CN114196422A - 液晶组合物及其液晶显示器件 - Google Patents
液晶组合物及其液晶显示器件 Download PDFInfo
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- CN114196422A CN114196422A CN202010981910.8A CN202010981910A CN114196422A CN 114196422 A CN114196422 A CN 114196422A CN 202010981910 A CN202010981910 A CN 202010981910A CN 114196422 A CN114196422 A CN 114196422A
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- Prior art keywords
- liquid crystal
- crystal composition
- compound
- carbon atoms
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 151
- 239000000203 mixture Substances 0.000 title claims abstract description 117
- 150000001875 compounds Chemical class 0.000 claims description 86
- 125000004432 carbon atom Chemical group C* 0.000 claims description 75
- 125000000217 alkyl group Chemical group 0.000 claims description 50
- 125000003342 alkenyl group Chemical group 0.000 claims description 22
- 125000003545 alkoxy group Chemical group 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 7
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 19
- 230000003287 optical effect Effects 0.000 abstract description 11
- 230000004044 response Effects 0.000 abstract description 9
- 238000012360 testing method Methods 0.000 description 32
- 238000009472 formulation Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- 239000004611 light stabiliser Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000000149 argon plasma sintering Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- 125000005449 2-fluoro-1,4-phenylene group Chemical group [H]C1=C([*:2])C([H])=C(F)C([*:1])=C1[H] 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 biphenylyl structure Chemical group 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000262 haloalkenyl group Chemical group 0.000 description 1
- 125000005291 haloalkenyloxy group Chemical group 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
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- C09K19/3001—Cyclohexane rings
- C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
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- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
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- G—PHYSICS
