TWI759324B - Retardation film with water vapor barrier properties and method for producing the same - Google Patents

Retardation film with water vapor barrier properties and method for producing the same Download PDF

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TWI759324B
TWI759324B TW106129728A TW106129728A TWI759324B TW I759324 B TWI759324 B TW I759324B TW 106129728 A TW106129728 A TW 106129728A TW 106129728 A TW106129728 A TW 106129728A TW I759324 B TWI759324 B TW I759324B
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片山雅章
後藤耕平
筒井皇晶
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日商日產化學工業股份有限公司
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Abstract

提供含有具有感光性側鏈的液晶性聚合物，而膜厚超過300nm且在50,000nm以下的具有水蒸氣障壁性的相位差膜。To provide a retardation film having water vapor barrier properties containing a liquid crystalline polymer having a photosensitive side chain and having a film thickness of more than 300 nm and 50,000 nm or less.

Description

具有水蒸氣障壁性之相位差膜及其製造方法Retardation film with water vapor barrier properties and method for producing the same

[0001] 本發明係關於具有水蒸氣障壁性的相位差膜及其製造方法。[0001] The present invention relates to a retardation film having water vapor barrier properties and a method for producing the same.

[0002] 在有機電致發光（EL）顯示器、液晶顯示器等之顯示裝置領域中，除了高精細化外，對輕量化、可撓性化等之要求日漸提高。在該情況，代替玻璃基板而樹脂基板受到注目。 　　[0003] 在有機EL顯示器用的基板，追求非常高的水蒸氣障壁性。以往，作為具有水蒸氣障壁性之樹脂基板，使用在由樹脂所構成的基材之表面形成有水蒸氣障壁層者。例如在專利文獻1，記載在基材之塑膠薄膜上依序具有以對向標靶濺鍍法形成的無機層、以真空蒸鍍法形成的無機層、以化學蒸鍍法形成的無機層及以真空蒸鍍法形成的無機層之氣體障壁性薄膜。但是該技術製造步驟繁雜，由生產性之觀點來看，有問題。 　　[0004] 在有機EL顯示器，為了抑制外光反射，提高視認性而使用相位差板。若能賦予相位差板高水蒸氣障壁性，則可同時具有作為有機EL顯示器的基板之機能與作為相位差膜的機能。但是使用無機材料的氣體障壁性薄膜因為柔軟性差、脆弱，有無法滿足對可撓性化等之要求的問題。 [先前技術文獻] [專利文獻] 　　[0005] [專利文獻1] 國際公開第2013/168739號[0002] In the field of display devices such as organic electroluminescence (EL) displays and liquid crystal displays, in addition to high definition, requirements for weight reduction, flexibility, and the like are increasing day by day. In this case, instead of a glass substrate, a resin substrate attracts attention. [0003] In substrates for organic EL displays, very high water vapor barrier properties are pursued. Conventionally, as a resin substrate having water vapor barrier properties, one having a water vapor barrier layer formed on the surface of a base material made of resin has been used. For example, in Patent Document 1, it is described that an inorganic layer formed by a counter-target sputtering method, an inorganic layer formed by a vacuum evaporation method, an inorganic layer formed by a chemical evaporation method, and Gas barrier thin film of inorganic layer formed by vacuum evaporation method. However, this technique has a complicated manufacturing process and has a problem from the viewpoint of productivity. [0004] In organic EL displays, retardation plates are used in order to suppress external light reflection and improve visibility. If high water vapor barrier properties can be imparted to the retardation plate, the function as a substrate of an organic EL display and the function as a retardation film can be simultaneously provided. However, the gas barrier thin film using an inorganic material has a problem of being unable to satisfy the requirements for flexibility and the like because of its low flexibility and fragility. [Prior Art Document] [Patent Document] [0005] [Patent Document 1] International Publication No. 2013/168739

[發明所欲解決之課題] 　　[0006] 本發明為有鑑於前述情況而成者，以提供可用比以往更低成本且簡單的方法製造、可以有機材料製造的具有水蒸氣障壁性的相位差膜、及其製造方法為目的。 [用以解決課題之手段] 　　[0007] 本發明者們為了達成前述目的而努力檢討之結果，發現含有具有指定的感光性側鏈的可表現液晶性之聚合物的相位差膜還具有水蒸氣障壁性，且可以更簡單的方法製造，完成本發明。 　　[0008] 因此，本發明提供下述具有水蒸氣障壁性的相位差膜及其製造方法。 　　1. 一種具有水蒸氣障壁性的相位差膜，其係含有具有感光性側鏈的液晶性聚合物，而膜厚超過300nm且在50,000nm以下。 　　2. 如1的相位差膜，其中，前述感光性側鏈為引起光交聯、光異構化或光-弗萊斯重排者。 　　3. 如2的相位差膜，其中，前述感光性側鏈為選自下述式（1）~（6）所表示之基的至少1種。

Figure 02_image001
（式中，A1 、A2 及A3 各自獨立，為單鍵、-O-、-CH2 -、 -C(=O)-O-、-O-C(=O)-、-C(=O)-NH-、-NH-C(=O)-、 -CH=CH-C(=O)-O-或-O-C(=O)-CH=CH-； 　　T1 為可被鹵素原子取代的碳數1~12的伸烷基； 　　T2 為單鍵、或可被鹵素原子取代的碳數1~12的伸烷基； 　　Y1 為選自苯基、萘基、聯苯基、呋喃基及吡咯基的1價芳香族基、碳數5~8的1價環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透過連結基A2 鍵結而成的基，鍵結於此等之氫原子的一部份可被-COOR0 （R0 為氫原子或碳數1~5的烷基。）、-NO2 、-CN、-CH=C(CN)2 、 -CH=CH-CN、鹵素原子、碳數1~5的烷基或碳數1~5的烷氧基取代； 　　Y2 為選自伸苯基、萘二基、亞聯苯基、呋喃二基及吡咯二基的2價芳香族基、碳數5~8的2價環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透過連結基A2 鍵結而成的基，鍵結於此等之氫原子的一部份可被-NO2 、-CN、 -CH=C(CN)2 、-CH=CH-CN、鹵素原子、碳數1~5的烷基或碳數1~5的烷氧基取代； 　　R為羥基或者碳數1~6的烷氧基、或與Y1 同定義； 　　X為單鍵、-C(=O)-O-、-O-C(=O)-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-C(=O)-O-或-O-C(=O)-CH=CH-，X之數為2以上時，各X可為相同亦可為相異； 　　Cou 為香豆素-6-基或香豆素-7-基，鍵結於此等之氫原子的一部份可被-NO2 、-CN、-CH=C(CN)2 、-CH=CH-CN、鹵素原子、碳數1~5的烷基或碳數1~5的烷氧基取代； 　　Q1 及Q2 各自獨立，為選自伸苯基、萘二基、亞聯苯基、呋喃二基及吡咯二基的2價芳香族基、碳數5~8的2價環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透過連結基A2 鍵結而成的基，但X為-CH=CH-CO-O-或 -O-CO-CH=CH-時，-CH=CH-鍵結側之Q1 或Q2 為2價芳香族基，Q1 之數為2以上時，各Q1 可為相同亦可為相異，Q2 之數為2以上時，各Q2 可為相同亦可為相異； 　　E為-C(=O)-O-或-O-C(=O)-； 　　W1 及W2 各自獨立，為伸苯基、萘二基、亞聯苯基、呋喃二基、吡咯二基、或由此等之取代基所選出的2~6個基透過連結基A2 鍵結而成的基； 　　a1為0或1； 　　a2為0~2的整數； 　　a1與a2皆為0且T2 為單鍵時，A1 為單鍵； 　　a1為1且T2 為單鍵時，A2 為單鍵； 　　b為0或1； 　　虛線為與主鏈之鍵結鍵。） 　　4. 如3的相位差膜，其中，前述感光性側鏈係選自下述式（7）~（10）所表示之基。
Figure 02_image003
（式中，A1 、A2 、A3 、Y1 、Y2 、R、X及虛線同前述，但n為0時，A2 為單鍵； 　　R1 為-NO2 、-CN、鹵素原子、碳數1~5的烷基、或碳數1~5的烷氧基； 　　c為1~12的整數； 　　m為0~2的整數； 　　m1及m2各自獨立，為1~3的整數； 　　d為0~4的整數； 　　n為0~12的整數。） 　　5. 如3的相位差膜，其中，前述感光性側鏈係選自下述式（11）~（13）所表示之基。
Figure 02_image005
（式中，A1 、R、R1 、X、c、d、m1及虛線同前述；e為0~6的整數。） 　　6. 如3的相位差膜，其中，前述感光性側鏈為下述式（14）或（15）所表示之基。
Figure 02_image007
（式中，A1 、R1 、Y1 、c、d、m1、m2及虛線同前述。） 　　7. 如3的相位差膜，其中，前述感光性側鏈為下述式（16）或（17）所表示之基。
Figure 02_image009
（式中，A1 、R1 、X、c、d、m及虛線同前述；f為0~5的整數。） 　　8. 如3的相位差膜，其中，前述感光性側鏈為下述式（18）或（19）所表示之基。
Figure 02_image011
（式中，A1 、A2 、E、R1 、Y1 、c、d、m1、m2及虛線同前述；g為0~5的整數。） 　　9. 如3的相位差膜，其中，前述感光性側鏈為下述式（20）所表示之基。
Figure 02_image013
（式中，A1 、R1 、X、Y1 、c、d、m及虛線同前述。） 　　10. 如1~9中任一的相位差膜，其中，前述液晶性聚合物再含有選自下述式（21）~（35）所表示之基的至少1種之液晶性側鏈。
Figure 02_image015
Figure 02_image017
（式中，A1 、A2 、E、R1 、c、d、e、m1、m2及虛線同前述； 　　R2 為氫原子、-NO2 、-CN、-CH=C(CN)2 、-CH=CH-CN、鹵素原子、苯基、萘基、聯苯基、呋喃基、1價的含有含氮雜環之基、碳數5~8的環狀脂肪族烴基、碳數1~12的烷基、或碳數1~12的烷氧基； 　　Y3 為苯基、萘基、聯苯基、呋喃基、1價的含有含氮雜環之基、碳數5~8的環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透過連結基A2 鍵結而成的基，鍵結於此等之氫原子的一部份可被-NO2 、-CN、鹵素原子、碳數1~5的烷基、或碳數1~5的烷氧基取代； 　　Z1 及Z2 各自獨立，為單鍵、-C(=O)-、-CH2 O-、-CH=N-或-CF2 -； 　　h為0~5的整數； 　　k各自獨立，為0~2的整數，但在式（25）及（26）中，全部的k之合計為2以上， 　　m3為1~3的整數。） 　　11. 如10的相位差膜，其中，前述液晶性聚合物為含有下述式（A）所表示之重複單位及下述式（B）所表示之重複單位者。
Figure 02_image019
（式中，RA 為選自式（1）~（6）所表示之基的至少1種，RB 為選自式（21）~（31）所表示之基的至少1種，MA 及MB 各自獨立，為來自聚合性基的基。） 　　12. 如11的相位差膜，其中，前述來自聚合性基的基為選自下述式所表示之基的至少1種。
Figure 02_image021
（式中，RC 為氫原子、碳數1~3的烷基、羧基或羧基甲基，RD 為單鍵、-C(=O)-O-、-C(=O)-NH-或伸苯基，RE 為羥基、碳數1~10的烷基或者烷氧基、或苯基，虛線為與RA 或RB 之鍵結鍵。） 　　13. 如1~12中任一的相位差膜，其中，前述液晶性聚合物表現液晶性的溫度範圍為50~300℃。 　　14. 一種有機EL顯示器，其係具備1~13中任一的相位差膜。 　　15. 一種具有水蒸氣障壁性的相位差膜之製造方法，其係包含： 　　將含有含具有感光性側鏈的液晶性聚合物的樹脂成分與有機溶劑的相位差膜形成用組成物塗佈於基材，形成膜厚超過300nm且為50,000nm以下的塗膜之步驟、 　　對前述塗膜照射偏光紫外線之步驟、及 　　將照射過前述偏光紫外線的膜加熱，得到膜厚超過300nm且為50,000nm以下的膜之步驟。 　　16. 如15的相位差膜之製造方法，其中，前述感光性側鏈為引起光交聯、光異構化或光-弗萊斯重排者。 　　17. 如16的相位差膜之製造方法，其中，前述感光性側鏈為選自前述式（1）~（6）所表示之基的至少1種。 　　18. 如14~17中任一的相位差膜之製造方法，其中，前述液晶性聚合物再含有選自前述式（21）~（35）所表示之基的至少1種之液晶性側鏈。 　　19. 如14~18中任一的相位差膜之製造方法，其中，前述液晶性聚合物表現液晶性的溫度範圍為50~300℃。 [發明之效果] 　　[0009] 本發明的相位差膜間具有高水蒸氣障壁性與作為相位差膜的機能，可適用在有機EL顯示器等之顯示裝置。又，本發明的相位差膜可以比以往更低成本且簡單的方法製造，生產性亦良好。 [實施發明之最佳形態] 　　[0010] [具有水蒸氣障壁性的相位差膜] 　　本發明之具有水蒸氣障壁性的相位差膜，含有具有感光性側鏈的液晶性聚合物，而膜厚超過300nm且在50,000nm以下。 　　[0011] 前述感光性側鏈的構造雖不特別限制，以感應光而引起交聯反應、異構化反應或光弗萊斯重排的構造為佳、引起交聯反應或光弗萊斯重排的構造更佳、引起交聯反應者更佳。 　　[0012] 前述感光性側鏈方面，以選自下述式（1）~（6）所表示之基的至少1種為佳。
Figure 02_image023
[0013] 式中，A1 、A2 及A3 各自獨立，為單鍵、-O-、-CH2 -、-C(=O)-O-、-O-C(=O)-、-C(=O)-NH-、-NH-C(=O)-、-CH=CH-C(=O)-O-或-O-C(=O)-CH=CH-。 　　[0014] T1 為可被鹵素原子取代的碳數1~12的伸烷基。T2 為單鍵、或可被鹵素原子取代的碳數1~12的伸烷基。 　　[0015] Y1 為選自苯基、萘基、聯苯基、呋喃基及吡咯基的1價芳香族基、碳數5~8的1價環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透過連結基A2 鍵結而成的基，鍵結於此等之氫原子的一部份可被-COOR0 （R0 為氫原子或碳數1~5的烷基。）、-NO2 、-CN、-CH=C(CN)2 、 -CH=CH-CN、鹵素原子、碳數1~5的烷基或碳數1~5的烷氧基取代。 　　[0016] Y2 為選自伸苯基、萘二基、亞聯苯基、呋喃二基及吡咯二基的2價芳香族基、碳數5~8的2價環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透過連結基A2 鍵結而成的基，鍵結於此等之氫原子的一部份可被-NO2 、-CN、-CH=C(CN)2 、-CH=CH-CN、鹵素原子、碳數1~5的烷基或碳數1~5的烷氧基取代。 　　[0017] R為羥基或者碳數1~6的烷氧基、或與Y1 同定義。 　　[0018] X為單鍵、-C(=O)-O-、-O-C(=O)-、-N=N-、 -CH=CH-、-C≡C-、-CH=CH-C(=O)-O-或-O-C(=O)-CH=CH-，X之數為2以上時，各X可為相同或相異。 　　[0019] Cou 為香豆素-6-基或香豆素-7-基，鍵結於此等之氫原子的一部份可被-NO2 、-CN、-CH=C(CN)2 、 -CH=CH-CN、鹵素原子、碳數1~5的烷基或碳數1~5的烷氧基取代。 　　[0020] Q1 及Q2 各自獨立，為選自伸苯基、萘二基、亞聯苯基、呋喃二基及吡咯二基的2價芳香族基、碳數5~8的2價環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透過連結基A2 鍵結而成的基，但X為-CH=CH-CO-O-或 -O-CO-CH=CH-時，-CH=CH-鍵結側之Q1 或Q2 為2價芳香族基，Q1 之數為2以上時，各Q1 可為相同亦可為相異，Q2 之數為2以上時，各Q2 可為相同或相異。 　　[0021] E為-C(=O)-O-或-O-C(=O)-。W1 及W2 各自獨立，為伸苯基、萘二基、亞聯苯基、呋喃二基、吡咯二基、或由此等之取代基所選出的2~6個基透過連結基A2 鍵結而成的基。 　　[0022] a1為0或1。a2為0~2的整數。a1與a2皆為0且T2 為單鍵時，A1 為單鍵。a1為1且T2 為單鍵時，A2 為單鍵。b為0或1。虛線為與主鏈之鍵結鍵。） 　　[0023] 前述感光性側鏈方面，以下述式（7）~（10）所表示者為佳。
Figure 02_image025
[0024] 式中，A1 、A2 、A3 、Y1 、Y2 、R、X及虛線同前述，但n為0時，A2 為單鍵。R1 為-NO2 、-CN、鹵素原子、碳數1~5的烷基、或碳數1~5的烷氧基。c為1~12的整數。m為0~2的整數。m1及m2各自獨立，為1~3的整數。d為0~4的整數。n為0~12的整數。 　　[0025] 前述碳數1~5的烷基方面，可舉例如甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、n-戊基等。前述碳數1~5的烷氧基方面，可舉例如甲氧基、乙氧基、n-丙氧基、異丙氧基、n-丁氧基、異丁氧基、sec-丁氧基、tert-丁氧基、n-戊基氧基等。 　　[0026] 前述感光性側鏈方面，下述式（11）~（13）所表示者亦佳。
