WO2016147165A1 - 잉크젯 헤드와 분말 상자-기반 ３ｄ 프린팅용 잉크 조성물 - Google Patents

잉크젯 헤드와 분말 상자-기반 ３ｄ 프린팅용 잉크 조성물 Download PDF

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Publication number
WO2016147165A1
WO2016147165A1 PCT/IB2016/051741 IB2016051741W WO2016147165A1 WO 2016147165 A1 WO2016147165 A1 WO 2016147165A1 IB 2016051741 W IB2016051741 W IB 2016051741W WO 2016147165 A1 WO2016147165 A1 WO 2016147165A1
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Prior art keywords
ink composition
present
adhesive
printing
catechol
Prior art date
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PCT/IB2016/051741
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English (en)
French (fr)
Inventor
이헌주
문명운
조원진
한상수
이해신
송인택
Original Assignee
한국과학기술연구원
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Application filed by 한국과학기술연구원 filed Critical 한국과학기술연구원
Priority to US15/308,414 priority Critical patent/US10472529B2/en
Publication of WO2016147165A1 publication Critical patent/WO2016147165A1/ko

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • 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
    • B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
    • 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
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/0009—After-treatment of articles without altering their shape; Apparatus therefor using liquids, e.g. solvents, swelling agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0032—Pigments, colouring agents or opacifiyng agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • B29K2105/0044—Stabilisers, e.g. against oxydation, light or heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0097—Glues or adhesives, e.g. hot melts or thermofusible adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/251—Particles, powder or granules

Definitions

  • the present invention relates to an ink composition containing a general adhesive suitable for a 3D printer and its use.
  • additive manufacturing is a technique of creating a desired shape through a process of assembling materials based on three-dimensional model data.
  • CAD Computer aided drawing
  • RP rapid prototyping
  • AM Lamination
  • the adhesive is sprayed with an inkjet printer to adhere only the desired parts and the powder is laminated.
  • the powder material in the part where the adhesive is not sprayed is removed by air pressure to obtain only the desired three-dimensional shape.
  • the adsorbent is cured to obtain the final three-dimensional structure, and the structure formed by applying adhesive is heat treated before removing the powder.
  • This method can recycle the powder material (usually 100 ⁇ or less) even if it is slightly lower than the lamination processing of the other method of numerical precision, and it is easy to process the structure floating in the three-dimensional structure hollow.
  • various functional materials can be formed, increasing interest in the use of inkjet heads and powder-box-based 3D printing techniques, amongst many methods of processing. It is becoming. [4] Numerous articles and patent documents are referenced and cited throughout the specification. The disclosures of cited articles and patent documents are shown in their entirety.
  • Polydopamine can function as an adhesive that effectively attaches a powder to various materials (e.g., polymers, metals, ceramics, composites, etc.) and when performing 3D printing using an ink composition containing the same
  • various materials e.g., polymers, metals, ceramics, composites, etc.
  • the present invention was completed by confirming that a more stable structure could be formed than a 3D printed structure made of a binder.
  • the object of the present invention is to provide an ink composition for 3D printing.
  • Another object of the present invention is to provide a method for manufacturing a structure using 3D printing.
  • Another object of the present invention is to provide a 3D printing system using the ink composition described above.
  • the present invention relates to adhesives, solvents, stabilizers and
  • An ink composition for 3D printing comprising a viscosity modifier, wherein the adhesive provides an ink composition which is a compound having a catechol group.
  • the present invention provides a method of manufacturing a structure using 3D printing, comprising the steps of: (a) preparing an ink composition as described above; And (b) manufacturing the part by introducing the composition into a 3D printer and applying powder continuously.
  • the present invention provides a 3D printing system using the ink composition described above.
  • the inventors have sought to develop a multifunctional adhesive that can be effectively applied to various functional materials used in 3D printing.
  • Polydopamine can function as an adhesive that effectively attaches a powder to various materials (e.g., polymers, metals, ceramics, composites, etc.) and when performing 3D printing using an ink composition containing the same In the binder It was confirmed that a more stable structure can be formed than the manufactured 3D printing structure.
  • 3D printing uses raw materials (eg, powder, plastics, polymers, metals, ceramics, glass,
  • plastics such as acrylonitrile butadiene styrene (ABS), poly lactic acid (PLA), acrylic, polycarbonate (PC), various metals, powders such as plaster, wax, rubber, wood (Sawdust), paper, glass, ceramic, etc.
  • 3D printing also includes powder bed & inkjet head 3D printing (PBP), selective laser sintering (SLS), digital light processing (DLP), Stereolithography (SLA), photopolymer jetting technology (PolyJet), fused deposition modeling (FDM),
  • PBP powder bed & inkjet head 3D printing
  • SLS selective laser sintering
  • DLP digital light processing
  • SLA Stereolithography
  • SLA photopolymer jetting technology
  • FDM fused deposition modeling
  • MJM multi jet modeling
  • LOM laminated object manufacturing
  • AOM anti-gravity object modeling
  • the system is an inkjet head and powder box-based 3D printing (PBP) system.
  • PBP powder box-based 3D printing
  • ink compositions for 3D printing comprising a functional adhesive component (or adhesive).
  • the ink compositions of the present invention include adhesives, solvents, stabilizers, and viscosity modifiers, more specifically 10-30 volume ⁇ 3 adhesives, 40-60 volume ⁇ 3 ⁇ 4 solvents, 5-10 volume ⁇ 3 ⁇ 4 stabilizer and 20-40 volume ⁇ 3 ⁇ 4 viscosity modifier, more specifically 10-15 volume ⁇ 3 ⁇ 4 adhesive, 45-55 volume ⁇ 3 ⁇ 4 solvent, 5-6 volume% stabilizer and 25-30 vol. ⁇ 3 ⁇ 4 viscosity modifier.
  • the mixing ratio of these components is 10-15% adhesive solution, 50% IPA (isopropyl alcohol), 5-6% 2-EHA (ethylhexanoic acrylate) and 25 It may be 2-ethylhexanoic acid.
  • the adhesive component of the present invention has excellent adhesion to various functional materials (eg, lime powder, polymer, metal, ceramic, composite material).
  • functional materials eg, lime powder, polymer, metal, ceramic, composite material.
