WO2017188550A1 - Binder composite and preparation method therefor - Google Patents

Binder composite and preparation method therefor Download PDF

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Publication number
WO2017188550A1
WO2017188550A1 PCT/KR2016/015009 KR2016015009W WO2017188550A1 WO 2017188550 A1 WO2017188550 A1 WO 2017188550A1 KR 2016015009 W KR2016015009 W KR 2016015009W WO 2017188550 A1 WO2017188550 A1 WO 2017188550A1
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Prior art keywords
poly
ink
ethylene glycol
binder
viscosity
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PCT/KR2016/015009
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French (fr)
Korean (ko)
Inventor
백운규
윤희성
최정현
선세호
김주현
Original Assignee
한양대학교 산학협력단
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Priority claimed from KR1020160146351A external-priority patent/KR20170123572A/en
Application filed by 한양대학교 산학협력단 filed Critical 한양대학교 산학협력단
Publication of WO2017188550A1 publication Critical patent/WO2017188550A1/en

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    • 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
    • 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
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials

Definitions

  • the present invention relates to a binder composite and a method for producing the same, and more particularly, to a binder composite comprising a thermoplastic binder mixed with PLA and PEG, ceramic particles and an antioxidant and a method for producing the same.
  • Three-dimensional printing technology such as FDM (Fused deposition modeling) to extrude and output the thermoplastic resin according to the printing method, SLA (Stereolithography) to irradiate and cure the light curable resin and plastic, ceramic, metal, or glass Laser is directly irradiated to the powder material, and classified into a SLS (Selective laser sintering) method for molding molten powder material.
  • FDM Freused deposition modeling
  • SLA Stepolithography
  • SLS Selective laser sintering
  • Plastics which are currently the most commonly used materials for three-dimensional printing, are inexpensive and have excellent processability, while molded articles made of plastic are weak in heat and low in strength.
  • molded articles made of ceramics are resistant to high temperatures and excellent in durability, and thus are most commonly used as materials for three-dimensional printing using the SLS method, but three-dimensional printing using the SLS method requires very expensive equipment, and ceramics. Silver is very high and inferior in workability.
  • the strength, surface properties, manufacturing time, resolution, or physical properties of the finished product pointed out as a problem of three-dimensional printing originate from the raw material, and recently, characteristics of a molded body manufactured by three-dimensional printing using various materials. Active research is being conducted on composite inks that can improve the quality of the resin.
  • Korean Patent Publication No. 10-2015-0042660 Applicant: Rocket, Inc., Appl. No. 10-2013-0121602
  • an ink for three-dimensional printing and a mixture of ceramic and poly (lactic acid) with ink.
  • the three-dimensional printing ink which improves the intensity
  • One technical problem to be solved by the present invention is to provide a method for producing a binder composite comprising an environmentally friendly organic binder.
  • Another technical problem to be solved by the present invention is to provide a method for producing a binder composite with easy viscosity control.
  • Another technical problem to be solved by the present invention is to provide a method for producing a binder composite that is easy to control the elastic modulus.
  • Another technical problem to be solved by the present invention is to provide a method for producing a binder composite with improved stability.
  • Another technical problem to be solved by the present invention is to provide a method for producing a binder composite with improved thermal properties.
  • Another technical problem to be solved by the present invention is to provide a method for producing a binder composite with improved mechanical properties.
  • the technical problem to be solved by the present invention is not limited to the above.
  • the present invention provides a method for producing a binder composite.
  • the manufacturing method of the binder composite preparing a thermoplastic binder mixed with Poly (lactic acid) and Poly (ethylene glycol) and to prevent oxidation of ceramic particles and Poly (lactic acid) in the thermoplastic binder. Adding an antioxidant to prepare the ink.
  • the manufacturing method of the binder composite may include adjusting the viscosity of the ink by adjusting the content or molecular weight of the poly (ethylene glycol).
  • the manufacturing method of the binder composite may include controlling the glass transition temperature and the melting point of the ink by controlling the content of the poly (ethylene glycol).
  • the manufacturing method of the binder composite may include controlling the fracture toughness of the molded product manufactured by using the ink by adjusting the content of the poly (ethylene glycol).
  • the manufacturing method of the binder composite may include adjusting the viscosity of the ink by adjusting the content of the antioxidant.
  • the manufacturing method of the binder composite may include adjusting the viscosity of the ink by adjusting the shape of the ceramic particles.
  • the manufacturing of the thermoplastic binder in which the poly (lactic acid) and the poly (ethylene glycol) are mixed may include heat treating the thermoplastic binder.
  • the method of manufacturing the binder composite may further include ball milling the ceramic particles before adding the ceramic particles to the thermoplastic binder.
  • the present invention provides a binder composite.
  • the binder composite may include a thermoplastic binder including poly (lactic acid) and poly (ethylene glycol), an ink including ceramic particles, and an antioxidant for preventing oxidation of the poly (lactic acid).
  • a thermoplastic binder including poly (lactic acid) and poly (ethylene glycol) an ink including ceramic particles
  • an antioxidant for preventing oxidation of the poly (lactic acid).
  • the viscosity of the ink decreases as the content of the poly (ethylene glycol) decreases, and includes increasing as the molecular weight of the poly (ethylene glycol) and the content of the antioxidant
  • the viscosity includes decreasing as the shape of the ceramic particles approaches a sphere, and the viscosity of the ink controls the content and molecular weight of the poly (ethylene glycol), the content of the antioxidant, and the shape of the ceramic particles. And include being adjusted.
  • the ceramic particles may include at least one of silica (SiO 2 ) particles, or zirconium silicate (ZrSiO 4 ) particles.
  • the binder composite according to the embodiment of the present invention includes a thermoplastic binder, ceramic particles, and an antioxidant in which poly (lactic acid) and poly (ethylene glycol) are mixed.
  • the viscosity of the ink may be adjusted by adjusting the content and molecular weight of the poly (ethylene glycol), the content of the antioxidant, and the shape of the ceramic particles. Accordingly, a binder composite may be provided in which the viscosity of the ink is adjusted to suit the purpose.
  • thermoplastic binder includes the poly (lactic acid) and the poly (ethylene glycol). Accordingly, a binder composite can be provided with improved thermal properties such as glass transition temperature and melting point, and mechanical properties such as fracture toughness of shaped bodies produced using the ink.
  • the thermoplastic binder includes the poly (lactic acid) and the poly (ethylene glycol).
  • the elastic modulus of the ink may be adjusted according to the molecular weight of the poly (ethylene glycol). Accordingly, a binder composite whose elastic modulus is adjusted to suit the purpose can be provided.
  • the binder composite according to the embodiment of the present invention includes the antioxidant for preventing oxidation of the thermoplastic binder. Accordingly, the binder composite may be provided to prevent the oxidation of the polymer chain of the thermoplastic binder, thereby maintaining the mechanical properties of the thermoplastic binder.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a binder composite according to an embodiment of the present invention.
  • FIG. 2 is a view for explaining the viscosity of the ink according to the poly (ethylene glycol) content of the binder composite prepared according to the embodiment of the present invention.
  • 3 is a view for explaining the viscosity of the ink according to the molecular weight of the poly (ethylene glycol) of the binder composite prepared according to the embodiment of the present invention.
  • FIG. 4 is a view for explaining the antioxidant effect of the ink according to the antioxidant content of the binder composite prepared according to the embodiment of the present invention.
  • FIG. 5 is a view for explaining the viscosity of the ink according to the antioxidant content of the binder composite prepared according to the embodiment of the present invention.
  • FIG. 6 is a view for explaining the elastic modulus of the ink according to the molecular weight of Poly (ethylene glycol) of the binder composite prepared according to the embodiment of the present invention.
  • FIG. 7 is a view illustrating the flexural strength and shrinkage rate of a molded article manufactured using ink according to the average particle size of the spherical silica particles constituting the ceramic particles added to the binder composite prepared according to the embodiment of the present invention. It is a drawing for
  • FIG. 8 is a view for explaining the viscosity of the ink according to the shape of the silica particles constituting the ceramic particles added to the binder composite prepared according to the embodiment and comparative example of the present invention.
  • FIG. 9 is a view for explaining the particle size distribution of the ceramic particles added to the binder composite prepared according to the embodiment of the present invention.
  • first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another. Thus, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment.
  • first component in one embodiment may be referred to as a second component in another embodiment.
  • second component in another embodiment.
  • Each embodiment described and illustrated herein also includes its complementary embodiment.
  • the term 'and / or' is used herein to include at least one of the components listed before and after.
  • FIG. 1 is a flowchart illustrating a method of manufacturing a binder composite according to an embodiment of the present invention.
  • thermoplastic binder in which poly (lactic acid) and poly (ethylene glycol) are mixed is manufactured (S110).
  • the poly (ethylene glycol) is a plasticizer, by lowering the glass transition temperature and melting point of the ink containing the poly (ethylene glycol), the processability of the ink can be improved.
  • the fracture toughness of the molded product manufactured using the ink may be controlled by the poly (ethylene glycol). In other words, as the content of the poly (ethylene glycol) is increased, the fracture toughness of the ink is increased, and the fracture toughness, which is the energy required to destroy the material, is increased, thereby increasing the amount of poly-ethylene glycol. Mechanical strength can be improved.
  • the viscosity of the ink is controlled by the poly (ethylene glycol), and accordingly, the materials constituting the ink may be uniformly mixed.
  • the molecular weight of the poly (ethylene glycol) may be adjusted to control the viscosity of the ink. In other words, as the molecular weight of the poly (ethylene glycol) increases, the viscosity of the ink increases, and as the molecular weight of the poly (ethylene glycol) decreases, the viscosity of the ink may decrease.
  • the manufacturing of the thermoplastic binder in which the poly (lactic acid) and the poly (ethylene glycol) are mixed may include heat treating the thermoplastic binder.
  • the heat treatment may be performed at 80 ° C.
  • An ink is manufactured by adding an antioxidant to prevent oxidation of ceramic particles and the poly (lactic acid) to the thermoplastic binder (S120).
  • the ceramic particles may include at least one of spherical silica (SiO 2 ) particles or zirconium silicate (ZrSiO 4 ) particles.
  • the antioxidant is a mixture of butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate and tert-butylhydroquinone (TBHQ), 2% ⁇ -tocopherol, 1% butylated hydroxytoluene (BHT) and 1% butylated hydroxyanisole
  • BHA butylated hydroxyanisole
  • BHT butylated hydroxytoluene
  • TBHQ tert-butylhydroquinone
  • BHA butylated hydroxyanisole
  • BHT butylated hydroxytoluene
  • BHT butylated hydroxyanisole
  • Tetrakis methylene (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate
  • the viscosity of the ink when using the spherical silica particles, compared to using amorphous silica particles, the viscosity of the ink can be reduced.
  • the closer the shape of the ceramic particles is to the spherical shape the lower the viscosity of the ink.
