KR101551255B1 - ceramic slurry composition with low viscosity for 3D printing - Google Patents
ceramic slurry composition with low viscosity for 3D printing Download PDFInfo
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Abstract
본 발명은 광경화형 세라믹 슬러리를 이용하여 복잡한 형상의 3차원 세라믹 조형물을 제작하기 위한 것으로서, 3D 프린팅용 세라믹 슬러리 조성물에 있어서, 무기입자 30~80중량부, 광경화성 수지 10~30중량부, 광개시제 및 광증감제 3~10중량부, 반응성 희석제 5~20중량부, 커플링제 0.05~3중량부 및 분산제 0.05~3중량부를 포함하여 이루어진 것을 특징으로 하는 3D 프린팅용 저점도 세라믹 슬러리 조성물 및 이를 DLP 방식을 이용한 3D 프린팅에 의해 조형물을 제조하는 것을 그 기술적 요지로 한다. 또한, 본 발명은 고농도 세라믹 슬러리의 저점도화를 실현하고, 고품질의 조형물을 성형하기 위한 세라믹 슬러리 조성물의 최적 비를 얻어 복잡한 형상의 3차원 세라믹 조형물을 제작할 수 있는 이점이 있다.A ceramic slurry composition for 3D printing comprising 30 to 80 parts by weight of an inorganic particle, 10 to 30 parts by weight of a photo-curing resin, a photoinitiator And 3 to 10 parts by weight of a photosensitizer, 5 to 20 parts by weight of a reactive diluent, 0.05 to 3 parts by weight of a coupling agent, and 0.05 to 3 parts by weight of a dispersing agent. The low viscosity ceramic slurry composition for DLP And a method of manufacturing a sculpture by 3D printing using the method. Further, the present invention has an advantage that a low viscosity of a high-concentration ceramic slurry can be realized and an optimal ratio of a ceramic slurry composition for forming a high-quality molding can be obtained and a three-dimensional ceramic molding of a complex shape can be produced.
Description
본 발명은 광경화형 세라믹 슬러리를 이용하여 복잡한 형상의 3차원 세라믹 조형물을 제작하기 위한 것으로서, 고농도 세라믹 슬러리의 저점도화를 위해 세라믹 슬러리 조성물의 최적 비를 구현하고, 반응성 희석제를 추가하여 세라믹 슬러리 조성물의 점도를 낮추기 위한 3D 프린팅용 저점도 세라믹 슬러리 조성물에 관한 것이다.The present invention relates to a method for producing a three-dimensional ceramic sculpture of complex shape by using a photocurable ceramic slurry, which realizes an optimum ratio of the ceramic slurry composition for lowering the viscosity of the high-concentration ceramic slurry, To a low viscosity ceramic slurry composition for 3D printing for lowering the viscosity.
전자, 정보통신 기술의 발달로 소형화, 고집적화된 전자부품 및 정밀 기계부품의 개발이 요구되고 있다.Development of miniaturized, highly integrated electronic parts and precision mechanical parts is required due to development of electronic and information communication technologies.
종래에는 상기의 전자부품 및 기계부품의 제작시, 필요한 부분까지 플라스틱을 사출 성형하여 제작하여 왔다.Conventionally, plastic parts have been manufactured by injection molding to the necessary parts at the time of manufacturing the above electronic parts and mechanical parts.
그러나, 사출 성형 방법은 금형 제작에 비용 및 시간이 많이 소요되며, 부품 간 편차가 심하고, 패턴 구현 시 복잡한 형태의 패턴 제작에는 한계가 있고, 금형의 경우 소모품으로 수명에도 한계가 있다.However, the injection molding method requires a lot of cost and time to manufacture the mold, there is a large deviation between the parts, there is a limit to the production of the complicated shape pattern when the pattern is realized, and the life time of the mold is also limited.
특히, 사출 부품의 경우에는 두께가 1mm 이상이어야 해서 슬림한 형태의 부품의 제작에는 어려움이 있어, 생산자와 소비자들의 다양한 요구를 충족시키지 못하고 있는 실정이다.Particularly, in the case of injection parts, the thickness must be 1 mm or more, which makes it difficult to manufacture slim parts, and thus it fails to meet various demands of the producers and consumers.
