KR101964941B1 - Composite material filament composition for 3d printer - Google Patents

Composite material filament composition for 3d printer Download PDF

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KR101964941B1
KR101964941B1 KR1020170131720A KR20170131720A KR101964941B1 KR 101964941 B1 KR101964941 B1 KR 101964941B1 KR 1020170131720 A KR1020170131720 A KR 1020170131720A KR 20170131720 A KR20170131720 A KR 20170131720A KR 101964941 B1 KR101964941 B1 KR 101964941B1
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South Korea
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phthalate
printer
plasticizer
acid
inorganic material
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KR1020170131720A
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Korean (ko)
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이봉춘
박광민
조영근
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(재)한국건설생활환경시험연구원
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10Processes of additive manufacturing
    • B29C64/106Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013Fillers, pigments or reinforcing additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016Plasticisers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • C08K5/101Esters; Ether-esters of monocarboxylic acids
    • C08K5/105Esters; Ether-esters of monocarboxylic acids with phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/005Additives being defined by their particle size in general

Abstract

The present invention provides a composite material filament composition for a 3D printer, comprising: a thermoplastic biodegradable polymer resin; an inorganic material; a plasticizer; and a lubricant. The thermoplastic biodegradable polymer resin includes at least one selected from the group consisting of combinations of polylactic acid (PLA), polybutylene adipate-co-terephthalate (PBAT), polyglycolic acid (PGA), polycaprolactone acid (PCL), aliphatic polyester acid (APES), polyhydroxyalkanoate (PHA), polybutylene succinate acid (PBS), and D-3-hydroxybutyrate acid (PHB).

Description

3D 프린터용 복합소재 필라멘트 조성물 {COMPOSITE MATERIAL FILAMENT COMPOSITION FOR 3D PRINTER}[0001] COMPOSITE MATERIAL FILAMENT COMPOSITION FOR 3D PRINTER [0002]

본 발명은 3D 프린터용 복합소재 필라멘트 조성물에 관한 것으로서, 보다 상세하게는, FDM(Fused Deposition Modeling) 방식 3D 프린터에 사용되는 필라멘트 조성물에 열가소성 생분해성 고분자 수지, 무기소재, 가소제 및 활제로 이루어지는 필라멘트 조성물을 공급하여 내후성, 불연성 및 표면 가공성이 향상되고, 복합수지의 혼합 균질성, 친환경성 내광성 및 내열성이 향상되는 제품을 공급할 수 있는 3D 프린터용 복합소재 필라멘트 조성물에 관한 것이다.The present invention relates to a composite filament composition for a 3D printer, and more particularly, to a filament composition for use in a FDM (Fused Deposition Modeling) type 3D printer, a filament composition comprising a thermoplastic biodegradable polymer resin, an inorganic material, a plasticizer, To a composite material filament composition for a 3D printer capable of supplying a product having improved weatherability, nonflammability and surface processability, and improved mixing homogeneity, environment-friendly light resistance and heat resistance of the composite resin.

일반적으로, 3D 프린터는 특수 소재를 순차적으로 분사하여 미세한 두께로 층층이 쌓아 올리면서 입체적인 형상물을 제작하는 장비로, 최근 다양한 분야에서 사용이 확산되고 있다.In general, a 3D printer is a device for producing a three-dimensional object by sequentially spraying a special material and accumulating a layer with a fine thickness, and its use is spreading in various fields in recent years.

이와 같은 3D 프린터의 확산과 함께 다양한 방식의 3D 프린터가 개발되어 이용되고 있으며, 이를 크게 출력방식에 따라 구분하면, FDM(적층방식), SLS(분말소결), SLA(광경화 적층방식) 그리고 DLP(액체수지)로 구분된다.Various 3D printers have been developed and used along with the proliferation of such 3D printers. FDM (lamination method), SLS (powder sintering), SLA (light curing lamination method) and DLP (Liquid resin).

먼저, FDM 방식은, 국내에서 가장 널리 적용되는 방식으로, 적층방식을 통해 쌓아올리는 방식으로, 3D프린터는 소재를 실처럼 가늘게 압출하여 한 줄씩 형상을 순차적으로 적층하여 제품을 출력한다.First, the FDM method is the most widely applied method in Korea, and is a method of stacking through a lamination method. In the 3D printer, the material is extruded like a thread to sequentially stack the shapes one by one and output the products.

FDM 방식의 3D 프린터에 적용되는 소재(필라멘트)는 대표적으로 PLA (Polylactic acid) 소재와 ABS(Acrylonitile Poly-Butadiens Styrene) 소재가 있다.Filaments applied to FDM-type 3D printers are typically made of PLA (Polylactic acid) and ABS (Acrylonitrile Poly-Butadiene Styrene).

