TWI797047B - Negative dielectric anisotropy liquid crystal composition, optical anisotropy and liquid crystal display device - Google Patents
Negative dielectric anisotropy liquid crystal composition, optical anisotropy and liquid crystal display device Download PDFInfo
- Publication number
- TWI797047B TWI797047B TW111131710A TW111131710A TWI797047B TW I797047 B TWI797047 B TW I797047B TW 111131710 A TW111131710 A TW 111131710A TW 111131710 A TW111131710 A TW 111131710A TW I797047 B TWI797047 B TW I797047B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- liquid crystal
- carbon atoms
- formula
- crystal composition
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Liquid Crystal Substances (AREA)
- Liquid Crystal (AREA)
Abstract
本發明涉及負介電各向異性液晶組合物、光學各向異構體及液晶顯示器件。本發明的負介電各向異性液晶組合物包含:至少一種式I所示化合物、至少一種式Ⅱ所示化合物以及至少一種式Ⅲ所示化合物。與現有技術相比,本發明的液晶組合物獲得了在維持合適的光學各向異性值、介電各向異性的基礎上獲得良好的低溫保存性、較快的聚合速率,進一步兼顧較高的可靠性、不容易發生預傾角的變化導致的顯示不良。The invention relates to a liquid crystal composition with negative dielectric anisotropy, an optical anisotropy and a liquid crystal display device. The negative dielectric anisotropy liquid crystal composition of the present invention comprises: at least one compound represented by formula I, at least one compound represented by formula II and at least one compound represented by formula III. Compared with the prior art, the liquid crystal composition of the present invention obtains good low-temperature preservation and faster polymerization rate on the basis of maintaining appropriate optical anisotropy value and dielectric anisotropy, and further takes into account higher Reliability and poor display caused by changes in pretilt angle are not easy to occur.
Description
本發明涉及液晶材料技術領域。更具體地,涉及液晶組合物、光學各向異構體及液晶顯示器件。 The invention relates to the technical field of liquid crystal materials. More specifically, it relates to liquid crystal compositions, optical anisotropes, and liquid crystal display devices.
液晶顯示器件中通常將像素製成多疇以改善視覺特性,因此設置突起等以分割像素。然而,當設置突起時,突起附近和分離部分之間存在預傾角差異,導致分離部分響應速度降低。 In liquid crystal display devices, pixels are usually made into multiple domains to improve visual characteristics, so protrusions and the like are provided to divide the pixels. However, when the protrusion is provided, there is a difference in pretilt angle between the vicinity of the protrusion and the separation part, resulting in a decrease in the response speed of the separation part.
之後開發了PSA(Polymer Sustained Alignment)液晶顯示裝置和PSVA(Polymer Stabilized Vertical Alignment)液晶顯示裝置。在PSA或PSVA液晶顯示裝置中,非聚合性液晶組合物和聚合性化合物設置在基板之間,任選地在基板之間施加電壓以使液晶分子取向。在取向狀態下,通過紫外線等照射使聚合性化合物聚合,並將液晶的取向狀態儲存在固化產物中。 Afterwards, a PSA (Polymer Sustained Alignment) liquid crystal display device and a PSVA (Polymer Stabilized Vertical Alignment) liquid crystal display device were developed. In a PSA or PSVA liquid crystal display device, a non-polymeric liquid crystal composition and a polymeric compound are disposed between substrates, and a voltage is optionally applied between the substrates to align the liquid crystal molecules. In the aligned state, the polymerizable compound is polymerized by irradiation with ultraviolet light or the like, and the aligned state of the liquid crystal is stored in the cured product.
這種液晶顯示器件仍然存在如長時間持續相同顯示時出現“殘影”等可靠性方面的問題,以及存儲穩定性、製造工藝引起的生產率等問題。 Such liquid crystal display devices still have problems in reliability such as "image sticking" when the same display is continued for a long time, storage stability, productivity due to manufacturing process, and the like.
關於可靠性,使用聚合引發劑的情況下,聚合引發劑及其分解產物是導致液晶顯示器件的電壓保持率降低和殘影的原因。另外,還已知殘影的發生與由含有聚合性化合物的液晶組合物中的液晶分子的預傾角的變化也是相關的。即,如果作為聚合性化合物的固化產物的聚合物是柔性的,當在形成顯示器件時長時間連續顯示相同圖案時,聚合物結構改變,結果,預傾角改變,優異預傾角會極大影響響應速度,從而影響顯示的可靠性。由此,為了解決預 傾角改變的問題,形成具有其中聚合物結構不改變的剛性結構的聚合物的聚合性化合物是有效的,但是這樣的情況下,存在液晶組合物的低溫儲存性劣化的問題。 With regard to reliability, when a polymerization initiator is used, the polymerization initiator and its decomposition products cause a decrease in the voltage retention ratio of the liquid crystal display device and cause image sticking. In addition, it is also known that the occurrence of image sticking is also related to the change in the pretilt angle of liquid crystal molecules in a liquid crystal composition containing a polymerizable compound. That is, if the polymer that is the cured product of the polymerizable compound is flexible, when the same pattern is continuously displayed for a long time when forming a display device, the polymer structure changes, and as a result, the pretilt angle changes, and an excellent pretilt angle greatly affects the response speed , thereby affecting the reliability of the display. Therefore, in order to solve the pre- As for the problem of changing the inclination angle, it is effective to form a polymerizable compound of a polymer having a rigid structure in which the polymer structure does not change, but in this case, there is a problem that the low-temperature storage property of the liquid crystal composition deteriorates.
因此,需要開發兼顧低溫存儲穩定性、製造工藝的生產率提高的含有聚合性化合物的液晶組合物。另外,還期望解決了長時間持續相同顯示時出現“殘影”等可靠性方面的問題的含有聚合性化合物的液晶組合物。 Therefore, there is a need to develop a liquid crystal composition containing a polymerizable compound that achieves both low-temperature storage stability and improved productivity of the manufacturing process. In addition, there is a demand for a liquid crystal composition containing a polymerizable compound that solves reliability problems such as "image sticking" that occurs when the same display is continued for a long period of time.
本發明的目的是提供一種含有聚合性化合物的液晶組合物,其具有優異的聚合反應速率從而製作工藝的生產率提高、低溫存儲穩定性。 An object of the present invention is to provide a liquid crystal composition containing a polymerizable compound, which has an excellent polymerization reaction rate, thereby improving the productivity of the manufacturing process, and having low-temperature storage stability.
進一步,本發明的液晶組合物用在PSA、PSVA顯示器件中時能夠獲得提高的紫外線照射後的VHR值,從而能夠減小/消除液晶顯示裝置的“殘影”等顯示不良的缺陷,可靠性提高。 Further, when the liquid crystal composition of the present invention is used in PSA, PSVA display device, can obtain the VHR value after the ultraviolet ray irradiation that improves, thereby can reduce/eliminate the defect of poor display such as " afterimage " of liquid crystal display device, reliability improve.
本發明人等為了解決上述課題而進行了深入研究,發現通過使用本申請的負介電各向異性液晶組合物可以解決上述課題,由此完成了本發明。 The inventors of the present invention conducted intensive studies to solve the above-mentioned problems, found that the above-mentioned problems can be solved by using the negative dielectric anisotropy liquid crystal composition of the present application, and completed the present invention.
