TWI754000B

TWI754000B - Polymerizable composition, liquid crystal composite, optical anisotropy, and liquid crystal display element

Info

Publication number: TWI754000B
Application number: TW107103564A
Authority: TW
Inventors: 矢野智広; 近藤史尚
Original assignee: 日商捷恩智股份有限公司; 日商捷恩智石油化學股份有限公司
Priority date: 2017-03-14
Filing date: 2018-02-01
Publication date: 2022-02-01
Also published as: CN110325507A; CN110325507B; JP6787478B2; JPWO2018168205A1; TW201840829A; WO2018168205A1

Abstract

一種式(1)所表示的聚合性化合物、包含該化合物及液晶組成物的聚合性組成物、由該聚合性組成物製備的液晶複合體、以及具有該液晶複合體的液晶顯示元件。 A polymerizable compound represented by formula (1), a polymerizable composition comprising the compound and a liquid crystal composition, a liquid crystal composite prepared from the polymerizable composition, and a liquid crystal display element having the liquid crystal composite.

(R¹)_c-MES-(SP¹-P¹)_a (1) (R ¹ ) _c -MES-(SP ¹ -P ¹ ) _a (1)

式(1)中，例如，R¹為氫、鹵素、-SP¹-P¹或碳數1至15的烷基，MES為具有至少一個環及N原子的的液晶原基，SP¹為單鍵或碳數1至10的伸烷基，P¹為聚合性基，a為0、1、2、3或4，c為0、1、2、3或4。 In formula (1), for example, R ¹ is hydrogen, halogen, -SP ¹ -P ¹ or an alkyl group having 1 to 15 carbon atoms, MES is a mesogen having at least one ring and an N atom, and SP ¹ is a single A bond or an alkylene group having 1 to 10 carbon atoms, P ¹ is a polymerizable group, a is 0, 1, 2, 3 or 4, and c is 0, 1, 2, 3 or 4.

Description

聚合性組成物、液晶複合體、光學各向異性體及液晶顯示元件 Polymerizable composition, liquid crystal composite, optical anisotropy and liquid crystal display elements

本發明是有關於一種聚合性化合物、包含該聚合性化合物及液晶組成物的聚合性組成物、由該聚合性組成物製備的液晶複合體、以及液晶顯示元件。 The present invention relates to a polymerizable compound, a polymerizable composition comprising the polymerizable compound and a liquid crystal composition, a liquid crystal composite prepared from the polymerizable composition, and a liquid crystal display element.

液晶顯示元件利用液晶組成物中液晶分子所具有的光學各向異性、介電各向異性等。基於液晶分子動作模式的分類為相變(phase change，PC)模式、扭轉向列(twisted nematic，TN)模式、超扭轉向列(super twisted nematic，STN)模式、雙穩態扭轉向列(bistable twisted nematic，BTN)模式、電控雙折射(electrically controlled birefringence，ECB)模式、光學補償彎曲(optically compensated bend，OCB)模式、共面切換(in-plane switching，IPS)模式、邊緣場切換(fringe field switching，FFS)模式、垂直配向(vertical alignment，VA)模式等。 The liquid crystal display element utilizes the optical anisotropy, dielectric anisotropy, and the like of liquid crystal molecules in the liquid crystal composition. The liquid crystal molecules are classified into phase change (PC) mode, twisted nematic (TN) mode, super twisted nematic (STN) mode, bistable twisted nematic (bistable) twisted nematic (BTN) mode, electrically controlled birefringence (ECB) mode, optically compensated bend (OCB) mode, in-plane switching (IPS) mode, fringe field switching (fringe) field switching, FFS) mode, vertical alignment (vertical alignment, VA) mode, etc.

於這些液晶顯示元件中，其初期配向一般是藉由聚醯亞胺配向膜而達成。另一方面，於不具有配向膜的液晶顯示元件中使用含有極性化合物及聚合物的液晶組成物或含有聚合性極性化合物的液晶組成物。首先，將添加有少量極性化合物及少量聚合性化合物或添加有少量聚合性極性化合物的組成物注入至元件中。此處，亦存在藉由極性化合物的作用而液晶分子配向的情況。接著，藉由對該組成物照射紫外線，聚合性化合物或聚合性極性化合物聚合。藉此，液晶分子進行配向，且該配向狀態得以穩定化，或注入後的配向得以穩定化。該組成物中，能夠利用極性化合物及聚合物或聚合性極性化合物來控制液晶分子的配向，故而元件的響應時間縮短，圖像的殘像得到改善。進而，不具有配向膜的元件中無需形成配向膜的步驟，且因不具有配向膜，故具有不存在由配向膜與組成物的相互作用引起的元件的電阻降低的優點。於具有TN、ECB、OCB、IPS、VA、FFS、FPA之類的模式的元件中可期待由極性化合物與聚合物的組合產生的此種優點。 In these liquid crystal display elements, the initial alignment is generally achieved by a polyimide alignment film. On the other hand, a liquid crystal composition containing a polar compound and a polymer or a liquid crystal composition containing a polymerizable polar compound is used in a liquid crystal display element that does not have an alignment film. First, a small amount of polar compounds and a small amount of polymerization will be added A compound or a composition added with a small amount of a polymeric polar compound is injected into the element. Here, there are cases where the liquid crystal molecules are aligned by the action of the polar compound. Next, the polymerizable compound or the polymerizable polar compound is polymerized by irradiating the composition with ultraviolet rays. Thereby, the liquid crystal molecules are aligned, and the alignment state is stabilized, or the alignment after injection is stabilized. In this composition, the alignment of the liquid crystal molecules can be controlled by the polar compound and the polymer or the polymerizable polar compound, so that the response time of the element is shortened, and the afterimage of the image is improved. Furthermore, a step of forming an alignment film is not required in an element without an alignment film, and since it does not have an alignment film, there is an advantage that the resistance of the element does not decrease due to the interaction between the alignment film and the composition. Such advantages resulting from the combination of polar compounds and polymers can be expected in devices with modes such as TN, ECB, OCB, IPS, VA, FFS, FPA.

使聚合物組合於液晶組成物的方法可應用於PS-TN、PS-IPS、PS-FFS、PSA-VA、PSA-OCB等多種動作模式的液晶顯示元件。對此種模式的元件使用的聚合性化合物要求優異的使液晶分子配向的能力、適當的聚合反應性、高轉化率及於液晶組成物中的高溶解性等特性。目前已開發有多種聚合性化合物，但期望開發進一步提升所述特性的化合物。 The method of incorporating a polymer into a liquid crystal composition can be applied to liquid crystal display elements of various operation modes such as PS-TN, PS-IPS, PS-FFS, PSA-VA, and PSA-OCB. The polymerizable compound used for the element of this mode is required to have characteristics such as excellent ability to align liquid crystal molecules, appropriate polymerization reactivity, high conversion rate, and high solubility in a liquid crystal composition. A variety of polymerizable compounds have been developed, but it is desired to develop compounds that further improve the properties.

[現有技術文獻] [Prior Art Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利特開2003-307720號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2003-307720

[專利文獻2]日本專利特開2004-131704號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2004-131704

[專利文獻3]日本專利特開2006-133619號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2006-133619

[專利文獻4]日本專利特表2010-537256號公報 [Patent Document 4] Japanese Patent Publication No. 2010-537256

[專利文獻5]日本專利特開平10-186330號公報 [Patent Document 5] Japanese Patent Laid-Open No. 10-186330

[專利文獻6]歐洲專利申請公開1889894號說明書 [Patent Document 6] Specification of European Patent Application Publication No. 1889894

[專利文獻7]中國專利申請公開第101671252號說明書 [Patent Document 7] Chinese Patent Application Publication No. 101671252 Specification

[專利文獻8]國際公開第2013/77343號 [Patent Document 8] International Publication No. 2013/77343

[專利文獻9]國際公開第2014/6962號 [Patent Document 9] International Publication No. 2014/6962

本發明的第一課題為提供一種聚合性化合物，其具有優異的使液晶分子配向的能力、適當的聚合反應性、高轉化率、高電壓保持率及於液晶組成物中的高溶解度的至少一種。第二課題為提供一種液晶複合體，其滿足向列相的上限溫度高、向列相的下限溫度低、黏度低、光學各向異性適當、介電各向異性大、彈性常數適當、比電阻大、預傾(pretilt)適當等物性的至少一種。該課題為提供一種關於至少兩種物性而具有適當的平衡的液晶複合體。第三課題為提供一種液晶顯示元件，其具有寬廣的元件可使用溫度範圍、短響應時間、低臨限電壓、高對比度及長壽命的至少一種。 The first object of the present invention is to provide a polymerizable compound having at least one of excellent ability to align liquid crystal molecules, appropriate polymerization reactivity, high conversion, high voltage retention, and high solubility in liquid crystal compositions . The second problem is to provide a liquid crystal composite which satisfies the requirements of high upper limit temperature of nematic phase, low lower limit temperature of nematic phase, low viscosity, suitable optical anisotropy, large dielectric anisotropy, suitable elastic constant, and specific resistance. At least one of physical properties such as large size and suitable pretilt. This subject is to provide a liquid crystal composite having an appropriate balance with respect to at least two physical properties. The third subject is to provide a liquid crystal display device having at least one of a wide usable temperature range, a short response time, a low threshold voltage, a high contrast ratio, and a long life.

項1. 一種聚合性化合物，其由下述式(1)表示：[化15] (R¹)_c-MES-(SP¹-P¹)_a (1) Item 1. A polymerizable compound represented by the following formula (1): [Chem. 15] (R ¹ ) _c -MES-(SP ¹ -P ¹ ) _a (1)

式(1)中，R¹為氫、鹵素、-SP¹-P¹或碳數1至15的烷基，於此烷基中，至少一個-CH₂-可經-O-或-S-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素或-SP¹-P¹取代；MES為具有至少一個環及N原子的液晶原基；SP¹為單鍵或碳數1至10的伸烷基，於此伸烷基中，至少一個-CH₂-可經-O-、-CO-、-COO-、-OCO-或-OCOO-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素取代；P¹為聚合性基；a為0、1、2、3或4；c為0、1、2、3或4。 In formula (1), R ¹ is hydrogen, halogen, -SP ¹ -P ¹ or an alkyl group having 1 to 15 carbon atoms, in this alkyl group, at least one -CH ₂ - may be via -O- or -S- Substituted, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by halogen or -SP ¹ -P ¹ ; MES has Mesogen group with at least one ring and N atom; SP ¹ is a single bond or an alkylene group having 1 to 10 carbon atoms, in this alkylene group, at least one -CH ₂ - can pass through -O-, -CO-, -COO-, -OCO- or -OCOO- substituted, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, in these groups at least one hydrogen may be substituted by halogen ; P ¹ is a polymerizable group; a is 0, 1, 2, 3 or 4; c is 0, 1, 2, 3 or 4.

項2. 如項1所述的聚合性化合物，其由下述式(1-1)表示：[化16]

Item 2. The polymerizable compound according to Item 1, which is represented by the following formula (1-1):

式(1-1)中，R⁵、R⁶及R⁷獨立地為氫、鹵素、-SP¹-P¹、-SP²-P²或碳數1至15的烷基，於此烷基中，至少一個-CH₂-可經-O-或-S-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素、-SP¹-P¹或-SP²-P²取代；a1及a2獨立地為0、1、2、3或4，a1與a2的合計為1~8；環A¹及環A²獨立地為由碳數3至18的脂環式烴、碳數6至18的芳香族烴或碳數3至18的雜芳香族烴所衍生的二價基，於此二價基中，至少一個氫可經鹵素、碳數1至12的烷基、碳數1至12的烷氧基、碳數1至12的烯基或碳數1至12的烯氧基取代，於這些一價烴基中，至少一個氫可經鹵素取代；Z¹及Z²獨立地為單鍵或碳數1至10的伸烷基，於此伸烷基中，至少一個-CH₂-可經-O-、-CO-、-COO-或-OCO-取代，至少一個-(CH₂)₂-可經-CH=CH-、-C(CH₃)=CH-、-CH=C(CH₃)-、-C(CH₃)=C(CH₃)-或-CH≡CH-取代，於這些二價基中，至少一個氫可經鹵素取代；b1及b2獨立地為0、1、2或3； SP¹及SP²獨立地為單鍵或碳數1至10的伸烷基，於此伸烷基中，至少一個-CH₂-可經-O-、-CO-、-COO-、-OCO-或-OCOO-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素取代；P¹及P²獨立地為由下述式(1a)、式(1b)、式(1c)、式(1d)或式(1e)表示的基團；

In formula (1-1), R ⁵ , R ⁶ and R ⁷ are independently hydrogen, halogen, -SP ¹ -P ¹ , -SP ² -P ² or an alkyl group having 1 to 15 carbon atoms, wherein the alkyl group is Among them, at least one -CH ₂ - can be substituted by -O- or -S-, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, among these groups, at least One hydrogen can be substituted by halogen, -SP ¹ -P ¹ or -SP ² -P ² ; a1 and a2 are independently 0, 1, 2, 3 or 4, and the total of a1 and a2 is 1~8; ring A ¹ and Ring A ² is independently a divalent group derived from an alicyclic hydrocarbon with a carbon number of 3 to 18, an aromatic hydrocarbon with a carbon number of 6 to 18 or a heteroaromatic hydrocarbon with a carbon number of 3 to 18, where the divalent In the group, at least one hydrogen may be substituted by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons or alkenyloxy having 1 to 12 carbons, in Among these monovalent hydrocarbon groups, at least one hydrogen may be substituted by halogen; Z ¹ and Z ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be replaced by a halogen. -O-, -CO-, -COO- or -OCO- substituted, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, -C(CH ₃ )=C(CH ₃ )- or -CH≡CH- substituted, in these divalent groups, at least one hydrogen can be substituted by halogen; b1 and b2 are independently 0, 1, 2 or 3; SP ¹ and SP ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, in this alkylene group, at least one -CH ₂ - may be through -O-, -CO-, -COO -, -OCO- or -OCOO- substituted, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, in these groups at least one hydrogen may be substituted by halogen; P ¹ and P ² are independently a group represented by the following formula (1a), formula (1b), formula (1c), formula (1d) or formula (1e);

式(1a)、式(1b)、式(1c)、式(1d)及式(1e)中，M¹及M²獨立地為氫、鹵素或碳數1至10的烷基，於此烷基中，至少一個-CH₂-可經-O-或-S-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素、-SP¹-P¹或-SP²-P²取代；R²、R³、R⁴及R⁸獨立地為氫或碳數1至15的直鏈狀、分支狀或環狀的烷基，於此烷基中，至少一個-CH₂-可經-O-或-S-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素取代。 In formula (1a), formula (1b), formula (1c), formula (1d) and formula (1e), M ¹ and M ² are independently hydrogen, halogen or an alkyl group having 1 to 10 carbon atoms, where the alkane In the group, at least one -CH ₂ - can be substituted by -O- or -S-, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, At least one hydrogen can be substituted by halogen, -SP ¹ -P ¹ or -SP ² -P ² ; R ² , R ³ , R ⁴ and R ⁸ are independently hydrogen or straight-chain or branched with 1 to 15 carbon atoms Or cyclic alkyl, in this alkyl, at least one -CH ₂ - can be substituted by -O- or -S-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡ C-substituted, in these groups at least one hydrogen may be replaced by halogen.

