KR20030022431A - Thermal crosslinking Polyimide Based Materials And Method For Fabricating Liquid Crystal Display Device By Said It - Google Patents

Thermal crosslinking Polyimide Based Materials And Method For Fabricating Liquid Crystal Display Device By Said It Download PDF

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KR20030022431A
KR20030022431A KR1020010050408A KR20010050408A KR20030022431A KR 20030022431 A KR20030022431 A KR 20030022431A KR 1020010050408 A KR1020010050408 A KR 1020010050408A KR 20010050408 A KR20010050408 A KR 20010050408A KR 20030022431 A KR20030022431 A KR 20030022431A
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liquid crystal
substrate
crystal display
display device
dianhydride
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KR100840669B1 (en
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김성진
김도성
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엘지.필립스 엘시디 주식회사
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    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1337Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723Polyimide, polyamide-imide
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509Filters, e.g. light shielding masks
    • G02F1/133514Colour filters
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1343Electrodes
    • G02F1/134309Electrodes characterised by their geometrical arrangement
    • G02F1/134336Matrix
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76Unipolar devices, e.g. field effect transistors
    • H01L29/772Field effect transistors
    • H01L29/78Field effect transistors with field effect produced by an insulated gate
    • H01L29/786Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F2201/00Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/12Constructional arrangements not provided for in groups G02F1/00 - G02F7/00 electrode
    • G02F2201/123Constructional arrangements not provided for in groups G02F1/00 - G02F7/00 electrode pixel

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Optics & Photonics (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Ceramic Engineering (AREA)
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  • Liquid Crystal (AREA)

Abstract

PURPOSE: A thermal crosslinking polyimide, and a method for manufacturing a liquid crystal display device using the same are provided to compensate a viewing angle without attaching a compensating film to an outer surface of a substrate, thereby reducing size and weight of the liquid crystal display device. CONSTITUTION: Gate wires and data wires(117) are formed on a first substrate(111), crossing each other to define pixels in matrix shape. A thin film transistor is formed at each crossing point of the gate wires and the data wires, and selectively turns on and off data signals of the data wires. A pixel electrode(119) is formed at each pixel. Black matrix(131) is formed on a second substrate(112) to prevent light loss. R,G,B color filter layers(132) are formed between the black matrixes to present colors. Common electrodes(133) apply regular voltage to a liquid crystal layer(150). A high molecular substance is applied to the first substrate or the second substrate. The high molecular substance includes a discotic liquid crystal derivative having a characteristic of compensating an optical viewing angle.

Description

열가교형 폴리이미드계 물질 및 이를 이용한 액정표시소자의 제조방법{Thermal crosslinking Polyimide Based Materials And Method For Fabricating Liquid Crystal Display Device By Said It}Thermal crosslinking polyimide material and method for manufacturing liquid crystal display device using the same {Thermal crosslinking Polyimide Based Materials And Method For Fabricating Liquid Crystal Display Device By Said It}

본 발명은 액정표시소자(LCD ; Liquid Crystal Display Device)에 관한 것으로, 특히 광시야각 보상기능을 가지는 배향막 및 이를 이용한 액정표시소자에 관한 것이다.The present invention relates to a liquid crystal display device (LCD), and more particularly, to an alignment layer having a wide viewing angle compensation function and a liquid crystal display device using the same.

최근, 액티브 매트릭스 액정표시소자는 그 성능이 급속하게 발전함에 따라, 평판 TV, 휴대용 컴퓨터, 모니터 등에 광범위하게 사용되고 있다.In recent years, active matrix liquid crystal display devices have been widely used in flat panel TVs, portable computers, monitors, and the like, as their performance is rapidly developed.

상기 액티브 매트릭스 액정표시소자 중 트위스티드 네마틱(TN : Twisted Nematic) 방식의 액정표시소자가 주로 사용되고 있는데, 트위스티드 네마틱 방식은 두 기판에 각각 전극을 설치하고 액정 방향자가 90°트위스트 되도록 배열한 다음, 전극에 전압을 가하여 액정 방향자를 구동하는 기술이다.Among the active matrix liquid crystal display devices, twisted nematic (TN) type liquid crystal display devices are mainly used. In the twisted nematic method, electrodes are disposed on two substrates and the liquid crystal directors are arranged to be twisted by 90 °. It is a technique of driving a liquid crystal director by applying a voltage to an electrode.

트위스티드 네마틱 방식 액정표시소자는 우수한 콘트라스트(contrast)와 색상 재현성을 제공한다는 이유로 각광받고 있지만, 시야각이 좁다는 고질적인 문제를 안고 있다.Twisted nematic liquid crystal display devices are spotlighted for providing excellent contrast and color reproducibility, but suffer from the chronic problem of narrow viewing angles.

이러한 TN방식의 시야각 문제를 해결하기 위해 디스코틱 액정을 사용한 보상필름이 사용되고 있다.In order to solve the viewing angle problem of the TN method, a compensation film using a discotic liquid crystal is used.

이하, 첨부된 도면을 참조하여 종래 기술에 의한 액정표시소자를 설명하면 다음과 같다.Hereinafter, a liquid crystal display device according to the related art will be described with reference to the accompanying drawings.

도 1은 종래 기술에 의한 액정표시소자의 단면도이다.1 is a cross-sectional view of a liquid crystal display device according to the prior art.