本發明一方面提供一種負介電各向異性液晶組合物,其包含:至少一種式I所示化合物;至少一種式Ⅱ所示化合物;以及,至少一種式Ⅲ所示化合物;
式I中,P1、P2各自獨立地表示丙烯酸酯基、甲基丙烯酸酯基、乙基丙烯酸酯基、丙基丙烯酸酯基、丁基丙烯酸酯基、戊基丙烯酸酯基、氟代丙烯酸酯基、氟代甲基丙烯酸酯基、氟代乙基丙烯酸酯基、氟代丙基丙烯酸酯基、氟代丁基丙烯酸酯基或氟代戊基丙烯酸酯基;Z1、Z2各自獨立地表示單鍵、碳原子數為1~8的直鏈亞烷基、碳原子數為1~8的直鏈亞烷氧基、碳原子數為2~8的直鏈亞烯基、或者碳原子數為2~8的直鏈亞烯氧基,其中一個或兩個不相鄰的-CH2-任選被-O-取代,任意的H任選被F原子取代;Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10各自獨立地表示-H、-F、-CH3、-CH2F、-CHF2、-CF3、-C2H5、-OCH3、-OCH2F、-OCHF2、-OCF3或者-OC2H5;n表示0、1或2;式II中,R3、R4各自獨立地表示碳原子數為1~5的烷基、碳原子數為1~5的烷氧基、碳原子數為2~5的烯基、或碳原子數為2~5的烯氧基;並且,R3、R4中任意碳原子上的H各自獨立地任選被F取代;環C、環D各自獨立地選自下述的基團組成的組:1,4-亞環己基、環己烯-1,4-二基、1,4-亞苯基、2-氟-1,4-亞苯基、2,3-二氟-1,4-亞苯基、氧雜環己烷-2,5-二基、1,3-二氧雜環己烷-2,5-二基、1-甲基環己烷-1,4-二基、2-甲基環己烷-1,4-二基、2-甲基苯-1,4-二基;p表示0、1、2或3;式Ⅲ中,R5、R6各自獨立地表示碳原子數為1~5的烷基、碳原子數為1~5的烷氧基、碳原子數為2~5的烯基、或碳原子數為2~5的烯氧基;並且,R5、R6中任意碳原子上的H各自獨立地任選被F取代;Z3表示單鍵或-CH2O-;q、r各自獨立地表示0、1或2;環E、環F各自獨立地選自下述的基團組成的組:1,4-亞環己基、環己烯-1,4-二基、1,4-亞苯基、2-氟-1,4-亞苯基、2,3-二氟-1,4-亞苯基、氧雜環己烷-2,5-二基、1,3-二氧雜環己烷-2,5-二基、1-甲基環己烷-1,4-二基、2-甲基環己烷-1,4-二基、2-甲基苯-1,4-二基。 In formula I, P 1 and P 2 each independently represent an acrylate group, a methacrylate group, an ethacrylate group, a propyl acrylate group, a butyl acrylate group, an amyl acrylate group, a fluoroacrylic acid group ester group, fluoromethacrylate group, fluoroethylacrylate group, fluoropropylacrylate group, fluorobutylacrylate group or fluoropentylacrylate group; Z 1 and Z 2 are independent means a single bond, a straight-chain alkylene group with 1 to 8 carbon atoms, a straight-chain alkyleneoxy group with 1 to 8 carbon atoms, a straight-chain alkenylene group with 2 to 8 carbon atoms, or a carbon Straight-chain alkenyleneoxy groups with 2~8 atoms, one or two non-adjacent -CH 2 - are optionally substituted by -O-, any H is optionally substituted by F atom; Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , and Y 10 each independently represent -H, -F, -CH 3 , -CH 2 F, -CHF 2 , -CF 3 , -C 2 H 5 , -OCH 3 , -OCH 2 F, -OCHF 2 , -OCF 3 or -OC 2 H 5 ; n represents 0, 1 or 2; in formula II, R 3 and R 4 are each independently represents an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkenyloxy group with 2 to 5 carbon atoms; and, H on any carbon atom in R 3 and R 4 is independently optionally substituted by F; ring C and ring D are each independently selected from the group consisting of the following groups: 1,4-cyclohexylene, cyclohexyl En-1,4-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, oxane- 2,5-diyl, 1,3-dioxane-2,5-diyl, 1-methylcyclohexane-1,4-diyl, 2-methylcyclohexane-1, 4-diyl, 2-methylbenzene-1,4-diyl; p represents 0, 1, 2 or 3; in formula III, R 5 and R 6 each independently represent an alkane with 1 to 5 carbon atoms group, an alkoxy group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or an alkenyloxy group with 2 to 5 carbon atoms; and, on any carbon atom in R 5 and R 6 H in each independently optionally substituted by F; Z 3 represents a single bond or -CH 2 O-; q, r independently represent 0, 1 or 2; ring E, ring F are each independently selected from the following groups Group consisting of: 1,4-cyclohexylene, cyclohexene-1,4-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro -1,4-phenylene, oxane-2,5-diyl, 1,3-dioxane-2,5-diyl, 1-methylcyclohexane-1, 4-diyl, 2-methylcyclohexane-1,4-diyl, 2-methylbenzene-1,4-diyl.
另一方面,本發明提供光學各向異構體,其由前述的負介電各向 異性液晶組合物的聚合物構成。 In another aspect, the present invention provides an optical anisotropy consisting of the aforementioned negative dielectric anisotropy Polymer composition of anisotropic liquid crystal composition.
又一方面,本發明提供液晶顯示器件,其為使用前述的的負介電各向異性液晶組合物,使所述負介電各向異性液晶組合物中的聚合性化合物聚合而被賦予液晶取向性能的液晶顯示器件。 In yet another aspect, the present invention provides a liquid crystal display device, which uses the above-mentioned negative dielectric anisotropy liquid crystal composition, and polymerizes the polymerizable compound in the negative dielectric anisotropy liquid crystal composition to give liquid crystal alignment performance liquid crystal display devices.
本發明的負介電各向異性液晶組合物具有優異的聚合反應速率、低溫存儲穩定性。進一步,本發明的液晶組合物用在PSA、PSVA等模式的液晶顯示器件中時能夠獲得提高的紫外線照射後的VHR值,從而能夠減小/消除液晶顯示裝置的“殘影”等顯示不良的缺陷。由本發明的負介電各向異性液晶組合物的聚合物構成的本發明的光學各向異構體中殘留的聚合物少,具有穩定的預傾角,低溫存儲穩定性良好。本發明的液晶顯示器件,製作工藝的生產率提高,並且“殘影”等顯示不良的缺陷減少。 The negative dielectric anisotropy liquid crystal composition of the present invention has excellent polymerization reaction rate and low-temperature storage stability. Further, when the liquid crystal composition of the present invention is used in liquid crystal display devices of modes such as PSA and PSVA, the VHR value after ultraviolet irradiation can be obtained to be improved, thereby reducing/eliminating the defects of poor display such as "image sticking" of the liquid crystal display device. defect. The optical anisotropy of the present invention composed of the polymer of the negative dielectric anisotropy liquid crystal composition of the present invention has little remaining polymer, has a stable pretilt angle, and has good low-temperature storage stability. In the liquid crystal display device of the present invention, the productivity of the manufacturing process is improved, and defects such as "image sticking" and other display defects are reduced.
[液晶組合物] [Liquid Crystal Composition]
本發明的負介電各向異性液晶組合物,其包含:至少一種式I所示化合物;至少一種式Ⅱ所示化合物;以及,至少一種式Ⅲ所示化合物。 The negative dielectric anisotropy liquid crystal composition of the present invention comprises: at least one compound represented by formula I; at least one compound represented by formula II; and at least one compound represented by formula III.
式I中,P1、P2各自獨立地表示聚合性基團,作為聚合性基團,可以列舉出如下的基團:丙烯酸酯基、甲基丙烯酸酯基、乙基丙烯酸酯基、丙基丙烯酸酯基、丁基丙烯酸酯基、戊基丙烯酸酯基、氟代丙烯酸酯基、氟代甲基丙烯酸酯基、氟代乙基丙烯酸酯基、氟代丙基丙烯酸酯基、氟代丁基丙烯酸酯基或氟代戊基丙烯酸酯基。 In formula I, P 1 and P 2 each independently represent a polymerizable group, as the polymerizable group, the following groups can be listed: acrylate group, methacrylate group, ethacrylate group, propyl group Acrylate, Butylacrylate, Amylacrylate, Fluoroacrylate, Fluoromethacrylate, Fluoroethylacrylate, Fluoropropylacrylate, Fluorobutyl Acrylate or fluoropentyl acrylate.
