TW201238980A - Composition for photoaligned film and optically anisotropic film - Google Patents
Composition for photoaligned film and optically anisotropic film Download PDFInfo
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201238980 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種新型之光配向膜用組成物及光學異 方性臈用組成物;並且,關於使用該組成物而得到之各種 之光學異方性膜、光學材料以及液晶胞。 【先前技術】 在近年來,在顯示器(除了液晶顯示器以外,也包含 ° 颂示器等。)領域,以各種之形式,來利用相位差 $視野角提升用膜、亮度提升用膜、偏光膜等之各種光 =異,性膜、導電性材料、非線性光學材料、光反應性致 器等之各種光學材料。此種光學異方性膜或光學材料係 ::有配向能之層(膜、基板表面等)之上…液晶性 θ色素$電性化合物等而進行製造,但是,向來, :θ、。配向層之方法係知道呈化學或物理地處理表面 =。作為此種方法係知道例如沿著某一方向,藉由布 寺而摩擦被覆於基板表面 m 败表面之聚醯亞胺等之高分子樹脂膜之 摩擦處理,使用在液晶 日日員不裝置用配向膜等之形成。 1一疋’在此種方法,由 製造生產魄η 、微、、田之塵埃發生而造成之液晶 生屋線之巧·染或者是ώ 晶體)有疋由於静電而造成之TFT (薄膜電 日體)兀件之破壞箄 良。 ’、成為引起液晶面板之製造製程之 題。 -者疋不谷易控制定量之配向等之問 於是,進行各種檢討,使用光反應性化合物(藉由光 4 201238980 照射而引起光異性化、光二量化、光分解等之化合物), ,,>、有液Ba專之配向能之光配向膜,來取代摩擦處理。 知道例如具有偶氮基之偶氮基苯化合物來作為引起光異性 化之化合物(非專利文獻丨)等、具有肉桂醯基之桂皮酸 街生物來作為引起光二量化之化合物(非專利文獻2) ' 具有香丑素基之香豆素衍生物(非專利文獻3)、具有芳 烯醯芳烴基之芳基丙烯醯芳烴衍生物(非專利文獻4 ) ^乍為引起光分解之化合物之光分解性聚醯亞胺(非專 利文獻5)等。 ^疋,像這樣 ” w机兀*兴性化、二量化或光分 "月格因此,在光配向膜之製造,有所謂材料選擇之 自由度變低之問題發生。 所謂Fnes (弗利斯)轉變係由苯盼醋來生成鄰— :嗣及/或對—苯盼酮之轉變反應,#由路易 觸1某(非專利文獻6卜在弗利斯轉變中,將藉由光而ί :二特別稱為光Fries (弗利斯)轉變 斯)轉變之反應機構係認為正如以下而透過自由基。201238980 6. Technical Field of the Invention The present invention relates to a novel composition for a photo-alignment film and an optical anisotropic composition; and various optical differences obtained by using the composition Square film, optical material and liquid crystal cell. [Prior Art] In recent years, in the field of displays (including liquid crystal displays, etc.), the phase difference of the viewing angle raising film, the brightness improving film, and the polarizing film are utilized in various forms. Various optical materials such as various types of light, such as a film, a conductive material, a nonlinear optical material, and a photoreactive device. Such an optical anisotropic film or optical material is produced by a layer having an alignment energy (film, substrate surface, etc.), a liquid crystal θ pigment, an electric compound, or the like, but is preferably θ. The method of the alignment layer is known to treat the surface chemically or physically. As such a method, for example, it is known that, in a certain direction, the rubbing treatment of a polymer resin film such as polyimide or the like which is coated on the surface of the substrate is rubbed by a cloth temple, and is used in the liquid crystal day and day. Formation of a film or the like. 1 疋 'In this method, the production of 魄η, micro, and the dust of the field caused by the occurrence of the dust of the liquid crystal living room line, dyed or ώ crystal) has a TFT due to static electricity (film electric day) Body) The damage of the pieces is good. ', has become the cause of the manufacturing process of the liquid crystal panel. - 疋 谷 谷 控制 控制 控制 控制 控制 控制 控制 控制 控制 易 易 易 易 易 易 易 易 易 易 谷 易 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 谷 光 光 光 光 光 光 谷 光 光 光 光 光 光;, there is a liquid alignment film with a liquid Ba to replace the friction treatment. For example, a azobenzene compound having an azo group is known as a cinnamic acid bacterium having a cinnamyl group as a compound which causes photo-analysis (Non-Patent Document 2). A coumarin derivative having a fragrant sulphate group (Non-Patent Document 3), an aryl propylene fluorene aromatic hydrocarbon derivative having an aryl olefin aryl hydrocarbon group (Non-Patent Document 4) ^ 光 is a photodecomposition of a compound which causes photolysis Polyimine (Non-Patent Document 5) and the like. ^疋, like this, “ww, 兴, 二, or quantitative”, in the manufacture of optical alignment films, there is a problem that the degree of freedom of material selection becomes lower. The so-called Fnes (Folly) The transformation is carried out by benzene vinegar to form a transition reaction between —-: and/or phenyl-p- ketone. ###################################################################### ί : The reaction mechanism that is particularly called the light Fries transition is considered to pass through free radicals as follows.
"!广' h 〇~jQ I"!广' h 〇~jQ I
〇^G— ..〇心〜Ια ^ 【先前技術文獻】 [非專利文獻】〇^G— ..〇心~Ια ^ [Prior Art Literature] [Non-patent Literature]
Langmuir, vol. 4 【非專利文獻1】K. Ichimura et al 201238980 page 1214 ( 1 988 ) 【非專利文獻 2】M. Schadt et al.,J. Appl. Phys., vol. 31, No. 7, page 21 55 ( 1 992 ) 【非專利文獻 3】M· Schadt et al·,Nature.,vol· 381, Page 21 2 ( 1 996 ) 【非專利文獻4】小川俊博等、液晶討論會演講預稿集、 2AB03 ( 1 997 ) 【非專利文獻5】第22回之液晶討論會演講預稿集、1672 頁 A1 7 ( 1 996 ) 【非專利文獻 6】THE MERCK INDEX FOURTEENTH EDITION, Organic Name Reactions 150 【發明内容】 【發明所欲解決之課題】 在前述之背景,本發明係提供一種包含材料選擇之自 由度非常高之光反應性化合物之光配向膜用組成物。此 外’本發明係提供一種使用該光配向膜用組成物之光配向 膜°此外’本發明係提供一種使用該光配向膜之相位差膜、 視野角提升用膜、亮度提升用膜、偏光膜等之各種光學異 方性膜和導電性材料、非線性光學材料、光反應性致動器 等之各種光學材料、以及使用該光配向膜之液晶胞。 此外’本發明係提供一種包含該光反應性化合物之光 干、方性膜用組成物以及使用該組成物之光學異方性膜。 【用以解決課題之手段】 6 201238980 本發明人們係全心地進行研究,結果發現:如果在聚 合物之側鏈之末端,使用藉由下列之化學式而表示且鍵結 具有苯紛性醋基之光反應性基之光反應性聚合物,來作為 光反應性化合物的話,則可以解決前述之課題;並且,還 重複地進行檢討而完成本發明。Langmuir, vol. 4 [Non-Patent Document 1] K. Ichimura et al 201238980 page 1214 (1 988) [Non-Patent Document 2] M. Schadt et al., J. Appl. Phys., vol. 31, No. 7 , page 21 55 (1 992) [Non-Patent Document 3] M. Schadt et al., Nature., vol. 381, Page 21 2 (1 996) [Non-Patent Document 4] Ogawa Junbo et al. Manuscript, 2AB03 (1 997) [Non-Patent Document 5] The 22nd Liquid Crystal Symposium Presentation Pre-Collection, 1672 Pages A1 7 (1 996) [Non-Patent Document 6] THE MERCK INDEX FOURTEENTH EDITION, Organic Name Reactions 150 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] In view of the foregoing, the present invention provides a composition for a photo-alignment film comprising a photoreactive compound having a very high degree of freedom in material selection. In addition, the present invention provides a photo-alignment film using the composition for a photo-alignment film. Further, the present invention provides a retardation film, a film for viewing angle enhancement, a film for brightness enhancement, and a polarizing film using the photo-alignment film. Various optical materials such as various optical anisotropic films and conductive materials, nonlinear optical materials, photoreactive actuators, and the like, and liquid crystal cells using the photoalignment film. Further, the present invention provides a light-dried, square film-containing composition comprising the photoreactive compound and an optical anisotropic film using the composition. [Means for Solving the Problem] 6 201238980 The inventors of the present invention conducted a thorough study and found that if it is at the end of the side chain of the polymer, it is represented by the following chemical formula and bonded with a benzene vinegar group. The photoreactive group photoreactive polymer can solve the above problems as a photoreactive compound, and the present invention can be completed by repeating the review.