  • the adhesive component In order to be sprayed onto an inkjet printer, the adhesive component must not block the spray nozzle. It should be able to show proper spreading during spraying and evaporate quickly after spraying, and to spread evenly into powder (powder) and not show any reaction other than powder and adhesion.
  • conventional adhesive ingredients can be molded by reacting only on specific powders.
  • the adhesive components of the present invention have excellent adhesion to almost any material, regardless of the hydrophilic / hydrophobic or surface tension or polarity of the powder material.
  • functional materials that were difficult or difficult to mold in three-dimensional structures can be processed with inkjet heads and powder-box-based 3D printing techniques.
  • the ink If included in the ink, it must not only be an anhydrous additive, but also have no effect on the pH of the ink. If a small amount of moisture is present, it can cause hydration and cause shrinkage, which can result in localization of the ink. This results in a change in density, which prevents the dispersion of additives from being uniformly maintained, resulting in irregular concentrations of the ink, as well as clogging of the nozzles, and in contact with air. As much as possible, the adhesive should be kept from contact with air as much as possible.
  • the ink composition of the present invention maintains an Ohnesorge number (Oh) of 1.0 or less, and more specifically, a Onesurge number in the range of 0.1-1.0.
  • the adhesive ingredient which may be used in the present invention includes a compound having a catechol group.
  • the term "compound comprising a catechol group” used in the present specification refers to a catechol molecule and / or a catechol derivative molecule.
  • a catechol molecule is also known as 1,2-dihydroxybenzene or pyrocatechol, and the catechol derivative comprises a benzene ring and two hydroxy groups bonded to the ring.
  • adhesive components that can be used in the present invention are dopamine, polydopamine,
  • Droxidopa 5-hydroxydopamine, deacetylated chitosan
  • Polydopamine or chitosan catechol is a compound synthesized in the hybridization and exhibits almost all surface adhesion, regardless of the specificity of the surface. It is known that the bonding force is maintained even in the water [JUNGKI RYU, et al.,
  • the term 'adhesive' used in the present invention can be injected through an inkjet head.
  • the ink compositions of the present invention may include solvents, ink stabilizers,
  • any solvent that can be used in the ink composition of the present invention may be any solvent that does not contain water, and more specifically includes an alcohol solvent.
  • Alcohol solvents include methanol, ethyl alcohol, methyl alcohol, glycerol, propylene glycol, isopropyl alcohol, isobutyl alcohol, polyvinyl alcohol, cyclonusanol, octyl alcohol, decanol, nucleatecanol, ethylene glycol, 1.2-octane Diols, 1,2-dodecanediol, 1,2-nuxadecanediol and combinations thereof, including but not limited to.
  • the term 'ink stabilizer' used in the present invention stably inhibits the state of ink for a long period of time by inhibiting the hydroxyl action that may occur in the ink composition.
  • An ink stabilizer that can be used in the ink composition of the present invention can be any ink stabilizer that is normally used in inkjet printing, and specifically, anhydrous 2-ethylnuclear acryl with ethyl nucleic acid added.
  • Acrylate anhydrous 2-EHA
  • 2-methoxyethanol (2-ME)
  • 2-butoxyethanol 2-butoxyethanol
  • hydroxyethyl cellulose methyl cellulose, ethyl
  • Water-soluble polymers such as styrene-maleic anhydride copolymer (SMA),
  • the ink stabilizer that may be used in the ink compositions of the present invention is anhydrous 2-ethylnuclear acrylate.
  • the one-stage number (01 ⁇ 80 6 101156) " of the ink composition of the present invention at room temperature (20-25 o C) must be maintained in the range of 0.1-1.0. This is a condition in which ink can be stably and wet without splashing when the ink is sprayed on the surface of the powder box without blocking between small spray nozzles.
  • Viscosity regulators that can be used in the ink compositions of the present invention are typically ink
  • viscosity modifier used in the composition may be used, for example 2-ethylhexanoic acid, 1,2-propanediol and its derivatives, 1,3-propanediol And derivatives thereof, and glycerol.
  • viscosity modifiers that may be used in the ink compositions of the present invention include ethylnuxanoic acid and 1,2-propanediol. .
  • dispersants may be additionally included if necessary to control the viscosity in the ink compositions of the present invention. It may be a dispersant and may include, for example, water-soluble acrylic resins, styrene-acryl copolymeric resins, polyester resins, polyamide resins, polyurethane resins, fluororesins, and the like.
  • the ink composition of the present invention may additionally include an oxidizing agent and a dye.
  • oxidants that can be used in the ink compositions of the present invention include a variety of materials suitable for ink compositions known in the art, including, for example, piperidine and derivatives thereof. It is not limited to this.
  • Dyes that may be included in the ink compositions of the present invention can be used in various configurations depending on the purpose or purpose, and the dyes that can be used in the present invention are dyes that are substantially insoluble in water. Its solubility in water at 25 0 C is below lg and may include yellow dyes, magenta dyes or cyan dyes.
  • the dyes that can be used in the ink compositions of the present invention include organic and inorganic dyes based on color inks.
  • red or magenta dyes are known as Pigment Red 3, 5, 19.
  • the ink composition of the present invention is suitable for a 3D printer.
  • the present invention provides a method of manufacturing a 3D structure that can be easily manufactured through 3D printing using the ink composition described above.
  • the ink composition of the present invention is prepared.
  • the ink composition is introduced into a spray nozzle part in a 3D printer.
  • the powder is applied continuously in a powder box to produce a 3D structure.
  • the ink composition of the present invention has a very good adhesion, and the final manufactured 3D structure is much more stable in structure than a conventional binder structure.
  • Commonly used binders include, for example, insoluble polymer binders, cellulose derivatives, and polyamides. And copolymers thereof, polyesters and copolymers thereof, phenolic resins, polyanhydrides, and the like.
  • the manufacturing method of the present invention may additionally include a post-processing processing step (c).
  • the post-processing step (c) may or may not be carried out, and may be applied in various ways in the art.
  • the post-processing material may be used as the post-processing material.
  • the structure may be polished, or the finished structure may be finished in finish type, or both steps may be performed.
  • the material after the process resins including epoxy resins, acrylic resins, dragon skin (Dragon Skin ®) and fiber-reinforced plastic (fiber reinforced plastics, frp), however, limited to It is not.
  • the finish type is a resin finish, sand-sprayed.
  • finish Includes but is not limited to finish (sand-blasted finish), resin dye finish, and integral color finish.
