WO2020042669A1 - Antimicrobial photocuring 3d printing material and preparation method therefor and 3d printing device - Google Patents

Antimicrobial photocuring 3d printing material and preparation method therefor and 3d printing device Download PDF

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Publication number
WO2020042669A1
WO2020042669A1 PCT/CN2019/086934 CN2019086934W WO2020042669A1 WO 2020042669 A1 WO2020042669 A1 WO 2020042669A1 CN 2019086934 W CN2019086934 W CN 2019086934W WO 2020042669 A1 WO2020042669 A1 WO 2020042669A1
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antibacterial
photocurable
printing
printing material
weight
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PCT/CN2019/086934
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French (fr)
Chinese (zh)
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崔可建
李屹
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深圳市绎立锐光科技开发有限公司
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Publication of WO2020042669A1 publication Critical patent/WO2020042669A1/en

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    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
    • C08F299/028—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight photopolymerisable compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B29C64/129—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask
    • B29C64/135—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • 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
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    • C08F2/00—Processes of polymerisation
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    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
    • C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
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    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
    • C08F299/0407—Processes of polymerisation
    • C08F299/0421—Polymerisation initiated by wave energy or particle radiation
    • C08F299/0428—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Definitions

  • the invention relates to an antibacterial light-curable 3D printing material, a preparation method thereof and a 3D printing device, and belongs to the technical field of 3D printing applications. Specifically, it relates to a visible light-curable 3D printing material with antibacterial properties, a preparation method thereof, and a 3D printing device for printing the material.
  • 3D Printing also known as Additive Manufacturing
  • Additive Manufacturing is an emerging Rapid Prototyping Technology. It has the advantages of high molding efficiency, low material cost, and the ability to produce complex structures. Unique manufacturing Its advantages have greatly favored it in various fields, and has been hailed as the symbol of the third industrial revolution.
  • 3D printing technology involves a variety of molding methods. Among them, based on the principle of light curing molding, the printing technologies based on light curing resin are mainly three-dimensional lithography (SLA), digital light processing (DLP), and three-dimensional inkjet printing (3DSP). . Compared with other molding methods, light-cured 3D printing molding has the advantages of high molding accuracy, fast printing speed, and mature technology. It is currently widely used in product design, mold manufacturing, scientific research, cultural creativity, medical treatment and many other fields.
  • SLA three-dimensional lithography
  • DLP digital light processing
  • 3DSP three-dimensional inkjet printing
  • UV curing 3D printing technology has the disadvantages of unfriendly environment, high equipment cost, and low curing depth.
  • the antibacterial components contained in them are often inorganic powders or particles. Certain absorption will greatly affect the efficiency of UV 3D printing.
  • the visible light 3D printing technology can effectively solve the problems caused by the above-mentioned ultraviolet curing, but there are currently no reports of antibacterial visible light curing 3D printing materials.
  • the photoinitiator in the material composition is mostly a small molecule compound.
  • the small molecule photoinitiator can easily migrate to the surface of the part and endanger the health of the contact.
  • Some researchers have grafted small molecule compounds with polymerizable monomers to synthesize macromolecular photoinitiators, which can effectively reduce the migration of photoinitiators, but the synthesis process of macromolecular photoinitiators is complicated and is not conducive to large-scale preparation.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide a new type of antibacterial photocurable 3D printing material.
  • the material can be cured by visible light, which can solve the problems of safety and printing efficiency in the prior art using ultraviolet light curing. ;
  • the material is cured by using a supramolecular photoinitiation system, which can solve the problem that conventional conventional photoinitiators easily migrate to the surface of the workpiece and cause health threats.
  • the material has significant antibacterial properties and can solve the problem that the product is easily infected with microorganisms. problem.
  • another object of the present invention is to provide a method for preparing the above-mentioned antibacterial photocurable 3D printing material, by which an antibacterial photocurable 3D printing material having the above-mentioned excellent properties can be prepared, and the preparation method is simple and easy.
  • a photoinitiator is prepared into a supramolecule through the action of host and guest, the preparation method is simple, and the anti-migration effect is remarkable.
  • another object of the present invention is to provide a 3D printing device for printing the above-mentioned antibacterial photocurable 3D printing material.
  • the 3D printing device can print using a visible light laser light source, and the container containing the material can heat the material.
  • the 3D printing device can improve the fluidity of the material.
  • the 3D printing device can print the antibacterial light-curable 3D printing material into a product with antibacterial properties and good mechanical properties.
  • the molding speed is fast, and one layer can be cured in 0.5 to 5 seconds. Printing efficiency High, overcome the problem of long curing time of similar UV products.
  • the present invention adopts the following technical solutions:
  • An antibacterial photocurable 3D printing material includes the following components by weight:
  • the supramolecular photo-initiating system is a supramolecular compound that is active under optical radiation in the visible light band.
  • the biocompatible oligomer / monomer is a biocompatible epoxy acrylate, a biocompatible polyurethane acrylate, a biocompatible polyester acrylate, a polyethylene glycol diacrylate, and a polyethylene glycol.
  • the supramolecular photoinitiation system is formed by a host compound encapsulating a guest photoinitiator;
  • the host compound is a gourd [5] urea, a gourd [6] urea, a gourd [7] urea, a gourd [8] ]
  • the guest photoinitiator is active below under visible light radiation
  • One or more of the following compounds dye / borate compounds, camphor quinone, fluorinated diphenyl titanocene, bis (pentafluorophenyl) titanocene, organic peroxy compounds.
  • the feeding ratio of the host compound of the supramolecular photoinitiation system and the guest photoinitiator of the supramolecular photoinitiation system is 1.1 to 1.5: 1, and more preferably 1.2 to 1.3: 1.
  • the content of the supramolecular photoinitiated system is preferably 0.5-2 parts by weight, and more preferably 0.5-1 parts by weight.
  • the antibacterial agent is silver (Ag) nanoparticles, cuprous oxide (Cu 2 O) nanoparticles, zinc oxide (ZnO) nanoparticles, magnesium-doped hydroxyphosphate lime, and quaternized mercapto silica.
  • silver (Ag) nanoparticles cuprous oxide (Cu 2 O) nanoparticles, zinc oxide (ZnO) nanoparticles, magnesium-doped hydroxyphosphate lime, and quaternized mercapto silica.
  • Cu 2 O cuprous oxide
  • ZnO zinc oxide
  • magnesium-doped hydroxyphosphate lime magnesium-doped hydroxyphosphate lime
  • quaternized mercapto silica quaternized mercapto silica.
  • the auxiliary agent includes one or more of a pigment, a filler, an antioxidant, an antifoaming agent, a wetting agent, and a polymerization inhibitor.
  • the pigment includes at least one of cadmium yellow, cadmium red, chrome green, and iron blue;
  • the filler includes at least one of calcium carbonate, barium sulfate, montmorillonite, and talc;
  • the consumer includes at least one of ethanol, n-butanol, silicone ester, and mineral oil;
  • the wetting agent includes at least one of lecithin, polyamino salt, and polyvalent carboxylic acid salt; and the polymerization inhibitor
  • the agent includes at least one of hydroxyanisole and hydroquinone.
  • the viscosity of the antibacterial photocurable 3D printing material at normal temperature is 20-5000 cps, preferably 100-1000 cps.
  • the present invention also provides a method for preparing the above-mentioned antibacterial photocurable 3D printing material, the method includes the following steps:
  • S1 Preparation of supramolecular photoinitiator system: Weigh a certain amount of small molecular photoinitiator as a guest photoinitiator, dissolve it in an organic solvent, adjust its pH value to 2 to 5, and then perform 500 to 2000 r / Add macrocyclic molecules as the host compound in batches while stirring at a min speed, continue stirring for 60 to 100 minutes after the host compound is added, then use a rotary evaporator to evaporate the solvent and dry to obtain the supramolecular photoinitiator system;
  • S2 Preparation of antibacterial photocurable 3D printing material: 100 parts by weight of biocompatible oligomer / monomer and 0.05-5 parts by weight of supramolecular light prepared in the above step S1 by mechanical stirring at normal temperature.
  • the initiation system, 5-30 parts by weight of the antibacterial agent, and 1-20 parts by weight of the admixture are mixed uniformly, and the stirring speed is 500-2000 r / min to obtain a homogeneous mixture, and the mixture is stored in a light-shielded state to obtain the antibacterial agent.
  • Photocurable 3D printing materials 100 parts by weight of biocompatible oligomer / monomer and 0.05-5 parts by weight of supramolecular light prepared in the above step S1 by mechanical stirring at normal temperature.
  • the initiation system, 5-30 parts by weight of the antibacterial agent, and 1-20 parts by weight of the admixture are mixed uniformly, and the stirring speed is 500-2000 r / min to obtain a homogeneous mixture, and the mixture is stored in
  • the pH value is preferably 2 to 3
  • the mixture is preferably stored in shading with tin foil.
  • the present invention further provides a 3D printing device for printing the above-mentioned antibacterial light-curable 3D printing material.
  • the 3D printing device includes a light source, a mechanical motion device, a software control system, and the antibacterial light.
  • the light source is a visible laser light source with a light emission wavelength of 415nm-750nm.
  • the container can heat the antibacterial photocurable 3D printing material contained therein, and the heating range is from room temperature to 70 ° C. to improve the fluidity of the antibacterial photocurable 3D printing material.
  • an antibacterial photocurable 3D printing material is provided.
  • the antibacterial light-curing 3D printing material is cured by visible light, which solves the problems of safety and printing efficiency in the prior art using ultraviolet light curing.
  • the printing speed is fast, and one layer can be cured in 0.5 to 5 seconds, which overcomes the UV similar
  • the problem of long product curing time uses a supramolecular photoinitiation system for curing, which solves the problem that the existing conventional photoinitiators easily migrate to the surface of the workpiece and cause a health threat to the contact of the workpiece.
  • the material has significant antibacterial properties, which solves the problem that the product is easily infected with microorganisms.
  • the present invention also provides a method for preparing the above-mentioned antibacterial photocurable 3D printing material, and an antibacterial photocurable 3D printing material having the above-mentioned excellent properties is prepared by the method, and the preparation method is simple and easy.
  • a photoinitiator is prepared into a supramolecule through the action of host and guest, the preparation method is simple, and the anti-migration effect is remarkable.
  • the present invention also provides a 3D printing device for printing the above-mentioned antibacterial light-curable 3D printing material.
  • the 3D printing device uses a visible light laser light source for printing, and the container containing the material can heat the material, which improves the material's performance. Flowability.
  • the 3D printing device can print the antibacterial photo-curable 3D printing material into a product with antibacterial performance and good mechanical properties. The printing efficiency is high and the molding speed is fast.
  • the present invention creatively proposes a visible light-curable 3D printing material having antibacterial properties for the first time.
