TWI710623B - Liquid crystal composition and its use, liquid crystal display element - Google Patents
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Abstract
本發明提供一種藉由聚合物的作用可達成液晶分子的垂直配向的液晶組成物、含有該組成物的液晶顯示元件。本發明是一種含有在分子末端的分支結構中具有聚合性基與極性基的化合物作為第一添加物,且具有負的介電各向異性的向列液晶組成物,該組成物亦可含有具有負的大介電各向異性的特定液晶性化合物作為第一成分,含有具有高的上限溫度或小的黏度的特定液晶性化合物作為第二成分,以及含有聚合性化合物作為第二添加物,而且本發明是一種含有該組成物的液晶顯示元件。 The present invention provides a liquid crystal composition capable of achieving vertical alignment of liquid crystal molecules through the action of a polymer, and a liquid crystal display element containing the composition. The present invention is a nematic liquid crystal composition containing a compound having a polymerizable group and a polar group in the branched structure of the molecular terminal as the first additive and having negative dielectric anisotropy. The composition may also contain A specific liquid crystal compound with a large negative dielectric anisotropy is used as the first component, a specific liquid crystal compound having a high upper limit temperature or a small viscosity is contained as a second component, and a polymerizable compound is contained as a second additive, and The present invention is a liquid crystal display element containing the composition.
Description
本發明是有關於一種液晶組成物、含有該組成物的液晶顯示元件等。尤其是有關於一種含有在分子末端的分支結構中具有聚合性基與極性基的化合物(或其聚合物),且藉由該化合物的作用可達成液晶分子的垂直配向的介電各向異性為負的液晶組成物,及液晶顯示元件。 The present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. In particular, it relates to a compound (or a polymer thereof) containing a polymerizable group and a polar group in the branch structure at the molecular end, and the vertical alignment of the liquid crystal molecule can be achieved by the action of the compound. The dielectric anisotropy is Negative liquid crystal composition, and liquid crystal display element.
液晶顯示元件中,基於液晶分子的運作模式的分類為相變(phase change,PC)、扭轉向列(twisted nematic,TN)、超扭轉向列(super twisted nematic,STN)、電控雙折射(electrically controlled birefringence,ECB)、光學補償彎曲(optically compensated bend,OCB)、面內切換(in-plane switching,IPS)、垂直配向(vertical alignment,VA)、邊緣場切換(fringe field switching,FFS)、電場感應光反應配向(field-induced photo-reactive alignment,FPA)等模式。基於元件的驅動方式的分類為被動矩陣(passive matrix,PM)及主動矩陣(active matrix,AM)。PM被分類為靜態式(static)、多工式(multiplex)等,AM被分類為薄膜電晶體(thin film transistor,TFT)、金屬-絕緣體-金屬(metal insulator metal,MIM)等。TFT的分類為非晶矽(amorphous silicon)及多晶矽(polycrystal silicon)。後者根據製造步驟而分類為高溫 型與低溫型。基於光源的分類為利用自然光的反射型、利用背光的透過型、及利用自然光與背光這兩者的半透過型。 In liquid crystal display elements, the classification based on the operation mode of liquid crystal molecules is phase change (PC), twisted nematic (TN), super twisted nematic (STN), and electrically controlled birefringence ( Electrically controlled birefringence (ECB), optically compensated bend (OCB), in-plane switching (IPS), vertical alignment (VA), fringe field switching (FFS), Field-induced photo-reactive alignment (FPA) and other modes. The classification based on the driving method of the element is a passive matrix (PM) and an active matrix (AM). PM is classified into static, multiplexed, etc., AM is classified into thin film transistor (TFT), metal insulator metal (MIM), etc. TFTs are classified into amorphous silicon and polycrystal silicon. The latter is classified as high temperature according to the manufacturing steps Type and low temperature type. The light source is classified into a reflective type using natural light, a transmissive type using backlight, and a semi-transmissive type using both natural light and backlight.