PLA 소재는 FDM 방식의 3D프린터에 가장 많이 사용되는 소재로, 친환경 수지로 녹아도 냄새가 나지 않고 유해요소가 거의 없다는 장점이 있다.PLA material is the most commonly used material for FDM type 3D printers. It has an advantage that it does not smell even if it is melted by environment friendly resin and there are few harmful elements.

한편, PLA 소재를 이용한 프린팅 제품은 후 가공이 어려워, 출력시 기밀성 및 표면 출력 상태가 양호할 것을 요한다.On the other hand, printing products using PLA materials are difficult to post-process and require good airtightness and surface output at the time of output.

그리고 ABS 소재는 기본적으로 Acrylonitile, Poly-Butadiene 및 Styrene로 이루어진 합성수지로, 후가공이 용이하나 소재를 출력시 냄새가 나며 , 상기 PLA 소재에 비하여 균열 및 수축현상이 크게 발생되는 단점이 있다.The ABS material is basically a synthetic resin made of Acrylonitile, Poly-Butadiene and Styrene. However, it has an unsatisfactory cracking and shrinking phenomenon as compared with the PLA material.

이외에도, FDM 방식의 3D 프린터는 Wood 소재 및 PVA (PolyVinyl Alcohol) 소재 등이 필라멘트로 구성되어 사용될 수 있다.In addition, FDM type 3D printers can be made of filament composed of wood material and PVA (polyvinyl alcohol) material.

한편, 3D 프린터의 방식 역시 FDM 방식 이외에, SLS(분말소결)방식, 액체 수지를 이용한 SLA방식 및 DLP방식 등이 있다.On the other hand, in addition to the FDM method, the 3D printer method also includes an SLS (powder sintering) method, an SLA method using a liquid resin, and a DLP method.

이에 본원 발명은 FDM 방식의 3D 프린터에 관한 것으로, 특히 FDM 방식의 프린터에 제공되는 PLA 소재의 필라멘트 조성물 및 이의 압출방법에 관한 것이다.Accordingly, the present invention relates to a 3D printer of FDM type, and more particularly to a filament composition of PLA material and an extrusion method thereof, which are provided in an FDM type printer.

3D프린터에 제공되는 필라멘트는 적정한 녹는점 특성에 따라, 프린팅 후 신속하게 고화되도록 하여, 변형 없이 치수 및 형태의 안정성을 확보하면서 프린팅 속도를 향상시킬 수 있도록 할 뿐만 아니라 제조 시 압출이 용이할 것이 요구된다.The filament provided in the 3D printer is required to be rapidly solidified after printing in accordance with proper melting point characteristics so that it is possible to improve the printing speed while ensuring dimensional stability and form stability without deformation, do.

한편 이러한 필라멘트에 대한 요구사항은 프린팅 대상물의 종류가 날로 확대됨에 따라 점차 증가하고 있는 추세이며, 이에 따라 상기 필라멘트 조성물에 대한 연구도 활발히 진행되고 있는 실정이다.On the other hand, the requirements for such filaments are gradually increasing as the type of printed objects is increasing day by day. Accordingly, studies on the filament compositions have been progressing actively.

상기한 문제점을 해결하기 위해 3D 프린터용 필라멘트 조성물의 압출방법이 개발되었으며, 종래기술에 따른 필라멘트 조성물은, 필라멘트 형태의 원재료를 압출하는 노즐과, 노즐을 가열하는 노즐 가열부와, 가열된 필라멘트를 노즐을 통해 압출하도록 가압력을 발생시키는 가압부를 포함하여 구성되는 3D 프린터를 통해 필라멘트를 압출하고, 필라멘트는, 폴리락트산(Polylactic acid) 90 내지 94 중량%와, 에틸렌 비스 스테아마이드(N,N Ethylene bis(stearamide)) 2 내지 5 중량%와, 산화방지제(Antioxidant) 2 내지 5 중량% 그리고 안료(Pigment) 2 내지 5 중량%를 포함한다.
In order to solve the above problems, a method for extruding a filament composition for a 3D printer has been developed. The filament composition according to the prior art includes a nozzle for extruding a raw material in a filament form, a nozzle heating part for heating the nozzle, The filament is extruded through a 3D printer including a pressurizing portion for generating a pressing force to be extruded through a nozzle, and the filament is formed by extruding 90 to 94% by weight of polylactic acid and 90 to 90% by weight of ethylene bis 2 to 5% by weight of stearamide, 2 to 5% by weight of an antioxidant and 2 to 5% by weight of a pigment.

본 발명의 배경기술은 대한민국 등록특허공보 제10-1757313호(2017년 07월 06일 공고, 발명의 명칭 : 3D 프린터용 필라멘트 조성물 및 이의 압출방법)에 개시되어 있다.
BACKGROUND ART [0002] The background art of the present invention is disclosed in Korean Patent Publication No. 10-1757313 (filed on Jul. 06, 2017, entitled "Filament composition for 3D printer and extrusion method thereof").