前述的“氟代”可以是單氟取代、多氟取代,也可以是全氟取代。 The aforementioned "fluoro" can be monofluoro, polyfluoro, or perfluoro.
這些基團通過自由基聚合、自由基加成聚合、陽離子聚合、陰離子聚合等而進行固化。尤其在紫外線聚合的情況下,優選P1、P2各自獨立地表示丙烯酸酯基或者甲基丙烯酸酯基。 These groups are cured by radical polymerization, radical addition polymerization, cationic polymerization, anionic polymerization, and the like. Especially in the case of ultraviolet polymerization, it is preferable that P 1 and P 2 each independently represent an acrylate group or a methacrylate group.
式I中,Z1、Z2各自獨立地表示單鍵、碳原子數為1~8的直鏈亞烷基、碳原子數為1~8的直鏈亞烷氧基、碳原子數為2~8的直鏈亞烯基、或者碳原子數為2~8的直鏈亞烯氧基,其中一個或兩個不相鄰的-CH2-任選被-O-取代,任意的H任選被F原子取代。優選地,Z1、Z2各自獨立地表示單鍵、碳原子數為1~5的直鏈亞烷基、碳原子數為1~5的直鏈亞烷氧基、碳原子數為2~5的直鏈亞烯基、或者碳原子數為2~5的直鏈亞烯氧基,其中一個或兩個不相鄰的-CH2-任選被-O-取代,任意的H任選被F原子取代。進一步優選地,Z1、Z2各自獨立地表示單鍵、碳原子數為1~3的直鏈亞烷基、碳原子數為1~3的直鏈亞烷氧基、碳原子數為2~4的直鏈亞烯基、或者碳原子數為2~4的直鏈亞烯氧基,其中一個或兩個不相鄰的-CH2-任選被-O-取代,任意的H任選被F原子取代。 In formula I, Z 1 and Z 2 each independently represent a single bond, a straight-chain alkylene group with 1 to 8 carbon atoms, a straight-chain alkyleneoxy group with 1 to 8 carbon atoms, and a straight-chain alkyleneoxy group with 2 carbon atoms. ~8 straight-chain alkenylene groups, or straight-chain alkenyleneoxy groups with 2~8 carbon atoms, wherein one or two non-adjacent -CH 2 -s are optionally substituted by -O-, and any H is any is substituted by an F atom. Preferably, Z 1 and Z 2 each independently represent a single bond, a straight-chain alkylene group with 1 to 5 carbon atoms, a straight-chain alkyleneoxy group with 1 to 5 carbon atoms, and a straight-chain alkyleneoxy group with 2 to 5 carbon atoms. 5 straight-chain alkenylene groups, or straight-chain alkenyleneoxy groups with 2 to 5 carbon atoms, wherein one or two non-adjacent -CH 2 - are optionally substituted by -O-, and any H is optionally replaced by an F atom. Further preferably, Z 1 and Z 2 each independently represent a single bond, a straight-chain alkylene group with 1 to 3 carbon atoms, a straight-chain alkyleneoxy group with 1 to 3 carbon atoms, and a straight-chain alkyleneoxy group with 2 carbon atoms. ~4 straight-chain alkenylene groups, or straight-chain alkenyleneoxy groups with 2~4 carbon atoms, wherein one or two non-adjacent -CH 2 -s are optionally substituted by -O-, and any H is any is substituted by an F atom.
作為前述的“碳原子數為1~3的直鏈亞烷基”,可以列舉出亞甲基、亞乙基、亞丙基。作為前述的“碳原子數為1~3的直鏈亞烷氧基”,可以列舉出例如亞甲基氧基、亞乙基氧基、亞丙基氧基。作為前述的“碳原子數為2~3的直鏈亞烯基”,有例如亞乙烯基、亞丙烯基、亞丁烯基。作為前述的“碳原子數為2~4的直鏈亞烯氧基”,可以列舉出例如亞乙烯基氧基、亞丙烯基氧基、亞丁烯 基氧基等。這些基團中一個或兩個不相鄰的-CH2-任選被-O-取代,任意的H任選被F原子取代。 Examples of the aforementioned "straight-chain alkylene group having 1 to 3 carbon atoms" include methylene group, ethylene group, and propylene group. Examples of the "straight-chain alkyleneoxy group having 1 to 3 carbon atoms" include methyleneoxy, ethyleneoxy, and propyleneoxy. Examples of the "straight-chain alkenylene group having 2 to 3 carbon atoms" include vinylene, propenylene and butenylene. Examples of the "straight-chain alkenyleneoxy group having 2 to 4 carbon atoms" include vinyleneoxy, propenyleneoxy, butenyleneoxy and the like. One or two non-adjacent -CH 2 -s in these groups are optionally substituted by -O-, and any H is optionally substituted by F atoms.
前述的式I所示化合物中,Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10各自獨立地表示-H、-F、-CH3、-CH2F、-CHF2、-CF3、-C2H5、-OCH3、-OCH2F、-OCHF2、-OCF3或者-OC2H5。其中,Y1、Y2任選相同或者不同。 Among the aforementioned compounds represented by formula I, Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , and Y 10 each independently represent -H, -F, -CH 3. -CH 2 F, -CHF 2 , -CF 3 , -C 2 H 5 , -OCH 3 , -OCH 2 F, -OCHF 2 , -OCF 3 or -OC 2 H 5 . Wherein, Y 1 and Y 2 are optionally the same or different.
本發明的負介電各向異性液晶組合物的一些實施方式中,優選地,式I所示化合物中Y1、Y2各自獨立地表示-H、-F、-CH3、-CF3、-OCH3、-C2H5、-OC2H5或者-OCF3。更優選Y1、Y2各自獨立地表示-H、-F、-CF3、或者-OCF3。進一步優選Y1、Y2各自獨立地為-H、或者、-F。 In some embodiments of the negative dielectric anisotropy liquid crystal composition of the present invention, preferably, Y 1 and Y 2 in the compound represented by formula I each independently represent -H, -F, -CH 3 , -CF 3 , -OCH 3 , -C 2 H 5 , -OC 2 H 5 or -OCF 3 . More preferably, Y 1 and Y 2 each independently represent -H, -F, -CF 3 , or -OCF 3 . More preferably, Y 1 and Y 2 are each independently -H or -F.
本發明的負介電各向異性液晶組合物的一些實施方式中,優選地,式I所示化合物中Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10表示-H或者-F。更優選Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10均為-H。 In some embodiments of the negative dielectric anisotropy liquid crystal composition of the present invention, preferably, Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , Y 10 in the compound represented by formula I Indicates -H or -F. More preferably, Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 8 , Y 9 , and Y 10 are all -H.
本發明的負介電各向異性液晶組合物的一些實施方式中,從獲得更快的聚合反應速率等方面考慮,n優選為0或者1,進一步優選n=1。 In some embodiments of the liquid crystal composition with negative dielectric anisotropy of the present invention, n is preferably 0 or 1, more preferably n=1, in view of obtaining a faster polymerization reaction rate and the like.
本發明的負介電各向異性液晶組合物的一些實施方式中,優選式I所示化合物為選自下述的式I-1~I-57所示化合物組成的組,其中P1、P2、Z1、Z2定義與前述相同。 In some embodiments of the negative dielectric anisotropy liquid crystal composition of the present invention, it is preferred that the compound represented by formula I is selected from the group consisting of compounds represented by the following formulas I-1 to I-57, wherein P 1 , P 2. The definitions of Z 1 and Z 2 are the same as above.
