KR102291561B1 - Composition for 3D Printing and Filament for 3D Printer - Google Patents

Composition for 3D Printing and Filament for 3D Printer Download PDF

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KR102291561B1
KR102291561B1 KR1020170126383A KR20170126383A KR102291561B1 KR 102291561 B1 KR102291561 B1 KR 102291561B1 KR 1020170126383 A KR1020170126383 A KR 1020170126383A KR 20170126383 A KR20170126383 A KR 20170126383A KR 102291561 B1 KR102291561 B1 KR 102291561B1
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filament
printer
composition
fluorescent material
diameter
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오종회
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코오롱플라스틱 주식회사
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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
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/071—Preforms or parisons characterised by their configuration, e.g. geometry, dimensions or physical properties
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    • 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
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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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
    • B29C2949/00—Indexing scheme relating to blow-moulding
    • B29C2949/07—Preforms or parisons characterised by their configuration
    • B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
    • C—CHEMISTRY; METALLURGY
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Abstract

본 발명은 3D 프린팅용 조성물 및 이를 이용한 3D 프린터용 필라멘트에 관한 것으로서, 구체적으로는 3D 프린팅을 통해 제조된 조형물에서 빛을 발광할 수 있는 특성을 가진 열적으로 안정한 3D 프린팅용 조성물 및 이를 이용한 3D 프린터용 필라멘트를 제공하는 것이다. The present invention relates to a composition for 3D printing and a filament for a 3D printer using the same, and more particularly, a thermally stable composition for 3D printing having a property of emitting light from a sculpture manufactured through 3D printing, and a 3D printer using the same It is to provide a filament for

Description

3D 프린터용 필라멘트 조성물 및 이를 이용한 3D 프린터용 필라멘트{Composition for 3D Printing and Filament for 3D Printer}Filament composition for 3D printer and filament for 3D printer using same

본 발명은 3D 프린터용 필라멘트 조성물 및 이를 이용한 3D 프린터용 필라멘트에 관한 것으로서, 보다 상세하게는 조형물에서 빛을 발광하는 특징을 가진 3D 프린팅용 조성물 및 이를 이용한 3D 프린터용 필라멘트에 관한 것이다.The present invention relates to a filament composition for a 3D printer and a filament for a 3D printer using the same, and more particularly, to a composition for 3D printing having a feature of emitting light from a sculpture and a filament for a 3D printer using the same.

3D(3-Dimension, 3 차원) 프린터는 활자나 그림을 인쇄하듯이 입력된 3 차원 도면을 바탕으로 실제 입체 모양을 그대로 제작하는 장비이다. 최근 3D 프린팅 기술은 상당히 핫 이슈가 되고 있으며, 자동차, 의료, 예술, 교육분야로 확대되고 있으며, 다양한 모형을 만들기 위한 용도로 광범위하게 사용하고 있다. 3D프린터의 원리는 가장 크게 절삭형과 적층형으로 나눌 수 있으며, 실제 적용되고 있는 3D프린터의 대부분은 재료 손실이 없는 적층형에 해당된다. A 3D (3-Dimension) printer is an equipment that produces a three-dimensional shape as it is based on an input three-dimensional drawing, just like printing type or picture. Recently, 3D printing technology has become a very hot issue and is being expanded to automobile, medical, art, and education fields, and is widely used for making various models. The principle of 3D printers can be divided into cutting type and stacking type, and most of the 3D printers that are actually applied fall into the layered type without material loss.

적층형 원리를 이용하는 방식도 약 20가지가 존재하지만, 이 가운데 가장 많이 사용되는 방식은 SLA(Stereolithography Apparatus), FDM(Fused Deposition Modeling) 혹은 FFF(Fused Filament Fabrication) 및 SLS(Selective Laser Sintering)방식이다.There are about 20 methods using the layered principle, but the most used methods are SLA (Stereolithography Apparatus), FDM (Fused Deposition Modeling) or FFF (Fused Filament Fabrication) and SLS (Selective Laser Sintering) method.

SLA의 경우 액체 상태의 광경화성 수지가 담긴 수조안에 레이저 빔을 투사하여 조형하는 방식으로서, 광경화성 수지인 에폭시 타입의 포토 폴리머가 주로 사용된다. 반면, 투입된 필라멘트상의 재료가 Z, Y, Z 축으로 움직이는 프린터의 노즐에서 용융상태로 토출되면서 3차원으로 조형되는 방식인 FDM(혹는 FFF)는 열가소성 플라스틱을 주 재료로 사용한다. 한편, SLS은 금속, 플라스틱, 세라믹 분말 등의 파우더 상 재료가 담긴 수조에 레이저를 쏘아 선택적으로 소결하는 방식으로 3D프린팅을 구현한다.In the case of SLA, a laser beam is projected into a tank containing a liquid photo-curable resin to form a model, and an epoxy-type photo polymer, which is a photo-curable resin, is mainly used. On the other hand, FDM (or FFF), a method in which the input filamentary material is discharged in a molten state from the nozzle of the printer moving in the Z, Y, and Z axes, is molded in three dimensions (or FFF) uses a thermoplastic plastic as its main material. On the other hand, SLS implements 3D printing by selectively sintering by firing a laser into a water tank containing powdery materials such as metal, plastic, and ceramic powder.

