KR100423213B1 - Method of manufacturing liquid crystal alignment film and liquid crystal display element - Google Patents
Method of manufacturing liquid crystal alignment film and liquid crystal display element Download PDFInfo
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- KR100423213B1 KR100423213B1 KR1019960021434A KR19960021434A KR100423213B1 KR 100423213 B1 KR100423213 B1 KR 100423213B1 KR 1019960021434 A KR1019960021434 A KR 1019960021434A KR 19960021434 A KR19960021434 A KR 19960021434A KR 100423213 B1 KR100423213 B1 KR 100423213B1
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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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- 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
- G02F1/133723—Polyimide, polyamide-imide
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Abstract
본 발명은 액정 배향막의 제조 방법 및 액정 표시 소자에 관한 것이다. 더욱 상세하게는, 러빙 처리를 실시하지 않고, 직선 편광된 자외선 조사에 의해 액정 배향능을 부여하는 것을 특징으로 하는 액정 배향막의 제조 방법 및 그 액정 배향막을 갖는 액정 표시 소자에 관한 것이다.The present invention relates to a method of manufacturing a liquid crystal alignment film and a liquid crystal display device. More specifically, the present invention relates to a process for producing a liquid crystal alignment film characterized by imparting liquid crystal aligning ability by linearly polarized ultraviolet irradiation without rubbing treatment, and a liquid crystal display device having the liquid crystal alignment film.
Description
본 발명은 액정 배향막의 제조 방법 및 액정 표시 소자에 관한 것이다. 더욱 상세하게는, 러빙 처리를 실시하지 않고 직선 편광된 자외선 조사에 의해 액정 배향능을 부여하는 것을 특징으로 하는 액정 배향막의 제조 방법 및 그 액정 배향막을 갖는 액정 표시 소자에 관한 것이다.The present invention relates to a method of manufacturing a liquid crystal alignment film and a liquid crystal display device. More specifically, the present invention relates to a process for producing a liquid crystal alignment film characterized by imparting liquid crystal aligning ability by linearly polarized ultraviolet irradiation without rubbing treatment, and a liquid crystal display device having the liquid crystal alignment film.
종래, 포지티브 유전 이방성을 갖는 네마틱형 액정을 액정 배향막을 갖는 투명 전극이 부착된 기판에서 샌드위치 구조로 하고, 액정 분자의 장축이 기판 사이에서 90°이상 연속적으로 비틀어지게하여 이루어진 TN(Twisted Nematic)형, STN(Super Twisted Nematic)형 액정 셀을 갖는 액정 표시 소자가 알려져 있다.Conventionally, a TN (twisted nematic) type liquid crystal display device has been proposed in which a nematic liquid crystal having positive dielectric anisotropy is made into a sandwich structure on a substrate to which a transparent electrode having a liquid crystal alignment film is attached and a long axis of the liquid crystal molecule is continuously twisted , And STN (Super Twisted Nematic) type liquid crystal cell are known.
상기, 액정 셀에서의 액정을 배향시키는 수단에는, 기판 표면에 유기막을 형성하고, 계속하여 그 유기막 표면을 레이온 등의 천으로 한 방향으로 문질러줌으로써 액정 배향능을 부여하는(러빙 처리 실시) 방법, 기판 표면에 산화규소를 시방(斜方) 증착하는 방법, 렁뮤어 프로젝트법(LB법)을 사용하여 장쇄 알킬기를 갖는 분자막을 형성하는 방법 등이 있으나, 처리하는 기판의 사이즈에 제약이 있거나, 처리 시간이나 처리 비용면에서 공업적으로는 러빙 처리에 의한 액정의 배향이 일반적이다.The means for orienting the liquid crystal in the liquid crystal cell includes a method in which an organic film is formed on the surface of the substrate and the surface of the organic film is rubbed in one direction with a cloth such as rayon to give a liquid crystal aligning ability , A method of obliquely depositing silicon oxide on the substrate surface, and a method of forming a molecular film having a long-chain alkyl group using the Lungmuir Project method (LB method). However, there is a limitation in the size of the substrate to be processed , And in terms of processing time and processing cost, alignment of liquid crystal by rubbing treatment is generally used industrially.
그러나, 액정의 배향을 러빙 처리에 의해 실시하면, 그 공정 중에 정전기가 발생하기 쉽다는 문제점이 있다. 정전기가 발생하면, 배향막 표면에 먼지가 부착하여, 표시 불량이 발생하는 원인이 되고, 또 TFT(박막 트렌지스터) 소자를 갖는 액정 셀의 경우, 발생된 정전기에 의해 TFT 소자의 회로 파괴가 일어나서, 수율 저하의 원인이 되기도 한다. 더욱이, 금후 점점 고정채화(高精彩化)되는 액정 표시 소자에 있어서는, 화소 밀도가 높아지기 때문에, 러빙 처리의 균일성이 문제가 된다. 본 발명의 목적은, 정전기가 발생하지 않고 생산성이 우수한 액정 배향막의 제조 방법 및 이 액정 배향막을 사용한 액정 표시 소자를 제공하는 것이다.However, if the orientation of the liquid crystal is performed by rubbing treatment, there is a problem that static electricity is liable to be generated during the process. In the case of a liquid crystal cell having a TFT (thin film transistor) element, circuit breakdown of the TFT element occurs due to the generated static electricity, so that the yield It also causes degradation. In addition, in a liquid crystal display element which is getting more and more finer (more refined) in the future, the pixel density becomes higher, so that the uniformity of the rubbing process becomes a problem. An object of the present invention is to provide a process for producing a liquid crystal alignment film which is free from static electricity and which is excellent in productivity, and a liquid crystal display device using the liquid crystal alignment film.
본 발명에서의 액정 배향막의 제조 방법은, 투명 전극이 부착된 기판 상에 자외선에 관능하는 유기 화합물을 함유하는 액정 배향제를 도포 및 건조하여 형성한 박막 상에, 직선 편광된 자외선을 조사함으로서 액정 배향능을 부여하는 액정 배향막의 제조 방법이다.The method for producing a liquid crystal alignment film in the present invention is a method for manufacturing a liquid crystal alignment film by applying linearly polarized ultraviolet rays onto a thin film formed by applying and drying a liquid crystal aligning agent containing an organic compound that is sensitive to ultraviolet rays on a substrate having a transparent electrode, And a liquid crystal alignment film.
또한, 본 발명에서의 액정 표시 소자는 상기의 액정 배향막을 갖는 것을 특징으로 한다.Further, the liquid crystal display element in the present invention is characterized by having the above liquid crystal alignment film.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
액정 배향제Liquid crystal aligning agent
본 발명의 액정 배향막을 형성하는 액정 배향제는, 자외선에 관능하는 유기 화합물을 함유한다. 여기서 "관능"이란 자외선 조사를 받으면, 광 여기 반응에 의해 에너지 준위가 높아지고, 이어서 에너지를 방출하여 안정 상태로 되돌아가는 것을 의미한다. 이와 같은 유기 화합물로서는, 칼콘(벤잘아세토페논) 구조, 스틸벤 구조, 안트라퀴논 구조 및 카르바졸 구조 중 어느 하나를 갖는 중합체를 예시할 수 있다. 바람직하게는 (1) 폴리아미드산 및 폴리이미드로부터 선택되는 적어도 1종의 중합체(2) 폴리에스테르 (3) 폴리아미드 중 어느 하나가 선택된다. 특히, 내열성이 우수하다는 점에서 폴리아미드산 및 폴리이미드가 바람직하다.The liquid crystal aligning agent for forming the liquid crystal alignment film of the present invention contains an organic compound that is sensitive to ultraviolet rays. Herein, " sensory " means that when the ultraviolet ray is irradiated, the energy level is increased by the photoexcitation reaction, and then the energy is released to return to the stable state. Examples of such organic compounds include polymers having either a chalcone (benzalacetophenone) structure, a stilbene structure, an anthraquinone structure, or a carbazole structure. Preferably, any one of (1) at least one polymer selected from polyamic acid and polyimide (2), and polyester (3) polyamide is selected. Particularly, polyamide acid and polyimide are preferable from the viewpoint of excellent heat resistance.
상기 폴리아미드산은 (a) 테트라카르복실산 이무수물과 (b) 디아민 화합물을 반응시켜 수득된다. 본 발명에서 사용되는 폴리아미드산은 (a) 테트라카르복실산 이무수물 성분과 (b) 디아민 성분 중 적어도 하나의 성분에 칼콘(벤잘아세토페논) 구조, 스틸벤 구조, 안트라퀴논 구조 및 카르바졸 구조를 갖는 화합물이 사용된다.The polyamic acid is obtained by reacting (a) a tetracarboxylic acid dianhydride and (b) a diamine compound. The polyamic acid used in the present invention is a polyamic acid having a chalcone (benzalacetophenone) structure, a stilbene structure, an anthraquinone structure and a carbazole structure in at least one of (a) a tetracarboxylic dianhydride component and (b) Is used.
