WO2020142888A1 - 一种用于3d打印的墨水材料、制备方法及用途 - Google Patents

一种用于3d打印的墨水材料、制备方法及用途 Download PDF

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Publication number
WO2020142888A1
WO2020142888A1 PCT/CN2019/070746 CN2019070746W WO2020142888A1 WO 2020142888 A1 WO2020142888 A1 WO 2020142888A1 CN 2019070746 W CN2019070746 W CN 2019070746W WO 2020142888 A1 WO2020142888 A1 WO 2020142888A1
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Prior art keywords
ink
printing
zein
printing according
ethanol
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Ceased
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PCT/CN2019/070746
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English (en)
French (fr)
Inventor
王瑾晔
王华杰
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Jiaxing Yaojiao Medical Device Co Ltd
Shanghai Jiao Tong University
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Jiaxing Yaojiao Medical Device Co Ltd
Shanghai Jiao Tong University
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Application filed by Jiaxing Yaojiao Medical Device Co Ltd, Shanghai Jiao Tong University filed Critical Jiaxing Yaojiao Medical Device Co Ltd
Priority to JP2021539145A priority Critical patent/JP7372976B2/ja
Priority to PCT/CN2019/070746 priority patent/WO2020142888A1/zh
Priority to CN201980077907.9A priority patent/CN113518804B/zh
Priority to US17/421,115 priority patent/US12552947B2/en
Publication of WO2020142888A1 publication Critical patent/WO2020142888A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/04—Printing inks based on proteins
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/01—Non-adhesive bandages or dressings
    • A61F13/01008—Non-adhesive bandages or dressings characterised by the material
    • A61F13/01012—Non-adhesive bandages or dressings characterised by the material being made of natural material, e.g. cellulose-, protein-, collagen-based
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/32—Proteins, polypeptides; Degradation products or derivatives thereof, e.g. albumin, collagen, fibrin, gelatin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/001—Use of materials characterised by their function or physical properties
    • A61L24/0036—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/10—Polypeptides; Proteins
    • A61L24/108—Specific proteins or polypeptides not covered by groups A61L24/102 - A61L24/106
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
    • A61L27/227—Other specific proteins or polypeptides not covered by A61L27/222, A61L27/225 or A61L27/24
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/146—Porous materials, e.g. foams or sponges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—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
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—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
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent

Definitions

  • the invention belongs to the field of biological manufacturing, and relates to an ink material that can be used for 3D printing, a preparation method, and the use of ink.
  • 3D printing technology is an emerging manufacturing technology that has emerged in recent years. It is based on computer-aided design, or output data to a 3D printer after obtaining data through an imaging diagnostic instrument such as a CT tomography scanner. Accurate 3D stacking with printing ink and rapid manufacturing of a given shape 3D digital molding technology.
  • the materials that can be used for 3D printing are synthetic polymers (such as polylactic acid (PLA), polycaprolactone (PCL)), natural polymers (such as: gelatin, collagen, chitosan, sodium alginate) , Cellulose) and inorganic materials (such as hydroxyapatite, tricalcium phosphate). Natural polymer materials have the characteristics of excellent biocompatibility, degradability and printing at lower temperatures. But its application is restricted due to poor mechanical properties. Finding a new bio-ink based on natural polymer materials is an urgent problem to be solved in the field of 3D printing.
  • Zein has proved to have application potential in the field of tissue engineering.
  • the three-dimensional porous scaffold prepared by the traditional compression molding method has excellent cell compatibility and mechanical properties, and can be used to repair bone defects.
  • the development of 3D-printable zein ink will greatly promote the wider application of this material in the field of biomedical engineering. After retrieval, only one conference paper is related to it (ESAFORM 2016: Proceedings of the 19 th International EASFORM Conference on Material Forming).
  • This work uses zein mixed with plasticizer glycerin as ink and prints at 130 °C . Zein at this temperature exhibits thermoplastic properties, which adversely affect its biocompatibility and degradation performance.
  • the present invention provides zein ink that can be used for 3D printing. It can be 3D printed under mild conditions, which not only does not affect the structure and properties of zein, but also helps maintain the activity of cells and active factors.
