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TWI798555B - Polymerizable compound, liquid crystal composition, liquid crystal display element and liquid crystal display - Google Patents

Polymerizable compound, liquid crystal composition, liquid crystal display element and liquid crystal display Download PDF

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TWI798555B
TWI798555B TW109117709A TW109117709A TWI798555B TW I798555 B TWI798555 B TW I798555B TW 109117709 A TW109117709 A TW 109117709A TW 109117709 A TW109117709 A TW 109117709A TW I798555 B TWI798555 B TW I798555B
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TW202130791A (en
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鮑永鋒
李明
王一平
孫新戰
姜軍
王東梅
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大陸商石家莊誠志永華顯示材料有限公司
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Abstract

本發明涉及可聚合化合物、液晶組合物、液晶顯示元件及液晶顯示器。本發明的可聚合化合物結構如下式I所示，其具有較高的溶解度，包含該可聚合化合物的液晶組合物具有大的預傾角，並能獲得良好的配向能力。 The present invention relates to a polymerizable compound, a liquid crystal composition, a liquid crystal display element and a liquid crystal display. The structure of the polymerizable compound of the present invention is shown in the following formula I, which has relatively high solubility, and the liquid crystal composition containing the polymerizable compound has a large pretilt angle and can obtain good alignment ability.

Figure 109117709-A0305-02-0001-1
Figure 109117709-A0305-02-0001-1

Description

可聚合化合物、液晶組合物、液晶顯示元件及液晶顯示器 Polymerizable compound, liquid crystal composition, liquid crystal display element and liquid crystal display

本發明屬於液晶顯示技術領域，具體涉及一種可聚合化合物、包含該可聚合化合物的液晶組合物，以及包含有該可聚合化合物或液晶組合物的液晶顯示元件或液晶顯示器。 The invention belongs to the field of liquid crystal display technology, and in particular relates to a polymerizable compound, a liquid crystal composition containing the polymerizable compound, and a liquid crystal display element or a liquid crystal display containing the polymerizable compound or the liquid crystal composition.

隨著顯示技術的發展，液晶顯示元件(Liquid Crystal Display，LCD)等平面顯示裝置因具有高畫質、省電、機身薄及應用範圍廣等優點，而被廣泛的應用於手機、電視、個人數位助理、數位相機、筆記型電腦、台式電腦等各種消費性電子產品，成為顯示裝置中的主流。 With the development of display technology, liquid crystal display (Liquid Crystal Display, LCD) and other flat display devices are widely used in mobile phones, TVs, Various consumer electronic products such as personal digital assistants, digital cameras, notebook computers, and desktop computers have become the mainstream of display devices.

反應性液晶(Reactive Mesogen,RM)目前是液晶顯示行業非常熱門且重要的研究方向，其可能應用的領域包括聚合物穩定配向(PSA)液晶顯示，聚合物穩定藍相(PS-BP)液晶顯示以及圖形化位元相差膜(Pattern Retarder Film)等。 Reactive liquid crystal (Reactive Mesogen, RM) is currently a very popular and important research direction in the liquid crystal display industry. Its possible application fields include polymer stabilized alignment (PSA) liquid crystal display, polymer stabilized blue phase (PS-BP) liquid crystal display And patterned bit phase difference film (Pattern Retarder Film) and so on.

但是，液晶化合物與RM混合後在PSA模式顯示器中的應用方面仍具有一些缺點。首先，到目前為止並不是所有RM都適合用於PSA顯示器；同時，如果採用紫外光(Ultraviolet light)而不添加光引發劑使RM進行聚合，則能夠選擇RM種類變得更少；另外，要求液晶化合物與所選擇的RM組合形成的液晶組合物具有優良的互溶性，因此需要RM有很好的溶解度；另外一個 問題是配向能力，這要求RM聚合後能形成較大的預傾角，如果在顯示器的製造過程中預傾角較小，這可對顯示性能產生負面影響，例如產生殘像，並因此降低了顯示品質。 However, the application of liquid crystal compounds mixed with RMs in PSA mode displays still has some disadvantages. First of all, not all RMs are suitable for PSA displays so far; at the same time, if the RMs are polymerized using Ultraviolet light without adding a photoinitiator, fewer RM types can be selected; in addition, the requirements The liquid crystal composition formed by the combination of the liquid crystal compound and the selected RM has excellent mutual solubility, so it is required that the RM has good solubility; another The problem is the alignment ability, which requires RM to be polymerized to form a large pretilt angle, if the pretilt angle is small during the display manufacturing process, this can negatively affect the display performance, such as afterimage generation, and thus reduce the display quality .

為了克服反應性液晶(RM)與液晶組合物互溶性差和形成配向能力差的問題，解決液晶顯示元件或液晶顯示器出現殘像等問題，獲得具有低互溶性好和獲得較大預傾角的液晶組合物，本發明人等進行了深入研究，發現通過在液晶組合物中含有本發明的化合物能夠解決該問題，藉以完成了本發明。 In order to overcome the problems of poor mutual solubility and poor alignment ability between reactive liquid crystals (RM) and liquid crystal compositions, solve problems such as afterimages in liquid crystal display elements or liquid crystal displays, and obtain liquid crystal combinations with low mutual solubility and large pretilt angles The inventors of the present invention conducted intensive studies and found that the problem can be solved by including the compound of the present invention in a liquid crystal composition, thereby completing the present invention.

具體地，本發明包含以下內容：本發明的第一方面，提供一種式I所示的可聚合化合物，

Figure 109117709-A0305-02-0003-2
Specifically, the present invention includes the following content: the first aspect of the present invention provides a polymerizable compound represented by formula I,
Figure 109117709-A0305-02-0003-2

其中，L1、L2、L3、L4各自獨立地表示F原子、Cl原子、-CN、具有1至25個C原子的直鏈烷基、具有3至25個C原子的支鏈烷基、具有3至25個C原子的環狀烷基、具有2至25個C原子的烯基或具有2至25個C原子的炔基，其中一個或多個不相鄰的-CH2-基團任選地被-O-、-S-、-NH-、-CO-、-CO-O-、-O-CO-、-O-CO-O-取代，和其中一個或多個H原子任選地被鹵素原子取代；r1、r3各自獨立地表示0、1、2、3或4； r2、r4各自獨立地表示0、1、2或3；x1、x2、x3、x4各自獨立地表示0、1或2，且x1+x2+x3+x4

Figure 109117709-A0305-02-0004-196
3；Sp1、Sp2、Sp3、Sp4、Sp5、Z1、Z2各自獨立地表示單鍵、具有1至25個C原子的直鏈烷基、具有3至25個C原子的支鏈烷基、具有3至25個C原子的環狀烷基、具有2至25個C原子的烯基或具有2至25個C原子的炔基，且其中一個或多個不相鄰的-CH2-基團任選地被-O-、-S-、-CO-、-CO-O-、-O-CO-、-O-CO-O-取代，其中一個或多個H原子任選被F原子或Cl原子取代；P1、P2、P3、P4各自獨立地表示可聚合基團。 Wherein, L 1 , L 2 , L 3 , and L 4 each independently represent an F atom, a Cl atom, -CN, a straight chain alkyl group having 1 to 25 C atoms, a branched chain alkyl group having 3 to 25 C atoms A group, a cyclic alkyl group having 3 to 25 C atoms, an alkenyl group having 2 to 25 C atoms or an alkynyl group having 2 to 25 C atoms, wherein one or more non-adjacent -CH 2 - The group is optionally substituted by -O-, -S-, -NH-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, and one or more of the H Atoms are optionally substituted by halogen atoms; r 1 , r 3 each independently represent 0, 1, 2, 3 or 4; r 2 , r 4 each independently represent 0, 1, 2 or 3; x 1 , x 2 , x 3 , x 4 independently represent 0, 1 or 2, and x 1 +x 2 +x 3 +x 4
Figure 109117709-A0305-02-0004-196
3; Sp 1 , Sp 2 , Sp 3 , Sp 4 , Sp 5 , Z 1 , and Z 2 each independently represent a single bond, a straight-chain alkyl group having 1 to 25 C atoms, an alkyl group having 3 to 25 C atoms Branched chain alkyl, cyclic alkyl having 3 to 25 C atoms, alkenyl having 2 to 25 C atoms or alkynyl having 2 to 25 C atoms, and one or more of the non-adjacent The -CH 2 - group is optionally substituted by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, wherein one or more H atoms Optionally substituted by an F atom or a Cl atom; P 1 , P 2 , P 3 , and P 4 each independently represent a polymerizable group.

本發明的第二方面，提供一種液晶組合物，所述液晶組合物包含一種或多種式I所示的可聚合化合物。 The second aspect of the present invention provides a liquid crystal composition, which contains one or more polymerizable compounds represented by formula I.

本發明的第三方面，提供一種液晶顯示元件或液晶顯示器，所述液晶顯示元件或液晶顯示器包含一種或多種式I所示的可聚合化合物或包含一種或多種式I所示的可聚合化合物的液晶組合物。 A third aspect of the present invention provides a liquid crystal display element or a liquid crystal display, the liquid crystal display element or liquid crystal display comprising one or more polymerizable compounds represented by formula I or comprising one or more polymerizable compounds represented by formula I liquid crystal composition.

本發明提供了一種新型的可聚合化合物，拓寬了RM種類的可選擇範圍，其與液晶母體組合物具有良好的互溶性，並且在聚合後能夠形成較大的預傾角，與現有技術相比，能夠獲得具有更高配向能力的液晶顯示元件等優良性能。 The present invention provides a new type of polymerizable compound, which broadens the range of options for RM types, has good miscibility with liquid crystal matrix compositions, and can form a larger pretilt angle after polymerization. Compared with the prior art, Excellent properties such as liquid crystal display elements with higher alignment ability can be obtained.

圖1示出式I-1-1所示可聚合化合物的1h-NMR譜圖； Fig. 1 shows the 1h -NMR spectrogram of polymerizable compound shown in formula I-1-1;

本發明公開了一種上述式I所示的可聚合化合物。 The present invention discloses a polymerizable compound represented by the above formula I.

