TWI530553B - Polymerizable liquid crystal composition and display device - Google Patents
Polymerizable liquid crystal composition and display device Download PDFInfo
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本創作係屬於一種液晶組合物,特別是關於一種包含可聚合化合物的聚合性液晶組合物及其在液晶顯示器件中的應用。 The present invention belongs to a liquid crystal composition, and more particularly to a polymerizable liquid crystal composition containing a polymerizable compound and its use in a liquid crystal display device.
液晶顯示元件可以在以鐘錶、電子計算器為代表的家庭用各種電器、測定機器、汽車用面板、文字處理劑、電腦、印表機、電視等中使用。作為夜景顯示方式,在其代表性的方式中,可以列舉PC(phase change,相變)、TN(twist nematic,扭曲向列)、STN(super twisted nematic,超扭曲向列)、ECB(electrically controlled birefringence,電控雙折射)、OCB(optically compensated bend,光學補償彎曲)、IPS(in-plane switching,共面轉變)、VA(vertical alignment,垂直配向)、CSH(color super homeotropic,彩色超垂面)等類模式。根據元件的驅動方式分為PM(passive matrix,被動矩陣)型和AM(active matrix,主動矩陣)型。PM分為靜態(static)和多路(multiplex)等類型。AM分為TFT(thin film transistor,薄膜電晶體)、MIM(metal insulator metal,金屬-絕緣層-金屬)等類型。TFT的類型有非晶矽(amorphous silicon)和多晶矽(polycrystal silicon)。後者根據製造工藝分為高溫型和低溫型。液晶顯示元件根據光源的類型分為利用自然光的反射型、利用背光的透過型、以及利用自然光和背光兩種光源的半透過型。 The liquid crystal display element can be used in various household electric appliances, measurement equipment, automobile panels, word processing agents, computers, printers, televisions, and the like represented by watches and clocks and electronic calculators. As a night view display mode, in a representative manner, PC (phase change), TN (twist nematic), STN (super twisted nematic), ECB (electrically controlled) can be cited. Birefringence, electronically controlled birefringence, OCB (optically compensated bend), IPS (in-plane switching), VA (vertical alignment), CSH (color super homeotropic) ) and other class patterns. According to the driving method of components, it is divided into PM (passive matrix) type and AM (active matrix) type. PM is divided into static (static) and multiplex (multiplex) types. The AM is classified into a TFT (thin film transistor), a MIM (metal insulator metal), and the like. The types of TFTs are amorphous silicon and polycrystalline silicon. The latter is classified into a high temperature type and a low temperature type according to a manufacturing process. The liquid crystal display element is classified into a reflection type using natural light, a transmission type using a backlight, and a semi-transmissive type using both natural light and backlight depending on the type of the light source.
在這些顯示方式中,IPS模式、ECB模式、VA模式或CSH模式等與現在常用的TN模式或STN模式不同在於,前者使用具有負介電各向異性的液晶材料。在這些顯示方式中,尤其是通過AM驅動的VA型顯示,在要求高速且寬視角的顯示元件中的應用,其中,最值得期待的是在電視等液晶元件中的應用。 Among these display modes, the IPS mode, the ECB mode, the VA mode, or the CSH mode are different from the conventional TN mode or the STN mode in that the former uses a liquid crystal material having a negative dielectric anisotropy. Among these display modes, in particular, an AM-driven VA-type display is used in a display element requiring a high-speed and wide viewing angle, and among them, the most desirable one is application to a liquid crystal element such as a television.