項3. 如項1所述的聚合性化合物，其由下述式(1-1-1) 至式(1-1-3)中的任一者表示：

Item 3. The polymerizable compound according to Item 1, which is represented by any one of the following formulae (1-1-1) to (1-1-3):

式(1-1-1)至式(1-1-3)中，R⁷為氫、鹵素、-SP¹-P¹、-SP²-P²或碳數1至15的烷基，於此烷基中，至少一個-CH₂-可經-O-或-S-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素、-SP¹-P¹或-SP²-P²取代；環A¹、環A²、環A³及環A⁴獨立地為由碳數3至18的脂環式烴、碳數6至18的芳香族烴或碳數3至18的雜芳香族烴所衍生的二價基，於此二價基中，至少一個氫可經鹵素、碳數1至12的烷基、碳數1至12的烷氧基、碳數1至12的烯基或碳數1至12的烯氧基取代，於這些一價烴基中，至少一個氫可經鹵素取代；Z¹、Z²、Z³及Z⁴獨立地為單鍵或碳數1至10的伸烷基，於此伸烷基中，至少一個-CH₂-可經-O-、-CO-、-COO-或-OCO-取代，至少一個-(CH₂)₂-可經-CH=CH-、-C(CH₃)=CH-、-CH=C(CH₃)-、 -C(CH₃)=C(CH₃)-或-CH≡CH-取代，於這些二價基中，至少一個氫可經鹵素取代；SP¹及SP²獨立地為單鍵或碳數1至10的伸烷基，於此伸烷基中，至少一個-CH₂-可經-O-、-CO-、-COO-、-OCO-或-OCOO-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素取代；P¹及P²獨立地為由下述式(1a)、式(1b)、式(1c)、式(1d)或式(1e)表示的基團；

In formula (1-1-1) to formula (1-1-3), R ⁷ is hydrogen, halogen, -SP ¹ -P ¹ , -SP ² -P ² or an alkyl group having 1 to 15 carbon atoms, in In this alkyl group, at least one -CH ₂ - can be substituted by -O- or -S-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-. wherein, at least one hydrogen may be substituted by halogen, -SP ¹ -P ¹ or -SP ² -P ² ; Ring A ¹ , Ring A ² , Ring A ³ and Ring A ⁴ are independently aliphatic with 3 to 18 carbon atoms Divalent radicals derived from cyclic hydrocarbons, aromatic hydrocarbons with 6 to 18 carbon atoms, or heteroaromatic hydrocarbons with 3 to 18 carbon atoms, in which at least one hydrogen Alkyl, alkoxy with 1 to 12 carbons, alkenyl with 1 to 12 carbons or alkenyl with 1 to 12 carbons are substituted, in these monovalent hydrocarbon groups, at least one hydrogen can be substituted by halogen; Z ¹ , Z ² , Z ³ and Z ⁴ are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be through -O-, -CO-, - COO- or -OCO- substituted, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, -C(CH ₃ )=C(CH ₃ )- or -CH≡CH- substituted, in these divalent groups, at least one hydrogen may be substituted by halogen; SP ¹ and SP ² are independently a single bond or an alkylene having 1 to 10 carbons base, in this alkylene, at least one -CH ₂ - can be substituted by -O-, -CO-, -COO-, -OCO- or -OCOO-, and at least one -(CH ₂ ) ₂ - can be substituted by - CH=CH- or -C≡C- substituted, in these groups, at least one hydrogen can be substituted by halogen; P ¹ and P ² are independently represented by the following formulas (1a), (1b), (1c) ), a group represented by formula (1d) or formula (1e);

項4. 如項1所述的聚合性化合物，其由下述式(1-1-4)至式(1-1-6)中的任一者表示：

Item 4. The polymerizable compound according to Item 1, which is represented by any one of the following formulae (1-1-4) to (1-1-6):

式(1-1-4)至式(1-1-6)中，R⁷為氫、鹵素、-SP¹-P¹、-SP²-P²或碳數1至15的烷基，於此烷基中，至少一個-CH₂-可經-O-或-S-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素、-SP¹-P¹或-SP²-P²取代；環A¹、環A²、環A³及環A⁴獨立地為由碳數3至18的脂環式烴、碳數6至18的芳香族烴或碳數3至18的雜芳香族烴所衍生的二價基，於此二價基中，至少一個氫可經鹵素、碳數1至12的烷基、碳數1至12的烷氧基、碳數1至12的烯基或碳數1至12的烯氧基取代，於這些一價烴基中，至少一個氫可經鹵素取代；SP¹及SP²獨立地為單鍵或碳數1至10的伸烷基，於此伸烷基中，至少一個-CH₂-可經-O-、-CO-、-COO-、-OCO-或-OCOO-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素取代；P¹及P²獨立地為由下述式(1a)、式(1b)、式(1c)、式(1d)或式(1e)表示的基團；

In formula (1-1-4) to formula (1-1-6), R ⁷ is hydrogen, halogen, -SP ¹ -P ¹ , -SP ² -P ² or an alkyl group having 1 to 15 carbon atoms, in In this alkyl group, at least one -CH ₂ - can be substituted by -O- or -S-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-. wherein, at least one hydrogen may be substituted by halogen, -SP ¹ -P ¹ or -SP ² -P ² ; Ring A ¹ , Ring A ² , Ring A ³ and Ring A ⁴ are independently aliphatic with 3 to 18 carbon atoms Divalent radicals derived from cyclic hydrocarbons, aromatic hydrocarbons with 6 to 18 carbon atoms, or heteroaromatic hydrocarbons with 3 to 18 carbon atoms, in which at least one hydrogen Alkyl, alkoxy with 1 to 12 carbons, alkenyl with 1 to 12 carbons or alkenyl with 1 to 12 carbons are substituted, in these monovalent hydrocarbon groups, at least one hydrogen can be substituted by halogen; SP ¹ and SP ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in this alkylene group, at least one -CH ₂ - may be via -O-, -CO-, -COO-, -OCO- Or -OCOO- substituted, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by halogen; P ¹ and P ² are independent is a group represented by the following formula (1a), formula (1b), formula (1c), formula (1d) or formula (1e);

項5. 如項1所述的聚合性化合物，其由式(1-1-4)至式(1-1-6)中的任一者表示：

Item 5. The polymerizable compound according to Item 1, which is represented by any one of formula (1-1-4) to formula (1-1-6):

式(1-1-4)至式(1-1-6)中，R⁷為氫、鹵素、-SP¹-P¹、-SP²-P²或碳數1至15的烷基，於此烷基中，至少一個-CH₂-可經-O-或-S-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素、-SP¹-P¹或-SP²-P²取代；環A¹及環A²獨立地為1,4-伸苯基，這些環上的至少一個氫可經鹵素取代；環A³及環A⁴獨立地為1,4-伸環己基、1,4-伸環己烯基或1,4-伸苯基，這些環上的至少一個氫可經鹵素取代；SP¹及SP²獨立地為單鍵或碳數1至10的伸烷基，於此伸烷基中，至少一個-CH₂-可經-O-、-CO-、-COO-、-OCO-或-OCOO-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素取代；P¹及P²獨立地為由下述式(1a)、式(1b)、式(1c)、式(1d) 或式(1e)表示的基團；

In formula (1-1-4) to formula (1-1-6), R ⁷ is hydrogen, halogen, -SP ¹ -P ¹ , -SP ² -P ² or an alkyl group having 1 to 15 carbon atoms, in In this alkyl group, at least one -CH ₂ - can be substituted by -O- or -S-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-. wherein, at least one hydrogen can be substituted by halogen, -SP ¹ -P ¹ or -SP ² -P ² ; Ring A ¹ and Ring A ² are independently 1,4-phenylene, and at least one hydrogen on these rings can be Substituted by halogen; Ring A ³ and Ring A ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenyl or 1,4-phenylene, and at least one hydrogen on these rings can be halogenated Substituted; SP ¹ and SP ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in this alkylene group, at least one -CH ₂ - can be changed to -OCO- or -OCOO- substituted, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by halogen; P ¹ and P ² is independently a group represented by the following formula (1a), formula (1b), formula (1c), formula (1d) or formula (1e);

項6. 如項1所述的聚合性化合物，其由下述式(1-1-7)表示：

Item 6. The polymerizable compound according to Item 1, which is represented by the following formula (1-1-7):

式(1-1-7)中，環A¹及環A²獨立地為1,4-伸苯基，這些環上的至少一個氫可經鹵素取代；SP¹及SP²獨立地為單鍵或碳數1至10的伸烷基，於此伸烷基中，至少一個-CH₂-可經-O-、-CO-、-COO-、-OCO-或-OCOO-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素取代；P¹及P²獨立地為由下述式(1a)、式(1b)、式(1c)、式(1d)或式(1e)表示的基團；

In formula (1-1-7), ring A ¹ and ring A ² are independently 1,4-phenylene, and at least one hydrogen on these rings may be substituted by halogen; SP ¹ and SP ² are independently single bonds Or alkylene with 1 to 10 carbon atoms, in this alkylene, at least one -CH ₂ - can be substituted by -O-, -CO-, -COO-, -OCO- or -OCOO-, at least one - (CH ₂ ) ₂ - may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by halogen; P ¹ and P ² are independently represented by the following formula (1a) , a group represented by formula (1b), formula (1c), formula (1d) or formula (1e);

式(1a)、式(1b)、式(1c)、式(1d)及式(1e)中，M¹及M²獨立地為氫、鹵素或碳數1至10的烷基，於此烷基中，至少一個-CH₂-可經-O-或-S-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素、-SP¹-P¹或-SP²-P²取代；R²、R³、R⁴及R⁸獨立地為氫或碳數1至15的直鏈狀、分支狀或環狀的烷基，於此烷基中，至少一個-CH₂-可經-O-或-S-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素取代。 In formula (1a), formula (1b), formula (1c), formula (1d) and formula (1e), M ¹ and M ² are independently hydrogen, halogen or an alkyl group having 1 to 10 carbon atoms, where the alkane In the group, at least one -CH ₂ - can be substituted by -O- or -S-, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, At least one hydrogen can be substituted by halogen, -SP ¹ -P ¹ or -SP ² -P ² ; R ² , R ³ , R ⁴ and R ⁸ are independently hydrogen or straight-chain or branched with 1 to 15 carbon atoms Or a cyclic alkyl group, in this alkyl group, at least one -CH ₂ - can be substituted by -O- or -S-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡ C-substituted, in these groups at least one hydrogen may be replaced by halogen.

項7. 一種聚合性組成物，其含有至少一種如項1至項6中任一項所述的聚合性化合物。 Item 7. A polymerizable composition comprising at least one polymerizable compound according to any one of Items 1 to 6.

項8. 如項7所述的聚合性組成物，其更含有選自下述式(2)~式(4)的任一者表示的化合物中的至少一種化合物。 Item 8. The polymerizable composition according to Item 7, further comprising at least one compound selected from the group consisting of compounds represented by any one of the following formulae (2) to (4).

式(2)至式(4)中，R¹¹及R¹²獨立地為碳數1至10的烷基或碳數2至10的烯基，於此烷基或烯基中，至少一個-CH₂-可經-O-取代，至少一個氫可經氟取代；環B¹、環B²、環B³及環B⁴獨立地為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、2,5-二氟-1,4-伸苯基或嘧啶-2,5-二基；Z¹¹、Z¹²及Z¹³獨立地為單鍵、-CH₂CH₂-、-CH=CH-、-C≡C-或-COO-。 In formula (2) to formula (4), R ¹¹ and R ¹² are independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in this alkyl group or alkenyl group, at least one -CH ₂ - may be substituted by -O-, at least one hydrogen may be substituted by fluorine; Ring B ¹ , Ring B ² , Ring B ³ and Ring B ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene , 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene or pyrimidine-2,5-diyl; Z ¹¹ , Z ¹² and Z ¹³ are independently single bonds , -CH ₂ CH ₂ -, -CH=CH-, -C≡C- or -COO-.

項9. 如項7或項8所述的聚合性組成物，其更含有選自由下述式(5)至式(7)的任一者表示的化合物中的至少一種化合物。 Item 9. The polymerizable composition of item 7 or item 8, further comprising optional At least one compound selected from compounds represented by any one of the following formula (5) to formula (7).

式(5)至式(7)中，R¹³為碳數1至10的烷基或碳數2至10的烯基，於此烷基及烯基中，至少一個-CH₂-可經-O-取代，至少一個氫可經氟取代；X¹¹為氟、氯、-OCF₃、-OCHF₂、-CF₃、-CHF₂、-CH₂F、-OCF₂CHF₂或-OCF₂CHFCF₃；環C¹、環C²及環C³獨立地為1,4-伸環己基、至少一個氫可經氟取代的1,4-伸苯基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基或嘧啶-2,5-二基；Z¹⁴、Z¹⁵及Z¹⁶獨立地為單鍵、-(CH₂)₂-、-CH=CH-、-C≡C-、-COO-、-CF₂O-、-OCF₂-、-CH₂O-或-(CH₂)₄-；L¹¹及L¹²獨立地為氫或氟。 In formulas (5) to (7), R ¹³ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in the alkyl and alkenyl groups, at least one -CH ₂ - may be through - O-substituted, at least one hydrogen may be substituted by fluorine; X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ or -OCF ₂ CHFCF ₃ ; Ring C ¹ , Ring C ² and Ring C ³ are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be substituted by fluorine, tetrahydropyran-2,5-di base, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are independently a single bond, -(CH ₂ ) ₂ -, -CH =CH-, -C≡C-, -COO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O- or -(CH ₂ ) ₄ -; L ¹¹ and L ¹² are independently hydrogen or fluorine .

項10. 如項7至項9中任一項所述的聚合性組成物，其更含有選自由下述式(8)表示的化合物的群組中的至少一種化合物。 Item 10. The polymerizable composition according to any one of Items 7 to 9, further comprising at least one compound selected from the group of compounds represented by the following formula (8).

式(8)中，R¹⁴為碳數1至10的烷基或碳數2至10的烯基，於此烷基及烯基中，至少一個-CH₂-可經-O-取代，至少一個氫可經氟取代；X¹²為-C≡N或-C≡C-C≡N；環D¹為1,4-伸環己基、至少一個氫可經氟取代的1,4-伸苯基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基或嘧啶-2,5-二基；Z¹⁷為單鍵、-(CH₂)₂-、-C≡C-、-COO-、-CF₂O-、-OCF₂-或-CH₂O-；L¹³及L¹⁴獨立地為氫或氟；i為1、2、3或4。 In formula (8), R ¹⁴ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, in the alkyl and alkenyl groups, at least one -CH ₂ - may be substituted by -O-, at least One hydrogen can be substituted by fluorine; X ¹² is -C≡N or -C≡CC≡N; Ring D ¹ is 1,4-cyclohexylene, at least one hydrogen can be substituted by fluorine, 1,4-phenylene, Tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; Z ¹⁷ is a single bond, -(CH ₂ ) ₂ -, -C≡C-, -COO-, -CF ₂ O-, -OCF ₂ - or -CH ₂ O-; L ¹³ and L ¹⁴ are independently hydrogen or fluorine; i is 1, 2, 3 or 4.

項11. 一種液晶複合體，其是藉由如項7至項10中任一項所述的聚合性組成物的聚合而生成。 Item 11. A liquid crystal composite produced by polymerization of the polymerizable composition according to any one of Items 7 to 10.

項12. 一種光學各向異性體，其是藉由如項7至項10 中任一項所述的聚合性組成物的聚合而生成。 Item 12. An optically anisotropic body, which is obtained by such as item 7 to item 10 It is produced by the polymerization of the polymerizable composition according to any one of them.

項13. 一種液晶顯示元件，其含有如項7至項10中任一項所述的聚合性組成物或如項11所述的液晶複合體。 Item 13. A liquid crystal display element comprising the polymerizable composition according to any one of Items 7 to 10 or the liquid crystal composite according to Item 11.

項14. 一種選自由如項1至項6中任一項所述的聚合性化合物、如項7至項10中任一項所述的聚合性組成物、以及如項11所述的液晶複合體所組成的群組中的至少一種的用途，其用於液晶顯示元件。 Item 14. One selected from the polymerizable compound as described in any one of Items 1 to 6, the polymerizable composition as described in any one of Items 7 to 10, and the liquid crystal composite as described in Item 11 Use of at least one of the group consisting of a liquid crystal display element.

本發明的第一優點為提供一種聚合性化合物，其具有優異的使液晶分子配向的能力、適當的聚合反應性、高轉化率、高電壓保持率及於液晶組成物中的高溶解度的至少一種。第二優點為液晶複合體滿足向列相的上限溫度高、向列相的下限溫度低、黏度低、光學各向異性適當、介電各向異性大、彈性常數適當、比電阻大、預傾適當等物性的至少一種。該優點為液晶複合體關於至少兩種物性而具有適當的平衡。第三優點為液晶顯示元件具有寬廣的元件可使用溫度範圍、短響應時間、低臨限電壓、高對比度及長壽命的至少一種。 A first advantage of the present invention is to provide a polymerizable compound having at least one of excellent ability to align liquid crystal molecules, appropriate polymerization reactivity, high conversion, high voltage retention, and high solubility in liquid crystal compositions . The second advantage is that the liquid crystal composite satisfies the high upper limit temperature of the nematic phase, the low temperature limit of the nematic phase, the low viscosity, the appropriate optical anisotropy, the large dielectric anisotropy, the appropriate elastic constant, the large specific resistance, and the pretilt. At least one of the appropriate equivalent properties. This advantage is that the liquid crystal composite has an appropriate balance with respect to at least two physical properties. The third advantage is that the liquid crystal display element has at least one of a wide element usable temperature range, a short response time, a low threshold voltage, a high contrast ratio, and a long lifetime.

該說明書中的用語的使用方法如下所述。液晶性化合物為具有向列相、層列相等液晶相的非聚合性化合物，以及雖不具有液晶相但為了調整上限溫度、下限溫度、黏度、介電各向異性等液晶組成物的物性而混合的非聚合性化合物的總稱。該化合物具有例如1,4-伸環己基或1,4-伸苯基之類的六員環，且其分子結構為棒狀(rod like)。液晶組成物為液晶性化合物的混合物。聚合性化合物是為了生成聚合物而添加於組成物的化合物。聚合性組成物是聚合性化合物、液晶組成物、添加物等的混合物。液晶複合體是藉由該聚合性組成物的聚合而生成的複合體。液晶顯示元件是液晶顯示面板及液晶顯示模組的總稱。向列相的上限溫度是液晶組成物、聚合性組成物或液晶複合體中的向列相-等向性相(isotropic phase)的相變溫度，有時簡稱為上限溫度。向列相的下限溫度有時簡稱為下限溫度。聚合反應性是指反應物進行聚合時的難易度。轉化率(inversion rate)是通過化學反應而消耗的反應物相對於反應物的重量比。 How to use the terms in this specification is as follows. Liquid crystal compounds are non-polymeric compounds with liquid crystal phases such as nematic phase and smectic phase, and although they do not have liquid crystal phases. There is a liquid crystal phase, but it is a general term for non-polymerizable compounds mixed to adjust the physical properties of liquid crystal compositions such as upper limit temperature, lower limit temperature, viscosity, and dielectric anisotropy. This compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. The liquid crystal composition is a mixture of liquid crystal compounds. The polymerizable compound is a compound added to the composition in order to generate a polymer. The polymerizable composition is a mixture of a polymerizable compound, a liquid crystal composition, additives, and the like. The liquid crystal composite is a composite produced by the polymerization of the polymerizable composition. A liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module. The upper limit temperature of the nematic phase is the phase transition temperature of the nematic phase-isotropic phase in the liquid crystal composition, the polymerizable composition, or the liquid crystal composite, and may be simply referred to as the upper limit temperature. The lower limit temperature of the nematic phase is sometimes simply referred to as the lower limit temperature. The polymerization reactivity refers to the ease with which the reactant is polymerized. The inversion rate is the weight ratio of the reactants consumed by the chemical reaction relative to the reactants.

