KR102048770B1 - Photo-curable resin ink composition for 3D printing with heat resisting and high mechanical property comprising dicyclopentadien epoxy acrylate - Google Patents

Photo-curable resin ink composition for 3D printing with heat resisting and high mechanical property comprising dicyclopentadien epoxy acrylate Download PDF

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KR102048770B1
KR102048770B1 KR1020180023524A KR20180023524A KR102048770B1 KR 102048770 B1 KR102048770 B1 KR 102048770B1 KR 1020180023524 A KR1020180023524 A KR 1020180023524A KR 20180023524 A KR20180023524 A KR 20180023524A KR 102048770 B1 KR102048770 B1 KR 102048770B1
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acrylate
epoxy
formula
epoxy acrylate
epoxycyclohexylmethyl
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KR20190109617A (en
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이종민
이환표
이상건
심종배
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애경화학 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof

Abstract

본 발명은 디싸이클로펜타디엔 에폭시 아크릴레이트를 포함하는 내열성과 기계적 물성이 우수한 3D프린팅용 광경화 수지 잉크조성물에 관한 것으로, 보다 상세하게는 디싸이클로펜타디엔 에폭시수지의 에폭시기를 완전 개환하여 아크릴레이트를 도입한 에폭시아크릴레이트 또는 에폭시기를 부분 개환하여 에폭시기와 아크릴기를 동시에 가지는 에폭시아크릴레이트와 아크릴 모노머를 포함하여 자외선 조사에 의한 라디칼 방식과 양이온 방식의 경화가 동시에 일어나는 디싸이클로펜타디엔 에폭시 아크릴레이트를 포함하는 내열성과 기계적 물성이 우수한 3D프린팅용 광경화 수지 잉크조성물에 관한 것이다.The present invention relates to a photocurable resin ink composition for 3D printing having excellent heat resistance and mechanical properties including dicyclopentadiene epoxy acrylate, and more particularly, to completely open the epoxy group of the dicyclopentadiene epoxy resin to form an acrylate. Including dicyclopentadiene epoxy acrylate which undergoes radical and cationic curing at the same time by ultraviolet irradiation, including epoxy acrylate or an epoxy monomer having an epoxy group and an acrylic group by partially opening the introduced epoxy acrylate or an epoxy group. The present invention relates to a photocurable resin ink composition for 3D printing having excellent heat resistance and mechanical properties.

Description

디싸이클로펜타디엔 에폭시 아크릴레이트를 포함하는 내열성과 기계적 물성이 우수한 3D프린팅용 광경화 수지 잉크조성물{Photo-curable resin ink composition for 3D printing with heat resisting and high mechanical property comprising dicyclopentadien epoxy acrylate}Photo-curable resin ink composition for 3D printing with heat resisting and high mechanical property comprising dicyclopentadien epoxy acrylate} with excellent heat resistance and mechanical properties including dicyclopentadiene epoxy acrylate

본 발명은 디싸이클로펜타디엔 에폭시 아크릴레이트를 포함하는 내열성과 기계적 물성이 우수한 3D프린팅용 광경화 수지 잉크조성물에 관한 것으로, 보다 상세하게는 디싸이클로펜타디엔 에폭시수지의 에폭시기를 완전 개환하여 아크릴레이트를 도입한 에폭시아크릴레이트 또는 에폭시기를 부분 개환하여 에폭시기와 아크릴기를 동시에 가지는 에폭시아크릴레이트와 아크릴 모노머를 포함하여 자외선 조사에 의한 라디칼 방식과 양이온 방식의 경화가 동시에 일어나는 디싸이클로펜타디엔 에폭시 아크릴레이트를 포함하는 내열성과 기계적 물성이 우수한 3D프린팅용 광경화 수지 잉크조성물에 관한 것이다.The present invention relates to a photocurable resin ink composition for 3D printing having excellent heat resistance and mechanical properties including dicyclopentadiene epoxy acrylate, and more particularly, to completely open the epoxy group of the dicyclopentadiene epoxy resin to form an acrylate. Including dicyclopentadiene epoxy acrylate which undergoes radical and cationic curing at the same time by ultraviolet irradiation, including epoxy acrylate or an epoxy monomer having an epoxy group and an acrylic group by partially opening the introduced epoxy acrylate or an epoxy group. The present invention relates to a photocurable resin ink composition for 3D printing having excellent heat resistance and mechanical properties.

일반적으로, 광경화 또는 UV경화 수지는 디스플레이 기판, 선박, 자동차 외장부품, 건축자재, 종이, 목재, 가구용, 방음벽, 광학재료, 화장품 용기를 비롯하여 다양한 산업분야에서 재료의 표면에 도포하여 얇은 박막을 형성함으로써 재료의 표면 특성을 보완하기 위한 코팅제로 널리 사용되고 있다.In general, photocuring or UV curing resins are applied to the surface of the material in a variety of industries, including display substrates, ships, automotive exterior parts, construction materials, paper, wood, furniture, soundproof walls, optical materials, cosmetics containers, to apply a thin film It is widely used as a coating agent to complement the surface properties of the material by forming.

뿐만 아니라, 상기 광경화 또는 UV경화 수지는 3차원 CAD 데이터를 기준으로 제어되는 3D 프린터로 3차원 인쇄하고 광경화 또는 UV경화시켜 마스터모델 등을 성형하는 3D 프린터용 잉크로도 널리 사용되고 있으며, 현재에도 이에 대한 연구가 활발히 진행되고 있다.In addition, the photocurable or UV curable resin is widely used as a 3D printer ink for forming a master model by three-dimensional printing and photocuring or UV curing with a 3D printer controlled based on three-dimensional CAD data, and In addition, research on this is being actively conducted.

종래, 3D 프린터로 상기 마스터모델을 인쇄할 수 있는 광경화 또는 UV경화 수지로는 한국공개특허 특2003-0009435에 삼차원 프린터에서 입체물을 형성시키는 화학 조성물로서, 성분이 비수성 유기 단량체 화합물을 포함하며, 상기 화합물이 알코올, 에스테르, 에테르, 실란, 비닐 단량체, 아크릴 단량체 또는 메타크릴레이트 단량체 중 하나 이상을 포함하되, 상기 아크릴 단량체가 트리(프로필렌 글리콜) 디아크릴레이트, 에틸렌 글리콜 페닐 에테르 아크릴레이트 또는 1,6 헥산디올 디아크릴레이트중 하나 이상을 포함하거나, 상기 메타크릴 단량체가 1,3 부틸렌 글리콜 디메타크릴레이트, 네오펜틸 글리콜 디메타크릴레이트, 부틸메타크릴레이트, 1,6 헥산디올 디메타크릴레이트 또는 디(프로필렌 글리콜) 알릴 에테르 메타크릴레이트중 하나 이상을 포함함을 특징으로 하는 삼차원 프린터용 광경화 조성물이 공지되어 있다.Conventionally, as a photocuring or UV curing resin which can print the master model with a 3D printer, it is a chemical composition for forming a three-dimensional object in a three-dimensional printer in Korean Patent Laid-Open Publication No. 2003-0009435, and the component includes a non-aqueous organic monomer compound. Wherein the compound comprises at least one of alcohol, ester, ether, silane, vinyl monomer, acrylic monomer or methacrylate monomer, wherein the acrylic monomer is tri (propylene glycol) diacrylate, ethylene glycol phenyl ether acrylate or 1 Or at least one of 6 hexanediol diacrylate, wherein the methacryl monomer is 1,3 butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, butyl methacrylate, 1,6 hexanediol dimethacrylate Containing at least one of acrylate or di (propylene glycol) allyl ether methacrylate There is known a photocuring composition for a three-dimensional printer.

또한, 한국공개특허 10-2012-0055242에는 광경화형 수지 조성물 100 중량부에 대하여, 아크릴계 화합물 50~80 중량부, 실세스퀴옥산 10~50 중량부, 광경화성 이형제 0.5~5 중량부 및 자외선 개시제 1~5 중량부를 포함하고, 상기 아크릴계 화합물은 단관능성 모노머, 이관능성 모노머, 삼관능성 모노머, 다관능성 모노머 및 이들의 혼합물로 구성된 군에서 선택되며, 상기 실세스퀴옥산은 아크릴레이트 또는 메타크릴레이트 기를 가지는 실세스퀴옥산 및 이들 의 혼합물로 구성된 군에서 선택되는 것을 특징으로 하는 광경화형 수지 조성물이 공지되어 있다.In addition, Korean Patent Laid-Open Publication No. 10-2012-0055242 discloses 50 to 80 parts by weight of an acrylic compound, 10 to 50 parts by weight of silsesquioxane, 0.5 to 5 parts by weight of a photocurable release agent, and an ultraviolet initiator based on 100 parts by weight of a photocurable resin composition. 1 to 5 parts by weight, wherein the acrylic compound is selected from the group consisting of monofunctional monomers, difunctional monomers, trifunctional monomers, polyfunctional monomers, and mixtures thereof, wherein the silsesquioxane is acrylate or methacrylate Photocurable resin compositions are known which are selected from the group consisting of silsesquioxanes having groups and mixtures thereof.

또한, 한국공개특허 10-2012-0137258에는 아크릴수지 기판 등의 기판에 대한 습윤 전개성이 우수한 광경화성 잉크젯 잉크이며, 기판으로의 밀착성이 우수한 표면 발액성 경화막을 형성할 수 있는 광경화성 잉크젯 잉크로서, 유기용매(A), 히드록시기를 갖는 2관능 이하의 (메타)아크릴레이트(B), 우레탄(메타)아크릴레이트(C), 계면활성제(D) 및 광중합 개시제(E)를 함유하고, 상기 우레탄(메타)아크릴레이트(C)가 화학식(2)로 표시되는 광경화성 잉크젯 잉크가 공지되어 있다.In addition, Korean Patent Laid-Open No. 10-2012-0137258 discloses a photocurable inkjet ink having excellent wettability with respect to substrates such as an acrylic resin substrate, and a photocurable inkjet ink capable of forming a surface-repellent cured film having excellent adhesion to a substrate. , An organic solvent (A), a bifunctional or less (meth) acrylate (B) having a hydroxy group, a urethane (meth) acrylate (C), a surfactant (D) and a photopolymerization initiator (E) are contained, and the urethane Photocurable inkjet inks in which (meth) acrylate (C) is represented by the formula (2) are known.

Figure 112018020077717-pat00001
Figure 112018020077717-pat00001

(화학식(2)에서, R1, R2 및 R3은 각각 독립적으로 탄소수 1 내지 20인 2가의 유기기이며, R4 및 R5는 각각 독립적으로 수소 또는 탄소수 1 내지 6의 알킬이며, m 및 n은 각각 독립적으로 1 내지 3의 정수이다.)(In formula (2), R1, R2 and R3 are each independently a divalent organic group having 1 to 20 carbon atoms, R4 and R5 are each independently hydrogen or alkyl having 1 to 6 carbon atoms, and m and n are each independently Is an integer of 1 to 3.)

또한, 한국공개특허 10-2016-0058595에는 피에조 헤드를 이용한 자외선 경화형 잉크젯 방식을 적용하여 3차원 연성 조형물을 형성하기 위한 컬러 잉크 조성물에 있어서, 아크릴레이트계 올리고머 13 내지 30 중량%; 아크릴레이트계 단관능 및 다관능 모노머 60 내지 80중량%; 안료 0.1 내지 2.0중량%; 광개시제 4 내지 12 중량%; 및 레벨링제 및 안정제를 포함하는 첨가제 1 내지 5 중량%를 포함하는 3차원 연성 조형물 형성용 잉크 조성물이 공지된 바 있다.In addition, Korean Patent Laid-Open Publication No. 10-2016-0058595, In the color ink composition for forming a three-dimensional flexible molding by applying an ultraviolet curable inkjet method using a piezo head, 13 to 30% by weight of an acrylate oligomer; 60 to 80% by weight of acrylate monofunctional and polyfunctional monomers; Pigment 0.1 to 2.0% by weight; 4-12 wt% photoinitiator; And an ink composition for forming a three-dimensional soft sculpture comprising 1 to 5% by weight of an additive comprising a leveling agent and a stabilizer.