최근에는 이러한 다양한 요구에 맞춰 3D 프린팅 기술에 대한 관심이 급증하고 있으며, 특히 본 발명에서는 광경화성 컴포지트 기반의 3D 프린팅 기술에 대해서 관심이 있으며, 그 중 액체 기반의 재료를 사용하는 DLP(Digital Light Processing) 방식의 3D 프린팅 기술에 대해서 살펴보고자 한다. In recent years, there has been a growing interest in 3D printing technology in response to these various demands. Particularly, in the present invention, there is an interest in 3D printing technology based on a photocurable composite, and DLP (Digital Light Processing ) Type of 3D printing technology.
DLP 방식에 의한 3D 프린팅 기술은 이미지 프로세싱 칩을 프로젝터에 장착하여 광경화성 수지에 마스크 이미지를 투영하여 경화시킴으로써 조형물을 제작하는 방식으로, 스팟(spot) 사이즈가 작은 마이크로 스팟형 디지털 빔을 이용하므로 고해상도 구현이 가능하여 작은 부품을 매우 정교하고 고품질로 생산할 수 있는 장점이 있다. 특히, 마이크로 전자부품 및 정밀 기계 부품의 제작에 활용성이 높은 특징이 있다.The DLP-based 3D printing technology uses a micro spot-type digital beam with a small spot size to mount a image processing chip on a projector and project a mask image onto a photocurable resin to cure it. It is possible to produce small parts with high precision. Particularly, it is highly applicable to the production of micro electronic parts and precision machine parts.
이러한 DLP 방식은 한 층이 경화가 되면 플랫폼이 상승하면서 새로운 슬러리가 다음 층을 형성하기 위해 조형물과 바닥판(bottom plate) 사이로 침투하게 되는데, 이때 슬러리의 농도가 맞지 않으면 여러가지 문제점이 야기되게 된다.In the DLP method, when a layer is cured, the platform rises and a new slurry penetrates between the molding and the bottom plate to form the next layer. If the concentration of the slurry is not proper, various problems are caused.
고농도의 점도가 높은 세라믹 슬러리의 경우 침투가 용이하지 않아 조형물 경화시 빈 공간이 생길 수 있으며, 이에 의해 조형물의 소결시 과도하게 수축되거나 크랙이 생길 염려가 있다. 즉, 고농도 슬러리의 경우 점도가 높아 정밀제어가 가능한 DLP 방식의 3D 프린팅으로 성형이 어려우며, 고품질의 정밀 부품의 제작이 제대로 이루어지지 않게 된다.In the case of a ceramic slurry having a high viscosity and a high viscosity, penetration is not easy and voids may be formed during curing of the molding, which may result in excessive shrinkage or cracking during sintering of the molding. That is, in the case of a high concentration slurry, it is difficult to form a DLP type 3D printing capable of precise control because of high viscosity, and high-quality precision parts can not be produced properly.
종래 기술인 US5496682는 "광중합을 이용한 3차원 소결 무기체 구조" 기술의 경우 광경화성 조성물의 경우 세라믹 또는 금속성 입자에 광경화성 모노머, 해교제 등이 사용되고 있다.Prior art US5496682 discloses a three-dimensional sintered inorganic structure using photopolymerization. In the case of photocurable compositions, photocurable monomers and peptizing agents are used for ceramics or metallic particles.
상기 종래 기술의 경우에도 세라믹 슬러리의 점도를 낮추기 위한 조성물이 포함되어 있지 않으며, 이에 의해 슬러리 내에 기포가 형성되어 조형물의 소결시 수축하게 되며, 제품의 불량을 야기하게 된다.Even in the case of the above-mentioned prior arts, a composition for lowering the viscosity of the ceramic slurry is not included, thereby forming bubbles in the slurry, resulting in shrinkage of the molding during sintering, resulting in defective products.
본 발명은 고농도 세라믹 슬러리의 저점도화를 위해 세라믹 슬러리 조성물의 최적 비를 구현하고, 반응성 희석제를 추가하여 세라믹 슬러리 조성물의 점도를 낮추기 위한 3D 프린팅용 저점도 세라믹 슬러리 조성물의 제공을 그 목적으로 한다.It is an object of the present invention to provide a low viscosity ceramic slurry composition for 3D printing for realizing an optimum ratio of a ceramic slurry composition for lowering the viscosity of a high-concentration ceramic slurry and adding a reactive diluent to lower the viscosity of the ceramic slurry composition.