칼콘 구조를 갖는 테트라카르복실산 이무수물로서, 예를 들면 3,3',4,4'-칼콘 테트라카르복실산 이무수물을 들 수 있다. 스틸벤 구조를 갖는 테트라카르복실산 이무수물로서는, 예를 들면 3,3',4,4'-스틸벤테트라카르복실산 이무수물을 들 수 있다. 안트라퀴논 구조를 갖는 테트라카르복실산 이무수물으로서는, 예를 들면 2,3,6,7-안트라퀴논테트라카르복실산 이무수물을 들 수 있다. 카르바졸 구조를 갖는 테트라카르복실산 이무수물로서는, 예를 들면 2,3,6,7-카르바졸테트라카르복실산 이무수물을 들 수 있다.Examples of the tetracarboxylic acid dianhydride having a chalcone structure include 3,3 ', 4,4'-chalcone tetracarboxylic dianhydride. Examples of the tetracarboxylic acid dianhydride having a stilbene structure include 3,3 ', 4,4'-stilbene tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride having an anthraquinone structure include 2,3,6,7-anthraquinonetetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride having a carbazole structure include 2,3,6,7-carbazole tetracarboxylic acid dianhydride.
칼콘 구조를 갖는 디아민 화합물로서는, 예를 들면 3,3'-디아미노칼콘, 4,4'-디아미노칼콘, 3,4'-디아미노칼콘, 3,4-디아미노칼콘 등을 들 수 있다. 스틸벤 구조를 갖는 디아민 화합물로서는, 예를 들면 3,3'-디아미노스틸벤, 4,4'-디아미노스틸벤, 4,4'-디아미노스틸벤-2,2'-술폰산,4,4'-비스(4-아미노-1-나프틸아조)-2,2'-스틸벤술폰산 등을 들 수 있다. 안트라퀴논 구조를 갖는 디아민 화합물로서는, 예를 들면 1,2-디아미노안트라퀴논, 1,4-디아미노안트라퀴논, 1,5-디아미노안트라퀴논, 1,4-디아미노안트라퀴논-2,3-디시아노-9,10-안트라퀴논 등을 들 수 있다. 카르바졸 구조를 갖는 디아민 화합물로서는, 예를 들면 3,6-디아미노카르바졸 등을 들 수 있다.Examples of the diamine compound having a chalcone structure include 3,3'-diamino chalcone, 4,4'-diamino chalcone, 3,4'-diamino chalcone, and 3,4-diamino chalcone . Examples of the diamine compound having a stilbene structure include 3,3'-diaminostilbene, 4,4'-diaminostilbene, 4,4'-diaminostilbene-2,2'-sulfonic acid, 4 , 4'-bis (4-amino-1-naphthylazo) -2,2'-stilbene sulfonic acid and the like. Examples of the diamine compound having an anthraquinone structure include 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 1,4-diaminoanthraquinone- 3-dicyano-9,10-anthraquinone, and the like. The diamine compound having a carbazole structure includes, for example, 3,6-diaminocarbazole.
본 발명에서 사용되는 폴리아미드산에는, 본 발명의 효과를 손상하지 않을 정도로 다른 테트라카르복실산 이무수물 및 디아민 화합물을 병용할 수 있다. 다른 테트라카르복실산 이무수물 및 디아민 화합물의 배합 비율은, 총 테트라카르복실산 이무수물 또는 총 디아민 화합물에 대하여 95 몰% 이하, 바람직하게는 90 몰% 이하의 양이다.The polyamic acid to be used in the present invention may be used in combination with other tetracarboxylic acid dianhydride and diamine compound to such an extent as not to impair the effect of the present invention. The mixing ratio of the other tetracarboxylic acid dianhydride and the diamine compound is 95 mol% or less, preferably 90 mol% or less, based on the total tetracarboxylic dianhydride or the total diamine compound.
다른 테트라카르복실산 이무수물으로서는, 예를 들면 2,3,5-트리카르복시 시클로펜틸카르복실산 이무수물, 부탄테트라카르복실산 이무수물, 1,2,3,4-시클로부탄테트라카르복실산 이무수물, 1,2,3,4-시클로펜탄테트라카르복실산 이무수물, 3,5,6-트리카르복시노르보르난-2-아세트산 이무수물, 2,3,4,5-테트라히드로푸란테트라카르복실산 이무수물, 1,3,3a,4,5,9b-헥사히드로-5-(테트라히드로-2,5-디옥소-3-푸라닐)-나프토[1,2-c]-푸란-1,3-디온, 5-(2,5-디옥소테트라히드로푸랄)-3-매틸-3-시클로헥센-1,2-디카르복실산 이무수물, 비시클로[2,2,2]-옥트-7-엔-2,3,5,6-테트라카르복실산 이무수물 등의 지방족 및 지환족 테트라카르복실산 이무수물; 피로멜리트산 이무수물, 3,3',4,4'-비페닐술폰테트라카르복실산 이무수물, 1,4,5,8-나프탈렌테트라카르복실산 이무수물, 2,3,6,7-나프탈렌테트라카르복실산 이무수물, 3,3',4,4'-비페닐에테르테트라카르복실산 이무수물, 3,3',4,4'-디메틸디페닐실란테트라카르복실산 이무수물, 3,3',4,4'-테트라페닐실란테트라카르복실산 이무수물, 1,2,3,4-푸란테트라카르복실산 이무수물, 4,4'-비스(3,4-디카르복시페녹시)디페닐술피드 이무수물, 4,4'-비스(3,4-디카르복시페녹시)디페닐술폰 이무수물, 4,4'-비스(3,4-디카르복시페녹시)디페닐프로판 이무수물, 3,3',4,4'-퍼플루오로이소프로필리덴테트라카르복실산 이무수물, 3,3',4,4'-비페닐테트라카르복실산 이무수물, 비스(프탈산)페닐포스핀옥시드 이무수물, p-페닐렌-비스(트리페닐프탈산) 이무수물, m-페닐렌-비스(트리페닐프탈산) 이무수물, 비스(트리페닐프탈산)-4,4'-디페닐에테르 이무수물, 비스(트리페닐프탈산)-4,4'디페닐메탄 이무수물 등의 방향족 테트라카르복실산 이무수물을 들 수 있다.Examples of other tetracarboxylic acid dianhydrides include 2,3,5-tricarboxycyclopentylcarboxylic acid dianhydride, butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid Dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 3,5,6-tricarboxy norbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetra Carboxylic acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ Furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3 -methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, bicyclo [ ] -Oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride; alicyclic and alicyclic tetracarboxylic acid dianhydrides; Pyromellitic dianhydride, 3,3 ', 4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7- Naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3 , 3 ', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy ) Diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride Water, 3,3 ', 4,4'-perfluoroisopropylidene tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, bis (phthalic acid) phenylphosphine P-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) imine And aromatic tetracarboxylic acid dianhydrides such as bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride and bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride.
이들 중, 2,3,5-트리카르복시시클로펜틸아세트산 이무수물, 부탄테트라카르복실산 이무수물, 1,2,3,4-시클로부탄테트라카르복실산 이무수물, 피로멜리트산 이무수물, 3,3',4,4'-비페닐술폰테트라카르복실산 이무수물, 1,4,5,8-나프탈렌테트라카르복실산 이무수물, 2,3,6,7-나프탈렌테트라카르복실산 이무수물, 3,3',4,4'-비페닐에테르테트라카르복실산 이무수물이 바람직하다. 이들은 단독 또는 2종 이상을 조합하여 사용할 수 있다.Of these, 2,3,5-tricarboxycyclopentylacetic dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 3, 3 ', 4,4'-biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride is preferable. These may be used alone or in combination of two or more.
다른 디아민 화합물로서는, 예를 들면 p-페닐렌디아민, m-페닐렌디아민, 4,4'-디아미노디페닐메탄, 4,4'-디아미노디페닐에탄, 4,4'-디아미노디페닐술피드, 4,4'-디아미노디페닐술폰, 3,3'-디메틸-4,4'디아미노비페닐, 4,4'-디아미노벤즈아닐리드, 4,4'-디아미노디페닐에테르, 1,5-디아미노나프탈렌, 3,3-디메틸-4,4'-디아미노비페닐, 5-아미노-1-(4'-아미노페닐)-1,3,3-트리메틸인단, 6-아미노-1-(4'-아미노페닐)-1,3,3-트리메틸인단, 3,4'-디아미노디페닐에테르, 2,2-비스(4-아비노페녹시)프로판, 2,2-비스[4-(4-아미노페녹시)페닐]프로판, 2,2-비스[4-(4-아미노페녹시)페닐]헥사플루오로프로판, 2,2-비스(4-아미노페닐)헥사플루오로프로판, 2,2-비스[4-(4-아미노페녹시)페닐]술폰, 1,4-비스(4-아미노페녹시)벤젠, 1,3-비스(4-아미노페녹시)벤젠, 1,3-비스(3-아미노페녹시)벤젠, 9,9-비스(4-아미노페닐)-10-히드로안트라센, 2,7-디아미노플루오렌, 9,9-비스(4-아미노페닐)플루오렌, 4,4'-메틸렌-비스(2-클로로아닐린), 2,2',5,5'-테트라클로로-4,4'-디아미노비페닐, 2,2'-디클로로-4,4'-디아미노-5,5'-디메톡시비페닐, 3,3'-디메톡시-4,4'-디아미노비페닐, 1,4,4'-(p-페닐렌이소프로필리덴)비스아닐린, 4,4'-(m-페닐렌이소프로필리덴)비스아닐린, 2,2'-비스[4-(4-아미노-2-트리플루오로메틸페녹시)페닐]헥사플루오로프로판, 4,4'-디아미노-2,2'-비스(트리플루오로메틸)비페닐, 4,4'-비스[(4-아미노-2-트리플루오로메틸)페녹시]-옥타플루오로비페닐 등의 방향족 디아민; 디아미노테트라페닐티오펜 등의 헤테로 원자를 갖는 방향족 디아민; 1,1-메타크실렌디아민, 1,3-프로판디아민, 테트라메틸렌디아민, 펜타메틸렌디아민, 헥사메틸렌디아민, 헵타메틸렌디아민, 옥타메틸렌디아민, 노나메틸렌디아민, 4,4-디아미노헵타메틸렌디아민, 1,4-디아미노시클로헥산, 이소포론디아민, 테트라히드로디시클로펜타디에닐렌디아민, 헥사히드로-4,7-메타노인다닐렌디메틸렌디아민, 트리시클로[6,2,1,02.7]-운데실렌디메틸디아민, 4,4'-메틸렌비스(시클로헥실아민) 등의 지방족 및 지환족 디아민; 디아미노헥사메틸디실록산 등의 디아미노오르가노실록산을 들 수 있다.Examples of other diamine compounds include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylethane, 4,4'- Phenyl sulfide, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenyl Ether, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether, 2,2-bis (4-avinophenoxy) propane, 2,2 Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenoxy) (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, , 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-amino Bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ' , 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'- 4,4'-diaminobiphenyl, 1,4,4 '- (p-phenyleneisopropylidene) bisaniline, 4,4' - (m-phenyleneisopropylidene) (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl , Aromatic diamines such as 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl; Aromatic diamines having a hetero atom such as diaminotetraphenylthiophene; Diaminodiphenylmethane diamine, 1,4-diaminoheptamethylene diamine, 1, 4-diaminoheptamethylene diamine, 1, 4-diaminoheptamethylene diamine, 1, , 4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenyldimethylenediamine, tricyclo [6,2,1,0 2,7 ] -undecylene Aliphatic and alicyclic diamines such as dimethyldiamine and 4,4'-methylenebis (cyclohexylamine); And diaminoorganosiloxane such as diaminohexamethyldisiloxane.