取储 (在化學^巾’ & A係非取代或取代脂環^烴或者是非取 代或取代芳香環,環B係非取代或取代芳香環。) 本發月之光反應性聚合物係其側鏈中之苯酚性酯基, 承受光之照射’藉由光裂解’經由自由基而成為分解物。 此外’在環B之笨㈣氫氧基之鄰位(或對位)為非取代 之狀態下’這些自由基之—部分係引起光Μα(弗利斯) 轉變,生成鄰-苯紛酮(或對—苯㈣)。因此,準備包 含該光反應性聚合物之光配向膜用或光學異方性膜用組成 物來塗佈於基材者’在這個照射光之狀態下在使用直線 偏光來作為引起這些-連串之反應之光之時,僅相對於該 直線偏光之偏光♦由g p X, , | . 苹呈冋軸地存在之苯酚性酯基係在該偏光 軸呈選擇性地引起光裂解或光裂解及A Fries (弗利斯) 轉變,因&,可以藉此而製造賦予液晶等之配向能之光配 向膜或光學異方性膜。本發明係根據此種認知而完成的。 201238980Storage (in the chemical ^ towel ' & A line unsubstituted or substituted alicyclic hydrocarbons or unsubstituted or substituted aromatic ring, ring B system unsubstituted or substituted aromatic ring.) This month's photoreactive polymer is The phenolic ester group in the side chain is subjected to irradiation of light 'by photolysis' to become a decomposition product via a radical. In addition, in the state in which the ortho (or para) of the hydroxyl group in the ring B is unsubstituted, the part of these radicals causes the Μα (Friss) transformation to form o-benzone ( Or p-benzene (four)). Therefore, the photo-alignment film or the optical anisotropic film composition containing the photoreactive polymer is applied to the substrate, and in the state of the irradiation light, linear polarized light is used as the cause of the series. At the time of the reaction light, only the polarized light relative to the linearly polarized light is gp X, , . The phenolic ester group present in the axis of the axis selectively causes photocleavage or photocleavage on the polarizing axis and A Fries is a light-aligning film or an optical anisotropic film which imparts an alignment energy to a liquid crystal or the like by & The present invention has been completed on the basis of such knowledge. 201238980
细一3?勘朗 也就是說’本發明係關於 [1 ]: 一種光配向膜用組成物,係將具有藉由通式(丨). m^PCr_〇--^WP (j) 千 W \〇^^z [在化學式中,Μ係形成均聚物或共聚物之主鏈之單體單 位,SPCR係間隔單位,環Α係非取代或取代脂環式烴或者 是非取代或取代芳香環,環B係非取代或取代芳香環,Z 係烷基、烷氧基、氰基、硝基、齒素原子、_ch=chzi、 -CeCZ1 (但是’ Ζι錢基、烧氧基、院氧基㈣、炫氧 基磺醯基、氱基、硝基或_素原子。)、__c〇〇Z2或—so』2 (但是,Z2係炫基。)。1所*千夕舌访。„ j所表不之重複早位之光反應性聚 合物予以包含而組成; [2]:前述[1]之光配向膜用組成物,係環a之取代基及 環B之取代基’分別獨立地成為由烷基、烷氧基、氰基、 硝基和齒素原子而選出之丨個或2個以上之基; [3 ].前述[1 ]之光配向膜用έ日占私 胰用組成物,係Μ成為由丙烯酸 酯、曱基丙稀酸酯、2 —教而祕缺〇 虱丙烯酸酯、2〜笨基丙烯酸酯、 8 201238980 丙烯醯基苯撐、丙烯醯胺、甲基丙烯醯胺、2 —氣丙烯醯胺、 2 —苯基丙烯醯胺、乙烯醚、笨乙烯衍生物、乙烯酯、順丁 烯二酸衍生物、富馬酸衍生物、矽氧烷、環氧化物而組成 之群組來選出之1種或2種以上之單體單位,spCR為由— (CH2 ) p (但疋,ph 1〜12之任何一個整數。)、1 2 ~丙烯、1,3— 丁烯、環戊烯一丨,2_二醯、環戊烯—1>3 —二醯、環己烯—丨,3一二醯、環己烯—丨,4—二醯、哌啶 ~1’4一二醯、哌嗪一1,4—二醯、1,2—苯撐、1,3_苯撐、 1 ’ 4本撐而組成之群組來選出之間隔單位,環a為藉由:Fine one 3? Surveying Lang means that 'this invention is related to [1]: a composition for optical alignment film, which will have the formula (丨). m^PCr_〇--^WP (j) thousand W \〇^^z [In the chemical formula, the lanthanide forms the monomer unit of the main chain of the homopolymer or copolymer, the SPCR system spacer unit, the cyclic oxime unsubstituted or substituted alicyclic hydrocarbon or the unsubstituted or substituted aromatic Ring, ring B is an unsubstituted or substituted aromatic ring, Z series alkyl, alkoxy, cyano, nitro, dentate atom, _ch=chzi, -CeCZ1 (but 'Ζι钱基, alkoxy, courtyard oxygen (4), oxooxysulfonyl, fluorenyl, nitro or _ atom.), __c〇〇Z2 or -so"2 (however, Z2 is a sleek base.). 1 * Qian Xi tongue visit. „ j indicates that the photoreactive polymer in the early position is included and composed; [2]: the composition for the photoalignment film of the above [1], the substituent of the ring a and the substituent of the ring B respectively Independently selected from the group consisting of an alkyl group, an alkoxy group, a cyano group, a nitro group and a dentate atom, or two or more groups; [3]. The light alignment film of the above [1] is used for the daytime private pancreas With the composition, the ruthenium is made of acrylate, mercapto acrylate, 2 - teaches the lack of acrylate, 2 ~ styrene acrylate, 8 201238980 propylene decyl benzene, acrylamide, methyl Acrylamide, 2-propene decylamine, 2-phenylpropene decylamine, vinyl ether, stupid ethylene derivative, vinyl ester, maleic acid derivative, fumaric acid derivative, decane, epoxy One or more monomer units selected from the group consisting of compounds, and spCR is composed of —(CH2) p (but 疋, any integer of ph 1 to 12), 1 2 to propylene, 1, 3—butene, cyclopentene monodecene, 2—bifluorene, cyclopentene-1” 2-diindole, cyclohexene-indole, 3 dioxin, cyclohexene-fluorene, 4-diindole, piperazine Acridine~1 The group consisting of 4-12, piperazine-1,4-diindole, 1,2-phenylene, 1,3_phenylene, 1'4 support, and the ring unit is selected by :
[但是’ X“〜Π系分別獨立地成為氣原子、院基、院氧基、 鹵素原子或氰基。]所表不之任何一種基,環B為藉由:[But the 'X' ~ Π is independently a gas atom, a hospital base, a hospital oxy group, a halogen atom or a cyano group.] Any one of the groups represented by the ring B is:
齒素原子或氰基,X係氮原子、 氧原子、硫原子。]所表示 201238980 之任何一種基; [4 ] ··前述[3 ]之光配向膜用組成物,係X1B和 Λ I至少 一種、X5B和ΧΙ2β之至少一種' 和Χ2“之至少—種、χ川 和之至少一種、Χ3丨Β和X3〇之至少一種以及 Β Λ 為氣原 子; [5 ]: —種光配向膜用組成物,係將具有藉由通式 a):A dentate atom or a cyano group, an X-type nitrogen atom, an oxygen atom, or a sulfur atom. Any of the groups of 201238980; [4] The composition for a photo-alignment film of the above [3], which is at least one of X1B and ΛI, at least one of X5B and ΧΙ2β, and at least one of Χ2, χ At least one of Chuanhe, at least one of Χ3丨Β and X3〇, and Β Λ is a gas atom; [5]: a composition for a photo-alignment film, which has the formula a):
及X1B〜X4B之各個係分別獨立地成為氫原子、烷基、烷氧 基、齒素原子或氰基,Z係烷基、烷氧基、氰基、硝基、 函素原子、—CH=CHZ1、-Csczl(但是,21係烷基、^氧 基、烷氧基幾基、烷氧基磺醯基、鼠基、硝基或函素原子。)、 —c〇ns〇3Z2(但是,22係院基。),p係卜12之任 何一個整數叫所表示之重複單位之光反應性聚合物予以包 含而組成。 [6]:前述[5]之光配向膜用組成物,係χΙΒ和χ“之至少 —種為氫原子; : 一種光配向膜,係準備在基材之表面來塗佈前述] 〜[6]中任-項之光配向膜心成物者,在這個照射直線偏 光而組成; 10 201238980 [8] . —種光學異方性膜或光學材料,係在前述[7]之光 配向膜,配向液晶性化合物、色素或導電性化合物而組成; [9] : 一種液晶胞,係前述[7]之光配向膜2片呈對向,’ 而使得某-邊之総向膜之直線偏光照射時之偏光轴之方 向和其他邊之光配向媒之直線偏光照射時之偏光轴之方 向’相互地形成規定之角度’在該對向之光配向膜之間, 填充液晶性化合物而組成; 通式 [10 ].-種光學異方性膜用組成物,係將具有藉由 (I) M—spcr—〇— [在化學式中’ Μ係形成均聚物或共聚物之主鏈之單體單 位’ SPCR係間隔單位,環U非取代或取代脂環式煙或者 是非取代或取代芳香環,環Β係非取代或取代芳香環,Ζ 係院基、烧氧基、氰基、硝基、_素原子、_CH=CHZ1、 -CSCZ1 (但是’ Z1係烷基、烷氧基、烷氧基羰基、烷氧 基續醯基、氰基、硝基或齒素原子〇、—⑽z^_s〇3z2 (但是’ Z2減基。)。]所表示之重複單位之光反應性聚 合物予以包含而組成; π 1 ].-種光學異方性膜,係準備在基材之表面來塗佈 刖述[10 ]之光學異方性膜用組成物,在這個照射直線偏光 之後’將包含於該光學異方性膜用組成物之液晶性化合 物’加熱至顯示液晶狀態之溫度以上,並且,該液晶性化 合物還冷卻至未滿顯示液晶狀態之溫度而組成。 11 201238980 【發明效果】 本發明係提供利用所謂 轉變之新型之生成機構之光 膜用組成物’不依賴習知之 桂醯基、芳基丙烯醯芳煙基 加簡單構造之苯酚性酯基, 設計光反應性聚合物之際, 性之自由度之特長。 此外,本發明之光學異 設置配向膜,因此,具有所 來得到光學異方性膜之特長 光裂解及光Fries (弗利斯彡 配向膜用組成物及光學異方性 光配向性基(例如偶氮基、肉 、香豆素基等),使用成為更 來作為光配向性基,因此,在 具有所謂格外地提高材料選擇 方性膜用組成物係不需要另外 謂能夠以簡便、進而低成本, 【實施方式】 【發明之實施形態】 在本發明之光反應性聚合物(I ) 批-» 、1」 在以下’顯不理 想之具體例。 一種光反應性聚合物係具有藉由通式(工_a)And each of X1B to X4B is independently a hydrogen atom, an alkyl group, an alkoxy group, a dentate atom or a cyano group, a Z-based alkyl group, an alkoxy group, a cyano group, a nitro group, a hydroxyl atom, or -CH= CHZ1, -Csczl (however, 21 is an alkyl group, an oxy group, an alkoxy group, an alkoxysulfonyl group, a murine group, a nitro group or a hydroxyl atom.), -c〇ns〇3Z2 (however, 22 Department bases.), any integer of the p system 12 is called a repeating unit of the photoreactive polymer to be included and composed. [6] The composition for a photo-alignment film according to the above [5], wherein at least one of the ruthenium and the ruthenium is a hydrogen atom; : a photo-alignment film prepared by coating the surface of the substrate] [6] The middle-item light-aligning film core is composed of a linearly polarized light in this illumination; 10 201238980 [8] . An optical anisotropic film or optical material, which is the light alignment film of the above [7], Oriented by a liquid crystal compound, a dye or a conductive compound; [9] : a liquid crystal cell which is opposite to the light alignment film of the above [7], and