종래의 액정표시소자는 도 1에서와 같이, 서로 대향 배치된 제 1 ,제 2 기판(11,12)과, 상기 두 기판 사이에 형성된 액정층(50)과, 상기 제 1 ,제 2기판(11,12) 외주면에 선택적으로 부착된 보상필름(42)과, 상기 보상필름(42)이 선택적으로 부착된 제 1 ,제 2 기판(11,12) 외주면에 각각 부착되어 특정 파장의 빛만을 투과시키는 편광판(51,52)이 구비된 액정표시소자에 있어서, 상기 제 1 기판(11) 상에는 매트릭스 형태로 배열되어 화소를 정의하는 게이트 배선(미도시) 및 데이터 배선(17)과, 상기 게이트 배선의 주사신호에 의해 데이터 배선(17)의 데이터 전압을 선택적으로 각 화소에 전달하는 스위칭 소자와, 상기 스위칭 소자와 연결되어 데이터 전압이 최종 인가되는 화소전극(19)이 형성되어 있고, 상기 제 2 기판(12) 상에는 빛샘을 방지하기 위해 액정의 배열을 제어할 수 없는 영역에 형성되는 블랙 매트릭스(31)와, 상기 블랙 매트릭스(31) 상에 색상을 구현하기 위한 R,G,B의 컬러필터층(32)과, 상기 컬러필터층(32) 상에서 상기 화소전극(19)과 대향되어 공통전압이 인가되는 공통전극(33)이 형성되어 있다.In the conventional liquid crystal display device, as shown in FIG. 1, the first and second substrates 11 and 12 disposed to face each other, the liquid crystal layer 50 formed between the two substrates, and the first and second substrates ( 11 and 12 are attached to the compensation film 42 selectively attached to the outer circumferential surface and the outer circumferential surfaces of the first and second substrates 11 and 12 to which the compensation film 42 is selectively attached to transmit only light having a specific wavelength. In the liquid crystal display device provided with the polarizing plates 51 and 52, a gate wiring (not shown) and a data wiring 17 arranged in a matrix form on the first substrate 11 to define pixels, and the gate wiring A switching element for selectively transferring the data voltage of the data line 17 to each pixel by a scan signal of the pixel; and a pixel electrode 19 connected to the switching element to finally apply a data voltage to the pixel, and the second On the substrate 12, an array of liquid crystals can be controlled to prevent light leakage. A black matrix 31 formed in a region that cannot be formed, a color filter layer 32 of R, G, and B for realizing color on the black matrix 31, and the pixel electrode on the color filter layer 32. A common electrode 33 to which a common voltage is applied is formed opposite to 19).

이 때, 상기 화소전극(19)에 인가된 데이터 전압과 상기 공통전극(33)에 인가된 공통전압에 의해 액정이 구동되는데, 액정 분자의 균일한 배향을 제어하기 위해 상기 화소전극(19) 또는 공통전극(33) 상면에 제 1 ,제 2 배향막(13a,13b)을 더 구비한다.At this time, the liquid crystal is driven by the data voltage applied to the pixel electrode 19 and the common voltage applied to the common electrode 33. The pixel electrode 19 or First and second alignment layers 13a and 13b are further provided on the upper surface of the common electrode 33.

상기 배향막으로는 폴리이미드(polyimide) 수지가 주로 이용되는데, 배향막에 비등방성을 부여하기 위해 러빙 공정을 행한다. 이러한 폴리이미드막의 두께는 겨우 수백 Å이다.A polyimide resin is mainly used as the alignment film, but a rubbing process is performed to provide anisotropy to the alignment film. The thickness of such a polyimide membrane is only several hundred micrometers.

상기 배향막은 액정과의 친화성 등이 우수한 폴리이미드(polyimide)계 유기고분자 물질이 주로 이용되는데, 일반적으로 폴리이미드산의 용액을 기판에 인쇄하고 건조시켜 이미드화하여 형성한다.The alignment layer is mainly used a polyimide organic polymer material having excellent affinity with liquid crystals, and is generally formed by imidizing a solution of polyimide acid on a substrate and drying it.

이후, 배향막에는 그 표면을 특수 형태의 천으로 러빙하는 러빙법에 의하여 배향패턴이 형성된다.Subsequently, an alignment pattern is formed on the alignment film by a rubbing method for rubbing the surface with a cloth of a special shape.

상기 러빙법은 실시가 용이하고 공정이 단순하기 때문에 액정표시소자의 제조에 널리 이용되고 있다.The rubbing method is widely used in the manufacture of liquid crystal display devices because of easy implementation and simple process.

한편, 상기 보상필름(42)은 TN 방식 액정표시소자에 있어서 협소한 시야각 문제를 해결하기 위해 구비한 것으로, 시각 방향에 따른 빛의 위상변화를 보상하여 시야각을 넓힌다.On the other hand, the compensation film 42 is provided to solve the narrow viewing angle problem in the TN-type liquid crystal display device, and compensates for the phase change of the light according to the visual direction to widen the viewing angle.

보상필름으로는 일축성 필름(uni-axial film), 이축성 필름(bi-axial film) 또는 와이드뷰 필름(wide view film) 등이 있으며, 네마틱 액정에 의한 빛의 위상을 보상하기 위해 주로 디스코틱(discotic) 액정을 사용하여 제작한다.Compensation films include uni-axial films, bi-axial films, or wide view films, and are mainly disco to compensate for the phase of light caused by nematic liquid crystals. It is produced using a tick liquid crystal.

