TW201632608A - Liquid crystal display element and method of manufacturing the same - Google Patents

Liquid crystal display element and method of manufacturing the same Download PDF

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TW201632608A
TW201632608A TW104139915A TW104139915A TW201632608A TW 201632608 A TW201632608 A TW 201632608A TW 104139915 A TW104139915 A TW 104139915A TW 104139915 A TW104139915 A TW 104139915A TW 201632608 A TW201632608 A TW 201632608A
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liquid crystal
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crystal display
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Shinichi Hirata
Yutaka Nagashima
Shinji Ogawa
Yoshinori Iwashita
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Dainippon Ink & Chemicals
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    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C—CHEMISTRY; METALLURGY
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    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
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    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

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Abstract

A liquid crystal display element, and a method of manufacturing the same, is provided which is not prone to the occurrence of drip marks during manufacturing and does not lead to a worsening of burn-in characteristics of the liquid crystal element, or of various liquid crystal display element characteristics such as dielectric anisotropy, viscosity, nematic phase maximum temperature, rotational viscosity ([gamma]1), etc. Further, this invention makes it possible to manufacture a liquid crystal display element which has excellent high-speed responsiveness as a liquid crystal display element, stable orientation and pre-tilt angle of the liquid crystal molecules, minimal occurrence of burn-in, and minimal occurrence of drip marks during manufacturing. The liquid crystal display element manufactured according to this invention can be used effectively as a display element in liquid crystal televisions, monitors, etc.

Description

液晶顯示元件及其製造方法 Liquid crystal display element and method of manufacturing same

本發明係關於一種作為液晶TV等之構成構件有用之液晶顯示元件及其製造方法。 The present invention relates to a liquid crystal display element useful as a constituent member of a liquid crystal TV or the like and a method of manufacturing the same.

液晶顯示元件以鐘錶、計算器為開端，用於各種測定機器、汽車用面板、文字處理機、電子記事本、印表機、電腦、電視、鐘錶、廣告顯示板等。作為液晶顯示方式，其具代表性者可列舉TN(Twisted Nematic，扭轉向列)型、STN(Super Twisted Nematic，超扭轉向列)型、使用TFT(Thin Film Transistor，薄膜電晶體)之垂直定向型(Vertical Aligned，VA)或IPS(In-Plane Switching，共平面切換)型等。業界要求該等液晶顯示元件所使用之液晶組成物對於水分、空氣、熱、光等外界因素穩定，又，於以室溫為中心之儘可能廣之溫度範圍內顯示出液晶相，低黏性且驅動電壓較低。進而，為了對於各液晶顯示元件將介電各向導性(△ε)或折射率異向性(△n)等設為最佳值，而由數種至數十種化合物構成液晶組成物。 The liquid crystal display element is started with a clock and a calculator, and is used for various measuring machines, automobile panels, word processors, electronic notebooks, printers, computers, televisions, clocks, advertisement display boards, and the like. Typical examples of the liquid crystal display method include a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, and a vertical orientation using a TFT (Thin Film Transistor). Vertical Aligned (VA) or IPS (In-Plane Switching) type. The liquid crystal composition used in these liquid crystal display elements is required to be stable to external factors such as moisture, air, heat, light, etc., and exhibits a liquid crystal phase in a temperature range as wide as possible around a room temperature, and has low viscosity. And the driving voltage is low. Further, in order to optimize the dielectric conductivity (Δε), the refractive index anisotropy (Δn), and the like for each liquid crystal display element, a liquid crystal composition is composed of several to several tens of compounds.

VA型顯示器中使用△ε為負之液晶組成物，而廣泛用於液晶TV等。另一方面，於全部驅動方式中，均要求低電壓驅動、高速應答、較廣之動作溫度範圍。即，要求△ε之絕對值較大、黏度(η)較小、及 較高之向列相-等向性液體相轉移溫度(Tni)。又，需要根據△n與單元間隙(d)之乘積即△n×d之設定，配合單元間隙將液晶組成物之△n調節在適當之範圍內。除此以外，於將液晶顯示元件應用於電視等中之情形時，由於重視高速應答性，故而要求旋轉黏度(γ1)較小之液晶組成物。 In the VA type display, a liquid crystal composition having a negative Δ ε is used, and is widely used for a liquid crystal TV or the like. On the other hand, in all driving methods, low voltage driving, high speed response, and a wide operating temperature range are required. That is, the absolute value of Δε is required to be large, the viscosity (η) is small, and the nematic phase-isotropic liquid phase transition temperature (T ni ) is high. Further, it is necessary to adjust the Δn of the liquid crystal composition to an appropriate range in accordance with the cell gap based on the setting of Δn × d which is the product of Δn and the cell gap (d). In addition, when a liquid crystal display element is applied to a television or the like, a liquid crystal composition having a small rotational viscosity (γ 1 ) is required because of high speed responsiveness.

另一方面，為了改善VA型顯示器之視野角特性，廣泛使用MVA(Multi-domain Vertical Alig nment，多域垂直定向)型之液晶顯示元件，其係藉由在基板上設置突起結構物，而將像素中之液晶分子之定向方向分割為多個。MVA型液晶顯示元件雖然於視野角特性方面優異，但於基板上之突起結構物附近及距其較遠之部位，液晶分子之應答速度不同，受到距突起結構物較遠而應答速度較慢之液晶分子之影響，存在整體之應答速度不足之問題，且存在由突起結構物引起之穿透率降低之問題。為了解決該問題，作為與通常之MVA型液晶顯示元件不同，不於單元中設置非透過性之突起結構物而於經分割之像素內賦予均勻之預傾角之方法，開發出PSA液晶顯示元件(polymer sustained alig nment，聚合物維持定向；包括PS液晶顯示元件(polymer stabilised，聚合物穩定化))。PSA液晶顯示元件係藉由將少量反應性單體添加至液晶組成物中，將該液晶組成物導入至液晶單元中後，一面於電極間施加電壓，一面利用活性能量線之照射使液晶組成物中之反應性單體聚合而製造。因此，可於分割像素中賦予合適之預傾角，結果可達成由提高穿透率而獲得之對比度之提高及由賦予均勻之預傾角而獲得之高速應答性(例如，參照專利文獻1)。然而，於PSA液晶顯示元件中，必須於液晶組成物中添加反應性單體，於要求較高之電壓保持率之主動矩陣液晶顯示元件中，問題較多，亦存在產生殘像等顯示不良之問 題。 On the other hand, in order to improve the viewing angle characteristics of a VA type display, a MVA (Multi-domain Vertical Aligament) type liquid crystal display element is widely used, which is provided by providing a protruding structure on a substrate. The orientation direction of the liquid crystal molecules in the pixel is divided into a plurality of directions. Although the MVA type liquid crystal display element is excellent in viewing angle characteristics, the response speed of the liquid crystal molecules is different in the vicinity of the protruding structure on the substrate and in a portion far from the substrate, and is distant from the protruding structure and has a slow response speed. The influence of the liquid crystal molecules has a problem that the overall response speed is insufficient, and there is a problem that the transmittance is lowered by the protruding structure. In order to solve this problem, a PSA liquid crystal display element has been developed as a method of providing a uniform pretilt angle in a divided pixel without providing a non-transmissive protruding structure in a cell, unlike a conventional MVA liquid crystal display device. Polymer sustained alig nment, the polymer maintains orientation; including PS liquid crystal display elements (polymer stabilised). In the PSA liquid crystal display device, a small amount of a reactive monomer is added to the liquid crystal composition, and the liquid crystal composition is introduced into the liquid crystal cell, and then a liquid crystal composition is applied by irradiation with an active energy ray while applying a voltage between the electrodes. The reactive monomer is polymerized and produced. Therefore, an appropriate pretilt angle can be imparted to the divided pixels, and as a result, an improvement in contrast obtained by increasing the transmittance and a high-speed response obtained by imparting a uniform pretilt angle can be achieved (for example, refer to Patent Document 1). However, in the PSA liquid crystal display device, it is necessary to add a reactive monomer to the liquid crystal composition, and in an active matrix liquid crystal display device requiring a high voltage holding ratio, there are many problems, and display defects such as afterimages are generated. ask question.

作為改良PSA液晶顯示元件之缺陷，不在液晶組成物中混入液晶材料以外之雜質而對液晶分子賦予均勻之預傾角之方法，開發出如下方式：於定向膜材料中混入反應性單體，將液晶組成物導入至液晶單元中後，一面於電極間施加電壓，一面利用活性能量線之照射使定向膜中之反應性單體聚合(例如，參照專利文獻2、3及4)。 As a method for improving the PSA liquid crystal display device, a method of imparting a uniform pretilt angle to liquid crystal molecules without mixing impurities other than the liquid crystal material in the liquid crystal composition has been developed, in which a reactive monomer is mixed into the alignment film material, and liquid crystal is incorporated. After the composition is introduced into the liquid crystal cell, the reactive monomer in the alignment film is polymerized by irradiation with an active energy ray while applying a voltage between the electrodes (see, for example, Patent Documents 2, 3, and 4).

另一方面，伴隨液晶顯示元件之大畫面化，液晶顯示元件之製造方法亦發生較大變化。即，於製造大型之面板之情形時，由於先前之真空注入法之製造製程需要大量時間，因此於大型面板之製造中，利用ODF(one-drop-fill)方式之製造方法逐漸成為主流(例如，參照專利文獻5)。由於該方式與真空注入法相比，可縮短注入時間，因此正成為液晶顯示元件之製造方法之主流。然而，滴加液晶組成物而形成之滴加痕於製作液晶顯示元件後亦以所滴加之形狀殘留於液晶顯示元件中之現象成為新問題。再者，所謂滴加痕係定義為於顯示黑色之情形時滴加液晶組成物之痕跡呈白色浮現之現象。尤其是於上文所述之於定向膜材料中添加反應性單體而對液晶分子賦予預傾角之方式中，由於液晶組成物在向基板滴加時，作為雜質之反應性單體存在於定向膜中，因此容易產生滴加痕之問題。又，通常滴加痕之產生亦多數係因液晶材料之選擇而產生，其原因尚不明確。 On the other hand, with the large screen of the liquid crystal display element, the manufacturing method of the liquid crystal display element has also largely changed. That is, in the case of manufacturing a large panel, since the manufacturing process of the prior vacuum injection method requires a large amount of time, in the manufacture of a large panel, a manufacturing method using an ODF (one-drop-fill) method has gradually become mainstream (for example, Refer to Patent Document 5). Since this method can shorten the injection time as compared with the vacuum injection method, it is becoming the mainstream of the manufacturing method of the liquid crystal display element. However, the phenomenon in which the dropping of the liquid crystal composition is dropped after the liquid crystal display element is formed and remains in the liquid crystal display element in the form of dropping is a new problem. Further, the so-called drop mark is defined as a phenomenon in which a trace of a liquid crystal composition is dropped in a white form when black is displayed. In particular, in the above-described manner of adding a reactive monomer to the alignment film material to impart a pretilt angle to the liquid crystal molecules, since the liquid crystal composition is dropped onto the substrate, the reactive monomer as an impurity exists in the orientation. In the film, the problem of dropping marks is likely to occur. Moreover, the occurrence of traces is usually caused by the selection of liquid crystal materials, and the reason is not clear.

作為滴加痕之抑制方法，揭示有如下方法：使混合於液晶組成物中之聚合性化合物聚合而於液晶組成物層中形成聚合物層，藉此抑制因與定向控制膜之關係而產生之滴加痕(例如，參照專利文獻6)。然而，若僅藉由該方法，則與PSA方式等同樣地存在由添加至液晶組成物中之反 應性單體引起之顯示之殘像的問題，關於滴加痕之抑制，其效果亦不充分，業界謀求開發出維持作為液晶顯示元件之基本特性，並且不易產生殘像或滴加痕之液晶顯示元件。進而，由於液晶顯示元件於其製造時及使用時會暴露於UV光下，因此重要的是不會因該等UV照射而產生劣化等，或即便產生亦不會對顯示造成影響。 As a method for suppressing the addition of the traces, there is disclosed a method of polymerizing a polymerizable compound mixed in a liquid crystal composition to form a polymer layer in the liquid crystal composition layer, thereby suppressing the relationship with the orientation control film. The mark is dropped (for example, refer to Patent Document 6). However, according to this method alone, there is a reaction added to the liquid crystal composition as in the PSA method or the like. The problem of the afterimage caused by the monomer is not sufficient, and the effect of the suppression of the drop mark is insufficient. The industry has sought to develop a liquid crystal which maintains the basic characteristics of the liquid crystal display element and is less likely to cause residual images or dripping marks. Display component. Further, since the liquid crystal display element is exposed to UV light at the time of its manufacture and use, it is important that deterioration or the like does not occur due to such UV irradiation, or that it does not affect the display even if it is generated.

因此，本發明人等於日本專利第05299595號公報(專利文獻12)等中提出一種液晶顯示元件，其於使垂直定向膜中含有反應性單體，將液晶組成物導入至液晶單元中後，一面於電極間施加電壓，一面藉由活性能量線之照射使定向膜中之反應性單體聚合之方式中，組合特定之液晶組成物。藉由該液晶顯示元件，可提供一種於不使介電各向導性、黏度、向列相上限溫度、旋轉黏度(γ1)等作為液晶顯示元件之各特性及液晶顯示元件之殘像特性變差之情況下，不易產生製造時之滴加痕的液晶顯示元件及其製造方法。然而，隨著對液晶顯示元件之要求變高，業界要求開發出作為液晶顯示元件之各特性進一步提高、尤其是可靠性更高之液晶組成物及液晶顯示元件。 Therefore, the inventors of the present invention have proposed a liquid crystal display element which has a reactive monomer contained in a vertical alignment film and introduces a liquid crystal composition into a liquid crystal cell, and a side of the invention is disclosed in Japanese Patent No. 05299595 (Patent Document 12). A specific liquid crystal composition is combined in a manner in which a voltage is applied between the electrodes and the reactive monomer in the alignment film is polymerized by irradiation with an active energy ray. With the liquid crystal display element, it is possible to provide various characteristics of the liquid crystal display element and the afterimage characteristics of the liquid crystal display element without changing the dielectric conductivity, the viscosity, the nematic phase upper limit temperature, the rotational viscosity (γ 1 ), and the like. In the case of a poor liquid crystal display element which is less likely to cause dripping at the time of manufacture, and a method of manufacturing the same. However, as the demand for liquid crystal display elements has increased, the industry has demanded the development of liquid crystal compositions and liquid crystal display elements which are further improved in various characteristics of liquid crystal display elements, particularly higher reliability.

[先前技術文獻] [Previous Technical Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本特開2002-357830號公報 [Patent Document 1] Japanese Laid-Open Patent Publication No. 2002-357830

[專利文獻2]日本特開2010-107536號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-107536

[專利文獻3]美國專利申請公開第2011/261295號說明書 [Patent Document 3] US Patent Application Publication No. 2011/261295

[專利文獻4]日本特開2011-227284號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2011-227284

[專利文獻5]日本特開平6-235925號公報 [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei 6-235925

[專利文獻6]日本特開2006-58755號公報 [Patent Document 6] Japanese Laid-Open Patent Publication No. 2006-58755

[專利文獻7]日本特開2011-95696號公報 [Patent Document 7] Japanese Laid-Open Patent Publication No. 2011-95696

[專利文獻8]日本特開2011-95697號公報 [Patent Document 8] Japanese Patent Laid-Open Publication No. 2011-95697

[專利文獻9]日本特開2009-139455號公報 [Patent Document 9] Japanese Patent Laid-Open Publication No. 2009-139455

[專利文獻10]日本特開2010-32860號公報 [Patent Document 10] Japanese Patent Laid-Open Publication No. 2010-32860

[專利文獻11]日本特開2010-107537號公報 [Patent Document 11] Japanese Patent Laid-Open Publication No. 2010-107537

[專利文獻12]日本專利05299595號公報 [Patent Document 12] Japanese Patent No. 05299595

本發明係鑒於上述情況而完成者，其目的在於提供一種於不使介電各向導性、黏度、向列相上限溫度、旋轉黏度(γ1)等作為液晶顯示元件之各特性及液晶顯示元件之殘像特性變差之情況下，不易產生製造時之滴加痕、作為液晶顯示元件之各特性較高、可靠性較高之液晶顯示元件及其製造方法。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid crystal display element and a liquid crystal display element which do not impart dielectric conductivity, viscosity, nematic phase upper limit temperature, rotational viscosity (γ 1 ), or the like. When the afterimage characteristics are deteriorated, it is difficult to cause dripping marks at the time of production, and the liquid crystal display element having high characteristics and high reliability as a liquid crystal display element and a method for producing the same.

本發明人等為了解決上述課題，對各種液晶組成物進行了研究，結果發現，藉由含有特定之聚合性化合物，可解決上述課題，從而完成本案發明。 In order to solve the above problems, the inventors of the present invention have studied various liquid crystal compositions, and as a result, have found that the above problems can be solved by including a specific polymerizable compound, and the present invention has been completed.

即，本發明係一種液晶顯示元件，其具備：具有第一基板與第二基板之一組基板、及夾持於上述基板間之液晶組成物層，於上述第一 基板與上述第二基板之至少一者具有電極，且於上述第一基板與上述第二基板之至少一者具有定向膜，該定向膜含有藉由使具有聚合性基之化合物之聚合性基聚合而控制上述液晶組成物層中之液晶分子之定向方向之聚合物，構成上述液晶組成物層之液晶組成物含有自下述通式(N-1)、通式(N-2)、及通式(N-3)所表示之化合物群中選擇之一種或兩種以上之化合物，且含有一種或兩種以上之通式(I)所表示之化合物作為上述具有聚合性基之化合物， That is, the present invention is a liquid crystal display device comprising: a group substrate having a first substrate and a second substrate; and a liquid crystal composition layer sandwiched between the substrates, and the first substrate and the second substrate At least one of the first substrate and the second substrate has an alignment film containing at least one of the first substrate and the second substrate, and the alignment film contains a polymerizable group polymerized by a polymerizable group to control the liquid crystal composition layer. The liquid crystal composition constituting the liquid crystal composition layer of the polymer in the orientation direction of the liquid crystal molecules is contained in the following general formula (N-1), general formula (N-2), and general formula (N-3) One or two or more compounds selected from the group consisting of one or two or more compounds represented by the formula (I) as the above-mentioned compound having a polymerizable group,

(式中，RN11、RN12、RN21、RN22、RN31及RN32分別獨立地表示碳原子數1~8之烷基，該烷基中之一個或非鄰接之兩個以上之-CH2-可分別獨立地被取代為-CH=CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-，AN11、AN12、AN21、AN22、AN31及AN32分別獨立地表示選自由(a)1,4-伸環己基(存在於該基中之一個-CH2-或未鄰接之兩個以上之-CH2-可被取代為-O-)、(b)1,4-伸苯基(存在於該基中之一個-CH=或未鄰接之兩個以上之-CH=可被取代為-N=)、及 (c)萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基或十氫萘-2,6-二基(存在於萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基中之一個-CH=或未鄰接之兩個以上之-CH=可被取代為-N=) (wherein R N11 , R N12 , R N21 , R N22 , R N31 and R N32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or more of the alkyl groups are not adjacent thereto - CH 2 - may be independently substituted with -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, A N11 , A N12 , A N21 , A N22 , A N31 and A N32 each independently represent a group selected from (a) 1,4-cyclohexylene (one of -CH 2 - present in the group or two or more -CH 2 - which may not be adjacent to - O-), (b) 1,4-phenylene (one present in the group -CH= or two or more non-contiguous -CH= may be substituted with -N=), and (c) naphthalene -2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (present in naphthalene-2,6-diyl or 1 , one of -2,3,4-tetrahydronaphthalene-2,6-diyl-CH= or two or more non-contiguous -CH= may be substituted by -N=)

所組成之群中之基，上述基(a)、基(b)及基(c)可分別獨立地經氰基、氟原子或氯原子取代，ZN11、ZN12、ZN21、ZN22、ZN31及ZN32分別獨立地表示單鍵、-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-、-CH=N-N=CH-、-CH=CH-、-CF=CF-或-C≡C-，XN21表示氫原子或氟原子，TN31表示-CH2-或氧原子，nN11、nN12、nN21、nN22、nN31及nN32分別獨立地表示0~3之整數，nN11+nN12、nN21+nN22及nN31+nN32分別獨立為1、2或3，於存在多個AN11~AN32、ZN11~ZN32之情形時，該等可相同，亦可不同)； The group (a), the group (b) and the group (c) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, respectively, Z N11 , Z N12 , Z N21 , Z N22 , Z N31 and Z N32 each independently represent a single bond, -CH 2 CH 2 -, -(CH 2 ) 4 -, -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -OCF 2 - , -CF 2 O-, -CH=NN=CH-, -CH=CH-, -CF=CF- or -C≡C-, X N21 represents a hydrogen atom or a fluorine atom, and T N31 represents -CH 2 - or The oxygen atoms, n N11 , n N12 , n N21 , n N22 , n N31 and n N32 each independently represent an integer of 0 to 3, n N11 +n N12 , n N21 +n N22 and n N31 +n N32 are each independently 1, 2 or 3, when there are multiple A N11 ~ A N32 , Z N11 ~ Z N32 , the same or different);

(式中，X10及X11分別獨立地表示氫原子或甲基，Sp3及Sp4分別獨立地表示單鍵、碳原子數1~8之伸烷基或-X-(CH2)t-(式中，t表示2~7之整數，X表示-O-、-OCOO-、-OCO-、或-COO-，X係鍵結於菲環上))。 (wherein X 10 and X 11 each independently represent a hydrogen atom or a methyl group, and Sp 3 and Sp 4 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -X-(CH 2 ) t - (where t represents an integer from 2 to 7, X represents -O-, -OCOO-, -OCO-, or -COO-, and X is bonded to the phenanthrene ring)).

又，本發明係一種液晶顯示元件之製造方法，其係藉由於第一基板與第二基板之至少一者塗佈定向材料並加熱而形成定向膜材料後，藉由至少一者具有電極之上述第一基板與上述第二基板夾持液晶組成物， 並對上述電極於施加電壓之狀態下照射活性能量線，藉此使上述定向膜材料中所含之具有聚合性基之化合物之聚合性基聚合而具有控制上述液晶組成物層中之液晶分子之定向方向之定向膜，上述液晶組成物含有自下述通式(N-1)、通式(N-2)、及通式(N-3)所表示之化合物群中選擇之一種或兩種以上之化合物，且含有一種或兩種以上之通式(I)所表示之化合物作為上述具有聚合性基之化合物， Moreover, the present invention is a method of fabricating a liquid crystal display device by forming at least one of the first substrate and the second substrate by applying an alignment material and heating to form an alignment film material. The liquid crystal composition is sandwiched between the first substrate and the second substrate, and the active energy ray is irradiated to the electrode in a state where a voltage is applied, whereby the polymerizable group of the polymerizable group contained in the alignment film material is made. And an alignment film having a direction of controlling the alignment direction of the liquid crystal molecules in the liquid crystal composition layer, wherein the liquid crystal composition contains the following general formula (N-1), general formula (N-2), and general formula (N- 3) one or two or more compounds selected from the group consisting of the compounds, and one or two or more compounds represented by the formula (I) are used as the compound having a polymerizable group,

(式中，RN11、RN12、RN21、RN22、RN31及RN32分別獨立地表示碳原子數1~8之烷基，該烷基中之一個或非鄰接之兩個以上之-CH2-可分別獨立地被取代為-CH=CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-，AN11、AN12、AN21、AN22、AN31及AN32分別獨立地表示選自由(a)1,4-伸環己基(存在於該基中之一個-CH2-或未鄰接之兩個以上之-CH2-可被取代為-O-)、(b)1,4-伸苯基(存在於該基中之一個-CH=或未鄰接之兩個以上之-CH=可被取代為-N=)、及(c)萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基或十氫萘-2,6-二基 (存在於萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基中之一個-CH=或未鄰接之兩個以上之-CH=可被取代為-N=) (wherein R N11 , R N12 , R N21 , R N22 , R N31 and R N32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or more of the alkyl groups are not adjacent thereto - CH 2 - may be independently substituted with -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, A N11 , A N12 , A N21 , A N22 , A N31 and A N32 each independently represent a group selected from (a) 1,4-cyclohexylene (one of -CH 2 - present in the group or two or more -CH 2 - which may not be adjacent to - O-), (b) 1,4-phenylene (one present in the group -CH= or two or more non-contiguous -CH= may be substituted with -N=), and (c) naphthalene -2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (present in naphthalene-2,6-diyl or 1 , one of -2,3,4-tetrahydronaphthalene-2,6-diyl-CH= or two or more non-contiguous -CH= may be substituted by -N=)

所組成之群中之基，上述基(a)、基(b)及基(c)可分別獨立地經氰基、氟原子或氯原子取代，ZN11、ZN12、ZN21、ZN22、ZN31及ZN32分別獨立地表示單鍵、-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-、-CH=N-N=CH-、-CH=CH-、-CF=CF-或-C≡C-，XN21表示氫原子或氟原子，TN31表示-CH2-或氧原子，nN11、nN12、nN21、nN22、nN31及nN32分別獨立地表示0~3之整數，nN11+nN12、nN21+nN22及nN31+nN32分別獨立為1、2或3，於存在多個AN11~AN32、ZN11~ZN32之情形時，該等可相同，亦可不同)； The group (a), the group (b) and the group (c) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, respectively, Z N11 , Z N12 , Z N21 , Z N22 , Z N31 and Z N32 each independently represent a single bond, -CH 2 CH 2 -, -(CH 2 ) 4 -, -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -OCF 2 - , -CF 2 O-, -CH=NN=CH-, -CH=CH-, -CF=CF- or -C≡C-, X N21 represents a hydrogen atom or a fluorine atom, and T N31 represents -CH 2 - or The oxygen atoms, n N11 , n N12 , n N21 , n N22 , n N31 and n N32 each independently represent an integer of 0 to 3, n N11 +n N12 , n N21 +n N22 and n N31 +n N32 are each independently 1, 2 or 3, when there are multiple A N11 ~ A N32 , Z N11 ~ Z N32 , the same or different);

(式中，X10及X11分別獨立地表示氫原子或甲基，Sp3及Sp4分別獨立地表示單鍵、碳原子數1~8之伸烷基或-X-(CH2)t-(式中，t表示2~7之整數，X表示-O-、-OCOO-、-OCO-、或-COO-，X係鍵結於菲環上))。 (wherein X 10 and X 11 each independently represent a hydrogen atom or a methyl group, and Sp 3 and Sp 4 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -X-(CH 2 ) t - (where t represents an integer from 2 to 7, X represents -O-, -OCOO-, -OCO-, or -COO-, and X is bonded to the phenanthrene ring)).

根據本發明，由於作為液晶顯示元件之高速應答性優異，殘像之產生較少，其製造時之滴加痕之產生較少，作為液晶顯示元件之各特性優異，又，可靠性較高，因此可有效地用作液晶TV、監視器等之顯示元 件。 According to the present invention, since the liquid crystal display element is excellent in high-speed responsiveness, the generation of afterimages is small, and the occurrence of dripping marks during production is small, and the characteristics of the liquid crystal display element are excellent, and reliability is high. Therefore, it can be effectively used as a display element of a liquid crystal TV, a monitor, or the like. Pieces.

又，根據本發明，可製造不易產生滴加痕之有效率之液晶顯示元件。 Moreover, according to the present invention, it is possible to manufacture an efficient liquid crystal display element which is less likely to cause dripping marks.

10‧‧‧液晶顯示元件 10‧‧‧Liquid display components

11‧‧‧第一基板 11‧‧‧First substrate

12‧‧‧第二基板 12‧‧‧second substrate

13‧‧‧液晶組成物層 13‧‧‧Liquid composition layer

14‧‧‧共用電極 14‧‧‧Common electrode

15‧‧‧像素電極 15‧‧‧pixel electrode

16‧‧‧垂直定向膜 16‧‧‧Vertical alignment film

17‧‧‧垂直定向膜 17‧‧‧Vertical alignment film

18‧‧‧彩色濾光片 18‧‧‧Color filters

19‧‧‧液晶分子 19‧‧‧ liquid crystal molecules

20‧‧‧聚合物層 20‧‧‧ polymer layer

21‧‧‧聚合物層 21‧‧‧ polymer layer

圖1係表示本發明之液晶顯示元件之一實施形態之概略立體圖。 Fig. 1 is a schematic perspective view showing an embodiment of a liquid crystal display element of the present invention.

圖2係表示本發明之液晶顯示元件所使用之狹縫電極(梳形電極)之一例的概略俯視圖。 Fig. 2 is a schematic plan view showing an example of a slit electrode (comb electrode) used in the liquid crystal display device of the present invention.

圖3係表示本發明之液晶顯示元件中之預傾角之定義的圖。 Fig. 3 is a view showing the definition of the pretilt angle in the liquid crystal display element of the present invention.

對本發明之液晶顯示元件及其製造方法之實施形態進行說明。 Embodiments of the liquid crystal display device of the present invention and a method of manufacturing the same will be described.

再者，本實施形態係為了使發明之主旨更好地理解而具體說明者，只要無特別指定，則並不限定本發明。 In addition, this embodiment is specifically described in order to better understand the gist of the invention, and the present invention is not limited unless otherwise specified.

[液晶顯示元件] [Liquid Crystal Display Element]

本發明之液晶顯示元件係具有夾持於一對基板之間之液晶組成物層者，其係基於藉由對液晶組成物層施加電壓，使液晶組成物層中之液晶分子發生弗里德里克斯(Freedericksz)轉變而發揮作為光學開關之功能之原理，於該方面可使用周知之慣用技術。 The liquid crystal display device of the present invention has a liquid crystal composition layer sandwiched between a pair of substrates, which is based on the application of a voltage to the liquid crystal composition layer to cause liquid crystal molecules in the liquid crystal composition layer to occur in Friedrich. Freedericksz is transformed to function as a function of an optical switch, and a well-known conventional technique can be used in this respect.

於兩個基板具有用以使液晶分子發生弗里德里克斯轉變之 電極的通常之垂直定向液晶顯示元件中，通常採用於兩個基板間垂直施加電荷之方式。於該情形時，一電極成為共用電極，另一電極成為像素電極。以下表示該方式最典型之實施形態。 The two substrates have a Friedrichs transformation for liquid crystal molecules In a generally vertical alignment liquid crystal display device of an electrode, a method of applying a charge perpendicularly between two substrates is generally employed. In this case, one electrode becomes a common electrode and the other electrode becomes a pixel electrode. The most typical embodiment of this mode is shown below.

圖1係表示本發明之液晶顯示元件之一實施形態之概略立體圖。 Fig. 1 is a schematic perspective view showing an embodiment of a liquid crystal display element of the present invention.

本實施形態之液晶顯示元件10係由如下構件概略構成：第一基板11、第二基板12、夾持於第一基板11與第二基板12之間之液晶組成物層13、設置於第一基板11之與液晶組成物層13相對向之面上之共用電極14、設置於第二基板12之與液晶組成物層13相對向之面上之像素電極15、設置於共用電極14之與液晶組成物層13相對向之面上之垂直定向膜16、設置於像素電極15之與液晶組成物層13相對向之面上之垂直定向膜17、視需要而形成於垂直定向膜16上之聚合物層20、形成於垂直定向膜17上之聚合物層21、及設置於第一基板11與共用電極14之間之彩色濾光片18。 The liquid crystal display element 10 of the present embodiment is configured by a first substrate 11 and a second substrate 12, and a liquid crystal composition layer 13 sandwiched between the first substrate 11 and the second substrate 12, and is provided in the first a common electrode 14 on the surface of the substrate 11 facing the liquid crystal composition layer 13 , a pixel electrode 15 provided on the surface of the second substrate 12 facing the liquid crystal composition layer 13 , and a liquid crystal provided on the common electrode 14 The vertical alignment film 16 on the surface of the composition layer 13 opposite thereto, the vertical alignment film 17 disposed on the surface of the pixel electrode 15 opposite to the liquid crystal composition layer 13, and the polymerization formed on the vertical alignment film 16 as needed The material layer 20, the polymer layer 21 formed on the vertical alignment film 17, and the color filter 18 disposed between the first substrate 11 and the common electrode 14.

作為第一基板11與第二基板12，可使用玻璃基板或塑膠基板。 As the first substrate 11 and the second substrate 12, a glass substrate or a plastic substrate can be used.

作為塑膠基板，可使用由丙烯酸樹脂、甲基丙烯酸樹脂、聚對苯二甲酸乙二酯、聚碳酸酯、環狀烯烴樹脂等樹脂構成之基板。 As the plastic substrate, a substrate made of a resin such as an acrylic resin, a methacrylic resin, polyethylene terephthalate, polycarbonate, or a cyclic olefin resin can be used.

共用電極14通常由添加銦之氧化錫(ITO)等具有透明性之材料構成。 The common electrode 14 is usually made of a material having transparency such as indium tin oxide (ITO).

像素電極15通常由添加銦之氧化錫(ITO)等具有透明性之材料構成。 The pixel electrode 15 is usually made of a material having transparency such as indium tin oxide (ITO).

像素電極15係以矩陣狀配設於第二基板12。像素電極15係藉由以TFT開關元件為代表之主動元件之汲極電極所控制，該TFT開關元件以矩陣狀具有作為位址訊號線之閘極線及作為資料線之源極線。再者，此處並未圖示TFT開關元件之構成。 The pixel electrodes 15 are arranged in a matrix on the second substrate 12. The pixel electrode 15 is controlled by a drain electrode of an active device typified by a TFT switching element having a gate line as an address signal line and a source line as a data line in a matrix. Furthermore, the configuration of the TFT switching elements is not shown here.

於為了提高視野角特性而進行將像素內之液晶分子之傾斜方向分割成數個區域之像素分割之情形時，可於各像素內設置具備具有條紋狀或V字狀圖案之狹縫(不形成電極之部分)之像素電極。 When the pixel is divided into a plurality of regions by dividing the oblique direction of the liquid crystal molecules in the pixel in order to improve the viewing angle characteristics, a slit having a stripe-like or V-shaped pattern may be provided in each pixel (the electrode is not formed). Part of the pixel electrode.

圖2係表示將像素內分割成4個區域之情形時之狹縫電極(梳形電極)之典型之形態的概略俯視圖。該狹縫電極藉由自像素之中央向4個方向呈梳齒狀地具有狹縫，而使未施加電壓時相對於基板大致垂直定向之各像素內之液晶分子伴隨電壓之施加將液晶分子之指向矢朝向4個不同之方向逐漸接近水平定向。其結果，由於可將像素內之液晶之定向方位分割成多個，因此具有極廣之視野角特性。 2 is a schematic plan view showing a typical form of a slit electrode (comb electrode) when the inside of the pixel is divided into four regions. The slit electrode has a slit in a comb shape in four directions from the center of the pixel, and the liquid crystal molecules in the respective pixels which are substantially perpendicularly oriented with respect to the substrate when no voltage is applied, the liquid crystal molecules are applied The directors are gradually approaching the horizontal orientation towards 4 different directions. As a result, since the directional orientation of the liquid crystal in the pixel can be divided into a plurality of directions, it has an extremely wide viewing angle characteristic.