종래기술에 따른 필라멘트 조성물은, 별도의 무기소재 및 가소제가 구비되지 않기 때문에 3D프린터에 의해 제조되는 제품의 내후성, 불연성 및 표면 가공성을 향상시키기 어렵고, 복합수지의 혼합 균질성, 친환경성, 내광성 및 내열성을 향상시키기 어려운 문제점이 있다.Since the filament composition according to the prior art does not have a separate inorganic material and plasticizer, it is difficult to improve the weather resistance, nonflammability and surface processability of a product manufactured by a 3D printer, and the mixed homogeneity, environment friendliness, light resistance, Which is difficult to improve.

따라서 이를 개선할 필요성이 요청된다.Therefore, there is a need for improvement.

본 발명은 FDM(Fused Deposition Modeling) 방식 3D 프린터에 사용되는 필라멘트 조성물에 열가소성 생분해성 고분자 수지, 무기소재, 가소제 및 활제로 이루어지는 필라멘트 조성물을 공급하여 내후성, 불연성 및 표면 가공성이 향상되고, 복합수지의 혼합 균질성, 친환경성 내광성 및 내열성이 향상되는 제품을 공급할 수 있는 3D 프린터용 복합소재 필라멘트 조성물을 제공하는데 그 목적이 있다.Disclosed is a filament composition for use in a FDM (Fused Deposition Modeling) 3D printer. The filament composition is made of a thermoplastic biodegradable polymer resin, an inorganic material, a plasticizer and a lubricant to improve the weather resistance, And to provide a composite material filament composition for a 3D printer capable of providing a product having improved uniformity of homogeneity, environment friendliness, light resistance and heat resistance.

본 발명은, 열가소성 생분해성 고분자 수지, 무기소재, 가소제 및 활제를 포함하여 이루어지고, 상기 열가소성 생분해성 고분자 수지는, 폴리유산 수지(Poly Lactic Acid, PLA), 폴리부틸렌 아디페이트-테레프탈레이드 수지(butylene adipate-co-terephthalate, PBAT), 폴리글리콜산 수지(Poly Glycolic Acid, PGA), 폴리카프로락톤 수지(Poly Caprolactone Acid, PCL), 지방족 폴리에스테르 수지(aliphatic polyester Acid, APES), 폴리히드록시알카노에이트 수지(Poly hydroxyalkanoat Acid, PHA), 폴리부틸렌 숙시네이트(Polybutylene succinate Acid, PBS) 및 D-3-히드록시 부틸레이트 수지(D-3-hydroxybutyrate Acid, PHB) 중에서 이들의 조합들로 이루어진 군에서 선택되는 1종 이상을 포함하는 것을 특징으로 한다.The present invention relates to a thermoplastic biodegradable polymer resin comprising a thermoplastic biodegradable polymer resin, an inorganic material, a plasticizer and a lubricant, wherein the thermoplastic biodegradable polymer resin is selected from the group consisting of Poly Lactic Acid (PLA), polybutylene adipate-terephthalide resin polyglycolic acid (PGA), polycaprolactone resin (PCL), aliphatic polyester resin (APES), polyhydroxy alcohols Polyhydroxyalkanoate resin (PHA), polybutylene succinate acid (PBS) and D-3-hydroxybutyrate acid (PHB). And at least one selected from the group consisting of

또한, 본 발명의 상기 3D 프린터용 복합소재 필라멘트 조성물은, 70 내지 90 중량부로 포함되는 상기 열가소성 생분해성 고분자 수지와, 10 내지 30 중량부로 포함되는 상기 무기소재 분말과, 5~10 중량부로 포함되는 상기 가소제와, 1~3 중량부로 포함되는 상기 활제를 포함하는 것을 특징으로 한다.In addition, the composite filament composition for 3D printer of the present invention may comprise the thermoplastic biodegradable polymer resin included in 70 to 90 parts by weight, the inorganic material powder contained in 10 to 30 parts by weight, and 5 to 10 parts by weight The plasticizer, and the lubricant contained in 1 to 3 parts by weight.

또한, 본 발명의 상기 무기소재는, 탈크(Talc), 탄산칼슘(Calcium carbonate, CaCO3), 무수석고(Calcium sulfate anhydrite, CaSO4), 동슬래그(Copper slag), 산화 티타늄(Titanium dioxide ,TiO2), 수산화 알루미늄(Aluminium hydroxide, Al(OH)3), 레드머드(Redmud) 및 애시(Ash)로 이루어진 난연성 무기소재 그룹에서 선택된 1종 이상을 포함하는 것을 특징으로 한다.The inorganic material of the present invention may be selected from the group consisting of talc, calcium carbonate, CaCO 3 , calcium sulfate anhydrite (CaSO 4 ), copper slag, titanium dioxide (TiO 2) 2 or a flame retardant inorganic material group consisting of aluminum hydroxide (Al (OH) 3 ), red mud, and ash.