이들 중, p-페닐렌디아민, 4,4'-디아미노디페닐메탄, 1,5-디아미노나프탈렌, 2,7-디아미노플루오렌, 4,4'-디아미노디페닐에테르, 4,4'-(p-페닐렌이소프로필리덴)비스아닐린, 2,2-비스[4-(4-아미노페녹시)페닐]헥사플루오로프로판, 2,2-비스(4-아미노페닐)헥사플루오로프로판, 2,2'-비스[4-(4-아미노-2-트리플루오로메틸페녹시)페닐]헥사플루오로프로판, 4,4'-디아미노-2,2'-비스(트리플루오로메틸)비페닐, 4,4'-비스[(4-아미노-2-트리플루오로메틸)페녹시]-옥타플루오로비페닐이 바람직하다. 이들은 단독 또는 2종 이상 조합하여 사용할 수 있다.Of these, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoro (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis 4,4'-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl is preferred. These may be used alone or in combination of two or more.
본 발명에서 사용되는 폴리이미드는, 상기 (a) 테트라카르복실산 이무수물 성분과, (b) 디아민 성분을 중축합시켜서 폴리아미드산을 수득하고, 이어서 필요에 따라 탈수제 및 이미드화 촉매의 존재하에서 가열하여, 이미드화를 실시함으로써 수득된다. 가열에 의해 이미드화를 실시할 경우의 반응 온도는 통상 60 내지 300℃, 바람직하게는 100 내지 170℃이다. 반응 온도가 60℃ 미만에서는 반응의 진행이 늦어지며, 또 300℃를 초과하면 폴리아미드산의 분자량이 크게 저하될 수 있다. 또, 탈수제 및 이미드화 촉매의 존재하에서 이미드화할 경우의 반응은, 유기 용매중에서 실시할 수 있다. 반응 온도는 통상 0 내지 180℃, 바람직하게는 60 내지 150℃이다. 상기 탈수제로서는, 무수 아세트산, 무수 프로피온산, 무수 트리플루오로아세트산 등의 산 무수물을 사용할 수 있다. 또한, 이미드화 촉매로서는, 예를 들면 피리딘, 콜리딘, 루티딘, 트리에틸아민 등의 3급 아민을 사용할 수 있으나,이들에 한정되는 것은 아니다. 탈수제의 사용량은 폴리아미드산의 반복 단위 1몰에 대하여 1.6 내지 20 몰로 하는 것이 바람직하다. 또한, 이미드화 촉매의 사용량은 사용하는 탈수제 1 몰에 대하여 0.5 내지 10 몰로 하는 것이 바람직하다. 이 이미드화 촉매 및 탈수제의 사용량에 따라, 폴리이미드 중의 아미드산 잔기의 함유율을 조정할 수 있다.The polyimide used in the present invention is obtained by polycondensing the tetracarboxylic dianhydride component (a) and the diamine component (b) to obtain a polyamic acid, and then, if necessary, in the presence of a dehydrating agent and an imidization catalyst Followed by heating and imidization. When the imidization is carried out by heating, the reaction temperature is usually 60 to 300 占 폚, preferably 100 to 170 占 폚. If the reaction temperature is less than 60 ° C, the progress of the reaction is delayed. If the reaction temperature exceeds 300 ° C, the molecular weight of the polyamic acid may be significantly lowered. The reaction in the case of imidation in the presence of a dehydrating agent and an imidation catalyst can be carried out in an organic solvent. The reaction temperature is usually from 0 to 180 ° C, preferably from 60 to 150 ° C. As the dehydrating agent, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. As the imidation catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used, but are not limited thereto. The amount of the dehydrating agent to be used is preferably 1.6 to 20 mol based on 1 mol of the repeating unit of the polyamic acid. The amount of the imidization catalyst to be used is preferably 0.5 to 10 mol based on 1 mol of the dehydrating agent used. Depending on the amount of the imidization catalyst and the dehydrating agent used, the content of the amide acid residue in the polyimide can be adjusted.
상기 폴리에스테르는 (c) 디카르복실산류(디카르복실산, 디카르복실산 에스테르 또는 디카르복실산 할로겐화물)와 (d) 2개의 히드록실기를 갖는 비페닐 화합물을 반응시켜 얻어진다. 본 발명에서 사용되는 폴리에스테르로는, (c) 디카르복실산류 화합물과 (d) 2개의 히드록실기를 갖는 비페닐 성분 중 적어도 1개의 성분에 칼콘(벤잘아세토페논) 구조, 스틸벤 구조, 안트라퀴논 구조 또는 카르바졸 구조를 갖는 화합물이 사용된다.The polyester is obtained by reacting (d) a dicarboxylic acid (dicarboxylic acid, dicarboxylic acid ester or dicarboxylic acid halide) and (b) a biphenyl compound having two hydroxyl groups. Examples of the polyester used in the present invention include a chalcone (benzalacetophenone) structure, a stilbene structure, a stilbene structure, and a stilbene structure in at least one of dicarboxylic acid compound (d) and biphenyl component having two hydroxyl groups A compound having an anthraquinone structure or a carbazole structure is used.
칼콘 구조를 갖는 카르복실산류 화합물로서는, 예를 들면 칼콘-3,3'-디카르복실산, 칼콘-3,4'-디카르복실산, 칼콘-4,4'-디카르복실산 및 각각의 알킬에스테르 등의 에스테르 화합물, 카르복실산 클로라이드 등의 카르복실산 할로겐화물을 들 수 있다. 스틸벤 구조를 갖는 카르복실산류 화합물로서는, 예를 들면 4,4'-스틸벤디카르복실산, 2,2'-트렌스-스틸벤디카르복실산, 2,4'-트렌스-스틸벤디카르복실산 및 각각의 알킬에스테르 등의 에스테르 화합물, 카르복실산 클로라이드 등의 카르복실산 할로겐화물을 들 수 있다.Examples of the carboxylic acid compound having a chalcone structure include chalcone-3,3'-dicarboxylic acid, chalcone-3,4'-dicarboxylic acid, chalcone-4,4'-dicarboxylic acid, Ester compounds such as alkyl esters of carboxylic acids, and carboxylic acid halides such as carboxylic acid chlorides. Examples of the carboxylic acid compound having a stilbene structure include 4,4'-stilbenedicarboxylic acid, 2,2'-trans-stilbenedicarboxylic acid, 2,4'-trans-stilbenedicarboxylic acid An ester compound such as a carboxylic acid, an ester compound such as an alkyl ester, and a carboxylic acid halide such as a carboxylic acid chloride.
안트라퀴논 구조를 갖는 카르복실산 화합물로서는, 예를 들면 1,2-안트라퀴논 디카르복실산, 1,3-안트라퀴논 디카르복실산, 1,4-안트라퀴논 디카르복실산,1,5-안트라퀴논 디카르복실산, 1,6-안트라퀴논 디카르복실산, 1,7-안트라퀴논 디카르복실산, 1,8-안트라퀴논 디카르복실산, 2,3-안트라퀴논 디카르복실산, 2,7-안트라퀴논 디카르복실산 및 각각의 알킬에스테르 등의 에스테르 화합물, 카르복실산 클로라이드 등의 카르복실산 할로겐화물을 들 수 있다.Examples of the carboxylic acid compound having an anthraquinone structure include 1,2-anthraquinone dicarboxylic acid, 1,3-anthraquinone dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid, 1,5 Anthraquinone dicarboxylic acid, 1,6-anthraquinone dicarboxylic acid, 1,6-anthraquinone dicarboxylic acid, 1,6-anthraquinone dicarboxylic acid, 1,6-anthraquinone dicarboxylic acid, Acid, 2,7-anthraquinonedicarboxylic acid and ester compounds such as alkyl esters, carboxylic acid halides such as carboxylic acid chlorides, and the like.
