KR101942244B1 - 3d 프린팅 지지체용 잉크 조성물 및 이를 이용한 3d 프린팅 제조방법 - Google Patents

3d 프린팅 지지체용 잉크 조성물 및 이를 이용한 3d 프린팅 제조방법 Download PDF

Info

Publication number
KR101942244B1
KR101942244B1 KR1020160023280A KR20160023280A KR101942244B1 KR 101942244 B1 KR101942244 B1 KR 101942244B1 KR 1020160023280 A KR1020160023280 A KR 1020160023280A KR 20160023280 A KR20160023280 A KR 20160023280A KR 101942244 B1 KR101942244 B1 KR 101942244B1
Authority
KR
South Korea
Prior art keywords
ink composition
poly
monomer
printing support
acrylate
Prior art date
Application number
KR1020160023280A
Other languages
English (en)
Other versions
KR20170100869A (ko
Inventor
김미경
김준형
백승아
박성은
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to KR1020160023280A priority Critical patent/KR101942244B1/ko
Publication of KR20170100869A publication Critical patent/KR20170100869A/ko
Application granted granted Critical
Publication of KR101942244B1 publication Critical patent/KR101942244B1/ko

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, e.g. INK-JET PRINTERS, THERMAL PRINTERS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/02—Esters of monocarboxylic acids
    • C08F18/04—Vinyl esters
    • C08F18/08—Vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultra-violet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5397—Phosphine oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L33/04—Homopolymers or copolymers of esters
    • 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
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/064—Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L33/04—Homopolymers or copolymers of esters
    • 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
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • 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
    • 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
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/06—Crosslinking by radiation

Abstract

잉크젯 방식의 3D 프린터에 사용 가능하며, 제팅성이 우수하고, 경화 후 물에 용해가 잘 되어 지지체의 제거가 용이한 3D 프린팅 지지체용 잉크 조성물 및 이를 이용한 3D 프린팅 제조방법이 개시된다. 상기 3D 프린팅 지지체용 잉크 조성물은, 아민 함유 단량체; 경화제; 및 아민 함유 중합체를 포함하는 수용성 중합체;를 포함한다.Disclosed is an ink composition for a 3D printing support which can be used in an inkjet type 3D printer, has excellent jetting property, is easily dissolved in water after curing, and can be easily removed, and a 3D printing manufacturing method using the ink composition. The ink composition for a 3D printing support comprises an amine-containing monomer; Curing agent; And a water-soluble polymer comprising an amine-containing polymer.

Description

3D 프린팅 지지체용 잉크 조성물 및 이를 이용한 3D 프린팅 제조방법{An Ink Composition for 3D Printing Support and the Manufacturing Method using the Same}TECHNICAL FIELD The present invention relates to an ink composition for a 3D printing support, and a 3D printing method using the composition.

본 발명은 3D 프린팅 지지체용 잉크 조성물 및 이를 이용한 3D 프린팅 제조방법에 관한 것으로서, 더욱 상세하게는, 잉크젯 방식의 3D 프린터에 사용 가능하며, 제팅성이 우수하고, 경화 후 물에 용해가 잘 되어 지지체의 제거가 용이한 3D 프린팅 지지체용 잉크 조성물 및 이를 이용한 3D 프린팅 제조방법에 관한 것이다.The present invention relates to an ink composition for a 3D printing support and a method for manufacturing 3D printing using the ink composition. More particularly, the present invention relates to an ink composition for a 3D printer which can be used in an inkjet 3D printer, has excellent jittering property, The present invention relates to an ink composition for a 3D printing support and a method of manufacturing 3D printing using the same.

3D 프린터(three dimentional printer)는 특정 물건을 3차원으로 찍어내는 프린터의 일종으로서, 입체적으로 만들어진 설계도를 종이에 인쇄하듯 3차원 공간 안에 실제 사물을 만들어낼 수 있는 기기이다. 잉크젯 프린터에서 디지털화된 파일이 전송되면 잉크를 종이 표면에 분사하여 2D 이미지를 인쇄하는 원리와 같이, 2D 프린터는 앞뒤(x축)와 좌우(y축)로만 운동하지만, 3D 프린터는 여기에 상하(z축) 운동을 더하여 입력한 3D 도면을 바탕으로 입체 물품을 만들어낸다. 이와 같은 3D 프린터로 조형물을 만들 때, 브릿지(bridge) 형태나 공중에 떠있는 모양의 구조물은 지지체(support) 재료를 필요로 하는데, 이러한 지지체 재료는 구조물 형성 시 잘 지지해주는 역할도 필요하지만, 나중에 잘 제거될 수도 있어야 한다.3D printers (three dimentional printers) are a type of printer that prints a specific object in three dimensions. It is a device that can create real objects in three-dimensional space like a three-dimensional printed design on paper. When a digitized file is transferred from an inkjet printer, 2D printers move only in front and back (x-axis) and left and right (y-axis), as in the principle of ejecting ink onto a paper surface to print 2D images. z axis) movements to create 3D objects based on the 3D drawings. When making a sculpture with such a 3D printer, a bridge structure or a structure floating in the air requires a support material. Such a support material also plays a role of supporting the structure well, It should be well removed.

대한민국 특허공개 10-2013-0141561호Korean Patent Publication No. 10-2013-0141561

앞서 살펴본 바와 같이, 3D 프린터로 브릿지 형태나 공중에 떠있는 모양의 조형물을 제작하고자 할 경우에는 지지체 재료가 필요하며, 이와 같은 지지체 재료로서 잉크젯(Inkjet) 방식의 3D 프린터에 사용할 수 있는 지지체 잉크가 필요하다. 하지만, 기존의 지지체 잉크는 수작업으로 지지체 부분을 뜯어내거나, 워터젯(water jet) 방식으로 지지체 부분을 일일이 제거하는 등 복잡한 제거 과정을 거쳐야 하는 문제가 있었다. 예를 들어, 한국공개특허 제2013-0141561호에서는 잉크젯 광조형품 제조 시 형상을 지지하는 서포트 재료에 대하여 개시하고 있으나, 이 경우 지지체 부분을 제거하는데 시간과 노력이 많이 들뿐만 아니라, 깨끗하게 제거하는 것도 쉽지 않고, 또한, 지지체가 수축되는 등의 문제가 있다. 따라서, 이러한 문제점을 해결하기 위하여, 광경화가 가능하면서도, 경화 후에 물에 담근 후 쉐이킹(shaking)을 하거나, 초음파 처리(sonication)를 하는 등의 간단한 방법으로 제거될 수 있는 잉크에 대한 연구의 필요성이 요구되고 있는 실정이다.As described above, when a 3D printer is used to produce a bridge or a floating object in the air, a support material is required. As the support material, a support ink usable in an inkjet type 3D printer need. However, the conventional support ink has to be subjected to a complicated removal process such as peeling off the support portion by hand or removing the support portion by water jet method. For example, Korean Patent Laid-Open Publication No. 2013-0141561 discloses a support material for supporting a shape in manufacturing an ink jet stereolithography product. However, in this case, in addition to a lot of time and effort for removing the support portion, It is not easy and there is a problem that the support shrinks or the like. Therefore, in order to solve such a problem, there is a need for studies on inks which can be photocured, can be removed by a simple method such as shaking after immersing in water after curing, or sonication It is a fact that is demanded.