液晶組成物藉由混合多種液晶性化合物來製備。液晶性化合物的比例(含量)由基於該液晶組成物的重量的重量百分率(重量%)來表示。可視需要於該組成物中添加光學活性化合物、抗氧化劑、紫外線吸收劑、光穩定劑、熱穩定劑、消泡劑、聚合性化合物、聚合起始劑、聚合抑制劑之類的添加物。添加物的比例(添加量)與液晶性化合物的比例同樣地，由基於液晶組成物的重量的重量百分率(重量%)來表示。有時亦使用重量百萬分率(ppm)。聚合起始劑及聚合抑制劑的比例例外地基於聚合性化合物的重量來表示。 The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. The ratio (content) of the liquid crystal compound is represented by the weight percentage (% by weight) based on the weight of the liquid crystal composition. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, defoaming agents, polymerizable compounds, polymerization initiators, and polymerization inhibitors may be added to the composition as needed. The ratio (addition amount) of the additive is represented by the weight percentage (% by weight) based on the weight of the liquid crystal composition similarly to the ratio of the liquid crystal compound. Parts per million by weight (ppm) are also sometimes used. The ratios of the polymerization initiator and the polymerization inhibitor are exceptionally expressed based on the weight of the polymerizable compound.

有時將式(1)所表示的化合物簡稱為化合物(1)。有時將選自式(1)所表示的化合物的群組中的至少一種化合物簡稱為「化合物(1)」。「化合物(1)」是指式(1)所表示的一種化合物、兩種化合物的混合物或三種以上化合物的混合物。對於其他式所表示的化合物亦相同。化合物(1-1)的環A¹或環A²中，將圓橫切的線是指-SP¹-P¹基可任意選擇六員環、縮合環等環上的鍵結位置。該規則亦適用於-SP²-P²基之類的記號。式(2)至式(8)中，由六邊形包圍的B¹、C¹、D¹等記號分別與環B¹、環C¹、環D¹等環對應。記號R¹¹被用於式(2)、式(3)等多個式。於這些化合物中，任意兩個R¹¹表示的兩個末端基可相同或亦可不同。式(8)中，當i為2時，兩個D¹存在於一個式中。於該化合物中，兩個D¹表示的兩個環可相同或亦可不同。該規則亦適用於i大於2時的D¹。該規則亦適用於-SP¹-P¹基之類的其他記號。 The compound represented by formula (1) may be simply referred to as compound (1). At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as "compound (1)" in some cases. "Compound (1)" refers to one compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulae. In ring A ¹ or ring A ² of compound (1-1), the line intersecting the circle means that the -SP ¹ -P ¹ group can arbitrarily select a bonding position on a ring such as a six-membered ring, a condensed ring, or the like. This rule also applies to notations such as -SP ² -P ² bases. In formulas (2) to (8), symbols such as B ¹ , C ¹ , and D ¹ surrounded by hexagons correspond to rings such as ring B ¹ , ring C ¹ , and ring D ¹ , respectively. The symbol R ¹¹ is used in a plurality of formulas such as formula (2) and formula (3). In these compounds, the two terminal groups represented by any two R ¹¹ may be the same or different. In formula (8), when i is 2, two D ¹ exist in one formula. In this compound, the two rings represented by the two D ¹ may be the same or different. This rule also applies to D ¹ when i is greater than 2. This rule also applies to other notations such as -SP ¹ -P ¹ bases.

「至少一個“A”可經“B”取代」的表述是指：當“A”的數量為1個時，“A”的位置為任意，當“A”的數量為兩個以上時，這些“A”的位置亦可無限制地自由選擇。「至少一個A可經B、C或D取代」的表述是指包括以下情況：至少一個A經B取代的情況、至少一個A經C取代的情況、及至少一個A經D取代的情況，進而多個A經B、C、D的至少兩者取代的情況。例如，至少一個-CH₂-(或-(CH₂)₂-)可經-O-(或-CH=CH-)取代的烷基包含烷基、烯基、烷氧基、烷氧基烷基、烷氧基烯基、烯氧基烷基(alkenyloxyalkyl)。此外，連續的兩個-CH₂-經-O-取代為-O-O-般的情況欠佳。於烷基等中，甲基部分(-CH₂-H)的-CH₂-經-O-取代為-O-H的情況亦欠佳。 The expression "at least one "A" may be substituted by "B"" means: when the number of "A" is one, the position of "A" is arbitrary, and when the number of "A" is two or more, these The position of "A" can also be freely chosen without restriction. The expression "at least one A may be substituted by B, C or D" is meant to include the following cases: the case where at least one A is substituted by B, the case where at least one A is substituted by C, and the case where at least one A is substituted by D, and further The case where multiple A's are substituted with at least two of B, C, and D. For example, alkyl groups in which at least one _-CH2- (or -( _CH2 ) _2- ) may be substituted with -O- (or -CH=CH-) include alkyl, alkenyl, alkoxy, alkoxyalkane group, alkoxyalkenyl, alkenyloxyalkyl. In addition, it is not preferable that two consecutive -CH ₂ - are substituted by -O- to -OO-. In an alkyl group etc., the case where _-CH2- of a methyl moiety ( _-CH2 -H) is substituted by -O- is also unfavorable.

2-氟-1,4-伸苯基是指下述兩種二價基。化學式中，氟可為朝左(L)，亦可為朝右(R)。該規則亦適用於四氫吡喃-2,5-二基之類的藉由自環去除兩個氫而衍生的左右非對稱的二價基。 The 2-fluoro-1,4-phenylene group refers to the following two divalent groups. In the chemical formula, fluorine can be left (L) or right (R). This rule also applies to left-right asymmetric divalent radicals such as tetrahydropyran-2,5-diyl, which are derived by removing two hydrogens from the ring.

鹵素是指氟、氯、溴及碘。較佳的鹵素為氟或氯。尤佳的鹵素為氟。 Halogen means fluorine, chlorine, bromine and iodine. Preferred halogens are fluorine or chlorine. A particularly preferred halogen is fluorine.

本發明亦包括以下項。 The present invention also includes the following items.

(a)所述聚合性組成物，其更含有光學活性化合物、抗氧化劑、紫外線吸收劑、光穩定劑、熱穩定劑、消泡劑、聚合起始劑、聚合抑制劑等添加物的至少一種。 (a) The polymerizable composition further comprising at least one of additives such as optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, thermal stabilizers, antifoaming agents, polymerization initiators, and polymerization inhibitors .

(b)所述聚合性組成物，其更含有至少一種聚合起始劑。 (b) The polymerizable composition, which further contains at least one polymerization initiator.

(c)所述聚合性組成物，其更含有並非由式(1)表示的聚合性化合物。 (c) The polymerizable composition further containing a polymerizable compound not represented by the formula (1).

(d)式(1)所表示的化合物的用途，其用於適合具有PSA模式的液晶顯示元件的聚合性組成物。 (d) Use of the compound represented by formula (1) in a polymerizable composition suitable for a liquid crystal display element having a PSA mode.

(e)式(1)所表示的化合物的用途，其用於具有PSA模式的液晶顯示元件。 (e) Use of the compound represented by formula (1) for a liquid crystal display element having a PSA mode.

(f)選自式(1)、式(1-1)及式(1-1-1)至式(1-1-7)的任一者所表示的化合物的群組中的至少一種化合物的用途，其用於具有PSA模式的液晶顯示元件。 (f) at least one compound selected from the group of compounds represented by formula (1), formula (1-1), and any one of formulas (1-1-1) to (1-1-7) , which is used in liquid crystal display elements with PSA mode.

(g)含有所述化合物的至少一種的聚合性組成物的用途，其用於具有PSA模式的液晶顯示元件。 (g) Use of the polymerizable composition containing at least one of the compounds described above for a liquid crystal display element having a PSA mode.

(h)藉由所述聚合性組成物的聚合而生成的液晶複合體的用途，其用於具有PSA模式的液晶顯示元件。 (h) Use of the liquid crystal composite produced by the polymerization of the polymerizable composition for a liquid crystal display element having a PSA mode.

(i)所述化合物、所述聚合性組成物、或所述液晶複合體的用途，其用於具有PS-TN、PS-IPS、PS-FFS、PSA-VA、或PSA-OCB模式的液晶顯示元件。 (i) Use of the compound, the polymerizable composition, or the liquid crystal composite for a liquid crystal having a PS-TN, PS-IPS, PS-FFS, PSA-VA, or PSA-OCB mode display element.

(j)含有式(1)所表示的化合物與選自式(2)、式(3)及式(4)的任一者所表示的化合物的群組中的至少一種化合物的組成物的用途，其用於具有PSA模式的液晶顯示元件。 (j) Use of a composition comprising a compound represented by formula (1) and at least one compound selected from the group of compounds represented by any one of formula (2), formula (3) and formula (4) , which is used in a liquid crystal display element having a PSA mode.

(k)含有式(1)所表示的化合物與選自式(5)、式(6)及式(7)的任一者所表示的化合物的群組中的至少一種化合物的組成物的用途，其用於具有PSA模式的液晶顯示元件。 (k) Use of a composition comprising a compound represented by formula (1) and at least one compound selected from the group of compounds represented by any one of formula (5), formula (6) and formula (7) , which is used in a liquid crystal display element having a PSA mode.

(l)含有式(1)所表示的化合物與選自式(8)所表示的化合物的群組中的至少一種化合物的組成物的用途，其用於具有PSA模式的液晶顯示元件。 (1) Use of a composition containing a compound represented by formula (1) and at least one compound selected from the group of compounds represented by formula (8) for a liquid crystal display element having a PSA mode.

以下，首先說明本發明的聚合性化合物，其後依序說明合成法、聚合性組成物、液晶複合體、液晶顯示元件。 Hereinafter, the polymerizable compound of the present invention will be described first, and then the synthesis method, polymerizable composition, liquid crystal composite, and liquid crystal display element will be described in order.

1.聚合性化合物 1. Polymeric compounds

一種聚合性化合物，其由下述式(1)表示：[化30](R¹)_c-MES-(SP¹-P¹)_a (1) A polymerizable compound represented by the following formula (1): [Chemical 30](R ¹ ) _c -MES-(SP ¹ -P ¹ ) _a (1)

第一，化合物(1)具有與液晶性化合物類似的棒狀的分子結構，故而於液晶組成物中的溶解度高。因此，化合物(1)適合作為具有PSA模式的元件所需的聚合性化合物。第二，化合物(1)具有適當的聚合性。因此，化合物(1)能夠穩定地保存。於聚合時，可容易地控制光反應的速度，能夠藉由適度地照射紫外線而使其聚合。另外，不需要過度的紫外線。 First, compound (1) has rod-like Molecular structure, so the solubility in liquid crystal composition is high. Therefore, the compound (1) is suitable as a polymerizable compound required for a device having a PSA mode. Second, the compound (1) has suitable polymerizability. Therefore, compound (1) can be stored stably. At the time of polymerization, the speed of the photoreaction can be easily controlled, and it can be polymerized by appropriately irradiating ultraviolet rays. Also, excessive UV light is not required.

化合物(1)中的較佳結構為式(1-1)，式(1-1)中的聚合性基P、連結基SP、環A、烷基R及鍵結基Z各自的較佳例如下所述。該例亦適用於化合物(1)的下位化合物。化合物(1)能夠藉由適當地組合所述基團的種類而任意地調整物性。由於化合物的物性不存在大的差異，故而化合物(1)可包含較天然豐度(natural abundance)的量更多的²H(氘)、¹³C等同位素。 The preferred structure in the compound (1) is the formula (1-1), and the preferred examples of each of the polymerizable group P, the linking group SP, the ring A, the alkyl group R and the linking group Z in the formula (1-1) are described below. This example also applies to the lower compound of compound (1). Compound (1) can arbitrarily adjust physical properties by appropriately combining the types of the groups. Since there is no large difference in the physical properties of the compounds, compound (1) may contain isotopes such as ² H (deuterium) and ¹³ C in greater amounts than the natural abundance.

式(1-1)中，P¹及P²獨立地為聚合性基。聚合性基的例子為丙烯醯氧基、甲基丙烯醯氧基、丙烯醯胺、甲基丙烯醯胺、乙烯基氧基、乙烯基羰基、氧雜環丙烷基、氧雜環丁烷基、3,4-環氧環己基、順丁烯二醯亞胺基或衣康酸酯基。於這些基團中，至少一個氫可經氟、甲基或三氟甲基取代。聚合性基的較佳例為丙烯醯氧基(下述式(1a))、氧雜環丙烷基(下述式(1b))、乙烯基氧基(下述式(1c))、順丁烯二醯亞胺基(下述式(1d))或衣康酸酯基(下述式(1e))。 In formula (1-1), P ¹ and P ² are independently polymerizable groups. Examples of the polymerizable group are acryloxy, methacryloyloxy, acrylamide, methacrylamide, vinyloxy, vinylcarbonyl, oxiranyl, oxetanyl, 3,4-Epoxycyclohexyl, maleimide or itaconate. In these groups, at least one hydrogen may be substituted with fluorine, methyl or trifluoromethyl. Preferable examples of the polymerizable group are acryloxy (formula (1a) below), oxiranyl group (formula (1b) below), vinyloxy (formula (1c) below), cis-butane An enediimide group (the following formula (1d)) or an itaconate group (the following formula (1e)).

此處，式(1a)~式(1e)中，M¹及M²獨立地為氫、鹵素或碳數1至10的烷基，於此烷基中，至少一個-CH₂-可經-O-或-S-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素、-SP¹-P¹或-SP²-P²取代；R²、R³、R⁴及R⁸獨立地為氫或碳數1至15的直鏈狀、分支狀或環狀的烷基，於此烷基中，至少一個-CH₂-可經-O-或-S-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素取代。 Here, in formulas (1a) to (1e), M ¹ and M ² are independently hydrogen, halogen or an alkyl group having 1 to 10 carbon atoms, and in this alkyl group, at least one -CH ₂ - may be through - O- or -S- substituted, at least one -(CH ₂ ) ₂ - may be substituted with -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted with halogen, -SP ¹ -P ¹ or -SP ² -P ² substituted; R ² , R ³ , R ⁴ and R ⁸ are independently hydrogen or a straight-chain, branched or cyclic alkyl group having 1 to 15 carbon atoms, in this alkyl group , at least one -CH ₂ - can be substituted by -O- or -S-, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, among these groups, at least one Hydrogen can be replaced by halogen.

式(1-1)中，SP¹及SP²獨立地為單鍵或碳數1至10的伸烷基，於此伸烷基中，至少一個-CH₂-可經-O-、-CO-、-COO-或-OCO-取代，至少一個-CH₂-CH₂-可經-CH=CH-或-C≡C-取代，於這些二價基中，至少一個氫可經鹵素或碳數1至3的烷基取代。 In formula (1-1), SP ¹ and SP ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in this alkylene group, at least one -CH ₂ - may be through -O-, -CO -, -COO- or -OCO- substituted, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, in these divalent groups, at least one hydrogen can be substituted by halogen or carbon Alkyl substitution of numbers 1 to 3.

SP¹或SP²的較佳例為：單鍵、-CH₂-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-(CH₂)₂-、-CH=CH-、-C≡C-、-CH₂CH₂O-、-OCH₂CH₂-、-CH=CH-O-、-O-CH=CH-、-C≡C-O-、-O-C≡C-、-(CH₂)₃-、-(CH₂)₃-O-、-O-(CH₂)₃-、-(CH₂)₄-、-(CH₂)₄O-或-O(CH₂)₄-。尤佳例為：單鍵、-CH₂-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-CH=CH-、-C≡C-、-CH₂CH₂O-、-OCH₂CH₂-、-CH=CH-O-或-O-CH=CH-。更佳例為：單鍵、-CH₂-、-CH=CH-、-CH=CH-O-、-O-CH=CH-、-CH₂CH₂O-或-OCH₂CH₂-。特佳例為單鍵。-CH=CH-的雙鍵的立體構型可為順式，亦可為反式。反式優於順式。 Preferred examples of SP ¹ or SP ² are: single bond, -CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -(CH ₂ ) ₂ -, -CH=CH -, -C≡C-, -CH ₂ CH ₂ O-, -OCH ₂ CH ₂ -, -CH=CH-O-, -O-CH=CH-, -C≡CO-, -OC≡C- , -(CH ₂ ) ₃ -, -(CH ₂ ) ₃ -O-, -O-(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -(CH ₂ ) ₄ O- or -O(CH ₂ ) _4- . Preferred examples are: single bond, -CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CH=CH-, -C≡C-, -CH ₂ CH ₂ O -, -OCH2CH2-, -CH= _CH - _O- or -O-CH=CH-. More preferred examples are: single bond, -CH ₂ -, -CH=CH-, -CH=CH-O-, -O-CH=CH-, -CH ₂ CH ₂ O- or -OCH ₂ CH ₂ -. A particularly good example is a single key. The three-dimensional configuration of the double bond of -CH=CH- may be cis or trans. Trans is better than cis.

式(1-1)中，R⁵、R⁶及R⁷獨立地為氫、鹵素、-SP¹-P¹、-SP²-P²或碳數1至15的烷基，於此烷基中，至少一個-CH₂-可經-O-或-S-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素、-SP¹-P¹或-SP²-P²取代。 In formula (1-1), R ⁵ , R ⁶ and R ⁷ are independently hydrogen, halogen, -SP ¹ -P ¹ , -SP ² -P ² or an alkyl group having 1 to 15 carbon atoms, wherein the alkyl group is Among them, at least one -CH ₂ - can be substituted by -O- or -S-, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, among these groups, at least One hydrogen may be substituted with halogen, -SP ¹ -P ¹ or -SP ² -P ² .