또한, 본 발명의 상기 무기소재는, 결정수를 포함하지 않고, 입자 크기는 635~400 mesh(20~38 μm)로 이루어지는 것을 특징으로 한다.Further, the inorganic material of the present invention does not contain crystal water and has a particle size of 635 to 400 mesh (20 to 38 μm).

또한, 본 발명의 상기 가소제는, 디에틸헥실프탈레이트(DEHP), 다이노말옥틸프탈레이트(DNOP), 프탈산부틸벤질(Butyl Benzyl Phthalate : BBP), 프탈산디부틸(Dibutyl Phthalate : DBP), DINP(Diisononyl phthalate), DIDP(Diisodecyl phthalate)로 이루어지는 프탈레이트계 가소제를 대체하여 2-(2-(2-페닐카르보닐옥시에톡시)에톡시)에틸 벤조에이트, 글리세릴 트리벤조에이트, 트리메틸올프로판 트리 벤조에이트, 이소노닐 벤조에이트, 1-메틸-2-(2-페닐카보닐옥시프로폭시)에틸 벤조에이트, 2, 2, 4-트리메틸-1, 3-펜탄디올 디벤조에이트, n-헥실 벤조에이트 및 트리메틸올 프로판트리벤조에이트 중에서 1종 이상을 포함하는 것을 특징으로 한다.The plasticizer of the present invention may be selected from the group consisting of diethylhexyl phthalate (DEHP), dynomal octyl phthalate (DNOP), butyl benzyl phthalate (BBP), dibutyl phthalate (DBP), diisononyl phthalate ) And DIDP (diisodecyl phthalate), which are used in place of the phthalate-based plasticizer, and 2- (2- (2-phenylcarbonyloxyethoxy) ethoxy) ethylbenzoate, glyceryl tribenzoate, trimethylolpropane tribenzoate, 2-ethylhexanoate, isononyl benzoate, 1-methyl-2- (2-phenylcarbonyloxypropoxy) ethylbenzoate, 2,2,4-trimethyl-1,3-pentanediol dibenzoate, And olpropane tribenzoate. ≪ IMAGE >

또한, 본 발명의 상기 활제는 티탄산염, 실란 및 인산염으로 이루어진 군에서 선택되는 1종 이상을 포함하는 것을 특징으로 한다.In addition, the lubricant of the present invention is characterized by containing at least one selected from the group consisting of titanate, silane, and phosphate.

본 발명에 따른 3D 프린터용 복합소재 필라멘트 조성물은, 무기소재가 포함되어 이루어지므로 3D 프린터용 필라멘트의 내후성, 불연성 및 표면 가공성이 향상되고, 가소제로 프탈레이트 성분이 없는 벤조에이트계 가소제를 첨가하므로 복합수지의 혼합 균질성, 친환경성, 내광성 및 내열성을 향상시킬 수 있는 이점이 있다.
Since the composite material filament composition for 3D printer according to the present invention includes an inorganic material, the benzoate plasticizer having no phthalate component is added as the plasticizer filament with improved weatherability, incombustibility and surface processability, And can improve the homogeneity of the mixture, the environment friendliness, the light resistance and the heat resistance.

이하, 첨부된 도면들을 참조하여 본 발명에 따른 3D 프린터용 복합소재 필라멘트 조성물의 일 실시예를 설명한다.Hereinafter, an embodiment of a composite material filament composition for a 3D printer according to the present invention will be described with reference to the accompanying drawings.

이러한 과정에서 도면에 도시된 선들의 두께나 구성요소의 크기 등은 설명의 명료성과 편의상 과장되게 도시되어 있을 수 있다.In this process, the thicknesses of the lines and the sizes of the components shown in the drawings may be exaggerated for clarity and convenience of explanation.

또한, 후술되는 용어들은 본 발명에서의 기능을 고려하여 정의된 용어들로써, 이는 사용자, 운용자의 의도 또는 관례에 따라 달라질 수 있다.In addition, the terms described below are terms defined in consideration of the functions of the present invention, which may vary depending on the intention or custom of the user, the operator.

그러므로 이러한 용어들에 대한 정의는 본 명세서 전반에 걸친 내용을 토대로 내려져야 할 것이다.Therefore, definitions of these terms should be made based on the contents throughout this specification.

본 발명의 일 실시예에 따른 3D 프린터용 복합소재 필라멘트 조성물은, 열가소성 생분해성 고분자 수지, 무기소재, 가소제 및 활제를 포함하여 이루어진다.A composite material filament composition for a 3D printer according to an embodiment of the present invention comprises a thermoplastic biodegradable polymer resin, an inorganic material, a plasticizer, and a lubricant.