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- 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
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- C09K2019/122—Ph-Ph
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- C09K2019/181—Ph-C≡C-Ph
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- C09K2019/2035—Ph-COO-Ph
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Abstract
本发明提供一种液晶组合物及其液晶显示器件,所述液晶组合物包含至少一种通式I的化合物和至少一种通式II的化合物。该液晶组合物在维持适当的清亮点、适当的光学各向异性和适当的介电各向异性绝对值的情况下,还具有较大的垂直介电(ε⊥)、较大的垂直介电与介电绝对值的比值(ε⊥/|Δε|)、较大的Kave值和较高的透过率,使得包含其的液晶显示器件在维持适当的可使用的温度范围和适当的阈值电压的情况下,具有较好的对比度、较快的响应速度和较好的透过率。
Description
技术领域
本发明涉及液晶领域,具体涉及液晶组合物和包含所述液晶组合物的液晶显示器件。
背景技术
液晶显示元件可以在钟表、电子计算器为代表的各种家庭用电器、测定机器、汽车用面板、文字处理机、电脑、打印机、电视等中使用。根据显示模式的类型,液晶显示元件可以分为PC(phase change,相变)、TN(twist nematic,扭曲向列)、STN(super twistednematic,超扭曲向列)、ECB(electrically controlled birefringence,电控双折射)、OCB(optically compensated bend,光学补偿弯曲)、IPS(in-plane switching,共面转变)、VA(vertical alignment,垂直配向)等类型。根据元件的驱动方式,液晶显示元件可以分为PM(passive matrix,被动矩阵)型和AM(active matrix,主动矩阵)型。PM分为静态(static)和多路(multiplex)等类型。AM分为TFT(thin film transistor,薄膜晶体管)、MIM(metalinsulator metal,金属-绝缘层-金属)等类型。TFT的类型包含非晶硅(amorphoussilicon)和多晶硅(polycrystal silicon)。后者根据制造工艺分为高温型和低温型。根据光源的类型,液晶显示元件可以分为利用自然光的反射型、利用背景光的透过型、以及利用自然光和背光两种光源的半透过型。
液晶显示元件含有具有向列相的液晶组合物,该组合物具有适当的特性。借由提高该组合物的特性,可获得具有良好特性的AM元件。组合物特性和AM元件特性的关联归纳于下表1中。
表1.组合物的特性与AM元件的特性
编号 | 组合物的特性 | AM元件的特性 |
1 | 向列相的温度范围广 | 可使用的温度范围广 |
2 | 粘度小 | 响应时间短 |
3 | 光学各向异性适当 | 对比度大 |
4 | 正或负的介电各向异性的绝对值大 | 阈值电压低、消耗电力小、对比度大 |
5 | 比电阻大 | 电压保持率大、对比率大 |
6 | 对紫外线及热稳定 | 寿命长 |
7 | 弹性常数大 | 对比度大、响应时间短 |
在液晶显示器件的应用中,对比度对视觉效果的影响非常关键。一般来说,对比度越大,图像越清晰醒目,色彩也越鲜明艳丽;而如果对比度小,则整个画面都灰蒙蒙的。高对比度对于图像的清晰度、细节表现、灰度层次表现都有很大的帮助。高对比度产品在黑白反差、清晰度、完整性等方面都具有优势。对比度对于动态视频显示效果的影响也较大,由于动态图像中明暗转换比较快,因此对比度越高,人的眼睛越容易分辨出这样的转换过程。
根据IPS模式的透过率公式Tr∝|Δε|/ε⊥(其中,Tr表示透过率,“∝”表示“反比例”关系,Δε表示介电各向异性,ε⊥表示垂直于分子轴方向的介电常数),若要提高液晶介质的透过率,可以试图降低液晶介质的Δε,但一般同一款产品的驱动电压的调整范围有限。另外,液晶分子在边缘电场垂直分量的作用下会向Z轴方向发生倾斜,导致其光学各向异性发生变化,根据公式(其中,χ即为液晶层光轴与偏光片光轴之间的夹角,Δn为光学各向异性,d为液晶盒的间距,λ为波长)可知,有效Δn*d会影响Tr,若要提升液晶的透过率,也可以考虑增大Δn*d,但每款产品的延迟量设计都是固定的。
另一方面,本领域技术人员基于传统的IPS-LCD漏光性能测试发现,造成液晶显示器件漏光问题的主要原因是:光散射(LC scattering)、摩擦均匀性(rubbinguniformity)、彩色滤光膜漏光(CF/TFT scattering)以及极化能力(polarize ability),其中,光散射在漏光性能的影响因素中占比达63%。
