KR20010088960A - Liquid Crystal Display using on the Photopolymer Based N-(phenyl)maleimide - Google Patents
Liquid Crystal Display using on the Photopolymer Based N-(phenyl)maleimide Download PDFInfo
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- KR20010088960A KR20010088960A KR1020010051494A KR20010051494A KR20010088960A KR 20010088960 A KR20010088960 A KR 20010088960A KR 1020010051494 A KR1020010051494 A KR 1020010051494A KR 20010051494 A KR20010051494 A KR 20010051494A KR 20010088960 A KR20010088960 A KR 20010088960A
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
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Abstract
Description
본 발명은N-(phenyl)maleimide계 수직광배향재료인 PMI5CA, poly{N- (phenyl)maleimide-co-3-[4-(pentyloxy)cinnamate]propyl-2-hydroxy-1-methacrylate}을 이용한 광배향 VA-LCD mode로서 낮은 임계치 전압, 빠른 응답속도 그리고 고콘트라스트에 관한 발명이다.The present invention is N - (phenyl) maleimide-based vertical photo alignment material is PMI5CA, using poly {N- (phenyl) maleimide- co-3- [4- (pentyloxy) cinnamate] propyl-2-hydroxy-1-methacrylate} The photoalignment VA-LCD mode is an invention regarding low threshold voltage, fast response speed and high contrast.
LCD는 평판표시 소자의 한 종류로 휴대화가 가능, 평판, 박형, 저소비전력, 고화질 등의 장점을 가지고 많은 정보표시 분야에 이용되고 있다. 박막 트랜지스터(thin-film-transister) 기술과 TN (twisted nematic) 모드를 사용한 TFT-LCD가 대화면, 고해상도, 풀컬러라는 고기능을 갖는 디스플레이에 적용되어 상품화되고 있다. 고품위 액정표시소자를 만들기 위해서는 액정의 균일한 배향이 필수적이다. 액정분자를 제어하기 위하여 현재 양산에 사용되고 있는 러빙처리법은 배향이 안정하며 공정이 단순하고 대량생산이 용이하다는 장점을 가지고 있다. 그러나 러빙처리법은 러빙천에 의한 먼지및 오물의 발생과 정전기로 인한 TFT 소자의 파괴, 그리고 배향의 얼룩 등의 문제가 심각하게 제기 되고 있으며, 특히 멀티도메인(Multi-domain)법으로 광시야각을 구현할 때 사진 식각법(Photolithography) 공정이 많이 추가되므로 생산성이 떨어지게 된다. 따라서 액정 배향 방법중 기존의 러빙천에 의한 러빙처리법의 한계를 극복할 수 있는 넌러빙 처리법(rubbing-free treatment)에 의한 액정배향 기술이 필요하게 되었다. 그래서 러빙처리법을 대신하여 액정을 배향시켜 러빙시 수반되는 먼지, 정전기등을 배제 할 수 있는 공정상의장점을 가지며, LCD의 시야각 개선을 위한 화소의 다분할화를 구현할 수 있는 기술로써 광중합 반응을 나타내는 고분자막에 직선 편광된 광을 조사하여 특정 방향을 향한 분자만을 중합 반응시켜 광학 이방성을 발생시키는 광중합법이 연구되고 있으며, 대표적으로 PVCi(poly vinyl cinnamate)등의 TN-LCD용의 광중합 재료로 개발되었다. 하지만 대부분 재료가 backbone 구조가 아크릴(acrylate) 계열의 유연한(flexible) chain으로 이루어져 있어서 실제 LCD 공정에 사용할 수 없다는 과제를 안고 있다. 또한 TN-LCD는 시야각이 협소하고 중간조표시에서 화상이 반전하는 문제점과 완벽한 동화상을 구현하기에는 응답속도가 느리다는 문제점을 가지고 있다. 그래서 광시야각, 고콘트라스트, 고속응답특성을 가진 VA mode가 많이 연구되고 있다. 하지만 VA mode는 단일 VA-LCD로는 광시야각을 확보 할수 없기 때문에 멀티 VA mode을 이용하게 된다. 특히 광배향법은 쉽게 멀티도메인을 통하여 도멘인을 구현 할 수 있다. 그러나 아직 VA-LCD용(수직배향 적용)의 광중합 재료는 미비한 현실이다.LCD is a kind of flat panel display device that can be portable, and has been used in many information display fields with advantages such as flat panel, thin film, low power consumption and high image quality. TFT-LCDs using thin-film-transister technology and twisted nematic (TN) mode have been applied to commercial displays having high-performance displays such as large screens, high resolution, and full color. In order to make a high quality liquid crystal display device, uniform alignment of liquid crystals is essential. The rubbing treatment method currently used in mass production to control liquid crystal molecules has the advantages of stable orientation, simple process, and easy mass production. However, the rubbing treatment method has serious problems such as dust and dirt generation by rubbing cloth, destruction of TFT devices due to static electricity, and staining of orientation. Especially, the multi-domain method can realize a wide viewing angle. When a