TW591083B - Liquid crystal-orienting agent and liquid crystal display element - Google Patents
Liquid crystal-orienting agent and liquid crystal display element Download PDFInfo
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- TW591083B TW591083B TW091116903A TW91116903A TW591083B TW 591083 B TW591083 B TW 591083B TW 091116903 A TW091116903 A TW 091116903A TW 91116903 A TW91116903 A TW 91116903A TW 591083 B TW591083 B TW 591083B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
- C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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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
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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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- Crystallography & Structural Chemistry (AREA)
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- Organic Chemistry (AREA)
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Abstract
Description
591083 A7 B7 五、發明説明(;| 【發明之技術領域】 本發明係有關液晶配向劑及液晶顯示元件之發明。更 詳細地說,係有關一種具有優良印刷性之液晶配向劑及由 其所製得之液晶顯示元件。 【先前技術】 目前,液晶顯示元件,已知例如係於設置有透明導電 膜之基板表面上形成液晶配向膜以作爲液晶顯示元件用基 板,並將該基板以2片對向配置之方式,於該間隙內形成 具有介電異向性之向列型液晶層以作爲三明治構造之晶 胞,使液晶分子之長軸由一側之基板向另一側基板連續地 扭轉9 0度,即具有T N型(Twisted Nematic )液晶晶胞之 丁 N型液晶顯示元件。又,例如使用添加有光學活性物質 之鏡像異構化劑之液晶時可使液晶分子之長軸於基板間達 成連續地扭轉1 8 0度以上之狀態,而利用此方式所產生 之多折射效果之S T N ( Super Twisted Nematic )型液晶顯 示元件等。此外,例如較T N型液晶顯示元件具有更低視 角依賴性之I P S ( In-Plane Switiching )型液晶顯示元件 或,垂直配向型液晶顯示元件亦已被開發。 前述液晶顯示元件中液晶配向膜材料中,已知例如以 往之聚醯亞胺、聚醯胺及聚酯等,特別是聚醯亞胺,因具 有優良之耐熱性、與液晶之親和性、機械性強度等,故受 到多數液晶顯示元件使用。聚醯亞胺所形成之液晶配向 膜,一般係將聚醯亞胺前驅物之聚醯胺酸或,可溶性聚醯 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁)591083 A7 B7 V. Description of the invention (; | [Technical Field of the Invention] The present invention relates to an invention of a liquid crystal alignment agent and a liquid crystal display element. More specifically, it relates to a liquid crystal alignment agent with excellent printability and its application. [Previous technology] At present, it is known that a liquid crystal display element is formed by, for example, forming a liquid crystal alignment film on a surface of a substrate provided with a transparent conductive film as a substrate for the liquid crystal display element, and the substrate is divided into two pieces. In the opposite arrangement method, a nematic liquid crystal layer having a dielectric anisotropy is formed in the gap as a unit cell of a sandwich structure, so that the long axis of the liquid crystal molecules is continuously twisted from one substrate to the other substrate. 90 degrees, that is, a N-type liquid crystal display element having a TN-type (Twisted Nematic) liquid crystal cell. In addition, for example, when a liquid crystal with an optically active substance isomerized is used, the long axis of the liquid crystal molecules can be on the substrate. The STN (Super Twisted Nematic) type liquid crystal display element that achieves a state of continuously reversing 180 degrees or more, and uses the multi-refraction effect produced by this method In addition, for example, an IPS (In-Plane Switiching) type liquid crystal display element having a lower viewing angle dependency than a TN type liquid crystal display element or a vertical alignment type liquid crystal display element has also been developed. The liquid crystal alignment film in the aforementioned liquid crystal display element Among materials, it is known that, for example, conventional polyimide, polyimide, polyester, etc., especially polyimide, because of its excellent heat resistance, affinity with liquid crystals, mechanical strength, etc. Use for display elements. The liquid crystal alignment film formed of polyimide is generally made of polyimide precursor of polyimide or soluble polyimide. The paper size applies to Chinese National Standard (CNS) A4 (210X297 mm). ) (Please read the notes on the back before filling this page)
、1T 經濟部智慧財產局員工消費合作社印製 -4 - 591083 A7 _B7_ 五、發明説明(^ 亞胺之有機溶媒溶液塗佈於基板上,再以加熱使其醯亞胺 化方式而製得。該液晶晶配向劑中,可再添加以提高對基 板水平性爲目的之矽烷偶合劑。 但,添加有矽烷偶合劑之液晶配向劑,雖可提高對基 板之水平性,但塗佈時極容易產生泡沬,此泡沬即爲液晶 配向膜容易形成砂孔之原因,此點將會造成液晶之配向 性、並使所製得液晶顯示元件之電特性降低之原因。 【發明之目的】 本發明之目的,即是以提供一種塗佈於基板時不會產 生泡沬’且具有良好塗佈性之之液晶配向劑爲目的。 本發明之其他目的及優點,將可經由以下說明而明 白。 【發明之內容】 依本發明之內容’本發明之上記目的及優點,係爲提 供一種液晶配向劑’其係含有(A )具有選自下記式(ϊ - 1 )所示重複單位與下記式(I - 2)所示重複單位中 之至少1種重複單位的聚合物,與 (B )具有聚醚鍵結之含矽化合物 之液晶配向劑; 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁) 丨痛·Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China-591083 A7 _B7_ V. Description of the Invention (^ The organic solvent solution of imine is coated on the substrate, and then it is made by heating it to imide. To this liquid crystal crystal alignment agent, a silane coupling agent for the purpose of improving the horizontality to the substrate can be added. However, the liquid crystal alignment agent added with the silane coupling agent can improve the horizontality to the substrate, but it is extremely easy to apply. The generation of bubbles, which is the reason for the easy formation of sand holes in the liquid crystal alignment film, will cause the alignment of the liquid crystal and reduce the electrical characteristics of the produced liquid crystal display element. [Objective of the Invention] The present invention The purpose is to provide a liquid crystal alignment agent that does not cause foaming when coated on a substrate and has good coating properties. Other objects and advantages of the present invention will be apparent from the following description. SUMMARY OF THE INVENTION According to the content of the present invention, 'the purpose and advantages of the present invention are to provide a liquid crystal alignment agent', which contains (A) having a weight selected from the following formula (ϊ-1) Unit and polymer of at least one repeating unit in the repeating unit shown in the following formula (I-2), and (B) a silicon-containing compound liquid crystal alignment agent having a polyether bond; This paper size applies to Chinese national standards ( CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) 丨 Pain ·
、1T 經濟部智慈財產局員工消費合作社印製 -5- 591083 A7 B7 五、發明説明( HOOC\ COOH/P\ 1 HNOC CONH——Q1 1-1)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs -5- 591083 A7 B7 V. Description of the invention (HOOC \ COOH / P \ 1 HNOC CONH——Q1 1-1)
Q 1爲2價之有機 (1-2) (請先閲讀背面之注意事項再填寫本頁) 經濟部智慈財產局員工消費合作社印製 (式中,P2爲4價之有機基,Q2爲2價之有機 基)。 【發明之實施形態】 以下,將對本發明作進一步之說明。 (A )聚合物 本發明所使用之聚合物,係含有選自上記式(I -1 )所示重複單位與上記式(I - 2)所示重複單位中之 至少1種重複單位者。例如,具有聚醯胺酸及/或聚醯胺 酸經脫水閉環(醯亞胺化)所得構造之醯亞胺化聚合物。 又’本發明中,「醯亞胺化聚合物」係包含重複單位全部 經醯亞胺化者,及部份經醯亞胺化者。或,醯亞胺環中之 一部份爲異醯亞胺環者亦可。 本纸張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -6 - 591083 A7 B7 五、發明説明() 4 (请先閱讀背面之注意事項再填寫本頁) 本發明中較佳使用之聚合物,係爲具有上記式(I -1 )所示重複單位與上記式(I - 2 )所示重複單位的聚 合物。具有前述聚合物之液晶配向劑,例如下記①〜③之聚 合物等。 ①兼具有聚醯胺酸與醯亞胺化聚合物之液晶配向劑。 © 具有聚醯胺酸之預聚合物與,具有醯亞胺構造之預 聚合物所形成之含嵌段共聚合物之液晶配向劑。 ® 含有聚醯胺酸經部份脫水閉環所得醯亞胺化聚合 物之液晶配向劑。 其中,又以①與②爲更佳,又以①爲最佳。 聚醯胺酸 本發明所使用之聚醯胺酸,係由四羧酸二酐與二胺反 應而得者。 〔四羧酸二酐〕 經濟部智慧財產局員工消費合作社印製 合成上記聚醯胺酸所使用之四羧酸二酐,例如丁烷四 羧酸二酐、1,2,3,4 一環丁烷四羧酸二酐、1,2 —二甲基—1,2,3,4 一環丁烷四羧酸二酐、1,3 _二甲基—1 ,2,3,4 一環丁烷四羧酸二酐、1 ,3 —二氯基一 1,2,3,4 一環丁烷四羧酸二酐、1, 2,3,4 一四甲基—1,2,3,4 —環丁烷四羧酸二 酐、1,2,3,4一環戊烷四羧酸二酐、1,2,4, 5 —環己烷四羧酸二酐、3,3’ ,4,4,—二環己基 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 591083 A7 B7 五、發明説明(^ (請先閲讀背面之注意事項再填寫本頁) 四羧酸二酐、2,3,5 -三羧基環戊基乙酸二酐、3, 5,6 -三羧基原菠烷一 2 -乙酸二酐、2,3,4,5 —四氫咲喃四殘酸二酐、1,3,3a,4,5,9b -六氫一 5 (四氫一 2,5 —二氧代一 3 -呋喃基)一萘〔 1,2 — c〕—咲喃—1,3 —二酮、1,3,3a, 4,5,9b—六氫一5 甲基—5 —(四氫—2,5 -二 氧代—3 -呋喃基)—萘〔1,2 — c〕一呋喃一 1,3 —二酮、1 ,3,3 a,4,5,9b —六氫—5 —乙基 —5 (四氫一 2,5 —二氧代—3 -咲喃基)一萘〔1 ’ 2 — c〕—呋喃—1,3 —二酮、1,3,3a,4, 5,9b -六氫—7 -甲基一 5 (四氫—2,5 -二氧代 —3 —呋喃基)—萘〔1,2 - c〕—呋喃一 1,3 —二 酮、1 ,3,3 a ,4,5,9b —六氫一甲基一5 (四 氫一 2,5 —二氧代—3 -呋喃基)一萘〔1,2 - c〕 —咲喃—1,3 —二酮、1,3,3a,4,5,9b -六氫一 7 —乙基—5 (四氫一 2,5 -二氧代一 3 -呋喃 基)—萘〔1,2 — c〕—呋喃一 1,3 —二酮、1, 經濟部智慧財產局0(工消費合作社印製 3 ’ 3a ’ 4 ’ 5 ’ 9b —六氯—8 —甲基—5 (四氨— 2,5 —二氧代一 3 —呋喃基)—萘〔1,2 - c〕一呋 喃—1,3 —二酮、1,3,3a,4,5,9b —六氫 —8 —乙基—5 (四氫一 2,5 -二氧代一 3 —呋喃基) —萘〔1,2 — c〕-呋喃—1,3 —二酮、1,3,3 a ’ 4 ’ 5 ’ 9b —六氨一5 ’ 8 — —^甲基一 5 (四氨— 2,5 —二氧代—3 -呋喃基)—萘〔1,2 — c〕—呋 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 591083 A7 B7 五、發明説明(g (請先閱讀背面之注意事項再填寫本頁) 喃一 1,3 -二酮、5 -(2,5 -二氧代四氫呋喃基) —3 -甲基—3 -環己烯—1,2 -二羧酸二酐、二環〔 2,2,2〕—辛—7 —烯一 2,3,5,6 -四羧酸二 酐、下記式(I )與(I I )所示化合物等脂肪族及脂環 式四羧酸無水物;Q 1 is a 2-valent organic (1-2) (Please read the notes on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (where P2 is a 4-valent organic base, Q2 is Divalent organic group). [Embodiments of the invention] The present invention will be further described below. (A) Polymer The polymer used in the present invention contains at least one repeating unit selected from the repeating unit represented by the above formula (I -1) and the repeating unit represented by the above formula (I-2). For example, a fluorinated polymer having a structure obtained by dehydration ring closure (fluoridation) of polyfluorinated acid and / or polyfluorinated acid. In the present invention, the "fluorene imidized polymer" includes those in which all of the repeating units are fluorinated and some are fluorinated. Alternatively, a part of the fluorene imine ring is an isofluorene ring. This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -6-591083 A7 B7 V. Description of the invention () 4 (Please read the notes on the back before filling this page) It is better to use in the invention The polymer is a polymer having a repeating unit represented by the above formula (I -1) and a repeating unit represented by the above formula (I-2). The liquid crystal alignment agent having the aforementioned polymer is, for example, a polymer of the following ① to ③. ① Liquid crystal alignment agent having both polyamidic acid and fluorinated imidized polymer. © A block copolymer-containing liquid crystal alignment agent formed from a prepolymer having a polyamidic acid and a prepolymer having a fluorimine structure. ® A liquid crystal alignment agent containing a polyimide polymer obtained by partial dehydration and ring closure. Among them, ① and ② are more preferable, and ① is the best. Polyamic acid The polyamino acid used in the present invention is obtained by reacting a tetracarboxylic dianhydride with a diamine. [Tetracarboxylic dianhydride] The tetracarboxylic dianhydride used in the synthesis of polyamic acid printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as butane tetracarboxylic dianhydride, 1, 2, 3, 4 Alkanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4 monocyclobutanetetracarboxylic dianhydride, 1,3_dimethyl-1,2,3,4 monocyclobutanetetra Carboxylic dianhydride, 1,3-dichloro-1,2,3,4 monocyclobutanetetracarboxylic dianhydride, 1,2,3,4 tetramethyl-1,2,3,4-cyclo Butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4, —The basic paper size of Dicyclohexane is applicable to China National Standard (CNS) A4 (210X297 mm) 591083 A7 B7 V. Description of the invention (^ (Please read the notes on the back before filling this page) Tetracarboxylic dianhydride, 2 , 3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxyoranidine- 2-acetic dianhydride, 2,3,4,5-tetrahydrofuran tetraresidic acid dianhydride, 1,3,3a, 4,5,9b -Hexahydro-5 (tetrahydro-2,5-dioxo-3 -furan Yl) mononaphthalene [1,2-c] -pyran-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5 methyl-5-(tetrahydro-2,5 -Dioxo-3-furyl) -naphthalene [1,2-c] -furan-1,3-dione, 1,3,3 a, 4,5,9b-hexahydro-5-ethyl- 5 (tetrahydro-2,5-dioxo-3-pyranyl) -naphthalene [1 '2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphthalene [1,2-c] -furan-1,3-dione, 1,3,3 a, 4,5,9b —Hexahydromonomethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphthalene [1,2, c] —pyran-1,3 —di Ketone, 1,3,3a, 4,5,9b -hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3 -furanyl) -naphthalene [1,2, c]- Furan-1,3-dione, 1, Intellectual Property Bureau of the Ministry of Economic Affairs 0 (printed by the Industrial and Consumer Cooperatives 3 '3a' 4 '5' 9b -hexachloro-8 -methyl-5 (tetraamine-2,5- Dioxo-3-furanyl) -naphthalene [1,2,- c] monofuran-1,3-dione, 1,3,3a, 4,5,9b -hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3 -furanyl) —Naphthalene [1,2, c] -furan-1,3-dione, 1,3,3 a '4' 5 '9b —hexamine-5' 8 — — ^ methyl-5 (tetraammine-2 , 5-dioxo-3-furanyl) -naphthalene [1,2-c] —The size of fur paper is subject to Chinese National Standard (CNS) A4 (210X297 mm) 591083 A7 B7 V. Description of the invention (g ( Please read the notes on the back before filling in this page.) 1,2,3 -dione, 5-(2,5 -dioxotetrahydrofuranyl) -3 -methyl -3 -cyclohexene -1,2,- Fatty acids such as dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-1,2,3,5,6-tetracarboxylic dianhydride, compounds represented by the following formulae (I) and (II) Family and alicyclic tetracarboxylic acid anhydrous;
(式中,R1與R3爲具有芳香環之2價有機基,R2 與R4爲氫原子或烷基,複數存在之R2與R4可各自爲相 同或相異)。 經濟部智慧財產局員工消費合作社印製 均苯四 甲 酸 二 酐 , 例 如 3 5 3 , 4 ,4 ♦ —_. 苯甲 酮四羧酸二 酐 3 5 3 4 > 4 — 聯 苯碩 四 羧酸 二 酐、 1, 4 5 5 5 8 — 萘 四 羧 酸 二 酐 \ 2 ,3 , 6, 7 - 萘四羧酸二 酐 3 5 3 贅 j 4 , 4 , — 聯 苯醚 四 羧酸 二 酐、 * 3, 3 贅 5 4 4 — 一 甲 基 二 苯 基 矽烷 四 羧酸 二 酐、 ‘3, 丨3 9 > 4 4 — 四 苯 基 矽 院 四 羧酸 二 酐、 1, 2, ,3, 丨4 — 呋 喃 四 羧 酸 二 酐 、 4 4 $ —雙 ( 3 , 4 - 二殘基苯氧基)二苯基硫醚二酐、 本紙張尺度適用中國國家標準(CNS ) A4規格(210X:Z97公釐) .4 ^1083 A7 ——^____£Z_ 五、發明説明(、 4,4’ 一雙(3,4 一二羧基苯氧基)二苯基碩二 酉干、4,4, 一雙(3,4 一二羧基苯氧基)二苯基硫醚 二酐、4,4’ 一雙(3,4 —二羧基苯氧基)二苯基丙 燒二酐、3, 3’ ,4,4’ 一全氟異亞丙基二苯二酸二 酐、3,3’ ,4,4,—二苯基四羧酸二酐、雙(苯二 酸)苯基膦氧化物二酐、p 一伸苯基一雙(三苯基苯二 酸)二酐、m —伸苯基一雙(三苯基苯二酸)二酐、雙 (三苯基苯二酸)-4,4’ —二苯基醚二酐、雙(三苯 基苯二酸)一 4,4’ 一二苯基甲烷二酐、乙二醇一雙 (脫水偏苯三酸酯)丙二醇-雙(脫水偏苯三酸酯)、 1 ’ 4 一丁二醇—雙(脫水偏苯三酸酯)、1,6 -己二 醇一雙(脫水偏苯三酸酯)、1,8 -辛二醇一雙(脫水 偏苯三酸酯)、2,2 -雙(4 一羥苯基)丙烷一雙(脫 水偏苯三酸酯)、下記式(1 )至(4 )所示化合物等芳 香族四羧酸二酐等。其可單獨使用1種或將2種以上組合 使用。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局g(工消費合作社印製 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -10- 591083 五、發明説明( Ο 0(In the formula, R1 and R3 are divalent organic groups having an aromatic ring, R2 and R4 are hydrogen atoms or alkyl groups, and plural R2 and R4 may be the same or different). Pyromellitic dianhydride printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as 3 5 3, 4, 4 ♦ —_. Benzophenone tetracarboxylic dianhydride 3 5 3 4 > 4 — Biphenylsulfonic tetracarboxylic acid Acid dianhydride, 1, 4 5 5 5 8 —naphthalene tetracarboxylic dianhydride \ 2, 3, 6, 7-naphthalene tetracarboxylic dianhydride 3 5 3 j 4, 4, — diphenyl ether tetracarboxylic acid dianhydride Anhydride, * 3, 3 and 5 4 4 —monomethyldiphenylsilane tetracarboxylic dianhydride, '3, 丨 3 9 > 4 4 —tetraphenylsilane tetracarboxylic dianhydride, 1, 2, , 3, 丨 4 — Furantetracarboxylic dianhydride, 4 4 $ —Bis (3, 4-diresidual phenoxy) diphenyl sulfide dianhydride, this paper size applies to China National Standard (CNS) A4 specifications (210X: Z97 mm) .4 ^ 1083 A7 —— ^ ____ £ Z_ V. Description of the invention (4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfonium dihydrazone, 4 , 4, bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4 'bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3 , 3 ' 4,4 'monoperfluoroisopropylenediphthalic dianhydride, 3,3', 4,4,4-diphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride , P-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4 ' —Diphenyl ether dianhydride, bis (triphenylphthalic acid) —4,4′—diphenylmethane dianhydride, ethylene glycol—bis (anhydrotrimellitic acid ester), propylene glycol—bis (anhydroanhydrobenzene) Triester), 1 '4-Butanediol-bis (anhydrotrimellitic acid ester), 1,6-Hexanediol-anhydrous (anhydrotrimellitic acid ester), 1,8-octanediol an-anhydrous (Dehydrated trimellitate), 2,4-bis (4-hydroxyphenyl) propane-bis (dehydrated trimellitate), aromatic tetracarboxylic compounds such as compounds represented by the following formulae (1) to (4) Acid dianhydride, etc. It can be used alone or in combination of two or more. (Please read the precautions on the back before filling this page) Intellectual Property Bureau of the Ministry of Economic Affairs (printed by the Industrial Cooperative Cooperative) Standard (CNS) A4 specification (210X297 PCT) -10-591083 V. invention is described (o 0
0 A7 B70 A7 B7
.CH3 、CH3(2) 經濟部智慧財產局員工消費合作社印製.CH3, CH3 (2) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs
(請先閲讀背面之注意事項再填寫本頁)(Please read the notes on the back before filling this page)
本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) ^ -11 - 591083 A7 __ B7 ____This paper size applies to China National Standard (CNS) A4 (210X 297 mm) ^ -11-591083 A7 __ B7 ____
五、發明説明(I (請先閱讀背面之注意事項再填寫本頁) 其中又以丁烷四羧酸二酐、1 ’ 2,3 ’ 4 一環丁院 四羧酸二酐、1,3 -二甲基—1,2,3,4 一環丁烷 四羧酸二酐、1,2,3,4 一環戊烷四羧酸二酐、2 ’ 3,5 -三羧基環戊基乙酸二酐、5— (2,5 -二氧代 四氫呋喃基)—3 -甲基一 3 -環己烯一 1,2 -二幾酸 二酐、1,3,3a,4,5,9b —六氫—5 —(四氫 一 2,5 -二氧代一 3 —呋喃基)—萘〔1,2 - c〕咲 喃一1,3 —二酮、1,3,3 a,4,5,9b -六氫 一 8 —甲基—5 —(四氫一 2,5 —二氧代—3 -咲喃 基)一萘〔1,2 — c〕呋喃—1,3 —二酮、1,3, 3a ,4,5 ,9b —六氫一5,8 —二甲基一 5 —(四 氫一 2,5 —二氧代-3 -呋喃基)—萘〔1,2 - c〕 呋喃—1,3 —二酮、二環〔2,2,2〕—辛一 7 一儲 一 2,3,5,6 —四羧酸二酐、偏苯四甲酸二酐、3 ’ 3’ ,4,4’ —二苯甲酮四羧酸二酐、3,3’ ,4, 經濟部智慧財產局Μ工消費合作社印製 4,—聯苯基硕四羧酸二酐、1,4,5,8 —萘四羧酸 二酐、上記式(I )所示化合物中之下記式(5 )至 (7)所示化合物,與上記式(I I)所示化合物中之下 記式(8 )所示化合物,因具有良好液晶配向性,故爲較 佳使用之化合物。特別是以1,2,3,4 -環丁烷四羧 酸二酐、2,3,5 —三羧基環戊基乙酸二酐、1,3, 3 a,4,5,9b —六氫-5—(四氫—2,5 —二氧 代一 3 -呋喃基)—萘〔1,2 — c〕呋喃—1,3 -二 酮、1,3,3 a,4,5,9b —六氫一 8 —甲基一 5 1紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐)~ — " -12- 591083 A7 B7 五、發明説明( 10 —(四氯一 2 ’ 5 — 一氧代一 3 -咲喃基)一蔡〔1 ’ 2 一 c〕呋喃—1,3 -二酮、偏苯四甲酸二酐、與下記式 (5 )所示化合物爲更佳。 Ο 0V. Description of the invention (I (please read the notes on the back before filling out this page) Among them, butane tetracarboxylic dianhydride, 1 '2, 3' 4 monocyclobutane tetracarboxylic dianhydride, 1, 3- Dimethyl-1,2,3,4 monocyclobutanetetracarboxylic dianhydride, 1,2,3,4 monocyclopentanetetracarboxylic dianhydride, 2 '3,5-tricarboxycyclopentylacetic dianhydride , 5- (2,5 -dioxotetrahydrofuryl) -3 -methyl- 3 -cyclohexene-1,2-dicarbic acid dianhydride, 1,3,3a, 4,5,9b -hexahydro —5 — (tetrahydro-2,5-dioxo-3furanyl) —naphthalene [1,2, c] pyran-1,3-dione, 1,3,3 a, 4, 5, 9b -hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3 -pyranyl) -naphthalene [1,2, c] furan-1,3-dione, 1, 3, 3a, 4, 5, 9b —hexahydro-5,8 —dimethyl-5 — (tetrahydro-2,5-dioxo-3 -furyl) —naphthalene [1,2, c] furan —1,3 —dione, bicyclo [2,2,2] —octyl-7, storage one 2,3,5,6-tetracarboxylic dianhydride, trimellitic dianhydride, 3 ′ 3 ′, 4, 4 '— Benzophenonetetracarboxylic dianhydride, 3,3 ', 4, printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Industrial and Commercial Cooperative, 4, 4-biphenylsulfonic tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetra Carboxylic dianhydride, compounds represented by the following formulae (5) to (7) among the compounds represented by the formula (I) above, and compounds represented by the following formula (8) among the compounds represented by the formula (II), because Good liquid crystal alignment, so it is a preferred compound. Especially 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1, 3, 3 a, 4, 5, 9b —hexahydro-5— (tetrahydro-2,5-dioxo-3—furanyl) —naphthalene [1,2, c] furan-1,3-dione 、 1,3,3 a, 4,5,9b —Hexahydro-8—Methyl-1 5 1 Paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) ~ — " -12- 591083 A7 B7 V. Description of the invention (10- (tetrachloro-2'5-monooxo-3-pyranyl) -Cai [1'2-c] furan-1,3-dione, trimellitic dianhydride And compounds represented by the following formula (5) are more preferred.