  • the problem to be solved by the present invention is to provide an ink material for 3D printing.
  • Another problem to be solved by the present invention is to provide a method for preparing the above ink material for 3D printing.
  • the third problem to be solved by the present invention is to provide the use of the above-mentioned 3D printing ink.
  • the ink for 3D printing of the present invention is a gel composed of alpha zein, which can be 3D printed at room temperature.
  • the gel is a gel formed by a mixed solution of ethanol and water containing 10 to 50% (w/v) alpha zein.
  • the mixed solution of ethanol and water and alpha zein are The volume to weight ratio, for example, 100ml of ethanol and water mixed solution contains 10-50 grams of alpha zein. It is recommended that the alpha zein gel contains 30 to 50% by weight of alpha zein.
  • the volume ratio of ethanol and water is 40-90: 10-60.
  • the recommended volume ratio of alcohol to water is 60 to 85: 15 to 40.
  • the preparation method of the ink material for 3D printing according to the present invention is achieved by the following steps: dissolving 10-50% zein in a mixed solution of ethanol and water, and recommending 10 at 5-95% At -50°C, let it stand for 1-10 days, 1-3 days is recommended, or stir the reaction for 30 minutes-24 hours to prepare an ink material that can be used for 3D printing; in the mixed solution, ethanol and water
  • the volume ratio is 40 to 90: 10 to 60.
  • the pore structure and porosity of the printed product can also be adjusted by adding a pore-forming agent to the prepared ink.
  • the recommended addition amount is 0-10% w/w of the quality of zein.
  • the pore-forming agent mannitol, ammonium bicarbonate, sodium chloride, sodium tartrate, sodium citrate and other water-soluble salts or sugar particles may also be known pore-forming agents such as paraffin particles or ice particles.
  • the 3D printing ink provided by the present invention can be used in the field of biomedicine, including:
  • the digital data obtained by an imaging diagnostic instrument such as a CT tomograph can be accurately and quickly manufactured to a predetermined shape by a 3D printer; 3D printing high resolution, internal pore structure and machinery Controllable tissue engineering substitutes and hemostatic materials.
  • an imaging diagnostic instrument such as a CT tomograph
  • 3D printing high resolution, internal pore structure and machinery Controllable tissue engineering substitutes and hemostatic materials.
  • tubular products such as nerve catheters, trachea, urethral tubes and blood vessels, etc.
  • membrane products such as artificial skin and hemostatic membrane materials
  • 3D stent products such as bone, cartilage, ears, hemostatic materials.
  • the gel-like ink can also be used without injection, directly used for deep and irregular wound penetration through injection or smear to stop bleeding, and cooperate with 3D printing products to stop bleeding.
  • the ink material has a zero shear viscosity of 30-5000Pa ⁇ s, 120-recommended 4000Pa ⁇ s.
  • the hemostatic mechanism is divided into the following steps: first, the release of ethanol contained in the gel causes the gel to solidify and precipitate protein components in the blood; then, a large number of platelets are adsorbed; and finally the fibrinogen is concentrated into fibrin, capturing red blood cells and other blood cells .
  • the product printed by using the above-mentioned ink for 3D printing provided by the present invention may be a single component product of alpha zein printed by one 3D printer nozzle, or may be printed by two or more 3D printer nozzles.
  • a multi-component product mixed with zein and other ink materials including: synthetic and natural polymers such as polylactic acid, sodium alginate, sodium carboxymethyl cellulose, gelatin, etc.).
  • the zein ink for 3D printing of the invention has rich raw materials and simple preparation method. Moreover, 3D bioprinting can be performed at room temperature without affecting the structure and properties of zein, which is beneficial for maintaining the activity of cells and active factors.
  • Figure 1 The alpha zein gel-like 3D printing ink material prepared in Example 2.
  • Figure 1-1 shows the 3D printed ink in the syringe
  • Figure 1-2 shows the 3D printed ink in the bottle.
  • Figure 2 3D printed tissue engineering tubular product of alpha zein ink prepared in Example 3.
  • Figure 3 The grid-type hemostatic membrane material prepared by 3D printing the alpha zein ink prepared in Example 4, black indicates the pore structure of the grid.