따라서, 본 발명의 목적은, 잉크젯 방식의 3D 프린터에 사용 가능하며, 제팅성이 우수하고, 경화 후 물에 용해가 잘 되어 지지체의 제거가 용이한 3D 프린팅 지지체용 잉크 조성물 및 이를 이용한 3D 프린팅 제조방법을 제공하는 것이다.Accordingly, an object of the present invention is to provide an ink composition for a 3D printing support which can be used in an ink jet 3D printer, has excellent jittering property, is easily dissolved in water after curing and can be easily removed, and 3D printing Method.

상기 목적을 달성하기 위하여, 본 발명은, 아민 함유 단량체; 경화제; 및 아민 함유 중합체를 포함하는 수용성 중합체를 포함하는 3D 프린팅 지지체용 잉크 조성물을 제공한다.In order to accomplish the above object, the present invention provides a resin composition comprising: an amine-containing monomer; Curing agent; And an amine-containing polymer. The present invention also provides an ink composition for a 3D printing support.

또한, 본 발명은, 상기 3D 프린팅 지지체용 잉크 조성물을 이용하는 것을 특징으로 하는 3D 프린팅 제조방법을 제공한다.In addition, the present invention provides a 3D printing manufacturing method using the ink composition for the 3D printing support.

본 발명에 따른 3D 프린팅 지지체용 잉크 조성물 및 이를 이용한 3D 프린팅 제조방법은, 잉크젯 방식의 3D 프린터에 사용 가능하며, 제팅성이 우수하고, 경화 후 물에 용해가 잘 되어 지지체의 제거가 용이하다는 장점이 있다.The ink composition for a 3D printing support according to the present invention and the method for manufacturing 3D printing using the same can be used in an inkjet 3D printer and have an excellent jittering property and an advantage of being easily dissolved in water after curing, .

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명에 따른 3D 프린팅 지지체용 잉크 조성물은, 아민 함유 단량체, 경화제 및 아민 함유 중합체를 포함하는 수용성 중합체를 포함한다.The ink composition for a 3D printing support according to the present invention comprises a water-soluble polymer comprising an amine-containing monomer, a curing agent and an amine-containing polymer.

본 발명에 따른 3D 프린팅 지지체용 잉크 조성물은, 상기와 같은 조성을 가짐으로써, 잉크젯 방식의 3D 프린터에 사용 가능하며, 제팅성이 우수하고, 경화 후 물에 용해가 잘 되어 지지체의 제거가 용이하다.The ink composition for a 3D printing support according to the present invention can be used in an ink jet 3D printer by having the composition as described above. The ink composition for a 3D printing support has excellent jittering property and is easily dissolved in water after curing to facilitate removal of the support.

상기 아민 함유 단량체(monomer)는 당업계에서 사용하는 것이라면 특별한 제한이 없으나, 바람직하게는 아민기를 하나 이상 포함하는 탄소수 1 내지 30의 단량체, 더욱 바람직하게는 아민기를 하나 이상 포함하는 탄소수 2 내지 10의 단량체일 수 있으며, 예를 들어, N,N-디메틸아크릴아미드(N,N-dimethylacrylamide, DMA), 디아세톤아크릴아미드(diacetone acrylamide, DAA), N-[3-(디메틸아미노)프로필]메타크릴아미드(N-[3-(dimethylamino)propyl]methacrylamide, DMAPMA), N-메틸-N-비닐아세트아미드(N-methyl-N-vinylacetamide, NMNVA), 2-(디메틸아미노)에틸아크릴레이트(2-(dimethylamino)ethylacrylate, DMAEA), N-비닐피롤리돈(N-vinyl pyrrolidone, VP), 4-아크릴로일모르폴린(4-acryloylmorpholine, ACMO), N-메타크릴로일모르폴린(N-methacryloylmorpholine), N-이소프로필아크릴아미드(N-isopropyl acrylamide, NIPA), 2-메틸-2-옥사졸린(2-methyl-2-oxazoline), 2-에틸-2-옥사졸린(2-ethyl-2-oxazoline), N-이소프로필-2-옥사졸린(N-isopropyl-2-oxazoline), 에틸렌이민(ethyleneimine, 또는 아지리딘(aziridine)) 및 이들의 혼합물 등이 있다.The amine-containing monomer is not particularly limited as long as it is used in the art, but it is preferably a monomer having 1 to 30 carbon atoms and at least one amine group, more preferably a monomer having 2 to 10 carbon atoms And may be, for example, monomers such as N, N-dimethylacrylamide (DMA), diacetone acrylamide (DAA), N- [3- (dimethylamino) Amide, N- dimethylamino propyl methacrylamide, DMAPMA, N-methyl-N-vinylacetamide, NMNVA, 2- (dimethylamino) ethyl acrylate (2- (dimethylamino) ethylacrylate, DMAEA), N-vinyl pyrrolidone (VP), 4-acryloylmorpholine (ACMO), N-methacryloylmorpholine ), N-isopropyl acrylamide (NIPA), 2-methyl-2-oxazoline 2-oxazoline, 2-ethyl-2-oxazoline, N-isopropyl-2-oxazoline, ethyleneimine or aziridine aziridine), and mixtures thereof.

상기 아민 함유 단량체는 본 발명에 따른 3D 프린팅 지지체용 잉크 조성물 전체 중량에 대하여 10 내지 99.9중량%로 포함될 수 있으며, 상기 아민 함유 단량체의 함량이 10중량% 미만이면 지지체 제거 시 물에 대한 용해 특성이 충분하지 못할 우려가 있고, 99.9중량%를 초과하면 경화 특성이 저하될 우려가 있다.The amine-containing monomer may be contained in an amount of 10 to 99.9% by weight based on the total weight of the ink composition for a 3D printing support according to the present invention. If the content of the amine-containing monomer is less than 10% by weight, There is a fear that it is not sufficient, and when it exceeds 99.9% by weight, the curing property may be deteriorated.