作為用以進行像素分割之方法，除了上述於像素電極設置狹縫之方法以外，可使用於像素內設置線性突起等結構物之方法、設置像素電極或共用電極以外之電極之方法等。藉由該等方法亦可分割液晶分子之定向方向，但就穿透率、製造之容易性而言，較佳為使用狹縫電極之構成。由於設置有狹縫之像素電極於未施加電壓時對液晶分子不具驅動力，因此無法對液晶分子賦予預傾角。然而，藉由併用本發明所使用之定向膜材料可賦予預傾角，並且藉由與經像素分割之狹縫電極組合，可達成由像素分割形成之廣視野角。 As a method for performing pixel division, in addition to the above-described method of providing a slit to a pixel electrode, a method of providing a structure such as a linear protrusion in a pixel, a method of providing an electrode other than a pixel electrode or a common electrode, or the like can be used. The alignment direction of the liquid crystal molecules can also be divided by these methods, but in terms of transmittance and ease of fabrication, it is preferable to use a slit electrode. Since the pixel electrode provided with the slit does not have a driving force for the liquid crystal molecules when no voltage is applied, it is impossible to impart a pretilt angle to the liquid crystal molecules. However, the pretilt angle can be imparted by using the alignment film material used in the present invention in combination, and by combining with the pixel-divided slit electrode, a wide viewing angle formed by pixel division can be achieved.

於本發明中，所謂具有預傾角，係指於未施加電壓之狀態 下，液晶分子之指向矢與垂直於基板面(第一基板11及第二基板12之與液晶組成物層13鄰接之面)之方向稍有不同之狀態。 In the present invention, the term "pretilt angle" refers to a state in which no voltage is applied. The direction of the liquid crystal molecules is slightly different from the direction perpendicular to the substrate surface (the surface of the first substrate 11 and the second substrate 12 adjacent to the liquid crystal composition layer 13).

(定向膜) (orientation film)

本發明之液晶顯示元件由於係垂直定向(VA)型液晶顯示元件，因此於未施加電壓時液晶分子之指向矢相對於基板面大致垂直定向。為了使液晶分子垂直定向，通常使用(垂直)定向膜。 Since the liquid crystal display element of the present invention is a vertical alignment (VA) type liquid crystal display element, the director of the liquid crystal molecules is oriented substantially vertically with respect to the substrate surface when no voltage is applied. In order to orient the liquid crystal molecules vertically, a (vertical) oriented film is usually used.

本發明係使用含有藉由使具有聚合性基之化合物之聚合性基聚合而控制上述液晶組成物層中之液晶分子之定向方向之聚合物的定向膜。即，本發明使用含有使具有聚合性基之化合物之聚合性基聚合而成之聚合物的定向膜，上述聚合物具有控制組成物中之液晶分子之定向方向之功能。 In the present invention, an oriented film containing a polymer which controls the orientation direction of liquid crystal molecules in the liquid crystal composition layer by polymerizing a polymerizable group of a compound having a polymerizable group is used. That is, in the present invention, an oriented film containing a polymer obtained by polymerizing a polymerizable group of a compound having a polymerizable group having a function of controlling the orientation direction of liquid crystal molecules in the composition is used.

作為形成垂直定向膜之材料(垂直定向膜材料)，可使用聚醯亞胺、聚醯胺、聚矽氧烷、聚合性液晶化合物之硬化物等。 As the material for forming the vertical alignment film (vertical alignment film material), a polyimide, a polyamide, a polyoxyalkylene, a cured product of a polymerizable liquid crystal compound, or the like can be used.

於使用聚醯亞胺作為形成垂直定向膜之定向膜材料之情形時，較佳為使用使四羧酸二酐及二異氰酸酯之混合物、聚醯胺酸、聚醯亞胺溶解或分散於溶劑中而成之聚醯亞胺溶液，於該情形時，聚醯亞胺溶液中之聚醯亞胺之含量較佳為1質量%以上且10質量%以下，更佳為3質量%以上且5質量%以下，進而較佳為10質量%以下。 In the case of using polyimine as the oriented film material for forming the vertical alignment film, it is preferred to dissolve or disperse the tetracarboxylic dianhydride and the mixture of diisocyanate, polylysine or polyimine in a solvent. In the case of the polyimine solution, the content of the polyimine in the polyimide reaction solution is preferably 1% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 5% by mass. % or less, further preferably 10% by mass or less.

又，於使用聚矽氧烷系材料作為形成垂直定向膜之定向膜材料之情形時，可使用使藉由以特定之調配量比混合具有烷氧基之矽化合物、醇衍生物及草酸衍生物並加熱而製造之聚矽氧烷溶解而成之聚矽氧烷溶液。 Further, in the case where a polyoxyalkylene-based material is used as the alignment film material for forming the vertical alignment film, a ruthenium compound, an alcohol derivative, and an oxalic acid derivative having an alkoxy group by mixing at a specific ratio can be used. And a polyoxyalkylene solution obtained by dissolving polysiloxane produced by heating.

於本發明之液晶顯示元件中，由聚醯亞胺等形成之上述垂直定向膜16、17含有藉由具有聚合性基之聚合性化合物之聚合所形成之聚合物等。該聚合性化合物係賦予將液晶分子之預傾角加以固定之功能者。即，使用狹縫電極等，可使像素內之液晶分子之指向矢於施加電壓時向不同方向傾斜。然而，即便於使用狹縫電極之構成中，於未施加電壓時，液晶分子亦相對於基板面而幾乎垂直地定向，不產生預傾角，於在電極間施加電壓而使液晶分子略微傾斜之狀態下，藉由照射紫外線等，使液晶組成物中之反應性單體聚合，而賦予合適之預傾角。 In the liquid crystal display device of the present invention, the vertical alignment films 16 and 17 formed of polyimide or the like contain a polymer formed by polymerization of a polymerizable compound having a polymerizable group. The polymerizable compound imparts a function of fixing the pretilt angle of the liquid crystal molecules. In other words, by using a slit electrode or the like, the director of the liquid crystal molecules in the pixel can be tilted in different directions when a voltage is applied. However, even in the configuration using the slit electrode, when no voltage is applied, the liquid crystal molecules are oriented almost perpendicularly with respect to the substrate surface, and no pretilt angle is generated, and a voltage is applied between the electrodes to slightly tilt the liquid crystal molecules. Next, the reactive monomer in the liquid crystal composition is polymerized by irradiation of ultraviolet rays or the like to give a suitable pretilt angle.

又，視需要可藉由將含有於液晶組成物中之聚合性化合物夾持於基板間後，一面施加電壓一面使聚合性化合物硬化，從而聚合性化合物一面相分離，一面使上述聚合物層20、21以聚合物之形式形成於上述垂直定向膜16、17之表面。 In addition, the polymerizable compound can be cured while the voltage is applied to the liquid crystal composition, and the polymerizable compound can be cured while applying a voltage, and the polymer layer 20 can be separated while the polymerizable compound is separated. 21 is formed on the surface of the above-mentioned vertical alignment films 16, 17 in the form of a polymer.

藉由上述垂直定向膜16、17中所含之聚合物、及視需要於所形成之上述垂直定向膜16、17之表面形成之上述聚合物層20、21，而成為液晶分子之定向性較高、殘像之產生較少、其製造時之滴加痕之產生較少者。 The orientation of the liquid crystal molecules is improved by the polymer contained in the vertical alignment films 16, 17 and the polymer layers 20, 21 formed on the surfaces of the vertically oriented films 16, 17 formed as needed. High and residual images are produced less, and the number of drops added during manufacture is less.

於本發明中，所謂大致垂直意指垂直定向之液晶分子之指向矢自垂直方向稍微傾斜而賦予預傾角之狀態。若將完全垂直定向之情形設為預傾角為90°、將水平定向(與基板面水平地定向)之情形設為預傾角為0°，則所謂大致垂直較佳為89.5~85°，更佳為89.5~87°。 In the present invention, the term "substantially perpendicular" means that the director of the vertically oriented liquid crystal molecules is slightly inclined from the vertical direction to give a pretilt angle. If the case of the full vertical orientation is set to a pretilt angle of 90° and a horizontal orientation (oriented horizontally with the substrate surface) is set to a pretilt angle of 0°, the so-called substantially vertical is preferably 89.5 to 85°, more preferably It is 89.5~87°.

含有具有聚合性基之聚合性化合物之聚合物之垂直定向膜16、17係藉由在垂直定向膜材料中混合之聚合性化合物之效果所形成者。 因此，推測垂直定向膜與聚合性化合物複雜地交聯而形成一種聚合物合金，但無法示出其準確之結構。 The vertical alignment films 16, 17 containing a polymer having a polymerizable group having a polymerizable group are formed by the effect of a polymerizable compound mixed in a vertically oriented film material. Therefore, it is presumed that the vertically oriented film is intricately crosslinked with the polymerizable compound to form a polymer alloy, but the exact structure cannot be shown.

又，視需要而形成之上述聚合物層20、21係含有於液晶組成物中之聚合性化合物於聚合時一面自液晶組成物相分離一面形成於上述垂直定向膜16、17之表面，但認為是否均勻地形成於垂直定向膜之整個面、是否以不均勻之海島結構形成係根據製造之條件而有所不同，無法示出其準確之結構。圖1係表示均勻形成之情形。 Further, the polymerizable layers 20 and 21 which are formed as needed in the liquid crystal composition are formed on the surface of the vertical alignment films 16 and 17 while being separated from the liquid crystal composition during polymerization. Whether or not it is uniformly formed on the entire surface of the vertically oriented film, whether or not the island structure is formed in a non-uniform manner differs depending on the conditions of manufacture, and the accurate structure cannot be shown. Figure 1 shows the case of uniform formation.

本發明所使用之定向膜必須具有使液晶組成物層中之液晶分子沿相對於基板面垂直之方向定向之垂直定向功能，並且進一步具有控制液晶分子之定向方向之定向控制功能。作為獲得具有上述垂直定向功能及定向控制功能之兩種功能之定向膜之方法，有通常使用之於定向膜材料中調配具有聚合性基之聚合性化合物之方法、使用側鏈部分具有交聯性官能基之聚合性化合物之聚合物作為定向膜材料之方法、使用聚合性液晶化合物之硬化物作為定向膜材料之方法。以下，對各方法進行說明。 The alignment film used in the present invention must have a vertical alignment function for orienting liquid crystal molecules in the liquid crystal composition layer in a direction perpendicular to the substrate surface, and further has an orientation control function for controlling the orientation direction of the liquid crystal molecules. As a method of obtaining an oriented film having two functions of the above-described vertical alignment function and orientation control function, there is a method of generally using a polymerizable compound having a polymerizable group in an alignment film material, and using a side chain portion to have crosslinkability A method of using a polymer of a polymerizable compound of a functional group as a method of orienting a film material, and using a cured product of a polymerizable liquid crystal compound as an oriented film material. Hereinafter, each method will be described.

(於定向膜材料中調配具有聚合性基之聚合性化合物之方法) (Method of formulating a polymerizable compound having a polymerizable group in an oriented film material)

作為於定向膜材料中調配具有聚合性基之聚合性化合物之方法，可列舉於上文所述之定向膜材料中調配具有聚合性基之聚合性化合物之方法。 As a method of formulating a polymerizable compound having a polymerizable group in the alignment film material, a method of formulating a polymerizable compound having a polymerizable group in the alignment film material described above can be mentioned.

定向膜材料所含之具有聚合性基之聚合性化合物可含有液晶原基性部位，亦可不含液晶原基性部位，重要的是作為具有聚合性基之化合物，而含有一種或兩種以上之通式(I)所表示之化合物， The polymerizable compound having a polymerizable group contained in the alignment film material may contain a liquid crystal primordial moiety or may not contain a liquid crystal primordial moiety, and it is important to contain one or two or more compounds as a polymerizable group. a compound represented by the formula (I),

(式中，X10及X11分別獨立地表示氫原子或甲基，Sp3及Sp4分別獨立地表示單鍵、碳原子數1~8之伸烷基或-X-(CH2)t-(式中，t表示2~7之整數，X表示-O-、-OCOO-、-OCO-、或-COO-，X係鍵結於菲環上)，式中之菲環中任意氫原子可被取代為氟原子)。由於通式(I)所表示之化合物之反應速度較快，因此藉由含有該化合物，可使定向膜中所形成之聚合物能量較少，即，可降低紫外線等之照射量。 (wherein X 10 and X 11 each independently represent a hydrogen atom or a methyl group, and Sp 3 and Sp 4 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -X-(CH 2 ) t - (where t represents an integer from 2 to 7, X represents -O-, -OCOO-, -OCO-, or -COO-, and X is bonded to the phenanthrene ring), and any hydrogen in the phenanthrene ring in the formula An atom can be substituted with a fluorine atom). Since the reaction rate of the compound represented by the general formula (I) is fast, by containing the compound, the energy of the polymer formed in the alignment film can be made small, that is, the irradiation amount of ultraviolet rays or the like can be reduced.

於上述通式(I)中，X10及X11分別獨立地表示氫原子或甲基，於重視反應速度之情形時，較佳為氫原子，於重視減少反應殘留量之情形時，較佳為甲基。 In the above formula (I), X 10 and X 11 each independently represent a hydrogen atom or a methyl group, and when a reaction rate is important, a hydrogen atom is preferred, and when it is important to reduce the residual amount of the reaction, it is preferred. Is a methyl group.

於上述通式(I)中，Sp3及Sp4分別獨立地表示單鍵、碳原子數1~8之伸烷基或-X-(CH2)t-(式中，t表示2~7之整數，X表示-O-、-OCOO-、或-COO-，X係鍵結於菲環上)，較佳為碳鏈並不太長，且較佳為單鍵或碳原子數1~5之伸烷基，更佳為單鍵或碳原子數1~3之伸烷基。又，於Sp3及Sp4表示-X-(CH2)t-之情形時，t亦較佳為1~5，更佳為1~3，且更佳為Sp3及Sp4之至少一者為單鍵，尤佳為均為單鍵。 In the above formula (I), Sp 3 and Sp 4 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -X-(CH 2 ) t - (wherein t represents 2 to 7). An integer, X represents -O-, -OCOO-, or -COO-, X is bonded to the phenanthrene ring), preferably the carbon chain is not too long, and is preferably a single bond or a carbon number of 1~ The alkyl group of 5 is more preferably a single bond or an alkyl group having 1 to 3 carbon atoms. Further, in the case where Sp 3 and Sp 4 represent -X-(CH 2 ) t -, t is preferably from 1 to 5, more preferably from 1 to 3, and more preferably at least one of Sp 3 and Sp 4 . The one is a single button, and the best one is a single button.

具體而言，上述通式(I)所表示之化合物較佳為以下之通式(I-1)~(I-52)所表示之化合物。 Specifically, the compound represented by the above formula (I) is preferably a compound represented by the following formula (I-1) to (I-52).

上述通式(I)所表示之化合物於形成定向膜之上述高分子化合物前驅物中之含量較佳為0.1~6質量%，更佳為0.5~5質量%，進而較佳為1~4質量%。 The content of the compound represented by the above formula (I) in the precursor of the polymer compound forming the alignment film is preferably from 0.1 to 6% by mass, more preferably from 0.5 to 5% by mass, even more preferably from 1 to 4% by mass. %.

作為定向膜材料所含之具有聚合性基之聚合性化合物，除了上述通式(I)所表示之化合物以外，亦可含有下述通式(V) The polymerizable compound having a polymerizable group contained in the alignment film material may contain the following formula (V) in addition to the compound represented by the above formula (I).

(式中，X7及X8分別獨立地表示氫原子或甲基，Sp1及Sp2分別獨立地表示單鍵、碳原子數1~8之伸烷基或-X-(CH2)s-(式中，s表示2~7之整數，X表示O、OCOO、OCO、或COO，X係鍵結於存在於U中之芳香環上)，U表示碳原子數2~20之直鏈或支鏈多元伸烷基、碳原子數3~20之直鏈或支鏈多元伸烯基或者碳原子數5~30之多元環狀取代基，多元伸 烷基中之伸烷基或多元伸烯基中之伸烯基可於氧原子不鄰接之範圍內被取代為-O-、-CO-、-CF2-，亦可被取代為碳原子數5~20之烷基(基中之伸烷基可於氧原子不鄰接之範圍內被取代為氧原子)、或環狀取代基，k表示0~5之整數)所表示之聚合性化合物。 (wherein, X 7 and X 8 each independently represent a hydrogen atom or a methyl group, and Sp 1 and Sp 2 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -X-(CH 2 ) s - (where s represents an integer from 2 to 7, X represents O, OCOO, OCO, or COO, X is bonded to an aromatic ring present in U), and U represents a linear chain of 2 to 20 carbon atoms. Or a branched polyalkylene group, a linear or branched polyalkylene group having 3 to 20 carbon atoms or a polyvalent cyclic substituent having 5 to 30 carbon atoms; an alkyl group or a plurality of stretches in a polyalkylene group The alkenyl group in the alkenyl group may be substituted with -O-, -CO-, -CF 2 - in the range in which the oxygen atoms are not adjacent, and may be substituted with an alkyl group having 5 to 20 carbon atoms. The alkylene group may be a polymerizable compound represented by an alkyl group which may be substituted with an oxygen atom in a range in which the oxygen atoms are not adjacent, or a cyclic substituent, and k represents an integer of 0 to 5.

於上述通式(V)中，X7及X8分別獨立地表示氫原子或甲基，於重視反應速度之情形時，較佳為氫原子，於重視減少反應殘留量之情形時，較佳為甲基。 In the above formula (V), X 7 and X 8 each independently represent a hydrogen atom or a methyl group, and when a reaction rate is important, a hydrogen atom is preferred, and when it is important to reduce the residual amount of the reaction, it is preferred. Is a methyl group.

於上述通式(V)中，Sp1及Sp2分別獨立地表示單鍵、碳原子數1~8之伸烷基或-X-(CH2)s-(式中，s表示2~7之整數，X表示O、OCOO、或COO，X係鍵結於存在於U中之芳香環上)，較佳為碳鏈並不太長，且較佳為單鍵或碳原子數1~5之伸烷基，更佳為單鍵或碳原子數1~3之伸烷基。又，於Sp1及Sp2表示-X-(CH2)s-之情形時，s亦較佳為1~5，更佳為1~3，且更佳為Sp1及Sp2之至少一者為單鍵，尤佳為均為單鍵。 In the above formula (V), Sp 1 and Sp 2 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -X-(CH 2 ) s - (wherein s represents 2 to 7). An integer, X represents O, OCOO, or COO, and X is bonded to an aromatic ring present in U), preferably the carbon chain is not too long, and is preferably a single bond or a carbon number of 1 to 5 The alkyl group is more preferably a single bond or an alkyl group having 1 to 3 carbon atoms. Further, when Sp 1 and Sp 2 represent -X-(CH 2 ) s -, s is also preferably 1 to 5, more preferably 1 to 3, and more preferably at least one of Sp 1 and Sp 2 The one is a single button, and the best one is a single button.

於上述通式(V)中，k表示0~5之整數，於重視液晶組成物層中之液晶分子之定向方向之控制性之情形時，較佳為k表示1~5之整數，更佳為k表示1~3之整數，進而較佳為k表示1。 In the above formula (V), k represents an integer of 0 to 5, and in the case of paying attention to the controllability of the orientation direction of the liquid crystal molecules in the liquid crystal composition layer, k is preferably an integer of 1 to 5, more preferably k is an integer from 1 to 3, and further preferably k is 1.

於上述通式(V)中，U表示碳原子數2~20之直鏈或支鏈多元伸烷基、碳原子數3~20之直鏈或支鏈多元伸烯基或者碳原子數5~30之多元環狀取代基，多元伸烷基中之伸烷基可於氧原子不鄰接之範圍內被取代為-O-、-CO-、-CF2-，亦可被取代為碳原子數5~20之烷基(基中之伸烷基可於氧原子不鄰接之範圍內被取代為氧原子)、或環狀取代基， 較佳為被取代為兩個以上之環狀取代基。 In the above formula (V), U represents a linear or branched polyalkylene group having 2 to 20 carbon atoms, a linear or branched polyalkylene group having 3 to 20 carbon atoms or a carbon number of 5~. a polyvalent cyclic substituent of 30, wherein the alkylene group in the polyalkylene group may be substituted with -O-, -CO-, -CF 2 - in the range in which the oxygen atoms are not adjacent, or may be substituted into a carbon atom. The alkyl group of 5 to 20 (the alkylene group in the group may be substituted with an oxygen atom in the range in which the oxygen atoms are not adjacent) or the cyclic substituent is preferably substituted with two or more cyclic substituents.

於上述通式(V)中，具體而言，U較佳為表示以下之式(Va-1)至式(Va-5)，更佳為表示式(Va-1)、式(Va-2)，尤佳為表示式(Va-1)。 In the above formula (V), specifically, U preferably represents the following formula (Va-1) to formula (Va-5), more preferably represents formula (Va-1), formula (Va-2) ), especially preferred is the expression (Va-1).

(式中，兩端係鍵結於Sp1或Sp2上(上述為k=1之情形)，於k為2~5之整數之情形時，連結基數相對應地增加；Z1、Z2及Z3分別獨立地表示-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-COO-、-CH2-OCO-或單鍵，式中之全部芳香環中任意氫原子可被取代為氟原子) (wherein, both ends are bonded to Sp 1 or Sp 2 (in the case of k = 1 above), and when k is an integer of 2 to 5, the number of linkages is correspondingly increased; Z 1 , Z 2 And Z 3 independently represent -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -CH 2 CH 2 -, -CF 2 CF 2 - , -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH 2 CH 2 -, -OCO-CH 2 CH 2 - , -CH 2 CH 2 -COO-, -CH 2 CH 2 -OCO-, -COO-CH 2 -, -OCO-CH 2 -, -CH 2 -COO-, -CH 2 -OCO- or a single bond, Any hydrogen atom in all aromatic rings in the formula may be substituted with a fluorine atom)

於上述U中，Z1、Z2及Z3分別獨立，較佳為-OCH2-、- CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-或單鍵，更佳為-COO-、-OCO-或單鍵，尤佳為單鍵。 In the above U, Z 1 , Z 2 and Z 3 are each independently, preferably -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, - CH 2 CH 2 -, -CF 2 CF 2 - or a single bond, more preferably -COO-, -OCO- or a single bond, particularly preferably a single bond.

於U具有上述環結構之情形時，上述Sp1及Sp2較佳為至少一者表示單鍵，亦較佳為兩者均為單鍵。 In the case where U has the above ring structure, it is preferred that at least one of Sp 1 and Sp 2 represents a single bond, and it is preferable that both of them are single bonds.

於上述通式(V)中，k表示0~5之整數，較佳為k為1之二官能化合物、或k為2之三官能化合物，更佳為k為1之二官能化合物。 In the above formula (V), k represents an integer of 0 to 5, preferably a difunctional compound in which k is 1, or a trifunctional compound in which k is 2, and more preferably a difunctional compound in which k is 1.

上述通式(V)所表示之化合物具體而言，較佳為以下之通式(Va-1-1)~(Va-5-3)所表示之化合物。 Specifically, the compound represented by the above formula (V) is preferably a compound represented by the following formula (Va-1-1) to (Va-5-3).

又，上述式(Va-1-1)~式(Va-5-3)所表示之化合物中，較佳為式(Va-1-1)~式(Va-2-11)所表示之化合物，更佳為式(Va-1-1)~式(Va-1-13)所表示之化合物。 Further, among the compounds represented by the above formula (Va-1-1) to formula (Va-5-3), preferred are compounds represented by formula (Va-1-1) to formula (Va-2-11). More preferably, it is a compound represented by the formula (Va-1-1) to the formula (Va-1-13).

上述通式(V)所表示之化合物於形成定向膜之定向膜材料中之含量較佳為0~6質量%，更佳為0.5~4質量%，進而較佳為1~2質量%。 The content of the compound represented by the above formula (V) in the alignment film material forming the alignment film is preferably from 0 to 6% by mass, more preferably from 0.5 to 4% by mass, still more preferably from 1 to 2% by mass.

上述具有聚合性基之聚合性化合物整體於形成定向膜之上 述高分子化合物前驅物中的含量較佳為0.1~6質量%，更佳為0.5~5質量%，進而較佳為1~4質量%。 The above polymerizable compound having a polymerizable group is entirely formed on the oriented film The content of the polymer compound precursor is preferably from 0.1 to 6% by mass, more preferably from 0.5 to 5% by mass, still more preferably from 1 to 4% by mass.

(使用側鏈部分具有交聯性官能基之聚合性化合物之聚合物作為定向膜材料之方法) (Method of using a polymer having a polymerizable compound having a crosslinkable functional group in a side chain portion as an oriented film material)

作為側鏈部分具有交聯性官能基之聚合性化合物，只要側鏈部分具有交聯性官能基(聚合性基)，則主鏈部分並無特別限定，較佳為使用具有上文所述之醯亞胺骨架或矽氧烷骨架作為主鏈部分之化合物，更佳為使用主鏈部分具有聚醯亞胺骨架之化合物。作為主鏈部分具有聚醯亞胺骨架且具有交聯性官能基作為側鏈之聚合性化合物，可列舉於構成聚醯亞胺結構之重複單位(主鏈部分)含有交聯性官能基作為側鏈之化合物。並且，該交聯性官能基成為聚合反應起始點，於定向膜材料中調配之具有聚合性基之聚合性化合物發生自由基反應，而形成側鏈，藉此具有控制液晶組成物層中之液晶分子之定向方向之定向控制功能。作為上述交聯性官能基，只要可進行自由基反應，則可具有任何結構，較佳為以下所示之(V2-1)~(V2-7)所表示之基，更佳為(V2-1)~(V2-3)所表示之基，進而較佳為(V2-1)或(V2-2)所表示之基。 The polymerizable compound having a crosslinkable functional group as a side chain moiety is not particularly limited as long as the side chain moiety has a crosslinkable functional group (polymerizable group), and it is preferred to use the above-mentioned one. The compound having a quinone imine skeleton or a siloxane skeleton as a main chain moiety is more preferably a compound having a polyimine skeleton in the main chain portion. A polymerizable compound having a polyimine skeleton in the main chain portion and a crosslinkable functional group as a side chain, and a repeating unit (main chain portion) constituting the polyimine structure has a crosslinkable functional group as a side. Chain compound. Further, the crosslinkable functional group becomes a polymerization initiation point, and a polymerizable compound having a polymerizable group which is formulated in the alignment film material undergoes a radical reaction to form a side chain, thereby having a control liquid crystal composition layer Orientation control function of the orientation direction of liquid crystal molecules. The crosslinkable functional group may have any structure as long as it can undergo a radical reaction, and is preferably a group represented by (V2-1) to (V2-7) shown below, and more preferably (V2- The group represented by 1) to (V2-3) is further preferably a group represented by (V2-1) or (V2-2).

(R1表示碳原子數1~5之烷基) (R 1 represents an alkyl group having 1 to 5 carbon atoms)

上述交聯性官能基只要經由共價鍵與主鏈部分鍵結即可，亦可直接鍵結於主鏈部分，亦可經由連結基鍵結於主鏈部分，作為連結基，較佳為使用-O-C6H4-或-O-C6H4-(R2O)r-(R2表示碳原子數1~20之伸烷基，r表示1以上之整數)。 The crosslinkable functional group may be bonded to the main chain moiety via a covalent bond, or may be directly bonded to the main chain moiety, or may be bonded to the main chain moiety via a linking group, and is preferably used as a linking group. -OC 6 H 4 - or -OC 6 H 4 -(R 2 O) r - (R 2 represents an alkylene group having 1 to 20 carbon atoms, and r represents an integer of 1 or more).

作為具有聚醯亞胺骨架作為主鏈且具有交聯性官能基作為側鏈之聚合性化合物，例如，可例示以下所示之通式(V2)所表示之化合物。 The polymerizable compound having a polyethylenimine skeleton as a main chain and having a crosslinkable functional group as a side chain, for example, a compound represented by the following formula (V2) can be exemplified.

(通式(V2)中，R3表示下述(V2-A)~(V2-F)所表示之基中之任一種，R4及R5分別獨立地表示碳原子數1~20之伸烷基，R6及R7分別獨立地表示上述(V2-1)~(V2-7)所表示之基中之任一種，n表示1以上之整數，m1及m2分別表示0或1，m3及m4分別表示0或1以上之整數，m5及m6分別表示0或1，但m5及m6之至少一者表示1) (In the formula (V2), R 3 represents any one of the groups represented by the following (V2-A) to (V2-F), and R 4 and R 5 each independently represent a stretch of 1 to 20 carbon atoms. The alkyl group, R 6 and R 7 each independently represent any one of the groups represented by the above (V2-1) to (V2-7), n represents an integer of 1 or more, and m1 and m2 represent 0 or 1, respectively, m3 And m4 respectively represent an integer of 0 or more, m5 and m6 respectively represent 0 or 1, but at least one of m5 and m6 represents 1)

作為與主鏈部分具有聚醯亞胺骨架且具有交聯性官能基作為側鏈之聚合性化合物一併調配於定向膜材料中之具有聚合性基之聚合性化合物，可列舉與上述通式(I)及上述通式(V)所表示之化合物相同者，其特徵在於必定含有通式(I)所表示之化合物。藉由含有該上述通式(I)所表示之化合物，可以較少之能量形成側鏈，即，可降低紫外線等之照射量。 The polymerizable compound having a polymerizable group which is blended in the alignment film material together with the polymerizable compound having a polyfluorene imine skeleton in the main chain portion and having a crosslinkable functional group as a side chain may be exemplified by the above formula ( I) is the same as the compound represented by the above formula (V), and is characterized in that it contains a compound represented by the formula (I). By containing the compound represented by the above formula (I), side chains can be formed with less energy, that is, the amount of irradiation of ultraviolet rays or the like can be reduced.

上述通式(I)所表示之化合物於定向膜材料中調配之調配量較佳為0.1~6質量%，更佳為0.5~5質量%，進而較佳為1~4質量%。 The compounding amount of the compound represented by the above formula (I) in the alignment film material is preferably from 0.1 to 6% by mass, more preferably from 0.5 to 5% by mass, still more preferably from 1 to 4% by mass.

上述具有聚合性基之聚合性化合物整體於定向膜材料中調配之調配量較佳為0.1~6質量%，更佳為0.5~5質量%，進而較佳為1~4 質量%。 The amount of the polymerizable compound having a polymerizable group as a whole is preferably 0.1 to 6% by mass, more preferably 0.5 to 5% by mass, even more preferably 1 to 4, based on the amount of the polymerizable compound. quality%.

再者，於使用側鏈部分具有交聯性官能基之聚合性化合物之聚合物作為該定向膜材料之情形時，亦可併用上文所述之公知之聚醯亞胺系材料。 Further, in the case where a polymer of a polymerizable compound having a crosslinkable functional group in a side chain portion is used as the material of the alignment film, a known polyamidene-based material as described above may be used in combination.

(使用聚合性液晶化合物之硬化物作為定向膜之方法) (Method of using a cured product of a polymerizable liquid crystal compound as an oriented film)

於使用聚合性液晶化合物之硬化物作為定向膜之情形時，可使用上文所述之由聚醯亞胺系材料或聚矽氧烷系材料構成之定向膜作為底塗定向膜。 In the case where a cured product of a polymerizable liquid crystal compound is used as the oriented film, an oriented film composed of a polyimide-based material or a polyoxyalkylene-based material as described above may be used as the undercoat alignment film.

於使用聚合性液晶化合物之硬化物作為定向膜之情形時，其特徵在於必定含有下述通式(V3)所表示之聚合性液晶化合物、及上述通式(I)所表示之化合物。藉由含有該上述通式(I)所表示之化合物，可以較少之能量獲得聚合性液晶化合物之硬化物，即，可降低紫外線等之照射量。 When a cured product of a polymerizable liquid crystal compound is used as the alignment film, it is characterized in that it contains a polymerizable liquid crystal compound represented by the following formula (V3) and a compound represented by the above formula (I). By containing the compound represented by the above formula (I), a cured product of the polymerizable liquid crystal compound can be obtained with less energy, that is, the amount of irradiation of ultraviolet rays or the like can be reduced.

於使用聚合性液晶化合物之硬化物製造定向膜之情形時，相對於上述通式(I)所表示之化合物及通式(V3)所表示之聚合性液晶化合物之總量，較佳為含有0.1~50質量%之上述通式(I)所表示之化合物，更佳為含有0.3~30質量%，進而較佳為含有0.5~10質量%。 In the case of producing an oriented film using a cured product of a polymerizable liquid crystal compound, the total amount of the polymerizable liquid crystal compound represented by the compound represented by the above formula (I) and the formula (V3) is preferably 0.1. The compound represented by the above formula (I) is preferably used in an amount of from 0.3 to 30% by mass, more preferably from 0.5 to 10% by mass.

作為形成定向膜之聚合性液晶化合物，具體而言，較佳為含有一種或兩種以上下述通式(V3) Specific examples of the polymerizable liquid crystal compound forming the alignment film include one or two or more of the following formula (V3).

(式中，X1表示氫原子或甲基，Sp5及Sp6分別獨立地表示單鍵、碳原 子數1~8之伸烷基或-O-(CH2)s-(式中，s表示2~7之整數，氧原子係鍵結於芳香環上)，Z4表示-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-COO-、-CH2-OCO-、-CY1=CY2-(Y1及Y2分別獨立地表示氫原子、氟原子)、-C≡C-或單鍵，Y表示碳原子數1~8之烷基、碳原子數2~8之烯基、碳原子數1~8之烷氧基、碳原子數2~8之烯氧基、氫原子、氟原子或氰基、或者以下之結構， (wherein, X 1 represents a hydrogen atom or a methyl group, and Sp 5 and Sp 6 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O-(CH 2 ) s - (wherein, s Indicates an integer from 2 to 7, the oxygen atom is bonded to the aromatic ring), and Z 4 represents -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -CF 2 O-, -OCF 2 - , -CH 2 CH 2 -, -CF 2 CF 2 -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO- CH 2 CH 2 -, -OCO-CH 2 CH 2 -, -CH 2 CH 2 -COO-, -CH 2 CH 2 -OCO-, -COO-CH 2 -, -OCO-CH 2 -, -CH 2 -COO-, -CH 2 -OCO-, -CY 1 =CY 2 - (Y 1 and Y 2 each independently represent a hydrogen atom, a fluorine atom), -C≡C- or a single bond, and Y represents a carbon number of 1 An alkyl group of ~8, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, a hydrogen atom, a fluorine atom or a cyano group, or the following structure,

(式中，X2表示氫原子或甲基)，C環表示1,4-伸苯基、反-1,4-伸環己基或單鍵，於C環中，1,4-伸苯基之任意氫原子可被取代為氟原子)所表示之聚合性液晶化合物。 (wherein, X 2 represents a hydrogen atom or a methyl group), and the C ring represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, and a 1,4-phenylene group in the C ring. Any of the hydrogen atoms may be substituted with a polymerizable liquid crystal compound represented by a fluorine atom.

