TWI570220B - A liquid crystal composition, and a display element or a display using the liquid crystal composition - Google Patents
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本發明關於一種液晶組合物及包含該液晶組合物的液晶顯示元件或液晶顯示器。 The present invention relates to a liquid crystal composition and a liquid crystal display element or liquid crystal display comprising the liquid crystal composition.
目前,液晶化合物的應用範圍拓展的越來越廣,其可應用於多種類型的顯示器、光電元件、感測器等中。用於上述顯示領域的液晶化合物的種類繁多,其中向列相液晶應用最為廣泛。向列相液晶已經應用在被動TN、STN矩陣顯示器和具有TFT主動矩陣的系統中。 At present, the application range of liquid crystal compounds is expanding wider and wider, and it can be applied to various types of displays, photoelectric elements, sensors, and the like. There are many kinds of liquid crystal compounds used in the above display field, and the nematic liquid crystal is most widely used. Nematic liquid crystals have been used in passive TN, STN matrix displays and systems with TFT active matrices.
對於薄膜電晶體技術(TFT-LCD)應用領域,近年來市場雖然已經非常巨大,技術也逐漸成熟,但人們對顯示技術的要求也在不斷的提高,尤其是在實現快速回應,降低驅動電壓以降低功耗等方面。液晶材料作為液晶顯示器重要的光電子材料之一,對改善液晶顯示器的性能發揮重要的作用。 For the application of thin film transistor technology (TFT-LCD), although the market has been very large in recent years, and the technology has gradually matured, people's requirements for display technology are also constantly improving, especially in achieving rapid response and reducing the driving voltage. Reduce power consumption and other aspects. As one of the important optoelectronic materials for liquid crystal displays, liquid crystal materials play an important role in improving the performance of liquid crystal displays.
作為液晶材料,需要具有良好的化學和熱穩定性以及對電場和電磁輻射的穩定性。而作為薄膜電晶體技術(TFT-LCD)用液晶材料,不僅需要具有如上穩定性外,還應具有較寬的向列相溫度範圍、合適的雙折射率異向性、非常高的電阻率、良好的抗紫外線性能、高電荷保持率以及低蒸汽壓等性能。 As a liquid crystal material, it is required to have good chemical and thermal stability as well as stability against electric fields and electromagnetic radiation. As a liquid crystal material for thin film transistor technology (TFT-LCD), it is not only required to have the above stability, but also has a wide nematic phase temperature range, a suitable birefringence anisotropy, a very high resistivity, Good UV resistance, high charge retention and low vapor pressure.
對於動態畫面顯示應用,消除顯示畫面殘影和拖尾,要求液晶具有很快的回應速度,因此要求液晶具有較低的旋轉黏度γ1;另外,對於可攜式設備,為了降低設備能耗,希望液晶的驅動電壓盡可能低;而對於電視等用途的顯 示器來說,對於液晶的驅動電壓要求不是那麼的低。 For the dynamic picture display application, eliminating the image sticking and smearing, the liquid crystal is required to have a fast response speed, so the liquid crystal is required to have a low rotational viscosity γ 1 ; in addition, for the portable device, in order to reduce the energy consumption of the device, It is desirable that the driving voltage of the liquid crystal be as low as possible; and for a display such as a television, the driving voltage requirement for the liquid crystal is not so low.