VA模式與IPS模式同樣是常黑,但不同的是,VA模式面板的液晶層中的液晶分子用負性液晶,透明電極設於上下基板,形成垂直於基板的電場。未加電時,液晶分子的長軸垂直於基板,而形成暗態;加電時,液晶分子的長軸向平行於基板的方向倒下。其初始配向同樣需要對基板進行摩擦,從而產生污染性、靜電等問題,預傾角也難以控制,為解決VA模式的初始配向問題,又有各種衍生模式,如多區域垂直配向(Multi-domain Vertical Alignment,MVA)、圖像垂直配向(Patterned Vertical Alignment,PVA)、聚合物穩定取向(Polymer Sustained Alignment,PSA)和聚合物穩定垂直配向(Polymer Stabilized Vertical Alignment,PSVA)。其中,PSA模式和PSVA模式以高穿透率、高對比和快回應等特點,漸漸成為主流。 The VA mode is almost always black as in the IPS mode, but the difference is that the liquid crystal molecules in the liquid crystal layer of the VA mode panel are made of negative liquid crystal, and the transparent electrodes are provided on the upper and lower substrates to form an electric field perpendicular to the substrate. When the power is not applied, the long axis of the liquid crystal molecules is perpendicular to the substrate to form a dark state; when power is applied, the long axis of the liquid crystal molecules falls parallel to the direction of the substrate. The initial alignment also requires friction on the substrate, which causes problems such as pollution and static electricity. The pretilt angle is also difficult to control. To solve the initial alignment problem of the VA mode, various derivative modes, such as multi-domain vertical alignment (Multi-domain Vertical) Alignment, MVA), Pattern Vertical Alignment (PVA), Polymer Sustained Alignment (PSA), and Polymer Stabilized Vertical Alignment (PSVA). Among them, PSA mode and PSVA mode have become mainstream with high penetration rate, high contrast and fast response.
聚合物穩定取向(Polymer Sustained Alignment,PSA)型液晶顯示裝置是為了控制液晶分子的預傾角(Pretilt angle)而具有在盒內形成聚合物結構的裝置,由於其快回應性、高對比的特性,而作為液晶顯示元件被應用。 A Polymer Sustained Alignment (PSA) type liquid crystal display device has a device for forming a polymer structure in a cell in order to control a pretilt angle of liquid crystal molecules. Due to its fast response and high contrast characteristics, It is applied as a liquid crystal display element.
PSA型液晶顯示元件的製造如下:將由液晶性化合物和聚合性化合物組成的聚合性組合物注入到基板間,施加電壓,在使液晶分子 取向的狀態下,使聚合性化合物聚合,固定液晶分子的取向。PSA型液晶顯示元件的顯示不良,即圖像殘留的原因,已知由雜質以及液晶分子的取向變化(預傾角的變化)導致。 The PSA type liquid crystal display device is produced by injecting a polymerizable composition composed of a liquid crystal compound and a polymerizable compound between substrates, and applying a voltage to cause liquid crystal molecules. In the oriented state, the polymerizable compound is polymerized to fix the orientation of the liquid crystal molecules. The display failure of the PSA type liquid crystal display element, that is, the cause of image sticking, is known to be caused by impurities and changes in the orientation of liquid crystal molecules (change in pretilt angle).
由分子的預傾角的變化引起的圖像殘留原因是:在構成元件的情況下,長時間持續顯示同一圖案時,聚合物的結構發生變化,其結果預傾角發生變化。因此,需要可形成具有聚合物結構不發生變化的剛直性的結構的聚合物的聚合性化合物。 The reason for the image sticking caused by the change in the pretilt angle of the molecule is that, in the case of constituting the element, when the same pattern is continuously displayed for a long time, the structure of the polymer changes, and as a result, the pretilt angle changes. Therefore, there is a need for a polymerizable compound which can form a polymer having a rigid structure in which the polymer structure does not change.
以往為了通過提高聚合物的剛直性來防止圖像殘留,對於使用具有具有環狀結構和聚合性官能團的1,4-亞苯基等結構的聚合性化合物來構成顯示器件,如JP2003-307720,使用具有聯芳基結構的聚合性化合物來構成顯示元件,如JP2008-116931,但是由於這些聚合性化合物對液晶性化合物的相溶性低,因而在製備液晶組合物時,產生該聚合性化合物析出的問題。 Conventionally, in order to prevent image sticking by increasing the rigidity of the polymer, a display device is formed using a polymerizable compound having a structure such as a 1,4-phenylene group having a cyclic structure and a polymerizable functional group, such as JP 2003-307720. A display element is formed using a polymerizable compound having a biaryl structure, such as JP 2008-116931, but since these polymerizable compounds have low compatibility with a liquid crystal compound, precipitation of the polymerizable compound occurs when a liquid crystal composition is prepared. problem.
