TWI770162B - Liquid crystal alignment film and method for producing the same - Google Patents

Liquid crystal alignment film and method for producing the same Download PDF

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TWI770162B
TWI770162B TW107113322A TW107113322A TWI770162B TW I770162 B TWI770162 B TW I770162B TW 107113322 A TW107113322 A TW 107113322A TW 107113322 A TW107113322 A TW 107113322A TW I770162 B TWI770162 B TW I770162B
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alignment film
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side chain
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鈴木暢
飯田敏行
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日商日東電工股份有限公司
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • G—PHYSICS
    • G02—OPTICS
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    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells

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Abstract

本發明之液晶配向膜含有側鏈型熱致性液晶聚合物、及熱致性液晶化合物之聚合物。側鏈型熱致性液晶聚合物具有含有液晶性片段側鏈之單體單元與含有非液晶性片段側鏈之單體單元。本發明之液晶配向膜之面內之遲相軸方向之折射率nx、面內之進相軸方向之折射率ny、及厚度方向之折射率nz滿足nx＞nz＞ny。NZ＝(nx－nz)/(nx－ny)所表示之NZ係數較佳為0.2～0.8。The liquid crystal alignment film of the present invention contains a side chain type thermotropic liquid crystal polymer and a polymer of a thermotropic liquid crystal compound. The side chain type thermotropic liquid crystal polymer has a monomer unit containing a liquid crystal segment side chain and a monomer unit containing a non-liquid crystal segment side chain. The refractive index nx in the in-plane slow axis direction, the in-plane refractive index ny in the in-plane advancing axis direction, and the refractive index nz in the thickness direction of the liquid crystal alignment film of the present invention satisfy nx>nz>ny. The NZ coefficient represented by NZ=(nx-nz)/(nx-ny) is preferably 0.2 to 0.8.

Description

液晶配向膜及其製造方法Liquid crystal alignment film and method for producing the same

本發明係關於一種液晶配向膜及其製造方法。The present invention relates to a liquid crystal alignment film and a manufacturing method thereof.

為了液晶顯示裝置之光學補償、有機EL(Electroluminescence，電致發光)元件之抗外界光反射等，業界使用有各種具有折射率各向異性之光學膜(相位差膜)。作為相位差膜，通常係將聚合物膜進行延伸而成者。就薄型化或輕量化之觀點而言，業界亦使用有使液晶分子以特定方向進行配向之液晶配向膜。 作為液晶配向膜，已知有於設置有配向膜之基板上，使液晶分子進行水平配向或垂直配向而成者。於專利文獻1中記載有於不具有垂直配向膜之基板上，自發地進行垂直配向之液晶性組合物。 關於厚度方向之折射率nz為面內之遲相軸方向之折射率nx與進相軸方向之折射率ny之中間值的相位差膜，由視認方向之變化所引起之延遲之變化較小，而用於顯示器之視角補償等。為了以1片膜實現nx＞nz＞ny之折射率各向異性，必須於膜內使分子沿面內方向與厚度方向配向。 對於聚合物膜，藉由將熱收縮性膜貼合於兩面，並以利用熱收縮性膜之收縮力使聚合物膜於厚度方向上膨脹之方式進行延伸之方法，可獲得具有nx＞nz＞ny之折射率各向異性之相位差膜。另一方面，不易使液晶分子沿多方向配向。具有nx＞nz＞ny之折射率各向異性之液晶配向膜僅為積層有複數個液晶配向膜之例(例如專利文獻2)、或使用有複數種向液性液晶化合物之例(例如專利文獻3)等。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利第4174192號 [專利文獻2]日本專利特開2008-122851號公報 [專利文獻3]WO2011/138869號說明書Various optical films (retardation films) with refractive index anisotropy are used in the industry for optical compensation of liquid crystal display devices, anti-reflection of external light of organic EL (Electroluminescence) elements, etc. The retardation film is usually obtained by extending a polymer film. From the viewpoint of thinning or weight reduction, a liquid crystal alignment film that aligns liquid crystal molecules in a specific direction is also used in the industry. As a liquid crystal alignment film, a liquid crystal molecule is known to be horizontally aligned or vertically aligned on a substrate on which the alignment film is provided. Patent Document 1 describes a liquid crystalline composition that spontaneously performs vertical alignment on a substrate without a vertical alignment film. Regarding the retardation film in which the refractive index nz in the thickness direction is the intermediate value of the refractive index nx in the in-plane slow axis direction and the refractive index ny in the advance axis direction, the change in retardation caused by the change in the visual direction is small, It is used for viewing angle compensation of displays, etc. In order to realize the refractive index anisotropy of nx>nz>ny with one film, it is necessary to align the molecules in the in-plane direction and the thickness direction in the film. For the polymer film, a method of attaching a heat-shrinkable film to both sides and extending the polymer film in the thickness direction using the shrinkage force of the heat-shrinkable film can obtain a method with nx>nz> A retardation film with refractive index anisotropy of ny. On the other hand, it is difficult to align liquid crystal molecules in multiple directions. The liquid crystal alignment film with the refractive index anisotropy of nx>nz>ny is only an example in which a plurality of liquid crystal alignment films are laminated (for example, Patent Document 2), or an example in which a plurality of liquid tropic liquid crystal compounds are used (for example, in Patent Document 2) 3) etc. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent No. 4174192 [Patent Document 2] Japanese Patent Laid-Open No. 2008-122851 [Patent Document 3] Specification No. WO2011/138869

[發明所欲解決之問題] 本發明之目的在於提供一種可實現薄型化且控制了折射率各向異性之液晶配向膜。 [解決問題之技術手段] 本發明係關於一種含有側鏈型熱致性液晶聚合物、及熱致性液晶化合物之聚合物之液晶配向膜。側鏈型熱致性液晶聚合物可較佳地使用具有含有液晶性片段側鏈之單體單元與含有非液晶性片段側鏈之單體單元者。熱致性液晶化合物之聚合物之含量較佳為側鏈型熱致性液晶聚合物之含量之1.2～20倍。 本發明之液晶配向膜之一實施形態中，面內之遲相軸方向之折射率nx、面內之進相軸方向之折射率ny、及厚度方向之折射率nz滿足nx＞nz＞ny。較佳為NZ＝(nx－nz)/(nx－ny)所表示之NZ係數為0.2～0.8。 液晶配向膜可藉由在未設置垂直配向膜之膜基板上，塗佈含有側鏈型熱致性液晶聚合物及光聚合性之熱致性液晶化合物之液晶性組合物(塗佈步驟)、對側鏈型熱致性液晶聚合物及熱致性液晶化合物進行加熱而使之配向(液晶配向步驟)、藉由光照射使熱致性液晶化合物進行聚合或交聯(光聚合步驟)而製作。 於本發明中，作為膜基板可使用延伸膜。用作膜基板之延伸膜之面內延遲例如較佳為10～1000 nm。有膜基板之面內延遲及面內雙折射越大，液晶配向膜之NZ係數越增大(接近1)之傾向。作為膜基板，例如可使用降𦯉烯系聚合物膜。 有利用加熱之液晶配向時之加熱溫度越高，液晶分子之水平配向性越增高，液晶配向膜之NZ係數越增大之傾向。較佳為液晶配向時之加熱溫度T(℃)與膜基板之面內雙折射Δn滿足T≧90－5×103 Δn。藉由將加熱溫度T調整為該範圍，容易獲得NZ係數大於0之液晶配向膜。 [發明之效果] 根據本發明，可獲得控制了折射率各向異性之液晶配向膜。THE PROBLEM TO BE SOLVED BY THE INVENTION The objective of this invention is to provide the liquid crystal alignment film which can realize thinning and control the anisotropy of refractive index. [Technical Means for Solving the Problem] The present invention relates to a liquid crystal alignment film containing a side chain type thermotropic liquid crystal polymer and a polymer of a thermotropic liquid crystal compound. The side chain type thermotropic liquid crystal polymer having a monomer unit containing a liquid crystal segment side chain and a monomer unit containing a non-liquid crystal segment side chain can be preferably used. The content of the polymer of the thermotropic liquid crystal compound is preferably 1.2 to 20 times the content of the side chain type thermotropic liquid crystal polymer. In one embodiment of the liquid crystal alignment film of the present invention, the refractive index nx in the in-plane slow axis direction, the in-plane refractive index ny in the advancing axis direction, and the refractive index nz in the thickness direction satisfy nx>nz>ny. Preferably, the NZ coefficient represented by NZ=(nx-nz)/(nx-ny) is 0.2 to 0.8. The liquid crystal alignment film can be prepared by coating a liquid crystal composition containing a side chain type thermotropic liquid crystal polymer and a photopolymerizable thermotropic liquid crystal compound on a film substrate without a vertical alignment film (coating step), The side chain type thermotropic liquid crystal polymer and the thermotropic liquid crystal compound are heated and aligned (liquid crystal alignment step), and the thermotropic liquid crystal compound is polymerized or crosslinked by light irradiation (photopolymerization step) . In the present invention, a stretched film can be used as the film substrate. The in-plane retardation of the stretched film used as the film substrate is preferably, for example, 10 to 1000 nm. The larger the in-plane retardation and in-plane birefringence of the film substrate, the higher the NZ coefficient of the liquid crystal alignment film (closer to 1). As the film substrate, for example, a noralkene-based polymer film can be used. There is a tendency that the higher the heating temperature during the liquid crystal alignment by heating, the higher the horizontal alignment of the liquid crystal molecules, and the higher the NZ coefficient of the liquid crystal alignment film. Preferably, the heating temperature T (° C.) during liquid crystal alignment and the in-plane birefringence Δn of the film substrate satisfy T≧90-5×10 3 Δn. By adjusting the heating temperature T to this range, it is easy to obtain a liquid crystal alignment film with a NZ coefficient greater than 0. [Effect of the Invention] According to the present invention, a liquid crystal alignment film whose refractive index anisotropy is controlled can be obtained.

