TWI507743B - Film, process for producing film and use thereof - Google Patents

Film, process for producing film and use thereof Download PDF

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TWI507743B
TWI507743B TW096110470A TW96110470A TWI507743B TW I507743 B TWI507743 B TW I507743B TW 096110470 A TW096110470 A TW 096110470A TW 96110470 A TW96110470 A TW 96110470A TW I507743 B TWI507743 B TW I507743B
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film
liquid crystal
alignment
group
crystal compound
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TW200741264A (en
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Koshiro Ochiai
Motohiro Yamahara
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Sumitomo Chemical Co
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal 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
    • 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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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Mathematical Physics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polarising Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Description

膜及膜之製造方法，以及其用途Film and film manufacturing method, and use thereof

本發明係有關膜(film)及膜之製造方法，以及其用途，並且係有關並非在膜之平面方向而是在膜之法線方向上能夠賦予高折射率的膜及膜之製造方法，以及其用途。The present invention relates to a method for producing a film and a film, and a use thereof, and to a method for producing a film and a film which are capable of imparting a high refractive index not in the planar direction of the film but in the normal direction of the film, and Its use.

液晶顯示裝置(後文稱為「LCD」)、或有機電致發光(後文稱為「EL」)等平面顯示裝置(後文稱為「FPD」)係比CRT更節省空間及消耗更少電力。因此近年來FPD廣泛地普及作為電腦、電視、行動電話、汽車導航或個人數位助理(PDA)的畫面。A flat display device (hereinafter referred to as "FPD") such as a liquid crystal display device (hereinafter referred to as "LCD") or organic electroluminescence (hereinafter referred to as "EL") is more space-saving and consumes less than a CRT. electric power. Therefore, in recent years, FPD has been widely used as a screen for computers, televisions, mobile phones, car navigation, or personal digital assistants (PDAs).

在FPD中，一般而言為了防止反射、視角擴大等，係使用各式各樣的光學膜。列舉例如使不同折射率之光學薄膜層多層化以減少在光干涉效果下之表面反射率的抗反射(Anti－reflection，後文稱為AR)膜等防止反射膜、只容許特定振動方向之光能夠透射而隔絕其他光的偏光膜、將STN方式或TN方式等之LCD之干涉色以光學方式進行色彩補償的相位差膜、使偏光膜與相位差膜一體化的橢圓偏光膜、以及使LCD之視角擴大的視角擴大膜等。In the FPD, in general, in order to prevent reflection, increase in viewing angle, and the like, various optical films are used. For example, an antireflection film such as an anti-reflection (hereinafter referred to as AR) film which is formed by multilayering an optical film layer having different refractive indexes to reduce surface reflectance under an optical interference effect, and only a specific vibration direction is allowed. a polarizing film capable of transmitting and isolating other light, a retardation film for optically compensating an interference color of an LCD such as an STN method or a TN method, an elliptically polarizing film for integrating a polarizing film and a retardation film, and an LCD The angle of view of the expanded view expands the film and the like.

再者，FPD所用的光學膜所追求的特性不只是因應如上所述的功能而異，還會依據適用的FPD種類而異。例如以在LCD中為了顯現廣視角而具備的光學補償膜為例，說明如下。在LCD方面，已提出有VA模式、TN模式、IPS模式等各式各樣液晶驅動方式者。在這些具各種驅動方式的LCD中，為了顯現廣視角而具備的光學補償膜係分別需求不同的特性。Furthermore, the characteristics pursued by the optical film used in the FPD vary not only in accordance with the functions described above, but also depending on the type of FPD to be applied. For example, an optical compensation film provided in order to visualize a wide viewing angle in an LCD will be described as follows. In terms of LCD, various liquid crystal driving methods such as VA mode, TN mode, and IPS mode have been proposed. In these LCDs having various driving methods, optical compensation films provided to exhibit a wide viewing angle require different characteristics.

具體而言，在VA模式LCD中，可利用使折射率在平面方向上變化的延伸膜進行光學補償。上述延伸膜係使用以往用來作為賦予光學補償效果之相位差膜的膜。上述延伸膜例如可藉由使聚乙烯醇、聚碳酸酯等膜進行延伸而得到。Specifically, in the VA mode LCD, optical stretching can be performed by using a stretching film that changes the refractive index in the planar direction. As the above-mentioned stretched film, a film which has been conventionally used as a retardation film for imparting an optical compensation effect is used. The stretched film can be obtained, for example, by stretching a film such as polyvinyl alcohol or polycarbonate.

另外，在TN模式LCD中，為了顯現廣視角，係以使用使折射率在傾斜方向上變化的光學膜為較佳。此等膜可列舉例如富士軟片股份公司的WV Film(商品名)、或新日本石油股份公司的NH Film(商品名)等。這些膜不是延伸膜，而是利用液晶分子之傾斜配向的光學補償膜。上述液晶分子係可使用在配向膜界面上呈水平配向，在空氣界面上呈垂直配向的傾斜配向液晶分子。藉此所得到的膜，會變成使折射率在傾斜方向上變化。Further, in the TN mode LCD, in order to develop a wide viewing angle, it is preferable to use an optical film which changes the refractive index in the oblique direction. Examples of such a film include WV Film (trade name) of Fujifilm Co., Ltd., and NH Film (trade name) of Nippon Oil Corporation. These films are not stretched films, but optical compensation films that utilize oblique alignment of liquid crystal molecules. The above liquid crystal molecules may use obliquely aligned liquid crystal molecules which are horizontally aligned at the interface of the alignment film and which are vertically aligned at the air interface. The film thus obtained becomes such that the refractive index changes in the oblique direction.

另一方面，在IPS模式LCD中，為了顯現廣視角，需要使在膜平面方向上之折射率變化為小且使折射率在法線方向上變化的光學補償膜。換言之，需要能在法線方向上控制光學異向性層(optical anisotropy)之傾斜角(亦即所謂折射率橢圓體)的膜。On the other hand, in the IPS mode LCD, in order to develop a wide viewing angle, an optical compensation film in which the refractive index in the film plane direction is changed to be small and the refractive index is changed in the normal direction is required. In other words, there is a need for a film that can control the tilt angle of an optical anisotropy (i.e., a so-called refractive index ellipsoid) in the normal direction.

然而，上述延伸膜雖然能使折射率在膜平面方向上增加，但無法使折射率在膜法線方向上增加。例如聚碳酸酯膜等雖然能使折射率在延伸方向上增加，但不能使折射率在膜法線方向上增加。因此，此類延伸膜可在VA模式LCD中實現廣視角，但是無法在TN型、IPS模式LCD中實現廣視角化。However, although the above-mentioned stretched film can increase the refractive index in the film plane direction, it cannot increase the refractive index in the film normal direction. For example, although a polycarbonate film or the like can increase the refractive index in the extending direction, the refractive index cannot be increased in the film normal direction. Therefore, such a stretched film can realize a wide viewing angle in a VA mode LCD, but it is not possible to realize a wide viewing angle in a TN type, IPS mode LCD.

再者，在上述利用液晶分子而成之光學補償膜的情形，為了使液晶分子配向而施加摩擦處理。因此，液晶分子在配向膜界面上會呈水平配向。所以，當使用在配向膜界面上呈水平配向且在空氣界面上也呈水平或者是垂直配向的液晶分子時，所得到的光學補償膜會成為水平配向及傾斜配向。因此，如上所述，雖然可使用於TN模式LCD的廣視角化，但無法用在IPS模式的LCD上。Further, in the case of the above optical compensation film using liquid crystal molecules, a rubbing treatment is applied in order to align liquid crystal molecules. Therefore, the liquid crystal molecules will be horizontally aligned at the interface of the alignment film. Therefore, when liquid crystal molecules which are horizontally aligned at the interface of the alignment film and which are horizontally or vertically aligned at the air interface are used, the obtained optical compensation film becomes horizontal alignment and oblique alignment. Therefore, as described above, although the wide viewing angle for the TN mode LCD can be made, it cannot be used in the IPS mode LCD.

如此一來，VA模式、TN模式LCD所使用的光學補償膜，無法用於實現IPS模式LCD的廣視角化。所以，提案有數個可對應IPS模式LCD之廣視角化的光學補償膜。As a result, the optical compensation film used in the VA mode and the TN mode LCD cannot be used to realize a wide viewing angle of the IPS mode LCD. Therefore, there are several optical compensation films that can be used for a wide viewing angle of the IPS mode LCD.

具體而言，專利文獻1係揭示使用長鏈烷基型樹枝狀聚合物衍生物以形成垂直配向膜，藉由將聚合性液晶化合物塗布在此垂直配向膜上而使前述液晶化合物呈垂直配向的垂直配向液晶膜。再者，該文獻中記載前述聚合性液晶化合物係具有例如以丙烯酸酯基或甲基丙烯酸酯基作為聚合性官能基的液晶性化合物，且較佳為使用在室溫下為向列型液晶性者作為液晶性化合物。此外，該文獻中記載在此所使用的向列型材料係與光聚合起始劑一起塗布在配向膜上而形成垂直配向液晶層。Specifically, Patent Document 1 discloses that a long-chain alkyl type dendrimer derivative is used to form a vertical alignment film, and the liquid crystal compound is vertically aligned by coating a polymerizable liquid crystal compound on the vertical alignment film. Vertical alignment of the liquid crystal film. In addition, it is described in the literature that the polymerizable liquid crystal compound has, for example, a liquid crystal compound having an acrylate group or a methacrylate group as a polymerizable functional group, and is preferably used as a nematic liquid crystal at room temperature. As a liquid crystal compound. Further, in this document, the nematic material used herein is coated on the alignment film together with a photopolymerization initiator to form a vertical alignment liquid crystal layer.

另外，專利文獻2係揭示在沒有設置垂直配向膜之基板上塗布側鏈型液晶聚合物，再使該液晶聚合物在液晶狀態下呈垂直配向後，在保持其配向狀態的狀態下固定化的垂直配向液晶膜。又，該文獻中記載上述側鏈型液晶聚合物係包含具有液晶性片段的單體單元，該液晶性片段含有包含液晶性片段側鏈的單體單元(a)與包含非液晶性片段側鏈的單體單元(b)。Further, Patent Document 2 discloses that a side chain type liquid crystal polymer is applied onto a substrate on which a vertical alignment film is not provided, and the liquid crystal polymer is vertically aligned in a liquid crystal state, and is then fixed while being in an aligned state. Vertical alignment of the liquid crystal film. Further, the above-described side chain type liquid crystal polymer includes a monomer unit having a liquid crystal segment containing a monomer unit (a) including a liquid crystal fragment side chain and a non-liquid crystal fragment side chain. Monomer unit (b).

再者，專利文獻3係揭示具備具有透光性之基材、以及形成於該基材上之第1雙折射率層的光學元件。又，揭示前述第1雙折射率層係由含有偶合劑且使分子形狀為棒狀之聚合性液晶呈垂直配向的交聯高分子所構成。此外，該文獻中記載在該光學元件中，前述交聯聚合物係具有使分子形狀為棒狀之聚合性液晶仍舊保持垂直配向之狀態而進行三維交聯的結構。Further, Patent Document 3 discloses an optical element including a light-transmitting substrate and a first birefringence layer formed on the substrate. Further, the first birefringence layer is composed of a crosslinked polymer containing a coupling agent and having a polymerized liquid crystal having a rod shape in a vertical alignment. Further, in the optical element, the crosslinked polymer has a structure in which a polymerizable liquid crystal having a rod shape in a molecular form is maintained in a vertical alignment state and is three-dimensionally crosslinked.

再者，專利文獻4係揭示具備具有透光性之基材、形成於該基材上之垂直配向膜、以及形成於該垂直配向膜上之第1雙折射率層的光學元件。另外，揭示前述垂直配向膜係藉由具有長鏈烷基的界面活性劑而形成。此外，該文獻中記載前述第1雙折射率層具有使分子形狀為棒狀之聚合性液晶仍舊保持垂直配向之狀態而進行三維交聯的結構。Further, Patent Document 4 discloses an optical element including a light-transmitting substrate, a vertical alignment film formed on the substrate, and a first birefringence layer formed on the vertical alignment film. Further, it is revealed that the above-mentioned vertical alignment film is formed by a surfactant having a long-chain alkyl group. In addition, it is described in the literature that the first birefringence layer has a structure in which a polymerizable liquid crystal having a rod shape is maintained in a vertical alignment state and is three-dimensionally crosslinked.

[專利文獻1]日本特開2002－174724號公報(平成14(2002)年6月21日公開)[專利文獻2]日本特開2002－174725號公報(平成14(2002)年6月21日公開)[專利文獻3]日本特開2005－165240號公報(平成17(2005)年6月23日公開)[專利文獻4]日本特開2005－165239號公報(平成17(2005)年6月23日公開)[Patent Document 1] Japanese Laid-Open Patent Publication No. 2002-174724 (published on Jun. 21, 2002). [Patent Document 2] JP-A-2002-174725 (June 21 (2002) June 21 [Patent Document 3] Japanese Laid-Open Patent Publication No. 2005-165240 (published on Jun. 23, 2005). [Patent Document 4] JP-A-2005-165239 (June 2005 (June 2005) Open on the 23rd)

然而，專利文獻1之垂直配向液晶膜的垂直配向膜係以長鏈烷基型樹枝狀聚合物衍生物所形成。此長鏈烷基型樹枝狀聚合物衍生物為特殊材料，有難以製造的問題。再者，由於專利文獻1所使用的液晶在該垂直配向用配向膜上呈垂直配向，所以無法調整其液晶分子之配向角。因此，無法控制相對於在光學異向性層之折射率橢圓體之膜平面的傾斜角，而無法配合液晶面板的特性改善視角。However, the vertical alignment film of the vertical alignment liquid crystal film of Patent Document 1 is formed of a long-chain alkyl type dendrimer derivative. This long-chain alkyl type dendrimer derivative is a special material and has a problem that it is difficult to manufacture. Further, since the liquid crystal used in Patent Document 1 is vertically aligned on the alignment film for vertical alignment, the alignment angle of the liquid crystal molecules cannot be adjusted. Therefore, the inclination angle with respect to the film plane of the refractive index ellipsoid in the optical anisotropic layer cannot be controlled, and the viewing angle cannot be improved in accordance with the characteristics of the liquid crystal panel.

另外，專利文獻2之垂直配向液晶膜的製造係可使用液晶聚合物。當使用液晶聚合物時，為了得到單疇(monodomain)的垂直液晶配向，必須使液晶聚合物變成液晶狀態，且必須在液晶配向步驟中以高溫加熱。因此，必須選定能長時間耐受此熱處理之基材，不能使用耐熱性低的膜。又，由於升溫會增加液晶化合物的流動性，所以與基底的密著性會降低，或因殘餘應力而使雙折射特性顯著地降低。Further, in the production of the vertical alignment liquid crystal film of Patent Document 2, a liquid crystal polymer can be used. When a liquid crystal polymer is used, in order to obtain a monodomain vertical liquid crystal alignment, it is necessary to change the liquid crystal polymer to a liquid crystal state, and it is necessary to heat at a high temperature in the liquid crystal alignment step. Therefore, it is necessary to select a substrate which can withstand such heat treatment for a long period of time, and a film having low heat resistance cannot be used. Further, since the temperature rise increases the fluidity of the liquid crystal compound, the adhesion to the substrate is lowered, or the birefringence characteristics are remarkably lowered by the residual stress.

專利文獻3之光學元件的雙折射層係即使不在垂直配向膜上亦可形成垂直配向者。因此，為了得到垂直配向，必須添加棒狀聚合性液晶，且摻入偶合劑。但是，偶合劑的雙折射異向性比棒狀聚合性液晶小。因此，會有所得到的光學元件之相位差值降低的問題。於是，為了在該光學元件中得到期望的相位差值，必須使膜厚比只有使用棒狀聚合性液晶的情況變得更厚。像這樣的光學元件會產生無法充分追求輕量化的問題。此外，在偶合劑的影響下，容易發生對基材可濕性亦產生變化、或產生彈性、與基底之密著性降低的問題。The birefringent layer of the optical element of Patent Document 3 can form a vertical alignment even if it is not on the vertical alignment film. Therefore, in order to obtain a vertical alignment, it is necessary to add a rod-shaped polymerizable liquid crystal and incorporate a coupling agent. However, the coupling agent has a smaller birefringence anisotropy than a rod-shaped polymerizable liquid crystal. Therefore, there is a problem that the phase difference of the obtained optical element is lowered. Therefore, in order to obtain a desired retardation value in the optical element, it is necessary to make the film thickness thicker than the case where only the rod-shaped polymerizable liquid crystal is used. An optical element like this causes a problem that the weight reduction cannot be sufficiently pursued. Further, under the influence of the coupling agent, there is a problem in that the wettability of the substrate is also changed, or the elasticity is generated and the adhesion to the substrate is lowered.

此外，在專利文獻4的光學元件中，垂直配向膜係以界面活性劑所形成。該界面活性劑係僅將基材表面予以覆蓋。因此，上述垂直配向膜為非常脆弱，會有例如無法耐受摩擦等處理的問題。再者，由於垂直配向膜係以界面活性劑所形成，所以會有與由棒狀聚合性液晶化合物所構成之雙折射層的黏合性不足的問題。Further, in the optical element of Patent Document 4, the vertical alignment film is formed of a surfactant. The surfactant only covers the surface of the substrate. Therefore, the above-mentioned vertical alignment film is very fragile, and there is a problem that processing such as friction cannot be tolerated. Further, since the vertical alignment film is formed of a surfactant, there is a problem that the adhesion to the birefringent layer composed of the rod-shaped polymerizable liquid crystal compound is insufficient.

如此，以往可適用於IPS模式廣視角化的光學補償膜係具有各式各樣的問題，因此尋求開發更適合的光學補償膜。As described above, the optical compensation film which can be applied to the IPS mode and has a wide viewing angle has various problems. Therefore, development of a more suitable optical compensation film has been sought.

另外，特別是近年來隨著FPD大型化的進展，新產生由光學膜所引起的問題。具體而言，當FPD進行大型化之際，從較廣之角度觀察顯示畫面整體時，就會產生顯示畫面有時會著色(亦稱為著色現象)，有時會黑白反轉(亦稱為反轉現象)的問題。再者，若使視角傾向於顯示畫面上方的反視角方向時，就會產生對比降低的問題。於是，為了解決此等問題，也經過很多關於光學膜之測試錯誤，以追求能在任意方向上賦予光學異向性的光學膜。此外，在此等光學膜中，除了光學補償效果及防止反射功能，亦追求視角相依性的改善及著色現象更進一步的改善。In addition, in particular, in recent years, with the progress of the large-scale FPD, problems caused by optical films have newly arisen. Specifically, when the FPD is enlarged, when the entire display screen is viewed from a wide angle, the display screen may be colored (also called a coloring phenomenon), and sometimes black and white is reversed (also called The problem of reversing the phenomenon). Furthermore, if the viewing angle tends to be displayed in the direction of the reverse viewing angle above the screen, a problem of contrast reduction occurs. Therefore, in order to solve such problems, many test errors concerning optical films have been made to pursue an optical film capable of imparting optical anisotropy in an arbitrary direction. Further, in these optical films, in addition to the optical compensation effect and the anti-reflection function, improvement in viewing angle dependence and further improvement in coloring phenomenon are also pursued.

本發明係鑑於上述問題點，而提供並非在光學膜之膜水平方向而是在膜法線方向上能夠賦予高折射率的膜及膜之製造方法，以及其用途。The present invention has been made in view of the above problems, and provides a method for producing a film and a film which can impart a high refractive index in the film normal direction, not in the film horizontal direction, and the use thereof.

本案發明者等鑑於上述課題進行深入研究的結果，獨自發現藉由在垂直配向用配向膜上形成混合配向性之棒狀聚合性液晶化合物層而得到折射率在法線方向上變化的膜，因而完成本發明。換言之，本發明包含於產業上有用的以下發明。As a result of intensive studies in view of the above-mentioned problems, the inventors of the present invention have found that a film having a refractive index in the normal direction is obtained by forming a rod-shaped polymerizable liquid crystal compound layer having a mixed orientation on the alignment film for vertical alignment. The present invention has been completed. In other words, the present invention encompasses the following inventions which are industrially useful.

(1)一種膜，係具有形成於垂直配向用配向膜上之光學異向性層的膜，其特徵為：上述光學異向性層係由含有包含從棒狀聚合性液晶化合物而來之結構單元的聚合物之層所構成，上述棒狀聚合性液晶化合物係作為單體並且為具有在水平配向膜上呈水平配向、在空氣界面上呈垂直配向之特性者，在膜平面之正交軸方向及膜厚方向的折射率分別為nx、ny、nz的情況下，滿足nz>nx及nz>ny。(1) A film comprising an optically anisotropic layer formed on an alignment film for a vertical alignment, wherein the optically anisotropic layer contains a structure comprising a rod-like polymerizable liquid crystal compound. a layer of a polymer layer of the unit, wherein the rod-shaped polymerizable liquid crystal compound is a monomer and has a property of being horizontally aligned on a horizontal alignment film and vertically aligned at an air interface, and an orthogonal axis at a film plane When the refractive indices in the direction and the film thickness direction are nx, ny, and nz, respectively, nz>nx and nz>ny are satisfied.

(2)如(1)記載之膜，其中，上述垂直配向用配向膜係垂直配向膜。(2) The film according to (1), wherein the alignment film for vertical alignment is a vertical alignment film.

(3)如(2)記載之膜，其中，相對於上述光學異向性層之折射率橢圓體之膜平面的傾斜角係90±5°。(3) The film according to (2), wherein the film angle with respect to the film plane of the refractive index ellipsoid of the optically anisotropic layer is 90 ± 5°.

(4)如(1)記載之膜，其中，上述垂直配向用配向膜係對於垂直配向膜施加摩擦處理而成之配向膜。(4) The film according to (1), wherein the alignment film for vertical alignment is an alignment film obtained by applying a rubbing treatment to the vertical alignment film.

(5)如(4)記載之膜，其中，相對於上述光學異向性層之折射率橢圓體之膜平面的傾斜角係45°至85°。(5) The film according to (4), wherein the film angle with respect to the film plane of the refractive index ellipsoid of the optically anisotropic layer is 45 to 85.