which causes a linear polarization of the edge of the film to the film The direction of the polarization axis and the direction of the polarization axis when the linear alignment of the light-aligning medium of the other side is 'formed at a predetermined angle to each other' is formed by filling the liquid crystal compound between the opposite photo-alignment films; The composition of the optical anisotropic film of the formula [10]. will have a monomer which is formed by (I) M-spcr-〇- [in the chemical formula, the main chain of the homopolymer or copolymer Unit 'SPCR line spacing unit, ring U non-substituted or substituted alicyclic smoke or unsubstituted or substituted aromatic , anthracycline unsubstituted or substituted aromatic ring, fluorene, alkoxy, cyano, nitro, _ atom, _CH=CHZ1, -CSCZ1 (but 'Z1 alkyl, alkoxy, alkoxy a photoreactive polymer of a repeating unit represented by a carbonyl group, an alkoxy fluorenyl group, a cyano group, a nitro group or a dentate atom 〇, —(10)z^_s〇3z2 (but 'Z2 minus group.). And the composition; π 1 ]-- an optical anisotropic film, which is prepared by coating the surface of the substrate with the composition of the optical anisotropic film described in [10], after which the linearly polarized light is irradiated The liquid crystal compound of the composition for an optical anisotropic film is heated to a temperature higher than the temperature at which the liquid crystal state is displayed, and the liquid crystal compound is further cooled to a temperature at which the liquid crystal state is not displayed. 11 201238980 [Effect of the invention] The present invention Provided by a composition for a light film which utilizes a novel generation mechanism called a conversion, a phenolic ester group which is not dependent on a conventional ruthenium base, an aryl propylene fluorene base, and a simple structure, and a photoreactive polymer is designed. The strength of the degree of freedom of sex. In addition, this hair Since the optical film is provided with an alignment film, it has the characteristic photocleavage and optical Fries of the optically anisotropic film (Flies aligning film composition and optical anisotropic photo-alignment group (for example, azo, meat, Since the coumarin group or the like is used as a photo-alignment group, it is not necessary to be simple and further low-cost, and it is not necessary to further improve the material selection method. [Embodiment of the Invention] In the photoreactive polymer (I) of the present invention, the batch-», 1" is not particularly preferred in the following. A photoreactive polymer has a general formula (work_a) )
[在化學式中,符號係具有相同於前面敘述之意義。]所表 示之重複單位。 在通式(I )(在也適合於通式(! —a)之狀態下, 12 201238980 形成均聚物 於該領域之 也包含通式(I—a)。在以下相同。),m係 或共聚物之主鏈之單體單位,通常如果是使用 單體單位的話,則皆可以適度地使用。作為此種單體單位 係列舉例如由丙烯酸g旨、曱基丙稀酸醋、2 __氯丙稀@ ^ 2 —笨基丙烯酸酯、丙烯醯胺、甲基丙烯醯脸、 ^ ^ ^ ~虱丙稀 醯胺、2 —苯基丙烯醯胺、乙烯醚、苯乙烯衍生物(例如〇 —曱基苯乙烯、ρ —苯乙烯磺酸酯)、順丁烯二酸衍生物(例 如順丁烯二酸酯、苯基馬來酸酐縮亞胺、環己基馬來酸酐 縮亞胺)、富馬酸衍生物(例如富馬酸酯)、石夕氧燒、環 氧化物而組成之群組來選出之1種或2種以上之翠體單 位。在Μ由1種之單體單位而組成之狀態下,通式(工) 之光反應性聚合物係均聚物,在Μ由2種以上之單體單位 而組成之狀態下,通式(I )之光反應性聚合物係共聚物。 在本發明之光反應性聚合物為共聚物之狀態下,此種共聚 物係也包含交互型、無規型、接枝型等之任何一種。在這 些單體單位中,最好是丙烯酸酯、曱基丙烯酸酯。 SPCR係繫接單體單位和光反應性基之間隔單位,通常 如果疋使用於該領域的話,則皆可以適度地使用。作為此 種間隔單位係列舉例如—(CH2)卜(但是,ρ係、卜12之 任何一個整數。)、i,2 _丙烯、j,3 —丁烯、環戊烯一工,2 -二醯、環戊烯—1,3-二醯、環己烯—κ 3—二醯、環己 烯一1,4一二醯、哌啶—h4—二醯、哌嗪— 14—二醯、^ =苯撐、1,3 -笨撐或丄,4 一苯撐等。在這些間隔單位中, 最好是一(CH2) ρ ~ (但是,ρ係i〜丨2之任何一個整數。)。 13 201238980 作為P係最好是3〜9之任何一個整數,其中,更加理想是 5〜7之任何一個整數,最佳理想是6。 環A係非取代或取代脂環式烴或者是非取代或取代芳 香%,其中,最好是非取代或取代芳香環,更加理想是非 取代芳香環。環B係非取代或取代芳香環,其中,最好是 非取代芳香環。環A及環B係皆正如藉由通式(1)所表 示而成為2價基,但是,在本說明書,所謂環A或環B成 為「非取代」係表示在形成這些2價基之鍵手以外之鍵手, 成為「非取代」。此外,在本說明書,記載在藉由構造式 而例舉環A及環B之狀態下,就形成2價基之這些鍵手而 言,主鏈側之鍵手係達到至左側’側鏈末端側之鍵手係達 到至右側。環A之取代基(Χ1Α〜Γ2Α)及環B之取代基(χ1Β 〜X )係分別獨立地成為由烷基、烷氧基、氰基、硝基和 南素原子而選出之基,其中,最好是烷氧基。作為環Α或 環B之整體係分別具有1個或2個以上之取代基。作為環 A或環B之理想之取代基之數目係1。 作為Z係列舉烷基、烷氧基 '氰基、硝基、齒素原子、 -•Ci^CHZ1、一 C^CZ1 (但是,Z1係烷基、烷氧基、烷氧基 羰基、烷氧基磺醯基、氰基、硝基或齒素原子。)、 或一S〇3Z2 (但是,Z2係烷基。),其中,最好是烷氧基。 作為Z1係在前述之記載中,最好是烷氧基。 作為R係列舉氫原子、甲基、笨基、氣原子,其中, 最好是氫原子、甲基》 在本說明書’作為烷基係列舉碳數1〜1 2之貌基,其 14 201238980 中’最好是列舉碳數1〜6,审Λ 更加理想是列舉碳數1〜4,爭 佳理想是列舉甲基。作為烷 某,其中,#征β 軋丞谅列舉妷數1〜12之烷氣 L匕 碳數1〜6,更加理想是碳數1〜4, 最佳理想是曱氧基。作盔 ^ _素原子係列舉氟原子、氣原子、 >臭原子、衫子,其中,最好是敦原子。 本發明之光反應性聚合物(1 或溶媒中’聚合以通式(n ): ⑼ Μ—SPCR-ο[In the chemical formula, the symbol system has the same meaning as described above. ] Repeated units indicated. In the state of the general formula (I) (in the state also suitable for the general formula (!-a), 12 201238980 forms a homopolymer in the field also includes the general formula (I-a). The same applies hereinafter.), m system Or the monomer unit of the main chain of the copolymer, if it is a monomer unit, can be used moderately. As such a monomer unit series, for example, acrylic acid, mercapto acrylate, 2 __ chloropropane @ ^ 2 - phenyl acrylate, acrylamide, methacryl oxime, ^ ^ ^ ~ Propylene amide, 2-phenylpropenylamine, vinyl ether, styrene derivatives (eg, fluorenyl styrene, ρ-styrene sulfonate), maleic acid derivatives (eg, cis-butane) a group consisting of a enedic acid ester, a phenyl maleic anhydride imide, a cyclohexyl maleic anhydride imide, a fumaric acid derivative (for example, a fumarate), an arsine, and an epoxide One or more types of green body units to be selected. In the state in which the ruthenium is composed of one type of monomer unit, the photoreactive polymer-based homopolymer of the formula (work) is in a state in which ruthenium is composed of two or more monomer units, and the formula ( A photoreactive polymer copolymer of I). In the state where the photoreactive polymer of the present invention is a copolymer, such a copolymer system also includes any of an interactive type, a random type, a graft type and the like. Among these monomer units, an acrylate or a mercapto acrylate is preferable. The SPCR system is an interval unit between a monomer unit and a photoreactive group, and can be suitably used if it is used in the field. As such a series of intervals, for example, -(CH2) (but, any one of ρ, Bu 12), i, 2 propylene, j, 3-butene, cyclopentene, 2 - 2 Anthraquinone, cyclopentene-1,3-dioxene, cyclohexene-κ3-diindole, cyclohexene-1,4-dioxin, piperidine-h4-dihydrazine, piperazine- 14-dioxin, ^ = phenylene, 1,3 - stupid or bismuth, 4 phenylene, etc. Among these interval units, it is preferable that one (CH2) ρ ~ (however, ρ is any integer of i to 丨2). 13 201238980 As the P system, it is preferable to use any integer of 3 to 9, wherein it is more desirable to be any integer of 5 to 7, and the best ideal is 6. The ring A is an unsubstituted or substituted alicyclic hydrocarbon or an unsubstituted or substituted aromatic, wherein an unsubstituted or substituted aromatic ring is preferred, and an unsubstituted aromatic ring is more preferred. The ring B is an unsubstituted or substituted aromatic ring, and among them, an unsubstituted aromatic ring is preferred. Both the ring A and the ring B are divalent groups as represented by the formula (1). However, in the present specification, the ring A or the ring B is "unsubstituted" and means a bond forming these divalent groups. The key hand other than the hand becomes "non-replacement". Further, in the present specification, in the state in which the ring A and the ring B are exemplified by the structural formula, the bond hands on the main chain side reach the left side side chain end when the bond hands forming the divalent group are formed. The key hand on the side reaches the right side. The substituent of the ring A (Χ1Α~Γ2Α) and the substituent of the ring B (χ1Β to X) are each independently selected from the group consisting of an alkyl group, an alkoxy group, a cyano group, a nitro group and a south atom, wherein Most preferably an alkoxy group. Each of the ring Α or the ring B has one or two or more substituents. The number of substituents which are ideal for ring A or ring B is 1. As the Z series, alkyl, alkoxy 'cyano, nitro, dentate atom, -•Ci^CHZ1, one C^CZ1 (however, Z1 alkyl, alkoxy, alkoxycarbonyl, alkoxy A sulfonyl group, a cyano group, a nitro group or a dentate atom.), or a S〇3Z2 (however, a Z2 alkyl group), wherein an alkoxy group is preferred. In the above description of the Z1 system, an alkoxy group is preferred. The R series is a hydrogen atom, a methyl group, a stupid group, or a gas atom, and among them, a hydrogen atom and a methyl group are preferred. In the present specification, the alkyl group is a carbon number of 1 to 12, which is 14 201238980. 