즉, 네마틱 액정은 양성 단축매질(positive uniaxial)로서 이상굴절률(extraordinary refractive index)이 정상굴절률(ordinary refractive index)보다 크고, 디스코틱 액정은 음성 단축매질(negative uniaxial)로서 이상굴절률이 정상굴절률보다 작기 때문에, 디스코틱 액정으로써 방향에 따른 네마틱 액정의 위상차 변화를 줄일 수 있다.In other words, nematic liquid crystals are positive uniaxial and have an extraordinary refractive index greater than ordinary refractive index, and discotic liquid crystals are negative uniaxial and have an abnormal refractive index more than normal refractive index. Since it is small, it can reduce the phase difference change of the nematic liquid crystal according to a direction as a discotic liquid crystal.

상기 보상필름(42)과 편광판(51,52)을 일체형으로 구성하여 기판의 외측면에 부착할 수도 있다.The compensation film 42 and the polarizing plates 51 and 52 may be integrally formed and attached to the outer surface of the substrate.

그러나, 상기와 같은 종래의 액정표시소자는 다음과 같은 문제점이 있다.However, the conventional liquid crystal display device as described above has the following problems.

첫째, 종래에는 TN방식 액정표시소자의 협소한 시야각 문제를 해결하기 위해 기판의 외측면에 보상필름을 더 부착하여 시야각을 보상하였으나, 상기 보상필름으로 틸트 복굴절을 보상하는 데에 한계가 있으며, 보상필름 제작도 용이하지 않아 어려움이 있다.First, in order to solve the narrow viewing angle problem of the TN type liquid crystal display device, a compensation film is further attached to the outer surface of the substrate to compensate the viewing angle, but there is a limitation in compensating the tilt birefringence with the compensation film. Film production is also difficult and difficult.

둘째, 소자에 보상필름이 추가적으로 더 구비되므로 경량박형화의 액정표시소자를 제작하는데 어려움이 있다.Second, since the compensation film is additionally provided in the device, it is difficult to manufacture a liquid crystal display device having a light weight and thinness.

셋째, 종래의 중합형 폴리이미드계 배향막은 내용매성, 치수안정성이 불안하여 세정 용매나 열에 의해 배향 상태가 흐트러지는데, 그로인해 불량이 발생한다.Third, the conventional polymerization type polyimide alignment film is unstable in solvent resistance and dimensional stability, so that the alignment state is disturbed by the cleaning solvent or heat, which causes defects.

본 발명은 상기와 같은 문제점을 해결하기 위하여 안출한 것으로, 광시야각 보상 특성을 가지는 가교형 폴리이미드계 물질 및 이를 이용한 액정표시소자의 제조방법을 제공하는데 그 목적이 있다.The present invention has been made to solve the above problems, and an object thereof is to provide a cross-linked polyimide material having a wide viewing angle compensation characteristics and a method of manufacturing a liquid crystal display device using the same.

도 1은 종래 기술에 의한 액정표시소자의 단면도.1 is a cross-sectional view of a liquid crystal display device according to the prior art.

도 2는 본 발명에 의한 액정표시소자의 단면도.2 is a cross-sectional view of a liquid crystal display device according to the present invention.

*도면의 주요 부분에 대한 부호설명* Explanation of symbols on the main parts of the drawings

111 : 제 1 기판 112 : 제 2 기판111: first substrate 112: second substrate

113 : 배향막 114 : 게이트 전극113 alignment film 114 gate electrode

115 : 게이트 절연막 116 : 반도체층115: gate insulating film 116: semiconductor layer

117 : 데이터 배선 117a : 소스 전극117: data wiring 117a: source electrode

117b : 드레인 전극 118 : 보호막117b: drain electrode 118: protective film

119 : 화소전극 131 : 블랙 매트릭스119: pixel electrode 131: black matrix

132 : 컬러필터층 133 : 공통전극132: color filter layer 133: common electrode

140 : 스페이서 141 : 씨일제140: spacer 141: sealant

150 : 액정층150: liquid crystal layer

상기와 같은 목적을 달성하기 위한 본 발명의 가교형 폴리이미드계 물질은 에폭시기(epoxy group)를 가지는 디스코틱(discotic) 액정 유도체를 포함하는 것을 특징으로 한다.Cross-linked polyimide material of the present invention for achieving the above object is characterized in that it comprises a discotic (discotic) liquid crystal derivative having an epoxy group (epoxy group).

그리고, 상기 가교형 폴리이미드계 물질을 이용한 액정표시소자의 제조방법은 대향 합착된 제 1 기판 및 제 2 기판 사이에 액정층이 구비된 액정표시소자에 있어서, 상기 제 1 기판 또는 제 2 기판의 내측면에 에폭시기를 가지는 디스코틱 액정 유도체를 포함하는 배향막을 형성하는 것을 특징으로 한다.In addition, a method of manufacturing a liquid crystal display device using the crosslinked polyimide material may include a liquid crystal layer provided between a first substrate and a second substrate that are opposed to each other. It is characterized by forming an alignment film containing a discotic liquid crystal derivative having an epoxy group on the inner side.

이하, 첨부된 도면을 참조하여 본 발명에 의한 가교형 폴리이미드계 물질 및이를 이용한 액정표시소자의 제조방법을 상세히 설명하면 다음과 같다.Hereinafter, a cross-linked polyimide material and a method of manufacturing a liquid crystal display device using the same according to the present invention will be described in detail with reference to the accompanying drawings.

도 2는 본 발명에 의한 액정표시소자의 단면도이다.2 is a cross-sectional view of a liquid crystal display device according to the present invention.