Figure 02_image027
（式中，A1 、X、R、R1 、c、d、m、m1及虛線同前述。e為0~6的整數。） 　　[0027] 前述感光性側鏈方面，下述式（14）或（15）所表示者亦佳。
Figure 02_image029
（式中，A1 、R1 、Y1 、c、d、m1、m2及虛線同前述。） 　　[0028] 前述感光性側鏈方面，下述式（16）或（17）所表示者亦佳。
Figure 02_image031
（式中，A1 、R1 、X、c、d、m及虛線同前述。f為0~5的整數。） 　　[0029] 前述感光性側鏈方面，下述式（18）或（19）所表示者亦佳。
Figure 02_image033
（式中，A1 、A2 、E、R1 、Y1 、c、d、m1、m2及虛線同前述。g為0~5的整數。） 　　[0030] 前述感光性側鏈方面，下述式（20）所表示者亦佳。
Figure 02_image035
（式中，A1 、R1 、X、Y1 、c、d、m及虛線同前述。） 　　[0031] 前述感光性側鏈，以與波長250~400nm範圍之光反應者為佳。 　　[0032] 前述感光性側鏈方面，尤以式（7）、（8）、（9）、（14）、（15）所表示者為佳。 　　[0033] 前述液晶性聚合物，主鏈鍵結有具有感光性之側鏈，感應光而可引起交聯反應、異構化反應、或光弗萊斯重排。具有感光性的側鏈的構造，雖不特別限制，以感應光而引起交聯反應或光弗萊斯重排的構造為佳、引起交聯反應者更佳。具有可表現液晶性之感光性側鏈的聚合物膜的構造為滿足該特性者則不特別限定，以側鏈構造具有剛性的液晶元成分為佳。 　　[0034] 前述液晶性聚合物，以在50~300℃的溫度範圍表現液晶性為佳。前述液晶性的表現溫度以60~280℃更佳、70~250℃又更佳、80~200℃再更佳。液晶性的表現溫度若在前述範圍，則即使暴露於熱或光等之外部壓力下，仍可製作長時間安定地維持得到的水蒸氣障壁性及相位差的薄膜。 　　[0035] 前述液晶性聚合物除前述感光性側鏈外，以含有具有剛性的液晶元部位的液晶性側鏈為佳。如此之側鏈方面，以選自下述式（21）~（35）所表示之基的至少1種為佳。
Figure 02_image037
[0036]
Figure 02_image039
[0037] 式中，A1 、A2 、E、R1 、c、d、e、m1、m2及虛線同前述。 　　[0038] R2 為氫原子、-NO2 、-CN、-CH=C(CN)2 、 -CH=CH-CN、鹵素原子、苯基、萘基、聯苯基、呋喃基、1價的含有含氮雜環之基、碳數5~8的環狀脂肪族烴基、碳數1~12的烷基、或碳數1~12的烷氧基。 　　[0039] Y3 為苯基、萘基、聯苯基、呋喃基、1價的含有含氮雜環之基、碳數5~8的環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透過連結基A2 鍵結而成的基，鍵結於此等之氫原子的一部份可被-NO2 、-CN、鹵素原子、碳數1~5的烷基、或碳數1~5的烷氧基取代。 　　[0040] Z1 及Z2 各自獨立，為單鍵、-C(=O)-、-CH2 O-、-CH=N-或-CF2 -。 　　[0041] h為0~5的整數。k各自獨立，為0~2的整數，但在式（25）及（26）中，全部的k之合計為2以上。m3為1~3的整數。 　　[0042] 前述液晶性側鏈方面，尤以式（21）、（22）、（23）、（24）、（27）、（29）、（30）、（31）所表示者為佳。 　　[0043] 前述液晶性聚合物為具有主鏈與鍵結於其上的側鏈者，且作為側鏈為含有前述感光性側鏈或液晶性側鏈者。前述聚合物方面，以含有前述側鏈的聚醯亞胺、聚酯、聚脲、或含有下述式（A）所表示之重複單位及下述式（B）所表示之重複單位者為佳。
Figure 02_image041
[0044] 式中，RA 為選自式（1）~（6）所表示之基的至少1種，RB 為選自式（21）~（35）所表示之基的至少1種，MA 及MB 各自獨立，為來自聚合性基的基。 　　[0045] 前述主鏈，以來自（甲基）丙烯酸、伊康酸、富馬酸、馬來酸、α-亞甲基-γ-丁內酯、乙烯、苯乙烯、馬來醯亞胺、降冰片烯等之自由基聚合性單體者或聚矽氧烷構造為佳。 　　[0046] 具體上，前述來自聚合性基的基以選自下述式所表示之基的至少1種為佳。
Figure 02_image043
[0047] 式中，RC 為氫原子、碳數1~3的烷基、羧基或羧基甲基，RD 為單鍵、-C(=O)-O-、-C(=O)-NH-或伸苯基，RE 為羥基、碳數1~10的烷基或者烷氧基、或苯基，虛線為與RA 或RB 之鍵結鍵。 　　[0048] 此等中，前述聚合性基方面，以來自（甲基）丙烯酸、α-亞甲基-γ-丁內酯、苯乙烯、馬來醯亞胺者為佳、來自（甲基）丙烯酸、α-亞甲基-γ-丁內酯、苯乙烯者更佳、來自（甲基）丙烯酸、α-亞甲基-γ-丁內酯者再更佳。 　　[0049] 前述液晶性聚合物中，前述感光性側鏈的含量以全側鏈中5mol%以上為佳、10mol%以上更佳。又，前述液晶性側鏈的含量以全側鏈中95mol%以下為佳、90mol%以下更佳。前述感光性側鏈及液晶性側鏈的含量，合計以全側鏈中70mol%以上為佳、80mol%以上更佳。 　　[0050] 前述液晶性聚合物，以前述感光性側鏈及液晶性側鏈之至少任一者含有極性基為佳。前述極性基方面，以羥基、羧基、醯胺基、胺基為佳、羧基更佳。又，前述液晶性聚合物在不阻礙液晶性程度，可含有交聯構造。前述交聯構造方面，可舉例如來自縮水甘油基等之含環氧乙烷環之基、含氧雜環丁烷環之基等者。 　　[0051] 前述液晶性聚合物，在不損及本發明之效果範圍，可含有前述感光性側鏈及液晶性側鏈以外的其他側鏈。如此之側鏈方面，可舉例如碳數1~15之直鏈狀或分枝狀的烷基、碳數1~15之直鏈狀或分枝狀的鹵素化烷基、碳數6~20的芳基、碳數2~20的雜芳基、碳數7~20的芳烷基、碳數3~20的雜芳烷基、縮水甘油基等之含環氧乙烷環之基、含氧雜環丁烷環之基等。前述液晶性聚合物中，其他側鏈的含量以全側鏈中30莫耳%以下為佳。 　　[0052] 前述烷基方面，可舉例如甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、sec-丁基、tert-丁基、n-戊基、n-己基、n-庚基、n-辛基、n-壬基、n-癸基、n-十一基、n-十二基、n-十三基、n-十四基、n-十五基等。前述鹵素化烷基方面，可舉例如此等之烷基的氫原子之一部份或全部被氟原子、氯原子、溴原子、碘原子等之鹵素原子取代的基。 　　[0053] 前述芳基方面，可舉例如苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基等。 　　[0054] 前述雜芳基方面，以含有氧原子、氮原子、硫原子、硒原子等者為佳，具體上，可舉例如2-噻吩基、3-噻吩基、2-呋喃基、3-呋喃基、2-噁唑基、4-噁唑基、5-噁唑基、3-異噁唑基、4-異噁唑基、5-異噁唑基、2-噻唑基、4-噻唑基、5-噻唑基、3-異噻唑基、4-異噻唑基、5-異噻唑基、2-咪唑基、4-咪唑基、2-吡啶基、3-吡啶基、4-吡啶基等。 　　[0055] 前述芳烷基方面，可舉例如苄基、苯乙基、萘基甲基、萘基乙基等。 　　[0056] 前述雜芳烷基方面，以含有氧原子、氮原子、硫原子、硒原子等者為佳，具體上，可舉例如噻吩基甲基、呋喃基甲基、噁唑基甲基、3-異噁唑基甲基、噻唑基甲基、異噻唑基甲基、咪唑基甲基、吡啶基甲基等。 　　[0057] 具有如此之側鏈的重複單位方面，以下述式（C）所表示者為佳。
Figure 02_image045
[0058] 式中，RC 為碳數1~15之直鏈狀或分枝狀的烷基、碳數1~15之直鏈狀或分枝狀的鹵素化烷基、碳數6~20的芳基、碳數2~20的雜芳基、碳數7~20的芳烷基、碳數3~20的雜芳烷基、縮水甘油基等之含環氧乙烷環之基、含氧雜環丁烷環之基等。MC 為來自聚合性基的基。前述聚合性基方面，可舉例如與MA 及MB 之說明中列舉者相同者。 　　[0059] 前述聚合物的重量平均分子量（Mw），考量得到的塗膜的強度、塗膜形成時之作業性及塗膜之均勻性，以2,000~1,000,000為佳、5,000~100,000更佳。又，本發明中，Mw為膠體滲透層析法（GPC）之聚苯乙烯換算測定值。 　　[0060] 前述聚合物可依據例如國際公開第2014/054785號記載之方法進行合成。 　　[0061] [具有水蒸氣障壁性的相位差膜之製造方法] 　　本發明的相位差膜之製造方法為包含下述步驟者。 　　[I] 將含有含前述液晶性聚合物的樹脂成分與有機溶劑的相位差膜形成用組成物塗佈於基材，形成膜厚超過300nm且為50,000nm以下的塗膜之步驟、 　　[II] 對前述塗膜照射偏光紫外線之步驟、及 　　[III] 將照射過前述偏光紫外線的膜加熱，得到膜厚超過300nm且為50,000nm以下的膜之步驟。 　　[0062] 步驟[I]中，前述基材方面，雖不特別限制，可使用玻璃基板或乙酸酯基板、丙烯酸基板、聚碳酸酯基板、聚對苯二甲酸乙二醇酯基板、聚萘二甲酸乙二醇脂基板、環烯烴聚合物基板、聚醯亞胺基板等之塑膠基板等。 　　[0063] 前述相位差膜形成用組成物，含有含前述液晶性聚合物的樹脂成分與有機溶劑。前述相位差膜形成用組成物，由適合於相位差膜之形成觀點來看，以前述聚合物溶於有機溶劑的溶液為佳。 　　[0064] 前述樹脂成分，可全部係前述液晶性聚合物，但在不損及液晶表現能力及感光性能力範圍，可含其以外之聚合物（以下稱其他聚合物。）。其他聚合物方面，可舉例如聚（甲基）丙烯酸酯、聚醯胺酸、聚醯亞胺等。前述樹脂成分含有其他聚合物時，樹脂成分中的其他聚合物的含量，以0.5~80質量%為佳、1~50質量%更佳。 　　[0065] 前述相位差膜形成用組成物中，前述樹脂成分的含量，以1~20質量%為佳、3~15質量%更佳、3~10質量%更佳。 　　[0066] 前述有機溶劑方面，可舉例如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、N-甲基己內醯胺、2-吡咯烷酮、N-乙基吡咯烷酮、N-乙烯基吡咯烷酮、二甲基亞碸、四甲基尿素、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、3-甲氧基-N,N-二甲基丙醯胺、3-乙氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺、1,3-二甲基-咪唑啉酮、乙基戊基酮、甲基壬基酮、甲基乙基酮、甲基異戊基酮、甲基異丙基酮、環己酮、碳酸乙烯酯、丙烯碳酸酯、二甘醇二甲醚、4-羥基-4-甲基-2-戊酮、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-tert-丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚等。此等可1種單獨使用，亦可2種以上混合使用。 　　[0067] 又，為了使膜厚的均勻性或表面平滑性提升，可添加貧溶劑。前述貧溶劑方面，可舉例如異丙基醇、甲氧基甲基戊醇、甲基溶纖劑、乙基溶纖劑、丁基溶纖劑、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二異丁基甲醇、丁基卡必醇、乙基卡必醇、乙基卡必醇乙酸酯、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇單丁基醚、丙二醇-tert-丁基醚、二丙二醇單甲基醚、二丙二醇二甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、二異丁烯、戊基乙酸酯、丁基丁酸酯、丁基醚、二異丁基酮、甲基環己烯、丙基醚、二己基醚、1-己醇、n-己烷、n-戊烷、n-辛烷、二乙基醚、乳酸甲基酯、乳酸乙基酯、乙酸甲基酯、乙酸乙基酯、乙酸n-丁基酯、乙酸丙二醇單乙基醚、丙酮酸甲基酯、丙酮酸乙基酯、3-甲氧基丙酸甲基酯、3-乙氧基丙酸甲基乙基酯、3-甲氧基丙酸乙基酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙基酯、3-甲氧基丙酸丁基酯、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二醇、2-（2-乙氧基丙氧基）丙醇、乳酸甲基酯、乳酸乙基酯、乳酸n-丙基酯、乳酸n-丁基酯、乳酸異戊基酯等之具有低表面張力的溶劑等。 　　[0068] 前述貧溶劑的含量，為了不使溶劑全體之溶解性顯著降低，以全溶劑中5~80質量%為佳、20~60質量%更佳。前述貧溶劑可1種單獨使用，亦可2種以上混合使用。 　　[0069] 前述相位差膜形成用組成物，由使膜厚的均勻性或表面平滑性提高之觀點來看，可含有氟系界面活性劑、矽酮系界面活性劑、非離子系界面活性劑等之界面活性劑。前述界面活性劑方面，可舉例如EFTOP（註冊商標）301、EF303、EF352（三菱材料電子化學品（股）製）、MEGAFAC（註冊商標）F171、F173、R-30（DIC（股）製）、Fluorad（註冊商標）FC430、FC431（3M公司製）、Asahiguard（註冊商標）AG710（旭硝子（股）製）、Surflon（註冊商標）S-382、SC101、SC102、SC103、SC104、SC105、SC106（AGC塞米化學（股）製）等。界面活性劑的含量，相對前述樹脂成分100質量份，以0.01~2質量份為佳、0.01~1質量份更佳。 　　[0070] 前述相位差膜形成用組成物，可含有含官能性矽烷之化合物。前述含官能性矽烷之化合物方面，可舉例如3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-（2-胺基乙基）-3-胺基丙基三甲氧基矽烷、N-（2-胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽烷基丙基三二乙三胺、N-三甲氧基矽烷基丙基三二乙三胺、10-三甲氧基矽烷基-1,4,7-三氮雜癸烷、10-三乙氧基矽烷基-1,4,7-三氮雜癸烷、9-三甲氧基矽烷基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽烷基-3,6-二氮雜壬基乙酸酯、N-苄基-3-胺基丙基三甲氧基矽烷、N-苄基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙（氧基乙烯）-3-胺基丙基三甲氧基矽烷、N-雙（氧基乙烯）-3-胺基丙基三乙氧基矽烷等。此等可1種單獨使用，亦可2種以上組合使用。 　　[0071] 前述含官能性矽烷之化合物的含量，相對前述樹脂成分100質量份，以0.1~30質量份為佳、1~20質量份更佳。若在前述範圍，則可得到密著性提升效果。 　　[0072] 前述相位差膜形成用組成物，進而以信賴性提升、抑制障壁性及相位差之降低等之目的，可含有酚醛樹脂系化合物或含環氧基之化合物、含氧雜環丁烷環之化合物等之添加劑。 　　[0073] 前述酚醛樹脂系化合物方面，可舉例如以下所示者，但不限於此等。
Figure 02_image047
[0074] 前述含環氧基之化合物方面，可舉例如乙二醇二縮水甘油基醚、聚乙二醇二縮水甘油基醚、丙二醇二縮水甘油基醚、三丙二醇二縮水甘油基醚、聚丙二醇二縮水甘油基醚、新戊二醇二縮水甘油基醚、1,6-己二醇二縮水甘油基醚、甘油二縮水甘油基醚、2,2-二溴新戊二醇二縮水甘油基醚、1,3,5,6-四縮水甘油基-2,4-己二醇、N,N,N’,N’-四縮水甘油基-m-二甲苯二胺、1,3-雙（N,N-二縮水甘油基胺基甲基）環己烷、N,N,N’,N’-四縮水甘油基-4,4’-二胺基二苯基甲烷等。 　　[0075] 前述相位差膜形成用組成物，進而可含有光增感劑。光增感劑方面，以無色增感劑及三重態增感劑為佳。前述光增感劑方面，可舉例如芳香族硝基化合物、香豆素（7-二乙基胺基-4-甲基香豆素、7-羥基4-甲基香豆素）、香豆素酮、羰基雙香豆素、芳香族2-羥基酮（2-羥基二苯甲酮）、經胺基取代的芳香族2-羥基酮（單-或二-p-（二甲基胺基）-2-羥基二苯甲酮）、苯乙酮、蒽醌、呫噸酮、噻噸酮、苯並蒽酮、噻唑啉衍生物（2-苯甲醯基亞甲基-3-甲基-β-萘並噻唑啉、2-（β-萘甲醯基亞甲基）-3-甲基苯並噻唑啉、2-（α-萘甲醯基亞甲基）-3-甲基苯並噻唑啉、2-（4-二苯甲醯基亞甲基）-3-甲基苯並噻唑啉、2-（β-萘甲醯基亞甲基）-3-甲基-β-萘並噻唑啉、2-（4-二苯甲醯基亞甲基）-3-甲基-β-萘並噻唑啉、2-（p-氟苯甲醯基亞甲基）-3-甲基-β-萘並噻唑啉）、噁唑啉衍生物（2-苯甲醯基亞甲基-3-甲基-β-萘並噁唑啉、2-（β-萘甲醯基亞甲基）-3-甲基苯並噁唑啉、2-（α-萘甲醯基亞甲基）-3-甲基苯並噁唑啉、2-（4-二苯甲醯基亞甲基）-3-甲基苯並噁唑啉、2-（β-萘甲醯基亞甲基）-3-甲基-β-萘並噁唑啉、2-（4-二苯甲醯基亞甲基）-3-甲基-β-萘並噁唑啉、2-（p-氟苯甲醯基亞甲基）-3-甲基-β-萘並噁唑啉）、苯並噻唑、硝基苯胺（m-或p-硝基苯胺、2,4,6-三硝基苯胺）、硝基苊（5-硝基苊）、2-[（m-羥基-p-甲氧基）苯乙烯基]苯並噻唑、安息香烷基醚、N-烷基化酞酮、苯乙酮縮酮（2,2-二甲氧基苯基乙酮）、萘衍生物（2-萘甲醇、2-萘羧酸）、蒽衍生物（9-蒽甲醇、9-蒽羧酸）、苯并哌喃、偶氮吲哚嗪、梅洛香豆素等。此等中，以芳香族2-羥基酮（二苯甲酮）、香豆素、香豆素酮、羰基雙香豆素、苯乙酮、蒽醌、呫噸酮、噻噸酮、及苯乙酮縮酮為佳。 　　[0076] 前述添加劑或光增感劑的含量，相對前述樹脂成分100質量份，以0.1~30質量份為佳、0.5~20質量份更佳。若在前述範圍，則可得到充分的效果，且亦不損及液晶性。 　　[0077] 前述相位差膜形成用組成物中，除前述者，在不損及本發明之效果範圍，可添加介電體或導電物質、進而交聯性化合物。 　　[0078] 將前述相位差膜形成用組成物塗佈於基材之方法不特別限制。塗佈方法方面，工業上，一般為網版印刷、凹板印刷、膠版印刷、柔版印刷、噴墨法等。其他塗佈方法方面，有浸漬法、模塗法、滾筒塗佈法、狹縫塗佈法、旋轉塗佈法、噴塗法等，可因應目的而使用此等。 　　[0079] 將前述相位差膜形成用組成物塗佈於基材上後，以加熱板、熱循環型烤箱、紅外線型烤箱等之加熱手段，較佳為在50~200℃、更佳為50~150℃，使溶劑蒸發，可得到塗膜。此時之溫度以比前述聚合物的液晶相表現溫度低為佳。 　　[0080] 塗膜之膜厚為超過300nm且在50,000nm以下，但其下限較佳為350nm、更佳為400nm、再佳為1,000nm、最佳為1,500nm。另一方面，其上限較佳為20,000nm、更佳為10,000nm、再佳為6,000nm、最佳為5,000nm。 　　[0081] 又，在步驟[I]之後、步驟[II]之前，可設置將形成有塗膜的基板冷卻至室溫的步驟。 　　[0082] 步驟[II]中，對塗膜之膜面照射偏光紫外線時，對基板從一定方向透過偏光板，照射偏光之紫外線。使用之紫外線方面，以波長100~400nm之範圍者為宜。波長因使用塗膜之種類，透過過濾器等選擇最佳者。例如為了可選擇性地引發光交聯反應，可選擇使用波長290~ 400nm之範圍的紫外線。紫外線方面，例如可使用由高壓水銀燈放射之光。 　　[0083] 偏光紫外線的照射量依存於使用之塗膜。照射量以在實現該塗膜中之與偏光紫外線的偏光方向平行方向的紫外線吸光度和與偏光紫外線的偏光方向垂直方向的紫外線吸光度的差即ΔA之最大值（以下亦稱ΔAmax）的偏光紫外線的量之1~70%之範圍內為佳、1~50%之範圍內更佳。 　　[0084] 步驟[III]中，藉由將照射前述偏光紫外線的塗膜加熱，可對塗膜賦予大的各向異性（相位差）。 　　[0085] 加熱，可使用加熱板、熱循環型烤箱、紅外線型烤箱等之加熱手段。加熱溫度，可考量使用的塗膜表現液晶性之溫度來決定。 　　[0086] 加熱溫度，以在前述液晶性聚合物表現液晶性的溫度（以下、稱液晶表現溫度。）之範圍內為佳。為塗膜般薄膜表面之情形，塗膜表面的液晶表現溫度，預想比大量觀察能表現液晶性的感光性的側鏈型高分子時的液晶表現溫度低。因此，加熱溫度以在塗膜表面的液晶表現溫度之溫度範圍內更佳。即、偏光紫外線照射後的加熱溫度的溫度範圍，以比使用的鏈型高分子的液晶表現溫度的溫度範圍的下限高10℃之溫度為下限，以比其液晶溫度範圍的上限低10℃之溫度為上限的範圍的溫度為佳。加熱溫度比上述溫度範圍低，則有塗膜之熱所致之各向異性的放大效果不足之傾向，又加熱溫度比上述溫度範圍過為高，則有塗膜之狀態接近等方性的液體狀態（各向同性相）之傾向，該場合，有因自組織化而難以朝向一方向再配向之情形。 　　