계속해서, 상기 경화제는 본 발명에 따른 3D 프린팅 지지체용 잉크 조성물에 포함되어, 다양한 경화 방식을 통한 경화 공정에 이용될 수 있도록 하는 것으로서, 경화 방식에 따라 다양한 것을 사용할 수 있으며, 통상의 경화제를 제한 없이 사용할 수 있다. 보다 구체적으로는, 상기 경화제로서 광 개시제를 사용할 수 있으며, 사용하는 광원에 맞추어 당업계에서 사용하는 것이라면 특별한 제한이 없으나, 바람직하게는 Irgacure 819(Bis acyl phosphine계), Darocur TPO(Mono acyl phosphine계), Irgacure 369(α-aminoketone계), Irgacure 184(α-hydroxyketone계), Irgacure 907(α-aminoketone계), Irgacure 2022(Bis acyl phosphine/α-hydroxyketone계), Irgacure 2100(Phosphine oxide계), Darocur ITX(isopropyl thioxanthone) 또는 이와 유사한 구조의 광개시제 등과 같은 상용품을 사용할 수 있다.The curing agent is included in the ink composition for a 3D printing support according to the present invention and can be used in a curing process through various curing methods. Various curing agents can be used depending on the curing method. Can be used without. More specifically, a photoinitiator can be used as the curing agent, and there is no particular limitation as long as it is used in the art depending on the light source to be used. Preferably, Irgacure 819 (bisacyl phosphine type), Darocur TPO (mono acyl phosphine type ), Irgacure 369 (a-aminoketone type), Irgacure 184 (a-hydroxyketone type), Irgacure 907 (a-aminoketone type), Irgacure 2022 (Bis acyl phosphine / Darocur ITX (isopropyl thioxanthone) or a similar photoinitiator may be used.

상기 경화제는 본 발명에 따른 3D 프린팅 지지체용 잉크 조성물 전체 중량에 대하여 0.01 내지 20중량%, 바람직하게는 1 내지 10중량%로 포함될 수 있다. 상기 경화제의 함량이 0.01중량% 미만이면 경화가 일어나지 않을 우려가 있고, 20 중량%를 초과하면 경화감도가 과도하게 상승하여 헤드(head)가 막힐 우려가 있다.The curing agent may be included in an amount of 0.01 to 20% by weight, preferably 1 to 10% by weight based on the total weight of the ink composition for a 3D printing support according to the present invention. If the content of the curing agent is less than 0.01% by weight, curing may not occur. If the content is more than 20% by weight, the curing sensitivity may excessively increase and the head may be clogged.

상기 아민 함유 중합체를 포함하는 수용성 중합체는, 잉크의 점도를 조절하고, 경화물이 물에 더욱 용이하게 용해될 수 있도록 하는 것으로서, 상기 아민 함유 단량체를 중합한 폴리머(polymer) 및 그밖에 수용성 폴리머, 즉, 아민 미함유 단량체를 중합한 수용성 폴리머 중 어느 하나 이상을 사용할 수 있으며, 통상의 아민 함유 단량체를 중합한 폴리머 및 통상의 수용성 폴리머를 제한 없이 사용할 수 있다. 한편, 상기 아민 함유 단량체를 중합한 폴리머 및 아민 미함유 단량체를 중합한 수용성 폴리머는, 하나의 단량체만을 중합시킨 단일 중합체(homo-polymer) 형태 이외에, 둘 이상의 단량체를 중합시킨 공중합체(co-polymer)의 형태일 수 있다.The water-soluble polymer containing the amine-containing polymer controls the viscosity of the ink and allows the cured product to be more easily dissolved in water. The water-soluble polymer includes a polymer obtained by polymerizing the amine-containing monomer and a water-soluble polymer , And a water-soluble polymer obtained by polymerizing an amine-free monomer, and polymers obtained by polymerizing ordinary amine-containing monomers and conventional water-soluble polymers can be used without limitation. On the other hand, the water-soluble polymer obtained by polymerizing the amine-containing monomer and the amine-free monomer may be a copolymer obtained by polymerizing two or more monomers in addition to a homo-polymer in which only one monomer is polymerized. ). ≪ / RTI >

이와 같이, 잉크의 점도 조절이 용이해지면, 잉크의 점도를 필요 수준으로 상승시킬 수 있으며(단, 잉크의 점도가 높을 경우에는, 헤드(head)를 가열하여 제팅(jetting)해야 한다), 잉크의 점도가 높아지면, 3D 조형물 제조 시 잉크가 지나치게 퍼지는 것을 방지할 수 있어, 해상도가 높은 정밀한 형상의 제조가 가능해질 뿐만 아니라, 잉크의 경화 감도 또한 향상되는 장점이 있다. 특히, 조형물의 엣지(edge) 부분에서 잉크가 흘러내리거나 원하지 않는 부분까지 퍼지는 것을 방지할 수 있고, 해상도를 높여서 조형물을 제조하면 1층(layer)의 높이가 높아지기 때문에, 3D 조형 속도를 높이는 것이 가능해진다.As described above, when the viscosity of the ink is easily controlled, the viscosity of the ink can be raised to a required level (if the viscosity of the ink is high, the head must be jetted by heating) When the viscosity is increased, it is possible to prevent the ink from spreading excessively in the production of 3D sculpture, and it is possible not only to manufacture a precise shape with high resolution, but also to improve the curing sensitivity of the ink. Particularly, it is possible to prevent the ink from flowing down to the edge portion of the molding or spreading to an undesired portion, and when the molding is manufactured with a higher resolution, the height of the first layer becomes higher, It becomes possible.

상기 수용성 중합체 중 상기 아민 함유 단량체를 중합한 폴리머의 예로는, 폴리비닐피롤리돈(polyvinyl pyrrolidone, PVP), 폴리(N,N-디메틸아크릴아미드)(poly(N,N-dimethylacrylamide), PDMA), 폴리(N-이소프로필아크릴아미드)(poly(N-isopropyl acrylamide), PNIPA), 폴리(N-아크릴로일모르폴린)(poly(N-acryloylmorpholine), PACMO), 폴리(N-메타크릴로일모르폴린)(poly(N-methacryloylmorpholine)), 폴리(2-메틸-2-옥사졸린)(poly(2-methyl-2-oxazoline)), 폴리(2-에틸-2-옥사졸린)(poly(2-ethyl-2-oxazoline)), 폴리(N-이소프로필-2-옥사졸린)(poly(N-isopropyl-2-oxazoline)), 폴리에틸렌이민(polyethylene imine, PEI), 폴리(2-이소프로페닐-2-옥사졸린-co-메틸메타크릴레이트)(poly(2-isopropenyl-2-oxazoline-co-methylmethacrylate)), 폴리(비닐피롤리돈-co-비닐아세테이트)(poly(vinyl pyrrolidone-co-vinyl acetate)) 및 폴리(N,N-디메틸아크릴아미드-co-2-히드록시에틸 메타크릴레이트)(poly(N,N-dimethylacrylamide-co-2-hydroxyethyl methacrylate)) 등이 있다.Examples of the polymer obtained by polymerizing the amine-containing monomer in the water-soluble polymer include polyvinyl pyrrolidone (PVP), poly (N, N-dimethylacrylamide) N-isopropyl acrylamide (PNIPA), poly (N-acryloylmorpholine), PACMO), poly (N-methacryloyl 2-oxazoline), poly (2-ethyl-2-oxazoline) (poly (N-methacryloylmorpholine) (2-ethyl-2-oxazoline), poly (N-isopropyl-2-oxazoline), polyethylene imine (PEI) Poly (2-isopropenyl-2-oxazoline-co-methylmethacrylate), poly (vinyl pyrrolidone- co-vinyl acetate) and poly (N, N-dimethylacrylamide-co-2-hydroxyethylmeta Poly (N, N-dimethylacrylamide-co-2-hydroxyethyl methacrylate)).