lot of photolithography process is added, productivity decreases. Therefore, there is a need for a liquid crystal alignment technique by a rubbing-free treatment that can overcome the limitation of the existing rubbing treatment method by the rubbing cloth of the liquid crystal alignment method. So, instead of rubbing treatment, it has the advantages of process to eliminate dust, static electricity, etc. accompanying by rubbing liquid crystal, and it shows photopolymerization reaction as a technology that can realize multi-division of pixel for improving the viewing angle of LCD. A photopolymerization method that produces optical anisotropy by polymerizing and reacting only molecules in a specific direction by irradiating linearly polarized light onto a polymer film has been studied. Representatively, it has been developed as a photopolymerization material for TN-LCD such as PVCi (poly vinyl cinnamate). . However, most materials have a problem that their backbone structure is composed of acrylate-based flexible chains, which cannot be used in actual LCD processes. In addition, TN-LCD has a problem that the viewing angle is narrow, the image is reversed in halftone display, and the response speed is slow to realize a perfect moving picture. Therefore, VA mode with wide viewing angle, high contrast, and high speed response has been studied. However, VA mode uses multi VA mode because it cannot secure wide viewing angle with a single VA-LCD. In particular, the photo-alignment method can easily implement domains through multi-domains. However, photopolymerization materials for VA-LCD (vertical alignment application) are still inadequate.
그래서 본 발명에서는N-(phenyl)maleimide를 포함하는 새로운 수직광배향재료인 PMI5CA를 개발하였다. 개발한 광중합 재료의 TGA 특성을 통해 약 300℃까지 열적 안전성을 얻을 수 있었다. PMI5CA 표면에 편광된 UV를 조사한 광배향 VA-LCD을 이용하여 양호한 V-T 및 응답특성을 얻을 수 있었으며, UV 조사기술을 이용한 멜티도메인법을 사용하여 쉽게 넓은 광시야각을 얻을 수 있다.Therefore, the present invention has developed a new vertical optical alignment material PMI5CA containing N- (phenyl) maleimide. Thermal stability up to about 300 ℃ was obtained through the TGA characteristics of the developed photopolymerized material. By using the photo-aligned VA-LCD irradiated with polarized UV on the surface of PMI5CA, good VT and response characteristics could be obtained, and a wide wide viewing angle could be easily obtained by using the Melti Domain method using UV irradiation technology.
그래서 본 개발에서는 고속응답, 광시야각 그리고 고콘트라스트 등을 구현할 수 있는 VA-LCD 구현을 위해N-(phenyl)maleimide계 수직광배향재료인 PMI5CA의 구조와 합성방법과 PMI5CA을 이용하여 VA-LCD의 구현에 관한 기술적인 방법과 대안을 제시한다.Therefore, in this development, the structure and synthesis method of PMI5CA, a N- (phenyl) maleimide-based vertical optical alignment material, and PMI5CA are used to implement VA-LCD that can realize high-speed response, wide viewing angle, and high contrast. We present technical methods and alternatives for implementation.
본 발명은 차세대에 필요한 LCD 개발의 목표인 넌러빙 배향, 광시야각, 고속응답 그리고 고콘트라스트 등을 구현할 수 있는 VA-LCD mode용 광중합 재료를 제안하고, 이 광중합 재료에 UV를 조사하여 광배향VA-LCD에 구현법에 대하여 자세히 설명한다.The present invention proposes a photopolymerization material for VA-LCD mode that can realize non-rubbing orientation, wide viewing angle, high-speed response and high contrast, which are the goals of LCD development for the next generation, and photo-alignment VA by irradiating UV to the photopolymerization material. -Details on how to implement the LCD.