  • the adhesive for 3D printers of the present invention can be used for bonding various materials having various functionalities, since conventional adhesives only react to special powders, so that the moldable material is limited. Therefore, the present invention is a functional adhesive.
  • the present invention provides a very interesting and surprising adhesive that enables the processing of a variety of materials, which are typically difficult or difficult to mold in three-dimensional structures, with inkjet heads and powder-based 3D printing techniques.
  • This invention is suitable for 3D printers. It relates to an ink composition containing a functional adhesive and its use.
  • the multifunctional adhesive of the present invention includes a compound having a catechol group and has excellent adhesion to various materials (e.g., gypsum powder, polymers, metals, ceramics, composite materials).
  • the ink composition of the present invention can be used as a
  • FIG. 1 is a schematic diagram of an inkjet head and a powder box-based 3D printing system.
  • FIG. 1 is a box containing a powdered material
  • 2 is a piston to adjust the height of the powder.
  • a device that enables lamination 3 a device for supplying powdered materials, and 4 a powdered material mainly made of plaster powder or polymer.
  • 5 is a device for evenly spreading the powder deposited by the roller
  • 6 is a device for supplying the adhesive liquid
  • 7 is a special adhesive liquid.
  • polydopamine can effectively attach Ti0 2 to the powder surface.
  • 9 and 10 are experimental results showing the stability of the 3D printing structure performed using an adhesive containing or not containing polydopamine, respectively.
  • FIG. 1 shows a simplified schematic of the present invention, which can be applied to a variety of materials, unlike conventional inkjet head and powder-based 3D printing techniques adhesives.
  • the solution may include ink stabilizers, solvents, viscosity modifiers, dyes, and the like, in addition to the adhesive solution.
  • Each of these components may have a difference in fraction depending on their application, but it is very important that the Ohnesorge number (Oh) ranges from 0.1 to 1.0 for spraying and evaporation without containing moisture. If the number exceeds the range of 1.0, the water droplets fall into the form of (satellite drops), and when the water chamber touches this surface, a popping phenomenon is not desirable.
  • the one-surge number is less than 0.1, the viscosity is high. Therefore, it is very important to formulate a one-surge number value in the range of 0.1-1.0 for uniform spraying.
  • the following formula is a formula for calculating one-surge number:
  • the present inventors investigated the function of the binder and polydopamine in the adhesion between the powder and Ti0 2 (2.5 mg). As shown in Figs. 4 and 5, it was confirmed that Ti0 2 was well adhered to the surface of the polydopamine powder as well as the conventional binder.
  • each component was mixed at room temperature for 24 hours in the composition as shown in Table 1.
  • the precipitate was centrifuged to wash the precipitate with ethanol. The procedure was performed five times.
  • the washed mixture was centrifuged at 1,200 rpm and 2,000 rpm to observe the settling state.
  • 3D printing was carried out in the absence (FIG. 9) and in the presence of polydopamine (FIG. 10) to investigate the stability of the manufactured 3D printing structure.
  • the pristine was well formed regardless of the presence or absence of polydopamine.
  • the 3D printing structure using the adhesive containing polydopamine was more stable than the 3D printing structure using the adhesive containing no polydopamine. 100 in each water It was confirmed that the 3D printing structure using the adhesive containing polydopamine retained the shape more stably when shaking at rpm (third panel of FIGS. 9 and 10).
  • the adhesive does not contain the control polydopamine.
  • 3D printing structures using are mostly stirred in water and then completely

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

요약서 본발명은 3D프린터에적합한다기능성접착제를포함하는잉크조성물및이의용도에 관한것이다. 본발명의다기능성접착제는카테콜기(catechol group)를가지는화합물을 포함하고, 다양한소재(예컨대, 석고가루, 폴리머, 금속, 세라믹, 복합소재)에대해뛰어난 접착력을가진다. 상기다기능성접착제를포함하는본발명의잉크조성물을이용하는 경우, 3차원구조로의성형이까다롭거나또는어려웠던다채로운기능성소재들에대한 가공공정이가능하다. 따라서, 본발명의잉크조성물은 3D프린터용기능성소재시장의 효과적인창출뿐아니라새로운응용분야(예컨대, 자동차, 의료, 패션, 항공/우주, 건축, 소비자가전, 엔터테인먼트, 등)로의적용가능성이매우높다. 14

Description

명세서
발명의명칭:잉크젯헤드와분말상자 -기반 3 D프린팅용잉크 조성물
기술분야
[1] 본발명은 3D프린터에적합한범용접착제를포함하는잉크조성물및이의 용도에관한것이다.
배경기술
[2] 적층가공 (Additive manufacturing, AM)이란, 3차원의모델자료를기반으로, 재료를뭉치는공정을통하여원하는형상을만드는기법으로,
절삭가공 (subtractive manufacturing)과같은전통적인가공공정의반대되는 개념이라할수있다.보통의경우한겹한겹차례로쌓아올리는방식으로 만들어지며 ,적층공법 (additive fabrication),적층공정 (additive processes), 적증기법 (additive technique),적증생산법 (additive layer manufacturing)이라고 불리기도한다. 3D프린터는 1980년대말컴퓨터의발달로,
컴퓨터지원설계 (computer aided drawing, CAD)데이터를빠른시간에저렴한 가격으로 3차원형상의축소된모델이나시제품 (prototype)에대한제작이 가능해지면서,산업용 3D프린터로써가장먼저사용되기시작했으며,주로 제품설계및검증단계에서의쾌속성형법 (rapid prototyping, RP)의한방법으로 널리이용되어왔다.적층가공 (AM)은기존다른가공공정에비해제작에 소요되는에너지가약 50%이상,소재는약 90%이상절감할수있다고알려져 있다.이러한이점들때문에지멘스 (Siemens), BMW,폭스바겐 (Volkswagen), GM. NASA, GE, BOSE, HP등자동차,항공우주,건축,가전제품에이르기까지 산업계를비롯한다양한분야에서널리사용되고있다.