'It is best to list the carbon number 1 to 6, and it is more desirable to enumerate the carbon number 1 to 4. The ideal is to cite the methyl group. As the alkane, among them, #################################################################### Helmet ^ _ prime atom series of fluorine atoms, gas atoms, > stinky atoms, shirts, of which, preferably, the atom. The photoreactive polymer (1 or solvent) of the present invention is polymerized by the formula (n): (9) Μ-SPCR-ο
,0 m [在化學式中,符號1 千夕i神工 ”有相问於則面敘述之意義。]所表 ^ ... 在M表示1種單體單位之狀態下, l a每個而得到之通 (1)之先反應性聚合物係成為均 =,在M表示2種以上之單體單位之狀態下, 之光反應性聚合物係成為聚合這些複數種之單 體早位之共聚物。聚 干 # Ink可以使用光或熱而實施。在聚合 氣程’裝入該單體哎泫拔笙 f 戈/合媒寻之方法係並無特別限定,可以 在I5則而預先投入全 A,廿 4至反應容器之後,開始進行聚 ° ’ ’ ,可以就該單體或溶姐笙·》 入々你 ^ M飞/合媒4之一部分而開始進行聚 合之後’藉由滴下或分钊浐λ哲 殘餘。 次 J技入荨之方法而呈階段性地追加 此外’在單體(π) 可以含有其他… I之際,並無必要’但是’ 體,此種早體係僅限定為具有聚合性之 不飽和鍵(例如7 p 之方面’並無特別限定,可以 > 士 f 、,. 烯性不飽和鍵)之化合物,在這個以外 是具有液晶性之化合物,或 201238980 者也可以是不具有液晶性之化合物。 作為此種單體係列舉例如曱基(曱基)丙稀酸酯、t —丁基(甲基)丙烯酸酯、硬脂醯(甲基)丙稀酸酯、環 己基(甲基)丙烯酸酯、乙氧基乙基(甲基)丙烯酸酯、 經乙基(甲基)丙稀酸酯、苯基(甲基)丙烯酸酯、N,n —二甲基丙烯醯胺等之(曱基)丙烯單體、苯乙烯、 曱基笨乙烯、ρ —笨乙烯磺酸、乙基乙烯醚、Ν —乙烯基咪 唑、乙烯基乙酸酯' 乙烯基吡啶、2 —乙烯基萘、氯乙烯、 氟乙烯、Ν—乙烯基咔唑、乙烯基胺、乙烯基笨酚、Ν—乙 烯基一2 —吼咯烷酮等之乙烯基系單體、4 —烯丙基—丨,2 一曱氧基苯、4 —烯丙基笨酚、4一曱氧基烯丙基笨等之 烯丙基系單體、苯基馬來酸酐縮亞胺、環己基馬來酸酐縮 亞胺等之馬來酸酐縮亞胺類。這些單體係可以單獨使用任 何一種’也可以併用2種以上而使用。 在聚合於溶液中之狀態下,可以無特別限定地使用通 用之有機溶媒。作為溶媒之具體例係列舉乙醇、丙醇、丁 醇等之醇糸溶媒、丙酮、曱基乙基曱酮、甲基異丁基甲酮、 f己_、環戊酮等之酮系溶媒、乙酸乙酯、丁基乙酸酯、 丙二醇單曱基醚乙酸酯等之酯系溶媒、二乙基醚、二甘醇 :甲:等之醚系溶媒、己烷、環己烷、甲基環己烷、曱苯、 浐苯等之烴糸溶媒、乙醯腈等之腈系溶媒、N 一甲基吡咯 =基乙酿胺等之醯胺系溶媒等。這些溶媒係可以 早使用任何一 #,也可以併用2種以上而使用。 在前述之聚合之際 可以使用光聚合起始劑。作為光 16 201238980 聚合起始劑係為了藉由少量之光照射而形成均勻膜,因 此’皆可以使用一般知道之通用之光聚合劑。作為具體例 係列舉例如2,2, 一偶氮二氮丁腈(AIBN) 、2,2’ 一偶氮 基雙(2,4 一二甲基戍腈)專之偶氮腈系光聚合起始劑、, 0 m [In the chemical formula, the symbol 1 千夕i 神工" has the meaning of the face-to-face description.] The table ^ ... In the state where M represents one type of monomer unit, each is obtained by la The first reactive polymer in (1) is a uniform =, and in the state where M represents two or more monomer units, the photoreactive polymer is a copolymer which polymerizes the early monomers of the plurality of monomers.聚干# Ink can be implemented by using light or heat. There is no particular limitation on the method of loading the monomer in the polymerization process, and it is possible to pre-inject all A in I5. After 廿4 to the reaction vessel, start the polymerization, and then start the polymerization on the monomer or the sputum, and then start the polymerization.浐λ哲 residual. The second J technique is added in stages. In addition, when the monomer (π) can contain other... I, there is no need to 'but' the body, such early system is only limited to have The unsaturated bond of polymerizability (for example, the aspect of 7 p is not particularly limited, and can be > f f,,. The compound of the saturated bond) may be a compound having liquid crystallinity other than this, or a compound having no liquid crystallinity may be used as a monomer of 201238980. As such a monomer series, for example, a mercapto (mercapto) acrylate, t — Butyl (meth) acrylate, stearin (meth) acrylate, cyclohexyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethyl (meth) acrylate Dilute ester, phenyl (meth) acrylate, N, n-dimethyl acrylamide, etc. (mercapto) propylene monomer, styrene, fluorenyl styrene, ρ - stupid vinyl sulfonic acid, ethyl Vinyl ether, hydrazine-vinylimidazole, vinyl acetate 'vinyl pyridine, 2-vinyl naphthalene, vinyl chloride, vinyl fluoride, fluorene vinyl carbazole, vinyl amine, vinyl phenol, hydrazine - ethylene a vinyl monomer such as 2-pyrrolidone, 4-allyl-indole, 2-monooxybenzene, 4-allylphenol, 4-monooxyallyl, etc. Maleic anhydride imide, such as allyl monomer, phenyl maleic anhydride imide, cyclohexyl maleic anhydride, or the like Any one of these single-systems may be used alone or in combination of two or more. In the state of being polymerized in a solution, a general-purpose organic solvent can be used without particular limitation. As a specific example of the solvent, ethanol and C are used. Alcohol oxime solvent such as alcohol or butanol, ketone solvent such as acetone, mercaptoethyl fluorenone, methyl isobutyl ketone, f hexyl or cyclopentanone, ethyl acetate, butyl acetate, propylene glycol An ester-based solvent such as mercaptoacetate, diethyl ether or diethylene glycol: an ether solvent such as methyl, cyclohexane, cyclohexane, methylcyclohexane, toluene, toluene or the like The oxime solvent, a nitrile-based solvent such as acetonitrile, or a guanamine-based solvent such as N-methylpyrrole = acetylamine. These solvents may be used alone or in combination of two or more. A photopolymerization initiator can be used in the above polymerization. As the light 16 201238980, a polymerization initiator is used to form a uniform film by irradiation with a small amount of light, and therefore, a generally known photopolymerization agent can be used. As a specific example, for example, 2,2, azobisazobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethyl phthalonitrile)-specific azonitrile-based photopolymerization Starting agent,
Irgacure907 ( Ciba Specialty Chemicals 公司製)、 Irgacure369 ( Ciba Specialty Chemicals 公司製)等之 α —胺基酮系光聚合起始劑、4 _苯氧基二氯乙醯苯、4 一 ^ —丁基—二氣乙醯笨、二乙氧基乙醯苯、1_ (4 —異丙基 苯基)一2—羥基一2 —曱基丙院一1—酮、1—羥基環己基 苯基酮、2 —苄基一2 —二曱基胺基一1— (4 一嗎啉苯基) 一 丁烷一1—酮等之乙醯苯系光聚合起始劑、苯偶因、苯偶 因甲基醚、苯偶因乙基醚、苯偶因異丙基醚、苄基二甲基 酮縮醇專之本偶因糸光聚合起始劑、二苯曱銅、苯醯安息 香酸、苯醯安息香酸甲酯、4一苯基二苯甲酮、羥基二苯曱 酮、丙烯化二笨曱酮、4 —笨醯一4’ 一曱基二苯基硫化物 等之二苯曱酮系光聚合起始劑、2 —氣代噻噸酮、2 —曱基 噻噸酮、異丙基噻噸酮、2, 4 —二異丙基噻噸酮等之.噻噸酮 系光聚合起始劑、2, 4, 6 —三氣一s—三嗪、2 —苯基一 4, 6 —雙(三氣甲基)~s —三嗪、2— (p—曱氧基笨基)一4, 6 —雙(二氯甲基)一s —三0秦、2_ (p—甲笨基)一 4,6 — 雙(三氣甲基)一s —三嗪、2 —胡椒基一4, 6 —雙(三氣甲 基)一 5—二°秦、2,4 —雙(三氯曱基)一6 —苯乙稀基一 s 一三嗪、2—(萘并一1 一醯)—4, 6—雙(三氣甲基)一s —三嗪、2— (4 -甲氧基—萘并―丨―醯)一4, 6 —雙(三 17 201238980 氯曱基)一 s —三嘻、2, 4 —三氣甲基一(胡椒基)一6—三 嗪、2, 4—三氯甲基(4’ 一曱氧基笨乙烯基)一 6—三嗪等 之三嗪系光聚合起始劑、咔唑系光聚合起始劑、咪唑系光 聚合起始劑等;以及醯氧基酯、醯基膦氧化物、甲基 苯基乙醛酸酯、苄基、9,1 0 —菲醌、樟腦醌、乙基蒽醌、 4, 4’ 一二乙基間苯二曱醯基笨、3, 3’ ,4,4’ 一四(t一丁 基過氧羰基)二苯甲酮、4, 4’ 一二乙基胺基二苯甲酮、噻 °頓明等之光聚合起始劑。光聚合起始劑係可以單獨地使用 任何一種,並且,也可以一併使用2種以上。 在前述聚合時之溫度係由於單體(jj)之種類、聚合 溶媒種類、起始劑種類等而不同,但是,最好是4〇〜15〇 °C ’更加理想是50〜i2〇t之範圍。 像這樣得到之本發明之光反應性聚合物(T )係除 光聚合起始劑、界面活性劑、溶媒等以外,還可以適度 、加通$ &含於II纟光及#而引起聚合之聚合性組成物 成分’成為光配向膜用組成物。這些任意成分之含有量 她特別限定’但是,通常最好是相對於聚合物(I ) 總重量而包含光聚合起始劑成為大約1〜大約1。重量% 界面活性劑成為大約〇 7η ' °·1大約5重量% ,溶媒成為大 70〜大約99重。 作為光聚合起始劑係可以同樣地使用前述者。 用α Φ活11劑係為了形成均勻膜,因此,皆可 硫酸:二用:界面活性劑。作為具體例係列舉例如月 .穌打、月桂基硫酸録、月桂基硫酸三乙醇胺、聚 18 201238980 乙細烧基驗硫酸鹽、烧基驗鱗酸醋、納油稀基號拍酸西旨 肉豆蔻酸鉀、椰子油脂肪酸鉀、鈉月桂醯肌氨酸酯等之苯 胺性界面活性劑;聚乙二醇單月桂酸酯、硬脂酸山梨糖醇 酐、肉豆蔻酸甘油酯、二油酸甘油酯 '山梨糖醇酐硬脂酸 醋、山梨糖醇酐油酸酯等之非離子性界面活性劑;硬脂醯 三甲基銨氣化物、氣化山茶基三甲基銨、氣化硬脂醯二甲 基苄基銨、十六烷基三甲基銨氯化物等之陽離子性界面活 性劑;月桂基甜菜鹼、烷基磺基甜菜鹼、椰子醯胺丙基甜 菜鹼、烷基二曱基胺基乙酸甜菜鹼等之烷基甜菜鹼'烷基 咪唑啉、月桂醯肌氨酸鈉、椰子硝銨乙酸鈉等之兩性界面 活性劑;以及 ΒΥΚ-361、ΒΥΚ— 306、BYK—3〇7 (日本 Βγκ 化學公司幻、Fluorad F_(住友3Μ公司製)、 FI 71、R〇8(大日本油墨化學工業公司製)等之界面活性劑。 這些界面活性劑係可以單獨地使用任何一種’並且,也可 以併用2種以上。 …料溶耗可以使用通常使用於該領域之溶媒,作為Α-amino ketone photopolymerization initiator, 4 _phenoxy dichloro acetophenone, 4 butyl butyl hydride, etc., Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Irgacure 369 (manufactured by Ciba Specialty Chemicals Co., Ltd.)醯乙醯, diethoxyethyl benzene, 1_(4-isopropylphenyl)-2-hydroxy-2-indolyl propyl 1-keto, 1-hydroxycyclohexyl phenyl ketone, 2 — Ethyl benzene photopolymerization initiator, benzoin, benzoin methyl ether, etc., benzyl 2- 2 - decylamino 1 - (4 morpholinyl phenyl) 1-butane-1-one , benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal, the exclusive photoinitiator, diphenyl sulfonium, benzoquinone benzoic acid, benzoquinone benzoic acid Dibenzophenone photopolymerization of methyl ester, 4-phenylbenzophenone, hydroxybenzophenone, propylene dicumenone, 4-alum, 4'-mercaptodiphenyl sulfide a thioxanthone-based photopolymerization initiator, a starting agent, a 2-oxothioxanthone, a 2-mercaptothioxanthone, an isopropylthioxanthone, a 2,4-diisopropylthioxanthone, 2, 4, 6 — three gas and one s Triazine, 2-phenyl- 4,6-bis(tris-methyl)~s-triazine, 2-(p-decyloxy)- 4,6-bis(dichloromethyl)-s —三0秦, 2_(p-甲笨基)-4,6 — bis(trimethylmethyl)-s-triazine, 2-pipeline--4,6-bis(tri-methyl)-5- 2°Q, 2,4-bis(trichloroindenyl)-6-styrene-s-triazine, 2-(naphtho-1)- 4,6-bis(tri-methyl) a s-triazine, 2-(4-methoxy-naphtho-indole-indole)-4,6-double (III 17 201238980 chloropurinyl)-s--tris-, 2,4-tris-methyl a triazine-based photopolymerization initiator, oxadiazole-based light, such as (pipeney-based)-6-triazine, 2,4-trichloromethyl (4'-fluorenyloxy) vinyl-6-triazine a polymerization initiator, an imidazole photopolymerization initiator, etc.; and a decyloxy ester, a mercaptophosphine oxide, a methylphenylglyoxylate, a benzyl group, a 9,10-phenanthrenequinone, a camphorquinone, a Base, 4, 4'-diethylisophthalonitrile, 3, 3', 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4, 4 -Diethyl amino benzophenone, Ming, etc. thiazol ° Dayton photopolymerization initiator. The photopolymerization initiator may be used singly or in combination of two or more kinds. The temperature at the time of the polymerization differs depending on the kind of the monomer (jj), the type of the polymerization solvent, the type of the initiator, and the like, but it is preferably 4 〇 15 15 ° ° C, and more preferably 50 to 2 〇 t range. The photoreactive polymer (T) of the present invention obtained in this manner can be used in addition to a photopolymerization initiator, a surfactant, a solvent, etc., and can be appropriately added, and the addition of $& The polymerizable component component ' becomes a composition for a photo-alignment film. The content of these optional components is particularly limited. However, it is usually preferred to include the photopolymerization initiator in an amount of from about 1 to about 1 with respect to the total weight of the polymer (I). The % by weight of the surfactant is about 5% by weight of 〇 7η ' °·1, and the solvent becomes from 70 to about 99. The foregoing can be used similarly as a photopolymerization initiator. In order to form a uniform film, the α Φ activating agent 11 is used for sulfuric acid: two-purpose: a surfactant. As a specific example series, for example, the moon, the sulphuric acid, the lauryl sulfate, the triethanolamine, the poly 18 201238980, the sulphate, the sulphur-based sulphuric acid vinegar, the naphtha Ananiline surfactant such as potassium myristate, coconut oil fatty acid potassium, sodium laurel sarcosinate; polyethylene glycol monolaurate, sorbitan stearate, myristate, dioleic acid a nonionic surfactant such as glyceride sorbitan stearate or sorbitan oleate; stearic acid trimethylammonium vapor, gasified camellyl trimethylammonium, gasification hard a cationic surfactant such as decyl dimethyl benzyl ammonium or cetyl trimethyl ammonium chloride; lauryl betaine, alkyl sulfobetaine, coconut amidinopropyl betaine, alkyl di An amphoteric surfactant such as an alkylbetaine such as decylaminoacetic acid betaine, a sodium alkyl laurate, a sodium citrate, and a sodium amphoteric acid sodium acetate; and ΒΥΚ-361, ΒΥΚ-306, BYK-3 〇7 (Japan Βγκ Chemical Company illusion, Fluorad F_ (manufactured by Sumitomo 3), FI 71. A surfactant such as R〇8 (manufactured by Dainippon Ink Chemicals Co., Ltd.). These surfactants may be used singly or in combination of two or more kinds. Solvent in this field, as
明之光配向膜用組成物, 種,並且,也可以併用2種以 可以藉由像這樣得到之本發明 19 201238980 塗佈於基板’纟酉己合需要而餾除溶媒之後,在這個照射直 線偏光’來成為光配向膜。 作為構成基板之基材係列舉例如石英玻璃、驗玻璃、 無鹼玻璃等之玻璃基材、聚醞亞胺、聚醯胺、丙烯樹脂、 聚乙稀醇、三乙酿基纖維素、聚乙稀對苯二甲㈣、環稀 烴聚,物、聚乙稀、聚碳酸㈣笨乙稀、聚三氟化氣化 乙烯等之樹脂基材、鐵、鋁、銅等之金屬基材等,更加理 想是玻璃基材。 作為光配向膜用組成物 一般知曉之任何一種方法, 法、模塗佈法、網版印刷法 之塗佈方法係可以是在該領域 例如有旋轉塗佈法、桿條塗佈 、噴射塗佈器法等。 、乾燥製程係可以藉由通常使用於該領域之任何—種方 法而實施,只要是形成樹脂層之膜的話,則並無特別限定。 直線偏光係也可以由對於該犋呈垂直之方向或者是由 傾斜之方向之任何一種而進行照射,但是’最好是由垂直 之方向而進行照射。 在本發明,所謂直線偏光係包含電場(或磁場)之振 動方向之面來特定於__錄夕本。士土 、種之先直線偏光係可以藉由在來 先源之光,使用偏光遽光片或偏光稜 光係如果是紅外線、可見光線…射之 外線笨、v 务、外線(近紫外線、遠紫 以 =)、Χ·線、電荷粒子線(例如電子線等)等之可 射而產生化學反應之照射線的話,則並無特別限 仁疋,通常大多是照射線具有 、有2〇〇nm〜500四之波長之 心、,4性之觀點來看的話,則最好是咖⑽至45〇nm 20 201238980 之近紫外線。作為光源係列舉例如氙燈、高壓水銀燈、超 高壓水銀燈、金屬齒化物燈等。由此種光源而得到之紫外 線或可見光係可以使用干涉濾光片或彩色濾光片等而限制 照射之波長範圍。 照射能量係配合光反應性聚合物(丨)之種類或膜厚 等而不同,但是,通常為大約10mJ/cn]2〜5〇〇〇mJ/cm2。 例如在包含藉由實施例丨而合成之聚[丨—[β _ [ 4 — [ 4 — (甲氧基)苯氧基羰基]笨氧基]己氧基羰基]一丨一甲基乙 烯]來組成之大約100ηιη厚度之薄膜之狀態下,成為大約 250〜4000mJ/cm2。 此外,在照射直線偏光之際,如果使用光罩的話,則 可以在光配向膜,沿| 2個以上之不同之方向,呈圖案狀 地產生液晶等之配向能。具體地說,可以藉由在塗佈、乾 燥本發明之光配向膜用組成物之後,在其上面,覆蓋光罩, 照射直線偏光’僅在曝光部分,賦予配向&,配合需要來 改變方肖,重複地進行這個複數二欠,而在複數個之方向, 呈圖案狀地產生配向能。 就本發明之光配向膜而言,其膜厚係最好是大約1 〇〜 ^約50〇nm,更加理想是大約1〇〇〜大約5〇〇μ,甚至最好 是大約100〜大約200nm之範圍。 可以藉由在像這樣得到之光配向膜上,準備塗佈液晶 )生化α物(包含成為色素之液晶性化合物或者是成為導電 I·生化口物之液晶性化合物)纟,加熱這個至該液晶性化合 物顯不液晶狀態之溫度以上,而在配向該m生化合物之 21 201238980 後,還冷卻至該液晶性化合物顯示液晶狀態之溫度未滿, 而固定液晶性化合物之該配向狀態,t作由該液晶性化合 物來組成之相位差膜、視野角提升用m、亮度提升用膜、 偏光膜等之各種光學異方性膜或導電性材料、非線性光學 材料、光反應性致動器等之各種光學材料。可以在塗佈液 晶性化合物之狀態下,由於要求而溶解於溶媒,進行塗佈。 作為此種溶媒係皆可以使用通常使用於該領域之溶媒。具 體地說,列舉前述者、也就是甲苯'乙苯、乙二醇單甲基 醚、乙二醇二甲基醚、丙二醇甲基醚、二丁基醚、丙酮、 甲基乙基曱酮、乙SI、丙醇、環己烷、環戊酮、甲基環己 烷、四氫化吱喃、二噁院、環己酮、n—己烷、乙酸乙醋、 乙酸丁醋、丙二醇甲基醚乙酸酷、甲氧基丁基乙酸㈠ -甲基口比㈣、二甲基乙醜胺等。這些係也可以單獨地 使用任何一種,並且,也可以併用2種以上。 此外,即使是藉由在並非液晶性化合物之色素或導電 性化合物之狀態下,混合這些色素或導電性化合物和液晶 化合物,相同於冑面之敘述而進行處王里,或者是這些色: 或導電性化合物’溶解於溶媒’這個塗佈於光配向臈上, 進行乾燥,也可以製作各種之光學異方㈣或光學材^ 在此,作為液晶性化合物、色素、導電性化合物係皆 可以適合使用通常使用於該領域者。例如作為液晶性化二 物係列舉氰基聯苯基型向列液晶等。作為色素―舉^ 偶氮基系色素(聚偶氮基系色素、二重氮系色素等)、窗 I系等之二色性色素等。作為導電性化合物係列舉例如: 22 201238980 Μ吩等。此外’作為溶媒係可以同樣地使用列舉 作為在塗佈液晶性化合物時之溶媒之前述者。 +就料樣得到之本發明之光學異方性膜及光學材料而 :’其厚度係配合用途等而不同,但般而言,最好 是0.1〜20·0„之範圍,更加理想是i 〇〜5 _之範圍。 此外,如果使用本發明之光配向膜的話,則可以製作 包含該光配向膜而組成之液晶胞。例如可以藉由該光配向 膜2片呈對向而使得某一邊之光配向膜之直線偏光照射時 之偏光軸之方向和其他邊之光配向膜之直線偏光照射時之 偏光軸之方向,相互地形成規^之角度(例如Μ。、18〇。 〜27(Γ之任何一種角度等),在該對向之光配向膜之間, 填充液晶性化合物,來製作液晶胞。 本發明之光反應性聚合物(!)係除了光聚合起始劑、 界面活性劑、溶媒等以外,還可以適度地添加通f包含於 藉由光及熱而引起聚合之聚合性組成物之成分,成為光學 異方性膜用組成物。這些任意成分之含有量係並無特別限 定,但是,通常最好是相對於聚合物(工)之總重量而包 含光聚合起始劑成為大、約i〜大約5重量%,界面活性劑 成為大約0.1〜大約1重量% ,溶媒成為大約50〜大約80 重里/"光聚合起始劑、界面活性劑、溶媒等之任意成分 係可以同樣地使用關於前述之光配向膜用組成物而列舉 者。但是,光反應性聚合物(Ϊ )係通常為液晶性化合物, 在其製造之際’在單體(Π)之聚合時而添加之其他單體 為無顯示液晶性之化合物之狀態下,可以藉由該其他單體 23 201238980 之添加量等而使得聚合物(i AU JA ^ ^ 成為無顯示液晶性之化合 物。像這樣,在聚合物(z ) ^ UL. At _ 為無顯示液晶性之化合物 之狀心下,在本光學異方性 . τ . 、用、·且成物之調製之際,該聚 合物(I )之一部分,置換# 風s + 換成為液晶性化合物,作為該光 子異方性膜用組成物之整體而15 - 顯不液晶性。作為像這樣添 加之液晶性化合物係皆可以、吞人 了 適合使用通常使用於該領域In the case of the bright-light aligning film composition, it is also possible to use two kinds of the present invention, and the present invention 19 201238980 can be applied to the substrate as needed to distill off the solvent. 