먼저, 디아민과 디안하이드라이드를 당량대 당량 반응으로 양측에 디아민을 갖는 화학식 1의 폴리이미드(polyimide)계 물질을 합성한다.First, a polyimide-based material of Chemical Formula 1 having diamine on both sides by an equivalent-to-equivalent reaction of diamine and dianhydride is synthesized.

여기서, 상기 디아민은 2,5-디아미노벤조니트릴(diaminobenzonitrile), 2-(트리플루오로메틸)-1,4-벤젠디아민(2-(trifluoromethyl)-1,4-benzenediamine), p-페닐렌디아민(p-phenyl1enediamine), 2-클로로-1,4-벤젠디아민(2-chloro-1,4-benzenediamine), 2-플루오르-1,4-벤젠디아민(2-fluoro-1,4-benzenediamine), m-페닐렌디아민(m-phenyl1enediamine), 2,5-디아미노톨루엔(2,5-diaminotoluene), 2,6-디아미노톨루엔(2,6-diaminotoluene), 4,4'-디아미노비페닐(4,4'-diaminobiphenyl), 3,3'-디메틸-4,4'-디아미노비페닐(3,3'-dimethyl-4,4'-diaminobiphenyl), 3,3'-디메톡시-4,4'-디아미노비페닐(3,3'-dimethoxy-4,4'-diaminobiphenyl), 디아미노디페닐메탄(diaminodiphenylmethane), 디아미노디페닐 에테르(diaminodiphenyl ether), 2,2-디아미노디페닐프로판(2,2-diaminodiphenylpropane), 비스(3,5-디에틸-4-아미노페닐)메탄(bis(3,5-diethyl-4-aminophenyl)methane), 디아미노디페닐술폰(diaminodiphenylsulfone), 디아미노나프탈렌(diaminonaphthalene), 1,4-비스(4-아미노페녹시)벤젠(1,4-bis(4-aminophenoxy)benzene), 4,4'-디아미노벤조페논(4,4'-diaminobenzophenone), 3,4'-디아미노벤조페논(3,4'-diaminobenzophenone), 1,4-비스(4-아미노페닐)벤젠(1,4-bis(4-aminophenyl)benzene), 9,10-비스(4-아미노페닐)안트라센(9,10-bis(4-aminophenyl)anthracene), 4,4'-비스(4-아미노페녹시)디페닐술폰(4,4'-bis(4-aminophenoxy)diphenylsulfone), 2,2-비스[4-(4-아미노페녹시)페닐]프로판(2,2-bis[4-(4-aminophenoxy)phenyl]propane), 2,2-비스(4-아미노페닐)헥사플루오르프로판(2,2-bis(4-aminophenyl)hexafluoropropane), 2,2-비스[4-(4-아미노페녹시)페닐]헥사플루오로프로판(2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane), 비스(4-아미노사이클로헥실)메탄(bis(4-aminocyclohexyl)methane) 등의 지방족고리 디아민(alicyclic diamine), 테트라메틸렌 디아민(tetramethylene diamine), 헥사메틸렌 디아민(hexamethylene diamine) 등의 지방족 디아민(aliphatic diamine), 비스(3-아미노프로필)테트라메틸디실록산(bis(3-aminopropyl)tetramethyldisiloxane) 등의 디아미노실록산(diaminosiloxane) 그리고, 상기 물질들의 유도체들로 이루어진 군으로부터 선택된다.Here, the diamine is 2,5-diaminobenzonitrile, 2- (trifluoromethyl) -1,4-benzenediamine (2- (trifluoromethyl) -1,4-benzenediamine), p-phenylene P-phenyl1enediamine, 2-chloro-1,4-benzenediamine, 2-fluoro-1,4-benzenediamine , m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4'-diamino ratio Phenyl (4,4'-diaminobiphenyl), 3,3'-dimethyl-4,4'-diaminobiphenyl (3,3'-dimethyl-4,4'-diaminobiphenyl), 3,3'-dimethoxy- 4,4'-diamino-4,4'-diaminobiphenyl, diaminodiphenylmethane, diaminodiphenyl ether, 2,2-diamino Diphenylpropane (2,2-diaminodiphenylpropane), bis (3,5-diethyl-4-aminophenyl) methane (bis (3,5-diethyl-4-aminophenyl) methane), diaminodiphenylsulfone one), diaminonaphthalene, 1,4-bis (4-aminophenoxy) benzene (4,4'-diaminobenzophenone (4,4) '-diaminobenzophenone), 3,4'-diaminobenzophenone, 1,4-bis (4-aminophenyl) benzene, 1,4-bis (4-aminophenyl) benzene, 9 , 10-bis (4-aminophenyl) anthracene (9,10-bis (4-aminophenyl) anthracene), 4,4'-bis (4-aminophenoxy) diphenylsulfone (4,4'-bis (4 -aminophenoxy) diphenylsulfone), 2,2-bis [4- (4-aminophenoxy) phenyl] propane (2,2-bis [4- (4-aminophenoxy) phenyl] propane), 2,2-bis (4 -Aminophenyl) hexafluoropropane (2,2-bis (4-aminophenyl) hexafluoropropane), 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (2,2-bis [4 Alicyclic diamines such as-(4-aminophenoxy) phenyl] hexafluoropropane), bis (4-aminocyclohexyl) methane, tetramethylene diamine, hexamethylene diamine aliphatic diamine such as hexamethylene diamine, diaminosiloxane such as bis (3-aminopropyl) tetramethyldisiloxane, and derivatives of the above materials. Selected from the group.