本發明之液晶配向膜含有側鏈型液晶聚合物與液晶化合物之聚合物。側鏈型液晶聚合物及液晶化合物(光聚合性液晶單體)均顯示出熱致性液晶性。液晶配向膜係藉由將包含液晶聚合物與液晶單體之液晶性組合物塗佈於基板上，並使其配向固定而製作。 [液晶性組合物] 液晶配向膜之製作中所使用之液晶性組合物包含側鏈型熱致性液晶聚合物、及光聚合性之熱致性液晶化合物(單體)。 ＜側鏈型液晶聚合物＞ 作為側鏈型熱致性液晶聚合物，可使用具有含有熱致性液晶性片段側鏈之單體單元與含有非液晶性片段側鏈之單體單元之共聚物。藉由聚合物於側鏈具有熱致性液晶性片段，於將液晶性組合物加熱至特定溫度時，側鏈型液晶聚合物進行配向。又，藉由側鏈型聚合物於側鏈具有非液晶性片段，非液晶性片段與光聚合性液晶單體相互作用，而產生使光聚合性液晶單體進行垂直配向之作用。 作為具有液晶性片段側鏈之單體，可列舉具有包含液晶原基之向列型液晶性之取代基之聚合性化合物。作為液晶原基，可列舉：聯苯基、苯基苯甲酸酯基、苯基環己烷基、氧化偶氮苯基、次甲基偶氮基、偶氮苯基、苯基嘧啶基、二苯基乙炔基、二苯基苯甲酸酯基、雙環己烷基、環己基苯基、聯三苯基等環狀結構。該等環狀單元之末端亦可具有氰基、烷基、烷氧基、鹵基等取代基。其中，作為液晶原基，較佳為具有聯苯基、苯基苯甲酸酯基者。 作為具有非液晶性片段側鏈之單體，可列舉具有碳數7以上之長鏈烷基等直鏈狀之取代基之聚合性化合物。作為液晶性單體及非液晶性單體之聚合性官能基，例如可列舉(甲基)丙烯醯基。 作為側鏈型熱致性液晶聚合物，可較佳地使用具有通式(I)所表示之液晶性單體單元與通式(II)所表示之非液晶性單體單元之共聚物。 [化1]

Figure 02_image001
[化2]
Figure 02_image003
於式(I)中，R1 為氫原子或甲基，R2 為氰基、氟基、碳數1～6之烷基、或碳數1～6之烷氧基，X1 為-CO2 -或-OCO-。a為1～6之整數，b及c分別獨立地為1或2。 於式(II)中，R3 為氫原子或甲基，R4 為碳數7～22之烷基、碳數1～22之氟烷基、或下述通式(III)所表示之基。 [化3]
Figure 02_image005
於式(III)中，R5 為碳數1～5之烷基，d為1～6之整數。 側鏈型液晶聚合物中之液晶性單體單元與非液晶性單體單元之比率並無特別限定，於非液晶性單體單元之比率較少之情形時，有伴隨側鏈型液晶聚合物之配向之光聚合性液晶單體之配向變得不充分之傾向，於液晶性單體單元之比率較少之情形時，側鏈型液晶聚合物不易顯示出液晶單域配向性。因此，非液晶性單體相對於液晶性單體單元與非液晶性單體單元之合計之比率以莫耳比計較佳為0.05～0.8，更佳為0.1～0.6，進而較佳為0.15～0.5。就同時實現液晶性組合物之成膜性與配向性之觀點而言，側鏈型液晶聚合物之重量平均分子量較佳為2000～100000左右，更佳為2500～50000左右。 側鏈型液晶聚合物可藉由各種公知之方法進行聚合。例如，於單體單元具有(甲基)丙烯醯基作為聚合性官能基之情形時，藉由利用光或熱之自由基聚合，可獲得具有液晶性片段及非液晶性片段之側鏈型液晶聚合物。 ＜光聚合性熱致性液晶單體＞ 光聚合性熱致性液晶單體於1分子中具有液晶原基與至少1個光聚合性官能基。作為液晶原基，可列舉上文作為側鏈型液晶聚合物之液晶性片段所述者。作為光聚合性官能基，可列舉：(甲基)丙烯醯基、環氧基、乙烯醚基等。其中，較佳為(甲基)丙烯醯基。 光聚合性液晶單體較佳為於1分子中具有2個以上之光聚合性官能基者。藉由使用包含2個以上之光聚合性官能基之液晶單體，而向光聚合後之液晶層中導入交聯結構，故而有液晶配向膜之耐久性提高之傾向。 作為於1分子中具有液晶原基與複數個(甲基)丙烯醯基之光聚合性液晶化合物，例如可列舉下述通式(IV)所表示之化合物。 [化4]
Figure 02_image007
於式(IV)中，R為氫原子或甲基，A及D分別獨立地為1,4-伸苯基或1,4-伸環己基，B為1,4-伸苯基、1,4-伸環己基、4,4'-伸聯苯基或4,4'-伸聯環己基，Y及Z分別獨立地為-COO-、-OCO-或-O-。g及h分別獨立地為2～6之整數。 作為上述通式(IV)所表示之光聚合性液晶單體之市售品，可例示BASF公司製造之「Paliocolor LC242」。 ＜組成＞ 液晶性組合物中之光聚合性液晶化合物與側鏈型液晶聚合物之比率並無特別限制。於側鏈型液晶聚合物之含量較多之情形時，由與聚合物之相互作用引起之垂直配向佔優勢，而有(nx－nz)/(nx－ny)所表示之NZ係數減小之傾向。另一方面，於光聚合性液晶化合物之含量較多之情形時，由基板之配向限制力所引起之液晶化合物之水平配向佔優勢，而有(nx－nz)/(nx－ny)所表示之NZ係數增大之傾向。為了獲得NZ係數為0.2～0.8之範圍之液晶配向膜，較佳為光聚合性液晶化合物之含量為側鏈型液晶聚合物之含量之1.2～20倍。為了獲得NZ係數接近0.5之液晶配向膜，光聚合性液晶化合物之含量較佳為側鏈型液晶聚合物之含量之1.3～10倍，更佳為1.4～9倍，進而較佳為1.5～8倍。 為了促進利用光照射之光聚合性液晶化合物之硬化，液晶性組合物較佳為含有光聚合起始劑。作為光聚合起始劑，例如可例示：BASF公司製造之Irgacure 907、Irgacure 184、Irgacure 651、Irgacure 369等。關於液晶性組合物中之光聚合起始劑之含量，相對於光聚合性液晶化合物100重量份，通常為0.5～20重量份左右，較佳為3～15重量份左右，更佳為5～10重量份左右。 藉由將側鏈型液晶聚合物、光聚合性液晶化合物及光聚合起始劑與溶劑混合，可製備液晶性組合物。溶劑只要係可溶解側鏈型液晶聚合物及光聚合性液晶化合物，且不會侵蝕膜基板(或侵蝕性較低)者，則並無特別限定，可列舉：氯仿、二氯甲烷、四氯化碳、二氯乙烷、四氯乙烷、三氯乙烯、四氯乙烯、氯苯、鄰二氯苯等鹵化烴類；苯酚、對氯苯酚等酚類；苯、甲苯、二甲苯、甲氧基苯、1,2-二甲氧基苯等芳香族烴類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮、環戊酮、2-吡咯啶酮、N-甲基-2-吡咯啶酮等酮系溶劑；乙酸乙酯、乙酸丁酯等酯系溶劑；第三丁醇、甘油、乙二醇、三乙二醇、乙二醇單甲醚、二乙二醇二甲醚、丙二醇、二丙二醇、2-甲基-2,4-戊二醇等醇系溶劑；二甲基甲醯胺、二甲基乙醯胺等醯胺系溶劑；乙腈、丁腈等腈系溶劑；二乙醚、二丁醚、四氫呋喃等醚系溶劑；乙基賽路蘇、丁基賽路蘇等。液晶性組合物之濃度通常為3～50重量%左右，較佳為7～35重量%左右。 [膜基板] 為了獲得具有nx＞nz＞ny之折射率各向異性之液晶配向膜，作為供塗佈液晶性組合物之基板，較佳為使用未設置垂直配向膜之延伸膜。藉由使用延伸膜基板，於光聚合性液晶化合物中，發揮由與側鏈型液晶聚合物之相互作用所引起之垂直配向作用、及由構成延伸膜基板之聚合物之分子配向所引起之水平配向作用。藉由使該等配向作用達到平衡，可調整光聚合性液晶化合物之配向，而控制液晶配向膜之折射率各向異性。 用作膜基板之延伸膜之面內延遲R0 通常為10 nm以上。有膜基板之面內延遲越大，構成膜之聚合物沿特定方向(遲相軸方向或進相軸方向)之配向性越大，伴隨其形成於膜基板上之液晶配向層之水平配向性越增大，NZ係數越增大(接近1)之傾向。於延伸膜之面內延遲過大之情形時，有不易控制液晶分子之配向性之傾向，故而延伸膜之面內延遲R0 較佳為1000 nm以下，更佳為500 nm以下，進而較佳為400 nm以下。 膜基板之厚度並無特別限定，若考慮處理性等，則通常為10～200 μm左右。延伸膜之面內雙折射Δn(將面內延遲R0 除以厚度而得之值)較佳為0.0001～0.05，更佳為0.0005～0.03，進而較佳為0.001～0.02。 構成膜基板之樹脂材料只要不溶解於液晶性組合物之溶劑中，且具有用以使液晶性組合物配向之加熱時之耐熱性，則並無特別限制，可列舉：聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯；聚乙烯、聚丙烯等聚烯烴；降𦯉烯系聚合物等環狀聚烯烴；二乙醯纖維素、三乙醯纖維素等纖維素系聚合物；丙烯酸系聚合物；苯乙烯系聚合物；聚碳酸酯、聚醯胺、聚醯亞胺等。其中，就容易獲得成形時之流動性優異，且平滑性較高之膜之方面而言，尤佳為使用降𦯉烯系聚合物膜作為膜基板。就將液晶配向膜轉印至其他基材等時之剝離性優異之方面而言，亦較佳為降𦯉烯系聚合物膜。作為降𦯉烯系聚合物，可列舉：日本Zeon製造之Zeonor、Zeonex、JSR製造之Arton等。 膜基板具有第一主面及第二主面，且於第一主面上塗佈液晶性組合物。膜基板之第一主面之算術平均粗糙度Ra較佳為3 nm以下，更佳為2 nm以下，進而較佳為1.5 nm以下。藉由在Ra較小而平滑性較高之膜基板面塗佈液晶性組合物，有液晶配向膜之配向缺陷減少之傾向。 藉由將膜進行延伸，使成膜時之模線等凹凸平滑化，故而有膜基板之Ra減小之傾向。因此，藉由使用延伸膜基板，可控制液晶配向膜之折射率各向異性，除此以外，有配向缺陷減少之傾向。就表面之均一性較高之方面而言，尤佳為使用雙軸延伸膜作為膜基板。 為了將算術平均粗糙度設為上述範圍，膜基板較佳為於內部不含填料者。不含填料而表面之平滑性較高之膜由於滑動性較低，故而存在產生黏連，或產生卷對卷製程中之搬送不良或捲繞不良之情形。為了防止由高平滑性所引起之黏連或搬送不良等，可列舉於膜基板貼合滑動性較高之其他膜之方法、或於膜基板設置易滑層之方法。於膜基板貼合其他膜之情形時，就抑制由接著層等向第一主面(供塗佈液晶性組合物之面)之轉印所引起之不良情況(液晶之配向不良或光學缺陷等)之觀點而言，較佳為貼合於第二主面(與液晶性組合物之塗佈面相反之側之面)。其中，於卷對卷製程中，於膜基板之捲取時，附著於第二主面之黏著劑等轉移至第一主面，而有可能導致配向不良或光學之缺陷。 因此，較佳為藉由在膜基板之至少一面設置易滑層，而改善滑動性。作為易滑層，例如可列舉於聚酯、聚胺基甲酸酯等黏合劑中含有平均粒徑為100 nm以下之微小填料者。就維持將垂直配向液晶膜轉印至其他基材等時之剝離性，且抑制自膜基板剝離時易滑層向垂直配向液晶膜之轉印等不良情況之觀點而言，膜基板較佳為於供塗佈液晶性組合物之面不具有易滑層。即，較佳為使用於第二主面具有易滑層，且於第一主面不具有易滑層之膜基板。 [於膜基板上之液晶配向膜之形成] 於膜基板上塗佈液晶性組合物，藉由加熱形成為液晶狀態而使液晶性分子配向，其後藉由冷卻使配向固定化，並藉由光照射使液晶單體進行聚合或交聯，藉此可獲得液晶配向膜。因此，液晶配向膜含有液晶聚合物與液晶化合物之聚合物。 於膜基板上塗佈液晶性組合物之方法並無特別限定，可採用旋轉塗佈、模嘴塗佈、接觸輥式塗佈、凹版塗佈、反向塗佈、噴塗、邁耶棒式塗佈、輥刀塗佈、氣刀塗佈等。於塗佈溶液後，去除溶劑，藉此於膜基板上形成液晶性組合物層。塗佈厚度較佳為以使溶劑乾燥後之液晶性組合物層之厚度(液晶配向膜之厚度)成為0.5～5 μm左右之方式加以調整。液晶配向膜之面內延遲係由面內雙折射(nx－ny)與厚度之積所表示，故而厚度越大，面內延遲越增大。又，如於下述實驗例中顯示結果般，有塗佈厚度越大，液晶配向膜之NZ係數越增大之傾向。 藉由對形成於膜基板上之液晶性組合物層進行加熱而成為液晶相，側鏈型液晶聚合物進行垂直配向。此時，藉由與側鏈型液晶聚合物之非液晶性片段之相互作用，於光聚合性液晶化合物中產生垂直配向作用。於使用無延伸膜基板之情形時，基板之配向限制力未起作用，故而側鏈型液晶聚合物與光聚合性液晶化合物之兩者進行垂直配向，而形成垂直配向液晶層。另一方面，於使用延伸膜基板之情形時，根據加熱溫度而液晶配向膜之折射率各向異性有所不同，有溫度越高，厚度方向之折射率nz越減小，(nx－nz)/(nx－ny)所表示之NZ係數越增大之傾向。 可認為加熱溫度越高則厚度方向之折射率nz越減小係由根據加熱溫度，光聚合性液晶化合物之配向行為有所不同所導致。即，可認為於加熱溫度較低之情形時，液晶單體之非液晶片段與光聚合性液晶化合物之相互作用較強，光聚合性液晶化合物中垂直配向佔優勢，相對於此，隨著加熱溫度增高，延伸膜基板之配向限制力之影響增強，光聚合性液晶化合物中水平配向佔優勢。作為溫度越高則膜基板之配向限制力之影響越增大之一個原因，可認為於高溫下，聚合性液晶化合物進行各向同性相轉移，藉由冷卻恢復至液晶相時容易受到膜基板之配向限制力之影響。 於本發明中，藉由利用上述見解，可控制液晶性組合物之配向，製作厚度方向之折射率nz具有面內之遲相軸方向之折射率nx與進相軸方向之折射率ny之中間值(NZ係數大於0且小於1)之液晶配向膜。 於使用延伸膜基板之情形時，除加熱溫度以外，液晶性組合物之組成、或延伸膜基板之面內延遲及面內雙折射亦會對液晶配向膜之折射率各向異性造成影響。因此，無法將於延伸膜基板上塗佈液晶性組合物後使液晶性化合物配向時之適當之溫度範圍一概而定，用於獲得NZ係數大於0之液晶配向膜之加熱溫度T較佳為70℃以上，更佳為75℃以上，進而較佳為80℃以上。又，加熱溫度T(℃)與膜基板之面內雙折射Δn較佳為滿足T≧90－5×103 Δn。加熱溫度T(℃)更佳為95－5×103 Δn以上，更佳為100－5×103 Δn以上，進而較佳為105－5×103 Δn以上。 於液晶分子均勻地進行水平配向之情形時，液晶配向膜成為nx＞nz＝ny(NZ＝1)之正A板。用於使垂直配向成分與水平配向成分共存，而獲得nz＞ny(NZ＜1)之液晶配向膜之加熱溫度T較佳為150℃以下，更佳為140℃以下，進而較佳為130℃以下。又，較佳為加熱溫度T(℃)與膜基板之面內雙折射Δn滿足T≦150－3×103 Δn。加熱溫度T(℃)更佳為140－3×103 Δn以下，更佳為135－3×103 Δn以下，進而較佳為130－3×103 Δn以下。 就與上述同樣之觀點而言，為了獲得NZ係數大於0且小於1之液晶配向膜，加熱溫度T(℃)較佳為(90－0.1×R0 )～(150－0.06×R0 )，更佳為(95－0.1×R0 )～(140－0.06×R0 )，進而較佳為(100－0.1×R0 )～(135－0.06×R0 )，尤佳為(105－0.1×R0 )～(130－0.06×R0 )。R0 為延伸膜基材之面內延遲(nm)。 於對液晶性組合物層進行加熱後，冷卻至液晶聚合物之玻璃轉移溫度以下之溫度，藉此使液晶性化合物之配向固定。冷卻方法並無特別限定，例如，只要自加熱氛圍中取出至室溫下即可。亦可進行空氣冷卻、水冷等強制冷卻。 對配向經固定之液晶性組合物層進行光照射，使光聚合性液晶化合物進行聚合或交聯，藉此使光聚合性液晶化合物之配向固定，液晶配向膜之耐久性提高。作為所照射之光，只要選擇光聚合起始劑發生裂解之波長之光即可，通常可使用紫外線。為了促進光聚合反應，光照射較佳為於氮氣等惰性氣體氛圍下進行。 [液晶配向膜之特性及用途] 藉由上述而獲得之液晶配向膜具有nx＞nz＞ny之折射率各向異性，可用作以視角補償等為目的之顯示器用光學膜。液晶配向膜之面內延遲例如為50～500 nm。於本發明中，藉由調整液晶性組合物之組成、延伸膜基材之面內延遲及面內雙折射、液晶性組合物之塗佈厚度、以及液晶配向時之加熱溫度等，可獲得具有所需之延遲及NZ係數之液晶配向膜。根據本發明，僅藉由使用相同之膜基板及液晶性組合物，調整液晶配向時之加熱溫度，可製作具有各種正面延遲或NZ係數之液晶配向膜，故而可提高生產性，對小批量生產等之應對亦較容易。 為了減小由視認方向所引起之延遲之變化，液晶配向膜之NZ係數較佳為0.2～0.8，更佳為0.3～0.7，進而較佳為0.4～0.6，尤佳為0.45～0.55。 液晶配向膜之面內延遲Ro及NZ係數之較佳之範圍根據使用目的等而有所不同。例如，於Ro為200～350 nm，NZ係數為0.4～0.6之情形時，適合作為由視認方向所引起之延遲之變化較少之λ/2相位差板，可適宜地用於IPS(In-Plane Switching，橫向電場效應)液晶顯示裝置之視角補償膜等。於Ro為120～170 nm，NZ係數為0.4～0.6之情形時，適合作為由視認方向所引起之延遲之變化較少之λ/4相位差板，藉由與偏光板積層，可獲得廣視角圓偏光板。廣視角圓偏光板可適宜地用於OLED(Organic Light Emitting Diode，有機發光二極體)之抗外界光反射膜等。 液晶配向膜可於與膜基板積層之狀態下使用，亦可自膜基板剝離而使用。液晶配向膜亦可自膜基板剝離，並與相位差膜、偏光板、玻璃等基材積層而使用。 [實施例] 以下，列舉液晶配向膜之製作例更詳細地說明本發明，但本發明並不限定於下述例。 [評價方法] (算術平均粗糙度) 根據使用掃描式探針顯微鏡(AFM)之1 μm見方之AFM觀察圖像，求出算術平均粗糙度。 (延遲) 延遲之測定係使用偏光相位差測定系統(Axometrics製造 製品名「AxoScan」)，於23℃之環境下，測定波長590 nm之值。液晶配向膜之延遲之測定係使用於在表面設置有黏著劑之玻璃板之黏著劑附設面上轉印有液晶配向膜之樣品，測定面內延遲R0 、及40°傾斜時之延遲，並根據該等測定值，將液晶配向膜之平均折射率設為1.52而算出折射率nx、ny、nz，並求出NZ＝(nx－nz)/(nx－ny)。 [液晶性組合物1～8之製備] 使下述化學式(為n＝0.35，為了便於說明而利用嵌段聚合物體表示)之重量平均分子量5000之側鏈型液晶聚合物與顯示熱致性向列型液晶相之聚合性液晶單體(BASF製造之「Paliocolor LC242」)合計100重量份、及光聚合起始劑(BASF製造之「Irgacure 907」)5重量份溶解於環戊酮400重量份中而製備液晶性組合物。如表1所示，將聚合物與單體之比變更為100/0～20/80之比，而製成液晶性組合物1～8。 [化5]