液晶顯示元件含有具有向列相的液晶組成物。該組成物具有適當的特性。藉由提高該組成物的特性,可獲得具有良好特性的AM元件。將兩者的特性中的關聯歸納於下述表1中。基於市售的AM元件來對組成物的特性進一步進行說明。向列相的溫度範圍與元件可使用的溫度範圍相關聯。向列相的較佳的上限溫度為約70℃以上,而且向列相的較佳的下限溫度為約-10℃以下。 組成物的黏度與元件的響應時間相關聯。為了以元件顯示動態影像(moving image),較佳為響應時間短。理想為短於1毫秒的響應時間。因此,較佳為組成物的黏度小。尤佳為低溫下的黏度小。 The liquid crystal display element contains a liquid crystal composition having a nematic phase. The composition has appropriate characteristics. By improving the characteristics of the composition, an AM device with good characteristics can be obtained. The relationship between the two characteristics is summarized in Table 1 below. The characteristics of the composition will be further described based on commercially available AM devices. The temperature range of the nematic phase is related to the temperature range in which the element can be used. The preferred upper limit temperature of the nematic phase is about 70°C or higher, and the preferred lower limit temperature of the nematic phase is about -10°C or lower. The viscosity of the composition is related to the response time of the device. In order to display moving images with components, it is preferable that the response time be short. Ideally, the response time is shorter than 1 millisecond. Therefore, it is preferable that the viscosity of the composition is small. It is particularly preferable that the viscosity at low temperature is small.
組成物的光學各向異性與元件的對比度比相關聯。根據元件的模式,而需要大的光學各向異性或小的光學各向異性、即適當的光學各向異性。組成物的光學各向異性(△n)與元件的單 元間隙(d)的積(△n×d)被設計成使對比度比為最大。適當的積的值依存於運作模式的種類。VA模式的元件中,該值為約0.30μm至約0.40μm的範圍,IPS模式或FFS模式的元件中,該值為約0.20μm至約0.30μm的範圍。該些情況下,對單元間隙小的元件而言較佳為具有大的光學各向異性的組成物。組成物的大的介電各向異性有助於元件的低臨限電壓、小的消耗電力與大的對比度比。因此,較佳為大的介電各向異性。組成物的大的比電阻有助於元件的大的電壓保持率與大的對比度比。因此,較佳為在初始階段中不僅在室溫下,而且在接近於向列相的上限溫度的溫度下亦具有大的比電阻的組成物。較佳為在長時間使用後,不僅在室溫下,而且在接近於向列相的上限溫度的溫度下亦具有大的比電阻的組成物。組成物對紫外線及熱的穩定性與元件的壽命相關聯。於該穩定性高時,元件的壽命長。此種特性對用於液晶投影機、液晶電視等的AM元件而言較佳。 The optical anisotropy of the composition is related to the contrast ratio of the element. Depending on the mode of the element, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy is required. The optical anisotropy (△n) of the composition and the single element The product (Δn×d) of the cell gap (d) is designed to maximize the contrast ratio. The appropriate product value depends on the type of operation mode. In the VA mode device, the value is in the range of about 0.30 μm to about 0.40 μm, and in the IPS mode or FFS mode device, the value is in the range of about 0.20 μm to about 0.30 μm. In these cases, for an element with a small cell gap, a composition having large optical anisotropy is preferable. The large dielectric anisotropy of the composition contributes to the low threshold voltage of the device, small power consumption, and large contrast ratio. Therefore, a large dielectric anisotropy is preferable. The large specific resistance of the composition contributes to the large voltage holding ratio and large contrast ratio of the element. Therefore, it is preferably a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage. It is preferably a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after long-term use. The stability of the composition to ultraviolet rays and heat is related to the life of the device. When the stability is high, the life of the device is long. Such characteristics are better for AM devices used in liquid crystal projectors, liquid crystal televisions, and the like.