상기 3가지 방식 중에서 열가소성 플라스틱을 필라멘트 형태로 제조하여 사용하는 FDM방식이 3D 프린터의 가격이 비교적 저렴하여 접근성이 뛰어나 가장 널리 대중화 되어있다. FDM방식에는 일반적으로 3D 조형물을 형상할 때 베드 접착력 및 층(layer)간 접착력이 우수하고, 형태안정성이 좋다는 이유로 폴리락트산(Polylactic acid, PLA), ABS(Acrylonitrile Butadiene Styrene), HDPE, 폴리카보네이트(Polycarbonate, PC) 등의 딱딱한 소재와 열가소성 탄성체와 같은 유연한 소재가 사용되고 있다.Among the above three methods, the FDM method, which manufactures and uses a thermoplastic plastic in the form of a filament, is the most widely popular because the price of a 3D printer is relatively low and accessibility is excellent. In the FDM method, polylactic acid (PLA), ABS (Acrylonitrile Butadiene Styrene), HDPE, polycarbonate ( Hard materials such as polycarbonate and PC) and flexible materials such as thermoplastic elastomers are used.

또한, 최근에는 다양한 기능을 가진 소재가 소개되고 있지만, 단순히 내열성, 고강도, 내충격 소재 등 기존 플라스틱의 한계를 벗어나지 못하는 한계를 가지고 있다. 한편, FDM용 필라멘트 중 PLA, ABS 등을 사용하여 축광형 안료를 첨가한 필라멘트가 판매되고 있다. In addition, although materials with various functions have been recently introduced, they have limitations that cannot escape the limitations of conventional plastics, such as simply heat-resistant, high-strength, and impact-resistant materials. On the other hand, among filaments for FDM, filaments containing a phosphorescent pigment using PLA, ABS, etc. are being sold.

하지만 본 필라멘트는 단순히 빛을 축광하였다가 어두운 환경이 조성이 되었을 때 야광을 나타내는 단순한 소재라 할 수 있다. UV 조사시 발광할 수 있는 물질을 이용한 사례가 있지만 이는 물질 자체를 사용하기 때문에 필라멘트 제조 혹은 필라멘트를 이용하여 3D 프린팅할 때 열적 안정성이 화보 되지 않아 성능이 구현 되지 않을 수 있다. 따라서 열적으로 안정하고 UV 조사시 발광할 수 있는 특수한 기능을 가진 소재에 대한 개발이 필요하다고 볼 수 있다.However, this filament can be said to be a simple material that shows luminescence when a dark environment is created after simply emitting light. There is a case of using a material that can emit light when irradiated with UV, but since the material itself is used, the performance may not be realized because the thermal stability is not pictorial when manufacturing a filament or 3D printing using a filament. Therefore, it is necessary to develop a material that is thermally stable and has a special function that can emit light when irradiated with UV.

이에, 본 발명을 통해 3D 프린팅을 통해 제조된 조형물에서 빛을 발광할 수 있는 특성을 가진 열적으로 안정한 3D 프린팅용 조성물 및 이를 이용한 3D 프린터용 필라멘트를 제공하고자 한다.Accordingly, an object of the present invention is to provide a thermally stable composition for 3D printing having a property of emitting light from a sculpture manufactured through 3D printing, and a filament for a 3D printer using the same.

본 발명의 바람직한 일 구현예는 플라스틱 수지 및 형광물질이 담지된 구형 비드를 포함하고, 상기 형광물질이 담지된 구형 비드는 플라스틱 수지 100 중량부 대비 2 내지 10 중량부로 포함하는 것인 3D 프린터용 필라멘트 조성물을 제공하는 것이다.A preferred embodiment of the present invention includes a plastic resin and a spherical bead supported with a fluorescent material, and the spherical bead supported with the fluorescent material is included in an amount of 2 to 10 parts by weight based on 100 parts by weight of the plastic resin. Filament for a 3D printer to provide a composition.

상기 플라스틱 수지는 PET(Polyethylene Terephtalate), PLA(Polylactic acid), ABS(Acrylonitrile Butadiene Styrene), PP(Polypropylene), PE(Polyethylene), HIPS(High Impact Polystyrene), EVA(Ethylene Vinyl Acetate), TPO(Thermoplastic Poly Olefin), PC(Polycarbonate), PETG(glycol- modified polyethylene terephthalate), Rubber, Nylon, PEN(polyethylene naphthalate), TPE(Thermo Plastic Elastomer) 및 이들의 조합으로 이루어진 군에서 선택된 1종 이상인 것을 특징으로 한다.The plastic resin is PET (Polyethylene Terephtalate), PLA (Polylactic acid), ABS (Acrylonitrile Butadiene Styrene), PP (Polypropylene), PE (Polyethylene), HIPS (High Impact Polystyrene), EVA (Ethylene Vinyl Acetate), TPO (Thermoplastic) Poly Olefin), PC (Polycarbonate), PETG (glycol-modified polyethylene terephthalate), Rubber, Nylon, PEN (polyethylene naphthalate), TPE (Thermo Plastic Elastomer), and characterized in that at least one selected from the group consisting of combinations thereof .

