KR0139148B1 - Liquid resin composition for stereolithography - Google Patents
Liquid resin composition for stereolithographyInfo
- Publication number
- KR0139148B1 KR0139148B1 KR1019940026355A KR19940026355A KR0139148B1 KR 0139148 B1 KR0139148 B1 KR 0139148B1 KR 1019940026355 A KR1019940026355 A KR 1019940026355A KR 19940026355 A KR19940026355 A KR 19940026355A KR 0139148 B1 KR0139148 B1 KR 0139148B1
- Authority
- KR
- South Korea
- Prior art keywords
- stereolithography
- resin composition
- liquid resin
- present
- weight
- Prior art date
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 17
- 239000011342 resin composition Substances 0.000 title claims abstract description 16
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 14
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 13
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 3
- 238000001459 lithography Methods 0.000 claims description 3
- 239000008280 blood Substances 0.000 claims 1
- 210000004369 blood Anatomy 0.000 claims 1
- -1 α-hydroxy acetyl Chemical group 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 10
- 239000000178 monomer Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical compound OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- 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 ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08F220/00—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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- 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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
- C08F299/028—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight photopolymerisable compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
본 발명은 스테레오리쏘그래피(Sterolithography)용 액상수지 조성물에 관한 것으로서, 더욱 상세하게는 우레탄 아크릴레이트와 에폭시 아크릴레이트 및 기타 광개시제 및 모노머로 이루어짐으로써 성형 후 고탄성율, 고정밀도, 저수축성 및 개선된 2차 가공성 등을 가지며 휨성질을 방지할 수 있는 스테레오리쏘그래피용 액상수지 조성물에 관한 것이다.The present invention relates to a liquid resin composition for stereolithography, and more particularly, consisting of urethane acrylate, epoxy acrylate, and other photoinitiators and monomers, high modulus, high precision, low shrinkage, and improved after molding. The present invention relates to a liquid resin composition for stereolithography having a difference in workability and preventing warpage properties.
Description
본 발명은 스테레오리쏘그래피(Sterolithography)용 액상수지 조성물에 관한 것으로서, 더욱 상세하게는 우레탄 아크릴레이트와 에폭시 아크릴레이트 및 기타 광개시제 및 헥산디올 디아크릴레이트로 이루어짐으로써 성형 후 고탄성율, 고정밀도, 저수축성 및 개선된 2차 가공성 등을 가지며 휨성질을 방지할 수 있는 스테레오리쏘그래피용 액상수지 조성물에 관한 것이다.The present invention relates to a liquid resin composition for stereolithography (Sterolithography), and more particularly, it consists of urethane acrylate, epoxy acrylate and other photoinitiator and hexanediol diacrylate, high elastic modulus, high precision, low shrinkage And it relates to a liquid resin composition for stereolithography having improved secondary processability and the like and can prevent the warpage properties.
지금까지 3차원 물체의 제조시 기존의 설계도면에 따라 제조하던 금형법은 소요시간과 인력, 정밀도면에서, 문제가 많았으나, 컴퓨터로 제어되는 레이저를 사용하여 액상수지 조성물을 박막경화 적층하여 3차원 물체를 제작하는 방법을 스테레오리쏘그래피라 한다.Until now, the mold method, which was manufactured according to the existing design drawings, had many problems in terms of time, manpower, and precision, but the liquid resin composition was thin-film cured and laminated using a computer controlled laser. The method of making a dimensional object is called stereolithography.
따라서, 스테레오리쏘그래피용 액상수지는 성형 후 성형물이 고탄성률, 고정밀도와 높은 경도를 가지며 우수한 2차 가공성과 저수축성 및 휨성질을 방지할 수 있는 성질이 요구된다.Therefore, the liquid resin for stereolithography is required to have a property that the molded article after molding has a high modulus of elasticity, high precision and high hardness, and can prevent excellent secondary workability, low shrinkage, and warpage properties.