  • Figure 4 A diagram of the hemostatic effect of the hemostatic membrane material described in Example 4 on skin bleeding.
  • FIG. 4-1 shows a photo of a rat’s skin bleeding
  • FIG. 4-2 shows a photo of a hemostatic film material on a rat’s skin bleeding.
  • Figure 5 3D products of various shapes produced by 3D printing of alpha zein ink prepared in Example 7.
  • Figure 6 The ⁇ -zein ink prepared in Example 8 was 3D printed to produce tissue-engineered artificial ears containing cells.
  • Fig. 6-1 shows the gel-like artificial ear photos immediately after printing
  • Fig. 6-2 shows the artificial ear photos after curing.
  • Fig. 7 A diagram of the hemostatic effect of the porous hemostatic material described in Example 7 and the alpha zein gel material prepared in Example 9 acting synergistically on a penetrating injury model.
  • FIG. 7-1 is a photograph of muscle damage
  • FIG. 7-2 is a photograph of the 3D printed ink of the present invention filled in the muscle, and the hemostatic membrane material of the present invention of Example 7 pasted on the surface.
  • An ink material that can be used for 3D printing is made of the following mass parts of raw materials: alpha zein 10g.
  • the preparation method of the ink material that can be used for 3D printing in this embodiment has the following steps:
  • Alpha zein was dissolved in 100 mL of an aqueous solution containing 40% ethanol and subjected to ultrasonic treatment at room temperature for 10 min to obtain a milky white solution. Then, the solution was left to stand at 10°C for 10 days to obtain an ink material usable for 3D printing.
  • the ink material had a zero shear viscosity of about 28 Pa ⁇ s.
  • An ink material that can be used for 3D printing is made of the following mass parts of raw materials: alpha zein 20g.
  • the preparation method of the ink material that can be used for 3D printing in this embodiment has the following steps:
  • the ink material has a zero shear viscosity of about 120 Pa ⁇ s.
  • An ink material that can be used for 3D printing is made of the following mass parts of raw materials: alpha zein 30g.
  • the preparation method of the ink material that can be used for 3D printing in this embodiment includes the following steps: dissolve alpha zein in 100 mL of a 70% volumetric ethanol aqueous solution, and perform ultrasonic treatment at room temperature for 10 min to obtain a transparent solution. Then, the solution was left to stand at 30°C and reacted for 2 days to obtain an ink material usable for 3D printing.
  • the ink material had a zero shear viscosity of about 389 Pa ⁇ s.
  • ink material prepared in this example mixed with pore-forming agent mannitol particles (accounting for 6% of the quality of zein, w/w), loaded into a printing nozzle, using a printing needle with a diameter of 0.5 mm, at 10 °C, At a printing speed of 8 mm/s and a printing pressure of 150 kPa, a tubular product was 3D printed at room temperature, and a porous tubular product was obtained after the pore-making agent was removed by boiling. As shown in Figure 2, it can be used as a tissue engineering nerve catheter.
  • An ink material that can be used for 3D printing is made of the following mass parts of raw materials: alpha zein 40g.
  • the preparation method of the ink material that can be used for 3D printing in this embodiment includes the following steps: dissolve ⁇ zein in 100 mL of a 80% volumetric ethanol aqueous solution, and perform ultrasonic treatment at room temperature for 10 min to obtain a transparent solution. Then, the solution was left to stand at 40°C for 4 days to obtain an ink material usable for 3D printing.
  • the ink material had a zero shear viscosity of about 1832 Pa ⁇ s.
  • a printing needle with a diameter of 0.33 mm under a condition of 20° C., printing speed of 8 mm/s, and printing pressure of 80 kPa, a grid-shaped film-like product was 3D printed, as shown in FIG. 3, used as a hemostatic membrane material.
  • Fig. 4 is a diagram showing the hemostatic effect of the hemostatic membrane material on the skin bleeding of rats.
  • An ink material that can be used for 3D printing is made of the following mass parts of raw materials: alpha zein 50g.
  • the preparation method of the ink material that can be used for 3D printing in this embodiment includes the following steps: dissolve ⁇ zein in 100 mL of an ethanol aqueous solution with a volume fraction of 85%, and perform ultrasonic treatment at room temperature for 10 min to obtain a transparent solution. Then, the solution was left to stand at 50°C for 8 days to obtain an ink material usable for 3D printing.