液晶化合物的黏度,尤其是旋轉黏度γ1直接影響液晶加電後的回應時間,不管是上升時間(ton)還是下降時間(toff),都與液晶的旋轉黏度γ1成正比關係,上升時間(ton)由於與液晶盒和驅動電壓有關,可以通過加大驅動電壓的方法與降低液晶盒盒厚來調節;而下降時間(toff)與驅動電壓無關,主要是與液晶的彈性常數與液晶盒盒厚有關,盒厚的下降會降低下降時間(toff),而不同顯示模式下,液晶分子的運動方式不一樣,TN、IPS、VA三種模式分別於平均彈性常數K、扭曲彈性常數、彎曲彈性常數成反比關係。 The viscosity of the liquid crystal compound, especially the rotational viscosity γ 1 directly affects the response time after the liquid crystal is powered on, whether it is the rise time (t on ) or the fall time (t off ), which is proportional to the rotational viscosity γ 1 of the liquid crystal, and rises. The time (t on ) is related to the liquid crystal cell and the driving voltage, and can be adjusted by increasing the driving voltage and reducing the thickness of the liquid crystal cell; and the falling time (t off ) is independent of the driving voltage, mainly the elastic constant of the liquid crystal. In relation to the thickness of the liquid crystal cell, the decrease in the thickness of the cell reduces the fall time (t off ), while in different display modes, the liquid crystal molecules move in different ways. The three modes of TN, IPS and VA are respectively the average elastic constant K and the torsional elasticity. The constant and the bending elastic constant are inversely proportional.
依照液晶連續體理論,各種不同的液晶在外力(電場、磁場)作用下發生形變後,會通過分子間的相互作用,會“回彈”回原來的形狀;同樣的,液晶也是由於分子間的相互作用力形成“黏度”。液晶分子的微小變化,會使液晶的常規參數性能發生明顯的變化,這些變化有的是有一定規律的,有的幾乎不易找到規律,對於液晶分子間的相互作用也會產生明顯的影響,這些影響非常微妙,至今也沒有形成很完善的理論解釋。 According to the theory of liquid crystal continuum, after different kinds of liquid crystals are deformed by external force (electric field, magnetic field), they will "rebound" back to the original shape through the interaction between molecules; similarly, the liquid crystal is also due to the intermolecular The interaction forces form a "viscosity." Small changes in liquid crystal molecules can cause significant changes in the performance of conventional parameters of liquid crystals. Some of these changes are regular, and some are almost impossible to find. They also have a significant impact on the interaction between liquid crystal molecules. These effects are very Subtle, so far has not formed a perfect theoretical explanation.
液晶的黏度與液晶分子結構有關,研究不同液晶分子形成的液晶體系的黏度與液晶分子結構之間的關係是液晶配方工程師的重要任務之一。 The viscosity of liquid crystals is related to the molecular structure of liquid crystals. It is one of the important tasks of liquid crystal formulators to study the relationship between the viscosity of liquid crystal systems formed by different liquid crystal molecules and the molecular structure of liquid crystals.
本發明需要解決的技術問題是提供一種液晶組合物及使用該液晶組合物的液晶顯示元件或液晶顯示器,該液晶組合物具有較低的黏度,可以實現快速回應,同時具有較大的介電異向性△ε、適中的光學異向性△n、高的對熱和光的穩定性、良好的抗紫外線性能、高電荷保持率以及低蒸汽壓等性能。 The technical problem to be solved by the present invention is to provide a liquid crystal composition and a liquid crystal display element or liquid crystal display using the liquid crystal composition, which has a low viscosity, can achieve a fast response, and has a large dielectric difference. Directional Δ ε, moderate optical anisotropy Δn, high stability to heat and light, good UV resistance, high charge retention, and low vapor pressure.
為解決上述技術問題,本發明所採用的技術手段是:
一種液晶組合物,包含一種或多種通式I化合物、一種或多種通式Ⅱ化合物、一種或多種通式Ⅲ化合物、一種或多種通式Ⅳ化合物,
本發明所提供的液晶組合物的△n[589nm,25℃]>0.08,△ε[1KHz,25℃]>2,清亮點Cp>70.0℃,旋轉黏度γ1[25℃]在40~110mPa.s之間。 The liquid crystal composition provided by the invention has Δn [589 nm, 25 ° C] > 0.08, Δ ε [1 KHz, 25 ° C] > 2, clearing point C p > 70.0 ° C, and rotational viscosity γ 1 [25 ° C] at 40~ 110mPa. Between s.