그러나, 상기한 3D프린팅용 경화형 수지조성물들은 경화메카니즘이 아크릴레이트 또는 메타크릴레이트 이중결합의 광경화 또는 UV경화에 의한 라디칼 연쇄중합반응만으로 경화되기 때문에 경화속도가 늦고 균일한 경화가 어려우며 이로 인하여 현상성(미세선폭 구현)과 수축률이 불량한 심각한 문제가 있었다.However, the above-mentioned curable resin compositions for 3D printing have a slow curing rate and difficulty in uniform curing because the curing mechanism is cured only by radical curing of photopolymerization or UV curing of acrylate or methacrylate double bonds. There was a serious problem with poor sex (implementation of fine wire width) and poor shrinkage.

한편, 에폭시 아크릴레이트는 에폭시 수지를 원료로 사용하며, 현재 가장 주된 에폭시 수지는 방향족 조성물인 BPA(bispenol-A) 계열이다. BPA계 에폭시 아크릴레이트는 기존의 BPA에폭시 수지의 기본 물성을 그대로 따른다. 따라서 경화반응의 속도가 빠르고, 저렴하며, 내열성, 경도 및 내약품성 등 이 우수하다는 장점이 있다. On the other hand, epoxy acrylate uses an epoxy resin as a raw material, and currently the main epoxy resin is a BPA (bispenol-A) based aromatic composition. BPA epoxy acrylate follows the basic properties of conventional BPA epoxy resin. Therefore, there is an advantage that the speed of the curing reaction is fast, inexpensive, and excellent in heat resistance, hardness and chemical resistance.

최근에는 굴절률이 높은 소재로서 굴절률을 제어할 수 있는 코팅 소재로의 수요가 증가하고 있다. 아크릴레이트 분자 설계를 통한 굴절률 향상이나 무기 나노입자를 분산시켜 굴절률을 조절하는 연구도 진행되고 있다. 이러한 연구 성과로 유리를 대체하는 고굴절 아크릴레이트를 코팅재로 사용하는 사례가 보고되었고 아크릴레이트 자체를 렌즈소재로 대체하는 연구도 있다.Recently, the demand for a coating material capable of controlling the refractive index as a material having a high refractive index is increasing. Research has also been conducted to improve the refractive index through the design of acrylate molecules or to control the refractive index by dispersing inorganic nanoparticles. As a result of this research, a case of using a high refractive acrylate that replaces glass as a coating material has been reported, and there is a study that replaces the acrylate itself with a lens material.

하지만 계 BPA 에폭시 아크릴레이트는 높은 분자량과 점도로 인해 취급하기 어렵다는 단점이 따라서 반응성 모노머를 희석제로 사용한다. 또한 BPA계 에폭시 아크릴레이트의 경화도가 높아지면 수축현상이 증가하고 부착력이 감소하며 brittle한 성질이 커져 경화 후 소재가 깨지거나 부서지기 쉬워진다. 이때 수축현상은 접착 면을 손상시키기 때문에 접착부나 코팅 면이 아예 떨어져나갈 수도 있다. 이러한 문제를 해결하기 위한 방법으로는 반응성 모노머의 관능기수나 사슬 길이를 조절하거나 반응성 모노머의 함량을 조절하여 가교 밀도를 제어하는 방법이 있다. However, BPA epoxy acrylates are difficult to handle due to their high molecular weight and viscosity, and thus use reactive monomers as diluents. In addition, as the hardness of BPA-based epoxy acrylate increases, shrinkage increases, adhesion decreases, and brittle properties increase, so that the material is easily broken or broken after curing. At this time, since the shrinkage damages the adhesive surface, the adhesive part or the coating surface may fall off at all. As a method for solving this problem, there is a method of controlling the crosslinking density by adjusting the functional group number or chain length of the reactive monomer or adjusting the content of the reactive monomer.

종래, 에폭시아크릴레이트와 반응성 모노머를 사용한 3D 광경화잉크 조성물을 살펴 보면, 한국공개특허 10-2008-0044303(2008년05월20일)에 a) 에폭시 함유 화합물 30-80 중량%; b) 이작용성 (메트)아크릴레이트 5-40 중량%; c) (1) 1 이상의 에폭시 또는 알코올 작용기를 함유하는 저분자량 내지 중분자량의 1 이상의 성분; 및 (2) 성분 (1)과는 상이하며 성분(1)보다 더 높은 분자량을 갖는 1 이상의 폴리올을 포함하는 폴리올 함유 혼합물 5-40 중량%; d) 양이온 광개시제; e) 자유 라디칼 광개시제; 및 경우에 따라 f) 1 이상의 안정화제를 포함하며, 상기 중량%는 광경화성 조성물의 전체 중량을 기준으로 하는, 광경화성 조성물이 공지되어 있다.Conventionally, looking at the 3D photocurable ink composition using an epoxy acrylate and a reactive monomer, a) 30-80% by weight of an epoxy-containing compound in Korea Patent Publication No. 10-2008-0044303 (May 20, 2008); b) 5-40% by weight bifunctional (meth) acrylate; c) (1) at least one component of low to medium molecular weight containing at least one epoxy or alcohol functional group; And (2) 5-40% by weight of a polyol containing mixture comprising one or more polyols different from component (1) and having a higher molecular weight than component (1); d) cationic photoinitiators; e) free radical photoinitiators; And optionally f) one or more stabilizers, wherein the weight percent is based on the total weight of the photocurable composition.

또한, 한국공개특허 10-2006-0125711(2006년12월06일)에는 (a) 양이온 경화성 화합물, (b) 아크릴레이트 함유 화합물, (c) 다관능성 히드록실 함유 화합물, (d) 양이온 광개시제, 및 (e) 자유 라디칼 광개시제를 포함하고, 100 그램 당, 바람직하게는 유기 부분 100 그램 당 양이온 경화성 기 0.54 당량 미만, 아크릴레이트기 0.10당량 미만 및 히드록실기 0.10 당량 미만을 갖는 광경화성 조성물이 공지되어 있다.In addition, Korean Patent Publication No. 10-2006-0125711 (December 06, 2006) discloses (a) a cation-curable compound, (b) an acrylate-containing compound, (c) a polyfunctional hydroxyl-containing compound, (d) a cationic photoinitiator, And (e) free radical photoinitiators, wherein the photocurable composition has less than 0.54 equivalents of cationically curable groups, less than 0.10 equivalents of acrylate groups and less than 0.10 equivalents of hydroxyl groups per 100 grams, preferably per 100 grams of organic moiety. It is.

그러나, 상기 에폭시 함유 화합물 또는 양이온 경화성 화합물을 포함하는 조성물은 에폭시아크릴레이트가 아닌 에폭시 화합물 자체를 아크릴레이트와 혼합하여 조성되는 것으로 에폭시아크릴레이트의 특성을 발휘하지 못하고, 특히 굴곡강도와 내열성에 있어서 미흡한 문제점이 있었다.However, the composition containing the epoxy-containing compound or the cation-curable compound is composed by mixing the epoxy compound itself, not the epoxy acrylate with the acrylate, and does not exhibit the properties of the epoxy acrylate, especially in flexural strength and heat resistance There was a problem.

또한, 한국공개특허 10-2016-0082280(2016년07월08일)에는 표면 개질된 무기 입자; 상기 표면 개질된 무기 입자와 가교 결합되는 광경화성 물질; 및 상기 광경화성 물질을 경화시키는 광개시제;를 포함하는 3차원 인쇄를 위한 잉크 조성물로서, 상기 상기 광경화성 물질은, 에폭시아크릴레이트계 화합물을 포함하는 조성물이 공지되어 있으나, 에폭시아크릴레이트를 사용하면서도 반응성 모노머를 사용하지 않아 에폭시아크릴레이트의 종래 문제점인 높은 분자량과 점도로 인한 사용상의 문제점이 있다.In addition, Korean Patent Publication No. 10-2016-0082280 (July 08, 2016), the surface-modified inorganic particles; A photocurable material crosslinked with the surface modified inorganic particles; And a photoinitiator for curing the photocurable material, wherein the photocurable material is a composition comprising an epoxyacrylate-based compound, although a composition comprising an epoxyacrylate-based compound is known, but is reactive There is a problem in use due to the high molecular weight and viscosity, which is a conventional problem of epoxy acrylate because no monomer is used.

상기한 문제점을 개선하기 위하여, 본 발명자들은 2016.09.07.에 출원번호 10-2016-0114889호로 양이온경화 및 자외선경화 메커니즘을 동시에 가지는 지환족 에폭시 아크릴계 화합물을 포함하는 현상성과 수축률이 우수한 3D프린팅용 수지 조성물을 개발하고 특허출원한 바 있으며, 또한, 2016.09.07.에 출원번호 10-2016-0114893호로 양이온경화 및 자외선경화 메커니즘을 동시에 가지는 지환족 에폭시 아크릴계 화합물을 개발하여 특허출원한 바 있다.In order to improve the above-mentioned problems, the inventors of the present invention, the application number 10-2016-0114889 on 2016.09.07. 3D printing resin having excellent developability and shrinkage rate including an alicyclic epoxy acrylic compound having a cation curing and UV curing mechanism at the same time The composition has been developed and patented, and in 2016.09.07., The application number 10-2016-0114893 has been developed and patented by developing an alicyclic epoxy acrylic compound having both a cation curing and ultraviolet curing mechanism.

그러나, 상기 특허출원번호 10-2016-0114889호는 지환족 에폭시 아크릴계 화합물을 사용하여 현상성과 수축률이 우수하고, 특허출원번호 10-2016-0114893호는 Bispheno A 에폭시수지의 양 말단 에폭시기를 개환하여 메틸메타크릴레이트를 도입한 에폭시아크릴레이트 올리고머를 사용하여 굴곡강도와 내열성을 향상시켰으나 지환족 에폭시 아크릴레이트 또는 Bispheno A 에폭시아크릴레이트는 여전히 내열성이 만족스럽지 못하고, 표면경도가 미흡하여 3D 프린팅시 미세선폭이 구현되지 못하는 문제점이 있었다. However, the patent application No. 10-2016-0114889 is excellent in developability and shrinkage rate using an alicyclic epoxy acrylic compound, and the patent application No. 10-2016-0114893 is a methyl ring by opening both terminal epoxy groups of Bispheno A epoxy resin Epoxy acrylate oligomers with methacrylates were used to improve flexural strength and heat resistance. However, cycloaliphatic epoxy acrylates or Bispheno A epoxy acrylates were still unsatisfactory in heat resistance and had poor surface hardness, resulting in fine line widths during 3D printing. There was a problem that could not be implemented.