  • the antioxidant may prevent oxidation of poly (lactic acid), thereby improving stability of the ink.
  • the viscosity of the ink may be adjusted by the antioxidant. In other words, as the content of the antioxidant is increased, the viscosity of the ink is increased, and as the content of the antioxidant is decreased, the viscosity of the ink can be decreased.
  • the ceramic particles may be added by being ball milled before being added to the thermoplastic binder.
  • the binder composite according to the embodiment of the present invention includes the thermoplastic binder including the poly (lactic acid) and the poly (ethylene glycol), the ceramic particles, and the antioxidant, but the content of the poly (ethylene glycol) And by adjusting the molecular weight, the content of the antioxidant, and the shape of the ceramic particles, the viscosity of the ink can be easily adjusted. Because of this, the viscosity of the ink is adjusted to suit the application can be provided a binder composite with improved processability.
  • the binder composite according to the embodiment of the present invention includes the poly (lactic acid) and the poly (ethylene glycol) as the thermoplastic binder, and includes the antioxidant for preventing oxidation of the thermoplastic binder.
  • the glass transition temperature and melting point of the binder composite according to the embodiment of the present invention are reduced, and the fracture toughness of the molded article manufactured using the ink can be improved and maintained.
  • the binder composite when the binder composite does not include the thermoplastic binder including the poly (lactic acid) and the poly (ethylene glycol), the glass transition temperature and melting point of the ink are increased and destroyed. Toughness may be lowered.
  • the polymer chain of the thermoplastic binder when it does not contain the antioxidant, the polymer chain of the thermoplastic binder is oxidized, the stability of the ink containing the thermoplastic binder is lowered, the fracture toughness of the molded article produced using the ink is weakened and mechanical The property cannot be maintained.
  • three-dimensional printing technology for the production of precision component materials used in various industries, such as electronics, automobiles, aviation, or medical may be a limitation.
  • the binder composite when the binder composite includes the poly (ethylene glycol) and the antioxidant, thermal properties such as glass transition temperature and melting point of the ink are improved, and the ink is used.
  • the mechanical properties such as the fracture toughness of the molded article produced by this can be improved and maintained.
  • FIG 2 is a view for explaining the viscosity of the ink according to the poly (ethylene glycol) content of the binder composite prepared according to an embodiment of the present invention
  • Figure 3 is prepared according to an embodiment of the present invention, the binder composite It is a figure for explaining the viscosity of the ink according to the molecular weight of poly (ethylene glycol).
  • the weight of the thermoplastic binder the content of the poly (lactic acid) is 90%, the ink of the poly (ethylene glycol) is 10%, and the content of the poly (lactic acid) is An ink of 80% and a poly (ethylene glycol) content of 20% was prepared. The viscosity according to the shear rate of the prepared inks was measured.
  • the poly (lactic acid) is 90% by weight based on the weight of the thermoplastic binder, and the poly (lactic acid) is 80%, compared to the ink having 10% of the poly (ethylene glycol). It can be seen that the viscosity of the ink in which the content of the poly (ethylene glycol) is 20%, that is, the ink in which the content of the poly (ethylene glycol) is increased is lowered. In other words, at a shear rate of 10 / s, the viscosity of the ink having 10% of poly (ethylene glycol) is 2.7 Pa ⁇ s, and the viscosity of the ink having 20% of poly (ethylene glycol) is 0.3 Pa ⁇ s, It can be seen that the viscosity of the ink is reduced.
  • the viscosity of the ink can be adjusted according to the content of the poly (ethylene glycol).
  • the viscosity of the ink may be decreased by increasing the content of the poly (ethylene glycol) or the viscosity of the ink may be increased by decreasing the content of the poly (ethylene glycol).
  • an ink including the poly (ethylene glycol) having a molecular weight of 200 and an ink including the poly (ethylene glycol) having a molecular weight of 20,000 were prepared.
  • the viscosity according to the shear rate of the prepared inks was measured.
  • the ink having a molecular weight of 200 of the poly (ethylene glycol) constituting the thermoplastic binder and the molecular weight of the poly (ethylene glycol) are The viscosity difference of 20,000 ink can be confirmed.
  • the molecular weight of the poly (ethylene glycol) is increased from 200 to 20,000, it can be seen that at the shear rate 10 / s, the viscosity of the ink is increased from 13 Pa.s to 62 Pa.s.
  • the viscosity of the ink can be adjusted according to the molecular weight of the poly (ethylene glycol).
  • the viscosity of the ink may be increased by increasing the molecular weight of the poly (ethylene glycol) or the content of the poly (ethylene glycol) may be decreased to decrease the viscosity of the ink.
  • Figure 4 is a view for explaining the antioxidant effect of the ink according to the antioxidant content of the binder composite, prepared according to an embodiment of the present invention
  • Figure 5 is an oxidation of the binder composite, prepared according to an embodiment of the present invention It is a figure for demonstrating the viscosity of ink according to inhibitor content.
  • an ink containing no antioxidant an ink containing 1% or 2% of an antioxidant, was prepared based on the weight of the ink. Molded bodies were prepared using the inks, and the molded bodies were photographed to evaluate browning phenomenon.
  • the polymer chain of the thermoplastic binder in which the poly (lactic acid) and the poly (ethylene glycol) are mixed is oxidized, and browning occurs in a molded article manufactured using the ink. You can see that.
  • the ink to which the antioxidant is added it is confirmed that oxidation of the polymer chain of the thermoplastic binder is prevented, so that browning phenomenon of the molded product manufactured using the ink is reduced. Accordingly, the oxidation of the polymer chain of the thermoplastic binder is prevented, so that the stability of the ink including the thermoplastic binder is improved, and the mechanical properties of the molded article manufactured using the ink can be maintained.
  • the preparation of the ink by adding the antioxidant is an effective method of preventing oxidation of the molded article produced using the ink, thereby suppressing browning phenomenon of the molded article.
  • an ink containing no antioxidant an ink containing 1% or 2% of an antioxidant, was prepared based on the weight of the ink. The viscosity according to the shear rate of the prepared inks was measured.
  • the ink having an antioxidant content of 1% is higher than the ink containing no antioxidant, and the ink having an antioxidant content of 2% is higher than the ink having an antioxidant content of 1%.
  • the viscosity of the ink can be adjusted according to the content of the antioxidant.
  • the viscosity of the ink may be increased by increasing the content of the antioxidant, or the viscosity of the ink may be decreased by decreasing the content of the antioxidant.
  • FIG. 6 is a view for explaining the elastic modulus of the ink according to the molecular weight of the poly (ethylene glycol) of the binder composite prepared according to the embodiment of the present invention.
  • an ink including the poly (lactic acid) and the ceramic particles and the poly (ethylene glycol) having a molecular weight of 200 was prepared, and the poly (lactic acid) and the ceramic particles were included.
  • an ink including the poly (ethylene glycol) having a molecular weight of 4,000, and preparing the ink including the poly (lactic acid) and the ceramic particles and containing the poly (ethylene glycol) having a molecular weight of 20,000 were not measured.
  • the elastic modulus of the ink containing the poly (ethylene glycol) having a molecular weight of 4,000 is greater than that of the ink containing the poly (ethylene glycol) having a molecular weight of 200, and the ink containing the poly (ethylene glycol) having a molecular weight of 4,000
  • the elastic modulus of the ink including the poly (ethylene glycol) having a molecular weight of 20,000 is large.
  • the elastic modulus of the ink containing the poly (ethylene glycol) having a molecular weight of 20,000 is confirmed to be close to the elastic modulus of the ink containing the poly (lactic acid) and not containing the poly (ethylene glycol) and the ceramic particles. Can be.
  • the elastic modulus of the ink according to the molecular weight of the poly (ethylene glycol) can be confirmed.
  • the molecular weight of the poly (ethylene glycol) is 200, 4,000, or 20,000, it can be seen that the elastic modulus of the ink increases as the molecular weight of the poly (ethylene glycol) increases.
  • the elastic modulus of the ink can be adjusted according to the molecular weight of the poly (ethylene glycol).
  • the elastic modulus of the ink may be increased by increasing the molecular weight of the poly (ethylene glycol) or the elastic modulus of the ink may be reduced by decreasing the molecular weight of the poly (ethylene glycol).
  • FIG. 7 illustrates the flexural strength and shrinkage rate of a molded article manufactured using ink according to the average particle size of spherical silica particles constituting ceramic particles added to a binder composite, prepared according to an embodiment of the present invention. It is a figure for following.
  • the ceramic particles were composed of a mixture of the spherical silica particles and the zircon silicate particles.
  • the spherical silica particles were composed of particles having an average particle size of 30 ⁇ m, 9 ⁇ m (99.6%, Sibelco, Belgium), or 0.3 ⁇ m (99.7%, Denka, Japan), and the zirconium silicate was an amorphous particle with an average particle size of 1 ⁇ m. (97%, Cenotec, Korea).
  • the bending strength of the molded bodies prepared from the ink to which the ceramic particles were added according to Examples 1 to 9 was measured by using a universal testing machine. Bending strength measurement standard is according to ASTM C1161-13, UTM used for bending strength measurement is equipped with 250kg load cell (H10SK, Hounsefield, England), and bending strength measurement is 80mm span size, 1mm / min cross-head Progress at speed.
  • the mixing ratio of the spherical silica particles having an average particle size of 30 ⁇ m, 9 ⁇ m, or 0.3 ⁇ m constituting the ceramic particles the bending strength and shrinkage rate of the molded product produced using the ink to which the ceramic particles are added are changed. You can see that.
  • the mixing ratio of the spherical silica particles having an average particle size of 30 ⁇ m, 9 ⁇ m, or 0.3 ⁇ m constituting the ceramic particles can be controlled.
  • a binder composite can be provided, which can produce a molded article in which bending strength and shrinkage rate are adjusted according to the use.
  • Figure 8 is a view for explaining the viscosity of the ink according to the shape of the silica particles constituting the ceramic particles added to the binder composite prepared according to the embodiment and comparative example of the present invention
  • Figure 9 is an embodiment of the present invention The figure for demonstrating the particle size distribution of the ceramic particle added to the binder composite manufactured according to this.
  • the spherical and amorphous silica to which the ceramic particles are added including the 52.5% spherical silica particles having a mean particle size of 30 ⁇ m, 22.5% of spherical silica particles having a particle size of 9 ⁇ m, and 25% of zirconium silicate particles having a size of 1 ⁇ m.
  • the ink (irregular) to which the ceramic particles containing particles were added was prepared. The viscosity according to the shear rate of the prepared inks was measured.
  • the ink to which the ceramic particles containing the spherical silica particles are added has a lower viscosity than the ink to which the ceramic particles containing the amorphous silica particles are added.
  • the shape of the silica particles included in the ceramic particles it is possible to adjust the viscosity of the ink to which the ceramic particles are added.
  • the viscosity of the ink may be decreased by adding the ceramic particles including the spherical silica particles, or the viscosity of the ink may be increased by adding the ceramic particles including the amorphous silica.