카르바졸 구조를 갖는 카르복실산 화합물로서는, 예를 들면 3,6-카르바졸 디카르복실산 및 그의 알킬 에스테르 등의 에스테르 화합물, 카르복실산 클로라이드 등의 카르복실산 할로겐화물을 들 수 있다.Examples of the carboxylic acid compound having a carbazole structure include ester compounds such as 3,6-carbazole dicarboxylic acid and alkyl esters thereof, and carboxylic acid halides such as carboxylic acid chlorides.
칼콘 구조를 갖는 비페닐 화합물로서는, 예를 들면 3,3'-디히드록시칼콘, 4,4'-디히드록시칼콘, 3,4'-디히드록시칼콘, 3,4-디히드록시칼콘 등을 들 수 있다.Examples of the biphenyl compound having a chalcone structure include 3,3'-dihydroxychalcone, 4,4'-dihydroxychalcone, 3,4'-dihydroxychalcone, 3,4-dihydroxychalcone And the like.
스틸벤 구조를 갖는 비페닐 화합물로서는, 예를 들면 3,3'-디히드록시스틸벤, 4,4'-디히드록시스틸벤, 3,4'-디히드록시스틸벤 등을 들 수 있다. 안트라퀴논 구조를 갖는 비페닐 화합물로서는, 예를 들면 1,2-디히드록시안트라퀴논, 1,4-디히드록시안트라퀴논, 1,5-디히드록시안트라퀴논 등을 들 수 있다. 카르바졸 구조를 갖는 비페닐 화합물로서는, 예를 들면 3,6-디히드록시카르바졸 등을 들 수 있다.Examples of the biphenyl compound having a stilbene structure include 3,3'-dihydroxystilbene, 4,4'-dihydroxystilbene, 3,4'-dihydroxystilbene and the like . Examples of the biphenyl compound having an anthraquinone structure include 1,2-dihydroxy anthraquinone, 1,4-dihydroxy anthraquinone, and 1,5-dihydroxy anthraquinone. The biphenyl compound having a carbazole structure includes, for example, 3,6-dihydroxycarbazole.
본 발명에서 사용되는 폴리에스테르에는, 본 발명의 효과를 손상하지 않는 정도의 다른 디카르복실산류 화합물 및 2개의 히드록실기를 갖는 비페닐 화합물을 병용할 수 있다.The polyester used in the present invention may be used in combination with other dicarboxylic acid compounds and biphenyl compounds having two hydroxyl groups to the extent that the effect of the present invention is not impaired.
다른 디카르복실산류 화합물로서는, 예를 들면 옥살산, 말론산, 디플루오로말론산, 알킬 말론산, 숙신산, 테트라플루오로 숙신산, 알킬 숙신산, (±)-말산, 메소-타르타르산, 이타콘산, 말레산, 메틸말레산, 푸마르산, 메틸푸마르산, 아세틸렌 디카르복실산, 글루타르산, 헥사플루오로글루타르산, 메틸글루타르산, 글루타콘산, 아디프산, 디티오아디프산, 메틸아디프산, 디메틸아디프산, 테트라메틸아디프산, 메틸렌아디프산, 무콘산, 갈락타르산, 피멜산, 수베르산, 퍼플루오로 수베르산, 3,3',6,6'-테트라메틸 수베르산, 아젤라산, 세바신산, 퍼플루오로 세바신산, 브라실산, 도데실 디카르복실산, 트리데실 카르복실산, 테트라데실 카르복실산 등의 지방족 카르복실산; 예를 들면, 시클로알킬 디카르복실산, 핀산, 헥사히드로프탈산, 1,4-(노르보넨)디카르복실산, 비시클로알킬 디카르복실산, 아다만탄 디카르복실산, 스피로헵탄 디카르복실산 등의 지환족 카르복실산;Examples of other dicarboxylic acid compounds include oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, (±) -malic acid, meso-tartaric acid, itaconic acid, Examples of the organic acid include at least one selected from the group consisting of acid, methylmaleic acid, fumaric acid, methylfumaric acid, acetylenedicarboxylic acid, glutaric acid, hexafluoroglutaric acid, methylglutaric acid, glutaconic acid, adipic acid, , Dimethyl adipic acid, tetramethyl adipic acid, methylene adipic acid, miconic acid, galactaric acid, pimelic acid, suberic acid, perfluorosuberic acid, 3,3 ', 6,6'-tetramethyl Aliphatic carboxylic acids such as suberic acid, azelaic acid, sebacic acid, perfluorosevacic acid, brassylic acid, dodecyldicarboxylic acid, tridecylcarboxylic acid, and tetradecylcarboxylic acid; For example, there may be mentioned cycloalkyl dicarboxylic acid, fumaric acid, hexahydrophthalic acid, 1,4- (norbornene) dicarboxylic acid, bicycloalkyldicarboxylic acid, adamantanedicarboxylic acid, spiroheptanedicarboxylic acid Alicyclic carboxylic acids such as carboxylic acids;
예를 들면, 프탈산, 이소프탈산, 디티오이소프탈산, 메틸이소프탈산, 디메틸이소프탈산, 클로로이소프탈산, 디클로로이소프탈산, 테레프탈산, 메틸테레프탈산, 디메틸테레프탈산, 클로로테레프탈산, 프로모테레프탈산, 나프탈렌 디카르복실산, 옥소플루오렌 디카르복실산, 안트라센 디카르복실산, 비페닐 디카르복실산, 비페닐렌 디카르복실산, 디메틸비페닐렌 디카르복실산, 4,4"-p-테레페닐렌 디카르복실산, 4,4"'-p-쿠와렐페닐 디카르복실산, 비벤질 디카르복실산, 아조벤젠 디카르복실산, 호모프탈산, 페닐렌 이아세트산, 페닐렌 디프로피온산, 나프탈렌 디카르복실산, 나프탈렌 디프로피온산, 비페닐 이아세트산, 비페닐 디프로피온산, 3,3'-[4,4'-(메틸렌디-p-비페닐렌)디프로피온산, 4,4'-비벤질 이아세트산, 3,3'-(4,4'-비벤질)디프로피온산, 옥시디-p-페닐렌 이아세트산 등의 방향족 디카르복실산 및 각각의 알킬에스테르 등의 에스테르 화합물, 카르복실산 클로라이드 등의 카르복실산 할로겐화물을 들 수 있다. 이들은 단독 또는 2종 이상을 조합하여 사용할 수 있다.For example, there can be mentioned, for example, aliphatic dicarboxylic acids such as phthalic acid, isophthalic acid, dithioisophthalic acid, methylisophthalic acid, dimethylisophthalic acid, chloroisophthalic acid, dichloroisophthalic acid, terephthalic acid, methylterephthalic acid, dimethyl terephthalic acid, chloroterephthalic acid, Fluorene dicarboxylic acid, anthracene dicarboxylic acid, biphenyl dicarboxylic acid, biphenylene dicarboxylic acid, dimethyl biphenylene dicarboxylic acid, 4,4 "-p-terphenylenedicarboxylic acid Acid, 4,4 "'- p-quinoledicarboxylic acid, bibenzyldicarboxylic acid, azobenzene dicarboxylic acid, homophthalic acid, phenylene diacetic acid, phenylene dicopropionic acid, naphthalene dicarboxylic acid , Naphthalene diphopropionic acid, biphenyl diacetic acid, biphenyl dicopropionic acid, 3,3 '- [4,4' - (methylene di-p-biphenylene) diphopropionic acid, 4,4'- , 3 '- (4,4'-bibenzyl) dipropionic acid, oxydip-phenyl This may be mentioned aromatic dicarboxylic acids and each of the carboxylic acid halide of the ester compound, carboxylic acid chloride such as alkyl esters such as acetate. These may be used alone or in combination of two or more.
다른 비페닐 화합물로서는, 예를 들면 카테콜, 알킬카테콜, 히드로퀴논 등의 다가 페놀류; 메틸렌 비스페놀, 이소프로필리덴 비스페놀, 부틸리덴비스페놀, 티오 비스페놀, 술피닐 비스페놀, 술포닐룬 비스페놀, 옥시비스페놀 등의 비스페놀류를 들 수 있다. 이들은 단독 또는 2종 이상을 조합하여 사용할 수 있다.Examples of other biphenyl compounds include polyhydric phenols such as catechol, alkyl catechol, and hydroquinone; And bisphenols such as methylene bisphenol, isopropylidene bisphenol, butyryliden bisphenol, thiobisphenol, sulfinyl bisphenol, sulfonylund bisphenol, and oxybisphenol. These may be used alone or in combination of two or more.