  • the material includes the following parts by weight: 100 parts by weight of biocompatible oligomer / monomer, 0.05-5 parts by weight of supramolecular photoinitiation system, 5-30 parts by weight of antibacterial agent, and 1-20 parts by weight of auxiliary agent Wherein the supramolecular photo-initiating system is a supramolecular compound that is active under optical radiation in the visible light band.
  • the supramolecular photo-initiated system in the present invention is a molecular complex system formed by self-assembly of a host compound and a guest compound through non-chemical bonds. That is, the supramolecular photoinitiator system in the present invention is a molecular complex system formed by self-assembly of macrocyclic molecules and small molecule photoinitiators through non-chemical bonds. Specifically, the supramolecular photoinitiator system of the present invention is formed by a host compound encapsulating a guest photoinitiator. Photoinitiator is the key component that initiates the polymerization reaction of oligomers / monomers.
  • the compatibility between small molecule photoinitiators and polymers in printed products is different, which is easy. Migration to the surface, which will bring certain chemical pollution and affect the antibacterial performance of the product.
  • the introduction of a supramolecular system initiator in 3D printing materials can effectively prevent the migration of initiator components to the surface of the product, avoid chemical pollution, and reduce the impact on the antibacterial performance of the product.
  • the present invention by making the macrocyclic and small molecule photoinitiators into a supramolecular photoinitiator system, the strong motion of the photoinitiator molecule is suppressed, and the surface migration phenomenon of the small molecule photoinitiator can be effectively reduced, thereby avoiding the production of Contacts cause health problems.
  • the feeding ratio of the host compound and the guest compound may be 1.1 to 1.5: 1, and more preferably 1.2 to 1.3: 1.
  • the pH required for the host compound and the guest compound to be blended is 2 to 5, more preferably 2 to 3, and a too low or too high pH is not conducive to the blending of the host compound and the guest compound.
  • the host compound may be one or more of cucurbituril, cyclodextrin, calixarene, and crown ether
  • the guest compound may be one of the following compounds that are active under visible light radiation
  • the cyclodextrin may be one or more of ⁇ -cyclodextrin, ⁇ -cyclodextrin, and ⁇ -cyclodextrin
  • the quinone compound may be, for example, camphorquinone (CQ); the above
  • the titanocene-based compound may be fluorinated diphenyl titanocene (Irgacure 784), bis (pentafluorophenyl) titanocene, or the like.
  • the content of the supramolecular photoinitiated system contained in the antibacterial visible light-curable 3D printing material of the present invention is preferably 0.5-2 parts by weight, and more preferably 0.5-1 parts by weight to achieve good Photo-initiating effect.
  • the content of the initiator is too small, the initiation speed is slow, and when it is too much, waste is generated, and the initiation speed is no longer increased.
  • the biocompatible oligomer / monomer refers to an oligomer / monomer that does not produce rejection, irritation, toxicity, and other effects when in contact with biological tissues, and is an antibacterial photocurable 3D printing material.
  • the weight part is based on the biocompatible oligomer / monomer, and is 100 parts by weight as described above.
  • the biocompatible oligomer / monomer may be a biocompatible epoxy acrylate, a biocompatible polyurethane acrylate, a biocompatible polyester acrylate, a polyethylene glycol diacrylate (PEGDA), a polyethylene One or more of glycol dimethacrylate (PEGDMA), polypropylene glycol diacrylate (PPGDA), and polypropylene glycol dimethacrylate (PEGDA).
  • the antibacterial agent may be silver (Ag) nanoparticles, cuprous oxide (Cu 2 O) nanoparticles, zinc oxide (ZnO) nanoparticles, magnesium One or more of doped hydroxyphosphate lime and quaternized mercapto silica hybrid particles.
  • the absorption of ultraviolet light by the nanoparticles is related to the particle size. As long as it is a nano-level particle, it will inevitably absorb ultraviolet light. Experiments show that if you want to significantly reduce UV absorption, you can only increase the particle size of the particle until the particle is no longer a nanoparticle, which will lose the performance of the nanoparticle and no antibacterial effect. In addition, adjusting ultraviolet light intensity and irradiation time can solve the problem of light curing and antibacterial, but it cannot be used for 3D printing. The reason is that, first, if the intensity of ultraviolet light increases, the heat will increase.
  • the antibacterial nanoparticles have a strong absorption of UV light. Therefore, in order to complete 3D printing, the content of the antibacterial nanoparticles is very limited. In other words, the antibacterial performance of printed products obtained by 3D printing by UV curing is not excellent.
  • the present invention proposes a method of curing with visible light, because the depth of visible light curing is much higher than that of ultraviolet light, and the antibacterial nanoparticles do not have the above-mentioned problems existing in ultraviolet light curing during visible light curing. Therefore, by introducing visible light as a 3D printing light source, the present invention can greatly increase the amount of antibacterial agent added and play an excellent antibacterial effect.
  • Adding antibacterial components to polymer systems by co-doping is the simplest, most direct, and most efficient way to prepare antibacterial materials.
  • the antibacterial properties of polymer products are directly proportional to the content of antibacterial components added. That is, the higher the antibacterial content, the better the antibacterial property.
  • the excessive addition of antibacterial components will affect the solidification depth of the material, and then affect the printing efficiency.
  • the use of visible light as the curing light source can significantly increase the curing depth of the material, and thus can support a higher amount of antibacterial components.
  • ultraviolet light is used for curing. Since the antibacterial photosensitive material has a certain absorption of ultraviolet light, which will greatly affect the efficiency of UV 3D printing, its addition amount is limited.
  • the present invention adopts visible light curing, which does not have the problems in the prior art. Therefore, the content of the above-mentioned antibacterial agent in the present invention may be 5-30 parts by weight, preferably 20-30 parts by weight, which is much larger than UV. Addition in curing. Therefore, compared with the UV curing 3D printing material in the prior art, a better antibacterial effect can be achieved.
  • the aforementioned auxiliary agents may include pigments (such as cadmium yellow, cadmium red, chrome green, iron blue, etc.), fillers (such as calcium carbonate, barium sulfate, montmorillonite, talc, etc.), antioxidants, and defoamers. (Such as ethanol, n-butanol, silicone esters, mineral oil, etc.), wetting agents (such as lecithin, polyamino salts, polyvalent carboxylic acid salts, etc.), polymerization inhibitors (such as hydroxyanisole, terephthalic acid, etc.) Phenol, etc.).
  • the content of the auxiliary agent is 1-20 parts by weight, and preferably 2-5 parts by weight.
  • the viscosity of the above-mentioned antibacterial photo-curable 3D printing material at normal temperature is 20-5000 cps, preferably 100-1000 cps, and the surface tension is moderate, which is suitable for visible light 3D printing.
  • the antibacterial light-curable 3D printing material has a fast curing speed under visible light conditions, and one layer can be cured in 0.5 to 5 seconds.
  • the antibacterial photo-curable 3D printing material of the present invention has good antibacterial properties, and is suitable for the preparation of articles in technical fields with relatively high antibacterial requirements in fields such as medical treatment and food.
  • the antibacterial light-curable 3D printing material of the present invention can be cured by visible light, avoiding problems such as poor safety caused by curing with ultraviolet light, and the printing speed is fast.
  • One layer can be cured in 0.5 to 5 seconds, which overcomes UV Long curing time of similar products.
  • the antibacterial photocurable 3D printing material of the present invention uses a supramolecular photoinitiator system instead of the small molecule photoinitiator in the prior art, which overcomes the fact that the small molecule photoinitiator can easily migrate to the surface of the article and endanger the contacts. Health issues.
  • the present invention also provides a method for preparing the above-mentioned antibacterial photocurable 3D printing material, including the following steps:
  • S1 Preparation of supramolecular photoinitiation system: Weigh a certain amount of guest compound, that is, small molecule photoinitiator, dissolve it in an organic solvent (preferably low boiling point solvents such as dichloromethane, methanol, ethyl acetate, etc.) and adjust The pH value of the system is 2 to 5, and more preferably 2 to 3.
  • the main compound, that is, the macrocyclic molecule is added in batches under stirring at a speed of 500 to 2000 r / min, and the stirring is continued for 60 to 100 minutes after the addition is completed.
  • the antibacterial visible light-curable 3D printing material of the present invention can be prepared, and the preparation method is simple and easy.
  • a photoinitiator is prepared into a supramolecule through the action of host and guest, the preparation method is simple, and the anti-migration effect is remarkable.
  • the present invention also provides a device for printing the above-mentioned antibacterial photocurable 3D printing material, which includes a light source, a mechanical motion device, a software control system, and a container for accommodating the antibacterial photocurable 3D printing material of the present invention.
  • the light source in cooperation with the mechanical motion device and the software control system, cures the antibacterial photo-curable 3D printing material provided by the container layer by layer while forming it to form a product.
  • the light source is a visible laser light source with a light emission wavelength of 415nm-750nm. It should be noted that the light source must be a solid-color laser light source, such as a blue laser light source.
  • the container containing the 3D printing material has the ability to heat the stored material, and the heating range is from room temperature to 70 ° C, and the fluidity of the printing material is significantly improved under heating.
  • room temperature refers to a temperature range of 23 ° C to 30 ° C.
  • the antibacterial photocurable 3D printing material of the present invention can be printed into an article with antibacterial performance and good mechanical properties by using the above-mentioned 3D printing device, with high printing efficiency and high molding speed.
  • calabash [8] urea and camphorquinone (CQ) were weighed out according to a ratio of 1.2: 1 and added and mixed in this order.
  • Ethyl acetate was used as the solvent, stirred for 45min, the solvent was evaporated, dried, and reserved .
  • biocompatible bisphenol A type epoxy acrylate 70 parts by weight of polyethylene glycol diacrylate (PEGDA), 1 part by weight of gourd [8] urea, and camphorquinone (CQ) were assembled Supramolecular photo-initiated system, 10 parts by weight of silver nanoparticles, and 2 parts by weight of the additive are stirred and mixed uniformly in a normal temperature environment to obtain a homogeneous mixture, which is stored in a light-shielded state for future use.
  • PEGDA polyethylene glycol diacrylate
  • CQ camphorquinone
  • the above mixture is added to a material container of a visible light 3D printing device, printing is performed at a room temperature (25 ° C), a layer is printed at a speed of 2 s, and finally a product is printed.
  • the following methods can be used to detect whether the product surface contains a photoinitiator: (1) The high-performance liquid chromatography (HPLC) is used to determine the characteristic retention time of the photoinitiator, and a series of samples with different concentrations are prepared and generated.