(6)一種膜，係具有形成於垂直配向用配向膜上之光學異向性層的膜，其特徵為：上述光學異向性層係由含有棒狀聚合性液晶化合物的層所構成，上述棒狀聚合性液晶化合物係具有在水平配向膜上呈水平配向、在空氣界面上呈垂直配向之特性者，在膜平面之正交軸方向及膜厚方向的折射率分別為nx、ny、nz的情況下，滿足nz>nx及nz>ny。(6) A film comprising an optically anisotropic layer formed on an alignment film for a vertical alignment, wherein the optically anisotropic layer is composed of a layer containing a rod-shaped polymerizable liquid crystal compound, The rod-shaped polymerizable liquid crystal compound has a characteristic of being horizontally aligned on the horizontal alignment film and vertically aligned at the air interface, and the refractive indices in the orthogonal axis direction and the film thickness direction of the film plane are nx, ny, and nz, respectively. In the case of nz>nx and nz>ny.

(7)如(1)至(6)中任一項記載之膜，其表現出逆波長分散。(7) The film according to any one of (1) to (6) which exhibits reverse wavelength dispersion.

(8)如(7)記載的膜，其中，上述光學異向性層含有包含從下述式(1)所示之聚合性化合物而來之結構單元的聚合物，P2－E2－X2－B2－A2－(G2)t－Y－(G1)s－A1－B1－X1－E1－P1 (1)(式中，Y表示2價基，s及t分別獨立地表示0或1的整數，G1及G2分別獨立地表示－CR1 R2 －，R1 及R2 分別獨立地表示碳數1至4的烷基、鹵素原子、氫原子，A1及A2分別獨立地表示2價環狀烴基、2價雜環基、亞甲基伸苯基、氧伸苯基、硫伸苯基，A1及A2亦可結合碳數1至5的烷基、碳數1至5的烷氧基、鹵素原子，B1及B2分別獨立地表示選自－CRR’－、－C≡C－、－CH＝CH－、－CH2 －CH2 －、－O－、－S－、－C(＝O)－、－C(＝O)－O－、－O－C(＝O)－、－O－C(＝O)－O－、－C(＝S)－、－C(＝S)－O－、－O－C(＝S)－、－O－C(＝S)－O－、－CH＝N－、－N＝CH－、－N＝N－、－N(→O)＝N－、－N＝N(→O)－、－C(＝O)－NR－、－NR－C(＝O)－、－OCH2 －、－NR－、－CH2 O－、－SCH2 －、－CH2 S－、－CH＝CH－C(＝O)－O－、－O－C(＝O)－CH＝CH－、單鍵所成組群中之2價基，R及R’分別獨立地表示氫原子或碳數1至4的烷基，X1及X2分別獨立地表示下述式(2)所示之2價基， (式中，A3表示2價環狀烴基、雜環基，B3表示與前述B1及B2相同的意義，n表示1至4的整數)，E1及E2分別獨立地表示碳數2至25的伸烷基，E1及E2亦可再結合碳數1至5的烷基、碳數1至5的烷氧基、鹵素原子，P1及P2表示氫原子或聚合性基，P1及P2至少有一個是聚合性基)。(8) The film according to the above aspect, wherein the optically anisotropic layer contains a polymer comprising a structural unit represented by the following formula (1), P2-E2-X2-B2 -A2-(G2)t-Y-(G1)s-A1-B1-X1-E1-P1 (1) (wherein Y represents a divalent group, and s and t each independently represent an integer of 0 or 1, G1 and G2 each independently represent -CR 1 R 2 -, and R 1 and R 2 each independently represent an alkyl group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom, and A1 and A2 each independently represent a divalent cyclic hydrocarbon group. , a divalent heterocyclic group, a methylene extended phenyl group, an oxygen extended phenyl group, a sulfur extended phenyl group, and A1 and A2 may also bond an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen. The atoms, B1 and B2, respectively, are independently selected from -CRR'-, -C≡C-, -CH=CH-, -CH 2 -CH 2 -, -O-, -S-, -C(=O) -, -C(=O)-O-, -O-C(=O)-, -O-C(=O)-O-, -C(=S)-, -C(=S)-O -, -O-C(=S)-, -O-C(=S)-O-, -CH=N-, -N=CH-, -N=N-, -N(→O)=N -, -N=N(→O)-, -C(=O)-NR-, -NR -C(=O)-, -OCH 2 -, -NR-, -CH 2 O-, -SCH 2 -, -CH 2 S-, -CH=CH-C(=O)-O-, -O -C(=O)-CH=CH-, a divalent group in a group of single bonds, R and R' each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X1 and X2 are independently a divalent group represented by the following formula (2), (wherein A3 represents a divalent cyclic hydrocarbon group or a heterocyclic group, B3 represents the same meaning as the above B1 and B2, and n represents an integer of 1 to 4), and E1 and E2 each independently represent a carbon number of 2 to 25 The alkyl group, E1 and E2 may further be bonded to an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom, and P1 and P2 each represent a hydrogen atom or a polymerizable group, and at least one of P1 and P2 is Polymerizable group).

(9)一種膜之製造方法，係具有形成於垂直配向用配向膜上之光學異向性層的膜之製造方法，其特徵為：至少包括(A)在垂直配向用配向膜上塗布含有棒狀聚合性液晶化合物之組成物的步驟、及(B)使上述步驟(A)所形成的塗膜在25℃至120℃下加熱10秒鐘至60分鐘的步驟；而上述棒狀聚合性液晶化合物係作為單體並且為具有在水平配向膜上呈水平配向、在空氣界面上呈垂直配向之特性者。(9) A method for producing a film comprising a film having an optically anisotropic layer formed on an alignment film for a vertical alignment, comprising at least (A) coating a bar containing a vertical alignment film a step of forming a composition of the polymerizable liquid crystal compound, and (B) a step of heating the coating film formed in the above step (A) at 25 ° C to 120 ° C for 10 seconds to 60 minutes; and the above rod-shaped polymerizable liquid crystal The compound is a monomer and has the property of being horizontally aligned on the horizontal alignment film and vertically aligned at the air interface.

(10)如(9)記載之膜之製造方法，其中，復包括(C)藉由光聚合使上述棒狀液晶化合物交聯的步驟。(10) The method for producing a film according to (9), which further comprises (C) a step of crosslinking the rod-like liquid crystal compound by photopolymerization.

(11)一種偏光膜，其特徵為由(1)至(8)中任一項記載之膜所積層而成。(11) A polarizing film comprising the film according to any one of (1) to (8).

(12)一種平面顯示裝置，其特徵為具備(1)至(8)中任一項記載之膜或(11)記載之偏光膜。(12) A flat display device comprising the film according to any one of (1) to (8) or the polarizing film according to (11).

(13)一種光學膜，係具備由液晶所構成且具有第1面及與第1面平行之第2面的光學異向性層、以及與光學異向性層第1面接觸的配向層之光學膜；其中，位於光學異向性層第1面附近的液晶係大致為水平配向，位於光學異向性層第2面附近的液晶係大致為垂直配向，在與光學膜垂直之第1方向的第1折射率(nz)、與光學膜第1方向成直角之第2方向的第2折射率(nx)、以及與光學膜第1方向和第2方向成直角之第3方向的第3折射率(ny)方面，第1折射率(nz)係比第2折射率(nx)及第3折射率(ny)大。(13) An optical film comprising: an optically anisotropic layer composed of a liquid crystal and having a first surface and a second surface parallel to the first surface; and an alignment layer in contact with the first surface of the optically anisotropic layer An optical film; wherein the liquid crystal system located in the vicinity of the first surface of the optically anisotropic layer is substantially horizontally aligned, and the liquid crystal system located in the vicinity of the second surface of the optically anisotropic layer is substantially vertically aligned, and is in a first direction perpendicular to the optical film. The first refractive index (nz), the second refractive index (nx) in the second direction at right angles to the first direction of the optical film, and the third direction in the third direction at right angles to the first and second directions of the optical film In terms of the refractive index (ny), the first refractive index (nz) is larger than the second refractive index (nx) and the third refractive index (ny).

在本發明之一側面上，藉由在硬化前將形成液晶用單體或低聚物(具體而言為棒狀聚合性液晶化合物)的配向性予以控制，而控制硬化後液晶層的配向性。硬化前單體的配向性與硬化後聚合物(亦即液晶)的配向性被認為是相同的。On one aspect of the present invention, the alignment of the liquid crystal layer after hardening is controlled by controlling the alignment of the liquid crystal monomer or oligomer (specifically, a rod-shaped polymerizable liquid crystal compound) before curing. . The alignment of the monomer before hardening and the alignment of the polymer after hardening (i.e., liquid crystal) are considered to be the same.

在本發明之膜中，於垂直配向用配向膜上形成有光學異向性層。上述光學異向性層，係含有在水平配向膜上呈水平配向且在空氣界面上呈垂直配向之棒狀聚合性液晶化合物的層。所以，會發揮在膜之平面方向能將折射率變化縮小、且在膜之法線方向能將折射率變化增大的效果。In the film of the present invention, an optically anisotropic layer is formed on the alignment film for vertical alignment. The optically anisotropic layer is a layer containing a rod-shaped polymerizable liquid crystal compound which is horizontally aligned on a horizontal alignment film and vertically aligned at an air interface. Therefore, the refractive index change can be reduced in the plane direction of the film, and the refractive index change can be increased in the normal direction of the film.

針對本發明之實施形態加以說明即如下述，但本發明不受該等所限定。The embodiments of the present invention are described below, but the present invention is not limited thereto.

<I.本發明之膜><I. Film of the invention>

本發明之膜，係具有形成於垂直配向用配向膜12上之光學異向性層11的膜。上述垂直配向用配向膜12係形成在支撐基材上。亦即，本發明的膜係由垂直配向用配向膜12及光學異向性層11依序積層在上述支撐基材上而成的膜。再者，在本發明之膜中，相對於光學異向性層11的面係空氣層。The film of the present invention is a film having an optically anisotropic layer 11 formed on the alignment film 12 for vertical alignment. The vertical alignment alignment film 12 is formed on a support substrate. In other words, the film of the present invention is a film in which the alignment film 12 for vertical alignment and the optically anisotropic layer 11 are sequentially laminated on the support substrate. Further, in the film of the present invention, the air layer is formed on the surface of the optically anisotropic layer 11.

另外，在本發明中，所謂「垂直配向用配向膜」係指包括使液晶分子呈垂直配向之配向膜(後文亦稱為「垂直配向膜」)、及經摩擦處理過之垂直配向膜的意思。In the present invention, the "alignment film for vertical alignment" means an alignment film including a liquid crystal molecule in a vertical alignment (hereinafter also referred to as a "vertical alignment film"), and a frictionally treated vertical alignment film. meaning.

上述光學異向性層11，係由含有棒狀聚合性液晶化合物14聚合之聚合物的層所構成。以上述棒狀聚合性液晶化合物14而言，如第1A圖所示，可使用具有在水平配向膜上呈水平配向且在空氣界面上呈垂直配向之特性的棒狀聚合性液晶化合物(圖中的橢圓)。只要使用像這樣的棒狀聚合性液晶化合物，當配向於沒有經摩擦處理過的垂直配向膜(垂直配向用配向膜)上時，如第1B圖所示，棒狀聚合性液晶化合物會呈向列垂直配向。另外，使該棒狀聚合性液晶化合物在經摩擦處理過的垂直配向膜(垂直配向用配向膜)上配向時，如第1C圖所示，棒狀聚合性液晶化合物在空氣層界面上仍舊保持垂直方向的分子配向，而在垂直配向用膜界面上會呈傾斜配向。此外，為了方便，在第1A圖至第1C圖中，將垂直配向用配向膜記載為「配向層」，棒狀聚合性液晶化合物記載為「液晶分子」，光學異向性層記載為「液晶層」。The optically anisotropic layer 11 is composed of a layer containing a polymer polymerized by the rod-shaped polymerizable liquid crystal compound 14. In the above-mentioned rod-shaped polymerizable liquid crystal compound 14, as shown in FIG. 1A, a rod-shaped polymerizable liquid crystal compound having a property of being horizontally aligned on a horizontal alignment film and vertically aligned at an air interface can be used (in the figure) Ellipse). When a rod-shaped polymerizable liquid crystal compound as described above is used, when it is aligned on a vertical alignment film (orthogonal alignment alignment film) which has not been subjected to rubbing treatment, as shown in FIG. 1B, the rod-shaped polymerizable liquid crystal compound will be oriented. Column vertical alignment. Further, when the rod-shaped polymerizable liquid crystal compound is aligned on the rubbed vertical alignment film (orthogonal alignment alignment film), as shown in FIG. 1C, the rod-shaped polymerizable liquid crystal compound remains at the air layer interface. Molecular alignment in the vertical direction and oblique alignment at the interface of the vertical alignment film. In addition, in the first to third drawings, the alignment film for vertical alignment is referred to as "alignment layer", the rod-like polymerizable liquid crystal compound is referred to as "liquid crystal molecule", and the optically anisotropic layer is referred to as "liquid crystal." Floor".

像這樣的本發明之膜，其特性為在膜平面之正交軸方向及膜厚方向之折射率分別為nx、ny、nz的情況下，滿足nz>nx及nz>ny。也就是在膜之平面方向上折射率變化小，而在膜法線方向上折射率變化大的膜。因此，本發明之膜能發揮在膜平面方向上折射率變化小，而在膜法線方向上折射率變化大的效果。所以，本發明之膜可用來作為適合IPS模式等液晶面板的光學膜。The film of the present invention has such a characteristic that when the refractive indices in the orthogonal axis direction and the film thickness direction of the film plane are nx, ny, and nz, respectively, nz>nx and nz>ny are satisfied. That is, a film having a small refractive index change in the plane direction of the film and a large refractive index change in the film normal direction. Therefore, the film of the present invention exhibits an effect that the refractive index change in the film plane direction is small and the refractive index changes greatly in the film normal direction. Therefore, the film of the present invention can be used as an optical film suitable for a liquid crystal panel such as an IPS mode.

再者，本發明之膜具有光學異向性。以上述光學異向性而言，列舉例如傾斜角、相位差值等。關於本發明之膜的光學異向性，係根據第2圖更詳細說明如下。Further, the film of the present invention has optical anisotropy. In the above optical anisotropy, for example, a tilt angle, a phase difference value, and the like are listed. The optical anisotropy of the film of the present invention will be described in more detail below based on Fig. 2 .

如第2圖所示，在表示膜1之光學特性的折射率橢圓體22中，定義三維主折射率na、nb、nc。將Y軸與主折射率nb的夾角定義為傾斜角23，從Z方向觀察時，定義出在膜上形成的垂直橢圓面24之長軸ny與短軸nx，將ny與nx之差和膜厚d的積(ny－nx)．d定義為相位差值。As shown in Fig. 2, three-dimensional principal refractive indices na, nb, and nc are defined in the refractive index ellipsoid 22 indicating the optical characteristics of the film 1. The angle between the Y-axis and the main refractive index nb is defined as the inclination angle 23, and when viewed from the Z direction, the major axis ny and the minor axis nx of the vertical elliptical surface 24 formed on the film are defined, and the difference between ny and nx and the film are defined. The product of thickness d (ny-nx). d is defined as the phase difference value.

相位差值的測定法，列舉例如橢圓偏光計測定等方法。傾斜角的測定法，列舉例如在相位差值的測定中，測定光入射角相依性，使用因理想折射率橢圓體之相位差值的入射角相依而變化的計算值，由曲線配適(carve fitting)計算出的方法等。The method of measuring the phase difference is, for example, a method such as measurement by an ellipsometer. For the measurement of the tilt angle, for example, in the measurement of the phase difference value, the incident angle dependence of the light is measured, and the calculated value is changed by the incident angle dependence of the phase difference value of the ideal refractive index ellipsoid, and the curve is fitted (carve) Fitting) The calculated method, etc.

通常，相位差值為5至700 nm左右，較佳為50至400 nm左右。Usually, the phase difference is about 5 to 700 nm, preferably about 50 to 400 nm.

後文更詳細說明構成本發明之膜的上述支撐基材、垂直配向用配向膜及光學異向性層。The above-mentioned support substrate, alignment film for vertical alignment, and optical anisotropic layer constituting the film of the present invention will be described in more detail later.

(I－1)支撐基材(I-1) support substrate

上述支撐基材，只要是能在該支撐基材上形成垂直配向用配向膜者即可，並沒有特別限定。可列舉例如玻璃、塑膠薄片、塑膠膜及透光性膜。又，上述透光性膜列舉例如聚乙烯、聚丙烯、降冰片烯系聚合物等聚烯烴膜；聚乙烯基醇膜、聚對苯二甲酸乙二酯膜、聚甲基丙烯酸酯膜、聚丙烯酸酯膜、纖維素酯膜、聚對萘二甲酸乙二酯膜、聚碳酸酯膜、聚碸膜、聚醚碸膜、聚醚酮膜、聚苯硫醚(polyphenylene sulfide)膜、聚苯醚(polyphenylene oxide)膜等。The support substrate is not particularly limited as long as it can form an alignment film for vertical alignment on the support substrate. For example, glass, a plastic sheet, a plastic film, and a translucent film are mentioned. Further, the translucent film is, for example, a polyolefin film such as polyethylene, polypropylene or a norbornene-based polymer; a polyvinyl alcohol film, a polyethylene terephthalate film, a polymethacrylate film, and a poly Acrylate film, cellulose ester film, polyethylene naphthalate film, polycarbonate film, polyfluorene film, polyether film, polyether ketone film, polyphenylene sulfide film, polyphenylene Polyphenylene oxide film or the like.

一般而言，使用有聚合性液晶化合物的光學異向性層係薄膜，例如即使在使用本發明之膜的貼合步驟、實施膜的搬運或保存等步驟等需要膜強度的步驟中，亦可藉由使用支撐基材而使膜容易處理且沒有破損等。In general, an optically anisotropic layer-form film using a polymerizable liquid crystal compound can be used, for example, in a step of requiring a film strength such as a bonding step using a film of the present invention, a step of transporting or storing a film, and the like. The film is easily handled without damage or the like by using a supporting substrate.

(I－2)垂直配向用配向膜(I-2) alignment film for vertical alignment

在本發明之膜中，垂直配向用配向膜係必須具有因光學異向性層之塗布等而不會溶解的耐溶劑性、並具有因除去溶劑或液晶配向之加熱處理而有的耐熱性、且不會因為摩擦等而產生剝落等，係聚合物或含有聚合物之組成物。In the film of the present invention, the alignment film for vertical alignment must have solvent resistance which is not dissolved by application of an optically anisotropic layer, etc., and has heat resistance due to heat treatment by removing a solvent or a liquid crystal alignment. It does not cause peeling or the like due to friction or the like, and is a polymer or a composition containing a polymer.

上述聚合物，只要是在上述支撐基材上形成者即可，並沒有特別限定。可列舉例如分子內具有醯胺鍵之聚醯胺或明膠類、分子內具有醯亞胺鍵之聚醯亞胺及乃其水解物之聚醯胺酸、聚乙烯基醇、聚丙烯醯胺、聚唑、聚伸乙亞胺、聚丙烯酸、聚丙烯酸酯類等聚合物。這些聚合物可單獨使用，亦可混合2種以上、或使用共聚物。這些聚合物可藉由脫水或脫胺等聚縮合反應，或是自由基聚合反應、陰離子聚合反應、陽離子聚合反應等連鎖聚合反應，配位聚合反應等而或開環聚合反應等而容易地得到。The polymer is not particularly limited as long as it is formed on the support substrate. For example, polyamine or gelatin having a guanamine bond in the molecule, polyimine having a quinone imine bond in the molecule, and polyglycolic acid, polyvinyl alcohol, polyacrylamide, or a hydrolyzate thereof, Gather A polymer such as azole, polyethylenimine, polyacrylic acid or polyacrylate. These polymers may be used singly or in combination of two or more kinds or using a copolymer. These polymers can be easily obtained by a polycondensation reaction such as dehydration or deamination, or a chain polymerization reaction such as a radical polymerization reaction, an anionic polymerization reaction or a cationic polymerization reaction, a coordination polymerization reaction or the like, or a ring-opening polymerization reaction or the like. .

另外，此等聚合物可導入如類固醇等脂環基、長鏈烷基、氟化烷基、芳環結構及含氟芳環結構等有機基。藉由導入如上述所示的結構，棒狀聚合性液晶化合物會變得更容易呈垂直配向。此外，即使藉由混入具有如類固醇等脂環基、長鏈烷基、氟化烷基、芳環結構及含氟芳環結構等有機基之化合物，或是製成添加有鎓鹽、銫離子、銣離子等無機鹽或有機酸鹽類之組成物，棒狀聚合性液晶化合物亦會變得更容易呈垂直配向。Further, these polymers may be introduced with an organic group such as an alicyclic group such as a steroid, a long-chain alkyl group, a fluorinated alkyl group, an aromatic ring structure, and a fluorine-containing aromatic ring structure. By introducing the structure as described above, the rod-shaped polymerizable liquid crystal compound becomes easier to be vertically aligned. Further, even by mixing a compound having an alicyclic group such as a steroid such as an alicyclic group, a long-chain alkyl group, a fluorinated alkyl group, an aromatic ring structure or a fluorine-containing aromatic ring structure, or by adding a cerium salt or a cerium ion In the case of an inorganic salt such as a cerium ion or a composition of an organic acid salt, the rod-shaped polymerizable liquid crystal compound also becomes more likely to be vertically aligned.

上述聚合物之具體例可列舉例如在日本特開2001－305549號公報、WO 2003－042752、日本特開2005－139228號公報、液晶第8卷第4號216頁等所揭示的聚醯亞胺及其聚醯胺酸，或是在日本特開2005－196015號公報、日本特開2005－315988號公報及日本特開2005－196016號公報等所揭示的聚乙烯基醇等。再者，後述實施例所使用的垂直配向用聚醯亞胺配向膜(商品名SE－5300，日產化學公司製造)等亦是垂直配向用的聚醯亞胺配向膜。Specific examples of the polymer include polyethylenimine disclosed in, for example, JP-A-2001-305549, WO 2003-042752, JP-A-2005-139228, Liquid Crystal No. 8, No. 4, page 216, and the like. And a polyvinyl alcohol or the like disclosed in JP-A-2005-196015, JP-A-2005-315988, and JP-A-2005-196016. Further, the polyimine alignment film for vertical alignment (trade name: SE-5300, manufactured by Nissan Chemical Co., Ltd.) used in the examples described later is also a polyimide film for vertical alignment.