  • the ink material had a zero shear viscosity of about 1623 Pa ⁇ s.
  • An ink material that can be used for 3D printing is made of the following mass parts of raw materials: alpha zein 20g.
  • the preparation method of the ink material that can be used for 3D printing in this embodiment includes the following steps: dissolve ⁇ zein in 100 mL of a 90% volumetric ethanol aqueous solution, and perform ultrasonic treatment at room temperature for 10 min to obtain a transparent solution. Then, the solution was stirred at 10°C for 12 hours to obtain an ink material usable for 3D printing.
  • the ink material had a zero shear viscosity of about 55 Pa ⁇ s.
  • An ink material that can be used for 3D printing is made of the following mass parts of raw materials: alpha zein 30g.
  • the preparation method of the ink material that can be used for 3D printing in this embodiment includes the following steps: dissolve ⁇ zein in 100 mL of a 65% volume aqueous solution of ethanol, and perform ultrasonic treatment at room temperature for 10 min to obtain a transparent solution. Then, the solution was placed at 20°C and stirred for 30 minutes to obtain an ink material usable for 3D printing.
  • the ink material had a zero shear viscosity of about 344 Pa ⁇ s.
  • the size of the printing needle is 0.5mm, and under the conditions of 50°C, printing speed of 8mm/s, and printing pressure of 200kPa, tissue engineering substitute is 3D printed.
  • FIG. 5 is a 3D hemostatic material of various sizes printed with the ink material of this embodiment.
  • the zein ink material is suitable for printing 3D stent products.
  • the stent has a compression strength of 3.34 ⁇ 1.25MPa, a compression modulus of 63.93 ⁇ 19.22MPa; a bending strength of 5.30 ⁇ 1.32MPa, a bending modulus of 52.07 ⁇ 11.07MPa; a tensile strength of 0.11 ⁇ 0.02MPa and a tensile modulus of 2.63 ⁇ 1.25MPa.
  • An ink material that can be used for 3D printing is made of the following mass parts of raw materials: alpha zein 30g.
  • the preparation method of the ink material that can be used for 3D printing in this embodiment includes the following steps: dissolve ⁇ zein in 100 mL of an ethanol aqueous solution with a volume fraction of 85%, and perform ultrasonic treatment at room temperature for 10 min to obtain a transparent solution. Then, the solution was stirred at 30°C for 6 hours to obtain an ink material usable for 3D printing.
  • the ink material had a zero shear viscosity of about 551 Pa ⁇ s.
  • Charged in the first print head in the ink materials may be used in 3D printing, the second print head charged with a mixture of sodium alginate cells (cell density of 1 ⁇ 10 6 / ml) ink materials, at 37 °C, Tissue engineering organs are 3D printed using a printing needle with a diameter of 0.33 mm, a printing speed of 8 mm/s, and a printing pressure of 80 kPa.
  • Figure 6 shows the printed artificial ear.
  • the ink material can be used alone or mixed with cells or other ink materials to 3D print out irregularly shaped tissue engineering substitutes.
  • An ink material that can be used for 3D printing is made of the following mass parts of raw materials: alpha zein 50g.
  • the preparation method of the ink material that can be used for 3D printing in this embodiment includes the following steps: dissolve ⁇ zein in 100 mL of a 90% volumetric ethanol aqueous solution, and perform ultrasonic treatment at room temperature for 10 min to obtain a transparent solution. Then, the solution was placed at 50°C and stirred for 4 hours to obtain a gel ink material.
  • the gel material has a zero-shear viscosity of about 3476 Pa ⁇ s. It can be used for deep layer and irregular wound penetration to stop bleeding by injection or smear. It can also be used together with 3D printing products (Figure 7).
  • Figure 7-1 is muscle The damaged photo
  • Figure 7-2 is filled with the 3D printed ink of the present invention
  • the 3D printed ink of Example 7 is pasted on the surface. .