0 (5)0 (5)
Ο 0 (6)Ο 0 (6)
(7) (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 〇 0(7) (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇 0
(8) 〔二胺〕 可用於合成上記聚醯胺酸之二胺,例如p 一苯二胺 m —苯二胺、4,4, 一二胺基二苯基甲烷、4,4, 二胺基二苯基乙烷、4,4’ —二胺基二苯基硫醚、4 本紙張尺度適用中國國家標準(CNS ) A4規格(210Χ;Ζ97公釐) -13- 591083 A7 B7_ 五、發明説明( 4,—二胺基二苯基碩、3,3’ —二甲基一 4,4,一 (請先閲讀背面之注意事項再填寫本頁) 二胺基聯苯基、4,4’ 一二胺基N —苯甲醯苯胺、4 ’ 4,—二胺基二苯基醚'1,5 -二胺基萘、2,2’ 一 二甲基—4,4,—二胺基聯苯基、3 ’ 3 —一甲基一 4,4,—二胺基聯苯基、2,2’ —二三氟甲基—4, 4,—二胺基聯苯基、3,3’ —二三氟甲基—4,4’ 一二胺基聯苯基、5 -胺基一 1 一(4’ 一胺基苯基)一 1,3,3 -三甲基茚滿、6 -胺—1 一(4’ —胺基苯 基)—1,3,3-三甲基茚滿、3,4’一二胺基二苯 基醚、3,3’ 一二胺基二苯甲酮、3,4’ —二胺基二 苯甲酮、4,4’ 一二胺基二苯甲酮、2,2’ —雙〔4 一(4 一胺基苯氧基)苯基〕丙烷、2,2’ 一雙〔4 一 (4 一胺基苯氧基)苯基〕六氟丙烷、2,2’ 一雙(4 一胺基苯基)六氟丙烷、2,2’ 一雙〔4—(4一胺基 苯氧基)苯基〕硕、1,4 一雙(4 一胺基苯氧基)苯、 經濟部智慧財產局8工消費合作社印製33· 1,3 -雙(4 —胺基苯氧基)苯、1,3 -雙(3 -胺 基苯氧基)苯、9,9 一雙(4 一胺基苯基)—1 0 -氫 蒽、2,7 -二胺基芴、9,9 —雙(4 —胺基苯基) 芴、4,4’—伸甲基—雙(2 -氯苯胺)、2,2’ , 5,5,—四氯—4,4’ —二胺基聯苯基、2,2,— 二氯—4,4’ _二胺基—5,5’ 一二甲氧基聯苯基、 3,3 -一甲氧基—4,4,—二胺基聯苯基、1, 4,4,—(p —伸苯基異亞丙基)雙苯胺、2,2,-雙〔4 一( 4 一胺基一 2 -三氟甲基苯氧基)苯基〕六氟 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -14- 591083 A7 B7 _ 五、發明説明(12) (請先閲讀背面之注意事項再填寫本頁) 丙烷、4,4’ —二胺基一 2,2’ 一雙(三氟甲基)聯 苯基、4,4’ 一雙〔(4 —胺基一 2 -三氟甲基)苯氧 基〕-八氟聯苯基等芳香族二胺類; 1 ,1 一伸甲氧基二胺、1 ,3 -丙二胺、四甲基二 胺、五甲基二胺、六甲基二胺、七甲基二胺、八甲基二 胺、九甲基二胺、4,4’ —二胺基七甲基二胺、1,4 -二胺基環己烷、異佛爾酮二胺、四氫二環戊二烯二胺、 六氫一 4,7 —甲醇基茚滿二伸甲基二胺、三環〔6 . 2.1.〇2’7〕—十一烯二甲基二胺、4,4’一伸甲 基雙(環己胺)等脂肪族與脂環式二胺; 經濟部智慧財產局S工消費合作社印製 2,3 —二胺基吡啶、2,6 -二胺基吡啶、3,4 —二胺基吡啶、2,4 —二胺基吡啶、5,6 —二胺基一 2,3-二胺基吡嗪、5,6-二胺基一 2,4 —二氫基 嘧啶、2,4 —二胺基—6 -二甲基胺基一 1,3,5 -三嗪、1,4 一雙(3 —胺丙基)哌嗪、2,4 —二胺基 —6 —異丙氧基—1,3,5 —三嗪、2,4—二胺基一 6 -甲氧基一 1 ,3,5 —三嗪、2,4 —二胺基一6 — 本基一 1,3,5 —三嗪、2,4 一二胺基一 6 —甲基一 s - 三嗪、2,4 一 二胺基—1,3,5-三嗪、4,6 一二胺基—2 —乙醯基—s —三嗪、2,4 —二胺基一 5 一苯基噻唑、2,6-二胺基嘌呤、5,6 —二胺基一 1,3 —二甲基尿嘧啶、3,5 -二胺基一 1,2,4一 三唑、6,9 —二胺基—2 -乙氧基吖啶丙醇酸酯、3, 8 —二胺基一 6 —苯基菲啶、1,4 一二胺基哌嗪、3, 3¾.本紙張尺度適用中國國家樣準(CNS ) A4規格(210X297公釐) -15- 591083 A7 B7 五 、發明説明j( 4(8) [Diamine] It can be used to synthesize the diamine of the polyamidic acid described above, such as p-phenylenediamine m-phenylenediamine, 4,4, diaminodiphenylmethane, 4,4, diamine Diphenyl ethane, 4,4'-diaminodiphenyl sulfide, 4 This paper size is applicable to China National Standard (CNS) A4 specifications (210 ×; Z97 mm) -13- 591083 A7 B7_ V. Invention Description (4,4-Diaminodiphenyl master, 3,3'-dimethyl-4,4,1 (Please read the precautions on the back before filling this page) Diaminobiphenyl, 4,4 'Monodiamino N-benzidine aniline, 4' 4, Diamino diphenyl ether '1,5-Diamino naphthalene, 2,2' Monodimethyl-4,4, -Diamine Dibiphenyl, 3 ′ 3-monomethyl-4,4, -diaminobiphenyl, 2,2′-ditrifluoromethyl-4, 4, diaminobiphenyl, 3, 3'-ditrifluoromethyl-4,4'-diaminobiphenyl, 5-amino-1 (4'monoaminophenyl) -1,3,3-trimethylindane, 6-Amine-1 mono (4'-aminophenyl) -1,3,3-trimethylindane, 3,4'-diaminodiphenyl ether 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2'-bis [4 one (4 Monoaminophenoxy) phenyl] propane, 2,2 'monobis [4 mono (4 monoaminophenoxy) phenyl] hexafluoropropane, 2,2' monobis (4 monoaminophenyl) ) Hexafluoropropane, 2,2 'bis [4- (4-aminophenoxy) phenyl], 1,4-bis (4-aminophenoxy) benzene, Intellectual Property Bureau of the Ministry of Economic Affairs 8 Industrial and consumer cooperatives printed 33.1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminoaminobenzene) Radicals) —1 0-hydroanthracene, 2,7-diaminofluorene, 9,9—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'-dimethoxy Phenylbiphenyl, 3,3-monomethoxy-4,4,4-diaminobiphenyl, 1,4,4,-(p-phenylene isopropylidene) bisaniline, 2,2 , -Double [4 one (4 one 2-a-trifluoromethylphenoxy) phenyl] hexafluoro This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) -14- 591083 A7 B7 _ 5. Description of the invention (12) (Please Please read the notes on the back before filling in this page) Propane, 4,4 '—diamino-1,2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino Aromatic diamines such as 1-trifluoromethyl) phenoxy] -octafluorobiphenyl; 1,1-dimethoxymethoxydiamine, 1,3-propanediamine, tetramethyldiamine, penta Methyldiamine, hexamethyldiamine, heptamethyldiamine, octamethyldiamine, nonamethyldiamine, 4,4'-diamino heptamethyldiamine, 1,4-diamine Cyclohexane, isophoronediamine, tetrahydrodicyclopentadienediamine, hexahydro-4,7-methanolylindanediethylenediamine, tricyclic [6. 2.1.〇2'7 ] —Undecenyl dimethyl diamine, 4,4'-methylene bis (cyclohexylamine) and other aliphatic and alicyclic diamines; printed by S Industrial Consumer Cooperative, Bureau of Intellectual Property, Ministry of Economic Affairs, 2, 3 — 2 Aminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine Pyridine, 2,4-diaminopyridine, 5,6-diamino-2,3-diaminopyrazine, 5,6-diamino-2,4-dihydropyrimidine, 2,4 — Diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy —1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6—benzyl-1,3, 5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2- Acetyl-s-triazine, 2,4-diamino-5 monophenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridinyl propionate, 3,8-diamino-6-phenylphenanthrene Pyridine, 1,4 diaminopiperazine, 3, 3¾. This paper size applies to China National Standard (CNS) A4 (210X297 mm) -15- 591083 A7 B7 V. Description of invention j (4
H2N NH2 (V) (式中,R7爲由一◦一 C〇〇一、一〇c〇~~、 -NHCO —、一 C〇NH —與一C〇一中所選出的2價 有機基,R8爲具有由膽固甾骨架、三氟甲基與氟基中所選 出基之1價有機基或碳數6至3 0之烷基)H2N NH2 (V) (wherein R7 is a divalent organic group selected from the group consisting of -CO1-, COCO- ~, -NHCO-, -CO-NH- and -CO-1, R8 is a monovalent organic group or an alkyl group having 6 to 30 carbon atoms having a group selected from a cholesteric skeleton, a trifluoromethyl group and a fluoro group)
H2N+CH R 〇—Si-H2N + CH R 〇—Si-
R 9 7q CH2j-NH2 (VI) (請先閲讀背面之注意事項再填寫本頁) (式中,R9爲碳數1至1 2之烴基,複數存在之 R9,可各別爲相同或不同,P爲1至3之整數,Q爲1至 2 0之整數) 經濟部智慧財產局員工消費合作社印製 又如下記式(9)至(1 3)所示化合物等。前述二 胺,可單獨或將2種以上組合使用皆可。 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -17- 591083 A7 B7 五、發明説明 \5 CH3R 9 7q CH2j-NH2 (VI) (Please read the notes on the back before filling out this page) (where R9 is a hydrocarbon group with 1 to 12 carbons, and the plural R9 may be the same or different, P is an integer from 1 to 3, and Q is an integer from 1 to 20) The compound printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the following formulas (9) to (1 3). The diamine may be used alone or in combination of two or more kinds. This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -17- 591083 A7 B7 V. Description of the invention \ 5 CH3
CH3 H3C CH ( CH2 )3 CHCH3 H3C CH (CH2) 3 CH
NH2 CH3 (9) CH3 H3C CH(CH2)3CH CH3 CH3NH2 CH3 (9) CH3 H3C CH (CH2) 3CH CH3 CH3
CH3CH3
H2NH2N
/—NH2/ —NH2
CH3 I H3c pH(CH2}3CH CH3 (11) (請先閱讀背面之注意事項再填寫本頁)CH3 I H3c pH (CH2) 3CH CH3 (11) (Please read the precautions on the back before filling this page)
C2H4 NH2V°O (12)C2H4 NH2V ° O (12)
H2NH2N
s- NH2s- NH2
(13) 經濟部智慧財產局員工消費合作社印製 (式中,y爲2至12之整數,z爲1至5之整數) 其中又以,P —苯二胺、m —苯二胺、4,4,—二 胺基二苯基甲烷、4,4’ 一二胺基二苯基硫醚、1,5 —二胺基萘、2,2’ —二甲基—4,4’ —二胺基聯苯 基、2,2’ —二三氟甲基—4,4’ —二胺基聯苯基、 2,7 —二胺基芴、4,4’ —二胺基二苯基醚、2, 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) -18- 591083 A7 B7 五、發明説明(16 ) 2,—雙〔4 一(4 一胺基苯氧基)苯基〕丙烷、9,9 一雙(4 一胺基苯基)芴、2,2,-雙(4 一胺苯基) 六氟丙烷、4,4’ 一(P -伸苯基二異亞丙基)雙苯 胺、4,4’ 一(m —伸苯基二異亞丙基)雙苯胺、1, 4 一環己烷二胺、4,4’ 一伸甲基雙(環己胺)、1, 4 —雙(4 一胺基苯氧基)苯、4,4,一雙(4 一胺基 苯氧基)聯苯基,上記式(9 )至(1 3 )所示化合物, 2,6 —二胺基吡啶、3,4 一二胺基吡啶、2,4 一二 胺基嘧啶、3,6 -二胺基吖啶、上記式(I I I )所示 化合物中之下記式(1 4 )所示化合物,上記式(I v) 所示化合物中之下記式(1 5 )所示化合物,及上記式 (V)所示化合物中,十二烷氧一 2,4 一二胺基苯、十 五烷氧一 2,4 —二胺基苯、十六烷氧一 2,4 一二胺基 苯、十八烷氧—2,4 —二胺基苯、十二烷氧一 2,5 — 二胺基苯、十五烷氧一 2,5 -二胺基苯、十六烷氧一 2 ’ 5 —二胺基苯、十六烷氧一 2,5 -二胺基苯、與下 記式(1 6 )至(2 1 )所示化合物爲佳。 m I * 丨i 1^1 LH ϋ— mi —ml ϋ (請先閲讀背面之注意事項再填寫本頁) 訂 P. 經濟部智慧財產局B(工消費合作社印製 β74本紙張尺度適用中國國家標準(CNS )八4規格(210 X 297公釐) -19- 591083 A7 B7 五、發明説明(17 COO —CH2CH2 —(~yrS N (14) Η2Ν~ν^ΝΗ2 h2nh〇~nLXcH2VCn~〇~nh2 (15) COO·Η2Ν--^Χ-ΝΗ2(13) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (where y is an integer from 2 to 12 and z is an integer from 1 to 5) where P—phenylenediamine, m—phenylenediamine, 4 4,4-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-di Amino biphenyl, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether 2. This paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210X 297 mm) -18- 591083 A7 B7 5. Description of the invention (16) 2, bis [4 one (4 monoaminophenoxy) Phenyl] propane, 9,9-bis (4-aminoaminophenyl) fluorene, 2,2, -bis (4-monoaminophenyl) hexafluoropropane, 4,4 '-(P-phenylene diiso Propylene) bisaniline, 4,4 'mono (m-phenylene diisopropylidene) bisaniline, 1,4 monocyclohexanediamine, 4,4' monomethylbis (cyclohexylamine), 1, 4-bis (4-aminophenoxy) benzene, 4,4,4-bis (4-aminophenoxy) biphenyl Group, the compounds represented by the above formulae (9) to (1 3), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diamine group Acridine, a compound represented by the following formula (1 4) among the compounds represented by the above formula (III), a compound represented by the following formula (1 5) among the compounds represented by the formula (I v), and the above formula (V) Among the compounds shown, dodecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecane Oxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, hexadecyloxy-2 '5-diamine Phenylbenzene, hexadecyloxy-2,5-diaminobenzene, and compounds represented by the following formulae (1 6) to (2 1) are preferred. m I * 丨 i 1 ^ 1 LH ϋ— mi —ml ϋ (Please read the notes on the back before filling out this page) Order P. Intellectual Property Bureau of the Ministry of Economy B (printed by the Industrial and Consumer Cooperatives β74 This paper is applicable to China Standard (CNS) 8 4 specifications (210 X 297 mm) -19- 591083 A7 B7 V. Description of the invention (17 COO —CH2CH2 — (~ yrS N (14) Η2Ν ~ ν ^ ΝΗ2 h2nh〇 ~ nLXcH2VCn ~ 〇 ~ nh2 (15) COO · Η2Ν-^ Χ-ΝΗ2
H3CH3C
CH3 H3C CH(CH2)3CH CH3 CH3 (16) CH3CH3 H3C CH (CH2) 3CH CH3 CH3 (16) CH3
H3C CH(CH2)3CHH3C CH (CH2) 3CH
H2NH2N
CH3 CH3 (17) CH3 H3C CH(CH2)3CH=C" <CH3CH3 CH3 (17) CH3 H3C CH (CH2) 3CH = C " < CH3
H3C CH3 H2N-J^JLNH2H3C CH3 H2N-J ^ JLNH2
H3C H2NH3C H2N
CH3 (18) CH3 I 丨 CH(CH2)3CH = ^CH3 =C\ ^CH3 (19) H3C CH3 經濟部智慧財產局員工消费合作社印製 COO 00c- rS H2N-X>-NH2 /CF3 V/ (20) COO -〇 00c- H2N -0- NH2 (21 ) (請先閲讀背面之注意事項再填寫本頁)CH3 (18) CH3 I 丨 CH (CH2) 3CH = ^ CH3 = C \ ^ CH3 (19) H3C CH3 Printed by COO 00c- rS H2N-X > -NH2 / CF3 V / ( 20) COO -〇00c- H2N -0- NH2 (21) (Please read the precautions on the back before filling this page)
本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -20- 591083 A7 B7 五、發明説明(18 ) 〔聚醯胺酸之合成〕 (請先閲讀背面之注意事項再填寫本頁) 用於聚醯胺酸之合成反應之四羧酸二酐與二胺化合物 之使用比例,以對包含於二胺化合物之胺基1當量,使用 0·2至2當量四羧酸二酐之酸酐基之比例爲佳,更佳爲 0.3至1.2當量之比例。 聚醯胺酸之合成反應,係於有機溶媒中,一般於 一 2 0 °C至1 5 0 t、較佳爲0至1 0 0 t之溫度條件下 進行。其中,有機溶媒只要可溶解合成之聚醯胺酸者即無 特別之限定,例如N -甲基—2 —吡咯烷酮、N,N —二 甲基乙烯醯胺、N,N —二甲基甲醯胺、二甲基磺氧化 物、r -丁內酯、四甲基脲、六甲基膦三醯胺等非質子系 極性溶媒;間甲酚、二甲苯酚、苯酚、鹵化苯酚等苯酚系 溶媒等。又,有機溶媒之使用量(a),一般於四羧酸二 酐與二胺化合物之總量爲(b )下,對反應溶液之全量 (a+b)以使用〇·1至30重量%之量爲佳。 經濟部智慧財產局8工消費合作社印製 又,前記有機溶媒中,可將聚醯胺酸之貧溶媒的醇 類、酮類、酯類、醚類、鹵化烴類、烴類等,於不會造成 生成之醯胺酸產生結晶之範圍下予以倂用。前述貧溶媒之 具體例,例如甲醇、乙醇、異丙醇、環己醇、乙二醇、丙 二醇、1 ,4 — 丁二醇、三乙醇、乙二醇單甲基醚、乳酸 乙酯、乳酸丁酯、丙酮、甲基乙基酮、甲基異丁酮、環己 酮、乙酸甲酯、乙酸乙酯、乙酸丁酯、甲基甲氧基丙酸 酯、乙基乙氧基丙酸酯、草酸二乙酯、丙二酸二乙酯、二 乙醚、乙二醇甲基醚、乙二醇乙基醚、乙二醇—η — 丁基 本纸張尺度適用中國國家樣準(CNS〉Α4規格(210X297公釐) 〜 經濟部智慧財產局員工消費合作社印製 591083 A7 B7 五、發明説明(19 ) 醚、乙二醇二甲基醚、乙二醇乙基醚乙酸酯、二乙二醇二 甲基醚、二乙二醇二乙基醚、二乙二醇單甲基醚、二乙二 醇單乙基醚、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基 醚乙酸酯、四氫呋喃、二氯甲烷、1,2 —二氯乙院、 1,4 一二氯丁烷、三氯乙烷、氯基苯、〇 -二氯基苯、 己烷、庚烷、辛烷、苯、甲苯、二甲苯等。 如上所示般,將聚醯胺酸溶解後即可製得反應溶液。 隨後,將此反應溶液注入大量貧溶媒中而得析出物,將此 析出物於減壓下乾燥後得聚醯胺酸。又,可將此聚醯胺酸 再溶解於有機溶媒中,隨後再以溶媒進行1次或多次析出 步驟,以對聚醯胺酸進行精製。 醯亞胺化聚合物 本發明所使用之醯亞胺化聚合物,係將四羧酸二酐與 二胺反應所製得之聚醯胺酸,經脫水閉環而製得者。 〔四羧酸二酐〕 上記合成醯亞胺化聚合物所使用之四羧酸二酐,例如 上記合成聚醯胺所使用之四羧酸二酐等。 本發明之合成醯亞胺化聚合物所使用之四羧酸二酐, 以使用脂環式四羧酸二酐爲佳。