종래의 수지로는 첫째, 우레탄 아크릴레이트와 광개시제 및 모노머로 이루어진 유형이 있으나 이 경우 성형물이 너무 유연하고 정밀도가 떨어지며 2차 가공성이 불량해지는 문제가 있으며, 또 하나의 유형으로 에폭시 아크릴레이트와 광개시제 및 모노머로 이루어지는 경우가 있으나 이 또한 성형물의 탄성율이 낮고, 수축율과 파손율이 높아 스테레오리쏘그래피용으로는 부적당한 문제가 있다.Conventional resins include, firstly, urethane acrylates, photoinitiators, and monomers, but in this case, the moldings are too flexible, have low precision, and have poor secondary processability. In another type, epoxy acrylates and photoinitiators and Although it may be made of a monomer, there is also a problem that the molded article has a low elastic modulus, a high shrinkage ratio and a high breakage ratio, and thus is unsuitable for stereolithography.
또한, 시클로에폭시 아크릴레이트와 양이온 광개시제로 이루어진 또 하나의 유형이 있으나 이 경우 수지보관 및 사용중 습기에 약하고 성형물의 수축성이 높으며 경화성이 낮아 바람직하지 않다.In addition, there is another type consisting of a cycloepoxy acrylate and a cationic photoinitiator, but in this case, it is not preferable to be susceptible to moisture during resin storage and use, high shrinkage of the molding, and low curability.
따라서. 본 발명자들은 상기와 같은 종래기술의 문제점을 극복하고자 노력한 결과 우레탄 아크릴레이트와 에폭시 아크릴레이트를 주성분으로 하고 여기에 광개시제와 헥산디올 디아크릴레이트를 첨가함으로써 성형 후 성형물의 탄성율과 정밀도가 우수하고 저수축성을 가지며 2차 가공성 등이 양호한 본 발명의 스테레오리쏘그래피용 액상수지 조성물을 개발함으로써 본 발명을 완성하였다.therefore. The present inventors have made efforts to overcome the problems of the prior art as a result of the urethane acrylate and epoxy acrylate as a main component and by adding a photoinitiator and hexanediol diacrylate to the molded article after molding, excellent elastic modulus and precision and low shrinkage The present invention was completed by developing a liquid resin composition for stereolithography of the present invention having a secondary processability and the like.
본 발명은 고탄성율과 고정밀도 등을 가지는 등 제반물성이 우수한 스테레오리쏘그래피용 액상수지 조성물을 제공하는데 그 목적이 있다.It is an object of the present invention to provide a liquid resin composition for stereolithography having excellent physical properties such as high elastic modulus and high precision.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 우레탄 아크릴레이트 10∼75중량%, 에폭시 아크릴레이트 10∼75%, 광개시제 1∼5중량 % 및 헥산디올 디아크릴레이트 5∼14중량%로 이루어진 스테레오리쏘그래피용 액상수지 조성물에 관한 것이다.The present invention relates to a liquid resin composition for stereolithography comprising 10 to 75% by weight of urethane acrylate, 10 to 75% of epoxy acrylate, 1 to 5% by weight of photoinitiator and 5 to 14% by weight of hexanediol diacrylate.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 우레탄 아크릴레이트와 에폭시 아크릴레이트를 주성분으로 하여 이루어짐으로써 고탄성률과 고정밀도를 가지는 등 제반물성이 우수하여 스테레오리쏘그래피용으로 적합한 액상수지 조성물에 관한 것으로서, 본 발명의 수지조성물 중 주성분의 하나인 우레탄 아크릴레이트의 함량이 10 중량% 미만이면(에폭시 아크릴레이트의 함량이 75중량%를 초과하면) 탄성률이 낮아지고 수축율과 파손율이 높아지는 문제가 있어 바람직하지 않다.The present invention relates to a liquid resin composition suitable for stereolithography, having excellent elasticity and high precision by being made of urethane acrylate and epoxy acrylate as main components, and comprising a major component of the resin composition of the present invention. If the content of one of the urethane acrylate is less than 10% by weight (the content of the epoxy acrylate exceeds 75% by weight) is not preferable because there is a problem that the elastic modulus is lowered, the shrinkage rate and the breakage rate is increased.