상기 형광물질은 Naphthalene계, Fluorescein계, Pyrene계, Thiophene계, Fluorene계, Carbazole계, quinine계, Resorufin계, Benzodiazole 계, Pentacene 계, Perylene계, Pyrazine계 및 이들의 조합으로 이루어진 군에서 선택되는 1종 이상인 방향족 유도체 화합물; 및 Ir, Zn, Li, Al, Ru, Pt 및 이들의 조합으로 이루어진 군에서 선택되는 1종 이상의 유기금속 복합체를 포함하는 것을 특징으로 한다.The fluorescent material is 1 selected from the group consisting of Naphthalene-based, Fluorescein-based, Pyrene-based, Thiophene-based, Fluorene-based, Carbazole-based, quinine-based, Resorufin-based, Benzodiazole-based, Pentacene-based, Perylene-based, Pyrazine-based, and combinations thereof. aromatic derivative compounds of more than one species; and Ir, Zn, Li, Al, Ru, Pt, and at least one organometallic complex selected from the group consisting of combinations thereof.

상기 구형 비드의 지름은 1 내지 20㎛이고, 종횡비가 0.8 내지 1인 것을 특징으로 한다.The spherical beads have a diameter of 1 to 20 μm, and an aspect ratio of 0.8 to 1.

상기 구형 비드는 폴리메틸메타크릴레이트(PMMA)인 것을 특징으로 한다.The spherical beads are characterized in that polymethyl methacrylate (PMMA).

본 발명의 다른 일 구현예는 상술한 3D 프린터용 필라멘트 조성물로부터 제조된 3D 프린터용 필라멘트를 제공하는 것이다.Another embodiment of the present invention is to provide a filament for a 3D printer prepared from the above-described filament composition for a 3D printer.

상기 필라멘트는 직경이 0.8 ~ 4.0mm인 것을 특징으로 한다.The filament is characterized in that the diameter is 0.8 ~ 4.0mm.

본 발명에 따르면 3D 프린터를 이용하여 개인이 원하는 조형물을 출력했을 때 자외선을 조사 하였을 때 여러가지 컬러가 발현되는 조형물을 출력할 수 있는 특수한 기능성을 가지며, 일반 발광소재와는 차별화된 열적 안정성이 우수한 UV 발광용 3D 프린팅용 조성물 및 이를 이용한 3D 프린터용 필라멘트를 제공할 수 있다.According to the present invention, when an individual's desired sculpture is output using a 3D printer, it has a special function to output a sculpture that expresses various colors when irradiated with ultraviolet rays, and has excellent thermal stability differentiated from general light emitting materials. It is possible to provide a composition for 3D printing for light emission and a filament for a 3D printer using the same.

본 발명에 의한 상기 3차원 프린팅용 조성물은 UV에 의해 발광하는 물질인 형광물질이 구형 비드에 담지화 되어 내열성이 우수하여, FDM 용 3D 프린터용 필라멘트 소재로 매우 적합하다고 할 수 있다.The composition for 3D printing according to the present invention is excellent in heat resistance as a fluorescent material, which is a material emitting light by UV, is supported on a spherical bead, and it can be said that it is very suitable as a filament material for a 3D printer for FDM.

나아가, 최종 제조된 조형물에서 UV 조사시 다양한 컬러를 발광할 수 있으므로 유아용 장남감, 학습용 모형 등에 유용하게 이용될 수 있으며, 3차원 프린팅 원리를 학습하는 교육용에도 매우 유리하게 접목할 수 있다.Furthermore, since various colors can be emitted when irradiated with UV in the final manufactured sculpture, it can be usefully used for toys for children, learning models, etc., and can be very advantageously applied to education for learning the 3D printing principle.

도 1은 본 발명의 일 구현예에 따른 PMMA 형광 비드를 포함하는 필라멘트와 일반 필라멘트의 UV 조사시 발광 특성을 나타낸 사진이다.
도 2는 본 발명의 일 구현예에 따른 조형물에 UV 조사시 발광 특성을 나타낸 사진이다. 1 is a photograph showing the luminescence characteristics of a filament including a PMMA fluorescent bead according to an embodiment of the present invention and a general filament upon UV irradiation.
Figure 2 is a photograph showing the light emitting characteristics when UV irradiation to the sculpture according to an embodiment of the present invention.

본 발명의 일 구현예에 따르면, 플라스틱 수지 및 형광물질이 담지된 구형 비드를 포함하고, 상기 형광물질이 담지된 구형 비드는 플라스틱 수지 100 중량부 대비 2 내지 10 중량부로 포함하는 것인 3D 프린터용 필라멘트 조성물을 제공하는 것이다. According to an embodiment of the present invention, it comprises a plastic resin and a spherical bead supported with a fluorescent material, and the spherical bead supported with the fluorescent material is included in an amount of 2 to 10 parts by weight based on 100 parts by weight of the plastic resin for a 3D printer To provide a filament composition.

본 발명은 플라스틱 수지에 형광물질을 담지화한 구형 비드를 포함하여 다양한 물질에 따라 구현하고자 하는 컬러를 선택적으로 제조 할 수 있게 된다. 또한 형광물질이 구형 비드에 담지화 되어 있기 때문에 FMD방식에 적용되는 필라멘트에 가장 적합하게 적용될 수 있다.According to the present invention, it is possible to selectively manufacture a color to be realized according to various materials, including spherical beads in which a fluorescent material is supported on a plastic resin. In addition, since the fluorescent material is supported on the spherical bead, it can be most suitably applied to the filament applied to the FMD method.