한국공개특허 특2003-0009435(2003년01년29일)Korean Patent Publication No. 2003-0009435 (January 29, 2003) 한국공개특허 10-2012-0055242(2012년05월31일)Korea Patent Publication 10-2012-0055242 (May 31, 2012) 한국공개특허 10-2012-0137258(2012년12월20일)Korea Patent Publication 10-2012-0137258 (December 20, 2012) 한국공개특허 10-2016-0058595(2016년05월25일)Korean Patent Publication 10-2016-0058595 (May 25, 2016) 한국공개특허 10-2008-0044303(2008년05월20일)Korea Patent Publication 10-2008-0044303 (May 20, 2008) 한국공개특허 10-2006-0125711(2006년12월06일)Korea Patent Publication 10-2006-0125711 (December 06, 2006) 한국공개특허 10-2016-0082280(2016년07월08일)Korea Patent Publication 10-2016-0082280 (July 08, 2016)

본 발명은 상기 문제점들을 해결하기 위하여, 디싸이클로펜타디엔 에폭시수지의 에폭시기를 완전 개환하여 아크릴레이트를 도입한 에폭시아크릴레이트 또는 에폭시기를 부분 개환하여 에폭시기와 아크릴기를 동시에 가지는 에폭시아크릴레이트와 아크릴 모노머를 포함하여 자외선 조사에 의한 라디칼 방식과 양이온 방식의 경화가 동시에 일어나는 디싸이클로펜타디엔 에폭시 아크릴레이트를 포함하는 내열성과 기계적 물성이 우수한 3D프린팅용 광경화 수지 잉크조성물을 제공하는 것을 해결하고자 하는 과제로 한다.In order to solve the above problems, the present invention includes an epoxy acrylate or an acrylic monomer having an epoxy group and an acrylic group at the same time by partially opening the epoxy acrylate or an epoxy group by completely opening the epoxy group of the dicyclopentadiene epoxy resin. It is an object of the present invention to provide a photocurable resin composition for 3D printing having excellent heat resistance and mechanical properties, including dicyclopentadiene epoxy acrylate, wherein curing of a radical method and a cationic method by ultraviolet irradiation occurs simultaneously.

본 발명은 상기 과제를 해결하기 위하여, 다음 [화학식 1], [화학식 2] 또는 [화학식 3]으로 표시되는 어느 하나 또는 둘 이상의 디싸이클로펜타디엔 에폭시아크릴레이트와 아크릴 모노머를 포함하여 구성되어 자외선 조사에 의한 라디칼 방식과 양이온 방식의 경화가 동시에 일어나는 3D프린팅용 광경화 수지 잉크조성물을 과제의 해결수단으로 한다.In order to solve the above problems, the present invention comprises any one or two or more dicyclopentadiene epoxy acrylate and an acrylic monomer represented by the following [Formula 1], [Formula 2] or [Formula 3] UV irradiation The photocurable resin ink composition for 3D printing in which the curing of the radical method and the cationic method by the same method occurs simultaneously.

[화학식 1][Formula 1]

Figure 112018020077717-pat00002
Figure 112018020077717-pat00002

[화학식 2][Formula 2]

Figure 112018020077717-pat00003
Figure 112018020077717-pat00003

[화학식 3][Formula 3]

Figure 112018020077717-pat00004
Figure 112018020077717-pat00004

상기 [화학식 1], [화학식 2], [화학식 3]에 있어서, n은 중량평균분자량 500 내지 2,000g/mol을 만족하는 유리수이다.In [Formula 1], [Formula 2], [Formula 3], n is a ratio of 500 to 2,000 g / mol weight average molecular weight satisfies.

상기 [화학식 1], [화학식 2] 또는 [화학식 3]으로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트는 다음 [화학식 4]로 표시되는 디싸이클로펜타디엔 에폭시수지에 아크릴산을 부가반응시켜 에폭시기를 개환하여 생성되는 것을 과제의 해결수단으로 한다. The dicyclopentadiene epoxy acrylate represented by the above [Formula 1], [Formula 2] or [Formula 3] is added to the dicyclopentadiene epoxy resin represented by the following [Formula 4] by acrylic acid to ring-open the epoxy group What is produced is taken as the solution means of a subject.

[화학식 4][Formula 4]

Figure 112018020077717-pat00005
Figure 112018020077717-pat00005

상기 화학식 4에 있어서, n은 중량평균분자량 500 내지 2,000g/mol을 만족하는 유리수이다.In Chemical Formula 4, n is a rational number satisfying a weight average molecular weight of 500 to 2,000 g / mol.

상기 [화학식 1]로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트와, 아크릴 모노머와, 에폭시화합물과, 에폭시아크릴레이트를 포함하여 구성되는 3D프린팅용 광경화 수지 잉크조성물을 과제의 해결수단으로 한다.The 3D printing photocurable resin ink composition containing the dicyclopentadiene epoxy acrylate, an acrylic monomer, an epoxy compound, and an epoxy acrylate represented by the said [Formula 1] is made into the solution.

상기 아크릴 모노머는 hydroxy ethyl acrylate, hydroxy propyl acrylate, ethyl hexyl acrylate, cyclic-trimethylolpropane-formal acrylate, benzyl acrylate, phenol acrylate, tetrahydrofurfuryl acrylate, nonyl phenol acrylate, ethoxy ethoxy ethyl acrylate, phenoxybenzyl acrylate, lsooctyl acrylate, isododecyl acrylate, lauryl acrylate, tetradecyl acrylate, cetyl acrylate, stearyl acrylate, icosyl acrylate, behenyl acrylate, 3,3,5-trimethyl cyclohexyl acrylate, caprolactone acrylate, 2-carboxyethyl acrylate, bisphenol A acrylate, Bisphenol A diacrylate, (Octahydro-4,7-methano-1H-indenediyl)bis(methylene)diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, hexanediol diacrylate, butanediol diacrylate, bisphenol fluorene diacrylate, neopentyl glycol diacrylate, hydroxy pivalic neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol tiriacrylate, trimethylolpropane triacrylate, glycerine triacrylate, tris(2-hydroxy ethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, methoxy PEG methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isodecyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate, stearyl methacrylate, 3,3,5 trimethyl cyclohexyl methacrylate, bisphenol A dimethacrylate, 1,6-hexandiol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylene propane trimethacrylate, glycerol trimethacrylate 중에서 선택되는 것을 과제의 해결수단으로 한다.The acrylic monomers are hydroxy ethyl acrylate, hydroxy propyl acrylate, ethyl hexyl acrylate, cyclic-trimethylolpropane-formal acrylate, benzyl acrylate, phenol acrylate, tetrahydrofurfuryl acrylate, nonyl phenol acrylate, ethoxy ethoxy ethyl acrylate, phenoxybenzyl acrylate, lsooctyl acrylate, isododecyl acrylate lauryl acrylate, tetradecyl acrylate, cetyl acrylate, stearyl acrylate, icosyl acrylate, behenyl acrylate, 3,3,5-trimethyl cyclohexyl acrylate, caprolactone acrylate, 2-carboxyethyl acrylate, bisphenol A acrylate, Bisphenol A diacrylate, (Octahydro-4,7 -methano-1H-indenediyl) bis (methylene) diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, hexanediol diacrylate, butanediol diacrylate, bisphenol fluorene diacrylate, neopentyl glycol diacrylate, hydroxy pivalic neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol tiriacrylate, trimethylo lpropane triacrylate, glycerine triacrylate, tris (2-hydroxy ethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, methoxy PEG methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isodecdecyl methacrylate, lauryl methacrylate, lauryl acetylacrylate stearyl methacrylate, 3,3,5 trimethyl cyclohexyl methacrylate, bisphenol A dimethacrylate, 1,6-hexandiol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, The solution to the problem is selected from polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylene propane trimethacrylate, and glycerol trimethacrylate.

상기 에폭시화합물은 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycycloheylmethyl acrylate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane, 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexanecarboxylate modified epsilon-caprolactone, 4-vinyl-1-cyclohexene 1,2-epoxide, 3-cyclohexen-1-carboxaldehyde, diglycidyl 1,2-cyclohexanedicarboxylate, tetrahydrophthalic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4-vinylcyclohexene dioxide, 1,2:5,6-diepoxyhexahydro-4,7-methanoindan, N,N-diglycidyl-4-glycidyloxyaniline, 4,4'-methylenebis(N,N-diglycidylaniline), 1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylate), 4,4'-(1-methylethylidene)bisphenol polymer with(chloromethyl)oxirane 중에서 선택되는 것을 과제의 해결수단으로 한다.The epoxy compound is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycycloheylmethyl acrylate, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexylmethyl) epoxy) cyclohexane, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate modified epsilon-caprolactone, 4-vinyl-1-cyclohexene 1,2-epoxide, 3-cyclohexen-1-carboxaldehyde, diglycidyl 1,2-cyclohexanedicarboxylate, tetrahydrophthalic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4-vinylcyclohexene dioxide, 1,2: 5,6-diepoxyhexahydro-4,7-methanoindan, N, N-diglycidyl-4-glycidyloxyaniline , 4,4'-methylenebis (N, N-diglycidylaniline), 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate), 4,4 '-(1-methylethylidene) bisphenol polymer with (chloromethyl) oxirane It is to solve the problem.

상기 에폭시아크릴레이트는 bisphenol A epoxy acrylate, bisphenol F epoxy acrylate, cresol novolac epoxy acrylate, phenol novolac epoxy acrylate, bisphenyl novlac epoxy acrylate, fatty acid epoxy acrylate, resorcinol epoxy acrylate 중에서 선택되는 것을 과제의 해결수단으로 한다.The epoxy acrylate is selected from bisphenol A epoxy acrylate, bisphenol F epoxy acrylate, cresol novolac epoxy acrylate, phenol novolac epoxy acrylate, bisphenyl novlac epoxy acrylate, fatty acid epoxy acrylate and resorcinol epoxy acrylate.

상기 [화학식 2] 및/또는 [화학식 3]으로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트와, 아크릴 모노머와, 글리시딜에테르화합물과, 옥세탄화합물과, 에폭시화합물과, 에폭시아크릴레이트, 광개시제와, 양이온개시제를 포함하여 구성되는 3D프린팅용 광경화 수지 잉크조성물을 과제의 해결수단으로 한다.Dicyclopentadiene epoxy acrylate, an acrylic monomer, a glycidyl ether compound, an oxetane compound, an epoxy compound, an epoxy acrylate, a photoinitiator represented by the above [Formula 2] and / or [Formula 3] A photocurable resin ink composition for 3D printing comprising a cationic initiator is a solution to the problem.

상기 아크릴 모노머는 hydroxy ethyl acrylate, hydroxy propyl acrylate, ethyl hexyl acrylate, cyclic-trimethylolpropane-formal acrylate, benzyl acrylate, phenol acrylate, tetrahydrofurfuryl acrylate, nonyl phenol acrylate, ethoxy ethoxy ethyl acrylate, phenoxybenzyl acrylate, lsooctyl acrylate, isododecyl acrylate, lauryl acrylate, tetradecyl acrylate, cetyl acrylate, stearyl acrylate, icosyl acrylate, behenyl acrylate, 3,3,5-trimethyl cyclohexyl acrylate, caprolactone acrylate, 2-carboxyethyl acrylate, bisphenol A acrylate, Bisphenol A diacrylate, (Octahydro-4,7-methano-1H-indenediyl)bis(methylene)diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, hexanediol diacrylate, butanedioldiacrylate, bisphenol fluorene diacrylate, neopentyl glycol diacrylate, hydroxy pivalic neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol tiriacrylate, trimethylolpropane triacrylate, glycerine triacrylate, tris(2-hydroxy ethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, methoxy PEG methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isodecyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate, stearyl methacrylate, 3,3,5 trimethyl cyclohexyl methacrylate, bisphenol A dimethacrylate, 1,6-hexandiol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylene propane trimethacrylate, glycerol trimethacrylate 중에서 선택되는 것을 과제의 해결수단으로 한다.The acrylic monomers are hydroxy ethyl acrylate, hydroxy propyl acrylate, ethyl hexyl acrylate, cyclic-trimethylolpropane-formal acrylate, benzyl acrylate, phenol acrylate, tetrahydrofurfuryl acrylate, nonyl phenol acrylate, ethoxy ethoxy ethyl acrylate, phenoxybenzyl acrylate, lsooctyl acrylate, isododecyl acrylate lauryl acrylate, tetradecyl acrylate, cetyl acrylate, stearyl acrylate, icosyl acrylate, behenyl acrylate, 3,3,5-trimethyl cyclohexyl acrylate, caprolactone acrylate, 2-carboxyethyl acrylate, bisphenol A acrylate, Bisphenol A diacrylate, (Octahydro-4,7 -methano-1H-indenediyl) bis (methylene) diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, hexanediol diacrylate, butanedioldiacrylate, bisphenol fluorene diacrylate, neopentyl glycol diacrylate, hydroxy pivalic neopentyl glycol diacrylate, 1,9-nonanediol diacrylate , tetraethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol tiriacrylate, trimethylol propane triacrylate, glycerine triacrylate, tris (2-hydroxy ethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, methoxy PEG methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isodecyl methacrylate, lauryl methacrylate stearyl methacrylate, 3,3,5 trimethyl cyclohexyl methacrylate, bisphenol A dimethacrylate, 1,6-hexandiol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, The solution to the problem is selected from polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylene propane trimethacrylate, and glycerol trimethacrylate.