於上述通式(V3)中，X1及X2分別獨立地表示氫原子或甲基，於重視反應速度之情形時，較佳為氫原子，於重視減少反應殘留量之情形時，較佳為甲基。 In the above formula (V3), X 1 and X 2 each independently represent a hydrogen atom or a methyl group, and when a reaction rate is important, a hydrogen atom is preferred, and when it is important to reduce the residual amount of the reaction, it is preferred. Is a methyl group.

於上述通式(V3)中，Sp5及Sp6分別獨立地表示單鍵、碳原子數1~8之伸烷基或-O-(CH2)s-(式中，s表示2~7之整數，氧原子係鍵結於芳香環上)，較佳為碳鏈並不太長，且較佳為單鍵或碳原子數1~5之伸烷基，更佳為單鍵或碳原子數1~3之伸烷基。又，於Sp5及Sp6表示-O-(CH2)s-之情形時，s亦較佳為1~5，更佳為1~3，且更佳為 Sp5及Sp6之至少一者為單鍵，尤佳為均為單鍵。 In the above formula (V3), Sp 5 and Sp 6 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O-(CH 2 ) s - (wherein s represents 2 to 7) An integer, the oxygen atom is bonded to the aromatic ring, preferably the carbon chain is not too long, and is preferably a single bond or an alkylene group having 1 to 5 carbon atoms, more preferably a single bond or a carbon atom. A number of 1-3 alkyl groups. Further, in the case where Sp 5 and Sp 6 represent -O-(CH 2 ) s -, s is also preferably from 1 to 5, more preferably from 1 to 3, and still more preferably at least one of Sp 5 and Sp 6 The one is a single button, and the best one is a single button.

於上述通式(V3)中，Z4表示-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-COO-、-CH2-OCO-、-CY1=CY2-(Y1及Y2分別獨立地表示氫原子、氟原子)、-C≡C-或單鍵，較佳為-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-或單鍵，更佳為-COO-、-OCO-或單鍵，尤佳為單鍵。 In the above formula (V3), Z 4 represents -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -CH 2 CH 2 -, - CF 2 CF 2 -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH 2 CH 2 -, -OCO- CH 2 CH 2 -, -CH 2 CH 2 -COO-, -CH 2 CH 2 -OCO-, -COO-CH 2 -, -OCO-CH 2 -, -CH 2 -COO-, -CH 2 -OCO -, -CY 1 = CY 2 - (Y 1 and Y 2 each independently represent a hydrogen atom, a fluorine atom), -C≡C- or a single bond, preferably -OCH 2 -, -CH 2 O-, - COO-, -OCO-, -CF 2 O-, -OCF 2 -, -CH 2 CH 2 -, -CF 2 CF 2 - or a single bond, more preferably -COO-, -OCO- or a single bond, especially Good for a single button.

於上述通式(V3)中，C環表示任意氫原子可被取代為氟原子之1,4-伸苯基、反-1,4-伸環己基或單鍵，較佳為1,4-伸苯基或單鍵。 In the above formula (V3), the C ring represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond in which an arbitrary hydrogen atom may be substituted with a fluorine atom, preferably 1,4- Stretch phenyl or single bond.

於C環表示單鍵以外之環結構之情形時，Z4亦較佳為單鍵以外之連結基，於C環為單鍵之情形時，Z4較佳為單鍵。 In the case where the C ring represents a ring structure other than a single bond, Z 4 is also preferably a linking group other than a single bond, and in the case where the C ring is a single bond, Z 4 is preferably a single bond.

Y表示碳原子數1~8之烷基、碳原子數2~8之烯基、碳原子數1~8之烷氧基、碳原子數2~8之烯氧基、氫原子、氟原子或氰基之化合物為單官能之聚合性液晶化合物，Y不具有聚合性骨架。另一方面，Y表示上文所述之聚合性骨架之化合物為二官能聚合性液晶化合物。於本發明中，可使用單官能之聚合性液晶化合物或二官能聚合性液晶化合物之任一者，就耐熱性之觀點而言，較佳為二官能聚合性液晶化合物，亦可同時使用該等兩者。 Y represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, a hydrogen atom, a fluorine atom or The cyano compound is a monofunctional polymerizable liquid crystal compound, and Y does not have a polymerizable skeleton. On the other hand, a compound in which Y represents a polymerizable skeleton as described above is a difunctional polymerizable liquid crystal compound. In the present invention, any of a monofunctional polymerizable liquid crystal compound or a difunctional polymerizable liquid crystal compound can be used. From the viewpoint of heat resistance, a difunctional polymerizable liquid crystal compound is preferable, and these may be used at the same time. Both.

就以上方面而言，作為具有環結構之聚合性液晶化合物，較 佳為以下之通式(V3-1)至(V3-6)所表示之化合物，尤佳為通式(V3-1)至(V3-4)所表示之化合物，最佳為通式(V3-2)所表示之化合物。 In the above aspect, as a polymerizable liquid crystal compound having a ring structure, The compound represented by the following general formulae (V3-1) to (V3-6) is particularly preferably a compound represented by the general formulae (V3-1) to (V3-4), and the most preferable one is a general formula (V3). -2) The compound represented.

(上述式中，Sp5及Sp6分別獨立地表示與上述所定義者相同者) (In the above formula, Sp 5 and Sp 6 each independently represent the same as defined above)

於使用聚合性液晶化合物之硬化物作為定向膜之情形時，於加熱定向膜形成材料中之聚合性液晶化合物而製成等向性液體後，必須降低溫度，將聚合性液晶化合物之定向設為垂直定向。其後，於施加自基板面傾斜特定角度之磁場之狀態下賦予預傾角，於該狀態下，照射紫外線使聚合性液晶化合物硬化，而製成定向膜。 When a cured product of a polymerizable liquid crystal compound is used as the alignment film, after heating the polymerizable liquid crystal compound in the alignment film forming material to form an isotropic liquid, it is necessary to lower the temperature and set the orientation of the polymerizable liquid crystal compound to Vertical orientation. Thereafter, a pretilt angle is applied in a state where a magnetic field inclined at a specific angle from the substrate surface is applied, and in this state, the polymerizable liquid crystal compound is cured by irradiation with ultraviolet rays to form an alignment film.

又，該定向膜可具有水平定向膜作為定向膜之基底層。具體而言，可具有如下水平定向膜：使用聚醯亞胺系水平定向定向膜材料等， 藉由旋轉塗佈法將水平定向膜材料塗佈於基板上，並藉由加熱等去除溶劑後，進行燒成而製成基底層，並進行摩擦處理而賦予水平定向性。 Further, the alignment film may have a horizontal alignment film as a base layer of the alignment film. Specifically, it may have a horizontal alignment film using a polyimine-based horizontal alignment film material or the like, The horizontal alignment film material is applied onto the substrate by a spin coating method, and the solvent is removed by heating or the like, and then fired to form a base layer, which is subjected to a rubbing treatment to impart horizontal orientation.

(為了於定向膜表面形成聚合物層而含有於液晶組成物中之聚合性化合物) (Polymerizable compound contained in the liquid crystal composition for forming a polymer layer on the surface of the alignment film)

於本發明之液晶顯示元件中，垂直定向膜含有藉由具有反應性基之聚合性化合物之聚合所形成之聚合物，藉由該聚合物，可賦予合適之預傾角，進而，視需要於液晶組成物中含有聚合性化合物，將該液晶組成物夾持於基板間後，一面施加電壓一面使該聚合性化合物硬化，藉此聚合性化合物一面相分離，一面以聚合物層之形式形成於上述垂直定向膜之表面，可進一步獲得液晶分子之定向性或預傾角之穩定性較高、殘像之產生較少、其製造時之滴加痕之產生較少的液晶顯示元件。 In the liquid crystal display device of the present invention, the vertical alignment film contains a polymer formed by polymerization of a polymerizable compound having a reactive group, by which a suitable pretilt angle can be imparted, and further, if necessary, liquid crystal The composition contains a polymerizable compound, and after the liquid crystal composition is sandwiched between the substrates, the polymerizable compound is cured while applying a voltage, whereby the polymerizable compound is formed as a polymer layer while being phase-separated. Further, the surface of the vertically oriented film can further obtain a liquid crystal display element in which the directivity of the liquid crystal molecules or the stability of the pretilt angle is high, the generation of residual images is small, and the occurrence of dripping marks at the time of manufacture is small.

形成上述聚合層之聚合性化合物可列舉具有一個反應性基之單官能性之聚合性化合物、二官能或三官能等具有兩個以上之反應性基之多官能性之聚合性化合物等，較佳為二官能或三官能等具有兩個以上之反應性基之多官能性之聚合性化合物。所使用之聚合性化合物可為一種，亦可為兩種以上。 The polymerizable compound which forms the above-mentioned polymerizable layer may, for example, be a monofunctional polymerizable compound having one reactive group, or a polyfunctional polymerizable compound having two or more reactive groups such as a difunctional or trifunctional group, and the like. It is a polyfunctional polymerizable compound having two or more reactive groups such as a difunctional or trifunctional group. The polymerizable compound to be used may be one type or two or more types.

作為形成聚合物層之聚合性化合物，較佳為含有上文所述之通式(I)所表示之化合物。藉由使用該上文所述之通式(I)所表示之化合物，可於定向膜之表面以較少之能量形成聚合物層，即，可降低紫外線等之照射量。 The polymerizable compound forming the polymer layer preferably contains the compound represented by the above formula (I). By using the compound represented by the above formula (I), the polymer layer can be formed with less energy on the surface of the alignment film, that is, the irradiation amount of ultraviolet rays or the like can be reduced.

又，作為形成聚合物層之聚合性化合物，較佳為與上文所述之通式(V)同樣之通式(V1) Further, as the polymerizable compound forming the polymer layer, the formula (V1) similar to the above formula (V) is preferred.

(式中，X7及X8分別獨立地表示氫原子或甲基，Sp1及Sp2分別獨立地表示單鍵、碳原子數1~8之伸烷基或-X-(CH2)r-(式中，r表示2~7之整數，X表示O、OCOO、OCO、或COO，X係鍵結於存在於U中之芳香環上)，U表示碳原子數2~20之直鏈或支鏈多元伸烷基、碳原子數3~20之直鏈或支鏈多元伸烯基或者碳原子數5~30之多元環狀取代基，多元伸烷基中之伸烷基或多元伸烯基中之伸烯基可於氧原子不鄰接之範圍內被取代為-O-、-CO-、-CF2-，亦可被取代為碳原子數5~20之烷基(基中之伸烷基可於氧原子不鄰接之範圍內被取代為氧原子)、或環狀取代基，k表示0~5之整數)所表示之聚合性化合物。 (wherein, X 7 and X 8 each independently represent a hydrogen atom or a methyl group, and Sp 1 and Sp 2 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -X-(CH 2 ) r - (wherein, r represents an integer from 2 to 7, X represents O, OCOO, OCO, or COO, X is bonded to an aromatic ring present in U), and U represents a linear chain of 2 to 20 carbon atoms. Or a branched polyalkylene group, a linear or branched polyalkylene group having 3 to 20 carbon atoms or a polyvalent cyclic substituent having 5 to 30 carbon atoms; an alkyl group or a plurality of stretches in a polyalkylene group The alkenyl group in the alkenyl group may be substituted with -O-, -CO-, -CF 2 - in the range in which the oxygen atoms are not adjacent, and may be substituted with an alkyl group having 5 to 20 carbon atoms. The alkylene group may be a polymerizable compound represented by an alkyl group which may be substituted with an oxygen atom in a range in which the oxygen atoms are not adjacent, or a cyclic substituent, and k represents an integer of 0 to 5.

於上述通式(V1)中，X7及X8分別獨立地表示氫原子或甲基，於重視反應速度之情形時，較佳為氫原子，於重視減少反應殘留量之情形時，較佳為甲基。 In the above formula (V1), X 7 and X 8 each independently represent a hydrogen atom or a methyl group, and when a reaction rate is important, a hydrogen atom is preferred, and when it is important to reduce the residual amount of the reaction, it is preferred. Is a methyl group.

於上述通式(V1)中，Sp1及Sp2分別獨立地表示單鍵、碳原子數1~8之伸烷基或-X-(CH2)r-(式中，r表示2~7之整數，X表示O、OCOO、或COO，X係鍵結於存在於U中之芳香環上)，較佳為碳鏈並不太長，且較佳為單鍵或碳原子數1~5之伸烷基，更佳為單鍵或碳原子數1~3之伸烷基。又，於Sp1及Sp2表示-X-(CH2)s-之情形時，r亦較佳為1~5，更佳為1~3，且更佳為Sp1及Sp2之至少一者為單鍵，尤佳為均為單鍵。 In the above formula (V1), Sp 1 and Sp 2 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -X-(CH 2 ) r - (wherein, r represents 2 to 7). An integer, X represents O, OCOO, or COO, and X is bonded to an aromatic ring present in U), preferably the carbon chain is not too long, and is preferably a single bond or a carbon number of 1 to 5 The alkyl group is more preferably a single bond or an alkyl group having 1 to 3 carbon atoms. Further, in the case where Sp 1 and Sp 2 represent -X-(CH 2 ) s -, r is preferably from 1 to 5, more preferably from 1 to 3, and still more preferably at least one of Sp 1 and Sp 2 . The one is a single button, and the best one is a single button.

於上述通式(V1)中，k表示0~5之整數，於重視液晶組 成物層中之液晶分子之定向方向之控制性之情形時，較佳為k表示1~5之整數，更佳為k表示1~3之整數，進而較佳為k表示1。 In the above formula (V1), k represents an integer of 0 to 5, and the liquid crystal group is emphasized. In the case where the orientation of the alignment direction of the liquid crystal molecules in the layer is controlled, k is preferably an integer of 1 to 5, more preferably k is an integer of 1 to 3, and further preferably k is 1.

於上述通式(V1)中，U表示碳原子數2~20之直鏈或支鏈多元伸烷基、碳原子數3~20之直鏈或支鏈多元伸烯基或者碳原子數5~30之多元環狀取代基，多元伸烷基中之伸烷基可於氧原子不鄰接之範圍內被取代為-O-、-CO-、-CF2-，亦可被取代為碳原子數5~20之烷基(基中之伸烷基可於氧原子不鄰接之範圍內被取代為氧原子)、或環狀取代基，較佳為被取代為兩個以上之環狀取代基。具體而言，U較佳為表示以下之式(V1a-1)至式(V1a-6)，更佳為表示式(V1a-1)、式(V1a-2)、式(V1a-6)，尤佳為表示式(V1a-1)。 In the above formula (V1), U represents a linear or branched polyalkylene group having 2 to 20 carbon atoms, a linear or branched polyalkylene group having 3 to 20 carbon atoms or a carbon number of 5~ a polyvalent cyclic substituent of 30, wherein the alkylene group in the polyalkylene group may be substituted with -O-, -CO-, -CF 2 - in the range in which the oxygen atoms are not adjacent, or may be substituted into a carbon atom. The alkyl group of 5 to 20 (the alkylene group in the group may be substituted with an oxygen atom in a range in which the oxygen atoms are not adjacent) or the cyclic substituent is preferably substituted with two or more cyclic substituents. Specifically, U preferably represents the following formula (V1a-1) to formula (V1a-6), and more preferably represents formula (V1a-1), formula (V1a-2), and formula (V1a-6). It is especially preferable to express the formula (V1a-1).

(式中，兩端係鍵結於Sp1或Sp2上(上述為k=1之情形)，於k為2~5之整數之情形時，連結基數相對應地增加；Z1、Z2及Z3分別獨立地表示-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2 -、-CF2CF2-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-COO-、-CH2-OCO-或單鍵，式中之全部芳香環中任意氫原子可被取代為氟原子) (wherein, both ends are bonded to Sp 1 or Sp 2 (in the case of k = 1 above), and when k is an integer of 2 to 5, the number of linkages is correspondingly increased; Z 1 , Z 2 And Z 3 independently represent -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -CH 2 CH 2 -, -CF 2 CF 2 - , -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH 2 CH 2 -, -OCO-CH 2 CH 2 - , -CH 2 CH 2 -COO-, -CH 2 CH 2 -OCO-, -COO-CH 2 -, -OCO-CH 2 -, -CH 2 -COO-, -CH 2 -OCO- or a single bond, Any hydrogen atom in all aromatic rings in the formula may be substituted with a fluorine atom)

於上述U中，Z1、Z2及Z3分別獨立，較佳為-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-或單鍵，更佳為-COO-、-OCO-或單鍵，尤佳為單鍵。 In the above U, Z 1 , Z 2 and Z 3 are each independently, preferably -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, - CH 2 CH 2 -, -CF 2 CF 2 - or a single bond, more preferably -COO-, -OCO- or a single bond, particularly preferably a single bond.

於U具有上述環結構之情形時，上述Sp1及Sp2較佳為至少一者表示單鍵，亦較佳為兩者均為單鍵。 In the case where U has the above ring structure, it is preferred that at least one of Sp 1 and Sp 2 represents a single bond, and it is preferable that both of them are single bonds.

上述通式(V1)所表示之化合物較佳為以下之通式(V1b)所表示之化合物。 The compound represented by the above formula (V1) is preferably a compound represented by the following formula (V1b).

(式中，X1及X2分別獨立地表示氫原子或甲基，Sp1b及Sp2b分別獨立地表示單鍵、碳原子數1~8之伸烷基或-O-(CH2)s-(式中，s表示2~7之整數，氧原子係鍵結於芳香環上)，Z4表示-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-COO-、-CH2-OCO -、-CY1=CY2-(Y1及Y2分別獨立地表示氫原子、氟原子)、-C≡C-或單鍵，C環表示1,4-伸苯基、反-1,4-伸環己基或單鍵，式中之全部1,4-伸苯基中任意氫原子可被取代為氟原子) (wherein X 1 and X 2 each independently represent a hydrogen atom or a methyl group, and Sp 1b and Sp 2b each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O-(CH 2 ) s - (wherein, s represents an integer from 2 to 7, the oxygen atom is bonded to the aromatic ring), and Z 4 represents -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -CF 2 O -, -OCF 2 -, -CH 2 CH 2 -, -CF 2 CF 2 -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH= CH-, -COO-CH 2 CH 2 -, -OCO-CH 2 CH 2 -, -CH 2 CH 2 -COO-, -CH 2 CH 2 -OCO-, -COO-CH 2 -, -OCO-CH 2 -, -CH 2 -COO-, -CH 2 -OCO -, -CY 1 =CY 2 - (Y 1 and Y 2 each independently represent a hydrogen atom, a fluorine atom), -C≡C- or a single bond, The C ring represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, and any hydrogen atom in the 1,4-phenylene group in the formula may be substituted with a fluorine atom)

於上述通式(V1b)中，X1及X2分別獨立地表示氫原子或甲基，較佳為均表示氫原子之二丙烯酸酯衍生物、或均表示甲基之二甲基丙烯酸酯衍生物，亦較佳為一者表示氫原子、另一者表示甲基之化合物。關於該等化合物之聚合速度，二丙烯酸酯衍生物最快，二甲基丙烯酸酯衍生物較慢，非對稱化合物為其中間，可根據其用途使用較佳之態樣。 In the above formula (V1b), X 1 and X 2 each independently represent a hydrogen atom or a methyl group, preferably a diacrylate derivative each representing a hydrogen atom, or a dimethacrylate derivative derived from a methyl group. The substance is also preferably a compound in which one represents a hydrogen atom and the other represents a methyl group. Regarding the polymerization rate of the compounds, the diacrylate derivative is the fastest, the dimethacrylate derivative is slow, and the asymmetric compound is in the middle thereof, and a preferred aspect can be used depending on the use thereof.

於上述通式(V1b)中，Sp1b及Sp2b分別獨立地表示單鍵、碳原子數1~8之伸烷基或-O-(CH2)s-，較佳為至少一者為單鍵，且較佳為均表示單鍵之化合物或者一者為單鍵、另一者表示碳原子數1~8之伸烷基或-O-(CH2)s-之態樣。於該情形時，較佳為碳原子數1~4之伸烷基，且s較佳為1~4。 In the above formula (V1b), Sp 1b and Sp 2b each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O-(CH 2 ) s -, preferably at least one of which is a single A bond, and preferably a compound which each represents a single bond or one of which is a single bond, and the other represents an alkylene group having 1 to 8 carbon atoms or -O-(CH 2 ) s -. In this case, an alkylene group having 1 to 4 carbon atoms is preferred, and s is preferably 1 to 4.

於上述通式(V1b)中，Z4表示-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-COO-、-CH2-OCO-、-CY1=CY2-、-C≡C-或單鍵，較佳為-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-或單鍵，更佳為-COO-、-OCO-或單鍵，尤佳為單鍵。 In the above formula (V1b), Z 4 represents -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -CH 2 CH 2 -, - CF 2 CF 2 -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH 2 CH 2 -, -OCO- CH 2 CH 2 -, -CH 2 CH 2 -COO-, -CH 2 CH 2 -OCO-, -COO-CH 2 -, -OCO-CH 2 -, -CH 2 -COO-, -CH 2 -OCO -, -CY 1 = CY 2 -, -C≡C- or a single bond, preferably -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -CH 2 CH 2 -, -CF 2 CF 2 - or a single bond, more preferably -COO-, -OCO- or a single bond, particularly preferably a single bond.

於C環表示單鍵以外之環結構之情形時，Z4亦較佳為單鍵 以外之連結基，於C環為單鍵之情形時，Z4較佳為單鍵。 In the case where the C ring represents a ring structure other than a single bond, Z 4 is also preferably a linking group other than a single bond, and in the case where the C ring is a single bond, Z 4 is preferably a single bond.

根據以上內容，於上述通式(V1b)中，較佳為C環表示單鍵、環結構由兩個環形成之情形，作為具有環結構之聚合性化合物，具體而言，較佳為以下之通式(V1b-1)至(V1b-6)所表示之化合物，尤佳為通式(V1b-1)至(V1b-4)所表示之化合物，最佳為通式(V1b-2)所表示之化合物。 In the above formula (V1b), it is preferred that the C ring represents a single bond and the ring structure is formed of two rings, and as the polymerizable compound having a ring structure, specifically, the following is preferable. The compounds represented by the formulae (V1b-1) to (V1b-6) are particularly preferably compounds represented by the formulae (V1b-1) to (V1b-4), and most preferably the formula (V1b-2) Expressed as a compound.

(Sp1b及Sp2b分別表示與通式(V1b)所記載之Sp1及Sp2相同之含義) (Sp 1b and Sp 2b respectively have the same meanings as Sp 1 and Sp 2 described in the general formula (V1b))

具體而言，上述通式(V1)所表示之化合物亦較佳為以下之通式(V1c)所表示之化合物。 Specifically, the compound represented by the above formula (V1) is also preferably a compound represented by the following formula (V1c).

(式中，X1、X2及X3分別獨立地表示氫原子或甲基，Sp1c、Sp2c及Sp3c分別獨立地表示單鍵、碳原子數1~8之伸烷基或-O-(CH2)s-(式中，s表示2~7之整數，氧原子係鍵結於芳香環上)，Z11表示-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-COO-、-CH2-OCO-、-CY1=CY2-、-C≡C-或單鍵，J環表示1,4-伸苯基、或單鍵，式中之全部1,4-伸苯基中任意氫原子可被取代為氟原子) (wherein, X 1 , X 2 and X 3 each independently represent a hydrogen atom or a methyl group, and Sp 1c , Sp 2c and Sp 3c each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O -(CH 2 ) s - (wherein s represents an integer from 2 to 7, the oxygen atom is bonded to the aromatic ring), and Z 11 represents -OCH 2 -, -CH 2 O-, -COO-, -OCO -, -CF 2 O-, -OCF 2 -, -CH 2 CH 2 -, -CF 2 CF 2 -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH- , -OCO-CH=CH-, -COO-CH 2 CH 2 -, -OCO-CH 2 CH 2 -, -CH 2 CH 2 -COO-, -CH 2 CH 2 -OCO-, -COO-CH 2 -, -OCO-CH 2 -, -CH 2 -COO-, -CH 2 -OCO-, -CY 1 =CY 2 -, -C≡C- or a single bond, the J ring represents 1,4-phenylene Or a single bond, wherein any hydrogen atom in the 1,4-phenylene group in the formula may be substituted with a fluorine atom)

為了於垂直定向膜表面形成聚合物層而使用之通式(I)所表示之化合物於液晶組成物中之含量之合計較佳為0~1質量%，更佳為0.03~0.8質量%，進而較佳為0.05~0.6質量%。 The total content of the compound represented by the formula (I) in the liquid crystal composition used for forming the polymer layer on the surface of the vertically oriented film is preferably from 0 to 1% by mass, more preferably from 0.03 to 0.8% by mass. It is preferably 0.05 to 0.6% by mass.

又，為了於垂直定向膜表面形成聚合物層而使用之通式(V1)所表示之聚合性化合物於液晶組成物中的含量之合計較佳為0~1質量%，更佳為0.03~0.8質量%，進而較佳為0.05~0.6質量%。 In addition, the total content of the polymerizable compound represented by the formula (V1) in the liquid crystal composition used for forming the polymer layer on the surface of the vertical alignment film is preferably 0 to 1% by mass, more preferably 0.03 to 0.8. The mass% is further preferably 0.05 to 0.6% by mass.

為了於垂直定向膜表面形成聚合物層而使用之聚合性化合物整體於液晶組成物中的含量之合計較佳為0~1質量%，更佳為0.03~0.8質量%，進而較佳為0.05~0.6質量%。 The total content of the polymerizable compound used for forming the polymer layer on the surface of the vertically oriented film in the liquid crystal composition is preferably 0 to 1% by mass, more preferably 0.03 to 0.8% by mass, still more preferably 0.05%. 0.6% by mass.

(液晶組成物) (liquid crystal composition)

本發明中之液晶組成物含有一種或兩種以上之通式(N-1)、通式(N-2)、及通式(N-3)所表示之化合物。 The liquid crystal composition of the present invention contains one or two or more compounds represented by the formula (N-1), the formula (N-2), and the formula (N-3).

式中，RN11、RN12、RN21、RN22、RN31及RN32分別獨立地表示碳原子數1~8之烷基，該烷基中之一個或非鄰接之兩個以上之-CH2-可分別獨立地被取代為-CH=CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-，AN11、AN12、AN21、AN22、AN31及AN32分別獨立地表示選自由(a)1,4-伸環己基(存在於該基中之一個-CH2-或未鄰接之兩個以上之-CH2-可被取代為-O-)、(b)1,4-伸苯基(存在於該基中之一個-CH=或未鄰接之兩個以上之-CH=可被取代為-N=)、及(c)萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基或十氫萘-2,6-二基(存在於萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基中之一個-CH=或未鄰接之兩個以上之-CH=可被取代為-N=) In the formula, R N11 , R N12 , R N21 , R N22 , R N31 and R N32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two or more non-adjacent-CH 2 - may be independently substituted with -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, A N11 , A N12 , A N21 , A N22 , A N31 and A N32 each independently represent a group selected from (a) 1,4-cyclohexylene (one of -CH 2 - present in the group or two or more of -CH 2 - which may not be adjacent may be substituted with -O -), (b) 1,4-phenylene (one present in the group -CH= or two or more non-contiguous -CH= may be substituted with -N=), and (c)naphthalene- 2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (present in naphthalene-2,6-diyl or 1, One of the 2,3,4-tetrahydronaphthalene-2,6-diyl-CH= or two or more non-contiguous -CH= may be substituted by -N=)

所組成之群中之基，上述基(a)、基(b)及基(c)可分別獨立地經氰基、氟原子或氯原子取代，ZN11、ZN12、ZN21、ZN22、ZN31及ZN32分別獨立地表示單鍵、-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-、-CH=N-N=CH-、-CH=CH-、-CF=CF-或-C≡C-，XN21表示氫原子或氟原子，TN31表示-CH2-或氧原子，nN11、nN12、nN21、nN22、nN31及nN32分別獨立地表示0~3之整數，nN11+nN12、nN21+nN22及nN31+nN32分別獨立為1、2或3，於存在多個AN11~AN32、ZN11~ZN32之情形時，該等可相同，亦可不同。 The group (a), the group (b) and the group (c) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, respectively, Z N11 , Z N12 , Z N21 , Z N22 , Z N31 and Z N32 each independently represent a single bond, -CH 2 CH 2 -, -(CH 2 ) 4 -, -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -OCF 2 - , -CF 2 O-, -CH=NN=CH-, -CH=CH-, -CF=CF- or -C≡C-, X N21 represents a hydrogen atom or a fluorine atom, and T N31 represents -CH 2 - or The oxygen atoms, n N11 , n N12 , n N21 , n N22 , n N31 and n N32 each independently represent an integer of 0 to 3, n N11 +n N12 , n N21 +n N22 and n N31 +n N32 are each independently 1, 2 or 3, when there are a plurality of A N11 ~ A N32 , Z N11 ~ Z N32 , the same may be the same or different.

通式(N-1)、(N-2)及(N-3)所表示之化合物較佳為△ε為負且其絕對值大於3之化合物。 The compound represented by the general formulae (N-1), (N-2) and (N-3) is preferably a compound in which Δε is negative and its absolute value is more than 3.

通式(N-1)、(N-2)及(N-3)中，RN11、RN12、RN21、RN22、RN31及RN32分別獨立，較佳為碳原子數1~8之烷基、碳原子數1~8之烷氧基、碳原子數2~8之烯基或碳原子數2~8之烯氧基，更佳為碳原子數1~5之烷基、碳原子數1~5之烷氧基、碳原子數2~5之烯基或碳原子數2~5之烯氧基，進而較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，進而更佳為碳原子數2~5之烷基或碳原子數2~3之烯基，尤佳為碳原子數為3之烯基(丙烯基)。 In the general formulae (N-1), (N-2) and (N-3), R N11 , R N12 , R N21 , R N22 , R N31 and R N32 are each independently, preferably having 1 to 8 carbon atoms. An alkyl group, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or carbon An alkoxy group having 1 to 5 atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or 2 to 2 carbon atoms. The alkenyl group of 5 is more preferably an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, and particularly preferably an alkenyl group having 3 carbon atoms (acryloyl group).

又，於其所鍵結之環結構為苯基(芳香族)之情形時，較佳為直鏈狀之碳原子數1~5之烷基、直鏈狀之碳原子數1~4之烷氧基及碳原子數4~5之烯基，於其所鍵結之環結構為環己烷、吡喃及二烷等飽和之 環結構之情形時，較佳為直鏈狀之碳原子數1~5之烷基、直鏈狀之碳原子數1~4之烷氧基及直鏈狀之碳原子數2~5之烯基。為了使向列相穩定化，較佳為碳原子及存在之情形時之氧原子之合計為5以下，且較佳為直鏈狀。 Further, in the case where the ring structure to which the bond is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms and a linear alkyl group having 1 to 4 carbon atoms are preferable. An oxy group and an alkenyl group having 4 to 5 carbon atoms, wherein the ring structure to which the bond is bonded is cyclohexane, pyran and In the case of a saturated ring structure such as an alkane, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear carbon atom number 2 are preferred. ~5 alkenyl. In order to stabilize the nematic phase, it is preferred that the total number of carbon atoms and oxygen atoms in the case of being present is 5 or less, and is preferably linear.

作為烯基，較佳為自式(R1)至式(R5)之任一者所表示之基中選擇。(各式中之黑點表示環結構中之碳原子) The alkenyl group is preferably selected from the group represented by any one of the formulae (R1) to (R5). (black dots in various formulas represent carbon atoms in the ring structure)

AN11、AN12、AN21、AN22、AN31及AN32分別獨立，於謀求增大△n之情形時，較佳為芳香族，為了改善應答速度，較佳為脂肪族，且較佳為表示反-1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、3-氟-1,4-伸苯基、3,5-二氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基、1,4-伸環己烯基、1,4-雙環[2.2.2]伸辛基、哌啶-1,4-二基、萘-2,6-二基、十氫萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基，更佳為表示下述結構， A N11 , A N12 , A N21 , A N22 , A N31 and A N32 are each independently. When it is desired to increase Δn, it is preferably aromatic, and in order to improve the response speed, it is preferably aliphatic, and preferably. To represent trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro -1,4-phenylene, 2,3-difluoro-1,4-phenylene, 1,4-cyclohexenyl, 1,4-bicyclo[2.2.2]exenyl, piperidine -1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, more preferably Indicates the following structure,

進而較佳為表示反-1,4-伸環己基或1,4-伸苯基。 Further preferably, it is a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

ZN11、ZN12、ZN21、ZN22、ZN31及ZN32分別獨立，較佳為表示-CH2O-、-CF2O-、-CH2CH2-、-CF2CF2-或單鍵，進而較佳為-CH2O-、-CH2CH2-或單鍵，尤佳為-CH2O-或單鍵。 Z N11 , Z N12 , Z N21 , Z N22 , Z N31 and Z N32 are each independently, preferably represent -CH 2 O-, -CF 2 O-, -CH 2 CH 2 -, -CF 2 CF 2 - or The single bond is further preferably -CH 2 O-, -CH 2 CH 2 - or a single bond, and more preferably -CH 2 O- or a single bond.

XN21較佳為氟原子。 X N21 is preferably a fluorine atom.

TN31較佳為氧原子。 T N31 is preferably an oxygen atom.

nN11+nN12、nN21+nN22及nN31+nN32較佳為1或2，且較佳為nN11為1且nN12為0之組合、nN11為2且nN12為0之組合、nN11為1且nN12為1之組合、nN11為2且nN12為1之組合、nN21為1且nN22為0之組合、nN21為2且nN22為0之組合、nN31為1且nN32為0之組合、nN31為2且nN32為0之組合。 n N11 +n N12 , n N21 +n N22 and n N31 +n N32 are preferably 1 or 2, and preferably n N11 is 1 and n N12 is a combination of 0, n N11 is 2 and n N12 is 0. a combination in which n N11 is 1 and n N12 is 1 combination, n N11 is 2 and n N12 is 1 combination, n N21 is 1 and n N22 is 0 combination, n N21 is 2, and n N22 is 0 combination. n N31 is 1 and n N32 is a combination of 0, n N31 is 2, and n N32 is a combination of 0.