상기 목적 달성을 위해 본 발명은, DLP 방식의 3D 프린터에 투입되어 소정 형상의 조형물로 제조되는 3D 프린팅용 세라믹 슬러리 조성물에 있어서, 바륨타이타네이트, PZT(lead zirconium titanate) 및 산화물 페라이트 중 어느 하나의 무기입자 30~80중량부, 광경화성 수지 10~30중량부, 광개시제 및 광증감제 3~10중량부, 반응성 희석제 5~20중량부, 커플링제 0.05~3중량부 및 분산제 0.05~3중량부를 포함하여 이루어지며, 상기 반응성 희석제는, 점도 5cps~50cps의 액상 모노아크릴레이트 또는 모노메타아크릴레이트를 사용하는 것을 특징으로 하는 3D 프린팅용 저점도 세라믹 슬러리 조성물을 기술적 요지로 한다.In order to achieve the above object, the present invention provides a ceramic slurry composition for 3D printing, which is produced by molding a predetermined shape into a 3D printer of DLP type, and is characterized in that any one of barium titanate, lead zirconium titanate (PZT) 10 to 30 parts by weight of a photo-curable resin, 3 to 10 parts by weight of a photoinitiator and a photosensitizer, 5 to 20 parts by weight of a reactive diluent, 0.05 to 3 parts by weight of a coupling agent and 0.05 to 3 parts by weight of a dispersant Wherein the reactive diluent is a liquid monoacrylate or monomethacrylate having a viscosity of 5 cps to 50 cps. The present invention also provides a low viscosity ceramic slurry composition for 3D printing.
또한, 상기 무기입자는, 세라믹계 분말로 싸이즈는 0.1~3㎛인 것을 특징으로 하며, 상기 세라믹계 분말은, 복합산화물계로 바륨타이타네이트, PZT(lead zirconium titanate) 또는 산화물 페라이트를 사용하는 것이 바람직하다.Further, the inorganic particles are ceramic-based powders and have a size of 0.1 to 3 μm. The ceramic-based powder is preferably a composite oxide system using barium titanate, lead zirconium titanate (PZT), or oxide ferrite desirable.
또한, 상기 광경화성 수지는, 광경화가 가능한 유기 관능기를 적어도 1관능기 이상 함유하는 에폭시계 아크릴 수지, 에테르계 아크릴 수지, 에스테르계 아크릴 수지 및 우레탄계 아크릴 수지 중에 어느 하나를 사용하는 것이 바람직하다.It is preferable that the photo-curing resin is any one of an epoxy-based acrylic resin, an ether-based acrylic resin, an ester-based acrylic resin and a urethane-based acrylic resin containing at least one functional group capable of photo-curing.
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또한, 상기 세라믹 슬러리 조성물에는, 레벨링제 0.05~3중량부가 더 포함되며, 소포제 0.05~3중량부 더 포함되는 것이 바람직하다.The ceramic slurry composition may further contain 0.05 to 3 parts by weight of a leveling agent and 0.05 to 3 parts by weight of a defoaming agent.
한편, 상기의 세라믹 슬러리 조성물은, DLP 방식의 3D 프린터에 투입되어 소정 형상의 조형물로 제조되고, 소결 공정을 거쳐 조형물의 완성이 이루어지게 되는 것이다.On the other hand, the ceramic slurry composition is put into a 3D printer of the DLP type, and is manufactured into a predetermined shaped product, and the finished product is completed through a sintering process.
본 발명은 고농도 세라믹 슬러리의 저점도화를 실현하고, 고품질의 조형물을 성형하기 위한 세라믹 슬러리 조성물의 최적 비를 얻어 복잡한 형상의 3차원 세라믹 조형물을 제작할 수 있는 효과가 있다.The present invention has an effect of realizing a low viscosity of a high-concentration ceramic slurry and obtaining an optimum ratio of a ceramic slurry composition for forming a high-quality molding, thereby producing a three-dimensional ceramic molding of a complex shape.
특히, 반응성 희석제를 추가하여 고농도 세라믹 슬러리를 저점도화하여, 마이크로 빔을 이용하는 DLP 방식을 이용한 3D 프린팅에 최적화된 광경화성 조성물을 제공하여, 고정밀, 고품질의 부품을 생산해낼 수 있는 효과가 있다.Particularly, a reactive diluent is added to lower the viscosity of the high-concentration ceramic slurry to provide a photo-curing composition optimized for 3D printing using a DLP method using a micro beam, thereby producing high-precision and high-quality parts.