最佳之具體例示如,2, 3,5 —三羧基環戊基乙酸二酐、l,3,3a,4, 5,9b —六氫—5 -(四氫—2,5 -二氧代一 3 —呋 喃基)—萘〔1,2 — c〕—呋喃—1,3 -二酮、1, 77本紙張尺度適用中國國家標準(CNS〉A4規格(210X297公釐) -22- (請先閲讀背面之注意事項再填寫本頁)This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -20-591083 A7 B7 V. Description of the Invention (18) [Synthesis of Polyamic Acid] (Please read the notes on the back before filling this page ) The ratio of tetracarboxylic dianhydride to diamine compound used in the synthesis reaction of polyamic acid is to use 1 equivalent of the amine group contained in the diamine compound and use 0.2 to 2 equivalents of tetracarboxylic dianhydride. The proportion of acid anhydride groups is preferred, and a ratio of 0.3 to 1.2 equivalents is more preferred. The synthesis reaction of the polyamic acid is carried out in an organic solvent, and is generally carried out at a temperature of 20 ° C to 150 t, preferably 0 to 100 t. Among them, the organic solvent is not particularly limited as long as it can dissolve the synthetic polyamino acid, for example, N-methyl-2-pyrrolidone, N, N-dimethylvinylamine, N, N-dimethylformamidine Aprotic polar solvents such as amines, dimethylsulfoxide, r-butyrolactone, tetramethylurea, and hexamethylphosphinetriamine; phenol solvents such as m-cresol, xylenol, phenol, and halogenated phenol Wait. In addition, the amount (a) of the organic solvent is generally used under the total amount of the tetracarboxylic dianhydride and the diamine compound (b), and the total amount (a + b) of the reaction solution is used in the range of 0.1 to 30% by weight. The amount is better. Printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In the previous organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc. of the poor solvents of polyamic acid can be used in the organic solvent. It is used in the range that will cause the generated glutamic acid to crystallize. Specific examples of the aforementioned lean solvent include, for example, methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethanol, ethylene glycol monomethyl ether, ethyl lactate, and lactic acid Butyl ester, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate , Diethyl oxalate, Diethyl malonate, Diethyl ether, Glycol methyl ether, Glycol ethyl ether, Glycol — η — Butyl This paper size is applicable to Chinese national standards (CNS> Α4 Specifications (210X297 mm) ~ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 591083 A7 B7 V. Description of the invention (19) Ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol Alcohol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol mono Ethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, 〇- Chlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, etc. As shown above, the polyamic acid is dissolved to prepare a reaction solution. Subsequently, this reaction solution is injected into a large amount of lean solvent The precipitate is obtained in the middle, and the precipitate is dried under reduced pressure to obtain polyamic acid. In addition, the polyamino acid may be re-dissolved in an organic solvent, and then one or more precipitation steps may be performed with the solvent. The polyimide polymer is used for the purification of polyamidic acid. The polyimide polymer used in the present invention is a polyamidic acid prepared by reacting a tetracarboxylic dianhydride with a diamine. [Tetracarboxylic dianhydride] The tetracarboxylic dianhydride used in the synthesis of fluorinated imidized polymers described above, such as the tetracarboxylic dianhydride used in the synthesis of polyfluorinated amines. Synthesis of the present invention As the tetracarboxylic dianhydride used in the fluorinated polymer, an alicyclic tetracarboxylic dianhydride is preferably used. The best specific examples are 2, 3, 5-tricarboxycyclopentylacetic dianhydride, l, 3,3a, 4,5,9b —hexahydro-5 — (tetrahydro-2,5-dioxo-3 —furanyl) — 〔1,2—c〕 —Furan-1,3-dione, 1,77 This paper size applies to Chinese national standards (CNS> A4 specification (210X297 mm) -22- (Please read the precautions on the back before filling (This page)
591083 A7 _Β7 五、發明説明(2〇 ) 3,3 a,4,5,9b —六氫一 8 —甲基一5 —(四氫 (請先閲讀背面之注意事項再填寫本頁} 〜2,5 —二氧代一 3 —呋喃基)—萘〔1,2 — c〕一 吹喃一 1,3 —二酮等。又,脂環式四羧酸二酐亦可與其 他四羧酸二酐合倂使用。 〔二胺〕 上記之合成醯亞胺化聚合物所使用之二胺,例如上記 之合成聚醯胺酸所使用之二胺等。 本發明之合成醯亞胺化聚合物所使用之二胺,亦可將 上記式(V )所示二胺與其他二胺倂用。較佳之其他二 胺,例如P-苯二胺、4,4’ 一二胺基二苯基甲烷、 4,4’ 一二胺基二苯基硫醚、1,5-二胺基萘、2, 2’ 一二甲基一4,4, 一二胺基連苯基、2,2,〜二 三氟甲基一 4,4’ —二胺基聯苯基、2,7 -二胺基 芴、4,4’ —二胺基二苯基醚、2,2,—雙〔4〜 經濟部智慈財產局8工消費合作杜印製 (4 一胺基苯氧基)苯基〕丙烷、9,9 一雙(4 一胺基 苯基)芴、2,2 -雙〔4 一(4 一胺基苯氧基)苯基〕 六氟丙烷、2,2 -雙(4 一胺基苯基)六氟丙烷、4, 4’ 一(p -伸苯基二異亞丙基)雙苯胺、4,4’ 一 (m -伸苯基二異亞丙基)雙苯胺、1,4 一環己烷二 胺、4,4,—伸甲基雙(環己胺)、1,4 一雙(4 — 胺基苯氧基)苯、4,4, 一雙(4一胺基苯氧基)聯苯 基’上記式(9)至(13)所示化合物,2,6 -二胺 基吡啶、3,4 一二胺基吡啶、2,4 —二胺基嘧啶、 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -23- 591083 A7 B7 五、發明説明(21 ) (锖先閱讀背面之注意事項再填寫本頁) 3,6 —二胺基吖啶、上記式(I I I )所示化合物中之 上記式(1 4 )所示化合物,上記式(I V )所示化合物 中之上記式(1 5 )所示化合物等。 本發明之醯亞胺化聚合物中,上記式(V )所示二胺 以對全體二胺較佳爲使用0 · 5重量%以上,更佳爲1重 量%以上。 〔醯亞胺化聚合物之合成〕 構成本發明之液晶配向劑之醯亞胺化聚合物,可將上 記聚醯胺酸經脫水閉環而製得。聚醯胺酸之脫水閉環’係 (i )將聚醯胺酸以加熱之方法,或(i i )將聚醯胺酸 溶解於有機溶媒中,再於此溶液中添加脫水劑與脫水閉環 觸媒,並於必要時以加熱方式進行。 經濟部智慧財產局g(工消費合作社印製 上記(i )之將聚醯胺酸加熱方法之反應溫度,一般 爲50至200 °C,較佳爲60至170 °C。反應溫度低 於5 0 °C時,則脫水閉環反應並未能充分進行,反應溫度 超過2 0 0 °C時,則所得醯亞胺化聚合物之分子量將會有 降低之情形。 又,上記’(i i )之於聚醯胺酸溶液中添加脫水劑與 脫水閉環觸媒之方法中,脫水劑例如可使用醋酸酐、無水 丙烯酸、無水三氟乙酸等酸酐,脫水劑之使用量,以對1 莫耳聚醯胺酸重複單位使用0·01至20莫耳爲佳。 又,脫水閉環觸媒,例如可使用吡啶、三甲基吡啶、二甲 基吡啶、三乙基胺等三級胺。但並不僅限定於此。脫水閉 -24 - 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 591083 Α7 Β7 五、發明説明(22 ) 環觸媒之使用量,以對1莫耳所使用之脫水劑使用 0·01至10莫耳爲佳。又,脫水閉環反應所使用之有 機溶媒,例如可使用合成聚醯胺酸之例示的有機溶媒等。 又,脫水閉環反應溫度,一般爲0至1 8 0°C,較佳爲 1 0至1 5 0 °C。又,本發明方法所製得之反應溶液,可 依與聚醯胺酸之精製方法進行相同之操作,以對醯亞胺化 聚合物進行精製。 本發明所使用之醯亞胺化聚合物,可使用部分脫水閉 環之醯亞胺化較低者亦可。本發明所使用之醯亞胺化聚合 物中,較佳之醯亞胺化率爲8 0 %以上,更佳爲8 5 %以 上。其中,「醯亞胺化率」係指對聚合物中重複單位之總 數,形成醯亞胺環之重複單位數目之比例,以%表示者。 此時,醯亞胺環之一部份可爲異醯亞胺環亦可。 末端修飾型之聚合物 上記聚醯亞胺酸與醯亞胺化聚合物,可爲經調整分子 量後所得之末端修飾型者。前述末端修飾型者,係指於合 成聚醯胺酸時,將酸一酐、單胺化合物 '單異氰酸酯化合 物等添加於反應系以合成者。其中,酸一酐例如馬來酸 酐、苯甲酸酐、衣康酸酐、η -癸基琥珀酸酐、η -十二 烷基琥珀酸酐、η -十四烷基琥珀酸酐、η 一十六烷基琥 珀酸酐等。又,單胺化合物例如苯胺、環己胺、η 一丁基 胺、η -戊基胺、η -己基胺、η -庚基胺、;q -辛基 胺、η -壬基胺、η -癸基胺、η——h—烷基胺、η —十 本紙張尺度適用中國國家標準(CNS ) Μ規格(210Χ297公釐) (請先閲讀背面之注意事項再填寫本頁) 訂 %r. 經濟部智慈財產局8工消費合作社印製 -25- _51 59l〇83 A7 五、發明説明(23 ) 二焼基胺、η —十三院基胺、η -十四院基胺、η--h五 (請先閲讀背面之注意事項再填寫本頁) 燒基胺、η —十六院基胺、η -十七焼基胺、η -十八院 基胺、η -二十烷基胺等。又,單異氰酸酯化合物,例如 苯基異氰酸酯、萘基異氰酸酯等。 聚合物之對數黏度 依上述方法所製得之聚醯胺酸與醯亞胺化聚合物,其 對數黏度之値一般爲〇 · 05至10d Ι/g, 較佳爲0.05至5dl/g。 本發明之對數黏度(7? ln)値,係使用N -甲基一 2 〜吡咯烷酮作爲溶媒,以濃度爲0·5g/l00ml之 溶液,於3 0 °C下進行黏度測定,並依下記式(i )計算 式所求得者。591083 A7 _B7 V. Description of the invention (20) 3, 3 a, 4, 5, 9b —Hexahydro-8 —Methyl-5 — (Tetrahydro (Please read the precautions on the back before filling out this page}) ~ 2 , 5-dioxo-3-furanyl) -naphthalene [1,2-c] -buffan-1,3-dione, etc. In addition, alicyclic tetracarboxylic dianhydride can also be used with other tetracarboxylic acids. The dianhydride is used in combination. [Diamine] The diamine used in the synthetic fluorinated imidized polymer described above, such as the diamine used in the synthetic polyfluorinated acid described above. The synthetic fluorinated imidized polymer of the present invention The diamine used can also be used with the diamine represented by the above formula (V) and other diamines. Other diamines are preferred, such as P-phenylenediamine, 4,4'-diaminodiphenylmethane , 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2, 2'-dimethyl-4,4, monodiaminodiphenyl, 2,2, ~ Ditrifluoromethyl-4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 2,2, -bis [4 ~ economy Produced by Du Zhizhi Property Bureau, 8 industrial and consumer cooperation Du printed (4 monoaminophenoxy Phenyl] propane, 9,9-bis (4-aminoaminophenyl) fluorene, 2,2-bis [4-mono (4-aminoaminophenoxy) phenyl] hexafluoropropane, 2,2-bis ( 4 monoaminophenyl) hexafluoropropane, 4, 4 'mono (p-phenylene diisopropylidene) bisaniline, 4,4' mono (m-phenylene diisopropylidene) bisaniline , 1,4-cyclohexanediamine, 4,4, -methylenebis (cyclohexylamine), 1,4-bis (4-aminophenoxy) benzene, 4,4, one-bis (4-1 Aminophenoxy) biphenyl 'Compounds represented by the above formulae (9) to (13), 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -23- 591083 A7 B7 V. Description of the invention (21) (锖 Please read the precautions on the back before filling this page) 3,6 —Diamino group Acridine, a compound represented by the above formula (1 4) among the compounds represented by the above formula (III), a compound represented by the above formula (1 5) among the compounds represented by the formula (IV), and the like. In a polymer, a diamine represented by the above formula (V) The total diamine is preferably 0.5% by weight or more, more preferably 1% by weight or more. [Synthesis of fluorene imidized polymer] The fluorene imidized polymer constituting the liquid crystal alignment agent of the present invention may be used. The polyamic acid described above is prepared by dehydration and ring closure. The dehydration and ring closure of the polyamic acid is (i) a method in which the polyamino acid is heated, or (ii) the polyamino acid is dissolved in an organic solvent, A dehydrating agent and a dehydrating closed-loop catalyst are added to the solution, and the heating is performed when necessary. The reaction temperature of the method for heating polyamic acid printed by the Intellectual Property Bureau of the Ministry of Economic Affairs (printed in the above (i) by the Industrial and Consumer Cooperatives) is generally 50 to 200 ° C, preferably 60 to 170 ° C. The reaction temperature is lower than 5 At 0 ° C, the dehydration ring-closing reaction does not proceed sufficiently. When the reaction temperature exceeds 200 ° C, the molecular weight of the fluorene imidized polymer obtained may decrease. Also, the above-mentioned '(ii) In the method of adding a dehydrating agent and a dehydrating closed-loop catalyst to a polyamic acid solution, for example, an acid anhydride such as acetic anhydride, anhydrous acrylic acid, and anhydrous trifluoroacetic acid can be used as the dehydrating agent. The repeating unit of the amino acid is preferably from 0.01 to 20 moles. For the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, trimethylpyridine, dimethylpyridine, and triethylamine can be used. Here, dehydration closed -24-This paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 591083 Α7 B7 V. Description of the invention (22) The amount of ring catalyst used, for the use of 1 Moore The dehydrating agent is preferably from 0.01 to 10 moles. Also, dehydration The organic solvent used in the ring-closing reaction can be, for example, an organic solvent exemplified for the synthesis of polyamic acid. The dehydration ring-closing reaction temperature is generally 0 to 180 ° C, preferably 10 to 150 °. C. In addition, the reaction solution prepared by the method of the present invention can be subjected to the same operation as the method of purifying polyfluorinated acid to purify the fluorinated imidized polymer. The fluorinated imidized polymerization used in the present invention It is also possible to use partially dehydrated and closed-loop fluorene imidization. The fluorene imidization polymer used in the present invention preferably has a fluorene imidization rate of 80% or more, more preferably 85%. Above, the "fluorenimide ratio" refers to the ratio of the total number of repeating units in the polymer to the number of repeating units forming a sulfonimide ring, expressed in%. At this time, a part of the sulfonimide ring It may be an isoamidine ring. The polymer of the terminal modification type may include polyimide acid and amidine polymer, which may be obtained by adjusting the molecular weight of the terminal modification type. The aforementioned terminal modification type is When synthesizing polyamidic acid, the acid monoanhydride and monoamine compound are used. Isocyanate compounds are added to the reaction system to synthesize. Among them, acid monoanhydrides such as maleic anhydride, benzoic anhydride, itaconic anhydride, η-decylsuccinic anhydride, η-dodecylsuccinic anhydride, η-tetradecane Succinic anhydride, η-hexadecyl succinic anhydride, etc. In addition, monoamine compounds such as aniline, cyclohexylamine, η-butylamine, η-pentylamine, η-hexylamine, η-heptylamine, q-octylamine, η-nonylamine, η-decylamine, η—h-alkylamine, η — ten paper sizes are applicable to China National Standard (CNS) M specifications (210 × 297 mm) (please first Read the notes on the back and fill out this page) Order% r. Printed by the 8th Industrial Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -25- _51 59l〇83 A7 V. Description of the invention (23) Dimethylamine, η — 13 Rhodium amine, η-fourteen amine, η--h five (please read the precautions on the back before filling this page) Benzylamine, η-hexadecyl amine, η-heptadecylamine, η-octadecylamine, η-icosylamine and the like. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate. Logarithmic Viscosity of Polymers The polyamidoacid and fluorinated imidized polymers prepared according to the above methods have a logarithmic viscosity of generally 0.05 to 10d Ι / g, preferably 0.05 to 5dl / g. The logarithmic viscosity (7? Ln) of the present invention uses N-methyl-2 ~ pyrrolidone as a solvent, and a solution with a concentration of 0.5 g / 100 ml is used to measure the viscosity at 30 ° C and according to the following formula (I) Those obtained by the calculation formula.