본 실시예의 열가소성 생분해성 고분자 수지는, 자연계에 존재하는 생물에 의해 소화분해 되어 최종적으로는 이산화탄소와 물이 될 수 있는 가소성 고분자수지(樹脂)의 일종이고, 종래의 플라스틱 결정이 자연계에서는 분해되지 않는 점과 소각 시 고열이나 독성가스 발생 등의 단점을 보완할 수 있는 성분이다.The thermoplastic biodegradable polymer resin of the present embodiment is a kind of plastic polymer resin (resin) that can be decomposed and decomposed by organisms existing in nature to be finally carbon dioxide and water, and the conventional plastic crystal is not decomposed in nature It is a component that can compensate for the disadvantages of point and incineration such as high temperature and toxic gas generation.

따라서 열가소성 생분해성 고분자 수지를 포함하는 필라멘트는, 친환경성을 향상시킬 수 있게 된다.Therefore, the filament containing the thermoplastic biodegradable polymer resin can improve the environmental friendliness.

본 실시예의 열가소성 생분해성 고분자 수지는, 폴리유산 수지(Poly Lactic Acid, PLA), 폴리부틸렌 아디페이트-테레프탈레이드 수지(butylene adipate-co-terephthalate, PBAT), 폴리글리콜산 수지(Poly Glycolic Acid, PGA), 폴리카프로락톤 수지(Poly Caprolactone Acid, PCL), 지방족 폴리에스테르 수지(aliphatic polyester Acid, APES), 폴리히드록시알카노에이트 수지(Poly hydroxyalkanoat Acid, PHA), 폴리부틸렌 숙시네이트(Polybutylene succinate Acid, PBS) 및 D-3-히드록시 부틸레이트 수지(D-3-hydroxybutyrate Acid, PHB) 중에서 이들의 조합들로 이루어진 군에서 선택되는 1종 이상을 포함하여 이루어진다.The thermoplastic biodegradable polymer resin of the present embodiment may be selected from polylactic acid (PLA), butylene adipate-co-terephthalate (PBAT), polyglycolic acid resin, PGA, poly caprolactone acid (PCL), aliphatic polyester acid (APES), polyhydroxyalkanoate resin (PHA), polybutylene succinate Acid, PBS) and D-3-hydroxybutyrate Acid (PHB). These compounds may be used alone or in combination of two or more thereof.

폴리유산 수지는, 유산의 중축합 혹은 락티드의 개환 중합으로 합성되는 생분해성 합성 고분자이고, 생분해성이며, 주로 의약용 재료로 사용된다.The poly (lactic acid) resin is a biodegradable synthetic polymer synthesized by polycondensation of lactic acid or ring-opening polymerization of lactide, is biodegradable, and is mainly used as a pharmaceutical material.

또한, 본 실시예의 3D 프린터용 복합소재 필라멘트 조성물은, 70 내지 90 중량부로 포함되는 열가소성 생분해성 고분자 수지와, 10 내지 30 중량부로 포함되는 무기소재 분말과, 5~10 중량부로 포함되는 가소제와, 1~3 중량부로 포함되는 활제를 포함한다.The composite filament composition for a 3D printer according to the present invention may further comprise a thermoplastic biodegradable polymer resin in an amount of 70 to 90 parts by weight, an inorganic material powder in 10 to 30 parts by weight, a plasticizer in 5 to 10 parts by weight, 1 to 3 parts by weight of a lubricant.

여기서, 무기소재는, 탈크(Talc), 탄산칼슘(Calcium carbonate, CaCO3), 무수석고(Calcium sulfate anhydrite, CaSO4), 동슬래그(Copper slag), 산화 티타늄(Titanium dioxide ,TiO2), 수산화 알루미늄(Aluminium hydroxide, Al(OH)3), 레드머드(Redmud) 및 애시(Ash)로 이루어진 난연성 무기소재 그룹에서 선택된 1종 이상을 포함하여 이루어진다.Here, the inorganic material is talc (Talc), calcium carbonate (Calcium carbonate, CaCO 3), anhydrite (Calcium sulfate anhydrite, CaSO 4), copper slag (Copper slag), titanium oxide (Titanium dioxide, TiO 2), hydroxide And a flame retardant inorganic material group composed of aluminum (Aluminum hydroxide, Al (OH) 3 ), Redmud and Ash.

여기서, 탈크는, 활석(滑石)을 분말로 분쇄한 것이며, 탈크의 성분 조성은 3MgO·4SiO·H2O이고, 백색~담황백색으로 그리즈와 같은 매끈매끈함이 있다.Here, talc is obtained by pulverizing talc into powder, and the composition of talc is 3MgO.4SiO.H2O, and there is smooth smoothness like grease with white to pale yellowish white.

또한, 본 실시예의 무기소재는, 결정수를 포함하지 않고, 입자 크기는 635~400 mesh(20~38 μm)로 이루어진다.The inorganic material of this embodiment does not contain crystal water and has a particle size of 635 to 400 mesh (20 to 38 mu m).