垂直配向用配向膜的厚度雖然沒有特別限定，但以10 nm至10000 nm為較佳，10 nm至1000 nm為更佳。只要在上述範圍內，就可使所得到的膜輕量化。再者，垂直配向用配向膜所具有的光學特性可減少對於所得到之膜的影響。Although the thickness of the alignment film for the vertical alignment is not particularly limited, it is preferably 10 nm to 10000 nm, and more preferably 10 nm to 1000 nm. As long as it is within the above range, the obtained film can be made lighter. Further, the optical characteristics of the alignment film for vertical alignment can reduce the influence on the obtained film.

上述垂直配向用配向膜視需要可進行摩擦處理。在未施加摩擦處理的垂直配向用配向膜上，若使後述棒狀聚合性液晶化合物在液晶狀態下配向時，該棒狀聚合性液晶化合物相對於垂直配向用配向膜呈向列垂直配向。因此，所得到的膜會變成垂直配向膜。The above alignment film for vertical alignment can be subjected to rubbing treatment as needed. When the rod-shaped polymerizable liquid crystal compound to be described later is aligned in a liquid crystal state, the rod-shaped polymerizable liquid crystal compound is aligned in a vertical direction with respect to the alignment film for vertical alignment on the alignment film for the vertical alignment which is not subjected to the rubbing treatment. Therefore, the obtained film becomes a vertical alignment film.

另一方面，在經摩擦處理過的垂直配向用配向膜上，若使後述棒狀聚合性液晶化合物在液晶狀態下配向時，該棒狀聚合性液晶化合物在空氣層界面上仍舊保持垂直配向的狀態，而在垂直配向用配向膜界面上會呈傾斜配向。因此，所得到的膜會變成傾斜配向膜。On the other hand, when the rod-shaped polymerizable liquid crystal compound described later is aligned in a liquid crystal state on the rubbing-treated vertical alignment alignment film, the rod-shaped polymerizable liquid crystal compound remains vertically aligned at the air layer interface. The state is inclined at the interface of the alignment film for vertical alignment. Therefore, the obtained film becomes a tilt alignment film.

亦即，本發明之膜包括垂直配向膜及傾斜配向膜兩者。That is, the film of the present invention includes both a vertical alignment film and a tilt alignment film.

(I－3)光學異向性層(I-3) Optical anisotropic layer

上述光學異向性層，係形成於上述垂直配向用配向膜上且具有光學異向性的層。上述光學異向性層係由含有一種聚合物之層所構成，而該聚合物含有從棒狀聚合性液晶化合物而來之結構單元。上述光學異向性層中，亦可含有包含從棒狀聚合性液晶化合物以外之化合物而來之結構單元的聚合物。例如，為了賦予本發明之膜期望的波長分散特性，亦可使用在從棒狀聚合性液晶化合物而來之結構單元中，復含有從特定聚合性化合物而來之結構單元的聚合物。另外，亦可含有與棒狀聚合性液晶化合物及特定聚合性化合物係相異的液晶化合物(後文為了便於說明，亦稱為「其他液晶化合物」)。此外，亦可含有聚合起始劑、聚合抑制劑、光敏劑、調平劑等。另外，後文敘述關於構成光學異向性層之化合物的詳細情形。The optically anisotropic layer is a layer formed on the vertical alignment alignment film and having optical anisotropy. The optically anisotropic layer is composed of a layer containing a polymer containing a structural unit derived from a rod-shaped polymerizable liquid crystal compound. The optically anisotropic layer may further contain a polymer containing a structural unit derived from a compound other than the rod-shaped polymerizable liquid crystal compound. For example, in order to impart desired wavelength dispersion characteristics to the film of the present invention, a polymer having a structural unit derived from a specific polymerizable compound in a structural unit derived from a rod-shaped polymerizable liquid crystal compound may be used. Further, a liquid crystal compound which is different from the rod-shaped polymerizable liquid crystal compound and the specific polymerizable compound may be contained (hereinafter referred to as "other liquid crystal compound" for convenience of explanation). Further, a polymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent and the like may be contained. Further, the details of the compound constituting the optically anisotropic layer will be described later.

只要以使上述光學異向性層的厚度變成所得到之膜之相位差值(相位差值(retardation value)，Re(λ))之期望值的方式，加以適當地調整即可。Re(λ)係依據下述數學式(a)而決定。所以，為了得到期望的Re(λ)，只要調整膜厚d即可。The thickness of the optically anisotropic layer may be appropriately adjusted so as to become a desired value of a phase difference (retardation value, Re(λ)) of the obtained film. Re(λ) is determined according to the following formula (a). Therefore, in order to obtain the desired Re(λ), it is only necessary to adjust the film thickness d.

Re(λ)＝d×△n(λ)………(a)(式中，Re(λ)表示在波長λ nm時的相位差值，d表示膜厚，△n(λ)表示在波長λ nm時的折射率異向性。)Re(λ)=d×Δn(λ) (a) (wherein, Re(λ) represents the phase difference at the wavelength λ nm, d represents the film thickness, and Δn(λ) represents the wavelength Refractive index anisotropy at λ nm.)

此外，在本發明之膜之較佳的一實施形態中，上述垂直配向用配向膜係垂直配向膜，上述棒狀聚合性液晶化合物之折射率橢圓體以具有相對於膜平面為90±5°之傾斜角為較佳。因此，該膜成為垂直配向膜。Further, in a preferred embodiment of the film of the present invention, the alignment film for vertical alignment is a vertical alignment film, and the refractive index ellipsoid of the rod-shaped polymerizable liquid crystal compound has a 90±5° with respect to the plane of the film. The tilt angle is preferred. Therefore, the film becomes a vertical alignment film.

另外，在其他實施形態中，上述垂直配向用配向膜係經磨擦處理過的垂直配向膜，上述棒狀聚合性液晶化合物之折射率橢圓體在垂直配向用配向膜界面上，以具有相對於膜平面為45°至85°之傾斜角為較佳。因此，該膜成為傾斜配向膜。Further, in another embodiment, the vertical alignment alignment film is a rubbed-treated vertical alignment film, and the refractive index ellipsoid of the rod-shaped polymerizable liquid crystal compound is on the interface of the alignment film for vertical alignment to have a film relative to the film. A plane angle of 45 to 85 is preferred. Therefore, the film becomes an inclined alignment film.

後文詳細說明可包含在上述光學異向性層中的棒狀聚合性液晶化合物、其他液晶化合物、聚合性化合物及其他組成化合物。The rod-shaped polymerizable liquid crystal compound, other liquid crystal compound, polymerizable compound, and other constituent compounds which may be contained in the above-mentioned optical anisotropic layer will be described in detail later.

(I－3－1)棒狀聚合性液晶化合物(I-3-1) rod-shaped polymerizable liquid crystal compound

在上述光學異向性層中所含的棒狀聚合性液晶化合物，係作為單體並且在水平配向膜上呈水平配向、在空氣界面上呈垂直配向的棒狀聚合性液晶化合物。上述「作為單體並且在水平配向膜上呈水平配向、在空氣界面上呈垂直配向的棒狀聚合性液晶化合物」係指例如在將表面進行水平處理過的玻璃基板上、或是在將聚乙烯基醇等會引起水平配向之配向膜作為水平配向膜而設置於表面上所成的基材上，將棒狀聚合性液晶化合物作為單體而塗布時，所得到之配向在配向膜上成為水平且在空氣界面上呈垂直配向的棒狀聚合性液晶化合物。棒狀聚合性液晶化合物即使聚合亦保持配向，在膜的法線方向上賦予高之折射率。The rod-shaped polymerizable liquid crystal compound contained in the optically anisotropic layer is a rod-like polymerizable liquid crystal compound which is a monomer and is horizontally aligned on a horizontal alignment film and vertically aligned at an air interface. The above-mentioned "rod-like polymerizable liquid crystal compound which is a monomer and is horizontally aligned on a horizontal alignment film and vertically aligned at an air interface" means, for example, on a glass substrate having a surface treated horizontally, or is to be aggregated. When an alignment film which causes a horizontal alignment, such as a vinyl alcohol, is provided as a horizontal alignment film on a substrate formed on the surface, and when a rod-shaped polymerizable liquid crystal compound is applied as a monomer, the obtained alignment becomes on the alignment film. A rod-shaped polymerizable liquid crystal compound which is horizontally aligned and vertically aligned at the air interface. The rod-shaped polymerizable liquid crystal compound maintains an alignment even when polymerized, and imparts a high refractive index in the normal direction of the film.

賦予此等所謂混合配向性的聚合性液晶化合物，係含有從單獨或2種以上之棒狀聚合性液晶化合物而來之結構單元的液晶，列舉例如日本特開2005－320317號公報或日本特開2001－55573號公報所示之聚合性液晶化合物。再者，亦可在棒狀聚合性液晶化合物中添加矽系低聚物化合物或含氟聚合物、(甲基)丙烯酸系單體、非離子性界面活性劑等，以控制配向。以此等方法而言，可列舉例如日本特開平9－288210號公報或日本特開平2006－16599號公報、日本特開平2005－196221號公報中所示的方法。The polymerizable liquid crystal compound to which the above-mentioned mixed-alignment is contained is a liquid crystal containing a structural unit derived from a single or two or more kinds of rod-shaped polymerizable liquid crystal compounds, and is disclosed, for example, in JP-A-2005-320317 or JP-A-. A polymerizable liquid crystal compound shown in JP-A-2001-55573. Further, a fluorene-based oligomer compound, a fluoropolymer, a (meth)acrylic monomer, a nonionic surfactant, or the like may be added to the rod-shaped polymerizable liquid crystal compound to control the alignment. For example, the method shown in Japanese Laid-Open Patent Publication No. Hei 9-288210, or Japanese Patent Application Laid-Open No. Hei No. Hei.

上述棒狀聚合性液晶化合物之具體例，可列舉如在液晶便覽(液晶便覽編集委員會編，丸善股份公司平成12年10月30日發行)之第3章 分子結構與液晶性質之3.2非手性棒狀液晶分子、3.3手性棒狀液晶分子中所記載之化合物中具有聚合性基的化合物。Specific examples of the above-mentioned rod-like polymerizable liquid crystal compound include, for example, the liquid crystal structure (edited by the Liquid Crystal Handbook Compilation Committee, Maruzen Co., Ltd., issued on October 30, 2009). Chapter 3: Molecular Structure and Liquid Crystal Properties 3.2 Achirality A compound having a polymerizable group among the compounds described in the rod-like liquid crystal molecules and the 3.3 chiral rod-like liquid crystal molecules.

更具體而言，可列舉如後述實施例使用的RMS－03－11(商品名，默克(Merck)股份有限公司製造)中所含的棒狀聚合性液晶化合物。More specifically, a rod-shaped polymerizable liquid crystal compound contained in RMS-03-11 (trade name, manufactured by Merck Co., Ltd.) used in the examples described later can be mentioned.

在本發明之膜中，以棒狀聚合性液晶化合物而言，並非以往使用的垂直配向性棒狀聚合性液晶化合物，是藉由使用如上述之混合配向性棒狀聚合性液晶化合物，而能夠在法線方向上任意控制該化合物經聚合所得到之光學異向性層中之折射率橢圓體的傾斜角。若更詳言之，就是在上述垂直配向用配向膜之中，在沒有經摩擦處理過的垂直配向膜上，若使上述棒狀聚合性液晶化合物在液晶狀態下配向時，上述棒狀聚合性液晶化合物相對於垂直配向用配向膜呈向列垂直配向後，會使該配向性仍舊保持並聚合而提供膜。另一方面，在經摩擦處理過的垂直配向膜上，若使上述棒狀聚合性液晶化合物在液晶狀態下配向時，上述棒狀聚合性液晶化合物在空氣層界面上仍舊保持垂直配向的狀態、且在垂直配向用配向膜界面上呈傾斜配向後，會使該配向性仍舊保持並聚合而提供膜。In the film of the present invention, the rod-like polymerizable liquid crystal compound is not a vertical alignment rod-shaped polymerizable liquid crystal compound which has been conventionally used, and can be obtained by using the above-described mixed alignment rod-shaped polymerizable liquid crystal compound. The tilt angle of the refractive index ellipsoid in the optically anisotropic layer obtained by polymerization of the compound is arbitrarily controlled in the normal direction. More specifically, in the vertical alignment film for vertical alignment, when the rod-shaped polymerizable liquid crystal compound is aligned in a liquid crystal state on a vertical alignment film which has not been subjected to rubbing treatment, the rod-like polymerizability is obtained. When the liquid crystal compound is vertically aligned with respect to the alignment film for vertical alignment, the alignment property is maintained and polymerized to provide a film. On the other hand, when the rod-shaped polymerizable liquid crystal compound is aligned in a liquid crystal state on the rubbed-treated vertical alignment film, the rod-shaped polymerizable liquid crystal compound maintains a vertical alignment state at the air layer interface. Moreover, after being oriented obliquely at the interface of the alignment film for vertical alignment, the alignment property is maintained and polymerized to provide a film.

因此，本發明之膜係成為在膜平面方向上折射率變化小，而在膜法線方向上折射率變化大的膜。Therefore, the film of the present invention is a film having a small change in refractive index in the film plane direction and a large refractive index change in the film normal direction.

再者，上述棒狀聚合性液晶化合物，亦可為任何聚合方式進行聚合者。可列舉例如熱聚合性棒狀聚合性液晶化合物或光聚合性棒狀聚合性液晶化合物。在本發明中，特別以光聚合性棒狀聚合性液晶化合物為較佳。據此，可在低溫下使棒狀聚合性液晶化合物聚合、固定化。所以，在上述支撐基材的選擇變寬的同時，在工業上亦為有利。Further, the rod-shaped polymerizable liquid crystal compound may be polymerized by any polymerization method. For example, a thermally polymerizable rod-shaped polymerizable liquid crystal compound or a photopolymerizable rod-shaped polymerizable liquid crystal compound can be mentioned. In the present invention, a photopolymerizable rod-like polymerizable liquid crystal compound is particularly preferred. According to this, the rod-shaped polymerizable liquid crystal compound can be polymerized and immobilized at a low temperature. Therefore, it is industrially advantageous while the selection of the above-mentioned support substrate is widened.

(I－3－2)其他液晶化合物(I-3-2) other liquid crystal compounds

在上述光學異向性層中所包含且含有從上述棒狀聚合性液晶化合物而來之結構單元的聚合物中，亦可含有從不同種類之液晶化合物而來的結構單元。The polymer contained in the optically anisotropic layer and containing the structural unit derived from the rod-shaped polymerizable liquid crystal compound may contain a structural unit derived from a different type of liquid crystal compound.

上述液晶化合物，例如以下述式(3)、式(4)、式(5)、式(6)、式(7)或式(8)所示之化合物為較佳。The liquid crystal compound is preferably a compound represented by the following formula (3), formula (4), formula (5), formula (6), formula (7) or formula (8), for example.

P11－E11－B11－A11－B12－A12－B14－A14－B15－E12－P12 (3) P11－B11－B11－A11－B12－A12－B14－A14－B13－F11 (4) P11－B11－A11－B12－A12－B14－A14－B13－F11 (5) P11－E11－B11－A11－B12－A12－F11 (6) P11－B11－A11－B12－A12－B13－F11 (7) P11－E11－B11－A11－B12－A12－B13－F11 (8)P11-E11-B11-A11-B12-A12-B14-A14-B15-E12-P12 (3) P11-B11-B11-A11-B12-A12-B14-A14-B13-F11 (4) P11-B11- A11-B12-A12-B14-A14-B13-F11 (5) P11-E11-B11-A11-B12-A12-F11 (6) P11-B11-A11-B12-A12-B13-F11 (7) P11- E11-B11-A11-B12-A12-B13-F11 (8)

另外，在上述式(3)、式(4)、式(5)、式(6)、式(7)及式(8)中，A11、A12及A14分別獨立地表示2價環狀烴基、2價雜環基、亞甲基伸苯基、氧伸苯基或硫伸苯基。在A11、A12及A14上亦可結合碳數1至5的烷基、碳數1至5的烷氧基或鹵素原子。Further, in the above formulas (3), (4), (5), (6), (7) and (8), A11, A12 and A14 each independently represent a divalent cyclic hydrocarbon group, A divalent heterocyclic group, a methylene-phenylene group, an oxygen-extended phenyl group or a sulfur-extended phenyl group. An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom may be bonded to A11, A12 and A14.

B11、B12、B13、B14及B15分別獨立地表示選自－CRR’－、－C≡C－、－CH＝CH－、－CH2 －CH2 －、－O－、－S－、－C(＝O)－、－C(＝O)－O－、－O－C(＝O)－、－O－C(＝O)－O－、－C(＝S)－、－C(＝S)－O－、－O－C(＝S)－、－O－C(＝S)－O－、－CH＝N－、－N＝CH－、－N＝N－、－N(→O)＝N－、－N＝N(→O)－、－C(＝O)－NR－、－NR－C(＝O)－、－OCH2 －、－NR－、－CH2 O－、－SCH2 －、－CH2 S－、－CH＝CH－C(＝O)－O－、－O－C(＝O)－CH＝CH－及單鍵所成組群(又，R及R’分別獨立地表示氫原子或碳數1至4的烷基)中之2價基。B11, B12, B13, B14 and B15 are each independently selected from -CRR'-, -C≡C-, -CH=CH-, -CH 2 -CH 2 -, -O-, -S-, -C (=O)-, -C(=O)-O-, -O-C(=O)-, -O-C(=O)-O-, -C(=S)-, -C(= S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CH=N-, -N=CH-, -N=N-, -N(→ O)=N-, -N=N(→O)-, -C(=O)-NR-, -NR-C(=O)-, -OCH 2 -, -NR-, -CH 2 O- , -SCH 2 -, -CH 2 S-, -CH=CH-C(=O)-O-, -O-C(=O)-CH=CH-, and a single bond group (again, R And R' each independently represents a divalent group in a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

E11及E12分別獨立地表示碳數2至25的伸烷基。此外，在E11及E12上亦可結合碳數1至5的烷基、碳數1至5的烷氧基或鹵素原子。E11 and E12 each independently represent an alkylene group having 2 to 25 carbon atoms. Further, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom may be bonded to E11 and E12.

式(4)至式(8)的P11表示聚合性基。式(3)的P11及P12表示氫原子或聚合性基，P11及P12至少有一個是聚合性基。P11 of the formula (4) to the formula (8) represents a polymerizable group. P11 and P12 in the formula (3) represent a hydrogen atom or a polymerizable group, and at least one of P11 and P12 is a polymerizable group.

F11表示氫原子、烷基、氰基、硝基、三氟甲基、氟原子等鹵素原子或氫原子。F11 represents a halogen atom or a hydrogen atom such as a hydrogen atom, an alkyl group, a cyano group, a nitro group, a trifluoromethyl group or a fluorine atom.

作為其他液晶化合物者，尤其是以下的式(3－1)至(3－6)、式(6－1)、式(6－2)、式(8－1)及式(8－2)中之任一者所示的液晶化合物， 或是下述式(3－7)至(3－12)、式(4－1)至(4－4)、式(5－1)、式(5－2)、式(7－1)及式(7－2)中之任一者所示的液晶化合物， 以容易取得故為較佳。As other liquid crystal compounds, in particular, the following formulas (3-1) to (3-6), formula (6-1), formula (6-2), formula (8-1), and formula (8-2) a liquid crystal compound as shown in any of Or the following formulas (3-7) to (3-12), formulas (4-1) to (4-4), formula (5-1), formula (5-2), and formula (7-1) And a liquid crystal compound represented by any one of the formula (7-2), It is preferred to be easy to obtain.

(I－3－3)聚合性化合物(I-3-3) polymerizable compound

在上述光學異向性層之聚合物中，為了賦予所得到的膜期望的波長分散特性，亦可使用復含有從特定聚合性液晶化合物而來之結構單元的聚合物。In the polymer of the optically anisotropic layer, a polymer containing a structural unit derived from a specific polymerizable liquid crystal compound may be used in order to impart desired wavelength dispersion characteristics to the obtained film.

上述「特定聚合性化合物」係指藉由一併使用於上述棒狀聚合性液晶化合物中，而能夠賦予所得到的膜期望的波長分散特性者。The above-mentioned "specific polymerizable compound" means a wavelength-dispersing property which can be imparted to a desired film by using it in the above-mentioned rod-shaped polymerizable liquid crystal compound.