PSVA使用了可聚合型化合物來控制液晶分子的排列方向:通過外加電場使液晶處於理想的排列狀態,在保持此狀態的同時進行UV曝光,使混合液晶中的可聚合型化合物聚合,從而“固化”住了液晶的理想排列狀態。 PSVA uses a polymerizable compound to control the alignment direction of liquid crystal molecules: the liquid crystal is in an ideal alignment state by an external electric field, and UV exposure is performed while maintaining this state, so that the polymerizable compound in the mixed liquid crystal is polymerized, thereby "cure". "The ideal arrangement of the LCD."
PSVA模式不需要摩擦配向工序,因此能夠避免TN、IPS等模式中由於摩擦帶來的靜電及污染等問題。 Since the PSVA mode does not require a rubbing alignment process, it is possible to avoid problems such as static electricity and contamination due to friction in modes such as TN and IPS.
令人遺憾的是,目前的聚合性液晶單體還存在很多缺陷,例如美國專利US6136225記載的聚合性液晶單體的熔點太高,實際生產中需要在80~90℃的溫度條件下才能進行操作,這大大增加了能耗,而且在高 溫下還容易引起配向不均、異常聚合等嚴重影響光學品質的缺陷。 Unfortunately, the current polymerizable liquid crystal monomer also has many defects. For example, the melting point of the polymerizable liquid crystal monomer described in US Pat. No. 6,136,225 is too high, and it is required to operate at a temperature of 80 to 90 ° C in actual production. This greatly increases energy consumption and is high Under temperature, it is easy to cause defects such as uneven alignment and abnormal polymerization, which seriously affect optical quality.
因此,試圖採用製作聚合性液晶組合物的方法來提高聚合性液晶的性能。日本專利JP2003193053提供了一種較低熔點的聚合性液晶組合物,但存在嚴重的配向不均的問題。美國專利US6090308提供了一種較低熔點的聚合性液晶組合物,但存在穩定性差、容易結晶等問題。 Therefore, attempts have been made to improve the performance of a polymerizable liquid crystal by a method of producing a polymerizable liquid crystal composition. Japanese Patent JP2003193053 provides a lower melting point polymerizable liquid crystal composition, but has a problem of severe misalignment. U.S. Patent No. 6,090,308 provides a lower melting point polymerizable liquid crystal composition, but has problems such as poor stability and easy crystallization.
現有技術中,一般都是使用單個可聚合化合物,以至於出現各種問題,如:聚合速度較慢或較快,不易控制,聚合後殘留量過高,並且還會出現各種顯示不良的現象,如殘影,顯示不均等。 In the prior art, a single polymerizable compound is generally used, so that various problems occur, such as: slower or faster polymerization, difficult to control, excessive residual amount after polymerization, and various display defects, such as various display defects, such as Afterimage, showing unevenness.
因此,非常需要一種新型聚合性液晶組合物,該液晶組合物沒有或者在很大程度上減少上述缺點。 Therefore, there is a great need for a novel polymerizable liquid crystal composition which does not or substantially reduces the above disadvantages.
本發明的目的是提供一種新型聚合性液晶組合物,所述聚合性液晶組合物包含至少兩種可聚合化合物,使得所述液晶組合物能夠控制聚合速率,降低聚合型化合物殘留,大大減少產生圖像殘影,圖像顯示不均等顯示不良問題的風險。 An object of the present invention is to provide a novel polymerizable liquid crystal composition comprising at least two polymerizable compounds, such that the liquid crystal composition can control the polymerization rate, reduce the residual of the polymerizable compound, and greatly reduce the generation of the pattern. Like afterimages, the image shows unequal risks showing poor problems.
為了完成上述發明目的,本發明提供一種聚合性液晶組合物,包含:至少一種通式I的化合物作為第一成分
在本發明的一些實施方案中,所述通式I的化合物占所述聚合性液晶組合物總重量的0.01-0.3%;所述通式Ⅱ的化合物占所述聚合性液晶組合物總重量的0.001-0.3%;所述通式Ⅲ的化合物占所述聚合性液晶組合物總重量的20-79.4%;以及所述通式Ⅳ的化合物占所述聚合性液晶組合物總重量的20-79.4%。 In some embodiments of the present invention, the compound of the formula I accounts for 0.01 to 0.3% by weight based on the total weight of the polymerizable liquid crystal composition; the compound of the formula II accounts for the total weight of the polymerizable liquid crystal composition. 0.001 to 0.3%; the compound of the formula III accounts for 20-79.4% by weight of the total of the polymerizable liquid crystal composition; and the compound of the formula IV accounts for 20-79.4 of the total weight of the polymerizable liquid crystal composition. %.