본 실시예의 가소제는, 디에틸헥실프탈레이트(DEHP), 다이노말옥틸프탈레이트(DNOP), 프탈산부틸벤질(Butyl Benzyl Phthalate : BBP), 프탈산디부틸(Dibutyl Phthalate : DBP), DINP(Diisononyl phthalate), DIDP(Diisodecyl phthalate)로 이루어지는 프탈레이트계 가소제를 대체하여 2-(2-(2-페닐카르보닐옥시에톡시)에톡시)에틸 벤조에이트, 글리세릴 트리벤조에이트, 트리메틸올프로판 트리 벤조에이트, 이소노닐 벤조에이트, 1-메틸-2-(2-페닐카보닐옥시프로폭시)에틸 벤조에이트, 2, 2, 4-트리메틸-1, 3-펜탄디올 디벤조에이트, n-헥실 벤조에이트 및 트리메틸올 프로판트리벤조에이트 중에서 1종 이상을 포함하여 이루어진다.The plasticizer of the present embodiment is a plasticizer such as diethylhexyl phthalate (DEHP), dynomal octyl phthalate (DNOP), butyl benzyl phthalate (BBP), dibutyl phthalate (DBP), DINP (Diisononyl phthalate) (2- (2-phenylcarbonyloxyethoxy) ethoxy) ethyl benzoate, glyceryl tribenzoate, trimethylolpropane tribenzoate, isononyl benzoate, diisodecyl phthalate, 2-methyl-2- (2-phenylcarbonyloxypropoxy) ethyl benzoate, 2,2,4-trimethyl-1,3-pentanediol dibenzoate, n-hexylbenzoate and trimethylolpropane tri Benzoate. ≪ / RTI >

디에틸헥실프탈레이트(DEHP)는, 프탈레이트 계통의 인공 화학물질로 무색무취한 액체이고, 다이에틸헥실프탈산이라고도 칭하며, 장난감이나 실내장식제 등 플라스틱 제품을 유연하게 하기 위한 가소제로 널리 사용된다.Diethylhexyl phthalate (DEHP) is a phthalate-based artificial chemical that is colorless and odorless liquid, also called diethylhexylphthalic acid, and widely used as a plasticizer to soften plastic products such as toys and upholstery.

또한, 본 실시예의 활제는 티탄산염, 실란 및 인산염으로 이루어진 군에서 선택되는 1종 이상을 포함하여 이루어진다.In addition, the lubricant of the present embodiment comprises at least one selected from the group consisting of titanate, silane, and phosphate.

티탄산염은, 이산화티탄과 다른 금속의 산화물로서 구성된 화합물로, 일반식 mMI2OㅇTiO2와 같은 화합물을 티탄산염이라 부르고, 보통 티탄산염이라 불리는 CaTiO3, BaTiO3 등은 페로브스카이드형 구조의 복산화물, MgTiO3 등은 티탄 철광형의 복산화물이다.
The titanate is a compound composed of titanium dioxide and an oxide of another metal. A compound such as mMI2O? TiO2 is called a titanate, and CaTiO3, BaTiO3 or the like commonly called titanate is a double oxide of a perovskite structure, MgTiO3 And the like are double oxides of titanium iron type.

<실시예><Examples>

본 실시예에 따른 3D 프린터용 복합소재 필라멘트 조성물은, 시차주사열량계(Differential Scanning Calorimeters, DSC) 열분석시 용융온도(Melting Temperature, Tm)가 160 내지 180℃인 폴리유산 수지(Poly Lactic Acid, PLA)를 70중량부, 입자크기가 635~400 mesh(20~38 μm)인 탄산칼슘 30중량부, 벤조에이트계 가소제는 PLA 대비 10중량부를 첨가하여 이루어지고, 유무기 소재는 160 내지 180℃에서 용용하여 필라멘트 조성물을 제조한다.The composite filament composition for a 3D printer according to this embodiment is obtained by mixing polylactic acid (PLA) having a melting temperature (Tm) of 160 to 180 DEG C upon thermal analysis by differential scanning calorimetry (DSC) ), 30 parts by weight of calcium carbonate having a particle size of 635 to 400 mesh (20 to 38 μm), 10 parts by weight of a benzoate plasticizer as a PLA, To prepare a filament composition.

이로써, FDM(Fused Deposition Modeling) 방식 3D 프린터에 사용되는 필라멘트 조성물에 열가소성 생분해성 고분자 수지, 무기소재, 가소제 및 활제로 이루어지는 필라멘트 조성물을 공급하여 내후성, 불연성 및 표면 가공성이 향상되고, 복합수지의 혼합 균질성, 친환경성 내광성 및 내열성이 향상되는 제품을 공급할 수 있는 3D 프린터용 복합소재 필라멘트 조성물을 제공할 수 있게 된다.Thus, a filament composition comprising a thermoplastic biodegradable polymer resin, an inorganic material, a plasticizer and a lubricant is supplied to a filament composition used in a FDM (Fused Deposition Modeling) type 3D printer to improve weather resistance, nonflammability and surface processability, It is possible to provide a composite material filament composition for a 3D printer capable of supplying a product having improved homogeneity, environment-friendly light resistance and heat resistance.