'Become a light alignment film. Examples of the substrate constituting the substrate include a glass substrate such as quartz glass, glass, and alkali-free glass, polyimide, polyamide, acrylic resin, polyethylene glycol, triethyl cellulose, and polyethylene. a resin substrate such as a terephthalic acid (tetra), a ring-shaped dilute hydrocarbon, a polyethylene, a polyethylene carbonate, a tetraphenyl ether, a polyfluorinated ethylene, or the like, and a metal substrate such as iron, aluminum or copper. More desirable is a glass substrate. As a method generally known as a composition for a photo-alignment film, a coating method of a method, a die coating method, or a screen printing method may be, for example, a spin coating method, a bar coating method, or a spray coating method in the field. Method and so on. The drying process can be carried out by any of the methods generally used in the field, and is not particularly limited as long as it is a film forming a resin layer. The linear polarizing system may be irradiated by any of the direction perpendicular to the crucible or the direction of the tilt, but it is preferable to irradiate it in the vertical direction. In the present invention, the linear polarization system includes a surface of a vibration direction of an electric field (or a magnetic field) to be specified in the __ 夕 夕. The first linear light system of the soil and the species can be used by the light source, the polarized light sheet or the polarized prism light system. If it is infrared light or visible light, the line is stupid, v, and outside (near ultraviolet light, far When purple is irradiated with a chemical reaction such as a ray, a ray, a charge, or a charged particle beam (for example, an electron beam), there is no particular limitation. Usually, the illuminating line has two illuminating lines. From the point of view of the wavelength of nm to 500, and the point of view of the four sexes, it is best to use near ultraviolet rays of coffee (10) to 45 〇 nm 20 201238980. As the light source series, for example, a xenon lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal toothed lamp, or the like can be cited. The ultraviolet light or visible light obtained by such a light source can be used to limit the wavelength range of the irradiation using an interference filter or a color filter. The irradiation energy differs depending on the type or film thickness of the photoreactive polymer (丨), but is usually about 10 mJ/cn] 2 to 5 μm J/cm 2 . For example, in the polymerization comprising the poly(丨-[β _ [ 4 —[ 4 —(methoxy)phenoxycarbonyl]]oxy]hexyloxycarbonyl]-indenylmethyl] synthesized by the examples] In the state of a film having a thickness of about 100 nm, it is about 250 to 4000 mJ/cm 2 . Further, when a linear ray is irradiated, if a reticle is used, the alignment energy of the liquid crystal or the like can be generated in a pattern in the direction of the photoalignment film in two or more directions. Specifically, after coating and drying the composition for a photo aligning film of the present invention, the reticle is covered thereon, and the linearly polarized light is irradiated, and only the exposed portion is imparted with the alignment & Xiao, repeating this complex two owes, and generating the aligning energy in a pattern in a plurality of directions. In the case of the photoalignment film of the present invention, the film thickness is preferably from about 1 Å to about 50 Å, more preferably from about 1 Torr to about 5 Å, even more preferably from about 100 Å to about 200 nm. The scope. By coating a liquid alignment film obtained in this manner, it is possible to apply a liquid crystal) biochemical alpha substance (including a liquid crystal compound which is a dye or a liquid crystal compound which becomes a conductive I·biochemical substance), and heat this to the liquid crystal. The compound is not more than the temperature of the liquid crystal state, and after being aligned with the 21 201238980 of the m compound, it is cooled until the liquid crystal compound shows that the temperature of the liquid crystal state is not full, and the alignment state of the liquid crystal compound is fixed. The retardation film, the viewing angle improvement m, the brightness enhancement film, the polarizing film, and the like, various optical anisotropic films, conductive materials, nonlinear optical materials, photoreactive actuators, and the like Various optical materials. The coating may be carried out by dissolving in a solvent in the state of applying a liquid crystal compound as required. As such a solvent system, a solvent which is generally used in the field can be used. Specifically, the foregoing, that is, toluene 'ethylbenzene, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether, dibutyl ether, acetone, methyl ethyl fluorenone, SI, propanol, cyclohexane, cyclopentanone, methylcyclohexane, tetrahydrofuran, dioxins, cyclohexanone, n-hexane, ethyl acetate, butyl acetate, propylene glycol methyl ether Acetic acid cool, methoxybutyl acetic acid (a) - methyl port ratio (tetra), dimethyl ethyl ugly amine and the like. Any of these may be used alone or in combination of two or more. Further, even if these dyes, conductive compounds, and liquid crystal compounds are mixed in a state in which a dye or a conductive compound of a liquid crystal compound is not present, the same as the description of the kneading surface, or these colors: or The conductive compound 'dissolved in the solvent' is applied to the optical alignment crucible and dried, and various optical anisotropy (IV) or optical material can be produced. Here, the liquid crystal compound, the dye, and the conductive compound can be suitably used. Use is usually used in the field. For example, as a liquid crystal compound, a cyanobiphenyl nematic liquid crystal or the like is used. The dye is a dichroic dye such as an azo-based dye (a polyazo-based dye or a diazo-based dye) or a window I-based product. As a series of conductive compounds, for example, 22 201238980 porphin and the like. Further, the above-mentioned solvent can be used in the same manner as the solvent in the case of applying the liquid crystalline compound. + The optical anisotropic film and the optical material of the present invention obtained in the same manner are different in thickness, and in general, it is preferably in the range of 0.1 to 20·0 Å, and more preferably i Further, if the photo-alignment film of the present invention is used, a liquid crystal cell comprising the photo-alignment film can be produced. For example, the photo-alignment film can be aligned to form one side. The direction of the polarization axis when the linear alignment film is irradiated with the polarized light and the direction of the polarization axis when the linear alignment light of the other side of the light alignment film is irradiated to each other to form an angle (for example, Μ., 18 〇. Any one of the angles, etc., is filled with a liquid crystal compound between the opposite photoalignment films to produce a liquid crystal cell. The photoreactive polymer (!) of the present invention is in addition to a photopolymerization initiator, interface activity. In addition to the agent, the solvent, and the like, a component which is contained in the polymerizable composition which is polymerized by light and heat, and which is a composition for an optical anisotropic film, may be added as appropriate. Special limit However, it is usually preferred that the photopolymerization initiator is included in a large amount, from about i to about 5% by weight based on the total weight of the polymer, the surfactant is from about 0.1 to about 1% by weight, and the solvent is about 50%. Any of the components of the photopolymerization initiator, the surfactant, the solvent, and the like may be similarly used in the above-mentioned composition for a photo-alignment film. However, the photoreactive polymer (Ϊ) The liquid crystal compound is usually a liquid crystal compound, and in the state of production, when the other monomer added during the polymerization of the monomer is a compound having no liquid crystal property, the addition of the other monomer 23 201238980 can be used. The amount of the polymer (i AU JA ^ ^ becomes a compound exhibiting no liquid crystallinity. Thus, in the case where the polymer (z) ^ UL. At _ is a compound having no liquid crystallinity, When the τ., the use, and the preparation of the product are modulated, one part of the polymer (I) is replaced with the liquid s + and replaced with a liquid crystal compound, and the photonic heterojunction film is integrated as a whole. 15 - No LCD As an additive such as coupled-based liquid crystal compounds can all, generally used for people to swallow for use in the field