本發明公開的可聚合化合物，較佳地，在式I所示的化合物中：L1、L2、L3、L4各自獨立地表示碳原子數為1-5的烷基、氟取代的碳原子數為1-5的烷基、碳原子數為2-5的烯基、碳原子數為1-5的烷氧基、氟取代的碳原子數為1-5的烷氧基、F原子或Cl原子；r1、r3各自獨立地表示0、1或2；r2、r4各自獨立地表示0或1；x1、x2、x3、x4各自獨立地表示0或1，且x1+x2+x3+x4

Figure 109117709-A0305-02-0005-197
3；Sp1、Sp2、Sp3、Sp4、Sp5、Z1、Z2各自獨立地表示單鍵、碳原子數為1-10的烷基、碳原子數為2-10的烯基或碳原子數為2-10的炔基，其中一個或多個不相鄰的-CH2-基團任選地被-O-、-CO-、-CO-O-、-O-CO-取代，一個或多個H原子任選被F原子取代；P1、P2、P3、P4各自獨立地表示
Figure 109117709-A0305-02-0005-4
、
Figure 109117709-A0305-02-0005-5
、
Figure 109117709-A0305-02-0005-6
、
Figure 109117709-A0305-02-0005-7
、
Figure 109117709-A0305-02-0005-8
、
Figure 109117709-A0305-02-0005-3
 In the polymerizable compound disclosed in the present invention, preferably, in the compound represented by formula I: L 1 , L 2 , L 3 , and L 4 each independently represent an alkyl group with 1-5 carbon atoms, fluorine-substituted Alkyl group with 1-5 carbon atoms, alkenyl group with 2-5 carbon atoms, alkoxy group with 1-5 carbon atoms, alkoxy group with 1-5 carbon atoms substituted by fluorine, F atom or Cl atom; r 1 , r 3 each independently represent 0, 1 or 2; r 2 , r 4 each independently represent 0 or 1; x 1 , x 2 , x 3 , x 4 each independently represent 0 or 1, and x 1 +x 2 +x 3 +x 4
Figure 109117709-A0305-02-0005-197
3; Sp 1 , Sp 2 , Sp 3 , Sp 4 , Sp 5 , Z 1 , and Z 2 each independently represent a single bond, an alkyl group with 1-10 carbon atoms, and an alkenyl group with 2-10 carbon atoms Or an alkynyl group with 2-10 carbon atoms, wherein one or more non-adjacent -CH 2 - groups are optionally replaced by -O-, -CO-, -CO-O-, -O-CO- Substitution, one or more H atoms are optionally substituted by F atoms; P 1 , P 2 , P 3 , and P 4 each independently represent
Figure 109117709-A0305-02-0005-4
,
Figure 109117709-A0305-02-0005-5
,
Figure 109117709-A0305-02-0005-6
,
Figure 109117709-A0305-02-0005-7
,
Figure 109117709-A0305-02-0005-8
,
Figure 109117709-A0305-02-0005-3

本發明公開的可聚合化合物，更佳地，其選自下述的式I-1-1至式I-17-3所示化合物所組成的群組，

Figure 109117709-A0305-02-0006-9
The polymerizable compound disclosed in the present invention, more preferably, is selected from the group consisting of compounds represented by the following formula I-1-1 to formula I-17-3,
Figure 109117709-A0305-02-0006-9

Figure 109117709-A0305-02-0007-10
Figure 109117709-A0305-02-0007-10

Figure 109117709-A0305-02-0008-11
Figure 109117709-A0305-02-0008-11

Figure 109117709-A0305-02-0009-12
Figure 109117709-A0305-02-0009-12

Figure 109117709-A0305-02-0010-14
Figure 109117709-A0305-02-0010-14

Figure 109117709-A0305-02-0011-15
Figure 109117709-A0305-02-0011-15

Figure 109117709-A0305-02-0012-16
Figure 109117709-A0305-02-0012-16

Figure 109117709-A0305-02-0013-17
Figure 109117709-A0305-02-0013-17

Figure 109117709-A0305-02-0014-18
Figure 109117709-A0305-02-0014-18

Figure 109117709-A0305-02-0015-19
Figure 109117709-A0305-02-0015-19

Figure 109117709-A0305-02-0016-20
Figure 109117709-A0305-02-0016-20

本發明還提供一種液晶組合物，該液晶組合物包含一種或多種前述的本發明的可聚合化合物。 The present invention also provides a liquid crystal composition comprising one or more of the aforementioned polymerizable compounds of the present invention.

做為本發明的一個方案的液晶組合物，含有前述的式I所示的化合物。液晶組合物中，除了式I所示的化合物之外，還可以含有式I所示的化合物之外的液晶化合物以及其他添加材料。 The liquid crystal composition as one aspect of the present invention contains the compound represented by the aforementioned formula I. In addition to the compound represented by the formula I, the liquid crystal composition may contain liquid crystal compounds other than the compound represented by the formula I and other additive materials.

較佳地，本發明的液晶組合物還包含一種或多種下述的式II所示化合物以及一種或多種下述的式III所示化合物，

Figure 109117709-A0305-02-0016-21
Preferably, the liquid crystal composition of the present invention further comprises one or more compounds represented by the following formula II and one or more compounds represented by the following formula III,
Figure 109117709-A0305-02-0016-21

Figure 109117709-A0305-02-0017-22
Figure 109117709-A0305-02-0017-22

式II中，R1、R2各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基；

Figure 109117709-A0305-02-0017-24
、
Figure 109117709-A0305-02-0017-25
各自獨立地表示
Figure 109117709-A0305-02-0017-26
或
Figure 109117709-A0305-02-0017-27
；式III中，R3、R4各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基，且R3、R4中任意一個或多個不相鄰的-CH2-任選被亞環戊基、亞環丁基或亞環丙基取代；Z1、Z2各自獨立地表示單鍵、-CH2CH2-、-CH2O-或-OCH2-；
Figure 109117709-A0305-02-0017-28
、
Figure 109117709-A0305-02-0017-29
各自獨立地表示
Figure 109117709-A0305-02-0017-30
、
Figure 109117709-A0305-02-0017-31
、
Figure 109117709-A0305-02-0017-32
、
Figure 109117709-A0305-02-0017-33
、
Figure 109117709-A0305-02-0017-23
 m1表示1或2，當m1表示2時，
Figure 109117709-A0305-02-0017-34
相同或不同；n1表示0、1或2，當n1表示2時，
Figure 109117709-A0305-02-0017-35
相同或不同。 In formula II, R 1 and R 2 each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, Alkoxy group with 1-10 carbon atoms substituted by fluorine, alkenyl group with 2-10 carbon atoms, alkenyl group with 2-10 carbon atoms substituted by fluorine, and alkenyl group with 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms;
Figure 109117709-A0305-02-0017-24
,
Figure 109117709-A0305-02-0017-25
express independently
Figure 109117709-A0305-02-0017-26
or
Figure 109117709-A0305-02-0017-27
; In formula III, R 3 and R 4 each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms replaced by fluorine, and an alkoxy group with 1-10 carbon atoms , alkoxy group with 1-10 carbon atoms substituted by fluorine, alkenyl group with 2-10 carbon atoms, alkenyl group with 2-10 carbon atoms substituted with fluorine, 3-8 carbon atoms Alkenyloxy or alkenyloxy with 3-8 carbon atoms substituted by fluorine, and any one or more non-adjacent -CH 2 - in R 3 and R 4 is optionally replaced by cyclopentylene, Substituted by cyclobutylene or cyclopropylene; Z 1 and Z 2 each independently represent a single bond, -CH 2 CH 2 -, -CH 2 O- or -OCH 2 -;
Figure 109117709-A0305-02-0017-28
,
Figure 109117709-A0305-02-0017-29
express independently
Figure 109117709-A0305-02-0017-30
,
Figure 109117709-A0305-02-0017-31
,
Figure 109117709-A0305-02-0017-32
,
Figure 109117709-A0305-02-0017-33
,
Figure 109117709-A0305-02-0017-23
 m 1 means 1 or 2, when m 1 means 2,
Figure 109117709-A0305-02-0017-34
same or different; n 1 means 0, 1 or 2, when n 1 means 2,
Figure 109117709-A0305-02-0017-35
same or different.

通過在本發明的液晶組合物中含有式II所示化合物、式III所示化合物的組合，獲得的液晶組合物具有低的旋轉黏度低藉以有利於提高液晶組合 物的反應速度，且具有負介電各項異性，能夠調節組合物的驅動電壓。 By containing the combination of the compound shown in the formula II and the compound shown in the formula III in the liquid crystal composition of the present invention, the obtained liquid crystal composition has a low rotational viscosity, which is beneficial to improve the liquid crystal composition. The reaction speed of the compound, and has a negative dielectric anisotropy, which can adjust the driving voltage of the composition.

本發明中，將除式I所示化合物之外的其他化合物的總質量記為100%，式I所示化合物的質量與其他化合物的總質量之間比值的百分數，記為液晶組合物中式I所示化合物的質量分數。例如，在液晶組合物中只包含有式I、式II及式III所示化合物的情況下，則式II和式III所示化合物的總含量記為100%，式I所示化合物的加入量與式II和式III所示化合物的總質量之間比值的百分數，記為式I所示化合物的質量分數。 In the present invention, the total mass of other compounds other than the compound shown in formula I is recorded as 100%, and the percentage of the ratio between the mass of the compound shown in formula I and the total mass of other compounds is recorded as formula I in the liquid crystal composition Mass fractions of the indicated compounds. For example, when the liquid crystal composition only contains compounds shown in formula I, formula II and formula III, the total content of compounds shown in formula II and formula III is recorded as 100%, and the amount of compound shown in formula I The percentage of the ratio to the total mass of the compounds represented by formula II and formula III is recorded as the mass fraction of the compound represented by formula I.

本發明的液晶組合物中，較佳地，前述式II所示化合物選自式II-1至式II-17所示化合物所組成的群組，

Figure 109117709-A0305-02-0018-36
In the liquid crystal composition of the present invention, preferably, the compound represented by the aforementioned formula II is selected from the group consisting of compounds represented by formula II-1 to formula II-17,
Figure 109117709-A0305-02-0018-36

Figure 109117709-A0305-02-0018-37
Figure 109117709-A0305-02-0018-37

Figure 109117709-A0305-02-0018-38
Figure 109117709-A0305-02-0018-38

Figure 109117709-A0305-02-0018-39
Figure 109117709-A0305-02-0018-39

Figure 109117709-A0305-02-0018-40
Figure 109117709-A0305-02-0018-40

Figure 109117709-A0305-02-0018-41
Figure 109117709-A0305-02-0018-41

Figure 109117709-A0305-02-0018-42
Figure 109117709-A0305-02-0018-42

Figure 109117709-A0305-02-0018-43
Figure 109117709-A0305-02-0018-43

Figure 109117709-A0305-02-0018-44
Figure 109117709-A0305-02-0018-44

Figure 109117709-A0305-02-0018-45
Figure 109117709-A0305-02-0018-45

Figure 109117709-A0305-02-0018-47
Figure 109117709-A0305-02-0018-47

Figure 109117709-A0305-02-0018-48
Figure 109117709-A0305-02-0018-48

Figure 109117709-A0305-02-0018-49
Figure 109117709-A0305-02-0018-49

Figure 109117709-A0305-02-0018-50
Figure 109117709-A0305-02-0018-50

Figure 109117709-A0305-02-0019-51
Figure 109117709-A0305-02-0019-51

Figure 109117709-A0305-02-0019-52
Figure 109117709-A0305-02-0019-52

Figure 109117709-A0305-02-0019-53
Figure 109117709-A0305-02-0019-53

較佳地，前述式III所示化合物選自式III-1至式III-15所示化合物所組成的群組，

Figure 109117709-A0305-02-0019-54
Preferably, the compound represented by the aforementioned formula III is selected from the group consisting of compounds represented by formula III-1 to formula III-15,
Figure 109117709-A0305-02-0019-54

Figure 109117709-A0305-02-0019-55
Figure 109117709-A0305-02-0019-55

Figure 109117709-A0305-02-0019-56
Figure 109117709-A0305-02-0019-56

Figure 109117709-A0305-02-0019-57
Figure 109117709-A0305-02-0019-57

Figure 109117709-A0305-02-0019-58
Figure 109117709-A0305-02-0019-58

Figure 109117709-A0305-02-0019-60
Figure 109117709-A0305-02-0019-60

Figure 109117709-A0305-02-0019-61
Figure 109117709-A0305-02-0019-61

Figure 109117709-A0305-02-0019-62
Figure 109117709-A0305-02-0019-62

Figure 109117709-A0305-02-0019-200
Figure 109117709-A0305-02-0019-200

Figure 109117709-A0305-02-0019-64
Figure 109117709-A0305-02-0019-64

Figure 109117709-A0305-02-0019-66
Figure 109117709-A0305-02-0019-66

Figure 109117709-A0305-02-0020-67
Figure 109117709-A0305-02-0020-67

Figure 109117709-A0305-02-0020-69
Figure 109117709-A0305-02-0020-69

Figure 109117709-A0305-02-0020-70
Figure 109117709-A0305-02-0020-70

Figure 109117709-A0305-02-0020-71
Figure 109117709-A0305-02-0020-71

其中，R31、R41各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基，並且R3、R4所示基團中任意一個或多個不相鄰的-CH2-任選被亞環戊基、亞環丁基或亞環丙基取代。 Wherein, R 31 and R 41 each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, a fluorine-substituted Alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkenyl groups with 2-10 carbon atoms substituted by fluorine, alkenyl groups with 3-8 carbon atoms An alkenyloxy group with 3-8 carbon atoms substituted by oxo or fluorine, and any one or more non-adjacent -CH 2 - in the groups represented by R 3 and R 4 is optionally replaced by a cyclopentylene group , cyclobutylene or cyclopropylene.