[0087] 又，液晶表現溫度係指在前述液晶性聚合物由固體相相轉變為液晶相之玻璃轉化溫度以上，且在由液晶相相轉變為各向同性相（Isotropic phase）之各向同性相轉化溫度以下的溫度。 　　[0088] 加熱後形成的塗膜之膜厚超過300nm而在50,000nm以下，但其下限較佳為350nm、更佳為400nm、再佳為1,000nm、最佳為1,500nm。另一方面，其上限較佳為20,000nm、更佳為10,000nm、再佳為6,000nm、最佳為5,000nm。 　　[0089] 以前述製造方法，可以高效率實現對塗膜導入各向異性。亦即表現相位差。而可以高效率製造附相位差膜的基材。 　　[0090] 如此而得到的本發明的相位差膜還為具有水蒸氣障壁性者。藉由液晶元骨架整齊地配向，可得到π共軛、π-π堆疊效果，故認為係障壁性提升者。具體上，前述相位差膜之膜厚為1,000nm時之水蒸氣透過率以500g/m2 ‧day以下為佳。又，本發明中，水蒸氣透過率係指依據JIS Z 0208「防溼包裝材料的透溼度試驗方法（杯式法）」，在溫度40℃、相對溼度90%之條件，測定的值。 　　[0091] 本發明之具有水蒸氣障壁性的相位差膜，尤其可用作為有機EL顯示器用相位差膜。具備本發明的相位差膜的有機EL顯示器，因為水蒸氣障壁性高，故成為信賴性優異者，可製造大屏幕且高精細的顯示器。[Problems to be Solved by the Invention] [0006] The present invention is made in view of the above-mentioned circumstances, and provides a retardation film having water vapor barrier properties that can be produced by a lower cost and simpler method than conventional ones and can be produced from organic materials , and its manufacturing method for the purpose. [MEANS TO SOLVE THE PROBLEM] [0007] As a result of diligently examining to achieve the aforementioned object, the present inventors found that a retardation film containing a polymer expressing liquid crystallinity having a specified photosensitive side chain also has water vapor. Barrier properties, and can be produced by a simpler method, the present invention is completed. Therefore, the present invention provides the following retardation film having water vapor barrier properties and a method for producing the same. 1. A retardation film having water vapor barrier properties, comprising a liquid crystalline polymer having a photosensitive side chain, and having a film thickness of more than 300 nm and 50,000 nm or less. 2. The retardation film according to 1, wherein the photosensitive side chain is one that causes photocrosslinking, photoisomerization, or photo-Fries rearrangement. 3. The retardation film according to 2, wherein the photosensitive side chain is at least one selected from groups represented by the following formulae (1) to (6).
Figure 02_image001
(In the formula, A 1 , A 2 and A 3 are each independently, and are a single bond, -O-, -CH 2 -, -C(=O)-O-, -OC(=O)-, -C(= O)-NH-, -NH-C(=O)-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-; T 1 can be substituted by halogen atom The alkylene of carbon number 1～12; T 2 is a single bond, or the alkylene of carbon number 1～12 that can be replaced by halogen atom; Y 1 is selected from phenyl, naphthyl, biphenyl, furan A monovalent aromatic group of a pyrrolyl group and a pyrrolyl group, a monovalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, or 2 to 6 groups selected from these substituents are bonded through a linking group A 2 A part of the hydrogen atoms bonded to these can be -COOR 0 (R 0 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.), -NO 2 , -CN, -CH=C(CN ) 2 , -CH=CH-CN, halogen atom, the alkyl group of carbon number 1～5 or the alkoxy group of carbon number 1～5 is substituted; Y 2 is selected from phenylene, naphthalenediyl, biphenylene , divalent aromatic groups of furan diyl and pyrrole diyl, divalent cyclic aliphatic hydrocarbon groups with 5 to 8 carbon atoms, or 2 to 6 groups selected from such substituents through the linking group A 2 bond A part of the hydrogen atoms bonded to these can be formed by -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen atom, carbon number 1~ The alkyl group of 5 or the alkoxy group of carbon number 1~5 is substituted; R is hydroxyl or the alkoxy group of carbon number 1~6, or the same definition as Y 1 ; X is a single bond, -C(=O)-O -, -OC(=O)-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or -OC(=O)-CH =CH-, when the number of X is 2 or more, each X may be the same or different; C ou is coumarin-6-yl or coumarin-7-yl, and is bonded to these hydrogen atoms A part of it can be replaced by -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen atom, alkyl group with 1~5 carbon atoms or alkoxy group with 1~5 carbon number Substituted; Q 1 and Q 2 are each independently, and are a bivalent aromatic group selected from phenylene, naphthalene diyl, biphenylene, furan diyl and pyrrole diyl, and a bivalent cyclic group having 5 to 8 carbon atoms. Aliphatic hydrocarbon group, or a group in which 2 to 6 groups selected from such substituents are bonded through linking group A 2 , but X is -CH=CH-CO-O- or -O-CO-CH When =CH-, Q 1 or Q 2 on the bonding side of -CH=CH- is a divalent aromatic group, and when the number of Q 1 is 2 or more, each Q 1 may be the same or different. When the number is 2 or more, each Q 2 may be the same or different; E is -C(=O)-O- or -OC(=O)-; W 1 and W 2 are each independently and are phenylene groups , naphthalenediyl, biphenylene, fur Pyranyl diyl, pyrrole diyl, or 2-6 groups selected from such substituents are bonded through linking group A 2 ; a1 is 0 or 1; a2 is an integer of 0-2; a1 When a2 and a2 are both 0 and T2 is a single bond, A1 is a single bond; when a1 is 1 and T2 is a single bond, A2 is a single bond; b is 0 or 1 ; The dotted line is the bond with the main chain key. ) 4. The retardation film according to 3, wherein the photosensitive side chain is selected from groups represented by the following formulae (7) to (10).
Figure 02_image003
(In the formula, A 1 , A 2 , A 3 , Y 1 , Y 2 , R, X and the dotted line are the same as above, but when n is 0, A 2 is a single bond; R 1 is -NO 2 , -CN, halogen Atom, an alkyl group with 1 to 5 carbon atoms, or an alkoxy group with 1 to 5 carbon atoms; c is an integer of 1 to 12; m is an integer of 0 to 2; m1 and m2 are each independently and are an integer of 1 to 3 d is an integer of 0 to 4; n is an integer of 0 to 12.) 5. The retardation film according to 3, wherein the photosensitive side chain is selected from those represented by the following formulae (11) to (13) base.
Figure 02_image005
(In the formula, A 1 , R , R 1 , X, c, d, m1 and the dotted line are the same as above; e is an integer of 0 to 6.) 6. The retardation film according to 3, wherein the photosensitive side chain is A base represented by the following formula (14) or (15).
Figure 02_image007
(In the formula, A 1 , R 1 , Y 1 , c, d, m1 , m2 and the dotted line are the same as above.) 7. The retardation film according to 3, wherein the photosensitive side chain is the following formula (16) or (17) represents the basis.
Figure 02_image009
(In the formula, A 1 , R 1 , X, c, d, m and the dotted line are the same as above; f is an integer of 0 to 5.) 8. The retardation film according to 3, wherein the photosensitive side chain is the following The basis represented by formula (18) or (19).
Figure 02_image011
(In the formula, A 1 , A 2 , E, R 1 , Y 1 , c, d, m1 , m2 and the dotted line are the same as above; g is an integer from 0 to 5.) 9. The retardation film according to 3, wherein, The said photosensitive side chain is a group represented by following formula (20).
Figure 02_image013
(In the formula, A 1 , R 1 , X, Y 1 , c, d, m and the dotted line are the same as described above.) 10. The retardation film according to any one of 1 to 9, wherein the liquid crystalline polymer further contains selected A liquid crystal side chain of at least one type of groups represented by the following formulae (21) to (35).
Figure 02_image015
Figure 02_image017
(In the formula, A 1 , A 2 , E, R 1 , c, d, e, m1, m2 and the dotted line are the same as above; R 2 is a hydrogen atom, -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen atom, phenyl group, naphthyl group, biphenyl group, furyl group, monovalent nitrogen-containing heterocyclic group, cyclic aliphatic hydrocarbon group with 5 to 8 carbon atoms, 1 carbon group ~12 alkyl groups, or alkoxy groups with 1~12 carbon atoms; Y 3 is phenyl, naphthyl, biphenyl, furyl, 1-valent nitrogen-containing heterocycle-containing groups, and 5~8 carbon atoms Cyclic aliphatic hydrocarbon group, or a group in which 2 to 6 groups selected from these substituents are bonded through a linking group A , -CN, halogen atom, alkyl with 1 to 5 carbons, or alkoxy with 1 to 5 carbons; Z 1 and Z 2 are each independently, and are single bonds, -C(=O)-, -CH 2 O-, -CH=N- or -CF 2 -; h is an integer from 0 to 5; k is independently an integer from 0 to 2, but in formulas (25) and (26), all k The total is 2 or more, and m3 is an integer of 1 to 3.) 11. The retardation film according to 10, wherein the liquid crystalline polymer contains a repeating unit represented by the following formula (A) and the following formula (B) The repeating unit indicated.
Figure 02_image019
(in the formula, R A is at least one selected from the groups represented by the formulae (1) to (6), R B is at least one selected from the groups represented by the formulas (21) to (31), and M A and M B are independently a group derived from a polymerizable group.) 12. The retardation film according to 11, wherein the group derived from the polymerizable group is at least one selected from groups represented by the following formula.