聚合物穩定配向(polymer sustained alignment,PSA)型的液晶顯示元件中,使用含有聚合物的液晶組成物。首先,將添加有少量聚合性化合物的組成物注入至元件中。其次,一邊對該元件的基板之間施加電壓,一邊對組成物照射紫外線。聚合性化合物進行聚合而於組成物中生成聚合物的網狀結構。該組成物中,可利用聚合物來控制液晶分子的配向,因此元件的響應時間縮短,圖像的殘像得到改善。於具有TN、ECB、OCB、IPS、VA、FFS、FPA之類的模式的元件中可期待聚合物的此種效果。 In a polymer sustained alignment (PSA) type liquid crystal display element, a liquid crystal composition containing a polymer is used. First, a composition containing a small amount of polymerizable compound is injected into the device. Next, while applying a voltage between the substrates of the element, ultraviolet rays are irradiated to the composition. The polymerizable compound is polymerized to form a polymer network structure in the composition. In this composition, the polymer can be used to control the alignment of liquid crystal molecules, so the response time of the element is shortened, and the afterimage of the image is improved. Such effects of polymers can be expected in devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
通用的液晶顯示元件中,液晶分子的垂直配向是藉由聚醯亞胺配向膜來達成。另一方面,於不具有配向膜的液晶顯示元件中,使用含有聚合物及極性化合物的液晶組成物。首先,將添加有少量聚合性化合物及少量極性化合物的組成物注入至元件中。此處,極性化合物吸附於基板表面並進行排列。依據該排列,液晶分子進行配向。其次,一邊對該元件的基板之間施加電壓,一邊對組成物照射紫外線。此處,聚合性化合物進行聚合,並使液晶分子的配向穩定化。該組成物中,可利用聚合物及極性化合物來控制液晶分子的配向,因此元件的響應時間縮短,圖像的殘像得到改善。進而,不具有配向膜的元件無需形成配向膜的步驟。 由於不存在配向膜,因此不存在元件的電阻因配向膜與組成物的相互作用而降低的情況。於具有TN、ECB、OCB、IPS、VA、FFS、FPA之類的模式的元件中可期待利用聚合物與極性化合物的組合的此種效果。 In general liquid crystal display devices, the vertical alignment of liquid crystal molecules is achieved by polyimide alignment films. On the other hand, in a liquid crystal display element without an alignment film, a liquid crystal composition containing a polymer and a polar compound is used. First, a composition containing a small amount of polymerizable compound and a small amount of polar compound is injected into the device. Here, the polar compounds are adsorbed on the surface of the substrate and arranged. According to this arrangement, the liquid crystal molecules are aligned. Next, while applying a voltage between the substrates of the element, ultraviolet rays are irradiated to the composition. Here, the polymerizable compound is polymerized and stabilizes the alignment of liquid crystal molecules. In this composition, polymers and polar compounds can be used to control the alignment of liquid crystal molecules, so the response time of the device is shortened, and the afterimage of the image is improved. Furthermore, an element without an alignment film does not require a step of forming an alignment film. Since there is no alignment film, the resistance of the device does not decrease due to the interaction between the alignment film and the composition. Such an effect of the combination of a polymer and a polar compound can be expected in devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.
具有TN模式的AM元件中使用具有正的介電各向異性的組成物。具有VA模式的AM元件中使用具有負的介電各向異性的組成物。具有IPS模式或FFS模式的AM元件中使用具有正或負的介電各向異性的組成物。聚合物穩定配向型的AM元件中使用具有正或負的介電各向異性的組成物。使用了具有負的介電各向異性的液晶化合物與具有極性基的聚合性化合物的液晶組成物的例子揭示於以下的專利文獻1至專利文獻2中。專利文獻1中揭示了於化合物的側方位具有聚合性基、於末端具有極性基的聚 合性自配向添加劑。專利文獻2中揭示了於化合物的兩末端分別具有聚合性基與極性基的聚合性自配向添加劑。專利文獻1及專利文獻2中記載的化合物與本發明中使用的化合物不同。 The AM device having the TN mode uses a composition having positive dielectric anisotropy. The AM device having the VA mode uses a composition having negative dielectric anisotropy. The AM device having the IPS mode or the FFS mode uses a composition having positive or negative dielectric anisotropy. A polymer stabilized alignment type AM device uses a composition having positive or negative dielectric anisotropy. Examples of a liquid crystal composition using a liquid crystal compound having negative dielectric anisotropy and a polymerizable compound having a polar group are disclosed in Patent Documents 1 to 2 below. Patent Document 1 discloses a polymer having a polymerizable group at the side of the compound and a polar group at the end. Synthetic self-aligning additives. Patent Document 2 discloses a polymerizable self-aligning additive having a polymerizable group and a polar group at both ends of the compound. The compounds described in Patent Document 1 and Patent Document 2 are different from the compounds used in the present invention.