本發明所提供的液晶組合物中通式I化合物質量百分比含量為5~30%,通式Ⅱ化合物質量百分比含量為5~20%,通式Ⅲ化合物質量百分比含量為5~30%,通式Ⅳ化合物質量百分比含量為20~50%。 The content of the compound of the formula I in the liquid crystal composition provided by the invention is 5-30%, the mass percentage of the compound of the formula II is 5-20%, and the mass percentage of the compound of the formula III is 5-30%. The IV compound has a mass percentage of 20 to 50%.
本發明所提供的液晶組合物的進一步改進在於:通式I化合物為式I1~I4化合物,通式Ⅱ化合物為式Ⅱ1~Ⅱ5通式化合物,通式Ⅲ化合物為式Ⅲ1~Ⅲ3通式化合物,通式Ⅳ化合物為式Ⅳ1~Ⅳ4化合物,
上述的通式I1~I4化合物的介電異向性△ε在25-30之間,而且同時具有低的旋轉黏度,清亮點在120℃以上,△n在0.2以上。通式I化合物有利於提高液晶組合物△ε、提高清亮點、提高△n。 The above compounds of the formulae I1 to I4 have a dielectric anisotropy Δ ε of between 25 and 30, and at the same time have a low rotational viscosity, a clearing point of 120 ° C or more, and a Δn of 0.2 or more. The compound of the formula I is advantageous for increasing the liquid crystal composition Δε, increasing the clearing point, and increasing Δn.
上述的通式Ⅱ1~Ⅱ5化合物的烷基鏈碳原子數多,液晶的清亮點Cp會較高,但是同時黏度會增大。 Polyalkyl number of chain carbon atoms Ⅱ1 ~ Ⅱ5 compound of the above formula, the clearing point of the liquid crystal C p will be higher, but at the same time increases the viscosity.
上述的式Ⅲ1~Ⅲ3所示化合物與式Ⅱ所示化合物相比具有更高的清亮點Cp,較低的黏度,尤其是具有更大的彈性常數。有利於提高回應速度。 A compound of formula with a compound represented by the above formulas Ⅱ Ⅲ1 ~ Ⅲ3 compared to a higher clearing point C p, low viscosity, in particular, has a larger spring constant. Helps improve response speed.
上述的式Ⅳ1~Ⅳ4化合物具有很低的旋轉黏度γ1、接近中性的介電異向性△ε、較小的光學異向性△n,在改善液晶黏度、低溫性能具有優勢。不同的烷基取代基對液晶的旋轉黏度γ1、清亮點Cp都具有影響,一般的較長的烷基鏈或烯基鏈會加大液晶的旋轉黏度γ1同時提高清亮點Cp。 The above compounds of the formulae IV1 to IV4 have a very low rotational viscosity γ 1 , a near-neutral dielectric anisotropy Δ ε, and a small optical anisotropy Δn, which are advantageous in improving liquid crystal viscosity and low temperature performance. Different alkyl substituents have an effect on the rotational viscosity γ 1 and clearing point C p of the liquid crystal. Generally, the longer alkyl chain or alkenyl chain increases the rotational viscosity γ 1 of the liquid crystal while increasing the clearing point C p .
本發明所提供的液晶組合物中還可以加入一種或多種式V所示化合物,且其質量百分比含量為1~15%,
上述技術手段的進一步改進在於:式V化合物為式V1~V8化合物,
V1至V7化合物均具有較大的彈性常數K(K11、K22、K33都較大),高的清亮點Cp(高於200℃),但是同時也具有偏大的黏度γ1,可用於調 節液晶的K值參數和清亮點Cp。V1至V7化合物介電異向性△ε基本接近中性,V1至V4化合物具有側向氟原子,有利於改善液晶的互溶性。 The V1 to V7 compounds all have large elastic constants K (both K11, K22, and K33 are large), high clearing point C p (higher than 200 ° C), but also have a large viscosity γ 1 , which can be used for adjustment. The K value parameter of the liquid crystal and the clearing point C p . The dielectric anisotropy Δ ε of the V1 to V7 compound is substantially close to neutral, and the V1 to V4 compound has a lateral fluorine atom, which is advantageous for improving the mutual solubility of the liquid crystal.