상기 글리시딜에테르화합물은 N-butyl glycidyl ether, aliphatic glycidyl ether(C8-C15), ethylhexyl glycidyl ether, phenyl glycidyl ether, o-cresyl glycidyl ether, m,p-cresyl glycidyl ether, p-tertiary butylphenyl glycidyl ether, 3-alkyl phenol glycidyl ether, octafluoropentyl glycidyl ether, o-phenyl phenol glycidyl ether, benzyl glycidyl ether, 0-sec-butyl phenyl glycidyl ether, 1,4-butanediol glycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexandiol dlycidyl ether, neopentyl glycol diglycidyl ether, 1,4-cyclohexane dimetanol diglycidyl ether, Propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, resorcinol diglycidyl ether, thio-dipheny diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, caster oil polyglycidyl ether, sorbitol polyglycidyl ether 중에서 선택되는 것을 과제의 해결수단으로 한다.The glycidyl ether compounds include N-butyl glycidyl ether, aliphatic glycidyl ether (C8-C15), ethylhexyl glycidyl ether, phenyl glycidyl ether, o-cresyl glycidyl ether, m, p-cresyl glycidyl ether, p-tertiary butylphenyl glycidyl ether , 3-alkyl phenol glycidyl ether, octafluoropentyl glycidyl ether, o-phenyl phenol glycidyl ether, benzyl glycidyl ether, 0-sec-butyl phenyl glycidyl ether, 1,4-butanediol glycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexandiol dlycidyl ether, neopentyl glycol diglycidyl ether, 1,4-cyclohexane dimetanol diglycidyl ether, Propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, resorcinol diglycidyl ether, thio-dipheny diglycidyl ether, trimethylollygyl tricilyyl ether polydci ether The solution selected from the group consisting of sorbitol polyglycidyl ether is to be solved.

상기 옥세탄화합물은 3-ethyl-hydroxymethyl oxethane, 1,4-bis{[(3-ethyloxetane-3-yl)methoxy]methyl}benzene, 3-ethyl-3-{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane, 3-ethyl-3-phenoxymethyl oxethane, 3-ethyl-3-(2-ethylhexyl)methyl oxethane, 3-ethyl-3-cyclohexyloxymethyloxetane, phenol novolac oxetane 중에서 선택되는 것을 과제의 해결수단으로 한다.The oxetane compound is 3-ethyl-hydroxymethyl oxethane, 1,4-bis {[(3-ethyloxetane-3-yl) methoxy] methyl} benzene, 3-ethyl-3-{[(3-ethyloxetane-3-yl ) Methoxy] methyl} oxetane, 3-ethyl-3-phenoxymethyl oxethane, 3-ethyl-3- (2-ethylhexyl) methyl oxethane, 3-ethyl-3-cyclohexyloxymethyloxetane, phenol novolac oxetane do.

상기 에폭시화합물은 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycycloheylmethyl acrylate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane, 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexanecarboxylate modified epsilon-caprolactone, 4-vinyl-1-cyclohexene 1,2-epoxide, 3-cyclohexen-1-carboxaldehyde, diglycidyl 1,2-cyclohexanedicarboxylate, tetrahydrophthalic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4-vinylcyclohexene dioxide, 1,2:5,6-diepoxyhexahydro-4,7-methanoindan, N,N-diglycidyl-4-glycidyloxyaniline, 4,4'-methylenebis(N,N-diglycidylaniline), 1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylate), 4,4'-(1-methylethylidene)bisphenol polymer with(chloromethyl)oxirane 중에서 선택되는 것을 과제의 해결수단으로 한다.The epoxy compound is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycycloheylmethyl acrylate, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexylmethyl) epoxy) cyclohexane, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate modified epsilon-caprolactone, 4-vinyl-1-cyclohexene 1,2-epoxide, 3-cyclohexen-1-carboxaldehyde, diglycidyl 1,2-cyclohexanedicarboxylate, tetrahydrophthalic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4-vinylcyclohexene dioxide, 1,2: 5,6-diepoxyhexahydro-4,7-methanoindan, N, N-diglycidyl-4-glycidyloxyaniline , 4,4'-methylenebis (N, N-diglycidylaniline), 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate), 4,4 '-(1-methylethylidene) bisphenol polymer with (chloromethyl) oxirane It is to solve the problem.

상기 에폭시아크릴레이트는 bisphenol A epoxy acrylate, bisphenol F epoxy acrylate, cresol novolac epoxy acrylate, phenol novolac epoxy acrylate, bisphenyl novlac epoxy acrylate, fatty acid epoxy acrylate, resorcinol epoxy acrylate 중에서 선택되는 것을 과제의 해결수단으로 한다.The epoxy acrylate is selected from bisphenol A epoxy acrylate, bisphenol F epoxy acrylate, cresol novolac epoxy acrylate, phenol novolac epoxy acrylate, bisphenyl novlac epoxy acrylate, fatty acid epoxy acrylate and resorcinol epoxy acrylate.

상기 광개시제는 phenylbis(2,4,6-trimehylbenzoyl), benzyl dimethyl ketal, hydroxy cyclohexyl phenyl ketone, hydroxyl dimethyl acetophenone, methyl-[4-mehylthio phenyl]-2-morpholine propanone, 2,4-diethylthioxanthone, isopropylthioxanthone propanone, ethyl-4-dimethylaminobenzoate, benzophenone, 4-phenylbenxophenone, 2,4,6-trimethylbenzoyl-diphenyl phosphine, methyl benzoylformate 중에서 선택되는 것을 과제의 해결수단으로 한다.The photoinitiator is phenylbis (2,4,6-trimehylbenzoyl), benzyl dimethyl ketal, hydroxy cyclohexyl phenyl ketone, hydroxyl dimethyl acetophenone, methyl- [4-mehylthio phenyl] -2-morpholine propanone, 2,4-diethylthioxanthone, isopropylthioxanthone propanone, The solution of the problem is selected from ethyl-4-dimethylaminobenzoate, benzophenone, 4-phenylbenxophenone, 2,4,6-trimethylbenzoyl-diphenyl phosphine, and methyl benzoylformate.

상기 양이온개시제는 Irgacure 250 또는 Irgacure 270(BASF) 중에서 선택되는 것을 과제의 해결수단으로 한다.The cationic initiator is selected from Irgacure 250 or Irgacure 270 (BASF) as a means of solving the problem.

본 발명의 디싸이클로펜타디엔 에폭시 아크릴레이트를 포함하는 내열성과 기계적 물성이 우수한 3D프린팅용 광경화 수지 잉크조성물은 디싸이클로펜타디엔 에폭시수지의 에폭시기를 완전 개환하여 아크릴레이트를 도입한 에폭시아크릴레이트 또는 에폭시기를 부분 개환하여 에폭시기와 아크릴기를 동시에 가지는 에폭시아크릴레이트와 아크릴 모노머를 포함하여 자외선 조사에 의한 라디칼 방식과 양이온 방식의 경화가 동시에 일어나도록 하고, 자외선 조사에 의한 라디칼 방식과 양이온 방식의 경화의 조절을 통해 수축률을 제어하고 내열성과 기계적 물성이 대폭 향상되는 우수한 효과가 있다.The photocurable resin ink composition for 3D printing having excellent heat resistance and mechanical properties including the dicyclopentadiene epoxy acrylate of the present invention is an epoxy acrylate or epoxy group in which an acrylate is introduced by completely opening an epoxy group of a dicyclopentadiene epoxy resin. Partial ring opening is carried out so that epoxy and acrylic monomers having epoxy and acrylic groups at the same time can be used to effect the curing of the radical method and the cationic method by UV irradiation. Through the control of the shrinkage rate and heat resistance and mechanical properties is greatly improved.

도 1은 본 발명의 디싸이클로펜타디엔 에폭시아크릴레이트의 CNMR 데이터
도 2는 본 발명의 디싸이클로펜타디엔 에폭시아크릴레이트의 TGA 그래프
도 3은 본 발명의 디싸이클로펜타디엔 에폭시아크릴레이트를 포함한 3D잉크조성물의 CNMR 데이터
도 4는 본 발명의 디싸이클로펜타디엔 에폭시아크릴레이트를 포함한 3D잉크조성물의 TGA 그래프
도 5는 본 발명의 3D프린팅용 수지 조성물 인쇄해상도 광학현미경사진1 is CNMR data of the dicyclopentadiene epoxy acrylate of the present invention
2 is a TGA graph of the dicyclopentadiene epoxyacrylate of the present invention
Figure 3 is CNMR data of the 3D ink composition containing the dicyclopentadiene epoxy acrylate of the present invention
Figure 4 is a TGA graph of the 3D ink composition containing the dicyclopentadiene epoxy acrylate of the present invention
Figure 5 is a print resolution optical micrograph of the resin composition for 3D printing of the present invention

본 발명은, 다음 [화학식 1], [화학식 2] 또는 [화학식 3]으로 표시되는 어느 하나 또는 둘 이상의 디싸이클로펜타디엔 에폭시아크릴레이트와 아크릴 모노머를 포함하여 구성되어 자외선 조사에 의한 라디칼 방식과 양이온 방식의 경화가 동시에 일어나는 3D프린팅용 광경화 수지 잉크조성물을 기술구성의 특징으로 한다.The present invention comprises any one or two or more dicyclopentadiene epoxy acrylate and an acrylic monomer represented by the following [Formula 1], [Formula 2] or [Formula 3], and the radical method and cation by ultraviolet irradiation The photocurable resin ink composition for 3D printing, which simultaneously undergoes curing of the anticorrosion method, is characterized by a technical configuration.

[화학식 1][Formula 1]

Figure 112018020077717-pat00006
Figure 112018020077717-pat00006

[화학식 2][Formula 2]

Figure 112018020077717-pat00007
Figure 112018020077717-pat00007

[화학식 3][Formula 3]

Figure 112018020077717-pat00008
Figure 112018020077717-pat00008

상기 [화학식 1], [화학식 2], [화학식 3]에 있어서, n은 중량평균분자량 500 내지 2,000g/mol을 만족하는 유리수이다.In [Formula 1], [Formula 2], [Formula 3], n is a ratio of 500 to 2,000 g / mol weight average molecular weight satisfies.

상기 [화학식 1], [화학식 2] 또는 [화학식 3]으로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트는 다음 [화학식 4]로 표시되는 디싸이클로펜타디엔 에폭시수지에 아크릴산을 부가반응시켜 에폭시기를 개환하여 생성되는 것을 기술구성의 특징으로 한다.The dicyclopentadiene epoxy acrylate represented by the above [Formula 1], [Formula 2] or [Formula 3] is added to the dicyclopentadiene epoxy resin represented by the following [Formula 4] by acrylic acid to ring-open the epoxy group It is characterized by the technical configuration that is generated.

[화학식 4][Formula 4]

Figure 112018020077717-pat00009
Figure 112018020077717-pat00009

상기 화학식 4에 있어서, n은 중량평균분자량 500 내지 2,000g/mol을 만족하는 유리수이다.In Chemical Formula 4, n is a rational number satisfying a weight average molecular weight of 500 to 2,000 g / mol.