本發明公開的液晶組合物中，較佳地，還包含一種或多種式IV所示的化合物，

Figure 109117709-A0305-02-0020-72
In the liquid crystal composition disclosed in the present invention, preferably, it also contains one or more compounds represented by formula IV,
Figure 109117709-A0305-02-0020-72

其中，R5、R6各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基，並且R5、R6中任意一個或多個不相鄰的-CH2-任選被亞環戊基、亞環丁基或亞環丙基替代；W表示-O-、-S-或-CH2O-。 Wherein, R 5 and R 6 each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, a fluorine-substituted Alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkenyl groups with 2-10 carbon atoms substituted by fluorine, alkenyl groups with 3-8 carbon atoms Alkenyloxy group with 3-8 carbon atoms substituted by oxo or fluorine, and any one or more non-adjacent -CH 2 - in R 5 and R 6 is optionally replaced by cyclopentylene, cyclobutylene group or cyclopropylene; W represents -O-, -S- or -CH 2 O-.

通過在本申請的液晶組合物中含有前述的式IV所示的化合物，藉以能夠使得液晶組合物具有較大的負的介電各向異性，有利於降低元件的驅動 電壓。 By including the compound shown in the aforementioned formula IV in the liquid crystal composition of the present application, the liquid crystal composition can be made to have a large negative dielectric anisotropy, which is beneficial to reduce the driving of the element. Voltage.

進一步地，前述式IV所示的化合物選自式IV-1至式IV-10所示化合物，

Figure 109117709-A0305-02-0021-73
其中，R51、R61表示碳原子數為1-6的烷基；本發明公開的液晶組合物中，較佳地，還包含一種或多種式V所示的化合物，
Figure 109117709-A0305-02-0021-74
 Further, the compound shown in the aforementioned formula IV is selected from the compounds shown in formula IV-1 to formula IV-10,
Figure 109117709-A0305-02-0021-73
 Wherein, R 51 and R 61 represent an alkyl group with 1-6 carbon atoms; the liquid crystal composition disclosed in the present invention preferably further contains one or more compounds represented by formula V,
Figure 109117709-A0305-02-0021-74

其中，R7、R8各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基；

Figure 109117709-A0305-02-0021-75
、
Figure 109117709-A0305-02-0021-76
各自獨立地表示
Figure 109117709-A0305-02-0021-77
、
Figure 109117709-A0305-02-0021-78
或
Figure 109117709-A0305-02-0021-79
。 Wherein, R 7 and R 8 each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, or an alkyl group with 1-10 carbon atoms substituted by fluorine. Alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkenyl groups with 2-10 carbon atoms substituted by fluorine, alkenyl groups with 3-8 carbon atoms Alkenyloxy group with 3-8 carbon atoms substituted by oxy group or fluorine;
Figure 109117709-A0305-02-0021-75
,
Figure 109117709-A0305-02-0021-76
express independently
Figure 109117709-A0305-02-0021-77
,
Figure 109117709-A0305-02-0021-78
or
Figure 109117709-A0305-02-0021-79
.

進一步地，上述式V所示的化合物較佳選自式V-1至式V-4所示 化合物所組成的群組，

Figure 109117709-A0305-02-0022-83
其中，R71、R81各自獨立的表示碳原子數為2-6的烷基或碳原子數為2-6的烯基；其中，做為碳原子數為2-6的烯基可以列舉出例如乙烯基、2-丙烯基或者3-戊烯基；R82表示碳原子數為1-5的烷氧基；通過在本發明的液晶組合物中含有式V所示的化合物，能夠獲得高的清晰點、高的彈性常數，尤其是展曲彈性常數K33，有利於提升液晶組合物的參數性能。 Further, the compound represented by the above formula V is preferably selected from the group consisting of compounds represented by formula V-1 to formula V-4,
Figure 109117709-A0305-02-0022-83
 Among them, R 71 and R 81 each independently represent an alkyl group with 2-6 carbon atoms or an alkenyl group with 2-6 carbon atoms; among them, the alkenyl group with 2-6 carbon atoms can be listed For example vinyl, 2-propenyl or 3-pentenyl; R 82 represents the alkoxyl group that carbon number is 1-5; By containing the compound shown in formula V in the liquid crystal composition of the present invention, can obtain high The clear point and high elastic constant, especially the splay elastic constant K 33 , are beneficial to improve the parameter performance of the liquid crystal composition.

本發明公開的液晶組合物中，較佳地，還包含一種或多種式VI所示化合物，

Figure 109117709-A0305-02-0022-80
其中，R9、R10各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基；
Figure 109117709-A0305-02-0022-84
表示
Figure 109117709-A0305-02-0022-193
、
Figure 109117709-A0305-02-0022-86
或
Figure 109117709-A0305-02-0022-85
。 In the liquid crystal composition disclosed in the present invention, preferably, it also contains one or more compounds represented by formula VI,
Figure 109117709-A0305-02-0022-80
 Wherein, R 9 and R 10 each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, or an alkyl group with 1-10 carbon atoms substituted by fluorine. Alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkenyl groups with 2-10 carbon atoms substituted by fluorine, alkenyl groups with 3-8 carbon atoms Alkenyloxy group with 3-8 carbon atoms substituted by oxy group or fluorine;
Figure 109117709-A0305-02-0022-84
express
Figure 109117709-A0305-02-0022-193
,
Figure 109117709-A0305-02-0022-86
or
Figure 109117709-A0305-02-0022-85
.

進一步地，前述式VI所示的化合物較佳選自式VI-1至VI-3所示化合物所組成的群組，

Figure 109117709-A0305-02-0022-81
Figure 109117709-A0305-02-0022-82
Figure 109117709-A0305-02-0023-88
 其中，R91、R101各自獨立地較佳表示碳原子數為2-6的烷基或原子數為2-6的烯基。 Further, the compound represented by the aforementioned formula VI is preferably selected from the group consisting of compounds represented by the formulas VI-1 to VI-3,
Figure 109117709-A0305-02-0022-81
Figure 109117709-A0305-02-0022-82
Figure 109117709-A0305-02-0023-88
 Among them, R 91 and R 101 each independently preferably represent an alkyl group with 2-6 carbon atoms or an alkenyl group with 2-6 atoms.

通過在液晶組合物中含有選自式VI-1至VI-3所示的化合物，能夠提高液晶組合物的清晰點。 The clear point of the liquid crystal composition can be improved by including the compound selected from the group consisting of formulas VI-1 to VI-3 in the liquid crystal composition.

較佳地，本發明的液晶組合物按照質量百分數包含：0.01-1%的式I所示化合物，30-60%的式II所示化合物，30-60%的式III所示化合物，1-10%的式VI所示化合物；較佳地，本發明的液晶組合物按照質量百分數包含：0.01-1%的式I所示化合物，15-60%的式II所示化合物，20-60%的式III所示化合物，1-15%的式IV所示化合物，1-10%的式VI所示化合物；較佳地，本發明的液晶組合物按照質量百分數包含：0.03-0.2%的式I所示化合物，35-45%的式II所示化合物，45-50%的式III所示化合物，2-10%的式IV所示化合物，2-5%的式VI所示化合物。 Preferably, the liquid crystal composition of the present invention comprises: 0.01-1% of the compound shown in formula I, 30-60% of the compound shown in formula II, 30-60% of the compound shown in formula III, 1- 10% of the compound shown in formula VI; preferably, the liquid crystal composition of the present invention comprises: 0.01-1% of the compound shown in formula I, 15-60% of the compound shown in formula II, 20-60% The compound shown in the formula III, 1-15% of the compound shown in the formula IV, 1-10% of the compound shown in the formula VI; preferably, the liquid crystal composition of the present invention comprises: 0.03-0.2% of the formula Compound shown in I, 35-45% compound shown in formula II, 45-50% compound shown in formula III, 2-10% compound shown in formula IV, 2-5% compound shown in formula VI.

較佳地，本發明的液晶組合物按照質量百分數包含：0.01-1%的式I所示化合物，15-60%的式II所示化合物，20-60%的式III所示化合物，1-30%的式V所示化合物，1-10%的式VI所示化合物；較佳地，本發明的液晶組合物按照質量百分數包含：0.03-0.2%的式I所示化合物，25-40%的式II所示化合物，35-50%的式III所示化合物，5-20%的式V所示化合物，2-5%的式VI所示化合物。 Preferably, the liquid crystal composition of the present invention comprises according to mass percentage: 0.01-1% of the compound shown in formula I, 15-60% of the compound shown in formula II, 20-60% of the compound shown in formula III, 1- 30% of the compound shown in formula V, 1-10% of the compound shown in formula VI; preferably, the liquid crystal composition of the present invention comprises: 0.03-0.2% of the compound shown in formula I, 25-40% Compound shown in formula II, 35-50% compound shown in formula III, 5-20% compound shown in formula V, 2-5% compound shown in formula VI.

較佳地，本發明的液晶組合物按照質量百分數包含：0.01-1%的式I所示化合物，15-60%的式II所示化合物，20-60%的式III所示化合物，1-15% 的式IV所示化合物，1-30%的式V所示化合物，1-10%的式VI所示化合物；較佳地，本發明的液晶組合物按照質量百分數包含：0.03-0.2%的式I所示化合物，20-40%的式II所示化合物，30-50%的式III所示化合物，2-10%的式IV所示化合物，5-20%的式V所示化合物，2-5%的式VI所示化合物。 Preferably, the liquid crystal composition of the present invention comprises according to mass percentage: 0.01-1% of the compound shown in formula I, 15-60% of the compound shown in formula II, 20-60% of the compound shown in formula III, 1- 15% The compound shown in the formula IV, 1-30% of the compound shown in the formula V, 1-10% of the compound shown in the formula VI; preferably, the liquid crystal composition of the present invention comprises: 0.03-0.2% of the compound shown in the formula The compound shown in I, the compound shown in 20-40% formula II, the compound shown in 30-50% formula III, the compound shown in 2-10% formula IV, the compound shown in 5-20% formula V, 2 -5% of the compound shown in formula VI.

本發明公開的液晶組合物中，還可以加入各種功能的摻雜劑，在含有摻雜劑的情況下，摻雜劑的含量較佳在液晶組合物中所占的質量百分比為0.01-1%，這些摻雜劑可以列舉出例如抗氧化劑、紫外線吸收劑、手性劑。 In the liquid crystal composition disclosed in the present invention, dopants with various functions can also be added. In the case of containing dopants, the content of the dopant is preferably 0.01-1% by mass in the liquid crystal composition. , These dopants include, for example, antioxidants, ultraviolet absorbers, and chiral agents.

抗氧化劑、紫外線吸收劑可以列舉出，

Figure 109117709-A0305-02-0024-89
t表示1-10的整數。 Examples of antioxidants and ultraviolet absorbers include,
Figure 109117709-A0305-02-0024-89
 t represents an integer of 1-10.