본 발명은 광경화형 세라믹 슬러리를 이용하여 복잡한 형상의 3차원 세라믹 조형물을 제작하기 위한 것으로서, 고농도 세라믹 슬러리의 저점도화를 위해 세라믹 슬러리 조성물의 최적 비를 구현하고, 반응성 희석제를 추가하여 세라믹 슬러리 조성물의 점도를 낮추기 위한 것이다.The present invention relates to a method for producing a three-dimensional ceramic sculpture of complex shape by using a photocurable ceramic slurry, which realizes an optimum ratio of the ceramic slurry composition for lowering the viscosity of the high-concentration ceramic slurry, This is to lower the viscosity.
이에 의해 본 발명은 세라믹 슬러리 조성물의 점도를 낮춰 조형물 경화시 세라믹 슬러리 조성물의 빠른 침투가 가능하여 조형물의 빈 공간을 없애고, 소결공정에 의한 조형물의 수축율을 최소화하여 고품질의 정밀한 조형물을 제조할 수 있는 것이다.Accordingly, the present invention can reduce the viscosity of the ceramic slurry composition and allow rapid penetration of the ceramic slurry composition during the curing of the molding material, thereby eliminating the void space of the molding material and minimizing the shrinkage rate of the molding material by the sintering process to produce a high- will be.
또한, 본 발명은 정밀한 형상 제어가 가능한 DLP 방식의 3D 프린팅 기술에 최적화된 세라믹 슬러리 조성물을 확보하여 복잡한 형상의 세라믹 조형물을 용이하게 성형할 수 있는 것이다.
The present invention also provides a ceramic slurry composition optimized for a DLP type 3D printing technology capable of precise shape control, thereby easily molding a ceramic molding of a complex shape.
이하에서는 본 발명에 대해 상세히 설명하고자 한다.Hereinafter, the present invention will be described in detail.
본 발명은 3D 프린팅용 세라믹 슬러리 조성물에 있어서, 무기입자 30~80중량부, 광경화성 수지 10~30중량부, 광개시제 및 광증감제 3~10중량부, 반응성 희석제 5~20중량부, 커플링제 0.05~3중량부 및 분산제 0.05~3중량부를 포함하여 이루어진 것을 특징으로 한다.The present invention relates to a ceramic slurry composition for 3D printing comprising 30 to 80 parts by weight of inorganic particles, 10 to 30 parts by weight of a photo-curing resin, 3 to 10 parts by weight of a photoinitiator and 5 to 20 parts by weight of a reactive diluent, 0.05 to 3 parts by weight and 0.05 to 3 parts by weight of a dispersing agent.
본 발명에 따른 세라믹 슬러리 조성물은 무용제형으로 무기입자, 광경화성 수지, 광개시제 및 광증감제, 반응성 희석제, 커플링제 및 분산제로 이루어진다.The ceramic slurry composition according to the present invention is composed of an inorganic particle, a photo-curing resin, a photoinitiator, a photosensitizer, a reactive diluent, a coupling agent, and a dispersant as a solventless formulation.
먼저, 상기 무기입자는 세라믹계 분말로, 세라믹 슬러리 내에서의 침강방지를 위해 싸이즈는 0.1~3㎛ 이내를 유지하도록 하며, 그 함량비는 30~80중량부로, 이보다 적은 경우에는 무기입자의 기능을 제대로 수행하지 못하며, 그 보다 많은 경우에는 경화가 제대로 이루어지지 않고, 소결시 파손될 염려가 있다.First, the inorganic particles are ceramic-based powders. The size of the inorganic particles is set to be within a range of 0.1 to 3 占 퐉 in order to prevent sedimentation in the ceramic slurry. The content ratio thereof is 30 to 80 parts by weight, And in many cases, hardening is not properly performed, and there is a fear that the sintering will be broken.