Figure 02_image009
[液晶性組合物9之製備] 使具有下述化學式所表示之重複單元之重量平均分子量5000之側鏈型液晶聚合物50重量份、BASF製造之「Paliocolor LC242」50重量份、及BASF製造之「Irgacure 907」5重量份溶解於環戊酮400重量份中而製備液晶性組合物9。 [化6]
Figure 02_image011
[實驗例1] 於在一面具有易滑層之雙軸延伸降𦯉烯系膜(日本Zeon製造之「Zeonor Film」、厚度：52 μm、面內延遲：50 nm、未形成易滑層之面之算術平均粗糙度：1.2 nm)之未形成易滑層之面，使用邁耶棒(＃4)塗佈上述液晶性組合物1～9，並於100℃下加熱2分鐘而使液晶配向。其後，冷卻至室溫而使配向固定，並於氮氣氛圍下照射700 mJ/cm2 之紫外線，使液晶單體進行光硬化，而製作液晶配向膜。 [實驗例2、3] 於實驗例2中使用＃8之邁耶棒，於實驗例3中使用＃12之邁耶棒，除此以外，以與實驗例1同樣之方式，實施液晶性組合物1～8之塗佈、加熱、冷卻及光硬化，而製作液晶配向膜。 [實驗例4] 於在一面具有易滑層之雙軸延伸降𦯉烯系膜(日本Zeon製造之「Zeonor Film」、厚度：34 μm、面內延遲：270 nm、未形成易滑層之面之算術平均粗糙度：0.9 nm)之未形成易滑層之面，使用＃12之邁耶棒輥塗佈液晶性組合物1～8，以與實驗例3同樣之方式製作液晶配向膜。 [實驗例5] 於未延伸之降𦯉烯系膜(日本Zeon製造之「Zeonor Film」、厚度：34 μm、面內延遲：0 nm、算術平均粗糙度2.3 nm)，使用＃12之邁耶棒輥塗佈液晶性組合物4，以與實驗例3同樣之方式製作液晶配向膜。 將實驗例1～5中所使用之基材之面內延遲R0 、液晶配向膜之厚度、及液晶配向膜之延遲之測定結果(面內延遲R0 及NZ)示於表1。 [表1]
Figure 107113322-A0304-0001
 [實驗例6～8] 於與實驗例1～3同樣之面內延遲為50 nm之雙軸延伸膜上，使用＃12之邁耶棒，塗佈液晶性組合物4(聚合物/單體之比為80/20)，並將其後之加熱溫度於70～120℃之範圍內變更。除此以外，以與實驗例3同樣之方式，製作液晶配向膜。將實驗例6～8之加熱溫度、及液晶配向膜之延遲之測定結果與實驗例3之結果(再次揭示)一併示於表2。 [表2]
Figure 107113322-A0304-0002
 於表1中，於將液晶性組合物中之熱致性液晶化合物之比率較小之液晶性組合物7、8塗佈於延伸膜基板上之情形時，於實驗例1～4中之任一者中，所獲得之液晶配向膜均為面內延遲R0 大致為0且NZ係數為負之正C板。於實驗例1～4中，可見隨著熱致性液晶化合物之比率增加，液晶配向膜之R0 增大，伴隨其而NZ係數增大之傾向。另一方面，於使用無延伸膜之實驗例5中，於熱致性液晶化合物之比率較大之情形時(單體/聚合物＝80/20)，液晶配向膜之R0 亦大致為0。 若對比實驗例1～3，則於使用相同之液晶性組合物之情形時，亦可見塗佈厚度越增大，液晶配向膜之NZ越增大之傾向。根據實驗例3與實驗例4之對比可知，延伸基板膜之面內雙折射越大，水平配向成分越增加，液晶配向膜之NZ係數越增大。 根據表2所示之結果可知，於使用相同之液晶性組合物之情形時，亦塗佈液晶性組合物後之加熱溫度越高，液晶配向膜之NZ係數越增大。 根據以上之結果可知，藉由調整於延伸膜基板上塗佈包含側鏈型熱致性液晶聚合物與熱致性液晶化合物之液晶性組合物後之加熱溫度等，可控制液晶配向膜之折射率各向異性。即，可知根據本發明，藉由調整液晶性組合物之組成、塗佈液晶性組合物之基板之面內延遲(面內雙折射)、塗佈厚度、及加熱溫度等，可獲得具有各種面內延遲及NZ係數之液晶配向膜。The liquid crystal alignment film of the present invention contains a side chain type liquid crystal polymer and a polymer of a liquid crystal compound. Both the side chain type liquid crystal polymer and the liquid crystal compound (photopolymerizable liquid crystal monomer) exhibit thermotropic liquid crystallinity. The liquid crystal alignment film is produced by coating a liquid crystal composition containing a liquid crystal polymer and a liquid crystal monomer on a substrate and fixing the alignment. [Liquid Crystal Composition] The liquid crystal composition used for the production of the liquid crystal alignment film contains a side chain type thermotropic liquid crystal polymer and a photopolymerizable thermotropic liquid crystal compound (monomer). <Side chain type liquid crystal polymer> As the side chain type thermotropic liquid crystal polymer, a copolymer having a monomer unit containing a side chain of a thermotropic liquid crystal segment and a monomer unit containing a side chain of a non-liquid crystal segment can be used . Since the polymer has a thermotropic liquid crystal segment in the side chain, when the liquid crystal composition is heated to a specific temperature, the side chain type liquid crystal polymer is aligned. Moreover, since the side chain type polymer has a non-liquid crystalline segment in the side chain, the non-liquid crystalline segment interacts with the photopolymerizable liquid crystal monomer, thereby producing the effect of vertically aligning the photopolymerizable liquid crystal monomer. As a monomer which has a liquid crystal segment side chain, the polymerizable compound which has a substituent which has a nematic liquid crystallinity containing a mesogen group is mentioned. As mesogen groups, biphenyl group, phenyl benzoate group, phenylcyclohexane group, azophenyl oxide group, methineazo group, azophenyl group, phenylpyrimidinyl group, Diphenylethynyl, diphenylbenzoate, bicyclohexyl, cyclohexylphenyl, triphenyl and other cyclic structures. The terminal of these cyclic units may also have substituents such as a cyano group, an alkyl group, an alkoxy group, and a halogen group. Among them, as the mesogen group, those having a biphenyl group and a phenylbenzoate group are preferable. As a monomer which has a non-liquid crystal segment side chain, the polymerizable compound which has linear substituents, such as a long-chain alkyl group with a carbon number of 7 or more, is mentioned. As a polymerizable functional group of a liquid crystalline monomer and a non-liquid crystalline monomer, a (meth)acryloyl group is mentioned, for example. As the side chain type thermotropic liquid crystal polymer, a copolymer having a liquid crystal monomer unit represented by the general formula (I) and a non-liquid crystal monomer unit represented by the general formula (II) can be preferably used. [hua 1]
Figure 02_image001
[hua 2]
Figure 02_image003
In formula (I), R 1 is a hydrogen atom or a methyl group, R 2 is a cyano group, a fluoro group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and X 1 is -CO 2 - or -OCO-. a is an integer of 1 to 6, and b and c are each independently 1 or 2. In formula (II), R 3 is a hydrogen atom or a methyl group, and R 4 is an alkyl group having 7 to 22 carbon atoms, a fluoroalkyl group having 1 to 22 carbon atoms, or a group represented by the following general formula (III) . [hua 3]
Figure 02_image005
In formula (III), R 5 is an alkyl group having 1 to 5 carbon atoms, and d is an integer of 1 to 6. The ratio of the liquid crystalline monomer unit to the non-liquid crystalline monomer unit in the side chain type liquid crystal polymer is not particularly limited. The orientation of the photopolymerizable liquid crystal monomer tends to be insufficient, and when the ratio of the liquid crystal monomer unit is small, the side chain type liquid crystal polymer is less likely to exhibit liquid crystal monodomain alignment. Therefore, the molar ratio of the non-liquid crystalline monomer to the total of the liquid crystalline monomer units and the non-liquid crystalline monomer units is preferably 0.05 to 0.8, more preferably 0.1 to 0.6, still more preferably 0.15 to 0.5 . The weight average molecular weight of the side chain type liquid crystal polymer is preferably about 2,000 to 100,000, more preferably about 2,500 to 50,000, from the viewpoint of simultaneously achieving the film-forming properties and the