또한, 상기 수용성 중합체 중 상기 아민 함유 단량체를 중합한 폴리머를 제외한 나머지 폴리머, 즉, 아민 미함유 단량체를 중합한 수용성 폴리머의 예로는, 폴리아크릴산(polyacrylic acid, PAA), 폴리(2-히드록시에틸아크릴레이트) 및 폴리(2-히드록시에틸메타아크릴레이트) 등이 있다.Examples of the water-soluble polymer obtained by polymerizing the polymer other than the polymer obtained by polymerizing the amine-containing monomer, that is, the amine-free monomer include polyacrylic acid (PAA), poly (2-hydroxyethyl Acrylate) and poly (2-hydroxyethyl methacrylate).

상기 수용성 중합체는 본 발명에 따른 3D 프린팅 지지체용 잉크 조성물 전체 중량에 대하여 0.01 내지 30중량%로 포함될 수 있는 것으로서, 상기 수용성 중합체의 함량이 상기 잉크 조성물 전체 중량에 대하여 0.01중량% 미만이면, 첨가에 따른 용해도 상승의 효과가 미미해질 우려가 있고, 30중량%를 초과할 경우에는, 잉크의 점도가 높아져 제팅(jetting)이 불가능해지는 문제가 있다.The water-soluble polymer may be contained in an amount of 0.01 to 30% by weight based on the total weight of the ink composition for a 3D printing support according to the present invention. When the content of the water-soluble polymer is less than 0.01% by weight based on the total weight of the ink composition, There is a possibility that the effect of increasing the solubility may be insignificant. When it exceeds 30% by weight, there is a problem that the viscosity of ink becomes high and jetting becomes impossible.

한편, 본 발명에 따른 3D 프린팅 지지체용 잉크 조성물은, 비닐기(vinyl group) 및 아크릴레이트기(acrylate group) 중 어느 하나 이상을 포함하는 단량체(즉, V/A 단량체)를 더욱 포함할 수 있으며, 이를 통해 경화 감도를 조절하고, 경화물의 강도(물렁물렁하거나 단단한 정도)와 같은 막의 특성을 조절할 수 있다는 특성을 가질 수 있다.Meanwhile, the ink composition for a 3D printing support according to the present invention may further comprise a monomer (i.e., a V / A monomer) containing at least one of a vinyl group and an acrylate group , Through which the curing sensitivity can be controlled and properties of the film such as the strength of the cured product (soft or hard) can be controlled.

상기 비닐기 및 아크릴레이트기 중 어느 하나 이상을 포함하는 단량체는, 당업계에서 사용하는 것이라면 특별한 제한이 없으나, 바람직하게는 비닐 아세테이트(vinyl acetate), 2-히드록시에틸(메타)아크릴레이트(2-hydroxyethyl(meth)acrylate), 2-히드록시메틸(메타)아크릴레이트(2-hydroxymethyl(meth)acrylate), 2-히드록시프로필(메타)아크릴레이트(2-hydroxypropyl(meth)acrylate), 4-히드록시부틸(메타)아크릴레이트(4-hydroxybutyl(meth)acrylate), 에틸-2-히드록시아크릴레이트(Ethyl-2-hydroxyacrylate), 2-(아크릴로일옥시)에틸 히드로겐 숙시네이트(2-(acryloyloxy)ethyl hydrogen succinate) 및 메타크릴레이트 산(methacylic acid)으로 이루어진 군으로부터 선택되는 어느 하나 이상을 사용할 수 있다.The monomer containing at least one of the vinyl group and the acrylate group is not particularly limited as long as it is used in the art, but it is preferably vinyl acetate, 2-hydroxyethyl (meth) acrylate (2 2-hydroxyethyl (meth) acrylate, 2-hydroxymethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, ethyl-2-hydroxyacrylate, 2- (acryloyloxy) ethylhydrogen succinate (2- acryloyloxy ethyl hydrogen succinate, and methacylic acid may be used.

상기 비닐기 및 아크릴레이트기 중 어느 하나 이상을 포함하는 단량체가 사용될 경우, 상기 비닐기 및 아크릴레이트기 중 어느 하나 이상을 포함하는 단량체는, 본 발명에 따른 3D 프린팅 지지체용 잉크 조성물 전체 중량에 대하여 0.01 내지 80중량%로 포함될 수 있는 것으로서, 상기 비닐기 및 아크릴레이트기 중 어느 하나 이상을 포함하는 단량체의 함량이 상기 잉크 조성물 전체 중량에 대하여 0.01중량% 미만이면, 단량체 첨가에 따른 충분한 효과를 얻기 힘들다는 문제가 있고, 80중량%를 초과할 경우에는 경화물이 물에 녹지 않는다는 문제가 있다.When the monomer containing at least one of the vinyl group and the acrylate group is used, the monomer containing at least one of the vinyl group and the acrylate group is preferably used in an amount of 0.01 to 80% by weight. When the content of the monomer containing at least one of the vinyl group and the acrylate group is less than 0.01% by weight based on the total weight of the ink composition, There is a problem that it is hard, and when it exceeds 80% by weight, there is a problem that the cured product is insoluble in water.

또한, 본 발명에 따른 3D 프린팅 지지체용 잉크 조성물은, 계면활성제, 가소제, (열)중합 방지제, 안정제, 소포제, 희석제, 점도 조절제 등의 첨가제를 더욱 포함할 수 있다. 상기 첨가제들은 경제적인 측면에서 상기 작용이 일어날 수 있는 최소한의 양을 포함할 수 있으며, 바람직하게는 잉크 조성물 전체 중량에 대하여 0.01 내지 5중량%로 포함될 수 있다.The ink composition for a 3D printing support according to the present invention may further contain additives such as a surfactant, a plasticizer, a (thermal) polymerization inhibitor, a stabilizer, a defoaming agent, a diluent, and a viscosity controlling agent. The additives may include the minimum amount in which the action can take place economically, and preferably 0.01 to 5% by weight based on the total weight of the ink composition.

이와 같이, 본 발명은 전술한 3D 프린팅 지지체용 잉크 조성물로 제조된 지지체를 제공하며, 상기 지지체는 3D 프린팅 공정에 사용되는 것이라면, 특별한 제한이 없다.Thus, the present invention provides a support made of an ink composition for a 3D printing support as described above, and the support is not particularly limited as long as it is used in a 3D printing process.