根据如下关系式:LC(其中,d表示液晶盒的间距,Δn表示光学各向异性,ne表示非寻常光折射率,no表示寻常光折射率,Kave表示平均弹性常数K11为斜展弹性常数,K22为扭曲弹性常数,K33为弯曲弹性常数)。由该关系式可知,LC Scattering与Kave成反比关系,在提高Kave的情况下,可以降低液晶材料的漏光。
此外,对比度(CR)与亮度(L)的关系式如下:
CR=L255/L0×100%,
其中,L255为开态亮度,L0为关态亮度。可以看出,显著影响CR的应该是L0的变化。在关态下,L0与液晶分子的介电性能无关,而与液晶材料本身的LC Scattering相关;LCScattering愈小,L0也愈小,CR从而也就会显著提高。
鉴于上述情况,常见的用来提高对比度和透过率的方式可以从如下两方面考虑:(1)保持液晶组合物的介电各向异性Δε不变,通过提高ε⊥可以有效地提高透过率;(2)提高液晶组合物的平均弹性常数Kave的值,使液晶分子的有序度更好、漏光更少,从而使透过率提高。
从液晶材料的制备角度出发,液晶材料的各项性能互相牵制影响,某项性能指标的提升可能会使其他性能发生变化。因此,制备各方面性能都合适的液晶材料往往需要创造性劳动。
发明内容
发明目的:本发明的目的在于提供一种液晶组合物,所述液晶组合物在维持适当的清亮点、适当的光学各向异性和适当的介电各向异性绝对值的情况下,还具有较大的垂直介电(ε⊥)、较大的垂直介电与介电绝对值的比值(ε⊥/|Δε|)、较大的Kave值和较高的透过率。
本发明的目的还在于提供一种包含上述液晶组合物的液晶显示器件。
技术方案:为了实现以上发明目的,本发明提供一种液晶组合物,所述液晶组合物包含:
至少一种通式I的化合物
至少一种通式II的化合物
其中,
R1表示含有2-12个碳原子的直链或支链的烯基、或含有2-11个碳原子的直链或支链的烯氧基;
R2表示含有1-12个碳原子的直链或支链的烷基、所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH2-可分别独立地被-CH=CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代;
R3和R4各自独立地表示含有1-11个碳原子的直链或支链的烷氧基;
L1、L2、L3和L4各自独立地表示-F、-Cl、-CF3、-OCF3或-CHF2;并且
n1表示0或1。
在本发明的一些实施方案中,L1和L2均为-F。
在本发明的一些实施方案中,优选地,R2表示含有1-10个碳原子的直链或支链的烷基、含有1-9个碳原子的直链或支链的烷氧基、或含有2-10个碳原子的直链或支链的烯基;进一步优选地,R2表示含有1-8个碳原子的直链或支链的烷基、含有1-7个碳原子的直链或支链的烷氧基、或含有2-8个碳原子的直链或支链的烯基。
在本发明的一些实施方案中,通式I的化合物选自由如下化合物组成的组:
其中,
a表示0-4的整数;并且
b表示1-4的整数。
在本发明的一些实施方案中,通式I的化合物占液晶组合物的重量百分比为0.1%-50%,例如,0.1%、0.5%、1%、2%、4%、6%、8%、10%、11%、12%、13%、14%、15%、16%、17%、18%、20%、22%、24%、25%、26%、28%、30%、32%、34%、35%、36%、38%、40%、42%、44%、46%、48%、50%;优选地,通式I的化合物占液晶组合物的重量百分比为0.5%-40%。
在本发明的一些实施方案中,液晶组合物包含至少两种通式I的化合物。
在本发明的一些实施方案中,液晶组合物包含至少一种通式I-1的化合物和/或通式I-2的化合物。
在本发明的一些实施方案中,在介电各向异性绝对值处于相同或近似水平的情况下,为了获得较大的垂直介电(ε⊥)、较大的垂直介电与介电绝对值的比值(ε⊥/|Δε|)、较大的Kave值和较高的透过率,液晶组合物优选包含至少一种通式I-2的化合物;特别优选包含至少一种a=0的通式I-2的化合物。
在本发明的一些实施方案中,L3和L4均为-F。
在本发明的一些实施方案中,在介电各向异性绝对值处于相同或近似水平的情况下,为了获得较大的垂直介电(ε⊥)、较大的垂直介电与介电绝对值的比值(ε⊥/|Δε|)、较大的Kave值和较高的透过率,液晶组合物优选包含至少两种通式II的化合物。
在本发明的一些实施方案中,在介电各向异性绝对值处于相同或近似水平的情况下,为了获得较大的垂直介电(ε⊥)、较大的垂直介电与介电绝对值的比值(ε⊥/|Δε|)、较大的Kave值和较高的透过率,液晶组合物优选包含至少一种n1表示0的通式II的化合物。
在本发明的一些实施方案中,在介电各向异性绝对值处于相同或近似水平的情况下,为了获得较大的垂直介电(ε⊥)、较大的垂直介电与介电绝对值的比值(ε⊥/|Δε|)、较大的Kave值和较高的透过率,液晶组合物优选包含至少一种a表示0的通式I-2的化合物和至少一种n1表示0的通式II的化合物。