alignment properties of the liquid crystal composition. The side chain type liquid crystal polymer can be polymerized by various known methods. For example, when the monomer unit has a (meth)acryloyl group as a polymerizable functional group, a side-chain type liquid crystal having a liquid crystal segment and a non-liquid crystal segment can be obtained by radical polymerization using light or heat polymer. <Photopolymerizable thermotropic liquid crystal monomer> The photopolymerizable thermotropic liquid crystal monomer has a mesogen group and at least one photopolymerizable functional group in one molecule. As a mesogen group, what was mentioned above as a liquid crystal segment of a side chain type liquid crystal polymer is mentioned. As a photopolymerizable functional group, a (meth)acryloyl group, an epoxy group, a vinyl ether group, etc. are mentioned. Among them, a (meth)acryloyl group is preferred. The photopolymerizable liquid crystal monomer preferably has two or more photopolymerizable functional groups in one molecule. By using a liquid crystal monomer containing two or more photopolymerizable functional groups, a crosslinked structure is introduced into the liquid crystal layer after photopolymerization, so that the durability of the liquid crystal alignment film tends to improve. As a photopolymerizable liquid crystal compound which has a mesogen group and a plurality of (meth)acryloyl groups in 1 molecule, the compound represented by following general formula (IV) is mentioned, for example. [hua 4]
Figure 02_image007
In formula (IV), R is a hydrogen atom or a methyl group, A and D are each independently 1,4-phenylene or 1,4-cyclohexylene, B is 1,4-phenylene, 1, 4-cyclohexylene, 4,4'-biphenylene or 4,4'-bicyclohexylene, Y and Z are each independently -COO-, -OCO- or -O-. g and h are each independently an integer of 2 to 6. As a commercial item of the photopolymerizable liquid crystal monomer represented by the said general formula (IV), "Paliocolor LC242" by BASF Corporation can be illustrated. <Composition> The ratio of the photopolymerizable liquid crystal compound and the side chain type liquid crystal polymer in the liquid crystal composition is not particularly limited. When the content of the side-chain type liquid crystal polymer is large, the vertical alignment caused by the interaction with the polymer is dominant, and the NZ coefficient represented by (nx-nz)/(nx-ny) decreases. tendency. On the other hand, in the case where the content of the photopolymerizable liquid crystal compound is large, the horizontal alignment of the liquid crystal compound caused by the alignment restriction force of the substrate is dominant, and it is represented by (nx-nz)/(nx-ny) The NZ coefficient tends to increase. In order to obtain a liquid crystal alignment film having an NZ coefficient in the range of 0.2 to 0.8, the content of the photopolymerizable liquid crystal compound is preferably 1.2 to 20 times the content of the side chain type liquid crystal polymer. In order to obtain a liquid crystal alignment film with a NZ coefficient close to 0.5, the content of the photopolymerizable liquid crystal compound is preferably 1.3 to 10 times that of the side chain type liquid crystal polymer, more preferably 1.4 to 9 times, and still more preferably 1.5 to 8 times. times. In order to promote hardening of the photopolymerizable liquid crystal compound by light irradiation, it is preferable that the liquid crystal composition contains a photopolymerization initiator. Examples of the photopolymerization initiator include Irgacure 907, Irgacure 184, Irgacure 651, and Irgacure 369 manufactured by BASF Corporation. The content of the photopolymerization initiator in the liquid crystal composition is usually about 0.5 to 20 parts by weight, preferably about 3 to 15 parts by weight, and more preferably about 5 to 5 parts by weight relative to 100 parts by weight of the photopolymerizable liquid crystal compound. About 10 parts by weight. A liquid crystal composition can be prepared by mixing a side chain type liquid crystal polymer, a photopolymerizable liquid crystal compound, and a photopolymerization initiator with a solvent. The solvent is not particularly limited as long as it dissolves the side-chain type liquid crystal polymer and the photopolymerizable liquid crystal compound, and does not corrode the film substrate (or has low corrosivity), and examples include: chloroform, dichloromethane, tetrachloride Carbon, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, o-dichlorobenzene and other halogenated hydrocarbons; phenol, p-chlorophenol and other phenols; benzene, toluene, xylene, methylbenzene, etc. Aromatic hydrocarbons such as oxybenzene and 1,2-dimethoxybenzene; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pyrrolidone, N- Ketone solvents such as methyl-2-pyrrolidone; ester solvents such as ethyl acetate and butyl acetate; tertiary butanol, glycerol, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethyl ether Alcohol-based solvents such as glycol dimethyl ether, propylene glycol, dipropylene glycol, and 2-methyl-2,4-pentanediol; amide-based solvents such as dimethylformamide and dimethylacetamide; acetonitrile, butyl Nitrile-based solvents such as nitrile; ether-based solvents such as diethyl ether, dibutyl ether, tetrahydrofuran, etc.; The concentration of the liquid crystal composition is usually about 3 to 50% by weight, preferably about 7 to 35% by weight. [Film substrate] In order to obtain a liquid crystal alignment film having refractive index anisotropy of nx>nz>ny, it is preferable to use a stretched film without a vertical alignment film as a substrate for coating the liquid crystal composition. By using the stretch film substrate, in the photopolymerizable liquid crystal compound, the vertical alignment effect caused by the interaction with the side chain type liquid crystal polymer and the horizontal alignment effect caused by the molecular alignment of the polymer constituting the stretch film substrate are exhibited Orientation. By balancing these alignment effects, the alignment of the photopolymerizable liquid crystal compound can be adjusted, and the refractive index anisotropy of the liquid crystal alignment film can be controlled. The in-plane retardation R 0 of the stretched film used as the film substrate is usually 10 nm or more. The greater the in-plane retardation of the film substrate, the greater the alignment of the polymer constituting the film along a specific direction (the direction of the slow axis or the direction of the advance axis), along with the horizontal alignment of the liquid crystal alignment layer formed on the film substrate. The larger the NZ coefficient is, the larger (closer to 1) the NZ coefficient