In (溶液流下時間/溶媒流下時間) V 1η = ( i ) (聚合物之重量濃度) 經濟部智慧財產局工消費合作社印製 (B )含矽化合物 本發明所使用之含矽化合物,係爲具有聚醚鍵結之聚 有機矽氧烷。上記聚有機矽氧烷,以支鏈具有聚醚鍵結者 爲佳。 上記含矽化合物,又以下記式(I I )所示化合物爲 最佳之化合物。 本紙張尺度適用中國國家標準(CNS〉八4規格(2丨〇>< 297公釐) -26- 591083 A7 B7_______ 五、發明説明(24 )In (solution flow time / solvent flow time) V 1η = (i) (weight concentration of polymer) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Industrial and Consumer Cooperatives (B) Silicon-containing compound The silicon-containing compound used in the present invention is Polyorganosiloxane with polyether bond. The polyorganosiloxane mentioned above is preferably a branch having a polyether bond. The above-mentioned silicon-containing compound and the compound represented by the following formula (I I) are the best compounds. This paper size applies to Chinese National Standards (CNS> 8-4 specifications (2 丨 〇 > < 297 mm) -26- 591083 A7 B7_______ V. Description of the invention (24)
H3C |-fOCmH2^(〇CnH2n^-B (請先閲讀背面之注意事項再填寫本頁) H3C-fsi-〇ysi-〇)^s|^CH3^ (II) ch3 ch3 (式中’ A爲單鍵、伸甲基或碳數2至5之伸烷基, B爲羥基或碳數1至3之烷基,a與13爲相互獨立之1至 1 0 0之數,c與d爲相互獨立之1至3之數,m與η爲 相互獨立之1至6之數) 上記式(I I )之Α所示之碳數2至5之伸烷基’例 如伸乙基、η -伸丙基、η〜伸丁基、伸戊基等。 又,上記式(I I)之Β所示碳數1至3之烷基,例 如甲基、乙基、η —丙基等。 經濟部智慧財產局員工消費合作社印製 上記式(I I )之a與b,其可爲相互獨立之1至 100之數,較佳爲30至80之數。又,c與d爲相互 獨立之1至3之數。此外,m與η爲相互獨立之1至6之 數,較佳爲1至3之數。特別是m爲1、η爲2之組合, m爲2、η爲3之組合爲更佳。 前述化合物,可單獨或將2種以上組合使用。 又,本發明所使用之(Β )含矽化合物,其分子量一 般爲500至50,000,較佳爲1,〇〇〇至 1 0,0 0 0 ° 本發明之液晶配向劑中,(Β )含矽化合物之添加 量’以對(Α)聚合物1〇〇重量份,一般爲〇 · 至 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) -27- 591083 A7 B7___ 五、發明説明(26 ) (請先閲讀背面之注意事項再填寫本頁) 聚丙二醇二縮水甘油醚、新戊二醇二縮水甘油醚、1,6 —己二醇二縮水甘油醚、丙三醇二縮水甘油醚、2,2 -二溴新戊二醇二縮水甘油醚、1,3,5,6 -四縮水甘 油基一2,4—己二醇、N,N,N, ,N,—四縮水甘 油基一 m —二甲苯二胺、1,3 -雙(N,N - —►縮水甘 油基胺甲基)環己烷、Ν,Ν,Ν’ ,Ν’ —四縮水甘油 基- 4,4 一二胺基二苯基甲烷等。前述含環氧基化合物 之添加量,以對聚合物1 0 0重量份,一般爲4 0重量份 以下,較佳爲0.1至30重量份。 液晶顯示元件 本發明之液晶顯示元件,例如可以下記方法製得。 經濟部智慧財4局g(工消費合作社印製 (1 )將經設有圖案化透明導電膜之基板之一側面, 將本發明之液晶配向劑,以較適當之印刷法等塗佈於其 上,隨後再對塗佈面加熱以形成塗膜。其中,基板例如可 使用寬幅玻璃或鈉鈣玻璃,或聚對苯二甲酸乙二醇酯、聚 對苯二甲酸丁二醇酯、聚醚碾、聚碳酸指數之等塑膠所構 成之透明基板。至於設置於基板一側面之透明導電膜,例 如可使用氧化錫(S η〇2 )所構成之N E S Α膜(美國 PPG公司商標)、氧化銦—氧化錫(In2〇3 — S η〇2)所構成之I T ◦膜等,前述透明導電膜之圖案, 可以蝕刻法或預先使用光罩予以形成等方法。塗佈液晶配 向劑之際,爲使基板表面與透明導電膜之塗膜的黏著性更 加良好,可於基板之前述表面上,預先塗佈官能性矽烷化 本紙張尺度適用中國國家標率(CNS ) A4規格(210X297公釐) -29- 591083 A7 B7 五、發明説明(27 ) (請先閲讀背面之注意事項再填寫本頁} 合物、官能性鈦化合物等。液晶配向劑塗佈後之加熱溫度 爲80至30CTC,較佳爲120至250 °C。又,含聚 醯胺酸之本發明液晶配向劑,係於塗佈後將有機溶媒去除 以形成配向膜之塗膜,以加熱方式進行脫水閉環,再經醯 亞胺化以形成塗膜亦可。所形成之塗膜之膜厚,一般爲 0 · 001 至 l//m,較佳爲 〇 · 005 至 0 . 5/zm。 (2 )於形成之塗膜面,可以捲附例如耐龍、螺縈、 棉等纖維所構成之布帛的滾筒依一定方向進行摩擦處理, 經由此處理,可對塗膜賦予具有液晶分子配向能,使其形 成液晶配向膜。 經濟部智慧財產局員工消費合作社印製 又,依本發明液晶配向劑所形成之液晶配向膜,例如 特開平6-222366號公報或特開平6-28193 7號公報所記載般,可經由紫外線之部分照射方式使預傾 角產生變化之處理,或如特開平5 - 1 0 7 5 4 4號公報 所記載般,對於經使用摩擦處理所得之液晶配向膜表面先 形成部分之光阻膜,再與先前摩擦處理不同方向下以摩擦 處理去除光阻膜,使液晶配向膜之液晶配向能產生變化方 式之處理,亦可改變液晶顯示元件之視角特性。 (3 )製作2片依上記方式形成液晶配向膜之基板, 使其液晶配向膜之摩擦方向形成直角或逆向之方式,將2 片基板介有間隙之方式對向配置,將2片基板之周邊部份 以密封劑黏合,表面基板與密封劑所區隔之間隙內注入液 晶’再將注入孔封閉以構成液晶晶胞。隨後,於液晶晶胞 外表面’即構成液晶晶胞基板之另一側面,將偏光板依該 本紙張尺度適用中國國家標準(CNS ) A4規格(210X29*7公釐) -30- 591083 A7 B7 五、發明説明(28 ) 偏光方向與該基板另一側面所形成之液晶配向膜的摩擦方 向爲相同或直角之方式貼合,而製得液晶顯示元件。 (請先閲讀背面之注意事項再填寫本頁) 其中,密封劑例可使用含有硬化劑與作爲調距之氧化 鋁球脂環氧樹脂等。 液晶形態,例如有矩陣型液晶與扭轉矩陣型液晶等, 其中又以矩陣型液晶爲佳,例如席夫系液晶、氧化偶氮系 液晶、聯苯系液晶、苯基環己烷系液晶、嘧啶系液晶、二 噁烷系液晶、雙環辛烷系液晶、立方體系液晶等。又,前 述液晶例如可添加氯化膽固留、膽固甾壬酯、膽固甾碳酸 酯等膽固留型液晶或商品名〔C — 1 5〕、〔 c B — 1 5 〕(美路可公司製)販賣之鏡像劑。此外,亦可使用例如 P -癸氧基亞苄基- P -胺基- 2 -甲基丁基苯乙烯酯等 強介電性液晶。 又’貼合於液晶晶胞外表面之偏光板,於使用聚乙嫌 醇延伸配向中,可再加入以乙酸纖維素保護膜挾夾吸有碘 之Η膜的偏光膜所得偏光板,或由Η膜本身構成之偏光板 等。 經濟部智慧財產^員工消費合作社印製 【實施例】 以下,本發明將以實施例做更具體之說明,但本發明 並不受此些實施例所限制。 合成例1 將四羧酸二酐之109 · 06g (0 · 5莫耳)均苯 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ' ,.-31 - 591083 A7 _B7___ 五、發明説明(29 ) (請先閲讀背面之注意事項再填寫本頁) 四甲酸二酐、98 . 06g (0 · 5 莫耳)1 ,2,3, 4 一環丁烷四羧酸二酐、二胺化合物之200 · 2g (1 _ 〇莫耳)4,4 一二胺基二苯基醚溶解於4500 g之N -甲基一2 —吡咯烷酮中,於6 0°C下反應6小 時。隨後,將反應溶液注入過量之甲醇中使反應產物產生 沉澱,再以甲醇洗淨,減壓下於4 0 °C下乾燥1 5小時後 得黏度對數0 · 88d Ι/g,醯亞胺化率爲0%之聚醯 胺酸(以下稱「聚醯胺酸(A—l)」)290g。 合成例2 將四羧酸二酐之109 . 06g (0 . 5莫耳)均苯 四甲酸二酐、98.06g(0.5莫耳)1,2,3, 4 —環丁烷四羧酸二酐、二胺化合物之198 · 27g (1莫耳)4,4’ —二胺基二苯基甲烷溶解於4500 經濟部智慧財產局員工消費合作社印製 g之N —甲基—2 —吡咯烷酮中,於6 Ot:下反應6小 時。隨後,將反應溶液注入過量之甲醇中使反應產物產生 沉澱,再以甲醇洗淨,減壓下於4 0 t下乾燥1 5小時後 得黏度對數0 . 92d Ι/g,醯亞胺化率爲〇%之聚醯 胺酸(以下稱「聚醯胺酸(A - 2)」)310g。 合成例3 將四羧酸二酐之196·12g(1·0莫耳)1, 2,3,4 —環丁烷四羧酸二酐、二胺化合物之 200.2g(1.0莫耳)4,4’ —二胺基二苯基醚 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ~ 591083 A7 __ _B7_ 五、發明説明(3〇 ) (請先閲讀背面之注意事項再填寫本頁) 溶解於4 5 0 0 g之N —甲基一 2 —吡咯烷酮中,於6 0 °c下反應6小時。隨後,將反應溶液注入過量之甲醇中使 反應產物產生沉澱,再以甲醇洗淨,減壓下於4 0 °C下乾 燥1 5小時後得黏度對數〇 · 9 0 d 1 / g,醯亞胺化率 爲0%之聚醯胺酸(以下稱「聚醯胺酸(A - 3)」) 2 9 〇 g 〇 合成例4 將四羧酸二酐之196.12g(1·0莫耳)1’ 2,3,4 一環丁烷四羧酸二酐、二胺化合物之2 1 2g (1.0莫耳)2,2’ 一 4,4’ —胺基聯苯基溶解於 4 5 0 0 g之N —甲基—2 —吡咯烷酮中,於6 0°C下反 應6小時。隨後,將反應溶液注入過量之甲醇中使反應產 物產生沉澱,再以甲醇洗淨,減壓下於4 0 °C下乾燥1 5 小時後得黏度對數0 · 9 9 d 1 / g,醯亞胺化率爲0 % 之聚醯胺酸(以下稱「聚醯胺酸(A - 4)」)290 g。 經濟部智慈財產局:貝工消費合作社印製 合成例5 將四羧酸二酐之224 · 17g (1 · 0莫耳)2 ’ 3,5 -三羧基環戊基乙酸二酐、二胺化合物之 200.2g(1.0莫耳)4,4’ 一二胺基二苯基醚 溶解於4 5 0 0 g之N -甲基—2 —吡咯烷酮中,於6 〇 。(:下反應6小時。隨後,將反應溶液注入過量之甲醇中使 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -33- 591083 A7 B7 五、發明説明(31 ) (請先閱讀背面之注意事項存填寫本I) 反應產物產生沉澱,再以甲醇洗淨,減壓下於4 0°C下乾 燥1 5小時後得黏度對數0 · 8 7 d 1、/ g,醯亞胺化率 爲0%之聚醯胺酸(以下稱「聚醯胺酸(A - 5 )」) 2 8 0 g ° 合成例6 將四羧酸二酐之224 . 17g (0 · 5莫耳)2, 3,5 —三羧基環戊基乙酸二酐、157 . 14g ( 0.5 莫耳)l,3,3a,4,5,9b —六氫一 5 -甲基—5 (四氫一 2,5 -二氧代—3_呋喃基)—萘〔 1,2 — c〕—呋喃一 1,3 -二酮、二胺化合物之 94.62g (0·875莫耳)p-伸苯基二胺、 32 · 02g (0 · 1 莫耳)2,2 —二三氟甲基一 4, 4 —二胺基聯苯基、6 · 43g (0 · 0 1莫耳)3,6 -雙(4 一胺基苯醯氧基)膽固烯(上記式(9 )所示化 合物,以下相同)、4 · 04g (0 · 015莫耳)十八 經濟部智慧財產局員工消費合作社印製 烷氧基一 2,5 -二胺基苯溶解於4500g之N -甲基 —2 -吡咯烷酮中,於6 0 °C下反應6小時。隨後,將反 應溶液注入過量之甲醇中使反應產物產生沉澱,再以甲醇 洗淨,減壓下於4 0 °C下乾燥1 5小時後得黏度對數 0 · 87d Ι/g,醯亞胺化率爲0%之聚醯胺酸410 g。將所得聚醯胺酸30g再溶解於570g之N -甲基 一 2 —吡咯烷酮中,再添加23 · 4g吡啶與18 . lg 乙酸酐後,於1 1 0 °C下進行4小時之脫水閉環反應,並 -34- 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 591083 A7 __B7 __ 五、發明説明(32 ) (請先閲讀背面之注意事項再填寫本頁) 進行前述相同之沉澱、洗淨、減壓後得黏度對數〇 · 80 d Ι/g,醯亞胺化率爲100 %之醯亞胺化聚合物(以 下稱「醯亞胺化聚合物(B— 1)」)17 · 5g。 合成例7 將四羧酸二酐之224 · 17g (0 . 5莫耳)2, 3,5 —三羧基環戊基乙酸二酐、157 · 14g ( 0 · 5 莫耳)1,3,3a,4,5,9b —六氫—5 — 甲基—5 (四氫一 2,5_二氧代一 3 —呋喃基)一萘〔 1,2 — c〕—呋喃—1,3 -二酮、二胺化合物之 94 · 62g (0 · 875莫耳)p -伸苯基二胺、 24 · 85g (0 · 1莫耳)雙胺基丙基四甲基二矽氧 經濟部智慧財4局K工消費合作社印製 烷、6 · 43g (0 · 0 1 莫耳)3,6 -雙(4 —胺基 苯醯氧基)膽固烯、4 . 04g (0 . 015莫耳)十八 烷氧基一 2,5 —二胺基苯溶解於4500g之N -甲基 一 2 -吡咯烷酮中,於6 0°C下反應6小時。隨後,將反 應溶液注入過量之甲醇中使反應產物產生沉澱,再以甲醇 洗淨,減壓下於4 0 °C下乾燥1 5小時後得黏度對數 0 · 82d Ι/g,醯亞胺化率爲0%之聚醯胺酸370 g。將所得聚醯胺酸30g再溶解於570g之N —甲基 一 2 —吡咯烷酮中,再添加23 · 4g吡啶與18 · lg 乙酸酐後,於1 1 0 °C下進行4小時之脫水閉環反應,並 進行前述相同之沉澱、洗淨、減壓後得黏度對數〇 · 7 7 d 1 / g,醯亞胺化率爲1 0 0 °/。之醯亞胺化聚合物(以 -35- 本纸張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 591083 A7 B7_ 五、發明説明(33 ) 下稱「醯亞胺化聚合物(B — 2)」)18 · 5g。 (請先閲讀背面之注意事項再填寫本頁) •合成例8 將四羧酸二酐之224 · 17g (1 · 0莫耳)2, 3,5 -三羧基環戊基乙酸二酐、二胺化合物之 107 · 06g (0 · 99莫耳)P —伸苯基二胺、 6 · 43g (0 · 01莫耳)3,6 —雙(4 —胺基苯醯 氧基)膽固烯溶解於4 5 0 0 g之N -甲基一 2 -吡咯院 酮中,於6 0 °C下反應6小時。隨後,將反應溶液注入過 量之甲醇中使反應產物產生沉澱,再以甲醇洗淨,減壓下 於4 0 t下乾燥1 5小時後得黏度對數0 . 9 0 d 1 / g,醯亞胺化率爲0%之聚醯胺酸4 1 0g。將所得聚醯 胺酸3 0 g再溶解於5 7 0 g之N -甲基—2 -吡咯烷酮 中,再添加23·4g吡啶與18.lg乙酸酐後,於 1 1 0 °C下進行4小時之脫水閉環反應,並進行前述相同 之沉澱、洗淨、減壓後得黏度對數0 . 8 5 d 1 / g,醯 經濟部智慧財產局員工消費合作社印製 亞胺化率爲1 〇 〇 %之醯亞胺化聚合物(以下稱「醯亞胺 化聚合物(B - 3)」)17.5g。 合成例9 將四羧酸二酐之224 · 17g (0 · 5莫耳)2, 3,5 —三羧基環戊基乙酸二酐、157 . I4g ( 0 · 5 莫耳)1,3,3a,4,5,9b —六氫—5 — 甲基_5 (四氫—2,5 —二氧代-3 —呋喃基)一萘〔 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -36 - 59l〇83 A7 B7 _________________ 五、發明説明(34 ) (請先閲讀背面之注意事項再填寫本頁) 1,2 — c〕一呋喃一 1,3 —二酮、二胺化合物之 89 . 21g (〇 · 825莫耳)P -伸苯基二胺、 32.02g(0.1莫耳)2’2’ 一二三氟甲基一 經濟部智慧財產局8工消費合作社印製 4,4,—二胺基聯苯基、25.34g(〇.〇6莫 耳)1— (3,5 -二胺基苯醯氧基)一 4 一(4 一三氟 甲基苯醯氧基)-環己烷(上記式(20)所示化合物, 以下相同)、4 · 04g (〇 · 〇15莫耳)十八烷氧基 一 2,5 -二胺基苯溶解於4500g之N -甲基—2 — 吡咯烷酮中,於6 0 °C下反應6小時。隨後,將反應溶液 注入過量之甲醇中使反應產物產生沉澱,再以甲醇洗淨, 減壓下於4 0 °C下乾燥1 5小時後得黏度對數0 · 9 0 d Ι/g,醯亞胺化率爲0%之聚醯胺酸4 1 0g。將所 得聚醯胺酸3 0g再溶解於570g之N -甲基一 2 -吡 咯烷酮中,再添加23·4g吡啶與18.lg乙酸酐 後,於1 1 0 °C下進行4小時之脫水閉環反應,並進行前 述相同之沉澱、洗淨、減壓後得黏度對數0 · 8 3 d 1 / g,醯亞胺化率爲1 0 0%之醯亞胺化聚合物(以下稱 「醯亞胺化聚合物(B — 4)」)17 · 5g。 實施例1 將合成例6所製得之醯亞胺化聚合物(B - 1 ) 1 0 0重量份與,上記式(I I )所示含矽化合物之 SH 3 77 1 (東麗—道康寧公司製)0 _ 075重量份 溶解於r - 丁內酯/N -甲基一 2 -吡咯烷酮/丁基溶纖 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ~ "" 591083 A7 B7 五、發明説明(35 ) (請先閲讀背面之注意事項再填寫本頁) 素(71/17/12 (重量比))混合溶媒中,使成固 型成分濃度爲4重量%之溶液’將此溶液以孔徑1 //m之 過濾器過濾,以製作本發明之液晶配向劑。將上記液晶配 向劑使用液晶配向膜印刷機(日本寫真印刷公司製)塗佈 於附有I T ◦膜透明電極之玻璃基板之透明電極面上,再 於8 0 t之熱壓板乾燥1分鐘後,於2 0 0 °C之熱壓板上 乾燥1 0分鐘,形成平均厚度6 0 0埃之被膜。將以基板 以倍率2 0倍之顯微鏡觀察結果,並未發現印刷斑紋與砂 孔,確認其印刷性極爲良好。 經濟部智慈財產局貨工消費合作社印製 將此被膜以捲附有耐龍型布帛之滾筒使用摩擦機器以 滾筒迴轉數5 0 0 r pm、平台移動速度3 cm/秒、壓 腳長0 . 4 m m之條件下進行摩擦處理,以形成液晶配向 膜。隨後,將形成上記液晶配向膜之基板浸漬於異丙醇中 1分鐘後,於1 0 0 °C之熱壓板上乾燥5分鐘。隨後,將 一對上記基板中具有液晶配向膜之外緣,塗佈置有直徑 5 · 5 // m氧化鋁球脂環氧樹脂黏著劑後,將液晶配向膜 面以相對面方式貼合,使黏著劑硬化。隨後,經由液晶注 入孔對一對基板間塡充矩陣型液晶(美路可公司製, M L C — 6 2 2 1 )後,使用丙烯系光硬化黏著劑將液晶 注入孔封閉,隨後對基板外側兩面上貼合偏向板,而完成 本發明之液晶顯示元件。 所製得之液晶顯示元件,經以交流6 . 0 V (波峰與 波峰)重疊之30Hz、3 · 0V之矩形波於70 °C之環 境溫度下施加5 0 0小時後,以目視方式觀察結果得知液 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -38- 591083 A7 B7 五、發明説明(36 ) 晶顯示元件並未發現有顯示不佳之情形。 實施例2至2 2,比較例1至2 將合成例1至9與比較例1至2所得之聚醯亞胺酸與 醯亞胺化聚合物,除改變含矽化合物之種類與添加量及液 晶配向膜之乾燥溫度以外,其他皆依實施例1相同方法製 得液晶配向劑,並對基板上所形成之被膜,觀察其是否產 生印刷斑紋或砂孔,再觀察所製得之液晶顯示元件是否有 顯示不良之情形。又,實施例5至2 2、比較例1至2 中,聚醯胺酸與醯亞胺化聚合物係使用聚醯胺酸:醯亞胺 化聚合物=4 : 1 (重量比)之比例。其結果同時記載於 表1中。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS ) A4規格(21 OX 297公釐) -39 - 591083H3C | -fOCmH2 ^ (〇CnH2n ^ -B (Please read the notes on the back before filling out this page) H3C-fsi-〇ysi-〇) ^ s | ^ CH3 ^ (II) ch3 ch3 (where A is Single bond, methyl group or alkylene group with 2 to 5 carbon atoms, B is a hydroxyl group or alkyl group with 1 to 3 carbon atoms, a and 13 are independent numbers from 1 to 100, and c and d are mutually Independent numbers of 1 to 3, m and η are independent numbers of 1 to 6) The alkylene groups of 2 to 5 carbon atoms represented by A in the above formula (II), such as ethylidene, η-propylene Group, η ~ butylene, pentyl and the like. Further, the alkyl group having 1 to 3 carbon atoms represented by B of the above formula (I I) includes, for example, methyl, ethyl, η-propyl, and the like. The a and b of the above-mentioned formula (I I) printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs may be numbers from 1 to 100 independently, preferably from 30 to 80. In addition, c and d are numbers of 1 to 3 independent of each other. In addition, m and η are numbers of 1 to 6 independently of each other, and preferably numbers of 1 to 3. In particular, a combination of m being 1 and η being 2 and a combination of m being 2 and η being 3 are more preferable. These compounds can be used alone or in combination of two or more. In addition, the (B) silicon-containing compound used in the present invention has a molecular weight of generally 500 to 50,000, preferably 1,000 to 10,000. In the liquid crystal alignment agent of the present invention, (B ) The amount of silicon-containing compound added is based on 100 parts by weight of (A) polymer, generally 0. to the paper size. Applicable to China National Standard (CNS) A4 specification (210X297 