在本发明的一些实施方案中,在介电各向异性绝对值处于相同或近似水平的情况下,为了获得较大的垂直介电(ε⊥)、较大的垂直介电与介电绝对值的比值(ε⊥/|Δε|)、较大的Kave值和较高的透过率,液晶组合物优选包含至少一种n1表示1的通式II的化合物。
在本发明的一些实施方案中,在介电各向异性绝对值处于相同或近似水平的情况下,为了获得较大的垂直介电(ε⊥)、较大的垂直介电与介电绝对值的比值(ε⊥/|Δε|)、较大的Kave值和较高的透过率,液晶组合物优选包含至少一种a表示0的通式I-2的化合物和至少一种n1表示1的通式II的化合物。
在本发明的一些实施方案中,在介电各向异性绝对值处于相同或近似水平的情况下,为了获得较大的垂直介电(ε⊥)、较大的垂直介电与介电绝对值的比值(ε⊥/|Δε|)、较大的Kave值和较高的透过率,液晶组合物优选包含至少一种n1表示0的通式II的化合物和至少一种n1表示1的通式II的化合物。
在本发明的一些实施方案中,通式II的化合物占液晶组合物的重量百分比为0.1%-60%,例如,0.1%、0.5%、1%、2%、4%、6%、8%、10%、11%、12%、13%、14%、15%、16%、17%、18%、20%、22%、24%、25%、26%、28%、30%、32%、34%、35%、36%、38%、40%、42%、44%、46%、48%、50%、50%、52%、54%、56%、58%、60%;优选地,通式II的化合物占液晶组合物的重量百分比为0.5%-40%。
在本发明的一些实施方案中,本发明的液晶组合物还包含至少一种通式M的化合物
其中,
RM1和RM2各自独立地表示含有1-12个碳原子的直链或支链的烷基、 所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH2-可分别独立地被-CH=CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代;
ZM1和ZM2各自独立地表示单键、-CO-O-、-O-CO-、-CH2O-、-OCH2-、-C≡C-、-CH=CH-、-CH2CH2-或-(CH2)4-;并且
本发明中的烯基优选地选自式(V1)至式(V9)中的任一者所表示的基团,特别优选为式(V1)、式(V2)、式(V8)或式(V9)。式(V1)至式(V9)所表示的基团如下所示:
其中,*表示所键结的环结构中的碳原子。
本发明中的烯氧基优选地选自式(OV1)至式(OV9)中的任一者所表示的基团,特别优选为式(OV1)、式(OV2)、式(OV8)或式(OV9)。式(OV1)至式(OV9)所表示的基团如下所示:
其中,*表示所键结的环结构中的碳原子。
在本发明的一些实施方案中,通式M的化合物选自由如下化合物组成的组:
在本发明的一些实施方案中,通式M的化合物占液晶组合物的重量百分比为1%-80%,例如,1%、2%、4%、6%、8%、10%、11%、12%、13%、14%、15%、16%、17%、18%、20%、22%、24%、25%、26%、28%、30%、32%、34%、35%、36%、38%、40%、42%、44%、46%、48%、50%、52%、54%、56%、58%、60%、62%、64%、66%、68%、70%、72%、74%、76%、78%、80%;优选地,通式M的化合物占液晶组合物的重量百分比为20%-70%。
在本发明的一些实施方案中,在介电各向异性绝对值处于相同或近似水平的情况下,为了获得较大的垂直介电(ε⊥)、较大的垂直介电与介电绝对值的比值(ε⊥/|Δε|)、较大的Kave值和较高的透过率,液晶组合物优选包含至少一种一侧端基为烯基的通式M-12的化合物。
在本发明的一些实施方案中,通式M的化合物的含量必须视低温下的溶解性、转变温度、电可靠性、双折射率、工艺适应性、滴下痕迹、烧屏、介电各向异性等所需的性能而适当进行调整。
关于通式M的化合物的含量,在需要保持本发明的液晶组合物的粘度较低、且响应时间较短时,优选其下限值较高且上限值较高;进一步地,在需要保持本发明的液晶组合物的清亮点较高、且温度稳定性良好时,优选其下限值较高且上限值较高;在为了将驱动电压保持为较低、且使介电各向异性的绝对值较大时,优选其下限值变低且上限值变低。
在本发明的一些实施方案中,RM1和RM2优选各自独立地为含有1-10个碳原子的直链或支链的烷基、含有1-9个碳原子的直链或支链的烷氧基、或含有2-10个碳原子的直链或支链的烯基;RM1和RM2进一步优选各自独立地为含有1-8个碳原子的直链或支链的烷基、含有1-7个碳原子的直链或支链的烷氧基、或含有2-8个碳原子的直链或支链的烯基;RM1和RM2再进一步优选各自独立地为含有1-5个碳原子的直链或支链的烷基、含有1-4个碳原子的直链或支链的烷氧基、或含有2-5个碳原子的直链或支链的烯基。
在本发明的一些实施方案中,RM1和RM2优选各自独立地为含有2-8个碳原子的直链的烯基;进一步优选各自独立地为含有2-5个碳原子的直链的烯基。
在本发明的一些实施方案中,优选地,RM1和RM2中的任一者为含有2-5个碳原子的直链的烯基,而另一者为含有1-5个碳原子的直链的烷基。
在本发明的一些实施方案中,RM1和RM2优选各自独立地为含有1-8个碳原子的直链的烷基、或含有1-7个碳原子的直链的烷氧基;进一步优选各自独立地为含有1-5个碳原子的直链的烷基、或含有1-4个碳原子的直链的烷氧基。