tends to be. When the in-plane retardation of the stretched film is too large, it tends to be difficult to control the alignment of the liquid crystal molecules. Therefore, the in-plane retardation R 0 of the stretched film is preferably 1000 nm or less, more preferably 500 nm or less, and more preferably below 400 nm. The thickness of the film substrate is not particularly limited, but is usually about 10 to 200 μm in consideration of handling properties and the like. The in-plane birefringence Δn (value obtained by dividing the in-plane retardation R 0 by the thickness) of the stretched film is preferably 0.0001-0.05, more preferably 0.0005-0.03, and still more preferably 0.001-0.02. The resin material constituting the film substrate is not particularly limited as long as it does not dissolve in the solvent of the liquid crystal composition and has heat resistance during heating for aligning the liquid crystal composition, and examples include: polyethylene terephthalate Polyesters such as diesters and polyethylene naphthalate; polyolefins such as polyethylene and polypropylene; cyclic polyolefins such as noralkene polymers; Polymer; acrylic polymer; styrene polymer; polycarbonate, polyamide, polyimide, etc. Among them, it is particularly preferable to use a noralkene-based polymer film as a film substrate, since it is easy to obtain a film having excellent fluidity during molding and high smoothness. A noralkene-based polymer film is also preferred in terms of excellent releasability when the liquid crystal alignment film is transferred to another base material or the like. As the noralkene-based polymer, Zeonor, Zeonex, and Arton manufactured by JSR, manufactured by Zeon Japan, etc. may be mentioned. The film substrate has a first main surface and a second main surface, and the liquid crystal composition is coated on the first main surface. The arithmetic mean roughness Ra of the first main surface of the film substrate is preferably 3 nm or less, more preferably 2 nm or less, and still more preferably 1.5 nm or less. By coating the liquid crystal composition on the surface of the film substrate with relatively small Ra and high smoothness, the alignment defects of the liquid crystal alignment film tend to be reduced. By extending the film, irregularities such as mold lines during film formation are smoothed, so that the Ra of the film substrate tends to decrease. Therefore, by using the stretched film substrate, the refractive index anisotropy of the liquid crystal alignment film can be controlled, and in addition, there is a tendency for alignment defects to decrease. It is particularly preferable to use a biaxially stretched film as a film substrate from the viewpoint of high uniformity of the surface. In order to make an arithmetic mean roughness into the said range, it is preferable that a film substrate does not contain a filler inside. Films with high surface smoothness without fillers may cause sticking due to low sliding properties, or may cause poor conveyance or poor winding in the roll-to-roll process. In order to prevent sticking or poor conveyance due to high smoothness, a method of attaching another film with high slidability to a film substrate, or a method of providing an easy-slip layer on the film substrate can be mentioned. When the film substrate is bonded to another film, it is possible to suppress defects (such as poor alignment of liquid crystals, optical defects, etc.) caused by transfer of the adhesive layer or the like to the first main surface (the surface on which the liquid crystal composition is applied). ), it is preferable to stick to the second main surface (surface on the opposite side to the coating surface of the liquid crystalline composition). Among them, in the roll-to-roll process, when the film substrate is wound up, the adhesive or the like attached to the second main surface is transferred to the first main surface, which may cause poor alignment or optical defects. Therefore, it is preferable to improve slidability by providing an easy-slip layer on at least one side of the film substrate. As the easy-slip layer, for example, those containing fine fillers having an average particle diameter of 100 nm or less in adhesives such as polyester and polyurethane can be mentioned. From the viewpoint of maintaining the releasability when the vertical alignment liquid crystal film is transferred to other substrates and the like and suppressing the transfer of the easy-slip layer to the vertical alignment liquid crystal film when peeling from the film substrate, etc., the film substrate is preferably There is no easy-slip layer on the surface for coating the liquid crystal composition. That is, it is preferable to use the film substrate which has an easy-slip layer on the 2nd main surface, and does not have an easy-slip layer on the 1st main surface. [Formation of liquid crystal alignment film on film substrate] The liquid crystal composition is coated on the film substrate, and the liquid crystal molecules are aligned by heating to form a liquid crystal state, and then the alignment is fixed by cooling, and the The light irradiation polymerizes or crosslinks the liquid crystal monomer, whereby a liquid crystal alignment film can be obtained. Therefore, the liquid crystal alignment film contains a liquid crystal polymer and a polymer of a liquid crystal compound. The method of coating the liquid crystal composition on the film substrate is not particularly limited, and spin coating, die nozzle coating, contact roll coating, gravure coating, reverse coating, spray coating, and Meyer bar coating can be used. Cloth, roll knife coating, air knife coating, etc. After coating the solution, the solvent is removed, thereby forming a liquid crystalline composition layer on the film substrate. The coating thickness is preferably adjusted so that the thickness of the liquid crystalline composition layer (the thickness of the liquid crystal alignment film) after drying of the solvent becomes about 0.5 to 5 μm. The in-plane retardation of the liquid crystal alignment film is represented by the product of the in-plane birefringence (nx-ny) and the thickness, so the greater the thickness, the greater the in-plane retardation. Moreover, as the result shown in the following experimental example, there exists a tendency for the NZ coefficient of a liquid crystal alignment film to become large as the coating thickness becomes large. By heating the liquid crystal composition layer formed on the film substrate, it becomes a liquid crystal phase, and the side chain type liquid crystal polymer is vertically aligned. At this time, a vertical alignment effect is produced in the photopolymerizable liquid crystal compound by interaction with the non-liquid