  • the ceramic particles were prepared including 52.5% spherical silica particles having an average particle size of 30 ⁇ m, 22.5% spherical silica particles having a size of 9 ⁇ m, and 25% zirconium silicate particles having a thickness of 1 ⁇ m.
  • the particle size distribution of the prepared ceramic particles was measured.
  • the particle size of the ceramic particles was measured from a minimum of 0.4 ⁇ m to a maximum of 100 ⁇ m.
  • the binder composite according to the embodiment of the present invention is excellent in mechanical properties and elastic modulus, and can be used in a three-dimensional printer process.

Abstract

A method for preparing a binder composite is provided. The method for preparing a binder composite comprises the steps of: preparing a thermoplastic binder in which poly(lactic acid) and poly(ethylene glycol) are mixed; and preparing an ink by adding, to the thermoplastic binder, ceramic particles and an antioxidant preventing the oxidation of the poly(lactic acid).

Description

바인더 복합물 및 그 제조 방법Binder Composite and Manufacturing Method Thereof
본 발명은 바인더 복합물 및 그 제조 방법에 관한 것으로, 보다 상세하게는, PLA 및 PEG가 혼합된 열가소성 바인더, 세라믹 입자 및 산화 방지제를 포함하는 바인더 복합물 및 그 제조 방법에 관한 것이다.The present invention relates to a binder composite and a method for producing the same, and more particularly, to a binder composite comprising a thermoplastic binder mixed with PLA and PEG, ceramic particles and an antioxidant and a method for producing the same.
3차원 프린팅 기술은, 프린팅 방식에 따라, 열가소성 수지를 압출하여 출력하는 FDM(Fused deposition modeling), 광경화성 수지에 빛을 조사하여 경화시키는 SLA(Stereolithography) 및 플라스틱, 세라믹, 금속, 또는 유리 등의 분말 재료에 직접적으로 레이저를 조사하여, 용융된 분말 재료를 조형하는 SLS(Selective laser sintering) 방식으로 분류된다.Three-dimensional printing technology, such as FDM (Fused deposition modeling) to extrude and output the thermoplastic resin according to the printing method, SLA (Stereolithography) to irradiate and cure the light curable resin and plastic, ceramic, metal, or glass Laser is directly irradiated to the powder material, and classified into a SLS (Selective laser sintering) method for molding molten powder material.
현재 3차원 프린팅의 재료로 가장 보편적으로 사용되는 플라스틱은 비용이 저렴하고 가공성이 우수한 반면, 플라스틱으로 제조된 성형체는 열에 약하고 강도가 낮다. 이와 달리, 세라믹으로 제조된 성형체는 고온에 강하고 내구성이 우수하여, SLS 방식을 이용한 3차원 프린팅의 재료로 가장 많이 이용되고 있으나, SLS 방식을 이용한 3차원 프린팅은 매우 고가의 기기가 필요하며, 세라믹은, 점도가 매우 높아 가공성이 떨어진다.Plastics, which are currently the most commonly used materials for three-dimensional printing, are inexpensive and have excellent processability, while molded articles made of plastic are weak in heat and low in strength. On the other hand, molded articles made of ceramics are resistant to high temperatures and excellent in durability, and thus are most commonly used as materials for three-dimensional printing using the SLS method, but three-dimensional printing using the SLS method requires very expensive equipment, and ceramics. Silver is very high and inferior in workability.
이와 같이, 3차원 프린팅의 문제로 지적되는 강도, 표면특성, 제조시간, 해상도, 또는 완제품의 물성 등은 원료 소재에서 비롯된 것으로, 최근, 다양한 재료를 이용하여, 3차원 프린팅으로 제조되는 성형체의 특성을 향상시킬 수 있는 복합 잉크에 대해 활발한 연구가 진행되고 있다.As such, the strength, surface properties, manufacturing time, resolution, or physical properties of the finished product pointed out as a problem of three-dimensional printing originate from the raw material, and recently, characteristics of a molded body manufactured by three-dimensional printing using various materials. Active research is being conducted on composite inks that can improve the quality of the resin.
예를 들어, 대한민국 특허 공개 번호 10-2015-0042660 (출원인: 주식회사 로킷, 출원번호: 10-2013-0121602)는 3차원 프린팅용 잉크에 관한 것으로, 세라믹 및 Poly(lactic acid)의 혼합물을 잉크로 사용함으로써, 상기 잉크로 제조되는 성형체의 강도를 향상시키는 3차원 프린팅용 잉크를 개시한다.For example, Korean Patent Publication No. 10-2015-0042660 (Applicant: Rocket, Inc., Appl. No. 10-2013-0121602) relates to an ink for three-dimensional printing, and a mixture of ceramic and poly (lactic acid) with ink. By using this, the three-dimensional printing ink which improves the intensity | strength of the molded object manufactured with the said ink is disclosed.
본 발명이 해결하고자 하는 일 기술적 과제는, 친환경 유기 바인더를 포함하는 바인더 복합물의 제조 방법을 제공하는 데 있다.One technical problem to be solved by the present invention is to provide a method for producing a binder composite comprising an environmentally friendly organic binder.
본 발명이 해결하고자 하는 다른 기술적 과제는, 점도 조절이 용이한 바인더 복합물의 제조 방법을 제공하는 데 있다.Another technical problem to be solved by the present invention is to provide a method for producing a binder composite with easy viscosity control.
본 발명이 해결하고자 하는 다른 기술적 과제는, 탄성률의 조절이 용이한 바인더 복합물의 제조 방법을 제공하는 데 있다.Another technical problem to be solved by the present invention is to provide a method for producing a binder composite that is easy to control the elastic modulus.
본 발명이 해결하고자 하는 다른 기술적 과제는, 안정성이 향상된 바인더 복합물의 제조 방법을 제공하는 데 있다.Another technical problem to be solved by the present invention is to provide a method for producing a binder composite with improved stability.
본 발명이 해결하고자 하는 또 다른 기술적 과제는, 열적 특성이 향상된 바인더 복합물의 제조 방법을 제공하는 데 있다.Another technical problem to be solved by the present invention is to provide a method for producing a binder composite with improved thermal properties.
본 발명이 해결하고자 하는 또 다른 기술적 과제는, 기계적 특성이 향상된 바인더 복합물의 제조 방법을 제공하는 데 있다.Another technical problem to be solved by the present invention is to provide a method for producing a binder composite with improved mechanical properties.
본 발명이 해결하고자 하는 기술적 과제는 상술된 것에 제한되지 않는다.The technical problem to be solved by the present invention is not limited to the above.
상기 기술적 과제를 해결하기 위해, 본 발명은 바인더 복합물의 제조 방법을 제공한다.In order to solve the above technical problem, the present invention provides a method for producing a binder composite.
일 실시 예에 따르면, 바인더 복합물의 제조 방법은, Poly(lactic acid) 및 Poly(ethylene glycol)이 혼합된 열가소성 바인더를 제조하는 단계 및 상기 열가소성 바인더에 세라믹 입자 및 Poly(lactic acid)의 산화를 방지하는 산화 방지제를 첨가하여 잉크를 제조하는 단계를 포함한다.According to one embodiment, the manufacturing method of the binder composite, preparing a thermoplastic binder mixed with Poly (lactic acid) and Poly (ethylene glycol) and to prevent oxidation of ceramic particles and Poly (lactic acid) in the thermoplastic binder. Adding an antioxidant to prepare the ink.
일 실시 예에 따르면, 바인더 복합물의 제조 방법은, 상기 Poly(ethylene glycol)의 함량 또는 분자량을 조절하여 상기 잉크의 점도를 조절하는 것을 포함할 수 있다.According to one embodiment, the manufacturing method of the binder composite may include adjusting the viscosity of the ink by adjusting the content or molecular weight of the poly (ethylene glycol).
일 실시 예에 따르면, 바인더 복합물의 제조 방법은, 상기 Poly(ethylene glycol)의 함량을 조절하여 상기 잉크의 유리 전이 온도 및 녹는점을 조절하는 것을 포함할 수 있다.According to one embodiment, the manufacturing method of the binder composite may include controlling the glass transition temperature and the melting point of the ink by controlling the content of the poly (ethylene glycol).
일 실시 예에 따르면, 바인더 복합물의 제조 방법은, 상기 Poly(ethylene glycol)의 함량을 조절하여, 상기 잉크를 이용하여 제조되는 성형체의 파괴 인성(fracture toughness)을 조절하는 것을 포함할 수 있다.According to one embodiment, the manufacturing method of the binder composite may include controlling the fracture toughness of the molded product manufactured by using the ink by adjusting the content of the poly (ethylene glycol).
일 실시 예에 따르면, 바인더 복합물의 제조 방법은, 상기 산화 방지제의 함량을 조절하여 상기 잉크의 점도를 조절하는 것을 포함할 수 있다.According to one embodiment, the manufacturing method of the binder composite may include adjusting the viscosity of the ink by adjusting the content of the antioxidant.
일 실시 예에 따르면, 바인더 복합물의 제조 방법은, 상기 세라믹 입자의 형상을 조절하여 상기 잉크의 점도를 조절하는 것을 포함할 수 있다.According to one embodiment, the manufacturing method of the binder composite may include adjusting the viscosity of the ink by adjusting the shape of the ceramic particles.
일 실시 예에 따르면, 상기 poly(lactic acid) 및 상기 poly(ethylene glycol)이 혼합된 상기 열가소성 바인더를 제조하는 단계는, 상기 열가소성 바인더를 열처리하는 단계를 포함할 수 있다.According to an embodiment, the manufacturing of the thermoplastic binder in which the poly (lactic acid) and the poly (ethylene glycol) are mixed may include heat treating the thermoplastic binder.
일 실시 예에 따르면, 상기 바인더 복합물의 제조 방법은, 상기 열가소성 바인더에 상기 세라믹 입자를 첨가하기 전, 상기 세라믹 입자를 볼밀하는 단계를 더 포함할 수 있다.According to an embodiment, the method of manufacturing the binder composite may further include ball milling the ceramic particles before adding the ceramic particles to the thermoplastic binder.
상기 기술적 과제를 해결하기 위해, 본 발명은 바인더 복합물을 제공한다.In order to solve the above technical problem, the present invention provides a binder composite.