式(1-1)中，a1及a2獨立地為0、1、2、3或4。-SP¹-P¹或-SP²-P²為參與聚合的一價基。-SP¹-P¹及-SP²-P²的合計個數(即a1+a2)為1至8。較佳例為1至6，尤佳例為1至3。更佳例為1或2。 In formula (1-1), a1 and a2 are independently 0, 1, 2, 3 or 4. -SP ¹ -P ¹ or -SP ² -P ² is a monovalent group participating in the polymerization. The total number of -SP ¹ -P ¹ and -SP ² -P ² (ie, a1+a2) is 1 to 8. Preferred examples are 1 to 6, and particularly preferred examples are 1 to 3. A more preferable example is 1 or 2.

式(1-1)中，環A¹及環A²獨立地為藉由自碳數3至18的脂環式烴、碳數6至18的芳香族烴或碳數3至18的雜芳香族烴去除兩個氫而衍生的二價基。於此二價基中，至少一個氫可經鹵素、碳數1至12的烷基、碳數1至12的烷氧基、碳數1至 12的烯基或碳數1至12的烯氧基取代，於這些一價烴基中，至少一個氫可經鹵素取代。進而，環A¹中，a1個氫可經-SP¹-P¹取代，環A²中，a2個氫可經-SP²-P²取代。 In formula (1-1), ring A ¹ and ring A ² are independently formed from alicyclic hydrocarbons having 3 to 18 carbon atoms, aromatic hydrocarbons having 6 to 18 carbon atoms, or heteroaromatic hydrocarbons having 3 to 18 carbon atoms. A divalent group derived from a family of hydrocarbons by removing two hydrogens. In this divalent group, at least one hydrogen may be through halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons or alkenyl having 1 to 12 carbons In these monovalent hydrocarbon groups, at least one hydrogen may be substituted with halogen. Furthermore, in ring A ¹ , a1 hydrogens may be substituted by -SP ¹ -P ¹ , and in ring A ² , a2 hydrogens may be substituted by -SP ² -P ² .

脂環式烴的例子為C_nH_2n所表示的環丙烷、環丁烷、環己烷、環庚烷、環辛烷等。其他例子為四氫萘等。芳香族烴的例子為苯、萘、蒽、菲、茀、二氫茚(indan)、茚、四氫萘等。雜芳香族烴的例子為吡啶、嘧啶、呋喃、吡喃、噻吩、苯并呋喃等。這些烴可經氟、氯、烷基之類的一價基取代。環A¹或環A²的較佳例為苯、氟苯、萘、茀、或菲。尤佳例為苯或環己烷。 Examples of alicyclic _hydrocarbons are cyclopropane represented by _CnH2n , cyclobutane, cyclohexane, cycloheptane, cyclooctane, and the like. Other examples are tetralin and the like. Examples of aromatic hydrocarbons are benzene, naphthalene, anthracene, phenanthrene, fortane, indan, indene, tetrahydronaphthalene, and the like. Examples of heteroaromatic hydrocarbons are pyridine, pyrimidine, furan, pyran, thiophene, benzofuran, and the like. These hydrocarbons may be substituted with monovalent groups such as fluorine, chlorine, alkyl and the like. Preferable examples of ring A ¹ or ring A ² are benzene, fluorobenzene, naphthalene, fluorine, or phenanthrene. A particularly preferred example is benzene or cyclohexane.

式(1-1)中，Z¹及Z²獨立地為單鍵或碳數1至10的伸烷基，於此伸烷基中，至少一個-CH₂-可經-O-、-CO-、-COO-或-OCO-取代，至少一個-(CH₂)₂-可經-CH=CH-、-C(CH₃)=CH-、-CH=C(CH₃)-、-C(CH₃)=C(CH₃)-或-CH≡CH-取代，於這些二價基中，至少一個氫可經鹵素取代。 In formula (1-1), Z ¹ and Z ² are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in this alkylene group, at least one -CH ₂ - may be via -O-, -CO -, -COO- or -OCO- substituted, at least one -(CH ₂ ) ₂ - may be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, -C (CH ₃ )=C(CH ₃ )- or -CH≡CH- substituted, in these divalent radicals, at least one hydrogen may be substituted by halogen.

Z¹及Z²的較佳例為：單鍵、碳數1至4的伸烷基、-COO-、-OCO-、-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-、-CH=CH-、-CH=CH-COO-、-OCO-CH=CH-、-C(CH₃)=CH-COO-、-OCO-CH=C(CH₃)-、-CH=C(CH₃)-COO-、-OCO-(CH₃)C=CH-、-C(CH₃)=C(CH₃)-COO-、-OCO-C(CH₃)=C(CH₃)-、-CO-CH=CH-、-CH=CH-CO-、-C(CH₃)=C(CH₃)-、-CH=CH-CH₂O-、-OCH₂-CH=CH-、-CH=CH-OCH₂-、-CH₂O-CH=CH-或-CH≡CH-。尤佳例為單鍵、乙烯、-COO-、-OCO-、-CH=CH-、-CH=CH-COO-、 -OCO-CH=CH-或-CH≡CH-。特佳例為單鍵。 Preferred examples of Z ¹ and Z ² are: single bond, alkylene having 1 to 4 carbon atoms, -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, - OCF ₂ -, -CH=CH-, -CH=CH-COO-, -OCO-CH=CH-, -C(CH ₃ )=CH-COO-, -OCO-CH=C(CH ₃ )-, -CH=C(CH ₃ )-COO-, -OCO-(CH ₃ )C=CH-, -C(CH ₃ )=C(CH ₃ )-COO-, -OCO-C(CH ₃ )=C (CH ₃ )-, -CO-CH=CH-, -CH=CH-CO-, -C(CH ₃ )=C(CH ₃ )-, -CH=CH-CH ₂ O-, -OCH ₂ - CH=CH-, -CH=CH-OCH ₂ -, -CH ₂ O-CH=CH- or -CH≡CH-. A particularly preferred example is a single bond, ethylene, -COO-, -OCO-, -CH=CH-, -CH=CH-COO-, -OCO-CH=CH- or -CH≡CH-. A particularly good example is a single key.

式(1-1)中，b1及b2獨立地為0、1、2或3。當b2為0時，該化合物具有b1個環A¹所表示的環。於該情況下，較佳的環A¹為藉由自萘、蒽、菲、苯之類的縮合環去除兩個氫而衍生的二價基。當b1及b2為1時，該化合物具有環A¹與環A²。於該情況下，較佳的環A¹或環A²為自苯、經氟或甲基之類的取代基取代的苯所衍生的二價基。當b1為1且b2為2時，該化合物具有環A¹、環A²及環A²此三環。較佳的環A¹或環A²為自苯、經氟之類的取代基取代的苯所衍生的二價基。 In formula (1-1), b1 and b2 are independently 0, 1, 2 or 3. When b2 is ⁰ , the compound has b1 rings represented by ring A1. In this case, preferable ring A ¹ is a divalent group derived by removing two hydrogens from a condensed ring such as naphthalene, anthracene, phenanthrene, and benzene. When b1 and b2 are 1, the compound has ring A ¹ and ring A ² . In this case, preferable ring A ¹ or ring A ² is a divalent group derived from benzene, benzene substituted with a substituent such as fluorine or methyl. When b1 is 1 and b2 is 2, the compound has three rings of ring A ¹ , ring A ² and ring A ² . Preferred ring A ¹ or ring A ² is a divalent group derived from benzene, benzene substituted with a substituent such as fluorine.

2.合成法 2. Synthesis

對化合物(1)或化合物(1-1)的合成法進行說明。化合物(1)可藉由將有機合成化學的方法適當組合來合成。於起始物質中導入目標末端基、環以及鍵結基的方法記載於侯本-懷爾(Houben-Wyle，「有機化學方法(Methoden der Organische Chemie)」，喬治.蒂姆出版社(Georg-Thieme Verlag)，斯圖加特(Stuttgart))、「有機合成」(Organic Syntheses，約翰威立父子出版公司(John Wily & Sons,Inc.))、「有機反應」(Organic Reactions，約翰威立父子出版公司)、「綜合有機合成」(Comprehensive Organic Synthesis，培格曼出版公司(Pergamon Press))、新實驗化學講座(丸善)等書中。 The synthesis method of compound (1) or compound (1-1) will be described. Compound (1) can be synthesized by appropriately combining methods of synthetic organic chemistry. The method for introducing target end groups, rings and bonding groups into starting materials is described in Houben-Wyle, "Methoden der Organische Chemie", Georg Tim Thieme Verlag, Stuttgart), Organic Syntheses (John Wily & Sons, Inc.), Organic Reactions (John Wily & Sons, Inc.) , "Comprehensive Organic Synthesis" (Comprehensive Organic Synthesis, Pergamon Press), New Experimental Chemistry Lectures (Maruzen) and other books.

2-1.鍵結基Z的生成 2-1. Generation of bonding group Z

生成化合物(1-1)中的鍵結基Z的方法的例子如下述流程所述。該流程中，MSG¹(或MSG²)為具有至少一個環的一價有機基。多個MSG¹(或MSG²)所表示的一價有機基可相同或亦可不同。化合物(1A)至化合物(1I)相當於化合物(1)。酯的生成中示出具有-COO-的化合物的合成法。具有-OCO-的化合物亦能夠利用該合成法來合成。對於其他非對稱的鍵結基亦相同。 An example of the method for generating the bonding group Z in the compound (1-1) is described in the following scheme. In this scheme, MSG ¹ (or MSG ² ) is a monovalent organic group having at least one ring. The monovalent organic groups represented by a plurality of MSG ¹ (or MSG ² ) may be the same or different. Compound (1A) to compound (1I) correspond to compound (1). The synthesis method of the compound having -COO- is shown in the production of ester. A compound having -OCO- can also be synthesized by this synthesis method. The same is true for other asymmetric bonding groups.

[化34]

[Chemical 34]

(1)單鍵的生成 (1) Generation of a single key

於碳酸鹽水溶液中，在四(三苯基膦)鈀之類的觸媒存在下，使芳基硼酸(21)與利用周知方法合成的化合物(22)反應而合成化合物(1A)。該化合物(1A)亦可藉由使利用周知方法合成的化合物(23)與正丁基鋰反應，繼而與氯化鋅反應，於二氯雙(三苯基膦)鈀之類的觸媒存在下使化合物(22)進行反應來合成。 Compound (1A) is synthesized by reacting arylboronic acid (21) with compound (22) synthesized by a known method in an aqueous carbonate solution in the presence of a catalyst such as tetrakis(triphenylphosphine)palladium. The compound (1A) can also be prepared in dichlorobis(tris(trichlorobis)) by reacting the compound (23) synthesized by a well-known method with n-butyllithium and then with zinc chloride. It is synthesized by reacting compound (22) in the presence of a catalyst such as phenylphosphine)palladium.

(2)-COO-的生成 (2) Generation of -COO-

使化合物(23)與正丁基鋰反應，繼而與二氧化碳反應而獲得羧酸(24)。於1,3-二環己基碳二亞胺(1,3-dicyclohexyl carbodiimide，DCC)與N,N-二甲基-4-胺基吡啶(N,N-dimethyl-4-amino pyridine，DMAP)的存在下，使化合物(24)與利用周知方法合成的苯酚(25)進行脫水縮合而合成化合物(1B)。 The carboxylic acid (24) is obtained by reacting compound (23) with n-butyllithium and then with carbon dioxide. In 1,3-dicyclohexylcarbodiimide (1,3-dicyclohexyl carbodiimide, DCC) and N,N-dimethyl-4-aminopyridine (N,N-dimethyl-4-amino pyridine, DMAP) Compound (1B) is synthesized by subjecting compound (24) to dehydration condensation with phenol (25) synthesized by a known method in the presence of .

(3)-CF₂O-的生成 (3) Generation of -CF ₂ O-

利用勞森試劑(Lawesson's reagent)之類的硫化劑來處理化合物(1B)而獲得化合物(26)。利用氟化氫吡啶錯合物及N-溴代丁二醯亞胺(N-bromo succinimide，NBS)來氟化化合物(26)而合成化合物(1C)(參照M.黑星(M.Kuroboshi)等人的「化學快報(Chemistry Letters，Chem.Lett.)」1992年第827期)。亦可利用(二乙基胺基)三氟化硫(DAST)來氟化化合物(26)而合成化合物(1C)(參照W.H.班尼爾(W.H.Bunnelle)等人的「有機化學期刊(Journal of Organic Chemistry，J.Org.Chem.)」1990年第55期第768頁)。亦可利用皮爾.基爾希(Peer.Kirsch)等人的「應用化學國際英文版(Angewandte Chemie International Edition in English，Angew.Chem.Int.Ed.)」2001年第40期第1480頁中記載的方法來生成該鍵結基。 Compound (26) is obtained by treating compound (1B) with a sulfurizing agent such as Lawesson's reagent. Compound (1C) was synthesized by fluorinating compound (26) using hydrogen fluoride pyridine complex and N-bromo succinimide (N-bromo succinimide, NBS) (refer to M. Kuroboshi et al. The "Chemistry Letters (Chemistry Letters, Chem. Lett.)" 1992 No. 827). Compound (1C) can also be synthesized by fluorinating compound (26) using (diethylamino)sulfur trifluoride (DAST) (refer to the Journal of Organic Chemistry by WH Bunnelle et al. Organic Chemistry, J. Org. Chem.)" 1990, No. 55, p. 768). Peer. Kirsch et al., "Angewandte Chemie International Edition in English, Angew. Chem. Int. Ed.", No. 40, 2001, p. 1480, can also be used method to generate the bond base.

(4)-CH=CH-的生成 (4) Generation of -CH=CH-

利用正丁基鋰對化合物(22)進行處理後，與N,N-二甲基甲醯胺(N,N-dimethylformamide，DMF)等甲醯胺反應而獲得醛(28)。利用三級丁醇鉀之類的鹼對以周知方法合成的鏻鹽(27)進行處理而產生磷葉立德(phosphorus ylide)，使該磷葉立德與醛(28)反應來合成化合物(1D)。根據反應條件會生成順式體，故而視需要利用周知方法將順式體異構化為反式體。 Compound (22) is treated with n-butyllithium, and then reacted with formamide such as N,N-dimethylformamide (N,N-dimethylformamide, DMF) to obtain aldehyde (28). The phosphonium salt (27) synthesized by a known method is treated with a base such as potassium tertiary butoxide to produce a phosphorus ylide, and the phosphorous ylide is reacted with the aldehyde (28) to synthesize the compound (1D). Since a cis-isomer is produced depending on the reaction conditions, the cis-isomer is isomerized into a trans-isomer by a known method as necessary.

(5)-CH₂O-的生成 (5) Generation of -CH ₂ O-

利用硼氫化鈉等還原劑將化合物(28)還原而獲得化合物(29)。利用氫溴酸等將該化合物(29)鹵化而獲得化合物(31)。於碳酸鉀等的存在下，使化合物(31)與化合物(30)反應而合成化合物(1E)。 Compound (29) is obtained by reducing compound (28) with a reducing agent such as sodium borohydride. Compound (31) is obtained by halogenating this compound (29) with hydrobromic acid or the like. Compound (1E) is synthesized by reacting compound (31) with compound (30) in the presence of potassium carbonate or the like.

(6)-CH=CH-COO-的生成 (6) Generation of -CH=CH-COO-

使氫化鈉等鹼作用於二乙基膦醯基乙酸乙酯來製備磷葉立德，使該磷葉立德與醛(32)反應而獲得酯(33)。於氫氧化鈉等鹼的存在下將酯(33)水解而獲得羧酸(34)。使該化合物與化合物(25)脫水縮合來合成化合物(1F)。 Phosphorus ylide is prepared by reacting ethyl diethylphosphonoacetate with a base such as sodium hydride, and this phosphorus ylide is reacted with aldehyde (32) to obtain ester (33). The carboxylic acid (34) is obtained by hydrolyzing the ester (33) in the presence of a base such as sodium hydroxide. Compound (1F) is synthesized by dehydrating and condensing this compound and compound (25).

(7)-C(CH₃)=CH-COO-的生成 (7) Generation of -C(CH ₃ )=CH-COO-

使氫化鈉等鹼作用於二乙基膦醯基乙酸乙酯來製備磷葉立德，使該磷葉立德與甲基酮(35)反應而獲得酯(36)。繼而於氫氧化鈉等鹼的存在下將酯(36)水解而獲得羧酸(37)，然後藉由與化合物(25)的脫水縮合來合成化合物(1G)。 Phosphorus ylide is prepared by acting a base such as sodium hydride on ethyl diethylphosphoronoacetate, and this phosphorus ylide is reacted with methyl ketone (35) to obtain ester (36). Next, ester (36) is hydrolyzed in the presence of a base such as sodium hydroxide to obtain carboxylic acid (37), and compound (1G) is synthesized by dehydration condensation with compound (25).

(8)-CH=C(CH₃)-COO-的生成 (8) Generation of -CH=C(CH ₃ )-COO-

於N,N-二環己基甲基胺(Cy₂ NMe)之類的鹼以及雙(三-第三丁基膦)鈀之類的觸媒的存在下，使利用周知方法所合成的化合物(38)與利用周知方法所合成的化合物(39)進行反應來合成化合物(1H)。 _The compound ( 38) Compound (1H) is synthesized by reacting with compound (39) synthesized by a known method.

(9)-C(CH₃)=C(CH₃)-COO-的生成 (9) Generation of -C(CH ₃ )=C(CH ₃ )-COO-

藉由使化合物(25)與丙酮酸脫水縮合而獲得化合物(40)。於鋅及四氯化鈦存在下使化合物(40)與化合物(35)反應，藉此而合成化合物(1I)。 Compound (40) is obtained by dehydrating condensation of compound (25) with pyruvic acid. Compound (1I) is synthesized by reacting compound (40) with compound (35) in the presence of zinc and titanium tetrachloride.