본 발명에서 사용되는 폴리에스테르는, 상기 (c) 디카르복실산류 화합물 성분과, (d) 2개의 히드록실기를 갖는 비페닐 화합물 성분을, 필요에 따라 촉매 존재하에서 가열하여 중축합시켜 수득된다. 디카르복실산과 비페닐 화합물과의 증축합의 경우는, 촉매로서 황산, p-톨루엔 술폰산 등의 프로톤산, 중금속의 산화물 또는 염, 티탄, 주석, 납 등의 유기 금속 화합물 등이 사용된다. 디카르복실산 에스테르와 비페닐 화합물과의 경우는, 촉매로서 납, 아연, 망간, 칼슘, 코발트, 카드뮴 등의 아세트산염이나 탄산염 화합물, 금속 마그네슘, 아연, 납, 안티몬, 게르마늄 등의 산화물이 사용된다. 디카르복실산 할로겐화물과 비페닐 화합물과의 경우는 촉매로서 피리딘,트리에틸아민 등의 염기성 촉매가 사용된다.The polyester used in the present invention is obtained by polycondensing the dicarboxylic acid compound component (c) and (d) a biphenyl compound component having two hydroxyl groups, if necessary, in the presence of a catalyst . When the dicarboxylic acid and the biphenyl compound are added together, protonic acids such as sulfuric acid and p-toluenesulfonic acid, oxides or salts of heavy metals, and organic metal compounds such as titanium, tin and lead are used as catalysts. In the case of the dicarboxylic acid ester and the biphenyl compound, an oxide such as an acetate such as lead, zinc, manganese, calcium, cobalt and cadmium, or a carbonate compound, metal magnesium, zinc, lead, antimony or germanium is used do. In the case of a dicarboxylic acid halide and a biphenyl compound, a basic catalyst such as pyridine or triethylamine is used as a catalyst.
상기 폴리아미드는 (e) 디카르복실산류(디카르복실산, 디카르복실산 에스테르, 디카르복실산 할로겐화물) 화합물과 (f) 디아민 화합물을 반응시켜 수득된다. 본 발명에서 사용되는 폴리아미드는 (e) 디카르복실산류 화합물 성분과 (f) 디아민 화합물 성분 중 적어도 하나의 성분에 칼콘(벤잘아세토페논) 구조, 스틸벤 구조, 안트라퀴논 구조 또는 카르바졸 구조를 갖는 화합물이 사용된다.The polyamide is obtained by reacting (e) a dicarboxylic acid (dicarboxylic acid, dicarboxylic acid ester, dicarboxylic acid halide) compound and (f) a diamine compound. The polyamide to be used in the present invention has a chalcone (benzalacetophenone) structure, a stilbene structure, an anthraquinone structure, or a carbazole structure in at least one component of (d) a dicarboxylic acid compound component and (f) Is used.
칼콘 구조, 스틸벤 구조, 안트라퀴논 구조 또는 카르바졸 구조를 갖는 디카르복실산류 화합물로서는 위에서 열거한 디카르복실산류 (d)가 사용된다.As the dicarboxylic acid compounds having a chalcone structure, a stilbene structure, an anthraquinone structure or a carbazole structure, the dicarboxylic acids (d) listed above are used.
칼콘 구조, 스틸벤 구조, 안트라퀴논 구조 또는 카르바졸 구조를 갖는 디아민 화합물로서는, 위에서 열거한 디아민 화합물 (b)가 사용된다.As the diamine compound having a chalcone structure, a stilbene structure, an anthraquinone structure or a carbazole structure, the diamine compound (b) listed above is used.
본 발명에서 사용되는 폴리아미드에는, 본 발명의 효과를 손상하지 않는 정도의 다른 디카르복실산류 화합물, 디아민 화합물을 병용할 수 있다.The polyamide to be used in the present invention may be used in combination with other dicarboxylic acid compounds and diamine compounds to the extent that the effect of the present invention is not impaired.
다른 디카르복실산류 화합물, 디아민 화합물로서는, 위에서 열거한 다른 디카르복실산류 화합물 및 디아민 화합물이 사용된다. 이들은 단독 또는 2종 이상을 조합하여 사용된다.As other dicarboxylic acid compounds and diamine compounds, other dicarboxylic acid compounds and diamine compounds listed above are used. These may be used alone or in combination of two or more.
본 발명에서 사용되는 폴리아미드는, 상기 (e) 디카르복실산류 화합물 성분과 (f) 디아민 성분을 필요에 따라 피리딘, 트리에틸아민 등의 염기성 촉매 존재하에서 중축합시켜 수득된다.The polyamide to be used in the present invention is obtained by polycondensing the dicarboxylic acid compound component (e) and the diamine component (f) in the presence of a basic catalyst such as pyridine or triethylamine, if necessary.
용제solvent
본 발명의 액정 배향막을 형성하는 액정 배향제는, 상기의 자외선에 관능하는 유기 화합물을 함유하는 중합체의 용액으로부터 이루어진다. 이때 사용되는 용제로서는, 그 중합체를 용해할 수 있는 유기 용제이면 특별한 제한은 없고, 단독 또는 2종 이상의 용제를 조합하여 사용된다.The liquid crystal aligning agent for forming the liquid crystal alignment film of the present invention is made of a solution of a polymer containing an organic compound that is sensitive to ultraviolet rays. The solvent to be used at this time is not particularly limited as long as it is an organic solvent capable of dissolving the polymer, and may be used alone or in combination of two or more solvents.
기타 첨가제Other additives
본 발명에서 사용되는 액정 배향제는, 프레틸트각의 안정화 및 도막 강도의 향상을 위해, 여러가지 열경화성 가교제를 함유할 수 있다. 열경화 가교제로서는, 다관능 에폭시 함유 화합물이 유효하며, 비스페놀 A형 에폭시 수지, 페놀 노볼락(novolac)형 에폭시 수지, 크레졸 노볼락형 에폭시 수지, 환상 지방족 에폭시 수지, 글리시딜 에스테르계 에폭시 수지, 글리시딜디아민계 에폭시 수지, 복소환식 에폭시 수지, 에폭시기 함유 아크릴 수지 등에 사용된다. 시판품으로서 예를 들면, 에포라이트 400E, 동 3002 (고에이샤 유시 가가꾸 고교(주) 제품), 에피코트 828, 동 152, 에폭시 노볼락 180S (유까 셀에폭시(주) 제품) 등을 들 수 있다.The liquid crystal aligning agent used in the present invention may contain various thermosetting crosslinking agents in order to stabilize the pretilt angle and to improve the film strength. As the thermosetting crosslinking agent, polyfunctional epoxy-containing compounds are effective, and examples thereof include bisphenol A type epoxy resins, phenol novolac type epoxy resins, cresol novolak type epoxy resins, cyclic aliphatic epoxy resins, glycidyl ester type epoxy resins, Glycidyldiamine-based epoxy resins, heterocyclic epoxy resins, epoxy group-containing acrylic resins, and the like. Examples of commercially available products include Epolite 400E and 3002 (manufactured by Goeisha Yushi Chemical Co., Ltd.), Epicote 828, Copper 152 and Epoxy novolac 180S (manufactured by Yuka Cell Epoxy Co., Ltd.) have.
다시, 전술한 다관능 에폭시 함유 화합물을 사용할 때, 가교 반응을 효율적으로 일으키기 위한 목적으로, 1-벤질-2-메틸이미다졸 등의 염기 촉매를 첨가할 수 있다.Further, when using the polyfunctional epoxy-containing compound described above, a base catalyst such as 1-benzyl-2-methylimidazole may be added for the purpose of effectively causing a crosslinking reaction.
또, 본 발명에서 사용되는 액정 배향제는, 기판과의 접착성을 개선하는 목적으로, 관능성 실란 함유 화합물을 함유할 수 있다. 관능성 실란 함유 화합물로서는, 예를 들면 3-아미노프로필 트리메톡시실란, 3-아미노프로필 트리에톡시실란, 2-아미노프로필 트리에톡시실란, 2-아미노프로필 트리메톡시실란, N-(2-아미노에틸)-3-아미노프로필 트리메톡시실란, N-(2-아미노에틸)-3-아미노프로필 메틸디메톡시실란, 3-우레이도프로필 트리메톡시실란, 3-우레이도프로필 트리에톡시실란, N-에톡시카르보닐-3-아미노프로필트리메톡시실란, N-에톡시카르보닐-3-아미노프로필트리에톡시실란, N-트리에톡시실릴프로필 트리에틸렌 트리아민, N-트리메톡시 실릴프로필 트리에틸렌 트리아민, 10-트리메톡시이시릴-1,4,7-트리아자데칸, 10-트리에톡시실릴-1,4,7-트리아자데칸, 9-트리메톡시실릴-3,6-디아자노닐아세테이트, 9-트리에톡시실릴-3,6-디아자노닐아세테이트, N-벤질-3-아미노프로필 트리메톡시실란, N-벤질-3-아미노프로필 트리에톡시실란, N-페닐-3-아미노프로필 트리메톡시실란, N-페닐-3-아미노프로필 트리에톡시실란, N-비스(옥시에틸렌)-3-아미노프로필트리메톡시실란, N-비스(옥시에틸렌)-3-아미노프로필 트리에톡시실란 등을 들 수 있고, 또한 일본국 특허 공개 제63-291922호에 기재된 테트라카르복실산 이 무수물과 아미노기 함유 실란 화합물과의 반응물등을 들 수 있다.The liquid crystal aligning agent used in the present invention may contain a functional silane-containing compound for the purpose of improving the adhesiveness with the substrate. Examples of the functional silane-containing compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyl triethylenetriamine, N- Trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3 , 6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3- (Oxyethylene) -3-aminopropyltriethoxysilane, and the tetracarboxylic acid described in JP-A-63-291922 is an anhydride and an amino group-containing And a reaction product with a silane compound.