일 실시 예에 따르면, 상기 바인더 복합물은, Poly(lactic acid) 및 Poly(ethylene glycol)을 포함하는 열가소성 바인더, 세라믹 입자 및 상기 Poly(lactic acid)의 산화를 방지하는 산화 방지제를 포함하는 잉크를 포함하되, 상기 잉크의 점도가, 상기 Poly(ethylene glycol)의 함량이 감소함에 따라 감소하고, 상기 Poly(ethylene glycol)의 분자량 및 상기 산화 방지제의 함량이 증가함에 따라 증가하는 것을 포함하고, 상기 잉크의 점도가, 상기 세라믹 입자의 형상이 구형에 가까울수록 감소하는 것을 포함하고, 상기 잉크의 점도는, 상기 Poly(ethylene glycol)의 함량 및 분자량, 상기 산화 방지제의 함량, 및 상기 세라믹 입자의 형상을 조절하여, 조절되는 것을 포함한다.According to an embodiment, the binder composite may include a thermoplastic binder including poly (lactic acid) and poly (ethylene glycol), an ink including ceramic particles, and an antioxidant for preventing oxidation of the poly (lactic acid). However, the viscosity of the ink, and decreases as the content of the poly (ethylene glycol) decreases, and includes increasing as the molecular weight of the poly (ethylene glycol) and the content of the antioxidant, The viscosity includes decreasing as the shape of the ceramic particles approaches a sphere, and the viscosity of the ink controls the content and molecular weight of the poly (ethylene glycol), the content of the antioxidant, and the shape of the ceramic particles. And include being adjusted.
일 실시 예에 따르면, 상기 세라믹 입자는 실리카(SiO2) 입자, 또는 지르콘실리케이트(ZrSiO4) 입자 중에서 적어도 어느 하나를 포함할 수 있다.According to one embodiment, the ceramic particles may include at least one of silica (SiO 2 ) particles, or zirconium silicate (ZrSiO 4 ) particles.
본 발명의 실시 예에 따른 바인더 복합물은, Poly(lactic acid) 및 Poly(ethylene glycol)가 혼합된 열가소성 바인더, 세라믹 입자 및 산화 방지제를 포함한다. 상기 잉크의 점도는, 상기 Poly(ethylene glycol)의 함량 및 분자량, 상기 산화 방지제의 함량, 및 상기 세라믹 입자의 형상을 조절하여, 조절될 수 있다. 이에 따라, 용도에 맞게 잉크의 점도가 조절되는, 바인더 복합물이 제공될 수 있다.The binder composite according to the embodiment of the present invention includes a thermoplastic binder, ceramic particles, and an antioxidant in which poly (lactic acid) and poly (ethylene glycol) are mixed. The viscosity of the ink may be adjusted by adjusting the content and molecular weight of the poly (ethylene glycol), the content of the antioxidant, and the shape of the ceramic particles. Accordingly, a binder composite may be provided in which the viscosity of the ink is adjusted to suit the purpose.
또한, 본 발명의 실시 예에 따른 바인더 복합물은, 상기 열가소성 바인더로 상기 Poly(lactic acid) 및 상기 Poly(ethylene glycol)를 포함한다. 이에 따라, 유리 전이 온도 및 녹는점과 같은 열적 특성, 및 상기 잉크를 이용하여 제조된 성형체의 파괴 인성과 같은 기계적 특성이 향상된, 바인더 복합물이 제공될 수 있다.In addition, the binder composite according to the embodiment of the present invention, the thermoplastic binder includes the poly (lactic acid) and the poly (ethylene glycol). Accordingly, a binder composite can be provided with improved thermal properties such as glass transition temperature and melting point, and mechanical properties such as fracture toughness of shaped bodies produced using the ink.
또한, 본 발명의 실시 예에 따른 바인더 복합물은, 상기 열가소성 바인더로 상기 Poly(lactic acid) 및 상기 Poly(ethylene glycol)를 포함한다. 상기 Poly(ethylene glycol)의 분자량에 따라 상기 잉크의 탄성률이 조절될 수 있다. 이에 따라, 용도에 맞게 탄성률이 조절된 바인더 복합물이 제공될 수 있다.In addition, the binder composite according to the embodiment of the present invention, the thermoplastic binder includes the poly (lactic acid) and the poly (ethylene glycol). The elastic modulus of the ink may be adjusted according to the molecular weight of the poly (ethylene glycol). Accordingly, a binder composite whose elastic modulus is adjusted to suit the purpose can be provided.
또한, 본 발명의 실시 예에 따른 바인더 복합물은, 상기 열가소성 바인더의 산화를 방지하기 위한 상기 산화 방지제를 포함한다. 이에 따라, 상기 열가소성 바인더의 고분자 체인의 산화가 방지되어, 상기 열가소성 바인더의 기계적 특성이 유지될 수 있는 바인더 복합물이 제공될 수 있다.In addition, the binder composite according to the embodiment of the present invention includes the antioxidant for preventing oxidation of the thermoplastic binder. Accordingly, the binder composite may be provided to prevent the oxidation of the polymer chain of the thermoplastic binder, thereby maintaining the mechanical properties of the thermoplastic binder.
도 1은 본 발명의 실시 예에 따른 바인더 복합물의 제조 방법을 설명하기 위한 순서도이다.1 is a flowchart illustrating a method of manufacturing a binder composite according to an embodiment of the present invention.
도 2는 본 발명의 실시 예에 따라 제조된 바인더 복합물의 Poly(ethylene glycol) 함량에 따른 잉크의 점도를 설명하기 위한 도면이다.2 is a view for explaining the viscosity of the ink according to the poly (ethylene glycol) content of the binder composite prepared according to the embodiment of the present invention.
도 3은 본 발명의 실시 예에 따라 제조된 바인더 복합물의 Poly(ethylene glycol) 분자량에 따른 잉크의 점도를 설명하기 위한 도면이다.3 is a view for explaining the viscosity of the ink according to the molecular weight of the poly (ethylene glycol) of the binder composite prepared according to the embodiment of the present invention.
도 4는 본 발명의 실시 예에 따라 제조된 바인더 복합물의 산화 방지제 함량에 따른 잉크의 산화 방지 효과를 설명하기 위한 도면이다.4 is a view for explaining the antioxidant effect of the ink according to the antioxidant content of the binder composite prepared according to the embodiment of the present invention.
도 5는 본 발명의 실시 예에 따라 제조된 바인더 복합물의 산화 방지제 함량에 따른 잉크의 점도를 설명하기 위한 도면이다.5 is a view for explaining the viscosity of the ink according to the antioxidant content of the binder composite prepared according to the embodiment of the present invention.
도 6은 본 발명의 실시 예에 따라 제조된 바인더 복합물의 Poly(ethylene glycol) 분자량에 따른 잉크의 탄성률을 설명하기 위한 도면이다.6 is a view for explaining the elastic modulus of the ink according to the molecular weight of Poly (ethylene glycol) of the binder composite prepared according to the embodiment of the present invention.
도 7은 본 발명의 실시 예에 따라 제조된 바인더 복합물에 첨가되는 세라믹 입자를 구성하는 구형 실리카 입자의 평균 입도에 따른, 잉크를 이용하여 제조된 성형체의 굽힘 강도(flexural strength) 및 수축률을 설명하기 위한 도면이다.7 is a view illustrating the flexural strength and shrinkage rate of a molded article manufactured using ink according to the average particle size of the spherical silica particles constituting the ceramic particles added to the binder composite prepared according to the embodiment of the present invention. It is a drawing for
도 8은 본 발명의 실시 예 및 비교 예에 따라 제조된 바인더 복합물에 첨가되는 세라믹 입자를 구성하는 실리카 입자의 형상에 따른 잉크의 점도를 설명하기 위한 도면이다.8 is a view for explaining the viscosity of the ink according to the shape of the silica particles constituting the ceramic particles added to the binder composite prepared according to the embodiment and comparative example of the present invention.
도 9는 본 발명의 실시 예에 따라 제조된 바인더 복합물에 첨가되는 세라믹 입자의 입도 분포를 설명하기 위한 도면이다.9 is a view for explaining the particle size distribution of the ceramic particles added to the binder composite prepared according to the embodiment of the present invention.
이하, 첨부된 도면들을 참조하여 본 발명의 바람직한 실시 예를 상세히 설명할 것이다. 그러나 본 발명의 기술적 사상은 여기서 설명되는 실시 예에 한정되지 않고 다른 형태로 구체화 될 수도 있다. 오히려, 여기서 소개되는 실시 예는 개시된 내용이 철저하고 완전해질 수 있도록 그리고 당업자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 제공되는 것이다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the technical idea of the present invention is not limited to the exemplary embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed contents are thorough and complete, and that the spirit of the present invention can be sufficiently delivered to those skilled in the art.
본 명세서에서, 어떤 구성요소가 다른 구성요소 상에 있다고 언급되는 경우에 그것은 다른 구성요소 상에 직접 형성될 수 있거나 또는 그들 사이에 제 3의 구성요소가 개재될 수도 있다는 것을 의미한다. 또한, 도면들에 있어서, 막 및 영역들의 두께는 기술적 내용의 효과적인 설명을 위해 과장된 것이다.In the present specification, when a component is mentioned to be on another component, it means that it may be formed directly on the other component or a third component may be interposed therebetween. In addition, in the drawings, the thicknesses of films and regions are exaggerated for effective explanation of technical contents.
또한, 본 명세서의 다양한 실시 예 들에서 제1, 제2, 제3 등의 용어가 다양한 구성요소들을 기술하기 위해서 사용되었지만, 이들 구성요소들이 이 같은 용어들에 의해서 한정되어서는 안 된다. 이들 용어들은 단지 어느 구성요소를 다른 구성요소와 구별시키기 위해서 사용되었을 뿐이다. 따라서, 어느 한 실시 예에 제 1 구성요소로 언급된 것이 다른 실시 예에서는 제 2 구성요소로 언급될 수도 있다. 여기에 설명되고 예시되는 각 실시 예는 그것의 상보적인 실시 예도 포함한다. 또한, 본 명세서에서 '및/또는'은 전후에 나열한 구성요소들 중 적어도 하나를 포함하는 의미로 사용되었다.In addition, in various embodiments of the present specification, terms such as first, second, and third are used to describe various components, but these components should not be limited by these terms. These terms are only used to distinguish one component from another. Thus, what is referred to as a first component in one embodiment may be referred to as a second component in another embodiment. Each embodiment described and illustrated herein also includes its complementary embodiment. In addition, the term 'and / or' is used herein to include at least one of the components listed before and after.
명세서에서 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한 복수의 표현을 포함한다. 또한, "포함하다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 구성요소 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징이나 숫자, 단계, 구성요소 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 배제하는 것으로 이해되어서는 안 된다. In the specification, the singular encompasses the plural unless the context clearly indicates otherwise. In addition, the terms "comprise" or "having" are intended to indicate that there is a feature, number, step, element, or combination thereof described in the specification, and one or more other features or numbers, steps, configurations It should not be understood to exclude the possibility of the presence or the addition of elements or combinations thereof.
또한, 하기에서 본 발명을 설명함에 있어 관련된 공지 기능 또는 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략할 것이다.In addition, in the following description of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted.
도 1은 본 발명의 실시 예에 따른 바인더 복합물의 제조 방법을 설명하기 위한 순서도이다.1 is a flowchart illustrating a method of manufacturing a binder composite according to an embodiment of the present invention.