mm) -27- 591083 A7 B7___ 5 、 Explanation (26) (please read the precautions on the back before filling this page) polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol Diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N,, N, —Tetraglycidyl-m —xylylenediamine, 1,3-bis (N, N — —►glycidylamine methyl) cyclohexane, Ν, Ν, Ν ′, Ν ′ —tetraglycidyl -4,4-diaminodiphenylmethane, etc. The aforementioned epoxy group-containing compound is added in an amount of 100 parts by weight to the polymer, generally 40 parts by weight or less, and preferably 0.1 to 30 parts by weight. Liquid crystal display element The liquid crystal display element of the present invention can be produced, for example, by the following method. The 4th Bureau of the Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperative) (1) The liquid crystal alignment agent of the present invention will be coated on one side of a substrate provided with a patterned transparent conductive film by a suitable printing method, etc. Then, the coating surface is heated to form a coating film. The substrate may be, for example, a wide glass or a soda lime glass, or polyethylene terephthalate, polybutylene terephthalate, poly Transparent substrate made of plastic such as ether mill and polycarbonate index. As for the transparent conductive film provided on one side of the substrate, for example, NES Α film (trademark of American PPG Corporation) composed of tin oxide (S η〇2), It is an IT film composed of indium oxide-tin oxide (In2 03-S η〇2), and the pattern of the transparent conductive film can be formed by etching or using a photomask in advance. When the liquid crystal alignment agent is applied In order to improve the adhesion between the substrate surface and the coating film of the transparent conductive film, a functional silane can be pre-coated on the aforementioned surface of the substrate. The paper size is applicable to China National Standard (CNS) A4 specifications (210X297 mm). ) -29- 59108 3 A7 B7 V. Description of the invention (27) (Please read the notes on the back before filling out this page} compounds, functional titanium compounds, etc. The heating temperature after the liquid crystal alignment agent is applied is 80 to 30CTC, preferably 120 Up to 250 ° C. In addition, the liquid crystal alignment agent of the present invention containing polyamidic acid removes the organic solvent to form a coating film of the alignment film after coating, dehydrates and closes the ring by heating, and then undergoes imidization to It is also possible to form a coating film. The film thickness of the formed coating film is generally from 0. 001 to 1 // m, preferably from 0.005 to 0.5 / zm. (2) On the surface of the formed coating film, it can be A roller that is wrapped with a fabric made of fibers such as nylon, snails, and cotton is rubbed in a certain direction. After this treatment, the coating film can be provided with liquid crystal molecular alignment energy to form a liquid crystal alignment film. Printed by the Consumer Cooperative of the Property Bureau. The liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention is, for example, described in Japanese Patent Application Laid-Open No. 6-222366 or Japanese Patent Application Laid-Open No. 6-28193 7. It can be partially irradiated with ultraviolet rays. Where the pretilt angle changes , Or as described in Japanese Patent Application Laid-Open No. 5-1 0 7 5 4 4, a portion of the photoresist film is formed on the surface of the liquid crystal alignment film obtained after the rubbing treatment, and then the rubbing treatment is used to remove it in a direction different from the previous rubbing treatment. The photoresist film can change the liquid crystal alignment of the liquid crystal alignment film, and can change the viewing angle characteristics of the liquid crystal display element. (3) Make two substrates that form the liquid crystal alignment film according to the method described above, and make the liquid crystal alignment film The rubbing direction is formed at right angles or in the opposite direction. The two substrates are arranged opposite to each other with a gap. The peripheral parts of the two substrates are bonded with a sealant. The liquid crystal is injected into the gap separated by the surface substrate and the sealant. The injection hole is closed to form a liquid crystal cell. Subsequently, on the outer surface of the liquid crystal cell, that is, the other side of the substrate of the liquid crystal cell, the polarizing plate is applied to the Chinese national standard (CNS) A4 specification (210X29 * 7 mm) according to the paper size. -30- 591083 A7 B7 V. Description of the invention (28) The polarization direction and the rubbing direction of the liquid crystal alignment film formed on the other side of the substrate are adhered in the same or right-angled manner to obtain a liquid crystal display element. (Please read the precautions on the back before filling out this page.) Among them, examples of sealants can include hardeners and aluminum oxide epoxy resins for pitch adjustment. Liquid crystal forms include, for example, matrix-type liquid crystals and twisted-matrix-type liquid crystals. Among them, matrix-type liquid crystals are preferred, such as Schiff-type liquid crystals, azo oxide-based liquid crystals, biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, and pyrimidines. Based liquid crystal, dioxane based liquid crystal, bicyclooctane based liquid crystal, cube based liquid crystal, and the like. In addition, the liquid crystal may be added with a cholesteric liquid crystal such as cholesteryl chloride, cholesteryl nonyl ester, or cholesteryl carbonate, or trade names [C — 1 5], [c B — 1 5] (Mei Lu Can be made by the company). In addition, for example, a strong dielectric liquid crystal such as P-decoxybenzylidene-P-amino-2-methylbutylstyrene can be used. The polarizing plate attached to the outer surface of the liquid crystal cell, and in the case of using polyethylene glycol to extend the alignment, a polarizing film obtained by adding a polarizing film with a protective film of cellulose acetate and a film of iodine absorbed by iodine, or a The polarizing plate formed by the diaphragm itself. Printed by the Intellectual Property of the Ministry of Economic Affairs ^ Employee Consumer Cooperatives [Embodiments] Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited by these examples. Synthesis Example 1 The paper size of 109 · 06g (0.5 · mol) of tetracarboxylic dianhydride is benzene. The Chinese paper standard (CNS) A4 specification (210X297 mm) is applied., --31-591083 A7 _B7___ V. Description of the Invention (29) (Please read the precautions on the back before filling out this page) Tetracarboxylic dianhydride, 98.06g (0.5 Moore) 1,2,3,4 Monocyclobutanetetracarboxylic dianhydride, two 200 · 2 g (1-mole) of 4,4-diaminodiphenyl ether of an amine compound was dissolved in 4500 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours. Subsequently, the reaction solution was poured into an excess of methanol to precipitate a reaction product, and the reaction product was washed with methanol and dried at 40 ° C under reduced pressure for 15 hours to obtain a logarithm of viscosity 0 · 88d Ι / g. 290 g of polyamic acid (hereinafter referred to as "polyamino acid (A-1)") at a rate of 0%. Synthesis Example 2 Tetracarboxylic dianhydride of 109.06 g (0.5 mol) of pyromellitic dianhydride and 98.06 g (0.5 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride 198.27g of diamine compound (1 mole) 4,4'-diaminodiphenylmethane was dissolved in 4500 g of N-methyl-2-pyrrolidone printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Reaction at 6 Ot: 6 hours. Subsequently, the reaction solution was poured into excess methanol to cause precipitation of the reaction product, and then washed with methanol, and dried under reduced pressure at 40 t for 15 hours to obtain a logarithm of viscosity 0.992d Ι / g. It was 310 g of polyamidic acid (hereinafter referred to as "polyamidic acid (A-2)"). Synthesis Example 3 196.12 g (1.0 mole) of tetracarboxylic dianhydride, 1, 2, 3, 4-cyclobutane tetracarboxylic dianhydride, 200.2 g (1.0 mole) of diamine compound 4, 4 '—Diaminodiphenyl ether This paper is in accordance with China National Standard (CNS) A4 specification (210X297 mm) ~ 591083 A7 __ _B7_ V. Description of the invention (3〇) (Please read the notes on the back before filling (This page) was dissolved in 4,500 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 6 hours. Subsequently, the reaction solution was poured into excess methanol to precipitate the reaction product, and the reaction product was washed with methanol and dried at 40 ° C under reduced pressure for 15 hours to obtain a logarithmic viscosity of 0.90 d 1 / g. Polyamidic acid having an imidization ratio of 0% (hereinafter referred to as "polyamidic acid (A-3)") 290 g Synthesis Example 4 196.12 g (1.0 mole) of tetracarboxylic dianhydride ) 1 '2,3,4 Monocyclobutanetetracarboxylic dianhydride, 2 1 2 g (1.0 mole) of 2, 2'-4,4 '—aminobiphenyl dissolved in 4 5 0 0 In g of N-methyl-2-pyrrolidone, react at 60 ° C for 6 hours. Subsequently, the reaction solution was poured into excess methanol to precipitate the reaction product, and the reaction product was washed with methanol, and dried at 40 ° C under reduced pressure for 15 hours to obtain a logarithm of viscosity 0.99 d 1 / g. 290 g of polyamic acid (hereinafter referred to as "poly (A-4)") having an amination rate of 0%. Bureau of Intellectual Property, Ministry of Economic Affairs: Printed Synthesis Example 5 by Shelley Consumer Cooperative, 224 · 17g (1.0 mole) of tetracarboxylic dianhydride 2 '3,5-tricarboxycyclopentylacetic dianhydride, diamine Of the compound, 200.2 g (1.0 mole) of 4,4'-diaminodiphenyl ether was dissolved in 4,500 g of N-methyl-2-pyrrolidone at 600. (: React for 6 hours. Then, inject the reaction solution into excess methanol to make the paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -33- 591083 A7 B7. V. Description of the invention (31)) (Please First read the precautions on the back and fill in this I) The reaction product precipitates, and then washed with methanol, dried at 40 ° C under reduced pressure for 15 hours to obtain the logarithm of viscosity 0 · 8 7 d 1, / g, 醯Polyamidic acid having an imidization rate of 0% (hereinafter referred to as "polyamidic acid (A-5)") 2 8 0 g ° Synthesis Example 6 224. 17 g of tetracarboxylic dianhydride (0.5 Mo (Ear) 2,3,5-tricarboxycyclopentylacetic dianhydride, 157.14g (0.5 mole) 1,3,3a, 4,5,9b -hexahydro-5 -methyl-5 (tetrahydro-1 94.62g (0.5875 moles) p-phenylene of 2,5-dioxo-3-furyl) -naphthalene [1,2-c] -furan-1,3-dione, diamine compound Diamine, 32.02g (0. 