在本發明的一些實施方案中,所述通式I的化合物選自由如下化合物組成中一種或多種的化合物:
在本發明的一些實施方案中,所述通式Ⅱ的化合物選自由如下化合物組成中一種或多種的化合物:
在本發明的一些實施方案中,所述通式Ⅲ的化合物選自由如下化合物組成中一種或多種的化合物:;以及
在本發明的一些實施方式中,所述Ⅳ的化合物選自由如下化合物組成中的一種或多種:
本發明的另一方面提供一種液晶顯示器,所述液晶顯示器包含本發明的聚合性液晶組合物。 Another aspect of the present invention provides a liquid crystal display comprising the polymerizable liquid crystal composition of the present invention.
在一些實施方案中,所述液晶顯示器件可以用於VA模式、PS-VA模式、PALC模式、FFS模式、IPS模式或ECB模式。 In some embodiments, the liquid crystal display device can be used in a VA mode, a PS-VA mode, a PALC mode, an FFS mode, an IPS mode, or an ECB mode.
與現有的聚合性液晶組合物相比,本發明的聚合性液晶組合物產生了有益的技術效果,即:本發明的液晶組合物通過對上述化合物進行組合實驗,通過與對照的比較,確定了包括上述液晶組合物的液晶介質,能夠控制聚合速率,降低聚合型化合物殘留,大大減少產生圖像殘影,圖像顯示不均等顯示不良問題的風險,並且所述聚合性液晶組合物具有良好的抗UV穩定性,較高的清亮點、合適的光學各向異性以及合適的介電各向異性。 The polymerizable liquid crystal composition of the present invention produces a beneficial technical effect as compared with the conventional polymerizable liquid crystal composition, that is, the liquid crystal composition of the present invention is determined by a combination experiment with the above compound and by comparison with a control. The liquid crystal medium including the liquid crystal composition described above can control the polymerization rate, reduce the residual of the polymerizable compound, and greatly reduce the risk of occurrence of image sticking, uneven display of images, and the like, and the polymerizable liquid crystal composition has good properties. UV stability, high clearing point, suitable optical anisotropy and suitable dielectric anisotropy.
在本發明中如無特殊說明,所述的比例均為重量比,所有溫度均為攝氏度溫度,所述的回應時間資料的測試選用的盒厚為4μm。 In the present invention, unless otherwise specified, the ratios are all by weight, all temperatures are in degrees Celsius, and the thickness of the test for the response time data is 4 μm.
以下將結合具體實施方案來說明本發明。需要說明的是,雖然,下文中已經用一般性說明及具體實施方案對本發明作了詳盡的描述,但是在本發明基礎上,可以對之作一些修改或改進,這對本領域技術人員而言是顯而易見的。因此,在不偏離本發明精神的基礎上所作出的這些修 改或改進,均屬於本發明要求保護的範圍。 The invention will now be described in connection with specific embodiments. It should be noted that, although the present invention has been described in detail below with reference to the general description and specific embodiments, some modifications or improvements may be made thereto based on the present invention. Obvious. Therefore, these repairs are made without departing from the spirit of the present invention. Modifications or improvements are within the scope of the claimed invention.
為便於表達,以下各實施例中,液晶組合物的基團結構用表1所列的代碼表示:
以如下結構式的化合物為例:
該結構式如用表2所列代碼表示,則可表達為:nCPUF,代碼中的n表示左端烷基的C原子數,例如n為“3”,即表示該烷基為-C3H7;代碼中的C代表環己烷基;
該結構式如用表2所列代碼表示,則可表達為:3C1OWO2,代碼中烷基為-C3H7;代碼中的C代表環己烷基;代碼中的W代表2,3-二氟-1,4-亞苯基;代碼中的O代表氧取代基。 The structural formula is expressed as the code listed in Table 2, and can be expressed as: 3C1OWO2, the alkyl group in the code is -C 3 H 7 ; C in the code represents cyclohexane group; W in the code represents 2, 3- 2 Fluorine-1,4-phenylene; O in the code represents an oxygen substituent.