在本发明的一些实施方案中,优选地,RM1和RM2中的任一者为含有1-5个碳原子的直链的烷基,而另一者为含有1-5个碳原子的直链的烷基、或含有1-4个碳原子的直链的烷氧基;进一步优选地,RM1和RM2两者均各自独立地为含有1-5个碳原子的直链的烷基。
在本发明的一些实施方案中,在重视可靠性时,优选RM1和RM2均为烷基;在重视降低化合物的挥发性的情形时,优选RM1和RM2均为烷氧基;在重视粘度降低的情形时,优选RM1和RM2中至少一者为烯基。
在本发明的一些实施方案中,本发明的液晶组合物还包含至少一种通式III的化合物:
其中,
R5和R6各自独立地表示含有1-12个碳原子的直链或支链的烷基、 所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH2-可分别独立地被-CH=CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代;
T1、T2、T3、T4、T5和T6各自独立地表示-H、含有1-3个碳原子的烷基或卤素;并且
在本发明的一些实施方案中,通式III的化合物选自由如下化合物组成的组:
在本发明的一些实施方案中,优选地,R5和R6各自独立地表示含有1-10个碳原子的直链或支链的烷基、含有1-9个碳原子的直链或支链的烷氧基、或含有2-10个碳原子的直链或支链的烯基;进一步优选地,R5和R6各自独立地表示含有1-8个碳原子的直链或支链的烷基、含有1-7个碳原子的直链或支链的烷氧基、或含有2-8个碳原子的直链或支链的烯基;再进一步优选地,R5和R6各自独立地表示含有1-5个碳原子的直链或支链的烷基、含有1-4个碳原子的直链或支链的烷氧基、或含有2-5个碳原子的直链或支链的烯基。
在本发明的一些实施方案中,通式III的化合物占液晶组合物的重量百分比为0%-30%,例如,0%、0.1%、1%、2%、4%、6%、8%、10%、11%、12%、13%、14%、15%、16%、17%、18%、20%、22%、24%、25%、26%、28%、30%;优选地,通式III的化合物占液晶组合物的重量百分比为0.1%-25%。
在本发明的一些实施方案中,本发明的液晶组合物还包含至少一种通式N的化合物
其中,
RN1和RN2各自独立地表示含有1-12个碳原子的直链或支链的烷基、 所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH2-可分别独立地被-CH=CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代;
环和环各自独立地表示其中中的一个或更多个-CH2-可被-O-替代,一个或更多个环中单键可被双键替代,其中中的一个或更多个-H可分别独立地被-F、-Cl或-CN取代,一个或更多个环中-CH=可被-N=替代;
ZN1和ZN2各自独立地表示单键、-CO-O-、-O-CO-、-CH2O-、-OCH2-、-CH=CH-、-C≡C-、-CH2CH2-、-CF2CF2-、-(CH2)4-、-CF2O-或-OCF2-;
LN1和LN2各自独立地表示-F、-Cl、-CF3、-OCF3或-CHF2;
LN3和LN4各自独立地表示-H、含有1-3个碳原子的烷基或卤素;
当nN1+nN2=0时,或者nN1+nN2=1,且通式N的化合物为双联苯结构时,RN1和RN2不为烷氧基;
当nN1表示2,nN2表示0,且通式N的化合物中存在双联苯结构时,RN1不为烯基或烯氧基;并且
当nN1+nN2=3时,通式N的化合物不为三联苯结构。
在本发明的一些实施方案中,通式N的化合物选自由如下化合物组成的组:
其中,
RN1’和RN2’各自独立的表示含有1-8个碳原子的直链或支链的烷基、或含有2-8个碳原子的直链或支链的烯基;并且
RN1”表示含有1-8个碳原子的直链或支链的烷基、或含有1-7个碳原子的直链或支链的烷氧基。
在本发明的一些实施方案中,通式N的化合物占液晶组合物的重量百分比为0.1%-60%,例如,0.1%、1%、2%、4%、6%、8%、10%、11%、12%、13%、14%、15%、16%、17%、18%、20%、22%、24%、25%、26%、28%、30%、32%、34%、35%、36%、38%、40%、42%、44%、46%、48%、50%、52%、54%、56%、58%、60%;优选地,通式N的化合物占液晶组合物的重量百分比为1%-55%。
在本发明的一些实施方案中,在需要保持本发明的液晶组合物粘度较低、且响应时间较短时,优选通式N的化合物的含量的下限值较低且上限值较低;进一步地,在需要保持本发明的液晶组合物的清亮点较高、且温度稳定性良好时,优选通式N的化合物的含量的下限值较低且上限值较低;另外,在为了将驱动电压保持为较低、而使介电各向异性的绝对值变大时,优选使通式N的化合物的含量的下限值变高且上限值变高。