1 mole) 2,2-ditrifluoromethyl-4, 4-diaminobiphenyl, 6.43g (0. 0 1 mole) 3,6-bi (4 monoaminophenylfluorenyloxy) cholestaene (a compound represented by the above formula (9), The same below), 4 · 04g (0 · 015 mole) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the 18th printed alkoxy-2,5-diaminobenzene dissolved in 4500g of N-methyl-2-pyrrolidone The reaction was carried out at 60 ° C for 6 hours. Subsequently, the reaction solution was poured into excess methanol to precipitate the reaction product, washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure to obtain the viscosity. Logarithm: 0.887 d / g, 410 g of polyamidic acid with a fluorinated imidization rate of 0%. 30 g of the polyamidic acid obtained was re-dissolved in 570 g of N-methyl-2-pyrrolidone, and 23. After 4 g of pyridine and 18.1 g of acetic anhydride, perform dehydration and closed-loop reaction at 110 ° C for 4 hours, and -34- This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 591083 A7 __B7 __ V. Description of the invention (32) (Please read the precautions on the back before filling in this page) After carrying out the same precipitation, washing and decompression as described above, the viscosity logarithm is 0.80 d Ι / g. 100% of fluorene imidized polymer (hereinafter referred to as "fluorene imidized polymer (B-1)") 17. 5 g. Synthesis Example 7 Carboxylic dianhydride: 224 · 17g (0.5 mole) 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 157 · 14g (0 · 5 mole) 1,3,3a, 4,5, 9b —hexahydro-5 —methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphthalene [1,2-c] -furan-1,3-dione, diamine compound 94 · 62g (0 · 875 mol) p-phenylene diamine, 24 · 85g (0 · 1 mol) bisaminopropyltetramethyldisilax Printed alkane, 6.43g (0. 0 1 mol) 3,6-bis (4-aminophenylfluorenyloxy) cholestaene, 4.04g (0.015 mol) octadecyloxy-1 2,5-Diaminobenzene was dissolved in 4500 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 6 hours. Subsequently, the reaction solution was poured into an excess of methanol to precipitate a reaction product, and the reaction product was washed with methanol, and dried at 40 ° C under reduced pressure for 15 hours to obtain a logarithm of viscosity 0.882d I / g. 370 g of polyamic acid at a rate of 0%. 30 g of the obtained polyamic acid was re-dissolved in 570 g of N-methyl-2-pyrrolidone, and 23.4 g of pyridine and 18.1 lg of acetic anhydride were added, followed by a dehydration ring-closure reaction at 110 ° C for 4 hours. After carrying out the same precipitation, washing, and decompression, the logarithm of viscosity was 0.77 d 1 / g, and the imidization ratio was 100 ° /. Zhiimide polymer (at -35- this paper size applies Chinese National Standard (CNS) A4 specification (210X297mm) 591083 A7 B7_ V. Description of the invention (33) hereinafter referred to as "醯 imide polymer ( B — 2) ") 18 · 5g. (Please read the precautions on the back before filling this page) • Synthesis Example 8 224 · 17g (1 · 0 mole) of tetracarboxylic dianhydride 2, 3, 5-tricarboxycyclopentylacetic dianhydride 107 · 06 g (0 · 99 mole) of P-amine compound, 6 · 43 g (0 · 01 mole) of P-phenylenediamine, 3,6-bis (4-aminophenylphenoxy) cholesterol dissolved In 4 500 g of N-methyl-2-pyrrolidinone, react at 60 ° C for 6 hours. Subsequently, the reaction solution was poured into excess methanol to precipitate the reaction product, and then washed with methanol, and dried under reduced pressure at 40 t for 15 hours to obtain a logarithm of viscosity 0.90 d 1 / g. Polyglycolic acid 4 0 0 g with a chemical conversion rate of 0%. 30 g of the obtained polyamic acid was re-dissolved in 570 g of N-methyl-2-pyrrolidone, and 23.4 g of pyridine and 18.lg of acetic anhydride were added, followed by 4 at 1 10 ° C. Hours of dehydration and closed-loop reaction, and after the same precipitation, washing, and decompression as described above, the viscosity logarithm is 0.85 d 1 / g. The imidization rate printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is 100%. 17.5 g of fluorene imidized polymer (hereinafter referred to as "fluorene imidized polymer (B-3)"). Synthesis Example 9 224 · 17 g (0.5 mole) of tetracarboxylic dianhydride 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 157.1 g (0.5 mole) of 1,3,3a , 4,5,9b —hexahydro-5 —methyl-5 (tetrahydro-2,5-dioxo-3 —furanyl) -naphthalene [This paper size applies to China National Standard (CNS) A4 specification (210X297 Mm) -36-59l〇83 A7 B7 _________________ V. Description of the invention (34) (Please read the notes on the back before filling out this page) 1,2-c] -furan-1,3-dione, diamine 89. 21g (.825 mol) of P-Phenylenediamine, 32.02g (0.1 mol) of 2'2'-ditrifluoromethyl- Printed by the Industrial Property Cooperative of the Ministry of Economic Affairs 4 4,4-diaminobiphenyl, 25.34g (0.06 mole) 1- (3,5-diaminophenylphenyloxy)-4-(4-trifluoromethylphenyloxy) ) -Cyclohexane (the compound represented by the above formula (20), the same applies hereinafter), 4 · 04 g (0. 15 mol) octadecyloxy-2,5-diaminobenzene was dissolved in 4500 g of N- Methyl-2-pyrrolidone, 6 hours at 60 ° C . Subsequently, the reaction solution was poured into excess methanol to precipitate the reaction product, and the reaction product was washed with methanol and dried at 40 ° C under reduced pressure for 15 hours to obtain a logarithm of viscosity 0.99 d Ι / g. 4 1 0 g of polyamic acid having an amination rate of 0%. 30 g of the obtained polyamic acid was re-dissolved in 570 g of N-methyl-2-pyrrolidone, and after adding 23.4 g of pyridine and 18.lg of acetic anhydride, dehydration and ring closure were performed at 110 ° C for 4 hours. The reaction is carried out by the same precipitation, washing, and decompression as described above to obtain a logarithmic viscosity of 0.83 d 1 / g and a fluorinated imidization polymer having a fluorinated imidization rate of 100% (hereinafter referred to as “fluorene” Aminated polymer (B-4) '') 17.5g. Example 1 100 parts by weight of the fluorene imidized polymer (B-1) obtained in Synthesis Example 6 and SH 3 77 1 (Toray—Dow Corning Corporation) containing a silicon-containing compound represented by the above formula (II) Made) 0 _ 075 parts by weight dissolved in r-butyrolactone / N-methyl-2-pyrrolidone / butyl cellulose solubilizer This paper is applicable to China National Standard (CNS) A4 (210X297 mm) ~ " " 591083 A7 B7 V. Description of the invention (35) (Please read the precautions on the back before filling out this page) In a mixed solvent (71/17/12 (weight ratio)), the solution with a solid content concentration of 4% by weight ' This solution was filtered through a filter with a pore size of 1 // m to make the liquid crystal alignment agent of the present invention. The above-mentioned liquid crystal alignment agent was coated on a transparent electrode surface of a glass substrate with a transparent electrode of IT using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.), and dried on a hot-pressed plate at 80 t for one minute. And dried on a hot platen at 200 ° C for 10 minutes to form a film with an average thickness of 600 angstroms. When the substrate was observed under a microscope at a magnification of 20 times, printing streaks and sand holes were not found, and it was confirmed that the printability was extremely good. Printed by the Goods and Consumers Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. This film is rolled on a roller with a dragon-proof cloth. Friction machine is used to rotate the roller at 5 0 0 r pm, the platform moving speed is 3 cm / second, and the presser foot length is 0. The rubbing treatment was performed under a condition of 4 mm to form a liquid crystal alignment film. Subsequently, the substrate on which the above-mentioned liquid crystal alignment film was formed was immersed in isopropyl alcohol for 1 minute, and then dried on a hot platen at 100 ° C for 5 minutes. Subsequently, a pair of the substrates with the outer edges of the liquid crystal alignment film are coated with an alumina epoxy resin adhesive with a diameter of 5 · 5 // m, and then the liquid crystal alignment film faces are bonded in an opposite way. Harden the adhesive. Subsequently, a matrix type liquid crystal (MLC-6 2 2 1) was filled between a pair of substrates through the liquid crystal injection hole, and then the liquid crystal injection hole was closed with an acrylic light-curing adhesive, and then the two outer surfaces of the substrate The deflection plate is bonded to the upper surface to complete the liquid crystal display element of the present invention. The obtained liquid crystal display element was subjected to a rectangular wave of 30Hz and 3.0V with alternating AC 6.0V (peak and peak) for 50 hours at an ambient temperature of 70 ° C, and the result was observed visually. I learned that the paper size of this paper is in accordance with the Chinese National Standard (CNS) A4 (210X297 mm) -38- 591083 A7 B7 V. Description of the invention (36) Crystal display elements have not been found to display poorly. Examples 2 to 22, Comparative Examples 1 to 2 The polyimide acids and fluoridimide polymers obtained in Synthesis Examples 1 to 9 and Comparative Examples 1 to 2 were used, except for changing the types and addition amounts of silicon-containing compounds and Except for the drying temperature of the liquid crystal alignment film, a liquid crystal alignment agent was prepared in the same manner as in Example 1, and the film formed on the substrate was observed to see whether it had printed streaks or sand holes, and then the obtained liquid crystal display element was observed. Is there any display failure? Moreover, in Examples 5 to 2, and Comparative Examples 1 to 2, the polyamidic acid and the fluorene imidized polymer system used polyamic acid: fluorene imidized polymer = 4: 1 (weight ratio) ratio . The results are also shown in Table 1. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (21 OX 297 mm) -39-591083