액정 배향막의 형성Formation of liquid crystal alignment film
본 발명의 액정 배향막은, 예를 들면 다음 방법에 의해 제조할 수 있다. 먼저, 투명 도전막이 설치된 기판의 투명 도전막에 상기 액정 배향제를 롤 코터법, 스피너법, 인쇄법 등에 의해 도포하고, 40 내지 200 ℃의 온도에서 가열하여 도막을 형성시킨다. 도막의 막 두께는, 통상 0.001 내지 1 ㎛, 바람직하게는 0.005 내지 0.5 ㎛이다.The liquid crystal alignment film of the present invention can be produced, for example, by the following method. First, the liquid crystal aligning agent is applied to a transparent conductive film of a substrate provided with a transparent conductive film by a roll coater method, a spinner method, a printing method, etc., and heated at a temperature of 40 to 200 캜 to form a coated film. The film thickness of the coating film is usually 0.001 to 1 mu m, preferably 0.005 to 0.5 mu m.
상기 기판으로서는, 예를 들면 플로우트 유리, 소다 유리 등의 유리, 폴리에틸렌 테레프탈레이트, 폴리부틸렌 테레프탈레이트, 폴리에테르술폰, 폴리카르보네이트 등의 플라스틱 필름 등으로 이루어진 투명 기판을 사용할 수 있다.As the substrate, for example, a transparent substrate made of glass such as float glass or soda glass, a plastic film such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, or polycarbonate can be used.
상기 투명 도전막으로서는, SnO2으로 제조된 NESA막, In2O3-SnO2으로 제조된 ITO막 등을 사용할 수 있으며, 이들의 투명 도전막의 패터닝에는 포토·에칭법, 미리 마스크를 사용하는 방법 등이 사용된다.As the transparent conductive film, a NESA film made of SnO 2 , an ITO film made of In 2 O 3 -SnO 2 , or the like can be used. The transparent conductive film can be patterned by a photo-etching method, a method using a mask Etc. are used.
액정 배향제의 도포시에는, 기판 및 투명 도전막과 도막과의 접착성을 더욱 양호하게 하기 위하여, 기판 및 투명 도전막상에 미리 관능성 실란 함유 화합물, 티타네이트 등을 도포할 수 있다.In applying the liquid crystal aligning agent, a functional silane-containing compound, titanate or the like may be previously coated on the substrate and the transparent conductive film in order to further improve the adhesion between the substrate and the transparent conductive film and the coating film.
다음에, 상기 도막에 직선 편광된 자외선을 조사하고, 필요에 따라서는 다시150 내지 250 ℃의 온도에서 가열 처리를 실시하여 액정 배향능을 부여한다. 본 발명에 있어서 사용되는 자외선은 150 nm 내지 450 nm의 파장을 갖는 자외선, 그 중에서도 190 nm 내지 380 nm의 파장을 갖는 자외선이 바람직하다.Next, the coating film is irradiated with linearly polarized ultraviolet rays, and if necessary, subjected to heat treatment at a temperature of 150 to 250 DEG C to impart liquid crystal aligning ability. The ultraviolet ray used in the present invention is preferably ultraviolet ray having a wavelength of 150 nm to 450 nm, particularly ultraviolet ray having a wavelength of 190 nm to 380 nm.
상기 광원으로서는, 예를 들면 저압 수은 램프, 고압 수은 램프, 중수소 램프, 메탈할라이드 램프, 아르곤 공명 램프, 크세논 램프, 엑시머 레이저 램프 등이 사용될 수 있다.As the light source, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser lamp and the like can be used.
액정 표시 소자Liquid crystal display element
본 발명의 액정 표시 소자는, 상기 액정 배향막이 형성된 기판 2장을 액정 배향막을 조사한 직선 편광 자외선의 편광 방향이 소정의 각도가 되도록 대향시켜, 기판 사이의 주변부를 밀봉제로 밀봉하고, 액정을 충전하며, 충전 구멍을 봉지하여 액정 셀을 구성한다. 그리하여, 그 양면에 편광판의 편광 방향이 각각 기판의 액정 배향막을 조사한 직선 편광 자외선의 편광 방향과 소정의 각도를 이루도록 편광판을 맞부쳐서 액정 표시 소자로 한다. 액정 배향막이 형성된 2장의 기판에서, 조사된 직선 편광 자외선의 편광 방향이 이룬 각도 및 각각의 기판과 편광판과의 각도를 조정함으로써 TN형 또는 STN형 액정 셀을 갖는 액정 표시 소자를 임의로 수득할 수 있다.In the liquid crystal display element of the present invention, two substrates on which the liquid crystal alignment film is formed are opposed to each other so that the polarization direction of the linearly polarized ultraviolet ray irradiated with the liquid crystal alignment film is a predetermined angle, the peripheral portion between the substrates is sealed with a sealant, , And filling holes are sealed to constitute a liquid crystal cell. Thus, the polarizing plate is brought into contact with the polarizing plate so that the polarizing direction of the polarizing plate has a predetermined angle with the polarizing direction of the linearly polarized ultraviolet ray irradiated to the liquid crystal alignment film of the substrate, respectively, on both sides thereof. A liquid crystal display element having a TN type or STN type liquid crystal cell can arbitrarily be obtained by adjusting the angle of polarization of the irradiated linearly polarized ultraviolet ray and the angle between each substrate and the polarizing plate in the two substrates on which the liquid crystal alignment film is formed .
상기 밀봉제로서는, 예를 들면 경화제 및 스페이서로서의 산화알루미늄구를 함유한 에폭시 수지 등을 사용할 수 있다.As the sealing agent, for example, an epoxy resin containing an aluminum oxide sphere as a curing agent and a spacer can be used.
상기 액정으로서는, 네마틱형 액정, 스멕티형 액정 등을 사용할 수 있다. TN형 액정 셀의 경우, 네마틱형 액정을 형성시키는 것이 바람직하며, 예를 들면 시프염기(Schiff base)계 액정, 아족시계 액정, 비페닐계 액정, 페닐시클로헥산계 액정, 에스테르계 액정, 다페닐계 액정, 비페닐시클로헥산계 액정, 피리미딘계 액정, 디옥산계 액정, 비시클로옥탄계 액정, 규반계 액정 등이 사용된다. 또한, STN형 액정 셀의 경우, 상기 액정에, 예를 들면 콜레스틸클로라이드, 콜레스테릴 노난에이트, 콜레스테릴 카르보네이트 등의 콜레스테릭 액정이나, 상품명 C-15, CB-15(멜크사 제품)로서 판매되고 있는 바와 같은 키랄제 등을 더 첨가하여 사용할 수 있다. 또한, p-데실록시벤질리덴-p-아미노-2-메틸부틸신나메이트 등의 강유전성 액정도 사용할 수 있다.As the liquid crystal, a nematic liquid crystal, a smectic liquid crystal or the like can be used. In the case of a TN type liquid crystal cell, it is preferable to form a nematic liquid crystal, and examples thereof include a Schiff base liquid crystal, an azeotropic liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, Based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, and quasi-system liquid crystal. In the case of the STN type liquid crystal cell, a cholesteric liquid crystal such as cholestyl chloride, cholesteryl nonanate, cholesteryl carbonate or the like such as cholesteric liquid crystal such as C-15, CB-15 And a chiral agent such as those sold under the trade name of Nippon Kayaku Co., Ltd. may be further added. Further, ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate can also be used.
액정 셀 외측에 사용되는 편광판으로서는, 폴리비닐알콜을 연신 배향시키면서, 요오드를 흡수시킨 H막이라 불리우는 편광막을 아세트산 셀룰로스 보호막으로 끼워넣은 편광판, 또는 H막 그 자체로 된 편광판 등을 들 수 있다.Examples of the polarizing plate used for the outside of the liquid crystal cell include a polarizing plate in which a polarizing film called an H film in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched state with a cellulose acetate protective film or a polarizing plate made of the H film itself.
본 발명에서의 액정 배향막의 제조 방법에 의하면, 종래의 러빙 처리시에 발생하는 정전기에 의한 먼지의 부착 및 TFT 소자의 회로 파괴가 발생하지 않으므로, 높은 수율로 배향막이 제조될 수 있다.According to the method for producing a liquid crystal alignment film in the present invention, adhesion of dust due to static electricity and rupture of circuit of the TFT element occurring in the conventional rubbing treatment does not occur, and therefore an alignment film can be produced with high yield.
실시예Example
이하, 본 발명을 실시예에 의해, 더욱 구체적으로 설명하지만, 본 발명은 이들 실시예에 제한되지 않는다.Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.
합성예 1Synthesis Example 1
폴리아미드산의 중합Polymerization of polyamic acid
2,3,5-트리카르복시시클로펜틸아세트산 이무수물 22.42 g과, 4,4'-디아미노스틸벤 21.02 g을 N-메틸-2-피롤리돈 400 g에 용해시켜, 60 ℃에서 6시간 반응시켰다.22.42 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 21.02 g of 4,4'-diaminostilbene were dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours .
다음에, 반응 혼합물을 과량의 메탄올에 넣고, 반응 생성물을 침전시켰다. 그후, 메탄올로 세정하고, 감압하 40 ℃에서 15시간 건조시켜, 중합체 Ia 35.21 g을 얻었다.Next, the reaction mixture was put into an excess amount of methanol, and the reaction product was precipitated. Thereafter, the resultant was washed with methanol, and dried at 40 캜 for 15 hours under reduced pressure to obtain 35.21 g of polymer Ia.
이미드화 반응Imidization reaction
수득된 중합체(Ia) 20.00 g에 N-메틸-2-피롤리돈 380 g, 피리딘 7.28 g및 무수 아세트산 9.40 g을 첨가하고, 120 ℃에서 4시간 이미드화 반응시켰다.To 20.00 g of the obtained polymer (Ia), 380 g of N-methyl-2-pyrrolidone, 7.28 g of pyridine and 9.40 g of acetic anhydride were added and imidized at 120 DEG C for 4 hours.