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Abstract

一种用于3D打印的墨水、制备方法及墨水的用途。该墨水是由α玉米醇溶蛋白，玉米蛋白重量0-10％的制孔剂，乙醇和水组成的凝胶。该制备方法包括：把10-50％重量的玉米醇溶蛋白溶解在含有40-90% (v/v）乙醇的水溶液中，加入玉米蛋白重量0-10%的制孔剂，在5-95℃恒温静置1-10天或者搅拌30分钟-24小时后，获得可用于3D打印的墨水材料。该方法条件温和、操作简单，所述的3D打印的墨水的力学性能和生物相容性好。可用于生物医学领域，在室温下3D打印制备组织工程替代物和止血材料。

Description

一种用于3D打印的墨水材料、制备方法及用途 技术领域
本发明属于生物制造领域，涉及一种可用于3D打印的墨水材料、制备方法及墨水的用途。
背景技术
3D打印技术是近年来兴起的一项新兴制造技术，是根据计算机辅助设计，或者通过影像诊断仪如CT断层扫描仪获得数据后再输出到3D打印机，用打印墨水精确3D堆积、快速制造既定形状的3D数字化成型技术。迄今为止，能够用于3D打印的材料有合成高分子(如：聚乳酸(PLA)、聚己内酯(PCL))、天然高分子(如：明胶、胶原蛋白、壳聚糖、海藻酸钠、纤维素)和无机材料(如羟基磷灰石、磷酸三钙)。天然高分子材料具有优良的生物相容性、可降解性和可在较低温度下打印等特点。但因力学性能差使其应用受到了限制。寻找新的基于天然高分子材料的生物墨水是3D打印领域亟待解决的问题。
玉米醇溶蛋白已被证明在组织工程领域具有应用潜力，如用传统的模压成型法制备的三维多孔支架具有优良的细胞相容性和力学性能，能用于骨缺损修复。开发可3D打印的玉米醇溶蛋白墨水将极大地推动该材料在生物医学工程领域更为广泛的应用。经检索，仅有一篇会议论文与之相关(ESAFORM 2016:Proceedings of the 19 th International EASFORM Conference on Material Forming)，该工作采用玉米蛋白与增塑剂甘油混合后作为墨水，在130℃温度下进行打印。该温度下的玉米蛋白呈现热塑性质，对其生物相容性和降解性能均有不良影响。本发明提供可用于3D打印的玉米蛋白墨水，可在温和条 件下进行3D打印，不仅不会影响玉米蛋白的结构和性质，而且利于维持细胞和活性因子活性。
发明内容
本发明要解决的问题是：提供一种用于3D打印的墨水材料。
本发明要解决的另一问题是：提供上述用于3D打印的墨水材料的制备方法。
本发明要解决的第三个问题是：提供上述3D打印墨水的用途。
本发明的用于3D打印的墨水是由α玉米醇溶蛋白组成的凝胶,该凝胶可以在室温下进行3D打印。具体的说，该凝胶是含有10～50％(w/v)的α玉米醇溶蛋白的乙醇和水混合溶液形成的凝胶，所述的乙醇和水混合溶液与α玉米醇溶蛋白是体积与重量之比，例如，100ml乙醇和水混合溶液中含有α玉米醇溶蛋白10-50克。推荐该α玉米醇溶蛋白凝胶中含有30～50％重量的α玉米醇溶蛋白。所述的乙醇和水混合溶液中，乙醇和水的体积比为40～90：10～60。推荐醇和水的体积比为60～85：15～40。
本发明所述的用于3D打印的墨水材料的制备方法是通过以下步骤实现的：把10～50％玉米醇溶蛋白溶解在乙醇和水的混合溶液中，在5～95℃下，推荐10-50℃下，静置反应1～10天，推荐1-3天，或者搅拌反应30分钟-24小时后，制得可用于3D打印的墨水材料；所述的混合溶液中，乙醇和水的体积比为40～90：10～60。所述的制备方法中，还可以通过在制得的墨水中加入制孔剂的方法调整打印产品的孔结构和孔隙率，推荐加入量为玉米醇溶蛋白质量的0-10％w/w。所述的制孔剂甘露醇、碳酸氢铵、氯化钠、酒石酸钠和柠檬酸钠等水溶性盐或糖的颗粒，也可用石蜡颗粒或冰颗粒等周知的制孔剂。