또한, 본 발명은 전술한 3D 프린팅 지지체용 잉크 조성물을 이용하는 것을 특징으로 하는 3D 프린팅 제조방법을 제공하며, 상기 제조방법은 3D 프린팅 공정과 관련된 제조방법이라면, 특별한 제한이 없다.In addition, the present invention provides a 3D printing manufacturing method using the ink composition for a 3D printing support as described above, and the manufacturing method is not particularly limited as long as it is a manufacturing method related to a 3D printing process.

이하 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변경 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as set forth in the appended claims. Such changes and modifications are intended to be within the scope of the appended claims.

실시예Example

잉크의 제조Manufacture of ink

하기 표 1에 나타낸 바와 같이, 아민 함유 단량체, 경화제, 수용성 중합체, 비닐기 및 아크릴레이트기 중 어느 하나 이상을 포함하는 단량체(V/A 단량체) 등을 혼합하여 실시예 1 내지 3의 잉크를 제조하였으며, 또한, 하기 표 1과 같은 조성으로 비교예 1 내지 3의 잉크를 제조하였다.As shown in Table 1 below, the inks of Examples 1 to 3 were prepared by mixing an amine-containing monomer, a curing agent, a water-soluble polymer, a monomer (V / A monomer) containing at least one of a vinyl group and an acrylate group, And the inks of Comparative Examples 1 to 3 were prepared with the compositions shown in Table 1 below.

아민 함유 단량체Amine containing monomer 경화제Hardener 수용성 중합체Water-soluble polymer V/A 단량체V / A monomer 기타Other 실시예 1Example 1 DMA + VP
(40.75 + 40.75 wt%)DMA + VP
(40.75 + 40.75 wt%) I 819
(3.5 wt%)I 819
(3.5 wt%) PVP
(15.0 wt%)PVP
(15.0 wt%) -- -- 실시예 2Example 2 DMA + VP
(35.75 + 35.75 wt%)DMA + VP
(35.75 + 35.75 wt%) I 819
(3.5 wt%)I 819
(3.5 wt%) PVP + Poly(2-ethyl-2-oxazoline)
(5.0 + 10.0 wt%)PVP + Poly (2-ethyl-2-oxazoline)
(5.0 + 10.0 wt%) -- Ethanol
(10.0 wt%)Ethanol
(10.0 wt%) 실시예 3Example 3 DMA
(58.33 wt%)DMA
(58.33 wt%) I 819
(3.5 wt%)I 819
(3.5 wt%) Poly(vinyl pyrrolidone-co-vinyl acetate)
(9 wt%)Poly (vinyl pyrrolidone-co-vinyl acetate)
(9 wt%) HEMA
(29.17 wt%)HEMA
(29.17 wt%) -- 비교예 1Comparative Example 1 DMA + VP
(48.25 + 48.25 wt%)DMA + VP
(48.25 + 48.25 wt%) I 819
(3.5 wt%)I 819
(3.5 wt%) -- -- -- 비교예 2Comparative Example 2 DMA
(76.5 wt%)DMA
(76.5 wt%) I 819
(3.5 wt%)I 819
(3.5 wt%) -- -- PD-6400
(20.0 wt%)PD-6400
(20.0 wt%) 비교예 3Comparative Example 3 -- I 819
(3.5 wt%)I 819
(3.5 wt%) -- DPHA 5 wt%
TPGDA 81.5 wt%DPHA 5 wt%
TPGDA 81.5 wt% PD-6400
(10.0 wt%)PD-6400
(10.0 wt%)

DMA: N,N-dimethyl acrylamideDMA: N, N-dimethyl acrylamide

VP: N-vinyl pyrrolidoneVP: N-vinyl pyrrolidone

PVP: polyvinyl pyrrolidonePVP: polyvinyl pyrrolidone

HEMA: 2-hydroxyethyl methacrylateHEMA: 2-hydroxyethyl methacrylate

DPHA: dipentaerythritol hexaacrylateDPHA: dipentaerythritol hexaacrylate

TPGDA: tripropylene glycol diacrylateTPGDA: tripropylene glycol diacrylate

PD-6400: Acrylic Resins(Almatex사, 미국)PD-6400: Acrylic Resins (Almatex, USA)

실험예Experimental Example

상기 실시예 1 내지 3 및 비교예 1 내지 3의 잉크를 이용하여 지지체를 제조하였으며, 제조된 지지체의 물에서의 용해도 및 경화도(경화감도) 등을 평가하여, 그 결과를 하기 표 2에 나타내었으며, 여기에 상기 제조된 각 잉크의 점도 또한 나타내었다.A support was prepared using the inks of Examples 1 to 3 and Comparative Examples 1 to 3, and the solubility and curing degree (curing sensitivity) of the prepared support in water were evaluated. The results are shown in Table 2 below , And the viscosity of each ink prepared above was also shown.

실험예 1. 물에서의 용해도 평가Experimental Example 1. Evaluation of solubility in water

상기 실시예 1 내지 3 및 비교예 1 내지 3에서 제조된 잉크를 스포이드로 필름(film) 기재에 떨어뜨린 후, 고압 수은등으로 1,000mJ/cm2 노광하였다. 이어서, 여러 층을 반복 형성하여 지지체 잉크 경화물 시편을 만들고, 이를 기재로부터 떼내어 물에 침지시킨 후, 잉크 경화물이 침지된 병을 초음파분쇄기(sonicator)에 넣고 60분 동안 초음파 처리(sonication)를 실시하여, 경화된 지지체 막이 물에 녹는지 확인하여 용해도를 평가하였으며, 그 결과를 하기 표 2에 나타내었다. 이때, 물에서 용해가 잘 된 경우는 ○ 표시, 용해가 미미하게 된 경우(즉, 일부 성분만이 녹았을 경우)는 △ 표시, 용해가 되지 않은 경우는 × 표시로 각각 나타내었다.The inks prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were dropped on a film substrate with a syringe and exposed to 1,000 mJ / cm 2 using a high-pressure mercury lamp. Subsequently, several layers were repeatedly formed to prepare a support ink cured specimen. The specimen was taken out from the substrate and immersed in water. The bottle in which the ink cured body was immersed was placed in an ultrasonic sonicator and subjected to sonication for 60 minutes. To confirm that the cured support membrane was dissolved in water, and the solubility was evaluated. The results are shown in Table 2 below. In this case, when the solution was well dissolved in water, the symbol was marked with?, When the solution became insignificant (i.e., when only a part of the component was dissolved), the symbol? Was indicated, and when no dissolution was observed, the symbol was marked.