또한, 상기 세라믹계 분말은, 모든 세라믹계 분말을 사용할 수 있으며, 상기 세라믹계 분말은, (a)산화물계로 알루미나, 지르코니아, 실리카, 코디에라이트, 뮬라이트, 마그네시아, 타이타니아 중 어느 하나이거나, (b)탄화물계로 SiC 또는 TiC이거나, (c)질화물계로 Si3N4, AlN, TiN 및 BN 중 어느 하나이거나, (d)복합산화물계로 바륨타이타네이트, PZT(lead zirconium titanate) 또는 산화물 페라이트이거나, (e)금속 산화물과 질화물의 화합물인 옥시나이트라이드계이거나, (f)유리계 분말로 글라스 세라믹 분말 또는 유리 프릿(frit)이거나, 또는 이들의 혼합물 중 어느 하나를 사용할 수 있다.The ceramic powder may be any one selected from the group consisting of (a) oxide, alumina, zirconia, silica, cordierite, mullite, magnesia and titania, SiC or TiC as the carbide system; (c) Si 3 N 4 , AlN, TiN and BN as the nitride system; (d) barium titanate, lead zirconium titanate (PZT) (e) an oxynitride compound which is a compound of a metal oxide and a nitride, or (f) a glass-ceramic powder or glass frit as the glass-based powder, or a mixture thereof.
그리고, 상기 광경화성 수지는 액상 형태로 제공되며, 광경화가 가능한 유기 관능기를 적어도 1관능기 이상 함유하는 에폭시계 아크릴 수지, 에테르계 아크릴 수지, 에스테르계 아크릴 수지 및 우레탄계 아크릴 수지 중 어느 하나를 사용한다.The photocurable resin is provided in a liquid form, and any one of epoxy-based acrylic resin, ether-based acrylic resin, ester-based acrylic resin and urethane-based acrylic resin containing at least one functional group capable of photo-curing is used.
구체적으로는 액상의 아크릴 모노머, 메타아크릴 모노머 등이 사용하며, 조형물의 강도 유지를 위하여 다관능 아크릴레이트를 사용하는 것이 바람직하다.Specifically, a liquid acrylic monomer, a methacrylic monomer, or the like is used, and a polyfunctional acrylate is preferably used to maintain the strength of the molding.
상기 광경화성 수지는 10~30중량부로 사용되며, 이 보다 적은 경우에는 광경화가 제대로 이루어지지 않으며, 점도가 높아져 세라믹 슬러리의 신속한 투입이 이루어지지 않게 된다. 더 많이 첨가하면 수지의 양이 너무 많아 소결 후 수축율이 너무 커져 조형물에 균열이 생기거나 형태 유지가 어렵게 된다.The photo-curing resin is used in an amount of 10 to 30 parts by weight. If it is less than 10 parts by weight, photo-curing is not properly carried out, the viscosity is increased, and the ceramic slurry can not be rapidly injected. If the amount of resin added is too large, the shrinkage ratio after sintering becomes too large, which may cause cracks in the molding or make it difficult to maintain the shape.
그리고, 상기 광개시제 및 광증감제는 자외선을 흡수하여 라디칼 혹은 양이온을 생성시켜 광중합을 개시하는 역할을 하는 것이면 모두 사용할 수 있으며, 예를 들어 벤조인이서 계열을 사용할 수 있다.The photoinitiator and photosensitizer may be any organic photoinitiator that absorbs ultraviolet light to generate radicals or cations to initiate photopolymerization. For example, a benzoin isocyanate series may be used.
상기 광개시제 및 광증감제는 3~10중량부로 사용되는 것이 바람직하며, 이 범위 내에서 적절한 에너지의 자외선을 가했을 시 광중합 반응이 가장 활발하였다.The photopolymerization initiator and the photosensitizer are preferably used in an amount of 3 to 10 parts by weight, and the photopolymerization reaction is most active when ultraviolet rays of appropriate energy are applied within this range.
그리고, 상기 반응성 희석제는 세라믹 슬러리 조성물의 점도와 반응성을 조절하기 위한 것으로서, 말단에 아크릴레이트기 또는 에폭시기를 포함하는 물질로 액상의 모노아크릴레이트 모노머, 모노메타아크릴레이트 모노머 등을 사용한다.The reactive diluent is used to control the viscosity and reactivity of the ceramic slurry composition, and a liquid monoacrylate monomer, monomethacrylate monomer, or the like is used as a material containing an acrylate group or an epoxy group at the terminal.
상기 반응성 희석제는 점도 5cps~50cps의 광경화가 가능하면서도 광경화성 수지의 성분인 다관능 아크릴레이트보다 점도가 낮아 고농도 슬러리 제작에 사용된다.The reactive diluent is capable of light curing at a viscosity of 5 cps to 50 cps and is lower in viscosity than a polyfunctional acrylate, which is a component of a photocurable resin, and is used for producing a high-concentration slurry.