進一步地,前述的式I所示化合物優選選自下述的式IA-1~IA-258所示化合物組成的組。 Further, the compound represented by the aforementioned formula I is preferably selected from the group consisting of compounds represented by the following formulas IA-1 to IA-258.
本發明的液晶組合物中,前述的式II所示化合物的結構式如下所示。 In the liquid crystal composition of the present invention, the structural formula of the compound represented by the aforementioned formula II is as follows.
式II中,R3、R4各自獨立地表示碳原子數為1~5的烷基、碳原子數為1~5的烷氧基、碳原子數為2~5的烯基、或碳原子數為2~5的烯氧基;並且,R3、R4中任意碳原子上的H各自獨立地任選被F取代;環C、環D各自獨立地選自下述的基團組成的組:1,4-亞環己基、環己烯-1,4-二基、1,4-亞苯基、2-氟-1,4-亞苯基、2,3-二氟-1,4-亞苯基、氧雜環己烷-2,5-二基、1,3-二氧雜環己烷-2,5-二基、1-甲基環己烷-1,4-二基、2-甲基環己烷-1,4-二基、2-甲基苯-1,4-二基;p表示0、1、2或者3。 In formula II, R 3 and R 4 each independently represent an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or a carbon atom Alkenyloxy groups with a number of 2 to 5; and, H on any carbon atom in R 3 and R 4 is independently optionally substituted by F; ring C and ring D are each independently selected from the following groups: Groups: 1,4-cyclohexylene, cyclohexene-1,4-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1, 4-phenylene, oxane-2,5-diyl, 1,3-dioxane-2,5-diyl, 1-methylcyclohexane-1,4-diyl base, 2-methylcyclohexane-1,4-diyl, 2-methylbenzene-1,4-diyl; p represents 0, 1, 2 or 3.
作為前述的R3、R4各自獨立地表示的“碳原子數為1~5的烷基”,可以為直鏈烷基、支鏈烷基或者環狀烷基,優選為直鏈烷基。作為這樣的直鏈烷基,可以列舉出例如甲基、乙基、正丙基、正丁基、正戊基。作為支鏈烷基,可以列舉出例如異丙基、異丁基、叔丁基等。作為環狀烷基,可以列舉出環丙基、環丁基、環戊基、甲基環丙基、甲基環丁基等。 The "alkyl group having 1 to 5 carbon atoms" independently represented by the aforementioned R 3 and R 4 may be a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group, and is preferably a straight-chain alkyl group. Examples of such straight-chain alkyl groups include methyl groups, ethyl groups, n-propyl groups, n-butyl groups, and n-pentyl groups. As a branched alkyl group, an isopropyl group, an isobutyl group, a tert-butyl group etc. are mentioned, for example. Cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopropyl, methylcyclobutyl etc. are mentioned as a cyclic alkyl group.
作為前述的R3、R4各自獨立地表示的“碳原子數為1~5的烷氧基”,可以列舉出例如甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、正戊氧基、叔戊氧基等。 Examples of the "alkoxy group having 1 to 5 carbon atoms" each independently represented by R 3 and R 4 above include methoxy, ethoxy, n-propoxy, isopropoxy, n- Butoxy, isobutoxy, n-pentoxy, tert-pentoxy, etc.
作為前述的R3、R4各自獨立地表示的“碳原子數為2~5的烯基”,可以列舉出例如乙烯基、丙烯基、丁烯基、2-甲基丙烯基、1-戊烯基、2-戊烯基、 2-甲基-1-丁烯基、3-甲基-1-丁烯基、2-甲基-2-丁烯基等。 Examples of the "alkenyl group having 2 to 5 carbon atoms" each independently represented by R 3 and R 4 above include vinyl, propenyl, butenyl, 2-methacryl, 1-pentyl Alkenyl, 2-pentenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl and the like.
作為前述的R3、R4各自獨立地表示的“碳原子數為2~5的烯氧基”,可以列舉出例如乙烯氧基、丙烯氧基、丁烯氧基、2-甲基丙烯氧基、1-戊烯氧基、2-戊烯氧基、2-甲基-1-丁烯氧基、3-甲基-1-丁烯氧基、2-甲基-2-丁烯氧基等。 Examples of the "alkenyloxy group having 2 to 5 carbon atoms" each independently represented by R3 and R4 above include ethyleneoxy, propyleneoxy, butenyloxy, 2-methacryloxy, Base, 1-pentenyloxy, 2-pentenyloxy, 2-methyl-1-butenyloxy, 3-methyl-1-butenyloxy, 2-methyl-2-butenyloxy Base etc.
作為前述的式Ⅱ所示的化合物,優選選自下述的式Ⅱ-1至Ⅱ-11所示化合物組成的組。其中,R3、R4的定義與前述相同。 The compound represented by the aforementioned formula II is preferably selected from the group consisting of compounds represented by the following formulas II-1 to II-11. Wherein, the definitions of R 3 and R 4 are the same as above.
(F)表示F或H。 (F) means F or H.
本發明的液晶組合物中,前述的式Ⅲ所示化合物的結構式如下所示。 In the liquid crystal composition of the present invention, the structural formula of the compound represented by the aforementioned formula III is as follows.
式Ⅲ中,R5、R6各自獨立地表示碳原子數為1~5的烷基、碳原子數為1~5的烷氧基、碳原子數為2~5的烯基、或碳原子數為2~5的烯氧基;並且,R5、R6中任意碳原子上的H各自獨立地任選被F取代;Z3表示單鍵或-CH2O-;q、r各自獨立地表示0、1或2;環E、環F各自獨立地選自下述的基團組成的組:1,4-亞環己基、環己烯-1,4-二基、1,4-亞苯基、2-氟-1,4-亞苯基、2,3-二氟-1,4-亞苯基、氧雜環己烷-2,5-二基、1,3-二氧雜環己烷-2,5-二基、1-甲基環己烷-1,4-二基、2-甲基環己烷-1,4-二基、2-甲基苯-1,4-二基。 In formula III, R 5 and R 6 each independently represent an alkyl group with 1 to 5 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, an alkenyl group with 2 to 5 carbon atoms, or a carbon atom The number is 2-5 alkenyloxy groups; and, the H on any carbon atom in R 5 and R 6 is independently optionally substituted by F; Z 3 represents a single bond or -CH 2 O-; q and r are independently means 0, 1 or 2; ring E and ring F are each independently selected from the group consisting of the following groups: 1,4-cyclohexylene, cyclohexene-1,4-diyl, 1,4- Phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, oxane-2,5-diyl, 1,3-dioxo Heterocyclohexane-2,5-diyl, 1-methylcyclohexane-1,4-diyl, 2-methylcyclohexane-1,4-diyl, 2-methylbenzene-1, 4-diradical.
作為前述的R5、R6各自獨立地表示的“碳原子數為1~5的烷基”,可以為直鏈烷基、支鏈烷基或者環狀烷基,優選為直鏈烷基。作為這樣的直鏈烷基,可以列舉出例如甲基、乙基、正丙基、正丁基、正戊基。作為支鏈烷基,可以列舉出例如異丙基、異丁基、叔丁基等。作為環狀烷基,可以列舉出環丙基、環丁基、環戊基、甲基環丙基、甲基環丁基等。 The "alkyl group having 1 to 5 carbon atoms" independently represented by the aforementioned R 5 and R 6 may be a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group, and is preferably a straight-chain alkyl group. Examples of such straight-chain alkyl groups include methyl groups, ethyl groups, n-propyl groups, n-butyl groups, and n-pentyl groups. As a branched alkyl group, an isopropyl group, an isobutyl group, a tert-butyl group etc. are mentioned, for example. Cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopropyl, methylcyclobutyl etc. are mentioned as a cyclic alkyl group.