[3] 이중에서도,잉크젯헤드와분말상자 -기반 3D프린팅기법은분말소재를
수백 μηι두께로일정하게펴준다음에,접착제를잉크젯프린터로분사하여 원하는부위만접착하여적층하는방식이다.접착제가분사되지않은부분의 분말소재는공기압에의해제거되어최종적으로원하는 3차원형상만을얻게 된다.보통은흡착제를통해 2차경화를거쳐최종 3차원구조를얻어내는데, 접착제를뿌려성형한구조물은분말을떨어내기전에열처리를하여
건조시키기도한다.이러한방식은수치정밀도가다른방식의적층가공에비해 다소떨어지더라도 (보통 100 μηι이하)분말재료를재활용할수있고, 3차원 구조중공중에떠있는구조물도쉽게가공이가능하기때문에,많이사용되고 있다.특히,분말형태의다양한기능성소재와접착제의개발이이루어질경우, 여러가지기능성소재의성형이가능하기때문에,수많은적측가공법중에서도 잉크젯헤드와분말상자 -기반 3D프린팅기법의웅용에대한관심이증폭되고 있다. [4] 본명세서전체에걸쳐다수의논문및특허문헌이참조되고그인용이 표시되어 있다.인용된논문및특허문헌의개시내용은그전체로서본
명세서에참조로삽입되어본발명이속하는기술분야의수준및본발명의 내용이보다명확하게설명된다.
발명의상세한설명
기술적과제
[5] 본발명자들은 3D프린팅에이용되는다양한기능성소재에대해효과적으로 적용할수있는다기능성접착제를개발하고자노력하였다.그결과,본
발명자들은카테콜기를포함하는화합물 (예컨대,흥합에서유래된
폴리도파민)이파우더와다양한소재 (예컨대,폴리머,금속,세라믹,복합소재, 등)를효과적으로부착시키는역할을하는접착체로기능할수있고이를 포함하는잉크조성물을이용하여 3D프린팅을실시하는경우종래의바인더로 제조된 3D프린팅구조체보다훨씬안정적인구조체를형성시킬수있다는것을 확인함으로써,본발명을완성하였다.
[6] 따라서 ,본발명의목적은 3D프린팅용잉크조성물을제공하는데있다.
[7] 본발명의다른목적은 3D프린팅을이용한구조체의제조방법을제공하는데 있다.
[8] 본발명의또다른목적은상술한잉크조성물을이용하는 3D프린팅시스템을 제공하는데있다.
[9] 본발명의다른목적및이점은하기의발명의상세한설명,청구범위및도면에 의해보다명확하게된다.
과제해결수단
[10] 본발명의일양태에따르면,본발명은접착제 ,용매,안정화제및
점도조절제를포함하는 3D프린팅용잉크조성물로,상기접착제는카테콜 기 (catechol group)를가지는화합물인것인잉크조성물을제공한다.
[11] 본발명의다른양태에따르면,본발명은다음의단계를포함하는 3D프린팅을 이용한구조체의제조방법을제공한다: (a)상술한잉크조성물을제조하는단계 ; 및 (b)상기조성물을 3D프린터에도입하고파우더를연속적으로적용하여 구조체 (part)를제조하는단계.
[12] 본발명의또다른양태에따르면,본발명은상술한잉크조성물을이용하는 3D프린팅시스템을제공한다.
[13] 본발명자들은 3D프린팅에이용되는다양한기능성소재에대해효과적으로 적용할수있는다기능성접착제를개발하고자노력하였다.그결과,본
발명자들은카테콜기를포함하는화합물 (예컨대,흥합에서유래된
폴리도파민)이파우더와다양한소재 (예컨대,폴리머,금속,세라믹,복합소재, 등)를효과적으로부착시키는역할을하는접착체로기능을할수있고이를 포함하는잉크조성물을이용하여 3D프린팅을실시하는경우종래의바인더로 제조된 3D프린팅구조체보다훨씬안정적인구조체를형성시킬수있다는것을 확인하였다.
[14] 3D프린팅은원료 (예컨대,파우더,플라스틱,폴리머,금속,세라믹,유리,
복합소재,등)를사출,적층또는웅고시켜 3차원형태의고체제품을제작하는 기술로,전통적인재료가공기술에비해가격,사용편리성,맞춤형제작가능성, 등의다양한측면에서더욱우수한기술이다 . 3D프린팅에이용될수있는 소재는매우다양한데,예를들어 ABS(acrylonitrile butadiene styrene), PLA(poly lactic acid),아크릴, PC(polycarbonate)같은플라스틱,다양한금속류,석고가루 같은파우더,왁스,고무,나무 (톱밥),종이,유리,세라믹,등을포함한다.또한, 3D 프린팅은사용되는소재에따라서 PBP(Powder bed & inkjet head 3D printing), SLS(selective laser sintering), DLP(digital light processing), SLA(stereolithography), PolyJet(photopolymer jetting technology), FDM(fused deposition modeling),
MJM(multi jet modeling), LOM(laminated object manufacturing), AOM(anti-gravity object modeling),등의방식으로구분될수있다.가장보편적인 3D프린팅 방식은 PBP, FDM (수지압출법 ), SLA (광경화수지조형 ), DLP (디지털광학기술), SLS (파우더기반쾌속조형기술),등이다.
[15] 본발명의어떤구현예에서,본발명의잉크조성물이이용되는 3D프린팅
시스템은잉크젯헤드및분말상자-기반된 3D프린팅 (PBP)시스템이다.
[16] 하지만, 3D프린팅기법은이용하는소재및구조체를형성시키는방식에서 다양할지라도,대체적으로매우느린적층속도,약한모형강도,재료및색상 흔용의어려움,고난도 3D그래픽설계기술의요구등과같은문제들,특히적층 속도및강도상에서큰문제를가진다.
[17] 본발명은 3D프린팅 (특히 , PBP)의상술한문제점을개선하고보다다양한
소재들에간편하고효과적으로적용가능한다기능성접착성분 (또는접착제)을 포함하는 3D프린팅용잉크조성물을제공한다.
[18] 본발명의어떤구현예에서,본발명의잉크조성물은접착제 ,용매,안정화제 및점도조절제를포함하고,보다구체적으로는 10-30부피 <¾접착제 , 40-60부피 <¾ 용매, 5-10부피 <¾안정화제및 20-40부피 <¾점도조절제를포함하며,보다더 구체적으로는 10-15부피 <¾접착제 , 45-55부피 <¾용매, 5-6부피 %안정화제및 25-30부피 <¾점도조절제를포함한다.예를들면,상기성분의흔합비는 10-15% 접착제용액, 50% IPA(isopropyl alcohol), 5-6% 2-EHA(ethylhexanoic acrylate)및 25-30%에틸핵사노익산 (2-ethylhexanoic acid)일수있다.