通式(N-1)所表示之化合物相對於本發明之組成物之總量(液晶組成物中所含之液晶化合物之總量。以下相同)之較佳含量之下限值為1質量%(以下將質量%簡記為%)、10%、20%、30%、40%、50%、55%、60%、65%、70%、75%、80%。較佳含量之上限值為95%、85%、75%、65%、55%、45%、35%、25%、20%。 The lower limit of the preferred content of the compound represented by the formula (N-1) relative to the total amount of the composition of the present invention (the total amount of the liquid crystal compound contained in the liquid crystal composition, the same applies hereinafter) is 1% by mass. (Here is the mass % abbreviated as %), 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%.

通式(N-2)所表示之化合物相對於本發明之組成物之總量之較佳含量之下限值為1質量%(以下將質量%簡記為%)、10%、20%、30%、40%、50%、55%、60%、65%、70%、75%、80%。較佳含量之上限值為95%、85%、75%、65%、55%、45%、35%、25%、20%。 The lower limit of the preferred content of the compound represented by the formula (N-2) with respect to the total amount of the composition of the present invention is 1% by mass (hereinafter, the mass % is abbreviated as %), 10%, 20%, 30 %, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%.

通式(N-3)所表示之化合物相對於本發明之組成物之總量之較佳含量之下限值為1質量%(以下將質量%簡記為%)、10%、20%、30%、40%、50%、55%、60%、65%、70%、75%、80%。較佳含量之上限值為95%、85%、75%、65%、55%、45%、35%、25%、20%。 The lower limit of the preferred content of the compound represented by the formula (N-3) with respect to the total amount of the composition of the present invention is 1% by mass (hereinafter, the mass % is abbreviated as %), 10%, 20%, 30 %, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%.

於將本發明之組成物之黏度保持為較低、需要應答速度較快之組成物之情形時，較佳為上述下限值較低，且上限值較低。進而，於將本發明之組成物之Tni保持為較高、需要溫度穩定性良好之組成物之情形時，較佳為上述下限值較低，且上限值較低。又，於為了將驅動電壓保持 為較低而欲增大介電各向導性時，較佳為提高上述下限值，且上限值較高。 In the case where the viscosity of the composition of the present invention is kept low and a composition requiring a fast response speed is required, it is preferred that the lower limit value is lower and the upper limit value is lower. Further, in the case where the composition of the present invention has a high T ni and a composition requiring good temperature stability, the lower limit value is preferably low and the upper limit value is low. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to increase the above lower limit value and to have a higher upper limit value.

通式(N-1)所表示之化合物較佳為自通式(N-1-1)~(N-1-21)所表示之化合物群中選擇之化合物。 The compound represented by the formula (N-1) is preferably a compound selected from the group consisting of compounds represented by the formulae (N-1-1) to (N-1-21).

通式(N-1-1)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-1) is the following compound.

(式中，RN111及RN112分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (wherein R N111 and R N112 each independently represent the same meaning as R N11 and R N12 in the formula (N-1))

RN111較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，且較佳為丙基或戊基。RN112較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基，且較佳為乙氧基或丁氧基。 R N111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and is preferably a propyl group or a pentyl group. R N112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and is preferably an ethoxy group or a butoxy group.

通式(N-1-1)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (N-1-1) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於重視△ε之改善之情形時，較佳為將含量設定為較高，於重視低溫下之溶解性之情形時，若將含量設定為較多，則效果較高，於重視TNI之情形時，若將含量設定為較少，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 When the improvement of Δε is emphasized, it is preferable to set the content to be high, and when the solubility in low temperature is emphasized, if the content is set to be large, the effect is high, and the case of paying attention to T NI is emphasized. When the content is set to be small, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

相對於本發明之組成物之總量之式(N-1-1)所表示之化 合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%、23%、25%、27%、30%、33%、35%。較佳含量之上限值相對於本發明之組成物之總量，為50%、40%、38%、35%、33%、30%、28%、25%、23%、20%、18%、15%、13%、10%、8%、7%、6%、5%、3%。 The expression expressed by the formula (N-1-1) with respect to the total amount of the composition of the present invention The lower limit of the preferred content of the compound is 5% by mass (hereinafter, the mass % is abbreviated as %), 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30% , 33%, 35%. The upper limit of the preferred content is 50%, 40%, 38%, 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18 with respect to the total amount of the composition of the present invention. %, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3%.

進而，通式(N-1-1)所表示之化合物較佳為自式(N-1-1.1)至式(N-1-1.14)所表示之化合物群中選擇之化合物，較佳為式(N-1-1.1)~(N-1-1.4)所表示之化合物，較佳為式(N-1-1.1)及式(N-1-1.3)所表示之化合物。 Further, the compound represented by the formula (N-1-1) is preferably a compound selected from the group consisting of compounds represented by the formula (N-1-1.1) to the formula (N-1-1.14), preferably a formula The compound represented by (N-1-1.1) to (N-1-1.4) is preferably a compound represented by the formula (N-1-1.1) and the formula (N-1-1.3).

式(N-1-1.1)~(N-1-1.4)所表示之化合物可單獨使用，亦可組合使用，相對於本發明之組成物之總量之單獨或該等化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%、23%、25%、27%、30%、33%、35%。較佳含量之上限值相對於本發明之組成物之總量，為50%、40%、38%、35%、33%、30%、28%、25%、23%、20%、18%、15%、13%、10%、8%、7%、6%、5%、3%。 The compounds represented by the formula (N-1-1.1) to (N-1-1.4) may be used singly or in combination, and the total amount of the composition of the present invention alone or the preferred content of the compounds may be used in combination. The lower limit value is 5% by mass (hereinafter, mass % is abbreviated as %), 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, and 35%. The upper limit of the preferred content is 50%, 40%, 38%, 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18 with respect to the total amount of the composition of the present invention. %, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3%.

通式(N-1-2)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-2) is the following compound.

(式中，RN121及RN122分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (wherein R N121 and R N122 each independently represent the same meaning as R N11 and R N12 in the formula (N-1))

RN121較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，且較佳為乙基、丙基、丁基或戊基。RN122較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基，且較佳為甲基、丙基、甲氧基、乙氧基或丙氧基。 R N121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group, a butyl group or a pentyl group. R N122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably a methyl group, a propyl group or a methoxy group. Ethoxy or propoxy.

通式(N-1-2)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (N-1-2) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於重視△ε之改善之情形時，較佳為將含量設定為較高，於重視低溫下之溶解性之情形時，若將含量設定為較少，則效果較高，於重視TNI之情形時，若將含量設定為較多，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 When the improvement of Δε is emphasized, it is preferable to set the content to be high, and when the solubility at low temperature is emphasized, if the content is set to be small, the effect is high, and the case of paying attention to T NI is emphasized. When the content is set to be large, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

相對於本發明之組成物之總量之式(N-1-2)所表示之化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、7%、10%、13%、15%、17%、20%、23%、25%、27%、30%、33%、35%、37%、40%、42%。較佳含量之上限值相對於本發明之組成物之總量，為50%、48%、45%、 43%、40%、38%、35%、33%、30%、28%、25%、23%、20%、18%、15%、13%、10%、8%、7%、6%、5%。 The lower limit of the preferred content of the compound represented by the formula (N-1-2) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass % is abbreviated as %), 7%, and 10%. , 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 37%, 40%, 42%. The upper limit of the preferred content is 50%, 48%, 45%, relative to the total amount of the composition of the present invention. 43%, 40%, 38%, 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6% 5%.

進而，通式(N-1-2)所表示之化合物較佳為自式(N-1-2.1)至式(N-1-2.13)所表示之化合物群中選擇之化合物，較佳為式(N-1-2.3)至式(N-1-2.7)、式(N-1-2.10)、式(N-1-2.11)及式(N-1-2.13)所表示之化合物，於重視△ε之改良之情形時，較佳為式(N-1-2.3)至式(N-1-2.7)所表示之化合物，於重視TNI之改良之情形時，較佳為式(N-1-2.10)、式(N-1-2.11)及式(N-1-2.13)所表示之化合物。 Further, the compound represented by the formula (N-1-2) is preferably a compound selected from the group consisting of compounds represented by the formula (N-1-2.1) to the formula (N-1-2.13), preferably a formula (N-1-2.3) to the compound represented by formula (N-1-2.7), formula (N-1-2.10), formula (N-1-2.11) and formula (N-1-2.13), In the case of the improvement of Δε, a compound represented by the formula (N-1-2.3) to the formula (N-1-2.7) is preferred, and in the case of the improvement of the TNI , the formula (N- 1-2.10), a compound represented by the formula (N-1-2.11) and the formula (N-1-2.13).

式(N-1-2.1)至式(N-1-2.13)所表示之化合物可單獨使用，亦可組合使用，相對於本發明之組成物之總量之單獨或該等化合 物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%、23%、25%、27%、30%、33%、35%。較佳含量之上限值相對於本發明之組成物之總量，為50%、40%、38%、35%、33%、30%、28%、25%、23%、20%、18%、15%、13%、10%、8%、7%、6%、5%、3%。 The compounds represented by the formula (N-1-2.1) to the formula (N-1-2.13) may be used singly or in combination, alone or in combination with respect to the total amount of the composition of the present invention. The lower limit of the preferred content of the substance is 5% by mass (hereinafter, the mass % is abbreviated as %), 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%. The upper limit of the preferred content is 50%, 40%, 38%, 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18 with respect to the total amount of the composition of the present invention. %, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3%.

通式(N-1-3)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-3) is the following compound.

(式中，RN131及RN132分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (wherein R N131 and R N132 each independently represent the same meaning as R N11 and R N12 in the formula (N-1))

RN131較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，且較佳為乙基、丙基或丁基。RN132較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基，且較佳為乙氧基、丙氧基或丁氧基。 R N131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R N132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group. base.

通式(N-1-3)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (N-1-3) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於重視△ε之改善之情形時，較佳為將含量設定為較高，於重視低溫下之溶解性之情形時，若將含量設定為較多，則效果較高，於重視TNI之情形時，若將含量設定為較多，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 When the improvement of Δε is emphasized, it is preferable to set the content to be high, and when the solubility in low temperature is emphasized, if the content is set to be large, the effect is high, and the case of paying attention to T NI is emphasized. When the content is set to be large, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

相對於本發明之組成物之總量之式(N-1-3)所表示之化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、30%、28%、25%、23%、20%、18%、15%、13%。 The lower limit of the preferred content of the compound represented by the formula (N-1-3) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, the mass % is abbreviated as %), 10%, 13% , 15%, 17%, 20%. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the composition of the present invention.

進而，通式(N-1-3)所表示之化合物較佳為自式(N-1-3.1)至式(N-1-3.11)所表示之化合物群中選擇之化合物，較佳為式(N-1-3.1)~(N-1-3.7)所表示之化合物，較佳為式(N-1-3.1)、式(N-1-3.2)、式(N-1-3.3)、式(N-1-3.4)及式(N-1-3.6)所表示之化合物。 Further, the compound represented by the formula (N-1-3) is preferably a compound selected from the group consisting of compounds represented by the formula (N-1-3.1) to the formula (N-1-3.11), preferably a formula The compound represented by (N-1-3.1) to (N-1-3.7) is preferably a formula (N-1-3.1), a formula (N-1-3.2), or a formula (N-1-3.3). A compound represented by the formula (N-1-3.4) and the formula (N-1-3.6).

式(N-1-3.1)~式(N-1-3.4)及式(N-1-3.6)所表示之化合物可單獨使用，亦可組合使用，較佳為式(N-1-3.1)及式(N-1-3.2)之組合、自式(N-1-3.3)、式(N-1-3.4)及式(N-1-3.6) 中選擇之兩種或三種之組合。相對於本發明之組成物之總量之單獨或該等化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、30%、28%、25%、23%、20%、18%、15%、13%。 The compounds represented by the formula (N-1-3.1) to the formula (N-1-3.4) and the formula (N-1-3.6) may be used singly or in combination, preferably the formula (N-1-3.1). Combination of formula (N-1-3.2), self-formula (N-1-3.3), formula (N-1-3.4) and formula (N-1-3.6) Choose between two or three of them. The lower limit of the preferred content of the individual or the compounds relative to the total amount of the composition of the present invention is 5% by mass (hereinafter, the mass % is abbreviated as %), 10%, 13%, 15%, 17%, 20%. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the composition of the present invention.

通式(N-1-4)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-4) is the following compound.

(式中，RN141及RN142分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (wherein R N141 and R N142 each independently represent the same meaning as R N11 and R N12 in the formula (N-1))

RN141及RN142分別獨立，較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基，且較佳為甲基、丙基、乙氧基或丁氧基。 R N141 and R N142 are each independently, preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably a methyl group or a C group. Base, ethoxy or butoxy.

通式(N-1-4)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (N-1-4) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於重視△ε之改善之情形時，較佳為將含量設定為較高，於重視低溫下之溶解性之情形時，若將含量設定為較多，則效果較高，於重視TNI之情形時，若將含量設定為較少，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 When the improvement of Δε is emphasized, it is preferable to set the content to be high, and when the solubility in low temperature is emphasized, if the content is set to be large, the effect is high, and the case of paying attention to T NI is emphasized. When the content is set to be small, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

相對於本發明之組成物之總量之式(N-1-4)所表示之化合物之較佳含量之下限值為3質量%(以下將質量%簡記為%)、5%、7%、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、30%、28%、25%、23%、20%、18%、15%、13%、11%、10%、8%。 The lower limit of the preferred content of the compound represented by the formula (N-1-4) with respect to the total amount of the composition of the present invention is 3% by mass (hereinafter, mass % is abbreviated as %), 5%, 7%. 10%, 13%, 15%, 17%, 20%. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 11%, 10 with respect to the total amount of the composition of the present invention. %,8%.

進而，通式(N-1-4)所表示之化合物較佳為自式(N-1-4.1)至式(N-1-4.14)所表示之化合物群中選擇之化合物，較佳為式(N-1-4.1)~(N-1-4.4)所表示之化合物，較佳為式(N-1-4.1)及式(N-1-4.2)所表示之化合物。 Further, the compound represented by the formula (N-1-4) is preferably a compound selected from the group consisting of compounds represented by the formula (N-1-4.1) to the formula (N-1-4.14), preferably a formula The compound represented by (N-1-4.1) to (N-1-4.4) is preferably a compound represented by the formula (N-1-4.1) and the formula (N-1-4.2).

式(N-1-4.1)~(N-1-4.4)所表示之化合物可單獨使用，亦可組合使用，相對於本發明之組成物之總量之單獨或該等化合物之較佳含量之下限值為3質量%(以下將質量%簡記為%)、5%、7%、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、30%、28%、25%、23%、20%、18%、15%、13%、11%、10%、8%。 The compounds represented by the formula (N-1-4.1) to (N-1-4.4) may be used singly or in combination, and the total amount of the composition of the present invention alone or the preferred content of the compounds may be used in combination. The lower limit value is 3% by mass (hereinafter, mass % is abbreviated as %), 5%, 7%, 10%, 13%, 15%, 17%, and 20%. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 11%, 10 with respect to the total amount of the composition of the present invention. %,8%.

通式(N-1-5)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-5) is the following compound.

(式中，RN151及RN152分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (wherein R N151 and R N152 each independently represent the same meaning as R N11 and R N12 in the formula (N-1))

RN151及RN152分別獨立，較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基，且較佳為乙基、丙基或丁基。 R N151 and R N152 are each independently, preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethyl group or a C group. Base or butyl.

通式(N-1-5)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (N-1-5) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於重視△ε之改善之情形時，較佳為將含量設定為較高，於重視低溫下之溶解性之情形時，若將含量設定為較少，則效果較高，於重視TNI之情形時，若將含量設定為較多，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 When the improvement of Δε is emphasized, it is preferable to set the content to be high, and when the solubility at low temperature is emphasized, if the content is set to be small, the effect is high, and the case of paying attention to T NI is emphasized. When the content is set to be large, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

相對於本發明之組成物之總量之式(N-1-5)所表示之化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、8%、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、33%、30%、28%、25%、23%、20%、18%、15%、13%。 The lower limit of the preferred content of the compound represented by the formula (N-1-5) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass % is abbreviated as %), 8%, and 10%. , 13%, 15%, 17%, 20%. The upper limit of the preferred content is 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the composition of the present invention.

進而，通式(N-1-5)所表示之化合物較佳為自式(N-1-5.1)至式(N-1-5.6)所表示之化合物群中選擇之化合物，較佳為式(N -1-3.2)及式(N-1-3.4)所表示之化合物。 Further, the compound represented by the formula (N-1-5) is preferably a compound selected from the group consisting of compounds represented by the formula (N-1-5.1) to the formula (N-1-5.6), preferably a formula (N -1-3.2) and a compound represented by the formula (N-1-3.4).

式(N-1-3.2)及式(N-1-3.4)所表示之化合物可單獨使用，亦可組合使用，相對於本發明之組成物之總量之單獨或該等化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、8%、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、33%、30%、28%、25%、23%、20%、18%、15%、13%。 The compounds represented by the formula (N-1-3.2) and the formula (N-1-3.4) may be used singly or in combination, and the total amount of the composition or the preferred amount of the compounds relative to the total amount of the composition of the present invention. The lower limit is 5% by mass (hereinafter, mass % is abbreviated as %), 8%, 10%, 13%, 15%, 17%, and 20%. The upper limit of the preferred content is 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the composition of the present invention.

通式(N-1-10)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-10) is the following compound.

(式中，RN1101及RN1102分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (wherein R N1101 and R N1102 each independently represent the same meaning as R N11 and R N12 in the formula (N-1))

RN1101較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，且較佳為乙基、丙基或丁基。RN1102較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基，且較佳為乙氧基、丙氧基或丁氧基。 R N1101 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R N1102 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group. base.

通式(N-1-10)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (N-1-10) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於重視△ε之改善之情形時，較佳為將含量設定為較高，於重視低溫下之溶解性之情形時，若將含量設定為較多，則效果較高，於重視TNI之情形時，若將含量設定為較多，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 When the improvement of Δε is emphasized, it is preferable to set the content to be high, and when the solubility in low temperature is emphasized, if the content is set to be large, the effect is high, and the case of paying attention to T NI is emphasized. When the content is set to be large, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

相對於本發明之組成物之總量之式(N-1-10)所表示之化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、30%、28%、25%、23%、20%、18%、15%、13%。 The lower limit of the preferred content of the compound represented by the formula (N-1-10) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass % is abbreviated as %), 10%, 13% , 15%, 17%, 20%. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the composition of the present invention.

進而，通式(N-1-10)所表示之化合物較佳為自式(N-1-10.1)至式(N-1-10.11)所表示之化合物群中選擇之化合物，較佳為式(N-1-10.1)~(N-1-10.5)所表示之化合物，較佳為式(N-1-10.1)及式(N-1-10.2)所表示之化合物。 Further, the compound represented by the formula (N-1-10) is preferably a compound selected from the group consisting of compounds represented by the formula (N-1-10.1) to the formula (N-1-10.11), preferably a formula The compound represented by (N-1-10.1) to (N-1-10.5) is preferably a compound represented by the formula (N-1-10.1) and the formula (N-1-10.2).

式(N-1-10.1)及式(N-1-10.2)所表示之化合物可單獨使用，亦可組合使用，相對於本發明之組成物之總量之單獨或該等化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、30%、28%、25%、23%、20%、18%、15%、13%。 The compounds represented by the formula (N-1-10.1) and the formula (N-1-10.2) may be used singly or in combination, and the total amount of the composition or the preferred amount of the compounds relative to the total amount of the composition of the present invention. The lower limit is 5% by mass (hereinafter, mass % is abbreviated as %), 10%, 13%, 15%, 17%, and 20%. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the composition of the present invention.

通式(N-1-11)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-11) is the following compound.

(式中，RN1111及RN1112分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (wherein R N1111 and R N1112 each independently represent the same meaning as R N11 and R N12 in the formula (N-1))

RN1111較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，且較佳為乙基、丙基或丁基。RN1112較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基，且較佳為乙氧基、丙氧基或丁氧基。 R N1111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R N1112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group. base.

通式(N-1-11)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (N-1-11) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於重視△ε之改善之情形時，較佳為將含量設定為較高，於重視低溫下之溶解性之情形時，若將含量設定為較多，則效果較高，於重視TNI之情形時，若將含量設定為較多，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 When the improvement of Δε is emphasized, it is preferable to set the content to be high, and when the solubility in low temperature is emphasized, if the content is set to be large, the effect is high, and the case of paying attention to T NI is emphasized. When the content is set to be large, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

相對於本發明之組成物之總量之式(N-1-11)所表示之化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、30%、28%、25%、23%、20%、18%、15%、13%。 The lower limit of the preferred content of the compound represented by the formula (N-1-11) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass % is abbreviated as %), 10%, 13% , 15%, 17%, 20%. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the composition of the present invention.

進而，通式(N-1-11)所表示之化合物較佳為自式(N-1-11.1)至式(N-1-11.15)所表示之化合物群中選擇之化合物，較佳為式(N-1-11.1)~(N-1-11.15)所表示之化合物，較佳為式(N-1-11.2)及式(N-1-11.4)所表示之化合物。 Further, the compound represented by the formula (N-1-11) is preferably a compound selected from the group consisting of compounds represented by the formula (N-1-11.1) to the formula (N-1-11.15), preferably a formula The compound represented by (N-1-11.1) to (N-1-11.15) is preferably a compound represented by the formula (N-1-11.2) and the formula (N-1-11.4).

式(N-1-11.2)及式(N-1-11.4)所表示之化合物可單獨使用，亦可組合使用，相對於本發明之組成物之總量之單獨或該等化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、30%、28%、25%、23%、20%、18%、15%、13%。 The compounds represented by the formula (N-1-11.2) and the formula (N-1-11.4) may be used singly or in combination, and the total amount of the composition or the preferred amount of the compounds relative to the total amount of the composition of the present invention. The lower limit is 5% by mass (hereinafter, mass % is abbreviated as %), 10%, 13%, 15%, 17%, and 20%. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the composition of the present invention.

通式(N-1-12)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-12) is the following compound.

(式中，RN1121及RN1122分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (wherein R N1121 and R N1122 each independently represent the same meaning as R N11 and R N12 in the formula (N-1))

RN1121較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，且較佳為乙基、丙基或丁基。RN1122較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基，且較佳為乙氧基、丙氧基或丁氧基。 R N1121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R N1122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group. base.

通式(N-1-12)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (N-1-12) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於重視△ε之改善之情形時，較佳為將含量設定為較高，於重視低溫下之溶解性之情形時，若將含量設定為較多，則效果較高，於重視TNI之情形時，若將含量設定為較多，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 When the improvement of Δε is emphasized, it is preferable to set the content to be high, and when the solubility in low temperature is emphasized, if the content is set to be large, the effect is high, and the case of paying attention to T NI is emphasized. When the content is set to be large, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

相對於本發明之組成物之總量之式(N-1-12)所表示之化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、30%、28%、25%、23%、20%、18%、15%、13%。 The lower limit of the preferred content of the compound represented by the formula (N-1-12) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass % is abbreviated as %), 10%, 13% , 15%, 17%, 20%. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the composition of the present invention.

通式(N-1-13)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-13) is the following compound.

(式中，RN1131及RN1132分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (Wherein, R N1131 and R N1132 each independently represent the same meaning as in the general formula (N-1) in the R N11 and R N12)

RN1131較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，且較佳為乙基、丙基或丁基。RN1132較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基，且較佳為乙氧基、丙氧基或丁氧基。 R N1131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R N1132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group. base.

通式(N-1-13)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (N-1-13) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於重視△ε之改善之情形時，較佳為將含量設定為較高，於重視低溫下之溶解性之情形時，若將含量設定為較多，則效果較高，於重視TNI之情形時，若將含量設定為較多，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 When the improvement of Δε is emphasized, it is preferable to set the content to be high, and when the solubility in low temperature is emphasized, if the content is set to be large, the effect is high, and the case of paying attention to T NI is emphasized. When the content is set to be large, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

相對於本發明之組成物之總量之式(N-1-13)所表示之化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、30%、28%、25%、23%、20%、18%、15%、13%。 The lower limit of the preferred content of the compound represented by the formula (N-1-13) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass % is abbreviated as %), 10%, 13% , 15%, 17%, 20%. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the composition of the present invention.

通式(N-1-14)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-14) is the following compound.

(式中，RN1141及RN1142分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (wherein R N1141 and R N1142 each independently represent the same meaning as R N11 and R N12 in the formula (N-1))

RN1141較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，且較佳為乙基、丙基或丁基。RN1142較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基，且較佳為乙氧基、丙氧基或丁氧基。 R N1141 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R N1142 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group. base.

通式(N-1-14)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (N-1-14) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於重視△ε之改善之情形時，較佳為將含量設定為較高，於重視低溫下之溶解性之情形時，若將含量設定為較多，則效果較高，於重視TNI之情形時，若將含量設定為較多，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 When the improvement of Δε is emphasized, it is preferable to set the content to be high, and when the solubility in low temperature is emphasized, if the content is set to be large, the effect is high, and the case of paying attention to T NI is emphasized. When the content is set to be large, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

相對於本發明之組成物之總量之式(N-1-14)所表示之化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、30%、28%、25%、23%、20%、18%、15%、13%。 The lower limit of the preferred content of the compound represented by the formula (N-1-14) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass % is abbreviated as %), 10%, 13% , 15%, 17%, 20%. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the composition of the present invention.

通式(N-1-15)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-15) is the following compound.

(式中，RN1151及RN1152分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (wherein R N1151 and R N1152 each independently represent the same meaning as R N11 and R N12 in the formula (N-1))

RN1151較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，且較佳為乙基、丙基或丁基。RN1152較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基，且較佳為乙氧基、丙氧基或丁氧基。 R N1151 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R N1152 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group. base.

通式(N-1-15)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (N-1-15) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於重視△ε之改善之情形時，較佳為將含量設定為較高，於重視低溫下之溶解性之情形時，若將含量設定為較多，則效果較高，於重視TNI之情形時，若將含量設定為較多，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 When the improvement of Δε is emphasized, it is preferable to set the content to be high, and when the solubility in low temperature is emphasized, if the content is set to be large, the effect is high, and the case of paying attention to T NI is emphasized. When the content is set to be large, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

相對於本發明之組成物之總量之式(N-1-15)所表示之化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、30%、28%、25%、23%、20%、18%、15%、13%。 The lower limit of the preferred content of the compound represented by the formula (N-1-15) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass % is abbreviated as %), 10%, 13% , 15%, 17%, 20%. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the composition of the present invention.

通式(N-1-16)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-16) is the following compound.

(式中，RN1161及RN1162分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (wherein R N1161 and R N1162 each independently represent the same meaning as R N11 and R N12 in the formula (N-1))

RN1161較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，且較佳為乙基、丙基或丁基。RN1162較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基，且較佳為乙氧基、丙氧基或丁氧基。 R N1161 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R N1162 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group. base.

通式(N-1-16)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (N-1-16) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於重視△ε之改善之情形時，較佳為將含量設定為較高，於重視低溫下之溶解性之情形時，若將含量設定為較多，則效果較高，於重視TNI之情形時，若將含量設定為較多，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 When the improvement of Δε is emphasized, it is preferable to set the content to be high, and when the solubility in low temperature is emphasized, if the content is set to be large, the effect is high, and the case of paying attention to T NI is emphasized. When the content is set to be large, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

相對於本發明之組成物之總量之式(N-1-16)所表示之化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、30%、28%、25%、23%、20%、18%、15%、13%。 The lower limit of the preferred content of the compound represented by the formula (N-1-16) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass % is abbreviated as %), 10%, 13% , 15%, 17%, 20%. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the composition of the present invention.

通式(N-1-17)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-17) is the following compound.

(式中，RN1171及RN1172分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (wherein R N1171 and R N1172 each independently represent the same meaning as R N11 and R N12 in the formula (N-1))

RN1171較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，且較佳為乙基、丙基或丁基。RN1172較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基，且較佳為乙氧基、丙氧基或丁氧基。 R N1171 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R N1172 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group. base.

通式(N-1-17)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (N-1-17) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於重視△ε之改善之情形時，較佳為將含量設定為較高，於重視低溫下之溶解性之情形時，若將含量設定為較多，則效果較高，於重視TNI之情形時，若將含量設定為較多，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 When the improvement of Δε is emphasized, it is preferable to set the content to be high, and when the solubility in low temperature is emphasized, if the content is set to be large, the effect is high, and the case of paying attention to T NI is emphasized. When the content is set to be large, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

相對於本發明之組成物之總量之式(N-1-17)所表示之化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、30%、28%、25%、23%、20%、18%、15%、13%。 The lower limit of the preferred content of the compound represented by the formula (N-1-17) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass % is abbreviated as %), 10%, 13% , 15%, 17%, 20%. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the composition of the present invention.

通式(N-1-18)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-18) is the following compound.

(式中，RN1181及RN1182分別獨立地表示與通式(N)中之RN11及RN12相同之含義) (wherein R N1181 and R N1182 each independently represent the same meaning as R N11 and R N12 in the formula (N))

RN1181較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，且較佳為乙基、丙基或丁基。RN1182較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基，且較佳為乙氧基、丙氧基或丁氧基。 R N1181 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group or a butyl group. R N1182 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group. base.

通式(N-1-18)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (N-1-18) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於重視△ε之改善之情形時，較佳為將含量設定為較高，於重視低溫下之溶解性之情形時，若將含量設定為較多，則效果較高，於重視TNI之情形時，若將含量設定為較多，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 When the improvement of Δε is emphasized, it is preferable to set the content to be high, and when the solubility in low temperature is emphasized, if the content is set to be large, the effect is high, and the case of paying attention to T NI is emphasized. When the content is set to be large, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

相對於本發明之組成物之總量之式(N-1-18)所表示之化合物之較佳含量之下限值為5質量%(以下將質量%簡記為%)、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為35%、30%、28%、25%、23%、20%、18%、15%、13%。 The lower limit of the preferred content of the compound represented by the formula (N-1-18) with respect to the total amount of the composition of the present invention is 5% by mass (hereinafter, mass % is abbreviated as %), 10%, 13% , 15%, 17%, 20%. The upper limit of the preferred content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% with respect to the total amount of the composition of the present invention.

通式(N-1-20)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-20) is the following compound.

(式中，RN1201及RN1202分別獨立地表示與通式(N)中之RN11及RN12相同之含義) (wherein R N1201 and R N1202 each independently represent the same meaning as R N11 and R N12 in the formula (N))

通式(N-1-21)所表示之化合物係下述化合物。 The compound represented by the formula (N-1-21) is the following compound.

(式中，RN1211及RN1212分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (wherein R N1211 and R N1212 each independently represent the same meaning as R N11 and R N12 in the formula (N-1))

通式(N-2)所表示之化合物較佳為自通式(N-2-1)~(N-2-3)所表示之化合物群中選擇之化合物。 The compound represented by the formula (N-2) is preferably a compound selected from the group consisting of compounds represented by the formulae (N-2-1) to (N-2-3).

通式(N-2-1)所表示之化合物係下述化合物。 The compound represented by the formula (N-2-1) is the following compound.

(式中，RN211及RN212分別獨立地表示與通式(N-2)中之RN21及RN22相同之含義) (wherein R N211 and R N212 each independently represent the same meaning as R N21 and R N22 in the formula (N-2))

通式(N-2-2)所表示之化合物係下述化合物。 The compound represented by the formula (N-2-2) is the following compound.

(式中，RN221及RN222分別獨立地表示與通式(N-2)中之RN21及RN22相同之含義) (wherein R N221 and R N222 each independently represent the same meaning as R N21 and R N22 in the formula (N-2))

通式(N-2-3)所表示之化合物係下述化合物。 The compound represented by the formula (N-2-3) is the following compound.

(式中，RN231及RN232分別獨立地表示與通式(N-3)中之RN31及RN32相同之含義) (wherein R N231 and R N232 each independently represent the same meaning as R N31 and R N32 in the formula (N-3))

通式(N-3)所表示之化合物較佳為自通式(N-3-1)~(N-3-2)所表示之化合物群中選擇之化合物。 The compound represented by the formula (N-3) is preferably a compound selected from the group consisting of compounds represented by the formulae (N-3-1) to (N-3-2).

通式(N-3-1)所表示之化合物係下述化合物。 The compound represented by the formula (N-3-1) is the following compound.

(式中，RN311及RN312分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (wherein R N311 and R N312 each independently represent the same meaning as R N11 and R N12 in the formula (N-1))

通式(N-3-2)所表示之化合物係下述化合物。 The compound represented by the formula (N-3-2) is the following compound.

(式中，RN321及RN322分別獨立地表示與通式(N-1)中之RN11及RN12相同之含義) (wherein R N321 and R N322 each independently represent the same meaning as R N11 and R N12 in the formula (N-1))

相對於本發明之組成物之總量(液晶組成物中所含之液晶化合物之總量)之通式(N-1)、通式(N-2)、及通式(N-3)所表示之化合物之含量之總量較佳為10~90質量%，進而較佳為20~80質量%，進而較佳為20~70質量%，進而較佳為20~60質量%，進而較佳為20~55質量%，進而較佳為25~55質量%，尤佳為30~55質量%。 The general formula (N-1), the general formula (N-2), and the general formula (N-3) with respect to the total amount of the composition of the present invention (the total amount of the liquid crystal compound contained in the liquid crystal composition) The total amount of the compound represented by the compound is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, still more preferably from 20 to 70% by mass, still more preferably from 20 to 60% by mass, and further preferably from 20 to 60% by mass. It is 20 to 55 mass%, more preferably 25 to 55 mass%, and particularly preferably 30 to 55 mass%.