종래 3D 프린팅 소재로 널리 사용되고 있는 소재는 단순 축광형 안료를 사용한 것으로, 단순히 빛을 축광한 후 어두운 환경에 들어갔을 때 야광을 발현하는 소재일 뿐이다. 또한, 이를 해결하기 위해 형광물질 자체를 도입하여, 필라멘트에 적용하였으며, 이는 필라멘트를 제조하는 압출과정과 3D 프린팅 시에 두번의 열을 받아 형광물질이 분해되기도 하여, UV 발광 특성이 저하되는 문제가 발생한다. A material widely used as a conventional 3D printing material uses a simple luminescent pigment, which is simply a material that emits luminescence when it enters a dark environment after luminescent light. In addition, in order to solve this problem, the fluorescent material itself was introduced and applied to the filament, which is subjected to heat twice during the extrusion process of manufacturing the filament and during 3D printing, and the fluorescent material is decomposed. Occurs.

그러나 본 발명의 3D 프린터용 필라멘트는 형광물질이 담지된 구형 비드를 포함하여, 통상 적용되고 있는 형광물질 자체를 적용하는 조성물 대비 우수한 열적 특성을 가지고 있고, 이러한 특성에 의해 두 번의 열이 가해지는 공정을 추가적으로 거치더라도 UV 발광 특성이 우수한 필라멘트를 제공할 수 있다.However, the filament for a 3D printer of the present invention, including the spherical bead supported with the fluorescent material, has excellent thermal properties compared to the composition to which the fluorescent material itself is usually applied, and the process in which heat is applied twice by these properties It is possible to provide a filament with excellent UV luminescence properties even if it is additionally passed through.

이하, 본 발명의 3D 프린터용 필라멘트 조성물 및 이를 이용한 FMD 방식의 3D 프린터용 필라멘트에 관하여 보다 구체적으로 설명한다.Hereinafter, the filament composition for a 3D printer of the present invention and a filament for a 3D printer of the FMD method using the same will be described in more detail.

본 발명의 상기 3D 프린터용 필라멘트 조성물은 플라스틱 수지를 기본 베이스 수지로 사용하는 것으로서 상기 플라스틱 수지는 PET(Polyethylene Terephtalate), PLA(Polylactic acid), ABS(Acrylonitrile Butadiene Styrene), PP(Polypropylene), PE(Polyethylene), HIPS(High Impact Polystyrene), EVA(Ethylene Vinyl Acetate), TPO(Thermoplastic Poly Olefin), PC(Polycarbonate), PETG(glycol- modified polyethylene terephthalate), Rubber, Nylon, PEN(polyethylene naphthalate), TPE(Thermo Plastic Elastomer) 및 이들의 조합으로 이루어진 군에서 선택된 1종 이상인 것이 좋다.The filament composition for the 3D printer of the present invention uses a plastic resin as a basic base resin, and the plastic resin is PET (Polyethylene Terephtalate), PLA (Polylactic acid), ABS (Acrylonitrile Butadiene Styrene), PP (Polypropylene), PE ( Polyethylene), HIPS (High Impact Polystyrene), EVA (Ethylene Vinyl Acetate), TPO (Thermoplastic Poly Olefin), PC (Polycarbonate), PETG (glycol-modified polyethylene terephthalate), Rubber, Nylon, PEN (polyethylene naphthalate), TPE ( It is preferable that at least one selected from the group consisting of Thermo Plastic Elastomer) and combinations thereof.

상기 형광물질이 담지된 구형 비드에서 형광물질은 방향족 유도체 화합물 및 유기금속 복합체를 포함하는 것이 바람직하다.In the spherical beads on which the fluorescent material is supported, the fluorescent material preferably includes an aromatic derivative compound and an organometallic complex.

상기 방향족 유도체 화합물은 Naphthalene계, Fluorescein계, Pyrene계, Thiophene계, Fluorene계, Carbazole계, quinine계, Resorufin계, Benzodiazole 계, Pentacene계, Perylene계, Pyrazine계 및 이들의 조합으로 이루어진 군에서 선택되는 1종 이상인 것을 들 수 있다.The aromatic derivative compound is selected from the group consisting of Naphthalene, Fluorescein, Pyrene, Thiophene, Fluorene, Carbazole, quinine, Resorufin, Benzodiazole, Pentacene, Perylene, Pyrazine, and combinations thereof. One or more types are mentioned.

상기 방향족 유도체 화합물의 보다 구체적인 일례를 들면, 아래와 같다.

Figure 112017095404116-pat00001
A more specific example of the aromatic derivative compound is given below.
Figure 112017095404116-pat00001

Figure 112017095404116-pat00002
Figure 112017095404116-pat00003
Figure 112017095404116-pat00002
Figure 112017095404116-pat00003

또한, 상기 유기금속 복합체는 Ir, Zn, Li, Al, Ru, Pt 등의 원소를 함유하는 유기금속 복합체일 수 있다. In addition, the organometallic complex may be an organometallic complex containing elements such as Ir, Zn, Li, Al, Ru, and Pt.