[現有技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1] 日本專利特開2015-168826號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2015-168826
[專利文獻2] 國際公開第2016/015803號手冊 [Patent Document 2] International Publication No. 2016/015803 Brochure
本發明所欲解決的課題在於提供一種液晶組成物,其使用在分子末端的分支結構中具有聚合性基與極性基的化合物(或其聚合物)來控制不具有配向膜的液晶顯示元件的液晶分子的配向,而且聚合性極性化合物顯示出良好的相容性。 The problem to be solved by the present invention is to provide a liquid crystal composition which uses a compound (or a polymer thereof) having a polymerizable group and a polar group in the branched structure of the molecular terminal to control the liquid crystal of a liquid crystal display element without an alignment film Molecular alignment, and polymerizable polar compounds show good compatibility.
本發明利用含有在分子末端的分支結構中具有聚合性基與極性基的化合物,且具有負的介電各向異性的液晶組成物來控制不具有配向膜的液晶顯示元件的液晶分子的配向。 The present invention utilizes a liquid crystal composition containing a compound having a polymerizable group and a polar group in a branched structure at the molecular end and has a negative dielectric anisotropy to control the alignment of liquid crystal molecules of a liquid crystal display element without an alignment film.
一種液晶組成物,其含有選自式(1-1)所表示的化合物的群組中的至少一種極性化合物作為第一添加物,而且具有負的介電各向異性,
式(1-1)中,R1為碳數1至15的烷基,所述R1中,至少一個-CH2-可經-O-或-S-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,至少一個氫可經鹵素取代;環A1及環A2獨立地為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、萘-2,6-二基、十氫萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、吡啶-2,5-二基、茀-2,7-二基、菲-2,7-二基、蒽-2,6-二基、全氫環戊并[a]菲-3,17-二基、或2,3,4,7,8,9,10,11,12,13,14,15,16,17-十四氫環戊并[a]菲-3,17-二基,該些環中,至少一個氫可經氟、氯、碳數1至12的烷基、碳數2至12的烯基、碳數1至11的烷氧基、或碳數2至11的烯氧基取代,該些基團中,至少一個氫可經氟或氯取代;a為0、1、2、3、或4;Z1為單鍵或碳數1至6的伸烷基,所述Z1中,至少一個-CH2-可經-O-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,Z1中至少一個氫可經氟或氯取代;Sp1為單鍵或碳數1至10的伸烷基,所述Sp1中,至少一個-CH2-可經-O-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,Sp1中至少一個氫可經鹵素
取代,Sp1中至少一個氫經選自式(1a)所表示的基團中的基團取代;
式(1a)中,Sp12為單鍵或碳數1至10的伸烷基,所述Sp12中,至少一個-CH2-可經-O-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,Sp12中至少一個氫可經鹵素取代;M11及M12獨立地為氫、鹵素、碳數1至5的烷基、或至少一個氫經鹵素取代的碳數1至5的烷基;R12為碳數1至15的烷基,所述R12中,至少一個-CH2-可經-O-或-S-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,至少一個氫可經鹵素取代;式(1-1)中,P11為選自式(1e)及式(1f)所表示的基團中的基團;
式(1e)及式(1f)中,Sp13為單鍵或碳數1至10的伸烷基,所述Sp13中,至少一個-CH2-可經-O-、-NH-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,Sp13中至少一個氫可經鹵素取代;M13及M14獨立地為氫、鹵素、碳數1至5的烷基、或至少一個氫經鹵素取代的碳數1至5的烷基;R13為選自式(1g)、式(1h)、及式(1i)所表示的基團中的基團;
式(1g)、式(1h)、及式(1i)中,Sp14及Sp15獨立地為單鍵或碳數1至10的伸烷基,所述伸烷 基中,至少一個-CH2-可經-O-、-NH-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,至少一個氫可經鹵素取代;式(1g)及式(1i)中,S1為>CH-或>N-,S2為>C<或>Si<;X1為-OH、-NH2、-OR15、-N(R15)2、-COOH、-SH、-B(OH)2、或-Si(R15)3;-OR15、-N(R15)2、及-Si(R15)3中,R15為氫或碳數1至10的烷基,所述R15中,至少一個-CH2-可經-O-取代,至少一個-CH2CH2-可經-CH=CH-取代,R15中至少一個氫可經鹵素取代。 