者’例如最好是由棒肤夕八I 之刀子而組成之液晶性化合物,或 者最好是向列液晶等。 可以藉由準備像這樣得到之本發明之光學異方性膜用 ’、且成物來塗佈於基板者’在這個照射直線偏光之後,將包 3於u玄光學異方性膜用組成物之液晶性化合物加熱至顯 不液晶狀態之溫度以上,而配向該液晶性化合物,並且, 藉由該液晶性化合物,冷卻至顯示液晶狀態之溫度未滿, 而固定該配向狀態,製作光學異方性膜。 構成基板之基材、塗佈方法、直線偏光之照射等係皆 相同於前述光配向膜之製作。此外,得到之光學異方性膜 之厚度範圍係相同於關於前述光學異方性膜而例舉者。 在以下,列舉實施例而具體地說明本發明,但是,本 發明係根本無限定於下列之實施例。 【實施例1】 4— (6 —羥基己氧基)安息香酸之合成:For example, it is preferably a liquid crystal compound composed of a knife of the skin of the skin, or a nematic liquid crystal. By preparing the optical anisotropic film of the present invention obtained as described above and applying it to the substrate by the article, after the linearly polarized light is irradiated, the package 3 is applied to the composition of the anisotropic optical film. The liquid crystal compound is heated to a temperature higher than the temperature at which the liquid crystal is not present, and is aligned with the liquid crystal compound, and the liquid crystal compound is cooled to a temperature at which the liquid crystal state is not formed, and the alignment state is fixed to produce an optical heterodyne. Sex film. The substrate constituting the substrate, the coating method, the irradiation of the linearly polarized light, and the like are all the same as those of the above-described photoalignment film. Further, the thickness range of the obtained optical anisotropic film is the same as that of the above-mentioned optical anisotropic film. In the following, the present invention will be specifically described by way of examples, but the present invention is not limited to the following examples at all. [Example 1] Synthesis of 4-(6-hydroxyhexyloxy)benzoic acid:
在水400.〇g,溶解4一經基安息香酸100.〇g (0.7莫 24 201238980 爾)和氫氧化針105.1g(i.6莫爾)。在該溶液,經過1 小時而滴下6 —氣己醇i〇8.8g(〇.8莫爾)。接著,在100 °C,進行加熱回流。在2 0小時後,冷卻反應液,激烈地進 行授拌,並且,在室溫,滴下35%鹽酸344. 6g( 1. 7莫爾)。 攄取析出之固體,藉由四氫化吱喃(THF ) 400g而進行再 結晶’得到4 — ( 6 —經基己氧基)安息香酸12 0 · 〇 g ( 0. 5 莫爾)而成為白色結晶。 良品率為69.5% ,熔點為135〜14(TC。 2. 4- [6- (2-曱基丙烯醯氧基)己氧基]安息香酸之 合成·In water 400. 〇g, dissolved 4 by benzoic acid 100. 〇g (0.7 Mo 24 201238980 er) and hydroxide needle 105.1 g (i. 6 Mohr). In the solution, 6-air hexanol i 8.8 g (〇.8 mole) was dropped over 1 hour. Then, heating and refluxing were carried out at 100 °C. After the lapse of 20 hours, the reaction mixture was cooled, and the mixture was vigorously stirred, and 34.5 ml of hydrochloric acid was added dropwise at room temperature, 34. 6 g (1.7 mol). The precipitated solid was taken up and recrystallized by 400 g of tetrahydrofurfuryl (THF) to give 4 - (6-pyridyloxy)benzoic acid 12 0 · 〇g (0.5 mil) and became white. crystallization. The yield is 69.5%, and the melting point is 135~14 (TC. 2. 4- [6-(2-Mercaptopropenyloxy)hexyloxy] benzoic acid.
在480. Og之THF,溶解4— ( 6 —羥基己氧基)安息香酸 120.0g(0.5莫爾)和三乙基胺815g(0_8莫爾)。在該 溶液’經過1小時而滴下曱基丙烯酸氯化物84. 2g ( 〇· 8莫 爾)。接著,加熱至4(TC。在4小時後,冷卻反應液,加 入水240. 〇g。在分離之有機層’加入1〇%鹽酸367. ( 1 莫爾)而進仃攪拌。濃縮分離之有機層,藉由甲笨4〇〇. 〇g 而對於殘〉查進行再結晶,得到4 — [ 6 — ( 2 —甲基丙稀酿氧 基)己氧基]安息香酸96.〇g( 0.3莫爾)而成為白色結晶。 良品率為62.2% ,熔點為81〇c。 3. 4:[6— (2—曱基丙烯醯氧基)己氧基]安息香酸4 ~(曱氧基)笨基酯之合成:In 480. Og of THF, 40.0 g (0.5 mole) of 4-(6-hydroxyhexyloxy)benzoic acid and 815 g (0-8 mole) of triethylamine were dissolved. 2 g (〇·8 莫尔) was added dropwise to the solution of the thioglycolic acid chloride after 1 hour. Then, it was heated to 4 (TC. After 4 hours, the reaction liquid was cooled, and water 240. 〇g was added. In the separated organic layer, 1% hydrochloric acid 367. (1 mol) was added and stirred, and concentrated. The organic layer is recrystallized from the residue by a 笨g. 〇g to obtain 4-(6-(2-methylpropanyloxy)hexyloxy]benzoic acid 96.〇g ( 0.3 moles and white crystals. The yield is 62.2% and the melting point is 81〇c. 3. 4:[6-(2-mercaptopropenyloxy)hexyloxy]benzoic acid 4 ~ (decyloxy) Synthesis of stupyl esters:
201238980 在二氣甲烷960g,溶解4~[6 —(2 —甲基丙烯醯氧基)己 氧基]安息香酸96.0g(0.3莫爾)、甲氧基氫醌38.9g(().3 莫爾)和N,N—二曱基胺基0比啶7· 7g ( 〇· i莫爾)。在該 溶液,加入二環己基碳化二亞胺(DCC) 71. lg( 〇. 3莫爾)。 在室溫而反應2小時之後,加入水288g。濃縮分離之有機 層,由甲苯1 00g而對於殘渣進行再結晶,得到4 — [ 6 — ( 2 一曱基丙烯醯氧基)己氧基]安息香酸4一(甲氧基)笨基 酯l〇3g(〇.2莫爾)而成為白色結晶。 良品率為79. 6% ’熔點為52。〇。 4.聚[H6 一 [4— [4〜(甲氧基)笨氧基幾基]苯氧基] 己氧基羰基]—1—甲基乙烯]之合成:201238980 In the second gas methane 960g, dissolved 4 ~ [6 - (2 - methacryloxy) hexyloxy] benzoic acid 96.0g (0.3 mole), methoxyhydroquinone 38.9g ((). 3 Mo And N,N-didecylamino group 0 to pyridine 7·7g (〇·i moir). In the solution, dicyclohexylcarbodiimide (DCC) 71. lg (〇. 3 moor) was added. After reacting at room temperature for 2 hours, 288 g of water was added. The separated organic layer was concentrated, and the residue was recrystallized from toluene (100 g) to give 4-(6-(2-mercaptopropenyloxy)hexyloxy]benzoic acid 4-(methoxy)phenyl ester. 〇3g (〇.2 moir) becomes white crystal. The yield was 79.6% and the melting point was 52. Hey. 4. Synthesis of poly[H6-[4-[4~(methoxy)phenyloxy]phenoxy]hexyloxycarbonyl]-1-methylethene]:
在環己酮412g’溶解4— [6_ (2_甲基丙稀醯氧3 己氧基]安息香酸4-(甲氧基)笨基醋1〇3g(〇2莫爾: 〇.8g (5毫莫爾)之咖。在該溶液,對於氮進行i小 接著’加熱至8°°C。在10小時後,冷卻反應浓 激烈地進行攪拌,並且’在室溫,滴下至正己燒崎。 =取分離之聚合物’在減壓下、抓,進行乾燥,而 到標記聚合物83.4g。良品率為81% 。 (重量平均分子量(MW)之測定) 使用凝膠過遽色譜法(GPC)而測定在前面敘述來得 之聚合物之重量平均分子量(,)。得到之重量平均分 26 201238980 量(MW)係 31 000。 (相轉變溫度之測定) 在使用示差掃描熱量測定(〜 % )而測定在前面敘述來 得到之聚合物之相轉變溫度之時,成為7〇〜i3〇c>c。 5·光配向臈用組成物之調製 將在前面敘述來得到之聚合物5g’溶解於叫之, 而成為光配向膜用組成物1。 6.光配向膜之製造 在石英玻璃基板上,使用旋轉涂 ό >此 ϋ佈崙,塗佈在前面敘 述來得到之光配向膜用組成物i ^ 叩战馬大約lOOnm厚度之 薄膜’進行乾燥。在得到之基板,使用格蘭.泰勒稜鏡,將 轉換成為直線偏光之紫外線⑴mW/em2),㈣於基板呈 垂直之方向開始,照射2〇〇秒 £ 在暴扳上’製造光配向 臈。 (苯曱酸酯骨格之光裂解等之確認)Dissolved in cyclohexanone 412g' 4-[6_(2-methylpropionyloxy 3 hexyloxy)benzoic acid 4-(methoxy) stupid vinegar 1〇3g (〇2mol: 〇.8g ( 5 millimoles of coffee. In this solution, i is small for nitrogen and then 'heated to 8 ° C. After 10 hours, the cooling reaction is vigorously stirred vigorously, and 'at room temperature, drip until it is simmered = The separated polymer was taken under reduced pressure, and dried to obtain 83.4 g of the labeled polymer. The yield was 81%. (Measurement of Weight Average Molecular Weight (MW)) Using gel chromatography ( The weight average molecular weight (.) of the polymer described above was determined by GPC. The weight average score obtained was 26 201238980 (MW) was 31 000. (Measurement of phase transition temperature) Determination using differential scanning calorimetry (~ % When the phase transition temperature of the polymer obtained as described above is measured, it becomes 7 〇 to i3 〇 c > c. 5. The preparation of the photo-alignment composition is dissolved in the polymer 5g' obtained as described above. As a result, it becomes a composition for a photo-alignment film 1. 6. Fabrication of a photo-alignment film on a quartz glass substrate Using a spin coating > this bismuth, coated with the film of the photoalignment film obtained by the above description, i ^ 叩 叩 大约 about 100 nm thick film. On the obtained substrate, use Gran Taylor.稜鏡, will be converted into linear polarized ultraviolet (1) mW / em2), (d) in the direction of the substrate in the vertical direction, 2 hrs of exposure, on the violent pull on the 'making light alignment 臈. (Phenyl phthalate backbone light cracking, etc. Confirmation)