본 발명은 도면에 도시되는 일 실시예를 참고로 하여 설명되었으나, 이는 예시적인 것에 불과하며, 당해 기술이 속하는 분야에서 통상의 지식을 가진 자라면 이로부터 다양한 변형 및 균등한 타 실시예가 가능하다는 점을 이해할 것이다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. .

또한, 3D 프린터용 복합소재 필라멘트 조성물을 예로 들어 설명하였으나, 이는 예시적인 것에 불과하며, 3D 프린터용 복합소재 필라멘트 조성물이 아닌 다른 제품에도 본 발명의 필라멘트 조성물이 사용될 수 있다.In addition, although the composite filament composition for 3D printer has been described as an example, the filament composition of the present invention can be also used for other products other than the composite filament composition for 3D printer.

따라서 본 발명의 진정한 기술적 보호범위는 아래의 특허청구범위에 의해서 정하여져야 할 것이다.Accordingly, the true scope of the present invention should be determined by the following claims.

Claims (6)

열가소성 생분해성 고분자 수지, 무기소재, 가소제 및 활제를 포함하여 이루어지고,
상기 열가소성 생분해성 고분자 수지는,
폴리유산 수지(Poly Lactic Acid, PLA), 폴리부틸렌 아디페이트-테레프탈레이드 수지(butylene adipate-co-terephthalate, PBAT), 폴리글리콜산 수지(Poly Glycolic Acid, PGA), 폴리카프로락톤 수지(Poly Caprolactone Acid, PCL), 지방족 폴리에스테르 수지(aliphatic polyester Acid, APES), 폴리히드록시알카노에이트 수지(Poly hydroxyalkanoat Acid, PHA), 폴리부틸렌 숙시네이트(Polybutylene succinate Acid, PBS) 및 D-3-히드록시 부틸레이트 수지(D-3-hydroxybutyrate Acid, PHB) 중에서 이들의 조합들로 이루어진 군에서 선택되는 1종 이상을 포함하고,
상기 3D 프린터용 복합소재 필라멘트 조성물은,
시차주사열량계(Differential Scanning Calorimeters, DSC) 열분석시 용융온도(Melting Temperature, Tm)가 섭씨 160 내지 180℃이고, 70 내지 90 중량부로 포함되는 상기 열가소성 생분해성 고분자 수지;
입자크기가 635~400 mesh이고, 10 내지 30 중량부로 포함되는 상기 무기소재 분말;
5~10 중량부로 포함되는 상기 가소제; 및
1~3 중량부로 포함되는 상기 활제를 포함하여 이루어지고,
상기 3D 프린터용 복합소재 필라멘트 조성물은, 섭씨 160 내지 180℃에서 용용하여 이루어지는 것을 특징으로 하는 3D 프린터용 복합소재 필라멘트 조성물.
A thermoplastic biodegradable polymer resin, an inorganic material, a plasticizer and a lubricant,
The thermoplastic biodegradable polymer resin may contain,
Polylactic acid (PLA), butylene adipate-terephthalate (PBAT), polyglycolic acid (PGA), polycaprolactone resin (Poly Caprolactone Aliphatic polyester resin (APES), polyhydroxyalkanoate resin (PHA), polybutylene succinate acid (PBS), and D-3-hydroxystearic acid Hydroxybutyrate (D-3-hydroxybutyrate, PHB), and combinations thereof.
In the composite filament composition for a 3D printer,
Differential Scanning Calorimeters (DSC) The thermoplastic biodegradable polymeric resin having a melting temperature (Tm) in the range of 160 to 180 DEG C and 70 to 90 parts by weight in thermal analysis;
The inorganic material powder having a particle size of 635 to 400 mesh and being contained in an amount of 10 to 30 parts by weight;
5 to 10 parts by weight of the plasticizer; And
1 to 3 parts by weight of the lubricant,
Wherein the composite filament composition for a 3D printer is obtained by dissolving at a temperature of 160 to 180 캜.
삭제delete 제1항에 있어서,
상기 무기소재는, 탈크(Talc), 탄산칼슘(Calcium carbonate, CaCO3), 무수석고(Calcium sulfate anhydrite, CaSO4), 동슬래그(Copper slag), 산화 티타늄(Titanium dioxide ,TiO2), 수산화 알루미늄(Aluminium hydroxide, Al(OH)3), 레드머드(Redmud) 및 애시(Ash)로 이루어진 난연성 무기소재 그룹에서 선택된 1종 이상을 포함하는 것을 특징으로 하는 3D 프린터용 복합소재 필라멘트 조성물.
The method according to claim 1,
The inorganic material may be at least one selected from the group consisting of talc, calcium carbonate, CaCO 3 , calcium sulfate anhydrite (CaSO 4 ), copper slag, titanium dioxide (TiO 2 ) And a flame retardant inorganic material group consisting of aluminum hydroxide, Al (OH) 3 , Redmud and Ash. The composite material filament composition for 3D printer according to claim 1,
제1항 또는 제3항에 있어서,
상기 무기소재는, 결정수를 포함하지 않고, 입자 크기는 635~400 mesh(20~38 μm)로 이루어지는 것을 특징으로 하는 3D 프린터용 복합소재 필라멘트 조성물.
The method according to claim 1 or 3,