In formula (1g), formula (1h), and formula (1i), Sp 14 and Sp 15 are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH 2 -Can be substituted by -O-, -NH-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -CH 2 CH 2 -can be -CH=CH- or -C≡C- Substitution, at least one hydrogen can be replaced by halogen; In formula (1g) and formula (1i), S 1 is >CH- or >N-, S 2 is >C< or >Si<; X 1 is -OH,- NH 2 , -OR 15 , -N(R 15 ) 2 , -COOH, -SH, -B(OH) 2 , or -Si(R 15 ) 3 ; -OR 15 , -N(R 15 ) 2 , and In -Si(R 15 ) 3 , R 15 is hydrogen or an alkyl group having 1 to 10 carbons. In said R 15 , at least one -CH 2 -may be substituted by -O-, and at least one -CH 2 CH 2- It may be substituted by -CH=CH-, and at least one hydrogen in R 15 may be substituted by halogen.
本發明為下述項等。 The present invention includes the following items.
項1.一種液晶組成物,其含有選自式(1-1)所表示的化合物的群組中的至少一種極性化合物作為第一添加物,而且具有負的介電各向異性,
式(1-1)中,
R1為碳數1至15的烷基,所述R1中,至少一個-CH2-可經-O-或-S-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,至少
一個氫可經鹵素取代;環A1及環A2獨立地為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、萘-2,6-二基、十氫萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、吡啶-2,5-二基、茀-2,7-二基、菲-2,7-二基、蒽-2,6-二基、全氫環戊并[a]菲-3,17-二基、或2,3,4,7,8,9,10,11,12,13,14,15,16,17-十四氫環戊并[a]菲-3,17-二基,該些環中,至少一個氫可經氟、氯、碳數1至12的烷基、碳數2至12的烯基、碳數1至11的烷氧基、或碳數2至11的烯氧基取代,該些基團中,至少一個氫可經氟或氯取代;a為0、1、2、3、或4;Z1為單鍵或碳數1至6的伸烷基,所述Z1中,至少一個-CH2-可經-O-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,Z1中至少一個氫可經氟或氯取代;Sp1為單鍵或碳數1至10的伸烷基,所述Sp1中,至少一個-CH2-可經-O-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,Sp1中至少一個氫可經鹵素取代,Sp1中至少一個氫經選自式(1a)所表示的基團中的基團取代;
式(1a)中,Sp12為單鍵或碳數1至10的伸烷基,所述Sp12中,至少一個-CH2-可經-O-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,Sp12中至少一個氫可經鹵素取代;M11及M12獨立地為氫、鹵素、碳數1至5的烷基、或至少一個氫經鹵素取代的碳數1至5的烷基;R12為碳數1至15的烷基,所述R12中,至少一個-CH2-可經-O-或-S-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,至少一個氫可經鹵素取代;式(1-1)中,P11為選自式(1e)及式(1f)所表示的基團中的基團;
式(1e)及式(1f)中,Sp13為單鍵或碳數1至10的伸烷基,所述Sp13中,至少一個-CH2-可經-O-、-NH-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,Sp13中至少一個氫可經鹵素取代;M13及M14獨立地為氫、鹵素、碳數1至5的烷基、或至少一個氫經鹵素取代的碳數1至5的烷基;R13為選自式(1g)、式(1h)、及式(1i)所表示的基團中的基團;
式(1g)、式(1h)、及式(1i)中,Sp14及Sp15獨立地為單鍵或碳數1至10的伸烷基,所述伸烷基中,至少一個-CH2-可經-O-、-NH-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,至少一個氫可經鹵素取代;式(1g)及式(1i)中,S1為>CH-或>N-,S2為>C<或>Si<; X1為-OH、-NH2、-OR15、-N(R15)2、-COOH、-SH、-B(OH)2、或-Si(R15)3;-OR15、-N(R15)2、及-Si(R15)3中,R15為氫或碳數1至10的烷基,所述R15中,至少一個-CH2-可經-O-取代,至少一個-CH2CH2-可經-CH=CH-取代,R15中至少一個氫可經鹵素取代。 In formula (1g), formula (1h), and formula (1i), Sp 14 and Sp 15 are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH 2 -Can be substituted by -O-, -NH-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -CH 2 CH 2 -can be -CH=CH- or -C≡C- Substitution, at least one hydrogen can be replaced by halogen; in formula (1g) and formula (1i), S 1 is >CH- or >N-, S 2 is >C< or >Si<; X 1 is -OH,- NH 2 , -OR 15 , -N(R 15 ) 2 , -COOH, -SH, -B(OH) 2 , or -Si(R 15 ) 3 ; -OR 15 , -N(R 15 ) 2 , and In -Si(R 15 ) 3 , R 15 is hydrogen or an alkyl group having 1 to 10 carbons. In said R 15 , at least one -CH 2 -may be substituted by -O-, and at least one -CH 2 CH 2- It may be substituted by -CH=CH-, and at least one hydrogen in R 15 may be substituted by halogen.