Figure 02_image021
(In the formula, R C is a hydrogen atom, an alkyl group with 1 to 3 carbon atoms, a carboxyl group or a carboxymethyl group, and R D is a single bond, -C(=O)-O-, -C(=O)-NH- or phenylene extension, R E is a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a phenyl group, and the dotted line is a bond with R A or R B. ) 13. Any of 1 to 12 The retardation film of , wherein the temperature range in which the liquid crystalline polymer exhibits liquid crystallinity is 50 to 300°C. 14. An organic EL display comprising the retardation film of any one of 1 to 13. 15. A method for producing a retardation film with water vapor barrier properties, comprising: applying a composition for forming a retardation film containing a resin component containing a liquid crystalline polymer having a photosensitive side chain and an organic solvent on a composition for forming a retardation film. A substrate, a step of forming a coating film with a film thickness exceeding 300 nm and a thickness of 50,000 nm or less, a step of irradiating the above-mentioned coating film with polarized ultraviolet rays, and heating the film irradiated with the above-mentioned polarized ultraviolet rays to obtain a film thickness exceeding 300 nm and 50,000 nm or less the membrane steps. 16. The method for producing a retardation film according to 15, wherein the photosensitive side chain is one that causes photocrosslinking, photoisomerization, or photo-Fries rearrangement. 17. The manufacturing method of the retardation film of 16 whose said photosensitive side chain is at least 1 sort(s) chosen from the group represented by said formula (1)-(6). 18. The method for producing a retardation film according to any one of 14 to 17, wherein the liquid crystalline polymer further contains at least one liquid crystalline side chain selected from the group consisting of groups represented by the aforementioned formulas (21) to (35). . 19. The method for producing a retardation film according to any one of 14 to 18, wherein the temperature range in which the liquid crystalline polymer exhibits liquid crystallinity is 50 to 300°C. [Effect of the Invention] [0009] The retardation films of the present invention have high water vapor barrier properties and functions as retardation films, and can be applied to display devices such as organic EL displays. In addition, the retardation film of the present invention can be produced by a simpler method at a lower cost than conventional ones, and the productivity is also good. [Best Mode for Carrying out the Invention] [0010] [Retardation Film with Water Vapor Barrier Properties] The retardation film with water vapor barrier properties of the present invention contains a liquid crystalline polymer having a photosensitive side chain, and the film thickness More than 300nm and below 50,000nm. Although the structure of the aforementioned photosensitive side chain is not particularly limited, the structure that induces a cross-linking reaction, an isomerization reaction or an optical Frys rearrangement by sensing light is preferably, and a cross-linking reaction or an optical Fleis rearrangement is caused. The structure of the row is better, and the one that causes a cross-linking reaction is better. [0012] The above-mentioned photosensitive side chain is preferably selected from at least one of the bases represented by the following formulas (1) to (6).
Figure 02_image023
In formula, A 1 , A 2 and A 3 are each independently, are single bond,-O-,-CH 2 -,-C(=O)-O-,-OC(=O)-,-C (=O)-NH-, -NH-C(=O)-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-. [0014] T 1 is an alkylene group having 1 to 12 carbon atoms that can be substituted by a halogen atom. T 2 is a single bond or an alkylene group having 1 to 12 carbon atoms which may be substituted by a halogen atom. Y 1 is a monovalent aromatic group selected from a phenyl group, a naphthyl group, a biphenyl group, a furanyl group and a pyrrolyl group, a monovalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, or the replacement thereof The 2~6 groups selected by the group are bonded through the linking group A 2 , and a part of the hydrogen atoms bonded to them can be -COOR 0 (R 0 is a hydrogen atom or a carbon number of 1~5 ), -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen atom, alkyl group with 1~5 carbon atoms or alkoxy group with 1~5 carbon atoms replace. Y 2 is a divalent aromatic group selected from phenylene, naphthalene diyl, biphenylene, furan diyl and pyrrole diyl, a divalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, or A group in which 2 to 6 groups selected from these substituents are bonded through a linking group A 2 , and a part of the hydrogen atoms bonded to these may be -NO 2 , -CN, -CH= C(CN) 2 , -CH=CH-CN, halogen atom, alkyl group having 1 to 5 carbon atoms, or alkoxy group having 1 to 5 carbon atoms. R is the alkoxyl group of hydroxyl or carbon number 1～6, or with Y 1 the same definition. X is single bond,-C(=O)-O-,-OC(=O)-,-N=N-,-CH=CH-,-C≡C-,-CH=CH-C (=O)-O- or -OC(=O)-CH=CH-, when the number of X is 2 or more, each X may be the same or different. C ou is coumarin-6-yl or coumarin-7-yl, and a part of the hydrogen atom that is bonded to these can be -NO 2 , -CN, -CH=C(CN) 2. Substitution of -CH=CH-CN, halogen atom, alkyl group with 1 to 5 carbon atoms or alkoxy group with 1 to 5 carbon atoms. Q 1 and Q 2 are each independently, and are bivalent aromatic groups selected from phenylene, naphthalene diyl, biphenylene, furan diyl and pyrrole diyl, and a bivalent ring having 5 to 8 carbon atoms aliphatic hydrocarbon group, or a group in which 2 to 6 groups selected from such substituents are bonded through the linking group A 2 , but X is -CH=CH-CO-O- or -O-CO- When CH=CH-, Q 1 or Q 2 on the bonding side of -CH=CH- is a divalent aromatic group, and when the number of Q 1 is 2 or more, each Q 1 may be the same or different, and Q 2 When the number is 2 or more, each Q 2 may be the same or different. E is-C(=O)-O- or-OC(=O)-. W 1 and W 2 are each independently, are phenylene, naphthalene diyl, biphenylene, furan diyl, pyrrole diyl, or 2 to 6 groups selected from such substituents through the linking group A 2 bonded base. a1 is 0 or 1. a2 is an integer from 0 to 2. When both a1 and a2 are 0 and T 2 is a single bond, A 1 is a single bond. When a1 is 1 and T 2 is a single bond, A 2 is a single bond. b is 0 or 1. The dotted line is the bond to the main chain. ) [0023] In terms of the aforementioned photosensitive side chain, those represented by the following formulae (7) to (10) are preferred.
Figure 02_image025
In the formula, A 1 , A 2 , A 3 , Y 1 , Y 2 , R, X and dotted line are the same as above, but when n is 0, A 2 is a single bond. R 1 is -NO 2 , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. c is an integer from 1 to 12. m is an integer from 0 to 2. m1 and m2 are independent of each other and are integers from 1 to 3. d is an integer from 0 to 4. n is an integer from 0 to 12. The aspect of the alkyl group of the aforementioned carbon number 1～5, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl , n-pentyl, etc. As the alkoxy group having 1 to 5 carbon atoms, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a sec-butoxy group can be mentioned. , tert-butoxy, n-pentyloxy, etc. In terms of the aforementioned photosensitive side chain, those represented by the following formulae (11) to (13) are also preferred.
Figure 02_image027
(In the formula, A 1 , X, R, R 1 , c, d, m, m1 and the dotted line are the same as described above. e is an integer of 0 to 6.) ) or (15) are also preferred.
Figure 02_image029
(In the formula, A 1 , R 1 , Y 1 , c, d, m1 , m2 and the dotted line are the same as described above.) [0028] Regarding the aforementioned photosensitive side chain, those represented by the following formula (16) or (17) are also good.
Figure 02_image031
(In the formula, A 1 , R 1 , X, c, d, m and the dotted line are the same as described above. f is an integer of 0 to 5.) [0029] Regarding the aforementioned photosensitive side chain, the following formula (18) or (19) ) is also good as indicated.
Figure 02_image033
(In the formula, A 1 , A 2 , E, R 1 , Y 1 , c, d, m1 , m2 and the dotted line are the same as above. g is an integer of 0 to 5.) [0030] In terms of the aforementioned photosensitive side chain, the following The one represented by the formula (20) is also preferable.
Figure 02_image035
(In the formula, A 1 , R 1 , X, Y 1 , c, d, m and the dotted line are the same as above.) [0031] The above-mentioned photosensitive side chains are preferably those that react with light in the wavelength range of 250 to 400 nm. Aspects of aforementioned photosensitive side chain, especially those represented by formula (7), (8), (9), (14), (15) are preferred. [0033] The main chain of the liquid crystalline polymer has a photosensitive side chain bonded to it, and can cause a crosslinking reaction, an isomerization reaction, or a photofries rearrangement in response to light. Although the structure of the side chain having photosensitivity is not particularly limited, a structure that induces a crosslinking reaction or a photofries rearrangement by sensing light is preferable, and a structure that induces a crosslinking reaction is more preferable. The structure of the polymer film having a photosensitive side chain capable of expressing liquid crystallinity is not particularly limited as long as it satisfies this characteristic, and a mesogen component having a rigid side chain structure is preferable. [0034] The aforementioned liquid crystalline polymer preferably exhibits liquid crystallinity in a temperature range of 50 to 300°C. The performance temperature of the aforementioned liquid crystallinity is more preferably 60-280°C, more preferably 70-250°C, and even more preferably 80-200°C. When the temperature at which liquid crystallinity is expressed is within the above-mentioned range, even if exposed to external pressure such as heat or light, a thin film that stably maintains the obtained water vapor barrier properties and retardation for a long period of time can be produced. [0035] In addition to the photosensitive side chain, the liquid crystalline polymer preferably contains a liquid crystalline side chain having a rigid mesogen moiety. In terms of such a side chain, at least one selected from groups represented by the following formulae (21) to (35) is preferred.
Figure 02_image037
[0036]
Figure 02_image039
In formula, A 1 , A 2 , E, R 1 , c, d, e, m , m , and dashed line are the same as above. R 2 is hydrogen atom,-NO 2 ,-CN,-CH=C(CN) 2 ,-CH=CH-CN, halogen atom, phenyl, naphthyl, biphenyl, furanyl, monovalent The group containing nitrogen-containing heterocyclic ring, cyclic aliphatic hydrocarbon group with carbon number 5~8, alkyl group with carbon number 1~12, or alkoxy group with carbon number 1~12. Y 3 is phenyl, naphthyl, biphenyl, furyl, monovalent nitrogen-containing heterocyclic base, cyclic aliphatic hydrocarbon group of carbon number 5～8, or the substituent of such The selected 2 to 6 groups are bonded through the linking group A 2 , and a part of the hydrogen atoms bonded to these can be -NO 2 , -CN, halogen atoms, and alkanes with 1 to 5 carbon atoms. group, or alkoxy group having 1 to 5 carbon atoms. Z 1 and Z 2 are each independently and are single bond, -C(=O)-, -CH 2 O-, -CH=N- or -CF 2 -. h is an integer of 0～5. k is independent of each other and is an integer of 0 to 2, but in formulas (25) and (26), the sum of all k is 2 or more. m3 is an integer from 1 to 3. [0042] In terms of the aforementioned liquid crystal side chains, those represented by formulas (21), (22), (23), (24), (27), (29), (30), and (31) are preferred. [0043] The liquid crystalline polymer has a main chain and a side chain bonded thereto, and the side chain contains the photosensitive side chain or the liquid crystal side chain. In terms of the aforementioned polymer, polyimide, polyester, polyurea containing the aforementioned side chain, or a repeating unit represented by the following formula (A) and a repeating unit represented by the following formula (B) are preferred. .
Figure 02_image041
In the formula, R A is at least one kind selected from the base represented by formula (1)～(6), and R B is at least one kind selected from the base expressed by formula (21)～(35), M A and M B are each independently a group derived from a polymerizable group. The aforementioned main chain is derived from (meth)acrylic acid, itaconic acid, fumaric acid, maleic acid, α-methylene-γ-butyrolactone, ethylene, styrene, maleimide, A radically polymerizable monomer such as norbornene or a polysiloxane structure is preferable. [0046] Specifically, the above-mentioned polymerizable group-derived group is preferably at least one selected from the group represented by the following formula.
Figure 02_image043
In formula, R C is hydrogen atom, the alkyl of carbon number 1～3, carboxyl or carboxymethyl, R D is single bond,-C(=O)-O-,-C(=O)- NH- or phenylene, R E is a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a phenyl group, and the dotted line is a bond with R A or R B. Among these, in the aspect of aforementioned polymerizable group, it is better to be from (meth)acrylic acid, α-methylene-γ-butyrolactone, styrene, maleimide, from (methyl) Acrylic acid, α-methylene-γ-butyrolactone, and styrene are more preferred, and those derived from (meth)acrylic acid and α-methylene-γ-butyrolactone are even more preferred. In the aforementioned liquid crystalline polymer, the content of the aforementioned photosensitive side chain is preferably more than 5 mol% in all side chains, more preferably more than 10 mol%. In addition, the content of the liquid crystal side chain is preferably 95 mol % or less, more preferably 90 mol % or less, in all side chains. The total content of the photosensitive side chain and the liquid crystal side chain is preferably 70 mol % or more, and more preferably 80 mol % or more in all side chains. [0050] The liquid crystal polymer preferably contains a polar group in at least one of the photosensitive side chains and the liquid crystal side chains. Regarding the aforementioned polar groups, hydroxyl, carboxyl, amide and amine groups are preferred, and carboxyl groups are more preferred. Moreover, the said liquid crystalline polymer may contain a crosslinked structure to the extent that it does not inhibit liquid crystallinity. As for the said crosslinked structure, the group containing an oxirane ring derived from a glycidyl group, etc., the group containing an oxetane ring, etc. are mentioned, for example. [0051] The liquid crystalline polymer may contain other side chains other than the photosensitive side chain and the liquid crystalline side chain within a range that does not impair the effects of the present invention. Such side chains include, for example, linear or branched alkyl groups having 1 to 15 carbon atoms, linear or branched halogenated alkyl groups having 1 to 15 carbon atoms, and halogenated alkyl groups having 6 to 20 carbon atoms. aryl, heteroaryl with carbon number 2~20, aralkyl group with carbon number 7~20, heteroaralkyl group with carbon number 3~20, glycidyl group, etc. oxetane ring base, etc. In the aforementioned liquid crystalline polymer, the content of other side chains is preferably 30 mol % or less in all side chains. Aspects of the aforementioned alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n- Fifteen bases, etc. The aforementioned halogenated alkyl group includes a group in which a part or all of the hydrogen atoms of the alkyl group are substituted by halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, and the like. Aspects of aforementioned aryl, such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, 1-phenanthryl, 2-phenanthryl, 3 -Ferky, 4-Ferky, 9-Ferky, etc. Aspects of the aforementioned heteroaryl groups, preferably those containing oxygen atoms, nitrogen atoms, sulfur atoms, selenium atoms, etc., specifically, for example, 2-thienyl, 3-thienyl, 2-furyl, 3- Furanyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazole base, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, etc. . The aforementioned aralkyl group, for example, benzyl, phenethyl, naphthylmethyl, naphthylethyl and the like can be mentioned. Aspects of the aforementioned heteroaralkyl groups are preferably those containing oxygen atoms, nitrogen atoms, sulfur atoms, selenium atoms, etc. Specifically, for example, thienylmethyl, furylmethyl, oxazolylmethyl, 3-isoxazolylmethyl, thiazolylmethyl, isothiazolylmethyl, imidazolylmethyl, pyridylmethyl and the like. In terms of the repeating unit having such a side chain, the one represented by the following formula (C) is preferable.