在本发明的一些实施方案中,优选地,RN1和RN2各自独立地表示含有1-10个碳原子的直链或支链的烷基、含有1-9个碳原子的直链或支链的烷氧基、或含有2-10个碳原子的直链或支链的烯基;进一步优选地,RN1和RN2各自独立地表示含有1-8个碳原子的直链或支链的烷基、含有1-7个碳原子的直链或支链的烷氧基、或含有2-8个碳原子的直链或支链的烯基;再进一步优选地,RN1和RN2各自独立地表示含有1-5个碳原子的直链或支链的烷基、含有1-4个碳原子的直链或支链的烷氧基、或含有2-5个碳原子的直链或支链的烯基。
在本发明的一些实施方案中,本发明的液晶组合物还包含至少一种通式A-1的化合物和/或通式A-2的化合物:
其中,
RA1和RA2各自独立地表示含有1-12个碳原子的直链或支链的烷基、 所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH2-可分别独立地被-CH=CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代,并且所述含有1-12个碳原子的直链或支链的烷基、中的一个或更多个-H可分别独立地被-F或-Cl取代;
环环环和环各自独立地表示其中 中的一个或更多个-CH2-可被-O-替代,一个或更多个环中单键可被双键替代,其中中的一个或更多个-H可分别独立地被-F、-Cl或-CN取代,一个或更多个环中-CH=可被-N=替代;
ZA11、ZA21和ZA22各自独立地表示单键、-CH2CH2-、-CF2CF2-、-CO-O-、-O-CO-、-O-CO-O-、-CH=CH-、-CF=CF-、-CH2O-或-OCH2-;
LA11、LA12、LA13、LA21和LA22各自独立地表示-H、含有1-3个碳原子的烷基或卤素;
XA1和XA2各自独立地表示卤素、含有1-5个碳原子的卤代烷基或卤代烷氧基、含有2-5个碳原子的卤代烯基或卤代烯氧基;
在本发明的一些实施方案中,通式A-1的化合物选自由如下化合物组成的组:
其中,
RA1表示含有1-8个碳原子的直链或支链的烷基,所述含有1-8个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH2-可分别独立地被-CH=CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代,并且存在于这些基团中的一个或更多个-H可分别独立地被-F或-Cl取代;
Rv和Rw各自独立地表示-CH2-或-O-;
LA11、LA12、LA11’、LA12’、LA14、LA15和LA16各自独立地表示-H或-F;
LA13和LA13’各自独立地表示-H或-CH3;
XA1表示-F、-CF3或-OCF3;并且
v和w各自独立地表示0或1。
在本发明的一些实施方案中,通式A-1的化合物占液晶组合物的重量百分比为0%-50%,例如,0%、0.1%、1%、2%、4%、6%、8%、10%、11%、12%、13%、14%、15%、16%、17%、18%、20%、22%、24%、25%、26%、28%、30%、32%、34%、35%、36%、38%、40%、42%、44%、46%、48%、50%。
关于通式A-1的化合物的优选含量,在将本发明的液晶组合物的粘度保持为较低、且响应速度较快的情况下,优选使其下限值略低、且使其上限值略低;进一步地,在将本发明的液晶组合物的清亮点保持为较高、且温度稳定性良好的情况下,优选使其下限值略低、且使其上限值略低;此外,为了将驱动电压保持为较低、而欲增大介电各向异性绝对值时,优选使其下限值略高、且使上限值略高。
在本发明的一些实施方案中,通式A-2的化合物选自由如下化合物组成的组:
其中,
RA2表示含有1-8个碳原子的直链或支链的烷基,所述含有1-8个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH2-可分别独立地被-CH=CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代,并且存在于这些基团中的一个或更多个-H可分别独立地被-F或-Cl取代;
LA21、LA22、LA23、LA24和LA25各自独立地表示-H或-F;并且
XA2表示-F、-CF3、-OCF3或-CH2CH2CH=CF2。
在本发明的一些实施方案中,通式A-2的化合物占液晶组合物的重量百分比为0%-50%,例如,0%、0.1%、1%、2%、4%、6%、8%、10%、11%、12%、13%、14%、15%、16%、17%、18%、20%、22%、24%、25%、26%、28%、30%、32%、34%、35%、36%、38%、40%、42%、44%、46%、48%、50%。
关于通式A-2的化合物的优选含量,在将本发明的液晶组合物的粘度保持为较低、且响应速度快的情况下,优选使其下限值略低、且使其上限值略低;进一步地,在将本发明的液晶组合物的清亮点保持为较高、且温度稳定性良好的情况下,优选使其下限值略低、且使上限值略低;此外,为了将驱动电压保持为较低、而欲增大介电各向异性的绝对值时,优选使其下限值略高、且使其上限值略高。
除上述化合物以外,本发明的液晶组合物也可含有通常的向列型液晶、近晶型液晶、胆固醇型液晶、掺杂剂、抗氧化剂、紫外线吸收剂、红外线吸收剂、聚合性单体或光稳定剂等。
如下显示优选加入到根据本发明的液晶组合物中的可能的掺杂剂:
在本发明的一些实施方案中,掺杂剂占液晶组合物的重量百分比为0%-5%;优选地,掺杂剂占液晶组合物的重量百分比为0.01%-1%。
另外,本发明的液晶组合物所使用的抗氧化剂、光稳定剂等添加剂优选以下物质:
其中,n表示1-12的正整数。
优选地,光稳定剂选自如下所示的光稳定剂:
在本发明的一些实施方案中,光稳定剂占液晶组合物的总重量百分比为0%-5%;优选地,光稳定剂占液晶组合物的总重量百分比为0.01%-1%;更优选地,光稳定剂占液晶组合物的总重量百分比为0.01%-0.1%。
在再一方面,本发明还提供一种液晶显示器件,所述液晶显示器件包含上述液晶组合物。
有益效果:
与现有技术相比,本发明的液晶组合物在维持适当的清亮点、适当的光学各向异性和适当的介电各向异性绝对值的情况下,还具有较大的垂直介电(ε⊥)、较大的垂直介电与介电绝对值的比值(ε⊥/|Δε|)、较大的Kave值和较高的透过率,使得包含其的液晶显示器件在维持适当的可使用的温度范围和适当的阈值电压的情况下,具有较好的对比度、较快的响应速度和较好的透过率。
具体实施方式
以下将结合具体实施方案来说明本发明。需要说明的是,下面的实施例为本发明的示例,仅用来说明本发明,而不用来限制本发明。在不偏离本发明主旨或范围的情况下,可进行本发明构思内的其他组合和各种改良。
为便于表达,以下各实施例中,各化合物的基团结构用表2所列的代码表示:
表2.化合物的基团结构代码
以如下结构式的化合物为例:
该结构式如用表2所列代码表示,则可表达为:nCCGF,代码中的n表示左端烷基的C原子数,例如n为“3”,即表示该烷基为-C3H7;代码中的C代表1,4-亚环己基,G代表2-氟-1,4-亚苯基,F代表氟。
以下实施例中测试项目的简写代号如下:
Cp 清亮点(向列相-各向同性相的转变温度,℃)
Δn 光学各向异性(589nm,25℃)
ε⊥ 垂直介电
Δε 介电各向异性(1KHz,25℃)
ε⊥/|Δε| 垂直介电与介电绝对值的比值
Kave 平均弹性常数
Tr 透过率(%)
其中,
Cp:通过熔点仪测试获得。
Δn:使用阿贝折光仪在钠光灯(589nm)光源下、在25℃测试得到。
Δε:Δε=ε∥-ε⊥,其中,ε∥为平行于分子轴的介电常数,ε⊥为垂直于分子轴的介电常数;测试条件:25℃、1KHz、盒厚6μm的VA型测试盒。
Tr:使用DMS 505光电综合测试仪测试调光器件的V-T曲线,全部取V-T曲线上透过率的最大值来作为液晶的透过率,测试盒为负性IPS型,盒厚3.5μm。
在以下的实施例中所采用的各成分,均可以通过公知的方法进行合成,或者通过商业途径获得。这些合成技术是常规的,所得到的各液晶化合物经测试符合电子类化合物标准。
按照以下实施例规定的各液晶组合物的配比制备液晶组合物。液晶组合物的制备是按照本领域的常规方法进行的,如采取加热、超声波、悬浮等方式按照比例混合制得。
对比例1
按表3中所列的各化合物及其重量百分数配制成对比例1的液晶组合物,并且将其填充于液晶显示器两基板之间进行性能测试。
表3.液晶组合物的配方及性能参数测试结果
实施例1
按表4中所列的各化合物及其重量百分数配制成实施例1的液晶组合物,并且将其填充于液晶显示器两基板之间进行性能测试。
表4.液晶组合物的配方及性能参数测试结果
由对比例1和实施例1的对比可知,相较于仅包含本发明通式I的化合物的液晶组合物,包含本发明通式I的化合物和通式II的化合物的液晶组合物在维持适当的清亮点、适当的光学各向异性和适当的介电各向异性绝对值的情况下,还具有较大的垂直介电(ε⊥)、较大的垂直介电与介电绝对值的比值(ε⊥/|Δε|)、较大的Kave值和较高的透过率。
对比例2
按表5中所列的各化合物及其重量百分数配制成对比例2的液晶组合物,并且将其填充于液晶显示器两基板之间进行性能测试。
表5.液晶组合物的配方及性能参数测试结果
实施例2
按表6中所列的各化合物及其重量百分数配制成实施例2的液晶组合物,并且将其填充于液晶显示器两基板之间进行性能测试。
表6.液晶组合物的配方及性能参数测试结果
由对比例2和实施例2的对比可知,相较于仅包含本发明通式II的化合物的液晶组合物,包含本发明通式I的化合物和通式II的化合物的液晶组合物在维持适当的清亮点、适当的光学各向异性和适当的介电各向异性绝对值的情况下,还具有较大的垂直介电(ε⊥)、较大的垂直介电与介电绝对值的比值(ε⊥/|Δε|)、较大的Kave值和较高的透过率。
实施例3
按表7中所列的各化合物及其重量百分数配制成实施例3的液晶组合物,并且将其填充于液晶显示器两基板之间进行性能测试。
表7.液晶组合物的配方及性能参数测试结果
实施例4
按表8中所列的各化合物及其重量百分数配制成实施例4的液晶组合物,并且将其填充于液晶显示器两基板之间进行性能测试。
表8.液晶组合物的配方及性能参数测试结果
实施例5
按表9中所列的各化合物及其重量百分数配制成实施例5的液晶组合物,并且将其填充于液晶显示器两基板之间进行性能测试。
表9.液晶组合物的配方及性能参数测试结果
实施例6
按表10中所列的各化合物及其重量百分数配制成实施例6的液晶组合物,并且将其填充于液晶显示器两基板之间进行性能测试。
表10.液晶组合物的配方及性能参数测试结果