此類聚合性化合物係下述式(1)所示之化合物，P2－E2－X2－B2－A2－(G2)t－Y－(G1)s－A1－B1－X1－E1－P1 (1)(式中，Y表示2價基，s及t分別獨立地表示0或1的整數，G1及G2分別獨立地表示－CR1 R2 －(又，R1 及R2 分別獨立地表示碳數1至4的烷基、鹵素原子或氫原子)，A1及A2分別獨立地表示2價環狀烴基、2價雜環基、亞甲基伸苯基、氧伸苯基或硫伸苯基，在A1及A2上亦可結合碳數1至5的烷基、碳數1至5的烷氧基或鹵素原子，B1及B2分別獨立地表示選自－CRR’－、－C≡C－、－CH＝CH－、－CH2 －CH2 －、－O－、－S－、－C(＝O)－、－C(＝O)－O－、－O－C(＝O)－、－O－C(＝O)－O－、－C(＝S)－、－C(＝S)－O－、－O－C(＝S)－、－O－C(＝S)－O－、－CH＝N－、－N＝CH－、－N＝N－、－N(→O)＝N－、－N＝N(→O)－、－C(＝O)－NR－、－NR－C(＝O)－、－OCH2 －、－NR－、－CH2 O－、－SCH2 －、－CH2 S－、－CH＝CH－C(＝O)－O－、－O－C(＝O)－CH＝CH－及單鍵所成組群(又，R及R’分別獨立地表示氫原子或碳數1至4的烷基)中之2價基，X1及X2分別獨立地表示下述式(2)所示之2價基， (式中，A3表示2價環狀烴基或雜環基，B3表示選自－CRR’－、－C≡C－、－CH＝CH－、－CH2 －CH2 －、－O－、－S－、－C(＝O)－、－C(＝O)－O－、－O－C(＝O)－、－O－C(＝O)－O－、－C(＝S)－、－C(＝S)－O－、－O－C(＝S)－、－O－C(＝S)－O－、－CH＝N－、－N＝CH－、－N＝N－、－N(→O)＝N－、－N＝N(→O)－、－C(＝O)－NR－、－NR－C(＝O)－、－OCH2 －、－NR－、－CH2 O－、－SCH2 －、－CH2 S－、－CH＝CH－C(＝O)－O－、－O－C(＝O)－CH＝CH－及單鍵所成組群(又，R及R’分別獨立地表示氫原子或碳數1至4的烷基)中之2價基，n表示1至4的整數)，E1及E2分別獨立地表示碳數2至25的伸烷基，在E1及E2上亦可再結合碳數1至5的烷基、碳數1至5的烷氧基或鹵素原子，P1及P2表示氫原子或聚合性基，P1及P2至少有一個是聚合性基)。Such a polymerizable compound is a compound represented by the following formula (1), P2-E2-X2-B2-A2-(G2)t-Y-(G1)s-A1-B1-X1-E1-P1 (1) Wherein Y represents a divalent group, s and t each independently represent an integer of 0 or 1, and G1 and G2 each independently represent -CR 1 R 2 - (again, R 1 and R 2 each independently represent carbon a number of 1 to 4 alkyl groups, a halogen atom or a hydrogen atom), and A1 and A2 each independently represent a divalent cyclic hydrocarbon group, a divalent heterocyclic group, a methylene extended phenyl group, an oxygen extended phenyl group or a sulfur extended phenyl group. Further, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom may be bonded to A1 and A2, and B1 and B2 each independently represent a group selected from -CRR'-, -C≡C-. , -CH=CH-, -CH 2 -CH 2 -, -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)- , -O-C(=O)-O-, -C(=S)-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)- O-, -CH=N-, -N=CH-, -N=N-, -N(→O)=N-, -N=N(→O)-, -C(=O)-NR- , -NR-C(=O)-, -OCH 2 -, -NR-, -CH 2 O-, -SCH 2 -, -C H 2 S-, -CH=CH-C(=O)-O-, -O-C(=O)-CH=CH- and a single bond group (again, R and R' are independently represented a divalent group of a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X1 and X2 each independently represent a divalent group represented by the following formula (2). (wherein A3 represents a divalent cyclic hydrocarbon group or a heterocyclic group, and B3 represents a group selected from -CRR'-, -C≡C-, -CH=CH-, -CH 2 -CH 2 -, -O-, - S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -O-C(=O)-O-, -C(=S)- , -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CH=N-, -N=CH-, -N=N- , -N(→O)=N-, -N=N(→O)-, -C(=O)-NR-, -NR-C(=O)-, -OCH 2 -, -NR-, -CH 2 O-, -SCH 2 -, -CH 2 S-, -CH=CH-C(=O)-O-, -O-C(=O)-CH=CH- and a single bond a group (again, R and R' each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), n represents an integer of 1 to 4, and E1 and E2 independently represent a carbon number of 2 to The alkylene group of 25 may further combine an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a halogen atom on E1 and E2, and P1 and P2 represent a hydrogen atom or a polymerizable group, P1 and At least one of P2 is a polymerizable group).

上述式(1)中的Y表示2價基，此基以具有彎曲結構者為較佳。在此，「彎曲結構」係指在含有A1(其為Y之結合基)之基團上所結合的結合基、與在含有A2(其為Y之結合基)之基團上所結合的結合基，兩者所形成之角度為100°至140°的結構。再者，上述角度係以110°至130°為較佳。只要在上述範圍內，當聚合性化合物與棒狀聚合性液晶化合物溶解在有機溶劑時的互溶性就會提高。因此，可使所得到的膜之相位差值提高。Y in the above formula (1) represents a divalent group, and this group is preferably a structure having a bent structure. Here, the "bending structure" means a combination of a bonding group bonded to a group containing A1 (which is a bonding group of Y) and a group bonded to a group containing A2 (which is a binding group of Y). Base, the angle formed by the two is 100 ° to 140 ° structure. Further, the above angle is preferably 110 to 130. When it is in the above range, the mutual solubility of the polymerizable compound and the rod-shaped polymerizable liquid crystal compound in an organic solvent is improved. Therefore, the phase difference of the obtained film can be increased.

具體的Y可例示如下述式(9)所示的2價基。Specific Y can be exemplified by a divalent group represented by the following formula (9).

以A1、A2、C1、D1、D2、(G1)s 、(G2)t 表示在含有A1(其為Y之結合基)之基團上所結合的結合基與在含有A2(其為Y之結合基)之基團上所結合的結合基團所形成的角度時，在上述式(1)中s＝t＝1的情況下，該角度可用下述式(9－1)的兩箭形符號表示。同樣地，在上述式(1)中s＝t＝0的情況下，該角度可用下述式(9－2)表示。A1, A2, C1, D1, D2, (G1) s , (G2) t represent a bonding group bonded to a group containing A1 (which is a bonding group of Y) and a group containing A2 (which is Y) When the angle formed by the bonding group bonded to the group of the group is bonded, in the case of s=t=1 in the above formula (1), the angle can be two arrows of the following formula (9-1). Symbolic representation. Similarly, in the case of s=t=0 in the above formula (1), the angle can be expressed by the following formula (9-2).

在上述式(9)中，C1表示4級碳原子或4級矽原子。其中，從容易製造的觀點來看，C1係以4級碳原子為較佳。In the above formula (9), C1 represents a 4-stage carbon atom or a 4-stage ruthenium atom. Among them, from the viewpoint of ease of production, C1 is preferably a 4-stage carbon atom.

在上述式(9)中，D1及D2分別表示環狀烴基、雜環基、碳數1至5的直鏈狀烴基或碳數1至5的分枝狀烴基。D1及D2中所使用的環狀烴基可列舉如環戊基、環己基等碳數5至12左右的環烷基；下述式中之任一者所示之碳數6至18左右的芳基等。In the above formula (9), D1 and D2 each represent a cyclic hydrocarbon group, a heterocyclic group, a linear hydrocarbon group having 1 to 5 carbon atoms or a branched hydrocarbon group having 1 to 5 carbon atoms. Examples of the cyclic hydrocarbon group used in D1 and D2 include a cycloalkyl group having a carbon number of from 5 to 12 such as a cyclopentyl group or a cyclohexyl group; and a carbon number of from 6 to 18 as shown in any one of the following formulae. Base.

再者，D1及D2中所使用的雜環基可列舉如5員環、6員環等下述式中之任一者所示之基。In addition, examples of the heterocyclic group used in D1 and D2 include a group represented by any one of the following formulae such as a 5-membered ring or a 6-membered ring.

D1與D2亦可用碳數1至5的烴基、胺基、醚基、硫醚基或單鍵而連結。再者，在D1及D2上亦可結合羥基、胺基、巰基、環狀烴基、碳數1至5的直鏈狀或分枝狀烷基、碳數1至5的直鏈狀或分枝狀烷氧基、三氟甲基、三氟甲氧基、氰基、硝基或鹵素原子。D1 and D2 may also be bonded by a hydrocarbon group having 1 to 5 carbon atoms, an amine group, an ether group, a thioether group or a single bond. Further, D1 and D2 may also be bonded to a hydroxyl group, an amine group, a mercapto group, a cyclic hydrocarbon group, a linear or branched alkyl group having 1 to 5 carbon atoms, or a linear or branched carbon number of 1 to 5. An alkoxy group, a trifluoromethyl group, a trifluoromethoxy group, a cyano group, a nitro group or a halogen atom.

在此，上述烴基可列舉如亞甲基、伸乙基、伸丙基等伸烷基；或是伸烷基的單鍵經雙鍵或三鍵所取代而成之連接基等。再者，上述環狀烴基可例示如與D1及D2中所使用者為同樣的環狀烴基。烷基、烷氧基、鹵素原子可同樣例示如作為取代於前述A1和A2中之基團所例示的烷基、烷氧基及鹵素原子。Here, the above hydrocarbon group may, for example, be an alkylene group such as a methylene group, an exoethyl group or a propyl group; or a linking group obtained by substituting a single bond of an alkyl group with a double bond or a triple bond. Further, the cyclic hydrocarbon group may be, for example, the same cyclic hydrocarbon group as those used in D1 and D2. The alkyl group, the alkoxy group, and the halogen atom may be exemplified by an alkyl group, an alkoxy group, and a halogen atom exemplified as a group substituted in the above A1 and A2.

上述式(9)所示之基團的具體例可列舉如下述式(D－1)至(D－18)所示之2價取代基 (在此，從容易製造之觀點來看，係例示如碳原子作為4級原子C1)，或是C1為碳原子且D1及D2都是苯基的取代基等。Specific examples of the group represented by the above formula (9) include divalent substituents represented by the following formulas (D-1) to (D-18). (herein, from the viewpoint of easy production, for example, a carbon atom is referred to as a four-order atom C1), or a substituent in which C1 is a carbon atom and D1 and D2 are both a phenyl group.

另外，前述例示結構中所含的氫原子之一部分亦可用甲基、乙基、異丙基、三級丁基等碳數1至4左右的烷基；甲氧基、乙氧基等碳數1至4左右的烷氧基；三氟甲基；三氟甲氧基；氰基；硝基；氟原子、氯原子、溴原子等鹵素原子所取代。Further, a part of the hydrogen atom contained in the above-exemplified structure may be an alkyl group having a carbon number of about 1 to 4 such as a methyl group, an ethyl group, an isopropyl group or a tertiary butyl group; and a carbon number such as a methoxy group or an ethoxy group; Alkoxy group of about 1 to 4; trifluoromethyl; trifluoromethoxy; cyano; nitro; substituted by a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

以Y而言，從容易製造的觀點來看，係以C1為碳原子且D1及D2或是苯基的取代基、或上述式(D－1)至(D－12)所示的取代基為較佳。尤其是從顯著表現出逆波長分散的觀點來看，係以上述式(D－1)至(D－12)所示的取代基為較佳。In the case of Y, from the viewpoint of easy production, a substituent represented by C1 as a carbon atom and D1 and D2 or a phenyl group, or a substituent represented by the above formula (D-1) to (D-12) It is better. In particular, from the viewpoint of remarkably exhibiting reverse wavelength dispersion, the substituents represented by the above formulas (D-1) to (D-12) are preferred.

在上述式(1)中的(G1)s 及(G2)t 中，s及t分別獨立地表示0或1的整數。In (G1) s and (G2) t in the above formula (1), s and t each independently represent an integer of 0 or 1.

在s及t為1的情況下，G1及G2分別獨立地為－CR1 R2 －。在此，R1 及R2 分別獨立地表示甲基、乙基等碳數1至4左右的烷基；氟原子、氯原子、溴原子等鹵素原子。In the case where s and t are 1, G1 and G2 are each independently -CR 1 R 2 -. Here, R 1 and R 2 each independently represent an alkyl group having a carbon number of about 1 to 4 such as a methyl group or an ethyl group; and a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

再者，在s及t為0的情況下，Y與A1為單鍵結合，且Y與A2為單鍵結合。Further, in the case where s and t are 0, Y and A1 are single-bonded, and Y and A2 are single-bonded.

在上述式(1)中，A1及A2分別獨立地表示2價環狀烴基、2價雜環基、亞甲基伸苯基、氧伸苯基或硫伸苯基。在此，亞甲基伸苯基、氧伸苯基或硫伸苯基中的亞甲基、醚基、硫醚基係與B1及B2結合。In the above formula (1), A1 and A2 each independently represent a divalent cyclic hydrocarbon group, a divalent heterocyclic group, a methylene extended phenyl group, an oxygen extended phenyl group or a sulfur extended phenyl group. Here, the methylene group, the ether group, and the thioether group in the methylene-phenylene group, the oxygen-extended phenyl group or the sulfur-extended phenyl group are bonded to B1 and B2.

A1及A2中所使用的2價環狀烴基，可列舉例如下述式中之任一者所示之碳數6至18左右的芳基 、由下述式所示之5員環和6員環等所構成的脂環基 、以及由下述式中之任一者所示之5員環和6員環等所構成的雜環基等。Examples of the divalent cyclic hydrocarbon group used in A1 and A2 include an aryl group having a carbon number of about 6 to 18 as shown in any one of the following formulas. An alicyclic group composed of a 5-membered ring and a 6-membered ring represented by the following formula And a heterocyclic group or the like which is composed of a 5-membered ring and a 6-membered ring represented by any one of the following formulae.

另外，以A1及A2而言，前述例示基團的氫原子之一部分亦可用甲基、乙基、異丙基、三級丁基等碳數1至4左右的烷基；甲氧基、乙氧基等碳數1至4左右的烷氧基；三氟甲基；三氟甲氧基；氰基；硝基；氟原子、氯原子、溴原子等鹵素原子所取代。Further, in the case of A1 and A2, a part of the hydrogen atom of the above-exemplified group may be an alkyl group having a carbon number of about 1 to 4 such as a methyl group, an ethyl group, an isopropyl group or a tertiary butyl group; methoxy group; An alkoxy group having a carbon number of from 1 to 4 such as an oxy group; a trifluoromethyl group; a trifluoromethoxy group; a cyano group; a nitro group; and a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

從容易製造的觀點來看，A1及A2以都是同種類之基團為較佳。特別是A1及A2為1,4－伸苯基、1,4－環伸己基、或是苯環之碳原子被1至3個氮原子所取代而成之2價基為較佳，又以1,4－伸苯基為更佳。From the standpoint of ease of manufacture, it is preferred that A1 and A2 are groups of the same kind. In particular, A1 and A2 are a 1,4-phenylene group, a 1,4-cyclohexyl group, or a divalent group in which a carbon atom of a benzene ring is substituted by 1 to 3 nitrogen atoms, and 1,4-phenylene is more preferred.

B1及B2分別獨立地表示選自－CRR’－、－C≡C－、－CH＝CH－、－CH2 －CH2 －、－O－、－S－、－C(＝O)－、－C(＝O)－O－、－O－C(＝O)－、－O－C(＝O)－O－、－C(＝S)－、－C(＝S)－O－、－O－C(＝S)－、－O－C(＝S)－O－、－CH＝N－、－N＝CH－、－N＝N－、－N(→O)＝N－、－N＝N(→O)－、－C(＝O)－NR－、－NR－C(＝O)－、－OCH2 －、－NR－、－CH2 O－、－SCH2 －、－CH2 S－、－CH＝CH－C(＝O)－O－、－O－C(＝O)－CH＝CH－、單鍵所成組群中之2價基。在此，R及R’分別獨立地表示氫原子或甲基、乙基等碳數1至4的烷基，或是氟原子、氯原子、溴原子等鹵素原子。B1 and B2 each independently represent a group selected from -CRR'-, -C≡C-, -CH=CH-, -CH 2 -CH 2 -, -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -O-C(=O)-O-, -C(=S)-, -C(=S)-O-, -O-C(=S)-, -O-C(=S)-O-, -CH=N-, -N=CH-, -N=N-, -N(→O)=N-, -N=N(→O)-, -C(=O)-NR-, -NR-C(=O)-, -OCH 2 -, -NR-, -CH 2 O-, -SCH 2 -, -CH 2 S-, -CH=CH-C(=O)-O-, -O-C(=O)-CH=CH-, a divalent group in a group formed by a single bond. Here, R and R' each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group, or a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

再者，從容易製造的觀點來看，B1及B2以都是同種類之基團為較佳。Further, from the viewpoint of easy production, it is preferred that B1 and B2 are groups of the same kind.

在上述式(1)中，s及t為0的情況下，B1及B2以－CRR’－、－O－、－S－或NR－為較佳。In the above formula (1), when s and t are 0, B1 and B2 are preferably -CRR'-, -O-, -S- or NR-.

當B1及B2為上述結合基團時，由於A1(A2)和B1(B2)之連結部、與B1(B2)和X1(X2)之連結部會成為彎曲，且可改變連接基Y處所產生的角度，故與混合之棒狀聚合性液晶化合物等之互溶性有提高的傾向，因而較佳。When B1 and B2 are the above-mentioned bonding group, since the joint portion of A1 (A2) and B1 (B2) and the joint portion of B1 (B2) and X1 (X2) may be bent, and the connection group Y may be changed. From the viewpoint of the above, the mutual solubility with the mixed rod-shaped polymerizable liquid crystal compound or the like tends to be improved, which is preferable.

在上述式(1)中，s及t為1的情況下，較佳而言，在G1及G2更進一步為亞甲基的情況下，B1及B2係以單鍵、－C≡C－、－O－C(＝O)－O－、－O－C(＝O)－或－O－C(＝O)－O－為較佳。In the above formula (1), when s and t are 1, preferably, when G1 and G2 are further methylene groups, B1 and B2 are a single bond, -C≡C-, -O-C(=O)-O-, -O-C(=O)- or -O-C(=O)-O- is preferred.

當B1及B2為上述結合基時，係由於容易製造且在上述式(1)中的X2－B2－A2及A1－B1－X1分別成為直線狀，故具有使配向性提高的傾向，因而較佳。When B1 and B2 are the above-mentioned bonding group, since X2-B2-A2 and A1-B1-X1 in the above formula (1) are linear, they have a tendency to improve the alignment property, and thus good.

在上述式(1)中，X1及X2表示下述式(2)所示之2價基。In the above formula (1), X1 and X2 represent a divalent group represented by the following formula (2).

在上述式(2)中，A3表示2價環狀烴基或2價雜環基。具體而言，A3可同樣例示如在A1及A2中所例示的2價環狀烴基及2價雜環基。從容易製造的觀點來看，以1,4－伸苯基、1,4－環伸己基、或是苯環之碳原子被1至3個氮原子所取代而成之2價基為較佳，以1,4－伸苯基為更佳。In the above formula (2), A3 represents a divalent cyclic hydrocarbon group or a divalent heterocyclic group. Specifically, A3 may also be exemplified by a divalent cyclic hydrocarbon group and a divalent heterocyclic group as exemplified in A1 and A2. From the viewpoint of ease of production, a divalent group in which a 1,4-phenylene group, a 1,4-cyclohexyl group, or a carbon atom of a benzene ring is substituted with 1 to 3 nitrogen atoms is preferred. It is more preferable to use 1,4-phenylene.

再者，從容易製造的觀點來看，X1及X2以都是同種類之2價基為較佳。Further, from the viewpoint of easy production, X1 and X2 are preferably both of the same type of divalent groups.

B3可與B1同樣地定義。其中，從容易製造的觀點來看，以－O－C(＝O)－、－C(＝O)－O－、－O－或單鍵為較佳。B3 can be defined in the same manner as B1. Among them, from the viewpoint of ease of production, -O-C(=O)-, -C(=O)-O-, -O- or a single bond is preferred.

n表示1至4的整數。在n為2以上時，如後述表1中的化合物(1－2)至(1－4)，由A3及B3所構成的結構單元亦可彼此相異。n represents an integer of 1 to 4. When n is 2 or more, the structural units composed of A3 and B3 may be different from each other as the compounds (1-2) to (1-4) in Table 1 to be described later.

將含有所得聚合性化合物之組成物予以澆鑄時，從容易處理的觀點來看，n以1或2為較佳。此外，從容易製造的觀點來看，n以1為較佳。When the composition containing the obtained polymerizable compound is cast, n is preferably 1 or 2 from the viewpoint of easy handling. Further, n is preferably 1 in terms of ease of manufacture.

E1及E2分別獨立地表示碳數2至25的伸烷基，較佳而言為碳數4至10的伸烷基。E1 and E2 each independently represent an alkylene group having 2 to 25 carbon atoms, preferably an alkylene group having 4 to 10 carbon atoms.

E1及E2的氫原子雖然亦可被烷基、烷氧基、三氟甲基、三氟甲氧基、氰基、硝基或鹵素原子所取代，但還是以保持氫原子原樣為較佳。Although the hydrogen atom of E1 and E2 may be substituted by an alkyl group, an alkoxy group, a trifluoromethyl group, a trifluoromethoxy group, a cyano group, a nitro group or a halogen atom, it is preferred to retain the hydrogen atom as it is.

從容易製造的方面來看，以E1及E2都是同種類之伸烷基時為較佳。From the standpoint of ease of manufacture, it is preferred that both E1 and E2 are the same type of alkylene group.

P1及P2表示氫原子或聚合性基團。P1 and P2 represent a hydrogen atom or a polymerizable group.

在本說明書中，「聚合性基」係指能夠使聚合性化合物及上述棒狀聚合性液晶化合物進行聚合之取代基。具體而言，可例示如乙烯基、對二苯乙烯基、丙烯醯基、甲基丙烯醯基、羧基、甲基羰基、羥基、醯胺基、碳數1至4的烷基胺基、胺基、環氧基、氧環丁基(oxetanyl)、醛基、異氰酸酯基及硫代異氰酸酯基等。In the present specification, the term "polymerizable group" means a substituent capable of polymerizing a polymerizable compound and the above rod-shaped polymerizable liquid crystal compound. Specifically, examples thereof include a vinyl group, a p-stilbene group, an acryloyl group, a methacryloyl group, a carboxyl group, a methylcarbonyl group, a hydroxyl group, a decylamino group, an alkylamino group having 1 to 4 carbon atoms, and an amine. A group, an epoxy group, an oxetanyl group, an aldehyde group, an isocyanate group, a thioisocyanate group or the like.

再者，為了使上述例示之基團與E1或E2連結，在聚合性基中也亦可含有在B1或B2中所例示之基團。Further, in order to link the above-exemplified group to E1 or E2, the polymerizable group may also contain a group exemplified in B1 or B2.

其中，以丙烯醯基或甲基丙烯醯基為較佳，丙烯醯基為更佳。只要使用這些基團，就能夠在進行光聚合時容易處理，而且亦容易製造。Among them, a propylene fluorenyl group or a methacryl fluorenyl group is preferred, and an acryl fluorenyl group is more preferred. By using these groups, it is easy to handle when photopolymerization is carried out, and it is easy to manufacture.

P1及P2以至少有一個是聚合性基為較佳，以P1和P2都是聚合性基團為更佳。藉此，可使所得到的膜之膜硬度成為良好者。It is preferable that at least one of P1 and P2 is a polymerizable group, and it is more preferable that both P1 and P2 are a polymerizable group. Thereby, the film hardness of the obtained film can be made good.

上述聚合性化合物之具體化合物，可列舉如表1至4所示的化合物等。Specific examples of the above polymerizable compound include compounds shown in Tables 1 to 4.

在上述光學異向性層中，可單獨含有從上述聚合性化合物而來之結構單元中之任一者，亦可含有從不同的複數個聚合性化合物而來之結構單元。其中，以含有從表1及表2記載之化合物而來之結構單元為較佳。只要使用此等化合物，本發明之膜即可顯著表現出逆波長分散。此外，含有從表1記載之化合物而來之結構單元為更佳。只要使用此等化合物，本發明之膜就可容易地製造。In the optically anisotropic layer, any one of the structural units derived from the polymerizable compound may be contained alone, or a structural unit derived from a plurality of different polymerizable compounds may be contained. Among them, a structural unit containing the compounds described in Tables 1 and 2 is preferred. As long as these compounds are used, the film of the present invention can remarkably exhibit reverse wavelength dispersion. Further, the structural unit derived from the compound described in Table 1 is more preferable. The film of the present invention can be easily produced by using these compounds.