실험예 2. 경화감도 평가Experimental Example 2. Evaluation of Curing Sensitivity

상기 실시예 1 내지 3 및 비교예 1 내지 3에서 제조된 잉크를 유리(glass)에 스핀 코팅한 후 365nm 파장의 LED 램프로 노광시켰으며, 노광량을 125mJ/cm2, 250mJ/cm2, 500mJ/cm2 및 1,000mJ/cm2로 각각 조절하면서 눈으로 경화 여부를 관찰하고 경화감도를 판단하였다. 이때, 잉크가 완전히 경화되기 시작했을 시의 해당 노광량을 하기 표 2에 나타내었다.Example 1 to 3 and Comparative Examples 1 to stylized the ink prepared in three exposure to the LED lamp of 365nm wavelength was applied by spin coating on a glass (glass), the exposure dose 125mJ / cm 2, 250mJ / cm 2, 500mJ / cm < 2 > and 1,000 mJ / cm < 2 >, respectively. The amount of exposure at the time when the ink starts to be completely cured is shown in Table 2 below.

실험예 3. 패턴 형성 평가Experimental Example 3. Pattern Formation Evaluation

상기 실시예 1 및 비교예 1에서 제조된 각 잉크를, 85V의 제팅(jetting) 전압 및 1,000Hz의 제팅 주파수 하에서 잉크 제트 헤드(Dimatix 30pL 128 nozzle head)를 통해 사출한 후, 395nm 파장의 LED 램프로 경화시켜(노광량: 2,000mJ/cm2) 형성된 패턴을 1,200dpi 및 600dpi의 해상도 조건에서 각각 평가하였으며, 그 결과를 하기 표 2에 나타내었다. 이때, 패턴이 정상적으로 형성된 경우는 ○ 표시로, 패턴이 정상적으로 형성되지 않은 경우는 × 표시로 각각 나타내었다.Each of the inks prepared in Example 1 and Comparative Example 1 was ejected through an ink jet head (Dimatix 30pL 128 nozzle head) under a jetting voltage of 85 V and a jetting frequency of 1,000 Hz, and then an LED lamp (Exposure amount: 2,000 mJ / cm 2 ) to evaluate the pattern at 1,200 dpi and 600 dpi, respectively, and the results are shown in Table 2 below. At this time, when the pattern was normally formed, it was indicated by?, And when the pattern was not normally formed, it was indicated by x.


점도(cP)
Viscosity (cP)
물에서의 용해도
Solubility in water
경화감도(mJ/cm2)
Curing sensitivity (mJ / cm 2 )
패턴 평가Pattern evaluation 1200 dpi1200 dpi 600 dpi600 dpi 실시예 1Example 1 25.025.0 ○○ 500500 ○○ ○○ 실시예 2Example 2 24.024.0 ○○ 500500 -- -- 실시예 3Example 3 19.219.2 ○○ 500500 -- -- 비교예 1Comparative Example 1 1.81.8 ○○ 10001000 ×× ○○ 비교예 2Comparative Example 2 22.022.0 △△ 500500 -- -- 비교예 3Comparative Example 3 45.545.5 ×× 500500 -- --

상기 표 2에 나타낸 바와 같이, 실시예 1 내지 3의 조성물로부터 각각 제조된 잉크 모두, 점도, 물에서의 용해도 및 경화감도가 우수한 것을 확인할 수 있다. 이에 반해, 비교예 1의 조성물로부터 제조된 잉크의 경우에는, 물에서의 용해도는 우수하지만, 경화감도와 점도가 상기 실시예 1 내지 3으로부터 제조된 잉크에 비해 현저히 낮은 것을 알 수 있다. 또한, 비교예 2 및 3의 조성물로부터 제조된 잉크의 경우에도, 경화감도나 점도는 우수하지만, 경화된 잉크 막 중 지지체 부분이 일부만 녹거나 전혀 녹지 않아, 물에서의 용해도가 좋지 못함을 확인할 수 있었다.As shown in Table 2, all of the inks prepared from the compositions of Examples 1 to 3 were found to be excellent in viscosity, solubility in water and curing sensitivity. On the contrary, in the case of the ink prepared from the composition of Comparative Example 1, although the solubility in water is excellent, the curing sensitivity and viscosity are remarkably lower than those of the inks prepared in Examples 1 to 3 above. Further, even in the case of the inks prepared from the compositions of Comparative Examples 2 and 3, although the curing sensitivity and viscosity were excellent, it was confirmed that the portion of the cured ink film only partially melted or not dissolved, and the solubility in water was poor there was.

또한, 잉크를 이용한 패턴 형성에 있어서, 실시예 1의 경우에는 1200dpi 해상도 조건에서 사각 형태의 패턴이 잘 형성되었지만(1층(layer) 높이: 65㎛), 비교예 1의 경우, 1200dpi 조건에서는 잉크가 너무 잘 퍼져 패턴이 무너짐으로써, 사각 형태의 패턴을 잘 형성할 수 없었다. 대신, 해상도를 600dpi로 줄일 경우 패턴이 형성되기는 하였으나, 이 경우에는 단위 면적에 토출된 drop의 수가 감소하였기 때문에, 1층의 높이는 43㎛에 불과하였다. 즉, 잉크의 점도가 높은 실시예 1의 경우는, 고해상도에서도 패턴을 잘 형성할 수 있었으며, 이 경우 1층의 높이가 더 높기 때문에 3D 조형물을 보다 빨리 제작할 수 있었다. 반면, 점도가 낮은 비교예 1의 경우는 잉크가 너무 잘 퍼져서 원하는 모양의 패턴 밖으로 잉크가 퍼지는 문제가 나타났으며, 잉크가 너무 잘 퍼지면 주변의 구조체 잉크 부분과도 섞일 수 있기 때문에, 비교예 1과 같은 잉크를 지지체용으로 사용하는 것은 바람직하지 않음을 알 수 있다.Further, in the case of the pattern formation using the ink, in the case of the embodiment 1, a square pattern was well formed (1200 dpi resolution) (one layer height: 65 μm), but in the case of the comparative example 1, And the pattern was collapsed, it was impossible to form a rectangular pattern well. Instead, when the resolution was reduced to 600 dpi, the pattern was formed. In this case, however, the number of droplets ejected per unit area decreased, so that the height of the first layer was only 43 탆. That is, in the case of Example 1 in which the viscosity of the ink is high, the pattern can be formed well at high resolution, and in this case, the height of the first layer is higher, so that the 3D sculpture can be manufactured faster. On the other hand, in the case of Comparative Example 1 in which the viscosity is low, the ink spreads too well and the ink spreads out of the desired pattern. When the ink spreads too much, It is not preferable to use the ink for the support.