藉由直線偏光照射而確認苯甲酸醋(酉旨)骨格之光裂 解二進而確認產生光Fries (弗利斯)轉變,因此,相同 ; 之敘述,藉由偏光顯微紅外線分光法而觀察在照射 、泉偏光時之薄膜變化。結果係正如圖丄之圖表所示。同 表係相對於照射之直線偏光紫外線之偏光軸而測定同 車方向之吸收(同軸光譜:Abs 1 )和垂直軸方向之吸收(垂 =軸光4. Abs2),藉由實線而表示前者,藉由虛線而表 丁後者。此外,為了進行比較,因此,一併顯示由Absl扣 除AbS2之值來成為5倍之值(差值光譜:Absl - Abs2 ( X 27 201238980 5”。得知如果藉由差值光譜的話,則在相對於昭 線偏光紫外線之變更軸呈同軸之同軸方向, .line -1 „ /χ* v 1 260cm 1 和1196cm附近之波峰,增加1 727 , 见之波峰。關於 該減少之波峰係藉由笨甲酸酯骨格之羥基而 <双之吸收波 峰,關於該增加之波峰係藉由幾基而造成之吸收波峰(圖 2)。因此,由該吸收波峰之減少’讀取相對於直線偏光紫 外線之偏光軸呈同軸地存在之苯甲酸s|骨格係引起以解 而消失-部分。此外’由該吸收波峰之增力。,讀取相對於 直線偏光紫外線之偏光軸呈同軸地存在之酯(笨甲酸酯) 之羰基係經過光裂解或光FriM f &刹虹、姑 曰 人巧fries C弗利斯)轉變而轉換成 為酮之羰基。 (光配向性之評價) 在則面敘述來知到之形成光配向膜之基板2片呈對向 而使得在照射直線偏光紫外線時之偏綠成為平行,製作 液晶胞,在該液晶胞’填充分散二色性色f DisperseIt is confirmed by linear polarized light irradiation that the light cleavage of the benzoic acid vinegar is confirmed to produce a light Fries transition, and therefore, the same; the description is observed by polarized microscopic infrared spectroscopy. The film changes when the spring is polarized. The results are shown in the chart below. The same watch system measures the absorption in the same direction (coaxial spectrum: Abs 1 ) and the absorption in the vertical axis direction (vertical = axis light 4. Abs2) with respect to the polarization axis of the linearly polarized ultraviolet light to be irradiated, and the former is represented by a solid line. The latter is represented by a dotted line. In addition, for comparison, therefore, the value of AbS2 is subtracted from Absl to be 5 times the value (difference spectrum: Absl - Abs2 (X 27 201238980 5). It is known that if the difference spectrum is used, then The axis of the polarized ultraviolet light relative to the Zhao line is coaxial with the coaxial direction, .line -1 „ /χ* v 1 260cm 1 and the peak near 1196cm, increase by 1 727, see the peak. The peak of the reduction is by stupid The hydroxyl group of the formate skeleton and the absorption peak of the double, the peak of the increase is caused by a few bases (Fig. 2). Therefore, the reduction of the absorption peak is 'read relative to the linear polarized ultraviolet light. The polarizing axis is coaxially present in the benzoic acid s|bone system, causing the solution to disappear and partially disappear. In addition, by the force of the absorption peak, the ester which is coaxially present with respect to the polarization axis of the linearly polarized ultraviolet light is read ( The carbonyl group of the benzoic acid ester is converted into a carbonyl group of a ketone by photocleavage or light FriM f & flashing, and the carbonyl group of the ketone. (Evaluation of optical alignment) Knowing that it forms light Of the substrate film 2 to such that the form of greenish upon irradiation of linearly polarized ultraviolet rays become parallel, a liquid crystal cell, the liquid crystal cell "fill f Disperse dispersion dichroic Xingse
Bluel4( Aldrich 公司劁s 氣)之液曰日E7(日本Merck公司製), 在加熱至8〇t為止而使得液晶呈等方相之後,冷卻至室溫 為止。 在藉由偏光顯微鏡而觀察該液晶胞之時,確認液晶配 向在垂直於照射之直線偏光之偏光軸之垂直方向。 7.液晶胞之製造 在前述6來得到之形成光配向膜之基板2片呈對向而 使得在照射直線偏光料線時之偏光軸成為直交,製作液 晶胞,在該液晶胞’填充液晶E7,製作tn型液晶。 28 201238980 藉由施加電壓至該TN型液晶胞之兩基板間,而確認呈 正確地驅動該液晶胞。 8. 光學異方性膜用組成物之調製 在前述4來得到之聚合物5g ’溶解於丨5g之THF而成 為光學異方性膜用組成物1。 9. 光學異方性膜之製造 在玻璃基板上,使用旋轉塗佈器,塗佈光學異方性臈 用組成物1而成為大約i. 2 " m之厚度,進行乾燥。在得到 之基板,使用格蘭·泰勒稜鏡,將轉換成為直線偏光之紫外 線(10mW/cm ),由對於基板呈垂直之方向開始,照射2⑽ 秒鐘。在80C加熱該基板20分鐘之後,冷卻至室溫為止。 在藉由偏光顯微鏡而觀察形成於基板上之膜之時,觀 察明暗,T以確認已經㊣夠製作光學#方性膜。在使用偏 光解析裝置OPTIPR〇(SYMTEC股份有限公司製)而測定製 作之光學異方性膜之雙重折射之時,顯示Δηυ5、^ =126nm之值,確認可以使用作為相位差膜。 【產業上之可利用性】 ....... 初殂成(4 係有用於使用這個而製造之光配向膜或光學異方性膜、上 及在該光配向膜來配向液晶性化合物等而 a 、 Ί成之相位』 膜、視野角提升用膜、亮度提升用膜、偏 膘等之各種j 學異方性膜、或者是導電性材料、非線 丨元學材料、光万 應性致動器等之各種光學材料之原料, ^ m β 卫且’像這樣得至 之光子異方性膜或光學材料係可以使 &用作為各種光學月 29 201238980 件’特別是使用在電腦或傳真機等之楼。。 松 啊盗、行動電話、 電子筆記本、液晶電視,攝錄放影機等之顯示穿置 【圖式簡單說明】 圖1係將在由實施例1之光配向膜用組成物丨而組成 之薄膜,藉由偏光顯微紅外線分光法而觀察在照射直線偏 光時之該薄膜之變化之結果予以顯示。 圖2係就實施例1之光反應性聚合物而言,顯示 1 260cnTi和1196^」之吸收波峰關於苯甲酸酯骨格之羥 基’ 1727CHT1之吸收波峰關於羰基。 【主要元件符號說明】 無 30Liquid No. E7 (manufactured by Merck Co., Ltd.) of Bluel 4 (Aldrich Co., Ltd.) was heated to 8 Torr until the liquid crystal was in an isotropic phase, and then cooled to room temperature. When the liquid crystal cell was observed by a polarizing microscope, it was confirmed that the liquid crystal alignment was perpendicular to the polarization axis of the linearly polarized light which was irradiated. 7. Production of liquid crystal cell The two substrates which form the photoalignment film obtained in the above-mentioned 6 are opposed to each other such that the polarizing axis of the linear polarizing material line is orthogonal, and a liquid crystal cell is produced, and the liquid crystal cell is filled with liquid crystal E7. , making tn type liquid crystal. 28 201238980 It is confirmed that the liquid crystal cell is correctly driven by applying a voltage between the two substrates of the TN type liquid crystal cell. 8. Preparation of composition for optical anisotropic film 5 g of the polymer obtained in the above 4 was dissolved in 5 g of THF to form an optical anisotropic film composition 1. 9. Production of optical anisotropic film On the glass substrate, the optical anisotropic composition 1 was applied by a spin coater to a thickness of about i. 2 " m, and dried. On the obtained substrate, Glan Taylor was used to convert the ultraviolet light (10 mW/cm) into a linearly polarized light, and the substrate was irradiated for 2 (10) seconds in a direction perpendicular to the substrate. After heating the substrate at 80 C for 20 minutes, it was cooled to room temperature. When the film formed on the substrate was observed by a polarizing microscope, the brightness and darkness were observed to confirm that the optical film was already produced. When the double refractive index of the optical anisotropic film produced was measured using a polarizing analyzer OPTIPR (manufactured by SYMTEC Co., Ltd.), the values of Δη υ 5 and 126 nm were displayed, and it was confirmed that it can be used as a retardation film. [Industrial Applicability] . . . (4) The photo-alignment film or optical anisotropic film produced by using this, and the alignment of the liquid crystal compound on the photo-alignment film. And a, the phase of the film, the film for the viewing angle, the film for brightness enhancement, the film for brightness enhancement, and various j-shaped films, or conductive materials, non-linear materials, and optical Materials for various optical materials such as actuators, ^ m β wei and 'photon anisotropic film or optical material system can be used as a variety of optical month 29 201238980 'special use in computers Or the floor of a fax machine, etc.. Display of the thief, mobile phone, electronic notebook, LCD TV, video recorder, etc. [Simplified description of the drawing] Fig. 1 is a light alignment film to be used in the embodiment 1. The film composed of the composition , is shown by a polarizing micro-infrared spectroscopy method as a result of observing the change of the film when the linearly polarized light is irradiated. Fig. 2 is a view showing the photoreactive polymer of Example 1. Showing absorption signals of 1 260cnTi and 1196^" About hydroxy benzoate skeleton of 'absorption peak of about 1727CHT1 carbonyl group. The main element 30 None REFERENCE NUMERALS
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