在此，以化合物(1－1)為例而說明表上的標記。「A1＝A2」係表示A1與A2為相同的伸苯基。「B1＝B2之A側」係表示酯基的醚部分結合在A(伸苯基)上。再者，「B1＝B2之X側」係表示酯基的羰基部分結合在X(二苯醚(phenyl ether)基)上。此外，沒有指定側的情況係表示可在任一個方向上取代。Here, the label on the table will be described by taking the compound (1-1) as an example. "A1=A2" means that A1 and A2 are the same stretching phenyl groups. "B1 = A side of B2" means that the ether moiety of the ester group is bonded to A (phenylene). Further, "X side of B1 = B2" means that the carbonyl moiety of the ester group is bonded to X (phenyl ether group). Further, the case where there is no designated side means that it can be substituted in either direction.

聚合性化合物係以表1或表2記載的化合物為較佳，以表1記載的化合物為更佳，以下述式(1－1)、(1－2)、(1－3)、(1－4)、(1－5)、(1－11)、(1－45)、(1－49)及(1－50)所示的化合物為特佳。The polymerizable compound is preferably a compound described in Table 1 or Table 2, and more preferably a compound described in Table 1, and the following formulas (1-1), (1-2), (1-3), and (1) The compounds represented by -4), (1-5), (1-11), (1-45), (1-49) and (1-50) are particularly preferred.

如上述式(1－1)所示之化合物，上述式(1)中s＝t＝0的聚合性化合物之製造方法，可列舉例如以提供C1、D1及D2結構之化合物而言係使用相對應之羰基化合物，使含有A1(A2)、B1(B2)、X1(X2)、E1(E2)及P1(P2)之化合物的鹵化物作用於羰基化合物，進行脫水縮合而獲得之方法等。含有A1(A2)、B1(B2)、X1(X2)、E1(E2)及P1(P2)之化合物，可藉由利用脫水縮合反應、酯化反應、威廉森(Williamson)反應、烏耳曼(Ullmann)反應、苄基化反應、薗頭(Sonogashira)反應、鈴木－宮浦反應、根岸反應、熊田反應、檜山反應、Buchwald－Hartwig反應、Wittig反應、Friedel－Craft反應、Heck反應、或醛醇(aldol)反應等，使含有A1(＝A2)、B1(＝B2)、X1(＝X2)、E1(＝E2)、P1(＝P2)之各結構單元的化合物結合而加以製造。The compound represented by the above formula (1-1), and the method for producing a polymerizable compound having s = t = 0 in the above formula (1), for example, are used in the case of a compound which provides a structure of C1, D1 and D2. The carbonyl compound is a method in which a halide containing a compound of A1 (A2), B1 (B2), X1 (X2), E1 (E2), and P1 (P2) is allowed to act on a carbonyl compound to carry out dehydration condensation. A compound containing A1 (A2), B1 (B2), X1 (X2), E1 (E2), and P1 (P2) can be utilized by dehydration condensation reaction, esterification reaction, Williamson reaction, and Ullmann (Ullmann) reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, root bank reaction, Xiongtian reaction, Laoshan reaction, Buchwald-Hartwig reaction, Wittig reaction, Friedel-Craft reaction, Heck reaction, or aldol (aldol) reaction or the like, and a compound containing each structural unit of A1 (=A2), B1 (=B2), X1 (=X2), E1 (=E2), and P1 (=P2) is bonded and produced.

如上述式(1－2)所示之化合物，上述式(1)中之s及t為1且G1及G2都是亞甲基鏈的聚合性化合物之製造方法，可列舉例如在前述羰基化合物中，使作為提供C2與A1(C3及A2)之結構單元的化合物的在苯環中具有碘的鹵化苄基與鹼金屬氫氧化物一起反應，合成含有A1(A2)、C1、G1(G2)、D1及D2之化合物，再與以其他方法所合成之含有B1(B2)、X1(X2)、E1(E2)及P1(P2)之化合物進行反應的方法；或是從以同樣地操作而得到之含有A1、A2、C1、G1、G2、D1及D2之化合物中，使提供B1(B2)、X1(X2)、E1(E2)及P1(P2)結構之化合物依序反應的方法。The compound represented by the above formula (1-2), a method for producing a polymerizable compound in which s and t in the above formula (1) are 1 and G1 and G2 are all a methylene chain, and examples thereof include the above-mentioned carbonyl compound. In the above, a halogenated benzyl group having iodine in a benzene ring as a compound providing a structural unit of C2 and A1 (C3 and A2) is reacted with an alkali metal hydroxide to synthesize A1(A2), C1, G1 (G2). a compound of D1 and D2, which is reacted with a compound containing B1 (B2), X1 (X2), E1 (E2) and P1 (P2) synthesized by other methods; or from the same operation A method for sequentially reacting a compound having a structure of B1 (B2), X1 (X2), E1 (E2), and P1 (P2) in a compound containing A1, A2, C1, G1, G2, D1, and D2 .

所得到的膜之波長分散特性，係依據從上述棒狀聚合性液晶化合物及聚合性化合物而來之結構單元之比率而決定者。本發明中，在不含有上述聚合性化合物的情況下，所得到的膜係表現出正波長分散的膜。另一方面，藉由使從上述聚合性化合物而來之結構單元之含量增加，而可任意調整從正波長分散至逆波長分散的波長分散特性。因此，本發明之膜，較佳為只含有能使上述聚合性化合物得到期望波長分散特性的量。賦予期望波長分散特性所需要的上述聚合性化合物的含量，可依如以下的方式決定。例如，調整含有上述棒狀聚合性液晶化合物與聚合性化合物之組成物中所含之從聚合性化合物而來之結構單元之比率，求出所得到的膜之相位差值。從結果來看，可決定從聚合性化合物而來之結構單元之含量。The wavelength dispersion property of the obtained film is determined by the ratio of the structural unit derived from the rod-shaped polymerizable liquid crystal compound and the polymerizable compound. In the present invention, when the polymerizable compound is not contained, the obtained film system exhibits a film having a positive wavelength dispersion. On the other hand, by increasing the content of the structural unit derived from the above polymerizable compound, the wavelength dispersion characteristics from the positive wavelength dispersion to the reverse wavelength dispersion can be arbitrarily adjusted. Therefore, the film of the present invention preferably contains only an amount which enables the polymerizable compound to have a desired wavelength dispersion property. The content of the above-mentioned polymerizable compound required to impart desired wavelength dispersion characteristics can be determined in the following manner. For example, the ratio of the structural unit derived from the polymerizable compound contained in the composition of the rod-shaped polymerizable liquid crystal compound and the polymerizable compound is adjusted, and the phase difference of the obtained film is determined. From the results, the content of the structural unit derived from the polymerizable compound can be determined.

(I－3－4)其他組成化合物(I-3-4) Other constituent compounds [聚合起始劑][Polymerization initiator]

在上述光學異向性層中，亦可含有用以使上述棒狀聚合性液晶化合物或聚合性化合物進行聚合的聚合起始劑。上述聚合性起始劑只要是能使用於使上述化合物聚合者即可，並沒有特別限定。本發明之膜之較佳的一實施形態，以棒狀聚合性液晶化合物有進行光聚合為較佳。因此，上述聚合起始劑係以光聚合起始劑為較佳。The optically anisotropic layer may further contain a polymerization initiator for polymerizing the rod-shaped polymerizable liquid crystal compound or the polymerizable compound. The polymerizable initiator is not particularly limited as long as it can be used to polymerize the above compound. In a preferred embodiment of the film of the present invention, photopolymerization of the rod-shaped polymerizable liquid crystal compound is preferred. Therefore, the above polymerization initiator is preferably a photopolymerization initiator.

上述光聚合起始劑可列舉例如苯偶姻(benzoin)類、二苯基酮類、苄基縮酮類、α－羥基酮類、α－胺基酮類、錪鎓鹽類、鋶鹽(sulfonium)類等，更具體而言，可列舉有Irgacure 907、Irgacure 184、Irgacure 651、Irgacure 250及Irgacure 369(以上全部都是Ciba Specialty Chemicals公司製造)，SEIKUOL BZ、SEIKUOL Z、SEIKUOL BEE(以上全部都是精工化學公司製造)，kayacure BP 100(日本化藥公司製造)，kayacure UVI－6992(Dow公司製造)，ADEKA OPTOMER SP－152、ADEKA OPTOMER SP－170(以上全部都是旭電化製造)等。Examples of the photopolymerization initiator include benzoin, diphenyl ketone, benzyl ketal, α-hydroxy ketone, α-amino ketone, sulfonium salt, and sulfonium salt. Further, sulfonium) and the like, more specifically, Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 250, and Irgacure 369 (all of which are manufactured by Ciba Specialty Chemicals Co., Ltd.), SEIKUOL BZ, SEIKUOL Z, and SEIKUOL BEE (all of the above) It is manufactured by Seiko Chemical Co., Ltd., kayacure BP 100 (manufactured by Nippon Kayaku Co., Ltd.), kayacure UVI-6992 (manufactured by Dow Co., Ltd.), ADEKA OPTOMER SP-152, and ADEKA OPTOMER SP-170 (all of which are manufactured by Asahi Chemical Co., Ltd.) .

藉由使用此類光聚合起始劑，可使上述棒狀聚合性液晶化合物及聚合性化合物進行光聚合。再者，此類聚合起始劑的含量，為了不使棒狀聚合性液晶性化合物的配向性紊亂，係以相對於後述含有聚合性化合物之組成物為10重量%以下為較佳。The rod-shaped polymerizable liquid crystal compound and the polymerizable compound can be photopolymerized by using such a photopolymerization initiator. In addition, it is preferable that the content of the polymerization initiator is 10% by weight or less based on the composition containing a polymerizable compound to be described later in order to prevent the alignment of the rod-like polymerizable liquid crystal compound.

[聚合抑制劑][Polymerization inhibitor]

在上述光學異向性層中，亦可含有聚合抑制劑。上述聚合抑制劑，並沒有特別限定，可列舉例如氫醌、具有烷基醚等取代基的氫醌類、如丁基鄰苯二酚等具有烷基醚等取代基的鄰苯二酚類、五倍子酚(pyrogallol)類、2,2,6,6－四甲基－1－哌啶基氧基自由基等自由基捕捉劑、硫酚類、β－萘胺類及β－萘酚類。In the above optically anisotropic layer, a polymerization inhibitor may also be contained. The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, hydroquinone having a substituent such as an alkyl ether, and catechol having a substituent such as an alkyl ether such as butyl catechol. A radical scavenger such as pyroallol or 2,2,6,6-tetramethyl-1-piperidinyloxy radical, thiophenols, β-naphthylamines, and β-naphthols.

藉由使用上述聚合抑制劑，可控制上述棒狀聚合性液晶化合物或聚合性化合物之聚合，可提高光學異向性層的穩定性。By using the polymerization inhibitor described above, polymerization of the rod-shaped polymerizable liquid crystal compound or the polymerizable compound can be controlled, and the stability of the optically anisotropic layer can be improved.

[光敏劑][Photosensitizer]

再者，在上述光學異向性層中，亦可含有光敏劑。上述光敏劑，並沒有特別限定，可列舉例如呫噸酮(xanthone)、噻噸酮(thioxanthone)等呫噸酮類，蒽，具有烷基醚等取代基的蒽類，吩噻(phenothiazine)，及紅螢烯。Further, a photosensitizer may be contained in the optically anisotropic layer. The photosensitizer is not particularly limited, and examples thereof include xanthone such as xanthone and thioxanthone, anthraquinone, an anthracene having a substituent such as an alkyl ether, and phenothiazine. (phenothiazine), and red fluorene.

藉由使用上述光敏劑，可使上述棒狀聚合性液晶化合物或聚合性化合物之聚合反應高靈敏度化。By using the photosensitizer described above, the polymerization reaction of the rod-shaped polymerizable liquid crystal compound or the polymerizable compound can be made highly sensitive.

[調平劑][leveling agent]

此外，在上述光學異向性層中，亦可含有調平劑。上述調平劑，並沒有特別限定，可添加以往周知的調平劑。上述調平劑可列舉例如輻射硬化塗料用添加劑(BYK－Chemie Japan公司製：BYK－352、BYK－353、BYK－361N)、塗料添加劑(Dow Corning Toray公司製：SH28PA、DC11PA、ST80PA)、及塗料添加劑(Shin－Etsu Silicones公司製：KP321、KP323、X22－161A、KF6001)等。Further, a leveling agent may be contained in the optically anisotropic layer. The leveling agent is not particularly limited, and a conventionally known leveling agent can be added. The leveling agent may, for example, be an additive for a radiation-curing coating (BYK-352, BYK-353, BYK-361N, BYK-Chemie Japan), a coating additive (SH28PA, DC11PA, ST80PA, manufactured by Dow Corning Toray Co., Ltd.), and Coating additives (manufactured by Shin-Etsu Silicones Co., Ltd.: KP321, KP323, X22-161A, KF6001) and the like.

藉由使用上述調平劑，可使光學異向性層平滑化。此外，在上述膜之製造過程中，可控制後述含有液晶化合物之組成物的流動性，或是可調整上述棒狀聚合性液晶化合物或聚合性化合物的交聯密度。The optically anisotropic layer can be smoothed by using the above-described leveling agent. Further, in the production process of the film, the fluidity of the composition containing the liquid crystal compound described later can be controlled, or the crosslinking density of the rod-shaped polymerizable liquid crystal compound or the polymerizable compound can be adjusted.

<II.本發明之膜之製造方法><II. Method for Producing Film of the Present Invention>

本發明之膜之製造方法，可使用適於製造上述本發明之膜者。具體而言，至少包含：(A)在垂直配向用配向膜上，塗布含有前述棒狀聚合性液晶化合物之組成物的步驟(後文亦稱為「含有液晶化合物之組成物的塗布步驟」)；以及(B)將以上述含有液晶化合物之組成物的塗布步驟所形成的塗膜在25℃至120℃下加熱10秒鐘至60分鐘的步驟(後文亦稱為「含有液晶化合物之組成物的加熱步驟」)。As the method for producing the film of the present invention, those suitable for producing the film of the present invention described above can be used. Specifically, it includes at least (A) a step of applying a composition containing the rod-like polymerizable liquid crystal compound on the alignment film for vertical alignment (hereinafter also referred to as "coating step of a composition containing a liquid crystal compound") And (B) a step of heating the coating film formed by the coating step of the composition containing the liquid crystal compound at 25 ° C to 120 ° C for 10 seconds to 60 minutes (hereinafter also referred to as "the composition containing the liquid crystal compound" Heating step of the object").

根據上述結構，在使用垂直配向膜作為垂直配向用配向膜時，可使棒狀聚合性液晶化合物在該垂直配向用配向膜上呈向列垂直配向。此外，如果使用經摩擦處理過的垂直配向膜作為上述垂直配向用配向膜，可使棒狀聚合性液晶化合物在空氣層界面上仍舊保持垂直配向，且在垂直配向用配向膜界面上呈傾斜配向。因此，根據上述結構，聚合前之未聚合膜及聚合膜都可製造成在膜平面方向上折射率變化小，而在膜法線方向上折射率變化大的膜。According to the above configuration, when the vertical alignment film is used as the alignment film for the vertical alignment, the rod-shaped polymerizable liquid crystal compound can be aligned vertically in the nematic alignment film. Further, if a rubbed-treated vertical alignment film is used as the alignment film for the vertical alignment, the rod-shaped polymerizable liquid crystal compound can maintain a vertical alignment at the interface of the air layer, and is inclinedly aligned at the interface of the alignment film for the vertical alignment. . Therefore, according to the above configuration, both the unpolymerized film and the polymer film before polymerization can be produced into a film having a small change in refractive index in the film plane direction and a large refractive index change in the film normal direction.

再者，如上所述，棒狀聚合性液晶化合物之配向只要利用有或沒有對垂直配向用配向膜進行摩擦處理就可以任意地在法線方向上控制光學異向性層中之折射率橢圓體的傾斜角。因此，可容易地製造具有所期望之光學異向性的膜。Further, as described above, the alignment of the rod-shaped polymerizable liquid crystal compound can arbitrarily control the refractive index ellipsoid in the optical anisotropic layer in the normal direction by using or without rubbing the alignment film for vertical alignment. The angle of inclination. Therefore, a film having a desired optical anisotropy can be easily produced.

上述垂直配向用配向膜及棒狀聚合性液晶化合物同樣可使用在<I.本發明之膜>所述者。因此，<I.本發明之膜>所述的垂直配向用配向膜之中，在沒有經摩擦處理過的垂直配向膜上所形成的光學異向性層，上述棒狀聚合性液晶化合物會相對於垂直配向用配向膜呈向列垂直配向。另一方面，在經摩擦處理過的垂直配向膜上所形成的光學異向性層，上述棒狀聚合性液晶化合物在空氣層界面上仍舊保持垂直配向，而在垂直配向用配向膜界面上呈傾斜配向。也就是說，在經由含有液晶化合物之組成物的塗布步驟及含有液晶化合物之組成物的加熱步驟而形成的光學異向性層，可任意在法線方向上控制光學異向性層中之折射率橢圓體的傾斜角。因此，可容易地製造在膜平面方向上折射率變化小，而在膜法線方向上折射率變化大的膜。The alignment film for vertical alignment and the rod-shaped polymerizable liquid crystal compound can be similarly used in the film of <I. The present invention>. Therefore, in the above-mentioned alignment film for vertical alignment, the optically anisotropic layer formed on the vertical alignment film which has not been subjected to the rubbing treatment, the rod-shaped polymerizable liquid crystal compound is relatively The alignment film for vertical alignment is oriented vertically in the nematic direction. On the other hand, in the optically anisotropic layer formed on the rubbed vertical alignment film, the rod-shaped polymerizable liquid crystal compound still maintains a vertical alignment at the interface of the air layer, and at the interface of the alignment film for the vertical alignment Tilt alignment. That is, the optically anisotropic layer formed by the coating step of the composition containing the liquid crystal compound and the heating step of the composition containing the liquid crystal compound can arbitrarily control the refraction in the optical anisotropic layer in the normal direction. Rate the tilt angle of the ellipsoid. Therefore, a film having a small change in refractive index in the film plane direction and a large refractive index change in the film normal direction can be easily produced.

此外，本發明之膜之製造方法中，除了上述含有液晶化合物之組成物的塗布步驟及含有液晶化合物之組成物的加熱步驟以外，亦可包含：(C)調製含有塗布在垂直配向用配向膜上之棒狀聚合性液晶化合物的組成物的步驟(後文亦稱為「含有液晶化合物之組成物的調製步驟」)、(D)使以含有液晶化合物之組成物的加熱步驟所得到之未聚合膜進行聚合的步驟(後文亦稱為「液晶化合物的聚合步驟」)、(E)將垂直配向膜予以摩擦的步驟(後文亦稱為「摩擦步驟」)、(F)使垂直配向用配向膜形成在支撐基材上的步驟(後文亦稱為「垂直配向用配向膜的形成步驟」)。這4個步驟可全部包含，亦可只包含任1個或2個。當然亦可全部都不包含在內。Further, in the method for producing a film of the present invention, in addition to the coating step of the composition containing the liquid crystal compound and the heating step of the composition containing the liquid crystal compound, (C) preparing and coating the alignment film for vertical alignment may be included. a step of forming a composition of a rod-like polymerizable liquid crystal compound (hereinafter also referred to as "a preparation step of a composition containing a liquid crystal compound"), and (D) a step of heating a composition containing a liquid crystal compound a step of polymerizing a polymer film (hereinafter also referred to as "polymerization step of a liquid crystal compound"), (E) a step of rubbing a vertical alignment film (hereinafter also referred to as "friction step"), and (F) a vertical alignment The step of forming an alignment film on the support substrate (hereinafter also referred to as "the step of forming the alignment film for vertical alignment"). These four steps may all be included, or may include only one or two. Of course, all of them are not included.

後文詳細敘述垂直配向用配向膜的形成步驟、摩擦步驟、含有液晶化合物之組成物的調製步驟、含有液晶化合物之組成物的塗布步驟、含有液晶化合物之組成物的加熱步驟、及液晶化合物的聚合步驟。The formation step of the alignment film for vertical alignment, the rubbing step, the preparation step of the composition containing the liquid crystal compound, the coating step of the composition containing the liquid crystal compound, the heating step of the composition containing the liquid crystal compound, and the liquid crystal compound will be described in detail later. Aggregation step.

(II－1)垂直配向用配向膜的形成步驟(II-1) Step of forming an alignment film for vertical alignment

在上述垂直配向用配向膜的形成步驟中，使垂直配向用配向膜形成在支撐基材上。上述支撐基材並沒有特別限定。例如可使用<I.本發明之膜>所例示的支撐基材。關於上述垂直配向用配向膜，亦沒有特別限定，例如可使用<I.本發明之膜>所例示的垂直配向用配向膜。如果使用此類垂直配向用配向膜，因為不需要藉由延伸而進行控制折射率，所以雙折射的面內偏差變小。因此，能發揮在支撐基材上提供亦可與FPD大型化相對應之大型光學膜的效果。In the step of forming the alignment film for vertical alignment described above, the alignment film for vertical alignment is formed on the support substrate. The above support substrate is not particularly limited. For example, a support substrate exemplified by <I. Film of the Invention> can be used. The alignment film for the vertical alignment is not particularly limited, and for example, the alignment film for vertical alignment exemplified in <I. The film of the present invention> can be used. If such an alignment film for vertical alignment is used, since it is not necessary to control the refractive index by stretching, the in-plane variation of birefringence becomes small. Therefore, it is possible to provide an effect of providing a large-sized optical film which can also correspond to the enlargement of the FPD on the support substrate.

在上述支撐基材上形成垂直配向用配向膜之方法，並沒有特別限定，可使用以往周知的方法。例如可在上述支撐基材上塗布垂直配向用配向膜的材料，之後藉由進行退火(anneal)而在上述支撐基材上形成垂直配向用配向膜。The method of forming the alignment film for vertical alignment on the above-mentioned support substrate is not particularly limited, and a conventionally known method can be used. For example, a material for the alignment film for vertical alignment may be applied onto the support substrate, and then an alignment film for vertical alignment may be formed on the support substrate by annealing.