本發明的液晶顯示元元件包含前述的本發明的可聚合化合物或者包含前述的本發明的液晶組合物，該顯示元元件為主動矩陣顯示元元件或被動矩陣顯示元元件。 The liquid crystal display element of the present invention comprises the aforementioned polymerizable compound of the present invention or the aforementioned liquid crystal composition of the present invention, and the display element is an active matrix display element or a passive matrix display element.

較佳地，本發明的液晶顯示元元件較佳主動矩陣液晶顯示元元件。 Preferably, the liquid crystal display element of the present invention is preferably an active matrix liquid crystal display element.

較佳地，本發明的主動矩陣顯示元元件為PSVA-TFT或IPS-TFT液晶顯示元元件。 Preferably, the active matrix display element of the present invention is a PSVA-TFT or IPS-TFT liquid crystal display element.

對於前述的本發明的液晶顯示元元件，只要在其使用的液晶組合物中含有本發明的式I所示化合物，則對其結構沒有任何限定，本領域具有通常知識者能夠根據所需的性能選擇合適的液晶顯示元元件的結構。 For the aforesaid liquid crystal display element of the present invention, as long as the compound shown in the formula I of the present invention is contained in the liquid crystal composition used in it, then its structure is not limited in any way, and those skilled in the art can determine the desired performance Select the appropriate structure of the liquid crystal display element.

做為本發明的液晶顯示器的一個實施方式，可以列舉，例如下述的結構：包括第一基板、第二基板，以及設置在第一基板和第二基板之間的液晶組合物，第一基板與第二基板平行相對設置，第一基板和第二基板的靠近液晶組合物一側設有配向層，第一基板設有公共電極、第二基板設有畫素電極，第一基板與第二基板之間散佈有間隔物。 As an embodiment of the liquid crystal display of the present invention, can enumerate, for example following structure: comprise the first substrate, the second substrate, and the liquid crystal composition that is arranged between the first substrate and the second substrate, the first substrate It is arranged in parallel with the second substrate, an alignment layer is provided on the side of the first substrate and the second substrate close to the liquid crystal composition, the first substrate is provided with a common electrode, and the second substrate is provided with a pixel electrode, and the first substrate and the second substrate are provided with an alignment layer. Spacers are interspersed between the substrates.

做為本發明的液晶顯示器的製備方法，本領域具有通常知識者能夠根據本領域的常識選擇合適的方法進行製備。做為本發明的液晶顯示器的製備方法的一個例子，例如，包括下述步驟的製備方法：在第一基板和第二基板的表面均勻塗布配向材料，配向材料可以選用聚醯亞胺，對均勻塗布的配向材料進行加熱固化，加熱溫度為210-250℃，形成配向層；在第二基板表面散佈間隔物，並沿第一基板的邊緣塗布邊框膠，並在100℃-150℃下進行固化；將第一基板和第二基板相對設置，貼合形成具有夾層空間的結構；將液晶組合物注入第一基板和第二基板之間的夾層空間，密封固化，藉以將液晶組合物密封在第一基板和第二基板之間，並同時進行加電、紫外光照射。紫外光照射分為第一階段紫外光照射(UV1)、第二階段紫外光照射(UV2) 的兩個階段。在UV1階段，紫外光波長為360nm-370nm，紫外光輻照度為60-72mw/cm2。做為紫外光照射的時間，可以為例如50-65s，較佳為50-60s。 As the preparation method of the liquid crystal display of the present invention, those skilled in the art can select an appropriate method for preparation according to common knowledge in the field. As an example of the preparation method of the liquid crystal display of the present invention, for example, the preparation method comprising the following steps: uniformly coating the alignment material on the surface of the first substrate and the second substrate, the alignment material can be selected from polyimide, for uniform The coated alignment material is heated and cured at 210-250°C to form an alignment layer; spacers are spread on the surface of the second substrate, and frame glue is coated along the edge of the first substrate, and cured at 100°C-150°C ; The first substrate and the second substrate are arranged oppositely, and bonded to form a structure with an interlayer space; the liquid crystal composition is injected into the interlayer space between the first substrate and the second substrate, sealed and solidified, so as to seal the liquid crystal composition in the second substrate between the first substrate and the second substrate, and carry out power supply and ultraviolet light irradiation at the same time. The ultraviolet light irradiation is divided into two stages: the first stage ultraviolet light irradiation (UV1) and the second stage ultraviolet light irradiation (UV2). In the UV1 stage, the wavelength of ultraviolet light is 360nm-370nm, and the irradiance of ultraviolet light is 60-72mw/cm 2 . The time for ultraviolet light irradiation may be, for example, 50-65s, preferably 50-60s.

在第一階段的光照射結束後進行第二階段光照射(UV2)，UV2中所使用的光可以列舉出例如紫外光。第二階段紫外光照射(UV2)紫外光波長例如為360nm-370nm，在UV2階段使用紫外光輻照度為例如3-8mw/cm2。通過採用這樣的輻照度，能夠使得未發生聚合的式I所示化合物緩慢的完全聚合，提高可聚合化合物的轉化率，藉以使得液晶組合物中不存在可聚合化合物的殘留。並且由於聚合緩慢，該過程不會對已經形成的預傾角產生影響。UV2階段的紫外光照射時間可以為例如100-150min。 The second-stage light irradiation (UV2) is performed after the first-stage light irradiation is completed, and the light used in UV2 includes, for example, ultraviolet light. In the second stage of ultraviolet irradiation (UV2), the wavelength of ultraviolet light is, for example, 360nm-370nm, and the irradiance of ultraviolet light used in the UV2 stage is, for example, 3-8mw/cm 2 . By adopting such irradiance, the compound represented by formula I that has not been polymerized can be slowly and completely polymerized, and the conversion rate of the polymerizable compound can be improved, so that there is no residue of the polymerizable compound in the liquid crystal composition. And because the polymerization is slow, the process has no effect on the pretilt angle already formed. The ultraviolet light irradiation time in the UV2 stage can be, for example, 100-150 min.

實施例 Example

為了更清楚地說明本發明，下面結合較佳實施例和附圖對本發明做進一步的說明。附圖中相似的部件以相同的附圖標記進行表示。本領域具有通常知識者應當理解，下面所具體描述的內容是說明性的而非限制性的，不應以此限制本發明的保護範圍。 In order to illustrate the present invention more clearly, the present invention will be further described below in conjunction with preferred embodiments and accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not limit the protection scope of the present invention.

本發明中，製備方法如無特殊說明則均為常規方法，所用的原料如無特別說明均可從公開的商業途徑獲得，百分比均是指質量百分比，溫度為攝氏度(℃)，液晶化合物也成為液晶單體，其他符號的具體意義及測試條件如下：Cp表示液晶清晰點(℃)，DSC定量法測試；△n表示光學各向異性，△n=ne-no，其中，no為尋常光的折射率，ne為非尋常光的折射率，測試條件為25±2℃，589nm，阿貝折射儀測試； △ε表示介電各向異性，△ε=ε∥-ε⊥，其中，ε∥為平行於分子軸的介電常數，ε⊥為垂直於分子軸的介電常數，測試條件為25±0.5℃，20微米垂直盒，INSTEC：ALCT-IR1測試；VHR表示電壓保持率(%)，測試條件為20±2℃、電壓為±5V、脈衝寬度為10ms、電壓保持時間16.7ms。測試設備為TOYO Model6254液晶性能綜合測試儀；γ1表示旋轉黏度(mPa．s)，測試條件為25±0.5℃，20微米垂直盒，INSTEC：ALCT-IR1測試。 In the present invention, the preparation method is a conventional method unless otherwise specified, and the raw materials used can be obtained from open commercial channels if not otherwise specified, and the percentages all refer to mass percentages, and the temperature is degrees Celsius (° C.), and the liquid crystal compound also becomes Liquid crystal monomer, the specific meanings and test conditions of other symbols are as follows: Cp means liquid crystal clear point (°C), tested by DSC quantitative method; △n means optical anisotropy, △n=n e -n o , where n o is The refractive index of ordinary light, ne is the refractive index of extraordinary light, the test condition is 25±2℃, 589nm, Abbe refractometer test; △ε means dielectric anisotropy, △ε=ε∥-ε⊥, Among them, ε∥ is the dielectric constant parallel to the molecular axis, ε⊥ is the dielectric constant perpendicular to the molecular axis, the test condition is 25±0.5°C, 20 micron vertical cell, INSTEC: ALCT-IR1 test; VHR means voltage hold Rate (%), the test condition is 20±2℃, the voltage is ±5V, the pulse width is 10ms, and the voltage hold time is 16.7ms. The test equipment is TOYO Model6254 liquid crystal performance comprehensive tester; γ1 means rotational viscosity (mPa.s), the test condition is 25±0.5°C, 20 micron vertical cell, INSTEC: ALCT-IR1 test.

本發明實施例中，液晶組合物的製備所用的設備和儀器為：液晶組合物的製備方法如下：將各可聚合化合物按照一定配比稱量後放入不鏽鋼燒杯中，將裝有各可聚合化合物的不鏽鋼燒杯置於磁力攪拌儀器上加熱融化，待不鏽鋼燒杯中的可聚合化合物融化後，往不鏽鋼燒杯中加入磁力轉子，將混合物攪拌均勻，冷卻到室溫後即得液晶組合物。 In the embodiment of the present invention, the equipment and instruments used for the preparation of the liquid crystal composition are as follows: the preparation method of the liquid crystal composition is as follows: put each polymerizable compound into a stainless steel beaker after weighing according to a certain proportion, and put each polymerizable compound into a stainless steel beaker. The stainless steel beaker of the compound is heated and melted on a magnetic stirring apparatus, and after the polymerizable compound in the stainless steel beaker is melted, a magnetic rotor is added to the stainless steel beaker, the mixture is stirred evenly, and the liquid crystal composition is obtained after cooling to room temperature.

本發明的實施例中的液晶顯示元件的製備方法如下：首先，在第一基板和第二基板的表面均勻塗布配向材料，配向材料可以選用聚醯亞胺，對均勻塗布的配向材料進行加熱固化，加熱溫度為230℃，形成配向層；其次，在第二基板表面散佈間隔物，並沿第一基板的邊緣塗布邊框膠，並在120℃下進行固化；然後，將第一基板和第二基板相對設置，貼合形成具有夾層空間的結構；最後，將液晶組合物注入第一基板和第二基板之間的夾層空間，密封固化，藉以將液晶組合物密封在第一基板和第二基板之間，並同時進行加電、紫外光照射。紫外光照射分為兩個階段，包括第一階段紫外光照射(UV1)、第二階段紫外光照射(UV2)。在UV1階段，以紫外光波長為365nm，輻照度為64mw/cm2進行光照射，在第一階段的光照射結束後進行第二階段光照射 (UV2)，UV2中使用波長365nm的紫外光，輻照度為5mw/cm2，光照射時間為100-150min。 The preparation method of the liquid crystal display element in the embodiment of the present invention is as follows: First, uniformly coat the alignment material on the surface of the first substrate and the second substrate, the alignment material can be polyimide, and heat and cure the evenly coated alignment material , the heating temperature is 230°C to form an alignment layer; secondly, spacers are spread on the surface of the second substrate, and frame glue is coated along the edge of the first substrate, and cured at 120°C; then, the first substrate and the second The substrates are arranged oppositely and bonded to form a structure with interlayer space; finally, the liquid crystal composition is injected into the interlayer space between the first substrate and the second substrate, sealed and cured, so that the liquid crystal composition is sealed on the first substrate and the second substrate Between, and at the same time, power-on, ultraviolet light irradiation. The ultraviolet light irradiation is divided into two stages, including the first stage ultraviolet light irradiation (UV1) and the second stage ultraviolet light irradiation (UV2). In the UV1 stage, the ultraviolet light is irradiated with a wavelength of 365nm and an irradiance of 64mw/ cm2 . After the first stage of light irradiation is completed, the second stage of light irradiation (UV2) is carried out. In UV2, ultraviolet light with a wavelength of 365nm is used. The irradiance is 5mw/cm 2 , and the light irradiation time is 100-150min.