다음에, 반응 혼합액을 과량의 메탄올에 넣고, 반응 생성물을 침전시켰다. 그후, 메탄올로 세정하고, 감압하에서 15시간 건조시켜, 중합체(IIa) 12.61 g을 얻었다.Next, the reaction mixture was poured into an excess amount of methanol, and the reaction product was precipitated. Thereafter, it was washed with methanol and dried under reduced pressure for 15 hours to obtain 12.61 g of polymer (IIa).
합성예 2Synthesis Example 2
폴리아미드산의 중합Polymerization of polyamic acid
2,3,5-트리카르복시시클로펜틸아세트산 이무수물 22.42 g과, 4,4'-디아미노안트라퀴논 23.83 g을 N-메틸-2-피롤리돈 400 g에 용해시켜, 60 ℃에서 6시간 반응시켰다.22.42 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 23.83 g of 4,4'-diaminoanthraquinone were dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours .
다음에, 반응 혼합물을 과량의 메탄올에 넣고, 반응 생성물을 침전시켰다. 그후, 메탄올로 세정하고 감압하 40 ℃에서 15시간 건조시켜, 중합체(Ib) 40.00 g을 얻었다.Next, the reaction mixture was put into an excess amount of methanol, and the reaction product was precipitated. Thereafter, the resultant was washed with methanol and dried under reduced pressure at 40 DEG C for 15 hours to obtain 40.00 g of polymer (Ib).
이미드화 반응Imidization reaction
수득된 중합체(Ib) 20.00 g에 N-메틸-2-피롤리돈 380 g, 피리딘 6.84 g 및 무수 아세트산 8.83 g을 첨가하고, 120 ℃에서 4시간 이미드화 반응시켰다.To 20.00 g of the obtained polymer (Ib), 380 g of N-methyl-2-pyrrolidone, 6.84 g of pyridine and 8.83 g of acetic anhydride were added and imidized at 120 캜 for 4 hours.
다음에, 반응 혼합액을 과량의 메탄올에 넣고, 반응 생성물을 침전시켰다. 그후, 메탄올로 세정하고, 감압하에서 15시간 건조시켜, 중합체(IIb) 16.67 g을 얻었다.Next, the reaction mixture was poured into an excess amount of methanol, and the reaction product was precipitated. Thereafter, it was washed with methanol and dried under reduced pressure for 15 hours to obtain 16.67 g of polymer (IIb).
합성예 3Synthesis Example 3
폴리아미드산의 중합Polymerization of polyamic acid
3,3',4,4'-벤조페논테트라카르복실산 이무수물 32.22 g과, p-페닐렌디아민 10.81 g을 N-메틸-2-피롤리돈 400 g에 용해시켜, 60℃에서 6시간 반응시켰다.32.22 g of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 10.81 g of p-phenylenediamine were dissolved in 400 g of N-methyl-2-pyrrolidone, Lt; / RTI >
다음에, 반응 혼합물을 과량의 메탄올에 넣고, 반응 생성물을 침전시켰다. 그후, 메탄올로 세정하고, 감압하의 40℃에서 15시간 건조시켜, 중합체(Ic) 36.00 g을 얻었다.Next, the reaction mixture was put into an excess amount of methanol, and the reaction product was precipitated. Thereafter, the resultant was washed with methanol and dried at 40 DEG C under reduced pressure for 15 hours to obtain 36.00 g of a polymer (Ic).
이미드화 반응Imidization reaction
수득된 중합체(Ic) 20.00 g에 N-메틸-2-피롤리돈 380 g, 피리딘 6.19 g 및 무수 아세트산 7.71 g을 첨가하고, 120℃에서 4시간 이미드화 반응시켰다.380 g of N-methyl-2-pyrrolidone, 6.19 g of pyridine and 7.71 g of acetic anhydride were added to 20.00 g of the obtained polymer (Ic), and imidization reaction was carried out at 120 DEG C for 4 hours.
다음에, 반응 혼합액을 과량의 메탄올에 넣고, 반응 생성물을 침전시켰다. 그후, 메탄올로 세정하고, 감압하에서 15시간 건조시켜, 중합체(IIc) 15.3 g을 얻었다.Next, the reaction mixture was poured into an excess amount of methanol, and the reaction product was precipitated. Thereafter, the resultant was washed with methanol and dried under reduced pressure for 15 hours to obtain 15.3 g of a polymer (IIc).
비교 합성예 1Comparative Synthesis Example 1
폴리아미드산의 중합Polymerization of polyamic acid
2,3,5-트리카르복시시클로펜틸아세트산 이무수물 22.42 g과, p-페닐렌디아민 10.81 g을 N-메틸-2-피롤리돈 300g에 용해시켜, 60 ℃에서 6시간 반응시켰다.22.42 g of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 10.81 g of p-phenylenediamine were dissolved in 300 g of N-methyl-2-pyrrolidone and reacted at 60 DEG C for 6 hours.
다음에, 반응 혼합물을 과량의 메탄올에 넣고, 반응 생성물을 침전시켰다. 그후, 메탄올로 세정하고, 감압하 40 ℃에서 15시간 건조시켜, 중합체(Ix) 27.44 g을 얻었다.Next, the reaction mixture was put into an excess amount of methanol, and the reaction product was precipitated. Thereafter, the resultant was washed with methanol and dried at 40 ° C under reduced pressure for 15 hours to obtain 27.44 g of polymer (Ix).
이미드화 반응Imidization reaction
수득된 중합체(Ix) 20.00 g에 N-메틸-2-피롤리돈 380 g, 피리딘 9.52 g 및 무수 아세트산 12.29 g을 첨가하고, 120 ℃에서 4시간 이미드화 반응시켰다.To 20.00 g of the obtained polymer (Ix), 380 g of N-methyl-2-pyrrolidone, 9.52 g of pyridine and 12.29 g of acetic anhydride were added and subjected to imidization reaction at 120 DEG C for 4 hours.
다음에, 반응 혼합액을 과량의 메탄올에 넣고, 반응 생성물을 침전시켰다. 그후, 메탄올로 세정하고, 감압하에서 15시간 건조시켜, 중합체(IIx) 15.27 g을 얻었다.Next, the reaction mixture was poured into an excess amount of methanol, and the reaction product was precipitated. Thereafter, it was washed with methanol and dried under reduced pressure for 15 hours to obtain 15.27 g of a polymer (IIx).
비교 실시예 1Comparative Example 1
합성예 1에서 수득된 중합체(IIa)를 γ-부티로락톤에 용해시켜, 고형분 농도 4 중량%의 용액으로 하고, 이 용액을 공경 1 ㎛의 필터로 여과하여, 액정 배향제 용액을 조제하였다.The polymer (IIa) obtained in Synthesis Example 1 was dissolved in? -Butyrolactone to prepare a solution having a solid concentration of 4% by weight, and this solution was filtered with a filter having an opening diameter of 1 占 퐉 to prepare a liquid crystal aligning agent solution.
이 용액을, ITO 막으로 된 투명 전극이 부착된 유리 기판상에 투명 전극면에, 막 두께가 0.1 ㎛가 되도록 스피너를 사용하여 도포하고, 180℃에서 1시간 건조하여 박막을 형성하였다.This solution was applied to a transparent electrode surface of a transparent electrode made of an ITO film on a transparent electrode surface using a spinner so as to have a thickness of 0.1 mu m and dried at 180 DEG C for 1 hour to form a thin film.
이 박막에, 나일론제의 천을 말아 붙인 롤이 있는 러빙 장치에 의해, 롤의 회전수 500 rpm, 스테이지의 이동 속도 1 cm/초로 러빙 처리를 실시하였다.The thin film was subjected to a rubbing treatment at a roll rotation speed of 500 rpm and at a stage moving speed of 1 cm / sec by a rubbing device having a nylon cloth roll attached thereto.
다음에, 한쌍의 러빙 처리된 기판의 액정 배향막을 갖는 각각의 외측 가장자리에, 직경 17 cm의 산화알루미늄구가 들어있는 에폭시 수지 접착제를 스크린 인쇄 도포한 후, 한쌍의 기판을 액정 배향막면이 서로 대향하도록, 더욱이 러빙 방향에 직교하도록 겹쳐서 맞추어 압착하여, 접착제를 경화시켰다.Next, an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 17 cm was applied to each outer edge of the pair of rubbed substrates having the liquid crystal alignment film by screen printing, and then the pair of substrates were laminated with the liquid crystal alignment film faces facing each other , And further pressed and bonded so as to be orthogonal to the rubbing direction to cure the adhesive.
이어서, 액정 주입구로부터 한쌍의 기판 사이에, 네마틱형 액정 (멀크사 제품 ZLI-1565)을 충전한 후, 에폭시계 접착제로 액정 주입구를 봉지하고, 기판의 외측의 양면에 편광판을, 편광판의 편광 방향이 각각의 기판의 액정 배향막의 러빙 방향과 일치하도록 붙여 맞추고, 액정 표시 소자를 제작한 결과, 액정의 배향성은 양호하였다. 전압 5 V를 인가한 결과, 인가한 전압의 ON-OFF에 응답하여, 액정 표시 소자의 명암의 변화가 관찰되었다.Subsequently, a nematic liquid crystal (ZL-1565 manufactured by MURSU CORPORATION) was filled between the pair of substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an epoxy adhesive, and a polarizing plate was provided on both sides of the outer side of the substrate, Were adhered so as to coincide with the rubbing direction of the liquid crystal alignment film of each substrate, and the liquid crystal display device was produced. As a result, the alignment property of the liquid crystal was good. As a result of applying a voltage of 5 V, a change in the contrast of the liquid crystal display element was observed in response to ON / OFF of the applied voltage.