以下實施例中測試專案的簡寫代號如下: The shorthand code for the test project in the following examples is as follows:
Cp(℃):清亮點(向列-各向同性相轉變溫度) Cp (°C): clearing point (nematic-isotropic phase transition temperature)
△n:折射率各向異性(589nm,25℃) Δn: refractive index anisotropy (589 nm, 25 ° C)
△ε:介電各向異性(1KHz,25℃) △ ε: dielectric anisotropy (1 kHz, 25 ° C)
ppm 濃度單位為0.0001% The ppm concentration unit is 0.0001%
在以下的實施例中所採用的各成分,均可以通過公知的方法進行合成,或者通過商業途徑獲得。這些合成技術是常規的,所得到各液晶化合物經測試符合電子類化合物標準。 The components used in the following examples can be synthesized by a known method or obtained commercially. These synthetic techniques are conventional, and each of the obtained liquid crystal compounds has been tested to meet the standards of electronic compounds.
按照以下實施例規定的各液晶組合物的配比,製備液晶組合物。所述液晶組合物的製備是按照本領域的常規方法進行的,如採取加熱、超聲波、懸浮等方式按照規定比例混合制得。 A liquid crystal composition was prepared in accordance with the ratio of each liquid crystal composition specified in the following examples. The preparation of the liquid crystal composition is carried out according to a conventional method in the art, such as heating, ultrasonic wave, suspension, etc., in a predetermined ratio.
按表2中所列的各化合物及重量百分數配製成液晶組合物
LC-1,如下表所示:
按表3中所列的各化合物及重量百分數配製成液晶組合物LC-2,如下表所示:
對照例1Comparative Example 1
在99.7%的LC-1中添加0.3%的化合物I-5,製備聚合性液晶組合物PLC-1:
PLC-1的物性參數為:△n:0.090,△ε:-3.0,Cp:79.0℃。 The physical property parameters of PLC-1 are: Δn: 0.090, Δε: -3.0, and Cp: 79.0 °C.
使用真空灌注法,將PLC-1注入到盒厚為3.8μm且塗覆有誘發垂面取向的聚醯亞胺取向膜的帶有ITO導電層(氧化銦錫導電層)的液晶盒中,測定該液晶盒的預傾角(晶體旋轉法)後(89.6°),向其施加頻率為60~1000HZ、10-30V交流電電壓,利用高壓汞燈對液晶盒照射紫外線,將液晶盒表面的照射強度調整為10~30mW/cm2,照射300s,然後測試紫外線照射後的液晶盒預傾角,得到液晶盒的預傾角為85.1°。 Using a vacuum infusion method, PLC-1 was injected into a liquid crystal cell with an ITO conductive layer (indium tin oxide conductive layer) having a thickness of 3.8 μm and coated with a polyimide-oriented alignment film which induces a homeotropic orientation. After the pretilt angle (crystal rotation method) of the liquid crystal cell (89.6°), a frequency of 60-1000 Hz and 10-30 V alternating current is applied thereto, and the liquid crystal cell is irradiated with ultraviolet light by a high-pressure mercury lamp to adjust the irradiation intensity of the surface of the liquid crystal cell. After 10 to 30 mW/cm 2 , the irradiation was performed for 300 s, and then the pretilt angle of the liquid crystal cell after the ultraviolet irradiation was measured, and the pretilt angle of the liquid crystal cell was 85.1°.
利用液相色譜分析,對液晶盒中,所含有的式I-5所示未聚合聚合性化合物的含量進行分析,檢測結果為1550ppm,由此可以得出I-5所示聚合性化合物未完全聚合。 The content of the non-polymerizable polymerizable compound represented by Formula I-5 contained in the liquid crystal cell was analyzed by liquid chromatography, and the detection result was 1550 ppm, whereby the polymerizable compound represented by I-5 was incomplete. polymerization.
實施例1Example 1
在99.7%的LC-1中添加0.20%的化合物I-5,0.10%化合物Ⅱ-1,製備聚合性液晶組合物PLC-2:
PLC-2的物性參數為:△n:0.090,△ε:-3.0,Cp:79.2℃。 The physical property parameters of PLC-2 are: Δn: 0.090, Δε: -3.0, and Cp: 79.2 °C.