상기 [화학식 1]로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트와, 아크릴 모노머와, 에폭시화합물과, 에폭시아크릴레이트를 포함하여 구성되는 3D프린팅용 광경화 수지 잉크조성물을 기술구성의 특징으로 한다.A photocurable resin ink composition for 3D printing comprising a dicyclopentadiene epoxy acrylate, an acrylic monomer, an epoxy compound, and an epoxy acrylate represented by the above [Formula 1] is characterized by a technical configuration.

상기 아크릴 모노머는 hydroxy ethyl acrylate, hydroxy propyl acrylate, ethyl hexyl acrylate, cyclic-trimethylolpropane-formal acrylate, benzyl acrylate, phenol acrylate, tetrahydrofurfuryl acrylate, nonyl phenol acrylate, ethoxy ethoxy ethyl acrylate, phenoxybenzyl acrylate, lsooctyl acrylate, isododecyl acrylate, lauryl acrylate, tetradecyl acrylate, cetyl acrylate, stearyl acrylate, icosyl acrylate, behenyl acrylate, 3,3,5-trimethyl cyclohexyl acrylate, caprolactone acrylate, 2-carboxyethyl acrylate, bisphenol A acrylate, Bisphenol A diacrylate, (Octahydro-4,7-methano-1H-indenediyl)bis(methylene)diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, hexanediol diacrylate, butanedioldiacrylate, bisphenol fluorene diacrylate, neopentyl glycol diacrylate, hydroxy pivalic neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol tiriacrylate, trimethylolpropane triacrylate, glycerine triacrylate, tris(2-hydroxy ethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, methoxy PEG methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isodecyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate, stearyl methacrylate, 3,3,5 trimethyl cyclohexyl methacrylate, bisphenol A dimethacrylate, 1,6-hexandiol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylene propane trimethacrylate, glycerol trimethacrylate 중에서 선택되는 것을 기술구성의 특징으로 한다.The acrylic monomers are hydroxy ethyl acrylate, hydroxy propyl acrylate, ethyl hexyl acrylate, cyclic-trimethylolpropane-formal acrylate, benzyl acrylate, phenol acrylate, tetrahydrofurfuryl acrylate, nonyl phenol acrylate, ethoxy ethoxy ethyl acrylate, phenoxybenzyl acrylate, lsooctyl acrylate, isododecyl acrylate lauryl acrylate, tetradecyl acrylate, cetyl acrylate, stearyl acrylate, icosyl acrylate, behenyl acrylate, 3,3,5-trimethyl cyclohexyl acrylate, caprolactone acrylate, 2-carboxyethyl acrylate, bisphenol A acrylate, Bisphenol A diacrylate, (Octahydro-4,7 -methano-1H-indenediyl) bis (methylene) diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, hexanediol diacrylate, butanedioldiacrylate, bisphenol fluorene diacrylate, neopentyl glycol diacrylate, hydroxy pivalic neopentyl glycol diacrylate, 1,9-nonanediol diacrylate , tetraethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol tiriacrylate, trimethylol propane triacrylate, glycerine triacrylate, tris (2-hydroxy ethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, methoxy PEG methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isodecyl methacrylate, lauryl methacrylate stearyl methacrylate, 3,3,5 trimethyl cyclohexyl methacrylate, bisphenol A dimethacrylate, 1,6-hexandiol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, The technical composition is characterized by selecting among polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylene propane trimethacrylate, and glycerol trimethacrylate.

상기 에폭시화합물은 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycycloheylmethyl acrylate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane, 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexanecarboxylate modified epsilon-caprolactone, 4-vinyl-1-cyclohexene 1,2-epoxide, 3-cyclohexen-1-carboxaldehyde, diglycidyl 1,2-cyclohexanedicarboxylate, tetrahydrophthalic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4-vinylcyclohexene dioxide, 1,2:5,6-diepoxyhexahydro-4,7-methanoindan, N,N-diglycidyl-4-glycidyloxyaniline, 4,4'-methylenebis(N,N-diglycidylaniline), 1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylate), 4,4'-(1-methylethylidene)bisphenol polymer with(chloromethyl)oxirane 중에서 선택되는 것을 기술구성의 특징으로 한다.The epoxy compound is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycycloheylmethyl acrylate, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexylmethyl) epoxy) cyclohexane, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate modified epsilon-caprolactone, 4-vinyl-1-cyclohexene 1,2-epoxide, 3-cyclohexen-1-carboxaldehyde, diglycidyl 1,2-cyclohexanedicarboxylate, tetrahydrophthalic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4-vinylcyclohexene dioxide, 1,2: 5,6-diepoxyhexahydro-4,7-methanoindan, N, N-diglycidyl-4-glycidyloxyaniline , 4,4'-methylenebis (N, N-diglycidylaniline), 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate), 4,4 '-(1-methylethylidene) bisphenol polymer with (chloromethyl) oxirane It is characterized by the technical configuration.

상기 에폭시아크릴레이트는 bisphenol A epoxy acrylate, bisphenol F epoxy acrylate, cresol novolac epoxy acrylate, phenol novolac epoxy acrylate, bisphenyl novlac epoxy acrylate, fatty acid epoxy acrylate, resorcinol epoxy acrylate 중에서 선택되는 것을 기술구성의 특징으로 한다.The epoxy acrylate is characterized in that the technical composition is selected from bisphenol A epoxy acrylate, bisphenol F epoxy acrylate, cresol novolac epoxy acrylate, phenol novolac epoxy acrylate, bisphenyl novlac epoxy acrylate, fatty acid epoxy acrylate, resorcinol epoxy acrylate.

상기 [화학식 2] 및/또는 [화학식 3]으로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트와, 아크릴 모노머와, 글리시딜에테르화합물과, 옥세탄화합물과, 에폭시화합물과, 에폭시아크릴레이트, 광개시제와, 양이온개시제를 포함하여 구성되는 3D프린팅용 광경화 수지 잉크조성물을 기술구성의 특징으로 한다.Dicyclopentadiene epoxy acrylate, an acrylic monomer, a glycidyl ether compound, an oxetane compound, an epoxy compound, an epoxy acrylate, a photoinitiator represented by the above [Formula 2] and / or [Formula 3] The photocurable resin ink composition for 3D printing comprising a cationic initiator is characterized by a technical configuration.

상기 아크릴 모노머는 hydroxy ethyl acrylate, hydroxy propyl acrylate, ethyl hexyl acrylate, cyclic-trimethylolpropane-formal acrylate, benzyl acrylate, phenol acrylate, tetrahydrofurfuryl acrylate, nonyl phenol acrylate, ethoxy ethoxy ethyl acrylate, phenoxybenzyl acrylate, lsooctyl acrylate, isododecyl acrylate, lauryl acrylate, tetradecyl acrylate, cetyl acrylate, stearyl acrylate, icosyl acrylate, behenyl acrylate, 3,3,5-trimethyl cyclohexyl acrylate, caprolactone acrylate, 2-carboxyethyl acrylate, bisphenol A acrylate, Bisphenol A diacrylate, (Octahydro-4,7-methano-1H-indenediyl)bis(methylene)diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, hexanediol diacrylate, butanedioldiacrylate,bisphenol fluorene diacrylate, neopentyl glycol diacrylate, hydroxy pivalic neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol tiriacrylate, trimethylolpropane triacrylate, glycerine triacrylate, tris(2-hydroxy ethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, methoxy PEG methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isodecyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate, stearyl methacrylate, 3,3,5 trimethyl cyclohexyl methacrylate, bisphenol A dimethacrylate, 1,6-hexandiol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylene propane trimethacrylate, glycerol trimethacrylate 중에서 선택되는 것을 기술구성의 특징으로 한다.The acrylic monomers are hydroxy ethyl acrylate, hydroxy propyl acrylate, ethyl hexyl acrylate, cyclic-trimethylolpropane-formal acrylate, benzyl acrylate, phenol acrylate, tetrahydrofurfuryl acrylate, nonyl phenol acrylate, ethoxy ethoxy ethyl acrylate, phenoxybenzyl acrylate, lsooctyl acrylate, isododecyl acrylate lauryl acrylate, tetradecyl acrylate, cetyl acrylate, stearyl acrylate, icosyl acrylate, behenyl acrylate, 3,3,5-trimethyl cyclohexyl acrylate, caprolactone acrylate, 2-carboxyethyl acrylate, bisphenol A acrylate, Bisphenol A diacrylate, (Octahydro-4,7 -methano-1H-indenediyl) bis (methylene) diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, hexanediol diacrylate, butanedioldiacrylate, bisphenol fluorene diacrylate, neopentyl glycol diacrylate, hydroxy pivalic neopentyl glycol diacrylate, 1,9-nonanediol diacrylate , tetraethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol tiriacrylate, trimethylolp ropane triacrylate, glycerine triacrylate, tris (2-hydroxy ethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, methoxy PEG methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isodecdecyl methacrylate, lauryl methacrylate, lauryl methacrylate stearyl methacrylate, 3,3,5 trimethyl cyclohexyl methacrylate, bisphenol A dimethacrylate, 1,6-hexandiol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, The technical composition is characterized by selecting among polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylene propane trimethacrylate, and glycerol trimethacrylate.

상기 글리시딜에테르화합물은 N-butyl glycidyl ether, aliphatic glycidyl ether(C8-C15), ethylhexyl glycidyl ether, phenyl glycidyl ether, o-cresyl glycidyl ether, m,p-cresyl glycidyl ether, p-tertiary butylphenylglycidyl ether, 3-alkyl phenol glycidyl ether, octafluoropentyl glycidyl ether, o-phenyl phenol glycidyl ether, benzyl glycidyl ether, 0-sec-butyl phenyl glycidyl ether, 1,4-butanediol glycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexandiol dlycidyl ether, neopentyl glycol diglycidyl ether, 1,4-cyclohexane dimetanol diglycidyl ether, Propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, resorcinol diglycidyl ether, thio-dipheny diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, caster oil polyglycidyl ether, sorbitol polyglycidyl ether 중에서 선택되는 것을 기술구성의 특징으로 한다.The glycidyl ether compounds include N-butyl glycidyl ether, aliphatic glycidyl ether (C8-C15), ethylhexyl glycidyl ether, phenyl glycidyl ether, o-cresyl glycidyl ether, m, p-cresyl glycidyl ether, p-tertiary butylphenylglycidyl ether, 3-alkyl phenol glycidyl ether, octafluoropentyl glycidyl ether, o-phenyl phenol glycidyl ether, benzyl glycidyl ether, 0-sec-butyl phenyl glycidyl ether, 1,4-butanediol glycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexandiol dlycidyl ether, neopentyl glycol diglycidyl ether, 1,4-cyclohexane dimetanol diglycidyl ether, Propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, resorcinol diglycidyl ether, thio-dipheny diglycidyl ether, trimethylolpropane triglycidyl ether, ethylene polygether ether The polyglycidyl ether is selected from the features of the technical configuration.

상기 옥세탄화합물은 3-ethyl-hydroxymethyl oxethane, 1,4-bis{[(3-ethyloxetane-3-yl)methoxy]methyl}benzene, 3-ethyl-3-{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane, 3-ethyl-3-phenoxymethyl oxethane, 3-ethyl-3-(2-ethylhexyl)methyl oxethane, 3-ethyl-3-cyclohexyloxymethyloxetane, phenol novolac oxetane 중에서 선택되는 것을 기술구성의 특징으로 한다.The oxetane compound is 3-ethyl-hydroxymethyl oxethane, 1,4-bis {[(3-ethyloxetane-3-yl) methoxy] methyl} benzene, 3-ethyl-3-{[(3-ethyloxetane-3-yl ) methoxy] methyl} oxetane, 3-ethyl-3-phenoxymethyl oxethane, 3-ethyl-3- (2-ethylhexyl) methyl oxethane, 3-ethyl-3-cyclohexyloxymethyloxetane, phenol novolac oxetane do.