更具體而言，通式(N-1)、通式(N-2)、及通式(N-3)所表示之化合物之含量之總量於組成物中，作為下限值，較佳為含有1質量%(以下將質量%簡記為%)以上，較佳為含有5%以上，較佳為含有10%以上，較佳為含有13%以上，較佳為含有15%以上，較佳為含有18%以上，較佳為含有20%以上，較佳為含有23%以上，較佳為含有25%以上，較佳為含有28%以上，較佳為含有30%以上，較佳為含有33%以上，較佳為含有35%以上，較佳為含有38%以上，較佳為含有40%以上。又，作為上限值，較佳為含有95%以下，較佳為含有90%以下，較佳為含有88%以下，較佳為含有85%以下，較佳為含有83%以下，較佳為含有80%以下，較佳為含有78%以下，較佳為含有75%以下，較佳為含有73%以下，較佳為含有70%以下，較佳為含有68%以下，較佳為含有65%以下，較佳為含有63%以下，較佳為含有60%以下，較佳為含有55%以下，較佳為含有50%以下，較佳為含有40%以下。 More specifically, the total amount of the compounds represented by the general formula (N-1), the general formula (N-2), and the general formula (N-3) is preferably the lower limit of the composition. The content is 1% by mass or less (hereinafter, the mass % is abbreviated as %) or more, preferably 5% or more, preferably 10% or more, preferably 13% or more, and more preferably 15% or more. It is contained in an amount of 18% or more, preferably 20% or more, preferably 23% or more, preferably 25% or more, preferably 28% or more, preferably 30% or more, preferably containing 33% or more, preferably 35% or more, preferably 38% or more, preferably 40% or more. Further, the upper limit is preferably 95% or less, preferably 90% or less, more preferably 88% or less, more preferably 85% or less, still more preferably 83% or less, and more preferably 80% or less, preferably 78% or less, preferably 75% or less, preferably 73% or less, preferably 70% or less, preferably 68% or less, preferably 65 or more. % or less is preferably 63% or less, preferably 60% or less, preferably 55% or less, preferably 50% or less, and more preferably 40% or less.

本發明中之液晶組成物較佳為含有一種或兩種以上之通式(L)所表示之化合物。通式(L)所表示之化合物相當於介電性大致中性之化合物(△ε之值為-2~2)。 The liquid crystal composition in the present invention preferably contains one or two or more compounds represented by the formula (L). The compound represented by the formula (L) corresponds to a compound having a substantially dielectric property (the value of Δε is -2 to 2).

(式中，RL1及RL2分別獨立地表示碳原子數1~8之烷基，該烷基中之一個或非鄰接之兩個以上之-CH2-可分別獨立地被取代為-CH=CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-，nL1表示0、1、2或3，AL1、AL2及AL3分別獨立地表示選自由(a)1,4-伸環己基(存在於該基中之一個-CH2-或未鄰接之兩個以上之-CH2-可被取代為-O-)、(b)1,4-伸苯基(存在於該基中之一個-CH=或未鄰接之兩個以上之-CH=可被取代為-N=)、及(c)萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基或十氫萘-2,6-二基(存在於萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基中之一個-CH=或未鄰接之兩個以上之-CH=可被取代為-N=) (wherein R L1 and R L2 each independently represent an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two or more non-contiguous -CH 2 - may be independently substituted with -CH =CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, n L1 represents 0, 1, 2 or 3, and A L1 , A L2 and A L3 are independently selected Free (a) 1,4-cyclohexylene (one present in the group -CH 2 - or two or more non-contiguous -CH 2 - may be substituted with -O-), (b) 1,4 - a phenyl group (one present in the group -CH= or two or more adjacent to -CH= may be substituted with -N=), and (c) naphthalene-2,6-diyl, 1, 2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (present in naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene) One of -2,6-diyl-CH= or two or more non-contiguous -CH= can be replaced by -N=)

所組成之群中之基，上述基(a)、基(b)及基(c)可分別獨立地經氰基、氟原子或氯原子取代，ZL1及ZL2分別獨立地表示單鍵、-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-、-CH=N-N=CH-、-CH=CH-、-CF=CF-或-C≡C-，於nL1為2或3而存在多個AL2之情形時，該等可相同，亦可不同，於nL1為2或3而存在多個ZL3之情形時，該等可相同，亦可不同，但不包括通式(N-1)、通式(N-2)及通式(N-3)所表示之化合物) The group (a), the group (b) and the group (c) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, and Z L1 and Z L2 each independently represent a single bond, -CH 2 CH 2 -, -(CH 2 ) 4 -, -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -OCF 2 -, -CF 2 O-, -CH=NN= CH-, -CH=CH-, -CF=CF- or -C≡C-, when n L1 is 2 or 3 and there are multiple A L2 , the same or different, in n L1 When there are a plurality of Z L3 in the case of 2 or 3, the same may be the same or different, but the general formula (N-1), the general formula (N-2) and the general formula (N-3) are not included. Compound represented)

通式(L)所表示之化合物可單獨使用，亦可組合使用。可組合之化合物之種類並無特別限制，係根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所需之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種。或於本發明之另一實施形態中為兩種、三種、四種、五種、六種、七種、八種、九種、十種以上。 The compounds represented by the formula (L) may be used singly or in combination. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one embodiment of the present invention. Or in another embodiment of the present invention, there are two, three, four, five, six, seven, eight, nine, ten or more.

於本發明之組成物中，通式(L)所表示之化合物之含量必須根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率、製程相容性、滴加痕、殘像、介電各向導性等所要求之性能進行適當調整。 In the composition of the present invention, the content of the compound represented by the formula (L) must be based on solubility at low temperature, transfer temperature, electrical reliability, birefringence, process compatibility, dropping marks, afterimage The performance required for dielectric guidance, etc., is appropriately adjusted.

相對於本發明之液晶組成物之總量之式(L)所表示之化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、10%、20%、30%、40%、50%、55%、60%、65%、70%、75%、80%。較佳含量之上限值為95%、85%、75%、65%、55%、45%、35%、25%。 The lower limit of the preferred content of the compound represented by the formula (L) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass % is abbreviated as %), 10%, 20%, 30%. 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%.

於將本發明之組成物之黏度保持為較低、需要應答速度較快之組成物之情形時，較佳為上述下限值較高，且上限值較高。進而，於將本發明之組成物之Tni保持為較高、需要溫度穩定性良好之組成物之情形時，較佳為上述下限值較高，且上限值較高。又，於為了將驅動電壓保持為較低而欲增大介電各向導性時，較佳為降低上述下限值，且上限值較低。 In the case where the viscosity of the composition of the present invention is kept low and a composition having a fast response speed is required, it is preferred that the lower limit value is higher and the upper limit value is higher. Further, in the case where the composition of the present invention has a high T ni and a composition requiring good temperature stability, the lower limit value is preferably higher and the upper limit value is higher. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable to lower the above lower limit value and to lower the upper limit value.

於重視可靠性之情形時，較佳為RL1及RL2均為烷基，於重視降低化合物之揮發性之情形時，較佳為烷氧基，於重視黏性之降低之情形時，較佳為至少一者為烯基。 In the case where reliability is important, it is preferred that both R L1 and R L2 are alkyl groups. When it is important to reduce the volatility of the compound, it is preferably an alkoxy group, and when the viscosity is lowered, Preferably, at least one of them is an alkenyl group.

RL1及RL2於其所鍵結之環結構為苯基(芳香族)之情形時，較佳為直鏈狀之碳原子數1~5之烷基、直鏈狀之碳原子數1~4之烷氧基及 碳原子數4~5之烯基，於其所鍵結之環結構為環己烷、吡喃及二烷等飽和之環結構之情形時，較佳為直鏈狀之碳原子數1~5之烷基、直鏈狀之碳原子數1~4之烷氧基及直鏈狀之碳原子數2~5之烯基。為了使向列相穩定化，較佳為碳原子及存在之情形時之氧原子之合計為5以下，且較佳為直鏈狀。 When R L1 and R L2 are in the case where the ring structure to which the bond is bonded is a phenyl group (aromatic), it is preferably a linear alkyl group having 1 to 5 carbon atoms and a linear carbon number of 1 to 1 ring. Alkoxy group of 4 and alkenyl group having 4 to 5 carbon atoms, wherein the ring structure to which the bond is bonded is cyclohexane, pyran and In the case of a saturated ring structure such as an alkane, a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear carbon atom number 2 are preferred. ~5 alkenyl. In order to stabilize the nematic phase, it is preferred that the total number of carbon atoms and oxygen atoms in the case of being present is 5 or less, and is preferably linear.

作為烯基，較佳為自式(R1)至式(R5)之任一者所表示之基中選擇。(各式中之黑點表示環結構中之碳原子) The alkenyl group is preferably selected from the group represented by any one of the formulae (R1) to (R5). (black dots in various formulas represent carbon atoms in the ring structure)

於重視應答速度之情形時，nL1較佳為0，為了改善向列相之上限溫度，較佳為2或3，為了取得該等之平衡，較佳為1。又，為了滿足作為組成物而要求之特性，較佳為組合不同之值之化合物。 In the case where the response speed is important, n L1 is preferably 0, and in order to improve the upper limit temperature of the nematic phase, it is preferably 2 or 3. In order to achieve the balance, it is preferably 1. Further, in order to satisfy the characteristics required as a composition, it is preferred to combine compounds having different values.

AL1、AL2及AL3於謀求增大△n之情形時，較佳為芳香族，為了改善應答速度，較佳為脂肪族，該等分別獨立，較佳為表示反-1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、3-氟-1,4-伸苯基、3,5-二氟-1,4-伸苯基、1,4-伸環己烯基、1,4-雙環[2.2.2]伸辛基、哌啶-1,4-二基、萘-2,6-二基、十氫萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基，更佳為表示下述結構， A L1 , A L2 and A L3 are preferably aromatic when it is desired to increase Δn, and are preferably aliphatic in order to improve the response speed, and are each independently independent, preferably representing trans-1,4- Cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene , 1,4-cyclohexene, 1,4-bicyclo[2.2.2]exenyl, piperidin-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2, 6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, more preferably represents the following structure,

進而較佳為表示反-1,4-伸環己基或1,4-伸苯基。 Further preferably, it is a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

於重視應答速度之情形時，ZL1及ZL2較佳為單鍵。 When it is important to pay attention to the response speed, Z L1 and Z L2 are preferably single bonds.

通式(L)所表示之化合物較佳為自通式(L-1)~(L-7)所表示之化合物群中選擇之化合物。 The compound represented by the formula (L) is preferably a compound selected from the group consisting of compounds represented by the formulae (L-1) to (L-7).

通式(L-1)所表示之化合物係下述化合物。 The compound represented by the formula (L-1) is the following compound.

(式中，RL11及RL12分別獨立地表示與通式(L)中之RL1及RL2相同之含義) (wherein R L11 and R L12 each independently represent the same meaning as R L1 and R L2 in the general formula (L))

RL11及RL12較佳為直鏈狀之碳原子數1~5之烷基、直鏈狀之碳原子數1~4之烷氧基及直鏈狀之碳原子數2~5之烯基。 R L11 and R L12 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

通式(L-1)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (L-1) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

較佳含量之下限值相對於本發明之液晶組成物之總量，為1質量%(以下將質量%簡記為%)、2%、3%、5%、7%、10%、15%、20%、25%、30%、35%、40%、45%、50%、55%。較佳含量之上限值相對於本發明之組成物之總量，為95%、90%、85%、80%、75%、70%、65%、60%、55%、50%、45%、40%、35%、30%、25%。 The lower limit of the preferred content is 1% by mass (hereinafter abbreviated as % by mass), 2%, 3%, 5%, 7%, 10%, 15% with respect to the total amount of the liquid crystal composition of the present invention. 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%. The upper limit of the preferred content is 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45 with respect to the total amount of the composition of the present invention. %, 40%, 35%, 30%, 25%.

於將本發明之組成物之黏度保持為較低、需要應答速度較快 之組成物之情形時，較佳為上述下限值較高，且上限值較高。進而，於將本發明之組成物之Tni保持為較高、需要溫度穩定性良好之組成物之情形時，較佳為上述下限值適中，且上限值適中。又，於為了將驅動電壓保持為較低而欲增大介電各向導性時，較佳為上述下限值較低，且上限值較低。 In the case where the viscosity of the composition of the present invention is kept low and a composition having a fast response speed is required, it is preferred that the lower limit value is higher and the upper limit value is higher. Further, in the case where the composition of the present invention has a high T ni and a composition requiring good temperature stability, the lower limit is preferably moderate and the upper limit is moderate. Further, in order to increase the dielectric specificity in order to keep the driving voltage low, it is preferable that the lower limit value is low and the upper limit value is low.

通式(L-1)所表示之化合物較佳為自通式(L-1-1)所表示之化合物群中選擇之化合物。 The compound represented by the formula (L-1) is preferably a compound selected from the group of compounds represented by the formula (L-1-1).

(式中RL12表示與通式(L-1)中之含義相同之含義) (wherein R L12 represents the same meaning as in the formula (L-1))

通式(L-1-1)所表示之化合物較佳為自式(L-1-1.1)至式(L-1-1.3)所表示之化合物群中選擇之化合物，較佳為式(L-1-1.2)或式(L-1-1.3)所表示之化合物，尤佳為式(L-1-1.3)所表示之化合物。 The compound represented by the formula (L-1-1) is preferably a compound selected from the group consisting of compounds represented by the formula (L-1-1.1) to the formula (L-1-1.3), preferably a formula (L). The compound represented by the formula (L-1-1.3) is preferably a compound represented by the formula (L-1-1.3).

相對於本發明之液晶組成物之總量之式(L-1-1.3)所表示之化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、2%、3%、5%、7%、10%。較佳含量之上限值相對於本發明之組成物之總量，為20%、15%、13%、10%、8%、7%、6%、5%、3%。 The lower limit of the preferred content of the compound represented by the formula (L-1-1.3) of the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass % is abbreviated as %), 2%, 3 %, 5%, 7%, 10%. The upper limit of the preferred content is 20%, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3% with respect to the total amount of the composition of the present invention.

通式(L-1)所表示之化合物較佳為自通式(L-1-2)所表示之化合物群中選擇之化合物。 The compound represented by the formula (L-1) is preferably a compound selected from the group of compounds represented by the formula (L-1-2).

(式中RL12表示與通式(L-1)中之含義相同之含義) (wherein R L12 represents the same meaning as in the formula (L-1))

相對於本發明之液晶組成物之總量之式(L-1-2)所表示之化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、5%、10%、15%、17%、20%、23%、25%、27%、30%、35%。較佳含量之上限值相對於本發明之組成物之總量，為60%、55%、50%、45%、42%、40%、38%、35%、33%、30%。 The lower limit of the preferred content of the compound represented by the formula (L-1-2) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass % is abbreviated as %), 5%, 10 %, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 35%. The upper limit of the preferred content is 60%, 55%, 50%, 45%, 42%, 40%, 38%, 35%, 33%, 30% with respect to the total amount of the composition of the present invention.

進而，通式(L-1-2)所表示之化合物較佳為自式(L-1-2.1)至式(L-1-2.4)所表示之化合物群中選擇之化合物，較佳為式(L-1-2.2)至式(L-1-2.4)所表示之化合物。尤其是式(L-1-2.2)所表示之化合物因尤其改善本發明之組成物之應答速度而較佳。又，於相較於應答速度而要求較高之Tni時，較佳為使用式(L-1-2.3)或式(L-1-2.4)所表示之化合物。為了使低溫下之溶解度良好，將式(L-1-2.3)及式(L-1-2.4)所表示之化合物之含量設為30質量%以上欠佳。 Further, the compound represented by the formula (L-1-2) is preferably a compound selected from the group consisting of compounds represented by the formula (L-1-2.1) to the formula (L-1-2.4), preferably a formula (L-1-2.2) to a compound represented by the formula (L-1-2.4). In particular, the compound represented by the formula (L-1-2.2) is preferred because it particularly improves the response speed of the composition of the present invention. Further, when T Ni is required to be higher than the response speed, it is preferred to use a compound represented by the formula (L-1-2.3) or the formula (L-1-2.4). In order to improve the solubility at a low temperature, the content of the compound represented by the formula (L-1-2.3) and the formula (L-1-2.4) is preferably 30% by mass or less.

相對於本發明之液晶組成物之總量之式(L-1-2.2)所表示之化合物之較佳含量之下限值為10質量%(以下將質量%簡記為%)、15%、18%、20%、23%、25%、27%、30%、33%、35%、38%、40%。較佳含量之上限值相對於本發明之組成物之總量，為60%、55%、50%、45%、43%、40%、38%、35%、32%、30%、27%、25%、22%。 The lower limit of the preferred content of the compound represented by the formula (L-1-2.2) of the total amount of the liquid crystal composition of the present invention is 10% by mass (hereinafter, the mass % is abbreviated as %), 15%, 18 %, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 38%, 40%. The upper limit of the preferred content is 60%, 55%, 50%, 45%, 43%, 40%, 38%, 35%, 32%, 30%, 27 with respect to the total amount of the composition of the present invention. %, 25%, 22%.

相對於本發明之液晶組成物之總量之式(L-1-1.3)所表示之化合物及式(L-1-2.2)所表示之化合物之合計之較佳含量之下限值為10質量%(以下將質量%簡記為%)、15%、20%、25%、27%、30%、35%、40%。較佳含量之上限值相對於本發明之組成物之總量，為60%、55%、50%、45%、43%、40%、38%、35%、32%、30%、27%、25%、22%。 The lower limit of the total content of the compound represented by the formula (L-1-1.3) and the compound represented by the formula (L-1-2.2) with respect to the total amount of the liquid crystal composition of the present invention is 10 mass. % (hereinafter, mass % is abbreviated as %), 15%, 20%, 25%, 27%, 30%, 35%, and 40%. The upper limit of the preferred content is 60%, 55%, 50%, 45%, 43%, 40%, 38%, 35%, 32%, 30%, 27 with respect to the total amount of the composition of the present invention. %, 25%, 22%.

通式(L-1)所表示之化合物較佳為自通式(L-1-3)所表示之化合物群中選擇之化合物。 The compound represented by the formula (L-1) is preferably a compound selected from the group of compounds represented by the formula (L-1-3).

(式中RL13及RL14分別獨立地表示碳原子數1~8之烷基或碳原子數1~8之烷氧基) (wherein R L13 and R L14 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms)

RL13及RL14較佳為直鏈狀之碳原子數1~5之烷基、直鏈狀之碳原子數1~4之烷氧基及直鏈狀之碳原子數2~5之烯基。 R L13 and R L14 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

相對於本發明之液晶組成物之總量之式(L-1-3)所表示之化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、5%、10%、13%、15%、17%、20%、23%、25%、30%。較佳含量之上限值相對於本發明之組成物之總量，為60%、55%、50%、45%、40%、37%、35%、33%、30%、27%、25%、23%、20%、17%、15%、13%、10%。 The lower limit of the preferred content of the compound represented by the formula (L-1-3) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass % is abbreviated as %), 5%, 10 %, 13%, 15%, 17%, 20%, 23%, 25%, 30%. The upper limit of the preferred content is 60%, 55%, 50%, 45%, 40%, 37%, 35%, 33%, 30%, 27%, 25 with respect to the total amount of the composition of the present invention. %, 23%, 20%, 17%, 15%, 13%, 10%.

進而，通式(L-1-3)所表示之化合物較佳為自式(L-1-3.1)至式(L-1-3.12)所表示之化合物群中選擇之化合物，較佳為式(L-1-3.1)、式(L-1-3.3)或式(L-1-3.4)所表示之化合物。尤其是式(L-1-3.1)所表示之化合物因尤其改善本發明之組成物之應答速度而較佳。又，於相較於應答速度而要求較高之Tni時，較佳為使用式(L-1-3.3)、式(L-1-3.4)、式(L-1-3.11)及式(L-1-3.12)所表示之化合物。為了使低溫下之溶解度良好，將式(L-1-3.3)、式(L-1-3.4)、式(L-1-3.11)及式(L-1-3.12)所表示之化合物之合計之含量設為20質量%以上欠佳。 Further, the compound represented by the formula (L-1-3) is preferably a compound selected from the group consisting of the compounds represented by the formula (L-1-3.1) to the formula (L-1-3.12), preferably a formula (L-1-3.1), a compound represented by the formula (L-1-3.3) or the formula (L-1-3.4). In particular, the compound represented by the formula (L-1-3.1) is preferred because it particularly improves the response speed of the composition of the present invention. Further, when T Ni is required to be higher than the response speed, it is preferred to use the formula (L-1-3.3), the formula (L-1-3.4), the formula (L-1-3.11), and the formula (L). The compound represented by L-1-3.12). In order to improve the solubility at a low temperature, the total of the compounds represented by the formula (L-1-3.3), the formula (L-1-3.4), the formula (L-1-3.11), and the formula (L-1-3.12) The content is set to be 20% by mass or less.

相對於本發明之液晶組成物之總量之式(L-1-3.1)所表示之化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、2%、3%、5%、7%、10%、13%、15%、18%、20%。較佳含量之上限值相對於本發明之組成物之總量，為20%、17%、15%、13%、10%、8%、7%、6%。 The lower limit of the preferred content of the compound represented by the formula (L-1-3.1) of the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass % is abbreviated as %), 2%, 3 %, 5%, 7%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 20%, 17%, 15%, 13%, 10%, 8%, 7%, 6% with respect to the total amount of the composition of the present invention.

通式(L-1)所表示之化合物較佳為自通式(L-1-4)及/或(L-1-5)所表示之化合物群中選擇之化合物。 The compound represented by the formula (L-1) is preferably a compound selected from the group consisting of compounds represented by the formula (L-1-4) and/or (L-1-5).

(式中RL15及RL16分別獨立地表示碳原子數1~8之烷基或碳原子數1~8之烷氧基) (wherein R L15 and R L16 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms)

RL15及RL16較佳為直鏈狀之碳原子數1~5之烷基、直鏈狀之碳原子數1~4之烷氧基及直鏈狀之碳原子數2~5之烯基。 R L15 and R L16 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

相對於本發明之液晶組成物之總量之式(L-1-4)所表示 之化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、5%、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為25%、23%、20%、17%、15%、13%、10%。 Represented by the formula (L-1-4) of the total amount of the liquid crystal composition of the present invention The lower limit of the preferred content of the compound is 1% by mass (hereinafter, the mass % is abbreviated as %), 5%, 10%, 13%, 15%, 17%, and 20%. The upper limit of the preferred content is 25%, 23%, 20%, 17%, 15%, 13%, 10% with respect to the total amount of the composition of the present invention.

相對於本發明之液晶組成物之總量之式(L-1-5)所表示之化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、5%、10%、13%、15%、17%、20%。較佳含量之上限值相對於本發明之組成物之總量，為25%、23%、20%、17%、15%、13%、10%。 The lower limit of the preferred content of the compound represented by the formula (L-1-5) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass % is abbreviated as %), 5%, 10 %, 13%, 15%, 17%, 20%. The upper limit of the preferred content is 25%, 23%, 20%, 17%, 15%, 13%, 10% with respect to the total amount of the composition of the present invention.

進而，通式(L-1-4)及(L-1-5)所表示之化合物較佳為自式(L-1-4.1)至式(L-1-5.3)所表示之化合物群中選擇之化合物，較佳為式(L-1-4.2)或式(L-1-5.2)所表示之化合物。 Further, the compounds represented by the formulae (L-1-4) and (L-1-5) are preferably from the group of compounds represented by the formula (L-1-4.1) to the formula (L-1-5.3). The compound selected is preferably a compound represented by the formula (L-1-4.2) or the formula (L-1-5.2).

相對於本發明之液晶組成物之總量之式(L-1-4.2)所表示之化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、2%、3%、5%、7%、10%、13%、15%、18%、20%。較佳含量之上限值相對於本發明之組成物之總量，為20%、17%、15%、13%、10%、8%、7%、6%。 The lower limit of the preferred content of the compound represented by the formula (L-1-4.2) of the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass % is abbreviated as %), 2%, 3 %, 5%, 7%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferred content is 20%, 17%, 15%, 13%, 10%, 8%, 7%, 6% with respect to the total amount of the composition of the present invention.

較佳為組合自式(L-1-1.3)、式(L-1-2.2)、式(L-1-3.1)、式(L-1-3.3)、式(L-1-3.4)、式(L-1-3.11)及式(L-1-3.12)所表示之化合物中選擇之兩種以上之化合物，較佳為組合自式(L-1-1.3)、式(L-1-2.2)、式(L-1-3.1)、式(L-1-3.3)、式(L-1-3.4)及式(L-1-4.2)所表示之化合物中選擇之兩種以上之化合物，該等化合物之合計含量之較佳含量之下限值相對於本發明之液晶組成物之總量，為1質量%(以下將質量%簡記為%)、2%、3%、5%、7%、10%、13%、15%、18%、20%、23%、25%、27%、30%、33%、35%，上限值相對於本發明之組成物之總量，為80%、70%、60%、50%、45%、40%、37%、35%、33%、30%、28%、25%、23%、20%。於重視組成物之可靠性之情形時，較佳為組合自式(L-1-3.1)、式(L-1-3.3)及式(L-1-3.4)所表示之化合物中選擇之兩種以上之化合物，於重視組成物之應答速度之情形時，較佳為組合自式(L-1-1.3)、式(L-1-2.2)所表示之化合物中選擇之兩種以上之化合物。 Preferably, it is a combination of the formula (L-1-1.3), the formula (L-1-2.2), the formula (L-1-3.1), the formula (L-1-3.3), the formula (L-1-3.4), Two or more compounds selected from the group consisting of the compounds represented by the formula (L-1-3.11) and the formula (L-1-3.12) are preferably a combination of the formula (L-1-1.3) and the formula (L-1- 2.2) Two or more compounds selected from the compounds represented by the formula (L-1-3.1), the formula (L-1-3.3), the formula (L-1-3.4), and the formula (L-1-4.2) The lower limit of the preferred content of the total content of the compounds is 1% by mass (hereinafter abbreviated as % by mass), 2%, 3%, 5%, and the total amount of the liquid crystal composition of the present invention. 7%, 10%, 13%, 15%, 18%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, the upper limit value relative to the total amount of the composition of the present invention, It is 80%, 70%, 60%, 50%, 45%, 40%, 37%, 35%, 33%, 30%, 28%, 25%, 23%, 20%. When the reliability of the composition is emphasized, it is preferred to combine the two selected from the compounds represented by the formula (L-1-3.1), the formula (L-1-3.3), and the formula (L-1-3.4). When the compound of the above formula is used, it is preferable to combine two or more compounds selected from the compounds represented by the formula (L-1-1.3) and the formula (L-1-2.2). .

通式(L-2)所表示之化合物係下述化合物。 The compound represented by the formula (L-2) is the following compound.

(式中，RL21及RL22分別獨立地表示與通式(L)中之RL1及RL2相同之含義) (wherein R L21 and R L22 each independently represent the same meaning as R L1 and R L2 in the general formula (L))

RL21較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，RL22較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基。 R L21 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R L22 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 to 5 carbon atoms or An alkoxy group having 1 to 4 carbon atoms.

通式(L-1)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (L-1) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於重視低溫下之溶解性之情形時，若將含量設定為較多，則效果較高，相反地，於重視應答速度之情形時，若將含量設定為較少，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 When the solubility in low temperature is emphasized, if the content is set to be large, the effect is high. Conversely, when the response speed is emphasized, if the content is set to be small, the effect is high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

相對於本發明之液晶組成物之總量之式(L-2)所表示之化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、2%、3%、5%、7%、10%。較佳含量之上限值相對於本發明之組成物之總量，為20%、15%、13%、10%、8%、7%、6%、5%、3%。 The lower limit of the preferred content of the compound represented by the formula (L-2) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass % is abbreviated as %), 2%, 3%, 5%, 7%, 10%. The upper limit of the preferred content is 20%, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3% with respect to the total amount of the composition of the present invention.

進而，通式(L-2)所表示之化合物較佳為自式(L-2.1)至式(L-2.6)所表示之化合物群中選擇之化合物，較佳為式(L-2.1)、式(L-2.3)、式(L-2.4)及式(L-2.6)所表示之化合物。 Further, the compound represented by the formula (L-2) is preferably a compound selected from the group consisting of compounds represented by the formula (L-2.1) to the formula (L-2.6), preferably a formula (L-2.1), A compound represented by the formula (L-2.3), the formula (L-2.4) and the formula (L-2.6).

通式(L-3)所表示之化合物係下述化合物。 The compound represented by the formula (L-3) is the following compound.

(式中，RL31及RL32分別獨立地表示與通式(L)中之RL1及RL2相同之含義) (wherein R L31 and R L32 each independently represent the same meaning as R L1 and R L2 in the general formula (L))

RL31及RL32分別獨立，較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基。 R L31 and R L32 are each independently, and are preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

通式(L-3)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (L-3) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

相對於本發明之液晶組成物之總量之式(L-3)所表示之化合物之較佳含量之下限值為1質量%、2%、3%、5%、7%、10%。較佳含 量之上限值相對於本發明之組成物之總量，為20%、15%、13%、10%、8%、7%、6%、5%、3%。 The lower limit of the preferred content of the compound represented by the formula (L-3) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass, 2%, 3%, 5%, 7%, and 10%. Preferred The upper limit of the amount is 20%, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3% with respect to the total amount of the composition of the present invention.

於獲得較高之雙折射率之情形時，若將含量設定為較多，則效果較高，相反地，於重視較高之Tni之情形時，若將含量設定為較少，則效果較高。進而，於改良滴加痕或殘像特性之情形時，較佳為將含量之範圍設定於中間。 In the case of obtaining a higher birefringence, if the content is set to be larger, the effect is higher. Conversely, when the higher T ni is emphasized, if the content is set to be less, the effect is higher. high. Further, in the case of improving the characteristics of the dropping or afterimage, it is preferred to set the range of the content in the middle.

進而，通式(L-3)所表示之化合物較佳為自式(L-3.1)至式(L-3.4)所表示之化合物群中選擇之化合物，較佳為式(L-3.2)至式(L-3.7)所表示之化合物。 Further, the compound represented by the formula (L-3) is preferably a compound selected from the group consisting of compounds represented by the formula (L-3.1) to the formula (L-3.4), preferably a formula (L-3.2) to A compound represented by the formula (L-3.7).

通式(L-4)所表示之化合物係下述化合物。 The compound represented by the formula (L-4) is the following compound.

(式中，RL41及RL42分別獨立地表示與通式(L)中之RL1及RL2相同之含義) (wherein R L41 and R L42 each independently represent the same meaning as R L1 and R L2 in the general formula (L))

RL41較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，RL42較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基。 R L41 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R L42 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 to 5 carbon atoms or An alkoxy group having 1 to 4 carbon atoms.

通式(L-4)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (L-4) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於本發明之組成物中，通式(L-4)所表示之化合物之含量必須根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率、製程相容性、滴加痕、殘像、介電各向導性等所要求之性能進行適當調整。 In the composition of the present invention, the content of the compound represented by the formula (L-4) must be based on solubility at low temperature, transfer temperature, electrical reliability, birefringence, process compatibility, dropping marks, The performance required for the afterimage, dielectric guidance, etc. is appropriately adjusted.

相對於本發明之液晶組成物之總量之式(L-4)所表示之化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、2%、3%、5%、7%、10%、14%、16%、20%、23%、26%、30%、35%、40%。相對於本發明之組成物之總量之式(L-4)所表示之化合物之較佳含量之上限值為50%、40%、35%、30%、20%、15%、10%、5%。 The lower limit of the preferred content of the compound represented by the formula (L-4) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass % is abbreviated as %), 2%, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35%, 40%. The upper limit of the preferred content of the compound represented by the formula (L-4) with respect to the total amount of the composition of the present invention is 50%, 40%, 35%, 30%, 20%, 15%, 10%. 5%.

通式(L-4)所表示之化合物較佳為例如式(L-4.1)至式(L-4.3)所表示之化合物。 The compound represented by the formula (L-4) is preferably a compound represented by the formula (L-4.1) to the formula (L-4.3), for example.

根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能，可含有式(L-4.1)所表示之化合物，亦可含有式(L-4.2)所表示之化合物，亦可含有式(L-4.1)所表示之化合物與式(L-4.2)所表示之化合物之兩者，亦可含有全部之式(L-4.1)至式(L-4.3)所表示之化合物。相對於本發明之組成物之總量之式(L-4.1)或式(L-4.2)所表示之化合物之較佳含量之下限值為3%、5%、7%、9%、11%、12%、13%、18%、21%，較佳之上限值為45、40%、35%、30%、25%、23%、20%、18%、15%、13%、10%、8%。 The compound represented by the formula (L-4.1) may be contained according to the properties required for solubility at low temperature, transfer temperature, electrical reliability, birefringence, etc., and may also contain a compound represented by the formula (L-4.2). Further, it may contain both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2), and may also contain all of the formulas (L-4.1) to (L-4.3). Compound. The lower limit of the preferred content of the compound represented by the formula (L-4.1) or the formula (L-4.2) with respect to the total amount of the composition of the present invention is 3%, 5%, 7%, 9%, and 11 %, 12%, 13%, 18%, 21%, preferably upper limit is 45, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10 %,8%.

於含有式(L-4.1)所表示之化合物與式(L-4.2)所表示之化合物之兩者之情形時，相對於本發明之液晶組成物之總量之兩化合物之較佳含量之下限值為15質量%(以下將質量%簡記為%)、19%、24%、30%，較佳之上限值為45、40%、35%、30%、25%、23%、20%、18%、15%、13%。 In the case where both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2) are contained, the preferred content of the two compounds relative to the total amount of the liquid crystal composition of the present invention is The limit is 15% by mass (hereinafter, the mass % is abbreviated as %), 19%, 24%, 30%, and preferably the upper limit is 45, 40%, 35%, 30%, 25%, 23%, 20%. 18%, 15%, 13%.

通式(L-4)所表示之化合物較佳為例如式(L-4.4)至式(L-4.6)所表示之化合物，較佳為式(L-4.4)所表示之化合物。 The compound represented by the formula (L-4) is preferably a compound represented by the formula (L-4.4) to the formula (L-4.6), and preferably a compound represented by the formula (L-4.4).

根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能，可含有式(L-4.4)所表示之化合物，亦可含有式(L-4.5)所表示之化合物，亦可含有式(L-4.4)所表示之化合物與式(L-4.5)所表示之化合物這兩者。 The compound represented by the formula (L-4.4) may be contained according to the properties required for solubility at a low temperature, transfer temperature, electrical reliability, birefringence, etc., and may also contain a compound represented by the formula (L-4.5). Further, both the compound represented by the formula (L-4.4) and the compound represented by the formula (L-4.5) may be contained.

相對於本發明之液晶組成物之總量之式(L-4.4)或式(L-4.5)所表示之化合物之較佳含量之下限值為3質量%(以下將質量%簡記為%)、5%、7%、9%、11%、12%、13%、18%、21%。較佳之上限值為45、40%、35%、30%、25%、23%、20%、18%、15%、13%、10%、8%。 The lower limit of the preferred content of the compound represented by the formula (L-4.4) or the formula (L-4.5) with respect to the total amount of the liquid crystal composition of the present invention is 3% by mass (hereinafter, the mass % is abbreviated as %) , 5%, 7%, 9%, 11%, 12%, 13%, 18%, 21%. Preferred upper limits are 45, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%.