項2.如項1所述的液晶組成物,其中第一添加物為選自式(1-2)至式(1-3)所表示的化合物的群組中的至少一種聚合性化合物,
式(1-2)及式(1-3)中,R1為碳數1至12的烷基,所述烷基中,至少一個-CH2-可經-O-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,該些基 團中,至少一個氫可經氟取代;環A1及環A2獨立地為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、萘-2,6-二基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、茀-2,7-二基、菲-2,7-二基、全氫環戊并[a]菲-3,17-二基、或2,3,4,7,8,9,10,11,12,13,14,15,16,17-十四氫環戊并[a]菲-3,17-二基,該些環中,至少一個氫可經氟、碳數1至8的烷基、碳數2至8的烯基、碳數1至7的烷氧基、或碳數2至7的烯氧基取代,該些基團中,至少一個氫可經氟取代;a為0、1、2、3、或4;Z1為單鍵或碳數1至6的伸烷基,所述Z1中,至少一個-CH2-可經-O-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,該些基團中,至少一個氫可經氟或氯取代;l為0、1、2、3、4、5、或6,所述伸烷基的至少一個-CH2-可經-O-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,該些基團中,至少一個氫可經氟取代;Sp12為單鍵或碳數1至5的伸烷基,所述伸烷基中,至少一個-CH2-可經-O-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,該些基團中,至少一個氫可經氟取代;M11及M12獨立地為氫、氟、甲基、乙基、或三氟甲基; R12為氫或碳數1至5的烷基,所述烷基中,至少一個-CH2-可經-O-或-S-取代,至少一個-(CH2)2-可經-CH=CH-或-C≡C-取代,該些基團中,至少一個氫可經氟取代;Sp13為單鍵或碳數1至5的伸烷基,所述伸烷基中,至少一個-CH2-可經-O-、-CO-、或-COO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,該些基團中,至少一個氫可經氟取代;M13及M14獨立地為氫、氟、甲基、乙基、或三氟甲基;Sp14為單鍵或碳數1至5的伸烷基,所述伸烷基中,至少一個-CH2-可經-O-、-CO-、或-COO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,該些基團中,至少一個氫可經氟取代;X1為-OH或-N(R15)2;-N(R15)2中,R15為氫或碳數1至5的烷基,所述烷基中,至少一個-CH2-可經-O-取代,至少一個-CH2CH2-可經-CH=CH-取代,該些基團中,至少一個氫可經氟取代。 In formula (1-2) and formula (1-3), R 1 is an alkyl group having 1 to 12 carbons. In the alkyl group, at least one -CH 2 -may be substituted by -O-, and at least one -CH 2 CH 2 -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine; ring A 1 and ring A 2 are independently 1,4-cyclohexylene , 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2, 5-diyl, phenanthrene-2,7-diyl, phenanthrene-2,7-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl, or 2,3,4,7,8 ,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, in these rings, at least one hydrogen can be fluorine, carbon Alkyl having 1 to 8, alkenyl having 2 to 8, alkoxy having 1 to 7, or alkenyl having 2 to 7, in these groups, at least one hydrogen may be substituted by fluoro substituents; a is 0, 1,. 4; Z is a single bond or an alkylene group having a carbon number of 1-6, Z is a 1, at least one -CH 2 - may be -O-, -CO-, -COO-, -OCO-, or -OCOO- substituted, at least one -CH 2 CH 2 -may be substituted with -CH=CH- or -C≡C-, in these groups, at least one hydrogen Can be substituted by fluorine or chlorine; l is 0, 1, 2, 3, 4, 5, or 6, and at least one -CH 2 -of the alkylene group can be substituted by -O-, -CO-, -COO-, -OCO- or -OCOO- substitution, at least one -CH 2 CH 2 -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine; Sp 12 is A single bond or an alkylene having 1 to 5 carbon atoms, in which at least one -CH 2 -may be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, At least one -CH 2 CH 2 -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine; M 11 and M 12 are independently hydrogen, fluorine, methyl Group, ethyl group, or trifluoromethyl group; R 12 is hydrogen or an alkyl group having 1 to 5 carbons. In the alkyl group, at least one -CH 2 -may be substituted by -O- or -S-, and at least one -(CH 2 ) 2 -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine; Sp 13 is a single bond or an alkylene having 1 to 5 carbon atoms In the alkylene group, at least one -CH 2 -can be substituted by -O-, -CO-, or -COO-, and at least one -CH 2 CH 2 -can be -CH=CH- or -C≡ C-substitution, in these groups, at least one hydrogen can be replaced by fluorine; M 13 and M 14 are independently hydrogen, fluorine, methyl, ethyl, or trifluoromethyl; Sp 14 is a single bond or carbon number 1 to 5 alkylene groups, In the alkylene, at least one -CH 2 -may be substituted by -O-, -CO-, or -COO-, and at least one -CH 2 CH 2 -may be -CH=CH- or -C≡C- Substitution, in these groups, at least one hydrogen may be substituted by fluorine; X 1 is -OH or -N(R 15 ) 2 ; in -N(R 15 ) 2 , R 15 is hydrogen or a carbon number of 1 to 5 In the alkyl group, at least one -CH 2 -may be substituted by -O-, at least one -CH 2 CH 2 -may be substituted by -CH=CH-, in these groups, at least one hydrogen may be substituted by Fluorine substitution.
項3.如項1所述的液晶組成物,其中第一添加物為選自式(1-4)至式(1-60)所表示的化合物的群組中的至少一種聚合性化合物,
式(1-4)至式(1-60)中,R1為碳數1至10的烷基;Z1、Z12、及Z13獨立地為單鍵、-CH2CH2-、或-(CH2)4-;Sp12、Sp13、及Sp14獨立地為單鍵或碳數1至5的伸烷基,所述伸烷基中,至少一個-CH2-可經-O-取代;L1、L2、L3、L4、L5、L6、L7、L8、L9、L10、L11、及L12獨 立地為氫、氟、甲基、或乙基; l為0、1、2、3、4、5、或6。 In formulas (1-4) to (1-60), R 1 is an alkyl group having 1 to 10 carbons; Z 1 , Z 12 , and Z 13 are independently a single bond, -CH 2 CH 2 -, or -(CH 2 ) 4 -; Sp 12 , Sp 13 , and Sp 14 are independently a single bond or an alkylene group having 1 to 5 carbon atoms, in which at least one -CH 2 -may be -O -Substitution; L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 , L 8 , L 9 , L 10 , L 11 , and L 12 are independently hydrogen, fluorine, methyl, or Ethyl; l is 0, 1, 2, 3, 4, 5, or 6.
項4.如項1至項3中任一項所述的液晶組成物,其中基於液晶組成物的重量,第一添加物的比例為10重量%以下。 Item 4. The liquid crystal composition according to any one of items 1 to 3, wherein the ratio of the first additive is 10% by weight or less based on the weight of the liquid crystal composition.