crystal segment of the side chain type liquid crystal polymer. When a substrate without an extension film is used, the alignment restriction force of the substrate does not work, so both the side chain type liquid crystal polymer and the photopolymerizable liquid crystal compound are vertically aligned to form a vertically aligned liquid crystal layer. On the other hand, when a stretched film substrate is used, the refractive index anisotropy of the liquid crystal alignment film varies depending on the heating temperature. The higher the temperature, the smaller the refractive index nz in the thickness direction, (nx−nz) The NZ coefficient represented by /(nx-ny) tends to increase. It is considered that the higher the heating temperature, the smaller the refractive index nz in the thickness direction is because the alignment behavior of the photopolymerizable liquid crystal compound is different depending on the heating temperature. That is, when the heating temperature is low, the interaction between the non-liquid crystal segment of the liquid crystal monomer and the photopolymerizable liquid crystal compound is strong, and the vertical alignment is dominant in the photopolymerizable liquid crystal compound. When the temperature is increased, the influence of the alignment restraint force of the stretched film substrate is enhanced, and the horizontal alignment is dominant in the photopolymerizable liquid crystal compound. As one of the reasons why the influence of the alignment restriction force of the film substrate increases as the temperature increases, it is considered that at high temperature, the polymerizable liquid crystal compound undergoes an isotropic phase transition, and is easily affected by the film substrate when it returns to the liquid crystal phase by cooling. The effect of alignment restriction force. In the present invention, by utilizing the above knowledge, the alignment of the liquid crystalline composition can be controlled so that the refractive index nz in the thickness direction is intermediate between the refractive index nx in the in-plane slow axis direction and the refractive index ny in the advance axis direction value (NZ coefficient is greater than 0 and less than 1) of the liquid crystal alignment film. When a stretched film substrate is used, in addition to the heating temperature, the composition of the liquid crystal composition, or the in-plane retardation and in-plane birefringence of the stretched film substrate will also affect the refractive index anisotropy of the liquid crystal alignment film. Therefore, the appropriate temperature range for aligning the liquid crystal compound after coating the liquid crystal composition on the stretched film substrate cannot be determined. The heating temperature T for obtaining the liquid crystal alignment film with the NZ coefficient greater than 0 is preferably 70 °C or higher, more preferably 75°C or higher, still more preferably 80°C or higher. In addition, it is preferable that the heating temperature T (° C.) and the in-plane birefringence Δn of the film substrate satisfy T≧90-5×10 3 Δn. The heating temperature T (° C.) is more preferably 95-5×10 3 Δn or more, more preferably 100-5×10 3 Δn or more, and still more preferably 105-5×10 3 Δn or more. When the liquid crystal molecules are uniformly aligned horizontally, the liquid crystal alignment film becomes a positive A plate with nx>nz=ny (NZ=1). The heating temperature T is preferably 150°C or lower, more preferably 140°C or lower, and more preferably 130°C for the coexistence of the vertical alignment component and the horizontal alignment component to obtain a liquid crystal alignment film with nz>ny (NZ<1). the following. Moreover, it is preferable that the heating temperature T (° C.) and the in-plane birefringence Δn of the film substrate satisfy T≦150−3×10 3 Δn. The heating temperature T (°C) is more preferably 140-3×10 3 Δn or less, more preferably 135-3×10 3 Δn or less, and still more preferably 130-3×10 3 Δn or less. From the same viewpoint as above, in order to obtain a liquid crystal alignment film with a NZ coefficient of more than 0 and less than 1, the heating temperature T (°C) is preferably (90-0.1×R 0 ) to (150-0.06×R 0 ), More preferably, it is (95-0.1×R 0 ) to (140-0.06×R 0 ), still more preferably (100-0.1×R 0 ) to (135-0.06×R 0 ), particularly preferably (105-0.1 ×R 0 ) to (130−0.06×R 0 ). R 0 is the in-plane retardation (nm) of the stretched film substrate. After heating the liquid crystalline composition layer, the alignment of the liquid crystalline compound is fixed by cooling to a temperature below the glass transition temperature of the liquid crystalline polymer. The cooling method is not particularly limited, and may be taken out from a heating atmosphere to room temperature, for example. Forced cooling such as air cooling and water cooling can also be performed. The alignment-fixed liquid crystal composition layer is irradiated with light to polymerize or cross-link the photopolymerizable liquid crystal compound, thereby fixing the alignment of the photopolymerizable liquid crystal compound and improving the durability of the liquid crystal alignment film. As the light to be irradiated, light with a wavelength at which the photopolymerization initiator is cleaved may be selected, and ultraviolet rays are usually used. In order to promote the photopolymerization reaction, light irradiation is preferably performed in an inert gas atmosphere such as nitrogen. [Characteristics and Uses of Liquid Crystal Alignment Film] The liquid crystal alignment film obtained by the above has the refractive index anisotropy of nx>nz>ny, and can be used as an optical film for displays for viewing angle compensation and the like. The in-plane retardation of the liquid crystal alignment film is, for example, 50 to 500 nm. In the present invention, by adjusting the composition of the liquid crystalline composition, the in-plane retardation and in-plane birefringence of the stretched film substrate, the coating thickness of the liquid crystalline composition, and the heating temperature during liquid crystal alignment, etc. The required retardation and NZ coefficient of the liquid crystal alignment film. According to the present invention, only by using the same film substrate and liquid crystal composition, and adjusting the heating temperature during liquid crystal alignment, liquid crystal alignment films with various front retardation or NZ coefficients can be produced, so that the productivity can be improved, and it is suitable for small batch production. It is also easier to wait. In order to reduce the change of retardation caused by the viewing direction, the NZ coefficient of the liquid crystal alignment film is