그리고, 상기 디안하이드라이드는 피로멜리틱 디안하이드라이드(pyromellitic dianhydride), 2,3,6,7-나프탈렌테트라카르복실릭 디안하이드라이드(2,3,6,7-naphthalenetetracarboxylic dianhydride), 1,2,5,6-나프탈렌테트라카르복실릭 디안하이드라이드(1,2,5,6-naphthalenetetracarboxylic dianhydride), 1,4,5,8-나프탈렌테트라카르복실릭 디안하이드라이드(1,4,5,8-naphthalenetetracarboxylic dianhydride), 3,3',4,4'-비페닐테트라카르복실릭 디안하이드라이드(3,3',4,4'-biphenyltetracarboxylic dianhydride), 2,3,2',3'-비페닐테트라카르복실릭 디안하이드라이드(2,3,2',3'-biphenyltetracarboxylic dianhydride), 비스(3,4-디카르복시페닐)에테르 디안하이드라이드(bis(3,4-dicarboxyphenyl)ether dianhydride), 비스(3,4-디카르복시페닐)디페닐술폰 디안하이드라이드(bis(3,4-dicarboxyphenyl)diphenylsulfone dianhydride), 비스(3,4-디카르복시페닐)메탄 디안하이드라이드(bis(3,4-dicarboxyphenyl)methane dianhydride), 2,2-비스(3,4-디카르복시페닐)프로판 디안하이드라이드(2,2-bis(3,4-dicarboxyphenyl)propane dianhydride), 1,1,1,3,3,3-헥사플루오르-2,2-비스(3,4-디카르복시페닐)프로판 디안하이드라이드(1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane dianhydride), 비스(3,4-디카르복시페닐)디메틸실란 디안하이드라이드(bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride), 2,3,4,5-피리딘테트라카르복실릭 디안하이드라이드(2,3,4,5-pyridinetetracarboxylic dianhydride), 1,2,3,4-부탄테트라카르복실릭 디안하이드라이드(1,2,3,4-butanetetracarboxylic dianhydride), 1,2,3,4-사이크로부탄테트라카르복실릭 디안하이드라이드(1,2,3,4-cyclobutanetetracarboxylic dianhydride), 1,2,3,4-사이크로펜탄테트라카르복실릭 디안하이드라이드(1,2,3,4-cyclopentanetetracarboxylic dianhydride), 1,2,4,5-사이크로헥산테트라카르복실릭 디안하이드라이드(1,2,4,5-cyclohexanetetracarboxylic dianhydride), 2,3,5-트리카르복시사이크로펜틸아세틱 에시드 디안하이드라이드(2,3,5-tricarboxycyclopentylacetic acid dianhydride), 3,4-디카르복시-1,2,3,4-테트라하이드로-1-나프탈렌숙시닉 디안하이드라이드(3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride) 등과 그 유도체들 및 Cl-, F- 유도체들로 이루어진 군으로부터 선택된다.In addition, the dianhydride is pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride (2,3,6,7-naphthalenetetracarboxylic dianhydride), 1,2 , 5,6-naphthalenetetracarboxylic dianhydride (1,2,5,6-naphthalenetetracarboxylic dianhydride), 1,4,5,8-naphthalenetetracarboxylic dianhydride (1,4,5,8 -naphthalenetetracarboxylic dianhydride), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (3,3', 4,4'-biphenyltetracarboxylic dianhydride), 2,3,2 ', 3'-ratio Phenyltetracarboxylic dianhydride (2,3,2 ', 3'-biphenyltetracarboxylic dianhydride), bis (3,4-dicarboxyphenyl) ether dianhydride (bis (3,4-dicarboxyphenyl) ether dianhydride), Bis (3,4-dicarboxyphenyl) diphenylsulfon dianhydride (bis (3,4-dicarboxyphenyl) diphenylsulfone dianhydride), bis (3,4-dicarboxyphenyl) methane dianhydride Bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 1 , 1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane dianhydride (1,1,1,3,3,3-hexafluoro-2,2 -bis (3,4-dicarboxyphenyl) propane dianhydride), bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride (bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride), 2,3,4,5-pyridine Tetracarboxylic dianhydride (2,3,4,5-pyridinetetracarboxylic dianhydride), 1,2,3,4-butanetetracarboxylic dianhydride (1,2,3,4-butanetetracarboxylic dianhydride), 1 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride (1,2,3,4-cyclobutanetetracarboxylic dianhydride) , 2,3,4-cyclopentanetetracarboxylic dianhydride), 1,2,4,5-cyclohexanetetracarboxyl 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,4- Dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic Dianhydride (3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride) and the like and derivatives thereof and Cl-, F- derivatives.

참고로, 틸트의 조절이나 용해도를 증가시키기 위해서 상기 두 모노머에 지방족 긴사슬(aliphatic long-chain)을 가지는 유도체를 더 포함하여도 된다.For reference, a derivative having an aliphatic long-chain in the two monomers may be further included to increase tilt control or solubility.

상기에서와 같은 형태로 합성된 중간체(oligomer)인 폴리이미드계 물질에 디스코틱 액정의 관능기를 합성시켜서 에폭시(epoxy)기를 도입한다.An epoxy group is introduced by synthesizing a functional group of a discotic liquid crystal to a polyimide material, which is an intermediate synthesized in the form as described above.