  • HPLC high-performance liquid chromatography
  • Standard curve (2) After printing, the surface of the product is washed with organic solvent, and the washing solution is concentrated and quantitatively calibrated with a volumetric flask; (3) A sample is taken from the solution obtained in (2) above for HPLC detection, and compared with the standard HPLC The characteristic peaks are compared, and the photoinitiator content is calculated with reference to the standard curve of the sample; (4) After the product is stored for 10 days (days) and 30 days, the surface of the product is washed with organic solvents, and the washing solution is concentrated and quantitatively calibrated with a volumetric flask; Take a sample from the solution obtained in (4) above for HPLC detection and compare it with the HPLC characteristic peak of the standard, and calculate the photoinitiator content with reference to the standard curve of the sample; (6) Compare the residual on the surface of the product at 0d, 10d, and 30d Initiator content.
  • cyclodextrin and camphorquinone (CQ) are weighed out according to a ratio of 1.3: 1 and mixed in this order. Using ethanol as a solvent, stirring for 50 minutes, evaporating the solvent, drying, and preparing for use.
  • Supramolecular photoinitiator assembled with 50 parts by weight of biocompatible aliphatic urethane acrylate, 50 parts by weight of polyethylene glycol dimethacrylate (PEGDMA), 2 parts by weight of cyclodextrin and camphorquinone (CQ)
  • PEGDMA polyethylene glycol dimethacrylate
  • CQ camphorquinone
  • the system, 15 parts by weight of cuprous oxide nanoparticles, and 2 parts by weight of the auxiliary agent are stirred and mixed uniformly in a normal temperature environment to obtain a homogeneous mixture, which is stored in a light-shielded state for future use.
  • Embodiment 1 can be used to detect whether the surface of the product in this embodiment contains a photoinitiator, and the specific detection method will not be described again.
  • calixarene and fluorinated diphenyltacene (Irgacure 784) were weighed out according to a ratio of 1.5: 1 and mixed in this order. Acetone was selected as the solvent, stirred for 55 minutes, and the solvent was evaporated to dryness. Dry and set aside.
  • Embodiment 1 can be used to detect whether the surface of the product in this embodiment contains a photoinitiator, and the specific detection method will not be described again.
  • the antibacterial photocurable 3D printing material according to the present invention was prepared, and the antibacterial photocurable 3D printing material of the present invention was used to produce a good antibacterial property in a visible light environment.
  • 3D printed products there is no need to use environmentally unfriendly ultraviolet light during the preparation of the product, and the surface of the product does not have small molecular photoinitiators, which avoids health problems caused by the contact of the product, so it greatly improves the existing technology. .

Abstract

Provided in the present invention is an antimicrobial photocuring 3D printing material, the material comprising the following components in parts by weight: 100 parts by weight of biocompatible oligomers/monomers, 0.05-5 parts by weight of supramolecular photoinitiator systems, 5-30 parts by weight of antimicrobial agents, and 1-20 parts by weight of auxiliaries, wherein the supramolecular photoinitiator systems are active supramolecular compounds under light radiation of a visible light waveband.

Description

一种抗菌性光固化3D打印材料及其制备方法和3D打印装置Antibacterial light-curable 3D printing material, preparation method thereof and 3D printing device 技术领域Technical field
本发明涉及一种抗菌性光固化3D打印材料及其制备方法和3D打印装置，属于3D打印应用技术领域。具体涉及一种具有抗菌性的可见光固化3D打印材料及其制备方法和打印该材料的3D打印装置。The invention relates to an antibacterial light-curable 3D printing material, a preparation method thereof and a 3D printing device, and belongs to the technical field of 3D printing applications. Specifically, it relates to a visible light-curable 3D printing material with antibacterial properties, a preparation method thereof, and a 3D printing device for printing the material.
背景技术Background technique
3D打印(3D Printing)，又称增材制造(Additive Manufacturing)，是一项新兴的快速成型(Rapid Prototyping Manufacturing)技术，具有成型效率高、材料成本低、可制备复杂结构等优点，独特的制造优势使其受到了各领域极大青睐，被誉为第三次工业革命的标志。3D打印技术涉及多种成型方式，其中基于光固化成型原理，以光固化树脂为原料的打印技术主要有立体光刻(SLA)、数字光处理(DLP)和三维喷墨打印(3DSP)三种。与其他成型方式相比，光固化3D打印成型具有成型精度高、打印速度快及工艺成熟等优点，目前被广泛应用于产品设计、模具制造、科学研究、文化创意、医疗等众多领域。3D Printing, also known as Additive Manufacturing, is an emerging Rapid Prototyping Technology. It has the advantages of high molding efficiency, low material cost, and the ability to produce complex structures. Unique manufacturing Its advantages have greatly favored it in various fields, and has been hailed as the symbol of the third industrial revolution. 3D printing technology involves a variety of molding methods. Among them, based on the principle of light curing molding, the printing technologies based on light curing resin are mainly three-dimensional lithography (SLA), digital light processing (DLP), and three-dimensional inkjet printing (3DSP). . Compared with other molding methods, light-cured 3D printing molding has the advantages of high molding accuracy, fast printing speed, and mature technology. It is currently widely used in product design, mold manufacturing, scientific research, cultural creativity, medical treatment and many other fields.
随着3D打印技术应用的不断拓展，3D打印产品已广泛进入人们的生活。在现代高度文明的社会中，人们对于生活用品是否环保和是否有害健康有着极大重视，开发具有抗菌性能的3D打印材料非常重要。在医疗领域，许多医疗用品和设备都很容易感染微生物，随着3D打印的医疗辅具和医疗植入物数量日益增多，进一步加剧了对抗菌性3D打印材料的需求。目前已有少量抗菌性光固化3D打印材料的相关报道，但这些材料大都需要使用紫外(UV)光固化3D打印技术。紫外光固化3D打印技术具有环境不友好，设备成本高以及固化深度低等不足，尤其是对于上述抗菌性光敏材料，其所包含的抗菌组分，常常是无机粉体或颗粒，对紫外光具有一定的吸收，从而会极大影响UV 3D打印的效率。如专利CN107312133A和CN205668388U所述，可见光3D打印技术可有效解决 上述紫外光固化引起的问题，但目前并未有抗菌性可见光固化3D打印材料的报道。With the continuous expansion of 3D printing technology applications, 3D printing products have widely entered people's lives. In a modern and highly civilized society, people pay great attention to whether the daily necessities are environmentally friendly and harmful to health. It is very important to develop antibacterial 3D printing materials. In the medical field, many medical supplies and equipment are easily infected with microorganisms. With the increasing number of 3D printed medical aids and medical implants, the demand for antibacterial 3D printing materials has been further intensified. There have been a few reports about antibacterial photocurable 3D printing materials, but most of these materials require the use of ultraviolet (UV) photocurable 3D printing technology. UV curing 3D printing technology has the disadvantages of unfriendly environment, high equipment cost, and low curing depth. Especially for the above-mentioned antibacterial photosensitive materials, the antibacterial components contained in them are often inorganic powders or particles. Certain absorption will greatly affect the efficiency of UV 3D printing. As described in the patents CN107312133A and CN205668388U, the visible light 3D printing technology can effectively solve the problems caused by the above-mentioned ultraviolet curing, but there are currently no reports of antibacterial visible light curing 3D printing materials.
现有技术中，材料构成中的光引发剂多为小分子化合物，在打印形成制件后，小分子光引发剂很容易迁移到制件表面，危害到接触者的健康。有研究人员将小分子化合物与可聚合单体接枝，合成了大分子光引发剂，可以有效减少光引发剂的迁移，但大分子光引发剂合成过程复杂，不利于规模化制备。In the prior art, the photoinitiator in the material composition is mostly a small molecule compound. After printing to form a part, the small molecule photoinitiator can easily migrate to the surface of the part and endanger the health of the contact. Some researchers have grafted small molecule compounds with polymerizable monomers to synthesize macromolecular photoinitiators, which can effectively reduce the migration of photoinitiators, but the synthesis process of macromolecular photoinitiators is complicated and is not conducive to large-scale preparation.
因此，亟待解决的一个问题是开发出一种能够减少或避免小分子光引发剂迁移到制件表面的具有抗菌性的可见光固化3D打印材料。Therefore, a problem that needs to be solved urgently is to develop an antibacterial visible light curing 3D printing material which can reduce or avoid the migration of small molecule photoinitiators to the surface of the workpiece.
发明内容Summary of the Invention
技术问题technical problem
本发明的目的在于克服现有技术的不足，提供一种新型的抗菌性光固化3D打印材料，该材料通过可见光固化，能够解决现有技术中采用紫外光固化所存在的安全性和打印效率问题；该材料使用超分子光引发体系进行固化，能够解决现有的常规光引发剂容易迁移到制件表面而引起健康威胁的问题；该材料具有显著的抗菌性，能够解决制件容易感染微生物的问题。The purpose of the present invention is to overcome the shortcomings of the prior art and provide a new type of antibacterial photocurable 3D printing material. The material can be cured by visible light, which can solve the problems of safety and printing efficiency in the prior art using ultraviolet light curing. ; The material is cured by using a supramolecular photoinitiation system, which can solve the problem that conventional conventional photoinitiators easily migrate to the surface of the workpiece and cause health threats. The material has significant antibacterial properties and can solve the problem that the product is easily infected with microorganisms. problem.
另外，本发明的另一个目的在于提供一种上述抗菌性光固化3D打印材料的制备方法，通过该方法能够制备出具有上述优异性能的抗菌性光固化3D打印材料，制备方法简便易行。同时，在该方法中，将光引发剂通过主客体作用制备成超分子，制备方法简单，防迁移效果显著。In addition, another object of the present invention is to provide a method for preparing the above-mentioned antibacterial photocurable 3D printing material, by which an antibacterial photocurable 3D printing material having the above-mentioned excellent properties can be prepared, and the preparation method is simple and easy. At the same time, in this method, a photoinitiator is prepared into a supramolecule through the action of host and guest, the preparation method is simple, and the anti-migration effect is remarkable.
此外，本发明的再一个目的在于提供一种用于打印上述抗菌性光固化3D打印材料的3D打印装置，所述3D打印装置能够采用可见光激光光源进行打印，且容纳材料的容器可加热材料，能够改善材料的流动性，通过该3D打印装置能够将上述抗菌性光固化3D打印材料打印成具有抗菌性能和良好机械性能的制件，成型速度快，0.5～5s即可固化一层，打印效率高，克服了UV同类产品固化时间长的问题。In addition, another object of the present invention is to provide a 3D printing device for printing the above-mentioned antibacterial photocurable 3D printing material. The 3D printing device can print using a visible light laser light source, and the container containing the material can heat the material. The 3D printing device can improve the fluidity of the material. The 3D printing device can print the antibacterial light-curable 3D printing material into a product with antibacterial properties and good mechanical properties. The molding speed is fast, and one layer can be cured in 0.5 to 5 seconds. Printing efficiency High, overcome the problem of long curing time of similar UV products.