상기 에폭시화합물은 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycycloheylmethyl acrylate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane, 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexanecarboxylate modified epsilon-caprolactone, 4-vinyl-1-cyclohexene 1,2-epoxide, 3-cyclohexen-1-carboxaldehyde, diglycidyl 1,2-cyclohexanedicarboxylate, tetrahydrophthalic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4-vinylcyclohexene dioxide, 1,2:5,6-diepoxyhexahydro-4,7-methanoindan, N,N-diglycidyl-4-glycidyloxyaniline, 4,4'-methylenebis(N,N-diglycidylaniline), 1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylate), 4,4'-(1-methylethylidene)bisphenol polymer with(chloromethyl)oxirane 중에서 선택되는 것을 기술구성의 특징으로 한다.The epoxy compound is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycycloheylmethyl acrylate, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexylmethyl) epoxy) cyclohexane, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate modified epsilon-caprolactone, 4-vinyl-1-cyclohexene 1,2-epoxide, 3-cyclohexen-1-carboxaldehyde, diglycidyl 1,2-cyclohexanedicarboxylate, tetrahydrophthalic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4-vinylcyclohexene dioxide, 1,2: 5,6-diepoxyhexahydro-4,7-methanoindan, N, N-diglycidyl-4-glycidyloxyaniline , 4,4'-methylenebis (N, N-diglycidylaniline), 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate), 4,4 '-(1-methylethylidene) bisphenol polymer with (chloromethyl) oxirane It is characterized by the technical configuration.

상기 에폭시아크릴레이트는 bisphenol A epoxy acrylate, bisphenol F epoxy acrylate, cresol novolac epoxy acrylate, phenol novolac epoxy acrylate, bisphenyl novlac epoxy acrylate, fatty acid epoxy acrylate, resorcinol epoxy acrylate 중에서 선택되는 것을 기술구성의 특징으로 한다.The epoxy acrylate is characterized in that the technical composition is selected from bisphenol A epoxy acrylate, bisphenol F epoxy acrylate, cresol novolac epoxy acrylate, phenol novolac epoxy acrylate, bisphenyl novlac epoxy acrylate, fatty acid epoxy acrylate, resorcinol epoxy acrylate.

상기 광개시제는 phenylbis(2,4,6-trimehylbenzoyl), benzyl dimethyl ketal, hydroxy cyclohexyl phenyl ketone, hydroxyl dimethyl acetophenone, methyl-[4-mehylthio phenyl]-2-morpholine propanone, 2,4-diethylthioxanthone, isopropylthioxanthone propanone, ethyl-4-dimethylaminobenzoate, benzophenone, 4-phenylbenxophenone, 2,4,6-trimethylbenzoyl-diphenyl phosphine, methyl benzoylformate 중에서 선택되는 것을 기술구성의 특징으로 한다.The photoinitiator is phenylbis (2,4,6-trimehylbenzoyl), benzyl dimethyl ketal, hydroxy cyclohexyl phenyl ketone, hydroxyl dimethyl acetophenone, methyl- [4-mehylthio phenyl] -2-morpholine propanone, 2,4-diethylthioxanthone, isopropylthioxanthone propanone, The technical composition is characterized by selecting among ethyl-4-dimethylaminobenzoate, benzophenone, 4-phenylbenxophenone, 2,4,6-trimethylbenzoyl-diphenyl phosphine and methyl benzoylformate.

상기 양이온개시제는 Irgacure 250 또는 Irgacure 270(BASF) 중에서 선택되는 것을 기술구성의 특징으로 한다.The cationic initiator is characterized in that the technical configuration is selected from Irgacure 250 or Irgacure 270 (BASF).

이하에서는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예 및 도면을 통하여 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며, 여기에서 설명하는 실시예 및 도면에 한정되지 않는다.Hereinafter will be described in detail with reference to the embodiments and drawings of the present invention so that those skilled in the art can easily practice. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

본 발명의 3D프린팅용 광경화 수지 잉크조성물은 다음 [화학식 1], [화학식 2] 또는 [화학식 3]으로 표시되는 어느 하나 또는 둘 이상의 디싸이클로펜타디엔 에폭시아크릴레이트와 아크릴 모노머를 포함하여 구성되어 자외선 조사에 의한 라디칼 방식과 양이온 방식의 경화가 동시에 일어나도록 구성된다.3D printing photocurable resin ink composition of the present invention comprises any one or two or more dicyclopentadiene epoxy acrylate and an acrylic monomer represented by the following [Formula 1], [Formula 2] or [Formula 3] It is comprised so that hardening of a radical system and a cationic system by ultraviolet irradiation may occur simultaneously.

[화학식 1][Formula 1]

Figure 112018020077717-pat00010
Figure 112018020077717-pat00010

[화학식 2][Formula 2]

Figure 112018020077717-pat00011
Figure 112018020077717-pat00011

[화학식 3][Formula 3]

Figure 112018020077717-pat00012
Figure 112018020077717-pat00012

상기 [화학식 1], [화학식 2], [화학식 3]에 있어서, n은 중량평균분자량 500 내지 2,000g/mol을 만족하는 유리수이다.In [Formula 1], [Formula 2], [Formula 3], n is a ratio of 500 to 2,000 g / mol weight average molecular weight satisfies.

이때, 상기 [화학식 1], [화학식 2] 또는 [화학식 3]으로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트는 다음 [화학식 4]로 표시되는 디싸이클로펜타디엔 에폭시수지에 아크릴산을 부가반응시켜 에폭시기를 개환하여 생성될 수 있다.At this time, the dicyclopentadiene epoxy acrylate represented by the above [Formula 1], [Formula 2] or [Formula 3] is an epoxy group by addition reaction of acrylic acid to the dicyclopentadiene epoxy resin represented by the following [Formula 4] It can be produced by ring opening.

[화학식 4][Formula 4]

Figure 112018020077717-pat00013
Figure 112018020077717-pat00013

상기 화학식 4에 있어서, n은 중량평균분자량 500 내지 2,000g/mol을 만족하는 유리수이다.In Chemical Formula 4, n is a rational number satisfying a weight average molecular weight of 500 to 2,000 g / mol.

한편, 본 발명은 상기 [화학식 1]로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트와, 아크릴 모노머와, 에폭시화합물과, 에폭시아크릴레이트를 포함하여 구성되는 3D프린팅용 광경화 수지 잉크조성물을 구성할 수도 있으며, 상기 [화학식 2] 및/또는 [화학식 3]으로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트와, 아크릴 모노머와, 글리시딜에테르화합물과, 옥세탄화합물과, 에폭시화합물과, 에폭시아크릴레이트, 광개시제와, 양이온개시제를 포함하여 구성되는 3D프린팅용 광경화 수지 잉크조성물을 구성할 수도 있다.On the other hand, the present invention may constitute a photocurable resin ink composition for 3D printing comprising a dicyclopentadiene epoxy acrylate, an acrylic monomer, an epoxy compound, and an epoxy acrylate represented by the above [Formula 1]. Dicyclopentadiene epoxy acrylate, an acrylic monomer, a glycidyl ether compound, an oxetane compound, an epoxy compound, an epoxy acrylate, and the like represented by the above [Formula 2] and / or [Formula 3], The photocurable resin ink composition for 3D printing including a photoinitiator and a cationic initiator can also be comprised.

이때, 상기 [화학식 1]로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트 화학구조골격에 에폭시기가 전부 개환되어 아크릴레이트되어 있으므로 아크릴 모노머와, 에폭시화합물과, 에폭시아크릴레이트만을 가교제로 첨가하여 경화시키며, 상기 [화학식 2] 및/또는 [화학식 3]으로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트는 에폭시기와 아크릴레이트기가 동시에 존재하므로 아크릴 모노머와, 글리시딜에테르화합물과, 옥세탄화합물과, 에폭시화합물과, 에폭시아크릴레이트, 광개시제와, 양이온개시제를 포함하여 자외선 조사에 의한 라디칼 방식과 양이온 방식의 경화가 동시에 일어나도록 경화시킨다.In this case, since all the epoxy groups are ring-opened and acrylated in the dicyclopentadiene epoxy acrylate chemical structure skeleton represented by the above [Formula 1], only the acrylic monomer, the epoxy compound, and the epoxy acrylate are added as a crosslinking agent and cured. The dicyclopentadiene epoxy acrylates represented by [Formula 2] and / or [Formula 3] exist simultaneously with an epoxy group and an acrylate group, thereby acryl monomer, glycidyl ether compound, oxetane compound, epoxy compound, Including an epoxy acrylate, a photoinitiator, and a cationic initiator, it is cured so that the curing of the radical method and the cationic method by ultraviolet irradiation occurs simultaneously.

[본 발명의 [화학식 1] 내지 [화학식 3]으로 표시되는 화합물의 합성예][Synthesis example of compound represented by [Formula 1] to [Formula 3] of the present invention]

질소분위기 하에서 상기 [화학식 4]로 표시되는 디싸이클로펜타디엔 에폭시수지와 중합금지제(HQMME)를 상온에서 균질하게 혼합하고, 균질하게 혼합된 혼합물을 1시간 동안 70℃까지 승온하였다. 그 다음, 상기 승온된 혼합물에 아크릴산(Acrylic acid)을 다음 [표 1]의 비율과 같이 투입하여 1.5시간 동안 반응시킨 후, 상기 반응된 반응혼합물을 30분 동안 90℃까지 승온하고, 2시간 동안 유지 반응시켰다. 상기 유지 반응된 반응혼합물을 1시간 동안 40℃까지 냉각시키고 본 발명의 [화학식 1] 내지 [화학식 3]으로 표시되는 화합물을 합성하였다.In a nitrogen atmosphere, the dicyclopentadiene epoxy resin and the polymerization inhibitor (HQMME) represented by the above [Formula 4] were homogeneously mixed at room temperature, and the homogeneously mixed mixture was heated up to 70 ° C. for 1 hour. Then, acrylic acid (Acrylic acid) was added to the heated mixture as shown in the following Table 1 and reacted for 1.5 hours, and then the reaction mixture was heated up to 90 ° C. for 30 minutes and then heated for 2 hours. The reaction was carried out for maintenance. The holding reaction mixture was cooled to 40 ° C. for 1 hour and a compound represented by [Formula 1] to [Formula 3] of the present invention was synthesized.

Figure 112018020077717-pat00014
Figure 112018020077717-pat00014

이때, 상기 아크릴산(Acrylic acid) 투입량에 따라 에폭시기가 완전 개환되어 아크릴레이트가 도입된 [화학식 1]로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트 또는 에폭시기가 부분 개환되어 에폭시기와 아크릴기를 동시에 가지는 [화학식 2] 또는 [화학식 3]으로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트가 생성될 수 있다.At this time, the dicyclopentadiene epoxy acrylate or the epoxy group represented by [Formula 1] in which the epoxy group is completely ring-opened according to the acrylic acid (Acrylic acid) input amount is partially ring-opened to have an epoxy group and an acrylic group at the same time. Or dicyclopentadiene epoxyacrylate represented by [Formula 3].

상기 합성된 [화학식 1]로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트는 [도 1]의 13C-NMR을 동해 확인할 수 있으며, 열변형온도도 [도 2]의 TGA 그래프를통해 확인할 수 있다.The dicyclopentadiene epoxy acrylate represented by the above [Formula 1] can be confirmed by 13 C-NMR of [FIG. 1], and the heat deformation temperature can also be confirmed through the TGA graph of [FIG. 2].