preferably 0.2-0.8, more preferably 0.3-0.7, still more preferably 0.4-0.6, particularly preferably 0.45-0.55. The preferable ranges of the in-plane retardation Ro and the NZ coefficient of the liquid crystal alignment film vary depending on the purpose of use and the like. For example, when Ro is 200 to 350 nm and the NZ coefficient is 0.4 to 0.6, it is suitable as a λ/2 retardation plate with little change in retardation due to the viewing direction, and can be suitably used for IPS (In- Plane Switching, lateral electric field effect), viewing angle compensation film for liquid crystal display devices, etc. When the Ro is 120-170 nm and the NZ coefficient is 0.4-0.6, it is suitable as a λ/4 retardation plate with little change in retardation caused by the viewing direction. By laminating with a polarizing plate, a wide viewing angle can be obtained. Circular polarizer. The wide viewing angle circular polarizer can be suitably used for the anti-reflection film of external light of OLED (Organic Light Emitting Diode, organic light emitting diode). The liquid crystal alignment film can be used in a state of being laminated with a film substrate, or it can be used by peeling off the film substrate. The liquid crystal alignment film can be peeled off from the film substrate, and used by laminating it with a base material such as a retardation film, a polarizing plate, and glass. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to the production examples of liquid crystal alignment films, but the present invention is not limited to the following examples. [Evaluation method] (Arithmetic mean roughness) The arithmetic mean roughness was determined from an AFM observation image of 1 μm square using a scanning probe microscope (AFM). (Retardation) The retardation was measured at a wavelength of 590 nm in an environment of 23° C. using a polarization retardation measuring system (product name “AxoScan” manufactured by Axometrics). The measurement of the retardation of the liquid crystal alignment film is to use the sample with the liquid crystal alignment film transferred on the adhesive attachment surface of the glass plate with the adhesive on the surface to measure the in-plane retardation R 0 and the retardation when tilted at 40°, and From these measured values, the average refractive index of the liquid crystal alignment film was set to 1.52, the refractive indices nx, ny, and nz were calculated, and NZ=(nx−nz)/(nx−ny) was obtained. [Preparation of Liquid Crystalline Compositions 1 to 8] A side chain type liquid crystal polymer having a weight average molecular weight of 5000 and a thermotropic nematic with the following chemical formula (n=0.35, represented by a block polymer body for convenience of description) A total of 100 parts by weight of the polymerizable liquid crystal monomer (“Paliocolor LC242” manufactured by BASF) and 5 parts by weight of a photopolymerization initiator (“Irgacure 907” manufactured by BASF) of the liquid crystal phase were dissolved in 400 parts by weight of cyclopentanone And a liquid crystal composition was prepared. As shown in Table 1, the ratio of the polymer and the monomer was changed to a ratio of 100/0 to 20/80 to prepare liquid crystal compositions 1 to 8. [hua 5]
Figure 02_image009
[Preparation of Liquid Crystalline Composition 9] 50 parts by weight of a side chain type liquid crystal polymer having a weight average molecular weight of 5000 of repeating units represented by the following chemical formula, 50 parts by weight of "Paliocolor LC242" manufactured by BASF, and BASF Liquid crystal composition 9 was prepared by dissolving 5 parts by weight of "Irgacure 907" in 400 parts by weight of cyclopentanone. [hua 6]
Figure 02_image011
[Experimental Example 1] On one side of a biaxially stretched normethylene film (“Zeonor Film” manufactured by Zeon Japan, thickness: 52 μm, in-plane retardation: 50 nm, and no easy-slip layer formed on one side) Arithmetic mean roughness: 1.2 nm) on the surface on which the easy-slip layer was not formed, the above-mentioned liquid crystal compositions 1 to 9 were applied using a Meyer bar (#4), and the liquid crystal was aligned by heating at 100° C. for 2 minutes. Then, the alignment was fixed by cooling to room temperature, and 700 mJ/cm 2 of ultraviolet rays were irradiated in a nitrogen atmosphere to photo-harden the liquid crystal monomer to prepare a liquid crystal alignment film. [Experimental Examples 2 and 3] The liquid crystal combination was carried out in the same manner as in Experimental Example 1, except that the #8 Meyer rod was used in Experimental Example 2 and the #12 Meyer rod was used in Experimental Example 3. The coating, heating, cooling and photohardening of the objects 1 to 8 were carried out to produce a liquid crystal alignment film. [Experimental Example 4] On one side of a biaxially stretched normethylene film (“Zeonor Film” manufactured by Zeon Japan, thickness: 34 μm, in-plane retardation: 270 nm, and no easy-slip layer formed on one side) The arithmetic mean roughness: 0.9 nm) on the surface where the easy-slip layer was not formed, the liquid crystal compositions 1 to 8 were coated with a #12 Meyer bar roll, and a liquid crystal alignment film was produced in the same manner as in Experimental Example 3. [Experimental Example 5] On an unstretched orphan-based film (“Zeonor Film” manufactured by Zeon, Japan, thickness: 34 μm, in-plane retardation: 0 nm, arithmetic mean roughness 2.3 nm), Meyer of #12 was used The liquid crystal composition 4 was bar-rolled, and a liquid crystal alignment film was produced in the same manner as in Experimental Example 3. Table 1 shows the measured results (in-plane retardation R 0 and NZ) of the in-plane retardation R 0 of the substrates used in Experimental Examples 1 to 5, the thickness of the liquid crystal alignment film, and the retardation of the liquid crystal alignment film. [Table 1]
Figure 107113322-A0304-0001
 [Experimental Examples 6 to 8] On a biaxially stretched film with an in-plane retardation of 50 nm, the same as in Experimental Examples 1 to 3, a Meyer bar of #12 was used, and a liquid crystalline composition 4 (polymer/monomer) was applied. The ratio is 80/20), and the subsequent heating temperature is changed within the range of 70 to 120°C. Except for this, in the same manner as in Experimental Example 3, a liquid crystal alignment film was produced. The measurement results of the heating temperature and the retardation of the liquid crystal alignment film of Experimental Examples 6 to 8 are shown in Table 2 together with the results of Experimental Example 3 (disclosed again). [Table 2]
Figure 107113322-A0304-0002