为实现上述目的，本发明采用如下技术方案：To achieve the above objective, the present invention adopts the following technical solutions:
一种抗菌性光固化3D打印材料，所述材料包括以下重量份的组分：An antibacterial photocurable 3D printing material, the material includes the following components by weight:
生物相容低聚物/单体100重量份，100 parts by weight of biocompatible oligomer / monomer,
超分子光引发体系0.05-5重量份，Supramolecular photoinitiation system 0.05-5 parts by weight,
抗菌剂5-30重量份，5-30 parts by weight of antibacterial agent,
助剂1-20重量份，1-20 parts by weight
其中所述超分子光引发体系为在可见光波段的光辐射下具有活性的超分子化合物。The supramolecular photo-initiating system is a supramolecular compound that is active under optical radiation in the visible light band.
根据本发明，所述生物相容低聚物/单体为生物相容环氧丙烯酸酯、生物相容聚氨酯丙烯酸酯、生物相容聚酯丙烯酸酯、聚乙二醇二丙烯酸酯、聚乙二醇二甲基丙烯酸酯、聚丙二醇二丙烯酸酯、聚丙二醇二甲基丙烯酸酯中的一种或多种。According to the present invention, the biocompatible oligomer / monomer is a biocompatible epoxy acrylate, a biocompatible polyurethane acrylate, a biocompatible polyester acrylate, a polyethylene glycol diacrylate, and a polyethylene glycol. One or more of alcohol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate.
根据本发明，所述超分子光引发体系为主体化合物包结客体光引发剂所形成的；所述主体化合物为葫芦[5]脲、葫芦[6]脲、葫芦[7]脲、葫芦[8]脲、α-环糊精、β-环糊精、γ-环糊精、杯环芳烃、冠醚中的一种或多种；所述客体光引发剂为下述在可见光辐射下具有活性的化合物中的一种或多种：染料/硼酸盐类化合物、樟脑醌、氟化二苯基二茂钛、双(五氟化苯基)二茂钛、有机过氧化合物。According to the present invention, the supramolecular photoinitiation system is formed by a host compound encapsulating a guest photoinitiator; the host compound is a gourd [5] urea, a gourd [6] urea, a gourd [7] urea, a gourd [8] ] One or more of urea, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, calixarene, crown ether; the guest photoinitiator is active below under visible light radiation One or more of the following compounds: dye / borate compounds, camphor quinone, fluorinated diphenyl titanocene, bis (pentafluorophenyl) titanocene, organic peroxy compounds.
根据本发明，所述超分子光引发体系的主体化合物和所述超分子光引发体系的客体光引发剂的加料比例为1.1～1.5:1，进一步优选为1.2～1.3:1。According to the present invention, the feeding ratio of the host compound of the supramolecular photoinitiation system and the guest photoinitiator of the supramolecular photoinitiation system is 1.1 to 1.5: 1, and more preferably 1.2 to 1.3: 1.
根据本发明，所述超分子光引发体系的含量优选为0.5-2重量份，进一步优选为0.5-1重量份。According to the present invention, the content of the supramolecular photoinitiated system is preferably 0.5-2 parts by weight, and more preferably 0.5-1 parts by weight.
根据本发明，所述抗菌剂为银(Ag)纳米颗粒、氧化亚铜(Cu 2O)纳米颗粒、氧化锌(ZnO)纳米颗粒、镁掺杂羟基磷石灰、季铵化巯基二氧化硅杂化粒子中的一种或多种。 According to the present invention, the antibacterial agent is silver (Ag) nanoparticles, cuprous oxide (Cu 2 O) nanoparticles, zinc oxide (ZnO) nanoparticles, magnesium-doped hydroxyphosphate lime, and quaternized mercapto silica. One or more of the particles.
根据本发明，所述助剂包括颜料、填料、抗氧化剂、消泡剂、润湿剂、阻聚剂中的一种或多种。According to the present invention, the auxiliary agent includes one or more of a pigment, a filler, an antioxidant, an antifoaming agent, a wetting agent, and a polymerization inhibitor.
根据本发明，所述颜料包括镉黄、镉红、铬绿、铁蓝中的至少一种；所述填料包括碳酸钙、硫酸钡、蒙脱土、滑石粉中的至少一种；所述消泡剂包括乙醇、正丁醇、有机硅酯、矿物油中的至少一种；所述润湿剂包括卵磷脂、多氨基盐、多价羧酸盐中的至少一种；以及所述阻聚剂包括羟基苯甲醚、对苯二酚中的至少一种。According to the present invention, the pigment includes at least one of cadmium yellow, cadmium red, chrome green, and iron blue; the filler includes at least one of calcium carbonate, barium sulfate, montmorillonite, and talc; the consumer The foaming agent includes at least one of ethanol, n-butanol, silicone ester, and mineral oil; the wetting agent includes at least one of lecithin, polyamino salt, and polyvalent carboxylic acid salt; and the polymerization inhibitor The agent includes at least one of hydroxyanisole and hydroquinone.
根据本发明，所述抗菌性光固化3D打印材料在常温下的粘度为20-5000cps，优选为100-1000cps。According to the present invention, the viscosity of the antibacterial photocurable 3D printing material at normal temperature is 20-5000 cps, preferably 100-1000 cps.
另一方面，本发明还提供了一种上述抗菌性光固化3D打印材料的制备方法，所述方法包括以下步骤：In another aspect, the present invention also provides a method for preparing the above-mentioned antibacterial photocurable 3D printing material, the method includes the following steps:
S1：制备超分子光引发体系：称取一定量的作为客体光引发剂的小分子光引发剂，将其溶解在有机溶剂中，调节其pH值为2～5，然后在进行500～2000r/min转速的搅拌的同时分批加入作为主体化合物的大环分子，在添加完主体化合物之后继续搅拌60～100min，然后使用旋转蒸发仪蒸去溶剂并干燥以得到所述超分子光引发体系；S1: Preparation of supramolecular photoinitiator system: Weigh a certain amount of small molecular photoinitiator as a guest photoinitiator, dissolve it in an organic solvent, adjust its pH value to 2 to 5, and then perform 500 to 2000 r / Add macrocyclic molecules as the host compound in batches while stirring at a min speed, continue stirring for 60 to 100 minutes after the host compound is added, then use a rotary evaporator to evaporate the solvent and dry to obtain the supramolecular photoinitiator system;
S2：制备抗菌性光固化3D打印材料：在常温下采用机械搅拌的方式将100重量份的生物相容低聚物/单体、0.05-5重量份的上述步骤S1中制备得到的超分子光引发体系、5-30重量份的抗菌剂、1-20重量份的助剂混合均匀，其中搅拌速度为500～2000r/min，从而得到均一态混合物，所述混合物遮光保存，从而得到所述抗菌性光固化3D打印材料，S2: Preparation of antibacterial photocurable 3D printing material: 100 parts by weight of biocompatible oligomer / monomer and 0.05-5 parts by weight of supramolecular light prepared in the above step S1 by mechanical stirring at normal temperature. The initiation system, 5-30 parts by weight of the antibacterial agent, and 1-20 parts by weight of the admixture are mixed uniformly, and the stirring speed is 500-2000 r / min to obtain a homogeneous mixture, and the mixture is stored in a light-shielded state to obtain the antibacterial agent. Photocurable 3D printing materials,
其中在所述步骤S1中，所述pH值优选为2～3，并且Wherein in the step S1, the pH value is preferably 2 to 3, and
其中在所述步骤S2中，所述混合物优选用锡箔纸遮光保存。Wherein, in the step S2, the mixture is preferably stored in shading with tin foil.
另一方面，本发明进一步提供了一种用于打印上述的抗菌性光固化3D打印材料的3D打印装置，所述3D打印装置包括光源、机械运动装置、软件控制系统和容纳所述抗菌性光固化3D打印材料的容器，所述光源在所述机械运动装置和所述软件控制系统的配合下，在使所述容器提供的所述抗菌性光固化3D打印材料逐层累积的同时将其固化以形成制件。In another aspect, the present invention further provides a 3D printing device for printing the above-mentioned antibacterial light-curable 3D printing material. The 3D printing device includes a light source, a mechanical motion device, a software control system, and the antibacterial light. A container for curing a 3D printing material, the light source, in cooperation with the mechanical motion device and the software control system, cures the antibacterial light-curable 3D printing material provided by the container layer by layer while curing it To form an article.
根据本发明，所述光源为发光波长为415nm-750nm的可见激光光源。According to the present invention, the light source is a visible laser light source with a light emission wavelength of 415nm-750nm.
根据本发明，所述容器能够加热所容纳的所述抗菌性光固化3D打印材料，加热范围为室温至70℃以改善所述抗菌性光固化3D打印材料的流动性。According to the present invention, the container can heat the antibacterial photocurable 3D printing material contained therein, and the heating range is from room temperature to 70 ° C. to improve the fluidity of the antibacterial photocurable 3D printing material.
本发明的有益效果：The beneficial effects of the present invention:
根据本发明的上述技术方案，提供了一种抗菌性光固化3D打印材料。所述抗菌性光固化3D打印材料通过可见光固化，解决了现有技术中采用紫外光固化所存在的安全性和打印效率问题，打印速度快，0.5～5s即可固化一层，克服了UV同类产品固化时间长的问题。该材料使用超分子光引发体系进行固化，解决了现有的常规光引发剂容易迁移到制件表面而引起制件接触者的健康威胁的问题。该材料具有显著的抗菌性，解决了制件容易感染微生物的问题。According to the above technical solution of the present invention, an antibacterial photocurable 3D printing material is provided. The antibacterial light-curing 3D printing material is cured by visible light, which solves the problems of safety and printing efficiency in the prior art using ultraviolet light curing. The printing speed is fast, and one layer can be cured in 0.5 to 5 seconds, which overcomes the UV similar The problem of long product curing time. The material uses a supramolecular photoinitiation system for curing, which solves the problem that the existing conventional photoinitiators easily migrate to the surface of the workpiece and cause a health threat to the contact of the workpiece. The material has significant antibacterial properties, which solves the problem that the product is easily infected with microorganisms.
此外，本发明还提供了一种上述抗菌性光固化3D打印材料的制备方法，通过该方法制备出了具有上述优异性能的抗菌性光固化3D打印材料，制备方法简便易行。同时，在该方法中，将光引发剂通过主客体作用制备成超分子，制备方法简单，防迁移效果显著。In addition, the present invention also provides a method for preparing the above-mentioned antibacterial photocurable 3D printing material, and an antibacterial photocurable 3D printing material having the above-mentioned excellent properties is prepared by the method, and the preparation method is simple and easy. At the same time, in this method, a photoinitiator is prepared into a supramolecule through the action of host and guest, the preparation method is simple, and the anti-migration effect is remarkable.