[3D프린팅용 수지 잉크조성물의 제조][Production of Resin Ink Composition for 3D Printing]

[실시예 1]에서 합성된 [화학식 1]로 표시되는 화합물 50g, 펜타에리트리톨트리아크릴레이트(PETA) 25g, 3,4-epoxycyclohexylmethyl methacrylate 25g, bisphenol A epoxy acrylate 25g을 혼합하여 수지조성물을 제조하고 이를 혼합물 1로 하였다.A resin composition was prepared by mixing 50 g of the compound represented by [Formula 1], 25 g of pentaerythritol triacrylate (PETA), 25 g of 3,4-epoxycyclohexylmethyl methacrylate, and 25 g of bisphenol A epoxy acrylate synthesized in [Example 1]. This was taken as mixture 1.

또한, [실시예 1]에서 합성된 [화학식 2] 및 [화학식 3]으로 표시되는 화합물의 혼합물 50g, 펜타에리트리톨트리아크릴레이트(PETA) 25g, 3,4-epoxycyclohexylmethyl methacrylate 25g, bisphenol A epoxy acrylate 25g, 네오펜틸글리콜디글리시딜에테르(NPGDGE) 25g을 균질하게 혼합하고 여기에 3-에틸하이드록시메틸옥세탄, 벤조페논 및 Irgacure 250를 적당량 혼합하여 수지조성물을 제조하고 이를 혼합물 2로 하였다.In addition, 50 g of a mixture of the compounds represented by [Formula 2] and [Formula 3] synthesized in [Example 1], 25 g of pentaerythritol triacrylate (PETA), 25 g of 3,4-epoxycyclohexylmethyl methacrylate, bisphenol A epoxy acrylate 25 g and 25 g of neopentyl glycol diglycidyl ether (NPGDGE) were mixed homogeneously, and 3-ethylhydroxymethyloxetane, benzophenone and Irgacure 250 were mixed in an appropriate amount to prepare a resin composition, which was referred to as Mixture 2.

상기 제조된 혼합물 1은 [도 3]의 13C-NMR을 동해 확인할 수 있으며, 열변형온도도 [도 4]의 TGA 그래프를통해 확인할 수 있다.The prepared mixture 1 can be confirmed by 13 C-NMR of [FIG. 3], the heat distortion temperature can also be confirmed through the TGA graph of [FIG. 4].

[굴곡강도, 열변형온도, 표면경도 비교시험][Comparison Test of Flexural Strength, Heat Deflection Temperature and Surface Hardness]

상기 [실시예 2] 에서 제조된 본 발명의 혼합물 1과 혼합물 2와 비교 실험을 위해 자사의 라디칼 경화 방식의 BPA 에폭시 아크릴계 혼합물의 굴곡강도, 열변형온도, 표면경도를 비교시험하고 그 결과를 다음 [표 2]와 [도 5]에 나타내었다.For comparative experiments with the mixture 1 and the mixture 2 of the present invention prepared in Example 2, the bending strength, heat deformation temperature and surface hardness of the radically curable BPA epoxy acrylic mixture were compared and tested. Table 2 and Figure 5 are shown.

Figure 112018020077717-pat00015
Figure 112018020077717-pat00015

상기 [표 2] 및 [도 5]에 나타난 바와 같이, 본 발명의 잉크조성물은 해상도(미세선폭)이 31~32㎛로서 우수함을 확인할 수 있으며, 굴곡강도, 열변형온도, 표면경도에 있어서도 우수함을 확인하였다. As shown in Table 2 and Figure 5, the ink composition of the present invention can be confirmed that the resolution (microwire width) is excellent as 31 ~ 32㎛, and also excellent in flexural strength, heat deformation temperature, surface hardness. It was confirmed.

이상의 설명은 본 발명의 기술사상을 예시적으로 설명한 것에 불과한 것으로서, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 수정 및 변형이 가능할 것이다. 따라서, 본 발명에 개시된 실시예 및 도면들은 본 발명의 기술 사상을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예 및 도면에 의하여 본 발명의 기술 사상의 범위가 한정되는 것은 아니다. 본 발명의 보호 범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술 사상은 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.The above description is merely illustrative of the technical idea of the present invention, and those skilled in the art to which the present invention pertains may make various modifications and changes without departing from the essential characteristics of the present invention. Therefore, the embodiments and the drawings disclosed in the present invention are not intended to limit the technical spirit of the present invention but to explain, and the scope of the technical idea of the present invention is not limited by these embodiments and the drawings. The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.

Claims (13)

다음 [화학식 1], [화학식 2] 또는 [화학식 3]으로 표시되는 어느 하나 또는 둘 이상의 디싸이클로펜타디엔 에폭시아크릴레이트와 아크릴 모노머를 포함하여 구성되어 자외선 조사에 의한 라디칼 방식과 양이온 방식의 경화가 동시에 일어나는 것을 특징으로 하는 3D프린팅용 광경화 수지 잉크조성물
[화학식 1]
Figure 112018020077717-pat00016

[화학식 2]
Figure 112018020077717-pat00017

[화학식 3]
Figure 112018020077717-pat00018

상기 [화학식 1], [화학식 2], [화학식 3]에 있어서, n은 중량평균분자량 500 내지 2,000g/mol을 만족하는 유리수이다.
Next, any one or two or more dicyclopentadiene epoxyacrylates represented by the following [Formula 1], [Formula 2] or [Formula 3] and acrylic monomers are included, and curing of the radical method and the cationic method by UV irradiation is performed. Photocurable resin composition for 3D printing, characterized in that occur simultaneously
[Formula 1]
Figure 112018020077717-pat00016

[Formula 2]
Figure 112018020077717-pat00017

[Formula 3]
Figure 112018020077717-pat00018

In [Formula 1], [Formula 2], [Formula 3], n is a ratio of 500 to 2,000 g / mol weight average molecular weight satisfies.
제1항에 있어서,
상기 [화학식 1], [화학식 2] 또는 [화학식 3]으로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트는 다음 [화학식 4]로 표시되는 디싸이클로펜타디엔 에폭시수지에 아크릴산을 부가반응시켜 에폭시기를 개환하여 생성되는 것을 특징으로 하는 3D프린팅용 광경화 수지 잉크조성물
[화학식 4]
Figure 112018020077717-pat00019

상기 화학식 4에 있어서, n은 중량평균분자량 500 내지 2,000g/mol을 만족하는 유리수이다.
The method of claim 1,
The dicyclopentadiene epoxy acrylate represented by the above [Formula 1], [Formula 2] or [Formula 3] is added to the dicyclopentadiene epoxy resin represented by the following [Formula 4] by acrylic acid to ring-open the epoxy group Photocurable resin ink composition for 3D printing produced
[Formula 4]
Figure 112018020077717-pat00019