Wherein the inorganic material does not contain crystal water and has a particle size of 635 to 400 mesh (20 to 38 mu m).
제1항에 있어서,
상기 가소제는, 디에틸헥실프탈레이트(DEHP), 다이노말옥틸프탈레이트(DNOP), 프탈산부틸벤질(Butyl Benzyl Phthalate : BBP), 프탈산디부틸(Dibutyl Phthalate : DBP), DINP(Diisononyl phthalate), DIDP(Diisodecyl phthalate)로 이루어지는 프탈레이트계 가소제를 대체하여 2-(2-(2-페닐카르보닐옥시에톡시)에톡시)에틸 벤조에이트, 글리세릴 트리벤조에이트, 트리메틸올프로판 트리 벤조에이트, 이소노닐 벤조에이트, 1-메틸-2-(2-페닐카보닐옥시프로폭시)에틸 벤조에이트, 2, 2, 4-트리메틸-1, 3-펜탄디올 디벤조에이트, n-헥실 벤조에이트 및 트리메틸올 프로판트리벤조에이트 중에서 1종 이상을 포함하는 것을 특징으로 하는 3D 프린터용 복합소재 필라멘트 조성물.
The method according to claim 1,
The plasticizer may be selected from the group consisting of diethylhexyl phthalate (DEHP), dynomal octyl phthalate (DNOP), butyl benzyl phthalate (BBP), dibutyl phthalate (DBP), DINP (Diisononyl phthalate), DIDP phthalate) as a substitute for a phthalate plasticizer, it is possible to use a phthalate-based plasticizer such as 2- (2- (2-phenylcarbonyloxyethoxy) ethoxy) ethylbenzoate, glyceryl tribenzoate, trimethylolpropane tribenzoate, isononyl benzoate, Methyl-2- (2-phenylcarbonyloxypropoxy) ethylbenzoate, 2,2,4-trimethyl-1,3-pentanediol dibenzoate, n-hexylbenzoate and trimethylolpropane tribenzoate Wherein the composite filament composition is at least one of the following.
제1항에 있어서,
상기 활제는 티탄산염, 실란 및 인산염으로 이루어진 군에서 선택되는 1종 이상을 포함하는 것을 특징으로 3D 프린터용 복합소재 필라멘트 조성물.
The method according to claim 1,
Wherein the lubricant comprises at least one selected from the group consisting of titanate, silane, and phosphate.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200122044A (en) * 2019-04-17 2020-10-27 에콜그린텍(주) Pla mask clip and its manufacturing method
WO2021054948A1 (en) * 2019-09-18 2021-03-25 Hewlett-Packard Development Company, L.P. Three-dimensional printing
CN112694724A (en) * 2020-12-08 2021-04-23 上海浦景化工技术股份有限公司 Degradable wire rod suitable for 3D prints
WO2024029811A1 (en) * 2022-08-02 2024-02-08 에스케이티비엠지오스톤 주식회사 Method for preparing biodegradable resin composition, biodegradable resin composition prepared thereby, and biodegradable molded product comprising same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015037574A1 (en) * 2013-09-11 2015-03-19 東レ株式会社 Material for fused-deposition-type three-dimensional modeling, and filament for fused-deposition-type 3d printing device
KR20150098142A (en) * 2014-02-19 2015-08-27 (주)비앤케이 Complex filament composition for fdm type 3d printer containing metal powder

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015037574A1 (en) * 2013-09-11 2015-03-19 東レ株式会社 Material for fused-deposition-type three-dimensional modeling, and filament for fused-deposition-type 3d printing device
KR20150098142A (en) * 2014-02-19 2015-08-27 (주)비앤케이 Complex filament composition for fdm type 3d printer containing metal powder

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200122044A (en) * 2019-04-17 2020-10-27 에콜그린텍(주) Pla mask clip and its manufacturing method
KR102194997B1 (en) 2019-04-17 2020-12-24 에콜그린텍(주) Pla mask clip and its manufacturing method
WO2021054948A1 (en) * 2019-09-18 2021-03-25 Hewlett-Packard Development Company, L.P. Three-dimensional printing
CN112694724A (en) * 2020-12-08 2021-04-23 上海浦景化工技术股份有限公司 Degradable wire rod suitable for 3D prints
WO2024029811A1 (en) * 2022-08-02 2024-02-08 에스케이티비엠지오스톤 주식회사 Method for preparing biodegradable resin composition, biodegradable resin composition prepared thereby, and biodegradable molded product comprising same

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