도 1은 본 발명의N-(phenyl)maleimide를 가지는 새로운 광중합 재료인 PMI5CA의 화학구조와 공중합Figure 1 of the present invention N - (phenyl) new photo polymerization material, the chemical structure and PMI5CA copolymer having a maleimide
도 2은 본 발명의 UV 조사 시스템.2 is a UV irradiation system of the present invention.
도 3은 본 발명의N-(phenyl)maleimide를 가지는 새로운 광중합 재료인 PMI5CA의 TGA 특성Figure 3 is N according to the present invention - a new photo polymerization material properties of the TGA PMI5CA with (phenyl) maleimide
도 4은 본 발명의N-(phenyl)maleimide를 가지는 새로운 광중합 재료인 PMI5CA 표면에서의 UV 조사에 의한 광중합 반응.Figure 4 of the present invention N-photo polymerization reaction caused by UV irradiation in the PMI5CA new surface material having a photo-polymerization (phenyl) maleimide.
도 5은 본 발명의N-(phenyl)maleimide를 가지는 새로운 광중합 재료인 PMI5CA 표면에서의 편광현미경 사진Figure 5 of the present invention is N-polarized light micrograph of the surface of PMI5CA new material having a photo-polymerization (phenyl) maleimide
도 6은 본 발명의 광배향 VA-LCD의 전압-투광율 특성 (보상 필름이 없는 경우)6 is a voltage-transmittance characteristic of the photoalignment VA-LCD of the present invention (without compensation film)
도 7은 러빙처리한 VA-LCD의 전압-투광율 특성 (보상필름이 없는 경우)Figure 7 shows the voltage-transmittance characteristics of the rubbing VA-LCD (without compensation film)
도 8은 본 발명의 광배향 VA-LCD의 응답특성 (보상필름이 없는 경우)8 is a response characteristic of the optical alignment VA-LCD of the present invention (when there is no compensation film)
도 9은 러빙처리한 VA-LCD의 응답특성 (보상필름이 없는 경우)Figure 9 shows the response characteristics of the rubbing VA-LCD (without compensation film)
이하 첨부된 도면에 의해 상세히 설명하면 다음과 같다.Hereinafter, described in detail by the accompanying drawings as follows.
도 1은N-(phenyl)maleimide계 수직 광배향재료인 PMI5CA의 구조와 공중합를 나타낸다. 먼저 4-pentyloxycinnamic acid 1.17g(5mmol)과 GMA 0.71g(5mmol)을 플라스크에 채운 후 3g의 1,4-dioxane에 녹이고 3급아민을 몇 방울 첨가한다. 반응물을 80℃에서 5시간 동안 교반 후 얼음욕조에 10분간 냉각한 다음 메탄올과 증류수를 같은 비율로 섞은 용액에 침전시킨 후 여과, 건조한다. 그 다음 질소 분위기에서,N-(phenyl)maleimide 0.692g (4mmol)과 PM5CA 1.504g (4mmol)를 플라스크에 채우고, 중합 개시제로 2,2'-azobisisobutyronitrile (AIBN) 1mmol을, 용제로 1,4-dioxane을 사용하여 60℃ 에서 12시간 동안 반응 시켰다. 반응 후 메탄올에 침전하여 여과 후 48시간 진공건조 시켰다. 도 1은 공중합과정과 PM5CA의 구조를 나타낸다.1 shows the structure and copolymerization of PMI5CA, an N- (phenyl) maleimide-based vertical photoalignment material. First, fill the flask with 1.17 g (5 mmol) of 4-pentyloxycinnamic acid and 0.71 g (5 mmol) of GMA, dissolve in 3 g of 1,4-dioxane and add a few drops of tertiary amine. The reaction was stirred at 80 ° C. for 5 hours, cooled in an ice bath for 10 minutes, precipitated in a solution mixed with methanol and distilled water in the same ratio, filtered and dried. Then in a nitrogen atmosphere, N - (phenyl) maleimide 0.692g (4mmol) and PM5CA 1.504g (4mmol) are charged in a flask and polymerization initiator to 2,2'-azobisisobutyronitrile (AIBN) 1mmol, as a solvent 1,4 The reaction was carried out at 60 ° C. for 12 hours using dioxane. After the reaction, precipitated in methanol, filtered and dried in vacuo for 48 hours. Figure 1 shows the copolymerization process and the structure of PM5CA.