또한, 우레탄 아크릴레이트의 함량이 75중량%를 초과하면(에폭시 아크릴레이트의 함량이 10중량%미만이면) 성형된 성형물이 너무 유연해지고 정밀도가 낮아질 뿐만아니라 2차 가공성이 불량해지는 문제가 있어 스테레오리쏘그래피용으로는 적당하지 않다.In addition, when the content of urethane acrylate exceeds 75% by weight (if the content of epoxy acrylate is less than 10% by weight), the molded molding becomes too flexible and has low precision, and there is a problem of poor secondary workability. It is not suitable for photography.
또한, 본 발명에서 보조성분으로 사용되는 광개시제로는 이소프로필 티옥산톤(Isopropyl thioxanthone) 또는 α,α-디메틸, α-하이드록시 아세토페논(α,α-Dimethyl, α- hydroxy acetophenone)을 사용하는데, 그 사용량이 1∼5중량% 범위를 벗어나면 물성에는 직접적으로 영향을 주지는 않지만 수지의 경화도에 영향을 주어 성형물의 정밀한 가공이 어렵다는 문제가 있다.In addition, the photoinitiator used as an auxiliary component in the present invention uses isopropyl thioxanthone or α, α-dimethyl, α-hydroxy acetophenone (α, α-Dimethyl, α-hydroxy acetophenone). If the amount is out of the range of 1 to 5% by weight, it does not directly affect the physical properties, but there is a problem that it is difficult to precisely process the molding due to the degree of curing of the resin.
그리고, 또 하나의 보조성분으로서 헥산디올 디아크릴레이트를 사용하는데 이는 수지조성물의 점도와 경화된 후의 물성을 조절하기 위해서이고 사용범위를 벗어나면 소기의 목적을 달성하기 어렵다.In addition, hexanediol diacrylate is used as another auxiliary component, which is to control the viscosity of the resin composition and physical properties after curing, and beyond the range of use, it is difficult to achieve the desired purpose.
이와 같은 본 발명의 스테레오리쏘그래피용 액상수지 조성물은 상기와 같은 조성으로 이루어짐으로써 성형 후 성형물이 고탄성율과 고정밀도를 가지고 경도와 2차 가공성이 우수할 뿐아니라 수축성이 낮고 휨성질을 방지할 수 있는 등 스테레오리쏘그래피용 액상수지에 적합한 제반물성을 가짐으로써 전자제품의 부품및 완제품의 모델링, 자동차 부품의 사전 모델링 또는 이러한 성형부품들의 상호결합 및 테스트 분야에 아주 유용하게 사용할 수 있다.Such a liquid lithography composition for stereolithography of the present invention is composed of the composition as described above, the molding after molding has a high modulus and high precision, as well as excellent hardness and secondary workability, it is possible to prevent the shrinkage and bending properties It has various physical properties suitable for liquid lithography for stereolithography, which makes it very useful for modeling electronic parts and finished products, pre-modeling of automotive parts, and mutual coupling and testing of these molded parts.
이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.
[참고예 1 : 우레탄 아크릴레이트의 합성]Reference Example 1: Synthesis of Urethane Acrylate
포리카보네이트 포리올 40g, 헥사메틸렌 디이소시아네이트 37g, 2-하이드록시 에틸메타아크릴레이트 23g을 반응기에 넣고 95℃로 6시간동안 교반한다.40 g of polycarbonate polyol, 37 g of hexamethylene diisocyanate, and 23 g of 2-hydroxy ethylmethacrylate were added to a reactor and stirred at 95 ° C. for 6 hours.