另外，本发明还提供了一种用于打印上述抗菌性光固化3D打印材料的3D打印装置，所述3D打印装置采用可见光激光光源进行打印，且容纳材料的容器可加热材料，改善了材料的流动性，通过该3D打印装置能够将上述抗菌性光固化3D打印材料打印成具有抗菌性能和良好机械性能的制件，打印效率高，成型速度快。In addition, the present invention also provides a 3D printing device for printing the above-mentioned antibacterial light-curable 3D printing material. The 3D printing device uses a visible light laser light source for printing, and the container containing the material can heat the material, which improves the material's performance. Flowability. The 3D printing device can print the antibacterial photo-curable 3D printing material into a product with antibacterial performance and good mechanical properties. The printing efficiency is high and the molding speed is fast.
具体实施方式detailed description
以下，更全面地说明本发明的一个或多个示例性实施例。如本领域技术人员应认识到的，只要不脱离本发明的精神或范围，可以以各种不同的方式对所述示例性实施例进行修改，本发明的精神或范围不限于本文所述的示例性实施例。In the following, one or more exemplary embodiments of the present invention are explained more fully. As those skilled in the art should realize, the described exemplary embodiments may be modified in various different ways without departing from the spirit or scope of the invention, and the spirit or scope of the invention is not limited to the examples described herein. Sexual embodiment.
如上所述，本发明创造性地首次提出了一种具有抗菌性的可见光固化3D打印材料。所述材料包括以下重量份的组分：生物相容低聚物/单体100重量份，超分子光引发体系0.05-5重量份，抗菌剂5-30重量份， 助剂1-20重量份，其中所述超分子光引发体系为在可见光波段的光辐射下具有活性的超分子化合物。As described above, the present invention creatively proposes a visible light-curable 3D printing material having antibacterial properties for the first time. The material includes the following parts by weight: 100 parts by weight of biocompatible oligomer / monomer, 0.05-5 parts by weight of supramolecular photoinitiation system, 5-30 parts by weight of antibacterial agent, and 1-20 parts by weight of auxiliary agent Wherein the supramolecular photo-initiating system is a supramolecular compound that is active under optical radiation in the visible light band.
需要指出的是，本发明中的超分子光引发体系是由主体化合物和客体化合物通过非化学键自组装而形成的分子配合物体系。也就是说，本发明中的超分子光引发体系是由大环分子和小分子光引发剂通过非化学键自组装而形成的分子配合物体系。具体地，本发明的超分子光引发体系是通过主体化合物包结客体光引发剂所形成。光引发剂是引发低聚物/单体发生聚合反应的关键组分，在使用常规小分子引发剂时，得到的打印制品中小分子光引发剂与聚合物之间的相容性存在差异，容易迁移到表面，从而带来一定的化学污染，影响制品的抗菌性能。在3D打印材料中引入超分子体系引发剂，可有效防止引发剂组分向制品表面的迁移，避免化学污染，减少对制品抗菌性能的影响。在本发明中，通过将大环分子和小分子光引发剂制成超分子光引发体系，抑制了光引发剂分子的强烈运动，可以有效减少小分子光引发剂的表面迁移现象，从而避免制件接触者产生健康问题。It should be noted that the supramolecular photo-initiated system in the present invention is a molecular complex system formed by self-assembly of a host compound and a guest compound through non-chemical bonds. That is, the supramolecular photoinitiator system in the present invention is a molecular complex system formed by self-assembly of macrocyclic molecules and small molecule photoinitiators through non-chemical bonds. Specifically, the supramolecular photoinitiator system of the present invention is formed by a host compound encapsulating a guest photoinitiator. Photoinitiator is the key component that initiates the polymerization reaction of oligomers / monomers. When conventional small molecule initiators are used, the compatibility between small molecule photoinitiators and polymers in printed products is different, which is easy. Migration to the surface, which will bring certain chemical pollution and affect the antibacterial performance of the product. The introduction of a supramolecular system initiator in 3D printing materials can effectively prevent the migration of initiator components to the surface of the product, avoid chemical pollution, and reduce the impact on the antibacterial performance of the product. In the present invention, by making the macrocyclic and small molecule photoinitiators into a supramolecular photoinitiator system, the strong motion of the photoinitiator molecule is suppressed, and the surface migration phenomenon of the small molecule photoinitiator can be effectively reduced, thereby avoiding the production of Contacts cause health problems.
需要说明的是，超分子光引发体系中的主体化合物和客体化合物理论比例为1:1，但考虑到反应的可逆性以及反应完整性，本发明将主体化合物稍作过量添加，过量过多则会产生浪费，增加成本。因此，为了制出具有合适性能的上述超分子光引发体系，所述主体化合物和所述客体化合物的加料比例可以为1.1～1.5:1，进一步优选可以为1.2～1.3:1。根据本发明，所述主体化合物和所述客体化合物配合所需要的pH值为2～5，进一步优选为2～3，pH过小或过大不利于主体化合物与客体化合物的配合。举例来说，所述主体化合物可以为葫芦脲、环糊精、杯环芳烃、冠醚中的一种或多种，并且所述客体化合物可以为下述在可见光辐射下具有活性的化合物中的一种或多种：染料/硼酸盐类化合物、醌类化合物、茂钛类化合物、有机过氧化合物。It should be noted that the theoretical ratio of the host compound and the guest compound in the supramolecular photo-initiated system is 1: 1, but in consideration of the reversibility of the reaction and the integrity of the reaction, the present invention adds the host compound slightly in excess. There will be waste and increase costs. Therefore, in order to produce the above-mentioned supramolecular photoinitiator system with suitable properties, the feeding ratio of the host compound and the guest compound may be 1.1 to 1.5: 1, and more preferably 1.2 to 1.3: 1. According to the present invention, the pH required for the host compound and the guest compound to be blended is 2 to 5, more preferably 2 to 3, and a too low or too high pH is not conducive to the blending of the host compound and the guest compound. For example, the host compound may be one or more of cucurbituril, cyclodextrin, calixarene, and crown ether, and the guest compound may be one of the following compounds that are active under visible light radiation One or more: dye / borate compounds, quinone compounds, titaniumcene compounds, organic peroxy compounds.
举例来说，上述环糊精可以为α-环糊精、β-环糊精、γ-环糊精中的一种或多种，并且上述醌类化合物例如可以为樟脑醌(CQ)；上述茂钛类化合物可以为氟化二苯基二茂钛(Irgacure 784)、双(五氟化苯基)二茂钛等。For example, the cyclodextrin may be one or more of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, and the quinone compound may be, for example, camphorquinone (CQ); the above The titanocene-based compound may be fluorinated diphenyl titanocene (Irgacure 784), bis (pentafluorophenyl) titanocene, or the like.
进一步需要指出的是，本发明的上述具有抗菌性的可见光固化3D打印材料中所含的超分子光引发体系的含量优选为0.5-2重量份，进一步优选为0.5-1重量份以实现良好的光引发效果，引发剂含量过少时，引发速度慢，过多时产生浪费，且不再增加引发速度。It should further be pointed out that the content of the supramolecular photoinitiated system contained in the antibacterial visible light-curable 3D printing material of the present invention is preferably 0.5-2 parts by weight, and more preferably 0.5-1 parts by weight to achieve good Photo-initiating effect. When the content of the initiator is too small, the initiation speed is slow, and when it is too much, waste is generated, and the initiation speed is no longer increased.
需要指出的是，所述生物相容低聚物/单体是指与生物组织相接触时，不产生排异、刺激、毒性等作用的低聚物/单体，抗菌性光固化3D打印材料一般用于打印与生物组织相接触的三维结构，因此需要选择与生物相容性好的低聚物及单体，减少打印制件与生物组织的排斥作用。根据本发明，为方便计量，以生物相容低聚物/单体为基准重量份，如上所述取为100重量份。其中所述生物相容低聚物/单体可以为生物相容环氧丙烯酸酯、生物相容聚氨酯丙烯酸酯、生物相容聚酯丙烯酸酯、聚乙二醇二丙烯酸酯(PEGDA)、聚乙二醇二甲基丙烯酸酯(PEGDMA)、聚丙二醇二丙烯酸酯(PPGDA)、聚丙二醇二甲基丙烯酸酯(PEGDA)中的一种或多种。It should be noted that the biocompatible oligomer / monomer refers to an oligomer / monomer that does not produce rejection, irritation, toxicity, and other effects when in contact with biological tissues, and is an antibacterial photocurable 3D printing material. Generally used for printing three-dimensional structures in contact with biological tissues, it is necessary to select oligomers and monomers with good biocompatibility to reduce the repellent effect of printed parts and biological tissues. According to the present invention, for convenience of measurement, the weight part is based on the biocompatible oligomer / monomer, and is 100 parts by weight as described above. The biocompatible oligomer / monomer may be a biocompatible epoxy acrylate, a biocompatible polyurethane acrylate, a biocompatible polyester acrylate, a polyethylene glycol diacrylate (PEGDA), a polyethylene One or more of glycol dimethacrylate (PEGDMA), polypropylene glycol diacrylate (PPGDA), and polypropylene glycol dimethacrylate (PEGDA).
为了使得本发明的抗菌性光固化3D打印材料具有良好的抗菌性能，上述抗菌剂可以为银(Ag)纳米颗粒、氧化亚铜(Cu 2O)纳米颗粒、氧化锌(ZnO)纳米颗粒、镁掺杂羟基磷石灰、季铵化巯基二氧化硅杂化粒子中的一种或多种。 In order to make the antibacterial photocurable 3D printing material of the present invention have good antibacterial performance, the antibacterial agent may be silver (Ag) nanoparticles, cuprous oxide (Cu 2 O) nanoparticles, zinc oxide (ZnO) nanoparticles, magnesium One or more of doped hydroxyphosphate lime and quaternized mercapto silica hybrid particles.
需要说明的是，纳米粒子对紫外光的吸收和粒径相关，只要是纳米级别的颗粒，都不免会进行紫外光吸收。实验表明，如果想要大幅减小UV吸收，那么只能增大颗粒粒径，直至该颗粒不再是纳米粒子，也就失去了纳米粒子的性能，起不到抗菌的效果了。另外，调节紫外光强度和辐照时间可以解决光固化抗菌问题，但是却不能用于3D打印。原因是，首先，如果紫外光强度升高，那么热量会增大，一方面3D打印制品很难承受如此大的热量，另一方面也很难找到大功率UV设备用于3D打印。其次，如果增加辐照时间，那么只能在一定固化厚度下有用，随着打印层厚度增加，增加UV光照时间作用很小，一味的增加时间，同样也不能完成3D打印。也就是说，利用UV固化进行3D打印，无法实现高掺杂抗菌材料的成型。It should be noted that the absorption of ultraviolet light by the nanoparticles is related to the particle size. As long as it is a nano-level particle, it will inevitably absorb ultraviolet light. Experiments show that if you want to significantly reduce UV absorption, you can only increase the particle size of the particle until the particle is no longer a nanoparticle, which will lose the performance of the nanoparticle and no antibacterial effect. In addition, adjusting ultraviolet light intensity and irradiation time can solve the problem of light curing and antibacterial, but it cannot be used for 3D printing. The reason is that, first, if the intensity of ultraviolet light increases, the heat will increase. On the one hand, it is difficult for 3D printed products to withstand such a large amount of heat, and on the other hand, it is difficult to find high-power UV equipment for 3D printing. Secondly, if the irradiation time is increased, it can only be useful at a certain curing thickness. As the thickness of the printing layer increases, the effect of increasing the UV light time is small. Blindly increasing the time cannot also complete 3D printing. In other words, the use of UV curing for 3D printing cannot achieve the molding of highly doped antibacterial materials.