本發明實施例中使用的液晶單體結構用代碼表示，液晶環結構、端基、連接基團的代碼表示方法見下表1、表2。 The structures of the liquid crystal monomers used in the embodiments of the present invention are represented by codes, and the code representation methods of liquid crystal ring structures, terminal groups, and linking groups are shown in Table 1 and Table 2 below.

Figure 109117709-A0305-02-0028-90
Figure 109117709-A0305-02-0028-90

Figure 109117709-A0305-02-0028-91
Figure 109117709-A0305-02-0028-91
Figure 109117709-A0305-02-0029-92
Figure 109117709-A0305-02-0029-92

舉例：

Figure 109117709-A0305-02-0029-202
，其代碼為CC-Cp-V1；
Figure 109117709-A0305-02-0029-96
，其代碼為PGP-Cprl-2；
Figure 109117709-A0305-02-0029-95
，其代碼為CPY-2-O2；
Figure 109117709-A0305-02-0029-97
，其代碼為CCY-3-O2；
Figure 109117709-A0305-02-0029-98
，其代碼為COY-3-O2；
Figure 109117709-A0305-02-0029-99
，其代碼為CCOY-3-O2；
Figure 109117709-A0305-02-0029-100
，其代碼為Sb-CpO-O4；
Figure 109117709-A0305-02-0030-102
，其代碼為Sc-CpO-O4；
Figure 109117709-A0305-02-0030-203
，其代碼為COYL-Cprl-O2；
Figure 109117709-A0305-02-0030-201
，其代碼為COYL-1-OV1。 Example:
Figure 109117709-A0305-02-0029-202
, whose code is CC-Cp-V1;
Figure 109117709-A0305-02-0029-96
, whose code is PGP-Cprl-2;
Figure 109117709-A0305-02-0029-95
, whose code is CPY-2-O2;
Figure 109117709-A0305-02-0029-97
, whose code is CCY-3-O2;
Figure 109117709-A0305-02-0029-98
, whose code is COY-3-O2;
Figure 109117709-A0305-02-0029-99
, whose code is CCOY-3-O2;
Figure 109117709-A0305-02-0029-100
, whose code is Sb-CpO-O4;
Figure 109117709-A0305-02-0030-102
, whose code is Sc-CpO-O4;
Figure 109117709-A0305-02-0030-203
, whose code is COYL-Cprl-O2;
Figure 109117709-A0305-02-0030-201
, whose code is COYL-1-OV1.

以下採用以下具體實施例來對本發明進行說明： Below adopt following specific embodiment to illustrate the present invention:

[液晶化合物] [Liquid crystal compound]

本發明的式I所示化合物可根據下述方案進行合成：

Figure 109117709-A0305-02-0030-199
Compound shown in formula I of the present invention can be synthesized according to following scheme:
Figure 109117709-A0305-02-0030-199

其中，L1、L2、L3、L4、r1、r3、r2、r4、x1、x2、x3、x4、Sp1、Sp2、Sp3、Sp4、Sp5、Z1、Z2、P1、P2、P3、P4各自獨立地與上述式I所示的可聚合化合物中的定義相同；S1、S2各自獨立地表示醛基、羥基、羧基；B1、B2、B3、B4各自獨立地表示羥基的保護基。 Among them, L 1 , L 2 , L 3 , L 4 , r 1 , r 3 , r 2 , r 4 , x 1 , x 2 , x 3 , x 4 , Sp 1 , Sp 2 , Sp 3 , Sp 4 , Sp 5 , Z 1 , Z 2 , P 1 , P 2 , P 3 , and P 4 are each independently as defined in the polymerizable compound shown in the above formula I; S 1 and S 2 each independently represent an aldehyde group, Hydroxy group, carboxyl group; B 1 , B 2 , B 3 , and B 4 each independently represent a protecting group for a hydroxyl group.

合成通式中原材料及試劑均可通過常規合成或商業途徑購買而得，此類方法原理、操作過程、常規後處理、過矽膠柱、重結晶提純等手段是本領域合成人員所熟知的，完全可以實現合成過程，得到目標產物。 The raw materials and reagents in the general synthesis formula can be purchased through conventional synthesis or commercial channels. Means such as such method principle, operation process, conventional post-treatment, silica gel column, recrystallization and purification are well known to those skilled in the art. The synthesis process can be realized to obtain the target product.

上述所有方法的所有步驟的反應均在溶劑中進行；所述溶劑均選自四氫呋喃、N,N-二甲基甲醯胺、乙醇、甲醇、二氯甲烷、丙酮、甲苯和去離子水中的至少一種。 The reactions of all the steps of the above-mentioned methods are carried out in a solvent; the solvent is selected from tetrahydrofuran, N,N-dimethylformamide, ethanol, methanol, methylene chloride, acetone, toluene and deionized water at least A sort of.

實施例1 Example 1

化合物結構式如下式I-1-1所示：

Figure 109117709-A0305-02-0031-106
The compound structural formula is shown in the following formula I-1-1:
Figure 109117709-A0305-02-0031-106

其製備路線如下：

Figure 109117709-A0305-02-0032-107
Its preparation route is as follows:
Figure 109117709-A0305-02-0032-107

製備的具體操作流程： The specific operation process of preparation:

中間體3 Intermediate 3

氮氣保護下，在5L三口瓶中投入0.4mol的中間體1、0.4mol的中間體2，2.0L甲苯，0.7L水，0.45mol碳酸鉀，催化劑0.5g，加熱回流反應3小時。靜置分液，柱層析分離，甲苯/乙醇重結晶，得到化合物3黃色固體。HPLC：92%，收率Y=80%。 Under the protection of nitrogen, 0.4 mol of intermediate 1, 0.4 mol of intermediate 2, 2.0 L of toluene, 0.7 L of water, 0.45 mol of potassium carbonate, and 0.5 g of catalyst were put into a 5 L three-necked flask, and heated to reflux for 3 hours. The liquid was separated by standing, separated by column chromatography, and recrystallized from toluene/ethanol to obtain compound 3 as a yellow solid. HPLC: 92%, yield Y=80%.

中間體4 Intermediate 4

氮氣保護下，在2L三口瓶中投0.22mol的中間體3、0.15mol的1,2-二溴乙烷、0.25mol的無水碳酸鉀，1.2L DMF，N2保護下控溫120℃反應4小時。反應完畢，降溫，邊攪拌邊倒入冰水中，攪拌30min，過濾，0.5L石油醚打漿，可得到化合物4，HPLC：96%，收率Y=86%。 Under the protection of nitrogen, put 0.22mol of intermediate 3, 0.15mol of 1,2-dibromoethane, 0.25mol of anhydrous potassium carbonate, 1.2L of DMF into a 2L three-necked flask, and react at 120°C under the protection of N2 . Hour. After the reaction is complete, cool down, pour into ice water while stirring, stir for 30 minutes, filter, and beat with 0.5L petroleum ether to obtain compound 4, HPLC: 96%, yield Y=86%.

中間體6 Intermediate 6

氮氣保護下，在2L三口瓶中投0.22mol的中間體4、0.15mol的中間體5、0.25mol的無水碳酸鉀，1.2L DMF，N2保護下控溫120℃反應4小時。反應完 畢，降溫，邊攪拌邊倒入冰水中，攪拌30min，過濾，0.5L石油醚打漿，可得到化合物4，HPLC：96%，收率Y=86%。 Under the protection of nitrogen, put 0.22 mol of intermediate 4, 0.15 mol of intermediate 5, 0.25 mol of anhydrous potassium carbonate, 1.2 L of DMF into a 2L three-necked flask, and react at 120°C for 4 hours under the protection of N 2 . After the reaction is complete, cool down, pour into ice water while stirring, stir for 30 minutes, filter, and beat with 0.5L petroleum ether to obtain compound 4, HPLC: 96%, yield Y=86%.

中間體7 Intermediate 7

將0.08mol中間體6、7g的Pd/C、0.3L的THF和0.3L的EtOH加入1L三口瓶中，N2置換三次，H2置換三次，40℃加氫脫苄，反應6小時。反應完畢，矽藻土過濾，濾液濃縮，PE：EA=10：1打漿，攪拌10min，得到化合物5，HPLC：98%，收率Y=80%。 Add 0.08 mol of intermediate 6, 7 g of Pd/C, 0.3 L of THF and 0.3 L of EtOH into a 1 L three-necked flask, replace with N 2 three times, H 2 three times, hydrodebenzylation at 40°C, and react for 6 hours. After the reaction was completed, filter with diatomaceous earth, concentrate the filtrate, beat PE:EA=10:1, and stir for 10 minutes to obtain compound 5, HPLC: 98%, yield Y=80%.

化合物I-1-1 Compound I-1-1

在500ml三口瓶中投0.03mol的中間體7、0.2mol的三乙胺、0.2L的DCM，N2保護下控溫0℃滴加0.2mol甲基丙烯醯氯。滴畢，室溫反應3小時。反應完畢，加水分液，水相用DCM萃取，合併有機相，飽和食鹽水洗一次，無水硫酸鈉乾燥，過濾，濾液濃縮，5倍甲苯45℃溶解，過50g矽膠柱，3倍甲苯沖柱，濃縮，3倍甲苯3倍乙醇加熱溶解，-20℃冰箱冷凍4h，吸慮，按照相同的方法再重結晶三次，晾乾，得白色固體化合物I-1-1，HPLC：99.1%，收率Y=45%。化合物I-1-1的1h-NMR譜圖如圖1所示。 Put 0.03mol of intermediate 7, 0.2mol of triethylamine, and 0.2L of DCM into a 500ml three-neck flask, and add 0.2mol of methacryloyl chloride dropwise at 0°C under the protection of N2 . After dropping, react at room temperature for 3 hours. After the reaction is complete, add water, extract the aqueous phase with DCM, combine the organic phases, wash once with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times of toluene at 45°C, pass through a 50 g silica gel column, and wash the column with 3 times of toluene. Concentrate, heat to dissolve with 3 times of toluene and 3 times of ethanol, refrigerate at -20°C for 4 hours, inhale, recrystallize three times according to the same method, and dry to obtain white solid compound I-1-1, HPLC: 99.1%, yield Y=45%. The 1h -NMR spectrum of compound I-1-1 is shown in Figure 1.

實施例2 Example 2

化合物結構式如下式I-2-1所示，

Figure 109117709-A0305-02-0033-108
The structural formula of the compound is shown in the following formula I-2-1,
Figure 109117709-A0305-02-0033-108

其製備路線如下：

Figure 109117709-A0305-02-0034-109
Its preparation route is as follows:
Figure 109117709-A0305-02-0034-109

製備的具體操作流程：同上(I-1-1操作)。 The specific operation process of preparation: same as above (I-1-1 operation).

中間體3 Intermediate 3

參考化合物I-1-1路線裡中間體3的合成 Synthesis of intermediate 3 in the route of reference compound I-1-1

中間體8 Intermediate 8

將原料1,2-二溴丙烷替換為1,2-二溴己烷，合成方法參照實施例1中的中間體4的合成。 The raw material 1,2-dibromopropane is replaced by 1,2-dibromohexane, and the synthesis method refers to the synthesis of intermediate 4 in Example 1.

中間體9 Intermediate 9

合成方法參照實施例1中的中間體6的合成。 The synthesis method refers to the synthesis of intermediate 6 in Example 1.