이때 발열이 심하므로 반응기 내온조절에 특히 주의한다. 6시간 후 반응기 내온을 55℃로 고정하고 %NCO를 30분 간격으로 측정하여 0.003% 이하에 도달했을때 토출하여 우레탄 아크릴레이트를 제조하였다.At this time, since the heat generation is severe, pay special attention to the temperature control of the reactor. After 6 hours, the reactor internal temperature was fixed at 55 ° C., and% NCO was measured at 30 minute intervals to discharge when it reached 0.003% or less to prepare a urethane acrylate.
[참고예 2 : 에폭시 아크릴레이트의 합성Reference Example 2: Synthesis of Epoxy Acrylate
반응기에 비스페놀-에프 타입의 에폭시수지 67g을 넣고 약 2시간동안 메타아크릴산 33g을 투입한다. 이때 반응기 내부의 온도는 130℃를 유지하면서 고속 교반기로 교반한다. 메타아크릴산의 투입이 끝나면 반응기의 온도를 70℃로 내린다음 10시간동안 교반하면서 분자량 분포를 조절한다. 분자량 조절이 끝났을 때 토출하여 에폭시 아크릴레이트를 제조하였다.67 g of bisphenol-F type epoxy resin was added to the reactor and 33 g of methacrylic acid was added for about 2 hours. At this time, the temperature inside the reactor is stirred with a high speed stirrer while maintaining 130 ℃. After the addition of methacrylic acid, the temperature of the reactor was lowered to 70 ° C. and the molecular weight distribution was adjusted while stirring for 10 hours. Epoxy acrylate was prepared by discharging when the molecular weight adjustment was completed.
[실시예 1∼6]EXAMPLES 1-6
다음 표 1의 배합비율에 따라 각 성분을 첨가하고 온도 50℃에서 저속 교반기를 사용하여 본 발명의 스테레오리쏘그래피용 액상수지 조성물을 제조하였다.Next, the components were added according to the mixing ratio of Table 1, and the liquid resin composition for stereolithography of the present invention was prepared using a low speed stirrer at a temperature of 50 ° C.
[비교예 1∼4][Comparative Examples 1 to 4]
종래의 수지와 조성성분의 함량이 본 발명의 범위를 벗어난 경우를 비교예로 하고, 그 배합비율을 다음 표 1에 나타내었다.The case where the content of the conventional resin and the composition component is out of the range of the present invention as a comparative example, the compounding ratio is shown in Table 1 below.
[표 1]TABLE 1
(주) (1) α,α-디메틸, α-하이드록시 아세토페논을 사용하였으며, He/Cd 레이저에 적용함.(Note) (1) α, α-dimethyl, α-hydroxy acetophenone was used and applied to He / Cd laser.
(2) 이소프로필 티옥산톤을 사용하였으며, Ar 레이저에 적용함.(2) Isopropyl thioxanthone was used and applied to Ar laser.
(3) 헥산디올 디아크릴레이트를 사용함.(3) Use hexanediol diacrylate.
[실험예]Experimental Example
상기 실시예 1∼6과 비교예 1∼4에서 제조된 액상수지 조성물을 성형하여 시편으로 만든 후 각 물성을 측정한 결과를 다음 표 2에 나타내었다.Table 1 shows the results of measuring the physical properties after molding the liquid resin compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4 to form specimens.
[표 2]TABLE 2
(주) (1) NETZSCH DSC에 의해 측정함.(Note) (1) Measured by NETZSCH DSC.
(2) ASTM D638M 방법에 의해 측정함.(2) Measured by ASTM D638M method.
(3) ASTM D2240 방법에 의해 측정함.(3) Measured by ASTM D2240 method.
(4) ASTM D256A 방법에 의해 측정함.(4) Measured by ASTM D256A method.