利用本发明提供的3D打印墨水，可用于生物医学领域，包括： 将影像诊断仪如CT断层扫描仪所获数字化数据通过3D打印机精准、快速制造既定形状；3D打印高分辨、内部孔隙结构和机械性能可控的组织工程替代物以及止血材料。如：管状产品(如神经导管、气管、尿道管和血管等)、膜状产品(如人造皮肤和止血膜材料)、3D支架产品(如骨、软骨、耳朵、止血材料)。支架孔隙率30-95％；压缩强度0.2MPa至20MPa、压缩模量10MPa至300MPa；弯曲强度0.5MPa至18MPa、弯曲模量15至100MPa；拉伸强度0MPa至2MPa、拉伸模量0MPa至20MPa。凝胶状墨水还可不打印，通过注射或涂抹方式直接用于深层且伤口不规则的贯穿伤止血、以及与3D打印产品协同止血，该墨水材料零剪切粘度30-5000Pa·s，推荐120-4000Pa·s。止血机理分为以下步骤：先是凝胶中所含乙醇的释放导致凝胶固化的同时沉淀了血液中的蛋白成分；然后是吸附大量血小板；最后纤维蛋白原浓缩成为纤维蛋白、捕获红血球等血球细胞。
利用本发明提供的上述可用于3D打印的墨水打印出的产品可以是由一个3D打印机喷头打印出α玉米醇溶蛋白单一组分产品，也可以是由两个或多个3D打印机喷头打印出α玉米醇溶蛋白和其它墨水材料(包括：合成和天然高分子如聚乳酸、海藻酸钠、羧甲基纤维素钠、明胶等)混合的多组分产品。
本发明的用于3D打印的玉米蛋白墨水，原料丰富，制备方法简便。而且可在室温条件下进行3D生物打印，不会影响玉米蛋白的结构和性质，利于维持细胞和活性因子活性。
附图说明
图1：实施例2制备的α玉米醇溶蛋白凝胶状3D打印墨水材料。
其中，图1-1表示注射器中的3D打印的墨水，图1-2表示瓶中3D打 印的墨水。
图2：实施例3制备的α玉米醇溶蛋白墨水经3D打印出的组织工程管状产品。
图3：实施例4制备的α玉米醇溶蛋白墨水经3D打印出的网格型止血膜材料，黑色表示网格的孔结构。
图4：利用实施例4所述止血膜材料对皮肤出血的止血效果图。
其中，图4-1表示大鼠皮肤出血的照片，图4-2表示止血膜材料对大鼠皮肤出血的止血照片。
图5：实施例7制备的α玉米醇溶蛋白墨水经3D打印出的各种形状3D产品。
图6：实施例8制备的α玉米醇溶蛋白墨水经3D打印出含细胞的组织工程人工耳。
其中，图6-1表示刚打印出时为凝胶态人工耳照片，图6-2表示固化后人工耳照片。
图7：利用实施例7所述多孔止血材料及实施例9制备的α玉米醇溶蛋白凝胶材料协同作用于贯穿伤模型的止血效果图。
其中，图7-1为肌肉损伤的照片，图7-2为肌肉内填入本发明的3D打印的墨水，表面贴上实施例7的本发明的止血膜材料的照片。
具体实施方式
下面通过实施例对本发明进行具体描述，以下实例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制。在阅读了本发明内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书的范围。
实施例1
一种可用于3D打印的墨水材料，由以下质量份数的原料制成：α玉米醇溶蛋白10g。
本实施例的可用于3D打印的墨水材料的制备方法，步骤如下：
将α玉米醇溶蛋白溶解在100mL体积分数为含有40％乙醇的水溶液中，经室温超声处理10min，得到乳白色溶液。然后，将该溶液置于10℃静置反应10天，得到可用于3D打印的墨水材料，该墨水材料零剪切粘度约28Pa·s。
实施例2
一种可用于3D打印的墨水材料，由以下质量份数的原料制成：α玉米醇溶蛋白20g。
本实施例的可用于3D打印的墨水材料的制备方法，步骤如下：