如此操作所得到的垂直配向用配向膜之厚度雖然沒有特別限定，但以10 nm至10000 nm為較佳，又以10 nm至1000 nm為更佳。只要在上述範圍，在後述之光學異向性層的形成步驟中，即可使棒狀聚合性液晶化合物於該垂直配向用配向膜上配向為所期望的角度。The thickness of the alignment film for vertical alignment obtained in this manner is not particularly limited, but is preferably 10 nm to 10000 nm, and more preferably 10 nm to 1000 nm. In the above range, in the step of forming the optically anisotropic layer to be described later, the rod-shaped polymerizable liquid crystal compound can be aligned at a desired angle on the alignment film for vertical alignment.

(II－2)摩擦步驟(II-2) Friction step

在摩擦步驟中，對於以上述垂直配向用配向膜的形成步驟所得到的垂直配向膜進行摩擦處理。藉此，在後述含有液晶化合物之組成物的加熱步驟中，可使棒狀聚合性液晶化合物在空氣層界面上仍舊保持垂直配向，而在該垂直配向用配向膜界面上呈傾斜配向。又，上述垂直配向用配向膜亦可不是以上述垂直配向用配向膜的形成步驟所得到者，而是具有同等物性之垂直配向用配向膜，且用其他方法準備者，例如市售品。In the rubbing step, the vertical alignment film obtained by the above-described step of forming the alignment film for vertical alignment is subjected to a rubbing treatment. Thereby, in the heating step of the composition containing the liquid crystal compound described later, the rod-shaped polymerizable liquid crystal compound can be maintained in the vertical alignment at the interface of the air layer, and is inclinedly aligned at the interface of the alignment film for the vertical alignment. In addition, the alignment film for vertical alignment may be obtained by a step of forming the alignment film for vertical alignment, or an alignment film for vertical alignment having the same physical properties, and may be prepared by another method, for example, a commercially available product.

對於上述垂直配向膜進行摩擦的方法，並沒有特別限定，可使用以往周知的方法。例如，可使用使纏繞有摩擦布的轉動摩擦輥與裝在工作台上輸送的垂直配向膜進行接觸的方法。The method of rubbing the above-mentioned vertical alignment film is not particularly limited, and a conventionally known method can be used. For example, a method of bringing a rotating friction roller wound with a rubbing cloth into contact with a vertical alignment film conveyed on a table can be used.

上述摩擦布並沒有特別限定，只要是能夠纏繞在摩擦輥上的布即可。上述摩擦布的材質可列舉如嫘縈、棉、羊毛、絲等各式各樣的材質。再者，即使是相同材質，依據布所使用的絲線的粗細或長度等，會改變其摩擦狀態。為了使摩擦狀態一致，絲線的粗細或長度係以一致為較佳。The rubbing cloth is not particularly limited as long as it is a cloth that can be wound around the rubbing roller. The material of the rubbing cloth may be various materials such as enamel, cotton, wool, and silk. Furthermore, even if it is the same material, the friction state will be changed depending on the thickness or length of the thread used for the cloth. In order to make the friction state uniform, the thickness or length of the wire is preferably uniform.

上述摩擦輥的直徑，一般而言，為了穩定地控制其轉動，係以直徑10 mm至300 mm為較佳。再者，藉由改變上述摩擦輥的直徑，可調整與配向膜接觸的角度或面積。The diameter of the above-mentioned friction roller is generally preferably 10 mm to 300 mm in diameter in order to stably control the rotation thereof. Further, by changing the diameter of the above friction roller, the angle or area in contact with the alignment film can be adjusted.

再者，上述摩擦輥的轉速雖然亦根據上述摩擦輥的直徑而定，但是為了使摩擦輥穩定地轉動，係以100至2000 rpm為較佳。再者，藉由改變上述摩擦輥的轉速，亦可調整摩擦輥的狀況。Further, although the rotation speed of the rubbing roller is also determined according to the diameter of the rubbing roller, it is preferably 100 to 2000 rpm in order to stably rotate the rubbing roller. Furthermore, the condition of the friction roller can also be adjusted by changing the rotational speed of the friction roller.

上述工作台的工作台速度及垂直配向膜的輸送速度，一般而言，由於垂直配向膜的輸送速度不論太慢或太快都難以穩定地輸送，因此以控制在0.1 m/分至10 m/分為較佳。再者，藉由改變工作台速度及垂直配向膜的輸送速度，可調整摩擦輥的狀況。The table speed of the above table and the conveying speed of the vertical alignment film are generally controlled at 0.1 m/min to 10 m/s because the conveying speed of the vertical alignment film is difficult to be stably conveyed either too slowly or too fast. Divided into better. Furthermore, the condition of the friction roller can be adjusted by changing the speed of the table and the conveying speed of the vertical alignment film.

此外，在上述例示的摩擦方法中，壓入量及接觸長度並沒有特別限定，只要依照摩擦布的絲線長度，以可得到所之期望摩擦效果的方式加以設定即可。又，上述「壓入量」係指使摩擦輥壓在垂直配向膜上的量，係以壓在配向膜上之摩擦布的毛長度表示。在上述摩擦方法中，可只壓摩擦布的與布呈垂直方向上絲線露出的部分。再者，上述「接觸長度」係表示摩擦輥與基材接觸的長度。上述接觸長度，可從摩擦輥與垂直配向膜接觸的長度改變至使摩擦輥完全壓住時摩擦輥與垂直配向膜接觸的長度為止。Further, in the friction method exemplified above, the amount of pressing and the length of contact are not particularly limited, and may be set so as to obtain a desired friction effect in accordance with the length of the wire of the rubbing cloth. Further, the above "pressing amount" means the amount by which the rubbing roller is pressed against the vertical alignment film, and is expressed by the length of the rubbing cloth pressed against the alignment film. In the above rubbing method, only the portion of the rubbing cloth which is exposed in the vertical direction with the cloth can be pressed. Further, the above "contact length" means the length of contact of the rubbing roller with the substrate. The above contact length may be changed from the length in which the rubbing roller is in contact with the vertical alignment film to the length in which the rubbing roller is in contact with the vertical alignment film when the rubbing roller is completely pressed.

像這樣，在上述摩擦步驟中，雖然用上述例示的方法對於上述垂直配向膜進行摩擦處理，但摩擦步驟中垂直配向膜的摩擦次數並沒有特別限定。換言之，在上述摩擦步驟中，可對垂直配向膜只進行1次摩擦處理，亦可為了控制配向而進行複數次的摩擦處理。As described above, in the rubbing step, although the vertical alignment film is subjected to rubbing treatment by the above-described method, the number of rubbing of the vertical alignment film in the rubbing step is not particularly limited. In other words, in the rubbing step, the vertical alignment film may be subjected to only one rubbing treatment, or a plurality of rubbing treatments may be performed for controlling the alignment.

(II－3)含有液晶化合物之組成物的調製步驟(II-3) Modification step of a composition containing a liquid crystal compound

在含有液晶化合物之組成物的調製步驟中，係調製含有棒狀聚合性液晶化合物之組成物。具體而言係調製使上述棒狀聚合性液晶化合物溶解在有機溶劑中的溶液。上述棒狀聚合性化合物只要使用<I.本發明之膜>所述的棒狀聚合性液晶化合物即可。再者，上述有機溶劑只要是能溶解上述棒狀聚合性液晶化合物者即可，並沒有特別限定。可列舉例如環戊酮、環己酮、甲基乙基酮、甲苯、乙酸乙酯、甲基溶纖劑、丁基溶纖劑、異丙醇、甲基戊基酮、二甲苯、乙腈、四氫呋喃、γ－丁內酯、二甲氧基乙烷、乳酸乙酯、氯仿、丙二醇單甲醚乙酸酯及丙二醇單甲醚等。這些有機溶劑可單獨使用，亦可組合多種而使用。In the preparation step of the composition containing the liquid crystal compound, a composition containing a rod-like polymerizable liquid crystal compound is prepared. Specifically, a solution in which the above rod-shaped polymerizable liquid crystal compound is dissolved in an organic solvent is prepared. The rod-shaped polymerizable compound may be a rod-shaped polymerizable liquid crystal compound as described in <I. The film of the invention>. In addition, the organic solvent is not particularly limited as long as it can dissolve the rod-shaped polymerizable liquid crystal compound. For example, cyclopentanone, cyclohexanone, methyl ethyl ketone, toluene, ethyl acetate, methyl cellosolve, butyl cellosolve, isopropanol, methyl amyl ketone, xylene, acetonitrile, tetrahydrofuran, Γ-butyrolactone, dimethoxyethane, ethyl lactate, chloroform, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether. These organic solvents may be used singly or in combination of two or more.

再者，雖然上述組成物中的棒狀聚合性液晶化合物濃度沒有特別限定，但是當上述濃度太低時，由於光學異向性層變得太薄，所以在液晶面板之光學補償方面所需要的光學異向性會有無法得到的傾向。相反地，當上述濃度太高時，由於含有液晶化合物之組成物的溶液黏度變得太高，所以會有容易產生塗布膜厚不均的傾向。因此，上述濃度係以5至50重量%為較佳。只要在上述範圍內，就不會發生如上述般的問題。In addition, although the concentration of the rod-like polymerizable liquid crystal compound in the above composition is not particularly limited, when the above concentration is too low, since the optical anisotropic layer becomes too thin, it is required for optical compensation of the liquid crystal panel. Optical anisotropy tends to be unavailable. On the other hand, when the concentration is too high, the viscosity of the solution containing the composition of the liquid crystal compound becomes too high, so that the coating film thickness tends to be uneven. Therefore, the above concentration is preferably from 5 to 50% by weight. As long as it is within the above range, the problem as described above does not occur.

在上述組成物中，亦可復含有特定之聚合性化合物及/或與上述棒狀聚合性液晶化合物為相異的複數液晶化合物。The above composition may further contain a specific polymerizable compound and/or a plurality of liquid crystal compounds different from the above-mentioned rod-shaped polymerizable liquid crystal compound.

上述液晶化合物，只要使用<I.本發明之膜>所述的其他液晶化合物即可。The liquid crystal compound may be any other liquid crystal compound described in <I. The film of the present invention>.

上述液晶化合物的含量，只要因應得到的膜所需求出的相位差值而適當地決定即可。具體而言，以賦予所期望之相位差值的方式，調整上述組成物中所含之從液晶化合物而來之結構單元的比率，求出所得到的光學膜之相位差值。根據此結果，可決定從上述液晶化合物而來之結構單元的含量。The content of the liquid crystal compound may be appropriately determined in accordance with the phase difference value required for the obtained film. Specifically, the ratio of the structural unit derived from the liquid crystal compound contained in the above composition is adjusted so as to impart a desired retardation value, and the phase difference of the obtained optical film is obtained. From this result, the content of the structural unit derived from the above liquid crystal compound can be determined.

通常，相位差值可藉由改變膜厚而加以控制。然而，若只控制膜厚，即使能任意地控制法線方向的相位差值，亦難以控制入射角改變時的相位差值，而非得要改變前述棒狀聚合性液晶化合物的化學結構。另一方面，藉由添加從上述液晶化合物而來之結構單元，不僅能任意地調整法線方向的相位差值，還能任意地調整在所有角度的相位差值。換言之，藉由添加從上述液晶化合物而來之結構單元，可任意地控制具有光學異向性層的折射率橢圓體的形狀。但是，在過度添加從上述液晶化合物而來之結構單元時，有時亦會無法得到本發明之垂直配向。因此，例如相對於從上述液晶化合物而來之結構單元與從棒狀聚合性液晶化合物而來之結構單元的合計100重量份，使從液晶化合物而來之結構單元的含量成為5至50重量份為較佳。藉由設為上述含量，而可任意地控制所得到的膜之折射率橢圓體的形狀。Generally, the phase difference value can be controlled by changing the film thickness. However, if only the film thickness is controlled, even if the phase difference value in the normal direction can be arbitrarily controlled, it is difficult to control the phase difference value when the incident angle is changed, instead of changing the chemical structure of the rod-shaped polymerizable liquid crystal compound. On the other hand, by adding the structural unit derived from the above liquid crystal compound, not only the phase difference value in the normal direction but also the phase difference value at all angles can be arbitrarily adjusted. In other words, the shape of the refractive index ellipsoid having the optically anisotropic layer can be arbitrarily controlled by adding the structural unit derived from the above liquid crystal compound. However, when the structural unit derived from the above liquid crystal compound is excessively added, the vertical alignment of the present invention may not be obtained. Therefore, for example, the content of the structural unit derived from the liquid crystal compound is 5 to 50 parts by weight based on 100 parts by weight of the total of the structural unit derived from the liquid crystal compound and the structural unit derived from the rod-shaped polymerizable liquid crystal compound. It is better. By setting the above content, the shape of the refractive index ellipsoid of the obtained film can be arbitrarily controlled.

上述聚合性化合物，只要使用<I.本發明之膜>所述的聚合性化合物即可。藉由使上述組成物含有此類聚合性化合物，而可製造具有任意波長分散特性的膜。The polymerizable compound may be a polymerizable compound described in <I. The film of the present invention>. By including such a polymerizable compound in the above composition, a film having dispersion characteristics at any wavelength can be produced.

上述聚合性化合物的含量，只要因應得到的膜所需求的波長分散特性而適當地決定即可。具體而言，以賦予所期望之波長分散特性的方式，調整上述組成物中所含之從聚合性化合物而來之結構單元的比率，求出所得到的光學膜之相位差值。根據此結果，可決定從上述聚合性化合物而來之結構單元的含量。The content of the polymerizable compound may be appropriately determined depending on the wavelength dispersion characteristics required for the obtained film. Specifically, the ratio of the structural unit derived from the polymerizable compound contained in the above composition is adjusted so as to impart desired wavelength dispersion characteristics, and the phase difference value of the obtained optical film is obtained. From this result, the content of the structural unit derived from the above polymerizable compound can be determined.

一般而言，不含有或只含有少量上述聚合性化合物的膜會表現出正波長分散。另一方面，藉由使從上述聚合性化合物而來之結構單元之含量增加，而可任意地調整從正波長分散至逆波長分散的波長分散特性。當得到表現出逆波長分散之膜時，例如相對於從上述聚合性化合物而來之結構單元與從棒狀聚合性液晶化合物而來之結構單元的合計100重量份，使從聚合性化合物而來之結構單元的含量成為5至50重量份為較佳。藉由設為上述含量，可使所得到的膜表現出逆波長分散，同時還可製造表現出大之相位差值的膜。In general, a film containing no or only a small amount of the above polymerizable compound exhibits a positive wavelength dispersion. On the other hand, by increasing the content of the structural unit derived from the above polymerizable compound, the wavelength dispersion characteristics from the positive wavelength dispersion to the reverse wavelength dispersion can be arbitrarily adjusted. When a film which exhibits a reverse wavelength dispersion is obtained, for example, 100 parts by weight of the total of the structural unit derived from the polymerizable compound and the structural unit derived from the rod-shaped polymerizable liquid crystal compound is obtained from the polymerizable compound. The content of the structural unit is preferably from 5 to 50 parts by weight. By setting the above content, the obtained film can exhibit reverse wavelength dispersion, and a film exhibiting a large retardation value can be produced.

再者，在本發明之膜之製造方法中，藉由上述組成物的組成變化而達到所得到的膜之波長分散特性(正波長分散至逆波長分散)。因此，用非常簡便的方法，就能發揮可任意地調整膜之波長分散特性的效果。Further, in the method for producing a film of the present invention, the wavelength dispersion characteristics (positive wavelength dispersion to reverse wavelength dispersion) of the obtained film are achieved by the composition change of the above composition. Therefore, the effect of arbitrarily adjusting the wavelength dispersion characteristics of the film can be exhibited by a very simple method.

再者，上述組成物中，亦可含有聚合起始劑、聚合抑制劑、光敏劑、調平劑等。Further, the above composition may further contain a polymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, and the like.

上述聚合起始劑，可使用<I.本發明之膜>所述的聚合起始劑。再者，上述聚合起始劑的添加量只要是適合棒狀聚合性液晶化合物及/或聚合性化合物之聚合反應的量，不會使棒狀聚合性液晶性化合物的配向性紊亂的程度即可。換言之，係以因應棒狀聚合性液晶化合物、聚合性化合物與聚合起始劑的種類，以及上述組成物的組成而適當地決定為較佳。如此，雖然聚合起始劑之添加量的具體數值沒有特別限定，但舉例來說，相對於棒狀聚合性液晶化合物100重量份，係以0.1重量份至30重量份為較佳，0.5重量份至10重量份為更佳。只要在上述範圍內，就不會使棒狀聚合性液晶性化合物的配向性紊亂，而能夠使棒狀聚合性液晶化合物聚合。As the polymerization initiator, a polymerization initiator described in <I. Film of the Invention> can be used. In addition, the amount of the polymerization initiator to be added is such an amount that it is suitable for the polymerization reaction of the rod-shaped polymerizable liquid crystal compound and/or the polymerizable compound, and the degree of alignment of the rod-shaped polymerizable liquid crystal compound is not disturbed. . In other words, it is preferable to appropriately determine the type of the rod-like polymerizable liquid crystal compound, the polymerizable compound, the polymerization initiator, and the composition of the above composition. Thus, the specific value of the amount of the polymerization initiator to be added is not particularly limited, and is preferably, for example, 0.1 part by weight to 30 parts by weight, based on 100 parts by weight of the rod-like polymerizable liquid crystal compound, of 0.5 part by weight. It is more preferably 10 parts by weight. When it is in the above range, the alignment property of the rod-shaped polymerizable liquid crystal compound is not disturbed, and the rod-shaped polymerizable liquid crystal compound can be polymerized.

上述聚合抑制劑可使用<I.本發明之膜>所述的聚合抑制劑。再者，上述聚合抑制劑的添加量並沒有特別限定，只要是不會使棒狀聚合性液晶性化合物的配向性紊亂，能調節棒狀聚合性液晶化合物及/或聚合性化合物之聚合反應，且能提高光學異向性層之穩定性的量即可。具體而言，相對於棒狀聚合性液晶化合物100重量份，係以0.1重量份至30重量份為較佳，0.5重量份至10重量份為更佳。只要在上述範圍內，就不會使棒狀聚合性液晶性化合物的配向性紊亂，而能夠控制棒狀聚合性液晶化合物之聚合反應，且提高光學異向性層之穩定性。As the above polymerization inhibitor, the polymerization inhibitor described in <I. Membrane of the invention> can be used. In addition, the amount of the polymerization inhibitor to be added is not particularly limited, and the polymerization reaction of the rod-shaped polymerizable liquid crystal compound and/or the polymerizable compound can be adjusted without distorting the alignment property of the rod-shaped polymerizable liquid crystal compound. Moreover, the amount of stability of the optically anisotropic layer can be increased. Specifically, it is preferably from 0.1 part by weight to 30 parts by weight, more preferably from 0.5 part by weight to 10 parts by weight, per 100 parts by weight of the rod-like polymerizable liquid crystal compound. When it is within the above range, the alignment of the rod-shaped polymerizable liquid crystal compound is not disturbed, and the polymerization reaction of the rod-shaped polymerizable liquid crystal compound can be controlled, and the stability of the optically anisotropic layer can be improved.

再者，上述光敏劑可使用<I.本發明之膜>所述的光敏劑。再者，上述光敏劑的添加量並沒有特別限定，只要不會使棒狀聚合性液晶性化合物的配向性紊亂，且能夠使棒狀聚合性液晶化合物及/或聚合性化合物之聚合反應高靈敏度化的量即可。具體而言，相對於棒狀聚合性液晶化合物100重量份，係以0.1重量份至30重量份為較佳，0.5重量份至10重量份為更佳。只要在上述範圍內，就不會使棒狀聚合性液晶性化合物的配向性紊亂，而能夠使棒狀聚合性液晶化合物之聚合反應高靈敏度化。Further, as the above photosensitizer, the photosensitizer described in <I. Film of the Invention> can be used. In addition, the amount of the photosensitizer to be added is not particularly limited as long as the alignment of the rod-shaped polymerizable liquid crystal compound is not disturbed, and the polymerization reaction of the rod-shaped polymerizable liquid crystal compound and/or the polymerizable compound can be made highly sensitive. The amount can be reduced. Specifically, it is preferably from 0.1 part by weight to 30 parts by weight, more preferably from 0.5 part by weight to 10 parts by weight, per 100 parts by weight of the rod-like polymerizable liquid crystal compound. When it is within the above range, the alignment of the rod-shaped polymerizable liquid crystal compound is not disturbed, and the polymerization reaction of the rod-shaped polymerizable liquid crystal compound can be made highly sensitive.

此外，上述調平劑可使用<I.本發明之膜>所述的調平劑。再者，上述調平劑的添加量並沒有特別限定，只要不會使棒狀聚合性液晶性化合物的配向性紊亂，能夠使光學異向性層平滑化、控制含有液晶化合物之組成物在塗布時的流動性、調整棒狀聚合性液晶性化合物之交聯密度的量即可。具體而言，相對於棒狀聚合性液晶化合物100重量份，係以0.1重量份至30重量份為較佳，0.5重量份至10重量份為更佳。只要在上述範圍內，就不會使棒狀聚合性液晶性化合物的配向性紊亂，而能夠使光學異向性層平滑化、控制含有液晶化合物之組成物在塗布時的流動性、調整棒狀聚合性液晶性化合物之交聯密度。Further, as the above leveling agent, the leveling agent described in <I. Film of the Invention> can be used. In addition, the amount of the leveling agent to be added is not particularly limited, and the optically anisotropic layer can be smoothed and the composition containing the liquid crystal compound can be controlled by coating without distorting the alignment property of the rod-shaped polymerizable liquid crystal compound. The fluidity at the time and the amount of crosslinking density of the rod-shaped polymerizable liquid crystal compound may be adjusted. Specifically, it is preferably from 0.1 part by weight to 30 parts by weight, more preferably from 0.5 part by weight to 10 parts by weight, per 100 parts by weight of the rod-like polymerizable liquid crystal compound. When it is within the above range, the alignment property of the rod-like polymerizable liquid crystal compound is not disturbed, and the optically anisotropic layer can be smoothed, and the fluidity at the time of coating of the composition containing the liquid crystal compound can be controlled, and the rod shape can be adjusted. The crosslinking density of the polymerizable liquid crystalline compound.