化合物I-2-1 Compound I-2-1

合成方法參照實施例1中的化合物I-1-1的合成。 The synthesis method refers to the synthesis of compound I-1-1 in Example 1.

實施例3 Example 3

化合物結構式如下式I-6-1所示：

Figure 109117709-A0305-02-0035-110
The structural formula of the compound is shown in the following formula I-6-1:
Figure 109117709-A0305-02-0035-110

其製備路線如下：

Figure 109117709-A0305-02-0035-112
Its preparation route is as follows:
Figure 109117709-A0305-02-0035-112

製備的具體操作流程： The specific operation process of preparation:

中間體15 Intermediate 15

氮氣保護下，在3L三口瓶中投0.25mol的膦鹽，加入1L降溫至0到-10℃之間，分批緩慢加入0.25mol的叔丁醇鉀，控溫0到-10℃之間反應1h，滴加中間體14(0.15mol)的THF溶液，自然升溫至室溫反應4小時。反應完畢，加水分液，乙酸乙酯萃取水相，合併有機相飽和氯化鈉洗，乾燥，旋幹，柱層析分離(石油醚、乙酸乙酯)，旋幹溶劑可得到化合物15，HPLC：95%，收率Y=80%。 Under the protection of nitrogen, put 0.25mol of phosphine salt into a 3L three-necked flask, add 1L to cool down to between 0 and -10°C, slowly add 0.25mol of potassium tert-butoxide in batches, and control the temperature between 0 and -10°C to react For 1 h, a THF solution of intermediate 14 (0.15 mol) was added dropwise, and the temperature was naturally raised to room temperature for 4 hours. After the reaction is complete, add water, extract the aqueous phase with ethyl acetate, combine the organic phases, wash with saturated sodium chloride, dry, spin dry, separate by column chromatography (petroleum ether, ethyl acetate), and spin dry the solvent to obtain compound 15. HPLC : 95%, yield Y=80%.

中間體16 Intermediate 16

氮氣保護下，在2L三口瓶中加入0.15mol的中間體15和0.15mol的中間體3，再加入0.2mol的三苯基膦，降溫至0℃，滴加0.2mol的DIAD，滴畢自然升至室溫反應3h。反應完畢。加水和乙酸乙酯分液，乙酸乙酯萃取水相，合併有機相乾燥，旋幹，柱層析分離(石油醚、乙酸乙酯)，旋幹溶劑得到化合物16，HPLC：95%，收率Y=70%。 Under the protection of nitrogen, add 0.15 mol of intermediate 15 and 0.15 mol of intermediate 3 into a 2L three-necked flask, then add 0.2 mol of triphenylphosphine, cool down to 0°C, add 0.2 mol of DIAD dropwise, and rise naturally after dropping Reaction at room temperature for 3h. The reaction is complete. Add water and ethyl acetate to separate the liquid, extract the aqueous phase with ethyl acetate, combine the organic phases to dry, spin dry, separate by column chromatography (petroleum ether, ethyl acetate), spin dry the solvent to obtain compound 16, HPLC: 95%, yield Y=70%.

中間體17 Intermediate 17

將0.07mol中間體16、6g的Pd/C、0.3L的THF和0.2L的EtOH加入1L三口瓶中，N2置換三次，H2置換三次，40℃加氫脫苄，反應6小時。反應完畢，矽藻土過濾，濾液濃縮，PE：EA=10：1打漿，攪拌10min，得到化合物17，HPLC：98%，收率Y=80%。 Add 0.07 mol of intermediate 16, 6 g of Pd/C, 0.3 L of THF and 0.2 L of EtOH into a 1 L three-neck flask, replace with N 2 three times, replace with H 2 three times, hydrodebenzyle at 40°C, and react for 6 hours. After the reaction was completed, filter with diatomaceous earth, concentrate the filtrate, beat PE:EA=10:1, and stir for 10 minutes to obtain compound 17, HPLC: 98%, yield Y=80%.

化合物I-6-1 Compound I-6-1

在500ml三口瓶中投0.04mol的中間體17、0.15mol的三乙胺、0.2L的DCM，N2保護下控溫0℃滴加0.2mol甲基丙烯醯氯。滴畢，室溫反應3小時。反應完畢，加水分液，水相用DCM萃取，合併有機相，飽和食鹽水洗一次，無水硫酸鈉乾燥，過濾，濾液濃縮，5倍甲苯45℃溶解，過50g矽膠柱，3倍甲苯沖柱，濃縮，3倍甲苯3倍醇加熱溶解，-20℃冰箱冷凍4h，吸慮，按照相同的方法再重結晶四次，晾乾，得白色固體化合物I-6-1，HPLC：99.2%，收率Y=45%。 Put 0.04mol of intermediate 17, 0.15mol of triethylamine, and 0.2L of DCM into a 500ml three-neck flask, and add 0.2mol of methacryloyl chloride dropwise at 0°C under the protection of N2 . After dropping, react at room temperature for 3 hours. After the reaction is complete, add water, extract the aqueous phase with DCM, combine the organic phases, wash once with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times of toluene at 45°C, pass through a 50 g silica gel column, and wash the column with 3 times of toluene. Concentrate, heat to dissolve with 3 times of toluene and 3 times of alcohol, refrigerate at -20°C for 4 hours, inhale, recrystallize four times according to the same method, and dry to obtain white solid compound I-6-1, HPLC: 99.2%, yield Rate Y=45%.

實施例4 Example 4

化合物結構式如下式I-7-1所示，

Figure 109117709-A0305-02-0037-113
The structural formula of the compound is shown in the following formula I-7-1,
Figure 109117709-A0305-02-0037-113

其製備路線如下：

Figure 109117709-A0305-02-0037-114
Its preparation route is as follows:
Figure 109117709-A0305-02-0037-114

製備的具體操作流程： The specific operation process of preparation:

中間體20 Intermediate 20

氮氣保護下，在5L三口瓶中投入0.4mol的中間體1、0.4mol的中間體19，2.0L甲苯，0.7L水，0.6mol碳酸鉀，催化劑0.35g，加熱回流反應3小時。靜置分液，柱層析分離，甲苯/乙醇重結晶，得到化合物20淡黃色固體。HPLC：96%，收率Y=85%。 Under nitrogen protection, 0.4 mol of intermediate 1, 0.4 mol of intermediate 19, 2.0 L of toluene, 0.7 L of water, 0.6 mol of potassium carbonate, and 0.35 g of catalyst were put into a 5 L three-necked flask, and heated to reflux for 3 hours. The liquid was separated by standing, separated by column chromatography, and recrystallized from toluene/ethanol to obtain compound 20 as a pale yellow solid. HPLC: 96%, yield Y=85%.

中間體21 Intermediate 21

在3L三口瓶中投0.2mol的中間體20、0.1mol的丙二醇、0.05mol的DMAP，1.0L THF，N2保護下控溫0℃滴加0.3molDCC的THF溶液。滴畢，室溫反應6小時。反應完畢，過濾，濾液濃縮，3倍乙醇重結晶，得到化合物21，GC：94%，收率Y=78%。 Put 0.2mol of intermediate 20, 0.1mol of propylene glycol, 0.05mol of DMAP, 1.0L of THF in a 3L three-necked flask, and add 0.3mol of DCC THF solution dropwise at 0°C under the protection of N2 . After dropping, react at room temperature for 6 hours. After the reaction was completed, it was filtered, the filtrate was concentrated, and recrystallized from 3 times ethanol to obtain compound 21, GC: 94%, yield Y=78%.

中間體23 Intermediate 23

在3L三口瓶中投0.1mol的中間體21、0.1mol的中間體22、0.05mol的DMAP，1.0L THF，N2保護下控溫0℃滴加0.3molDCC的THF溶液。滴畢，室溫反應6小時。反應完畢，過濾，濾液濃縮，3倍乙醇重結晶，得到化合物23，GC：94%，收率Y=78%。 In a 3L three-necked flask, 0.1mol of intermediate 21, 0.1mol of intermediate 22, 0.05mol of DMAP, 1.0L of THF, and 0.3mol of THF solution of DCC were added dropwise at 0°C under the protection of N2 . After dropping, react at room temperature for 6 hours. After the reaction was completed, it was filtered, the filtrate was concentrated, and recrystallized from 3 times ethanol to obtain compound 23, GC: 94%, yield Y=78%.

中間體24 Intermediate 24

將0.06mol化合物23、6g的Pd/C、0.3L的THF和0.2L的EtOH加入1L三口瓶中，N2置換三次，H2置換三次，40℃加氫脫苄，反應6小時。反應完畢，矽藻土過濾，濾液濃縮，PE：EA=10：1打漿，攪拌10min，得到化合物24，HPLC：98%，收率Y=86%。 Add 0.06 mol of compound 23, 6 g of Pd/C, 0.3 L of THF and 0.2 L of EtOH into a 1 L three-neck flask, replace with N 2 three times, replace with H 2 three times, hydrodebenzyle at 40°C, and react for 6 hours. After the reaction was completed, filter with diatomaceous earth, concentrate the filtrate, beat PE:EA=10:1, and stir for 10 minutes to obtain compound 24, HPLC: 98%, yield Y=86%.

化合物I-7-1 Compound I-7-1

在500ml三口瓶中投0.02mol的中間體24、0.1mol的三乙胺、0.2L的DCM，N2保護下控溫0℃滴加0.1mol甲基丙烯醯氯。滴畢，室溫反應3小時。反應完畢，加水分液，水相用DCM萃取，合併有機相，飽和食鹽水洗一次，無水硫酸鈉乾燥，過濾，濾液濃縮，5倍甲苯45℃溶解，過50g矽膠柱，3倍甲苯沖柱，濃縮，3倍甲苯3倍醇加熱溶解，-20℃冰箱冷凍4h，吸慮，按照相同的方法再重結晶四次，晾乾，得白色固體化合物I-7-1，HPLC：99.0%，收率Y=50%。 Put 0.02mol of intermediate 24, 0.1mol of triethylamine, and 0.2L of DCM into a 500ml three-neck flask, and add 0.1mol of methacryloyl chloride dropwise at 0°C under the protection of N2 . After dropping, react at room temperature for 3 hours. After the reaction is complete, add water, extract the aqueous phase with DCM, combine the organic phases, wash once with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times of toluene at 45°C, pass through a 50 g silica gel column, and wash the column with 3 times of toluene. Concentrate, heat to dissolve with 3 times of toluene and 3 times of alcohol, refrigerate at -20°C for 4 hours, inhale, recrystallize four times according to the same method, and dry to obtain white solid compound I-7-1, HPLC: 99.0%, yield Rate Y=50%.

實施例5 Example 5

化合物結構式如下式I-8-1所示，

Figure 109117709-A0305-02-0039-115
The structural formula of the compound is shown in the following formula I-8-1,
Figure 109117709-A0305-02-0039-115

其製備路線如下：

Figure 109117709-A0305-02-0039-117
Its preparation route is as follows:
Figure 109117709-A0305-02-0039-117

製備的具體操作流程。 The specific operation process of the preparation.

中間體26的合成參照實施例4中的中間體21，將原料丙二醇替換為1，6-己二醇。 The synthesis of intermediate 26 refers to intermediate 21 in Example 4, and the raw material propylene glycol is replaced by 1,6-hexanediol.

中間體27的合成參照實施例4中的中間體23。 The synthesis of intermediate 27 refers to intermediate 23 in Example 4.

中間體28的合成參照實施例4中的中間體24。 The synthesis of intermediate 28 refers to intermediate 24 in Example 4.

化合物I-8-1的合成參照實施例4中的化合物I-7-1。 The synthesis of compound I-8-1 refers to compound I-7-1 in Example 4.