本發明所提供的液晶組合物,還可以包含式Ⅵ化合物,且其質量百分比含量為1~20%,
式Ⅵ所示化合物進一步限定為以下式Ⅵ1-Ⅵ3的化合物:
式Ⅵ1~Ⅵ3所示化合物普遍具有與其他液晶良好的互溶性,隨著氟原子取代基的增加,Ⅵ1、Ⅵ2、Ⅵ3介電異向性△ε逐漸增大,Ⅵ1為5左右,Ⅵ3達到12左右;光學異向性△n在合適的範圍之內,隨著氟原子取代基的增加Ⅵ1、Ⅵ2、Ⅵ3有減小趨勢,接近或稍大於混合液晶的△n,在0.11至0.13之間。 The compounds represented by formulas VI1 to VI3 generally have good mutual solubility with other liquid crystals. With the increase of fluorine atom substituents, the dielectric anisotropy Δε of VI1, VI2 and VI3 gradually increases, VI1 is about 5, and VI3 reaches 12. The optical anisotropy Δn is within a suitable range, and as the fluorine atom substituent increases, VI1, VI2, and VI3 have a decreasing tendency, which is close to or slightly larger than Δn of the mixed liquid crystal, and is between 0.11 and 0.13.
上述液晶組合物的各成分的比例不同時,會表現出略有差異的 性能,比如介電異向性△ε、光學異向性△n、液晶的向列相轉化為液體的轉變溫度清亮點Cp、低溫下穩定性都會有所差異,可以應用於不同類型的顯示元件,但是相同的特點是其旋轉黏度γ1較低。應用於液晶顯示元件,可以實現快速回應。 When the ratio of each component of the liquid crystal composition is different, a slightly different performance is exhibited, such as dielectric anisotropy Δ ε, optical anisotropy Δn, and a transition temperature of a liquid crystal which is converted into a liquid. C p and stability at low temperatures will vary and can be applied to different types of display elements, but the same feature is lower rotational viscosity γ 1 . Applied to liquid crystal display elements for fast response.
本發明所提供的液晶化合物中還可以加入各種功能的摻雜劑,摻雜劑含量優選0.01~1%之間,這些摻雜劑主要是抗氧化劑、紫外線吸收劑、手性劑。 The liquid crystal compound provided by the invention may also be added with dopants of various functions, and the dopant content is preferably between 0.01 and 1%. These dopants are mainly antioxidants, ultraviolet absorbers, and chiral agents.
抗氧化劑、紫外線吸收劑優選:
手性劑優選(左旋或右旋):
本發明還關於包含上述任意一種液晶組合物的液晶顯示元件或顯示器,該液晶顯示元件或顯示器為主動矩陣顯示元件或顯示器、被動矩陣顯示元件或顯示器。該液晶顯示元件或顯示器優選主動矩陣定址液晶顯示元件或顯示器。 The invention further relates to a liquid crystal display element or display comprising any of the above liquid crystal compositions, the liquid crystal display element or display being an active matrix display element or display, a passive matrix display element or a display. The liquid crystal display element or display is preferably an active matrix addressed liquid crystal display element or display.
該主動矩陣顯示元件或顯示器具體為TN-TFT或IPS-TFT液晶顯示元件或顯示器。 The active matrix display element or display is specifically a TN-TFT or IPS-TFT liquid crystal display element or display.