도 1을 참조하면, Poly(lactic acid) 및 Poly(ethylene glycol)가 혼합된 열가소성 바인더가 제조된다(S110). 일 실시 예에 따르면, 상기 Poly(ethylene glycol)은 가소제로써, 상기 Poly(ethylene glycol)을 포함하는 잉크의 유리 전이 온도 및 녹는점을 낮춰, 상기 잉크의 가공성이 향상될 수 있다. 또한, 일 실시 예에 따르면, 상기 Poly(ethylene glycol)에 의해, 상기 잉크를 이용하여 제조되는 성형체의 파괴 인성(fracture toughness)이 조절될 수 있다. 다시 말하면, 상기 Poly(ethylene glycol)의 함량이 증가됨에 따라, 상기 잉크의, 파괴 인성이 증가되고, 재료를 파괴하는 데 필요한 에너지인 파괴 인성이 증가됨에 따라, 상기 잉크를 이용하여 제조되는 성형체의 기계적 강도가 향상될 수 있다.Referring to FIG. 1, a thermoplastic binder in which poly (lactic acid) and poly (ethylene glycol) are mixed is manufactured (S110). According to one embodiment, the poly (ethylene glycol) is a plasticizer, by lowering the glass transition temperature and melting point of the ink containing the poly (ethylene glycol), the processability of the ink can be improved. In addition, according to an embodiment, the fracture toughness of the molded product manufactured using the ink may be controlled by the poly (ethylene glycol). In other words, as the content of the poly (ethylene glycol) is increased, the fracture toughness of the ink is increased, and the fracture toughness, which is the energy required to destroy the material, is increased, thereby increasing the amount of poly-ethylene glycol. Mechanical strength can be improved.
또한, 일 실시 예에 따르면, 상기 잉크의 점도가, 상기 Poly(ethylene glycol)에 의해 조절되고, 이에 따라, 상기 잉크를 구성하는 물질들이 균일하게 혼합될 수 있다. 다시 말하면, 상기 Poly(ethylene glycol)의 함량이 증가됨에 따라, 상기 잉크의 점도가 감소되고, 상기 Poly(ethylene glycol)의 함량이 감소됨에 따라, 상기 잉크의 점도가 증가될 수 있다. 또한, 일 실시 예에 따르면, 상기 Poly(ethylene glycol)의 분자량이 조절되어 상기 잉크의 점도가 조절될 수 있다. 다시 말하면, 상기 Poly(ethylene glycol)의 분자량이 증가됨에 따라, 상기 잉크의 점도가 증가되고, 상기 Poly(ethylene glycol)의 분자량이 감소됨에 따라, 상기 잉크의 점도가 감소될 수 있다.In addition, according to one embodiment, the viscosity of the ink is controlled by the poly (ethylene glycol), and accordingly, the materials constituting the ink may be uniformly mixed. In other words, as the content of the poly (ethylene glycol) increases, the viscosity of the ink decreases, and as the content of the poly (ethylene glycol) decreases, the viscosity of the ink may increase. In addition, according to one embodiment, the molecular weight of the poly (ethylene glycol) may be adjusted to control the viscosity of the ink. In other words, as the molecular weight of the poly (ethylene glycol) increases, the viscosity of the ink increases, and as the molecular weight of the poly (ethylene glycol) decreases, the viscosity of the ink may decrease.
일 실시 예에 따르면, 상기 poly(lactic acid) 및 상기 poly(ethylene glycol)이 혼합된 상기 열가소성 바인더를 제조하는 단계는, 상기 열가소성 바인더를 열처리하는 단계를 포함할 수 있다. 예를 들어, 상기 열처리는 80℃에서 수행될 수 있다.According to an embodiment, the manufacturing of the thermoplastic binder in which the poly (lactic acid) and the poly (ethylene glycol) are mixed may include heat treating the thermoplastic binder. For example, the heat treatment may be performed at 80 ° C.
상기 열가소성 바인더에 세라믹 입자 및 상기 Poly(lactic acid)의 산화를 방지하는 산화 방지제를 첨가하여 잉크가 제조된다(S120). 예를 들어, 상기 세라믹 입자는 구형(spherical) 실리카(SiO2) 입자 또는 지르콘실리케이트(ZrSiO4) 입자 중에서 적어도 어느 하나 이상을 포함할 수 있다. An ink is manufactured by adding an antioxidant to prevent oxidation of ceramic particles and the poly (lactic acid) to the thermoplastic binder (S120). For example, the ceramic particles may include at least one of spherical silica (SiO 2 ) particles or zirconium silicate (ZrSiO 4 ) particles.
예를 들어, 상기 산화 방지제는 butylated hydroxyanisole(BHA), butylated hydroxytoluene(BHT), propyl gallate 및 tert-butylhydroquinone(TBHQ)의 혼합물, 2% α-tocopherol, 1% butylated hydroxytoluene(BHT) 및 1% butylated hydroxyanisole(BHA)의 혼합물 또는 tris(2,4-di-tert-butylphenyl)phosphate 및 Tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy-hydrocinnam ate)]methane의 혼합물 중에서 적어도 어느 하나 이상을 포함할 수 있다.For example, the antioxidant is a mixture of butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), propyl gallate and tert-butylhydroquinone (TBHQ), 2% α-tocopherol, 1% butylated hydroxytoluene (BHT) and 1% butylated hydroxyanisole At least one of a mixture of (BHA) or a mixture of tris (2,4-di-tert-butylphenyl) phosphate and Tetrakis [methylene (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)] methane It may include.
일 실시 예에 따르면, 상기 세라믹 입자의 형상에 있어서, 비정형 실리카 입자를 이용하는 것에 비해, 상기 구형 실리카 입자를 이용할 시, 상기 잉크의 점도가 감소될 수 있다. 다시 말하면, 상기 세라믹 입자의 형상이 구형에 가까울수록, 상기 잉크의 점도가 감소될 수 있다. According to one embodiment, in the shape of the ceramic particles, when using the spherical silica particles, compared to using amorphous silica particles, the viscosity of the ink can be reduced. In other words, the closer the shape of the ceramic particles is to the spherical shape, the lower the viscosity of the ink.
상기 산화 방지제는 Poly(lactic acid)의 산화를 방지하여, 상기 잉크의 안정성을 향상시킬 수 있다. 일 실시 예에 따르면, 상기 산화 방지제에 의해 상기 잉크의 점도가 조절될 수 있다. 다시 말하면, 상기 산화 방지제의 함량이 증가됨에 따라, 상기 잉크의 점도가 증가되고, 상기 산화 방지제의 함량이 감소됨에 따라, 상기 잉크의 점도가 감소될 수 있다.The antioxidant may prevent oxidation of poly (lactic acid), thereby improving stability of the ink. According to one embodiment, the viscosity of the ink may be adjusted by the antioxidant. In other words, as the content of the antioxidant is increased, the viscosity of the ink is increased, and as the content of the antioxidant is decreased, the viscosity of the ink can be decreased.
일 실시 예에 따르면, 상기 세라믹 입자는, 상기 열가소성 바인더에 첨가되기 전, 볼밀(ball mill)되어 첨가될 수 있다.According to an embodiment of the present disclosure, the ceramic particles may be added by being ball milled before being added to the thermoplastic binder.
본 발명의 실시 예에 따른 바인더 복합물은, 상기 Poly(lactic acid) 및 상기 Poly(ethylene glycol)을 포함하는 상기 열가소성 바인더, 상기 세라믹 입자 및 상기 산화 방지제를 포함하되, 상기 Poly(ethylene glycol)의 함량 및 분자량, 상기 산화 방지제의 함량, 및 상기 세라믹 입자의 형상을 조절하여, 상기 잉크의 점도가 용이하게 조절될 수 있다. 이로 인해, 잉크의 점도가 용도에 적합하게 조절되어 가공성이 향상된 바인더 복합물이 제공될 수 있다.The binder composite according to the embodiment of the present invention includes the thermoplastic binder including the poly (lactic acid) and the poly (ethylene glycol), the ceramic particles, and the antioxidant, but the content of the poly (ethylene glycol) And by adjusting the molecular weight, the content of the antioxidant, and the shape of the ceramic particles, the viscosity of the ink can be easily adjusted. Because of this, the viscosity of the ink is adjusted to suit the application can be provided a binder composite with improved processability.
또한, 본 발명의 실시 예에 따른 바인더 복합물은, 상기 열가소성 바인더로 상기 Poly(lactic acid) 및 상기 Poly(ethylene glycol)를 포함하고, 상기 열가소성 바인더의 산화를 방지하기 위한 상기 산화 방지제를 포함한다. 이로 인해, 본 발명의 실시 예에 따른 바인더 복합물의 유리 전이 온도 및 녹는점이 감소되며, 상기 잉크를 이용하여 제조된 성형체의 파괴 인성이 향상되고, 유지될 수 있다.In addition, the binder composite according to the embodiment of the present invention includes the poly (lactic acid) and the poly (ethylene glycol) as the thermoplastic binder, and includes the antioxidant for preventing oxidation of the thermoplastic binder. As a result, the glass transition temperature and melting point of the binder composite according to the embodiment of the present invention are reduced, and the fracture toughness of the molded article manufactured using the ink can be improved and maintained.
본 발명의 실시 예와 달리, 바인더 복합물로, 상기 Poly(lactic acid) 및 상기 Poly(ethylene glycol)을 포함하는 상기 열가소성 바인더를 포함하지 못하는 경우, 상기 잉크의 유리 전이 온도 및 녹는점이 증가되고, 파괴 인성이 저하될 수 있다. 또는, 상기 산화 방지제를 포함하지 못하는 경우, 상기 열가소성 바인더의 고분자 체인이 산화되어, 상기 열가소성 바인더를 포함하는 상기 잉크의 안정성이 저하되고, 상기 잉크를 이용해 제조된 성형체의, 파괴 인성이 약화되어 기계적 특성이 유지될 수 없다. 이로 인해, 전자, 자동차, 항공, 또는 의료 등 다양한 산업군에서 이용되는 정밀 부품 소재의 생산을 위한 3차원 프린팅 기술에 제약이 될 수 있다.Unlike an embodiment of the present invention, when the binder composite does not include the thermoplastic binder including the poly (lactic acid) and the poly (ethylene glycol), the glass transition temperature and melting point of the ink are increased and destroyed. Toughness may be lowered. Alternatively, when it does not contain the antioxidant, the polymer chain of the thermoplastic binder is oxidized, the stability of the ink containing the thermoplastic binder is lowered, the fracture toughness of the molded article produced using the ink is weakened and mechanical The property cannot be maintained. As a result, three-dimensional printing technology for the production of precision component materials used in various industries, such as electronics, automobiles, aviation, or medical, may be a limitation.