[19] 본발명의접착성분은다양한기능성소재 (예컨대,석회가루,폴리머,금속, 세라믹,복합소재)에뛰어난접착성을가진다.잉크젯프린터로분사되기 위해서,상기접착성분은분사노즐을막지말아야하며 ,분사시적절한퍼짐 현상을나타내고분사후에빠르게증발해야한다.또한,분말 (파우더)내로 골고루퍼져야하며분말과접착이외에어떠한반웅도보이지말아야한다. 통상적으로,종래의접착성분은특정분말에대해서만반웅하여서성형가능한 소재가매우제한적이었지만,본발명의접착성분은분말소재의 친수성 /소수성이나표면장력,또는극성에상관없이거의대부분의물질에대해 우수한접착력을가진다.따라서,본발명의접착성분을포함하는접착제를 이용하는경우종래에는 3차원구조로성형이까다롭거나어려웠던기능성 소재를잉크젯헤드와분말상자 -기반 3D프린팅기법으로가공이가능하다.
[20] 또한,잉크젯프린터로분사가가능해야하는접착제가잉크젯프린터용
잉크에포함되는경우,무수 (anhydrous)첨가물이어야할뿐아니라잉크의 pH에 영향을미치지않아야한다.적은양의수분이존재하는경우수산화작용을 유발하여웅축현상이일어날수있고,이로인해잉크의국부적인밀도변화가 초래되며,첨가물의분산을일정하게유지하지못하도록한다.그결과,잉크의 불규칙적인농도를초래할뿐아니라노즐의막힘현상을유발할수있다.또한, 공기와의접촉도상술한현상을유발할수있기때문에접착액이공기와 접촉하는것도최대한으로막아야한다.
[21] 본발명의어떤구현예에서,본발명의잉크조성물은 1.0이하의오네서지 넘버 (Ohnesorge number, Oh)를유지하고,보다더구체적으로는 0.1-1.0범위의 오네서지넘버를유지한다.
[22] 본발명에서이용될수있는접착성분은카테콜기 (catechol group)를가지는 화합물을포함한다.본명세서에서사용되는용어 "카테콜기를포함하는 화합물 "은카테콜분자및 /또는카테콜유도체분자를포함하는접착력을가지는 분자를의미한다.카테콜분자는 1,2-디하이드록시벤젠또는피로카테콜로도 알려져 있으며,카테콜유도체는벤젠고리와상기고리에결합된두개의 하이드록시기를포함하는분자를가지는물질이다.보다구체적으로,본 발명에서이용될수있는접착성분은도파민,폴리도파민,
디하이드록시벤젠 (dihydroxybenzene),알파-메틸도파민,노레피네프린, 디하이드록시페닐알라닌,알파-메틸도파 (alpha-methyldopa),
드록시도파 (droxidopa), 5-하이드록시도파민,탈아세틸화키토산
카테콜 (Chitosan-catechol),히알루론산카테콜 (Hyaluronic Acid-catechol)및 알지네이트카테콜 (Alginate-catechol)로구성된군으로부터선택되는최소 하나의화합물을포함하고,보다더구체적으로는폴리도파민,탈아세틸화 키토산카테콜,히알루론산카테콜및알지네이트카테콜을포함하지만,이에 한정되는것은아니다.폴리도파민이나키토산카테콜은흥합에서합성되는 물질로,표면의특수성에상관없이거의모든표면우수한접합력을나타내며, 물속에서도접합력이지속된다고알려져있다 [JUNGKI RYU,등,
'Mussel-Inspired Polydopamine Coating as a Universal Route to Hydroxyapatite Crystallization', ADV. FUNCT. MATER., vol. 20: 2132-2139(2010); Kazunori Yamada,등, 'Chitosan Based Water-Resistant Adhesive Analogy to Mussel Glue', Biomacromolecules, vol. 1 (2): 252-258(2000)].
[23] 본발명에서사용되는용어 '접착액'은잉크젯헤드를통하여분사가가능한 잉크형태의접착제가포함된분사용용액을의미하고,본명세서에서 '접착 성분'또는 '접착제 '와상호흔용되어사용된다.
[24] 상기접착제이외에도,본발명의잉크조성물은용매,잉크안정화제및
점도조절제를포함한다.
[25] 본발명의어떤구현예에서,본발명의잉크조성물에사용할수있는용매는 물을포함하지않는용매라면어떠한것도이용가능하고,보다구체적으로는 알코올계용매를포함한다.예를들어,상기알코올계용매는메탄올,에틸알콜, 메틸알콜,글리세롤,프로필렌글리콜,이소프로필알콜,이소부틸알콜, 폴리비닐알콜,사이클로핵사놀,옥틸알콜,데카놀,핵사테카놀,에틸렌글리콜, 1.2-옥테인디올, 1,2-도데케인디올, 1,2-핵사데케인디올및이의흔합물을 포함하지만,이에한정되는것은아니다.
[26] 본발명에서사용되는용어 '잉크안정화제 '는잉크조성물에서발생할수있는 수산화작용을억제하여잉크의상태를오랜기간동안안정적으로
유지시켜주는물질을의미한다.본발명의잉크조성물에사용할수있는잉크 안정화제는통상적으로잉크젯프린팅에서사용되는잉크안정화제라면어떠한 것도이용할수있고,구체적으로는에틸핵산이추가된무수 2-에틸핵실 아크릴레이트 (anhydrous 2-EHA), 2-메톡시에탄올 (2-methoxyethanol, 2-ME), 2-부톡시에탄올,하이드록시에틸셀를로오스,메틸셀를로오스,에틸
셀를로오스,전분,카제인 (casein),젤라틴,폴리비닐알코올및
SMA(styrene-maleic anhydride copolymer)같은수용성들리머들,
하이드록시프로필-변형된구아검,아라비아검및잔탄검을포함하지만,이에 한정되는것은아니다.본발명의어떤구현예에서,본발명의잉크조성물에 사용할수있는잉크안정화제는무수 2-에틸핵실아크릴레이트및
2-메톡시에탄올을포함한다.