Figure 02_image045
In formula, R C is the straight-chain or branched alkyl of carbon number 1～15, the straight-chain or branched halogenated alkyl of carbon number 1～15, carbon number 6～20 aryl, heteroaryl with carbon number 2~20, aralkyl group with carbon number 7~20, heteroaralkyl group with carbon number 3~20, glycidyl group, etc. oxetane ring base, etc. MC is a group derived from a polymerizable group. As for the above-mentioned polymerizable group, for example, the same ones as those listed in the description of M A and M B can be mentioned. The weight-average molecular weight (Mw) of the aforementioned polymer, considering the strength of the obtained coating film, the workability when the coating film is formed, and the uniformity of the coating film, is preferably 2,000-1,000,000, more preferably 5,000-100,000. In addition, in this invention, Mw is the polystyrene conversion measurement value of colloid permeation chromatography (GPC). The aforementioned polymer can be synthesized according to, for example, the method described in International Publication No. 2014/054785. [Manufacturing method of retardation film having water vapor barrier properties] The manufacturing method of the retardation film of the present invention includes the following steps. [I] A step of applying a composition for forming a retardation film containing a resin component containing the liquid crystalline polymer and an organic solvent to a substrate to form a coating film having a thickness of more than 300 nm and 50,000 nm or less, [II] The step of irradiating the above-mentioned coating film with polarized ultraviolet rays, and [III] The step of heating the film irradiated with the above-mentioned polarized ultraviolet rays to obtain a film having a film thickness of more than 300 nm and 50,000 nm or less. In the step [1], the aforementioned substrate, although not particularly limited, can use a glass substrate or an acetate substrate, an acrylic substrate, a polycarbonate substrate, a polyethylene terephthalate substrate, a polynaphthalene substrate Plastic substrates such as ethylene glycol dicarboxylate substrates, cycloolefin polymer substrates, polyimide substrates, etc. [0063] The composition for forming a retardation film contains a resin component containing the liquid crystalline polymer and an organic solvent. The above-mentioned composition for forming a retardation film is preferably a solution in which the above-mentioned polymer is dissolved in an organic solvent from the viewpoint of being suitable for the formation of a retardation film. [0064] The above-mentioned resin components may be all of the above-mentioned liquid crystalline polymers, but may contain other polymers (hereinafter referred to as other polymers) within the scope of not impairing the liquid crystal expressing ability and photosensitivity ability. As for other polymers, for example, poly(meth)acrylate, polyamic acid, polyimide, etc. may be mentioned. When the resin component contains another polymer, the content of the other polymer in the resin component is preferably 0.5 to 80% by mass, more preferably 1 to 50% by mass. [0065] In the composition for forming a retardation film, the content of the resin component is preferably 1 to 20 mass %, more preferably 3 to 15 mass %, and more preferably 3 to 10 mass %. For the aforementioned organic solvent, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactamide , 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfoxide, hexamethyl sulfoxide, γ-butyrolactone, 3-methyl sulfite Oxy-N,N-dimethylpropionamide, 3-ethoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, 1, 3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, Propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether Wait. These may be used individually by 1 type, and may mix and use 2 or more types. [0067] Furthermore, in order to improve the uniformity of the film thickness or the surface smoothness, a poor solvent may be added. As the above-mentioned poor solvent, for example, isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve can be mentioned. Acetate, diisobutyl methanol, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl base ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether base ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether , dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate Esters, Methyl Acetate, Ethyl Acetate, N-Butyl Acetate, Propylene Glycol Monoethyl Ether, Methyl Pyruvate, Ethyl Pyruvate, Methyl 3-Methoxypropionate, 3 -Methylethyl ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, Butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy- 2-Propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. have low surface tension solvent, etc. The content of the above-mentioned poor solvent, in order not to significantly reduce the solubility of the entire solvent, is preferably 5 to 80 mass % in the total solvent, more preferably 20 to 60 mass %. The above-mentioned poor solvents may be used alone or in combination of two or more. The above-mentioned retardation film forming composition can contain fluorine-based surfactant, silicone-based surfactant, nonionic surfactant from the viewpoint of making the uniformity of film thickness or surface smoothness improve and other surfactants. As the above-mentioned surfactant, for example, EFTOP (registered trademark) 301, EF303, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), MEGAFAC (registered trademark) F171, F173, and R-30 (manufactured by DIC Corporation) , Fluorad (registered trademark) FC430, FC431 (manufactured by 3M Corporation), Asahiguard (registered trademark) AG710 (manufactured by Asahi Glass Co., Ltd.), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 ( AGC Semi Chemical (stock) system) and so on. The content of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the aforementioned resin component. [0070] The composition for forming a retardation film may contain a functional silane-containing compound. For the aforementioned functional silane-containing compounds, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltrimethoxysilane, Propyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethine Methoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxysilane Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxy Silyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-di Azanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis( oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, etc. These may be used individually by 1 type, and may be used in combination of 2 or more types. [0071] The content of the functional silane-containing compound is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the aforementioned resin component. If it is the said range, the adhesiveness improvement effect can be acquired. The composition for forming a retardation film may contain a phenolic resin-based compound or an epoxy group-containing compound, an oxetane-containing compound for the purpose of improving reliability, inhibiting barrier properties and reducing retardation, etc. Additives such as ring compounds. [0073] The above-mentioned phenolic resin compounds include, but are not limited to, those shown below.
Figure 02_image047
In the aspect of the aforementioned epoxy group-containing compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, poly Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether base ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3- Bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. [0075] The composition for forming a retardation film may further contain a photosensitizer. In terms of photosensitizers, colorless sensitizers and triplet sensitizers are preferred. As the aforementioned photosensitizers, for example, aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), coumarin ketones, carbonyl dicoumarins, aromatic 2-hydroxy ketones (2-hydroxybenzophenone), amine-substituted aromatic 2-hydroxy ketones (mono- or di-p-(dimethylamino) )-2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzoxanthone, thiazoline derivatives (2-benzylmethylene-3-methyl) -β-Naphthothiazoline, 2-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3-methylbenzene thiazoline, 2-(4-dibenzylmethylene)-3-methylbenzothiazoline, 2-(β-naphthylmethylene)-3-methyl-β-naphthalene thiazoline, 2-(4-dibenzylmethylene)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzylmethylene)-3-methyl -β-naphthothiazoline), oxazoline derivatives (2-benzylmethylene-3-methyl-β-naphthoxazoline, 2-(β-naphthoylmethylene) )-3-methylbenzoxazoline, 2-(α-naphthoylmethylene)-3-methylbenzoxazoline, 2-(4-dibenzylmethylene) -3-Methylbenzoxazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthoxazoline, 2-(4-dibenzylmethylene base)-3-methyl-β-naphthoxazoline, 2-(p-fluorobenzylmethylene)-3-methyl-β-naphthoxazoline), benzothiazole, nitro Nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline), nitroacenaphthene (5-nitroacenaphthene), 2-[(m-hydroxy-p-methoxy)benzene Vinyl]benzothiazole, benzoin alkyl ethers, N-alkylated phthalones, acetophenone ketals (2,2-dimethoxyphenylethanone), naphthalene derivatives (2-naphthalene methanol, 2 -naphthalene carboxylic acid), anthracene derivatives (9-anthracene methanol, 9-anthracene carboxylic acid), benzopyran, azoindolizine, merlotcoumarin, etc. Among these, aromatic 2-hydroxy ketones (benzophenone), coumarin, coumarin ketone, carbonyl dicoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and benzene Acetone ketal is preferred. [0076] The content of the aforementioned additives or photosensitizers, relative to 100 parts by mass of the aforementioned resin components, is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 20 parts by mass. In the aforementioned range, sufficient effects can be obtained without impairing the liquid crystallinity. [0077] In the above-mentioned composition for forming a retardation film, in addition to the above, a dielectric material or a conductive substance, and further a crosslinkable compound may be added within the range that does not impair the effect of the present invention. [0078] The method for applying the aforementioned composition for forming a retardation film to a substrate is not particularly limited. In terms of coating methods, industrially, screen printing, gravure printing, offset printing, flexographic printing, inkjet printing, etc. are generally used. As for other coating methods, there are a dip method, a die coating method, a roll coating method, a slit coating method, a spin coating method, a spray coating method, and the like, and these can be used according to the purpose. After the above-mentioned phase difference film forming composition is coated on the base material, with heating means such as a hot plate, a thermal cycle oven, an infrared oven, etc., preferably at 50 ~ 200 ℃, more preferably 50 At ~150℃, the solvent is evaporated to obtain a coating film. The temperature at this time is preferably lower than the temperature at which the liquid crystal phase of the polymer appears. [0080] The thickness of the coating film is more than 300 nm and below 50,000 nm, but the lower limit is preferably 350 nm, more preferably 400 nm, still more preferably 1,000 nm, and most preferably 1,500 nm. On the other hand, the upper limit is preferably 20,000 nm, more preferably 10,000 nm, still more preferably 6,000 nm, and most preferably 5,000 nm. [0081] Furthermore, after the step [I] and before the step [II], a step of cooling the substrate on which the coating film is formed to room temperature may be provided. [0082] In step [II], when the film surface of the coating film is irradiated with polarized ultraviolet rays, the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction. As for the ultraviolet rays used, those with a wavelength in the range of 100~400nm are suitable. The wavelength is selected according to the type of coating film used, through filters, etc. to select the best one. For example, in order to selectively initiate the photocrosslinking reaction, ultraviolet rays having a wavelength of 290 to 400 nm can be selected. For ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used. [0083] The irradiation amount of polarized ultraviolet rays depends on the coating film used. The irradiation amount is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays, that is, the maximum value of ΔA (hereinafter also referred to as ΔAmax) in the coating film. The amount is preferably within the range of 1~70%, more preferably within the range of 1~50%. [0084] In step [III], by heating the coating film irradiated with the polarized ultraviolet rays, a large anisotropy (retardation) can be imparted to the coating film. [0085] For heating, heating means such as a hot plate, a thermal cycle oven, an infrared oven, etc. can be used. The heating temperature can be determined in consideration of the temperature at which the coating film to be used exhibits liquid crystallinity. [0086] The heating temperature is preferably within the range of the temperature at which the liquid crystalline polymer exhibits liquid crystallinity (hereinafter referred to as the liquid crystal expression temperature). In the case of a thin film surface like a coating film, the liquid crystal expression temperature on the coating film surface is expected to be lower than the liquid crystal expression temperature when a large amount of photosensitivity side chain type polymers that express liquid crystallinity are observed. Therefore, it is more preferable that the heating temperature is within the temperature range of the temperature of the liquid crystal on the surface of the coating film. That is, the temperature range of the heating temperature after polarized ultraviolet irradiation is set to a temperature that is 10°C higher than the lower limit of the temperature range of the liquid crystal display temperature of the chain polymer to be used, and a temperature that is 10°C lower than the upper limit of the liquid crystal temperature range. The temperature in the range where the temperature is the upper limit is preferable. If the heating temperature is lower than the above temperature range, the amplification effect of the anisotropy caused by the heat of the coating film tends to be insufficient, and if the heating temperature is too high than the above temperature range, the state of the coating film is close to the isotropic liquid. The tendency of the state (isotropic phase), in this case, it may be difficult to re-align in one direction due to self-organization. In addition, the liquid crystal expression temperature refers to above the glass transition temperature at which the liquid crystal polymer changes from the solid phase phase to the liquid crystal phase, and the isotropy at which the liquid crystal phase transitions to the isotropic phase (Isotropic phase). temperature below the phase inversion temperature. [0088] The thickness of the coating film formed after heating is more than 300 nm and less than 50,000 nm, but the lower limit is preferably 350 nm, more preferably 400 nm, still more preferably 1,000 nm, and most preferably 1,500 nm. On the other hand, the upper limit is preferably 20,000 nm, more preferably 10,000 nm, still more preferably 6,000 nm, and most preferably 5,000 nm. [0089] With the above-described production method, the introduction of anisotropy into the coating film can be achieved with high efficiency. That is, the phase difference is expressed. As a result, the substrate with retardation film can be produced efficiently. [0090] The retardation film of the present invention thus obtained is also one having water vapor barrier properties. The π-conjugation and π-π stacking effects can be obtained by neatly aligning the mesogen skeleton, so it is considered that the barrier property is improved. Specifically, the water vapor transmission rate when the film thickness of the retardation film is 1,000 nm is preferably 500 g/m 2 ·day or less. In the present invention, the water vapor transmission rate refers to a value measured under the conditions of a temperature of 40°C and a relative humidity of 90% in accordance with JIS Z 0208 "Moisture Permeability Test Method for Moisture-Proof Packaging Materials (Cup Method)". [0091] The retardation film with water vapor barrier properties of the present invention is particularly useful as a retardation film for organic EL displays. Since the organic EL display provided with the retardation film of this invention has high water vapor barrier property, it is excellent in reliability, and a large-screen and high-definition display can be manufactured.

[實施例] 　　[0092] 以下舉實施例及比較例將本發明更具體說明，但本發明不限於下述實施例。又，數平均分子量（Mn）及重量平均分子量（Mw）係使用昭和電工（股）製Shodex GPC-101（溶劑：四氫呋喃、檢量線：標準聚苯乙烯）進行測定。 　　[0093] [1] 單體的合成 [合成例1-1] 單體MA1的合成 　　依據國際公開第2011/084546號記載之方法，合成下述式所表示之單體MA1。

Figure 02_image049
[0094] [合成例1-2] 單體MA2的合成 　　依據特開平9-118717號公報記載之方法，合成下述式所表示之單體MA2。
Figure 02_image051
[0095] [合成例1-3] 單體MA3的合成 　　依據Macromolecules (2012), 45(21), pp. 8547-8554記載之方法，合成下述式所表示之單體MA3。
Figure 02_image053
[0096] [合成例1-4] 單體MA4的合成 　　依據國際公開第2013/133078號記載之方法，合成下述式所表示之單體MA4。
Figure 02_image055
[0097] [合成例1-4] 單體MA5的合成 　　依據國際公開第2013/133078號記載之方法，合成下述式所表示之單體MA5。
Figure 02_image057
[0098] [2] 聚合物的合成 [合成例2-1] 聚合物P1的合成 　　將單體MA1 6.64g及單體MA2 9.19g溶於四氫呋喃（THF）146.42g，以隔膜泵進行脫氣後，加入2,2’-偶氮二異丁腈（AIBN）0.82g，再進行脫氣。之後，在60℃進行8小時反應。將得到的反應溶液滴下至甲醇300mL，將得到的沈澱物進行過濾、以甲醇洗淨、及減壓乾燥，得到粉末狀的聚合物P1（收量12.67g、收率80%）。聚合物P1的組成比為單體MA1：單體MA2=40：60。又，聚合物P1的Mn為16,000、Mw/Mn為1.75。 　　[0099] [合成例2-2] 聚合物P2的合成 　　除作為原料，使用單體MA1 1.66g及單體MA3 2.06g以外，以與實施例1同樣方法，得到粉末狀的聚合物P2。聚合物P2的組成比為單體MA1：單體MA3=50：50。又，聚合物P2的Mn為27,000、Mw/Mn為2.25。 　　[0100] [合成例2-3] 聚合物P3的合成 　　在具備冷卻管的燒瓶，加入單體MA4 2.16g（4.8 mmol）、單體MA5 1.80g（3.6 mmol）、n-十二基丙烯酸酯0.84g（3.6 mmol）、N-甲基-2-吡咯烷酮（NMP）48.0g、及AIBN0.10g，將燒瓶內進行氮取代後，在60℃進行20小時攪拌使其反應。將得到的反應溶液投入400mL之甲醇，使白色粉末沈澱。將該白色粉末過濾後，在室溫進行真空乾燥，得到下述式所表示之聚合物P3（收量3.60g、收率75%）。聚合物P3的Mn為13,258、Mw/Mn為2.0。