(II－4)含有液晶化合物之組成物的塗布步驟(II-4) Coating step of a composition containing a liquid crystal compound

在含有液晶化合物之組成物的塗布步驟中，將以上述含有液晶化合物之組成物的調製步驟所調製的組成物塗布在垂直配向用配向膜上。藉此可使含有上述組成物的塗膜形成在垂直配向用配向膜上。在此，上述組成物亦可不是以含有液晶化合物之組成物的調製步驟所調製者，而是具有同等組成之組成物，且用其他方法所製備之含有棒狀聚合性液晶化合物之組成物，例如可使用市售品。In the coating step of the composition containing the liquid crystal compound, the composition prepared by the above-described preparation step of the composition containing the liquid crystal compound is applied onto the alignment film for vertical alignment. Thereby, the coating film containing the above composition can be formed on the alignment film for vertical alignment. Here, the composition may not be prepared by a preparation step containing a composition of a liquid crystal compound, but a composition having an equivalent composition, and a composition containing a rod-like polymerizable liquid crystal compound prepared by another method, For example, a commercially available product can be used.

將上述組成物塗布在垂直配向用配向膜上的方法，並沒有特別限定，可使用以往周知的方法。例如，可使用擠壓式塗布(extrusion coating)法、直接凹版塗布法(direct gravure coating)、反轉凹版塗布法、CAP塗布法、模具式塗布(die coating)法、浸塗法、棒式塗布法及旋轉塗布法等。The method of applying the above composition to the alignment film for vertical alignment is not particularly limited, and a conventionally known method can be used. For example, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, a die coating method, a dip coating method, a bar coating method, or the like can be used. Method and spin coating method.

再者，上述組成物的塗布量並沒有特別限定，只要使所得到的膜成為能賦予期望相位差值之膜厚的方式，用適當量塗布即可。如上所述，藉由調整膜厚，可決定所得到的膜之相位差值(retardation值，Re(λ))。In addition, the coating amount of the above-mentioned composition is not particularly limited, and the obtained film may be applied in an appropriate amount so as to have a film thickness capable of imparting a desired retardation value. As described above, by adjusting the film thickness, the retardation value (Re(λ)) of the obtained film can be determined.

塗布上述組成物所形成的層厚度，如上所述，會因為所得到的膜之相位差值而有所不同。在本發明中，上述厚度係以0.1至10 μm為較佳，0.5至2 μm為更佳。只要在上述範圍內，就能夠成為上述本發明之膜的相位差值。The layer thickness formed by coating the above composition differs as described above due to the phase difference of the obtained film. In the present invention, the above thickness is preferably 0.1 to 10 μm, more preferably 0.5 to 2 μm. As long as it is within the above range, the phase difference value of the film of the present invention described above can be obtained.

如上所述，在含有液晶化合物之組成物的塗布步驟中，係於積層在任意支撐基材上而成的垂直配向用配向膜上積層光學異向性層(液晶層)。因此，製造液晶元件，與將液晶化合物注入該液晶元件中之方法相比，可降低生產成本。此外，卷片(Roll film)之膜的生產是有可能的。As described above, in the coating step of the composition containing the liquid crystal compound, an optically anisotropic layer (liquid crystal layer) is laminated on the alignment film for vertical alignment which is laminated on an arbitrary supporting substrate. Therefore, the production of the liquid crystal element can reduce the production cost as compared with the method of injecting the liquid crystal compound into the liquid crystal element. In addition, the production of a film of a roll film is possible.

(II－5)含有液晶化合物之組成物的加熱步驟(II-5) Heating step of the composition containing the liquid crystal compound

在含有液晶化合物之組成物的加熱步驟中，係將在上述含有液晶化合物之組成物的塗布步驟中形成的上述塗膜予以加熱。藉此使上述塗膜中所含的溶劑乾燥，可得到棒狀聚合性液晶化合物為未聚合狀態下的未聚合膜。本發明中亦包含如此操作所得到的未聚合膜。上述未聚合膜會表現出向列相等液晶相，因為單疇配向而具有雙折射性。再者，上述未聚合膜通常在10至120℃左右，較佳為在25至80℃的低溫下進行配向。因此，本發明可使用耐熱性低的基材作為上述支撐基材。In the heating step of the composition containing the liquid crystal compound, the coating film formed in the coating step of the composition containing the liquid crystal compound described above is heated. By drying the solvent contained in the coating film, the rod-shaped polymerizable liquid crystal compound is obtained as an unpolymerized film in an unpolymerized state. The unpolymerized film obtained in this manner is also included in the present invention. The above unpolymerized film exhibits a nematic liquid crystal phase, and has birefringence because of single domain alignment. Further, the above unpolymerized film is usually subjected to alignment at a low temperature of about 10 to 120 ° C, preferably at a low temperature of 25 to 80 ° C. Therefore, in the present invention, a substrate having low heat resistance can be used as the above-mentioned support substrate.

在含有液晶化合物之組成物的加熱步驟中，只要以能夠得到具有上述物性之未聚合膜的條件作為加熱上述組成物的方法或加熱條件等即可。具體而言，加熱溫度係以10至120℃為較佳，以25至80℃為更佳。再者，加熱時間係以10秒鐘至60分鐘為較佳，以30秒鐘至30分鐘為更佳。只要加熱溫度及加熱時間在上述範圍內，即可使用耐熱性不一定足夠的支撐基材作為上述支撐基材。In the heating step of the composition containing the liquid crystal compound, the method of heating the composition, the heating conditions, and the like may be used as conditions for obtaining the unpolymerized film having the above physical properties. Specifically, the heating temperature is preferably from 10 to 120 ° C, more preferably from 25 to 80 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes. As long as the heating temperature and the heating time are within the above range, a supporting substrate which is not necessarily sufficient in heat resistance can be used as the supporting substrate.

(II－6)液晶化合物的聚合步驟(II-6) Polymerization step of liquid crystal compound

在液晶化合物的聚合步驟中，使以上述含有液晶化合物之組成物的加熱步驟所得到的未聚合膜進行聚合、硬化。藉此而成為使棒狀聚合性液晶化合物之配向性固定化的膜，亦即聚合膜。因此，可製造在膜平面方向上折射率變化小，而在膜法線方向上折射率變化大的聚合膜。In the polymerization step of the liquid crystal compound, the unpolymerized film obtained by the heating step of the composition containing the liquid crystal compound described above is polymerized and cured. Thereby, it is a film which fixes the orientation of the rod-shaped polymerizable liquid crystal compound, that is, a polymer film. Therefore, it is possible to manufacture a polymer film having a small change in refractive index in the film plane direction and a large refractive index change in the film normal direction.

使未聚合膜進行聚合的方法，係依據棒狀聚合性液晶化合物及聚合性化合物的種類來決定。例如，可藉由光聚合或熱聚合使上述未聚合膜聚合。在本發明中，特別是以藉由光聚合使未聚合膜聚合為較佳。據此，由於可在低溫下使未聚合膜進行聚合，所以支撐基材之耐熱性的選擇範圍會變寬。再者，工業上的製造亦會變得容易。The method of polymerizing the unpolymerized film is determined depending on the type of the rod-shaped polymerizable liquid crystal compound and the polymerizable compound. For example, the above unpolymerized film can be polymerized by photopolymerization or thermal polymerization. In the present invention, in particular, it is preferred to polymerize the unpolymerized film by photopolymerization. According to this, since the unpolymerized film can be polymerized at a low temperature, the selection range of the heat resistance of the support substrate is widened. Furthermore, industrial manufacturing will also become easier.

使未聚合膜進行光聚合的方法並沒有特別限定，可使用以往周知的方法。例如可用紫外線照射未聚合膜，而使未聚合膜聚合。The method of photopolymerizing the unpolymerized film is not particularly limited, and a conventionally known method can be used. For example, the unpolymerized film may be irradiated with ultraviolet rays to polymerize the unpolymerized film.

如此，在本發明之膜之製造方法中，並沒有使用液晶聚合物作為液晶化合物。再者，可藉由光聚合使棒狀聚合性液晶化合物交聯。因此，能發揮雙折射之變化不容易受到熱影響的效果。再者，垂直配向用配向膜可不使用界面活性劑等表面處理劑。也就是說，本發明之膜之配向膜(垂直配向用配向膜)因為支撐基材與配向膜的密著性、及配向膜與光學異向性層的密著性良好，所以膜之製造容易。此外，根據本發明之膜之製造方法，與利用延伸膜而期望得到同等性能者相比，可在薄膜狀態下製造具有期望相位差值的光學補償膜。Thus, in the method for producing a film of the present invention, a liquid crystal polymer is not used as the liquid crystal compound. Further, the rod-shaped polymerizable liquid crystal compound can be crosslinked by photopolymerization. Therefore, it is possible to exert the effect that the change in birefringence is not easily affected by heat. Further, the alignment film for vertical alignment may not use a surface treatment agent such as a surfactant. In other words, the alignment film of the film of the present invention (alignment film for vertical alignment) is easy to manufacture because the adhesion between the support substrate and the alignment film and the adhesion between the alignment film and the optically anisotropic layer are good. . Further, according to the method for producing a film of the present invention, an optical compensation film having a desired retardation value can be produced in a film state as compared with a case where it is desired to obtain equivalent performance by using a stretched film.

<III.本發明之膜之用途><III. Use of the film of the present invention>

本發明之膜可廣泛用來作為具有優異波長分散特性之光學膜。上述光學膜可列舉抗反射(AR)膜等防止反射膜、偏光膜、相位差膜、橢圓偏光膜、視角擴大膜及透射型液晶顯示器之視角補償用光學補償膜等。The film of the present invention can be widely used as an optical film having excellent wavelength dispersion characteristics. Examples of the optical film include an antireflection film such as an antireflection (AR) film, a polarizing film, a retardation film, an elliptically polarizing film, a viewing angle widening film, and an optical compensation film for viewing angle compensation of a transmissive liquid crystal display.

此外，本發明之膜亦可利用在反射型液晶顯示器及有機電致發光(EL)顯示器之相位差板，以及具備該相位差板或上述光學膜的平面顯示裝置。上述平面顯示裝置並沒有特別限定，可列舉例如液晶顯示裝置(LCD)、有機電致發光(EL)者。Further, the film of the present invention can also be used in a phase difference plate of a reflective liquid crystal display or an organic electroluminescence (EL) display, and a flat display device including the phase difference plate or the optical film. The flat display device is not particularly limited, and examples thereof include a liquid crystal display device (LCD) and an organic electroluminescence (EL).

如此，推測本發明之膜可具有範圍廣泛的用途。其中，例如關於由本發明之膜積層所構成的偏光膜、以及具備本發明之膜或偏光膜的平面顯示裝置，係如後文說明。Thus, it is speculated that the film of the present invention can have a wide range of uses. Among them, for example, a polarizing film composed of the film laminate of the present invention and a flat display device including the film or polarizing film of the present invention will be described later.

(III－1)偏光膜(III-1) Polarizing film

雖然根據第3A圖至第3E圖，說明本發明之偏光膜的實施形態如下，但本發明之偏光膜並不限定於此。Although the embodiment of the polarizing film of the present invention is described below with reference to FIGS. 3A to 3E, the polarizing film of the present invention is not limited thereto.

本發明之偏光膜係具有偏光功能的膜，亦即藉由在偏光層之單面或雙面上直接或使用黏合劑貼合而得到者。The polarizing film of the present invention is a film having a polarizing function, that is, a film obtained by laminating one surface or both surfaces of a polarizing layer directly or by using an adhesive.

列舉例如第3A圖至第3E圖所示：(1)使膜1與偏光層2直接貼合的實施形態(第3A圖)；(2)使膜1與偏光層2經由黏合層或黏著層3而貼合的實施形態(第3B圖)；(3)使膜1與膜1’直接貼合，此外再使膜1’與偏光層2直接貼合的實施形態(第3C圖)；(4)使膜1與膜1’經由黏合層3而貼合，此外再使偏光層2直接貼合在膜1’上的實施形態(第3D圖)；及(5)使膜1與膜1’經由黏合層3而貼合，此外再使膜1’與偏光層2經由黏合層3’而貼合的實施形態(第3E圖)等。For example, as shown in FIGS. 3A to 3E, (1) an embodiment in which the film 1 and the polarizing layer 2 are directly bonded together (FIG. 3A); (2) the film 1 and the polarizing layer 2 are bonded via an adhesive layer or an adhesive layer. 3, the bonded embodiment (Fig. 3B); (3) the embodiment in which the film 1 and the film 1' are directly bonded together, and the film 1' and the polarizing layer 2 are directly bonded together (Fig. 3C); 4) an embodiment in which the film 1 and the film 1' are bonded via the adhesive layer 3, and the polarizing layer 2 is directly bonded to the film 1' (Fig. 3D); and (5) the film 1 and the film 1 are bonded 'An embodiment (Fig. 3E) in which the film 1' and the polarizing layer 2 are bonded together via the adhesive layer 3'.

為了便於說明，相同的元件(element)係附上相同的引用號碼。For ease of explanation, the same elements are attached with the same reference numerals.

在第3F圖中，使用液晶層11作為膜1，而膜1不包含配向層12。膜1與偏光層2係經由一對黏合層或黏著層3而使其貼合。In the 3F drawing, the liquid crystal layer 11 is used as the film 1, and the film 1 does not include the alignment layer 12. The film 1 and the polarizing layer 2 are bonded via a pair of adhesive layers or adhesive layers 3.

在第3G圖中，使用液晶層11作為膜1，膜1亦可不包含配向層12。經由黏合層或黏著層3使一對膜1貼合，此外，藉由黏合層或黏著層3使偏光層2貼合在其外側。In the 3G diagram, the liquid crystal layer 11 is used as the film 1, and the film 1 may not include the alignment layer 12. The pair of films 1 are bonded via the adhesive layer or the adhesive layer 3, and the polarizing layer 2 is bonded to the outside thereof by the adhesive layer or the adhesive layer 3.

第3H圖係表示與第3F圖同樣的構造。但是與第3F圖不同，係使用包含支撐膜13、在支撐膜13之表面上形成的配向膜12、以及在配向膜12之表面上形成的液晶層11作為膜1A的積層構造(laminated structure)。The 3H figure shows the same structure as the 3F figure. However, unlike the 3F, the alignment film 12 including the support film 13, the surface formed on the support film 13, and the liquid crystal layer 11 formed on the surface of the alignment film 12 are used as a laminated structure of the film 1A. .

第3I圖係表示與第3G圖同樣的構造。但是與第3G圖不同，係使用包含支撐膜13、在支撐膜13之表面上形成的配向膜12、以及在配向膜12之表面上形成的液晶層11作為膜1A的積層構造(laminated structure)。Fig. 3I shows the same structure as Fig. 3G. However, unlike the 3G diagram, the alignment film 12 including the support film 13, the surface formed on the support film 13, and the liquid crystal layer 11 formed on the surface of the alignment film 12 are used as a laminated structure of the film 1A. .

第3J圖及第3K圖係表示與第3G圖同樣的構造。但是2片膜之中的一片係使用液晶層11作為膜1，另一片則是使用包含支撐膜13、在支撐膜13之表面上形成的配向膜12、以及在配向膜12之表面上形成的液晶層11作為膜1A。The 3Jth and 3Kth drawings show the same structure as the 3Gth diagram. However, one of the two films uses the liquid crystal layer 11 as the film 1, and the other one uses the alignment film 12 including the support film 13, formed on the surface of the support film 13, and formed on the surface of the alignment film 12. The liquid crystal layer 11 serves as the film 1A.

上述偏光層2，只要是具有偏光功能的膜即可，並沒有特別限定。例如可使用使碘或二色性染料吸附在聚乙烯基醇系之膜上並加以延伸的膜、或使聚乙烯基醇系之膜加以延伸並吸附碘或二色性染料的膜作為上述偏光層2。The polarizing layer 2 is not particularly limited as long as it has a polarizing function. For example, a film in which iodine or a dichroic dye is adsorbed on a polyvinyl alcohol-based film and stretched, or a film in which a polyvinyl alcohol-based film is stretched and adsorbs iodine or a dichroic dye can be used as the polarized light. Layer 2.

上述黏合層3及黏合層3’所使用的黏合劑並沒有特別限定，但是以透明性高、耐熱性優異的黏合劑為較佳。此類黏合劑可使用例如丙烯酸系、環氧系或聚胺酯(urethane)系黏合劑等。The adhesive used for the adhesive layer 3 and the adhesive layer 3' is not particularly limited, but a binder having high transparency and excellent heat resistance is preferable. As such a binder, for example, an acrylic, epoxy or urethane-based adhesive can be used.

再者，在上述偏光膜中，如第3C圖至第3E圖所示，視需要也可貼合1層至3層本發明之膜。Further, in the above polarizing film, as shown in Figs. 3C to 3E, one to three layers of the film of the present invention may be bonded as needed.

(III－2)平面顯示裝置(III-2) Flat display device

本發明之平面顯示裝置係具備本發明之膜或偏光膜者。可列舉例如具備使本發明之偏光膜與液晶面板貼合而成之液晶面板的液晶顯示裝置、以及具備使本發明之偏光膜與發光層貼合而成之有機電致發光(後文稱為「EL」)面板的有機EL顯示裝置。The flat display device of the present invention is provided with the film of the present invention or a polarizing film. For example, a liquid crystal display device including a liquid crystal panel in which a polarizing film of the present invention and a liquid crystal panel are bonded together, and an organic electroluminescence including a polarizing film of the present invention and a light-emitting layer are exemplified (hereinafter referred to as "EL" panel organic EL display device.

以本發明之平面顯示裝置之實施形態而言，以下詳細敘述關於液晶顯示裝置及有機EL顯示裝置，但本發明並不限定於此。In the embodiment of the flat display device of the present invention, the liquid crystal display device and the organic EL display device will be described in detail below, but the present invention is not limited thereto.

[實施形態1][Embodiment 1]

實施形態1之液晶顯示裝置具備第4圖所示的液晶面板。上述液晶面板係經由黏著層或黏合層5使偏光膜4與液晶面板6貼合而成。根據上述結構，使用未圖示的電極，藉由對液晶面板施加電壓，驅動液晶分子，可發揮光閥的效果。The liquid crystal display device of the first embodiment includes the liquid crystal panel shown in Fig. 4 . The liquid crystal panel is formed by bonding the polarizing film 4 and the liquid crystal panel 6 via an adhesive layer or an adhesive layer 5. According to the above configuration, by applying an electric voltage to the liquid crystal panel by using an electrode (not shown), the liquid crystal molecules are driven, and the effect of the light valve can be exhibited.

[實施形態2][Embodiment 2]

實施形態2之有機EL顯示裝置具備第5圖所示的有機EL面板。上述有機EL面板係經由黏著層或黏合層5使偏光膜4、發光層7貼合而成。The organic EL display device of the second embodiment includes the organic EL panel shown in Fig. 5. The organic EL panel is formed by bonding the polarizing film 4 and the light-emitting layer 7 via an adhesive layer or an adhesive layer 5.

在上述有機EL面板中，偏光膜4具有作為廣頻帶圓形偏光板的功能。再者，上述發光層7係至少1層由導電性有機化合物所構成的層。In the above organic EL panel, the polarizing film 4 has a function as a wide-band circular polarizing plate. Further, the light-emitting layer 7 is a layer composed of at least one layer of a conductive organic compound.

另外，本發明並不限定於以上說明的各個結構，可在申請專利範圍所示的範圍內進行各種變更，適當組合不同實施形態中分別揭示的技術手段所得到的實施形態亦包含在本發明之技術範圍內。Further, the present invention is not limited to the respective configurations described above, and various modifications can be made within the scope of the claims, and the embodiments obtained by appropriately combining the technical means disclosed in the different embodiments are also included in the present invention. Within the technical scope.

[實施例][Examples]

根據實施例及比較例、以及第6圖及第7圖更具體說明本發明，但本發明並不限定於此。同業者可在不脫離本發明之範圍的情況下，進行各種變更、修正及改變。另外，在以下的實施例及比較例中，波長分散特性進行如下。The present invention will be more specifically described based on examples, comparative examples, and FIGS. 6 and 7, but the present invention is not limited thereto. Various changes, modifications, and changes can be made by those skilled in the art without departing from the scope of the invention. Further, in the following examples and comparative examples, the wavelength dispersion characteristics were as follows.

[波長分散特性之測定][Measurement of Wavelength Dispersion Characteristics]

使用測定儀器(KOBRA－WR，王子計測機器公司製造)，在585.6 nm的波長下測定所製造膜之相位差值的入射角相依性。第6圖及第7圖表示相對於快軸而使入射角變化時，波長585.6 nm的相位差值[Re(λ)]。同時，使用測定儀器(KOBRA－WR，王子計測機器公司製造)，在585.6 nm的波長下測定所製造膜之正面相位差值Ro(nm)。The incident angle dependence of the phase difference of the produced film was measured at a wavelength of 585.6 nm using a measuring instrument (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.). Fig. 6 and Fig. 7 show the phase difference [Re(λ)] at a wavelength of 585.6 nm when the incident angle is changed with respect to the fast axis. At the same time, the front phase difference Ro (nm) of the produced film was measured at a wavelength of 585.6 nm using a measuring instrument (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.).

再者，使用測定儀器(光譜式橢圓偏光計：M－220，日本分光公司製造)，測定所製造之膜之相位差值的入射角相依性，分別測定在膜平面之正交軸方向及膜厚方向的折射率nx、ny、nz。Further, using a measuring instrument (spectral ellipsometer: M-220, manufactured by JASCO Corporation), the incident angle dependence of the phase difference of the produced film was measured, and the direction of the orthogonal axis of the film plane and the film were measured. The refractive index nx, ny, nz in the thick direction.