作為前述的R5、R6各自獨立地表示的“碳原子數為1~5的烷氧基”,可以列舉出例如甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、正戊氧基、叔戊氧基等。 Examples of the "alkoxy group having 1 to 5 carbon atoms" each independently represented by R 5 and R 6 above include methoxy, ethoxy, n-propoxy, isopropoxy, n- Butoxy, isobutoxy, n-pentoxy, tert-pentoxy, etc.
作為前述的R5、R6各自獨立地表示的“碳原子數為2~5的烯基”,可以列舉出例如乙烯基、丙烯基、丁烯基、2-甲基丙烯基、1-戊烯基、2-戊烯基、2-甲基-1-丁烯基、3-甲基-1-丁烯基、2-甲基-2-丁烯基等。 Examples of the "alkenyl group having 2 to 5 carbon atoms" each independently represented by the aforementioned R 5 and R 6 include vinyl, propenyl, butenyl, 2-methacryl, 1-pentyl Alkenyl, 2-pentenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl and the like.
作為前述的R5、R6各自獨立地表示的“碳原子數為2~5的烯氧基”,可以列舉出例如乙烯氧基、丙烯氧基、丁烯氧基、2-甲基丙烯氧基、1-戊烯氧基、2-戊烯氧基、2-甲基-1-丁烯氧基、3-甲基-1-丁烯氧基、2-甲基-2-丁烯氧基等。 Examples of the "alkenyloxy group having 2 to 5 carbon atoms" each independently represented by R 5 and R 6 above include ethyleneoxy, propyleneoxy, butenyloxy, 2-methacryloxy, Base, 1-pentenyloxy, 2-pentenyloxy, 2-methyl-1-butenyloxy, 3-methyl-1-butenyloxy, 2-methyl-2-butenyloxy Base etc.
優選地,前述的式Ⅲ所示的化合物選自下述的式Ⅲ-1至Ⅲ-17所示化合物組成的組。其中,R5、R6的定義與前述相同。 Preferably, the compound represented by the aforementioned formula III is selected from the group consisting of the compounds represented by the following formulas III-1 to III-17. Wherein, the definitions of R 5 and R 6 are the same as above.
前述的負介電各向異性液晶組合物的一個實施方式中,式I所示化合物、式II所示化合物、式III所示化合物例如可以以下述的比例含有:相對於100質量份液晶組合物,所述式I所示化合物為0.001~1質量份,所述式Ⅱ所示化合物為10~60質量份,所述式Ⅲ所示化合物為10~70質量份。 In one embodiment of the foregoing negative dielectric anisotropy liquid crystal composition, the compound represented by formula I, the compound represented by formula II, and the compound represented by formula III can be contained in the following ratio, for example: relative to 100 parts by mass of the liquid crystal composition , the compound represented by the formula I is 0.001-1 parts by mass, the compound represented by the formula II is 10-60 parts by mass, and the compound represented by the formula III is 10-70 parts by mass.
本發明的負介電各向異性液晶組合物的一些實施方式中,還可以含有下述的式Ⅳ-1~Ⅳ-50所示的化合物。 In some embodiments of the negative dielectric anisotropy liquid crystal composition of the present invention, compounds represented by the following formulas IV-1 to IV-50 may also be included.
其中,R1’表示H或者碳原子數為1~8的烷基或碳原子數為2~8的烯基,並且任選4個以下H被F取代; R2’表示H或者碳原子數為1~8的烷基或碳原子數為2~8的烯基,其中一個或兩個不相鄰的-CH2-任選被-O-所取代,並且任選4個以下H被F取代。 Among them, R 1 ' represents H or an alkyl group with 1 to 8 carbon atoms or an alkenyl group with 2 to 8 carbon atoms, and optionally 4 or less Hs are replaced by F; R 2 ' represents H or carbon atoms An alkyl group of 1 to 8 or an alkenyl group with a carbon number of 2 to 8, wherein one or two non-adjacent -CH 2 -s are optionally substituted by -O-, and optionally 4 or less Hs are replaced by F replace.
本發明的負介電各向異性液晶組合物的一些實施方式中,各組分可以以下述的質量配比的方式含有:相對於100質量份負介電各向異性液晶組合物,前述式I所示化合物為0.001~0.3質量份,前述式Ⅱ所示化合物為20~60質量份,前述式Ⅲ所示化合物為20~60質量份,前述式Ⅳ所示的化合物為1~20質量份。 In some embodiments of the negative dielectric anisotropy liquid crystal composition of the present invention, each component may be contained in the following mass ratio: relative to 100 parts by mass of the negative dielectric anisotropy liquid crystal composition, the aforementioned formula I 0.001-0.3 parts by mass of the compound shown, 20-60 parts by mass of the compound shown in the aforementioned formula II, 20-60 parts by mass of the compound shown in the aforementioned formula III, and 1-20 parts by mass of the compound shown in the aforementioned formula IV.
本發明的負介電各向異性液晶組合物的一些實施方式中,還任選含有一種或多種下述的式V-1~V-78所示的化合物:
本發明的負介電各向異性液晶組合物的一些實施方式中,含有前述的式V所示的化合物的情況下,可以按照下述的質量配比含有各組分:相對於100質量份負介電各向異性液晶組合物,前述式I所示化合物為0.001~0.3質量份,前述式Ⅱ所示化合物為20~60質量份,前述式Ⅲ所示化合物為20~60質量份,前述式Ⅳ所示的化合物為1~20質量份,前述式V所示的化合物為1~10質量份。 In some embodiments of the negative dielectric anisotropy liquid crystal composition of the present invention, when containing the compound represented by the aforementioned formula V, each component can be contained according to the following mass ratio: relative to 100 parts by mass of negative Dielectrically anisotropic liquid crystal composition, the compound shown in the aforementioned formula I is 0.001~0.3 parts by mass, the compound shown in the aforementioned formula II is 20~60 parts by mass, the compound shown in the aforementioned formula III is 20~60 parts by mass, the compound shown in the aforementioned formula The compound represented by IV is 1 to 20 parts by mass, and the compound represented by the aforementioned formula V is 1 to 10 parts by mass.
本發明的負介電各向異性液晶組合物中,可選的,還可以加入各種功能的添加劑,這些添加劑可以列舉出例如UV穩定劑、抗氧化劑、手性摻雜劑、聚合起始劑,可以含有它們中的一種,或者多種。 In the negative dielectric anisotropy liquid crystal composition of the present invention, optionally, additives of various functions can also be added, and these additives can enumerate such as UV stabilizers, antioxidants, chiral dopants, polymerization initiators, One or more of them may be included.
[光學各向異構體] [Optical anisotropes]
本發明的光學各向異構體通過使用本發明的負介電各向異性液晶組合物聚合而成。通過在本發明的負介電各向異性液晶組合物取向的狀態下使其中的聚合性化合物聚合而製造得到前述的光學各向異構體。本發明的光學各向異構體具有光學各向異性。這樣的光學各向異構體例如可以如下製造:將本發明的負介電各向異性液晶組合物夾於利用布等對形成有有機薄膜的基板表面進行了摩擦處理的基板間,然後使本發明的液晶組合物聚合。 The optical anisotropy of the present invention is polymerized by using the negative dielectric anisotropy liquid crystal composition of the present invention. The aforementioned optical anisotropy is produced by polymerizing the polymerizable compound in the negative dielectrically anisotropic liquid crystal composition of the present invention in an aligned state. The optical anisotropy of the present invention has optical anisotropy. Such an optical anisotropy can be produced, for example, by sandwiching the negative dielectric anisotropy liquid crystal composition of the present invention between substrates on which the surface of the substrate on which the organic thin film is formed is rubbed with cloth or the like, and then making the composition The inventive liquid crystal composition is polymerized.