하지만, 본 발명의 실시 예와 같이, 바인더 복합물이, 상기 Poly(ethylene glycol) 및 상기 산화 방지제를 포함하는 경우, 상기 잉크의 유리 전이 온도 및 녹는점과 같은 열적 특성이 향상되고, 상기 잉크를 이용하여 제조된 성형체의 파괴 인성과 같은 기계적 특성이 향상되고, 유지될 수 있다.However, as in the embodiment of the present invention, when the binder composite includes the poly (ethylene glycol) and the antioxidant, thermal properties such as glass transition temperature and melting point of the ink are improved, and the ink is used. The mechanical properties such as the fracture toughness of the molded article produced by this can be improved and maintained.
이하, 본 발명의 실시 예에 따른 바인더 복합물의 구체적인 실험 예들이 설명된다. Hereinafter, specific experimental examples of the binder composite according to the embodiment of the present invention will be described.
도 2는 본 발명의 실시 예에 따라 제조된, 바인더 복합물의 Poly(ethylene glycol) 함량에 따른 잉크의 점도를 설명하기 위한 도면이고, 도 3은 본 발명의 실시 예에 따라 제조된, 바인더 복합물의 Poly(ethylene glycol) 분자량에 따른 잉크의 점도를 설명하기 위한 도면이다.2 is a view for explaining the viscosity of the ink according to the poly (ethylene glycol) content of the binder composite prepared according to an embodiment of the present invention, Figure 3 is prepared according to an embodiment of the present invention, the binder composite It is a figure for explaining the viscosity of the ink according to the molecular weight of poly (ethylene glycol).
도 2를 참조하면, 상기 열가소성 바인더의 중량 대비, 상기 Poly(lactic acid)의 함량이 90%이고, 상기 Poly(ethylene glycol)의 함량이 10%인 잉크, 및 상기 Poly(lactic acid)의 함량이 80%이고, 상기 Poly(ethylene glycol)의 함량이 20%인 잉크를 제조하였다. 제조된 상기 잉크들의 shear rate에 따른 점도를 측정하였다.Referring to Figure 2, the weight of the thermoplastic binder, the content of the poly (lactic acid) is 90%, the ink of the poly (ethylene glycol) is 10%, and the content of the poly (lactic acid) is An ink of 80% and a poly (ethylene glycol) content of 20% was prepared. The viscosity according to the shear rate of the prepared inks was measured.
상기 열가소성 바인더의 중량 대비, 상기 Poly(lactic acid)의 함량이 90%이고, 상기 Poly(ethylene glycol)의 함량이 10%인 잉크에 비해, 상기 Poly(lactic acid)의 함량이 80%이고, 상기 Poly(ethylene glycol)의 함량이 20%인 잉크, 즉, 상기 Poly(ethylene glycol)의 함량이 증가된 잉크의 점도가 낮아진 것을 확인할 수 있다. 다시 말하면, shear rate 10/s에서, 상기 Poly(ethylene glycol)이 10%인 잉크의 점도는 2.7Pa·s이고, 상기 Poly(ethylene glycol)이 20%인 잉크의 점도는 0.3Pa·s으로, 잉크의 점도가 감소한 것을 확인 수 있다. The poly (lactic acid) is 90% by weight based on the weight of the thermoplastic binder, and the poly (lactic acid) is 80%, compared to the ink having 10% of the poly (ethylene glycol). It can be seen that the viscosity of the ink in which the content of the poly (ethylene glycol) is 20%, that is, the ink in which the content of the poly (ethylene glycol) is increased is lowered. In other words, at a shear rate of 10 / s, the viscosity of the ink having 10% of poly (ethylene glycol) is 2.7 Pa · s, and the viscosity of the ink having 20% of poly (ethylene glycol) is 0.3 Pa · s, It can be seen that the viscosity of the ink is reduced.
이에 따라, 상기 Poly(ethylene glycol)의 함량에 따라 상기 잉크의 점도가 조절될 수 있는 것을 알 수 있다. 다시 말하면, 상기 Poly(ethylene glycol)의 함량을 증가시켜 상기 잉크의 점도를 감소시키거나, 상기 Poly(ethylene glycol)의 함량을 감소시켜 상기 잉크의 점도를 증가시킬 수 있다.Accordingly, it can be seen that the viscosity of the ink can be adjusted according to the content of the poly (ethylene glycol). In other words, the viscosity of the ink may be decreased by increasing the content of the poly (ethylene glycol) or the viscosity of the ink may be increased by decreasing the content of the poly (ethylene glycol).
도 3을 참조하면, 분자량이 200인 상기 Poly(ethylene glycol)을 포함하는 잉크, 및 분자량이 20,000인 상기 Poly(ethylene glycol)을 포함하는 잉크를 제조하였다. 제조된 상기 잉크들의 shear rate에 따른 점도를 측정하였다. Referring to FIG. 3, an ink including the poly (ethylene glycol) having a molecular weight of 200 and an ink including the poly (ethylene glycol) having a molecular weight of 20,000 were prepared. The viscosity according to the shear rate of the prepared inks was measured.
상기 잉크의 중량 대비 상기 세라믹 입자가 70%이고, 상기 열가소성 바인더가 30%일 경우, 상기 열가소성 바인더를 구성하는 상기 Poly(ethylene glycol)의 분자량이 200인 잉크와 상기 Poly(ethylene glycol)의 분자량이 20,000인 잉크의 점도 차이를 확인할 수 있다. 다시 말하면, 상기 Poly(ethylene glycol)의 분자량이 200에서 20,000으로 증가됨에 따라, shear rate 10/s에서, 잉크의 점도가 13Pa·s에서 62Pa·s로 증가된 것을 확인할 수 있다.When the ceramic particles are 70% by weight and the thermoplastic binder is 30% by weight of the ink, the ink having a molecular weight of 200 of the poly (ethylene glycol) constituting the thermoplastic binder and the molecular weight of the poly (ethylene glycol) are The viscosity difference of 20,000 ink can be confirmed. In other words, as the molecular weight of the poly (ethylene glycol) is increased from 200 to 20,000, it can be seen that at the shear rate 10 / s, the viscosity of the ink is increased from 13 Pa.s to 62 Pa.s.
이에 따라, 상기 Poly(ethylene glycol)의 분자량에 따라 상기 잉크의 점도가 조절될 수 있는 것을 알 수 있다. 다시 말하면, 상기 Poly(ethylene glycol)의 분자량을 증가시켜 상기 잉크의 점도를 증가시키거나, 상기 Poly(ethylene glycol)의 함량을 감소시켜 상기 잉크의 점도를 감소시킬 수 있다.Accordingly, it can be seen that the viscosity of the ink can be adjusted according to the molecular weight of the poly (ethylene glycol). In other words, the viscosity of the ink may be increased by increasing the molecular weight of the poly (ethylene glycol) or the content of the poly (ethylene glycol) may be decreased to decrease the viscosity of the ink.
도 4는 본 발명의 실시 예에 따라 제조된, 바인더 복합물의 산화 방지제 함량에 따른 잉크의 산화 방지 효과를 설명하기 위한 도면이고, 도 5는 본 발명의 실시 예에 따라 제조된, 바인더 복합물의 산화 방지제 함량에 따른 잉크의 점도를 설명하기 위한 도면이다.4 is a view for explaining the antioxidant effect of the ink according to the antioxidant content of the binder composite, prepared according to an embodiment of the present invention, Figure 5 is an oxidation of the binder composite, prepared according to an embodiment of the present invention It is a figure for demonstrating the viscosity of ink according to inhibitor content.
도 4를 참조하면, 상기 잉크의 중량 대비, 상기 산화 방지제를 포함하지 않는 잉크, 상기 산화 방지제의 함량이 1%, 또는 2%인 잉크를 제조하였다. 상기 잉크들을 이용하여 성형체들을 제조하고, 갈변 현상을 평가하기 위해 제조된 성형체들을 촬영하였다.Referring to FIG. 4, an ink containing no antioxidant, an ink containing 1% or 2% of an antioxidant, was prepared based on the weight of the ink. Molded bodies were prepared using the inks, and the molded bodies were photographed to evaluate browning phenomenon.
상기 산화 방지제가 첨가되지 않은 잉크의 경우, 상기 Poly(lactic acid) 및 상기 Poly(ethylene glycol)가 혼합된 상기 열가소성 바인더의 고분자 체인이 산화되어, 상기 잉크를 이용하여 제조된 성형체에 갈변 현상이 발생하는 것을 확인할 수 있다. 반면, 상기 산화 방지제가 첨가된 잉크의 경우, 상기 열가소성 바인더의 고분자 체인의 산화가 방지되어, 상기 잉크를 이용하여 제조된 성형체의 갈변 현상이 저하된 것을 확인할 수 있다. 이에 따라, 상기 열가소성 바인더의 고분자 체인의 산화가 방지되어, 상기 열가소성 바인더를 포함하는 상기 잉크의 안정성이 향상되고, 상기 잉크를 이용하여 제조된 성형체의 기계적 특성이 유지될 수 있다.In the case of the ink to which the antioxidant is not added, the polymer chain of the thermoplastic binder in which the poly (lactic acid) and the poly (ethylene glycol) are mixed is oxidized, and browning occurs in a molded article manufactured using the ink. You can see that. On the other hand, in the case of the ink to which the antioxidant is added, it is confirmed that oxidation of the polymer chain of the thermoplastic binder is prevented, so that browning phenomenon of the molded product manufactured using the ink is reduced. Accordingly, the oxidation of the polymer chain of the thermoplastic binder is prevented, so that the stability of the ink including the thermoplastic binder is improved, and the mechanical properties of the molded article manufactured using the ink can be maintained.
따라서, 상기 산화 방지제를 첨가하여 상기 잉크를 제조하는 것이, 상기 잉크를 이용하여 제조된 성형체의 산화를 방지하여, 성형체의 갈변 현상을 억제하는데 효율적인 방법임을 알 수 있다. Therefore, it can be seen that the preparation of the ink by adding the antioxidant is an effective method of preventing oxidation of the molded article produced using the ink, thereby suppressing browning phenomenon of the molded article.
도 5를 참조하면, 상기 잉크의 중량 대비, 상기 산화 방지제를 포함하지 않는 잉크, 상기 산화 방지제의 함량이 1%, 또는 2%인 잉크를 제조하였다. 제조된 상기 잉크들의 shear rate에 따른 점도를 측정하였다.Referring to FIG. 5, an ink containing no antioxidant, an ink containing 1% or 2% of an antioxidant, was prepared based on the weight of the ink. The viscosity according to the shear rate of the prepared inks was measured.