Figure 02_image059
[0101] [合成例2-4] 聚合物P4的合成 　　在具備冷卻管的燒瓶，加入單體MA4 1.80g（4 mmol）、單體MA5 1.50g（3 mmol）、n-十二基丙烯酸酯 0.48g（2 mmol）、糠基甲基丙烯酸酯（東京化成工業（股））0.17g（1 mmol）、NMP40.0g、及AIBN 0.085g，將燒瓶內進行氮取代後，在60℃進行20小時攪拌使其反應。將得到的反應溶液投入400mL之甲醇，使白色粉末沈澱。將該白色粉末過濾後，在室溫進行真空乾燥，得到下述式所表示之聚合物P4 （收量2.80g、收率71%）。聚合物P4的Mn為12,000、Mw/Mn為2.00。
Figure 02_image061
[0102] [3] 相位差膜形成用組成物的調製 [調製例1] 相位差膜形成用組成物C1的調製 　　於NMP7.5g中加入聚合物P1 1.5g，在室溫進行1小時攪拌使其溶解。於該溶液，加入丁基溶纖劑（BC）1.0g，進行攪拌，得到相位差膜形成用組成物C1。 　　[0103] [調製例2] 相位差膜形成用組成物C2的調製 　　於丙二醇單甲基醚（PGME）3.2g中，加入聚合物P2 1.0g，在室溫進行1小時攪拌使其溶解。於該溶液，加入環己酮（CHN）1.4g，進行攪拌，得到相位差膜形成用組成物C2。 　　[0104] [調製例3] 相位差膜形成用組成物C3之調製 　　於甲苯5.0g中，加入聚合物P3 1.0g，在室溫進行1小時攪拌使其溶解。於該溶液，加入CHN2.3g，進行攪拌，得到相位差膜形成用組成物C3。 　　[0105] [調製例4] 相位差膜形成用組成物C4之調製 　　於甲苯5.0g中，加入聚合物P4 1.0g，在室溫進行1小時攪拌使其溶解。於該溶液，加入CHN2.3g，進行攪拌，得到相位差膜形成用組成物C4。 　　[0106] [4] 水蒸氣障壁性的評估 [實施例1-1] 　　將相位差膜形成用組成物C1旋轉塗佈於基材之厚度80μm的乙酸酯薄膜（HOLBEIN ART MATERIALS公司製），在70℃的加熱板進行3分鐘乾燥，形成膜厚1,000nm之聚合物層。接著對塗膜面透過偏光板，照射313nm之紫外線10 mJ/cm2 後，在140℃的加熱板進行10分鐘加熱，製作膜厚1,000nm之附水蒸氣障壁性相位差膜的薄膜F1。 　　使用得到的附水蒸氣障壁性相位差膜的薄膜，根據JIS Z 0208「防溼包裝材料的透溼度試驗方法（杯式法）」之諸條件，用下述手法，評估水蒸氣障壁性。 　　使用透溼面積28.27cm2 之正六角形型的塗膜薄膜，在螺絲式的透溼杯封入作為吸溼劑的氯化鈣約20g，重複1小時以上間隔的秤量操作，由杯之質量增加算出水蒸氣透過率。結果如表1。 　　水蒸氣透過率[g/m2 ‧day]=（m/s）/t 　　　m：一定秤量間隔之增加質量（g） 　　　s：透溼面積（m2 ） 　　　t：一定量間隔時間（h）/24（h） 　　[0107] [實施例1-2] 　　除取代相位差膜形成用組成物C1，而使用相位差膜形成用組成物C2，且使313nm之紫外線照射為4 mJ/cm2 以外，以與實施例1-1同樣方法，製作附水蒸氣障壁性相位差膜的薄膜F2-1，並評估水蒸氣障壁性。結果如表1。 　　[0108] [實施例1-3] 　　除取代相位差膜形成用組成物C1，而使用相位差膜形成用組成物C2，且使313nm之紫外線照射為7 mJ/cm2 以外，以與實施例1-1同樣方法，製作附水蒸氣障壁性相位差膜的薄膜F2-2，並評估水蒸氣障壁性。結果如表1。 　　[0109] [實施例1-4] 　　除取代相位差膜形成用組成物C1，而使用相位差膜形成用組成物C2以外，以與實施例1-1同樣方法，製作附水蒸氣障壁性相位差膜的薄膜F2-3，並評估水蒸氣障壁性。結果如表1。 　　[0110] [實施例1-5] 　　除取代相位差膜形成用組成物C1，而使用相位差膜形成用組成物C3，且使313nm之紫外線照射為100 mJ/cm2 以外，以與實施例1-1同樣方法，製作附水蒸氣障壁性相位差膜的薄膜F3，並評估水蒸氣障壁性。結果如表1。 　　[0111] [實施例1-6] 　　除取代相位差膜形成用組成物C1，而使用相位差膜形成用組成物C4，且使313nm之紫外線照射為100 mJ/cm2 以外，以與實施例1-1同樣方法，製作附水蒸氣障壁性相位差膜的薄膜F4，並評估水蒸氣障壁性。結果如表1。 　　[0112] [比較例1-1] 　　除不進行紫外線的照射以外，以與實施例1-1同樣方法，製作薄膜F1’，並評估水蒸氣障壁性。結果如表1。 　　[0113] [比較例1-2] 　　除不進行紫外線的照射以外，以與實施例1-4同樣方法，製作薄膜F2’，並評估水蒸氣障壁性。結果如表1。 　　[0114] [比較例1-3] 　　除不進行紫外線的照射以外，以與實施例1-5同樣方法，製作膜F3’，並評估水蒸氣障壁性。結果如表1。 　　[0115] [比較例1-4] 　　除不進行紫外線的照射以外，以與實施例1-6同樣方法，製作膜F4’，並評估水蒸氣障壁性。結果如表1。 　　[0116] 結果如表1。又，將不形成相位差膜時的水蒸氣透過率作為參考一併記載於表1。 　　[0117]
Figure 02_image063
[0118] [5] 相位差值的評估 [實施例2-1] 　　將相位差膜形成用組成物C1旋轉塗佈於長40mm×寬30mm×厚度0.7mm且形成有ITO膜的玻璃基板，在70℃的加熱板進行3分鐘乾燥，形成膜厚1,000nm之聚合物層。接著對塗膜面透過偏光板，照射313nm之紫外線10 mJ/cm2 後，在140℃的加熱板進行10分鐘加熱，製作膜厚1,000nm的附相位差膜的玻璃基板G1。 　　對得到的附相位差膜的玻璃基板，使用穆勒矩陣/旋光儀（Axometrics公司製、製品名Axoscan），評估相位差值。又，測定波長為550nm、測定溫度為23℃。結果如表2。 　　[0119] [實施例2-2] 　　除取代相位差膜形成用組成物C1，而使用相位差膜形成用組成物C2，且使313nm之紫外線照射為4 mJ/cm2 以外，以與實施例2-1同樣方法，製作附相位差膜的玻璃基板G2-1，並評估相位差值。結果如表2。 　　[0120] [實施例2-3] 　　除取代相位差膜形成用組成物C1，而使用相位差膜形成用組成物C2，且使313nm之紫外線照射為7 mJ/cm2 以外，以與實施例2-1同樣方法，製作附相位差膜的玻璃基板G2-2，並評估相位差值。結果如表2。 　　[0121] [實施例2-4] 　　除取代相位差膜形成用組成物C1，而使用相位差膜形成用組成物C2以外，以與實施例2-1同樣方法，製作附相位差膜的玻璃基板G2-3，並評估相位差值。結果如表2。 　　[0122] [實施例2-5] 　　除取代相位差膜形成用組成物C1，而使用相位差膜形成用組成物C3，且使313nm之紫外線照射為100 mJ/cm2 以外，以與實施例2-1同樣方法，製作附相位差膜的玻璃基板G3，並評估相位差值。結果如表2。 　　[0123] [實施例2-6] 　　除取代相位差膜形成用組成物C1，而使用相位差膜形成用組成物C4，且使313nm之紫外線照射為100 mJ/cm2 以外，以與實施例1-1同樣方法，製作附相位差膜的玻璃基板G4，並評估相位差值。結果如表2。 　　[0124] [比較例2-1] 　　除不進行紫外線的照射以外，以與實施例2-1同樣方法，製作附相位差膜的玻璃基板G1’，並評估相位差值。結果如表2。 　　[0125] [比較例2-2] 　　除不進行紫外線的照射以外，以與實施例2-4同樣方法，製作附相位差膜的玻璃基板G2’，並評估相位差值。結果如表2。 　　[0126] [比較例2-3] 　　除不進行紫外線的照射以外，以與實施例2-5同樣方法，製作附相位差膜的玻璃基板G3’，並評估相位差值。結果如表2。 　　[0127] [比較例2-4] 　　除不進行紫外線的照射以外，以與實施例2-6同樣方法，製作附相位差膜的玻璃基板G4’，並評估相位差值。結果如表2。 　　[0128]
Figure 02_image065
[0129] 如表1及表2所示結果，可知本發明的相位差膜水蒸氣障壁性優異、且可得到作為相位差膜之機能。[Examples] [0092] The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using Shodex GPC-101 (solvent: tetrahydrofuran, calibration curve: standard polystyrene) manufactured by Showa Denko Co., Ltd. [1] Synthesis of Monomer [Synthesis Example 1-1] Synthesis of Monomer MA1 According to the method described in International Publication No. 2011/084546, a monomer MA1 represented by the following formula was synthesized.
Figure 02_image049
[Synthesis Example 1-2] Synthesis of Monomer MA2 According to the method described in Japanese Unexamined Patent Publication No. Hei 9-118717, the monomer MA2 represented by the following formula was synthesized.
Figure 02_image051
[Synthesis Example 1-3] Synthesis of Monomer MA3 According to the method described in Macromolecules (2012), 45(21), pp. 8547-8554, the monomer MA3 represented by the following formula was synthesized.
Figure 02_image053
[Synthesis Example 1-4] Synthesis of Monomer MA4 According to the method described in International Publication No. 2013/133078, a monomer MA4 represented by the following formula was synthesized.
Figure 02_image055
[Synthesis Example 1-4] Synthesis of Monomer MA5 According to the method described in International Publication No. 2013/133078, a monomer MA5 represented by the following formula was synthesized.
Figure 02_image057
[2] Synthesis of polymer [Synthesis example 2-1] Synthesis of polymer P1 6.64 g of monomer MA1 and 9.19 g of monomer MA2 were dissolved in 146.42 g of tetrahydrofuran (THF), and degassed with a diaphragm pump. , and 0.82 g of 2,2'-azobisisobutyronitrile (AIBN) was added, followed by degassing. After that, the reaction was carried out at 60°C for 8 hours. The obtained reaction solution was dropped into 300 mL of methanol, and the obtained precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain a powdery polymer P1 (yield 12.67 g, yield 80%). The composition ratio of the polymer P1 is monomer MA1:monomer MA2=40:60. Moreover, Mn of the polymer P1 was 16,000, and Mw/Mn was 1.75. [Synthesis Example 2-2] Synthesis of Polymer P2 A powdery polymer P2 was obtained in the same manner as in Example 1, except that 1.66 g of the monomer MA1 and 2.06 g of the monomer MA3 were used as raw materials. The composition ratio of the polymer P2 is monomer MA1:monomer MA3=50:50. Moreover, Mn of the polymer P2 was 27,000, and Mw/Mn was 2.25. [Synthesis Example 2-3] Synthesis of Polymer P3 In a flask equipped with a cooling tube, 2.16 g (4.8 mmol) of monomer MA4, 1.80 g (3.6 mmol) of monomer MA5, and n-dodecyl acrylate were added 0.84 g (3.6 mmol), 48.0 g of N-methyl-2-pyrrolidone (NMP), and 0.10 g of AIBN were substituted with nitrogen in the flask, and then reacted by stirring at 60° C. for 20 hours. The obtained reaction solution was put into 400 mL of methanol to precipitate a white powder. After filtering this white powder, it vacuum-dried at room temperature, and obtained the polymer P3 represented by the following formula (yield 3.60g, yield 75%). The Mn of the polymer P3 was 13,258, and the Mw/Mn was 2.0.
Figure 02_image059
[Synthesis Example 2-4] Synthesis of Polymer P4 In a flask equipped with a cooling tube, 1.80 g (4 mmol) of monomer MA4, 1.50 g (3 mmol) of monomer MA5, and n-dodecyl acrylate were added 0.48 g (2 mmol), furfuryl methacrylate (Tokyo Chemical Industry Co., Ltd.) 0.17 g (1 mmol), 40.0 g of NMP, and 0.085 g of AIBN, nitrogen-substituted in the flask, followed by 20 at 60°C. It was stirred for hours to react. The obtained reaction solution was put into 400 mL of methanol to precipitate a white powder. After filtering this white powder, it vacuum-dried at room temperature, and obtained the polymer P4 represented by the following formula (yield 2.80g, yield 71%). The Mn of the polymer P4 was 12,000, and the Mw/Mn was 2.00.
Figure 02_image061
[3] Preparation of the composition for forming a retardation film [Preparation Example 1] Preparation of the composition C1 for forming a retardation film In 7.5 g of NMP, 1.5 g of the polymer P1 was added, and the mixture was stirred for 1 hour at room temperature. it dissolves. To this solution, 1.0 g of butyl cellosolve (BC) was added and stirred to obtain a composition C1 for forming a retardation film. [Preparation Example 2] The preparation of the composition C2 for forming a retardation film was dissolved in 3.2 g of propylene glycol monomethyl ether (PGME), 1.0 g of the polymer P2 was added, and stirred at room temperature for 1 hour. To this solution, 1.4 g of cyclohexanone (CHN) was added and stirred to obtain a retardation film-forming composition C2. [Preparation Example 3] The preparation of the composition C3 for forming a retardation film was prepared in 5.0 g of toluene, 1.0 g of the polymer P3 was added, and the mixture was dissolved by stirring at room temperature for 1 hour. To this solution, 2.3 g of CHN was added and stirred to obtain a composition C3 for forming a retardation film. [Preparation Example 4] The composition C4 for forming a retardation film was prepared in 5.0 g of toluene, 1.0 g of the polymer P4 was added, and the mixture was stirred at room temperature for 1 hour to dissolve. To this solution, 2.3 g of CHN was added and stirred to obtain a retardation film-forming composition C4. [4] Evaluation of water vapor barrier properties [Example 1-1] The composition C1 for forming a retardation film was spin-coated on an acetate film having a thickness of 80 μm on a base material (manufactured by HOLBEIN ART MATERIALS Co., Ltd.), Drying was performed on a hot plate at 70° C. for 3 minutes to form a polymer layer with a film thickness of 1,000 nm. Next, the coated surface was irradiated with 10 mJ/cm 2 of ultraviolet rays at 313 nm through a polarizing plate, and then heated on a hot plate at 140° C. for 10 minutes to produce a thin film F1 with a water vapor barrier retardation film with a thickness of 1,000 nm. Using the obtained film with a retardation film with water vapor barrier property, the water vapor barrier property was evaluated by the following method according to the conditions of JIS Z 0208 "Moisture Permeability Test Method for Moisture-Proof Packaging Materials (Cup Method)". Using a regular hexagonal coating film with a moisture permeable area of 28.27cm 2 , enclose about 20 g of calcium chloride as a moisture absorbent in a screw-type moisture permeable cup, repeat the weighing operation at intervals of more than 1 hour, and calculate from the increase in the mass of the cup water vapor transmission rate. The results are shown in Table 1. Water vapor transmission rate [g/m 2 ‧day]=(m/s)/t m: increased mass at a certain weighing interval (g) s: moisture permeable area (m 2 ) t: certain interval time (h)/24 (h) [0107] [Example 1-2] In place of the retardation film-forming composition C1, the retardation film-forming composition C2 was used, and the 313 nm ultraviolet rays were irradiated at 4 mJ/cm 2 , and In the same manner as in Example 1-1, a thin film F2-1 with a water vapor barrier retardation film was produced, and the water vapor barrier properties were evaluated. The results are shown in Table 1. [Example 1-3] In addition to replacing the composition C1 for forming a retardation film, and using the composition C2 for forming a retardation film, and making the ultraviolet irradiation of 313nm to be 7 mJ/cm , the same as the embodiment 1-1 In the same way, the film F2-2 with the retardation film with water vapor barrier property was produced, and the water vapor barrier property was evaluated. The results are shown in Table 1. [Example 1-4] Except that the composition C1 for forming a retardation film was replaced, and the composition C2 for forming a retardation film was used, in the same manner as in Example 1-1, a water vapor barrier phase was produced. The film F2-3 of the poor film was evaluated and the water vapor barrier property was evaluated. The results are shown in Table 1. [Example 1-5] In addition to replacing the composition C1 for forming a retardation film, and using the composition C3 for forming a retardation film, and making the ultraviolet irradiation of 313nm to be 100 mJ /cm , the same as the embodiment 1-1 In the same manner, a film F3 with a water vapor barrier retardation film was produced, and the water vapor barrier property was evaluated. The results are shown in Table 1. [Example 1-6] In addition to replacing the composition C1 for forming a retardation film, and using the composition C4 for forming a retardation film, and making the ultraviolet irradiation of 313nm to be 100 mJ /cm , the same as the embodiment 1-1 In the same manner, the film F4 with the retardation film with water vapor barrier property was produced, and the water vapor barrier property was evaluated. The results are shown in Table 1. [Comparative Example 1-1] A thin film F1' was produced in the same manner as in Example 1-1 except that no ultraviolet irradiation was performed, and the water vapor barrier properties were evaluated. The results are shown in Table 1. [Comparative Example 1-2] A thin film F2' was produced in the same manner as in Example 1-4 except that no ultraviolet irradiation was performed, and the water vapor barrier properties were evaluated. The results are shown in Table 1. [Comparative Example 1-3] A film F3' was produced in the same manner as in Example 1-5 except that no ultraviolet irradiation was performed, and the water vapor barrier properties were evaluated. The results are shown in Table 1. [Comparative Example 1-4] A film F4' was produced in the same manner as in Example 1-6 except that no ultraviolet irradiation was performed, and the water vapor barrier properties were evaluated. The results are shown in Table 1. Result is as table 1. In addition, the water vapor transmission rate when the retardation film is not formed is also described in Table 1 as a reference. [0117]
Figure 02_image063
[5] Evaluation of the retardation value [Example 2-1] The composition C1 for forming a retardation film was spin-coated on a glass substrate having a length of 40 mm x width of 30 mm x thickness of 0.7 mm and an ITO film formed thereon. Drying was performed on a hot plate at 70° C. for 3 minutes to form a polymer layer with a film thickness of 1,000 nm. Next, the coating film surface was irradiated with 10 mJ/cm 2 of ultraviolet rays at 313 nm through a polarizing plate, and then heated on a hot plate at 140° C. for 10 minutes to produce a glass substrate G1 with a retardation film with a film thickness of 1,000 nm. The retardation value was evaluated with respect to the obtained glass substrate with retardation film using a Mueller matrix/polarimeter (manufactured by Axometrics, product name Axoscan). Moreover, the measurement wavelength was 550 nm, and the measurement temperature was 23 degreeC. The results are shown in Table 2. [Example 2-2] In addition to replacing the composition C1 for forming a retardation film, and using the composition C2 for forming a retardation film, and making the ultraviolet irradiation of 313nm to be 4 mJ/cm , with the same embodiment as the example 2-1 In the same way, glass substrate G2-1 with retardation film was produced, and the retardation value was evaluated. The results are shown in Table 2. [Example 2-3] In addition to replacing the composition C1 for forming a retardation film, and using the composition C2 for forming a retardation film, and making the ultraviolet irradiation of 313nm be 7 mJ/cm 2 , with the embodiment 2-1 In the same way, glass substrate G2-2 with retardation film was produced, and the retardation value was evaluated. The results are shown in Table 2. [Example 2-4] In addition to replacing the composition C1 for forming a retardation film, and using the composition C2 for forming a retardation film, in the same manner as in Example 2-1, a glass with a retardation film was produced Substrate G2-3, and evaluate the retardation value. The results are shown in Table 2. [Example 2-5] In addition to replacing the composition C1 for forming a retardation film, and using the composition C3 for forming a retardation film, and making the ultraviolet irradiation of 313nm to be 100 mJ /cm , with the same embodiment as the example 2-1 In the same way, the glass substrate G3 with retardation film was produced, and the retardation value was evaluated. The results are shown in Table 2. [Example 2-6] In addition to replacing the composition C1 for forming a retardation film, and using the composition C4 for forming a retardation film, and making the ultraviolet irradiation of 313nm to be 100 mJ /cm , with the embodiment 1-1 In the same way, the glass substrate G4 with retardation film was produced, and the retardation value was evaluated. The results are shown in Table 2. [Comparative Example 2-1] In the same manner as in Example 2-1, except that no ultraviolet irradiation was performed, a glass substrate G1' with a retardation film was produced, and the retardation value was evaluated. The results are shown in Table 2. [Comparative Example 2-2] In the same manner as in Example 2-4, except that no ultraviolet irradiation was performed, a glass substrate G2' with a retardation film was produced, and the retardation value was evaluated. The results are shown in Table 2. [Comparative Example 2-3] In the same manner as in Example 2-5, except that no ultraviolet irradiation was performed, a retardation film-attached glass substrate G3' was produced, and the retardation value was evaluated. The results are shown in Table 2. [Comparative Example 2-4] In the same manner as in Example 2-6, except that no ultraviolet irradiation was performed, a retardation film-attached glass substrate G4' was produced, and the retardation value was evaluated. The results are shown in Table 2. [0128]
Figure 02_image065
As shown in Table 1 and Table 2, it can be seen that the retardation film of the present invention is excellent in water vapor barrier property and can function as a retardation film.