상기 반응성 희석제는 5~20중량부를 사용하며, 이 보다 낮은 경우에는 세라믹 슬러리 조성물의 점도에 거의 영향을 미치지 않으며, 이 보다 높은 경우에는 세라믹 슬러리 조성물의 점도가 너무 낮아져 광경화가 제대로 이루어지지 않게 된다.The reactive diluent is used in an amount of 5 to 20 parts by weight, and if it is lower than the above range, the viscosity of the ceramic slurry composition is hardly affected. If it is higher than the above range, the viscosity of the ceramic slurry composition becomes too low.
그리고, 세라믹 슬러리 조성물에는 커플링제 0.05~3중량부, 분산제 0.05~3중량부가 혼합되어, 무기입자에 유기 작용기를 생성하여 액상의 광경화성 수지에 무기입자가 잘 분산되도록 한다. 각 커플링제와 분산제의 양은 무기입자가 가장 잘 분산될 수 있는 양이다.0.05 to 3 parts by weight of a coupling agent and 0.05 to 3 parts by weight of a dispersing agent are mixed in the ceramic slurry composition to generate an organic functional group in the inorganic particles to allow the inorganic particles to be well dispersed in the liquid photocurable resin. The amount of each coupling agent and dispersant is an amount by which the inorganic particles can be best dispersed.
또한, 상기 세라믹 슬러리 조성물에는 레벨링제 0.05~3중량부가 더 포함되며, 소포제 0.05~3중량부가 더 포함된다.The ceramic slurry composition further contains 0.05 to 3 parts by weight of a leveling agent and 0.05 to 3 parts by weight of a defoaming agent.
상기 레벨링제는 세라믹 슬러리의 슬립성을 향상시켜 광경화시 세라믹 슬러리의 신속한 투입이 가능하도록 하며, 소포제는 세라믹 슬러리 내의 기포 제거로 성형성을 향상시키고, 제품의 불량률을 최소화할 수 있다.The leveling agent improves the slipperiness of the ceramic slurry so that the ceramic slurry can be rapidly injected during the photo-curing. The defoaming agent improves the formability by removing bubbles in the ceramic slurry and can minimize the defective rate of the product.
본 발명에 따른 상기의 최적화된 성분비를 갖는 세라믹 슬러리 조성물은 점도가 500cps~3000cps, 바람직하게는 1000cps 이하로 형성되며, DLP 방식의 3D 프린터에 투입되어 소정 형상의 조형물로 제조되고, 소결 공정을 거쳐 조형물을 완성하게 된다.The ceramic slurry composition having the optimized composition ratio according to the present invention has a viscosity of 500 cps to 3000 cps, preferably 1000 cps or less. The ceramic slurry composition is put into a DLP type 3D printer to be manufactured into a predetermined shape product, And the sculpture is completed.
여기에서 소결 공정은 500℃~2000℃ 사이의 온도에서 이루어지며, 소결 공정이 완료되면 광경화성 수지를 비롯한 유기물 성분은 모두 없어지고, 무기물 성분 만이 소결 공정에 의해 결합되어 단단하게 성형되게 된다.
Here, the sintering process is performed at a temperature between 500 ° C and 2000 ° C. When the sintering process is completed, all the organic components including the photo-curing resin disappear, and only the inorganic component is combined by the sintering process to be hardened.
한편, 본 발명의 일실시예로, 무기입자로 입자 싸이즈가 1㎛인 알루미나 분말 60중량부, 광경화성 수지로 트리메틸올프로판 트리아크릴레이트(trimethylolpropane triacrylate, SR351) 20중량부, 광개시제로 Irgacure 907 5중량부, 광증감제로 Darocur ITX 2중량부, 반응성 희석제 Glycidyl methacrylate, SR379, 10중량부, 커플링제 KBM-503, 1중량부, 분산제 BYK-111, 0.5중량부, 레벨링제 BYK-UV3530, 1중량부, 소포제 BYK-353, 0.5중량부로 혼합하였다. 본 발명의 일실시예 의한 세라믹 슬러리 조성물의 점도는 1000cps 이하였다.
In an embodiment of the present invention, 60 parts by weight of alumina powder having a particle size of 1 mu m as inorganic particles, 20 parts by weight of trimethylolpropane triacrylate (SR351) as a photocurable resin, Irgacure 907 5 1 part by weight of a reactive diluent Glycidyl methacrylate, SR379, 10 parts by weight of a coupling agent KBM-503, 0.5 parts by weight of a dispersing agent BYK-111, 0.5 parts by weight of a leveling agent BYK-UV3530, 1 part by weight , And 0.5 part by weight of antifoaming agent BYK-353. The viscosity of the ceramic slurry composition according to one embodiment of the present invention was 1000 cps or less.