於含有式(L-4.4)所表示之化合物與式(L-4.5)所表示之化合物之兩者之情形時，相對於本發明之液晶組成物之總量之兩化合物之較佳含量之下限值為15質量%(以下將質量%簡記為%)、19%、24%、30%，較佳之上限值為45、40%、35%、30%、25%、23%、20%、18%、15%、13%。 In the case where both the compound represented by the formula (L-4.4) and the compound represented by the formula (L-4.5) are contained, the preferred content of the two compounds relative to the total amount of the liquid crystal composition of the present invention is The limit is 15% by mass (hereinafter, the mass % is abbreviated as %), 19%, 24%, 30%, and preferably the upper limit is 45, 40%, 35%, 30%, 25%, 23%, 20%. 18%, 15%, 13%.

通式(L-4)所表示之化合物較佳為式(L-4.7)至式(L-4.10)所表示之化合物，尤佳為式(L-4.9)所表示之化合物。 The compound represented by the formula (L-4) is preferably a compound represented by the formula (L-4.7) to the formula (L-4.10), and more preferably a compound represented by the formula (L-4.9).

通式(L-5)所表示之化合物係下述化合物。 The compound represented by the formula (L-5) is the following compound.

(式中，RL51及RL52分別獨立地表示與通式(L)中之RL1及RL2相同之含義) (wherein R L51 and R L52 each independently represent the same meaning as R L1 and R L2 in the general formula (L))

RL51較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，RL52較佳為碳原子數1~5之烷基、碳原子數4~5之烯基或碳原子數1~4之烷氧基。 R L51 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R L52 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 to 5 carbon atoms or An alkoxy group having 1 to 4 carbon atoms.

通式(L-5)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (L-5) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

於本發明之組成物中，通式(L-5)所表示之化合物之含量必須根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率、製程相容性、滴加痕、殘像、介電各向導性等所要求之性能進行適當調整。 In the composition of the present invention, the content of the compound represented by the formula (L-5) must be based on solubility at low temperature, transfer temperature, electrical reliability, birefringence, process compatibility, dropping marks, The performance required for the afterimage, dielectric guidance, etc. is appropriately adjusted.

相對於本發明之液晶組成物之總量之式(L-5)所表示之化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、2%、3%、5%、7%、10%、14%、16%、20%、23%、26%、30%、35%、40%。相對於本發明之組成物之總量之式(L-5)所表示之化合物之較佳含量之上限值為50%、40%、35%、30%、20%、15%、10%、5%。 The lower limit of the preferred content of the compound represented by the formula (L-5) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass % is abbreviated as %), 2%, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35%, 40%. The upper limit of the preferred content of the compound represented by the formula (L-5) with respect to the total amount of the composition of the present invention is 50%, 40%, 35%, 30%, 20%, 15%, 10%. 5%.

通式(L-5)所表示之化合物較佳為式(L-5.1)或式(L-5.2)所表示之化合物，尤佳為式(L-5.1)所表示之化合物。 The compound represented by the formula (L-5) is preferably a compound represented by the formula (L-5.1) or the formula (L-5.2), and more preferably a compound represented by the formula (L-5.1).

相對於本發明之液晶組成物之總量之該等化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、2%、3%、5%、7%。該等化合物之較佳含量之上限值為20%、15%、13%、10%、9%。 The lower limit of the preferred content of the compounds relative to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter referred to as % by mass), 2%, 3%, 5%, and 7%. The upper limit of the preferred content of the compounds is 20%, 15%, 13%, 10%, 9%.

通式(L-5)所表示之化合物較佳為式(L-5.3)或式(L-5.4)所表示之化合物。 The compound represented by the formula (L-5) is preferably a compound represented by the formula (L-5.3) or the formula (L-5.4).

相對於本發明之液晶組成物之總量之該等化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、2%、3%、5%、7%。該等化合物之較佳含量之上限值為20%、15%、13%、10%、9%。 The lower limit of the preferred content of the compounds relative to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter referred to as % by mass), 2%, 3%, 5%, and 7%. The upper limit of the preferred content of the compounds is 20%, 15%, 13%, 10%, 9%.

通式(L-5)所表示之化合物較佳為自式(L-5.5)至式(L -5.7)所表示之化合物群中選擇之化合物，尤佳為式(L-5.7)所表示之化合物。 The compound represented by the formula (L-5) is preferably from the formula (L-5.5) to the formula (L). The compound selected from the group of compounds represented by -5.7) is preferably a compound represented by the formula (L-5.7).

相對於本發明之液晶組成物之總量之該等化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、2%、3%、5%、7%。該等化合物之較佳含量之上限值為20%、15%、13%、10%、9%。 The lower limit of the preferred content of the compounds relative to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter referred to as % by mass), 2%, 3%, 5%, and 7%. The upper limit of the preferred content of the compounds is 20%, 15%, 13%, 10%, 9%.

通式(L-6)所表示之化合物係下述化合物。 The compound represented by the formula (L-6) is the following compound.

(式中，RL61及RL62分別獨立地表示與通式(L)中之RL1及RL2相同之含義，XL61及XL62分別獨立地表示氫原子或氟原子) (wherein R L61 and R L62 each independently represent the same meaning as R L1 and R L2 in the formula (L), and X L61 and X L62 each independently represent a hydrogen atom or a fluorine atom)

RL61及RL62分別獨立，較佳為碳原子數1~5之烷基或碳原子數2~5之烯基，較佳為XL61及XL62中一者為氟原子，另一者為氫原子。 R L61 and R L62 are each independently, preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably one of X L61 and X L62 is a fluorine atom, and the other is A hydrogen atom.

通式(L-6)所表示之化合物可單獨使用，亦可組合兩種以上之化合物而使用。可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能適當組合而使用。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種、五種以上。 The compound represented by the formula (L-6) may be used singly or in combination of two or more kinds of compounds. The type of the compound which can be combined is not particularly limited, and it is suitably used in combination according to the required properties such as solubility at low temperature, transfer temperature, electrical reliability, and birefringence. The type of the compound to be used is, for example, one, two, three, four, or five or more kinds of embodiments of the present invention.

相對於本發明之液晶組成物之總量之式(L-6)所表示之化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、2%、3%、5%、7%、10%、14%、16%、20%、23%、26%、30%、35%、40%。相對於本發明之組成物之總量之式(L-6)所表示之化合物之較佳含量之上限值為50%、40%、35%、30%、20%、15%、10%、5%。於重點在於增大△n之情形時，較佳為增多含量，於重點在於低溫下之析出之情形時，較佳為含量較少。 The lower limit of the preferred content of the compound represented by the formula (L-6) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass % is abbreviated as %), 2%, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35%, 40%. The upper limit of the preferred content of the compound represented by the formula (L-6) with respect to the total amount of the composition of the present invention is 50%, 40%, 35%, 30%, 20%, 15%, 10%. 5%. When the focus is on increasing the Δn, it is preferable to increase the content, and when the emphasis is on the precipitation at a low temperature, the content is preferably small.

通式(L-6)所表示之化合物較佳為式(L-6.1)至式(L-6.9)所表示之化合物。 The compound represented by the formula (L-6) is preferably a compound represented by the formula (L-6.1) to the formula (L-6.9).

可組合之化合物之種類並無特別限制，較佳為自該等化合物中含有一種~三種，進而較佳為含有一種~四種。又，由於所選之化合物之分子量分佈較廣對溶解性亦有效，因此較佳為例如自式(L-6.1)或(L-6.2)所表示之化合物中選擇一種化合物，自式(L-6.4)或(L-6.5)所表示之化合物中選擇一種化合物，自式(L-6.6)或式(L-6.7)所表示之化合物中選擇一種化合物，自式(L-6.8)或(L-6.9)所表示之化合物中選擇一種化合物，並將該等適當組合。其中，較佳為含有式(L-6.1)、式 (L-6.3)式(L-6.4)、式(L-6.6)及式(L-6.9)所表示之化合物。 The type of the compound which can be combined is not particularly limited, and it is preferred to contain one to three kinds from the compounds, and more preferably one to four. Further, since the molecular weight distribution of the selected compound is also effective for solubility, it is preferred to select, for example, a compound selected from the formula (L-6.1) or (L-6.2), from the formula (L- Select a compound from the compounds represented by 6.4) or (L-6.5), and select a compound from the compound represented by formula (L-6.6) or (L-6.7), from formula (L-6.8) or (L) -6.9) One of the compounds indicated is selected and these are appropriately combined. Among them, it is preferred to contain the formula (L-6.1), (L-6.3) A compound represented by the formula (L-6.4), the formula (L-6.6) and the formula (L-6.9).

進而，通式(L-6)所表示之化合物較佳為例如式(L-6.10)至式(L-6.17)所表示之化合物，其中較佳為式(L-6.11)所表示之化合物。 Further, the compound represented by the formula (L-6) is preferably a compound represented by the formula (L-6.10) to the formula (L-6.17), and among them, a compound represented by the formula (L-6.11) is preferred.

相對於本發明之液晶組成物之總量之該等化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、2%、3%、5%、7%。該等化合物之較佳含量之上限值為20%、15%、13%、10%、9%。 The lower limit of the preferred content of the compounds relative to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter referred to as % by mass), 2%, 3%, 5%, and 7%. The upper limit of the preferred content of the compounds is 20%, 15%, 13%, 10%, 9%.

通式(L-7)所表示之化合物係下述化合物。 The compound represented by the formula (L-7) is the following compound.

(式中，RL71及RL72分別獨立地表示與通式(L)中之RL1及RL2相同之含義，AL71及AL72分別獨立地表示與通式(L)中之AL2及AL3相同之含義，AL71及AL72上之氫原子可分別獨立地被取代為氟原子，ZL71表示與通式(L)中之ZL2相同之含義，XL71及XL72分別獨立地表示氟原子或氫原子) (wherein R L71 and R L72 each independently represent the same meaning as R L1 and R L2 in the general formula (L), and A L71 and A L72 independently represent A L2 in the general formula (L) and A L3 has the same meaning, the hydrogen atoms on A L71 and A L72 can be independently substituted into a fluorine atom, Z L71 represents the same meaning as Z L2 in the general formula (L), and X L71 and X L72 are independently Represents a fluorine atom or a hydrogen atom)

式中，RL71及RL72分別獨立，較佳為碳原子數1~5之烷基、碳原子數2~5之烯基或碳原子數1~4之烷氧基，AL71及AL72分別獨立，較佳為1,4-伸環己基或1,4-伸苯基，AL71及AL72上之氫原子可分別獨立地被取代為氟原子，QL71較佳為單鍵或COO-，較佳為單鍵，XL71及XL72較佳為氫原子。 In the formula, R L71 and R L72 are each independently, preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and A L71 and A L72. Separately, preferably 1,4-cyclohexylene or 1,4-phenylene, the hydrogen atoms on A L71 and A L72 can be independently substituted into a fluorine atom, and Q L71 is preferably a single bond or COO. Preferably, it is a single bond, and X L71 and X L72 are preferably a hydrogen atom.

可組合之化合物之種類並無特別限制，根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率等所要求之性能而組合。所使用之化合物之種類例如作為本發明之一實施形態為一種、兩種、三種、四種。 The type of the compound which can be combined is not particularly limited, and is combined according to the properties required at the low temperature such as solubility, transfer temperature, electrical reliability, and birefringence. The types of the compounds to be used are, for example, one, two, three, or four as one embodiment of the present invention.

於本發明之液晶組成物中，通式(L-7)所表示之化合物之含量必須根據低溫下之溶解性、轉移溫度、電性可靠性、雙折射率、製程相容性、滴加痕、殘像、介電各向導性等所要求之性能進行適當調整。 In the liquid crystal composition of the present invention, the content of the compound represented by the formula (L-7) must be based on solubility at low temperature, transfer temperature, electrical reliability, birefringence, process compatibility, and trace addition. The performance required for the afterimage, the dielectric image, and the like are appropriately adjusted.

相對於本發明之組成物之總量之式(L-7)所表示之化合物之較佳含量之下限值為1質量%(以下將質量%簡記為%)、2%、3%、5%、7%、10%、14%、16%、20%。相對於本發明之組成物之總量之式(L-7)所表示之化合物之較佳含量之上限值為30%、25%、23%、20%、18%、15%、 10%、5%。 The lower limit of the preferred content of the compound represented by the formula (L-7) with respect to the total amount of the composition of the present invention is 1% by mass (hereinafter, the mass % is abbreviated as %), 2%, 3%, and 5 %, 7%, 10%, 14%, 16%, 20%. The upper limit of the preferred content of the compound represented by the formula (L-7) with respect to the total amount of the composition of the present invention is 30%, 25%, 23%, 20%, 18%, 15%, 10%, 5%.

於期待本發明之組成物為較高之Tni之實施形態之情形時，較佳為使式(L-7)所表示之化合物之含量較多，於期待低黏度之實施形態之情形時，較佳為使含量較少。 In the case where the composition of the present invention is expected to have a higher T ni embodiment, it is preferred that the compound represented by the formula (L-7) is contained in a large amount, and in the case of an embodiment in which a low viscosity is desired, It is preferred to make the content small.

進而，通式(L-7)所表示之化合物較佳為式(L-7.1)至式(L-7.4)所表示之化合物，較佳為式(L-7.2)所表示之化合物。 Further, the compound represented by the formula (L-7) is preferably a compound represented by the formula (L-7.1) to the formula (L-7.4), and preferably a compound represented by the formula (L-7.2).

進而，通式(L-7)所表示之化合物較佳為式(L-7.11)至式(L-7.13)所表示之化合物，較佳為式(L-7.11)所表示之化合物。 Further, the compound represented by the formula (L-7) is preferably a compound represented by the formula (L-7.11) to the formula (L-7.13), and preferably a compound represented by the formula (L-7.11).

進而，通式(L-7)所表示之化合物為式(L-7.21)至式(L-7.23)所表示之化合物。較佳為式(L-7.21)所表示之化合物。 Further, the compound represented by the formula (L-7) is a compound represented by the formula (L-7.21) to the formula (L-7.23). A compound represented by the formula (L-7.21) is preferred.

進而，通式(L-7)所表示之化合物較佳為式(L-7.31)至式(L-7.34)所表示之化合物，較佳為式(L-7.31)或/及式(L-7.32)所表示之化合物。 Further, the compound represented by the formula (L-7) is preferably a compound represented by the formula (L-7.31) to the formula (L-7.34), preferably a formula (L-7.31) or/and a formula (L-). 7.32) Compounds indicated.

進而，通式(L-7)所表示之化合物較佳為式(L-7.41)至式(L-7.44)所表示之化合物，較佳為式(L-7.41)或/及式(L-7.42)所表示之化合物。 Further, the compound represented by the formula (L-7) is preferably a compound represented by the formula (L-7.41) to the formula (L-7.44), preferably a formula (L-7.41) or/and a formula (L-). 7.42) Compounds indicated.

本發明之液晶組成物中之添加劑(抗氧化劑、UV吸收劑等)較佳為100ppm~1質量%。 The additive (antioxidant, UV absorber, etc.) in the liquid crystal composition of the present invention is preferably from 100 ppm to 1% by mass.

本發明中之液晶組成物係可於較廣之範圍內使用向列相-等向性液體相轉移溫度(Tni)者，但向列相-等向性液體相轉移溫度(Tni)較佳為60~120℃，更佳為70~100℃，尤佳為70~85℃。 The liquid crystal composition of the present invention can use a nematic phase-isotropic liquid phase transfer temperature (T ni ) in a wide range, but the nematic phase-isotropic liquid phase transition temperature (T ni ) is relatively Preferably, it is 60 to 120 ° C, more preferably 70 to 100 ° C, and particularly preferably 70 to 85 ° C.

本發明中之液晶組成物之介電各向導性△ε於25℃下較佳為-2.0~-6.0，更佳為-2.5~-5.0，尤佳為-2.5~-3.5。 The dielectric specificity Δ ε of the liquid crystal composition of the present invention is preferably -2.0 to -6.0 at 25 ° C, more preferably -2.5 to -5.0, and particularly preferably -2.5 to -3.5.

本發明中之液晶組成物之折射率異向性△n於25℃下較佳為0.08~0.13，更佳為0.09~0.12。若進一步詳細而言，則於應對較薄之單元間隙之情形時，本發明中之液晶組成物之折射率異向性於25℃下較佳為0.10~0.12，若進一步詳細而言，則於應對較薄之單元間隙(單元間隙為3.4μm以下)之情形時，較佳為約0.9至約0.12左右，於應對較厚之單元間隙(單元間隙為3.5μm以上)之情形時，較佳為約0.08至約0.1左右。 The refractive index anisotropy Δn of the liquid crystal composition in the present invention is preferably from 0.08 to 0.13, more preferably from 0.09 to 0.12 at 25 °C. In more detail, the refractive index anisotropy of the liquid crystal composition of the present invention is preferably 0.10 to 0.12 at 25 ° C in the case of dealing with a thin cell gap, and in further detail, In the case of dealing with a thin cell gap (cell gap of 3.4 μm or less), it is preferably about 0.9 to about 0.12, and in the case of dealing with a thick cell gap (cell gap is 3.5 μm or more), it is preferably It is about 0.08 to about 0.1.

本發明之液晶組成物之旋轉黏度(γ1)之上限值較佳為150(mPa．s)以下，更佳為130(mPa．s)以下，尤佳為120(mPa．s)以下。 另一方面，該旋轉黏度(γ1)之下限值較佳為20(mPa．s)以上，更佳為30(mPa．s)以上，進而較佳為40(mPa．s)以上，更進而較佳為50(mPa．s)以上，進而更佳為60(mPa．s)以上，尤佳為70(mPa．s)以上。 The upper limit of the rotational viscosity (γ 1 ) of the liquid crystal composition of the present invention is preferably 150 (mPa·s) or less, more preferably 130 (mPa·s) or less, and particularly preferably 120 (mPa·s) or less. On the other hand, the lower limit of the rotational viscosity (γ 1 ) is preferably 20 (mPa·s) or more, more preferably 30 (mPa·s) or more, and still more preferably 40 (mPa·s) or more. Further, it is preferably 50 (mPa.s) or more, more preferably 60 (mPa.s) or more, and still more preferably 70 (mPa.s) or more.

本發明之液晶組成物中，旋轉黏度與折射率異向性之函數Z較佳為表示特定之值。 In the liquid crystal composition of the present invention, the function Z of the rotational viscosity and the refractive index anisotropy preferably represents a specific value.

(上述數式中，γ1表示旋轉黏度，△n表示折射率異向性) (In the above formula, γ 1 represents rotational viscosity, and Δn represents refractive index anisotropy)

Z較佳為13000以下，更佳為12000以下，尤佳為11000以下。 Z is preferably 13,000 or less, more preferably 12,000 or less, and still more preferably 11,000 or less.

於本發明之液晶組成物用於主動矩陣顯示元件之情形時，需具有1011(Ω．m)以上之比電阻，較佳為1012(Ω．m)，更佳為1013(Ω．m)以上。 When the liquid crystal composition of the present invention is used for an active matrix display device, it is required to have a specific resistance of 10 11 (Ω·m) or more, preferably 10 12 (Ω·m), more preferably 10 13 (Ω. m) above.

本發明之液晶組成物係可於較廣之範圍內使用向列相-等向性液體相轉移溫度(TNI)者，但該相轉移溫度(TNI)較佳為60~120℃，更佳為70~110℃，尤佳為75~100℃。 The liquid crystal composition of the present invention can use a nematic phase-isotropic liquid phase transfer temperature (T NI ) in a wide range, but the phase transition temperature (T NI ) is preferably 60 to 120 ° C, more Good is 70~110°C, especially preferably 75~100°C.

[液晶顯示元件之製造方法] [Method of Manufacturing Liquid Crystal Display Element]

繼而，參照圖1，對本發明之液晶顯示元件之製造方法進行說明。 Next, a method of manufacturing a liquid crystal display element of the present invention will be described with reference to Fig. 1 .

於第一基板11之形成有共用電極14之面及第二基板12之形成有像素電極15之面塗佈含有具有聚合性基之聚合性化合物的定向膜材料、或聚合性液晶化合物並加熱，藉此形成垂直定向膜16、17。再者，於 使用聚合性液晶化合物作為定向膜之情形時，亦可具有通常之定向膜作為基底定向膜。 An alignment film material containing a polymerizable compound having a polymerizable group or a polymerizable liquid crystal compound is applied to the surface of the first substrate 11 on which the common electrode 14 is formed and the surface of the second substrate 12 on which the pixel electrode 15 is formed, and heated. Thereby, the vertical alignment films 16, 17 are formed. Furthermore, When a polymerizable liquid crystal compound is used as the alignment film, it is also possible to have a usual alignment film as the substrate alignment film.

此處，首先，製備含有成為第一高分子化合物之高分子化合物前驅物、及/或上述通式(V2)所表示之化合物與上述通式(I)所表示之化合物及視需要之通式(V)所表示之化合物等聚合性化合物、或具有光聚合性及光交聯性之化合物之定向膜材料、或由通式(I)所表示之化合物及聚合性液晶化合物構成之定向膜材料。 Here, first, a polymer compound precursor which is a first polymer compound, and/or a compound represented by the above formula (V2) and a compound represented by the above formula (I) are prepared, and a general formula as required. Orientation film material such as a polymerizable compound such as a compound represented by (V) or a compound having photopolymerization and photocrosslinkability, or an oriented film material composed of a compound represented by the formula (I) and a polymerizable liquid crystal compound .

於第一高分子化合物為聚醯亞胺之情形時，作為高分子化合物前驅物，例如，可列舉四羧酸二酐及二異氰酸酯之混合物、或聚醯胺酸、或使聚醯亞胺溶解或分散於溶劑中而成之聚醯亞胺溶液等。該聚醯亞胺溶液中之聚醯亞胺之含量較佳為1質量%以上且10質量%以下，更佳為3質量%以上且5質量%以下。 In the case where the first polymer compound is a polyimine, the polymer compound precursor may, for example, be a mixture of tetracarboxylic dianhydride and diisocyanate, or polylysine, or dissolve the polyimine. Or a polyimine solution or the like dispersed in a solvent. The content of the polyimine in the polyimine solution is preferably 1% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 5% by mass or less.

又，於第一高分子化合物為聚矽氧烷之情形時，作為高分子化合物前驅物，例如，可列舉藉由將具有烷氧基之矽化合物、具有鹵代烷氧基之矽化合物、醇及草酸以特定之調配量比加以混合並加熱而合成聚矽氧烷，並將其溶解於溶劑中而成之聚矽氧烷溶液等。 In the case where the first polymer compound is a polyoxymethane, examples of the polymer compound precursor include a fluorene compound having an alkoxy group, a hydrazine compound having a halogenated alkoxy group, an alcohol, and oxalic acid. A polyoxane solution obtained by mixing and heating at a specific blending ratio to obtain a polyoxyalkylene oxide and dissolving it in a solvent.

再者，可視需要而於定向膜材料中添加具有光交聯性之化合物、光聚合起始劑、溶劑等。 Further, a compound having photocrosslinkability, a photopolymerization initiator, a solvent, or the like may be added to the alignment film material as needed.

製備定向膜材料後，以覆蓋共用電極14、以及像素電極15及其狹縫部(省略圖示)之方式將該定向膜材料分別塗佈或印刷於第一基板11及第二基板12後，進行加熱等處理。藉此，所塗佈或印刷之定向膜材料所含之高分子化合物前驅物及/或上述通式(V2)所表示之化合物、或 聚合性液晶化合物聚合及硬化而成為高分子化合物，形成混合存在高分子化合物與通式(I)所表示之化合物及視需要之通式(V)所表示之化合物、或通式(I)所表示之化合物及聚合性液晶化合物經半硬化之垂直定向膜16、17。 After the alignment film material is prepared, the alignment film material is applied or printed on the first substrate 11 and the second substrate 12 so as to cover the common electrode 14 and the pixel electrode 15 and the slit portion (not shown). Heat and other treatments. Thereby, the polymer compound precursor contained in the coated or printed alignment film material and/or the compound represented by the above formula (V2), or The polymerizable liquid crystal compound is polymerized and cured to form a polymer compound, and a polymer compound and a compound represented by the formula (I) and, if necessary, a compound represented by the formula (V) or a compound of the formula (I) are formed. The compound and the polymerizable liquid crystal compound are semi-hardened vertical alignment films 16, 17.

此處，於進行加熱處理之情形時，其溫度較佳為80℃以上，更佳為150~200℃。 Here, in the case of performing heat treatment, the temperature thereof is preferably 80 ° C or higher, more preferably 150 to 200 ° C.

再者，於該階段形成使液晶組成物層中之液晶分子相對於基板面沿垂直方向定向之垂直定向功能。其後，可視需要實施摩擦等處理。 Further, at this stage, a vertical alignment function of orienting the liquid crystal molecules in the liquid crystal composition layer in the vertical direction with respect to the substrate surface is formed. Thereafter, treatment such as friction may be performed as needed.

繼而，使第一基板11與第二基板12重疊，將含有液晶分子之液晶組成物層13密封於該等之間。 Then, the first substrate 11 and the second substrate 12 are overlapped, and the liquid crystal composition layer 13 containing liquid crystal molecules is sealed between them.

具體而言，對第一基板11與第二基板12之任一者之形成有垂直定向膜16、17之面散佈用以確保單元間隙之間隔突起物、例如塑膠珠粒等，並且藉由例如網版印刷法，使用環氧接著劑等印刷密封部。 Specifically, the surface of the first substrate 11 and the second substrate 12 on which the vertical alignment films 16 and 17 are formed is dispersed to ensure a gap between the cell gaps, for example, plastic beads, etc., and by, for example, In the screen printing method, a sealing portion such as an epoxy adhesive is used.

其後，以使垂直定向膜16、17相對向之方式，經由間隔突起物及密封部將第一基板11與第二基板12貼合，並注入含有液晶分子及視需要之聚合性化合物之液晶組成物。 Thereafter, the first substrate 11 and the second substrate 12 are bonded to each other via the spacer protrusions and the sealing portion so that the vertical alignment films 16 and 17 face each other, and liquid crystal containing liquid crystal molecules and, if necessary, a polymerizable compound is injected. Composition.

其後，進行加熱等使密封部硬化，藉此將液晶組成物密封於第一基板11與第二基板12之間。 Thereafter, the sealing portion is cured by heating or the like, whereby the liquid crystal composition is sealed between the first substrate 11 and the second substrate 12.

繼而，使用電壓施加手段，於共用電極14與像素電極15之間施加電壓。電壓例如係以5~30(V)之大小施加。上述施加亦存在對第一基板與第二基板大致垂直地施加電荷之情形。藉此，產生相對於第一基板11中之與液晶組成物層13鄰接之面(與液晶組成物層13相對向之面)、 及第二基板12之與液晶組成物層13鄰接之面(與液晶組成物層13相對向之面)成特定角度之方向之電場，液晶分子19自第一基板11與第二基板12之法線方向朝特定方向傾斜而定向。此時，液晶分子19之傾斜角與藉由下文所述之步驟對液晶分子19賦予之預傾角θ大致相等。因此，藉由適當調節電壓之大小，可控制液晶分子19之預傾角θ之大小(參照圖3)。 Then, a voltage is applied between the common electrode 14 and the pixel electrode 15 by using a voltage application means. The voltage is applied, for example, in a size of 5 to 30 (V). The above application also has a case where charges are applied substantially perpendicularly to the first substrate and the second substrate. Thereby, a surface adjacent to the liquid crystal composition layer 13 in the first substrate 11 (opposite to the liquid crystal composition layer 13) is generated, And an electric field in a direction of a specific angle of the surface of the second substrate 12 adjacent to the liquid crystal composition layer 13 (the surface facing the liquid crystal composition layer 13), the liquid crystal molecules 19 from the first substrate 11 and the second substrate 12 The line direction is oriented obliquely in a particular direction. At this time, the tilt angle of the liquid crystal molecules 19 is substantially equal to the pretilt angle θ imparted to the liquid crystal molecules 19 by the steps described below. Therefore, by appropriately adjusting the magnitude of the voltage, the magnitude of the pretilt angle θ of the liquid crystal molecules 19 can be controlled (refer to Fig. 3).

進而，於施加電壓之狀態下，例如自第一基板11之外側向液晶組成物層13照射紫外光UV，藉此使垂直定向膜16、17中之通式(I)所表示之化合物及視需要之通式(V)所表示之化合物或聚合性液晶化合物、及液晶組成物中之聚合性化合物聚合，而生成高分子聚合物。 Further, in a state where a voltage is applied, for example, the liquid crystal composition layer 13 is irradiated with ultraviolet light UV from the outer side of the first substrate 11, whereby the compound represented by the general formula (I) in the vertical alignment films 16 and 17 and the apparent The compound represented by the formula (V), the polymerizable liquid crystal compound, and the polymerizable compound in the liquid crystal composition are polymerized to form a polymer.

於該情形時，所照射之紫外光UV之強度可固定，亦可不固定，改變照射強度時之各強度下之照射時間亦為任意，於採用2個階段以上之照射步驟之情形時，較佳為第2階段後之照射步驟之照射強度選擇弱於第1階段之照射強度之強度，並且較佳為第2階段後之總照射時間長於第1階段之照射時間且照射總能量較大。又，於不連續地改變照射強度之情形時，較理想為全部照射步驟時間之前半部分之平均照射光強度強於後半部分之平均照射強度，更理想為剛開始照射後之強度最強，進而較佳為隨著照射時間經過，照射強度一直持續減少至某特定值。該情形時之紫外線UV強度較佳為2mW/cm-2~100mW/cm-2，更佳為多階段照射之情形時之第1階段、或不連續地改變照射強度之情形時之全部照射步驟中之最高照射強度為10mW/cm-2~100mW/cm-2，且多階段照射之情形時之第2階段後、或不連續地改變照射強度之情形時之最低照射強度為2mW/cm-2~50mW/cm-2。又，照射總能量較佳為10J~300J，更佳為50J~250J， 進而較佳為100J~250J。 In this case, the intensity of the ultraviolet light UV to be irradiated may be fixed or unfixed, and the irradiation time at each intensity when the irradiation intensity is changed is also arbitrary, and in the case of using the irradiation step of two or more stages, it is preferable. The intensity of the irradiation intensity after the second stage is selected to be weaker than the intensity of the first stage, and it is preferable that the total irradiation time after the second stage is longer than the irradiation time of the first stage and the total irradiation energy is large. Further, in the case of discontinuously changing the irradiation intensity, it is preferable that the average irradiation light intensity in the first half of the entire irradiation step time is stronger than the average irradiation intensity in the second half portion, and more preferably the intensity after the first irradiation is the strongest, and thus As the irradiation time passes, the illumination intensity continues to decrease to a certain value. In this case, the ultraviolet light intensity is preferably 2 mW/cm -2 to 100 mW/cm -2 , more preferably the first stage in the case of multi-stage irradiation, or the entire irradiation step in the case of discontinuously changing the irradiation intensity. the maximum illumination intensity of 10mW / cm -2 ~ 100mW / cm -2, the second stage of the case 2 and the multi-stage irradiation, or discontinuously changing the minimum intensity of the irradiation intensity of the irradiation case 2mW / cm - 2 ~ 50mW / cm -2 . Further, the total irradiation energy is preferably from 10 J to 300 J, more preferably from 50 J to 250 J, further preferably from 100 J to 250 J.

於該情形時，施加電壓可為交流，亦可為直流。 In this case, the applied voltage may be alternating current or direct current.

其結果，具有與垂直定向膜16、17之定向控制部固著之含有垂直定向膜材料之定向控制功能(省略圖示)，進而，視需要於其表面形成聚合物層20、21。該定向控制部於非驅動狀態下，具有對液晶組成物層13中之位於與聚合物層20、21(垂直定向膜16、17)之界面附近之液晶分子19賦予預傾角θ之功能(定向控制功能)。再者，此處係自第一基板11之外側照射紫外光UV，但亦可自第二基板12之外側照射紫外光UV，亦可自第一基板11及第二基板12之兩塊基板之外側照射紫外光UV。 As a result, the orientation control function (not shown) including the vertical alignment film material fixed to the orientation control portions of the vertical alignment films 16 and 17 is provided, and further, the polymer layers 20 and 21 are formed on the surface thereof as needed. The orientation control portion has a function of imparting a pretilt angle θ to the liquid crystal molecules 19 located in the vicinity of the interface with the polymer layers 20, 21 (vertical alignment films 16, 17) in the non-driving state. control function). In addition, ultraviolet light UV is irradiated from the outer side of the first substrate 11 , but ultraviolet light UV may be irradiated from the outer side of the second substrate 12 , or two substrates of the first substrate 11 and the second substrate 12 may be used. The outside is irradiated with UV light UV.

如上所述，於本發明之液晶顯示元件中，液晶組成物層13中之液晶分子19具有特定之預傾角θ。藉此，與完全未實施預傾處理之液晶顯示元件及具備該液晶顯示元件之液晶顯示裝置相比，可大幅提高對驅動電壓之應答速度。 As described above, in the liquid crystal display device of the present invention, the liquid crystal molecules 19 in the liquid crystal composition layer 13 have a specific pretilt angle θ. As a result, the response speed to the driving voltage can be greatly improved as compared with the liquid crystal display device in which the pretilt treatment is not performed and the liquid crystal display device including the liquid crystal display device.

於本發明之液晶顯示元件中，作為構成垂直定向膜16、17之高分子化合物前驅物，較佳為非感光性之聚醯亞胺前驅物。 In the liquid crystal display device of the present invention, as the polymer compound precursor constituting the vertical alignment films 16, 17, a non-photosensitive polyimide precursor is preferable.

[實施例] [Examples]

以下，藉由實施例及比較例進一步對本發明進行具體說明，但本發明並不限定於以下之實施例。又，以下之實施例及比較例之組成物中之「%」意指「質量%」。 Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples. Further, "%" in the compositions of the following examples and comparative examples means "% by mass".

於以下之實施例及比較例中，分別以如下方式定義Tni、△n、△ε、η、γ1。 In the following examples and comparative examples, T ni , Δn, Δε, η, and γ 1 were defined as follows.

Tni：向列相-等向性液體相轉移溫度(℃) T ni : nematic phase-isotropic liquid phase transfer temperature (°C)

Tcn：固相-向列相轉移溫度(℃) T cn : solid phase-nematic phase transfer temperature (°C)

△n：25℃下之折射率異向性 △n: refractive index anisotropy at 25 ° C

△ε：25℃下之介電各向導性 △ ε: Dielectric conductivity at 25 ° C

γ1：25℃下之旋轉黏度(mPa．s) γ 1 : rotational viscosity (mPa.s) at 25 ° C

K33：20℃下之彎曲之彈性常數(pN) K 33 : elastic constant (pN) of bending at 20 ° C

照射UV前電壓保持率(初期VHR)：於頻率60Hz、施加電壓1V之條件下343K下之電壓保持率(%) Voltage holding ratio before UV irradiation (initial VHR): Voltage holding ratio (%) at 343 K at a frequency of 60 Hz and an applied voltage of 1 V

照射UV後VHR：對以下之實施例、比較例之液晶顯示元件照射UV後，在與上述VHR測定方法相同之條件下進行測定。 VHR after UV irradiation: After irradiating UV to the liquid crystal display elements of the following examples and comparative examples, the measurement was performed under the same conditions as the above-described VHR measurement method.