實施例6 Example 6

化合物結構式如下式I-10-1所示，

Figure 109117709-A0305-02-0040-118
The structural formula of the compound is shown in the following formula I-10-1,
Figure 109117709-A0305-02-0040-118

其製備路線如下：

Figure 109117709-A0305-02-0040-119
Its preparation route is as follows:
Figure 109117709-A0305-02-0040-119

製備的具體操作流程： The specific operation process of preparation:

中間體30 Intermediate 30

在3L三口瓶中投0.3mol的中間體3、0.2mol的己二酸、0.06mol的DMAP，1.0L THF，N2保護下控溫0℃滴加0.4mol DCC的THF溶液。滴畢，室溫反應6小時。反應完畢，過濾，濾液濃縮，3倍乙醇重結晶，得到化合物30，GC：93%，收率Y=85%。 In a 3L three-necked flask, 0.3mol of intermediate 3, 0.2mol of adipic acid, 0.06mol of DMAP, 1.0L of THF, and 0.4mol of DCC THF solution were added dropwise at 0°C under the protection of N2 . After dropping, react at room temperature for 6 hours. After the reaction was completed, it was filtered, the filtrate was concentrated, and recrystallized from 3 times ethanol to obtain compound 30, GC: 93%, yield Y=85%.

中間體31 Intermediate 31

在3L三口瓶中投0.2mol的中間體30、0.2mol的中間體5、0.06mol的DMAP，1.0L THF，N2保護下控溫0℃滴加0.4molDCC的THF溶液。滴畢，室溫反應6小時。反應完畢，過濾，濾液濃縮，3倍乙醇重結晶，得到化合物31，GC：93%，收率Y=85%。 In a 3L three-necked flask, 0.2mol of intermediate 30, 0.2mol of intermediate 5, 0.06mol of DMAP, 1.0L of THF, and 0.4mol of THF solution of DCC were added dropwise at 0°C under the protection of N2 . After dropping, react at room temperature for 6 hours. After the reaction was completed, it was filtered, the filtrate was concentrated, and recrystallized from 3 times ethanol to obtain compound 31, GC: 93%, yield Y=85%.

中間體32 Intermediate 32

將0.05mol中間體27、6.0g的Pd/C、0.3L的THF和0.2L的EtOH加入1L三口瓶中，N2置換三次，H2置換三次，40℃加氫脫苄，反應6小時。反應完畢，矽藻土過濾，濾液濃縮，PE：EA=10：1打漿，攪拌10min，得到化合物28，HPLC：97%，收率Y=85%。 Add 0.05mol of intermediate 27, 6.0g of Pd/C, 0.3L of THF and 0.2L of EtOH into a 1L three-neck flask, replace with N 2 three times, H 2 three times, hydrodebenzylation at 40°C, and react for 6 hours. After the reaction was completed, filter with diatomaceous earth, concentrate the filtrate, beat PE:EA=10:1, and stir for 10 minutes to obtain compound 28, HPLC: 97%, yield Y=85%.

化合物I-10-1 Compound I-10-1

在500ml三口瓶中投0.03mol的中間體28、0.2mol的三乙胺、0.2L的DCM，N2保護下控溫0℃滴加0.2mol甲基丙烯醯氯。滴畢，室溫反應3小時。反應完畢，加水分液，水相用DCM萃取，合併有機相，飽和食鹽水洗一次，無水硫酸鈉乾燥，過濾，濾液濃縮，5倍甲苯45℃溶解，過50g矽膠柱，3倍甲苯沖柱，濃縮，3倍甲苯3倍醇加熱溶解，-20℃冰箱冷凍4h，吸慮，按照相同的方法再重結晶四次，晾乾，得白色固體化合物I-10-1，HPLC：99.1%，收率Y=47%。 Put 0.03mol of intermediate 28, 0.2mol of triethylamine, and 0.2L of DCM into a 500ml three-neck flask, and add 0.2mol of methacryloyl chloride dropwise at 0°C under the protection of N2 . After dropping, react at room temperature for 3 hours. After the reaction is complete, add water, extract the aqueous phase with DCM, combine the organic phases, wash once with saturated brine, dry over anhydrous sodium sulfate, filter, concentrate the filtrate, dissolve 5 times of toluene at 45°C, pass through a 50 g silica gel column, and wash the column with 3 times of toluene. Concentrate, heat to dissolve with 3 times of toluene and 3 times of alcohol, refrigerate at -20°C for 4 hours, inhale, recrystallize four times according to the same method, and dry to obtain white solid compound I-10-1, HPLC: 99.1%, yield Rate Y=47%.

製備液晶組合物： Preparation of liquid crystal composition:

母體液晶組合物 Matrix liquid crystal composition

液晶組合物的配方及相應的性能如下表3所示。 The formula and corresponding properties of the liquid crystal composition are shown in Table 3 below.

Figure 109117709-A0305-02-0041-120
Figure 109117709-A0305-02-0041-120
Figure 109117709-A0305-02-0042-121
Figure 109117709-A0305-02-0042-121

對比化合物： Comparative compound:

Figure 109117709-A0305-02-0042-122
Figure 109117709-A0305-02-0042-122

Figure 109117709-A0305-02-0042-123
Figure 109117709-A0305-02-0042-123

為了測量溶解性，實施例1、2、3、4、5、6中的單體I-1-1、I-2-1、I-6-1、I-7-1、I-8-1、I-10-1以及習知技術中的單體RM-1、RM-2各自以0.1至2.0重量%的不同濃度溶解於母體液晶組合物中。樣品在室溫(RT)下儲存1000小時並且檢查它們是否保持為均一的溶液。然後，離心並且過濾樣品，並測定上清液中剩餘單體的濃度。1000小時後RT下的最大剩餘單體濃度：

Figure 109117709-A0305-02-0042-124
Figure 109117709-A0305-02-0043-125
 In order to measure the solubility, the monomers I-1-1, I-2-1, I-6-1, I-7-1, I-8- 1. I-10-1 and monomers RM-1 and RM-2 in the prior art are each dissolved in the matrix liquid crystal composition at different concentrations of 0.1 to 2.0% by weight. The samples were stored at room temperature (RT) for 1000 hours and checked whether they remained a homogeneous solution. The samples were then centrifuged and filtered, and the concentration of residual monomer in the supernatant was determined. Maximum residual monomer concentration at RT after 1000 hours:
Figure 109117709-A0305-02-0042-124
Figure 109117709-A0305-02-0043-125

可以看到根據本發明的單體比習知技術的單體表現出明顯更好的溶解性。可以看到，本發明的單體都顯示出

Figure 109117709-A0305-02-0043-198
0.40%的剩餘濃度，這比通常用於PSA顯示器中的0.3%的RM濃度較高，滿足工業需求，而單體RM-1、RM-2具比通常使用的0.30%的RM濃度要低。 It can be seen that the monomers according to the invention exhibit significantly better solubility than the monomers of the prior art. It can be seen that the monomers of the present invention all show
Figure 109117709-A0305-02-0043-198
The residual concentration of 0.40%, which is higher than the 0.3% RM concentration commonly used in PSA displays, meets industrial needs, while the monomer RM-1 and RM-2 have a lower RM concentration than the 0.30% commonly used.

向測試母體液晶組合物分別添加一定量的式I所示可聚合化合物：I-1-1、I-2-1、I-6-1、I-7-1、I-8-1、I-10-1做為實施例7-12；做為對比，分別向測試母體液晶組合物中添加一定量的RM-1、RM-2、RM-3做為對比例1、對比例2、對比例3，以上述提到的液晶組合物製備方法製備成液晶組合物。 Add a certain amount of polymerizable compounds shown in formula I to the test matrix liquid crystal composition: I-1-1, I-2-1, I-6-1, I-7-1, I-8-1, I -10-1 is used as embodiment 7-12; as a comparison, a certain amount of RM-1, RM-2, and RM-3 are added to the test matrix liquid crystal composition respectively as comparative example 1, comparative example 2, and Example 3, a liquid crystal composition was prepared by the above-mentioned liquid crystal composition preparation method.

將液晶組合物進行填充製備液晶顯示元件，測試初始預傾角(此處表示90°與下述預傾角資料的差值，即下述預傾角資料越小，實際預傾角越大)，然後在UV1制程進行UV光照射，促使可聚合化合物聚合，利用聚合後形成的膜對液晶進行配向，UV2製程後，測試預傾角。液晶組合物實施例與對比例的預傾角資料見表5。 Fill the liquid crystal composition to prepare a liquid crystal display element, test the initial pretilt angle (here represents the difference between 90° and the following pretilt angle data, that is, the smaller the following pretilt angle data, the larger the actual pretilt angle), and then in UV1 The process is irradiated with UV light to promote the polymerization of the polymerizable compound, and the film formed after polymerization is used to align the liquid crystal. After the UV2 process, the pretilt angle is tested. See Table 5 for the pretilt angle data of the liquid crystal composition examples and comparative examples.

Figure 109117709-A0305-02-0043-126
Figure 109117709-A0305-02-0043-126
Figure 109117709-A0305-02-0044-127
Figure 109117709-A0305-02-0044-127

可以看出，本發明的可聚合化合物在製備液晶顯示元件等應用時，具有較大的預傾角，顯示出良好的配向性。 It can be seen that the polymerizable compound of the present invention has a relatively large pretilt angle and shows good alignment when used in the preparation of liquid crystal display elements and the like.

顯然，本發明的上述實施例僅僅是為清楚地說明本發明所作的舉例，而並非是對本發明的實施方式的限定，對於所屬領域的普通具有通常知識者來說，在上述說明的基礎上還可以做出其它不同形式的變化或變動，這裡無法對所有的實施方式予以窮舉，凡是屬於本發明的技術方案所引伸出的顯而易見的變化或變動仍處於本發明的保護範圍之列。 Apparently, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, rather than limiting the implementation of the present invention. Other changes or changes in different forms can be made, and all implementation modes cannot be exhausted here, and all obvious changes or changes derived from the technical solutions of the present invention are still within the scope of protection of the present invention.