In Chemical Formula 4, n is a rational number satisfying a weight average molecular weight of 500 to 2,000 g / mol.
제1항에 있어서,
상기 아크릴 모노머는 hydroxy ethyl acrylate, hydroxy propyl acrylate, ethyl hexyl acrylate, cyclic-trimethylolpropane-formal acrylate, benzyl acrylate, phenol acrylate, tetrahydrofurfuryl acrylate, nonyl phenol acrylate, ethoxy ethoxy ethyl acrylate, phenoxybenzyl acrylate, lsooctyl acrylate, isododecyl acrylate, lauryl acrylate, tetradecyl acrylate, cetyl acrylate, stearyl acrylate, icosyl acrylate, behenyl acrylate, 3,3,5-trimethyl cyclohexyl acrylate, caprolactone acrylate, 2-carboxyethyl acrylate, bisphenol A acrylate, Bisphenol A diacrylate, (Octahydro-4,7-methano-1H-indenediyl)bis(methylene)diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, hexanediol diacrylate, butanedioldiacrylate,bisphenolfluorene diacrylate, neopentyl glycol diacrylate, hydroxy pivalic neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol tiriacrylate, trimethylolpropane triacrylate, glycerine triacrylate, tris(2-hydroxy ethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, methoxy PEG methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isodecyl methacrylate, lauryl methacrylate, tetradecyl methacrylate, cetyl methacrylate, stearyl methacrylate, 3,3,5 trimethyl cyclohexyl methacrylate, bisphenol A dimethacrylate, 1,6-hexandiol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylene propane trimethacrylate, glycerol trimethacrylate 중에서 선택되는 것을 특징으로 하는 3D프린팅용 광경화 수지 잉크조성물
The method of claim 1,
The acrylic monomers are hydroxy ethyl acrylate, hydroxy propyl acrylate, ethyl hexyl acrylate, cyclic-trimethylolpropane-formal acrylate, benzyl acrylate, phenol acrylate, tetrahydrofurfuryl acrylate, nonyl phenol acrylate, ethoxy ethoxy ethyl acrylate, phenoxybenzyl acrylate, lsooctyl acrylate, isododecyl acrylate lauryl acrylate, tetradecyl acrylate, cetyl acrylate, stearyl acrylate, icosyl acrylate, behenyl acrylate, 3,3,5-trimethyl cyclohexyl acrylate, caprolactone acrylate, 2-carboxyethyl acrylate, bisphenol A acrylate, Bisphenol A diacrylate, (Octahydro-4,7 -methano-1H-indenediyl) bis (methylene) diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, hexanediol diacrylate, butanedioldiacrylate, bisphenolfluorene diacrylate, neopentyl glycol diacrylate, hydroxy pivalic neopentyl glycol diacrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol tiriacrylate, trimethylolpr opane triacrylate, glycerine triacrylate, tris (2-hydroxy ethyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, methoxy PEG methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isodecyl methacrylate, lauryl methacrylate stearyl methacrylate, 3,3,5 trimethyl cyclohexyl methacrylate, bisphenol A dimethacrylate, 1,6-hexandiol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, Photocurable resin composition for 3D printing, characterized in that selected from polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylene propane trimethacrylate, glycerol trimethacrylate
제3항에 있어서,
상기 [화학식 1]로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트와, 아크릴 모노머와, 에폭시화합물과, 에폭시아크릴레이트를 포함하여 구성되는 것을 특징으로 하는 3D프린팅용 광경화 수지 잉크조성물
The method of claim 3,
3D printing photocurable resin ink composition comprising a dicyclopentadiene epoxy acrylate, an acrylic monomer, an epoxy compound, and an epoxy acrylate represented by the above [Formula 1]
제4항에 있어서,
상기 에폭시화합물은 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycycloheylmethyl acrylate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane, 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexanecarboxylate modified epsilon-caprolactone, 4-vinyl-1-cyclohexene 1,2-epoxide, 3-cyclohexen-1-carboxaldehyde, diglycidyl 1,2-cyclohexanedicarboxylate, tetrahydrophthalic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4-vinylcyclohexene dioxide, 1,2:5,6-diepoxyhexahydro-4,7-methanoindan, N,N-diglycidyl-4-glycidyloxyaniline, 4,4'-methylenebis(N,N-diglycidylaniline), 1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylate), 4,4'-(1-methylethylidene)bisphenol polymer with(chloromethyl)oxirane 중에서 선택되는 것을 특징으로 하는 3D프린팅용 광경화 수지 잉크조성물
The method of claim 4, wherein
The epoxy compound is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycycloheylmethyl acrylate, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexylmethyl) epoxy) cyclohexane, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate modified epsilon-caprolactone, 4-vinyl-1-cyclohexene 1,2-epoxide, 3-cyclohexen-1-carboxaldehyde, diglycidyl 1,2-cyclohexanedicarboxylate, tetrahydrophthalic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4-vinylcyclohexene dioxide, 1,2: 5,6-diepoxyhexahydro-4,7-methanoindan, N, N-diglycidyl-4-glycidyloxyaniline , 4,4'-methylenebis (N, N-diglycidylaniline), 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate), 4,4 '-(1-methylethylidene) bisphenol polymer with (chloromethyl) oxirane Photocurable resin composition for 3D printing
제4항에 있어서,
상기 에폭시아크릴레이트는 bisphenol A epoxy acrylate, bisphenol F epoxy acrylate, cresol novolac epoxy acrylate, phenol novolac epoxy acrylate, bisphenyl novlac epoxy acrylate, fatty acid epoxy acrylate, resorcinol epoxy acrylate 중에서 선택되는 것을 특징으로 하는 3D프린팅용 광경화 수지 잉크조성물
The method of claim 4, wherein
The epoxy acrylate is selected from bisphenol A epoxy acrylate, bisphenol F epoxy acrylate, cresol novolac epoxy acrylate, phenol novolac epoxy acrylate, bisphenyl novlac epoxy acrylate, fatty acid epoxy acrylate and resorcinol epoxy acrylate. Resin Ink Composition
제3항에 있어서,
상기 [화학식 2] 및/또는 [화학식 3]으로 표시되는 디싸이클로펜타디엔 에폭시아크릴레이트와, 아크릴 모노머와, 글리시딜에테르화합물과, 옥세탄화합물과, 에폭시화합물과, 에폭시아크릴레이트, 광개시제와, 양이온개시제를 포함하여 구성되는 것을 특징으로 하는 3D프린팅용 광경화 수지 잉크조성물
The method of claim 3,
Dicyclopentadiene epoxy acrylate, an acrylic monomer, a glycidyl ether compound, an oxetane compound, an epoxy compound, an epoxy acrylate, a photoinitiator represented by the above [Formula 2] and / or [Formula 3] , 3D printing photocurable resin ink composition comprising a cationic initiator
제7항에 있어서,
상기 글리시딜에테르화합물은 N-butyl glycidyl ether, aliphatic glycidyl ether(C8-C15), ethylhexyl glycidyl ether, phenyl glycidyl ether, o-cresyl glycidyl ether, m,p-cresyl glycidyl ether, p-tertiary butylphenylglycidylether, 3-alkyl phenol glycidyl ether, octafluoropentyl glycidyl ether, o-phenyl phenol glycidyl ether, benzyl glycidyl ether, 0-sec-butyl phenyl glycidyl ether, 1,4-butanediol glycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexandiol dlycidyl ether, neopentyl glycol diglycidyl ether, 1,4-cyclohexane dimetanol diglycidyl ether, Propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, resorcinol diglycidyl ether, thio-dipheny diglycidyl ether, trimethylolpropane triglycidyl ether, glycerol polyglycidyl ether, caster oil polyglycidyl ether, sorbitol polyglycidyl ether 중에서 선택되는 것을 특징으로 하는 3D프린팅용 광경화 수지 잉크조성물
The method of claim 7, wherein
The glycidyl ether compound is N-butyl glycidyl ether, aliphatic glycidyl ether (C8-C15), ethylhexyl glycidyl ether, phenyl glycidyl ether, o-cresyl glycidyl ether, m, p-cresyl glycidyl ether, p-tertiary butylphenylglycidylether, 3 -alkyl phenol glycidyl ether, octafluoropentyl glycidyl ether, o-phenyl phenol glycidyl ether, benzyl glycidyl ether, 0-sec-butyl phenyl glycidyl ether, 1,4-butanediol glycidyl ether, ethylene glycol diglycidyl ether, 1,6-hexandiol dlycidyl ether , neopentyl glycol diglycidyl ether, 1,4-cyclohexane dimetanol diglycidyl ether, Propylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, resorcinol diglycidyl ether, thio-dipheny diglycidyl ether, trimethylolpropane triglyciylyl ether, glycerol polyd ether Photocurable resin composition for 3D printing, characterized in that selected from ether
제7항에 있어서,
상기 옥세탄화합물은 3-ethyl-hydroxymethyl oxethane, 1,4-bis{[(3-ethyloxetane-3-yl)methoxy]methyl}benzene, 3-ethyl-3-{[(3-ethyloxetane-3-yl)methoxy]methyl}oxetane, 3-ethyl-3-phenoxymethyl oxethane, 3-ethyl-3-(2-ethylhexyl)methyl oxethane, 3-ethyl-3-cyclohexyloxymethyloxetane, phenol novolac oxetane 중에서 선택되는 것을 특징으로 하는 3D프린팅용 광경화 수지 잉크조성물
The method of claim 7, wherein
The oxetane compound is 3-ethyl-hydroxymethyl oxethane, 1,4-bis {[(3-ethyloxetane-3-yl) methoxy] methyl} benzene, 3-ethyl-3-{[(3-ethyloxetane-3-yl ) methoxy] methyl} oxetane, 3-ethyl-3-phenoxymethyl oxethane, 3-ethyl-3- (2-ethylhexyl) methyl oxethane, 3ethyl-3-cyclohexyloxymethyloxetane, phenol novolac oxetane Photocurable Resin Ink Composition
제7항에 있어서,
상기 에폭시화합물은 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycycloheylmethyl acrylate, 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane, 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexanecarboxylate modified epsilon-caprolactone, 4-vinyl-1-cyclohexene 1,2-epoxide, 3-cyclohexen-1-carboxaldehyde, diglycidyl 1,2-cyclohexanedicarboxylate, tetrahydrophthalic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4-vinylcyclohexene dioxide, 1,2:5,6-diepoxyhexahydro-4,7-methanoindan, N,N-diglycidyl-4-glycidyloxyaniline, 4,4'-methylenebis(N,N-diglycidylaniline), 1,4-cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylate), 4,4'-(1-methylethylidene)bisphenol polymer with(chloromethyl)oxirane 중에서 선택되는 것을 특징으로 하는 3D프린팅용 광경화 수지 잉크조성물
The method of claim 7, wherein
The epoxy compound is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycycloheylmethyl acrylate, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexylmethyl) epoxy) cyclohexane, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate modified epsilon-caprolactone, 4-vinyl-1-cyclohexene 1,2-epoxide, 3-cyclohexen-1-carboxaldehyde, diglycidyl 1,2-cyclohexanedicarboxylate, tetrahydrophthalic acid diglycidyl ester, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester, 4-vinylcyclohexene dioxide, 1,2: 5,6-diepoxyhexahydro-4,7-methanoindan, N, N-diglycidyl-4-glycidyloxyaniline , 4,4'-methylenebis (N, N-diglycidylaniline), 1,4-cyclohexanedimethanol bis (3,4-epoxycyclohexanecarboxylate), 4,4 '-(1-methylethylidene) bisphenol polymer with (chloromethyl) oxirane Photocurable resin composition for 3D printing
제7항에 있어서,
상기 에폭시아크릴레이트는 bisphenol A epoxy acrylate, bisphenol F epoxy acrylate, cresol novolac epoxy acrylate, phenol novolac epoxy acrylate, bisphenyl novlac epoxy acrylate, fatty acid epoxy acrylate, resorcinol epoxy acrylate 중에서 선택되는 것을 특징으로 하는 3D프린팅용 광경화 수지 잉크조성물
The method of claim 7, wherein
The epoxy acrylate is selected from bisphenol A epoxy acrylate, bisphenol F epoxy acrylate, cresol novolac epoxy acrylate, phenol novolac epoxy acrylate, bisphenyl novlac epoxy acrylate, fatty acid epoxy acrylate and resorcinol epoxy acrylate. Resin Ink Composition
제7항에 있어서,
상기 광개시제는 phenylbis(2,4,6-trimehylbenzoyl), benzyl dimethyl ketal, hydroxy cyclohexyl phenyl ketone, hydroxyl dimethyl acetophenone, methyl-[4-mehylthio phenyl]-2-morpholine propanone, 2,4-diethylthioxanthone, isopropylthioxanthone propanone, ethyl-4-dimethylaminobenzoate, benzophenone, 4-phenylbenxophenone, 2,4,6-trimethylbenzoyl-diphenyl phosphine, methyl benzoylformate 중에서 선택되는 것을 특징으로 하는 3D프린팅용 광경화 수지 잉크조성물
The method of claim 7, wherein
The photoinitiator is phenylbis (2,4,6-trimehylbenzoyl), benzyl dimethyl ketal, hydroxy cyclohexyl phenyl ketone, hydroxyl dimethyl acetophenone, methyl- [4-mehylthio phenyl] -2-morpholine propanone, 2,4-diethylthioxanthone, isopropylthioxanthone propanone, Photocurable resin composition for 3D printing, characterized in that selected from ethyl-4-dimethylaminobenzoate, benzophenone, 4-phenylbenxophenone, 2,4,6-trimethylbenzoyl-diphenyl phosphine, methyl benzoylformate
제7항에 있어서,
상기 양이온개시제는 Irgacure 250 또는 Irgacure 270(BASF) 중에서 선택되는 것을 특징으로 하는 3D프린팅용 광경화 수지 잉크조성물The method of claim 7, wherein
The cationic initiator is selected from Irgacure 250 or Irgacure 270 (BASF) photocurable resin composition for 3D printing
KR1020180023524A 2018-02-27 2018-02-27 Photo-curable resin ink composition for 3D printing with heat resisting and high mechanical property comprising dicyclopentadien epoxy acrylate KR102048770B1 (en)

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CN110684401A (en) * 2019-11-25 2020-01-14 武汉绿之美铸造材料有限公司 Ink for acrylic acid 3D printing
CA3185920A1 (en) * 2021-06-09 2022-12-09 Altana New Technologies Gmbh Dual cure epoxy inkjet composition
CN114752018A (en) * 2022-03-17 2022-07-15 深圳市泓和顺科技有限公司 Preparation method of UV resin with rapid curing and low shrinkage
CN114621402B (en) * 2022-04-25 2023-07-25 哈尔滨工业大学 Interpenetrating network reinforced shape memory epoxy resin and preparation method thereof
CN114958073B (en) * 2022-05-16 2023-03-24 深圳九星印刷包装集团有限公司 Ultraviolet radiation indicating ink and ultraviolet radiation indicating device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011509313A (en) 2007-11-27 2011-03-24 ハンツマン・アドバンスド・マテリアルズ・アメリカズ・エルエルシー Photocurable resin composition for producing a three-dimensional article having high transparency
JP2014088567A (en) 2013-12-13 2014-05-15 Jnc Corp Photocurable ink for ink-jet
JP6268508B2 (en) 2015-12-24 2018-01-31 三菱ケミカル株式会社 Photosensitive coloring composition, cured product, colored spacer, image display device

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05247120A (en) * 1992-03-03 1993-09-24 Tosoh Corp Production of dicyclopentadieneepoxy (meth)acrylate polymer
KR100838878B1 (en) 2000-04-14 2008-06-16 제트 코포레이션 Compositions for three-dimensional printing of solid objects
US7232850B2 (en) 2003-10-03 2007-06-19 Huntsman Advanced Materials Americas Inc. Photocurable compositions for articles having stable tensile properties
CN101263428A (en) 2005-09-13 2008-09-10 亨斯迈先进材料（瑞士）有限公司 Photocurable compositions for preparing ABS-like articles
KR20120055242A (en) 2010-11-23 2012-05-31 한국생명공학연구원 Photocurable resin composition and method for preparing self-duplicable replica mold using same
JP5927783B2 (en) 2011-06-10 2016-06-01 Jnc株式会社 Photo-curable inkjet ink
KR20160058595A (en) 2014-11-17 2016-05-25 대한잉크 주식회사 The 3D Full Color Ink Composition and 3D soft sculpture formed by using the same
KR20160082280A (en) 2014-12-29 2016-07-08 삼성전자주식회사 Ink compositions for 3d printing, 3d printer and method for controlling of the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011509313A (en) 2007-11-27 2011-03-24 ハンツマン・アドバンスド・マテリアルズ・アメリカズ・エルエルシー Photocurable resin composition for producing a three-dimensional article having high transparency
JP2014088567A (en) 2013-12-13 2014-05-15 Jnc Corp Photocurable ink for ink-jet
JP6268508B2 (en) 2015-12-24 2018-01-31 三菱ケミカル株式会社 Photosensitive coloring composition, cured product, colored spacer, image display device

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