另外,通過電場控制取向狀態的情況下,可以使用具有電極層的基板。這種情況下,優選在電極上形成有聚醯亞胺薄膜等有機薄膜。 In addition, when the orientation state is controlled by an electric field, a substrate having an electrode layer can be used. In this case, it is preferable to form an organic thin film such as a polyimide thin film on the electrode.
作為使本發明的液晶組合物聚合的方法,從快速聚合的角度考慮,優選通過照射紫外線、電子射線等活性能量射線進行聚合的方法。在使液晶聚合物夾持於2片基板的狀態下進行聚合的情況下,使至少照射面側的基板對活性能量射線具有透過性。活性能量射線的照射強度及時間等根據需要適宜確定即可。 As a method of polymerizing the liquid crystal composition of the present invention, a method of polymerizing by irradiating active energy rays such as ultraviolet rays and electron beams is preferable from the viewpoint of rapid polymerization. When superposing|polymerizing in the state which sandwiched a liquid crystal polymer between two board|substrates, at least the board|substrate of an irradiation surface side is made transparent to an active energy ray. The irradiation intensity and time of active energy rays may be appropriately determined as needed.
通過這樣的方法製造的本發明的光學各向異構體可以從基板剝離後單獨使用,也可以不剝離而使用。另外,也可將其貼合於其他基板進行使用。 The optical anisotropy of the present invention produced by such a method may be used alone after peeling off the substrate, or may be used without peeling off. In addition, it can also be used by bonding it to other substrates.
[液晶顯示器件] [Liquid crystal display device]
本發明的液晶顯示器件為使用前述的本發明的負介電各向異性液晶組合物,使負介電各向異性液晶組合物中的聚合性化合物聚合而被賦予液晶取向性能的液晶顯示器件。 The liquid crystal display device of the present invention is a liquid crystal display device provided with liquid crystal alignment performance by polymerizing a polymerizable compound in the negative dielectric anisotropy liquid crystal composition using the above-mentioned negative dielectric anisotropy liquid crystal composition of the present invention.
本發明的液晶顯示器件的驅動方式優選為例如PS-VA模式、PVA模式、或者、或者PS-IPS模式。 The driving mode of the liquid crystal display device of the present invention is preferably, for example, PS-VA mode, PVA mode, or, or PS-IPS mode.
實施例 Example
為了更清楚地說明本發明,下面結合優選實施例對本發明做進一步的說明。本領域技術人員應當理解,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. 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.
下述的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(℃),液晶化合物也為液晶單體。 The following preparation methods are conventional methods unless otherwise specified, and the raw materials used can be obtained from public commercial sources unless otherwise specified, and the percentages refer to mass percentages, the temperature is degrees Celsius (°C), and the liquid crystal compound is also a liquid crystal monomer.
實施例及對比例中製備了不同組成的負介電各向異性液晶組合物,其中,各例中所使用的具體化合物的單體結構、用量(質量份)、所得的液晶介質的性能參數測試結果分別如後述的表所示。 Negative dielectric anisotropy liquid crystal compositions of different compositions were prepared in the examples and comparative examples, wherein, the monomer structure, dosage (mass parts) of the specific compounds used in each example, and the performance parameter test of the obtained liquid crystal medium The results are shown in the tables described later.
各實施例中所涉溫度單位為℃,其他符號的具體意義及測試條件如下:G1(mPa.s)表示液晶化合物的旋轉粘滯係數,測定方法:儀器設備INSTEC:ALCT-IR1、測試盒盒厚18微米垂直盒、溫度25℃,簡寫為“G1”;K11為扭曲彈性常數,K33為展曲彈性常數,測試條件為:25℃、INSTEC:ALCT-IR1、18微米垂直盒;△ε表示介電各向異性,△ε=ε∥-ε⊥,其中,ε∥為平行于分子軸的介電常數,ε⊥為垂直于分子軸的介電常數,測試條件:25℃、INSTEC:ALCT-IR1、18微米垂直盒;△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:589nm、25±0.2℃。 The unit of temperature involved in each embodiment is °C, and the specific meanings and test conditions of other symbols are as follows: G1 (mPa.s) represents the rotational viscosity coefficient of the liquid crystal compound, and the measurement method: Instrument and equipment INSTEC: ALCT-IR1, test box 18 micron thick vertical box, temperature 25°C, abbreviated as "G1"; K 11 is the torsional elastic constant, K 33 is the spread elastic constant, the test conditions are: 25°C, INSTEC: ALCT-IR1, 18 micron vertical box; △ ε means dielectric anisotropy, △ε=ε ∥ -ε ⊥ , where ε ∥ is the dielectric constant parallel to the molecular axis, ε ⊥ is the dielectric constant perpendicular to the molecular axis, test conditions: 25℃, INSTEC : ALCT-IR1, 18 micron vertical cell; △n represents 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, test conditions : 589nm, 25±0.2°C.
Tni:向列相-各向同性液體相轉變溫度(℃)。 Tni: nematic phase-isotropic liquid phase transition temperature (° C.).
低溫保存性:將含聚合性化合物的液晶組合物的實施例在-20℃下冷卻240小時後,觀察有無聚合性化合物的析出,作為低溫保存性的指標。將無析出且不會引起亮點等顯示不良的情況標記為○,將存在析出的情況標記為×。 Low-temperature storage stability: After cooling the examples of the liquid crystal composition containing the polymerizable compound at -20°C for 240 hours, the presence or absence of precipitation of the polymerizable compound was observed, which was used as an indicator of low-temperature storage stability. The case where there was no precipitation and did not cause display defects such as bright spots was marked as ◯, and the case where there was precipitation was marked as ×.
聚合反應速率:在紫外線波長主波段=365nm、照度值為2mW/cm2、照射總能量分別為3J、6J、及9J的固定照射條件下,分別照射對比例1以及實施例的液晶組合物,然後通過測量高效液相色譜得到照射前後聚合性單體的濃度,計算比值(照射後聚合性單體的濃度(%)/照射前聚合性單體的濃度(%)),根據公式:反應聚合轉化率=1-(照射後聚合性單體的濃度/照射前聚合性單體的濃度)計算得到聚合反應速率。 Polymerization reaction rate: Under the fixed irradiation conditions of ultraviolet wavelength main band=365nm, illuminance value of 2mW/cm 2 , and total irradiation energy of 3J, 6J, and 9J, respectively, the liquid crystal compositions of Comparative Example 1 and Example were irradiated, Then obtain the concentration of polymerizable monomers before and after irradiation by measuring high-performance liquid chromatography, and calculate the ratio (concentration of polymerizable monomers after irradiation (%)/concentration of polymerizable monomers before irradiation (%)), according to the formula: reaction polymerization Conversion rate=1-(concentration of polymerizable monomer after irradiation/concentration of polymerizable monomer before irradiation) to calculate the polymerization reaction rate.
VHR測試:測試紫外光照射前後的電壓保持率(%),測試條件為60±2℃、電壓為±5V、脈衝寬度為1ms、電壓保持時間16.7ms。測試設備為VHR-AMP01液晶VHR測試儀。VHR惡化使用紫外光365nm波長,照射光強為2.5Mw/cm2進行光輻照,輻照時間為34分鐘。 VHR test: test the voltage retention rate (%) before and after ultraviolet light irradiation, the test condition is 60±2°C, the voltage is ±5V, the pulse width is 1ms, and the voltage retention time is 16.7ms. The test equipment is VHR-AMP01 liquid crystal VHR tester. For the deterioration of VHR, ultraviolet light with a wavelength of 365nm was used for light irradiation with an irradiation intensity of 2.5Mw/cm 2 and an irradiation time of 34 minutes.