여기서, 상기 디스코틱 액정은 관능기로써 에폭시계열을 가지는 것으로 하기의 화학식 2의 군으로부터 선택된다.Here, the discotic liquid crystal has an epoxy series as a functional group is selected from the group of the following formula (2).

여기서, R은 에폭시기를 가지는Where R has an epoxy group

(n은 정수) 중 어느 하나이다. (n is an integer).

즉, 양측에 디아민을 가지는 폴리이미드계 물질과 에폭시기를 가지는 디스코틱 액정의 유도체를 열을 가하면서 적당한 용매에 녹이면, 폴리이미드의 아민이 디스코틱 액정의 에폭시기와 결합하는데, 이러한 과정의 반복에 의해 광시야각 보상특성을 가지는 열가교형 폴리이미드계 물질이 만들어진다.In other words, when a derivative of a polyimide-based material having a diamine and a discotic liquid crystal having an epoxy group is dissolved in a suitable solvent while being heated, the amine of the polyimide binds to the epoxy group of the discotic liquid crystal by repeating this process. A thermal crosslinked polyimide-based material having wide viewing angle compensation characteristics is made.

상기 용매로는 NMP(N-methylpyrrolidinone), 감마-부틸락톤(γ-butyllactone), BC(Butyl Cellosolve) 등을 사용하며, 상기 용매에 녹여서 1∼30wt%의 용액상을 제조한다.As the solvent, NMP (N-methylpyrrolidinone), gamma-butyllactone (γ-butyllactone), BC (Butyl Cellosolve) and the like are used, and dissolved in the solvent to prepare a solution phase of 1 to 30wt%.

상기 용액상을 이용하여 기판 상에 도포하여 배향막을 형성한 후, 경화시켜 용매를 증발시키면 광시야각 특성을 갖는 가교형 폴리이미드계 배향막이 형성된다.The solution phase is applied onto a substrate to form an alignment layer, and then cured to evaporate the solvent to form a crosslinked polyimide alignment layer having a wide viewing angle characteristic.

이와같이 형성된 배향막은 빛의 방향에 따른 빛의 위상을 보상하여 광시야각을 구현한다.The alignment layer formed as described above compensates for the phase of light according to the direction of light to implement a wide viewing angle.

상기 실시예에서는 1종의 중간체에 1종의 디스코틱 액정을 합성하였지만, 2종 이상의 중간체를 도입하거나 또는 2종 이상의 디스코틱 액정을 도입하여 합성하여도 된다.In the above embodiment, one kind of discotic liquid crystal is synthesized in one kind of intermediate, but two or more kinds of intermediates may be introduced or two or more kinds of discotic liquid crystals may be introduced.

본 발명에 의한 배향막 물질을 액정표시소자의 제조방법에 적용하면 다음과같다.The alignment film material according to the present invention is applied to the method of manufacturing a liquid crystal display device as follows.

먼저, 제 1 기판(111) 상에 서로 절연되는 게이트 배선(미도시) 및 데이터 배선(114)을 수직 교차 형성하여 매트릭스 배열 형태의 화소를 정의하고, 상기 두 배선의 교차점에 게이트 배선의 게이트 전압에 따라 데이터 배선의 데이터 신호를 선택적으로 온/오프(on/off)하는 박막트랜지스터를 형성한 뒤, 각 화소에 상기 박막트랜지스터에 연결되는 화소전극(119)을 형성한다.First, the gate wiring (not shown) and the data wiring 114 which are insulated from each other on the first substrate 111 are vertically formed to define a pixel in a matrix array form, and the gate voltage of the gate wiring is formed at the intersection of the two wirings. As a result, a thin film transistor for selectively turning on / off a data signal of a data line is formed, and then a pixel electrode 119 connected to the thin film transistor is formed in each pixel.

이 때, 상기 박막트랜지스터는 상기 게이트 배선에서 분기된 게이트 전극(114)과, 상기 게이트 전극(114)을 포함한 전면에 형성된 게이트 절연막(115)과, 상기 게이트 전극(114) 상부의 게이트 절연막 상에 형성된 반도체층(116)과, 상기 데이터 배선(117)에서 연장되어 형성된 소스/드레인 전극(117a,117b)으로 이루어진다. 상기 반도체층(116) 위에는 na-Si의 오믹콘택층을 형성할 수도 있다.In this case, the thin film transistor is formed on the gate electrode 114 branched from the gate wiring, the gate insulating film 115 formed on the entire surface including the gate electrode 114, and the gate insulating film on the gate electrode 114. The semiconductor layer 116 is formed and source / drain electrodes 117a and 117b extending from the data line 117. An ohmic contact layer of n + a-Si may be formed on the semiconductor layer 116.

다음, 제 2 기판(112) 상에 빛샘을 막기 위해 형성된 블랙 매트릭스(131)와, 상기 블랙 매트릭스(131) 사이에 형성되어 색상을 표현하는 R,G,B의 컬러필터층(132)과, 상기 화소전극(119)에 대향하여 액정층(150)에 일정 전압을 인가하는 공통전극(133)을 형성한다.Next, a black matrix 131 formed to prevent light leakage on the second substrate 112, a color filter layer 132 of R, G, and B formed between the black matrix 131 to express color, and The common electrode 133 that applies a predetermined voltage to the liquid crystal layer 150 is formed to face the pixel electrode 119.