상기 유기금속 복합체의 보다 구체적인 일례를 들면, 아래와 같다.A more specific example of the organometallic complex is as follows.

Figure 112017095404116-pat00004
Figure 112017095404116-pat00004

Figure 112017095404116-pat00005
Figure 112017095404116-pat00005

상술한 방향족 유도체 화합물과 유기금속 복합체를 포함하는 형광물질은 다음과 같은 모식도에 의한 기작으로 UV에 반응하여 빛을 발광하게 된다.The fluorescent substance including the above-described aromatic derivative compound and the organometallic complex emits light in response to UV by a mechanism according to the schematic diagram as follows.

<모식도><Schematic diagram>

Figure 112017095404116-pat00006
Figure 112017095404116-pat00006

상기 모식도를 참조로 상세하게 설명하면, 바닥상태의 에너지 준위에 있는 형광물질 속의 전자가 외부에서 들어오는 자외선에 의하여 여기된 상위 에너지 준위인 S1 상태로 흥분되게 된다. 이후 일정시간이 지나게 되면(빛과 같은 속도) 다시 바닥 상태의 에너지 S0 상태로 돌아오게 되는데 이때 나오는 빛이 형광이며, 또한 계간교차를 통해 제3의 에너지 준위인 T1을 거쳐 S0와 같은 바닥상태의 에너지 준위로 돌아오면서 나오는 빛이 인광이다.When described in detail with reference to the schematic diagram, electrons in the fluorescent material in the ground state energy level are excited to the upper energy level S1 state excited by ultraviolet rays coming from the outside. After a certain period of time (same speed as light), the energy returns to the ground state energy S0 again. The light emitted at this time is fluorescence, and also passes through the third energy level, T1, to the ground state such as S0 through inter-quaternary crossing. The light emitted as it returns to the energy level is phosphorescence.

상기 방향족 유도체 및 유기금속 복합체를 포함하는 형광 물질이 담지된 구형 비드는 상기 플라스틱 수지 100 중량부 대비 2 내지 10중량부, 바람직하게는 2 내지 5중량부로 포함되는 것이 좋다. 상기 구형 비드 의 함량이 상기 범위를 만족할 경우 필라멘트 제조가 용이하며, 생산성이 우수할 뿐만 아니라, 최종 조형물을 출력한 후 UV 조사시 발광특성이 우수하다. 또한, 상기 구형 비드의 함량이 2중량부 미만일 경우에 발광 정도가 낮고, 상기 10중량부를 초과하는 경우 필라멘트의 강도가 저하되거나 경제적인 측면에서 제조원가가 올라가는 단점을 가지고 있다. The spherical beads carrying the fluorescent material containing the aromatic derivative and the organometallic complex are preferably included in an amount of 2 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the plastic resin. When the content of the spherical beads satisfies the above range, filament manufacturing is easy, and productivity is excellent, and the light emitting characteristic is excellent when UV irradiation is performed after outputting the final molded object. In addition, when the content of the spherical beads is less than 2 parts by weight, the light emission degree is low, and when it exceeds 10 parts by weight, the strength of the filament is lowered or the manufacturing cost is increased in economic terms.

또한, 상기 구형 비드는 지름이 1 내지 20㎛, 바람직하게는 1 내지 10㎛인 것이 좋다. 상기 지름이 1㎛ 미만일 경우, 투입시 비산이 되어, 일정한 함량을 투입하기 어려운 문제가 있고, 20㎛를 초과하는 경우 필라멘트 제조시 분산이 잘 되지 않아 뭉침 현상으로 필라멘트의 강도가 저하되는 문제를 야기할 수 있다. In addition, the spherical beads have a diameter of 1 to 20 μm, preferably 1 to 10 μm. If the diameter is less than 1㎛, there is a problem that it is scattered during input, and it is difficult to inject a certain amount. can do.

또한, 상기 구형 입자의 종횡비가 0.8 내지 1, 바람직하게는 0.9 내지 1인 것이 좋다. 상기 종횡비가 0.8 미만일 경우 분산문제가 발생하여 색 발광 및 필라멘트 강도가 저하되는 문제를 야기할 수 있다. In addition, the aspect ratio of the spherical particles is preferably 0.8 to 1, preferably 0.9 to 1. When the aspect ratio is less than 0.8, a dispersion problem may occur, which may cause a problem in that color emission and filament strength are lowered.

상기 구형 비드는 폴리메틸메타크릴레이트(PMMA)인 것이 발광특성 및 공정안정성 점에서 좋다. The spherical bead is preferably polymethyl methacrylate (PMMA) in terms of light emitting characteristics and process stability.

본 발명의 다른 일 구현예에 따르면, 상술한 3D 프린터용 필라멘트 조성물로부터 제조된 3D 프린터용 필라멘트를 제공하는 것이다.According to another embodiment of the present invention, it is to provide a filament for a 3D printer prepared from the above-described filament composition for a 3D printer.

상기 필라멘트는 직경이 0.8 ~ 4.0mm, 바람직하게는 1.5 내지 2.0, 더욱 바람직하게는 1.7 내지 1.8인 것이 좋다.The filament has a diameter of 0.8 to 4.0 mm, preferably 1.5 to 2.0, and more preferably 1.7 to 1.8.