由此可见，对于3D打印技术来说，如果采用UV固化方式，由于抗菌性纳米颗粒对于UV光具有强烈吸收，因此为了能够完成3D打印，抗菌性纳米颗粒的添加含量非常有限。也就是说，采用UV固化方式进行3D打印得到的打印制品的抗菌性能并不会优异。It can be seen that, for the 3D printing technology, if the UV curing method is adopted, the antibacterial nanoparticles have a strong absorption of UV light. Therefore, in order to complete 3D printing, the content of the antibacterial nanoparticles is very limited. In other words, the antibacterial performance of printed products obtained by 3D printing by UV curing is not excellent.
有鉴于此，本发明提出了利用可见光固化的方式，原因是可见光固化深度远远高于紫外光，并且抗菌性纳米粒子在可见光固化时不存在紫外光固化时所存在的上述问题。因此，本发明通过引进可见光作为3D打印光源，可大大提高抗菌剂添加量，起到优异的抗菌效果。In view of this, the present invention proposes a method of curing with visible light, because the depth of visible light curing is much higher than that of ultraviolet light, and the antibacterial nanoparticles do not have the above-mentioned problems existing in ultraviolet light curing during visible light curing. Therefore, by introducing visible light as a 3D printing light source, the present invention can greatly increase the amount of antibacterial agent added and play an excellent antibacterial effect.
在聚合物体系中通过共掺杂方式加入抗菌组分，是最简便、最直接、最高效的制备抗菌材料的方式，通常情况下聚合物制品的抗菌性与所添加的抗菌组分含量成正比，即抗菌剂含量越高，抗菌性越好。但抗菌组分添加量过多会影响材料的固化深度，进而影响打印效率。采用可见光为固化光光源，可以显著提高材料的固化深度，从而可以支持更高的抗菌组分添加量。在现有技术中，使用紫外光进行固化，由于抗菌性光敏材料对紫外光具有一定的吸收，从而会极大影响UV 3D打印的效率，所以其添加量有限。相对地，本发明采用可见光固化，不存在现有技术中的所述问题，因此本发明中的上述抗菌剂的含量可以为5-30重量份，优选为20-30重量份，远远大于UV固化中的添加量。因此，与现有技术中的UV固化3D打印材料相比可以实现更好的抗菌效果。Adding antibacterial components to polymer systems by co-doping is the simplest, most direct, and most efficient way to prepare antibacterial materials. Generally, the antibacterial properties of polymer products are directly proportional to the content of antibacterial components added. That is, the higher the antibacterial content, the better the antibacterial property. However, the excessive addition of antibacterial components will affect the solidification depth of the material, and then affect the printing efficiency. The use of visible light as the curing light source can significantly increase the curing depth of the material, and thus can support a higher amount of antibacterial components. In the prior art, ultraviolet light is used for curing. Since the antibacterial photosensitive material has a certain absorption of ultraviolet light, which will greatly affect the efficiency of UV 3D printing, its addition amount is limited. In contrast, the present invention adopts visible light curing, which does not have the problems in the prior art. Therefore, the content of the above-mentioned antibacterial agent in the present invention may be 5-30 parts by weight, preferably 20-30 parts by weight, which is much larger than UV. Addition in curing. Therefore, compared with the UV curing 3D printing material in the prior art, a better antibacterial effect can be achieved.
根据本发明，上述助剂可以包括颜料(如镉黄、镉红、铬绿、铁蓝等)、填料(如碳酸钙、硫酸钡、蒙脱土、滑石粉等)、抗氧化剂、消泡剂(如乙醇、正丁醇、有机硅酯、矿物油等)、润湿剂(如卵磷脂、多氨基盐、多价羧酸盐等)、阻聚剂(如羟基苯甲醚、对苯二酚等)中的一种或多种。另外，上述助剂的含量为1-20重量份，优选为2-5重量份。According to the present invention, the aforementioned auxiliary agents may include pigments (such as cadmium yellow, cadmium red, chrome green, iron blue, etc.), fillers (such as calcium carbonate, barium sulfate, montmorillonite, talc, etc.), antioxidants, and defoamers. (Such as ethanol, n-butanol, silicone esters, mineral oil, etc.), wetting agents (such as lecithin, polyamino salts, polyvalent carboxylic acid salts, etc.), polymerization inhibitors (such as hydroxyanisole, terephthalic acid, etc.) Phenol, etc.). In addition, the content of the auxiliary agent is 1-20 parts by weight, and preferably 2-5 parts by weight.
需要指出的是，上述抗菌性光固化3D打印材料在常温下的粘度为20-5000cps，优选为100-1000cps，表面张力适中，适合用于可见光3D打印。It should be noted that the viscosity of the above-mentioned antibacterial photo-curable 3D printing material at normal temperature is 20-5000 cps, preferably 100-1000 cps, and the surface tension is moderate, which is suitable for visible light 3D printing.
根据本发明，上述抗菌性光固化3D打印材料在可见光条件下的固化速度快，0.5～5s即可固化一层。According to the present invention, the antibacterial light-curable 3D printing material has a fast curing speed under visible light conditions, and one layer can be cured in 0.5 to 5 seconds.
如上所述，本发明的抗菌性光固化3D打印材料具有良好的抗菌性，适用于对诸如医疗、食品等领域抗菌性要求比较高的技术领域的制件的制备。此外，本发明的抗菌性光固化3D打印材料可以通过可见光来固化，避免了使用紫外光来固化而导致的安全性差等问题，并且打印速度快，0.5～5s即可固化一层，克服了UV同类产品固化时间长的问题。另外，本发明的抗菌性光固化3D打印材料使用超分子光引发体系代替现有技术中的小分子光引发剂，克服了小分子光引发剂很容易迁移到制件表面，危害到接触者的健康的问题。As mentioned above, the antibacterial photo-curable 3D printing material of the present invention has good antibacterial properties, and is suitable for the preparation of articles in technical fields with relatively high antibacterial requirements in fields such as medical treatment and food. In addition, the antibacterial light-curable 3D printing material of the present invention can be cured by visible light, avoiding problems such as poor safety caused by curing with ultraviolet light, and the printing speed is fast. One layer can be cured in 0.5 to 5 seconds, which overcomes UV Long curing time of similar products. In addition, the antibacterial photocurable 3D printing material of the present invention uses a supramolecular photoinitiator system instead of the small molecule photoinitiator in the prior art, which overcomes the fact that the small molecule photoinitiator can easily migrate to the surface of the article and endanger the contacts. Health issues.
另外，本发明还提供了一种上述抗菌性光固化3D打印材料的制备方法，包括如下步骤：In addition, the present invention also provides a method for preparing the above-mentioned antibacterial photocurable 3D printing material, including the following steps:
S1：超分子光引发体系的制备：称取一定量的客体化合物，即小分子光引发剂，将其溶解在有机溶剂(优选二氯甲烷、甲醇、乙酸乙酯等低沸点溶剂)中，调节体系pH值至2～5，进一步优选为2～3，在500～2000r/min转速的搅拌下分批加入主体化合物，即大环分子，加料完毕后继续搅拌60～100min，使用旋转蒸发仪，在减压情况下保持温度在30～50℃蒸去溶剂，取出样品后在真空干燥箱60～80℃下干燥8～12h以得到所述超分子光引发体系。需要指出的是，在该步骤中，各组分的添加顺序不能改变，否则将会影响到超分子光引发体系的形成，对最终的防迁移造成影响。S1: Preparation of supramolecular photoinitiation system: Weigh a certain amount of guest compound, that is, small molecule photoinitiator, dissolve it in an organic solvent (preferably low boiling point solvents such as dichloromethane, methanol, ethyl acetate, etc.) and adjust The pH value of the system is 2 to 5, and more preferably 2 to 3. The main compound, that is, the macrocyclic molecule is added in batches under stirring at a speed of 500 to 2000 r / min, and the stirring is continued for 60 to 100 minutes after the addition is completed. Using a rotary evaporator, The solvent was distilled off at a temperature of 30-50 ° C under reduced pressure, and the sample was taken out and dried in a vacuum drying box at 60-80 ° C for 8-12 hours to obtain the supramolecular photoinitiator system. It should be noted that in this step, the order of addition of each component cannot be changed, otherwise the formation of supramolecular photo-initiated system will be affected, and the final anti-migration will be affected.
S2：3D打印材料的制备：在常温环境中采用机械搅拌的方式将100重量份的生物相容低聚物/单体、0.05-5重量份的上述步骤S1中制备得到的超分子光引发体系、5-30重量份的抗菌剂、1-20重量份的助剂混合均匀，其中搅拌速度为500～2000r/min，得到均一态混合物，混合物遮光保存，优选用锡箔纸遮光保存，从而得到所述抗菌性光固化3D打印材料。需要指出的是，在该步骤中，上述组分添加顺序的改变不会对材料性能造成影响。S2: Preparation of 3D printing material: 100 parts by weight of biocompatible oligomers / monomers and 0.05-5 parts by weight of the supramolecular photoinitiator system prepared in the above step S1 by mechanical stirring in a normal temperature environment 5 to 30 parts by weight of antibacterial agent and 1 to 20 parts by weight of the admixture are uniformly mixed, wherein the stirring speed is 500 to 2000 r / min to obtain a homogeneous mixture, and the mixture is stored in a light-shielded state, preferably in a tin foil paper, so as to obtain The antibacterial photocurable 3D printing material is described. It should be noted that, in this step, the change of the above-mentioned component addition order will not affect the material properties.
通过使用上述方法可以制备出本发明的具有抗菌性的可见光固化3D打印材料，制备方法简便易行。同时，在该方法中，将光引发剂通过主客体作用制备成超分子，制备方法简单，防迁移效果显著。By using the above method, the antibacterial visible light-curable 3D printing material of the present invention can be prepared, and the preparation method is simple and easy. At the same time, in this method, a photoinitiator is prepared into a supramolecule through the action of host and guest, the preparation method is simple, and the anti-migration effect is remarkable.