상기 산화 방지제를 포함하지 않는 잉크보다 상기 산화 방지제의 함량이 1%인 잉크의 점도가 높고, 상기 산화 방지제의 함량이 1%인 잉크보다 상기 산화 방지제의 함량이 2%인 잉크의 점도가 높은 것을 확인할 수 있다. 즉, 상기 산화 방지제의 함량에 따라, 상기 잉크의 점도가 조절되는 것을 확인할 수 있다. 다시 말하면, shear rate 10/s에서, 상기 산화 방지제가 첨가되지 않은 잉크의 점도는 1Pa·s인 것에 반해, 상기 산화 방지제가, 상기 잉크의 중량 대비 2% 첨가된 잉크의 점도는 38Pa·s인 것을 확인할 수 있다.The ink having an antioxidant content of 1% is higher than the ink containing no antioxidant, and the ink having an antioxidant content of 2% is higher than the ink having an antioxidant content of 1%. You can check it. That is, according to the content of the antioxidant, it can be confirmed that the viscosity of the ink is adjusted. In other words, at a shear rate of 10 / s, the viscosity of the ink to which the antioxidant is not added is 1 Pa.s, whereas the viscosity of the ink to which the antioxidant is added 2% to the weight of the ink is 38 Pa.s. You can see that.
이에 따라, 상기 산화 방지제의 함량에 따라 상기 잉크의 점도가 조절될 수 있는 것을 알 수 있다. 다시 말하면, 상기 산화 방지제의 함량을 증가시켜 상기 잉크의 점도를 증가시키거나, 상기 산화 방지제의 함량을 감소시켜 상기 잉크의 점도를 감소시킬 수 있다.Accordingly, it can be seen that the viscosity of the ink can be adjusted according to the content of the antioxidant. In other words, the viscosity of the ink may be increased by increasing the content of the antioxidant, or the viscosity of the ink may be decreased by decreasing the content of the antioxidant.
도 6은 본 발명의 실시 예에 따라 제조된, 바인더 복합물의 Poly(ethylene glycol) 분자량에 따른 잉크의 탄성률을 설명하기 위한 도면이다.6 is a view for explaining the elastic modulus of the ink according to the molecular weight of the poly (ethylene glycol) of the binder composite prepared according to the embodiment of the present invention.
도 6을 참조하면, 상기 Poly(lactic acid) 및 상기 세라믹 입자를 포함하고, 분자량이 200인 상기 Poly(ethylene glycol)을 포함하는 잉크를 제조하였고, 상기 Poly(lactic acid) 및 상기 세라믹 입자를 포함하고, 분자량이 4,000인 상기 Poly(ethylene glycol)을 포함하는 잉크를 제조하였고, 상기 Poly(lactic acid) 및 상기 세라믹 입자를 포함하고, 분자량이 20,000인 상기 Poly(ethylene glycol)을 포함하는 잉크를 제조하였고, 제조된 상기 잉크들 및 상용화된, 상기 Poly(lactic acid)를 포함하고 상기 Poly(ethylene glycol) 및 상기 세라믹 입자는 포함하지 않는 잉크의 탄성 강도를 측정하였다.Referring to FIG. 6, an ink including the poly (lactic acid) and the ceramic particles and the poly (ethylene glycol) having a molecular weight of 200 was prepared, and the poly (lactic acid) and the ceramic particles were included. And an ink including the poly (ethylene glycol) having a molecular weight of 4,000, and preparing the ink including the poly (lactic acid) and the ceramic particles and containing the poly (ethylene glycol) having a molecular weight of 20,000. In addition, the elastic strengths of the inks prepared and commercialized, the inks including the poly (lactic acid) and the poly (ethylene glycol) and the ceramic particles were not measured.
분자량이 200인 상기 Poly(ethylene glycol)을 포함하는 잉크보다 분자량이 4,000인 상기 Poly(ethylene glycol)을 포함하는 잉크의 탄성계수가 크고, 분자량이 4,000인 상기 Poly(ethylene glycol)을 포함하는 잉크보다 분자량이 20,000인 상기 Poly(ethylene glycol)을 포함하는 잉크의 탄성계수가 크다. 분자량이 20,000인 상기 Poly(ethylene glycol)을 포함하는 잉크의 탄성계수는, 상기 Poly(lactic acid)를 포함하고 상기 Poly(ethylene glycol) 및 상기 세라믹 입자는 포함하지 않는 잉크의 탄성계수에 근사한 것을 확인할 수 있다. 즉, 상기 Poly(ethylene glycol)의 분자량에 따른 상기 잉크의 탄성계수를 확인할 수 있다. 다시 말하면, 상기 Poly(ethylene glycol)의 분자량이 200, 4,000, 또는 20,000인 경우, 상기 Poly(ethylene glycol)의 분자량이 증가함에 따라 상기 잉크의 탄성 계수가 증가하는 것을 확인할 수 있다.The elastic modulus of the ink containing the poly (ethylene glycol) having a molecular weight of 4,000 is greater than that of the ink containing the poly (ethylene glycol) having a molecular weight of 200, and the ink containing the poly (ethylene glycol) having a molecular weight of 4,000 The elastic modulus of the ink including the poly (ethylene glycol) having a molecular weight of 20,000 is large. The elastic modulus of the ink containing the poly (ethylene glycol) having a molecular weight of 20,000 is confirmed to be close to the elastic modulus of the ink containing the poly (lactic acid) and not containing the poly (ethylene glycol) and the ceramic particles. Can be. That is, the elastic modulus of the ink according to the molecular weight of the poly (ethylene glycol) can be confirmed. In other words, when the molecular weight of the poly (ethylene glycol) is 200, 4,000, or 20,000, it can be seen that the elastic modulus of the ink increases as the molecular weight of the poly (ethylene glycol) increases.
이에 따라, 상기 Poly(ethylene glycol)의 분자량에 따라 상기 잉크의 탄성률이 조절될 수 있는 것을 알 수 있다. 다시 말하면, 상기 Poly(ethylene glycol)의 분자량을 증가시켜 상기 잉크의 탄성률을 증가시키거나, 상기 Poly(ethylene glycol)의 분자량을 감소시켜 상기 잉크의 탄성률을 감소시킬 수 있다.Accordingly, it can be seen that the elastic modulus of the ink can be adjusted according to the molecular weight of the poly (ethylene glycol). In other words, the elastic modulus of the ink may be increased by increasing the molecular weight of the poly (ethylene glycol) or the elastic modulus of the ink may be reduced by decreasing the molecular weight of the poly (ethylene glycol).
도 7은 본 발명의 실시 예에 따라 제조된, 바인더 복합물에 첨가되는 세라믹 입자를 구성하는 구형 실리카 입자의 평균 입도에 따른, 잉크를 이용하여 제조된 성형체의 굽힘 강도(flexural strength) 및 수축률을 설명하기 위한 도면이다.FIG. 7 illustrates the flexural strength and shrinkage rate of a molded article manufactured using ink according to the average particle size of spherical silica particles constituting ceramic particles added to a binder composite, prepared according to an embodiment of the present invention. It is a figure for following.
도 7 및 아래 <표 1>을 참조하면, 상기 세라믹 입자는 상기 구형 실리카 입자 및 상기 지르콘실리케이트 입자의 혼합물로 구성되었다. 상기 구형 실리카 입자는 평균 입도가 30μm, 9μm (99.6%, Sibelco, Belgium), 또는 0.3μm (99.7%, Denka, Japan)인 입자들로 구성되었고, 상기 지르콘실리케이트는 비정형 입자로, 평균 입도가 1μm (97%, Cenotec, Korea)인 입자이다. 아래 <표 1>과 같은 구성의 상기 구형 실리카 입자를 포함하는, 상기 세라믹 입자가 첨가된 잉크를 제조하여, 상기 구형 실리카 입자의 평균 입도에 따른, 상기 잉크를 이용하여 제조된 성형체의 굽힘 강도 및 수축률을 확인하였다. 상기 세라믹 입자는 상기 구형 실리카 입자 75%와 상기 지르콘실리케이트 입자 25%로 구성되었다.Referring to Figure 7 and Table 1 below, the ceramic particles were composed of a mixture of the spherical silica particles and the zircon silicate particles. The spherical silica particles were composed of particles having an average particle size of 30 μm, 9 μm (99.6%, Sibelco, Belgium), or 0.3 μm (99.7%, Denka, Japan), and the zirconium silicate was an amorphous particle with an average particle size of 1 μm. (97%, Cenotec, Korea). Bending strength of the molded article produced using the ink according to the average particle size of the spherical silica particles, by manufacturing the ink containing the spherical silica particles having the configuration as shown in Table 1 below, and Shrinkage was confirmed. The ceramic particles consisted of 75% of the spherical silica particles and 25% of the zirconium silicate particles.
구분division Sample No.Sample No. 0.3μm 실리카 입자0.3μm silica particles 9.0μm 실리카 입자9.0μm silica particles 30.0μm 실리카 입자30.0μm silica particles
실시 예 1Example 1 A50A50 -- 20wt%20wt% 55wt%55wt%
실시 예 2Example 2 A51A51 10wt%10wt% 10wt%10wt% 55wt%55wt%
실시 예 3Example 3 A52A52 -- 55wt%55wt% 20wt%20wt%
실시 예 4Example 4 A53A53 10wt%10wt% 55wt%55wt% 10wt%10wt%
실시 예 5Example 5 A54A54 5wt%5wt% 35wt%35wt% 35wt%35wt%
실시 예 6Example 6 A55A55 2.5wt%2.5wt% 27.5wt%27.5wt% 45wt%45wt%
실시 예 7Example 7 A56A56 7.5wt%7.5wt% 22.5wt%22.5wt% 45wt%45wt%
실시 예 8Example 8 A57A57 2.5wt%2.5wt% 45wt%45wt% 27.5wt%27.5wt%
실시 예 9Example 9 A58A58 7.5wt%7.5wt% 45wt%45wt% 22.5wt%22.5wt%
실시 예 1 내지 9에 따른 상기 세라믹 입자가 첨가된 잉크로 제조된 성형체들의 굽힘 강도는, 만능시험기(Universal Testing Machine)를 이용하여 측정되었다. 굽힘 강도 측정 규격은 ASTM C1161-13에 따르며, 굽힘 강도 측정에 사용된 UTM은 250kg의 로드셀(H10SK, Hounsefield, England)이 장착되었고, 굽힘 강도 측정은 80mm의 스팬 크기로 1mm/min의 cross-head 속도로 진행하였다.The bending strength of the molded bodies prepared from the ink to which the ceramic particles were added according to Examples 1 to 9 was measured by using a universal testing machine. Bending strength measurement standard is according to ASTM C1161-13, UTM used for bending strength measurement is equipped with 250kg load cell (H10SK, Hounsefield, England), and bending strength measurement is 80mm span size, 1mm / min cross-head Progress at speed.
상기 세라믹 입자를 구성하는, 평균 입도가 30μm, 9μm, 또는 0.3μm인 상기 구형 실리카 입자의 혼합 비율에 따라, 상기 세라믹 입자가 첨가된 상기 잉크를 이용하여 제조되는 성형체의 굽힘 강도 및 수축률이 변화되는 것을 확인할 수 있다.According to the mixing ratio of the spherical silica particles having an average particle size of 30 μm, 9 μm, or 0.3 μm constituting the ceramic particles, the bending strength and shrinkage rate of the molded product produced using the ink to which the ceramic particles are added are changed. You can see that.