使用真空灌注法,將PLC-2注入到盒厚為3.8μm且塗覆有誘發垂面取向的聚醯亞胺取向膜的帶有ITO導電層(氧化銦錫導電層)的液晶盒中, 測定該液晶盒的預傾角(晶體旋轉法)後(89.6°),向其施加頻率為60~1000HZ、10-30V交流電電壓,利用高壓汞燈對液晶盒照射紫外線,將液晶盒表面的照射強度調整為10~30mW/cm2,照射300s,然後測試紫外線照射後的液晶盒預傾角,得到液晶盒的預傾角為80.2°。 Using a vacuum infusion method, PLC-2 was injected into a liquid crystal cell with an ITO conductive layer (indium tin oxide conductive layer) having a thickness of 3.8 μm and coated with a polyimide-oriented oriented film which induces a homeotropic orientation. After the pretilt angle (crystal rotation method) of the liquid crystal cell (89.6°), a frequency of 60-1000 Hz and 10-30 V alternating current is applied thereto, and the liquid crystal cell is irradiated with ultraviolet light by a high-pressure mercury lamp to adjust the irradiation intensity of the surface of the liquid crystal cell. For 10 to 30 mW/cm 2 , the irradiation was performed for 300 s, and then the pretilt angle of the liquid crystal cell after the ultraviolet irradiation was measured, and the pretilt angle of the liquid crystal cell was 80.2°.
利用液相色譜分析,對液晶盒中,所含有的化合物I-5與化合物Ⅱ-1所示未聚合的聚合性化合物的含量進行分析,檢測結果為60ppm。 The content of the unpolymerized polymerizable compound represented by the compound I-5 and the compound II-1 contained in the liquid crystal cell was analyzed by liquid chromatography, and the result was 60 ppm.
實施例2Example 2
在99.7%的LC-1中添加0.20%的化合物I-5,0.10%化合物II-4,製備聚合性液晶組合物PLC-3:
PLC-3的物性參數為:△n:0.090,△ε:-3.0,Cp:79.1℃。 The physical property parameters of PLC-3 are: Δn: 0.090, Δε: -3.0, and Cp: 79.1 °C.
使用真空灌注法,將PLC-3注入到盒厚為3.8μm且塗覆有誘發垂面取向的聚醯亞胺取向膜的帶有ITO導電層(氧化銦錫導電層)的液晶盒中,測定該液晶盒的預傾角(晶體旋轉法)後(89.6°),向其施加頻率為60~1000HZ、10-30V交流電電壓,利用高壓汞燈對液晶盒照射紫外線,將液晶盒表面的照射強度調整為10~30mW/cm2,照射300s,然後測試紫外線照射後的液晶盒預傾角,得到液晶盒的預傾角為81.0°。 Using a vacuum infusion method, PLC-3 was injected into a liquid crystal cell with an ITO conductive layer (indium tin oxide conductive layer) having a thickness of 3.8 μm and coated with a polyimide-oriented oriented film which induces a homeotropic orientation. After the pretilt angle (crystal rotation method) of the liquid crystal cell (89.6°), a frequency of 60-1000 Hz and 10-30 V alternating current is applied thereto, and the liquid crystal cell is irradiated with ultraviolet light by a high-pressure mercury lamp to adjust the irradiation intensity of the surface of the liquid crystal cell. It was irradiated for 10 s for 10 to 30 mW/cm 2 , and then the pretilt angle of the liquid crystal cell after ultraviolet irradiation was measured to obtain a pretilt angle of the liquid crystal cell of 81.0°.
利用液相色譜分析,對液晶盒中,所含有的化合物I-5與化合物Ⅱ-4所示未聚合的聚合性化合物的含量進行分析,檢測結果為80ppm。 The content of the unpolymerized polymerizable compound represented by the compound I-5 and the compound II-4 contained in the liquid crystal cell was analyzed by liquid chromatography, and the detection result was 80 ppm.