Claims (8)

一種可聚合化合物，其選自下述的式I-1-1、I-2-1、I-6-1、I-7-1、I-8-1、I-10-1所示化合物所組成的群組，
Figure 109117709-A0305-02-0045-128
 A polymerizable compound, which is selected from the compounds shown in the following formulas I-1-1, I-2-1, I-6-1, I-7-1, I-8-1, and I-10-1 formed by the group,
Figure 109117709-A0305-02-0045-128
 一種液晶組合物，其包含一種或複數種請求項1-所述之可聚合化合物。 A liquid crystal composition comprising one or more polymerizable compounds described in Claim 1-. 根據請求項2所述之液晶組合物，還包含一種或複數種下述的 式II所示化合物以及一種或複數種下述的式III所示化合物，
Figure 109117709-A0305-02-0046-131
Figure 109117709-A0305-02-0046-132
 式II中，R1、R2各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基；
Figure 109117709-A0305-02-0046-133
、
Figure 109117709-A0305-02-0046-134
各自獨立地表示
Figure 109117709-A0305-02-0046-135
或
Figure 109117709-A0305-02-0046-136
；式III中，R3、R4各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基，且R3、R4中任意一個或複數個不相鄰的-CH2-任選被亞環戊基、亞環丁基或亞環丙基取代；Z1、Z2各自獨立地表示單鍵、-CH2CH2-、-CH2O-或-OCH2-；
Figure 109117709-A0305-02-0046-140
、
Figure 109117709-A0305-02-0046-141
各自獨立地表示
Figure 109117709-A0305-02-0046-142
、
Figure 109117709-A0305-02-0046-143
、
Figure 109117709-A0305-02-0046-144
、
Figure 109117709-A0305-02-0046-146
、
Figure 109117709-A0305-02-0046-195
 m1表示1或2，當m1表示2時，
Figure 109117709-A0305-02-0046-137
相同或不同；n1表示0、1或2，當n1表示2時，
Figure 109117709-A0305-02-0046-138
相同或不同。 According to the liquid crystal composition described in Claim 2, further comprising one or more compounds represented by the following formula II and one or more compounds represented by the following formula III,
Figure 109117709-A0305-02-0046-131
Figure 109117709-A0305-02-0046-132
 In formula II, R 1 and R 2 each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, Alkoxy group with 1-10 carbon atoms substituted by fluorine, alkenyl group with 2-10 carbon atoms, alkenyl group with 2-10 carbon atoms substituted by fluorine, and alkenyl group with 3-8 carbon atoms Alkenyloxy or fluorine-substituted alkenyloxy with 3-8 carbon atoms;
Figure 109117709-A0305-02-0046-133
,
Figure 109117709-A0305-02-0046-134
express independently
Figure 109117709-A0305-02-0046-135
or
Figure 109117709-A0305-02-0046-136
; In formula III, R 3 and R 4 each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, and an alkoxy group with 1-10 carbon atoms , alkoxy group with 1-10 carbon atoms substituted by fluorine, alkenyl group with 2-10 carbon atoms, alkenyl group with 2-10 carbon atoms substituted with fluorine, 3-8 carbon atoms Alkenyloxy or alkenyloxy with 3-8 carbon atoms substituted by fluorine, and any one or a plurality of non-adjacent -CH 2 - in R 3 and R 4 is optionally replaced by cyclopentylene, Substituted by cyclobutylene or cyclopropylene; Z 1 and Z 2 each independently represent a single bond, -CH 2 CH 2 -, -CH 2 O- or -OCH 2 -;
Figure 109117709-A0305-02-0046-140
,
Figure 109117709-A0305-02-0046-141
express independently
Figure 109117709-A0305-02-0046-142
,
Figure 109117709-A0305-02-0046-143
,
Figure 109117709-A0305-02-0046-144
,
Figure 109117709-A0305-02-0046-146
,
Figure 109117709-A0305-02-0046-195
 m 1 means 1 or 2, when m 1 means 2,
Figure 109117709-A0305-02-0046-137
same or different; n 1 means 0, 1 or 2, when n 1 means 2,
Figure 109117709-A0305-02-0046-138
same or different. 根據請求項3所述之液晶組合物，其中所述式II所示化合物選自式II-1至式II-17所示化合物所組成的群組，
Figure 109117709-A0305-02-0046-139
Figure 109117709-A0305-02-0047-147
Figure 109117709-A0305-02-0047-148
Figure 109117709-A0305-02-0047-149
Figure 109117709-A0305-02-0047-150
Figure 109117709-A0305-02-0047-152
Figure 109117709-A0305-02-0047-153
Figure 109117709-A0305-02-0047-154
Figure 109117709-A0305-02-0047-155
Figure 109117709-A0305-02-0047-156
Figure 109117709-A0305-02-0047-157
Figure 109117709-A0305-02-0047-158
Figure 109117709-A0305-02-0047-159
Figure 109117709-A0305-02-0047-160
Figure 109117709-A0305-02-0047-161
Figure 109117709-A0305-02-0047-162
Figure 109117709-A0305-02-0047-163
 所述式III所示化合物選自式III-1至式III-15所示化合物所組成的群組，
Figure 109117709-A0305-02-0047-164
Figure 109117709-A0305-02-0047-165
Figure 109117709-A0305-02-0047-166
Figure 109117709-A0305-02-0047-167
Figure 109117709-A0305-02-0048-168
Figure 109117709-A0305-02-0048-169
Figure 109117709-A0305-02-0048-170
Figure 109117709-A0305-02-0048-171
Figure 109117709-A0305-02-0048-172
Figure 109117709-A0305-02-0048-173
Figure 109117709-A0305-02-0048-175
Figure 109117709-A0305-02-0048-176
Figure 109117709-A0305-02-0048-177
Figure 109117709-A0305-02-0048-178
Figure 109117709-A0305-02-0048-179
 其中，R31、R41各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基，並且其中任意一個或複數個不相鄰的-CH2-任選被亞環戊基、亞環丁基或亞環丙基取代。 According to the liquid crystal composition described in claim 3, wherein the compound shown in formula II is selected from the group consisting of compounds shown in formula II-1 to formula II-17,
Figure 109117709-A0305-02-0046-139
Figure 109117709-A0305-02-0047-147
Figure 109117709-A0305-02-0047-148
Figure 109117709-A0305-02-0047-149
Figure 109117709-A0305-02-0047-150
Figure 109117709-A0305-02-0047-152
Figure 109117709-A0305-02-0047-153
Figure 109117709-A0305-02-0047-154
Figure 109117709-A0305-02-0047-155
Figure 109117709-A0305-02-0047-156
Figure 109117709-A0305-02-0047-157
Figure 109117709-A0305-02-0047-158
Figure 109117709-A0305-02-0047-159
Figure 109117709-A0305-02-0047-160
Figure 109117709-A0305-02-0047-161
Figure 109117709-A0305-02-0047-162
Figure 109117709-A0305-02-0047-163
 The compound shown in the formula III is selected from the group consisting of the compounds shown in the formula III-1 to the formula III-15,
Figure 109117709-A0305-02-0047-164
Figure 109117709-A0305-02-0047-165
Figure 109117709-A0305-02-0047-166
Figure 109117709-A0305-02-0047-167
Figure 109117709-A0305-02-0048-168
Figure 109117709-A0305-02-0048-169
Figure 109117709-A0305-02-0048-170
Figure 109117709-A0305-02-0048-171
Figure 109117709-A0305-02-0048-172
Figure 109117709-A0305-02-0048-173
Figure 109117709-A0305-02-0048-175
Figure 109117709-A0305-02-0048-176
Figure 109117709-A0305-02-0048-177
Figure 109117709-A0305-02-0048-178
Figure 109117709-A0305-02-0048-179
 Wherein, R 31 and R 41 each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, a fluorine-substituted Alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkenyl groups with 2-10 carbon atoms substituted by fluorine, alkenyl groups with 3-8 carbon atoms An alkenyloxy group with 3-8 carbon atoms substituted by oxo or fluorine, and any one or a plurality of non-adjacent -CH 2 -s are optionally replaced by cyclopentylene, cyclobutylene or cyclopropylene base substitution. 根據請求項1-4任一項所述之液晶組合物，其中所述液晶組合 物還包含一種或複數種式IV所示的化合物，
Figure 109117709-A0305-02-0049-181
 其中，R5、R6各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基，並且其中任意一個或複數個不相鄰的-CH2-任選被亞環戊基、亞環丁基或亞環丙基替代；W表示-O-、-S-或-CH2O-。 The liquid crystal composition according to any one of claims 1-4, wherein the liquid crystal composition further comprises one or more compounds represented by formula IV,
Figure 109117709-A0305-02-0049-181
 Wherein, R 5 and R 6 each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, a fluorine-substituted Alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkenyl groups with 2-10 carbon atoms substituted by fluorine, alkenyl groups with 3-8 carbon atoms An alkenyloxy group with 3-8 carbon atoms substituted by oxo or fluorine, and any one or a plurality of non-adjacent -CH 2 -s are optionally replaced by cyclopentylene, cyclobutylene or cyclopropylene Substitution; W represents -O-, -S- or -CH 2 O-. 根據請求項5所述之液晶組合物，其中所述液晶組合物還包含一種或複數種式V所示的化合物，
Figure 109117709-A0305-02-0049-182
 其中，R7、R8各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基；
Figure 109117709-A0305-02-0049-183
、
Figure 109117709-A0305-02-0049-184
各自獨立地表示
Figure 109117709-A0305-02-0049-185
、
Figure 109117709-A0305-02-0049-186
或
Figure 109117709-A0305-02-0049-187
。 The liquid crystal composition according to claim 5, wherein the liquid crystal composition further comprises one or more compounds represented by formula V,
Figure 109117709-A0305-02-0049-182
 Wherein, R 7 and R 8 each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, or an alkyl group with 1-10 carbon atoms substituted by fluorine. Alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkenyl groups with 2-10 carbon atoms substituted by fluorine, alkenyl groups with 3-8 carbon atoms Alkenyloxy group with 3-8 carbon atoms substituted by oxy group or fluorine;
Figure 109117709-A0305-02-0049-183
,
Figure 109117709-A0305-02-0049-184
express independently
Figure 109117709-A0305-02-0049-185
,
Figure 109117709-A0305-02-0049-186
or
Figure 109117709-A0305-02-0049-187
. 根據請求項6所述之液晶組合物，其中所述液晶組合物還包含一種或複數種式VI所示化合物，
Figure 109117709-A0305-02-0049-188
 其中，R9、R10各自獨立地表示碳原子數為1-10的烷基、氟取代的碳原子數為1-10的烷基、碳原子數為1-10的烷氧基、氟取代的碳原子數為1-10的烷氧基、碳原子數為2-10的鏈烯基、氟取代的碳原子數為2-10的鏈烯基、碳原子數為3-8的鏈烯氧基或氟取代的碳原子數為3-8的鏈烯氧基；
Figure 109117709-A0305-02-0050-189
表示
Figure 109117709-A0305-02-0050-190
、
Figure 109117709-A0305-02-0050-191
或
Figure 109117709-A0305-02-0050-192
；F1、F2、F3各自獨立地表示H原子或F原子，且F2、F3不同時為F原子。 The liquid crystal composition according to claim 6, wherein the liquid crystal composition further comprises one or more compounds represented by formula VI,
Figure 109117709-A0305-02-0049-188
 Wherein, R 9 and R 10 each independently represent an alkyl group with 1-10 carbon atoms, an alkyl group with 1-10 carbon atoms substituted by fluorine, an alkoxy group with 1-10 carbon atoms, or an alkyl group with 1-10 carbon atoms substituted by fluorine. Alkoxy groups with 1-10 carbon atoms, alkenyl groups with 2-10 carbon atoms, alkenyl groups with 2-10 carbon atoms substituted by fluorine, alkenyl groups with 3-8 carbon atoms Alkenyloxy group with 3-8 carbon atoms substituted by oxy group or fluorine;
Figure 109117709-A0305-02-0050-189
express
Figure 109117709-A0305-02-0050-190
,
Figure 109117709-A0305-02-0050-191
or
Figure 109117709-A0305-02-0050-192
; F 1 , F 2 , and F 3 each independently represent an H atom or an F atom, and F 2 and F 3 are not F atoms at the same time. 一種液晶顯示元件，其包含請求項1所述之可聚合化合物，或者請求項2-7中任一項所述之液晶組合物，所述顯示元件為主動矩陣顯示元件或被動矩陣顯示元件。 A liquid crystal display element, which comprises the polymerizable compound described in Claim 1, or the liquid crystal composition described in any one of Claims 2-7, and the display element is an active matrix display element or a passive matrix display element.
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Publication number Priority date Publication date Assignee Title
CN105358523A (en) * 2013-07-10 2016-02-24 捷恩智株式会社 Polymerizable compound, polymerizable composition, and liquid crystal display element
TW201928027A (en) * 2017-12-20 2019-07-16 大陸商石家莊誠志永華顯示材料有限公司 Liquid crystal composition and liquid crystal display element

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105358523A (en) * 2013-07-10 2016-02-24 捷恩智株式会社 Polymerizable compound, polymerizable composition, and liquid crystal display element
TW201928027A (en) * 2017-12-20 2019-07-16 大陸商石家莊誠志永華顯示材料有限公司 Liquid crystal composition and liquid crystal display element

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