2-2.連結基SP及聚合性基P的生成 2-2. Generation of linking group SP and polymerizable group P

聚合性基P的較佳例為丙烯醯氧基(1a)、氧雜環丙烷基(1b)、乙烯基氧基(1c)、順丁烯二醯亞胺基(1d)或衣康酸酯基(1e)。 Preferred examples of the polymerizable group P are acryloxy (1a), oxiranyl (1b), vinyloxy (1c), maleimide (1d) or itaconate base (1e).

該聚合性基藉由連結基SP而鍵結於環的化合物的合成方法的例子如下所述。首先，示出連結基SP為單鍵的例子。 Examples of the synthesis method of the compound in which the polymerizable group is bonded to the ring via the linking group SP are as follows. First, an example in which the linking group SP is a single bond is shown.

(1)單鍵的生成 (1) Generation of a single key

生成單鍵的方法如下述流程所述。該流程中，MSG¹為具有至少一個環的一價有機基。化合物(1S)至化合物(1Z)相當於化合物(1)。 The method of generating a single bond is described in the following scheme. In this scheme, MSG ¹ is a monovalent organic group having at least one ring. Compound (1S) to compound (1Z) correspond to compound (1).

連結基SP為單鍵的化合物的合成法如以上所述。生成其他連結基的方法可參考連結基Z的合成法來合成。 The synthesis method of the compound in which the linking group SP is a single bond is as described above. The method of generating other linking groups can be synthesized by referring to the synthesis method of linking group Z.

2-3.MES的生成 2-3. Generation of MES

化合物(1)中的MES為具有至少一個環及N原子的液晶原基。較佳例為以下(1J)。化合物(1J)相當於化合物(1)。於環A¹及環A²均為芳香族烴的情況下，例如可藉由以下的流程來合成。 MES in compound (1) is a mesogen group having at least one ring and an N atom. A preferable example is the following (1J). Compound (1J) corresponds to compound (1). When both ring A ¹ and ring A ² are aromatic hydrocarbons, it can be synthesized by, for example, the following scheme.

2-4.環A¹及環A²的生成 2-4. Generation of Ring A ¹ and Ring A ²

關於作為環A¹及環A²的、1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、2-氟-1,4-伸苯基、2-甲基-1,4-伸苯基、2-乙基-1,4-伸苯基、萘-2,6-二基、十氫萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、吡啶-2,5-二基、全氫環戊[a]菲-3,17-二基、2,3,4,7,8,9,10,11,12,13,14,15,16,17-十四氫環戊[a]菲-3,17-二基等環，起始物質已有市售、或合成法已廣為人知。 About Ring A ¹ and Ring A ² , 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2 -Methyl-1,4-phenylene, 2-ethyl-1,4-phenylene, naphthalene-2,6-diyl, decalin-2,6-diyl, 1,2,3 ,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, Pyridine-2,5-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl, 2,3,4,7,8,9,10,11,12,13,14,15,16 ,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl and other rings, starting materials are commercially available, or synthetic methods are widely known.

化合物(1)與類似的化合物相比具有適當的聚合反應性、高轉化率及於液晶組成物中的高溶解度。化合物(1)關於所述至少兩種物性而具有適當的平衡。因此，化合物(1)可添加於PSA模式用液晶組成物中。 Compound (1) has appropriate polymerization reactivity, high conversion, and high solubility in liquid crystal compositions compared with similar compounds. Compound (1) has an appropriate balance with respect to the at least two physical properties. Therefore, the compound (1) can be added to the liquid crystal composition for PSA mode.

3.聚合性組成物 3. Polymeric composition

聚合性組成物包含化合物(1)的至少一種作為第一成分。該組成物的成分可僅為第一成分。該組成物亦可包含第二成分、第三成分等其他成分。第二成分等的種類依存於目標聚合物的用途。該聚合性組成物亦可更包含與化合物(1)不同的其他聚合性化合物作為第二成分。其他聚合性化合物的較佳例為丙烯酸酯、甲基丙烯酸酯、乙烯基化合物、乙烯基氧基化合物、丙烯基醚、環氧化合物(氧雜環丙烷、氧雜環丁烷)及乙烯基酮。尤佳例為具有至少一個丙烯醯氧基的化合物及具有至少一個甲基丙烯醯氧基的化合物。尤佳例中亦包含具有丙烯醯氧基及甲基丙烯醯氧基兩者的化合物。 The polymerizable composition contains at least one compound (1) as a first component. The components of the composition may be only the first component. The composition may also contain other components such as the second component and the third component. The type of the second component and the like depends on the application of the target polymer. The polymerizable composition may further contain another polymerizable compound different from the compound (1) as the second component. Preferred examples of other polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes) and vinyl ketones . Particularly preferred examples are compounds having at least one acryloxy group and compounds having at least one methacryloyloxy group. A particularly preferred example also includes a compound having both acryloxy and methacryloyloxy.

其他聚合性化合物的追加例為化合物(M-1)至化合物(M-12)。於化合物(M-1)至化合物(M-12)中，R²⁵、R²⁶及R²⁷獨立地為氫或甲基；u、x及y獨立地為0或1；v及w獨立地為1 至10的整數；L²¹、L²²、L²³、L²⁴、L²⁵及L²⁶獨立地為氫或氟。 Additional examples of other polymerizable compounds are compound (M-1) to compound (M-12). In compound (M-1) to compound (M-12), R ²⁵ , R ²⁶ and R ²⁷ are independently hydrogen or methyl; u, x and y are independently 0 or 1; v and w are independently An integer from 1 to 10; L ²¹ , L ²² , L ²³ , L ²⁴ , L ²⁵ and L ²⁶ are independently hydrogen or fluorine.

當聚合性組成物的第二成分為具有液晶相的聚合性化合物時，藉由一邊控制液晶分子的配向一邊使其進行聚合而生成光學各向異性體。該光學各向異性體可用於相位差膜、偏光元件、圓偏光元件、橢圓偏光元件、抗反射膜、選擇反射膜、色補償膜、視角補償膜等。出於調整光學各向異性體的物性的目的，亦可將聚合起始劑等添加物添加於聚合性組成物中。 When the second component of the polymerizable composition is a polymerizable compound having a liquid crystal phase, an optically anisotropic body is generated by polymerizing the liquid crystal molecules while controlling the alignment. The optically anisotropic body can be used in retardation films, polarizing elements, circular polarizing elements, elliptically polarizing elements, anti-reflection films, selective reflection films, color compensation films, viewing angle compensation films, and the like. For the purpose of adjusting the physical properties of the optically anisotropic body, the Additives such as polymerization initiators are added to the polymerizable composition.

聚合性組成物亦可包含液晶組成物作為第二成分。在以用於PS-TN、PS-IPS、PS-FFS、PSA-VA、PSA-OCB等模式的液晶顯示元件為目的的情況下，聚合性組成物較佳包含化合物(1)作為成分A，且更包含選自以下所示的成分B、成分C及成分D中的化合物。成分B為化合物(2)至化合物(4)。成分C為化合物(5)至化合物(7)。成分D為化合物(8)。當製備此種聚合性組成物時，考慮到介電各向異性的正負、介電各向異性的大小等，較佳選擇成分B、成分C及成分D。適當地選擇了成分的聚合性組成物具有高上限溫度、低下限溫度、低黏度、適當的光學各向異性(即大的光學各向異性或小的光學各向異性)、大的正或負介電各向異性及適當的彈性常數(即大的彈性常數或小的彈性常數) The polymerizable composition may contain a liquid crystal composition as a second component. When it is intended to be used in liquid crystal display elements of modes such as PS-TN, PS-IPS, PS-FFS, PSA-VA, PSA-OCB, etc., the polymerizable composition preferably contains compound (1) as component A, Furthermore, the compound selected from the group consisting of component B, component C, and component D shown below is included. Ingredient B is compound (2) to compound (4). Ingredient C is compound (5) to compound (7). Ingredient D is compound (8). When preparing such a polymerizable composition, Component B, Component C, and Component D are preferably selected in consideration of the positive and negative of the dielectric anisotropy, the magnitude of the dielectric anisotropy, and the like. Properly selected polymeric compositions have high upper limit temperature, low lower limit temperature, low viscosity, appropriate optical anisotropy (ie, large optical anisotropy or small optical anisotropy), large positive or negative optical anisotropy Dielectric anisotropy and appropriate elastic constant (ie large elastic constant or small elastic constant)

聚合性組成物是藉由在液晶組成物中添加化合物(1)來製備。亦可視需要於該組成物中添加添加物。此種組成物中，基於液晶組成物的重量，化合物(1)即成分A的添加量為0.01重量%~20重量%的範圍，尤佳的添加量為0.0133重量%~10重量%的範圍，特佳的添加量為0.05重量%~5重量%的範圍。亦可更添加與化合物(1)不同的其他聚合性化合物的至少一種。於該情況下，化合物(1)與其他聚合性化合物的合計添加量較佳在所述範圍內。適當選擇其他聚合性化合物即可調整生成的聚合物的物性。其他聚合性化合物的例子如前述為丙烯酸酯、甲基丙烯酸酯等。該例子中亦包含化合物(M-1)至化合物(M-12)。 The polymerizable composition is prepared by adding the compound (1) to the liquid crystal composition. Additives may also be added to the composition as required. In such a composition, based on the weight of the liquid crystal composition, the compound (1), that is, component A, is added in an amount in the range of 0.01% by weight to 20% by weight, and preferably in an amount in the range of 0.0133% by weight to 10% by weight, A particularly preferable addition amount is in the range of 0.05% by weight to 5% by weight. At least one kind of other polymerizable compounds different from the compound (1) may be further added. In this case, the total addition amount of the compound (1) and other polymerizable compounds is preferably within the above-mentioned range. The physical properties of the resulting polymer can be adjusted by appropriately selecting another polymerizable compound. Examples of other polymerizable compounds are, as mentioned above, acrylates, methacrylates, and the like. Compounds (M-1) to (M-12) are also included in this example.

成分B是兩個末端基為烷基等的化合物。成分B的較佳例可列舉：化合物(2-1)至化合物(2-11)、化合物(3-1)至化合物(3-19)、或化合物(4-1)至化合物(4-7)。於成分B的化合物中，R¹¹及R¹²獨立地為碳數1至10的烷基或碳數2至10的烯基，於該烷基或烯基中，至少一個-CH₂-可經-O-取代，至少一個氫可經氟取代。 Component B is a compound whose two terminal groups are alkyl groups or the like. Preferred examples of component B include compound (2-1) to compound (2-11), compound (3-1) to compound (3-19), or compound (4-1) to compound (4-7) ). In the compound of component B, R ¹¹ and R ¹² are independently an alkyl group having 1 to 10 carbons or an alkenyl group having 2 to 10 carbons, and in the alkyl or alkenyl group, at least one -CH ₂ - may be -O-Substituted, at least one hydrogen may be replaced by fluorine.

[化40]

[Chemical 40]

成分B由於介電各向異性的絕對值小，故而為接近中性的化合物。化合物(2)主要具有調整黏度或調整光學各向異性的效果。化合物(3)及化合物(4)具有藉由提高上限溫度而擴大向列相的溫度範圍的效果、或調整光學各向異性的效果。 Component B is a nearly neutral compound because the absolute value of the dielectric anisotropy is small. The compound (2) mainly has the effect of adjusting the viscosity or adjusting the optical anisotropy. Compound (3) and compound (4) have the effect of expanding the temperature range of the nematic phase by raising the upper limit temperature, or the effect of adjusting the optical anisotropy.

增加成分B的含量，則隨之組成物的介電各向異性減小，但黏度減小。因此，只要滿足元件的臨限電壓的要求值，則含量較多者較佳。因此，於製備PS-IPS、PSA-VA等模式用組成物的情況下，基於液晶組成物的重量，成分B的含量較佳為30重量%以上，尤佳為40重量%以上。 As the content of component B increases, the dielectric anisotropy of the composition decreases small, but the viscosity decreases. Therefore, as long as the required value of the threshold voltage of the element is satisfied, a larger content is preferable. Therefore, in the case of preparing a mode composition such as PS-IPS and PSA-VA, the content of Component B is preferably 30 wt % or more, particularly preferably 40 wt % or more, based on the weight of the liquid crystal composition.

成分C是於右末端具有鹵素或含氟基的化合物。成分C的較佳例可列舉：化合物(5-1)至化合物(5-16)、化合物(6-1)至化合物(6-113)、或化合物(7-1)至化合物(7-57)。於成分C的化合物中，R¹³為碳數1至10的烷基或碳數2至10的烯基，於該烷基及烯基中，至少一個-CH₂-可經-O-取代，且至少一個氫可經氟取代；X¹¹為氟、氯、-OCF₃、-OCHF₂、-CF₃、-CHF₂、-CH₂F、-OCF₂CHF₂或-OCF₂CHFCF₃。 Component C is a compound having a halogen or fluorine-containing group at the right terminal. Preferred examples of component C include compound (5-1) to compound (5-16), compound (6-1) to compound (6-113), or compound (7-1) to compound (7-57) ). In the compound of component C, R ¹³ is an alkyl group having 1 to 10 carbons or an alkenyl group having 2 to 10 carbon atoms, and in the alkyl and alkenyl groups, at least one -CH ₂ - may be substituted by -O-, and at least one hydrogen may be substituted by fluorine; X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ or -OCF ₂ CHFCF ₃ .

[化41]

[Chemical 41]

[化42]

[Chemical 42]

[化43]

[Chemical 43]

[化44]

[Chemical 44]

[化45]

[Chemical 45]

[化46]

[Chemical 46]

成分C由於介電各向異性為正，對熱、光等的穩定性甚佳，故而用於製備PS-IPS、PS-FFS、PSA-OCB等模式用組成物。基於液晶組成物的重量，成分C的含量宜為1重量%~99重量%的範圍，較佳為10重量%~97重量%的範圍，尤佳為40重量%~95重量%的範圍。於將成分C添加於介電各向異性為負的組成物中的情況下，基於液晶組成物的重量，成分C的含量較佳為30重量%以下。藉由添加成分C，能夠調整組成物的彈性常數，且調整元件的電壓-透過率曲線。 Component C has a positive dielectric anisotropy and is very stable to heat and light, so it is used to prepare PS-IPS, PS-FFS, PSA-OCB and other mode compositions. Based on the weight of the liquid crystal composition, the content of component C is preferably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, and particularly preferably in the range of 40% by weight to 95% by weight. When adding Component C to a composition having a negative dielectric anisotropy, the content of Component C is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding the component C, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the element can be adjusted.

成分D是右末端基為-C≡N或-C≡C-C≡N的化合物(8)。成分D的較佳例可列舉化合物(8-1)至化合物(8-64)。成分D的化合物中，R¹⁴為碳數1至10的烷基或碳數2至10的烯基，於該烷基及烯基中，至少一個-CH₂-可經-O-取代，且至少一個氫可經氟取代；X¹²為-C≡N或-C≡C-C≡N。 Component D is a compound (8) whose right terminal group is -C≡N or -C≡CC≡N. Preferred examples of component D include compound (8-1) to compound (8-64). In the compound of component D, R ¹⁴ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in the alkyl and alkenyl groups, at least one -CH ₂ - may be substituted by -O-, and At least one hydrogen may be substituted with fluorine; X ¹² is -C≡N or -C≡CC≡N.

[化47]

[Chemical 47]

成分D由於介電各向異性為正，且其值大，故而主要用於製備PS-TN等模式用組成物。添加該成分D即可增大組成物的介電各向異性。成分D具有擴大液晶相的溫度範圍、調整黏度或調整光學各向異性的效果。成分D亦可用於調整元件的電壓-透過率曲線。 Since the dielectric anisotropy of Component D is positive and its value is large, it is mainly used to prepare a composition for mode such as PS-TN. Addition of this component D increases the dielectric anisotropy of the composition. Component D has the effect of expanding the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component D can also be used to adjust the voltage-transmittance curve of the device.

於製備PS-TN等模式用組成物的情況下，基於液晶組成物的重量，成分D的含量宜為1重量%~99重量%的範圍，較佳為10重量%~97重量%的範圍，尤佳為40重量%~95重量%的範圍。於將成分D添加於介電各向異性為負的組成物的情況下，基於液晶組成物的重量，成分D的含量較佳30重量%以下。藉由添加成分D，能夠調整組成物的彈性常數，且調整元件的電壓-透過率曲線。 In the case of preparing a mode composition such as PS-TN, based on the weight of the liquid crystal composition, the content of component D is preferably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, The range of 40% by weight to 95% by weight is particularly preferable. around. When the component D is added to a composition having a negative dielectric anisotropy, the content of the component D is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding the component D, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the element can be adjusted.

聚合性組成物的製備可利用使所需成分在高於室溫的溫度下溶解等方法來進行。根據用途，亦可於該組成物中添加添加物。添加物的例子為：光學活性化合物、抗氧化劑、紫外線吸收劑、光穩定劑、熱穩定劑、消泡劑、聚合起始劑、聚合抑制劑等。此種添加物已為本領域技術人員所熟知，並記載於文獻中。 The preparation of the polymerizable composition can be carried out by a method such as dissolving the desired components at a temperature higher than room temperature. Additives may be added to the composition according to the application. Examples of additives are: optically active compounds, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, antifoaming agents, polymerization initiators, polymerization inhibitors, and the like. Such additives are well known to those skilled in the art and are described in the literature.