A B 五、發明説明(37 )表1 經濟部智慧財產局員工消費合作社印製 聚合物 含矽化合物(重量份) 印刷性 顯示不佳 實施例2 B-2 C-K0.075) 良好 /γγΓ- IiTF j \w 實施例3 B-3 C-K0.075) 良好 4m* 111II y ι 實施例4 B-4 C-l(0.075) 良好 赃 實施例5 A-1 、 B-1 C-K0.075) 良好 dnL· TTTl: J \ w 實施例6 A-2 、 B-1 C-K0.075) 良好 inL ιΤΓΓ 實施例7 A-3 、 B-1 C-K0.075) 良好 4rrc. 11111 實施例7 A-4 、 B-1 C-l(0.080) 良好 迦 J\\\ 實施例8 A-5 、 B-1 C-l(0.080) 良好 4cnl lilt J INN 實施例9 A-1 、 B-2 C-K0.080) 良好 >frrf 111 rr 實施例1 0 A-2 、 B-2 C-K0.080) 良好 M J 實施例1 1 A-3 、 B-2 C-l(0.080) 良好 無 J\\\ 實施例1 2 A-4 、 B-2 C-l(0.075) 良好 4πΐ. Ill Γ J INN 實施例1 3 A-5 、 B-2 C-K0.075) 良好 4nt Π ΠΓ 實施例1 4 A-1 、 B-3 C-K0.075) 良好 itnt Π M J l 實施例1 5 Α·2 、 B-3 C-K0.075) 良好 M j \\\ 實施例1 6 A-3 、 Β-3 C-l(0.075) 良好 /frrr Mil J l \N 實施例1 7 A-4 、 B-3 C-l(0.075) 良好 dfral tttr j \\\ 實施例1 8 A-5 、 B-3 C-K0.075) 良好 >frrr lilt 實施例1 9 A-3 、 B-4 C-K0.075) 良好 /frrr ΙΙΠΓ J k NN 實施例2 0 A-4 、 B-4 C-K0.075) 良好 >6nr 實施例2 1 A-1 、 B-1 C-l(0.075) 良好 >fnT- II1Γ 實施例2 2 Α·4 、 B-4 C-K0.075) 良好 4ttL tin二 J \ w 比較例1 A-1 、 B-1 _ 有斑紋 M J i ΛΝ 比較例2 A-3 、 B-2 有斑紋 4rrr /fn-r 1111Γ 111 J \\\ Jv\\ 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁) -40 591083 A7 B7__ 五、發明説明(38 ) C— 1 : SH3 77 1 (東麗一道康寧公司一聚矽氧 公司製) (請先閱讀背面之注意事項再填寫本頁) C 一 2 : SH190 (東麗一道康寧公司一聚矽氧公 司製) 【發明之效果】 本發明之液晶配向劑,可製得塗佈於基板上時,可得 到不具有印刷斑紋、砂孔等印刷性良好之液晶配向膜。 本發明之液晶顯示元件,除適用於T N型與S T N型 液晶顯示元件以外,亦可選擇所使用之液晶,而用於製得 SH(Super Homeotropic)型、IPS(In-Plane Switching)型、強介 電性與反強介電性之液晶顯示元件。 此外,本發明之液晶顯示元件,可有效地用於各種裝 置,例如桌上型計算機、手錶、時鐘、數目顯示板、文字 處理機、個人電腦、液晶電視等顯示裝置。 經濟部智慧財產局肖工消費合作社印製 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) -41 -AB 5. Description of the invention (37) Table 1 Printed polymer containing silicon compounds (parts by weight) of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printability shows poor Example 2 B-2 C-K0.075) Good / γγΓ- IiTF j \ w Example 3 B-3 C-K0.075) Good 4m * 111II y ι Example 4 B-4 Cl (0.075) Good example 5 A-1, B-1 C-K0.075) Good dnL · TTTT1: J \ w Example 6 A-2, B-1 C-K0.075) Good inL ιΓΓΓ Example 7 A-3, B-1 C-K0.075) Good 4rrc. 11111 Example 7 A-4, B-1 Cl (0.080) Good J J \\\\ Example 8 A-5, B-1 Cl (0.080) Good 4cnl lilt J INN Example 9 A-1, B-2 C-K0. 080) Good > frrf 111 rr Example 1 0 A-2, B-2 C-K0.080) Good MJ Example 1 1 A-3, B-2 Cl (0.080) Good J \\\ Example 1 2 A-4, B-2 Cl (0.075) Good 4πΐ. Ill Γ J INN Example 1 3 A-5, B-2 C-K0.075) Good 4nt Π Γ Example 1 4 A-1, B -3 C-K0.075) Good itnt Π MJ l Example 1 5 Α · 2, B-3 C-K0.075) Good M j \\\ Example 1 6 A-3, β-3 Cl (0.075 ) OK / frr r Mil J l \ N Example 1 7 A-4, B-3 Cl (0.075) Good dfral tttr j \\\ Example 1 8 A-5, B-3 C-K0.075) Good > frrr lilt Example 1 9 A-3, B-4 C-K0.075) Good / frrr ΙΠΠΓ J k NN Example 2 0 A-4, B-4 C-K0.075) Good > 6nr Example 2 1 A -1, B-1 Cl (0.075) Good > fnT-II1Γ Example 2 2 Α · 4, B-4 C-K0.075) Good 4ttL tin II J \ w Comparative Example 1 A-1, B-1 _ Speckled MJ i ΛΝ Comparative Example 2 A-3, B-2 Speckled 4rrr / fn-r 1111Γ 111 J \\\ Jv \\ This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ( Please read the precautions on the back before filling this page) -40 591083 A7 B7__ V. Description of the invention (38) C— 1: SH3 77 1 (manufactured by Toray Co., Ltd., a polysilicon company) (Please read the back Please fill in this page again for precautions) C-2: SH190 (manufactured by Toray Co., Ltd. and Polysilicon Co., Ltd.) [Effect of the invention] The liquid crystal alignment agent of the present invention can be obtained when coated on a substrate. LCD with good printability such as printing streaks and sand holes Film. The liquid crystal display element of the present invention is applicable to TN type and STN type liquid crystal display elements. The liquid crystal used can also be selected, and used to obtain SH (Super Homeotropic) type, IPS (In-Plane Switching) type, strong Dielectric and anti-ferroelectric liquid crystal display elements. In addition, the liquid crystal display element of the present invention can be effectively used in various devices, such as display devices such as desktop computers, watches, clocks, number display boards, word processors, personal computers, and LCD televisions. Printed by Xiao Gong Consumer Cooperative, Bureau of Intellectual Property, Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) -41-
本纸張尺度適用中國國家標準(CNS ) A4規格(21〇X297公楚) 裝 訂 591083 A7 B7This paper size is in accordance with Chinese National Standard (CNS) A4 (21 × 297). Binding 591083 A7 B7
五、發明説明(13) 6 -二胺基吖啶、雙(4 -胺基苯基)苯基胺與下記式 (I I I )〜(I V )所示化合物等,分子內具有2個一 級胺基與該1級胺基以外之氮原子之二胺;V. Description of the invention (13) 6-diaminoacridine, bis (4-aminophenyl) phenylamine and compounds represented by the following formulae (III) to (IV), etc., have two primary amine groups in the molecule A diamine with a nitrogen atom other than the primary amine group;
H2N NH2 (III) I---------4衣—— (請先閲讀背面之注意事項再填寫本頁) (式中,R 5爲具有由吡啶、嘧啶、三嗪、哌啶與哌嗪 中所選出之含有氮原子之環構造的1價有機基,X爲2價 有機基)H2N NH2 (III) I --------- 4 clothing—— (Please read the precautions on the back before filling this page) (where R 5 is a compound with pyridine, pyrimidine, triazine, piperidine A monovalent organic group having a nitrogen atom-containing ring structure selected from piperazine, and X is a divalent organic group)
、1T 0x_r6'x"0 (iv) 線 (式中,R 6爲具有由吡啶、嘧啶、三嗪、哌啶與哌嗪 中所選出之含有氮原子之環構造的2價有機基,X爲2價 有機基,複數存在之X,可爲相同或不同皆可) 下記式(V )所示單取代苯二胺類;下記式(V I ) 所示二胺基有機矽氧烷; 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) -16- 591083 A7 B7 珍」二 五、發明説明(25) 2重量份,較佳爲0 · 05至1重量份,更佳爲〇 . 05 至0 · 5重量份。低於0 · 0 1重量份時,印刷性之改良 效果會有不充分之情形產生,超過1 0重量份時,會有增 黏之情形產生。 液晶配向劑 本發明之液晶配向劑中,上記(A )聚合物與(B ) 含矽化合物,一般係以溶解於有機溶媒之方式構成。 製作本發明之液晶配向劑時之溫度,一般爲0 °C至 2 0 0 °C,較佳爲2 0 °C至6 0它之範圍。 構成本發明液晶配向劑之有機溶媒,例如可聚醯胺酸 合成反應時所使用之有機溶媒等。又,聚醯胺酸之合成反 應中可倂用之貧溶媒亦可做適當選擇後使用。 本發明之液晶配向劑中固型成分之濃度,在考慮黏 度、揮發性等條件下,較佳爲1至1 0重量%之範圍。 即,本發明之液晶配向劑,係以塗佈於基板表面,以作爲 液晶配向膜之方式形成塗膜,故固型成分低於1重量% 時’因塗膜之膜厚過薄故未能得到良好之液晶配向膜, 又’液晶配向劑之黏度過大時其塗佈特性亦會產生劣化情 形。 本發明之液晶配向劑,就提高對基板表面黏著性之觀 點而言,以使用含有環氧基之化合物爲佳。前述含有環氧 基之化合物,例如乙二醇二縮水甘油醚、聚乙二醇二縮水 甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、 本紙張尺度適用中國國家標準(CNS ) Α4規格(21〇χ297公釐) 批衣-- (請先閲讀背面之注意事項再填寫本頁) 訂 線 -28-, 1T 0x_r6'x " 0 (iv) line (where R 6 is a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine, and piperazine, and X is Divalent organic group, X in plural may be the same or different) Mono-substituted phenylenediamines represented by the following formula (V); Diamine-based organosiloxanes represented by the following formula (VI); Applicable to China National Standard (CNS) A4 specification (210X297 mm) -16-591083 A7 B7 Zhen "25. Description of the invention (25) 2 parts by weight, preferably 0.05 to 1 part by weight, more preferably 0. 05 to 0 · 5 parts by weight. If it is less than 0 · 0 1 parts by weight, the effect of improving printability may be insufficient, and when it exceeds 10 parts by weight, it may be thickened. Liquid crystal alignment agent In the liquid crystal alignment agent of the present invention, the polymer (A) and the silicon-containing compound (B) described above are generally constituted by being dissolved in an organic solvent. The temperature when manufacturing the liquid crystal alignment agent of the present invention is generally in the range of 0 ° C to 200 ° C, and preferably in the range of 20 ° C to 60 °. The organic solvent constituting the liquid crystal alignment agent of the present invention can be, for example, an organic solvent used in the synthesis reaction of poly (fluorinated acid). In addition, a poor solvent that can be used in the synthesis reaction of polyamic acid can also be used after being appropriately selected. The concentration of the solid component in the liquid crystal alignment agent of the present invention is preferably in the range of 1 to 10% by weight in consideration of viscosity, volatility and the like. That is, the liquid crystal alignment agent of the present invention is formed on the substrate surface to form a coating film as a liquid crystal alignment film. Therefore, when the solid content is less than 1% by weight, 'the film thickness of the coating film is too thin, so it cannot be used. A good liquid crystal alignment film is obtained, and when the viscosity of the liquid crystal alignment agent is too large, its coating characteristics may also deteriorate. The liquid crystal alignment agent of the present invention is preferably a compound containing an epoxy group in terms of improving the adhesion to the substrate surface. The aforementioned epoxy-containing compounds, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, this paper standard applies to China National Standard (CNS) A4 Specifications (21〇χ297mm) Approved clothing-(Please read the precautions on the back before filling this page) Thread 28-
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CN101821672B (en) * | 2007-10-19 | 2012-05-30 | Jsr株式会社 | Liquid crystal aligning agent, method for producing liquid crystal alignment film, and liquid crystal display device |
TWI381041B (en) * | 2004-07-08 | 2013-01-01 | Jsr Corp | Liquid crystal alignment agent and liquid crystal display element |
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JP4671015B2 (en) * | 2003-12-17 | 2011-04-13 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
JP4868107B2 (en) * | 2004-03-09 | 2012-02-01 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
JP4793536B2 (en) * | 2004-11-10 | 2011-10-12 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
JP4844728B2 (en) * | 2006-05-15 | 2011-12-28 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
JP5013105B2 (en) * | 2007-03-06 | 2012-08-29 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
CN101802691B (en) | 2007-08-21 | 2012-04-18 | Jsr株式会社 | Liquid crystal aligning agent, method for producing liquid crystal alignment film, and liquid crystal display device |
WO2009069724A1 (en) * | 2007-11-27 | 2009-06-04 | Jsr Corporation | Liquid crystal aligning agent, method for forming liquid crystal alignment film, and liquid crystal display device |
JP4678450B2 (en) * | 2008-01-30 | 2011-04-27 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
JP5365774B2 (en) * | 2008-11-14 | 2013-12-11 | Jsr株式会社 | Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element |
KR101856727B1 (en) | 2016-06-21 | 2018-05-10 | 주식회사 엘지화학 | Liquid crystal alignment composition, method of preparing liquid crystal alignment film, and liquid crystal alignment film using the same |
CN108490652B (en) * | 2018-02-09 | 2020-05-22 | 深圳市华星光电半导体显示技术有限公司 | Gamma automatic adjustment method and system |
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JPS6466620A (en) * | 1987-09-08 | 1989-03-13 | Asahi Glass Co Ltd | Liquid crystal display element |
JPH04146993A (en) * | 1990-10-09 | 1992-05-20 | Nissan Chem Ind Ltd | Orienting agent for filmy liquid crystal display cell |
JPH07270803A (en) * | 1994-03-30 | 1995-10-20 | Sumitomo Bakelite Co Ltd | Liquid crystal orienting agent and its production |
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2001
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TWI381041B (en) * | 2004-07-08 | 2013-01-01 | Jsr Corp | Liquid crystal alignment agent and liquid crystal display element |
CN101821672B (en) * | 2007-10-19 | 2012-05-30 | Jsr株式会社 | Liquid crystal aligning agent, method for producing liquid crystal alignment film, and liquid crystal display device |
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KR100841868B1 (en) | 2008-06-27 |
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