상기 표 1과 표 2에 나타낸 것을 분석해 보면, 상기 실시예 1과 4는 우레탄 아크릴레이트가 다량 함유된 것을 특징으로 하며, 경도와 인장강도는 비교적 낮으나, 탁월한 내충격성을 가지므로 경화물의 용융에 있어서 유연성을 요구하는 분야에 적용될 수 있다.Analyzing what is shown in Table 1 and Table 2, Examples 1 and 4 are characterized by containing a large amount of urethane acrylate, the hardness and tensile strength is relatively low, but has excellent impact resistance in the melting of the cured product Applicable to applications requiring flexibility.
또한, 실시예 2와 5는 우레탄 아크릴레이트 53∼55 중량%, 에폭시 아크릴레이트 29∼35 중량%를 함유하는 것을 특징으로 하며, 좋은 인장강도, 경도와 내충격성을 가지므로 경화물의 응용에 있어서 적당한 강도와 유연성을 동시에 요구되는 경우 적용된다.In addition, Examples 2 and 5 are characterized by containing 53 to 55% by weight of urethane acrylate and 29 to 35% by weight of epoxy acrylate, and have good tensile strength, hardness and impact resistance, and thus are suitable for the application of the cured product. Applies when both strength and flexibility are required.
그리고, 실시예 3과 6은 에폭시 아크릴레이트가 다량 함유된 것을 특징으로 하며, 비교적 낮은 내충격성을 가지나 탁월한 경도와 인장강도를 가지므로 경화물의 응용에 있어서 우수한 경도가 요구되는 경우 적용된다.In addition, Examples 3 and 6 are characterized in that the epoxy acrylate is contained in a large amount, has a relatively low impact resistance, but has excellent hardness and tensile strength is applied when excellent hardness is required in the application of the cured product.
이에 대해 비교예 1은 우레탄 아크릴레이트를 77 중량% 사용하므로 현저한 유연성의 증가를 보이나 인장강도와 경도가 아주 감소하므로 경화물이 너무 유연하여 목적한 바의 용도로는 적용하기 어렵고, 비교예 2는 에폭시 아크릴레이트를 79 중량% 사용하므로 경도, 인장강도가 증가하여 아주 강한 경화물을 얻을 수 있으나, 상대적으로 내충격성이 감소하여 작은 충격에도 경화물이 파손되므로 이의 응용에는 부적합하다.On the contrary, in Comparative Example 1, since the urethane acrylate is used by 77% by weight, a marked increase in flexibility is shown, but the tensile strength and hardness are very reduced, so that the cured product is too flexible, and thus it is difficult to be applied to the intended use. Since 79% by weight of epoxy acrylate is used, the hardness and tensile strength are increased to obtain a very strong cured product. However, the impact resistance is reduced and the cured product is broken even in a small impact, which is not suitable for its application.
또한, 비교예 3은 모노머를 19 중량% 사용하므로 경화물의 물성은 지장이 없으나 점도의 감소로 인해 경화 시스템에 적용시 적층의 두께가 감소되므로 견고한 경화물을 제작하기 어려울 뿐아니라, 생산성이 저하되어 적용하기 어렵고, 비교예 4는 모노머를 4 중량% 사용하므로 경화물의 물성에는 사용에 지장이 없으나 점도 상승으로 인하여 경화 시스템에 적용시 적층의 두께증가로 정확한 경화물은 제작할 수 없으므로 본 발명에의 적용은 부적합하다.In addition, Comparative Example 3 uses 19% by weight of monomer, so that the physical properties of the cured product are not affected, but the thickness of the laminate is reduced when applied to the cured system due to the decrease in viscosity, making it difficult to produce a solid cured product and reducing productivity. Since it is difficult to apply, Comparative Example 4 uses 4% by weight of monomer, there is no problem in the properties of the cured product, but the exact cured product can not be produced due to the increase in thickness of the laminate when applied to the cured system due to the increase in viscosity. Is not suitable.
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