另外，本发明还提出了一种用于打印上述抗菌性光固化3D打印材料的装置，其包括光源、机械运动装置、软件控制系统和容纳本发明的抗菌性光固化3D打印材料的容器，所述光源在所述机械运动装置和所述软件控制系统的配合下，在使所述容器提供的所述抗菌性光固化3D打印材料逐层累积的同时将其固化以形成制件。根据本发明，所述光源为发光波长为415nm-750nm的可见激光光源。需要指出的是，所述光源必须为纯色激光光源，例如蓝色激光光源。根据本发明，所述容纳3D打印材料的容器，具有加热所容纳的材料的能力，加热范围为室温至70℃，加热下打印用材料的流动性得到明显改善。在本发明中，室温指的是23℃至30℃的温度范围。In addition, the present invention also provides a device for printing the above-mentioned antibacterial photocurable 3D printing material, which includes a light source, a mechanical motion device, a software control system, and a container for accommodating the antibacterial photocurable 3D printing material of the present invention. The light source, in cooperation with the mechanical motion device and the software control system, cures the antibacterial photo-curable 3D printing material provided by the container layer by layer while forming it to form a product. According to the present invention, the light source is a visible laser light source with a light emission wavelength of 415nm-750nm. It should be noted that the light source must be a solid-color laser light source, such as a blue laser light source. According to the present invention, the container containing the 3D printing material has the ability to heat the stored material, and the heating range is from room temperature to 70 ° C, and the fluidity of the printing material is significantly improved under heating. In the present invention, room temperature refers to a temperature range of 23 ° C to 30 ° C.
根据本发明，利用上述3D打印装置能够将本发明的抗菌性光固化3D打印材料打印成具有抗菌性能和良好机械性能的制件，打印效率高，成型速度快。According to the present invention, the antibacterial photocurable 3D printing material of the present invention can be printed into an article with antibacterial performance and good mechanical properties by using the above-mentioned 3D printing device, with high printing efficiency and high molding speed.
以下，将参照具体实施例来对本发明进行详细说明。Hereinafter, the present invention will be described in detail with reference to specific embodiments.
实施例1Example 1
在本实施例中，按照1.2:1的比例称取葫芦[8]脲与樟脑醌(CQ)并按该顺序进行加料混合，选用乙酸乙酯作为溶剂，搅拌45min，蒸干溶剂，干燥，备用。In this example, the calabash [8] urea and camphorquinone (CQ) were weighed out according to a ratio of 1.2: 1 and added and mixed in this order. Ethyl acetate was used as the solvent, stirred for 45min, the solvent was evaporated, dried, and reserved .
然后，将30重量份的生物相容双酚A型环氧丙烯酸酯、70重量份的聚乙二醇二丙烯酸酯(PEGDA)、1重量份的葫芦[8]脲与樟脑醌(CQ)组装的超分子光引发体系、10重量份的银纳米颗粒、2重量份的助剂在常温环境中搅拌混合均匀，得到均一态混合物，遮光保存备用。Then, 30 parts by weight of biocompatible bisphenol A type epoxy acrylate, 70 parts by weight of polyethylene glycol diacrylate (PEGDA), 1 part by weight of gourd [8] urea, and camphorquinone (CQ) were assembled Supramolecular photo-initiated system, 10 parts by weight of silver nanoparticles, and 2 parts by weight of the additive are stirred and mixed uniformly in a normal temperature environment to obtain a homogeneous mixture, which is stored in a light-shielded state for future use.
将上述混合物加入到可见光3D打印装置的材料容器中，保持室温(25℃)打印，打印一层速度为2s，最后打印成制品。The above mixture is added to a material container of a visible light 3D printing device, printing is performed at a room temperature (25 ° C), a layer is printed at a speed of 2 s, and finally a product is printed.
可以通过以下方法来检测本实施例中的制品表面是否含有光引发剂：(1)采用高效液相色谱法(HPLC)测定光引发剂的特征保留时间，配制一系列不同浓度的样品，并生成标准曲线；(2)打印完成后，用有机溶剂洗涤制品表面，浓缩洗涤液后用容量瓶定量标定；(3)从上述(2)所得溶液中取样品进行HPLC检测，并与标准品的HPLC特征峰进行对比， 参考样品的标准曲线计算光引发剂含量；(4)在制品储存10d(天)、30d后，用有机溶剂洗涤制品表面，浓缩洗涤液后用容量瓶定量标定；(5)从上述(4)所得溶液中取样品进行HPLC检测，并与标准品的HPLC特征峰进行对比，参考样品的标准曲线计算光引发剂含量；(6)对比0d、10d、30d时制品表面残留的引发剂含量。The following methods can be used to detect whether the product surface contains a photoinitiator: (1) The high-performance liquid chromatography (HPLC) is used to determine the characteristic retention time of the photoinitiator, and a series of samples with different concentrations are prepared and generated. Standard curve; (2) After printing, the surface of the product is washed with organic solvent, and the washing solution is concentrated and quantitatively calibrated with a volumetric flask; (3) A sample is taken from the solution obtained in (2) above for HPLC detection, and compared with the standard HPLC The characteristic peaks are compared, and the photoinitiator content is calculated with reference to the standard curve of the sample; (4) After the product is stored for 10 days (days) and 30 days, the surface of the product is washed with organic solvents, and the washing solution is concentrated and quantitatively calibrated with a volumetric flask; Take a sample from the solution obtained in (4) above for HPLC detection and compare it with the HPLC characteristic peak of the standard, and calculate the photoinitiator content with reference to the standard curve of the sample; (6) Compare the residual on the surface of the product at 0d, 10d, and 30d Initiator content.
根据测试，本实施例的打印制件表面在0d到30day内未检测出小分子光引发剂。同时，本实施例的打印制件具有良好的抗菌性。According to tests, no small-molecule photoinitiator was detected on the surface of the printed article in this example within 0d to 30days. At the same time, the printed article of this embodiment has good antibacterial properties.
实施例2Example 2
在本实施例中，按照1.3:1的比例称取环糊精与樟脑醌(CQ)并按该顺序进行加料混合，选用乙醇作为溶剂，搅拌50min，蒸干溶剂，干燥，备用。In this embodiment, cyclodextrin and camphorquinone (CQ) are weighed out according to a ratio of 1.3: 1 and mixed in this order. Using ethanol as a solvent, stirring for 50 minutes, evaporating the solvent, drying, and preparing for use.
将50重量份的生物相容脂肪族聚氨酯丙烯酸酯、50重量份的聚乙二醇二甲基丙烯酸酯(PEGDMA)、2重量份的环糊精与樟脑醌(CQ)组装的超分子光引发体系、15重量份的氧化亚铜纳米颗粒、2重量份的助剂在常温环境中搅拌混合均匀，得到均一态混合物，遮光保存备用。Supramolecular photoinitiator assembled with 50 parts by weight of biocompatible aliphatic urethane acrylate, 50 parts by weight of polyethylene glycol dimethacrylate (PEGDMA), 2 parts by weight of cyclodextrin and camphorquinone (CQ) The system, 15 parts by weight of cuprous oxide nanoparticles, and 2 parts by weight of the auxiliary agent are stirred and mixed uniformly in a normal temperature environment to obtain a homogeneous mixture, which is stored in a light-shielded state for future use.
将上述混合物加入到可见光3D打印装置的材料容器中，调整材料温度到35℃后打印，打印一层速度为2s，最后打印成制品。Add the above mixture to a material container of a visible light 3D printing device, adjust the material temperature to 35 ° C, print, print a layer at a speed of 2s, and finally print it into a product.
同样可以采用实施例1中的检测方法来检测本实施例中的制品表面是否含有光引发剂，具体检测方法不再赘述。Similarly, the detection method in Embodiment 1 can be used to detect whether the surface of the product in this embodiment contains a photoinitiator, and the specific detection method will not be described again.
根据测试，本实施例的打印制件表面在0d到30day内未检测出小分子光引发剂。同时，本实施例的打印制件具有良好的抗菌性。According to tests, no small-molecule photoinitiator was detected on the surface of the printed article in this example within 0d to 30days. At the same time, the printed article of this embodiment has good antibacterial properties.
实施例3Example 3
在本实施例中，按照1.5:1的比例称取杯环芳烃与氟化二苯基二茂钛(Irgacure 784)并按该顺序进行加料混合，选用丙酮作为溶剂，搅拌55min，蒸干溶剂，干燥，备用。In this example, calixarene and fluorinated diphenyltacene (Irgacure 784) were weighed out according to a ratio of 1.5: 1 and mixed in this order. Acetone was selected as the solvent, stirred for 55 minutes, and the solvent was evaporated to dryness. Dry and set aside.
将70重量份的生物相容聚酯丙烯酸酯、30重量份的聚丙二醇二丙烯酸酯(PPGDA)、1.5重量份的杯环芳烃与氟化二苯基二茂钛(Irgacure  784)、10重量份的氧化锌纳米颗粒、2重量份的助剂在常温环境中搅拌混合均匀，得到均一态混合物，遮光保存备用。70 parts by weight of biocompatible polyester acrylate, 30 parts by weight of polypropylene glycol diacrylate (PPGDA), 1.5 parts by weight of calixarene and fluorinated diphenyltitanocene (Irgacure 784), 10 parts by weight The zinc oxide nanoparticles and 2 parts by weight of the additive are stirred and mixed uniformly in a normal temperature environment to obtain a homogeneous mixture, which is stored in a light-shielded state for future use.
将上述混合物加入到可见光3D打印装置的材料容器中，调整材料温度到55℃后打印，打印一层速度为2s，最后打印成制品。Add the above mixture to a material container of a visible light 3D printing device, adjust the material temperature to 55 ° C, print, print a layer at a speed of 2s, and finally print into a product.
同样可以采用实施例1中的检测方法来检测本实施例中的制品表面是否含有光引发剂，具体检测方法不再赘述。Similarly, the detection method in Embodiment 1 can be used to detect whether the surface of the product in this embodiment contains a photoinitiator, and the specific detection method will not be described again.
根据测试，本实施例的打印制件表面在0d到30day内未检测出小分子光引发剂。同时，本实施例的打印制件具有良好的抗菌性。According to tests, no small-molecule photoinitiator was detected on the surface of the printed article in this example within 0d to 30days. At the same time, the printed article of this embodiment has good antibacterial properties.
由此可见，在上述各个实施例中，都制备出了根据本发明的抗菌性光固化3D打印材料，并且使用本发明的抗菌性光固化3D打印材料在可见光环境下制备出了具有良好抗菌性的3D打印制品，制品制备过程中不需要使用环境不友好的紫外光，该制品表面没有小分子光引发剂，避免了制件接触者产生健康问题，因此对现有技术提供了极大的改进。It can be seen that in each of the above embodiments, the antibacterial photocurable 3D printing material according to the present invention was prepared, and the antibacterial photocurable 3D printing material of the present invention was used to produce a good antibacterial property in a visible light environment. 3D printed products, there is no need to use environmentally unfriendly ultraviolet light during the preparation of the product, and the surface of the product does not have small molecular photoinitiators, which avoids health problems caused by the contact of the product, so it greatly improves the existing technology. .