光學活性化合物具有藉由使液晶分子產生螺旋結構來賦予所需扭轉角而防止逆扭轉的效果。添加光學活性化合物即可調整螺旋節距(helical pitch)。出於調整螺旋節距的溫度依存性的目的，亦可添加兩種以上的光學活性化合物。光學活性化合物的較佳例可列舉下述化合物(Op-1)至化合物(Op-18)。於化合物(Op-18)中，環J為1,4-伸環己基或1,4-伸苯基，R²⁸為碳數1至10的烷基。 The optically active compound has an effect of preventing reverse twist by imparting a desired twist angle by generating a helical structure in liquid crystal molecules. The helical pitch can be adjusted by adding an optically active compound. For the purpose of adjusting the temperature dependence of the helical pitch, two or more optically active compounds may be added. Preferable examples of the optically active compound include the following compounds (Op-1) to (Op-18). In compound (Op-18), ring J is 1,4-cyclohexylene or 1,4-phenylene, and R ²⁸ is an alkyl group having 1 to 10 carbons.

[化49]

[Chemical 49]

抗氧化劑對於維持大的電壓保持率而言有效。抗氧化劑的較佳例可列舉：下述化合物(AO-1)及化合物(AO-2)；易璐諾斯(IRGANOX)415、IRGANOX 565、IRGANOX 1010、IRGANOX 1035、IRGANOX 3114、以及IRGANOX 1098(商品名：巴斯夫(BASF)公司)。紫外線吸收劑對於防止上限溫度的下降而言有效。紫外線吸收劑的較佳例為：二苯甲酮衍生物、苯甲酸酯衍生物、***衍生物等。具體例可列舉下述化合物(AO-3)及化合物(AO-4)；地奴彬(Tinuvin)329、Tinuvin P、Tinuvin 326、Tinuvin 234、Tinuvin 213、Tinuvin 400、Tinuvin 328及Tinuvin 99-2(商品名：巴斯夫公司)；及1,4-二氮雜雙環[2.2.2]辛烷(1,4-diazabicyclo[2.2.2]octane，DABCO)。 Antioxidants are effective for maintaining a large voltage holding ratio. Preferable examples of antioxidants include the following compounds (AO-1) and compounds (AO-2); IRGANOX 415, IRGANOX 565, IRGANOX 1010, IRGANOX 1035, IRGANOX 3114, and IRGANOX 1098 (trade name: BASF). The ultraviolet absorber is effective in preventing the lowering of the upper limit temperature. Preferable examples of the ultraviolet absorber are: benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like. Specific examples include the following compounds (AO-3) and compounds (AO-4): Tinuvin 329, Tinuvin P, Tinuvin 326, Tinuvin 234, Tinuvin 213, Tinuvin 400, Tinuvin 328 and Tinuvin 99-2 (trade name: BASF Corporation); and 1,4-diazabicyclo[2.2.2]octane (1,4-diazabicyclo[2.2.2]octane, DABCO).

為了維持大的電壓保持率，較佳為具有立體阻礙的胺之類的光穩定劑。光穩定劑的較佳例可列舉：下述化合物(AO-5)及化合物(AO-6)；TINUVIN 144、TINUVIN 765、以及TINUVIN 770DF(商品名：巴斯夫公司)。熱穩定劑亦對於維持大的電壓保持率而言有效，較佳例可列舉易璐佛斯(IRGAFOS)168(商品名：巴斯夫公司)。消泡劑對於防止起泡而言有效。消泡劑的較佳例為二甲基矽酮油、甲基苯基矽酮油等。 In order to maintain a large voltage holding ratio, a light stabilizer such as an amine having steric hindrance is preferable. Preferable examples of the light stabilizer include the following compound (AO-5) and compound (AO-6); TINUVIN 144, TINUVIN 765, and TINUVIN 770DF (trade name: BASF). A thermal stabilizer is also effective for maintaining a large voltage holding ratio, and a preferred example thereof includes IRGAFOS 168 (trade name: BASF). Antifoaming agents are effective in preventing foaming. Preferred examples of the defoaming agent are dimethyl silicone oil, methyl phenyl silicone oil, and the like.

化合物(AO-1)中，R²⁹為碳數1至20的烷基、碳數1至20的烷氧基、-COOR³²或-CH₂CH₂COOR³²，此處R³²為碳數1至20的烷基。化合物(AO-2)及化合物(AO-5)中，R³⁰為碳數1至20的烷基。化合物(AO-5)中，R³¹為氫、甲基或O(氧自由基)，環K及環L為1,4-伸環己基或1,4-伸苯基，x為0、1或2。 In compound (AO-1), R ²⁹ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, -COOR ³² or -CH ₂ CH ₂ COOR ³² , where R ³² is a carbon number of 1 to 20 alkyl groups. In compound (AO-2) and compound (AO-5), R ³⁰ is an alkyl group having 1 to 20 carbon atoms. In compound (AO-5), R ³¹ is hydrogen, methyl or O (oxygen radical), ring K and ring L are 1,4-cyclohexylene or 1,4-phenylene, x is 0, 1 or 2.

4.液晶複合體 4. Liquid crystal complex

化合物(1)具有適當的聚合反應性、高轉化率及於液晶組成物中的高溶解度。藉由使包含化合物(1)及液晶組成物的聚合性組成物聚合而生成液晶複合體。化合物(1)藉由聚合而於液晶組成物中生成聚合物。該聚合物具有使液晶分子的初期配向穩定化的效果。另外，若一邊施加電場一邊進行聚合，則亦可產生預傾。藉由熱、光等來引起聚合。較佳的反應為光聚合。亦可於施加電場或磁場的狀態下進行聚合。 Compound (1) has appropriate polymerization reactivity, high conversion, and high solubility in liquid crystal compositions. The liquid crystal composite is produced by polymerizing the polymerizable composition containing the compound (1) and the liquid crystal composition. The compound (1) produces a polymer in the liquid crystal composition by polymerization. This polymer has the effect of stabilizing the initial alignment of liquid crystal molecules. In addition, pretilt may also be generated when polymerization is performed while applying an electric field. Polymerization is induced by heat, light, or the like. A preferred reaction is photopolymerization. The polymerization can also be carried out in the state where an electric field or a magnetic field is applied.

可調整化合物(1)的聚合反應性及轉化率。化合物(1)適合自由基聚合。化合物(1)可藉由添加聚合起始劑而快速聚合。使反應溫度最佳化即可減少化合物(1)的殘存量。光自由基聚合起始劑的例子為：巴斯夫公司的德牢固(Darocur)系列中的TPO、1173及4265，易璐佳(Irgacure)系列中的184、369、500、651、784、819、907、1300、1700、1800、1850及2959。 The polymerization reactivity and conversion rate of compound (1) can be adjusted. Compound (1) is suitable for free radical polymerization. Compound (1) can be rapidly polymerized by adding a polymerization initiator. The residual amount of compound (1) can be reduced by optimizing the reaction temperature. Examples of photo-radical polymerization initiators are: TPO, 1173 and 4265 in BASF's Darocur series, 184, 369, 500, 651, 784, 819, 907 in Irgacure series , 1300, 1700, 1800, 1850 and 2959.

光自由基聚合起始劑的追加例為：4-甲氧基苯基-2,4-雙(三氯甲基)三嗪、2-(4-丁氧基苯乙烯基)-5-三氯甲基-1,3,4-噁二唑、9-苯基吖啶、9,10-苯并啡嗪(9,10-benzophenazine)、二苯甲酮/米其勒酮(benzophenone/michler’s ketone)混合物、六芳基聯咪唑/巰基苯并咪唑混合物、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、苯偶醯二甲基縮酮、2-甲基-1-[4-(甲基硫基)苯基]-2-嗎啉基丙烷-1-酮、2,4-二乙基氧雜蒽酮/對二甲基胺基苯甲酸甲酯混合物、二苯甲酮/甲基三乙醇胺混合物。 Additional examples of photo-radical polymerization initiators are: 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxystyryl)-5-triazine Chloromethyl-1,3,4-oxadi azole, 9-phenylacridine, 9,10-benzophenazine, benzophenone/michler's ketone mixture, hexaarylbiimidazole/mercaptobenzene Mixture of imidazoles, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, benzalkonium dimethyl ketal, 2-methyl-1-[4-( Methylthio)phenyl]-2-morpholinopropan-1-one, 2,4-diethylxanthone/methyl p-dimethylaminobenzoate mixture, benzophenone/methyl triethanolamine mixture.

可藉由在聚合性組成物中添加光自由基聚合起始劑後，在施加電場的狀態下照紫外線來進行聚合。但是，未反應的聚合起始劑或聚合起始劑的分解產物可能會使元件產生圖像的殘像等顯示不良。為了避免所述顯示不良，亦可於不添加聚合起始劑的狀態下進行光聚合。所照射的光的較佳波長為150nm~500nm的範圍，尤佳波長為250nm~450nm的範圍，特佳波長為300nm~400nm的範圍。 Polymerization can be performed by adding a photo-radical polymerization initiator to the polymerizable composition and then irradiating with ultraviolet rays in a state where an electric field is applied. However, the unreacted polymerization initiator or the decomposition product of the polymerization initiator may cause poor display such as image afterimage in the element. In order to avoid the display failure, photopolymerization may be performed without adding a polymerization initiator. The preferred wavelength of the irradiated light is in the range of 150 nm to 500 nm, the particularly preferred wavelength is in the range of 250 nm to 450 nm, and the particularly preferred wavelength is in the range of 300 nm to 400 nm.

保管聚合性化合物時，為了防止聚合，亦可添加聚合抑制劑。聚合性化合物通常是以未去除聚合抑制劑的狀態添加於組成物中。聚合抑制劑的例子為對苯二酚、甲基對苯二酚之類的對苯二酚衍生物、4-第三丁基鄰苯二酚、4-甲氧基苯酚、啡噻嗪等。 When storing the polymerizable compound, a polymerization inhibitor may be added in order to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of the polymerization inhibitor are hydroquinone, hydroquinone derivatives such as methyl hydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine, and the like.

5.液晶顯示元件 5. Liquid crystal display element

液晶顯示元件中的聚合物的效果解釋如下。聚合性組成物為液晶性化合物、聚合性化合物等的混合物。若將該組成物注入至液晶單元，則藉由所使用的單元與組成物各自的特性而顯示出多種初期配向。於該狀態下對組成物照射紫外線，使聚合性化合物聚合。此時，亦可對單元施加電場。結果，於聚合性組成物中生成聚合物的網狀結構。藉由該網狀結構的效果，液晶分子以紫外線照射前的狀態得以穩定化。另外，初期配向為無規配向，但藉由紫外線照射而亦可形成均質配向或垂直配向等各種有秩序的配向。如此，藉由紫外線照射而使聚合性組成物聚合即可獲得以多種配向狀態穩定化的液晶顯示元件。 The effect of the polymer in the liquid crystal display element is explained as follows. The polymerizable composition is a mixture of liquid crystal compounds, polymerizable compounds, and the like. When the composition is injected into a liquid crystal cell, various initial alignments are exhibited depending on the characteristics of the used cell and the composition. In this state, ultraviolet rays are irradiated to the composition to make the polymerizable compound polymerization. At this time, an electric field may also be applied to the cell. As a result, a polymer network structure is formed in the polymerizable composition. By the effect of this network structure, the liquid crystal molecules are stabilized in the state before ultraviolet irradiation. In addition, the initial alignment is random alignment, but various ordered alignments such as homogeneous alignment and vertical alignment can also be formed by ultraviolet irradiation. In this way, a liquid crystal display element stabilized in various alignment states can be obtained by polymerizing the polymerizable composition by ultraviolet irradiation.

聚合性組成物的聚合較佳於顯示元件中進行。其中一例如下所述。準備具有兩塊玻璃基板的顯示元件，所述玻璃基板的至少任一者具備透明電極。製備以化合物(1)、液晶組成物、添加物等為成分的聚合性組成物。將該組成物注入顯示元件中。對該顯示元件照紫外線，使化合物(1)聚合。藉由該聚合而生成液晶複合體。利用該方法，可容易地製作具有液晶複合體的液晶顯示元件。該方法中，亦可省略配向膜的摩擦處理，且亦可無配向膜。 The polymerization of the polymerizable composition is preferably performed in a display element. One example is as follows. A display element having two glass substrates, at least one of which is provided with a transparent electrode, is prepared. A polymerizable composition containing the compound (1), a liquid crystal composition, an additive, and the like as components is prepared. The composition is injected into the display element. This display element is irradiated with ultraviolet rays to polymerize the compound (1). A liquid crystal composite is produced by this polymerization. By this method, a liquid crystal display element having a liquid crystal composite can be easily produced. In this method, the rubbing treatment of the alignment film may be omitted, and there may be no alignment film.

當基於液晶組成物的重量而聚合性化合物的添加量為0.1重量%至2重量%的範圍時，製作PSA模式的液晶顯示元件。PSA模式的元件可以主動矩陣(active matrix，AM)、被動矩陣(passive matrix，PM)之類的驅動方式驅動。此種元件可應用於反射型、透過型、半透過型的任一類型。藉由增加聚合性化合物的添加量，亦可製作高分子分散(polymer dispersed)模式的元件。 When the addition amount of the polymerizable compound is in the range of 0.1 wt % to 2 wt % based on the weight of the liquid crystal composition, a PSA mode liquid crystal display element is produced. The elements in the PSA mode can be driven by an active matrix (AM), passive matrix (PM) or the like. This type of element can be applied to any type of reflection type, transmission type, and semi-transmission type. By increasing the addition amount of the polymerizable compound, a polymer dispersed mode device can also be produced.

[實施例] [Example]

藉由實施例來對本發明進一步進行詳細說明。本發明不受這些實施例的限制。本發明包含實施例1的組成物與實施例2的組成物的混合物。本發明亦包含將實施例的組成物的至少兩種混合而成的混合物。所合成的化合物是藉由核磁共振(nuclear magnetic resonance，NMR)分析等方法來鑑定。化合物、組成物及元件的物性是利用下述所記載的方法來測定。 The present invention will be further described in detail by means of examples. The present invention does not Limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes mixtures obtained by mixing at least two of the compositions of the examples. The synthesized compounds were identified by methods such as nuclear magnetic resonance (NMR) analysis. The physical properties of compounds, compositions, and elements were measured by the methods described below.

NMR分析 NMR analysis

測定時使用布魯克拜厄斯賓(Bruker BioSpin)公司製造的DRX-500。¹H-NMR的測定中，使試樣溶解於CDCl₃等氘化溶媒中，於室溫下以500MHz、累計次數16次的條件進行測定。使用四甲基矽烷作為內部標準。¹⁹F-NMR的測定中，使用CFCl₃作為內部標準，以累計次數24次進行。核磁共振光譜的說明中，s是指單峰(singlet)，d是指雙重峰(doublet)，t是指三重峰(triplet)，q是指四重峰(quartet)，quin是指五重峰(quintet)，sex是指六重峰(sextet)，m是指多重峰(multiplet)，br是指寬峰(broad)。 For the measurement, DRX-500 manufactured by Bruker BioSpin was used. In the measurement of ¹ H-NMR, a sample is dissolved in a deuterated solvent such as CDCl ₃ , and the measurement is performed at room temperature under the conditions of 500 MHz and 16 cumulative times. Tetramethylsilane was used as an internal standard. In the measurement of ¹⁹ F-NMR, CFCl ₃ was used as an internal standard, and the cumulative number of times was 24 times. In the description of NMR spectra, s means singlet, d means doublet, t means triplet, q means quartet, and quin means quintet. (quintet), sex means sextet, m means multiplet, br means broad.

高效液相層析法(HPLC)分析 High performance liquid chromatography (HPLC) analysis

測定中使用島津製作所製造的普洛敏思(Prominence)(LC-20AD；SPD-20A)。管柱使用YMC製造的YMC-Pack ODS-A(長度150mm、內徑4.6mm、粒徑5μm)。析出液是將乙腈與水適當混合來使用。檢測器適當使用紫外線(UV)檢測器、折射率(RI)檢測器、電暈檢測器(CORONA detector)等。於使用UV檢測器的情況下，檢測波長設為254nm。試樣溶解於乙腈中，製備成0.1重量%的溶液，將該溶液1μL導入至試樣室中。記錄器使用島津製作所製造的C-R7Aplus。 For the measurement, Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used. As the column, YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 μm) manufactured by YMC was used. The precipitate was used by appropriately mixing acetonitrile and water. As the detector, an ultraviolet (UV) detector, a refractive index (RI) detector, a corona detector (CORONA detector) or the like is appropriately used. In the case of using a UV detector, the detection wavelength was set to 254 nm. The sample was dissolved in acetonitrile to prepare a 0.1% by weight solution, and 1 μL of this solution was introduced into the sample chamber. Recorder C-R7Aplus manufactured by Shimadzu was used.

紫外可見分光分析 UV-Vis spectroscopic analysis

測定中使用島津製作所製造的法瑪斯派克(PharmaSpec)UV-1700。檢測波長設為190nm至700nm。試樣溶解於乙腈中，製備成0.01mmol/L的溶液，加入至石英槽(光程長度為1cm)中進行測定。 For the measurement, PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used. The detection wavelength was set to 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare a solution of 0.01 mmol/L, and it was put into a quartz cell (optical path length: 1 cm) for measurement.

測定試樣 Measurement sample

測定相結構及轉變溫度(透明點、熔點、聚合起始溫度等)時，將化合物本身用作試樣。測定液晶性化合物的上限溫度、黏度、光學各向異性、介電各向異性等物性時，將該化合物與母液晶的混合物用作試樣。測定液晶組成物的物性時，將組成物本身用作試樣。 When measuring the phase structure and transition temperature (clearing point, melting point, polymerization initiation temperature, etc.), the compound itself was used as a sample. When measuring physical properties such as the upper limit temperature, viscosity, optical anisotropy, and dielectric anisotropy of the liquid crystal compound, a mixture of the compound and mother liquid crystal is used as a sample. When measuring the physical properties of the liquid crystal composition, the composition itself was used as a sample.