도 2는 본 발명의 UV 조사 시스템을 나타낸다. PM5CA를 스핀코팅법으로 ITO(indium- tin-oxide) 전극 위에 500Å으로 코팅하여, 150℃에서 1시간 동안 열처리한 기판을 280nm의 파장을 가진 편광 UV광을 경사 조사시켰다. 기판에 UV 를1분, 5분, 10분 20분을 조사하였으며, 사용한 UV의 에너지 밀도는 5.38 mW/㎠ 이다.2 shows a UV irradiation system of the present invention. PM5CA was coated on the indium tin oxide oxide (ITO) electrode by spin coating at 500 kPa, and the substrate heat-treated at 150 ° C. for 1 hour was irradiated with polarized UV light having a wavelength of 280 nm. The substrate was irradiated with UV for 1 minute, 5 minutes, and 10 minutes 20 minutes, and the energy density of the used UV was 5.38 mW / cm 2.
도 3는N-(phenyl)maleimide계 수직 광배향재료인 PMI5CA 기판에 UV 조사하여 4-domain 형성하는 방법을 나타낸다. Photomask를 도 3의 1st domain과 같이 만들고 UV를 조사하면 구멍난 부분만 UV가 조사되고 나머지 부분은 mask로 가려지므로 구명난 부분만 광배향이 된다. 두 번째는 photomask의 위치를 2nd domain 같이 만들고 UV를 조사하면 2번째부분에 광배향이 되며, 나머지 부분도 mask의 위치만 변화시키고 UV 조사하면 쉽게 4-domain을 구현 할 수 있다.3 shows a method of forming 4-domain by UV irradiation on a PMI5CA substrate which is an N- (phenyl) maleimide-based vertical photoalignment material. When the photomask is made as in the 1st domain of FIG. 3 and irradiated with UV, only pores are irradiated with UV, and the remaining parts are masked, so only the rescued parts are photo-oriented. The second is to make the photomask position like 2nd domain, and if it is irradiated with UV, it becomes photo-alignment in the second part, and the remaining part can be easily realized by changing only the position of mask and irradiating UV.
도 4는 본 발명의N-(phenyl)maleimide를 가지는 새로운 광중합 재료인 PMI5CA의 TGA곡선을 나타낸다. 새로운 광폴리머인 PMI5CA는 약 300℃까지 열적 안정을 얻었다.4 N of the present invention shows the TGA curves of PMI5CA a new material having a photo-polymerization (phenyl) maleimide. The new photopolymer, PMI5CA, achieved thermal stability up to about 300 ° C.
도 5는 본 발명의N-(phenyl)maleimide를 가지는 새로운 광중합 재료인 PMI5CA 표면에서의 UV 조사에 의한 광중합 반응을 나타낸다. UV 스펙트럼은 250∼350nm사이의 자외선 전영역에서 흡수가 일어남을 알 수 있다. 특히 그림에서 cinnamate group의 스펙트럼 피크가 250∼350nm임을 알수 있었으며, UV 조사시간이 증가함에따라 C=C bond가 감소함을 알 수 있었다.5 is a N of the present invention shows a photo polymerization reaction caused by UV irradiation in the PMI5CA new surface material having a photo-polymerization (phenyl) maleimide. The UV spectrum can be seen that the absorption occurs in the entire ultraviolet region between 250 ~ 350nm. In particular, it can be seen that the spectral peak of the cinnamate group is 250-350 nm, and the C = C bond decreases with increasing UV irradiation time.
도 6는 본 발명의N-(phenyl)maleimide를 가지는 새로운 광중합 재료인 PMI5CA 표면에서의 편광현미경 사진을 나타낸다. 인가전압 5 (V)에 대한 on-off 특성은 매우 양호한 콘트라스트를 나타내었다.Figure 6 is N of the present invention shows a polarization microscopic photograph of the surface of PMI5CA new material having a photo-polymerization (phenyl) maleimide. The on-off characteristic for the applied voltage 5 (V) showed very good contrast.