3D 프린터용으로 사용되는 필라멘트의 굵기는 1.75mm가 일반적으로 사용되지만 필라멘트는 직경은 0.8 ~ 4.0mm의 범위로 만들 수 있다. 상기 필라멘트의 직경이 0.8mm 미만일 경우 필라멘트가 미세하게 되어 출력시간이 길어지며, 4.0mm를 초과할 경우 굵은 필라멘트를 출력할 수 있는 프린터가 제한적일 것이다. 또한, 출력을 함에 있어 결정화가 느려지기 때문에 정밀한 조형물을 기대하기 어렵다.The thickness of the filament used for 3D printers is generally 1.75mm, but the diameter of the filament can be made in the range of 0.8 ~ 4.0mm. If the diameter of the filament is less than 0.8mm, the filament becomes fine and the printing time becomes longer, and when it exceeds 4.0mm, the printer capable of outputting a thick filament will be limited. In addition, since crystallization is slow in printing, it is difficult to expect precise sculptures.

실시예Example

이하, 실시예를 통하여 본 발명을 더욱 상세히 설명 하고자 한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로서, 이에 의해 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention in more detail, and the present invention is not limited thereto.

3D 프린터용 필라멘트는 하기 실시예 1 내지 3 및 비교예 1 내지 6로 표기된 조성물을 각각 사용하여, 스크류 직경 30mm, 스크류 길이 105mm의 단축압출기(single screw extruder)로 압출한 후 길이 4m의 냉각수조에서 냉각하고 권취하여 직경 1.75mm로 제조하였다. 하기 표 1에 기재된 함량은 수지 100중량부에 대한 중량부이다. The filament for 3D printer was extruded with a single screw extruder having a screw diameter of 30 mm and a screw length of 105 mm using the compositions shown in Examples 1 to 3 and Comparative Examples 1 to 6, respectively, and then in a cooling water bath having a length of 4 m. It was cooled and wound to prepare a diameter of 1.75 mm. The contents shown in Table 1 below are parts by weight based on 100 parts by weight of the resin.

필라멘트 제조에 적용한 조성물은 표 1 과 같으며 하기 측정 방법으로 측정하였다.The composition applied to the filament production is shown in Table 1 and was measured by the following measurement method.

실시예1Example 1 실시예2Example 2 실시예3Example 3 비교예1Comparative Example 1 비교예2Comparative Example 2 비교예3Comparative Example 3 비교예4Comparative Example 4 비교예5Comparative Example 5 비교예6Comparative Example 6 PET계수지PET resin 100100 00 100100 100100 100100 100100 100100 00 00 PLA계수지PLA resin 00 100100 00 00 00 00 00 100100 100100 형광비드1 Fluorescent Bead 1 22 22 1010 0.50.5 00 00 1515 1515 00 형광비드2Fluorescent Bead 2 00 00 00 00 22 00 00 00 22 형광물질fluorescent substance 00 00 00 00 00 22 00 00 00

주석) 형광비드1: 형광물질이 담지된 PMMA 구형 비드(ASP 社의 BL-5BU; 블루 발광 비드, 지름이 5㎛이고, 종횡비가 1임)Note) Fluorescent bead 1: PMMA spherical bead supported with fluorescent material (BL-5BU of ASP company; blue light emitting bead, diameter 5㎛, aspect ratio 1)

형광비드2: 형광물질이 담지된 PMMA 구형 비드(ASP社의 BL-25BU; 블루 발광 비드 지름이 25㎛이고, 종횡비가 1임)Fluorescent bead 2: PMMA spherical bead supported with fluorescent material (BL-25BU of ASP company; blue light emitting bead diameter is 25㎛, aspect ratio is 1)

형광물질: SMT 社 의 BLUE 400; 블루 발광 물질Fluorescent material: BLUE 400 from SMT; blue luminescent material

PET계 수지: Kolon 社의 KE101(상품명); PEN-PET 계 플라스틱 수지PET-based resin: KE101 (trade name) from Kolon; PEN-PET plastic resin

PLA계 수지: 네이처웍스 社 PLA4032D 플라스틱 수지PLA-based resin: Natureworks PLA4032D plastic resin

이어서 3차원 프린터(ALMOND, Opencreators 社)를 이용하여 정육면체의 3D 조형물을 제작하고, 하기와 같은 측정방법에 의해 물성을 측정하였다.Then, using a three-dimensional printer (ALMOND, Opencreators), a cube-shaped 3D object was produced, and the physical properties were measured by the following measurement method.

측정방법How to measure

(1) 필라멘트 강도: 필라멘트 제작 후 5cm 의 길이로 무작위로 5개를 샘플링 한 후 400N의 힘으로 구부렸을 때 파손 횟수를 평가하였다. (1) Filament strength: After the filament was made, 5 samples were randomly sampled with a length of 5 cm, and the number of breakages was evaluated when bent with a force of 400N.