母液晶是使用下述的母液晶(A)或母液晶(B)等。將母液晶(A)及母液晶(B)的成分的比例以重量%表示。 As the mother liquid crystal, the following mother liquid crystal (A), mother liquid crystal (B), or the like is used. The ratio of the components of mother liquid crystal (A) and mother liquid crystal (B) is expressed in % by weight.

測定方法 test methods

以下述方法進行物性的測定。這些方法大多是日本電子資訊技術產業協會(JEITA；Japan Electronics and Information Technology Industries Association)審議製定的JEITA規格(JEITA．ED-2521B)中記載的方法，或者將其修飾而成的方法。用於測定的TN元件上未安裝薄膜電晶體(Thin Film Transistor，TFT)。 The physical properties were measured by the following methods. Many of these methods are methods described in the JEITA standard (JEITA.ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (JEITA; Japan Electronics and Information Technology Industries Association), or modified methods. A thin film transistor (TFT) was not mounted on the TN element used for the measurement.

(1)相結構 (1) Phase structure

於具備偏光顯微鏡的熔點測定裝置的加熱板(梅特勒(Mettler)公司，FP-52型加熱台)上放置試樣。一邊以3℃/分鐘的速度對該試樣進行加熱，一邊利用偏光顯微鏡來觀察相狀態及其變化，來確定相的種類。 The sample was placed on a heating plate (Mettler, FP-52 type heating stage) equipped with a melting point measuring device of a polarizing microscope. side at 3°C/min The sample was heated at a speed of 100 Å, and the phase state and its changes were observed with a polarizing microscope to determine the type of phase.

(2)轉變溫度(℃) (2) Transformation temperature (°C)

測定時使用珀金埃爾默(Perkin Elmer)公司製造的掃描熱量計戴蒙德(Diamond)DSC系統、或SSI奈米技術(SSI Nanotechnology)公司製造的高感度示差掃描熱量計X-DSC7000。以3℃/min的速度使試樣升降溫。藉由外推求出隨著試樣的相變化所產生的吸熱峰、或放熱峰的起始點而確定轉變溫度。化合物的熔點、聚合起始溫度亦使用該裝置來測定。有時將化合物自固體轉變為層列相、向列相等液晶相的溫度簡稱為「液晶相的下限溫度」。有時將化合物自液晶相轉變為液體的溫度簡稱為「透明點」。 For the measurement, a scanning calorimeter Diamond DSC system manufactured by Perkin Elmer, or a high-sensitivity differential scanning calorimeter X-DSC7000 manufactured by SSI Nanotechnology was used. The sample was heated and cooled at a rate of 3°C/min. The transition temperature is determined by extrapolating the starting point of an endothermic peak or an exothermic peak generated with the phase change of the sample. The melting point and polymerization initiation temperature of the compound were also measured using this apparatus. The temperature at which the compound changes from a solid to a smectic phase or a nematic phase liquid crystal phase is sometimes simply referred to as "the lower limit temperature of the liquid crystal phase". The temperature at which a compound changes from a liquid crystal phase to a liquid is sometimes abbreviated as "clear point".

結晶表示為C。於對結晶的種類加以區別的情況下，分別表示為C₁、C₂。層列相表示為S，向列相表示為N。層列相中，於對層列A相、層列B相、層列C相、或層列F相加以區別的情況下，分別表示為S_A、S_B、S_C、或S_F。液體(等向性)表示為I。轉變溫度例如表述為「C 50.0 N 100.0 I」。這表示，自結晶至向列相的轉變溫度為50.0℃，自向列相至液體的轉變溫度為100.0℃。 Crystals are denoted as C. When distinguishing the types of crystals, they are represented by C ₁ and C ₂ , respectively. The smectic phase is denoted S and the nematic phase is N. Among the smectic phases, when the smectic A phase, the smectic B phase, the smectic C phase, or the smectic F addition are distinguished, they are represented as S _A , S _B , S _C , or _SF , respectively. Liquids (isotropy) are denoted I. The transition temperature is expressed as "C 50.0 N 100.0 I", for example. This means that the transition temperature from crystalline to nematic phase is 50.0°C, and the transition temperature from nematic phase to liquid is 100.0°C.

(3)向列相的上限溫度(T_NI或NI；℃) (3) Upper limit temperature of nematic phase (T _NI or NI; °C)

於具備偏光顯微鏡的熔點測定裝置的加熱板上放置試樣，以1℃/分的速度進行加熱。測定試樣的一部分自向列相變化為等向性液體時的溫度。有時將向列相的上限溫度簡稱為「上限溫度」。當試樣為液晶性化合物與母液晶的混合物時，以記號T_NI表示。當試樣為液晶性化合物與成分B、成分C、成分D之類的化合物的混合物時，以記號NI表示。 The sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope, and heated at a rate of 1°C/min. The temperature at which a part of the sample changes from the nematic phase to an isotropic liquid is measured. The upper limit temperature of the nematic phase is sometimes abbreviated as "upper limit temperature". When the sample is a mixture of a liquid crystal compound and a mother liquid crystal, it is represented by the symbol T _NI . When the sample is a mixture of a liquid crystal compound and a compound such as Component B, Component C, and Component D, it is represented by the symbol NI.

(4)向列相的下限溫度(T_C；℃) (4) Lower limit temperature of nematic phase (TC; ° _C )

將具有向列相的試樣於0℃、-10℃、-20℃、-30℃及-40℃的冷凍器中保管10天後，觀察液晶相。例如，當試樣於-20℃下為向列相的狀態而於-30℃下變化為結晶或層列相時，將T_C記載為≦-20℃。有時將向列相的下限溫度簡稱為「下限溫度」。 After storing the sample having a nematic phase in a freezer at 0°C, -10°C, -20°C, -30°C, and -40°C for 10 days, the liquid crystal phase was observed. For example, when the sample is in the state of nematic phase at -20°C and changes to crystalline or smectic phase at -30°C, T _C is described as ≦-20°C. The lower limit temperature of the nematic phase is sometimes abbreviated as "lower limit temperature".

(5)黏度(體積黏度；η；於20℃下測定；mPa．s) (5) Viscosity (bulk viscosity; η; measured at 20°C; mPa.s)

使用東京計器股份有限公司製造的E型旋轉黏度計來測定黏度。 The viscosity was measured using an E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd.

(6)光學各向異性(折射率各向異性；於25℃下測定；△n) (6) Optical anisotropy (refractive index anisotropy; measured at 25°C; Δn)

使用波長589nm的光，利用在接目鏡上安裝有偏光板的阿貝折射計(abbe refractometer)來進行測定。將主稜鏡的表面向一個方向摩擦後，將試樣滴加於主稜鏡上。折射率(n∥)是在偏光的方向與摩擦的方向平行時測定。折射率(n⊥)是在偏光的方向與摩擦的方向垂直時測定。光學各向異性(△n)的值是由△n=n∥-n⊥的式子來計算。 The measurement was performed with an Abbe refractometer with a polarizing plate attached to the eyepiece using light having a wavelength of 589 nm. After rubbing the surface of the main pole in one direction, drop the sample on the main pole. The refractive index (n∥) was measured when the direction of polarized light was parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of polarized light was perpendicular to the direction of rubbing. The value of optical anisotropy (Δn) is calculated by the formula of Δn=n∥-n⊥.

(7)比電阻(ρ；於25℃下測定；Ωcm) (7) Specific resistance (ρ; measured at 25°C; Ωcm)

於具備電極的容器中注入試樣1.0mL。對該容器施加直流電壓(10V)，測定10秒後的直流電流。比電阻是由下式來算出。(比電阻)={(電壓)×(容器的電容)}/{(直流電流)×(真空的介電常數)}。 1.0 mL of the sample was poured into a container equipped with an electrode. A DC voltage (10V) was applied to this container, and the DC current after 10 seconds was measured. The specific resistance is calculated by the following formula. (Compare resistance)={(voltage)×(capacitance of container)}/{(direct current)×(dielectric constant of vacuum)}.

(8)電壓保持率(VHR-1；於25℃下測定；%) (8) Voltage holding ratio (VHR-1; measured at 25°C; %)

用於測定的TN元件具有聚醯亞胺配向膜，並且兩塊玻璃基板的間隔(單元間隙)為5μm。在放入試樣後，利用以紫外線硬化的黏接劑來密封該元件。對該元件進行400秒的紫外線照射。照射紫外線時，使用豪雅冠得光電子學(HOYA CANDEO OPTRONICS)股份有限公司製造的EXECURE4000-D型水銀氙燈。對該元件施加脈衝電壓(5V、60微秒)來進行充電。利用高速電壓計在16.7毫秒之間測定所衰減的電壓，求出單位週期中的電壓曲線與橫軸之間的面積A。面積B為未衰減時的面積。電壓保持率是由面積A相對於面積B的百分率來表示。 The TN element used for the measurement had a polyimide alignment film, and the interval (cell gap) between the two glass substrates was 5 μm. After placing the sample, the element is sealed with a UV-curable adhesive. The element was irradiated with ultraviolet rays for 400 seconds. When irradiating ultraviolet rays, EXECUURE4000-D mercury-xenon lamps manufactured by HOYA CANDEO OPTRONICS Co., Ltd. were used. The element was charged by applying a pulse voltage (5 V, 60 microseconds). The decayed voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve per unit cycle and the horizontal axis was obtained. Area B is the area without attenuation. Voltage retention is expressed as the percentage of area A relative to area B.

(9)電壓保持率(VHR-2；於80℃下測定；%) (9) Voltage holding ratio (VHR-2; measured at 80°C; %)

除了代替25℃而於80℃下進行測定以外，利用所述方法來測定電壓保持率。由記號VHR-2來表示結果。 The voltage holding ratio was measured by the above-described method, except that the measurement was performed at 80°C instead of 25°C. The results are represented by the notation VHR-2.

(10)黏度(旋轉黏度；γ1；於25℃下測定；mPa．s) (10) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa.s)

依據M.今井(M.Imai)等人的「分子晶體與液晶(Molecular Crystals and Liquid Crystals)」第259期第37頁(1995年)中記載的方法來進行測定。於扭轉角為0度並且兩塊玻璃基板的間隔(單元間隙)為5μm的TN元件中放入試樣。在16V至19.5V的範圍內以0.5V為單位對該元件階段性地施加電壓。不施加電壓0.2秒後，以僅施加1個矩形波(矩形脈衝；0.2秒)與不施加電壓(2秒)的條件反覆施加。測定藉由該施加而產生的暫態電流(transient current)的峰值電流(peak current)及峰值時間(peak time)。由這些測定值與M.今井等人的論文第40頁的計算式(8)來獲得旋轉黏度的值。該計算所需的介電各向異性的值是使用該經測定旋轉黏度的元件，以下述方法求出。 The measurement was performed according to the method described in "Molecular Crystals and Liquid Crystals", No. 259, p. 37 (1995) by M. Imai et al. A sample was placed in a TN element with a twist angle of 0 degrees and a gap (cell gap) between two glass substrates of 5 μm. A voltage is applied to the element stepwise in a range of 16V to 19.5V in units of 0.5V. After no voltage is applied for 0.2 seconds, only one rectangular wave (rectangular pulse; 0.2 seconds) is applied and no voltage is applied. The conditions of pressure (2 seconds) were repeatedly applied. The peak current (peak current) and peak time (peak time) of the transient current (transient current) generated by the application were measured. The value of rotational viscosity was obtained from these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al. The value of the dielectric anisotropy required for the calculation was obtained by the following method using the element whose rotational viscosity was measured.

(11)介電各向異性(△ε；於25℃下測定) (11) Dielectric anisotropy (Δε; measured at 25°C)

於兩塊玻璃基板的間隔(單元間隙)為9μm，並且扭轉角為80度的TN元件中放入試樣。對該元件施加正弦波(10V、1kHz)，2秒後測定液晶分子的長軸方向的介電常數(ε∥)。對該元件施加正弦波(0.5V、1kHz)，2秒後測定液晶分子的短軸方向的介電常數(ε⊥)。介電各向異性的值是由△ε=ε∥-ε⊥的式子來計算。 A sample was placed in a TN element with a twist angle of 80 degrees at a distance (cell gap) between two glass substrates of 9 μm. A sine wave (10 V, 1 kHz) was applied to this element, and the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured after 2 seconds. A sine wave (0.5 V, 1 kHz) was applied to this element, and the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecules was measured after 2 seconds. The value of dielectric anisotropy is calculated by the formula Δε=ε∥-ε⊥.

(12)彈性常數(K；於25℃下測定；pN) (12) Elastic constant (K; measured at 25°C; pN)

測定時使用橫河惠普(Yokogawa-Hewlett-Packard)股份有限公司製造的HP4284A型電感電容電阻(LCR)計。於兩塊玻璃基板的間隔(單元間隙)為20μm的水平配向元件中放入試樣。對該元件施加0伏特至20伏特電荷，測定靜電電容及施加電壓。使用「液晶裝置手冊」(日刊工業新聞社)第75頁的式(2.98)、式(2.101)，將所測定的靜電電容(C)及施加電壓(V)的值進行擬合(fitting)，由式(2.99)獲得K₁₁及K₃₃的值。繼而，在第171頁的式(3.18)中，使用剛才求出的K₁₁及K₃₃的值來算出K₂₂。彈性常數K由以上述方式求出的K₁₁、K₂₂及K₃₃的平均值來表示。 The HP4284A type inductance-capacitance-resistance (LCR) meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. was used for the measurement. A sample was placed in a horizontal alignment element whose interval (cell gap) between two glass substrates was 20 μm. A charge of 0 to 20 volts was applied to the element, and the capacitance and the applied voltage were measured. Using equations (2.98) and (2.101) on page 75 of the "Handbook of Liquid Crystal Devices" (Nikkan Kogyo Shimbun), the measured values of electrostatic capacitance (C) and applied voltage (V) were fitted. The values of K ₁₁ and K ₃₃ are obtained from the formula (2.99). Next, in equation (3.18) on page 171, K ₂₂ is calculated using the values of K ₁₁ and K ₃₃ obtained just now. The elastic constant K is represented by the average value of K ₁₁ , K ₂₂ , and K ₃₃ obtained as described above.

(13)臨限電壓(Vth；於25℃下測定；V) (13) Threshold voltage (Vth; measured at 25°C; V)

測定時使用大塚電子股份有限公司製造的LCD5100型亮度計。光源為鹵素燈。於兩塊玻璃基板的間隔(單元間隙)為0.45/△n(μm)，且扭轉角為80度的正常顯白模式(normally white mode)的TN元件中放入試樣。對該元件施加的電壓(32Hz、矩形波)是以0.02V為單位，自0V階段性地增加至10V。此時，自垂直方向對元件照射光，測定透過元件的光量。製成當該光量達到最大時透過率為100%，且當該光量為最小時透過率為0%的電壓-透過率曲線。臨限電壓由透過率達到90%時的電壓來表示。 For the measurement, an LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source is a halogen lamp. A sample was placed in a normally white mode TN element with an interval (cell gap) between two glass substrates of 0.45/Δn (μm) and a twist angle of 80 degrees. The voltage (32 Hz, rectangular wave) applied to the element was increased in steps from 0V to 10V in units of 0.02V. At this time, the element was irradiated with light from a vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was prepared in which the transmittance was 100% when the light amount reached the maximum, and the transmittance was 0% when the light amount was the minimum. The threshold voltage is represented by the voltage at which the transmittance reaches 90%.

(14)響應時間(τ；於25℃下測定；ms) (14) Response time (τ; measured at 25°C; ms)

測定時使用大塚電子股份有限公司製造的LCD5100型亮度計。光源為鹵素燈。低通濾波器(Low-pass filter)設定為5kHz。於兩塊玻璃基板的間隔(單元間隙)為5.0μm且扭轉角為80度的正常顯白模式(normally white mode)的TN元件中放入試樣。對該元件施加矩形波(60Hz、5V、0.5秒)。此時，自垂直方向對元件照射光，測定透過元件的光量。當該光量達到最大時視作透過率為100%，當該光量為最小時視作透過率為0%。上升時間(τr：rise time；毫秒)是透過率自90%變化為10%所需要的時間。下降時間(τf：fall time；毫秒)是透過率自10%變化為90%所需要的時間。響應時間是由以所述方式求出的上升時間與下降時間之和來表示。 For the measurement, an LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source is a halogen lamp. The low-pass filter is set to 5kHz. A sample was placed in a TN element of a normally white mode with an interval (cell gap) of two glass substrates of 5.0 μm and a twist angle of 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to the element. At this time, the element was irradiated with light from a vertical direction, and the amount of light transmitted through the element was measured. When the light amount reaches the maximum, the transmittance is regarded as 100%, and when the light amount is the minimum, the transmittance is regarded as 0%. Rise time (τr: rise time; milliseconds) is the time required for the transmittance to change from 90% to 10%. The fall time (τf: fall time; milliseconds) is the time required for the transmittance to change from 10% to 90%. The response time is represented by the sum of the rise time and fall time obtained in the manner described above.

(15)室溫相容性 (15) Room temperature compatibility

製備以化合物的比例成為20重量%、15重量%、10重量%、 5重量%、3重量%、以及1重量%的方式將母液晶與化合物混合而成的試樣，於室溫下放置1日後，觀察結晶或層列相是否析出。 The ratio of the compound is 20% by weight, 15% by weight, 10% by weight, 10% by weight, Samples in which the mother liquid crystal and the compound were mixed at 5 wt %, 3 wt %, and 1 wt % were allowed to stand at room temperature for 1 day, and it was observed whether crystals or smectic phases were precipitated.