對比例2Comparative example 2
在99.7%的LC-2中添加0.3%的式I-6,製備聚合性液晶組合物PLC-4:
PLC-4的物性參數為:△n:0.098,△ε:-2.6,Cp:74.9℃ The physical property parameters of PLC-4 are: Δn: 0.098, △ ε: -2.6, Cp: 74.9 ° C
使用真空灌注法,將PLC-4注入到盒厚為3.8μm且塗覆有誘發垂面取向的聚醯亞胺取向膜的帶有ITO導電層(氧化銦錫導電層)的液晶盒中,測定該液晶盒的預傾角(晶體旋轉法)後(89.6°),向其施加頻率為60~1000HZ、10-30V交流電電壓,利用高壓汞燈對液晶盒照射紫外線,將液晶盒表面的照射強度調整為10~30mW/cm2,照射300s,然後測試紫外線照射後的液晶盒預傾角,得到液晶盒1的預傾角為87.9°。 Using a vacuum infusion method, PLC-4 was injected into a liquid crystal cell with an ITO conductive layer (indium tin oxide conductive layer) having a thickness of 3.8 μm and coated with a polyimide-oriented oriented film which induces a homeotropic orientation. After the pretilt angle (crystal rotation method) of the liquid crystal cell (89.6°), a frequency of 60-1000 Hz and 10-30 V alternating current is applied thereto, and the liquid crystal cell is irradiated with ultraviolet light by a high-pressure mercury lamp to adjust the irradiation intensity of the surface of the liquid crystal cell. It was irradiated for 10 s for 10 to 30 mW/cm 2 , and then the pretilt angle of the liquid crystal cell after ultraviolet irradiation was measured, and the pretilt angle of the liquid crystal cell 1 was 87.9°.
利用液相色譜分析,對液晶盒中,所含有的化合物I-6所示未聚合聚合性化合物的含量進行分析,檢測結果為1735ppm,由此可以得出化合物I-6所示聚合性化合物未完全聚合。 The content of the unpolymerized polymerizable compound represented by the compound I-6 contained in the liquid crystal cell was analyzed by liquid chromatography, and the result was 1735 ppm, whereby the polymerizable compound represented by the compound I-6 was not obtained. Completely polymerized.
實施例3Example 3
在99.7%的LC-2中添加0.20%的化合物I-6,0.10%化合物Ⅱ-7,製備聚合性液晶組合物PLC-5:
PLC-5的物性參數為:△n:0.098,△ε:-2.6,Cp:75.2℃ The physical properties of PLC-5 are: △n: 0.098, △ ε: -2.6, Cp: 75.2 °C
使用真空灌注法,將PLC-5注入到盒厚為3.8μm且塗覆有誘發垂面取向的聚醯亞胺取向膜的帶有ITO導電層(氧化銦錫導電層)的液晶盒中,測定該液晶盒的預傾角(晶體旋轉法)後(89.6°),向其施加頻率為60~1000HZ、10-30V交流電電壓,利用高壓汞燈對液晶盒照射紫外線,將液晶盒表面的照射強度調整為10~30mW/cm2,照射300s,然後測試紫外線照射後的液晶盒預傾角,得到液晶盒的預傾角為82.5°。 Using a vacuum infusion method, PLC-5 was injected into a liquid crystal cell with an ITO conductive layer (indium tin oxide conductive layer) having a thickness of 3.8 μm and coated with a polyimide-oriented oriented film which induces a homeotropic orientation. After the pretilt angle (crystal rotation method) of the liquid crystal cell (89.6°), a frequency of 60-1000 Hz and 10-30 V alternating current is applied thereto, and the liquid crystal cell is irradiated with ultraviolet light by a high-pressure mercury lamp to adjust the irradiation intensity of the surface of the liquid crystal cell. It is 10~30mW/cm 2 , irradiated for 300s, and then the pre-tilt angle of the liquid crystal cell after ultraviolet irradiation is tested, and the pretilt angle of the liquid crystal cell is 82.5°.
利用液相色譜分析,對液晶盒中,所含有的化合物I-6與Ⅱ-7所示未聚合的聚合性化合物的含量進行分析,檢測結果為85ppm。 The content of the unpolymerized polymerizable compound represented by the compounds I-6 and II-7 contained in the liquid crystal cell was analyzed by liquid chromatography, and the detection result was 85 ppm.