(2) UV 조사시 발광 특성: BOTECK 사의 Super Light-LUX 장비를 활용하여 UVA, UVB 파장을 조사하였을 때지름 4.5mm 길이 37mm의 조형물에서 발생되는 빛의 밝기 수준을 지름 4.5mm, 길이 37mm 의 블루 케미라이트와 비교하여 아래와 같이 평가하였다. 단, 빛의 세기는 블루 케미라이트가 발광할 때 블루 케미라이트의 표면으로부터 발광되는 빛의 길이를 측정하고, 이와 같은 방법으로 조형물이 발광할 때, 조형물의 표면으로부터 발광되는 빛의 길이를 측정하여 이들의 측정치를 아래와 같이 평가하였다. 또한, 상기 빛의 길이는 발광 전과 후를 사진으로 찍은 후, 10배로 확대하여 물체의 표면으로부터 발광되는 빛의 길이를 줄자로 측정하였다 (2) Luminescence characteristics during UV irradiation: When irradiated with UVA and UVB wavelengths using BOTECK's Super Light-LUX equipment, the brightness level of light generated from a sculpture with a diameter of 4.5mm and a length of 37mm is determined to be blue with a diameter of 4.5mm and a length of 37mm. It was evaluated as follows in comparison with Chemirite. However, the intensity of light is measured by measuring the length of light emitted from the surface of the blue chemilite when the blue chemilite emits light, and when the sculpture emits light in this way, the length of light emitted from the surface of the sculpture is measured. These measurements were evaluated as follows. In addition, the length of the light was measured by measuring the length of the light emitted from the surface of the object by magnifying 10 times after taking a picture before and after light emission.

높음: 블루 케미라이트의 빛의 길이(약 4mm) 보다 긴 경우High: Longer than the light length of blue chemilight (about 4mm)

보통: 블루 케미라이트의 빛의 길이(약 4mm)와 동일한 경우Normal: When the light length of the blue chemilight is equal to about 4mm

낮음: 블루 케미라이트의 빛의 길이(약 4mm)보다 짧은 경우Low: shorter than the light length of blue chemilight (about 4mm)

(3) 가공안정성: 실시예 및 비교예에 따라 제조된 필라멘트를 분쇄 후 압출하는 공정을 1회 및 3회로 각각 실시한 후, 4.5mm의 길이 및 37mm의 크기로 조형물을 출력하였다. 상기 1회 공정을 실시한 조형물과 3회 공정을 실시한 조형물의 발광특성을 측정한 후, 아래 수식에 의해 백분율로 계산하여 아래와 같이 평가하였다. 이때, 상기 발광특성은 조형물의 발광 전과 후를 사진으로 찍은 후, 10배로 확대하여 물체의 표면으로부터 발광되는 빛의 길이를 줄자로 측정하였다.(3) Processing stability: After pulverizing and extruding the filaments prepared according to Examples and Comparative Examples once and three times, respectively, a sculpture having a length of 4.5 mm and a size of 37 mm was output. After measuring the light emitting characteristics of the sculpture subjected to the process once and the sculpture subjected to the process three times, it was calculated as a percentage by the following formula and evaluated as follows. At this time, the light emission characteristics were measured by measuring the length of the light emitted from the surface of the object by measuring the length of the light emitted from the surface of the object by magnifying 10 times after taking a photograph of the before and after light emission of the sculpture.

<수식><Formula>

가공안정성(%)= (3회 공정시의 발광특성 측정값/1회 공정시의 발광특성 측정값)×100Processing stability (%) = (Measured value of luminescence characteristics in 3 processes / Measurement of luminescence characteristics in 1 process) × 100

우수: 90% 이상인 경우Excellent: over 90%

보통: 50% 이상 90% 미만인 경우Normal: More than 50% and less than 90%

나쁨: 50% 미만인 경우Bad: less than 50%

(4) 프린팅 적합성: 아래와 같은 기준으로 프린팅 적합성을 평가하였다.(4) Printing suitability: Printing suitability was evaluated based on the following criteria.

적합: 파손횟수 1회 이하, 발광특성 높음 및 가공안정성 우수인 경우Suitable: In case of less than 1 breakage, high luminous properties and excellent processing stability

부적합: 파손횟수 2 이상, 발광특성 보통 이하 및 가공안정성 보통 이하인 경우Unsuitable: When the number of breakages is 2 or more, the luminescence properties are below average, and the processing stability is below average.

실시예1Example 1 실시예2Example 2 실시예3Example 3 비교예1Comparative Example 1 비교예2Comparative Example 2 비교예3Comparative Example 3 비교예4Comparative Example 4 비교예5Comparative Example 5 비교예6Comparative Example 6 필라멘트 강도filament strength 00 00 1One 00 22 1One 22 22 22 발광 특성Luminescent properties 높음height 높음height 높음height 낮음lowness 높음height 높음height 높음height 높음height 높음height 가공안정성Processing stability 우수Great 우수Great 우수Great 우수Great 우수Great 나쁨bad 우수Great 우수Great 우수Great 프린팅 적합성Printing suitability 적합fitness 적합fitness 적합fitness 부적합incongruity 부적합incongruity 부적합incongruity 부적합incongruity 부적합incongruity 부적합incongruity

상기 표 1의 결과를 통해 확인할 수 있듯이, 실시예 1 내지 3과 같이 PMMA 비드의 함량이 2 내지 10 중량부 이내일 때와 PMMA 비드의 입자 사이즈가 1 내지 20㎛ 이내 일 때 프린팅 적합성이 적합으로 평가되었다.As can be seen from the results in Table 1 above, as in Examples 1 to 3, when the content of PMMA beads is within 2 to 10 parts by weight and when the particle size of PMMA beads is within 1 to 20 μm, the printing suitability is suitable. was evaluated.