Claims (15)

一種具有水蒸氣障壁性的相位差膜，其特徵係含有具有感光性側鏈的液晶性聚合物，前述感光性側鏈為引起光交聯、光異構化或光-弗萊斯重排者，前述感光性側鏈為選自下述式(2)~(6)所表示之基的至少1種，
Figure 106129728-A0305-02-0050-1
Figure 106129728-A0305-02-0050-2
Figure 106129728-A0305-02-0050-3
Figure 106129728-A0305-02-0050-4
Figure 106129728-A0305-02-0050-5
 (式中，A1、A2及A3各自獨立，為單鍵、-O-、-CH2-、-C(=O)-O-、-O-C(=O)-、-C(=O)-NH-、-NH-C(=O)-、-CH=CH-C(=O)-O-或-O-C(=O)-CH=CH-；T1為可被鹵素原子取代的碳數1~12的伸烷基； T2為單鍵、或可被鹵素原子取代的碳數1~12的伸烷基；Y1為選自苯基、萘基、聯苯基、呋喃基及吡咯基的1價芳香族基、碳數5~8的1價環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透過連結基A2鍵結而成的基，鍵結於此等之氫原子的一部份可被-COOR0(R0為氫原子或碳數1~5的烷基)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素原子、碳數1~5的烷基或碳數1~5的烷氧基取代；Y2為選自伸苯基、萘二基、亞聯苯基、呋喃二基及吡咯二基的2價芳香族基、碳數5~8的2價環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透過連結基A2鍵結而成的基，鍵結於此等之氫原子的一部份可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素原子、碳數1~5的烷基或碳數1~5的烷氧基取代；R為羥基或者碳數1~6的烷氧基、或與Y1同定義；X為單鍵、-C(=O)-O-、-O-C(=O)-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-C(=O)-O-或-O-C(=O)-CH=CH-，X之數為2以上時，各X可為相同亦可為相異；Cou為香豆素-6-基或香豆素-7-基，鍵結於此等之氫原子的一部份可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素原子、碳數1~5的烷基或碳數1~5的烷氧基取代；Q1及Q2各自獨立，為選自伸苯基、萘二基、亞聯苯基、呋喃二基及吡咯二基的2價芳香族基、碳數5~8的2價環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透 過連結基A2鍵結而成的基，但X為-CH=CH-CO-O-或-O-CO-CH=CH-時，-CH=CH-鍵結側之Q1或Q2為2價芳香族基，Q1之數為2以上時，各Q1可為相同亦可為相異，Q2之數為2以上時，各Q2可為相同亦可為相異；E為-C(=O)-O-或-O-C(=O)-；W1及W2各自獨立，為伸苯基、萘二基、亞聯苯基、呋喃二基、吡咯二基、或由此等之取代基所選出的2~6個基透過連結基A2鍵結而成的基；a1為0或1；a2為0~2的整數；a1與a2皆為0且T2為單鍵時，A1為單鍵；a1為1且T2為單鍵時，A2為單鍵；b為0或1；虛線為與主鏈之鍵結鍵)而膜厚超過300nm且在50,000nm以下。 A retardation film with water vapor barrier properties, which is characterized by containing a liquid crystalline polymer with photosensitive side chains, and the photosensitive side chains are those that cause photocrosslinking, photoisomerization or photo-Fries rearrangement , the above-mentioned photosensitive side chain is at least one selected from the group represented by the following formulas (2) to (6),
Figure 106129728-A0305-02-0050-1
Figure 106129728-A0305-02-0050-2
Figure 106129728-A0305-02-0050-3
Figure 106129728-A0305-02-0050-4
Figure 106129728-A0305-02-0050-5
 (In the formula, A 1 , A 2 and A 3 are each independently, and are a single bond, -O-, -CH 2 -, -C(=O)-O-, -OC(=O)-, -C(= O)-NH-, -NH-C(=O)-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-; T 1 can be substituted by halogen atom The alkylene of carbon number 1～12; T 2 is a single bond, or the alkylene of carbon number 1～12 that can be substituted by halogen atom; Y 1 is selected from phenyl, naphthyl, biphenyl, furan A monovalent aromatic group of a pyrrolyl group and a pyrrolyl group, a monovalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, or 2 to 6 groups selected from these substituents are bonded through a linking group A 2 A part of the hydrogen atoms bonded to these can be -COOR 0 (R 0 is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms), -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen atom, the alkyl group of carbon number 1～5 or the alkoxy group of carbon number 1～5 is substituted; Y 2 is selected from phenylene, naphthalenediyl, biphenylene, A divalent aromatic group of furandiyl and pyrrole diyl, a divalent cyclic aliphatic hydrocarbon group with 5 to 8 carbon atoms, or 2 to 6 groups selected from such substituents are bonded through a linking group A 2 A part of the hydrogen atoms bonded to these can be formed by -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen atom, carbon number 1~5 The alkyl group or the alkoxy group with the carbon number of 1~5 is substituted; R is the hydroxyl group or the alkoxy group with the carbon number 1~6, or the same definition as Y 1 ; X is a single bond, -C(=O)-O- , -OC(=O)-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or -OC(=O)-CH= CH-, when the number of X is 2 or more, each X may be the same or different; C ou is coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to these A part can be substituted by -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen atom, alkyl group with 1~5 carbon atoms or alkoxy group with 1~5 carbon atoms ; Q 1 and Q 2 are each independently, and are bivalent aromatic groups selected from phenylene, naphthalene diyl, biphenylene, furan diyl and pyrrole diyl, and bivalent cyclic aliphatic groups with 5 to 8 carbon atoms A family of hydrocarbon groups, or a group in which 2 to 6 groups selected from such substituents are bonded through the linking group A 2 , but X is -CH=CH-CO-O- or -O-CO-CH= In the case of CH-, Q 1 or Q 2 on the bonding side of -CH=CH- is a divalent aromatic group, and when the number of Q 1 is 2 or more, each Q 1 may be the same or different, and the number of Q 2 When it is 2 or more, each Q 2 can be the same or different; E is -C(=O)-O- or -OC(=O)-; W 1 and W 2 are each independently and are phenylene, Naphthalenediyl, biphenylene, furandiyl, pyrrolediyl, or 2 to 6 groups selected from such substituents through the linking group A 2 A bonded base; a1 is 0 or 1; a2 is an integer from 0 to 2 ; when both a1 and a2 are 0 and T2 is a single bond, A1 is a single bond; a1 is 1 and T2 is a single bond , A 2 is a single bond; b is 0 or 1; the dotted line is a bond with the main chain) and the film thickness exceeds 300 nm and is below 50,000 nm. 如請求項1記載的相位差膜，其中，前述感光性側鏈係選自下述式(8)~(10)所表示之基，
Figure 106129728-A0305-02-0053-6
Figure 106129728-A0305-02-0053-7
Figure 106129728-A0305-02-0053-8
 (式中，A1、A2、A3、Y1、Y2、R、X及虛線同前述，但n為0時，A2為單鍵；R1為-NO2、-CN、鹵素原子、碳數1~5的烷基、或碳數1~5的烷氧基；c為1~12的整數；m為0~2的整數；m1及m2各自獨立，為1~3的整數；d為0~4的整數；n為0~12的整數)。 The retardation film according to claim 1, wherein the photosensitive side chain is selected from groups represented by the following formulae (8) to (10),
Figure 106129728-A0305-02-0053-6
Figure 106129728-A0305-02-0053-7
Figure 106129728-A0305-02-0053-8
 (In the formula, A 1 , A 2 , A 3 , Y 1 , Y 2 , R, X and the dotted line are the same as above, but when n is 0, A 2 is a single bond; R 1 is -NO 2 , -CN, halogen Atom, an alkyl group with 1 to 5 carbon atoms, or an alkoxy group with 1 to 5 carbon atoms; c is an integer of 1 to 12; m is an integer of 0 to 2; m1 and m2 are each independently and are an integer of 1 to 3 ; d is an integer from 0 to 4; n is an integer from 0 to 12). 如請求項1記載的相位差膜，其中，前述感光性側鏈係選自下述式(11)~(13)所表示之基，
Figure 106129728-A0305-02-0054-9
Figure 106129728-A0305-02-0054-10
Figure 106129728-A0305-02-0054-11
 (式中，A1、X、R及虛線同前述；R1為-NO2、-CN、鹵素原子、碳數1~5的烷基、或碳數1~5的烷氧基；c為1~12的整數；d為0~4的整數；e為0~6的整數；m為0~2的整數；m1為1~3的整數)。 The retardation film according to claim 1, wherein the photosensitive side chain is selected from groups represented by the following formulae (11) to (13),
Figure 106129728-A0305-02-0054-9
Figure 106129728-A0305-02-0054-10
Figure 106129728-A0305-02-0054-11
 (in the formula, A 1 , X, R and the dotted line are the same as above; R 1 is -NO 2 , -CN, a halogen atom, an alkyl group with 1 to 5 carbon atoms, or an alkoxy group with 1 to 5 carbon atoms; c is An integer from 1 to 12; d is an integer from 0 to 4; e is an integer from 0 to 6; m is an integer from 0 to 2; m1 is an integer from 1 to 3). 如請求項1記載的相位差膜，其中，前述感光性側鏈為下述式(14)或(15)所表示之基，
Figure 106129728-A0305-02-0054-58
Figure 106129728-A0305-02-0054-13
 (式中，A1、Y1及虛線同前述； R1為-NO2、-CN、鹵素原子、碳數1~5的烷基、或碳數1~5的烷氧基；c為1~12的整數、d為0~4的整數；m1及m2各自獨立，為1~3的整數)。 The retardation film according to claim 1, wherein the photosensitive side chain is a group represented by the following formula (14) or (15),
Figure 106129728-A0305-02-0054-58
Figure 106129728-A0305-02-0054-13
 (in the formula, A 1 , Y 1 and the dotted line are the same as above; R 1 is -NO 2 , -CN, a halogen atom, an alkyl group with 1 to 5 carbon atoms, or an alkoxy group with 1 to 5 carbon atoms; c is 1 An integer of ~12, d is an integer of 0 to 4; m1 and m2 are independent of each other and are an integer of 1 to 3). 如請求項1記載的相位差膜，其中，前述感光性側鏈為下述式(16)或(17)所表示之基，
Figure 106129728-A0305-02-0055-59
Figure 106129728-A0305-02-0055-15
 (式中，A1、X及虛線同前述；R1為-NO2、-CN、鹵素原子、碳數1~5的烷基、或碳數1~5的烷氧基；d為0~4的整數；f為0~5的整數；c為1~12的整數；m為0~2的整數)。 The retardation film according to claim 1, wherein the photosensitive side chain is a group represented by the following formula (16) or (17),
Figure 106129728-A0305-02-0055-59
Figure 106129728-A0305-02-0055-15
 (in the formula, A 1 , X and the dotted line are the same as above; R 1 is -NO 2 , -CN, a halogen atom, an alkyl group with 1 to 5 carbon atoms, or an alkoxy group with 1 to 5 carbon atoms; d is 0~ 4 is an integer; f is an integer from 0 to 5; c is an integer from 1 to 12; m is an integer from 0 to 2). 如請求項1記載的相位差膜，其中，前述感光性側鏈為下述式(18)或(19)所表示之基，
Figure 106129728-A0305-02-0056-16
Figure 106129728-A0305-02-0056-17
 (式中，A1、A2、E、Y1及虛線同前述；R1為-NO2、-CN、鹵素原子、碳數1~5的烷基、或碳數1~5的烷氧基；c為1~12的整數；d為0~4的整數；g為0~5的整數；m1及m2各自獨立，為1~3的整數)。 The retardation film according to claim 1, wherein the photosensitive side chain is a group represented by the following formula (18) or (19),
Figure 106129728-A0305-02-0056-16
Figure 106129728-A0305-02-0056-17
 (In the formula, A 1 , A 2 , E, Y 1 and the dotted line are the same as above; R 1 is -NO 2 , -CN, halogen atom, alkyl group with 1 to 5 carbon atoms, or alkoxy group with 1 to 5 carbon atoms base; c is an integer from 1 to 12; d is an integer from 0 to 4; g is an integer from 0 to 5; m1 and m2 are independently an integer from 1 to 3). 如請求項1記載的相位差膜，其中，前述感光性側鏈為下述式(20)所表示之基，
Figure 106129728-A0305-02-0056-60
 (式中，A1、X、Y1及虛線同前述；R1為-NO2、-CN、鹵素原子、碳數1~5的烷基、或碳數1~5的烷氧基；c為1~12的整數；d為0~4的整數；m為0~2的整數)。 The retardation film according to claim 1, wherein the photosensitive side chain is a group represented by the following formula (20),
Figure 106129728-A0305-02-0056-60
 (In the formula, A 1 , X, Y 1 and the dotted line are the same as above; R 1 is -NO 2 , -CN, halogen atom, alkyl group with 1 to 5 carbon atoms, or alkoxy group with 1 to 5 carbon atoms; c is an integer from 1 to 12; d is an integer from 0 to 4; m is an integer from 0 to 2). 如請求項1~7中任1項記載的相位差膜，其中，前述液 晶性聚合物再含有選自下述式(21)~(35)所表示之基的至少1種之液晶性側鏈，
Figure 106129728-A0305-02-0057-19
Figure 106129728-A0305-02-0057-20
Figure 106129728-A0305-02-0057-21
Figure 106129728-A0305-02-0057-22
Figure 106129728-A0305-02-0057-23
Figure 106129728-A0305-02-0057-24
Figure 106129728-A0305-02-0057-25
Figure 106129728-A0305-02-0058-26
Figure 106129728-A0305-02-0058-27
Figure 106129728-A0305-02-0058-28
Figure 106129728-A0305-02-0058-29
Figure 106129728-A0305-02-0058-30
Figure 106129728-A0305-02-0058-31
Figure 106129728-A0305-02-0058-32
Figure 106129728-A0305-02-0058-34
 (式中，A1及A2各自獨立，為單鍵、-O-、-CH2-、-C(=O)-O-、-O-C(=O)-、-C(=O)-NH-、-NH-C(=O)-、-CH=CH-C(=O)-O-或-O-C(=O)-CH=CH-；E為-C(=O)-O-或-O-C(=O)-；R1為-NO2、-CN、鹵素原子、碳數1~5的烷基、或碳數1~5的烷氧基； R2為氫原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素原子、苯基、萘基、聯苯基、呋喃基、1價的含有含氮雜環之基、碳數5~8的環狀脂肪族烴基、碳數1~12的烷基、或碳數1~12的烷氧基；Y3為苯基、萘基、聯苯基、呋喃基、1價的含有含氮雜環之基、碳數5~8的環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透過連結基A2鍵結而成的基，鍵結於此等之氫原子的一部份可被-NO2、-CN、鹵素原子、碳數1~5的烷基、或碳數1~5的烷氧基取代；Z1及Z2各自獨立，為單鍵、-C(=O)-、-CH2O-、-CH=N-或-CF2-；c為1~12的整數；d為0~4的整數；e為0~6的整數；h為0~5的整數；k各自獨立，為0~2的整數，但在式(25)及(26)中，全部的k之合計為2以上；m1及m2各自獨立，為1~3的整數；m3為1~3的整數)。 The retardation film according to any one of claims 1 to 7, wherein the liquid crystalline polymer further contains at least one liquid crystalline side chain selected from groups represented by the following formulae (21) to (35) ,
Figure 106129728-A0305-02-0057-19
Figure 106129728-A0305-02-0057-20
Figure 106129728-A0305-02-0057-21
Figure 106129728-A0305-02-0057-22
Figure 106129728-A0305-02-0057-23
Figure 106129728-A0305-02-0057-24
Figure 106129728-A0305-02-0057-25
Figure 106129728-A0305-02-0058-26
Figure 106129728-A0305-02-0058-27
Figure 106129728-A0305-02-0058-28
Figure 106129728-A0305-02-0058-29
Figure 106129728-A0305-02-0058-30
Figure 106129728-A0305-02-0058-31
Figure 106129728-A0305-02-0058-32
Figure 106129728-A0305-02-0058-34