[27] 접착제가첨가된잉크조성물에 있어서,잉크의점성 (viscosity)과
표면장력 (surface tension)이매우중요하고,이를위해상온 (20-25oC)에서본 발명의잉크조성물의오네서지넘버(01 ^80 6 101156]")가0.1-1.0의범위를 유지시켜야한다.이는잉크가자그마한분사노즐사이를막히지않고 통과하면서도분말상자내분말표면에뿌려졌을때,튀지않고안정적으로 젖을수있는조건에해당한다.
[28] 본발명의잉크조성물에사용할수있는점도조절제는통상적으로잉크
조성물에서사용되는점도조절제라면어떠한것도이용할수있고,예를들어 에틸핵사노익산 (2-ethylhexanoic acid), 1,2-프로판디올 (1,2 propanediol)및이의 유도체, 1,3-프로판디올및이의유도체,및글리세롤을포함하지만,이에 한정되는것은아니다.본발명의어떤구현예에서,본발명의잉크조성물에 사용할수있는점도조절제는에틸핵사노익산및 1,2-프로판디올을포함한다.
[29] 추가적으로,본발명의잉크조성물에서점도를조절하기위해필요하다면 분산제 (dispersant)도추가적으로포함할수있다.상기분산제는레진 -타입 분산제일수있고,예를들어수용성아크릴성레진, SM공중합체 (styrene-acryl copolymeric)레진,폴리에스테르레진,폴리아미드레진,폴리우레탄레진, 플루오로레진,등을포함할수있다.
[30] 또한,본발명의잉크조성물은산화제및염료를추가적으로포함할수있다. 본발명의어떤구현예에서,본발명의잉크조성물에사용할수있는산화제는 당업계에공지된잉크조성물에적합한다양한물질을포함하며,예를들어 피페리딘 (piperidine)및이의유도체들을포함하지만,이에한정되는것은 아니다.
[31] 본발명의잉크조성물에포함될수있는염료 (dye)는목적또는용도에따라 다양하게구성하여이용할수있으며,본발명에서사용할수있는상기염료는 물에실질적으로불용인염료이고,구체적으로는 250C에서물로의용해도가 l g 이하로,엘로염료,마젠타염료또는시안염료를포함할수있다.
[32] 본발명의어떤구현예에서,본발명의잉크조성물에사용할수있는염료는 컬러인텍스에기재되는유기및무기염료를포함한다.예를들어,적색또는 마젠타염료는 Pigment Red 3, 5, 19, 22, 31, 38, 43, 48: 1, 48:2, 48:3, 48:4, 48:5, 49:1, 53: 1, 57: 1, 57:2, 58:4, 63: 1, 81, 81: 1, 81:2, 81:3, 81:4, 88, 104, 108, 112, 122, 123, 144, 146, 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, Pigment Orange 13, 16, 20, 36을;청색 또는시안염료는 Pigment Blue 1, 15, 15: 1, 15:2, 15:3, 15:4, 15:6, 16, 17-1, 22, 27, 28, 29, 36, 60을;녹색염료는 Pigment Green 7, 26, 36, 50을;황색염료는 Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137, 138, 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193을;흑색염료는 Pigment Black 7, 28, 26을;백색염료는 Pigment White 6, 18, 21을포함하지만, 이에한정되는것은아니다.
[33] 상술한바와같이,본발명의잉크조성물은 3D프린터에적합한구성및
특성을가진다.이에따라,본발명은상술한잉크조성물을이용하는 3D 프린팅을통해 3D구조체를용이하게제조할수있는 3D구조체의제조방법을 제공한다.
[34] 먼저,본발명의잉크조성물을제조한다.
[35] 본발명의 3D구조체제조방법은상술한잉크조성물을이용하기때문에 ,이둘 사이에공통된내용은본명세서의과도한복잡성을피하기위하여그기재를 생략한다.
[36] 다음으로,상기잉크조성물을 3D프린터내분사노즐파트에도입하고
파우더를분말상자에서연속적으로적용시켜 3D구조체를제조한다.본발명의 잉크조성물이매우우수한접착능을가져최종적으로제조된 3D구조체가물 속에서종래의바인더를이용한구조체보다훨씬더안정적인구조체를 이룬다는것을확인하였다 (참고도 9및도 10).통상적으로이용될수있는 바인더는,예를들어불용성폴리머바인더,셀를로오스유도체들,폴리아미드류 및이의공중합체,폴리에스테르및이의공중합체,페놀성레진,폴리무수물, 등을포함한다.
[37] 본발명의어떤구현예에서,본발명의제조방법은공정후 (post-processing) 처리단계 (c)를추가적으로포함할수있다.
[38] 상기공정후처리단계 (c)는실시할수도있고실시하지않을수도있으며 , 당업계에서실시되는다양한방식을적용시킬수있다.예를들어,상기공정후 물질 (post-processing material)로상기구조체를연마시키거나,또는피니시 타입 (finish type)으로상기공정된구조체를마감하거나,또는상기두단계를 모두실시할수도있다.
[39] 본발명의어떤구현예에서 ,상기공정후물질은레진,에폭시레진,아크릴성 레진,드래곤스킨 (Dragon Skin®)및섬유강화플라스틱 (fiber reinforced plastics, frp)을포함하지만,이에한정되는것은아니다.
[40] 본발명의어떤구현예에서,상기피니시타입은레진피니시,모래 -분사
피니시 (sand-blasted finish),레진염료피니시및인테그럴컬러피니시 (integral color finish)를포함하지만,이에한정되는것은아니다.
[41] 본발명의 3D프린터용접착제는종래의접착제가특수한분말에만반웅하기 때문에성형이가능한소재가한정적이었다면,본발명은다양한기능성을갖는 각종소재의접합에사용이가능한다기능성접착제이다.따라서,본발명은 통상적으로 3차원구조로성형이까다롭거나어려웠던다양한소재를잉크젯 헤드와분말상자 -기반 3D프린팅기법으로가공할수있도록해주는매우 흥미롭고놀라운접착제를제공한다.
발명의효과
[42] 본발명의특징및이점을요약하면다음과같다:
[43] (a)본발명은 3D프린터에적합한다기능성접착제를포함하는잉크조성물및 이의용도에관한것이다.
[44] (b)본발명의다기능성접착제는카테콜기 (catechol group)를가지는화합물을 포함하고,다양한소재 (예컨대,석고가루,폴리머,금속,세라믹,복합소재)에 대해뛰어난접착력을가진다.