[實施例1：垂直配向膜之製造][Example 1: Production of Vertical Alignment Film]

將垂直配向用聚醯亞胺配向膜用之溶液(SE－5300，日產化學公司製造)塗布在玻璃基板上之後，進行退火，得到厚度為104 nm的垂直配向用配向膜。接著，不進行摩擦處理，藉由旋轉塗布法塗布含有在水平配向膜上呈水平配向且在空氣界面上呈垂直配向之棒狀聚合性液晶化合物的組成物RMS－03－011(默克股份有限公司製造)，在55℃下乾燥1分鐘。藉由偏光顯微鏡確認所得到的未聚合膜為單疇。接著照射紫外線，製造膜厚為1.2 μm的膜。所得到的膜沒有不均，可均勻地塗布，在室內放置30天亦未見到剝落等現象，為密著性良好者。A solution for a vertical alignment using a polyimide film (SE-5300, manufactured by Nissan Chemical Co., Ltd.) was applied onto a glass substrate, and then annealed to obtain a vertical alignment film having a thickness of 104 nm. Next, the composition RMS-03-011 containing a rod-like polymerizable liquid crystal compound which is horizontally aligned on the horizontal alignment film and vertically aligned at the air interface is applied by a spin coating method without a rubbing treatment (Merck Co., Ltd.) Made by the company), dried at 55 ° C for 1 minute. It was confirmed by a polarizing microscope that the obtained unpolymerized film was a single domain. Then, ultraviolet rays were irradiated to produce a film having a film thickness of 1.2 μm. The obtained film had no unevenness, was uniformly applied, and was not left to be peeled off even after being left indoors for 30 days, and was excellent in adhesion.

利用上述方法測定所得到的膜之入射角相依性。其結果示於第6圖及表5。該圖是以入射角0°為中心，當對於膜之入射角繼續變大時，可知相位差值會變大。此膜之傾斜角顯示為90°。The incident angle dependence of the obtained film was measured by the above method. The results are shown in Fig. 6 and Table 5. The graph is centered on the incident angle of 0°, and when the incident angle to the film continues to increase, it is known that the phase difference value becomes large. The tilt angle of this film is shown to be 90°.

利用上述方法測定所得到的膜之正面相位差值Ro，結果為0 nm。從此等結果可知相對於膜平面之折射率橢圓體的傾斜角為90°。The front phase difference value Ro of the obtained film was measured by the above method, and the result was 0 nm. From these results, it is understood that the inclination angle of the refractive index ellipsoid with respect to the film plane is 90°.

[實施例2至4：傾斜配向膜之製造][Examples 2 to 4: Production of inclined alignment film]

將垂直配向用聚醯亞胺配向膜(SE－5300，日產化學公司製造)塗布在玻璃基板上之後，進行退火，得到厚度為104 nm的膜。用嫘縈(吉川化工製造，YA－20－R)對該配向膜進行表5所示的摩擦處理一次，接著，藉由旋轉塗布法塗布含有在水平配向膜上呈水平配向，在空氣界面上呈垂直配向之棒狀聚合性液晶化合物的組成物RMS－03－011(默克股份有限公司製造)，在55℃下乾燥1分鐘。藉由偏光顯微鏡確認所得到的未聚合膜為單疇。接著照射紫外線，使聚合性液晶化合物聚合，製造膜厚為1.2 μm的光學膜。所得到的膜沒有不均，可均勻地塗布，在室內放置30天亦未見到剝落等現象，為密著性良好者。The vertical alignment was applied to a glass substrate by a polyimide film (SE-5300, manufactured by Nissan Chemical Co., Ltd.), and then annealed to obtain a film having a thickness of 104 nm. The alignment film was subjected to the rubbing treatment shown in Table 5 once by 嫘萦 (manufactured by Yoshikawa Chemical Co., Ltd., YA-20-R), and then coated by a spin coating method to be horizontally aligned on the horizontal alignment film at the air interface. The composition of the rod-like polymerizable liquid crystal compound which was vertically aligned, RMS-03-011 (manufactured by Merck & Co., Inc.), was dried at 55 ° C for 1 minute. It was confirmed by a polarizing microscope that the obtained unpolymerized film was a single domain. Then, ultraviolet rays were irradiated to polymerize the polymerizable liquid crystal compound to produce an optical film having a film thickness of 1.2 μm. The obtained film had no unevenness, was uniformly applied, and was not left to be peeled off even after being left indoors for 30 days, and was excellent in adhesion.

利用上述方法測定所得到的膜之入射角相依性。另外，以第7圖及表5顯示實施例2之膜的結果作為其結果之一例。再者，實施例3及4的結果示於表5。實施例2至4之膜分別以入射角在－19°、－6°、－10°時為中心，當對於膜之入射角繼續變大時，可知相位差值會變大。此膜之傾斜角分別顯示為71°、84°、80°。The incident angle dependence of the obtained film was measured by the above method. Further, the results of the film of Example 2 are shown in Fig. 7 and Table 5 as an example of the results. Further, the results of Examples 3 and 4 are shown in Table 5. The films of Examples 2 to 4 were centered at -19, -6, and -10, respectively, and when the incident angle to the film continued to increase, the phase difference was increased. The inclination angles of the films were shown to be 71°, 84°, and 80°, respectively.

再者，亦利用上述方法測定所得到的光學膜之正面相位差值Ro。結果，實施例2至4之膜的Ro分別為18 nm、5 nm、9 nm。從這些結果可知在實施例2至4中，相對於膜平面之折射率橢圓體的傾斜角為71°、84°、80°。Further, the front phase difference value Ro of the obtained optical film was also measured by the above method. As a result, the films of the films of Examples 2 to 4 were 18 nm, 5 nm, and 9 nm, respectively. From these results, it is understood that in Examples 2 to 4, the inclination angles of the refractive index ellipsoid with respect to the film plane were 71°, 84°, and 80°.

[比較例1][Comparative Example 1]

除了使用表6之塗布液代替組成物RMS－03－011(默克股份有限公司製造)以作為含有液晶化合物之組成物以外，與實施例1同樣地實施以製造膜。藉由偏光顯微鏡確認所得到的未聚合膜不是單疇。A film was produced in the same manner as in Example 1 except that the composition liquid of Table 6 was used instead of the composition RMS-03-011 (manufactured by Merck & Co., Ltd.) as a composition containing a liquid crystal compound. It was confirmed by a polarizing microscope that the obtained unpolymerized film was not a single domain.

(產業上利用的可能性)(the possibility of industrial use)

本發明之膜，係並非在膜平面方向上而是在膜法線方向上能夠賦予高折射率的膜。因此，本發明可用來作為抗反射(AR)膜等防止反射膜、偏光膜、相位差膜、橢圓偏光膜、視角擴大膜等具有優異波長分散特性的光學膜。此外，本發明亦可利用在反射型液晶顯示器及有機電致發光(EL)顯示器之相位差板或具備此等相位差板的平面顯示裝置(FPD)。The film of the present invention is a film which is capable of imparting a high refractive index in the film normal direction, not in the film plane direction. Therefore, the present invention can be used as an optical film having excellent wavelength dispersion characteristics such as an antireflection (AR) film such as an antireflection film, a polarizing film, a retardation film, an elliptically polarizing film, and a viewing angle widening film. Further, the present invention can also be applied to a phase difference plate of a reflective liquid crystal display or an organic electroluminescence (EL) display or a flat display device (FPD) having such a phase difference plate.

1、1’、1A．．．膜1, 1', 1A. . . membrane

2．．．偏光層2. . . Polarizing layer

3、3’．．．黏著層或黏合層3, 3’. . . Adhesive layer or adhesive layer

4．．．偏光膜4. . . Polarizing film

5．．．黏著層或黏合層5. . . Adhesive layer or adhesive layer

6．．．液晶面板6. . . LCD panel

7．．．發光層7. . . Luminous layer

11．．．液晶層11. . . Liquid crystal layer

12．．．配向層或配向膜12. . . Alignment layer or alignment film

13．．．支撐膜13. . . Support film

14．．．棒狀聚合性液晶化合物14. . . Rod-shaped polymerizable liquid crystal compound

22．．．折射率橢圓體twenty two. . . Refractive index ellipsoid

24．．．垂直橢圓面twenty four. . . Vertical elliptical surface

d．．．膜厚d. . . Film thickness

na、nb、nc．．．三維主折射率Na, nb, nc. . . Three-dimensional principal refractive index

nx．．．長軸Nx. . . Long axis

ny．．．短軸Ny. . . Short axis

第1A圖第1A圖為表示膜之配向之一例的剖面圖。Fig. 1A is a cross-sectional view showing an example of alignment of a film.

第1B圖第1B圖為表示膜之配向之另一例的剖面圖。Fig. 1B is a cross-sectional view showing another example of the alignment of the film.

第1C圖第1C圖為表示膜之配向之另一例的剖面圖。Fig. 1C is a cross-sectional view showing another example of the alignment of the film.

第2圖第2圖為表示本發明之膜之雙折射性的圖。Fig. 2 is a view showing the birefringence of the film of the present invention.

第3A圖為表示本發明之膜之使用狀態的剖面圖。Fig. 3A is a cross-sectional view showing the state of use of the film of the present invention.

第3B圖為表示本發明之膜之使用狀態的剖面圖。Fig. 3B is a cross-sectional view showing the state of use of the film of the present invention.

第3C圖為表示本發明之膜之使用狀態的剖面圖。Fig. 3C is a cross-sectional view showing the state of use of the film of the present invention.

第3D圖為表示本發明之膜之使用狀態的剖面圖。Fig. 3D is a cross-sectional view showing the state of use of the film of the present invention.

第3E圖為表示本發明之膜之使用狀態的剖面圖。Fig. 3E is a cross-sectional view showing the state of use of the film of the present invention.

第3F圖為表示本發明之膜之使用狀態的剖面圖。Fig. 3F is a cross-sectional view showing the state of use of the film of the present invention.

第3G圖為表示本發明之膜之使用狀態的剖面圖。Fig. 3G is a cross-sectional view showing the state of use of the film of the present invention.

第3H圖為表示本發明之膜之使用狀態的剖面圖。Fig. 3H is a cross-sectional view showing the state of use of the film of the present invention.

第3I圖為表示本發明之膜之使用狀態的剖面圖。Fig. 3I is a cross-sectional view showing the state of use of the film of the present invention.

第3J圖為表示本發明之膜之使用狀態的剖面圖。Fig. 3J is a cross-sectional view showing the state of use of the film of the present invention.

第3K圖為表示本發明之膜之使用狀態的剖面圖。Fig. 3K is a cross-sectional view showing the state of use of the film of the present invention.

第4圖為液晶面板的剖面圖。Fig. 4 is a cross-sectional view of the liquid crystal panel.

第5圖為有機EL面板的剖面圖。Fig. 5 is a cross-sectional view of the organic EL panel.

第6圖為顯示實施例1所製造之光學膜之相位差值之入射角相依性的圖。Fig. 6 is a graph showing the incident angle dependence of the retardation values of the optical films produced in Example 1.

第7圖為顯示實施例2所製造之光學膜之相位差值之入射角相依性的圖。Fig. 7 is a graph showing the incident angle dependence of the retardation values of the optical films produced in Example 2.

11．．．液晶層11. . . Liquid crystal layer

12．．．配向層或配向膜12. . . Alignment layer or alignment film

14．．．棒狀聚合性液晶化合物14. . . Rod-shaped polymerizable liquid crystal compound

Claims (12)

一種光學膜，係具有形成於垂直配向用配向膜上之光學異向性層的膜，其特徵為：該光學異向性層係由含有包含從棒狀聚合性液晶化合物而來之結構單元的聚合物之層所構成，該棒狀聚合性液晶化合物係作為單體並且為具有在水平配向膜上呈水平配向、在空氣界面上呈垂直配向之特性者，在膜平面之正交軸方向及膜厚方向的折射率分別為nx、ny、nz的情況下，滿足nz>nx及nz>ny，且在沒有經摩擦處理過的垂直配向用配向膜上，使上述棒狀聚合性液晶化合物在液晶狀態下配向時，上述棒狀聚合性液晶化合物相對於垂直配向用配向膜呈向列垂直配向，而在經摩擦處理過的垂直配向用配向膜上，使上述棒狀聚合性液晶化合物在液晶狀態下配向時，在空氣層界面上仍舊保持垂直方向的分子配向，而在垂直配向用配向膜之界面上則呈傾斜配向者。 An optical film comprising an optically anisotropic layer formed on an alignment film for a vertical alignment, characterized in that the optically anisotropic layer is composed of a structural unit containing a rod-like polymerizable liquid crystal compound. a layer of a polymer, which is a monomer and has a property of being horizontally aligned on a horizontal alignment film and vertically aligned at an air interface, in the direction of the orthogonal axis of the film plane and When the refractive indices in the film thickness direction are respectively nx, ny, and nz, the above-mentioned rod-shaped polymerizable liquid crystal compound is obtained by satisfying nz>nx and nz>ny, and on the alignment film for vertical alignment without rubbing treatment. In the alignment in the liquid crystal state, the rod-shaped polymerizable liquid crystal compound is aligned in the vertical direction with respect to the alignment film for vertical alignment, and the rod-shaped polymerizable liquid crystal compound is allowed to be in the liquid crystal on the rubbed vertical alignment film. In the state of alignment, the molecular alignment in the vertical direction is maintained at the interface of the air layer, and the oblique alignment is provided at the interface of the alignment film for the vertical alignment. 如申請專利範圍第1項之光學膜，其中，該垂直配向用配向膜係垂直配向膜。 The optical film of claim 1, wherein the vertical alignment alignment film is a vertical alignment film. 如申請專利範圍第2項之光學膜，其中，相對於該光學異向性層之折射率橢圓體之膜平面的傾斜角係90±5°。 The optical film of claim 2, wherein the film angle with respect to the film plane of the refractive index ellipsoid of the optically anisotropic layer is 90 ± 5°. 如申請專利範圍第1項之光學膜，其中，該垂直配向用配向膜係對於垂直配向膜施加摩擦處理而成之配向膜。 The optical film of claim 1, wherein the vertical alignment alignment film is an alignment film obtained by applying a rubbing treatment to the vertical alignment film. 如申請專利範圍第4項之光學膜，其中，相對於該光學 異向性層之折射率橢圓體之膜平面的傾斜角係45°至85°。 An optical film according to claim 4, wherein the optical film is opposite to the optical The angle of inclination of the film plane of the refractive index ellipsoid of the anisotropic layer is 45° to 85°. 一種光學膜，係具有形成於垂直配向用配向膜上之光學異向性層的膜，其特徵為：該光學異向性層係由含有棒狀聚合性液晶化合物的層所構成，該棒狀聚合性液晶化合物係具有在水平配向膜上呈水平配向、在空氣界面上呈垂直配向之特性者，在膜平面之正交軸方向及膜厚方向的折射率分別為nx、ny、nz的情況下，滿足nz>nx及nz>ny，且在沒有經摩擦處理過的垂直配向用配向膜上，使上述棒狀聚合性液晶化合物在液晶狀態下配向時，上述棒狀聚合性液晶化合物相對於垂直配向用配向膜呈向列垂直配向，而在經摩擦處理過的垂直配向用配向膜上，使上述棒狀聚合性液晶化合物在液晶狀態下配向時，在空氣層界面上仍舊保持垂直方向的分子配向，而在垂直配向用配向膜之界面上則呈傾斜配向者。 An optical film comprising an optically anisotropic layer formed on an alignment film for a vertical alignment, wherein the optically anisotropic layer is composed of a layer containing a rod-shaped polymerizable liquid crystal compound. The polymerizable liquid crystal compound has a characteristic of being horizontally aligned on the horizontal alignment film and vertically aligned at the air interface, and the refractive indices in the orthogonal axis direction and the film thickness direction of the film plane are nx, ny, and nz, respectively. When the rod-shaped polymerizable liquid crystal compound is aligned in a liquid crystal state, the rod-shaped polymerizable liquid crystal compound is aligned with respect to nz>nx and nz>ny, and the alignment film for the vertical alignment is not subjected to the rubbing treatment. The alignment film for the vertical alignment is oriented in the vertical direction of the alignment, and when the rod-shaped polymerizable liquid crystal compound is aligned in the liquid crystal state on the rubbed-treated alignment film for the vertical alignment, the vertical direction is maintained at the interface of the air layer. Molecular alignment, and oblique alignment on the interface of the alignment film for vertical alignment. 如申請專利範圍第1至6項中任一項之光學膜，其呈現逆波長分散者。 The optical film of any one of claims 1 to 6 which exhibits a reverse wavelength dispersion. 如申請專利範圍第7項之光學膜，其中，該光學異向性層含有包含從下述式(1)所示之聚合性化合物而來之結構單元的聚合物，P2-E2-X2-B2-A2-(G2)t-Y-(G1)s-A1-B1-X1-E1-P1 (1)(式中，Y表示2價基，s及t分別獨立地表示0或1的整數，G1及G2分別獨立地表示-CR1 R2 -，R1 及R2 分 別獨立表示碳數1至4的烷基、鹵素原子、氫原子，A1及A2分別獨立地表示2價環狀烴基、2價雜環基、亞甲基伸苯基、氧伸苯基、硫伸苯基，在A1及A2上亦可結合碳數1至5的烷基、碳數1至5的烷氧基、鹵素原子，B1及B2分別獨立地表示選自-CRR’-、-C≡C-、-CH=CH-、-CH2 -CH2 -、-O-、-S-、-C(=O)-、-C(=O)-O-、-O-C(=O)-、-O-C(=O)-O-、-C(=S)-、-C(=S)-O-、-O-C(=S)-、-O-C(=S)-O-、-CH=N-、-N=CH-、-N=N-、-N(→O)=N-、-N=N(→O)-、-C(=O)-NR-、-NR-C(=O)-、-OCH2 -、-NR-、-CH2 O-、-SCH2 -、-CH2 S-、-CH=CH-C(=O)-O-、-O-C(=O)-CH=CH-、單鍵所成組群中之2價基，R及R’分別獨立地表示氫原子或碳數1至4的烷基，X1及X2分別獨立表示下述式(2)所示之2價基， (式中，A3表示2價環狀烴基、雜環基，B3表示與前述B1及B2相同的意義，n表示1至4的整數)，E1及E2分別獨立地表示碳數2至25的伸烷基，在E1及E2上亦可再結合碳數1至5的烷基、碳數1至5的烷氧基、鹵素原子，P1及P2表示氫原子或聚合性基，P1及P2至少有一個是聚合性基)。The optical film according to claim 7, wherein the optically anisotropic layer contains a polymer comprising a structural unit derived from a polymerizable compound represented by the following formula (1), P2-E2-X2-B2 -A2-(G2)tY-(G1)s-A1-B1-X1-E1-P1 (1) (wherein Y represents a divalent group, and s and t each independently represent an integer of 0 or 1, G1 and G2 independently represents -CR 1 R 2 -, and R 1 and R 2 each independently represent an alkyl group having 1 to 4 carbon atoms, a halogen atom, and a hydrogen atom, and A1 and A2 each independently represent a divalent cyclic hydrocarbon group and a divalent value. a heterocyclic group, a methylene-phenylene group, an oxygen-extended phenyl group, a sulfur-extended phenyl group, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a halogen atom may be bonded to A1 and A2. , B1 and B2 are independently represented by -CRR'-, -C≡C-, -CH=CH-, -CH 2 -CH 2 -, -O-, -S-, -C(=O)-, respectively. , -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -C(=S)-, -C(=S)-O-, -OC( =S)-, -OC(=S)-O-, -CH=N-, -N=CH-, -N=N-, -N(→O)=N-, -N=N(→O )-, -C(=O)-NR-, -NR-C(=O)-, -OCH 2 -, -NR-, -CH 2 O-, -SCH 2 -, -CH 2 S-, - CH=CH-C(=O)-O-, -OC(=O)-CH=CH-, the two-valent group in the group of single bonds, R and R' are independent Represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, the X1 and X2 each independently represented by the following formula (2) shown in the divalent group, (wherein A3 represents a divalent cyclic hydrocarbon group or a heterocyclic group, B3 represents the same meaning as the above B1 and B2, and n represents an integer of 1 to 4), and E1 and E2 each independently represent a carbon number of 2 to 25 The alkyl group may further combine an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom in E1 and E2, and P1 and P2 each represent a hydrogen atom or a polymerizable group, and P1 and P2 have at least One is a polymerizable group). 一種光學膜之製造方法，係具有形成於垂直配向用配向膜上之光學異向性層的膜之製造方法，其特徵為至少包含：(A)在垂直配向用配向膜上塗布含有棒狀聚合性液晶化合物之組成物的步驟，以及(B)使上述步驟(A)所形成的塗膜在25℃至120℃下加熱10秒鐘至60分鐘的步驟；其中，該棒狀聚合性液晶化合物係作為單體並且為具有在水平配向膜上呈水平配向、在空氣界面上呈垂直配向之特性，且在沒有經摩擦處理過的垂直配向用配向膜上，使上述棒狀聚合性液晶化合物在液晶狀態下配向時，上述棒狀聚合性液晶化合物相對於垂直配向用配向膜呈向列垂直配向，而在經摩擦處理過的垂直配向用配向膜上，使上述棒狀聚合性液晶化合物在液晶狀態下配向時，在空氣層界面上仍舊保持垂直方向的分子配向，而在垂直配向用配向膜之界面上則呈傾斜配向者。 A method for producing an optical film, comprising a method for producing a film having an optically anisotropic layer formed on an alignment film for vertical alignment, comprising at least (A) coating a rod-shaped polymerization on a vertical alignment alignment film; a step of forming a composition of the liquid crystal compound, and (B) a step of heating the coating film formed in the above step (A) at 25 ° C to 120 ° C for 10 seconds to 60 minutes; wherein the rod-shaped polymerizable liquid crystal compound The above-mentioned rod-shaped polymerizable liquid crystal compound is used as a monomer and has a property of being horizontally aligned on a horizontal alignment film and vertically aligned at an air interface, and on a vertical alignment alignment film which has not been subjected to rubbing treatment, In the alignment in the liquid crystal state, the rod-shaped polymerizable liquid crystal compound is aligned in the vertical direction with respect to the alignment film for vertical alignment, and the rod-shaped polymerizable liquid crystal compound is allowed to be in the liquid crystal on the rubbed vertical alignment film. In the state of alignment, the molecular alignment in the vertical direction is maintained at the interface of the air layer, and the oblique alignment is provided at the interface of the alignment film for the vertical alignment. 如申請專利範圍第9項之光學膜之製造方法，其中，復包含(C)藉由光聚合使上述棒狀液晶化合物交聯的步驟。 The method for producing an optical film according to claim 9, wherein the step (C) is a step of crosslinking the rod-like liquid crystal compound by photopolymerization. 一種偏光膜，其特徵為由申請專利範圍第1至8項中任一項之光學膜所積層而成。 A polarizing film characterized by being laminated by an optical film according to any one of claims 1 to 8. 一種平面顯示裝置，其特徵為具備申請專利範圍第1至8項中任一項之光學膜或申請專利範圍第11項之偏光膜。A flat display device comprising the optical film of any one of claims 1 to 8 or the polarizing film of claim 11 of the patent application.
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