 In Table 1, when the liquid crystal compositions 7 and 8 with a smaller ratio of the thermotropic liquid crystal compound in the liquid crystal composition were applied on the stretched film substrate, any one of the experimental examples 1 to 4 was used. In one, the obtained liquid crystal alignment films are all positive C plates with in-plane retardation R 0 approximately 0 and NZ coefficient being negative. In Experimental Examples 1 to 4, as the ratio of the thermotropic liquid crystal compound increases, the R 0 of the liquid crystal alignment film increases, and the NZ coefficient tends to increase accordingly. On the other hand, in Experimental Example 5 using a non-stretching film, when the ratio of the thermotropic liquid crystal compound is large (monomer/polymer=80/20), the R 0 of the liquid crystal alignment film is also approximately 0 . Comparing Experimental Examples 1 to 3, when the same liquid crystal composition is used, it can be seen that the larger the coating thickness is, the larger the NZ of the liquid crystal alignment film tends to be. According to the comparison between Experimental Example 3 and Experimental Example 4, the larger the in-plane birefringence of the stretched substrate film, the more the horizontal alignment component increases, and the more the NZ coefficient of the liquid crystal alignment film increases. According to the results shown in Table 2, when the same liquid crystal composition was used, the higher the heating temperature after coating the liquid crystal composition, the higher the NZ coefficient of the liquid crystal alignment film. From the above results, it can be seen that the refraction of the liquid crystal alignment film can be controlled by adjusting the heating temperature after coating the liquid crystal composition comprising the side chain type thermotropic liquid crystal polymer and the thermotropic liquid crystal compound on the stretched film substrate. Rate anisotropy. That is, according to the present invention, it was found that by adjusting the composition of the liquid crystalline composition, the in-plane retardation (in-plane birefringence), the coating thickness, the heating temperature, etc. Internal retardation and NZ coefficient of liquid crystal alignment film.

Claims (8)

一種液晶配向膜，其係包含液晶層者，該液晶層含有側鏈型熱致性液晶聚合物、及熱致性液晶化合物之聚合物，且上述側鏈型熱致性液晶聚合物具有含有液晶性片段側鏈之單體單元與含有非液晶性片段側鏈之單體單元，上述液晶層單層面內之遲相軸方向之折射率nx、面內之進相軸方向之折射率ny、及厚度方向之折射率nz滿足0.2≦(nx-nz)/(nx-ny)≦0.8。 A liquid crystal alignment film, which comprises a liquid crystal layer, the liquid crystal layer contains a side chain type thermotropic liquid crystal polymer and a polymer of a thermotropic liquid crystal compound, and the side chain type thermotropic liquid crystal polymer has a liquid crystal polymer containing a liquid crystal The monomer unit of the side chain of the liquid crystal segment and the monomer unit containing the side chain of the non-liquid crystal segment, the refractive index nx in the direction of the slow axis in the single layer of the liquid crystal layer, the refractive index ny in the direction of the advance axis in the plane, And the refractive index nz in the thickness direction satisfies 0.2≦(nx-nz)/(nx-ny)≦0.8. 如請求項1之液晶配向膜，其中上述側鏈型熱致性液晶聚合物具有下述通式(I)所表示之液晶性單體單元與下述通式(II)所表示之非液晶性單體單元，
Figure 107113322-A0305-02-0020-1
Figure 107113322-A0305-02-0020-2
 R1及R3分別獨立地為氫原子或甲基，X1為-CO2-基或-OCO-基， R2為氰基、氟基、碳數1~6之烷基、或碳數1~6之烷氧基，a為1~6之整數，b及c分別獨立地為1或2，R4為碳數7~22之烷基、碳數1~22之氟烷基、或下述通式(III)所表示之基，
Figure 107113322-A0305-02-0021-3
 R5為碳數1~5之烷基，d為1~6之整數。 The liquid crystal alignment film according to claim 1, wherein the side chain type thermotropic liquid crystal polymer has a liquid crystal monomer unit represented by the following general formula (I) and a non-liquid crystallinity represented by the following general formula (II) monomer unit,
Figure 107113322-A0305-02-0020-1
Figure 107113322-A0305-02-0020-2
 R 1 and R 3 are each independently a hydrogen atom or a methyl group, X 1 is a -CO 2 - group or -OCO- group, R 2 is a cyano group, a fluoro group, an alkyl group having 1 to 6 carbon atoms, or a carbon number Alkoxy of 1 to 6, a is an integer of 1 to 6, b and c are independently 1 or 2, R 4 is an alkyl group of 7 to 22 carbon atoms, a fluoroalkyl group of 1 to 22 carbon atoms, or The group represented by the following general formula (III),
Figure 107113322-A0305-02-0021-3
 R 5 is an alkyl group having 1 to 5 carbon atoms, and d is an integer of 1 to 6. 如請求項1或2之液晶配向膜，其中以重量比計，上述熱致性液晶化合物之聚合物之含量相對於上述側鏈型熱致性液晶聚合物之含量為1.2~20倍。 The liquid crystal alignment film of claim 1 or 2, wherein the content of the polymer of the thermotropic liquid crystal compound is 1.2 to 20 times the content of the side chain type thermotropic liquid crystal polymer in terms of weight ratio. 如請求項1或2之液晶配向膜，其面內延遲為50~500nm。 As in the liquid crystal alignment film of claim 1 or 2, the in-plane retardation is 50-500 nm. 一種液晶配向膜之製造方法，其係如請求項1至4中任一項之液晶配向膜之製造方法，且具有：塗佈步驟，其係於具有第一主面與第二主面且未設置垂直配向膜之膜基板之第一主面上，塗佈含有側鏈型熱致性液晶聚合物及光聚合性之熱致性液晶化合物之液晶性組合物；液晶配向步驟，其係對上述側鏈型熱致性液晶聚合物及熱致性液晶化合物進行加熱而使之配向；及光聚合步驟，其係藉由光照射使上述熱致性液晶化合物進行聚合或 交聯；且上述膜基板為延伸膜。 A method for producing a liquid crystal alignment film, which is the method for producing a liquid crystal alignment film according to any one of claims 1 to 4, and has: a coating step, which is formed on a liquid crystal alignment film having a first main surface and a second main surface without The first main surface of the film substrate on which the vertical alignment film is arranged is coated with a liquid crystal composition containing a side chain type thermotropic liquid crystal polymer and a photopolymerizable thermotropic liquid crystal compound; the liquid crystal alignment step is performed on the above-mentioned The side chain type thermotropic liquid crystal polymer and the thermotropic liquid crystal compound are heated to align them; and the photopolymerization step is to polymerize the above-mentioned thermotropic liquid crystal compound by light irradiation or cross-linked; and the above-mentioned film substrate is a stretched film. 如請求項5之液晶配向膜之製造方法，其中上述膜基板具有10~1000nm之面內延遲。 The method for producing a liquid crystal alignment film according to claim 5, wherein the film substrate has an in-plane retardation of 10 to 1000 nm. 如請求項5或6之液晶配向膜之製造方法，其中上述液晶配向步驟中之加熱溫度T(℃)與上述膜基板之面內雙折射△n滿足T≧90-5×103△n。 The method for producing a liquid crystal alignment film according to claim 5 or 6, wherein the heating temperature T (°C) in the liquid crystal alignment step and the in-plane birefringence Δn of the film substrate satisfy T≧90-5×10 3 Δn. 如請求項5或6之液晶配向膜之製造方法，其中上述膜基板為降
Figure 107113322-A0305-02-0022-4
烯系聚合物膜。 The method for producing a liquid crystal alignment film according to claim 5 or 6, wherein the above-mentioned film substrate is a
Figure 107113322-A0305-02-0022-4
Vinyl polymer film.
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