[45] (c)상기다기능성접착제를포함하는본발명의잉크조성물을이용하는경우,
3차원구조로의성형이까다롭거나또는어려웠던다채로운기능성소재들에 대한가공공정이가능하다.
[46] (d)따라서 ,본발명의잉크조성물은 3D프린터용기능성소재시장의
효과적인창출뿐아니라새로운웅용분야 (예컨대,자동차,의료,패션, 항공 /우주,건축,소비자가전,엔터테인먼트,등)로의적용가능성이매우높다. 도면의간단한설명
[47] 도 1은잉크젯헤드와분말상자기반 3D프린팅시스템의개략도이다.도의 1은 분말상태의재료를담고있는상자, 2는피스톤으로분말의높이를조절하여 적층이가능하게하는장치, 3은분말상의재료를공급하는장치, 4는 분말상태의재료로주로석고가루나폴리머가쓰인다. 5는롤러로공금된 분말을고르게펴주는장치이며, 6은접착액을공급하는장치이고, 7은특수한 접착액이다.
[48] 도 2-5는폴리도파민의접착효과를보여주는결과이다.종래의바인더와
비교하여,폴리도파민은효과적으로 Ti02를파우더표면에부착시킬수있다.
[49] 도 6-8는폴리도파민이 Ti02의파우더부착을효과적으로유발할수있다는 것을보여주는원심분리결과이다.
[50] 도 9및도 10은각각폴리도파민을포함하지않거나또는포함하는접착제를 이용하여실시된 3D프린팅구조체의안정성을보여주는실험결과이다.
발명의실시를위한최선의형태
[51] 이하,실시예를통하여본발명을더욱상세히설명하고자한다.이들실시예는 오로지본발명을보다구체적으로설명하기위한것으로,본발명의요지에 따라본발명의범위가이들실시예에의해제한되지않는다는것은당업계에서 통상의지식을가진자에있어서자명할것이다.
[52] 실시예
[53] 실시예 1:폴리도파민접착제의특성분석
[54] 도 1은본발명의간략한계략도로기존에한정된소재에국한되었던,잉크젯 헤드와분말상자 -기반 3D프린팅기법의접착제와달리여러가지소재에 적용이가능함을보여준다.통상적으로접착제는잉크젯헤드를통하여분사가 가능한잉크형태의접착제를포함하는분사용용액을의미한다.상기용액은 접착액이외에도잉크안정화제,용매,점도조절제,염료,등을포함할수있다. 상기각성분들은그용도에따라분률의차이가발생할수있지만,수분을 포함하지않고분사와증발을위해서오네서지넘버 (Ohnesorge number, Oh)가 0.1-1.0의범위에해당하는것이매우중요하다.오네서지넘버가 1.0의범위를 초과할경우,잔물방을 (satellite drops)형태로떨어져물방을이표면에닿을때 터지는현상이발생하여바람직하지않다.또한,오네서지넘버가 0.1이하의 경우에는점성이높아분사가되지않고물방을형성을방해한다.따라서 , 균일한분사를위해서는오네서지넘버값이 0.1-1.0의범위에해당하도록 조성하는것이매우중요하다.하기도식은오네서지넘버를계산하는수식이다:
[55]
Figure imgf000009_0001
\ incrt ia 3urfa.cc tension
[56] 상기식에서 ^는점성계수 , σ는표면에너지 , ρ는밀도, L은특성길이, Re는
레이놀드수 (Reynolds number),및 We는웨버수 (Weber number)를의미한다 [B. Derby and N. Reis, "Inkjet Printing of Highly Loaded Particulate Suspensions", MRS SwZfeftVz, pp. 815-818(2003)].상기도식을이용하여구성성분에따라오네서지 넘버를계산할수있다.
[57] 종래의잉크젯헤드와분말상자 -기반 3D프린팅시스템은분말상태의
소재 (4)와특수한접착액 (7)의특정한화학반웅 (즉,자가 -수화 (self-hydration) 반웅)에의하여결합하는방식이었다 (도 1 도 2에서볼수있듯이,본
발명자들은종래의바인더 (VisiJet PXLTM clear; 3D systems,미국)와 250 mg 파우더 (석고가루 (CaS04); 3D systems,미국)를흔합하는경우상기바인더성분 내에물성분을함유하고있어상기흔합을통해특정화학반웅이발생하고그 결과상기파우더표면에로드형태의변형이일어난다는것을확인할수 있었다.이는 CaS04가바인더성분에의해자가 -수화반웅이일어나재결정 형태의석고 (gypsum)로변하기때문이다.이에반해,에탄올에녹여진 폴리도파민 (polydopamine, 2 mg/ml; Sigma-Aldrich,미국)과파우더를흔합시킨 경우물성분이없기때문에파우더표면에로드형태의변형이관찰되지 않았다 (도 3).
[58] 상기폴리도파민이종래의바인더와유사,동일또는우수한접착기능을할수 있는지를조사하기위해,본발명자들은파우더와 Ti02(2.5 mg)간의부착에서의 바인더및폴리도파민의기능을조사하였다.도 4및도 5에서보여지듯이, 종래의바인더뿐아니라폴리도파민도파우더표면에 Ti02를잘부착시킨다는 것을확인할수있었다.
[59] 실시예 2:폴리도파민접착제의부착력분석
[60] 범용접착제로서폴리도파민의기능성을보다정확하게확인하기위해 ,하기 표 1과같은조성으로각구성성분을상온에서 24시간동안흔합시켰다.상기 흔합액을원심분리하여침전시킨침전물을에탄올로세척하는과정을 5번에 걸쳐서실시하였다.상기세척된흔합물을 1,200 rpm및 2,000 rpm에서 원심분리시켜침전상태를관찰하였다.
[61] [표 1]
Figure imgf000011_0001
[62] 폴리도파민의우수한부착력효과.
[63] 보다상세하게는, 1,200 rpm에서침전시킨경우첨가된도파민 (2 mg/ml;용매 , 에탄올)에의해 Ti02(2.5 mg)가파우더 (250 mg)에안정적으로결합됨에따라 뚜렷한침전물을형성하였음을확인할수있었지만,도파민접착제가없는경우 Ti02의파우더흡착이일어나지않아 1,200 rpm에서침전되지않았다 (도 6). 2,000 rpm에서침전시키는경우,도파민이첨가된경우에만침전물을얻을수있었고 산화제가추가적으로첨가된시료보다도파민만을첨가한시료에서보다 안정적으로침전물을얻을수있었다.여전히도파민접착제가없는경우는 Ti02 의파우더흡착이일어나지않아 2,000 rpm에서도어떠한침전물을얻을수 없었다 (도 7).