실시예 1Example 1
합성예 1에서 수득된 중합체(IIa)를 사용하여, 비교 실시예 1과 동일하게 기판상에 박막을 형성하였다.Using the polymer (IIa) obtained in Synthesis Example 1, a thin film was formed on the substrate in the same manner as in Comparative Example 1.
박막 표면에, Hg-Xe 램프보다, 그렌레이져 프리즘 GLP-0-10-15-AN(시그마 광기 제품)에 의해, 365 nm의 파장을 주로 하는, 직선 편광된 자외선 0.5 J/㎠를 조사하였다.On the surface of the thin film, a linearly polarized ultraviolet ray with a wavelength of 365 nm was irradiated at 0.5 J / cm 2 by a Granger laser prism GLP-0-10-15-AN (Sigma Photovoltaics) rather than an Hg-Xe lamp.
다음에, 액정 배향막을 겹쳐 맞추는 방향을 러빙 방향 대신에 자외선의 편광 방향에 따른 것 이외는, 비교 실시예 1과 동일한 방법으로 액정 표시 소자를 제작한 결과, 액정 배향성은 양호하였다. 비교 실시예 1과 동일한 조건으로 전압을 인가한 결과, 인가한 전압의 ON-OFF에 응답하여, 액정 표시 소자의 명암의 변화가 관찰되었다.Next, a liquid crystal display device was produced in the same manner as in Comparative Example 1 except that the direction in which the liquid crystal alignment film was superimposed was changed to the direction of polarization of the ultraviolet ray instead of the rubbing direction. As a result, the liquid crystal alignment property was good. As a result of applying a voltage under the same conditions as in Comparative Example 1, a change in the contrast of the liquid crystal display element was observed in response to ON / OFF of the applied voltage.
실시예 2 내지 3Examples 2 to 3
합성예 2 내지 3에서 수득된 중합체(IIb) 내지 (IIc)를 사용한 것 이외는, 실시예 1과 동일하게 액정 표시 소자를 제작한 결과, 액정의 배향성은 양호하였다. 실시예 1과 동일한 조건으로 전압을 인가한 결과, 인가한 전압의 ON-OFF에 응답하여, 액정 표시 소자의 명암의 변화가 관찰되었다.A liquid crystal display device was produced in the same manner as in Example 1 except that the polymers (IIb) to (IIc) obtained in Synthesis Examples 2 to 3 were used, and as a result, the alignment properties of the liquid crystal were good. As a result of applying a voltage under the same conditions as in Example 1, a change in the contrast of the liquid crystal display element was observed in response to ON / OFF of the applied voltage.
비교 실시예 2Comparative Example 2
비교 합성예 1에서 수득된 중합체(IIx)를 사용하여, 실시예 1과 동일하게 기판상에 박막을 형성하고, 직선 편광 자외선을 조사하여 액정 배향막을 형성하고, 그것을 사용하여 액정 표시 소자를 제작한 결과, 액정의 배향은 관찰되지 않았다.Using the polymer (IIx) obtained in Comparative Synthesis Example 1, a thin film was formed on a substrate in the same manner as in Example 1, and a liquid crystal alignment film was formed by irradiating linearly polarized ultraviolet rays. As a result, alignment of liquid crystal was not observed.
본 발명에 있어서의 액정 배향막의 제조 방법에 의하면, 종래의 러빙 처리시에 발생하는 정전기에 의한 먼지의 부착, TFT 소자의 회로 파괴가 발생하지 않으므로, 높은 수율로 배향막을 제조할 수 있다. 또, 본 발명에서의 액정 배향막은 면내 균일성이 우수하기 때문에, TN형, STN형, 또는 IPS (In-Plane Switching)형 등의 표시용으로 사용했을 경우에 높은 표시 품위를 갖는 액정 표시 소자가 수득되고, 여러가지 장치에 유효하게 사용되며, 예를 들면 탁상 계산기, 팔목시계, 탁상시계, 계수 표시판, 워드프로세서, 퍼스날 컴퓨터 및 액정 TV 등의 표시 장치에 적합하게 사용된다.According to the method for producing a liquid crystal alignment film of the present invention, adhesion of dust due to static electricity and breakage of circuit of the TFT element occurring during the conventional rubbing treatment does not occur, so that an alignment film can be produced with a high yield. In addition, since the liquid crystal alignment layer in the present invention is excellent in in-plane uniformity, a liquid crystal display element having a high display quality when used for displays such as TN type, STN type, IPS (In-Plane Switching) And is effectively used in various apparatuses and is suitably used for display devices such as a desk calculator, a wristwatch, a desk clock, a coefficient display board, a word processor, a personal computer, and a liquid crystal TV.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101445245B1 (en) | 2006-03-16 | 2014-09-26 | 제이엔씨 주식회사 | Light aligning film and liquid crystal display device |
| KR20140130007A (en) | 2013-12-23 | 2014-11-07 | 한국생산기술연구원 | Photo-alignment apparatus using pulse ｕｖ |
| US9494420B2 (en) | 2013-04-30 | 2016-11-15 | Korea Institute Of Industrial Technology | Optical alignment device using UV pulse |
| US10247868B2 (en) | 2013-07-02 | 2019-04-02 | Korea Institute Of Industrial Technology | Optical alignment method and patterned retarder manufacturing method using polarized pulse UV |
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| US5807498A (en) * | 1996-03-29 | 1998-09-15 | Alliant Techsystems Inc. | Process and materials for aligning liquid crystals and liquid crystal optical elements |
| JP4605677B2 (en) * | 1999-11-29 | 2011-01-05 | 経済産業大臣 | Liquid crystal alignment treatment method |
| JP2001290155A (en) * | 2000-04-10 | 2001-10-19 | Agency Of Ind Science & Technol | Method for forming liquid crystal alignment layer |
| JP2002107733A (en) * | 2000-09-29 | 2002-04-10 | Sony Corp | Liquid crystal display device |
| JP4013052B2 (en) * | 2002-09-25 | 2007-11-28 | 日産化学工業株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| KR101212135B1 (en) * | 2005-06-14 | 2012-12-14 | 엘지디스플레이 주식회사 | Liquid Crystal Display Device, and method of fabricating the same |
| JP5481771B2 (en) * | 2006-03-16 | 2014-04-23 | Ｊｎｃ株式会社 | Photo-alignment film and liquid crystal display element |
| KR100882586B1 (en) | 2007-10-10 | 2009-02-13 | 제일모직주식회사 | Photoalignment agent of liquid crystal, photoalignment film of liquid crystal including the same, and liquid crystal display including the same |
| KR100913605B1 (en) | 2007-12-07 | 2009-08-26 | 제일모직주식회사 | Photoalignment agent of liquid crystal, photoalignment film of liquid crystal including the same, and liquid crystal display including the same |
| KR101288558B1 (en) | 2008-12-12 | 2013-07-22 | 제일모직주식회사 | Liquid crystal photo-alignment agent, and liquid crystal photo-alignment film manufactured using same |
| CN102102019A (en) | 2009-12-16 | 2011-06-22 | 第一毛织株式会社 | Liquid crystal photo-alignment agent, liquid crystal photo-alignment layer, and liquid crystal display device |
| CN102559205B (en) | 2010-12-29 | 2014-07-30 | 第一毛织株式会社 | Liquid crystal alignment agent, liquid crystal alignment film manufactured using the same, and liquid crystal display device |
| KR101444190B1 (en) | 2011-12-19 | 2014-09-26 | 제일모직 주식회사 | Liquid crystal alignment agent, liquid crystal alignment film using the same, and liquid crystal display device including the liquid crystal alignment film |
| KR102143667B1 (en) * | 2012-08-21 | 2020-08-11 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
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| KR950015150U (en) * | 1993-11-18 | 1995-06-17 | 엘지전자주식회사 | Large-area photocurable polymer alignment film manufacturing device |
| KR100304510B1 (en) * | 1993-05-27 | 2002-09-05 | 제이에스알 가부시끼가이샤 | A liquid crystal alignment method using a liquid crystal alignment film and a liquid crystal alignment device using the liquid crystal alignment film |
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| KR100304510B1 (en) * | 1993-05-27 | 2002-09-05 | 제이에스알 가부시끼가이샤 | A liquid crystal alignment method using a liquid crystal alignment film and a liquid crystal alignment device using the liquid crystal alignment film |
| KR950015150U (en) * | 1993-11-18 | 1995-06-17 | 엘지전자주식회사 | Large-area photocurable polymer alignment film manufacturing device |
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| KR101445245B1 (en) | 2006-03-16 | 2014-09-26 | 제이엔씨 주식회사 | Light aligning film and liquid crystal display device |
| US9494420B2 (en) | 2013-04-30 | 2016-11-15 | Korea Institute Of Industrial Technology | Optical alignment device using UV pulse |
| US10247868B2 (en) | 2013-07-02 | 2019-04-02 | Korea Institute Of Industrial Technology | Optical alignment method and patterned retarder manufacturing method using polarized pulse UV |
| KR20140130007A (en) | 2013-12-23 | 2014-11-07 | 한국생산기술연구원 | Photo-alignment apparatus using pulse ｕｖ |
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