Claims (17)

  1. 아민 함유 단량체;
    경화제;
    폴리비닐피롤리돈, 폴리(N,N-디메틸아크릴아미드), 폴리(N-이소프로필아크릴아미드), 폴리(N-아크릴로일모르폴린), 폴리(N-메타크릴로일모르폴린), 폴리(2-메틸-2-옥사졸린), 폴리(2-에틸-2-옥사졸린), 폴리(N-이소프로필-2-옥사졸린) 및 폴리에틸렌이민으로 이루어진 군으로부터 선택되는 폴리머; 및
    폴리아크릴산, 폴리(2-히드록시에틸아크릴레이트) 및 폴리(2-히드록시에틸메타아크릴레이트)로 이루어진 군으로부터 선택되는 폴리머를 포함하는 3D 프린팅 지지체용 잉크 조성물.    Amine-containing monomers;
    Curing agent;
    (N, N-dimethylacrylamide), poly (N-isopropylacrylamide), poly (N-acryloylmorpholine), poly (N-methacryloylmorpholine) A polymer selected from the group consisting of poly (2-methyl-2-oxazoline), poly (2-ethyl-2-oxazoline), poly (N-isopropyl-2-oxazoline) and polyethyleneimine; And
    An ink composition for a 3D printing support comprising a polymer selected from the group consisting of polyacrylic acid, poly (2-hydroxyethyl acrylate), and poly (2-hydroxyethyl methacrylate).
  2. 청구항 1에 있어서, 상기 아민 함유 단량체의 함량은, 상기 3D 프린팅 지지체용 잉크 조성물 전체 중량에 대하여 10 내지 99.9중량%인 것인, 3D 프린팅 지지체용 잉크 조성물.The ink composition according to claim 1, wherein the content of the amine-containing monomer is 10 to 99.9% by weight based on the total weight of the ink composition for the 3D printing support.
  3. 청구항 1에 있어서, 상기 경화제의 함량은, 상기 3D 프린팅 지지체용 잉크 조성물 전체 중량에 대하여 0.01 내지 20중량%인 것인, 3D 프린팅 지지체용 잉크 조성물.The ink composition according to claim 1, wherein the content of the curing agent is 0.01 to 20% by weight based on the total weight of the ink composition for the 3D printing support.
  4. 청구항 1에 있어서, 상기 2종의 폴리머의 함량은, 상기 3D 프린팅 지지체용 잉크 조성물 전체 중량에 대하여 0.01 내지 30중량%인 것인, 3D 프린팅 지지체용 잉크 조성물.The ink composition for a 3D printing support according to claim 1, wherein the content of the two polymers is 0.01 to 30% by weight based on the total weight of the ink composition for the 3D printing support.
  5. 청구항 1에 있어서, 상기 아민 함유 단량체는 아민기를 하나 이상 포함하는 탄소수 1 내지 30의 단량체인 것인, 3D 프린팅 지지체용 잉크 조성물.The ink composition according to claim 1, wherein the amine-containing monomer is a monomer having from 1 to 30 carbon atoms and at least one amine group.
  6. 청구항 1에 있어서, 상기 아민 함유 단량체는 N,N-디메틸아크릴아미드, 디아세톤아크릴아미드, N-[3-(디메틸아미노)프로필]메타크릴아미드, N-메틸-N-비닐아세트아미드, 2-(디메틸아미노)에틸아크릴레이트, N-비닐피롤리돈, 4-아크릴로일모르폴린, N-메타크릴로일모르폴린, N-이소프로필아크릴아미드, 2-메틸-2-옥사졸린, 2-에틸-2-옥사졸린, N-이소프로필-2-옥사졸린, 에틸렌이민 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것인, 3D 프린팅 지지체용 잉크 조성물.[2] The method of claim 1, wherein the amine-containing monomer is selected from the group consisting of N, N-dimethylacrylamide, diacetone acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- (Dimethylamino) ethyl acrylate, N-vinylpyrrolidone, 4-acryloylmorpholine, N-methacryloylmorpholine, N-isopropylacrylamide, 2- Ethyl-2-oxazoline, N-isopropyl-2-oxazoline, ethyleneimine, and mixtures thereof.
  7. 청구항 1에 있어서, 상기 경화제는 광 개시제인 것인, 3D 프린팅 지지체용 잉크 조성물.The ink composition of claim 1, wherein the curing agent is a photoinitiator.
  8. 청구항 1에 있어서, 상기 3D 프린팅 지지체용 잉크 조성물은, 비닐기 및 아크릴레이트기 중 어느 하나 이상을 포함하는 단량체를 더욱 포함하는 것인, 3D 프린팅 지지체용 잉크 조성물.The ink composition according to claim 1, wherein the ink composition for a 3D printing support further comprises a monomer comprising at least one of a vinyl group and an acrylate group.
  9. 청구항 8에 있어서, 상기 비닐기 및 아크릴레이트기 중 어느 하나 이상을 포함하는 단량체는, 비닐 아세테이트, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시메틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 에틸-2-히드록시아크릴레이트, 2-(아크릴로일옥시)에틸 히드로겐 숙시네이트 및 메타크릴레이트 산으로 이루어진 군으로부터 선택되는 어느 하나 이상인 것인, 3D 프린팅 지지체용 잉크 조성물.[9] The method according to claim 8, wherein the monomer containing at least one of the vinyl group and the acrylate group is at least one monomer selected from the group consisting of vinyl acetate, 2-hydroxyethyl (meth) acrylate, 2-hydroxymethyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, ethyl-2-hydroxyacrylate, 2- (acryloyloxy) ethylhydrogen succinate and methacrylate acid Wherein the ink composition is at least one selected from the group consisting of the ink composition and the ink composition.
  10. 청구항 8에 있어서, 상기 비닐기 및 아크릴레이트기 중 어느 하나 이상을 포함하는 단량체의 함량은, 3D 프린팅 지지체용 잉크 조성물 전체 중량에 대하여 0.01 내지 80중량%인 것인, 3D 프린팅 지지체용 잉크 조성물.The ink composition according to claim 8, wherein the content of the monomer containing at least one of the vinyl group and the acrylate group is 0.01 to 80% by weight based on the total weight of the ink composition for a 3D printing support.
  11. 청구항 1에 있어서, 상기 3D 프린팅 지지체용 잉크 조성물은 첨가제를 더욱 포함하는 것인, 3D 프린팅 지지체용 잉크 조성물.The ink composition of claim 1, wherein the ink composition for the 3D printing support further comprises an additive.
  12. 청구항 11에 있어서, 상기 첨가제는 계면활성제, 가소제, (열)중합 방지제, 안정제, 소포제, 희석제 및 점도 조절제로 이루어진 군으로부터 선택되는 어느 하나 이상인 것인, 3D 프린팅 지지체용 잉크 조성물.12. The ink composition according to claim 11, wherein the additive is at least one selected from the group consisting of a surfactant, a plasticizer, a (thermal) polymerization inhibitor, a stabilizer, a defoaming agent, a diluent and a viscosity modifier.
  13. 청구항 1 내지 12 중 어느 한 항에 따른 3D 프린팅 지지체용 잉크 조성물을 이용하는 것인 3D 프린팅 제조방법.A method of making 3D printing using an ink composition for a 3D printing support according to any one of claims 1 to 12.
  14. 삭제delete
  15. 삭제delete
  16. 삭제delete
  17. 삭제delete
KR1020160023280A 2016-02-26 2016-02-26 3d 프린팅 지지체용 잉크 조성물 및 이를 이용한 3d 프린팅 제조방법 KR101942244B1 (ko)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020160023280A KR101942244B1 (ko) 2016-02-26 2016-02-26 3d 프린팅 지지체용 잉크 조성물 및 이를 이용한 3d 프린팅 제조방법