이와 같이 본 발명은 광경화형 세라믹 슬러리를 이용하여 복잡한 형상의 3차원 세라믹 조형물을 제작하기 위한 것으로서, 고농도 세라믹 슬러리의 저점도화를 실현하고, 고품질의 조형물을 성형하기 위한 세라믹 슬러리 조성물의 최적 비를 구현하고자 하는 것이다.As described above, the present invention is to produce a three-dimensional ceramic sculpture of complex shape using a photocurable ceramic slurry, realizes low viscosity of a high-concentration ceramic slurry, and realizes an optimum ratio of a ceramic slurry composition for molding a high quality sculpture I would like to.
특히, 반응성 희석제를 추가하여 고농도 세라믹 슬러리를 저점도화하여, 마이크로 빔을 이용하는 DLP 방식을 이용한 3D 프린팅에 최적화된 광경화성 조성물을 제공하여, 고정밀, 고품질의 부품을 생산해낼 수 있게 된다.In particular, by adding a reactive diluent, the high-concentration ceramic slurry can be made to have a low viscosity, and a photo-curable composition optimized for 3D printing using a DLP method using a micro beam can be provided, so that high-precision and high-quality parts can be produced.
Claims (9)
바륨타이타네이트, PZT(lead zirconium titanate) 및 산화물 페라이트 중 어느 하나의 무기입자 30~80중량부, 광경화성 수지 10~30중량부, 광개시제 및 광증감제 3~10중량부, 반응성 희석제 5~20중량부, 커플링제 0.05~3중량부 및 분산제 0.05~3중량부를 포함하여 이루어지며,
상기 반응성 희석제는,
점도 5cps~50cps의 액상 모노아크릴레이트 또는 모노메타아크릴레이트를 사용하는 것을 특징으로 하는 3D 프린팅용 저점도 세라믹 슬러리 조성물.CLAIMS 1. A ceramic slurry composition for 3D printing, which is injected into a DLP type 3D printer and is manufactured into a predetermined shape,
30 to 80 parts by weight of any one of barium titanate, lead zirconium titanate (PZT) and oxide ferrite, 10 to 30 parts by weight of a photocurable resin, 3 to 10 parts by weight of a photoinitiator and a photosensitizer, 0.05 to 3 parts by weight of a coupling agent and 0.05 to 3 parts by weight of a dispersant,
The reactive diluent may include,
Characterized in that a liquid monoacrylate or monomethacrylate having a viscosity of 5 cps to 50 cps is used as the low viscosity ceramic slurry composition for 3D printing.
세라믹계 분말로 싸이즈는 0.1~3㎛인 것을 특징으로 하는 3D 프린팅용 저점도 세라믹 슬러리 조성물.The method according to claim 1,
The ceramic slurry composition for 3D printing according to claim 1, wherein the ceramic-based powder has a size of 0.1 to 3 占 퐉.
(a)산화물계로 알루미나, 지르코니아, 실리카, 코디에라이트, 뮬라이트, 마그네시아, 타이타니아 중 어느 하나이거나,
(b)탄화물계로 SiC 또는 TiC이거나,
(c)질화물계로 Si3N4, AlN, TiN 및 BN 중 어느 하나이거나,
(d)복합산화물계로 바륨타이타네이트, PZT(lead zirconium titanate) 또는 산화물 페라이트이거나,
(e)금속 산화물과 질화물의 화합물인 옥시나이트라이드계이거나,
(f)유리계 분말로 글라스 세라믹 분말 또는 유리 프릿(frit)이거나,
또는 이들의 혼합물 중 어느 하나인 것을 특징으로 하는 3D 프린팅용 저점도 세라믹 슬러리 조성물.The ceramic powder according to claim 2, wherein the ceramic-
(a) an oxide system selected from the group consisting of alumina, zirconia, silica, cordierite, mullite, magnesia, and titania,
(b) SiC or TiC as the carbide,
(c) a nitride based one of Si 3 N 4 , AlN, TiN, and BN,
(d) complex oxides such as barium titanate, lead zirconium titanate (PZT) or oxide ferrite,
(e) an oxynitride compound which is a compound of a metal oxide and a nitride,
(f) glass-based powder, glass-ceramic powder or glass frit,
Or a mixture thereof. ≪ RTI ID = 0.0 > 11. < / RTI >
광경화가 가능한 유기 관능기를 적어도 1관능기 이상 함유하는 에폭시계 아크릴 수지, 에테르계 아크릴 수지, 에스테르계 아크릴 수지 및 우레탄계 아크릴 수지 중에 어느 하나를 사용하는 것을 특징으로 하는 3D 프린팅용 저점도 세라믹 슬러리 조성물.The photocurable resin composition according to claim 1,
A low viscosity ceramic slurry composition for 3D printing, characterized in that any one of epoxy-based acrylic resin, ether-based acrylic resin, ester-based acrylic resin and urethane-based acrylic resin containing at least one functional group capable of photo-curing is used.