虽然具体示出和说明了本发明构思的示例性实施例，但是本领域普通技术人员将会理解，在不脱离所附权利要求书的精神和范围的情况下，可以在其中产生形式和细节上的改变。Although exemplary embodiments of the present inventive concept have been shown and described in detail, those of ordinary skill in the art will understand that forms and details may be made therein without departing from the spirit and scope of the appended claims. Change.

Claims (13)

  1. 一种抗菌性光固化3D打印材料，所述材料包括以下重量份的组分：An antibacterial photocurable 3D printing material, the material includes the following components by weight:
    生物相容低聚物/单体100重量份，100 parts by weight of biocompatible oligomer / monomer,
    超分子光引发体系0.05-5重量份，Supramolecular photoinitiation system 0.05-5 parts by weight,
    抗菌剂5-30重量份，5-30 parts by weight of antibacterial agent,
    助剂1-20重量份，1-20 parts by weight
    其中所述超分子光引发体系为在可见光波段的光辐射下具有活性的超分子化合物。The supramolecular photo-initiating system is a supramolecular compound that is active under optical radiation in the visible light band.
  2. 如权利要求1所述的抗菌性光固化3D打印材料，其特征在于，The antibacterial photocurable 3D printing material according to claim 1, wherein:
    所述生物相容低聚物/单体为生物相容环氧丙烯酸酯、生物相容聚氨酯丙烯酸酯、生物相容聚酯丙烯酸酯、聚乙二醇二丙烯酸酯、聚乙二醇二甲基丙烯酸酯、聚丙二醇二丙烯酸酯、聚丙二醇二甲基丙烯酸酯中的一种或多种。The biocompatible oligomer / monomer is biocompatible epoxy acrylate, biocompatible polyurethane acrylate, biocompatible polyester acrylate, polyethylene glycol diacrylate, polyethylene glycol dimethyl One or more of acrylate, polypropylene glycol diacrylate, and polypropylene glycol dimethacrylate.
  3. 如权利要求1所述的抗菌性光固化3D打印材料，其特征在于，所述超分子光引发体系为主体化合物包结客体光引发剂所形成的；所述主体化合物为葫芦[5]脲、葫芦[6]脲、葫芦[7]脲、葫芦[8]脲、α-环糊精、β-环糊精、γ-环糊精、杯环芳烃、冠醚中的一种或多种；所述客体光引发剂为下述在可见光辐射下具有活性的化合物中的一种或多种：染料/硼酸盐类化合物、樟脑醌、氟化二苯基二茂钛、双(五氟化苯基)二茂钛、有机过氧化合物。The antibacterial photocurable 3D printing material according to claim 1, wherein the supramolecular photoinitiation system is formed by a host compound encapsulating a guest photoinitiator; the host compound is a gourd [5] urea, Cucurbit [6] urea, Cucurbit [7] urea, Cucurbit [8] urea, one or more of α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, calixarene, crown ether; The guest photoinitiator is one or more of the following compounds which are active under visible light radiation: dyes / borate compounds, camphorquinone, fluorinated diphenyl titanocene, bis (pentafluorinated benzene) Group) titanocene, organic peroxy compounds.
  4. 如权利要求3所述的抗菌性光固化3D打印材料，其特征在于，The antibacterial photocurable 3D printing material according to claim 3, wherein
    所述超分子光引发体系的主体化合物和所述超分子光引发体系的客体光引发剂的加料比例为1.1～1.5:1，进一步优选为1.2～1.3:1。The feeding ratio of the host compound of the supramolecular photoinitiation system and the guest photoinitiator of the supramolecular photoinitiation system is 1.1 to 1.5: 1, and more preferably 1.2 to 1.3: 1.
  5. 如权利要求1所述的抗菌性光固化3D打印材料，其特征在于，The antibacterial photocurable 3D printing material according to claim 1, wherein:
    所述超分子光引发体系的含量优选为0.5-2重量份，进一步优选为0.5-1重量份。The content of the supramolecular photoinitiation system is preferably 0.5-2 parts by weight, and more preferably 0.5-1 part by weight.
  6. 如权利要求1所述的抗菌性光固化3D打印材料，其特征在于，The antibacterial photocurable 3D printing material according to claim 1, wherein:
    所述抗菌剂为银(Ag)纳米颗粒、氧化亚铜(Cu 2O)纳米颗粒、氧化锌(ZnO)纳米颗粒、镁掺杂羟基磷石灰、季铵化巯基二氧化硅杂化粒子中的一种或多种。 The antibacterial agent is one of silver (Ag) nanoparticles, cuprous oxide (Cu 2 O) nanoparticles, zinc oxide (ZnO) nanoparticles, magnesium-doped hydroxyphosphate lime, and quaternized mercapto silica hybrid particles. One or more.
  7. 如权利要求1所述的抗菌性光固化3D打印材料，其特征在于，The antibacterial photocurable 3D printing material according to claim 1, wherein:
    所述助剂包括颜料、填料、抗氧化剂、消泡剂、润湿剂、阻聚剂中的一种或多种。The auxiliary agent includes one or more of pigments, fillers, antioxidants, defoamers, wetting agents, and polymerization inhibitors.
  8. 如权利要求7所述的抗菌性光固化3D打印材料，其特征在于，The antibacterial photocurable 3D printing material according to claim 7, wherein:
    所述颜料包括镉黄、镉红、铬绿、铁蓝中的至少一种；所述填料包括碳酸钙、硫酸钡、蒙脱土、滑石粉中的至少一种；所述消泡剂包括乙醇、正丁醇、有机硅酯、矿物油中的至少一种；所述润湿剂包括卵磷脂、多氨基盐、多价羧酸盐中的至少一种；以及所述阻聚剂包括羟基苯甲醚、对苯二酚中的至少一种。The pigment includes at least one of cadmium yellow, cadmium red, chrome green, and iron blue; the filler includes at least one of calcium carbonate, barium sulfate, montmorillonite, and talc; the defoamer includes ethanol At least one of n-butanol, silicone ester, and mineral oil; the wetting agent includes at least one of lecithin, polyamino salt, and polyvalent carboxylic acid salt; and the polymerization inhibitor includes hydroxybenzene At least one of methyl ether and hydroquinone.
  9. 如权利要求1所述的抗菌性光固化3D打印材料，其特征在于，The antibacterial photocurable 3D printing material according to claim 1, wherein:
    所述抗菌性光固化3D打印材料在常温下的粘度为20-5000cps，优选为100-1000cps。The viscosity of the antibacterial photocurable 3D printing material at normal temperature is 20-5000 cps, preferably 100-1000 cps.
  10. 一种如权利要求1～9中任一项所述的抗菌性光固化3D打印材料的制备方法，所述方法包括以下步骤：A method for preparing an antibacterial photocurable 3D printing material according to any one of claims 1 to 9, the method comprising the following steps:
    S1：制备超分子光引发体系：称取一定量的作为客体光引发剂的小分子光引发剂，将其溶解在有机溶剂中，调节其pH值为2～5，然后在进行500～2000r/min转速的搅拌的同时分批加入作为主体化合物的大环分子，在添加完主体化合物之后继续搅拌60～100min，然后使用旋转蒸发仪蒸去溶剂并干燥以得到所述超分子光引发体系；S1: Preparation of supramolecular photoinitiator system: Weigh a certain amount of small molecular photoinitiator as a guest photoinitiator, dissolve it in an organic solvent, adjust its pH value to 2 to 5, and then perform 500 to 2000 r / Add macrocyclic molecules as the host compound in batches while stirring at a min speed, continue stirring for 60 to 100 minutes after the host compound is added, then use a rotary evaporator to evaporate the solvent and dry to obtain the supramolecular photoinitiator system;
    S2：制备抗菌性光固化3D打印材料：在常温下采用机械搅拌的方式将100重量份的生物相容低聚物/单体、0.05-5重量份的上述步骤S1中制备得到的超分子光引发体系、5-30重量份的抗菌剂、1-20重量份的助剂混合均匀，其中搅拌速度为500～2000r/min，从而得到均一态混合物，所述混合物遮光保存，从而得到所述抗菌性光固化3D打印材料，S2: Preparation of antibacterial photocurable 3D printing material: 100 parts by weight of biocompatible oligomer / monomer and 0.05-5 parts by weight of supramolecular light prepared in the above step S1 by mechanical stirring at normal temperature. The initiation system, 5-30 parts by weight of the antibacterial agent, and 1-20 parts by weight of the admixture are mixed uniformly, and the stirring speed is 500-2000 r / min to obtain a homogeneous mixture, and the mixture is stored in a light-shielded state to obtain the antibacterial Photocurable 3D printing materials,
    其中在所述步骤S1中，所述pH值优选为2～3，并且Wherein in the step S1, the pH value is preferably 2 to 3, and
    其中在所述步骤S2中，所述混合物优选用锡箔纸遮光保存。Wherein, in the step S2, the mixture is preferably stored in shading with tin foil.
  11. 一种用于打印如权利要求1～9中任一项所述的抗菌性光固化3D打印材料的3D打印装置，所述3D打印装置包括光源、机械运动装置、软件控制系统和容纳所述抗菌性光固化3D打印材料的容器，所述光源在所述机械运动装置和所述软件控制系统的配合下，在使所述容器提供的所述抗菌性光固化3D打印材料逐层累积的同时将其固化以形成制件。A 3D printing device for printing the antibacterial photocurable 3D printing material according to any one of claims 1 to 9, the 3D printing device comprising a light source, a mechanical motion device, a software control system, and a housing of the antibacterial A container for a photocurable 3D printing material, the light source, in cooperation with the mechanical motion device and the software control system, accumulates the antibacterial photocurable 3D printing material provided by the container layer by layer while accumulating layer by layer. It cures to form an article.
  12. 如权利要求11所述的3D打印装置，其特征在于，所述光源为发光波长为415nm-750nm的可见激光光源。The 3D printing device according to claim 11, wherein the light source is a visible laser light source having a light emission wavelength of 415nm-750nm.
  13. 如权利要求11所述的3D打印装置，其特征在于，所述容器能够加热所容纳的所述抗菌性光固化3D打印材料，加热范围为室温至70℃以改善所述抗菌性光固化3D打印材料的流动性。The 3D printing device according to claim 11, wherein the container is capable of heating the antibacterial photocurable 3D printing material contained therein, and the heating range is from room temperature to 70 ° C to improve the antibacterial photocurable 3D printing. Material fluidity.
PCT/CN2019/086934 2018-08-31 2019-05-15 Antimicrobial photocuring 3d printing material and preparation method therefor and 3d printing device WO2020042669A1 (en)

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