이후, 상기의 다양한 패턴들이 형성되어 있는 제 1 기판(111) 또는 제 2 기판(112) 상에 광시야각 보상 특성을 가지는 디스코틱(discotic) 액정 유도체를 포함하는 고분자 물질을 회전도포법, 코팅법 등을 이용하여 도포한다.Subsequently, a spin coating method and a coating method are performed on a polymer material including a discotic liquid crystal derivative having a wide viewing angle compensation characteristic on the first substrate 111 or the second substrate 112 on which the various patterns are formed. The coating is carried out using the back.

상기 고분자 물질은 디안하이드라이드와 디아민이 부분적으로 합성된 폴리이미드와 디스코틱 액정을 열을 가하면서 NMP, γ-butyllactone, BC 등에 녹여 1∼30wt%의 용액상의 고분자 물질을 제조한다.The polymer material is dissolved in NMP, γ-butyllactone, BC and the like by heating polyimide and discotic liquid crystal partially synthesized with dianhydride and diamine to prepare a solution-like polymer material of 1 to 30 wt%.

이 때, 틸트의 조절이나 용해도를 증가시키기 위해서 지방족 긴사슬을 가지는 유도체를 포함하여 상기 폴리이미드를 합성하여도 된다.At this time, in order to adjust the tilt and increase the solubility, the polyimide may be synthesized including a derivative having an aliphatic long chain.

이와같이, 디스코틱 액정과 폴리이미드간의 열가교 반응을 유도함으로서 내용매성, 치수 안정성이 뛰어날 뿐만 아니라, 시야각 보상 특성을 가지는 배향막을 얻을 수 있다.In this manner, by inducing a thermal crosslinking reaction between the discotic liquid crystal and the polyimide, an alignment film having excellent solvent resistance and dimensional stability as well as viewing angle compensation characteristics can be obtained.

계속하여, 기판 상에 용액 상태로 도포된 고분자 물질을 경화시켜 내부에 남아 있는 용매를 완전 제거하여 고분자 물질을 고밀도화시킴으로써 배향막(113)을 형성한다.Subsequently, the alignment layer 113 is formed by curing the polymer material applied in a solution state on the substrate to completely remove the solvent remaining therein and densifying the polymer material.

다음, 상기 배향막(113)을 러빙 처리하거나 광조사하여 배향처리한 후, 상기 제 1 기판(111)의 가장자리에 씨일제(141)를 형성하고 제 2 기판(112)의 액티브 영역에 스페이서(140)를 균일하게 산포한 뒤, 제 1 ,제 2 기판(111,112)을 대향 합착시킨다.Next, after the alignment layer 113 is rubbed or irradiated with light to form an alignment process, a sealant 141 is formed at an edge of the first substrate 111 and the spacer 140 is formed in an active region of the second substrate 112. ) Is uniformly distributed, and the first and second substrates 111 and 112 are opposed to each other.

마지막으로, 대향 합착된 두 기판 사이에 액정을 주입하여 액정층(150)을 형성하고 밀봉처리하면 액정표시소자가 완성된다.Finally, a liquid crystal is injected between two oppositely bonded substrates to form the liquid crystal layer 150 and the sealing process is completed.

상기 액정은 통상 네마틱 구조를 가지는 액정으로서 상기한 액정으로는 양의 유전율 이방성, 음의 유전율 이방성을 가지는 것이 가능하고, 카이랄 도펀트(chiral dopant)를 첨가하는 것도 가능하다.The liquid crystal is usually a liquid crystal having a nematic structure, and the liquid crystal may have positive dielectric anisotropy and negative dielectric anisotropy, and chiral dopants may be added.

이와같이 형성된 액정표시소자는 배향막 자체에서 시야각을 보상해주므로 기판 외측면에 시야각 보상을 위한 보상필름을 더 부착하지 않아도 되며 소자의 경량박형화가 이루어진다.Since the liquid crystal display device formed as described above compensates the viewing angle in the alignment layer itself, it is not necessary to attach a compensation film for the viewing angle compensation on the outer surface of the substrate, and the device is made thin.

참고로, 상기 배향막은 러빙배향막으로 사용하여도 되고 광배향막으로 사용하여도 되며, TN(twisted nematic), STN(super twisted nematic), OCB(optically compensated birefrigence), VA(vertical alignment), FLC(ferroelectric liquid crystal display), AFLC(Anti-ferroelectric Liquid Crystal), PDLC(polymer dispersed liquid crystal display), a-Si TFT, poly-Si TFT, MIM(metal-insulator-metal) 등 시야각 보상이 이루어져야 하는 모드에 효과적이다.For reference, the alignment layer may be used as a rubbing alignment layer or a photoalignment layer, and may include twisted nematic (TN), super twisted nematic (STN), optically compensated birefrigence (OCB), vertical alignment (VA), and ferroelectric (FLC). Effective for modes that require viewing angle compensation, including liquid crystal display (AFLC), anti-ferroelectric liquid crystal (AFLC), polymer dispersed liquid crystal display (PDLC), a-Si TFT, poly-Si TFT, and metal-insulator-metal (MIM) to be.

상기와 같은 본 발명에 의한 가교형 폴리이미드계 물질 및 이를 이용한 액정표시소자의 제조방법은 다음과 같은 효과가 있다.The cross-linked polyimide material and the method of manufacturing the liquid crystal display device using the same according to the present invention as described above have the following effects.

첫째, 시야각 보상이 가능한 배향막을 제공하므로 기판 외측면에 시야각 보상을 위한 보상필름을 더 부착하지 않아도 되므로 소자의 경량 박형화가 가능하다.First, since the alignment film capable of viewing angle compensation is provided, it is not necessary to further attach a compensation film for viewing angle compensation on the outer surface of the substrate, thereby enabling a lighter and thinner device.