레벨링제 0.05~3중량부가 더 포함되는 것을 특징으로 하는 3D 프린팅용 저점도 세라믹 슬러리 조성물.The ceramic slurry composition according to claim 1,
0.05 to 3 parts by weight of a leveling agent is added to the low-viscosity ceramic slurry composition for 3D printing.
소포제 0.05~3중량부 더 포함되는 것을 특징으로 하는 3D 프린틴용 저점도 세라믹 슬러리 조성물.The ceramic slurry composition according to claim 1,
0.05 to 3 parts by weight of an antifoaming agent is further included in the low viscosity ceramic slurry composition for 3D printing.
500cps~3000cps인 것을 특징으로 하는 3D 프린팅용 저점도 세라믹 슬러리 조성물.The ceramic slurry composition according to claim 1,
Wherein the low-viscosity ceramic slurry composition is in the range of 500 cps to 3000 cps.
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|---|---|---|---|---|
| CN106495670A (en) * | 2016-10-13 | 2017-03-15 | 深圳市撒比斯科技有限公司 | For the adhesive of photocuring pottery 3D printing, its preparation method and application |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4390565A (en) | 1982-08-26 | 1983-06-28 | Lord Corporation | Photocurable compositions for use as ceramic ink vehicles |
| KR100808954B1 (en) | 2000-02-08 | 2008-03-04 | 훈츠만 어드밴스트 머티리얼스(스위처랜드)게엠베하 | Liquid, radiation-curable composition, especially for stereolithography |
| EP2301742A1 (en) * | 2003-07-23 | 2011-03-30 | DSM IP Assets B.V. | Viscosity reducible radiation curable resin composition |
-
2013
- 2013-12-30 KR KR1020130166360A patent/KR101551255B1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4390565A (en) | 1982-08-26 | 1983-06-28 | Lord Corporation | Photocurable compositions for use as ceramic ink vehicles |
| KR100808954B1 (en) | 2000-02-08 | 2008-03-04 | 훈츠만 어드밴스트 머티리얼스(스위처랜드)게엠베하 | Liquid, radiation-curable composition, especially for stereolithography |
| EP2301742A1 (en) * | 2003-07-23 | 2011-03-30 | DSM IP Assets B.V. | Viscosity reducible radiation curable resin composition |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106495670A (en) * | 2016-10-13 | 2017-03-15 | 深圳市撒比斯科技有限公司 | For the adhesive of photocuring pottery 3D printing, its preparation method and application |
| KR101831819B1 (en) * | 2017-01-10 | 2018-02-23 | 경상대학교산학협력단 | The composition for 3D printing using epoxy resin, manufacturing method thereof, and manufacturing method of epoxy fiber |
| KR20190034913A (en) | 2017-09-25 | 2019-04-03 | 주식회사 엠오피(M.O.P Co., Ltd.) | Ceramic/metal slurry composition for digital light processing type 3D printer using surface modified pigment |
| KR20200128235A (en) | 2019-04-22 | 2020-11-12 | 한국화학연구원 | 3D printing Ink Composition for Preparing Catalyst Structure and Method for Preparing Catalyst Structure Using Same |
| KR20220060117A (en) * | 2020-11-04 | 2022-05-11 | 한국세라믹기술원 | Photocurable ceramic complex ink composition and manufacturing method of printed circuit board |
| KR102457877B1 (en) * | 2020-11-04 | 2022-10-24 | 한국세라믹기술원 | Photocurable ceramic complex ink composition and manufacturing method of printed circuit board |
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