由於採用了上述技術手段,本發明取得的技術進步是:本發明所提供的液晶組合物具有較低的黏度,可以實現快速回應,同時具有適中的介電異向性△ε、適中的光學異向性△n、高的對熱和光的穩定性。 The technical progress achieved by the present invention is that the liquid crystal composition provided by the invention has low viscosity and can achieve fast response, and has moderate dielectric anisotropy Δ ε and moderate optical difference. Directional Δn, high stability to heat and light.
包含本發明所提供之液晶組合物的液晶材料,不但具有良好的化學和熱穩定性以及對電場和電磁輻射的穩定性。而且,作為薄膜電晶體技術(TFT-LCD)用液晶材料,還具有較寬的向列相溫度範圍、合適的雙折射率異向性、非常高的電阻率、良好的抗紫外線性能、高電荷保持率以及低蒸汽壓等性能。 The liquid crystal material comprising the liquid crystal composition provided by the present invention not only has good chemical and thermal stability and stability against electric fields and electromagnetic radiation. Moreover, as a liquid crystal material for thin film transistor technology (TFT-LCD), it also has a wide nematic phase temperature range, suitable birefringence anisotropy, very high resistivity, good ultraviolet resistance, and high charge. Maintainability and low vapor pressure.
下面結合具體實施例對本發明做進一步詳細說明,但本發明並不限於以下實施例。所述方法如無特別說明均為常規方法。所述原料如無特別說明均能從公開商業途徑而得。所述百分比如無特別說明,均為質量百分比。 The present invention will be further described in detail below with reference to specific embodiments, but the invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The raw materials can be obtained from an open commercial route unless otherwise specified. The percentages are all percentages by mass unless otherwise stated.
下述實施例中,Cp表示清亮點,直接使用WRX-1S顯微熱分析儀測定,設定升溫速率為3℃/min。△n表示光學異向性(589nm,20℃),△ε表示介電異向性(25℃,1KHz,HP4284A,5.2微米TN左旋盒),γ1表示20℃時旋轉黏度(mpas),VHR(%)代表電荷保持率(5V,60Hz,20℃),ρ(×1013Ω.cm)代表電阻率(20℃),電壓保持率VHR(%)的測試儀與電阻率ρ(×1013Ω.cm)均為TOYO06254和TOYO6517型液晶物性評價系統(測試溫度20℃,時間16ms,測試盒為7.0微米)。 In the following examples, C p denotes clearing point, directly WRX-1S microscopic thermal analyzer measurement, is set a heating rate of 3 ℃ / min. Δn represents optical anisotropy (589 nm, 20 ° C), Δ ε represents dielectric anisotropy (25 ° C, 1 KHz, HP 4284 A, 5.2 μm TN left-handed box), and γ 1 represents rotational viscosity (mpas) at 20 ° C, VHR (%) represents charge retention (5V, 60Hz, 20°C), ρ(×10 13 Ω.cm) represents resistivity (20°C), voltage retention rate VHR(%) of the tester and resistivity ρ(×10 13 Ω.cm) are TOYO06254 and TOYO6517 liquid crystal physical property evaluation systems (test temperature 20 ° C, time 16 ms, test box 7.0 microns).
本發明申請實施例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(一)、表(二)。 The structure of the liquid crystal monomer in the embodiment of the present invention is represented by a code, and the code representation methods of the liquid crystal ring structure, the terminal group and the linking group are shown in the following Table (1) and Table (2).
舉例:表示為3CCV1,記為3B B(3F)B(3F,5F)Q B(3F,5F)F。 Example: Expressed as 3CCV1, It is recorded as 3B B(3F)B(3F, 5F)QB(3F, 5F)F.
由以上實施例可以看出:本發明的液晶組合物具有較低的旋轉黏度γ1,用於液晶顯示,可以實現快速回應。尤其適合於TN、IPS模式用液晶材料。 It can be seen from the above examples that the liquid crystal composition of the present invention has a low rotational viscosity γ 1 for liquid crystal display and can achieve a fast response. It is especially suitable for liquid crystal materials for TN and IPS modes.
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