[64] 또한,상기표 1의시료 1내지시료 4에서괄호안의성분을먼저흔합시키고 건조시켰다.상기건조된흔합물을에탄올에다시흔합시킨후원심분리시켰다. 2,000 rpm에서원심분리시킨경우,시료 1내지시료 4모두잘침전되어 용이하게분리할수있었다.더욱이,건조시킨후 Ti02를첨가한경우 (즉,시료 2 및시료 4)도 Ti02가잘부착되어침전됨을확인할수있었다 (도 8).이에반해, 도파민을포함하지않는시료 5는여전히침전물을형성하지않았다.
[65] 실시예 3:폴리도파민접착제를이용한 3D프린팅
[66] 본발명자들은 3D프린팅적용시폴리도파민의효과를입증하기위해
폴리도파민의부존재 (도 9)및존재 (도 10)하에서 3D프린팅을실시하고이를 통해제조된 3D프린팅구조체의안정성을조사하였다.폴리도파민의존재또는 부존재와상관없이원형 (pristine)은잘형성되었지만,물속에담지시킨경우 (도 9및도 10의두번째패널)폴리도파민을포함하는접착제를사용한 3D프린팅 구조체가폴리도파민을포함하지않는접착제를사용한 3D프린팅구조체보다 보다안정된구조를이루었다.더욱이,상기구조체를각각물속에서 100 rpm으로교반 (shaking)시키는경우폴리도파민을포함하는접착제를사용한 3D 프린팅구조체가더욱안정적으로형태를유지하는것을확인하였다 (도 9및도 10의세번째패널).대조군인폴리도파민을포함하지않는접착제를사용한 3D 프린팅구조체는물에서교반시킨후대부분그구조형태가완전히
파괴되었으며 ,상온건조후에도 3D구조를유지하지못했다 (도 9의네번째 패널).이와대조적으로,폴리도파민을포함하는접착제를사용한 3D프린팅 구조체는교반후에도형태를보다더안정적으로유지했을뿐아니라,상온에서 건조후에도그구조를유지하였다 (도 10의네번째패널).따라서,본발명자들은 폴리도파민을포함하는접착제가 3D프리팅에효과적으로적용가능하다는 것을실질적으로확인하였다.
[67] 이상으로본발명의내용의특정한부분을상세히기술하였는바,당업계의 통상의지식을가진자에게있어서,이러한구체적기술은단지일구현예일 뿐이며,이에의해본발명의범위가제한되는것이아닌점은명백할것이다. 따라서,본발명의실질적인범위는첨부된청구항과그의등가물에의하여 정의된다고할것이다.

Claims

청구범위
[청구항 1] 접착제,용매,안정화제및점도조절제를포함하는 3D프린팅용잉크
조성물로,상기접착제는카테콜기 (catechol group)를가지는화합물인 것인잉크조성물.
[청구항 2] 제 1항에 있어서,상기잉크조성물은 10-30부피 <¾접착제 , 40-60부피 <¾ 용매, 5-10부피 <¾안정화제및 20-40부피 <¾점도조절제를포함하는것인 잉크조성물.
[청구항 3] 제 1항에 있어서,상기잉크조성물은 0.1-1.0의오네서지넘버 (Ohnesorge number, Oh)를유지하는것인잉크조성물.
[청구항 4] 제 1항에 있어서,상기접착제는폴리도파민 (poly-dopamine),
탈아세틸화된키토산카테콜 (Chitosan-catechol),히알루론산 카테콜 (Hyaluronic Acid-catechol)또는알지네이트
카테콜 (Alginate-catechol)인것인잉크조성물.
[청구항 5] 제 1항에 있어서,상기용매는알코올계용매인것인잉크조성물.
[청구항 6] 제 1항에 있어서,상기안정화제는무수 2-에틸핵실아크릴레이트 (2-EHA)
또는 2-메톡시에탄올 (2-methoxyethanol, 2-ME)인것인잉크조성물.
[청구항 7] 제 1항에 있어서,상기점도조절제는에틸핵사노익산또는
1,2-프로판디올인것인잉크조성물.
[청구항 8] 제 1항에 있어서,상기잉크조성물은산화제또는염료를추가적으로
포함하는것인잉크조성물.
[청구항 9] 제 8항에 있어서,상기산화제는피페리딘 (piperidine)인것인잉크조성물.
[청구항 10] 제 8항에 있어서,상기염료는컬러인텍스에기재되는유기또는무기 안료인것인잉크조성물.
[청구항 11] 다음의단계를포함하는 3D프린팅을이용한구조체의제조방법 :
(a)제 1항내지제 10항중어느하나의항의잉크조성물을제조하는단계 ;
(b)상기조성물을 3D프린터에도입하고파우더를연속적으로적용하여 구조체 (part)를제조하는단계.
[청구항 12] 제 11항에 있어서,상기제조방법은공정후 (post-processing)처리단계
(c)를추가적으로포함하는것인제조방법.
[청구항 13] 제 12항에 있어서,상기가공후처리단계 (c)는공정후
물질 (post-processing material)로상기구조체를연마시키는단계 (c-1)및 피니시타입 (finish type)으로상기공정된구조체를마감하는단계 (c-2)중 어느하나또는모두를포함하는것인제조방법 .
[청구항 14] 제 13항에 있어서,상기공정후물질은레진,에폭시레진,아크릴성레진, 드래곤스킨 (Dragon Skin®)또는섬유강화플라스틱 (fiber reinforced plastics, frp)인것인제조방법 .
[청구항 15] 제 13항에 있어서,상기피니시타입은레진피니시,모래 -분사 피니시 (sand-blasted finish),레진염료피니시또는인테그럴컬러 피니시 (integral color finish)를포함하는것인제조방법 .
[청구항 16] 제 1항내지제 10항중어느하나의항의잉크조성물을이용하는 3D 프린팅시스템.
[청구항 17] 제 16항에 있어서,상기 3D프린팅시스템은잉크젯헤드및분말 상자-기반된 3D프린팅시스템인것인 3D프린팅시스템.
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