1.化合物(1)的實施例 1. Examples of compound (1)

[合成例1]化合物(No.1)的合成

[Synthesis Example 1] Synthesis of Compound (No. 1)

將化合物(50)(3.94g、19.58mmol)、三乙基胺(4.36g、43.1mmol)、及二氯甲烷(100ml)加入容器中，一邊攪拌一邊滴加甲基丙烯醯氯(4.09g、39.16mmol)。其後，於室溫下攪拌1小時後，對混合物進行過濾、濃縮。利用矽膠層析法(甲苯)將所獲得的殘渣純化，獲得化合物(No.1)(2.2g)。 Compound (50) (3.94 g, 19.58 mmol), triethylamine (4.36 g, 43.1 mmol), and dichloromethane (100 ml) were added to a vessel, and methacryloyl chloride (4.09 g, 4.09 g, 100 ml) was added dropwise with stirring. 39.16 mmol). Then, after stirring at room temperature for 1 hour, the mixture was filtered and concentrated. The obtained residue was purified by silica gel chromatography (toluene) to obtain Compound (No. 1) (2.2 g).

此外，化合物(50)為周知化合物，若為本領域技術人員，則可容易地獲取。 In addition, compound (50) is a well-known compound and can be easily obtained by those skilled in the art.

¹H-NMR(CDCl₃；δppm)：7.03(d,8H),6.33(s,2H),5.74(s,2H),5.69(s,1H),2.06(s,6H). ¹ H-NMR (CDCl ₃ ; δppm): 7.03 (d, 8H), 6.33 (s, 2H), 5.74 (s, 2H), 5.69 (s, 1H), 2.06 (s, 6H).

化合物(No.1)的物性如下所述。 The physical properties of compound (No. 1) are as follows.

相變溫度：C 91.0 C 99.2 I Phase transition temperature: C 91.0 C 99.2 I

室溫相容性：5重量% Room temperature compatibility: 5% by weight

電壓保持率：95% Voltage retention rate: 95%

測定電壓保持率時使用的組成物是使用在母液晶(B)中添加0.4%的化合物(No.1)而成者。 The composition used for measuring the voltage holding ratio was obtained by adding 0.4% of the compound (No. 1) to the mother liquid crystal (B).

可藉由與合成例1中所記載的方法相同的方法來合成以下所示的化合物No.2至化合物No.54。 Compound No. 2 to Compound No. 54 shown below can be synthesized by the same method as that described in Synthesis Example 1.

[化54]

[Chemical 54]

[化55]

[Chemical 55]

[比較實驗1] [Comparative Experiment 1]

對日本專利特開2004-131704號公報(專利文獻2)中所揭示的比較化合物(R-1)測定室溫相容性，結果相對於母液晶(A)，結晶以1重量%析出。另外，藉由與實施例1相同的方法測定電壓保持率而得的結果為80%。化合物(No.1)的室溫相容性為結晶以5重量%析出，且電壓保持率為95%，據此而認為進一步具有於液晶組成物中的高溶解度及高電壓保持率。 The room temperature compatibility was measured with respect to the comparative compound (R-1) disclosed in Japanese Patent Laid-Open No. 2004-131704 (Patent Document 2), and as a result, crystals were deposited at 1 wt % with respect to the mother liquid crystal (A). In addition, as a result of measuring the voltage holding ratio by the same method as Example 1, it was 80%. Room temperature compatibility of compound (No.1) is crystalline Precipitated at 5% by weight, and the voltage retention rate was 95%, it is considered that it has further high solubility and high voltage retention rate in the liquid crystal composition.

2.聚合性組成物的實施例 2. Examples of polymerizable compositions

該實施例中的化合物是基於下述表的定義，由記號來表示。表中，與1,4-伸環己基有關的立體構型為反式。於實施例中，記號後的括號內的編號與化合物的編號對應。記號(-)是指其他液晶性化合物。液晶性化合物的含量(百分率)是基於液晶組成物的重量的重量百分率(重量%)。最後，總結組成物的物性值。物性是依據先前記載的方法來測定，將測定值(並不外推)直接記載。 The compounds in this example are represented by symbols based on the definitions in the following table. In the table, the steric configuration related to 1,4-cyclohexylene is trans. In the Examples, the numbers in parentheses after the symbols correspond to the numbers of the compounds. The symbol (-) refers to other liquid crystal compounds. The content (percentage) of the liquid crystal compound is a percentage by weight (% by weight) based on the weight of the liquid crystal composition. Finally, the physical property values of the composition are summarized. The physical properties were measured in accordance with the previously described methods, and the measured values (not extrapolated) were directly described.

[表1]

[Table 1]

[使用例1] [Example 1 of use]

2-HB-C (8-1) 6%

2-HB-C (8-1) 6%

以0.05重量%的比例於所述組成物中添加化合物(No.1)。 The compound (No. 1) was added to the composition at a ratio of 0.05% by weight.

NI=97.3℃；η=18.3mPa．s；△n=0.103；△ε=4.7 NI=97.3℃; η=18.3mPa. s;△n=0.103;△ε=4.7

[使用例2] [Use example 2]

以0.3重量%的比例於所述組成物中添加化合物(No.2)。 Compound (No. 2) was added to the composition at a ratio of 0.3% by weight.

NI=75.1℃；η=17.6mPa．s；△n=0.115；△ε=4.9 NI=75.1℃; η=17.6mPa. s;△n=0.115;△ε=4.9

[使用例3] [Use example 3]

以1重量%的比例於所述組成物中添加化合物(No.8)。 Compound (No. 8) was added to the composition in a ratio of 1% by weight.

NI=82.1℃；η=24.0mPa．s；△n=0.113；△ε=5.2 NI=82.1℃; η=24.0mPa. s;△n=0.113;△ε=5.2

[使用例4] [Use example 4]

5-HB-CL (5-2) 13%

5-HB-CL (5-2) 13%

以3重量%的比例於所述組成物中添加化合物(No.1)。 The compound (No. 1) was added to the composition at a ratio of 3% by weight.

NI=118.1℃；η=19.6mPa．s；△n=0.091；△ε=3.6 NI=118.1℃; η=19.6mPa. s;△n=0.091;△ε=3.6

[使用例5] [Use example 5]

以5重量%的比例於所述組成物中添加化合物(No.1)。 Compound (No. 1) was added to the composition at a ratio of 5% by weight.

NI=93.9℃；η=34.3mPa．s；△n=0.115；△ε=9.2 NI=93.9℃; η=34.3mPa. s;△n=0.115;△ε=9.2

[使用例6] [Use example 6]

以0.1重量%的比例於所述組成物中添加化合物(No.8)。 Compound (No. 8) was added to the composition at a ratio of 0.1% by weight.

NI=87.5℃；η=14.9mPa．s；△n=0.092；△ε=4.4 NI=87.5℃; η=14.9mPa. s;△n=0.092;△ε=4.4

[使用例7] [Use example 7]

以0.5重量%的比例於所述組成物中添加化合物(No.2)。 Compound (No. 2) was added to the composition at a ratio of 0.5% by weight.

NI=75.8℃；η=22.3mPa．s；△n=0.103；△ε=9.0 NI=75.8℃; η=22.3mPa. s;△n=0.103;△ε=9.0

[使用例8] [Use example 8]

以2重量%的比例於所述組成物中添加化合物(No.1)。 Compound (No. 1) was added to the composition at a ratio of 2% by weight.

NI=71.9℃；η=26.3mPa．s；△n=0.098；△ε=8.5 NI=71.9℃; η=26.3mPa. s;△n=0.098;△ε=8.5

[使用例9] [Use example 9]

5-HB-CL (5-2) 14%

5-HB-CL (5-2) 14%

以1.5重量%的比例於所述組成物中添加化合物(No.1)。 Compound (No. 1) was added to the composition at a ratio of 1.5% by weight.

NI=72.9℃；η=15.1mPa．s；△n=0.074；△ε=3.0 NI=72.9℃; η=15.1mPa. s;△n=0.074;△ε=3.0

[使用例10] [Example 10 of use]

以0.5重量%的比例於所述組成物中添加化合物(No.8)。 Compound (No. 8) was added to the composition at a ratio of 0.5% by weight.

NI=72.6℃；η=19.1mPa．s；△n=0.069；△ε=5.9 NI=72.6℃; η=19.1mPa. s;△n=0.069;△ε=5.9

[使用例11] [Example 11 of use]

以1重量%的比例於所述組成物中添加化合物(No.2)。 Compound (No. 2) was added to the composition at a ratio of 1% by weight.

NI=84.1℃；η=13.9mPa．s；△n=0.131；△ε=8.8 NI=84.1℃; η=13.9mPa. s;△n=0.131;△ε=8.8

[使用例12] [Example 12 of use]

NI=84.7℃；η=17.0mPa．s；△n=0.113；△ε=8.0 NI=84.7℃; η=17.0mPa. s;△n=0.113;△ε=8.0

[使用例13] [Example 13 of use]

NI=82.5℃；η=18.3mPa．s；△n=0109；△ε=9.4 NI=82.5℃; η=18.3mPa. s;△n=0109;△ε=9.4

[產業上之可利用性] [Industrial Availability]

可藉由使含有聚合性化合物(1)及液晶組成物的聚合性組成物進行聚合，來製作具有PSA等模式的液晶顯示元件。於最佳的態樣中，該元件具有寬廣的元件可使用溫度範圍、短響應時間、高電壓保持率、低臨限電壓、高對比度及長壽命。因此，化合物(1)可用於液晶投影機、液晶電視等。化合物(1)亦可用作光學各向異性體的原料。 A liquid crystal display element having modes such as PSA can be produced by polymerizing the polymerizable composition containing the polymerizable compound (1) and the liquid crystal composition. In its best form, the device has a wide device usable temperature range, short response time, high voltage retention, low threshold voltage, high contrast, and long lifetime. Therefore, the compound (1) can be used for liquid crystal projectors, liquid crystal televisions, and the like. Compound (1) can also be used as a raw material for an optically anisotropic body.

Claims

一種聚合性組成物，其含有下述式(1-1-4)至式(1-1-6)中的任一者表示的聚合性化合物以及選自由下述式(2)至式(8)的任一者表示的化合物中的至少一種化合物：

式(1a)、式(1b)、式(1c)、式(1d)及式(1e)中，M¹及M²獨立地為氫、鹵素或碳數1至10的烷基，於此烷基中，至少一個-CH₂-可經-O-或-S-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素、-SP¹-P¹或-SP²-P²取代；R²、R³、R⁴及R⁸獨立地為氫或碳數1至15的直鏈狀、分支狀或環狀的烷基，於此烷基中，至少一個-CH₂-可經-O-或-S-取代，至少一個-(CH₂)₂-可經-CH=CH-或-C≡C-取代，於這些基團中，至少一個氫可經鹵素取代；

式(2)至式(4)中，R¹¹及R¹²獨立地為碳數1至10的烷基或碳數2至10的烯基，於此烷基或烯基中，至少一個-CH₂-可經-O-取代，至少一個氫可經氟取代；環B¹、環B²、環B³及環B⁴獨立地為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、2,5-二氟-1,4-伸苯基或嘧啶-2,5-二基；Z¹¹、Z¹²及Z¹³獨立地為單鍵、-CH₂CH₂-、-CH=CH-、-C≡C-或-COO-；

式(5)至式(7)中，R¹³為碳數1至10的烷基或碳數2至10的烯基，於此烷基及烯基中，至少一個-CH₂-可經-O-取代，至少一個氫可經氟取代； X¹¹為氟、氯、-OCF₃、-OCHF₂、-CF₃、-CHF₂、-CH₂F、-OCF₂CHF₂或-OCF₂CHFCF₃；環C¹、環C²及環C³獨立地為1,4-伸環己基、至少一個氫可經氟取代的1,4-伸苯基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基或嘧啶-2,5-二基；Z¹⁴、Z¹⁵及Z¹⁶獨立地為單鍵、-(CH₂)₂-、-CH=CH-、-C≡C-、-COO-、-CF₂O-、-OCF₂-、-CH₂O-或-(CH₂)₄-；L¹¹及L¹²獨立地為氫或氟；

式(8)中，R¹⁴為碳數1至10的烷基或碳數2至10的烯基，於此烷基及烯基中，至少一個-CH₂-可經-O-取代，至少一個氫可經氟取代；X¹²為-C≡N或-C≡C-C≡N；環D¹為1,4-伸環己基、至少一個氫可經氟取代的1,4-伸苯基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基或嘧啶-2,5-二基；Z¹⁷為單鍵、-(CH₂)₂-、-C≡C-、-COO-、-CF₂O-、-OCF₂-或-CH₂O-；L¹³及L¹⁴獨立地為氫或氟；i為1、2、3或4。 A polymerizable composition comprising a polymerizable compound represented by any one of the following formulae (1-1-4) to (1-1-6) and a polymerizable compound selected from the group consisting of the following formulae (2) to (8) ) at least one of the compounds represented by any one of:

In formula (1a), formula (1b), formula (1c), formula (1d) and formula (1e), M ¹ and M ² are independently hydrogen, halogen or an alkyl group having 1 to 10 carbon atoms, where the alkane In the group, at least one -CH ₂ - can be substituted by -O- or -S-, at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, At least one hydrogen can be substituted by halogen, -SP ¹ -P ¹ or -SP ² -P ² ; R ² , R ³ , R ⁴ and R ⁸ are independently hydrogen or straight-chain or branched with 1 to 15 carbon atoms Or cyclic alkyl, in this alkyl, at least one -CH ₂ - can be substituted by -O- or -S-, and at least one -(CH ₂ ) ₂ - can be substituted by -CH=CH- or -C≡ C-substituted, in these groups, at least one hydrogen may be replaced by halogen;

In formula (2) to formula (4), R ¹¹ and R ¹² are independently an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in this alkyl group or alkenyl group, at least one -CH ₂ - may be substituted by -O-, at least one hydrogen may be substituted by fluorine; Ring B ¹ , Ring B ² , Ring B ³ and Ring B ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene , 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene or pyrimidine-2,5-diyl; Z ¹¹ , Z ¹² and Z ¹³ are independently single bonds , -CH ₂ CH ₂ -, -CH=CH-, -C≡C- or -COO-;

In formulas (5) to (7), R ¹³ is an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and in the alkyl and alkenyl groups, at least one -CH ₂ - may be through - O-substituted, at least one hydrogen may be substituted by fluorine; X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ or -OCF ₂ CHFCF ₃ ; Ring C ¹ , Ring C ² and Ring C ³ are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be substituted by fluorine, tetrahydropyran-2,5-di base, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are independently a single bond, -(CH ₂ ) ₂ -, -CH =CH-, -C≡C-, -COO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O- or -(CH ₂ ) ₄ -; L ¹¹ and L ¹² are independently hydrogen or fluorine ;

In formula (8), R ¹⁴ is an alkyl group having ₁ to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. One hydrogen can be substituted by fluorine; X ¹² is -C≡N or -C≡CC≡N; Ring D ¹ is 1,4-cyclohexylene, at least one hydrogen can be substituted by fluorine, 1,4-phenylene, Tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; Z ¹⁷ is a single bond, -(CH ₂ ) ₂ -, -C≡C-, -COO-, -CF ₂ O-, -OCF ₂ - or -CH ₂ O-; L ¹³ and L ¹⁴ are independently hydrogen or fluorine; i is 1, 2, 3 or 4.

如申請專利範圍第1項所述的聚合性組成物，其中在式(1-1-4)至式(1-1-6)中，環A¹及環A²獨立地為1,4-伸苯基，這些環上的至少一個氫可經鹵素取代；環A³及環A⁴獨立地為1,4-伸環己基、1,4-伸環己烯基或1,4-伸苯基，這些環上的至少一個氫可經鹵素取代。 The polymerizable composition according to claim 1, wherein in formula (1-1-4) to formula (1-1-6), ring A ¹ and ring A ² are independently 1,4- Phenylene, at least one hydrogen on these rings can be substituted by halogen; Ring A ³ and Ring A ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene radicals, at least one hydrogen on these rings may be substituted with halogen.

如申請專利範圍第1項所述的聚合性組成物，其中在式(1-1-4)中，R⁷為氫；環A¹及環A²獨立地為1,4-伸苯基，這些環上的至少一個氫可經鹵素取代。 The polymerizable composition according to claim 1, wherein in formula (1-1-4), R ⁷ is hydrogen; Ring A ¹ and Ring A ² are independently 1,4-phenylene, At least one hydrogen on these rings may be substituted with halogen.

一種液晶複合體，其是藉由如申請專利範圍第1項至第3項中任一項所述的聚合性組成物的聚合而生成。 A liquid crystal composite produced by the polymerization of the polymerizable composition according to any one of claims 1 to 3 of the patent application scope.

一種光學各向異性體，其是藉由如申請專利範圍第1項至第3項中任一項所述的聚合性組成物的聚合而生成。 An optically anisotropic body produced by the polymerization of the polymerizable composition according to any one of claims 1 to 3 of the scope of application.

一種液晶顯示元件，其含有如申請專利範圍第1項至第3項中任一項所述的聚合性組成物或如申請專利範圍第4項所述的液晶複合體。 A liquid crystal display element comprising the polymerizable composition according to any one of claims 1 to 3 or the liquid crystal composite according to claim 4.

一種選自由如申請專利範圍第1項至第3項中任一項所述的聚合性組成物、以及如申請專利範圍第4項所述的液晶複合體所組成的群組中的至少一種的用途，其用於液晶顯示元件。 At least one kind selected from the group consisting of the polymerizable composition described in any one of the first to third items in the scope of the patent application, and the liquid crystal composite as described in the fourth item of the patent application scope. It is used for liquid crystal display elements.