实施例7
按表11中所列的各化合物及其重量百分数配制成实施例7的液晶组合物,并且将其填充于液晶显示器两基板之间进行性能测试。
表11.液晶组合物的配方及性能参数测试结果
实施例8
按表12中所列的各化合物及其重量百分数配制成实施例8的液晶组合物,并且将其填充于液晶显示器两基板之间进行性能测试。
表12.液晶组合物的配方及性能参数测试结果
实施例9
按表13中所列的各化合物及其重量百分数配制成实施例9的液晶组合物,并且将其填充于液晶显示器两基板之间进行性能测试。
表13.液晶组合物的配方及性能参数测试结果
综上,本发明的液晶组合物在维持适当的清亮点、适当的光学各向异性和适当的介电各向异性绝对值的情况下,还具有较大的垂直介电(ε⊥)、较大的垂直介电与介电绝对值的比值(ε⊥/|Δε|)、较大的Kave值和较高的透过率,尤其是,当液晶组合物中含有通式I-2的化合物时,性能提升更显著,包含本发明液晶组合物的液晶显示器件在维持适当的可使用的温度范围和适当的阈值电压的情况下,具有较好的对比度、较快的响应速度和较好的透过率。
以上实施方式只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人了解本发明内容并加以实施,并不能以此限制本发明的保护范围,凡根据本发明精神实质所做的等效变化或修饰,都应涵盖在本发明的保护范围内。
Claims (10)
1.一种液晶组合物,其特征在于,所述液晶组合物包含
至少一种通式I的化合物
至少一种通式II的化合物
其中,
R1表示含有2-12个碳原子的直链或支链的烯基、或含有2-11个碳原子的直链或支链的烯氧基;
R2表示含有1-12个碳原子的直链或支链的烷基、或所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH2-可分别独立地被-CH=CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代;
R3和R4各自独立地表示含有1-11个碳原子的直链或支链的烷氧基;
L1、L2、L3和L4各自独立地表示-F、-Cl、-CF3、-OCF3或-CHF2;并且
n1表示0或1。
3.根据权利要求2所述的液晶组合物,其特征在于,所述液晶组合物包含至少一种通式I-2的化合物。
4.根据权利要求1所述的液晶组合物,其特征在于,所述液晶组合物包含至少两种通式II的化合物。
5.根据权利要求4所述的液晶组合物,其特征在于,所述液晶组合物包含至少一种n1表示1的通式II的化合物。
6.根据权利要求1所述的液晶组合物,其特征在于,所述液晶组合物还包含至少一种通式M的化合物
其中,
RM1和RM2各自独立地表示含有1-12个碳原子的直链或支链的烷基、或所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH2-可分别独立地被-CH=CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代;
ZM1和ZM2各自独立地表示单键、-CO-O-、-O-CO-、-CH2O-、-OCH2-、-C≡C-、-CH=CH-、-CH2CH2-或-(CH2)4-;并且
8.根据权利要求7所述的液晶组合物,其特征在于,所述通式I的化合物占所述液晶组合物的重量百分比为0.1%-50%;所述通式II的化合物占所述液晶组合物的重量百分比为0.1%-60%;所述通式M的化合物占液晶组合物的重量百分比为1%-80%;并且所述通式III的化合物占所述液晶组合物的重量百分比为0.1%-30%。
9.根据权利要求1所述的液晶组合物,其特征在于,所述液晶组合物还包含至少一种通式N的化合物
其中,
RN1和RN2各自独立地表示含有1-12个碳原子的直链或支链的烷基、或所述含有1-12个碳原子的直链或支链的烷基中的一个或不相邻的两个以上的-CH2-可分别独立地被-CH=CH-、-C≡C-、-O-、-CO-、-CO-O-或-O-CO-替代;
环和环各自独立地表示其中中的一个或更多个-CH2-可被-O-替代,一个或更多个环中单键可被双键替代,其中中的一个或更多个-H可分别独立地被-F、-Cl或-CN取代,一个或更多个环中-CH=可被-N=替代;
ZN1和ZN2各自独立地表示单键、-CO-O-、-O-CO-、-CH2O-、-OCH2-、-CH=CH-、-C≡C-、-CH2CH2-、-CF2CF2-、-(CH2)4-、-CF2O-或-OCF2-;
LN1和LN2各自独立地表示-F、-Cl、-CF3、-OCF3或-CHF2;
LN3和LN4各自独立地表示-H、含有1-3个碳原子的烷基或卤素;
当nN1+nN2=0时,或者nN1+nN2=1,且所述通式N的化合物为双联苯结构时,RN1和RN2不为烷氧基;
当nN1表示2,nN2表示0,且所述通式N的化合物中存在双联苯结构时,RN1不为烯基或烯氧基;并且
当nN1+nN2=3时,所述通式N的化合物不为三联苯结构。
10.一种包含权利要求1-9中任一项所述的液晶组合物的液晶显示器件。
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