實施例中各負介電各向異性液晶組合物的製備方法如下:將各液晶單體按照一定配比稱量後放入不銹鋼燒杯中,將裝有各液晶單體的不銹鋼燒杯置於磁力攪拌儀器上加熱融化,待不銹鋼燒杯中的液晶單體大部份融化後,往不銹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。 The preparation method of each negative dielectric anisotropic liquid crystal composition in the examples is as follows: each liquid crystal monomer is weighed according to a certain ratio and put into a stainless steel beaker, and the stainless steel beaker containing each liquid crystal monomer is placed in a magnetic stirring Heat and melt on the instrument. After most of the liquid crystal monomers in the stainless steel beaker are melted, add a magnetic rotor to the stainless steel beaker, stir the mixture evenly, and obtain the liquid crystal composition after cooling to room temperature.
實施例中所使用的液晶單體的結構用下述代碼表示,液晶環結構、端基、連接基團的代碼表示方法見下表(一)、表(二)。 The structures of liquid crystal monomers used in the examples are represented by the following 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.
舉例:
按照下述的表1~10所示的配比,製備實施例1~8以及對比例1~2的液晶組合物。 According to the proportions shown in the following Tables 1-10, the liquid crystal compositions of Examples 1-8 and Comparative Examples 1-2 were prepared.
將前述製備的實施例以及對比例的液晶組合物填充於液晶顯示器兩基板間進行性能測試,得到的測試結果如下表所示。需要說明的是,對比例2中不含有聚合性單體,因此,沒有進行聚合反應速率測試。 The liquid crystal compositions of the above-mentioned examples and comparative examples were filled between the two substrates of the liquid crystal display for performance testing, and the test results obtained are shown in the table below. It should be noted that Comparative Example 2 does not contain a polymerizable monomer, therefore, no polymerization rate test was performed.
如上述的表11所示,實施例1~8的液晶組合物與對比例1的液晶組合物相比,實施例1~8中的含有聚合性單體化合物的組合物經紫外線(UV)照射能量3J~9J後,其聚合反應速率均快於對比例1,可以縮短現有量產聚合物穩定排列制程時間。 As shown in the above-mentioned Table 11, compared with the liquid crystal composition of Examples 1 to 8 and the liquid crystal composition of Comparative Example 1, the composition containing the polymerizable monomer compound in Examples 1 to 8 was irradiated with ultraviolet rays (UV). After the energy is 3J~9J, the polymerization reaction rate is faster than that of Comparative Example 1, which can shorten the process time for the stable alignment of existing mass-produced polymers.
進而,對在實施例1~實施例8中所獲得的液晶顯示器件中殘存的聚合性化合物的量進行確認,結果殘留量充分少。 Furthermore, the amount of the polymerizable compound remaining in the liquid crystal display devices obtained in Examples 1 to 8 was confirmed, and the remaining amount was sufficiently small.
另外,與比較例1相比,實施例1~8的液晶組合物顯示出更優異的低溫保存性。 Moreover, compared with the comparative example 1, the liquid crystal composition of Examples 1-8 showed the more excellent low-temperature storage property.
根據以上確認到,本發明的液晶組合物在用於PS-VA液晶顯示器件、PS-VA顯示器件等時能夠獲得良好的低溫保存性、較快的聚合速率。 From the above, it was confirmed that when the liquid crystal composition of the present invention is used in PS-VA liquid crystal display devices, PS-VA display devices, etc., it can obtain good low-temperature storage stability and a relatively fast polymerization rate.
進一步,實施例1~8的組合物的經紫外線(UV)照射後的VHR比含有現有技術中使用的聚合性單體化合物的對比例1的組合物更高,這也說明了實施例1~8的液晶組合物具有高電壓保持率等性能,具有較高的可靠性,不容易發生預傾角的變化導致的顯示不良。 Further, the VHR of the compositions of Examples 1-8 after ultraviolet (UV) irradiation is higher than that of the composition of Comparative Example 1 containing the polymerizable monomer compound used in the prior art, which also shows that the compositions of Examples 1-8 The liquid crystal composition of 8 has properties such as a high voltage retention rate, has high reliability, and is not prone to display defects caused by changes in the pretilt angle.
本發明雖未窮盡要求保護的所有液晶混合物,但是本領域技術人員可以預見的是,在已公開的上述實施例基礎上,僅結合自身的專業嘗試即能以類似的方法得到其他同類液晶材料而不需要付出創造性勞動。此處由於篇幅有限,僅列舉代表性的實施方式。 Although the present invention does not exhaust all the liquid crystal mixtures claimed for protection, those skilled in the art can foresee that, on the basis of the above-mentioned disclosed embodiments, other liquid crystal materials of the same type can be obtained in a similar way only in combination with their own professional attempts. No creative labor is required. Due to limited space, only representative implementations are listed here.
Claims (11)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210034488.4 | 2022-01-13 | ||
CN202210034488.4A CN114350380B (en) | 2022-01-13 | 2022-01-13 | Negative dielectric anisotropic liquid crystal composition, optical anisotropic isomer and liquid crystal display device |
Publications (2)
Publication Number | Publication Date |
---|---|
TWI797047B true TWI797047B (en) | 2023-03-21 |
TW202328405A TW202328405A (en) | 2023-07-16 |
Family
ID=81109048
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW111131710A TWI797047B (en) | 2022-01-13 | 2022-08-23 | Negative dielectric anisotropy liquid crystal composition, optical anisotropy and liquid crystal display device |
Country Status (3)
Country | Link |
---|---|
CN (1) | CN114350380B (en) |
TW (1) | TWI797047B (en) |
WO (1) | WO2023134596A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114394953A (en) * | 2022-01-13 | 2022-04-26 | 烟台显华科技集团股份有限公司 | Polymerizable compound, composition, and liquid crystal display device |
CN114350380B (en) * | 2022-01-13 | 2024-08-16 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropic liquid crystal composition, optical anisotropic isomer and liquid crystal display device |
CN115305096B (en) * | 2022-09-01 | 2024-04-26 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropic liquid crystal composition and liquid crystal display device |
CN115287083B (en) * | 2022-09-01 | 2024-03-01 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropic liquid crystal composition and liquid crystal display device |
CN116083091B (en) * | 2022-12-26 | 2024-07-05 | 北京八亿时空液晶科技股份有限公司 | High-contrast negative liquid crystal composition and application thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111592517A (en) * | 2019-02-20 | 2020-08-28 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound containing dibenzofuran structure and preparation method and application thereof |
CN111592890A (en) * | 2019-02-20 | 2020-08-28 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound and preparation method and application thereof |
TW202138546A (en) * | 2020-04-09 | 2021-10-16 | 大陸商北京八億時空液晶科技股份有限公司 | Liquid crystal compound having negative dielectric anisotropy, and application thereof |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5693865B2 (en) * | 2010-03-24 | 2015-04-01 | 株式会社Adeka | Liquid crystal composition containing polymerizable compound and liquid crystal display device using the liquid crystal composition |
WO2013011893A1 (en) * | 2011-07-20 | 2013-01-24 | Dic株式会社 | (meth)acrylate compound, radical-polymerizable composition, cured product and plastic lens |
JP5828906B2 (en) * | 2013-02-15 | 2015-12-09 | Dic株式会社 | Liquid crystal composition and liquid crystal display device using the same |
CN104342167B (en) * | 2013-08-02 | 2016-12-28 | 江苏和成显示科技股份有限公司 | Polymerizable liquid crystal compound and display device thereof |
JP6202309B2 (en) * | 2013-08-23 | 2017-09-27 | Dic株式会社 | Liquid crystal composition and liquid crystal display device using the same |
KR20160058112A (en) * | 2013-10-08 | 2016-05-24 | 디아이씨 가부시끼가이샤 | Nematic liquid crystal composition and liquid crystal display element using same |
JP6745814B2 (en) * | 2015-11-10 | 2020-08-26 | Dic株式会社 | Nematic liquid crystal composition and liquid crystal display device using the same |