實施例4Example 4
在99.7%的LC-2中添加0.20%的式I-6,0.10%式Ⅱ-4,製備聚合性液晶組合物PLC-6:
PLC-6的物性參數為:△n:0.098,△ε:-2.6,Cp:75.2℃。 The physical property parameters of PLC-6 were: Δn: 0.098, Δε: -2.6, and Cp: 75.2 °C.
使用真空灌注法,將PLC-6注入到盒厚為3.8μm且塗覆有誘發垂面取向的聚醯亞胺取向膜的帶有ITO導電層(氧化銦錫導電層)的液晶盒中,測定該液晶盒的預傾角(晶體旋轉法)後(89.6°),向其施加頻率為60~1000HZ、10-30V交流電電壓,利用高壓汞燈對液晶盒照射紫外線,將 液晶盒表面的照射強度調整為10~30mW/cm2,照射300s,然後測試紫外線照射後的液晶盒預傾角,到液晶盒的預傾角為83.7°。 Using a vacuum infusion method, PLC-6 was injected into a liquid crystal cell with an ITO conductive layer (indium tin oxide conductive layer) having a thickness of 3.8 μm and coated with a polyimide-oriented oriented film which induces a homeotropic orientation. After the pretilt angle (crystal rotation method) of the liquid crystal cell (89.6°), a frequency of 60-1000 Hz and 10-30 V alternating current is applied thereto, and the liquid crystal cell is irradiated with ultraviolet light by a high-pressure mercury lamp to adjust the irradiation intensity of the surface of the liquid crystal cell. It is 10~30mW/cm 2 , irradiated for 300s, and then the pre-tilt angle of the liquid crystal cell after ultraviolet irradiation is tested, and the pretilt angle to the liquid crystal cell is 83.7°.
利用液相色譜分析,對液晶盒中,所含有的化合物I-6與化合物Ⅱ-4所示未聚合的聚合性化合物的含量進行分析,檢測結果為90ppm。 The content of the unpolymerized polymerizable compound represented by the compound I-6 and the compound II-4 contained in the liquid crystal cell was analyzed by liquid chromatography, and the result was 90 ppm.
實施例5Example 5
將對比例1、對比例2、實施例1、實施例2、實施例3以及實施例4的聚合性液晶組合物PLC-1、PLC-2、PLC-3、PLC-4、PLC-5以及PLC-6,利用真空灌注法注入到液晶盒中,對液晶盒施加電壓,通過觀察,將曝光後預傾角與聚合性化合物殘留的關係如表4所示。 The polymerizable liquid crystal compositions PLC-1, PLC-2, PLC-3, PLC-4, PLC-5 of Comparative Example 1, Comparative Example 2, Example 1, Example 2, Example 3, and Example 4 were used. PLC-6 was injected into the liquid crystal cell by a vacuum infusion method, and a voltage was applied to the liquid crystal cell. The relationship between the pretilt angle after exposure and the residual of the polymerizable compound was observed as shown in Table 4.
通過以上對比例和實施例可以看出,本發明提供的聚合性液晶組合物,能夠控制聚合速率,降低聚合型化合物殘留,大大減少產生圖像殘影,圖像顯示不均等問題,並且所述聚合性液晶組合物具有良好的抗紫外線穩定性,較高的清亮點、合適的光學各向異性以及合適的介電各向異性。 It can be seen from the above comparative examples and examples that the polymerizable liquid crystal composition provided by the present invention can control the polymerization rate, reduce the residual of the polymeric compound, greatly reduce the occurrence of image sticking, uneven image display, and the like. The polymerizable liquid crystal composition has good ultraviolet stability, a high clearing point, suitable optical anisotropy, and suitable dielectric anisotropy.
唯,以上該者,僅為本創作之較佳實施例而已,並非用以限定本創作實施之範圍,故該所屬技術領域中具有通常知識者,或是熟悉此技術所作出等效或輕易的變化者,在不脫離本創作之精神與範圍下所作之均等變化與修飾,皆應涵蓋於本創作之專利範圍內。 The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Therefore, it is common knowledge in the technical field or equivalent or easy to be familiar with the technology. The change and modification of the changer without departing from the spirit and scope of this creation shall be covered by the scope of the patent of this creation.
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