이에 따라, 상기 세라믹 입자를 구성하는, 평균 입도가 30μm, 9μm, 또는 0.3μm인 상기 구형 실리카 입자의 혼합 비율을 조절하여, 상기 세라믹 입자가 첨가된 상기 잉크를 이용하여 제조되는 성형체의 굽힘 강도 및 수축률을 조절할 수 있다. 이로 인해, 용도에 맞게 굽힘 강도 및 수축률이 조절된 성형체를 제조할 수 있는, 바인더 복합물이 제공될 수 있다.Accordingly, by adjusting the mixing ratio of the spherical silica particles having an average particle size of 30μm, 9μm, or 0.3μm constituting the ceramic particles, the bending strength of the molded article produced using the ink to which the ceramic particles are added and Shrinkage can be controlled. Thereby, a binder composite can be provided, which can produce a molded article in which bending strength and shrinkage rate are adjusted according to the use.
도 8은 본 발명의 실시 예 및 비교 예에 따라 제조된 바인더 복합물에 첨가되는 세라믹 입자를 구성하는 실리카 입자의 형상에 따른 잉크의 점도를 설명하기 위한 도면이고, 도 9는 본 발명의 실시 예에 따라 제조된 바인더 복합물에 첨가되는 세라믹 입자의 입도 분포를 설명하기 위한 도면이다.8 is a view for explaining the viscosity of the ink according to the shape of the silica particles constituting the ceramic particles added to the binder composite prepared according to the embodiment and comparative example of the present invention, Figure 9 is an embodiment of the present invention The figure for demonstrating the particle size distribution of the ceramic particle added to the binder composite manufactured according to this.
도 8을 참조하면, 평균 입도가, 30μm인 구형 실리카 입자 52.5%, 9μm인 구형 실리카 입자 22.5% 및 1μm인 지르콘실리케이트 입자 25%를 포함하는 상기 세라믹 입자가 첨가된 상기 잉크(spherical) 및 비정형 실리카 입자를 포함하는 상기 세라믹 입자가 첨가된 상기 잉크(irregular)를 제조하였다. 제조된 상기 잉크들의 shear rate에 따른 점도를 측정하였다.Referring to FIG. 8, the spherical and amorphous silica to which the ceramic particles are added, including the 52.5% spherical silica particles having a mean particle size of 30 μm, 22.5% of spherical silica particles having a particle size of 9 μm, and 25% of zirconium silicate particles having a size of 1 μm. The ink (irregular) to which the ceramic particles containing particles were added was prepared. The viscosity according to the shear rate of the prepared inks was measured.
상기 구형 실리카 입자를 포함하는 상기 세라믹 입자가 첨가된 잉크는, 비정형 실리카 입자를 포함하는 세라믹 입자가 첨가된 잉크에 비해 점도가 낮은 것을 확인할 수 있다.It is confirmed that the ink to which the ceramic particles containing the spherical silica particles are added has a lower viscosity than the ink to which the ceramic particles containing the amorphous silica particles are added.
이에 따라, 상기 세라믹 입자에 포함되는 상기 실리카 입자의 형상을 선택하여, 상기 세라믹 입자가 첨가된 상기 잉크의 점도를 조절할 수 있다. 다시 말하면, 상기 구형 실리카 입자를 포함하는 상기 세라믹 입자를 첨가하여, 상기 잉크의 점도를 감소시키거나, 상기 비정형 실리카를 포함하는 상기 세라믹 입자를 첨가하여, 상기 잉크의 점도를 증가시킬 수 있다.Accordingly, by selecting the shape of the silica particles included in the ceramic particles, it is possible to adjust the viscosity of the ink to which the ceramic particles are added. In other words, the viscosity of the ink may be decreased by adding the ceramic particles including the spherical silica particles, or the viscosity of the ink may be increased by adding the ceramic particles including the amorphous silica.
도 9를 참조하면, 평균 입도가, 30μm인 구형 실리카 입자 52.5%, 9μm인 구형 실리카 입자 22.5% 및 1μm인 지르콘실리케이트 입자 25%를 포함하는 상기 세라믹 입자가 제조되었다. 제조된 상기 세라믹 입자의 입도 분포를 측정하였다.Referring to FIG. 9, the ceramic particles were prepared including 52.5% spherical silica particles having an average particle size of 30 μm, 22.5% spherical silica particles having a size of 9 μm, and 25% zirconium silicate particles having a thickness of 1 μm. The particle size distribution of the prepared ceramic particles was measured.
상기 세라믹 입자의 입도는 최소 0.4μm에서 최대 100μm로 측정되었다.The particle size of the ceramic particles was measured from a minimum of 0.4μm to a maximum of 100μm.
이상, 본 발명을 바람직한 실시 예를 사용하여 상세히 설명하였으나, 본 발명의 범위는 특정 실시 예에 한정되는 것은 아니며, 첨부된 특허청구범위에 의하여 해석되어야 할 것이다. 또한, 이 기술분야에서 통상의 지식을 습득한 자라면, 본 발명의 범위에서 벗어나지 않으면서도 많은 수정과 변형이 가능함을 이해하여야 할 것이다.As mentioned above, although this invention was demonstrated in detail using the preferable embodiment, the scope of the present invention is not limited to a specific embodiment, Comprising: It should be interpreted by the attached Claim. In addition, those skilled in the art should understand that many modifications and variations are possible without departing from the scope of the present invention.
본 발명의 실시 예에 따른 바인더 복합물은, 기계적 특성 및 탄성율이 우수하여, 3차원 프린터 공정에 이용될 수 있다. The binder composite according to the embodiment of the present invention is excellent in mechanical properties and elastic modulus, and can be used in a three-dimensional printer process.

Claims (10)

  1. Poly(lactic acid) 및 Poly(ethylene glycol)가 혼합된 열가소성 바인더를 제조하는 단계; 및Preparing a thermoplastic binder in which poly (lactic acid) and poly (ethylene glycol) are mixed; And
    상기 열가소성 바인더에 세라믹 입자 및 Poly(lactic acid)의 산화를 방지하는 산화 방지제를 첨가하여 잉크를 제조하는 단계를 포함하는 바인더 복합물의 제조 방법.Method for producing a binder composite comprising the step of preparing an ink by adding an antioxidant to prevent oxidation of ceramic particles and Poly (lactic acid) to the thermoplastic binder.
  2. 제1항에 있어서, The method of claim 1,
    상기 Poly(ethylene glycol)의 함량 또는 분자량을 조절하여 상기 잉크의 점도를 조절하는 것을 포함하는 바인더 복합물의 제조 방법.Method of manufacturing a binder composite comprising adjusting the viscosity of the ink by adjusting the content or molecular weight of the poly (ethylene glycol).
  3. 제1항에 있어서, The method of claim 1,
    상기 Poly(ethylene glycol)의 함량을 조절하여 상기 잉크의 유리 전이 온도 및 녹는점을 조절하는 것을 포함하는 바인더 복합물의 제조 방법.Method of manufacturing a binder composite comprising adjusting the content of the poly (ethylene glycol) to control the glass transition temperature and melting point of the ink.
  4. 제1항에 있어서, The method of claim 1,
    상기 Poly(ethylene glycol)의 함량을 조절하여, 상기 잉크를 이용하여 제조되는 성형체의 파괴 인성(fracture toughness)을 조절하는 것을 포함하는 바인더 복합물의 제조 방법.Adjusting the content of the poly (ethylene glycol), the manufacturing method of the binder composite comprising controlling the fracture toughness (fracture toughness) of the molded product produced using the ink.
  5. 제1항에 있어서, The method of claim 1,
    상기 산화 방지제의 함량을 조절하여 상기 잉크의 점도를 조절하는 것을 포함하는 바인더 복합물의 제조 방법.Method of producing a binder composite comprising adjusting the content of the antioxidant to adjust the viscosity of the ink.
  6. 제1항에 있어서, The method of claim 1,
    상기 세라믹 입자의 형상을 조절하여 상기 잉크의 점도를 조절하는 것을 포함하는 바인더 복합물의 제조 방법.And controlling the viscosity of the ink by controlling the shape of the ceramic particles.
  7. 제1항에 있어서, The method of claim 1,
    상기 poly(lactic acid) 및 상기 poly(ethylene glycol)이 혼합된 상기 열가소성 바인더를 제조하는 단계는,Preparing the thermoplastic binder in which the poly (lactic acid) and the poly (ethylene glycol) is mixed,
    상기 열가소성 바인더를 열처리하는 단계를 포함하는 바인더 복합물의 제조 방법.Method for producing a binder composite comprising the step of heat-treating the thermoplastic binder.
  8. 제1항에 있어서, The method of claim 1,
    상기 열가소성 바인더에 상기 세라믹 입자를 첨가하기 전, 상기 세라믹 입자를 볼밀(ball mill)하는 단계를 더 포함하는 바인더 복합물의 제조 방법.And ball milling the ceramic particles prior to adding the ceramic particles to the thermoplastic binder.
  9. Poly(lactic acid) 및 Poly(ethylene glycol)을 포함하는 열가소성 바인더, 세라믹 입자 및 상기 Poly(lactic acid)의 산화를 방지하는 산화 방지제를 포함하는 잉크를 포함하되,Including a thermoplastic binder including poly (lactic acid) and Poly (ethylene glycol), ink containing ceramic particles and an antioxidant for preventing oxidation of the poly (lactic acid),
    상기 잉크의 점도가, 상기 Poly(ethylene glycol)의 함량이 증가함에 따라 감소하고, 상기 Poly(ethylene glycol)의 분자량 및 상기 산화 방지제의 함량이 증가함에 따라 증가하고, 상기 세라믹 입자의 형상이 구형에 가까울수록 감소하는 것을 포함하고,The viscosity of the ink decreases with increasing content of the poly (ethylene glycol), increases with increasing molecular weight of the poly (ethylene glycol) and the content of the antioxidant, and the shape of the ceramic particles is spherical. Close to decreasing,
    상기 잉크의 점도는, 상기 Poly(ethylene glycol)의 함량 및 분자량, 상기 산화 방지제의 함량, 및 상기 세라믹 입자의 형상을 조절하여, 조절되는 것을 포함하는 바인더 복합물.The viscosity of the ink, the binder composite comprising adjusting by adjusting the content and molecular weight of the poly (ethylene glycol), the content of the antioxidant, and the shape of the ceramic particles.
  10. 제9항에 있어서, The method of claim 9,
    상기 세라믹 입자는 실리카(SiO2) 입자, 또는 지르콘실리케이트(ZrSiO4) 입자 중에서 적어도 어느 하나를 포함하는 바인더 복합물.The ceramic particles include at least one of silica (SiO 2 ) particles, or zirconium silicate (ZrSiO 4 ) particles.
PCT/KR2016/015009 2016-04-28 2016-12-21 Binder composite and preparation method therefor WO2017188550A1 (en)

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