将α玉米醇溶蛋白溶解在100mL体积分数为含有65％乙醇的水溶液中，经室温超声处理10min，得到透明溶液。然后，将该溶液置于20℃静置反应1天，得到可用于3D打印的墨水材料，为凝胶状，如图1所示。该墨水材料零剪切粘度约120Pa·s。
实施例3
一种可用于3D打印的墨水材料，由以下质量份数的原料制成：α玉米醇溶蛋白30g。
本实施例的可用于3D打印的墨水材料的制备方法，步骤如下：将α玉米醇溶蛋白溶解在100mL体积分数为70％的乙醇水溶液中，经室温超声处理10min，得到透明溶液。然后，将该溶液置于30℃静置反应2天，得到可用于3D打印的墨水材料，该墨水材料零剪切粘度约389Pa·s。
利用本实施例制得的墨水材料，与制孔剂甘露醇颗粒(占玉米蛋白质量的6％，w/w)混合后，装入打印喷头中，利用直径0.5mm打印针头，在10℃、打印速度8mm/s、打印压力150kPa条件下，室温3D打印出管状产品，水煮法除去制孔剂后得到多孔管状产品。如图2所示，可作为组织工程神经导管等。
实施例4
一种可用于3D打印的墨水材料，由以下质量份数的原料制成：α玉米醇溶蛋白40g。
本实施例的可用于3D打印的墨水材料的制备方法，步骤如下：将α玉米醇溶蛋白溶解在100mL体积分数为80％的乙醇水溶液中，经室温超声处理10min，得到透明溶液。然后，将该溶液置于40℃静置反应4天，得到可用于3D打印的墨水材料，该墨水材料零剪切粘度约1832Pa·s。利用直径0.33mm打印针头，在20℃、打印速度8mm/s、打印压力80kPa条件下，3D打印出网格型膜状产品，如图3所示，用作止血膜材料。图4是利用该止血膜材料对大鼠皮肤出血的止血效果图。
实施例5
一种可用于3D打印的墨水材料，由以下质量份数的原料制成：α玉米醇溶蛋白50g。
本实施例的可用于3D打印的墨水材料的制备方法，步骤如下：将α玉米醇溶蛋白溶解在100mL体积分数为85％的乙醇水溶液中，经室温超声处理10min，得到透明溶液。然后，将该溶液置于50℃静置反应8天，得到可用于3D打印的墨水材料，该墨水材料零剪切粘度约1623Pa·s。
实施例6
一种可用于3D打印的墨水材料，由以下质量份数的原料制成：α玉米醇溶蛋白20g。
本实施例的可用于3D打印的墨水材料的制备方法，步骤如下：将α玉米醇溶蛋白溶解在100mL体积分数为90％的乙醇水溶液中，经室温超声处理10min，得到透明溶液。然后，将该溶液置于10℃搅拌12小时，得到可用于3D打印的墨水材料，该墨水材料零剪切粘度约55Pa·s。
实施例7
一种可用于3D打印的墨水材料，由以下质量份数的原料制成：α玉米醇溶蛋白30g。
本实施例的可用于3D打印的墨水材料的制备方法，步骤如下：将α玉米醇溶蛋白溶解在100mL体积分数为65％的乙醇水溶液中，经室温超声处理10min，得到透明溶液。然后，将该溶液置于20℃搅拌30分钟，得到可用于3D打印的墨水材料，该墨水材料零剪切粘度约344Pa·s。打印针头尺寸为0.5mm，在50℃、打印速度8mm/s、打印压力200kPa条件下，3D打印出组织工程替代物。图5是用本实施例墨水材料打印出的各种尺寸3D止血材料，可以看出，玉米醇溶蛋白墨水材料适用于打印3D支架产品。支架压缩强度3.34±1.25MPa、压缩模量63.93±19.22MPa；弯曲强度5.30±1.32MPa、弯曲模量52.07±11.07MPa；拉伸强度0.11±0.02MPa、拉伸模量2.63±1.25MPa。
实施例8
一种可用于3D打印的墨水材料，由以下质量份数的原料制成： α玉米醇溶蛋白30g。
本实施例的可用于3D打印的墨水材料的制备方法，步骤如下：将α玉米醇溶蛋白溶解在100mL体积分数为85％的乙醇水溶液中，经室温超声处理10min，得到透明溶液。然后，将该溶液置于30℃搅拌6小时，得到可用于3D打印的墨水材料，该墨水材料零剪切粘度约551Pa·s。