또한, 보상필름 사용에 따른 비용 및 공정추가 등을 해소할 수 있다.In addition, it is possible to solve the costs and process additions due to the use of compensation film.

둘째, 본발명에 의한 배향막은 열가교형 폴리이미드로써 열안정성을 가지고 있어 배향이 흐트러지지 않고 내용매성이 뛰어나 세정용매의 선정이 용이하다.Second, the alignment film according to the present invention is a thermally cross-linked polyimide, which has thermal stability, so that the alignment is not disturbed, the solvent resistance is excellent, and the cleaning solvent is easily selected.

Claims (10)

에폭시기(epoxy group)를 가지는 디스코틱(discotic) 액정 유도체를 포함하는 것을 특징으로 하는 열가교형 폴리이미드계 물질.A thermal crosslinked polyimide material comprising a discotic liquid crystal derivative having an epoxy group. 「여기서, 상기 디스코틱 액정은"The discotic liquid crystal is 의 군으로부터 선택된다.It is selected from the group of. 이 때, R은Where R is 중 어느 하나이고, n은 정수이다.」And n is an integer. 제 1 항에 있어서, 상기 디스코틱(discotic)은 하기의 화학식1로 표시되는 이미드 중간체로 이루어진 것을 특징으로 하는 열가교형 폴리이미드계 물질.The method of claim 1, wherein the discotic (discotic) is a thermal crosslinked polyimide material, characterized in that consisting of the imide intermediate represented by the formula (1). [화학식 1][Formula 1] 제 2 항에 있어서, 상기 이미드 중간체는 디아민과 디안하이드라이드의 합성체인 것을 특징으로 하는 열가교형 폴리이미드계 물질.3. The thermally crosslinked polyimide material according to claim 2, wherein the imide intermediate is a composite of diamine and dianhydride. 대향 합착된 제 1 기판 및 제 2 기판 사이에 액정층이 구비된 액정표시소자에 있어서,A liquid crystal display device comprising a liquid crystal layer between a first bonded substrate and a second substrate opposed to each other, 상기 제 1 기판 또는 제 2 기판의 내측면에 에폭시기를 가지는 디스코틱 액정 유도체를 포함하는 배향막을 형성하는 것을 특징으로 하는 액정표시소자의 제조방법.An alignment film comprising a discotic liquid crystal derivative having an epoxy group is formed on the inner surface of the first substrate or the second substrate. 제 4 항에 있어서, 상기 제 1 기판 상에 박막트랜지스터와 화소전극을 더 형성하는 것을 특징으로 하는 액정표시소자의 제조방법.The method of claim 4, further comprising forming a thin film transistor and a pixel electrode on the first substrate. 제 1 항에 있어서, 상기 배향막은 화학식 1로 표시되는 이미드 중간체와 화학식 2의 군으로부터 선택되는 디스코틱 액정을 합성하여 제조하는 것을 특징으로 하는 액정표시소자의 제조방법.The method of claim 1, wherein the alignment layer is manufactured by synthesizing an imide intermediate represented by Chemical Formula 1 and a discotic liquid crystal selected from the group of Chemical Formula 2. [화학식 1][Formula 1] [화학식 2][Formula 2] 이 때, R은Where R is 중 어느 하나이고, n은 정수이다.And n is an integer. 제 6 항에 있어서, 상기 이미드 중간체는 디안하이드라이드(dianhydride)와 디아민(diamine)을 합성하여 제조하는 것을 특징으로 하는 액정표시소자의 제조방법.The method of claim 6, wherein the imide intermediate is prepared by synthesizing dianhydride and diamine. 제 6 항에 있어서, 상기 이미드 중간체에 지방족 긴사슬(aliphatic long-chain)을 가지는 유도체를 더 포함하여 합성하는 것을 특징으로 하는 액정표시소자의 제조방법.The method of claim 6, further comprising a derivative having an aliphatic long-chain in the imide intermediate to synthesize the liquid crystal display device. 제 4 항에 있어서, 상기 배향막은 2종 이상의 디스코틱 액정 유도체를 포함하는 것을 특징으로 하는 액정표시소자의 제조방법.The method of claim 4, wherein the alignment layer comprises two or more discotic liquid crystal derivatives. 제 4 항에 있어서, 상기 배향막은 2종 이상의 이미드 중간체를 포함하는 것을 특징으로 하는 액정표시소자의 제조방법.The method of claim 4, wherein the alignment layer comprises two or more kinds of imide intermediates.
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KR101334945B1 (en) * 2006-11-02 2013-11-29 삼성디스플레이 주식회사 Alignment Layer and Liquid Crystal Display Apparatus Having the Same
KR101355145B1 (en) * 2006-12-27 2014-02-04 삼성디스플레이 주식회사 Array substrate and colorfilter substrate, liquid crystal display having the same and method of fabricating the same
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KR101334945B1 (en) * 2006-11-02 2013-11-29 삼성디스플레이 주식회사 Alignment Layer and Liquid Crystal Display Apparatus Having the Same
US8704985B2 (en) 2006-11-02 2014-04-22 Samsung Display Co., Ltd. Alignment layer and liquid crystal display having the same
US9732276B2 (en) 2006-11-02 2017-08-15 Samsung Display Co., Ltd. Alignment layer and liquid crystal display having the same
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