於以下之實施例及比較例中，藉由下述方法，對液晶顯示元件之殘像、滴加痕及預傾角進行評價。 In the following examples and comparative examples, the afterimage, the dropping marks, and the pretilt angle of the liquid crystal display element were evaluated by the following methods.

(殘像) (afterimage)

液晶顯示元件之殘像評價係使特定之固定圖案於顯示區域內顯示1000小時後，藉由目視根據以下之4個等級評價進行整個畫面之均勻顯示時之固定圖案之殘影之等級。 The afterimage evaluation of the liquid crystal display element was performed by displaying the specific fixed pattern in the display area for 1,000 hours, and then visually evaluating the level of the residual image of the fixed pattern when the entire screen was uniformly displayed based on the following four levels.

◎：無殘影 ◎: no residual image

○：有極少殘影且為可容許之等級 ○: There is very little afterimage and it is a tolerable level

△：有殘影，為無法容許之等級 △: There is a residual image, which is an unacceptable level.

×：有殘影，非常差 ×: There is a residual image, very bad

(滴加痕) (drops)

液晶顯示裝置之滴加痕之評價係藉由目視，根據以下之4個等級評價整個面顯示為黑色之情形時呈白色浮現之滴加痕。 The evaluation of the dropping marks of the liquid crystal display device was carried out by visual observation, and the white marks which appeared in the case where the entire surface was displayed in black were evaluated according to the following four levels.

◎：無殘影 ◎: no residual image

○：有極少殘影且為可容許之等級 ○: There is very little afterimage and it is a tolerable level

△：有殘影，為無法容許之等級 △: There is a residual image, which is an unacceptable level.

×：有殘影，非常差 ×: There is a residual image, very bad

(預傾角) (pretilt angle)

隨機對液晶顯示元件之面內計測5個部位，以平均值作為預傾角。又，於評價預傾角之穩定性之情形時，比較應力前後之預傾角之變化。應力係藉由將液晶顯示裝置投入保持為70℃之烘箱內，並施加168小時之1kHz、30V之矩形波而賦予。 Five parts were randomly measured in the plane of the liquid crystal display element, and the average value was used as the pretilt angle. Further, in the case of evaluating the stability of the pretilt angle, the change in the pretilt angle before and after the stress is compared. The stress was applied by placing the liquid crystal display device in an oven maintained at 70 ° C and applying a rectangular wave of 1 kHz and 30 V for 168 hours.

預傾變化角(°)：應力後之預傾角-應力前之預傾角 Pretilt angle of change (°): pretilt angle after stress - pretilt angle before stress

再者，於實施例中，化合物之記載使用以下之簡稱。再者，n表示自然數。 Further, in the examples, the description of the compounds is as follows. Furthermore, n represents a natural number.

(側鏈) (side chain)

(連結基) (link base)

(環結構) (ring structure)

(實施例1) (Example 1)

製作第一基板(共用電極基板)，其具備由透明之共用電極構成之透明電極層及彩色濾光片層；及第二基板(像素電極基板)，其具備具有藉由主動元件驅動之透明像素電極之像素電極層。 Manufacturing a first substrate (common electrode substrate) including a transparent electrode layer and a color filter layer formed of a transparent common electrode; and a second substrate (pixel electrode substrate) having a transparent pixel driven by an active device The pixel electrode layer of the electrode.

於像素電極基板中，作為各像素電極，使用為了分割液晶分子之定向而以像素電極存在不具有電極之狹縫之方式蝕刻ITO而成者。 In the pixel electrode substrate, as the respective pixel electrodes, in order to divide the alignment of the liquid crystal molecules, the ITO is etched so that the pixel electrodes have slits having no electrodes.

藉由旋轉塗佈法，將含有聚醯亞胺前驅物及具有聚合性基之聚合性化合物之垂直定向膜材料分別塗佈於共用電極基板及像素電極基板，並以200℃加熱該塗佈膜，藉此使垂直定向膜材料中之聚醯亞胺前驅物硬化，而於各基板之表面形成100nm±20nm之垂直定向膜。於該階段，該垂直定向膜中之具有聚合性基之聚合性化合物並未硬化。 The vertical alignment film material containing the polyimide precursor and the polymerizable compound having a polymerizable group is applied to the common electrode substrate and the pixel electrode substrate by a spin coating method, and the coating film is heated at 200 ° C. Thereby, the polyimide precursor in the vertical alignment film material is hardened, and a vertical alignment film of 100 nm ± 20 nm is formed on the surface of each substrate. At this stage, the polymerizable compound having a polymerizable group in the vertically oriented film is not hardened.

作為垂直定向膜形成材料，使用於含有3%之聚醯亞胺前驅 物之聚醯亞胺溶液(商品名：JALS2131-R6，JSR公司製造)中含有3.0%之以下之式(I-1)所表示之化合物之溶液。 Used as a vertically oriented film forming material for precursors containing 3% polyimine The polyimine solution (trade name: JALS2131-R6, manufactured by JSR Corporation) contains a solution of a compound represented by the formula (I-1) of 3.0% or less.

將含有以下之表所示之化學式所表示之化合物之液晶組成物(LC-A)夾持於形成有垂直定向膜之共用電極基板及像素電極基板後，使密封材料硬化，而形成液晶組成物層。此時，使用厚度3.0μm之間隔件，將液晶組成物層之厚度設為3.0μm。 The liquid crystal composition (LC-A) containing the compound represented by the chemical formula shown in the following table is sandwiched between the common electrode substrate and the pixel electrode substrate on which the vertical alignment film is formed, and then the sealing material is cured to form a liquid crystal composition. Floor. At this time, the thickness of the liquid crystal composition layer was set to 3.0 μm using a spacer having a thickness of 3.0 μm.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照 射紫外線，使上述式(I-1)所表示之化合物硬化。使用牛尾電機(Ushio)公司製造之UIS-S251IRZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射300秒之紫外線，而獲得實施例1之液晶顯示元件。藉由該步驟，形成含有上述式(I-1)所表示之化合物之垂直定向膜，並對液晶組成物層中之液晶分子賦予預傾角。 Photographing the obtained liquid crystal display element in a state where a rectangular alternating electric field is applied The compound represented by the above formula (I-1) is cured by ultraviolet rays. Using the UIS-S251IRZ manufactured by Ushio Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, the liquid crystal display element was irradiated with ultraviolet rays for 300 seconds at 20 mW, and the liquid crystal display of Example 1 was obtained. element. By this step, a vertical alignment film containing the compound represented by the above formula (I-1) is formed, and a pretilt angle is imparted to the liquid crystal molecules in the liquid crystal composition layer.

此處，預傾角係以如圖3所示之方式定義。於進行完全垂直定向之情形時，預傾角(θ)成為90°，於賦予預傾角之情形時，預傾角(θ)變得小於90°。 Here, the pretilt angle is defined in the manner as shown in FIG. In the case of performing a completely vertical orientation, the pretilt angle (θ) becomes 90°, and when the pretilt angle is given, the pretilt angle (θ) becomes less than 90°.

實施例1之液晶顯示元件沿如圖2所示之像素電極之狹縫，於4個區塊內朝向不同方向具有預傾角，上述聚合性化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The liquid crystal display element of the first embodiment has a pretilt angle in different directions in the four blocks along the slit of the pixel electrode as shown in FIG. 2, and after the hardening of the polymerizable compound, even in the state of cutting off the alternating electric field The pretilt angle is also maintained.

將實施例1之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表2。其結果，實施例1之液晶顯示元件所使用之液晶組成物於照射UV前後未見VHR之大幅降低。研究其原因在於：由於定向膜材料中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之具有聚合性基之聚合性化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 1, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 2 below. As a result, the liquid crystal composition used in the liquid crystal display device of Example 1 did not show a significant decrease in VHR before and after the irradiation of UV. The reason for the investigation is that since the polymerizable compound represented by the formula (I) is contained in the alignment film material, the total energy of the UV irradiation when the polymerizable compound having a polymerizable group in the alignment film is polymerized can be suppressed to be low. Therefore, decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(比較例1) (Comparative Example 1)

作為垂直定向膜形成材料，使用於含有3%之聚醯亞胺前驅物之聚醯亞胺溶液(商品名：JALS2131-R6，JSR公司製造)中含有3.0%之以下之式(Va-1-1)所表示之化合物之溶液，除此以外，以與實施例1同樣之方式，獲得比較例1之液晶顯示元件。 As a material for the vertical alignment film formation, a polyimine solution (trade name: JALS2131-R6, manufactured by JSR Corporation) containing 3% of a polyimide precursor is contained in a formula of 3.0% or less (Va-1- A liquid crystal display element of Comparative Example 1 was obtained in the same manner as in Example 1 except for the solution of the compound shown in the above.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述定向膜中之具有反應性基之聚合性化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射600秒之紫外線，而獲得比較例1之液晶顯示元件。再者，在與實施例1相同之條件(20mW下300秒)下對液晶顯示元件照射紫外線，進行了預傾角之賦予，但定向膜中之具有反應性基之聚合性化合物之硬化不充分，並未穩定地賦予預傾角，因此維持預傾角需要20mW下600秒之照射。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied, and the polymerizable compound having a reactive group in the alignment film is cured. The liquid crystal display element of Comparative Example 1 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. Further, under the same conditions as in Example 1 (300 seconds at 20 mW), the liquid crystal display element was irradiated with ultraviolet rays to impart a pretilt angle, but the curing of the polymerizable compound having a reactive group in the alignment film was insufficient. The pretilt angle is not stably imparted, so maintaining the pretilt angle requires 600 seconds of irradiation at 20 mW.

將比較例1之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像 評價示於以下之表3。其結果，由於比較例1之定向膜材料中不含通式(I)所表示之聚合性化合物，因此，用以使定向膜中之具有聚合性之聚合性化合物硬化之UV照射總能量變大，結果可見VHR之降低，確認到由液晶組成物中之液晶化合物之分解引起之物性降低。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Comparative Example 1, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element, and the afterimage The evaluation is shown in Table 3 below. As a result, since the polymerizable compound represented by the general formula (I) is not contained in the alignment film material of Comparative Example 1, the total energy of UV irradiation for hardening the polymerizable polymerizable compound in the alignment film becomes large. As a result, it was confirmed that the VHR was lowered, and it was confirmed that the physical properties caused by the decomposition of the liquid crystal compound in the liquid crystal composition were lowered.

(實施例2) (Example 2)

製備含有以下之表所示之化合物之液晶組成物(LC-A2)，並使用該液晶組成物。除此以外之條件係設為與實施例1相同，而獲得實施例2之液晶顯示元件。 A liquid crystal composition (LC-A2) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. The other conditions were the same as in Example 1, and the liquid crystal display element of Example 2 was obtained.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述式(I-1)所表示之化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射300秒之紫外線，而獲得實施例2之液晶顯示元件。實施例2之液晶顯示元件與實施例1同樣地具有預傾角，上述聚合性化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied, and the compound represented by the above formula (I-1) is cured. The liquid crystal display element of Example 2 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 300 seconds at 20 mW. The liquid crystal display element of Example 2 had a pretilt angle similarly to Example 1, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut.

將實施例2之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表5。其結果，實施例2之液晶顯示元件所使用之液晶組成 物於照射UV前後未見VHR之降低。研究其原因在於：由於定向膜材料中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之具有聚合性基之聚合性化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 2, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 5 below. As a result, the liquid crystal composition used in the liquid crystal display element of Example 2 No decrease in VHR was observed before and after irradiation with UV. The reason for the investigation is that since the polymerizable compound represented by the formula (I) is contained in the alignment film material, the total energy of the UV irradiation when the polymerizable compound having a polymerizable group in the alignment film is polymerized can be suppressed to be low. Therefore, decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(實施例3) (Example 3)

製備含有以下之表所示之化合物之液晶組成物(LC-A3)，並使用該液晶組成物。除此以外之條件係設為與實施例1相同，而獲得實施例3之液晶顯示元件。 A liquid crystal composition (LC-A3) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. The other conditions were the same as in Example 1, and the liquid crystal display element of Example 3 was obtained.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述式(I-1)所表示之化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射300秒之紫外線，而獲得實施例3之液晶顯示元件。實施例3之液晶顯示元件與實施例1同樣地具有預傾角，上述聚合性化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied, and the compound represented by the above formula (I-1) is cured. The liquid crystal display element of Example 3 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 300 seconds at 20 mW. The liquid crystal display element of Example 3 had a pretilt angle similarly to Example 1, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut.

將實施例3之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表7。其結果，實施例3之液晶顯示元件所使用之液晶組成 物於照射UV前後未見VHR之大幅降低。研究其原因在於：由於定向膜材料中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之具有聚合性基之聚合性化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 3, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 7 below. As a result, the liquid crystal composition used in the liquid crystal display element of Example 3 There was no significant decrease in VHR before and after UV exposure. The reason for the investigation is that since the polymerizable compound represented by the formula (I) is contained in the alignment film material, the total energy of the UV irradiation when the polymerizable compound having a polymerizable group in the alignment film is polymerized can be suppressed to be low. Therefore, decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(實施例4) (Example 4)

製備含有以下之表所示之化合物之液晶組成物(LC-A4)，並使用該液晶組成物。又，作為垂直定向膜形成材料，使用於含有3%之聚醯亞胺前驅物之聚醯亞胺溶液(商品名：JALS2131-R6，JSR公司製造)中含有1.5%之以下之式(I-1)所表示之化合物、及1.5%之式(Va-1-1)所表示之化合物之溶液。除此以外之條件係設為與實施例1相同，而獲得實施例4之液晶顯示元件。 A liquid crystal composition (LC-A4) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. Further, as a material for vertically oriented film formation, a polyimine solution (trade name: JALS2131-R6, manufactured by JSR Corporation) containing 3% of a polyimide precursor is contained in a formula of 1.5% or less (I- 1) A compound represented by the compound and 1.5% of a compound represented by the formula (Va-1-1). The other conditions were the same as in Example 1, and the liquid crystal display element of Example 4 was obtained.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述式(I-1)所表示之化合物及式(Va-1-1)所表示之化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射300秒之紫外線，而獲得實施例4之液晶顯示元件。實施例4之液晶顯示元件與實施例1同樣地具有預傾角，上述聚合性化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied, and the compound represented by the above formula (I-1) and the compound represented by the formula (Va-1-1) are cured. The liquid crystal display element of Example 4 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 300 seconds at 20 mW. The liquid crystal display element of Example 4 had a pretilt angle similarly to Example 1, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut.

將實施例4之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表9。其結果，實施例4之液晶顯示元件所使用之液晶組成物於照射UV前後未見VHR之大幅降低。研究其原因在於：由於定向膜材料中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之具有聚 合性基之聚合性化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 4, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 9 below. As a result, the liquid crystal composition used in the liquid crystal display element of Example 4 showed no significant decrease in VHR before and after the irradiation of UV. The reason for the research is that since the oriented film material contains the polymerizable compound represented by the general formula (I), the alignment film can be made to have a poly When the polymerizable compound of the conjugated group is polymerized, the total energy of the UV irradiation is suppressed to be low, so that the decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(實施例5) (Example 5)

製備含有以下之表所示之化合物之液晶組成物(LC-A5)，並使用該液晶組成物。又，作為垂直定向膜形成材料，使用於含有3%之聚醯亞胺前驅物之聚醯亞胺溶液(商品名：JALS2131-R6，JSR公司製造)中含有3.0%之以下之式(I-21)所表示之化合物之溶液。除此以外之條件係設為與實施例1相同，而獲得實施例5之液晶顯示元件。 A liquid crystal composition (LC-A5) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. Further, as a material for vertically oriented film formation, a polyimine solution (trade name: JALS2131-R6, manufactured by JSR Corporation) containing 3% of a polyimide precursor is contained in a formula of 3.0% or less (I- 21) A solution of the compound indicated. The other conditions were the same as in Example 1, and the liquid crystal display element of Example 5 was obtained.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述式(I-21)所表示之化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射300秒之紫外線，而獲得實施例5之液晶顯示元件。實施例5之液晶顯示元件與實施例1同樣地具有預傾角，上述聚合性化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied, and the compound represented by the above formula (I-21) is cured. The liquid crystal display element of Example 5 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 300 seconds at 20 mW. The liquid crystal display element of Example 5 had a pretilt angle similarly to Example 1, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut.

將實施例5之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表11。其結果，實施例5之液晶顯示元件所使用之液晶組 成物於照射UV前後未見VHR之大幅降低。研究其原因在於：由於定向膜材料中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之具有聚合性基之聚合性化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 5, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 11 below. As a result, the liquid crystal group used in the liquid crystal display element of Example 5 The product did not show a significant decrease in VHR before and after UV irradiation. The reason for the investigation is that since the polymerizable compound represented by the formula (I) is contained in the alignment film material, the total energy of the UV irradiation when the polymerizable compound having a polymerizable group in the alignment film is polymerized can be suppressed to be low. Therefore, decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(實施例6) (Example 6)

製備含有以下之表所示之化合物之液晶組成物(LC-A6)，並使用該液晶組成物。除此以外之條件係設為與實施例5相同，而獲得實施例6之液晶顯示元件。 A liquid crystal composition (LC-A6) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. The other conditions were the same as in Example 5, and the liquid crystal display element of Example 6 was obtained.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述式(I-21)所表示之化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射300秒之紫外線，而獲得實施例6之液晶顯示元件。實施例6之液晶顯示元件與實施例5同樣地具有預傾角，上述聚合性化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied, and the compound represented by the above formula (I-21) is cured. The liquid crystal display element of Example 6 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 300 seconds at 20 mW. The liquid crystal display element of Example 6 had a pretilt angle similarly to Example 5, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut.

將實施例6之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表13。其結果，實施例6之液晶顯示元件所使用之液晶組成物於照射UV前後未見VHR之大幅降低。研究其原因在於：由於定向膜 材料中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之具有聚合性基之聚合性化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 6, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 13 below. As a result, the liquid crystal composition used in the liquid crystal display device of Example 6 showed no significant decrease in VHR before and after the irradiation of UV. The reason for the study is: due to the orientation film Since the polymerizable compound represented by the formula (I) is contained in the material, the total energy of the UV irradiation when the polymerizable compound having a polymerizable group in the alignment film is polymerized can be suppressed to be low, so that the liquid crystal composition can be suppressed. Decomposition of liquid crystal compounds.

(實施例7) (Example 7)

製備含有以下之表所示之化合物之液晶組成物(LC-B)，並使用該液晶組成物。又，作為垂直定向膜形成材料，使用於含有3%之聚醯亞胺前驅物之聚醯亞胺溶液(商品名：JALS2131-R6，JSR公司製造)中含有3.0%之以下之式(I-33)所表示之化合物之溶液。除此以外之條件係設為與實施例1相同，而獲得實施例7之液晶顯示元件。 A liquid crystal composition (LC-B) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. Further, as a material for vertically oriented film formation, a polyimine solution (trade name: JALS2131-R6, manufactured by JSR Corporation) containing 3% of a polyimide precursor is contained in a formula of 3.0% or less (I- 33) A solution of the compound indicated. The other conditions were the same as in Example 1, and the liquid crystal display element of Example 7 was obtained.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述式(I-33)所表示之化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射300秒之紫外線，而獲得實施例7之液晶顯示元件。實施例7之液晶顯示元件與實施例1同樣地具有預傾角，上述聚合性化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied, and the compound represented by the above formula (I-33) is cured. The liquid crystal display element of Example 7 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 300 seconds at 20 mW. The liquid crystal display element of Example 7 had a pretilt angle similarly to Example 1, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut.

將實施例7之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表15。其結果，實施例7之液晶顯示元件所使用之液晶組 成物於照射UV前後未見VHR之大幅降低。研究其原因在於：由於定向膜材料中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之具有聚合性基之聚合性化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 7, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 15 below. As a result, the liquid crystal group used in the liquid crystal display element of Example 7 The product did not show a significant decrease in VHR before and after UV irradiation. The reason for the investigation is that since the polymerizable compound represented by the formula (I) is contained in the alignment film material, the total energy of the UV irradiation when the polymerizable compound having a polymerizable group in the alignment film is polymerized can be suppressed to be low. Therefore, decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(比較例2) (Comparative Example 2)

作為垂直定向膜形成材料，使用於含有3%之聚醯亞胺前驅物之聚醯亞胺溶液(商品名：JALS2131-R6，JSR公司製造)中含有3.0%之以下之式(Va-1-1)所表示之化合物之溶液，除此以外，以與實施例7同樣之方式，獲得比較例2之液晶顯示元件。 As a material for the vertical alignment film formation, a polyimine solution (trade name: JALS2131-R6, manufactured by JSR Corporation) containing 3% of a polyimide precursor is contained in a formula of 3.0% or less (Va-1- A liquid crystal display element of Comparative Example 2 was obtained in the same manner as in Example 7 except for the solution of the compound shown in the above.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述定向膜中之具有反應性基之聚合性化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射600秒之紫外線，而獲得比較例2之液晶顯示元件。再者，在與實施例7相同之條件(20mW下300秒)下對液晶顯示元件照射紫外線，進行了預傾角之賦 予，但定向膜中之具有反應性基之聚合性化合物之硬化不充分，並未穩定地賦予預傾角，因此維持預傾角需要20mW下600秒之照射。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied, and the polymerizable compound having a reactive group in the alignment film is cured. The liquid crystal display element of Comparative Example 2 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. Further, under the same conditions as in Example 7 (300 seconds at 20 mW), the liquid crystal display element was irradiated with ultraviolet rays, and the pretilt angle was imparted. However, the curing of the polymerizable compound having a reactive group in the alignment film is insufficient, and the pretilt angle is not stably imparted. Therefore, it is necessary to irradiate at 20 mW for 600 seconds while maintaining the pretilt angle.

將比較例2之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表16。其結果，由於比較例2之定向膜材料中不含通式(I)所表示之聚合性化合物，因此，用以使定向膜中之具有聚合性之聚合性化合物硬化之UV照射總能量變大，結果可見VHR之降低，確認到由液晶組成物中之液晶化合物之分解引起之物性降低。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Comparative Example 2, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 16 below. As a result, since the polymerizable compound represented by the formula (I) is not contained in the alignment film material of Comparative Example 2, the total energy of UV irradiation for hardening the polymerizable polymerizable compound in the alignment film becomes large. As a result, it was confirmed that the VHR was lowered, and it was confirmed that the physical properties caused by the decomposition of the liquid crystal compound in the liquid crystal composition were lowered.

(實施例8) (Example 8)

製備含有以下之表所示之化合物之液晶組成物(LC-B2)，並使用該液晶組成物。除此以外之條件係設為與實施例1相同，而獲得實施例8之液晶顯示元件。 A liquid crystal composition (LC-B2) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. The other conditions were the same as in Example 1, and the liquid crystal display element of Example 8 was obtained.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述式(I-1)所表示之化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射300秒之紫外線，而獲得實施例8之液晶顯示元件。實施例8之液晶顯示元件與實施例1同樣地具有預傾角，上述聚合性化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied, and the compound represented by the above formula (I-1) is cured. The liquid crystal display element of Example 8 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 300 seconds at 20 mW. The liquid crystal display element of Example 8 had a pretilt angle similarly to Example 1, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut.

將實施例8之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表18。其結果，實施例8之液晶顯示元件所使用之液晶組成物於照射UV前後未見VHR之降低。研究其原因在於：由於定向膜材料 中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之具有聚合性基之聚合性化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 8, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 18 below. As a result, the liquid crystal composition used in the liquid crystal display element of Example 8 did not show a decrease in VHR before and after the irradiation of UV. The reason for the study is: due to the orientation of the film material Since the polymerizable compound represented by the formula (I) is contained, the total energy of the UV irradiation when the polymerizable compound having a polymerizable group in the alignment film is polymerized can be suppressed to be low, so that the liquid crystal composition can be suppressed. Decomposition of liquid crystal compounds.

(實施例9) (Example 9)

製作第一基板(共用電極基板)，其具備由透明之共用電極構成之透明電極層及彩色濾光片層；及第二基板(像素電極基板)，其具備具有藉由主動元件驅動之透明像素電極之像素電極層。 Manufacturing a first substrate (common electrode substrate) including a transparent electrode layer and a color filter layer formed of a transparent common electrode; and a second substrate (pixel electrode substrate) having a transparent pixel driven by an active device The pixel electrode layer of the electrode.

於像素電極基板中，作為各像素電極，使用為了分割液晶分子之定向而以像素電極存在不具有電極之狹縫之方式蝕刻ITO而成者。 In the pixel electrode substrate, as the respective pixel electrodes, in order to divide the alignment of the liquid crystal molecules, the ITO is etched so that the pixel electrodes have slits having no electrodes.

藉由旋轉塗佈法，將含有聚醯亞胺前驅物及具有聚合性基之聚合性化合物之垂直定向膜材料分別塗佈於共用電極基板及像素電極基板，並以200℃加熱該塗佈膜，藉此使垂直定向膜材料中之聚醯亞胺前驅物硬化，而於各基板之表面形成100nm之垂直定向膜。於該階段，該垂直定向膜中具有聚合性基之聚合性化合物並未硬化。 The vertical alignment film material containing the polyimide precursor and the polymerizable compound having a polymerizable group is applied to the common electrode substrate and the pixel electrode substrate by a spin coating method, and the coating film is heated at 200 ° C. Thereby, the polyimide precursor in the vertical alignment film material is hardened, and a vertical alignment film of 100 nm is formed on the surface of each substrate. At this stage, the polymerizable compound having a polymerizable group in the vertical alignment film is not hardened.

作為垂直定向膜形成材料，使用含有3%之以下之式所表示之聚醯亞胺衍生物、3.0%之式(I-1)所表示之聚合性化合物之N-甲基-2-吡咯啶酮溶液。 As the material for the vertical alignment film formation, N-methyl-2-pyrrolidine having a polyimine derivative represented by a formula of 3% or less and 3.0% of a polymerizable compound represented by the formula (I-1) is used. Ketone solution.

將含有以下所示之化學式所表示之化合物之液晶組成物(LC-A)夾持於形成有垂直定向膜之共用電極基板及像素電極基板後，使密封材料硬化，而形成液晶組成物層。此時，使用厚度3.0μm之間隔件，將液晶組成物層之厚度設為3.0μm。 The liquid crystal composition (LC-A) containing the compound represented by the chemical formula shown below is sandwiched between the common electrode substrate and the pixel electrode substrate on which the vertical alignment film is formed, and then the sealing material is cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.0 μm using a spacer having a thickness of 3.0 μm.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述具有反應性基之聚合性化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射300秒之紫外線，而獲得實施例9之液晶顯示元件。藉由該步驟，形成含有具有聚醯亞胺骨架作為主鏈、具有聚合性基作為側鏈之聚合性化合物之聚合物之垂直定向膜，並對液晶組成物層中之液晶分子賦予預傾角。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the above-mentioned polymerizable compound having a reactive group. The liquid crystal display element of Example 9 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 300 seconds at 20 mW. By this step, a vertical alignment film containing a polymer having a polyethylenimine skeleton as a main chain and a polymerizable compound having a polymerizable group as a side chain is formed, and a pretilt angle is imparted to the liquid crystal molecules in the liquid crystal composition layer.

實施例9之液晶顯示元件沿如圖2所示之像素電極之狹縫，於4個區塊內朝向不同方向具有預傾角，上述聚合性化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The liquid crystal display element of the ninth embodiment has a pretilt angle in different directions in the four blocks along the slit of the pixel electrode as shown in FIG. 2, and after the hardening of the polymerizable compound, even in the state of cutting off the alternating electric field The pretilt angle is also maintained.

將實施例9之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表20。其結果，實施例9之液晶顯示元件所使用之液晶組成物於照射UV前後未見VHR之大幅降低。研究其原因在於：由於定向膜材料中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之具有聚合性基之聚合性化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 9, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 20 below. As a result, the liquid crystal composition used in the liquid crystal display device of Example 9 showed no significant decrease in VHR before and after the irradiation of UV. The reason for the investigation is that since the polymerizable compound represented by the formula (I) is contained in the alignment film material, the total energy of the UV irradiation when the polymerizable compound having a polymerizable group in the alignment film is polymerized can be suppressed to be low. Therefore, decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(比較例3) (Comparative Example 3)

作為垂直定向膜形成材料，使用含有3%之下述之式所表示之聚醯亞胺衍生物、及3%之式(Va-1-1)所表示之聚合性化合物之N-甲基-2-吡咯啶酮溶液，除此以外，以與實施例9同樣之方式，獲得比較例3之液晶顯示元件。 As the material for the vertical alignment film formation, a polyethylenimine derivative represented by the following formula of 3% and a N-methyl group of a polymerizable compound represented by the formula (Va-1-1) of 3% are used. A liquid crystal display element of Comparative Example 3 was obtained in the same manner as in Example 9 except for the 2-pyrrolidone solution.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述定向膜中之具有反應性基之聚合性化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射600秒之紫外線，而獲得比較例3之液晶顯示元件。再者，在與實施例9相同之條件(20mW下300秒)下對液晶顯示元件照射紫外線，進行了預傾角之賦予，但定向膜中之具有反應性基之聚合性化合物之硬化不充分，並未穩定地賦予預傾角，因此維持預傾角需要20mW下600秒之照射。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied, and the polymerizable compound having a reactive group in the alignment film is cured. The liquid crystal display element of Comparative Example 3 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. Further, the liquid crystal display element was irradiated with ultraviolet rays under the same conditions as in Example 9 (300 seconds at 20 mW), and the pretilt angle was imparted, but the curing of the polymerizable compound having a reactive group in the alignment film was insufficient. The pretilt angle is not stably imparted, so maintaining the pretilt angle requires 600 seconds of irradiation at 20 mW.

將比較例3之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像 評價示於以下之表21。其結果，由於比較例3之定向膜材料中不含通式(I)所表示之聚合性化合物，因此，用以使定向膜中之具有聚合性之聚合性化合物硬化之UV照射總能量變大，結果可見VHR之降低，確認到由液晶組成物中之液晶化合物之分解引起之物性降低。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Comparative Example 3, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element, and the afterimage The evaluation is shown in Table 21 below. As a result, since the polymerizable compound represented by the general formula (I) is not contained in the alignment film material of Comparative Example 3, the total energy of UV irradiation for hardening the polymerizable polymerizable compound in the alignment film becomes large. As a result, it was confirmed that the VHR was lowered, and it was confirmed that the physical properties caused by the decomposition of the liquid crystal compound in the liquid crystal composition were lowered.

(實施例10) (Embodiment 10)

製備含有以下之表所示之化合物之液晶組成物(LC-A3)，並使用該液晶組成物。除此以外之條件係設為與實施例9相同，而獲得實施例10之液晶顯示元件。 A liquid crystal composition (LC-A3) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. The other conditions were the same as in Example 9, and the liquid crystal display element of Example 10 was obtained.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述具有反應性基之聚合性化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射600秒之紫外線，而獲得實施例10之液晶顯示元件。實施例10之液晶顯示元件與實施例9同樣地具有預傾角，上述聚合性化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the above-mentioned polymerizable compound having a reactive group. The liquid crystal display element of Example 10 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. The liquid crystal display element of Example 10 had a pretilt angle similarly to Example 9, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut.

將實施例10之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表23。其結果，實施例10之液晶顯示元件所使用之液晶組 成物於照射UV前後未見VHR之大幅降低。研究其原因在於：由於定向膜材料中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之具有聚合性基之聚合性化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 10, the VHR before and after the irradiation of UV, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 23 below. As a result, the liquid crystal group used in the liquid crystal display element of Example 10 The product did not show a significant decrease in VHR before and after UV irradiation. The reason for the investigation is that since the polymerizable compound represented by the formula (I) is contained in the alignment film material, the total energy of the UV irradiation when the polymerizable compound having a polymerizable group in the alignment film is polymerized can be suppressed to be low. Therefore, decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(實施例11) (Example 11)

製備含有以下之表所示之化合物之液晶組成物(LC-A6)，並使用該液晶組成物。又，作為垂直定向膜形成材料，使用含有3%之以下之式所表示之聚醯亞胺衍生物及3%之以下之式(I-21)所表示之聚合性化合物之N-甲基-2-吡咯啶酮溶液。除此以外之條件係設為與實施例9相同，而獲得實施例11之液晶顯示元件。 A liquid crystal composition (LC-A6) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. In addition, as the material for the vertical alignment film formation, a polyethylenimine derivative represented by a formula of 3% or less and a N-methyl group of a polymerizable compound represented by the formula (I-21) of 3% or less are used. 2-pyrrolidone solution. The other conditions were the same as in Example 9, and the liquid crystal display element of Example 11 was obtained.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述具有反應性基之聚合性化合物硬化。使用牛尾電機公司 製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射600秒之紫外線，而獲得實施例11之液晶顯示元件。實施例11之液晶顯示元件與實施例9同樣地具有預傾角，上述聚合性化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the above-mentioned polymerizable compound having a reactive group. Using Oxtail Motor Company The manufactured UIS-S2511RZ was used as an irradiation device, and USH-250BY manufactured by Oxtail Electric Co., Ltd. was used as an ultraviolet lamp, and the liquid crystal display element was irradiated with ultraviolet rays for 600 seconds at 20 mW to obtain a liquid crystal display element of Example 11. The liquid crystal display element of Example 11 had a pretilt angle similarly to Example 9, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut.

將實施例11之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表25。其結果，實施例11之液晶顯示元件所使用之液晶組成物於照射UV前後未見VHR之大幅降低。研究其原因在於：由於定向膜材料中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之具有聚合性基之聚合性化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 11, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 25 below. As a result, the liquid crystal composition used in the liquid crystal display device of Example 11 showed no significant decrease in VHR before and after the irradiation of UV. The reason for the investigation is that since the polymerizable compound represented by the formula (I) is contained in the alignment film material, the total energy of the UV irradiation when the polymerizable compound having a polymerizable group in the alignment film is polymerized can be suppressed to be low. Therefore, decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(實施例12) (Embodiment 12)

製備含有以下之表所示之化合物之液晶組成物(LC-B)，並使用該液晶組成物。又，作為垂直定向膜形成材料，使用含有3%之以下之式所表示之聚醯亞胺衍生物及3%之以下之式(I-33)所表示之聚合性化合物之N-甲基-2-吡咯啶酮溶液。除此以外之條件係設為與實施例9相同，而獲得實施例12之液晶顯示元件。 A liquid crystal composition (LC-B) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. In addition, as the material for the vertical alignment film formation, a poly-imine derivative represented by a formula of 3% or less and a N-methyl group of a polymerizable compound represented by the formula (I-33) of 3% or less are used. 2-pyrrolidone solution. The other conditions were the same as in Example 9, and the liquid crystal display element of Example 12 was obtained.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述具有反應性基之聚合性化合物硬化。使用牛尾電機公司 製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射600秒之紫外線，而獲得實施例12之液晶顯示元件。實施例12之液晶顯示元件與實施例9同樣地具有預傾角，上述聚合性化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the above-mentioned polymerizable compound having a reactive group. Using Oxtail Motor Company The manufactured UIS-S2511RZ was used as an irradiation device, and the liquid crystal display element of Example 12 was obtained by using USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. The liquid crystal display element of Example 12 had a pretilt angle similarly to Example 9, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut.