在第一打印喷头中装入上述可用于3D打印的墨水材料，在第二打印喷头中装入混有细胞的海藻酸钠(细胞密度1*10 6个/ml)墨水材料，在37℃，利用直径0.33mm打印针头，打印速度8mm/s、打印压力80kPa条件下3D打印出组织工程器官，图6为打印出的人工耳。该墨水材料可单独或与细胞或其它墨水材料混合，3D打印出不规则形状的组织工程替代物。
实施例9
一种可用于3D打印的墨水材料，由以下质量份数的原料制成：α玉米醇溶蛋白50g。
本实施例的可用于3D打印的墨水材料的制备方法，步骤如下：将α玉米醇溶蛋白溶解在100mL体积分数为90％的乙醇水溶液中，经室温超声处理10min，得到透明溶液。然后，将该溶液置于50℃搅拌4小时，得到凝胶墨水材料。该凝胶材料零剪切粘度约3476Pa·s，可通过注射或涂抹方式用于深层且伤口不规则的贯穿伤止血，也可与3D打印产品共同使用(图7)，图7-1为肌肉损伤的照片，图7-2为填入本发明的3D打印的墨水，表面贴上实施例7的3D打印的墨水。。

Claims (12)

  1. 一种用于3D打印的墨水，其特征是：所述的墨水是α玉米醇溶蛋白，乙醇和水混合而成的凝胶。
  2. 如权利要求1所述的用于3D打印的墨水,其特征在于：该α玉米醇溶蛋白凝胶中含有10～50％重量的α玉米醇溶蛋白，还含有玉米蛋白重量0-10％的制孔剂，其余为体积计数的乙醇和水；乙醇和水的体积比为40～90：10～60；所述的制孔剂为甘露醇、碳酸氢铵、氯化钠、酒石酸钠或柠檬酸钠的水溶性盐或糖的颗粒、石蜡颗粒或冰颗粒。
  3. 如权利要求2所述的用于3D打印的墨水,其特征在于：该α玉米醇溶蛋白凝胶中含有30～50％的α玉米醇溶蛋白。
  4. 如权利要求2所述的用于3D打印的墨水,其特征在于：所述的乙醇和水的体积比为60～85：15～40。
  5. 如权利要求1或2所述的用于3D打印的墨水,其特征在于：是一种在室温下进行3D打印的墨水。
  6. 如权利要求1所述的用于3D打印的墨水,其特征在于：所述的该墨水材料零剪切粘度30-5000Pa·s。
  7. 一种如权利要求1或2所述的用于3D打印的墨水的制备方法，其特征在于是通过以下步骤实现的：把10～50％玉米醇溶蛋白溶解在乙醇和水的混合溶液中，在5～95℃下，恒温静置反应1～10天，或者搅拌反应30分钟-24小时后，制得可用于3D打印的墨水材料，再加入玉米蛋白重量0-10％的制孔剂；所述的混合溶液中，乙醇和水的体积比为40～90：10～60。
  8. 如权利要求7所述的一种可用于3D打印的墨水的制备方法，其特征在于所述的静置反应温度为10～50℃，静置反应1～3天。
  9. 如权利要求1或7所述的一种用于3D打印的墨水的用途，其特征在于制备生物医用材料。
  10. 如权利要求9所述的一种用于3D打印的墨水的用途，其特征在于所述的3D打印产品为管状、膜状、3D支架的组织工程替代物或止血材料。
  11. 如权利要求9或10所述的一种用于3D打印的墨水的用途，其特征在于所述的组织工程替代物是神经导管、人造气管、人造尿道管、人造血管、人造皮肤、止血膜材料、人造骨、人造软骨、人造耳朵。
  12. 如权利要求1所述的一种可用于3D打印的墨水的用途，其特征在于通过注射或涂抹方式直接用于深层且伤口不规则的贯穿伤止血、与权利要求9所述的3D打印产品的协同止血。
PCT/CN2019/070746 2019-01-08 2019-01-08 一种用于3d打印的墨水材料、制备方法及用途 Ceased WO2020142888A1 (zh)

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