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR1020160023280A KR101942244B1 (ko) 2016-02-26 2016-02-26 3d 프린팅 지지체용 잉크 조성물 및 이를 이용한 3d 프린팅 제조방법
CN201780004085.2A CN108350297A (zh) 2016-02-26 2017-02-17 用于3d打印支撑体的墨组合物和使用其的3d打印生产方法
EP17756761.7A EP3421555A4 (en) 2016-02-26 2017-02-17 Ink composition for 3d printing supporter and 3d printing production method using same
JP2018526057A JP2018537313A (ja) 2016-02-26 2017-02-17 Ink composition for 3D printing support and method for producing 3D printing using the same
US16/062,807 US20200131386A1 (en) 2016-02-26 2017-02-17 Ink composition for 3d printing supporter and 3d printing production method using same
PCT/KR2017/001810 WO2017146423A1 (ko) 2016-02-26 2017-02-17 3d 프린팅 지지체용 잉크 조성물 및 이를 이용한 3d 프린팅 제조방법

Publications (2)

Publication Number Publication Date
KR20170100869A KR20170100869A (ko) 2017-09-05
KR101942244B1 true KR101942244B1 (ko) 2019-01-28

Family

ID=59685409

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020160023280A KR101942244B1 (ko) 2016-02-26 2016-02-26 3d 프린팅 지지체용 잉크 조성물 및 이를 이용한 3d 프린팅 제조방법

Country Status (6)

Country Link
US (1) US20200131386A1 (ko)
EP (1) EP3421555A4 (ko)
JP (1) JP2018537313A (ko)
KR (1) KR101942244B1 (ko)
CN (1) CN108350297A (ko)
WO (1) WO2017146423A1 (ko)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW202000800A (zh) * 2018-06-14 2020-01-01 日商捷恩智股份有限公司 聚合性組成物、噴墨用墨水、耐熱性可溶構件、帶支撐部的立體結構物、及立體造形物的製造方法
US20200384696A1 (en) 2018-07-18 2020-12-10 Kj Chemicals Corporation Active energy ray-curable resin composition and ink for three-dimensional molding support materials
CN109593168B (zh) * 2018-11-23 2020-11-17 珠海赛纳三维科技有限公司 3d喷墨打印用耐高温光固化材料及其制备方法、3d打印制品及3d打印机
KR102188574B1 (ko) * 2019-03-12 2020-12-08 울산과학기술원 바이오 프린팅용 잉크 조성물 및 그로부터 형성된 하이드로젤

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015078255A (ja) 2013-10-15 2015-04-23 コニカミノルタ株式会社 三次元造形用インクジェットインク組成物および三次元造形物の製造方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4403384B2 (ja) * 2003-03-07 2010-01-27 リコープリンティングシステムズ株式会社 三次元積層造形方法
AT412399B (de) * 2003-06-18 2005-02-25 Stampfl Juergen Dipl Ing Dr Mit strahlung härtbare wasserlösliche und/oder schmelzbare zusammensetzung und deren verwendung für rapid prototyping verfahren
JP2010155889A (ja) * 2008-12-26 2010-07-15 Japan Fine Coatings Co Ltd 光硬化性液状樹脂組成物およびインクジェット光造形法による支持体の製造方法
EP2632696B1 (en) * 2010-10-27 2020-07-29 Rize Inc. Process and apparatus for fabrication of three-dimensional objects
JP5890990B2 (ja) * 2010-11-01 2016-03-22 株式会社キーエンス インクジェット光造形法における、光造形品形成用モデル材、光造形品の光造形時の形状支持用サポート材および光造形品の製造方法
KR102037558B1 (ko) * 2015-07-20 2019-10-28 주식회사 엘지화학 3d 프린팅 지지체용 잉크 조성물 및 이를 이용한 3d 프린팅 제조방법
KR102053481B1 (ko) * 2015-11-03 2019-12-06 주식회사 엘지화학 3차원 조형물의 형성 방법

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015078255A (ja) 2013-10-15 2015-04-23 コニカミノルタ株式会社 三次元造形用インクジェットインク組成物および三次元造形物の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF APPLIED POLYMER(2005)

Also Published As

Publication number Publication date
KR20170100869A (ko) 2017-09-05
EP3421555A1 (en) 2019-01-02
US20200131386A1 (en) 2020-04-30
CN108350297A (zh) 2018-07-31
WO2017146423A1 (ko) 2017-08-31
JP2018537313A (ja) 2018-12-20
EP3421555A4 (en) 2019-01-16

Similar Documents

Publication Publication Date Title
EP2819822B1 (en) Cationic polymerizable compositions and methods of use thereof
US8142860B2 (en) 3D-inkjet printing methods
EP2305762B1 (en) UV curable inkjet compositions for high-density print heads
US8679357B2 (en) Nanoimprinting method and method for producing substrates utilizing the nanoimprinting method
JP5702520B2 (ja) インクジェット印刷
JP4779136B2 (ja) インクジェット用インク
JP5999100B2 (ja) 活性光線硬化型インクジェットインク及びそれを用いた画像形成方法
JP4643140B2 (ja) 紫外線硬化性ホットメルト組成物
US8425790B2 (en) Ink-jet ink composition for etching resist
EP2153991B1 (en) Imaging apparatus and method for making flexographic printing masters
CN102218905B (zh) 记录方法、记录装置、油墨组
JP2004291625A (ja) 三次元積層造形装置
US20130310517A1 (en) Methods for manufacturing curable inks for digital offset printing applications and the inks made therefrom
JP5668328B2 (ja) 造形用スラリー及び造形方法
EP1574553B1 (en) Ink-jet ink and recording method
JP6268953B2 (ja) 重合性インク組成物、インクカートリッジ、及びインクジェットプリンタ
JP6679234B2 (ja) Model material resin composition, support material resin composition, stereolithography product, and method for producing stereolithography product
US9815314B2 (en) Methods for printing articles
JP5626520B2 (ja) 紫外線硬化型インクジェット用インク組成物
JP2008001003A (ja) インクジェット画像記録方法
TWI435918B (zh) 噴墨用墨水
JP5664850B2 (ja) 紫外線硬化型インクジェット用インク組成物
WO2016121587A1 (ja) 三次元造型サポート材用活性エネルギー線硬化性樹脂組成物
US20140232790A1 (en) Inkjet recording method and inkjet recording device
US7431759B2 (en) High elongation vacuum formable digital ink

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
AMND Amendment
E601 Decision to refuse application
AMND Amendment
X701 Decision to grant (after re-examination)
GRNT Written decision to grant