JP2021028299A (en) * | 2017-11-30 | 2021-02-25 | Jnc株式会社 | Compound having dibenzothiophene ring, liquid crystal composition and liquid crystal display element |
CN108084029B (en) * | 2017-12-20 | 2021-08-31 | 石家庄诚志永华显示材料有限公司 | Liquid crystal composition and liquid crystal display element |
JP7070122B2 (en) * | 2017-12-22 | 2022-05-18 | Dic株式会社 | Polymerizable compounds and liquid crystal compositions containing them |
CN110295046A (en) * | 2018-03-23 | 2019-10-01 | 石家庄诚志永华显示材料有限公司 | Liquid-crystal composition |
CN110343531A (en) * | 2018-04-02 | 2019-10-18 | 北京八亿时空液晶科技股份有限公司 | A kind of dibenzothiophenes class can poly- property compound and its application |
CN110386917A (en) * | 2018-04-16 | 2019-10-29 | 北京八亿时空液晶科技股份有限公司 | A kind of novel dibenzothiophenes class can poly- property compound and its application |
CN110577832A (en) * | 2018-06-11 | 2019-12-17 | 石家庄诚志永华显示材料有限公司 | negative dielectric anisotropy liquid crystal composition, liquid crystal display element and liquid crystal display |
CN108865177B (en) * | 2018-08-13 | 2020-06-09 | 石家庄晶奥量新材料有限公司 | Liquid-crystalline medium and use in liquid-crystal displays |
CN110922983A (en) * | 2018-09-20 | 2020-03-27 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition containing dibenzothiophene polymerizable monomer and application thereof |
CN109503534A (en) * | 2018-12-19 | 2019-03-22 | 西安瑞立电子材料有限公司 | Polymerizable compound and liquid crystal media |
CN109943346A (en) * | 2019-03-05 | 2019-06-28 | 曹亚宁 | Compound, liquid crystal media, liquid crystal display device and electronic equipment |
JP2021051281A (en) * | 2019-09-20 | 2021-04-01 | Jnc株式会社 | Horizontal alignment type liquid crystal display element, liquid crystal composition, display device, and method of manufacturing horizontal alignment type liquid crystal display element |
CN112980464A (en) * | 2019-12-30 | 2021-06-18 | 石家庄诚志永华显示材料有限公司 | Negative liquid crystal composition, liquid crystal display element and liquid crystal display |
CN112940755A (en) * | 2019-12-30 | 2021-06-11 | 石家庄诚志永华显示材料有限公司 | Liquid crystal composition, liquid crystal display element and liquid crystal display |
CN113493693A (en) * | 2020-04-01 | 2021-10-12 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition containing polymerizable compound and application thereof |
KR20210125922A (en) * | 2020-04-09 | 2021-10-19 | 메르크 파텐트 게엠베하 | Liquid-crystalline medium |
CN112143508B (en) * | 2020-10-09 | 2022-03-18 | 烟台显华科技集团股份有限公司 | Liquid crystal compound with negative dielectric anisotropy, liquid crystal composition and liquid crystal display device |
JP2022065315A (en) * | 2020-10-15 | 2022-04-27 | Dic株式会社 | Polymerizable compound and liquid crystal composition containing the same |
CN113403088B (en) * | 2021-06-17 | 2022-12-30 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropy liquid crystal composition and liquid crystal display device |
CN113736479B (en) * | 2021-07-23 | 2023-12-15 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropic liquid crystal composition and liquid crystal display device |
CN113512430B (en) * | 2021-08-17 | 2023-05-02 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropic liquid crystal composition and liquid crystal display device |
CN114394953A (en) * | 2022-01-13 | 2022-04-26 | 烟台显华科技集团股份有限公司 | Polymerizable compound, composition, and liquid crystal display device |
CN114350380B (en) * | 2022-01-13 | 2024-08-16 | 烟台显华科技集团股份有限公司 | Negative dielectric anisotropic liquid crystal composition, optical anisotropic isomer and liquid crystal display device |
-
2022
- 2022-01-13 CN CN202210034488.4A patent/CN114350380B/en active Active
- 2022-08-23 TW TW111131710A patent/TWI797047B/en active
-
2023
- 2023-01-08 WO PCT/CN2023/071140 patent/WO2023134596A1/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111592517A (en) * | 2019-02-20 | 2020-08-28 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound containing dibenzofuran structure and preparation method and application thereof |
CN111592890A (en) * | 2019-02-20 | 2020-08-28 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound and preparation method and application thereof |
TW202138546A (en) * | 2020-04-09 | 2021-10-16 | 大陸商北京八億時空液晶科技股份有限公司 | Liquid crystal compound having negative dielectric anisotropy, and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN114350380A (en) | 2022-04-15 |
CN114350380B (en) | 2024-08-16 |
WO2023134596A1 (en) | 2023-07-20 |
TW202328405A (en) | 2023-07-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI797047B (en) | Negative dielectric anisotropy liquid crystal composition, optical anisotropy and liquid crystal display device | |
TWI797046B (en) | Negative dielectric anisotropy liquid crystal composition, optical anisotropy and liquid crystal display device | |
KR100670983B1 (en) | Polymerizable compound, polymerizable liquid crystal composition containing the compound, and optical anisotropic body | |
CN103834414B (en) | Liquid crystal medium, stabilizing method thereof and liquid crystal display | |
TWI607078B (en) | Liquid-crystalline medium, method for the stabilisation thereof, and liquid-crystal display | |
JP6248557B2 (en) | Liquid crystalline compound having vinyloxy, liquid crystal composition, and liquid crystal display device | |
JP7414743B2 (en) | Thiophene compounds, liquid crystal media, and liquid crystal displays containing the same | |
CN111732569B (en) | Liquid crystalline compound having dibenzothiophene ring, liquid crystal composition, and liquid crystal display element | |
CN110527522B (en) | Liquid crystal compound, liquid crystal composition and liquid crystal display device | |
KR20190003393A (en) | Liquid-crystalline medium and liquid-crystal display comprising the same | |
KR20200007697A (en) | Thiophene compound, liquid-crystalline medium and liquid-crystal display comprising the same | |
TW201606057A (en) | Nematic liquid crystal composition and liquid crystal display element using same | |
TW201443204A (en) | Liquid crystal compound having xanthene skeleton and exhibiting negative dielectric anisotropy, liquid crystal composition, and LCD device | |
KR101982119B1 (en) | Positive dielectric liquid crystal composition | |
CN109181713A (en) | A kind of liquid-crystal composition and its application | |
JPWO2019167640A1 (en) | Polymerizable compound, liquid crystal composition and liquid crystal display device using the same | |
WO2022068499A1 (en) | Thiophene-containing liquid crystal compound, preparation method therefor and use thereof | |
TW201806984A (en) | Polymerizable compound and liquid crystal composition using same | |
JP2019533741A (en) | Liquid crystal medium, liquid crystal compound, and liquid crystal display including the same | |
CN109181712B (en) | Benzofuran liquid crystal compound with difluoromethyl ether bridge bond and composition thereof | |
JP6701611B2 (en) | Liquid crystal composition and liquid crystal display device | |
TW202307181A (en) | Positive dielectric anisotropy liquid crystal compound, liquid crystal composition and liquid crystal display device | |
JP2018002670A (en) | Liquid crystal compound | |
TW202106864A (en) | Polymerizable liquid crystal composition and liquid crystal display element, and compound | |
WO2020121639A1 (en) | Polymerizable compound-containing liquid crystal composition, liquid crystal display device, and polymerizable compound |