도 7 과 도 8에는 본 발명의N-(phenyl)maleimide를 가지는 새로운 광중합 재료인 PMI5CA 표면을 이용한 광중합 VA-LCD와 러빙 VA-LCD 의 전압-투과율 곡선을 나타낸다. 도 7 에서 보는 바와 같이, 1분간 PUV(polarized UV) 조사한 광배향 VA-LCD는 임계치 전압(V10)은 2.35 [V]로 러빙한 VA-LCD보다 (V10: 2.56 [V])보다 낮은 임계치 전압을 얻었다. 즉 PMI5CA 표면에 1분간 PUV 조사한 광중합 VA-LCD가 양호한 전압 대투과율 곡선을 얻을 수 있다.7 and 8, the N of the present invention shows a transmittance curve - (phenyl) new photo polymerization material of a photo-polymerization surface PMI5CA VA-LCD of the VA-LCD using a rubbing voltage having a maleimide. As shown in FIG. 7, the photo-aligned VA-LCD irradiated with PUV (polarized UV) for 1 minute was lower than the V-LCD (V 10 : 2.56 [V]) which had a threshold voltage (V 10 ) of 2.35 [V]. The threshold voltage was obtained. That is, the photopolymerization VA-LCD irradiated with PUV on the surface of PMI5CA for 1 minute can obtain a good voltage-to-transmission curve.
도 9과 도 10에는 본 발명의N-(phenyl)maleimide를 가지는 새로운 광중합 재료인 PMI5CA 표면을 이용한 광중합 VA- LCD와 러빙 처리한 VA-LCD의 응답특성을 나타낸다. 1분간 PUV 조사한 광배향 VA-LCD가 가장 양호한 응답 특성을 얻었으며, 응답 속도도 40.9[ms]로 러빙 VA-LCD와 비슷한 응답속도를 나타내었다. 그러므로 액정의 유전율, 셀갭을 적절히 조절함으로써 고속응답을 얻을 수 있다.Figure 9 and Figure 10, the N of the present invention represents a (phenyl) new photopolymerizable material, and photopolymerization VA- LCD rubbing a VA-LCD of the response characteristics with PMI5CA surface with a maleimide. The PUV-irradiated photo-aligned VA-LCD obtained the best response, and the response speed was 40.9 [ms], which was similar to rubbing VA-LCD. Therefore, high-speed response can be obtained by appropriately adjusting the dielectric constant and cell gap of the liquid crystal.
또한 도 3과 같은 UV 조사기술을 이용하여 쉽게 멀티도메인을 만들 수가 있어, 우수한 광시야각을 얻을 수 있다.In addition, it is possible to easily create a multi-domain using the UV irradiation technology as shown in Figure 3, it is possible to obtain an excellent wide viewing angle.
따라서, 본 발명은N-(phenyl)maleimide를 가지는 새로운 광중합 재료인 PMI5CA 표면을 이용한 광배향법으로 고속응답, 고콘트라스트 그리고 UV 조사기술을 이용한 멀티도메인법으로 넓은 광시야각을 실현할 수 있다.Accordingly, the invention is N - it is possible to realize a (phenyl) high-speed response, high contrast and a wide viewing angle in a multi-domain method using UV irradiation to the photo alignment method using a new photo polymerization PMI5CA surface material having a maleimide.
본 발명은N-(phenyl)maleimide를 가지는 새로운 광중합 재료인 PMI5CA 표면을 이용한 VA-LCD 모드에 관한 발명이다. 이 재료은 기존의 아크릴 재료와 달리N-(phenyl)maleimide을 backbone으로 이용하여 열적 안전성과 좋은 액정배향특성을 얻었다. 이 광중합 재료를 이용한 VA-LCD는 기존의 VA 모드의 장점인 고속응답과 고콘트라스트 특성을 향상시킬 수 있으며, 보상필름을 사용하지 않고 UV 조사기술을 이용한 멀티도메인 방법을 이용하여 넓은 광시야각을 쉽게 얻을 수 있다. 따라서 본 발명은 액정 디스플레이에서 안고 있는 문제인 광시야각 및 고콘트라스트 등의 문제를 해결하며, 셀 제작의 공정 수를 최소한으로 줄일 수 있는 매우 우수한 광배향 VA-LCD 재료이며, 액정표시장치의 산업에 크게 기여할 것으로 기대된다.The present invention is N - the invention relates to a VA-LCD mode using a new photo polymerization PMI5CA surface material having a (phenyl) maleimide. Unlike conventional acrylic materials, this material uses N- (phenyl) maleimide as backbone to obtain thermal stability and good liquid crystal orientation. VA-LCD using this photopolymerization material can improve the high-speed response and high contrast characteristics, which are advantages of the existing VA mode, and easily use a wide domain angle using a multi-domain method using UV irradiation technology without using a compensation film. You can get it. Accordingly, the present invention solves problems such as wide viewing angle and high contrast, which are problems in liquid crystal displays, and is an excellent optical alignment VA-LCD material that can reduce the number of cell manufacturing processes to a minimum. It is expected to contribute.
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