 (wherein, A 1 and A 2 are each independently, and are a single bond, -O-, -CH 2 -, -C(=O)-O-, -OC(=O)-, -C(=O)- NH-, -NH-C(=O)-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-; E is -C(=O)-O- or -OC(=O)-; R 1 is -NO 2 , -CN, a halogen atom, an alkyl group with 1 to 5 carbon atoms, or an alkoxy group with 1 to 5 carbon atoms; R 2 is a hydrogen atom, -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen atom, phenyl, naphthyl, biphenyl, furyl, monovalent nitrogen-containing heterocyclic group, carbon number 5-8 cyclic aliphatic hydrocarbon group, carbon number 1-12 alkyl group, or carbon number 1-12 alkoxy group; Y 3 is phenyl, naphthyl, biphenyl, furyl, monovalent containing A nitrogen-containing heterocyclic group, a cyclic aliphatic hydrocarbon group with 5 to 8 carbon atoms, or a group in which 2 to 6 groups selected from such substituents are bonded through the linking group A 2 , and it is bonded here. A part of the hydrogen atoms of the same can be substituted by -NO 2 , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; Z 1 and Z 2 are each independently, and are Single bond, -C(=O)-, -CH 2 O-, -CH=N- or -CF 2 -; c is an integer from 1 to 12; d is an integer from 0 to 4; e is an integer from 0 to 6 Integer; h is an integer of 0 to 5; k is independently an integer of 0 to 2, but in formulas (25) and (26), the sum of all k is 2 or more; m1 and m2 are independently 1 an integer of ~3; m3 is an integer of 1 to 3). 如請求項8記載的相位差膜，其中，前述液晶性聚合物為含有下述式(A)所表示之重複單位及下述式(B)所表示之重複單位者，
Figure 106129728-A0305-02-0060-35
 (式中，RA為選自式(1)~(6)所表示之基的至少1種，RB為選自式(21)~(31)所表示之基的至少1種，MA及MB各自獨立，為來自聚合性基的基)。 The retardation film according to claim 8, wherein the liquid crystalline polymer contains a repeating unit represented by the following formula (A) and a repeating unit represented by the following formula (B),
Figure 106129728-A0305-02-0060-35
 (wherein, R A is at least one selected from the group represented by the formulae (1) to (6), R B is at least one selected from the group represented by the formula (21) to (31), and M A and M B are each independently a group derived from a polymerizable group). 如請求項9記載的相位差膜，其中，前述來自聚合性基的基為選自下述式所表示之基的至少1種，
Figure 106129728-A0305-02-0060-61
 (式中，RC為氫原子、碳數1~3的烷基、羧基或羧基甲基，RD為單鍵、-C(=O)-O-、-C(=O)-NH-或伸苯基，RE為羥基、碳數1~10的烷基或者烷氧基、或苯基，虛線為與RA或RB之鍵結鍵)。 The retardation film according to claim 9, wherein the group derived from the polymerizable group is at least one selected from the group consisting of groups represented by the following formula,
Figure 106129728-A0305-02-0060-61
 (In the formula, R C is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a carboxyl group or a carboxymethyl group, and R D is a single bond, -C(=O)-O-, -C(=O)-NH- or phenyl extension, R E is a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a phenyl group, and the dotted line is a bond with R A or R B ). 如請求項1~7中任1項記載的相位差膜，其中，前述液晶性聚合物表現液晶性的溫度範圍為50~300℃。 The retardation film according to any one of claims 1 to 7, wherein the temperature range in which the liquid crystalline polymer exhibits liquid crystallinity is 50 to 300°C. 一種有機電致發光顯示器，其特徵係具備請求項1~11中任1項記載的相位差膜。 An organic electroluminescence display comprising the retardation film according to any one of claims 1 to 11. 一種具有水蒸氣障壁性的相位差膜之製造方法，其特 徵係含有：將含有含具有感光性側鏈的液晶性聚合物的樹脂成分與有機溶劑的相位差膜形成用組成物塗佈於基材，形成膜厚超過300nm且為50,000nm以下的塗膜之步驟、對前述塗膜照射偏光紫外線之步驟、及將照射過前述偏光紫外線的膜加熱，得到膜厚超過300nm且為50,000nm以下的膜之步驟，前述感光性側鏈為引起光交聯、光異構化或光-弗萊斯重排者，前述感光性側鏈為選自下述式(2)~(6)所表示之基的至少1種，
Figure 106129728-A0305-02-0061-37
Figure 106129728-A0305-02-0061-38
Figure 106129728-A0305-02-0061-39
Figure 106129728-A0305-02-0061-40
Figure 106129728-A0305-02-0061-41
 (式中，A1、A2及A3各自獨立，為單鍵、-O-、-CH2-、-C(=O)-O-、-O-C(=O)-、-C(=O)-NH-、-NH-C(=O)-、 -CH=CH-C(=O)-O-或-O-C(=O)-CH=CH-；T1為可被鹵素原子取代的碳數1~12的伸烷基；T2為單鍵、或可被鹵素原子取代的碳數1~12的伸烷基；Y1為選自苯基、萘基、聯苯基、呋喃基及吡咯基的1價芳香族基、碳數5~8的1價環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透過連結基A2鍵結而成的基，鍵結於此等之氫原子的一部份可被-COOR0(R0為氫原子或碳數1~5的烷基)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素原子、碳數1~5的烷基或碳數1~5的烷氧基取代；Y2為選自伸苯基、萘二基、亞聯苯基、呋喃二基及吡咯二基的2價芳香族基、碳數5~8的2價環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透過連結基A2鍵結而成的基，鍵結於此等之氫原子的一部份可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素原子、碳數1~5的烷基或碳數1~5的烷氧基取代；R為羥基或者碳數1~6的烷氧基、或與Y1同定義；X為單鍵、-C(=O)-O-、-O-C(=O)-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-C(=O)-O-或-O-C(=O)-CH=CH-，X之數為2以上時，各X可為相同亦可為相異；Cou為香豆素-6-基或香豆素-7-基，鍵結於此等之氫原子的一部份可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素原子、碳數1~5的烷基或碳數1~5的烷氧基取代；Q1及Q2各自獨立，為選自伸苯基、萘二基、亞聯苯 基、呋喃二基及吡咯二基的2價芳香族基、碳數5~8的2價環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透過連結基A2鍵結而成的基，但X為-CH=CH-CO-O-或-O-CO-CH=CH-時，-CH=CH-鍵結側之Q1或Q2為2價芳香族基，Q1之數為2以上時，各Q1可為相同亦可為相異，Q2之數為2以上時，各Q2可為相同亦可為相異；E為-C(=O)-O-或-O-C(=O)-；W1及W2各自獨立，為伸苯基、萘二基、亞聯苯基、呋喃二基、吡咯二基、或由此等之取代基所選出的2~6個基透過連結基A2鍵結而成的基；a1為0或1；a2為0~2的整數；a1與a2皆為0且T2為單鍵時，A1為單鍵；a1為1且T2為單鍵時，A2為單鍵；b為0或1；虛線為與主鏈之鍵結鍵)。 A method for producing a retardation film having water vapor barrier properties, comprising: applying a composition for forming a retardation film comprising a resin component containing a liquid crystalline polymer having a photosensitive side chain and an organic solvent on a base material, the steps of forming a coating film with a film thickness exceeding 300 nm and 50,000 nm or less, the step of irradiating the above-mentioned coating film with polarized ultraviolet rays, and heating the film irradiated with the above-mentioned polarized ultraviolet rays to obtain a film thickness exceeding 300 nm and 50,000 nm or less In the step of filming, the photosensitive side chain is one that causes photocrosslinking, photoisomerization or photo-Fries rearrangement, and the photosensitive side chain is selected from the group represented by the following formulas (2) to (6). at least one of the bases,
Figure 106129728-A0305-02-0061-37
Figure 106129728-A0305-02-0061-38
Figure 106129728-A0305-02-0061-39
Figure 106129728-A0305-02-0061-40
Figure 106129728-A0305-02-0061-41
 (In the formula, A 1 , A 2 and A 3 are each independently, and are a single bond, -O-, -CH 2 -, -C(=O)-O-, -OC(=O)-, -C(= O)-NH-, -NH-C(=O)-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-; T 1 can be substituted by halogen atom The alkylene of carbon number 1～12; T 2 is single bond, or the alkylene of carbon number 1～12 that can be substituted by halogen atom; Y 1 is selected from phenyl, naphthyl, biphenyl, furan A monovalent aromatic group of a pyrrolyl group and a pyrrolyl group, a monovalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, or 2 to 6 groups selected from these substituents are bonded through a linking group A 2 A part of the hydrogen atoms bonded to these can be -COOR 0 (R 0 is a hydrogen atom or an alkyl group with 1 to 5 carbon atoms), -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen atom, the alkyl group of carbon number 1～5 or the alkoxy group of carbon number 1～5 is substituted; Y 2 is selected from phenylene, naphthalenediyl, biphenylene, A divalent aromatic group of furandiyl and pyrrole diyl, a divalent cyclic aliphatic hydrocarbon group with 5 to 8 carbon atoms, or 2 to 6 groups selected from such substituents are bonded through a linking group A 2 A part of the hydrogen atoms bonded to these can be formed by -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen atom, carbon number 1~5 The alkyl group or the alkoxy group with the carbon number of 1~5 is substituted; R is the hydroxyl group or the alkoxy group with the carbon number 1~6, or the same definition as Y 1 ; X is a single bond, -C(=O)-O- , -OC(=O)-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or -OC(=O)-CH= CH-, when the number of X is 2 or more, each X may be the same or different; C ou is coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to these A part can be substituted by -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen atom, alkyl group with 1~5 carbon atoms or alkoxy group with 1~5 carbon atoms ; Q 1 and Q 2 are each independently, and are bivalent aromatic groups selected from phenylene, naphthalene diyl, biphenylene, furan diyl and pyrrole diyl, and bivalent cyclic aliphatic groups with 5 to 8 carbon atoms A family of hydrocarbon groups, or a group in which 2 to 6 groups selected from such substituents are bonded through the linking group A 2 , but X is -CH=CH-CO-O- or -O-CO-CH= In the case of CH-, Q 1 or Q 2 on the bonding side of -CH=CH- is a divalent aromatic group, and when the number of Q 1 is 2 or more, each Q 1 may be the same or different, and the number of Q 2 When it is 2 or more, each Q 2 can be the same or different; E is -C(=O)-O- or -OC(=O)-; W 1 and W 2 are each independently and are phenylene, Naphthalenediyl, biphenylene, furandiyl, pyrrolediyl, or 2 to 6 groups selected from such substituents through the linking group A 2 A bonded base; a1 is 0 or 1; a2 is an integer from 0 to 2 ; when both a1 and a2 are 0 and T2 is a single bond, A1 is a single bond; a1 is 1 and T2 is a single bond , A 2 is a single bond; b is 0 or 1; the dotted line is the bond with the main chain). 如請求項13記載的相位差膜之製造方法，其中，前述液晶性聚合物再含有選自下述式(21)~(35)所表示之基的至少1種之液晶性側鏈，
Figure 106129728-A0305-02-0064-42
Figure 106129728-A0305-02-0064-43
Figure 106129728-A0305-02-0064-44
Figure 106129728-A0305-02-0064-45
Figure 106129728-A0305-02-0064-46
Figure 106129728-A0305-02-0064-47
Figure 106129728-A0305-02-0064-48
Figure 106129728-A0305-02-0065-50
Figure 106129728-A0305-02-0065-51
Figure 106129728-A0305-02-0065-52
Figure 106129728-A0305-02-0065-53
Figure 106129728-A0305-02-0065-54
Figure 106129728-A0305-02-0065-55
Figure 106129728-A0305-02-0065-56
Figure 106129728-A0305-02-0065-57
 (式中，A1及A2各自獨立，為單鍵、-O-、-CH2-、-C(=O)-O-、-O-C(=O)-、-C(=O)-NH-、-NH-C(=O)-、-CH=CH-C(=O)-O-或-O-C(=O)-CH=CH-；E為-C(=O)-O-或-O-C(=O)-；R1為-NO2、-CN、鹵素原子、碳數1~5的烷基、或碳數1~5的烷氧基； R2為氫原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素原子、苯基、萘基、聯苯基、呋喃基、1價的含有含氮雜環之基、碳數5~8的環狀脂肪族烴基、碳數1~12的烷基、或碳數1~12的烷氧基；Y3為苯基、萘基、聯苯基、呋喃基、1價的含有含氮雜環之基、碳數5~8的環狀脂肪族烴基、或由此等之取代基所選出的2~6個基透過連結基A2鍵結而成的基，鍵結於此等之氫原子的一部份可被-NO2、-CN、鹵素原子、碳數1~5的烷基、或碳數1~5的烷氧基取代；Z1及Z2各自獨立，為單鍵、-C(=O)-、-CH2O-、-CH=N-或-CF2-；c為1~12的整數；d為0~4的整數；e為0~6的整數；h為0~5的整數；k各自獨立，為0~2的整數，但在式(25)及(26)中，全部的k之合計為2以上；m1及m2各自獨立，為1~3的整數；m3為1~3的整數)。 The method for producing a retardation film according to claim 13, wherein the liquid crystalline polymer further contains at least one liquid crystalline side chain selected from groups represented by the following formulae (21) to (35),
Figure 106129728-A0305-02-0064-42
Figure 106129728-A0305-02-0064-43
Figure 106129728-A0305-02-0064-44
Figure 106129728-A0305-02-0064-45
Figure 106129728-A0305-02-0064-46
Figure 106129728-A0305-02-0064-47
Figure 106129728-A0305-02-0064-48
Figure 106129728-A0305-02-0065-50
Figure 106129728-A0305-02-0065-51
Figure 106129728-A0305-02-0065-52
Figure 106129728-A0305-02-0065-53
Figure 106129728-A0305-02-0065-54
Figure 106129728-A0305-02-0065-55
Figure 106129728-A0305-02-0065-56
Figure 106129728-A0305-02-0065-57
 (wherein, A 1 and A 2 are each independently, and are a single bond, -O-, -CH 2 -, -C(=O)-O-, -OC(=O)-, -C(=O)- NH-, -NH-C(=O)-, -CH=CH-C(=O)-O- or -OC(=O)-CH=CH-; E is -C(=O)-O- or -OC(=O)-; R 1 is -NO 2 , -CN, a halogen atom, an alkyl group with 1 to 5 carbon atoms, or an alkoxy group with 1 to 5 carbon atoms; R 2 is a hydrogen atom, -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH-CN, halogen atom, phenyl, naphthyl, biphenyl, furyl, monovalent nitrogen-containing heterocyclic group, carbon number 5-8 cyclic aliphatic hydrocarbon group, carbon number 1-12 alkyl group, or carbon number 1-12 alkoxy group; Y 3 is phenyl, naphthyl, biphenyl, furyl, monovalent containing A nitrogen-containing heterocyclic group, a cyclic aliphatic hydrocarbon group with 5 to 8 carbon atoms, or a group in which 2 to 6 groups selected from such substituents are bonded through the linking group A 2 , and it is bonded here. A part of the hydrogen atoms of the same can be substituted by -NO 2 , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms; Z 1 and Z 2 are each independently, and are Single bond, -C(=O)-, -CH 2 O-, -CH=N- or -CF 2 -; c is an integer from 1 to 12; d is an integer from 0 to 4; e is an integer from 0 to 6 Integer; h is an integer of 0 to 5; k is independently an integer of 0 to 2, but in formulas (25) and (26), the sum of all k is 2 or more; m1 and m2 are independently 1 an integer of ~3; m3 is an integer of 1 to 3). 如請求項13或14記載的相位差膜之製造方法，其中，前述液晶性聚合物表現液晶性的溫度範圍為50~300℃。 The manufacturing method of the retardation film of Claim 13 or 14 whose temperature range in which the said liquid crystalline polymer expresses liquid crystallinity is 50-300 degreeC.
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