또한, 형광물질을 PMMA 비드에 담지화 한 필라멘트의 내열 특성이 더 우수하다는 결과를 얻을 수 있었다. 또한 PMMA 형광 비드를 포함하는 필라멘트와 일반 필라멘트의 UV 조사시 발광 특성을 도 1에 나타내었으며, 조형물에 UV 조사시 발광 특성을 도 2에 나타내었다.In addition, it was possible to obtain a result that the heat resistance property of the filament supported on the PMMA bead with a fluorescent material was better. In addition, the luminescent properties of the filament including the PMMA fluorescent bead and the general filament upon UV irradiation are shown in FIG.

Claims (7)

플라스틱 수지 및 형광물질이 담지된 구형 비드를 포함하고,
상기 형광물질이 담지된 구형 비드는 지름이 1 내지 20㎛이며, 플라스틱 수지 100 중량부 대비 2 내지 10 중량부로 포함하는 것인 3D 프린터용 필라멘트 조성물.It includes a plastic resin and a spherical bead supported with a fluorescent material,
The spherical beads supported with the fluorescent material have a diameter of 1 to 20 μm, and the filament composition for a 3D printer comprising 2 to 10 parts by weight based on 100 parts by weight of the plastic resin. 제1항에 있어서, 상기 플라스틱 수지는 PET(Polyethylene Terephtalate), PLA(Polylactic acid), ABS(Acrylonitrile Butadiene Styrene), PP(Polypropylene), PE(Polyethylene), HIPS(High Impact Polystyrene), EVA(Ethylene Vinyl Acetate), TPO(Thermoplastic Poly Olefin), PC(Polycarbonate), PETG(glycol- modified polyethylene terephthalate), Rubber, Nylon, PEN(polyethylene naphthalate), TPE(Thermo Plastic Elastomer) 및 이들의 조합으로 이루어진 군에서 선택된 1종 이상인 것을 특징으로 하는 3D 프린터용 필라멘트 조성물.According to claim 1, wherein the plastic resin is PET (Polyethylene Terephtalate), PLA (Polylactic acid), ABS (Acrylonitrile Butadiene Styrene), PP (Polypropylene), PE (Polyethylene), HIPS (High Impact Polystyrene), EVA (Ethylene Vinyl) Acetate), TPO (Thermoplastic Poly Olefin), PC (Polycarbonate), PETG (glycol-modified polyethylene terephthalate), Rubber, Nylon, PEN (polyethylene naphthalate), TPE (Thermo Plastic Elastomer), and combinations thereof 1 selected from the group consisting of Filament composition for 3D printer, characterized in that more than species. 제1항에 있어서, 상기 형광물질은 Naphthalene계, Fluorescein계, Pyrene계, Thiophene계, Fluorene계, Carbazole계, quinine계, Resorufin계, Benzodiazole 계, Pentacene 계, Perylene계, Pyrazine계 및 이들의 조합으로 이루어진 군에서 선택되는 1종 이상인 방향족 유도체 화합물; 및 Ir, Zn, Li, Al, Ru, Pt 및 이들의 조합으로 이루어진 군에서 선택되는 1종 이상의 유기금속 복합체를 포함하는 것을 특징으로 하는 3D 프린터용 필라멘트 조성물.According to claim 1, wherein the fluorescent material is Naphthalene, Fluorescein, Pyrene, Thiophene, Fluorene, Carbazole, quinine, Resorufin, Benzodiazole, Pentacene, Perylene, Pyrazine, and combinations thereof. at least one aromatic derivative compound selected from the group consisting of; and Ir, Zn, Li, Al, Ru, Pt, and at least one organometallic complex selected from the group consisting of combinations thereof. 제1항에 있어서, 상기 구형 비드의 지름은 1 내지 20㎛이며, 종횡비가 0.8 내지 1인 것을 특징으로 하는 3D 프린터용 필라멘트 조성물.The filament composition for a 3D printer according to claim 1, wherein the spherical bead has a diameter of 1 to 20 μm, and an aspect ratio of 0.8 to 1. 제1항에 있어서, 상기 구형 비드는 폴리메틸메타크릴레이트(PMMA)인 것을 특징으로 하는 3D 프린터용 필라멘트 조성물.The filament composition for a 3D printer according to claim 1, wherein the spherical beads are polymethyl methacrylate (PMMA). 제1항 내지 제5항 중 어느 한 항에 따른 3D 프린터용 필라멘트 조성물로부터 제조된 3D 프린터용 필라멘트.A filament for a 3D printer prepared from the filament composition for a 3D printer according to any one of claims 1 to 5. 제6항에 있어서, 상기 필라멘트는 직경이 0.8 ~ 4.0mm인 것을 특징으로 하는 3D 프린터용 필라멘트.The filament for a 3D printer according to claim 6, wherein the filament has a diameter of 0.8 to 4.0 mm.
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