將實施例12之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表27。其結果，實施例12之液晶顯示元件所使用之液晶組成物於照射UV前後未見VHR之大幅降低。研究其原因在於：由於定向膜材料中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之具有聚合性基之聚合性化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 12, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 27 below. As a result, the liquid crystal composition used in the liquid crystal display device of Example 12 showed no significant decrease in VHR before and after the irradiation of UV. The reason for the investigation is that since the polymerizable compound represented by the formula (I) is contained in the alignment film material, the total energy of the UV irradiation when the polymerizable compound having a polymerizable group in the alignment film is polymerized can be suppressed to be low. Therefore, decomposition of the liquid crystal compound constituting the liquid crystal composition can be suppressed.

(比較例4) (Comparative Example 4)

作為垂直定向膜形成材料，使用含有3%之下述之式所表示之聚醯亞胺衍生物、及3%之式(Va-1-1)所表示之聚合性化合物之N-甲基-2-吡咯啶酮溶液，除此以外，以與實施例12同樣之方式，獲得比較例4之液晶顯示元件。 As the material for the vertical alignment film formation, a polyethylenimine derivative represented by the following formula of 3% and a N-methyl group of a polymerizable compound represented by the formula (Va-1-1) of 3% are used. A liquid crystal display element of Comparative Example 4 was obtained in the same manner as in Example 12 except for the 2-pyrrolidone solution.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述定向膜中之具有反應性基之聚合性化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射600秒之紫外線，而獲得比較例4之液晶顯示元件。再者，在與實施例12相同之條件(20mW下300秒)下對液晶顯示元件照射紫外線，進行了預傾角之賦予，但定向膜中之具有反應性基之聚合性化合物之硬化不充分，並未穩定地賦予預傾角，因此維持預傾角需要20mW下600秒之照射。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied, and the polymerizable compound having a reactive group in the alignment film is cured. The liquid crystal display element of Comparative Example 4 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. Further, under the same conditions as in Example 12 (300 seconds at 20 mW), the liquid crystal display element was irradiated with ultraviolet rays to impart a pretilt angle, but the curing of the polymerizable compound having a reactive group in the alignment film was insufficient. The pretilt angle is not stably imparted, so maintaining the pretilt angle requires 600 seconds of irradiation at 20 mW.

將比較例4之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表28。其結果，由於比較例4之定向膜材料中不含通式(I)所表示之聚合性化合物，因此，用以使定向膜中之具有聚合性之聚合性化合物硬化之UV照射總能量變大，結果可見VHR之降低，確認到由液晶組成物中之液晶化合物之分解引起之物性降低。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Comparative Example 4, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 28 below. As a result, since the polymerizable compound represented by the general formula (I) is not contained in the alignment film material of Comparative Example 4, the total energy of UV irradiation for hardening the polymerizable polymerizable compound in the alignment film becomes large. As a result, it was confirmed that the VHR was lowered, and it was confirmed that the physical properties caused by the decomposition of the liquid crystal compound in the liquid crystal composition were lowered.

(實施例13) (Example 13)

製作第一基板(共用電極基板)，其具備由透明之共用電極構成之透明電極層及彩色濾光片層；及第二基板(像素電極基板)，其具備具有藉由主動元件驅動之透明像素電極之像素電極層。 Manufacturing a first substrate (common electrode substrate) including a transparent electrode layer and a color filter layer formed of a transparent common electrode; and a second substrate (pixel electrode substrate) having a transparent pixel driven by an active device The pixel electrode layer of the electrode.

藉由旋轉塗佈法將含有聚合性液晶化合物及聚合起始劑之垂直定向膜材料分別塗佈於共用電極基板及像素電極基板，而形成厚度200nm之垂直定向膜之前驅物層。作為垂直定向膜形成材料，使用3.0%之以下之式(I-1)所表示之聚合性化合物及97.0%之UCL-011-K1(DIC股份有限公司製造)聚合性化合物。 A vertical alignment film material containing a polymerizable liquid crystal compound and a polymerization initiator was applied to the common electrode substrate and the pixel electrode substrate by a spin coating method to form a vertical alignment film precursor layer having a thickness of 200 nm. As the material for the vertical alignment film formation, a polymerizable compound represented by the formula (I-1) of 3.0% or less and a polymerizable compound of 97.0% of UCL-011-K1 (manufactured by DIC Corporation) were used.

藉由70℃之恆溫槽將塗佈有垂直定向膜形成材料之各基板加熱15分鐘，藉此將所塗佈之垂直定向膜形成材料中之聚合性液晶化合物製成等向性液體。 Each substrate coated with the vertically oriented film forming material was heated by a thermostat at 70 ° C for 15 minutes, whereby the polymerizable liquid crystal compound in the applied vertical alignment film forming material was made into an isotropic liquid.

其後，以10℃/min之速度將溫度降低至室溫，將垂直定向膜形成材料中之聚合性液晶化合物之定向設為垂直定向。 Thereafter, the temperature was lowered to room temperature at a rate of 10 ° C/min, and the orientation of the polymerizable liquid crystal compound in the vertically oriented film forming material was set to a vertical orientation.

對像素電極基板及共用電極基板分別施加自基板面傾斜70° 之磁場，而對聚合性液晶化合物賦予預傾角。於該狀態下，照射紫外線使聚合性液晶化合物硬化，而形成垂直定向膜。 Applying a tilt of 70° from the substrate surface to the pixel electrode substrate and the common electrode substrate The magnetic field imparts a pretilt angle to the polymerizable liquid crystal compound. In this state, the ultraviolet ray is irradiated to cure the polymerizable liquid crystal compound to form a vertical alignment film.

將含有以下所示之化學式所表示之化合物之液晶組成物(LC-A)夾持於形成有垂直定向膜之共用電極基板及像素電極基板後，使密封材料硬化，而形成液晶組成物層。此時，使用厚度3.0μm之間隔件，將液晶組成物層之厚度設為3.0μm。 The liquid crystal composition (LC-A) containing the compound represented by the chemical formula shown below is sandwiched between the common electrode substrate and the pixel electrode substrate on which the vertical alignment film is formed, and then the sealing material is cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.0 μm using a spacer having a thickness of 3.0 μm.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述聚合性化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射300秒之紫外線，而獲得實施例 13之液晶顯示元件。藉由該步驟，形成含有聚合性液晶化合物之聚合物之垂直定向膜，並對液晶組成物層中之液晶分子賦予預傾角。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the polymerizable compound. The UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. was used as an irradiation device, and USH-250BY manufactured by Oxtail Electric Co., Ltd. was used as an ultraviolet lamp, and the liquid crystal display element was irradiated with ultraviolet rays for 300 seconds at 20 mW to obtain an example. 13 liquid crystal display elements. By this step, a vertical alignment film of a polymer containing a polymerizable liquid crystal compound is formed, and a liquid crystal molecule in the liquid crystal composition layer is given a pretilt angle.

實施例13之液晶顯示元件沿如圖2所示之像素電極之狹縫，於4個區塊內朝向不同方向具有預傾角，上述聚合性液晶化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The liquid crystal display element of the thirteenth embodiment has a pretilt angle in different directions in four blocks along the slit of the pixel electrode as shown in FIG. 2, and the state of the alternating electric field is cut even after the hardening of the polymerizable liquid crystal compound. The pretilt angle is also maintained.

將實施例13之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表。其結果，實施例13之液晶顯示元件所使用之液晶組成物於照射UV前後未見VHR之大幅降低。研究其原因在於：由於定向膜材料中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之聚合性液晶化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 13, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in the following table. As a result, the liquid crystal composition used in the liquid crystal display element of Example 13 showed no significant decrease in VHR before and after the irradiation of UV. The reason for the study is that since the polymerizable compound represented by the formula (I) is contained in the alignment film material, the total energy of the UV irradiation when the polymerizable liquid crystal compound in the alignment film is polymerized can be suppressed to be low, so that it can be suppressed. The decomposition of the liquid crystal compound constituting the liquid crystal composition.

(比較例5) (Comparative Example 5)

作為垂直定向膜形成材料，使用100%之UCL-011-K1(DIC股份有限公司製造)，除此以外，以與實施例13同樣之方式，獲得比較例5之液晶顯示元件。 A liquid crystal display element of Comparative Example 5 was obtained in the same manner as in Example 13 except that 100% of UCL-011-K1 (manufactured by DIC Corporation) was used as the material for the vertical alignment film formation.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述聚合性化合物硬化。使用牛尾電機公司製造之UIS- S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射600秒之紫外線，而獲得比較例5之液晶顯示元件。再者，在與實施例13相同之條件(20mW下300秒)下對液晶顯示元件照射紫外線，進行了預傾角之賦予，但定向膜中之聚合性液晶化合物之硬化不充分，並未穩定地賦予預傾角，因此維持預傾角需要20mW下600秒之照射。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the polymerizable compound. Using UIS- manufactured by Niuwei Motor Co., Ltd. S2511RZ was used as an irradiation device, and USH-250BY manufactured by Oxtail Electric Co., Ltd. was used as an ultraviolet lamp, and the liquid crystal display element was irradiated with ultraviolet rays for 600 seconds at 20 mW to obtain a liquid crystal display element of Comparative Example 5. Further, under the same conditions as in Example 13 (300 seconds at 20 mW), the liquid crystal display element was irradiated with ultraviolet rays, and the pretilt angle was imparted. However, the curing of the polymerizable liquid crystal compound in the alignment film was insufficient, and it was not stably The pretilt angle is imparted, so maintaining the pretilt angle requires 600 seconds of illumination at 20 mW.

將比較例5之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表31。其結果，由於比較例5之定向膜材料中不含通式(I)所表示之聚合性化合物，因此用以使定向膜中之聚合性液晶化合物硬化之UV照射總能量變大，結果可見VHR之降低，確認到由液晶組成物中之液晶化合物之分解引起之物性降低。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Comparative Example 5, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 31 below. As a result, since the polymerizable compound represented by the formula (I) is not contained in the alignment film material of the comparative example 5, the total energy of the UV irradiation for hardening the polymerizable liquid crystal compound in the alignment film is increased, and as a result, VHR can be seen. As a result of the decrease, it was confirmed that the physical properties caused by the decomposition of the liquid crystal compound in the liquid crystal composition were lowered.

(實施例14) (Example 14)

製備含有以下之表所示之化合物之液晶組成物(LC-A3)，並使用該液晶組成物，除此以外，設為與實施例13相同之條件，而獲得實施例14之液晶顯示元件。 A liquid crystal display device of Example 14 was obtained under the same conditions as those in Example 13 except that the liquid crystal composition (LC-A3) containing the compound shown in the following Table was used.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述聚合性化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射300秒之紫外線，而獲得實施例14之液晶顯示元件。實施例14之液晶顯示元件與實施例13同樣地具有預傾角，上述聚合性化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the polymerizable compound. The liquid crystal display element of Example 14 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 300 seconds at 20 mW. The liquid crystal display element of Example 14 had a pretilt angle similarly to that of Example 13, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut.

將實施例14之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表33。其結果，實施例14之液晶顯示元件所使用之液晶組 成物於照射UV前後未見VHR之大幅降低。研究其原因在於：由於定向膜材料中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之聚合性液晶化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 14, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 33 below. As a result, the liquid crystal group used in the liquid crystal display element of Example 14 The product did not show a significant decrease in VHR before and after UV irradiation. The reason for the study is that since the polymerizable compound represented by the formula (I) is contained in the alignment film material, the total energy of the UV irradiation when the polymerizable liquid crystal compound in the alignment film is polymerized can be suppressed to be low, so that it can be suppressed. The decomposition of the liquid crystal compound constituting the liquid crystal composition.

(實施例15) (Example 15)

製備含有以下之表所示之化合物之液晶組成物(LC-A6)，並使用該液晶組成物。作為垂直定向膜形成材料，使用3.0%之以下之式(I-21)所表示之聚合性化合物及97.0%之UCL-011-K1(DIC股份有限公司製造)聚合性化合物。除此以外，設為與實施例13相同之條件，而獲得實施例15之液晶顯示元件。 A liquid crystal composition (LC-A6) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. As the material for the vertical alignment film formation, a polymerizable compound represented by the formula (I-21) of 3.0% or less and a polymerizable compound of 97.0% of UCL-011-K1 (manufactured by DIC Corporation) were used. Otherwise, the same conditions as in Example 13 were carried out, and a liquid crystal display element of Example 15 was obtained.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述聚合性化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射300秒之紫外線，而獲得實施例15之液晶顯示元件。實施例15之液晶顯示元件與實施例13同樣地具有預傾角，上述聚合性化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the polymerizable compound. The liquid crystal display element of Example 15 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 300 seconds at 20 mW. The liquid crystal display element of Example 15 had a pretilt angle similarly to that of Example 13, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut.

將實施例15之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表35。其結果，實施例15之液晶顯示元件所使用之液晶組成物於照射UV前後未見VHR之大幅降低。研究其原因在於：由於定向膜材料中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之聚合性液晶化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 15, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 35 below. As a result, the liquid crystal composition used in the liquid crystal display device of Example 15 showed no significant decrease in VHR before and after the irradiation of UV. The reason for the study is that since the polymerizable compound represented by the formula (I) is contained in the alignment film material, the total energy of the UV irradiation when the polymerizable liquid crystal compound in the alignment film is polymerized can be suppressed to be low, so that it can be suppressed. The decomposition of the liquid crystal compound constituting the liquid crystal composition.

(實施例16) (Embodiment 16)

製備含有以下之表所示之化合物之液晶組成物(LC-B)，並使用該液晶組成物。作為垂直定向膜形成材料，使用3.0%之以下之式(I-33)所表示之聚合性化合物及97.0%之UCL-011-K1(DIC股份有限公司製造)聚合性化合物。除此以外，設為與實施例13相同之條件，而獲得實施例16之液晶顯示元件。 A liquid crystal composition (LC-B) containing a compound shown in the following table was prepared, and the liquid crystal composition was used. As the material for the vertical alignment film formation, a polymerizable compound represented by the formula (I-33) of 3.0% or less and a polymerizable compound of 97.0% of UCL-011-K1 (manufactured by DIC Corporation) were used. Otherwise, the same conditions as in Example 13 were carried out, and a liquid crystal display element of Example 16 was obtained.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述聚合性化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射300秒之紫外線，而獲得實施例16之液晶顯示元件。實施例16之液晶顯示元件與實施例13同樣地具有預傾角，上述聚合性化合物之硬化後，即便於切斷交流電場之狀態下，預傾角亦得以維持。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the polymerizable compound. The liquid crystal display element of Example 16 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 300 seconds at 20 mW. The liquid crystal display element of Example 16 had a pretilt angle similarly to Example 13, and after the curing of the polymerizable compound, the pretilt angle was maintained even in the state where the AC electric field was cut.

將實施例16之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表37。其結果，實施例16之液晶顯示元件所使用之液晶組成物於照射UV前後未見VHR之大幅降低。研究其原因在於：由於定向膜材料中含有通式(I)所表示之聚合性化合物，因此可將使定向膜中之聚合性液晶化合物聚合時之UV照射總能量抑制為較低，故而可抑制構成液晶組成物之液晶化合物之分解。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Example 16, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 37 below. As a result, the liquid crystal composition used in the liquid crystal display device of Example 16 showed no significant decrease in VHR before and after the irradiation of UV. The reason for the study is that since the polymerizable compound represented by the formula (I) is contained in the alignment film material, the total energy of the UV irradiation when the polymerizable liquid crystal compound in the alignment film is polymerized can be suppressed to be low, so that it can be suppressed. The decomposition of the liquid crystal compound constituting the liquid crystal composition.

(比較例6) (Comparative Example 6)

作為垂直定向膜形成材料，使用100%之UCL-011-K1(DIC股份有限公司製造)，除此以外，以與實施例16同樣之方式，獲得比較例6之液晶顯示元件。 A liquid crystal display element of Comparative Example 6 was obtained in the same manner as in Example 16 except that 100% of UCL-011-K1 (manufactured by DIC Corporation) was used as the material for the vertical alignment film formation.

於施加矩形交流電場之狀態下對所獲得之液晶顯示元件照射紫外線，使上述聚合性化合物硬化。使用牛尾電機公司製造之UIS-S2511RZ作為照射裝置，並且使用牛尾電機公司製造之USH-250BY作為紫外線燈，以20mW對液晶顯示元件照射600秒之紫外線，而獲得比較例6之液晶顯示元件。再者，在與實施例16相同之條件(20mW下300秒)下對液晶顯示元件照射紫外線，進行了預傾角之賦予，但定向膜中之聚合性液晶化合物之硬化不充分，並未穩定地賦予預傾角，因此維持預傾角需 要20mW下600秒之照射。 The obtained liquid crystal display element is irradiated with ultraviolet rays in a state where a rectangular alternating electric field is applied to cure the polymerizable compound. The liquid crystal display element of Comparative Example 6 was obtained by using the UIS-S2511RZ manufactured by Oxtail Electric Co., Ltd. as an irradiation device, and using the USH-250BY manufactured by Oxtail Electric Co., Ltd. as an ultraviolet lamp, and irradiating the liquid crystal display element with ultraviolet rays for 600 seconds at 20 mW. Further, under the same conditions as in Example 16 (300 seconds at 20 mW), the liquid crystal display element was irradiated with ultraviolet rays, and the pretilt angle was imparted. However, the curing of the polymerizable liquid crystal compound in the alignment film was insufficient, and it was not stably Give pretilt angle, so maintaining pretilt angle It takes 600 seconds to shine at 20mW.

將比較例6之液晶顯示元件所使用之液晶組成物之各物性、照射UV前後之VHR、及所獲得之液晶顯示元件之滴加痕評價、殘像評價示於以下之表38。其結果，由於比較例6之定向膜材料中不含通式(I)所表示之聚合性化合物，因此用以使定向膜中之聚合性液晶化合物硬化之UV照射總能量變大，結果可見VHR之降低，確認到由液晶組成物中之液晶化合物之分解引起之物性降低。 The physical properties of the liquid crystal composition used in the liquid crystal display device of Comparative Example 6, the VHR before and after the UV irradiation, and the evaluation of the dropping of the obtained liquid crystal display element and the afterimage evaluation are shown in Table 38 below. As a result, since the polymerizable compound represented by the formula (I) is not contained in the alignment film material of Comparative Example 6, the total energy of UV irradiation for hardening the polymerizable liquid crystal compound in the alignment film is increased, and as a result, VHR can be seen. As a result of the decrease, it was confirmed that the physical properties caused by the decomposition of the liquid crystal compound in the liquid crystal composition were lowered.

10‧‧‧液晶顯示元件 10‧‧‧Liquid display components

11‧‧‧第一基板 11‧‧‧First substrate

12‧‧‧第二基板 12‧‧‧second substrate

13‧‧‧液晶組成物層 13‧‧‧Liquid composition layer

14‧‧‧共用電極 14‧‧‧Common electrode

15‧‧‧像素電極 15‧‧‧pixel electrode

16‧‧‧垂直定向膜 16‧‧‧Vertical alignment film

17‧‧‧垂直定向膜 17‧‧‧Vertical alignment film

18‧‧‧彩色濾光片 18‧‧‧Color filters

19‧‧‧液晶分子 19‧‧‧ liquid crystal molecules

20‧‧‧聚合物層 20‧‧‧ polymer layer

21‧‧‧聚合物層 21‧‧‧ polymer layer

Claims (12)

一種液晶顯示元件，其具備具有第一基板與第二基板之一組基板、及夾持於上述基板間之液晶組成物層，於上述第一基板與上述第二基板之至少一者具有電極，且於上述第一基板與上述第二基板之至少一者具有定向膜，該定向膜含有藉由使具有聚合性基之化合物之聚合性基聚合而控制上述液晶組成物層中之液晶分子之定向方向的聚合物，構成上述液晶組成物層之液晶組成物含有選自下述通式(N-1)、通式(N-2)、及通式(N-3)所表示之化合物群中之一種或兩種以上之化合物，且含有一種或兩種以上之通式(I)所表示之化合物作為上述具有聚合性基之化合物； (式中，RN11、RN12、RN21、RN22、RN31及RN32分別獨立地表示碳原子數1~8之烷基，該烷基中之一個或非鄰接之兩個以上之-CH2-可分別獨立地被取代為-CH=CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-，AN11、AN12、AN21、AN22、AN31及AN32分別獨立地表示選自由 (a)1,4-伸環己基(存在於該基中之一個-CH2-或未鄰接之兩個以上之-CH2-可被取代為-O-)、(b)1,4-伸苯基(存在於該基中之一個-CH=或未鄰接之兩個以上之-CH=可被取代為-N=)、及(c)萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基或十氫萘-2,6-二基(存在於萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基中之一個-CH=或未鄰接之兩個以上之-CH=可被取代為-N=)所組成之群中之基，上述基(a)、基(b)及基(c)可分別獨立地經氰基、氟原子或氯原子取代，ZN11、ZN12、ZN21、ZN22、ZN31及ZN32分別獨立地表示單鍵、-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-、-CH=N-N=CH-、-CH=CH-、-CF=CF-或-C≡C-，XN21表示氫原子或氟原子，TN31表示-CH2-或氧原子，nN11、nN12、nN21、nN22、nN31及nN32分別獨立地表示0~3之整數，nN11+nN12、nN21+nN22及nN31+nN32分別獨立為1、2或3，於存在多個AN11~AN32、ZN11~ZN32之情形時，該等可相同，亦可不同)； (式中，X10及X11分別獨立地表示氫原子或甲基，Sp3及Sp4分別獨 立地表示單鍵、碳原子數1~8之伸烷基或-X-(CH2)t-(式中，t表示2~7之整數，X表示-O-、-OCOO-、-OCO-、或-COO-，X鍵結於菲環上)，式中之菲環中任意氫原子可被取代為氟原子)。 A liquid crystal display device comprising: a group substrate having a first substrate and a second substrate; and a liquid crystal composition layer sandwiched between the substrates, wherein at least one of the first substrate and the second substrate has an electrode. And an alignment film having at least one of the first substrate and the second substrate, wherein the alignment film comprises controlling the orientation of liquid crystal molecules in the liquid crystal composition layer by polymerizing a polymerizable group of a compound having a polymerizable group The polymer in the direction, the liquid crystal composition constituting the liquid crystal composition layer contains a compound group selected from the group consisting of the following general formula (N-1), general formula (N-2), and general formula (N-3); One or two or more compounds, and one or two or more compounds represented by the formula (I) are used as the above-mentioned polymerizable group; (wherein R N11 , R N12 , R N21 , R N22 , R N31 and R N32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or more of the alkyl groups are not adjacent thereto - CH 2 - may be independently substituted with -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, A N11 , A N12 , A N21 , A N22 , A N31 and A N32 each independently represent a group selected from (a) 1,4-cyclohexylene (one of -CH 2 - present in the group or two or more -CH 2 - which may not be adjacent to - O-), (b) 1,4-phenylene (one present in the group -CH= or two or more non-contiguous -CH= may be substituted with -N=), and (c) naphthalene -2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (present in naphthalene-2,6-diyl or 1 a group of 2,3,4-tetrahydronaphthalene-2,6-diyl-CH= or two or more non-contiguous -CH= can be substituted with -N=) The above group (a), the group (b) and the group (c) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, and Z N11 , Z N12 , Z N21 , Z N22 , Z N31 and Z N32 are each independently It represents a single bond, -CH 2 CH 2 -, - (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO- -OCF 2 -, - CF 2 O -, - CH = NN = CH -, - CH = CH -, - CF = CF- or -C≡C-, X N21 represents a hydrogen atom or a fluorine atom, T N31 represents - CH 2 - or an oxygen atom, n N11 , n N12 , n N21 , n N22 , n N31 and n N32 each independently represent an integer from 0 to 3, n N11 +n N12 , n N21 +n N22 and n N31 +n N32 is independently 1, 2 or 3, and when there are multiple A N11 ~ A N32 , Z N11 ~ Z N32 , the same or different); (wherein X 10 and X 11 each independently represent a hydrogen atom or a methyl group, and Sp 3 and Sp 4 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -X-(CH 2 ) t - (wherein t represents an integer from 2 to 7, X represents -O-, -OCOO-, -OCO-, or -COO-, X is bonded to the phenanthrene ring), and any hydrogen atom in the phenanthrene ring in the formula Can be replaced by a fluorine atom). 如申請專利範圍第1項之液晶顯示元件，其具有多個像素，該像素中具有預傾角不同之兩個以上之區域。 A liquid crystal display element according to claim 1, which has a plurality of pixels having two or more regions having different pretilt angles. 如申請專利範圍第1或2項之液晶顯示元件，其中，上述第一基板具有共用電極，第二基板具有像素電極。 The liquid crystal display device of claim 1 or 2, wherein the first substrate has a common electrode and the second substrate has a pixel electrode. 如申請專利範圍第3項之液晶顯示元件，其於上述共用電極與上述像素電極間具有上述定向膜，該定向膜係對上述第一基板與上述第二基板大致垂直地施加電荷而控制上述液晶組成物層中之液晶分子者。 The liquid crystal display device of claim 3, wherein the alignment film is provided between the common electrode and the pixel electrode, and the alignment film applies an electric charge substantially perpendicularly to the first substrate and the second substrate to control the liquid crystal. The liquid crystal molecules in the composition layer. 如申請專利範圍第1至4項中任一項之液晶顯示元件，其中，上述定向膜含有控制上述液晶組成物層中之液晶分子之定向方向之聚合物，或由聚合性液晶化合物之硬化物形成。 The liquid crystal display element according to any one of claims 1 to 4, wherein the alignment film contains a polymer which controls an orientation direction of liquid crystal molecules in the liquid crystal composition layer, or a cured product of a polymerizable liquid crystal compound form. 如申請專利範圍第5項之液晶顯示元件，其含有具有聚合性基之化合物的聚合物、或含有具有聚醯亞胺骨架作為主鏈且具有交聯性官能基作為側鏈之聚合性化合物的聚合物來作為控制上述液晶組成物層中之液晶分子之定向方向的聚合物。 A liquid crystal display element according to claim 5, which comprises a polymer having a polymerizable group or a polymerizable compound having a polyimine skeleton as a main chain and having a crosslinkable functional group as a side chain. The polymer serves as a polymer for controlling the orientation direction of the liquid crystal molecules in the liquid crystal composition layer. 如申請專利範圍第1至6項中任一項之液晶顯示元件，其進而於上述定向膜表面具有控制液晶分子之定向並使其穩定化之一種或兩種以上之聚合性化合物的聚合物。 The liquid crystal display element according to any one of the first to sixth aspects of the invention, further comprising a polymer of one or two or more polymerizable compounds which control the orientation of the liquid crystal molecules and stabilize the surface of the alignment film. 一種液晶顯示元件之製造方法，其係藉由於第一基板與第二基板之至少一者塗佈定向材料並加熱而形成定向膜材料後，藉由至少一者具有 電極之上述第一基板與上述第二基板夾持液晶組成物，並於施加電壓之狀態下對上述電極照射活性能量線，藉此使上述定向膜材料中所含之具有聚合性基之化合物之聚合性基聚合而具有控制上述液晶組成物層中之液晶分子之定向方向之定向膜，上述液晶組成物含有選自下述通式(N-1)、通式(N-2)、及通式(N-3)所表示之化合物群中之一種或兩種以上之化合物，且含有一種或兩種以上之通式(I)所表示之化合物作為上述具有聚合性基之化合物， (式中，RN11、RN12、RN21、RN22、RN31及RN32分別獨立地表示碳原子數1~8之烷基，該烷基中之一個或非鄰接之兩個以上之-CH2-可分別獨立地被取代為-CH=CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-，AN11、AN12、AN21、AN22、AN31及AN32分別獨立地表示選自由(a)1,4-伸環己基(存在於該基中之一個-CH2-或未鄰接之兩個以上之-CH2-可被取代為-O-)、 (b)1,4-伸苯基(存在於該基中之一個-CH=或未鄰接之兩個以上之-CH=可被取代為-N=)、及(c)萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基或十氫萘-2,6-二基(存在於萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基中之一個-CH=或未鄰接之兩個以上之-CH=可被取代為-N=)所組成之群中之基，上述基(a)、基(b)及基(c)可分別獨立地經氰基、氟原子或氯原子取代，ZN11、ZN12、ZN21、ZN22、ZN31及ZN32分別獨立地表示單鍵、-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-OCF2-、-CF2O-、-CH=N-N=CH-、-CH=CH-、-CF=CF-或-C≡C-，XN21表示氫原子或氟原子，TN31表示-CH2-或氧原子，nN11、nN12、nN21、nN22、nN31及nN32分別獨立地表示0~3之整數，nN11+nN12、nN21+nN22及nN31+nN32分別獨立為1、2或3，於存在多個AN11~AN32、ZN11~ZN32之情形時，該等可相同，亦可不同)； (式中，X10及X11分別獨立地表示氫原子或甲基，Sp3及Sp4分別獨立地表示單鍵、碳原子數1~8之伸烷基或-X-(CH2)t-(式中，t表示2~7之整數，X表示-O-、-OCOO-、-OCO-、或-COO-， X鍵結於菲環上)，式中之菲環中任意氫原子可被取代為氟原子)。 A method for manufacturing a liquid crystal display device, wherein the first substrate having the electrode and the above is formed by forming at least one of the first substrate and the second substrate by applying an alignment material and heating to form an alignment film material The liquid crystal composition is sandwiched between the second substrate, and the electrode is irradiated with an active energy ray in a state where a voltage is applied, thereby polymerizing the polymerizable group of the polymerizable group contained in the alignment film material to control the above. An alignment film of an alignment direction of liquid crystal molecules in the liquid crystal composition layer, wherein the liquid crystal composition is selected from the group consisting of the following general formula (N-1), general formula (N-2), and general formula (N-3) One or two or more compounds of the compound group, and one or two or more compounds represented by the formula (I) are used as the above-mentioned compound having a polymerizable group, (wherein R N11 , R N12 , R N21 , R N22 , R N31 and R N32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or more of the alkyl groups are not adjacent thereto - CH 2 - may be independently substituted with -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, A N11 , A N12 , A N21 , A N22 , A N31 and A N32 each independently represent a group selected from (a) 1,4-cyclohexylene (one of -CH 2 - present in the group or two or more -CH 2 - which may not be adjacent to - O-), (b) 1,4-phenylene (one present in the group -CH= or two or more adjacent to -CH= may be substituted with -N=), and (c) naphthalene -2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (present in naphthalene-2,6-diyl or 1 a group of 2,3,4-tetrahydronaphthalene-2,6-diyl-CH= or two or more non-contiguous -CH= can be substituted with -N=) The above-mentioned group (a), the group (b) and the group (c) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, and Z N11 , Z N12 , Z N21 , Z N22 , Z N31 and Z N32 are each independently Represents a single bond, -CH 2 CH 2 -, -(CH 2 ) 4 -, -OCH 2 -, -CH 2 O-, -COO-, -OCO- , -OCF 2 -, -CF 2 O-, -CH=NN=CH-, -CH=CH-, -CF=CF- or -C≡C-, X N21 represents a hydrogen atom or a fluorine atom, and T N31 represents -CH 2 - or an oxygen atom, n N11 , n N12 , n N21 , n N22 , n N31 and n N32 each independently represent an integer from 0 to 3, n N11 + n N12 , n N21 + n N22 and n N31 + n N32 is independently 1, 2 or 3, and when there are multiple A N11 ~ A N32 , Z N11 ~ Z N32 , the same or different); (wherein X 10 and X 11 each independently represent a hydrogen atom or a methyl group, and Sp 3 and Sp 4 each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -X-(CH 2 ) t - (where t represents an integer from 2 to 7, X represents -O-, -OCOO-, -OCO-, or -COO-, X is bonded to the phenanthrene ring), and any hydrogen atom in the phenanthrene ring of the formula Can be replaced by a fluorine atom). 如申請專利範圍第8項之液晶顯示元件之製造方法，其中，上述定向膜材料含有控制上述液晶組成物層中之液晶分子之定向方向之聚合物，或由聚合性液晶化合物之硬化物形成。 The method for producing a liquid crystal display device according to claim 8, wherein the alignment film material contains a polymer which controls an orientation direction of liquid crystal molecules in the liquid crystal composition layer, or is formed of a cured product of a polymerizable liquid crystal compound. 如申請專利範圍第9項之液晶顯示元件之製造方法，其中，該液晶顯示元件含有具有聚合性基之化合物的聚合物、或含有具有聚醯亞胺骨架作為主鏈且具有交聯性官能基作為側鏈之聚合性化合物的聚合物來作為控制上述液晶組成物層中之液晶分子之定向方向的聚合物。 The method for producing a liquid crystal display element according to claim 9, wherein the liquid crystal display element contains a polymer having a polymerizable group or a polyethylenimine skeleton as a main chain and has a crosslinkable functional group. A polymer which is a side chain polymerizable compound is used as a polymer which controls the orientation direction of the liquid crystal molecules in the liquid crystal composition layer. 如申請專利範圍第9或10項之液晶顯示元件之製造方法，其中，該液晶顯示元件進而於上述定向膜表面具有控制液晶分子之定向並使其穩定化之一種或兩種以上之聚合性化合物之聚合物。 The method for producing a liquid crystal display device according to the ninth or tenth aspect, wherein the liquid crystal display device further has one or two or more polymerizable compounds which control the orientation of the liquid crystal molecules and stabilize the surface of the alignment film. The polymer. 如申請專利範圍第9至11項中任一項之液晶顯示元件之製造方法，其中，上述活性能量線為紫外線，其強度為2mW/cm-2~100mW/cm-2，照射總能量為10J~300J。 The method for producing a liquid crystal display device according to any one of claims 9 to 11, wherein the active energy ray is ultraviolet ray, the intensity is 2 mW/cm -2 to 100 mW/cm -2 , and the total irradiation energy is 10 J. ~300J.
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