項5.如項1至項4中任一項所述的液晶組成物,其含有選自式(2)所表示的化合物的群組中的至少一種化合物作為第一成分,
式(2)中,R3及R4獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、或碳數2至12的烯氧基;環C及環E獨立地為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、至少一個氫經氟或氯取代的1,4-伸苯基、或四氫吡喃-2,5-二基;環D為2,3-二氟-1,4-伸苯基、2-氯-3-氟-1,4-伸苯基、2,3-二氟-5-甲基-1,4-伸苯基、3,4,5-三氟萘-2,6-二基、或7,8-二氟色原烷-2,6-二基;Z2及Z3獨立地為單鍵、-CH2CH2-、-CH2O-、-OCH2-、-COO-、或-OCO-;b為1、2、或3,c為0或1,而且b與c之和為3以下。 In formula (2), R 3 and R 4 are independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an alkene having 2 to 12 carbons. Oxy; ring C and ring E are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-in which at least one hydrogen is substituted by fluorine or chlorine Phenylene, or tetrahydropyran-2,5-diyl; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene , 2,3-Difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2 ,6-diyl; Z 2 and Z 3 are independently a single bond, -CH 2 CH 2 -, -CH 2 O-, -OCH 2 -, -COO-, or -OCO-; b is 1, 2, Or 3, c is 0 or 1, and the sum of b and c is 3 or less.
項6.如項1至項5中任一項所述的液晶組成物,其含有選自式(2-1)至式(2-22)所表示的化合物的群組中的至少一
種化合物作為第一成分,
式(2-1)至式(2-22)中,R3及R4獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、或碳數2至12的烯氧基。 In formulas (2-1) to (2-22), R 3 and R 4 are independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and an alkenyl group having 2 to 12 carbons. , Or an alkenyloxy group having 2 to 12 carbons.
項7.如項5或項6所述的液晶組成物,其中基於液晶組成物的重量,第一成分的比例為10重量%至90重量%的範圍。 Item 7. The liquid crystal composition according to Item 5 or 6, wherein the ratio of the first component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition.
項8.如項1至項7中任一項所述的液晶組成物,其含有選自式(3)所表示的化合物的群組中的至少一種化合物作為第二成分,
式(3)中,R5及R6獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、至少一個氫經氟或氯取代的碳數1至12的烷基、或至少一個氫經氟或氯取代的碳數2至12的烯基;環F及環G獨立地為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、或2,5-二氟-1,4-伸苯基;Z4為單鍵、-CH2CH2-、-CH2O-、-OCH2-、-COO-、或-OCO-;d為1、2、或3。 In formula (3), R 5 and R 6 are independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, and at least one hydrogen is substituted by fluorine or chlorine The alkyl group having 1 to 12 carbons, or the alkenyl group having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; ring F and ring G are independently 1,4-cyclohexylene, 1,4-alkylene Phenyl, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z 4 is a single bond, -CH 2 CH 2 -, -CH 2 O-, -OCH 2 -, -COO-, or -OCO-; d is 1, 2, or 3.
項9.如項1至項8中任一項所述的液晶組成物,其含有選自式(3-1)至式(3-13)所表示的化合物的群組中的至少一種化合物作為第二成分, Item 9. The liquid crystal composition according to any one of items 1 to 8, which contains at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-13) as The second component,
式(3-1)至式(3-13)中,R5及R6獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、至少一個氫經氟或氯取代的碳數1至12的烷基、或至少一個氫經氟或氯取代的碳數2至12的烯基。 In formulas (3-1) to (3-13), R 5 and R 6 are independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and an alkenyl group having 2 to 12 carbons. , Alkyl groups having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or alkenyl groups having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.
項10.如項8或項9中任一項所述的液晶組成物,其中基於液晶組成物的重量,第二成分的比例為10重量%至90重量%的範圍。 Item 10. The liquid crystal composition according to any one of Item 8 or Item 9, wherein the ratio of the second component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition.
項11.如項1至項10中任一項所述的液晶組成物,其含有選自式(4)所表示的化合物的群組中的至少一種聚合性化合物作為第二添加物,
式(4)中,環J及環P獨立地為環己基、環己烯基、苯基、1-萘基、2-萘基、四氫吡喃-2-基、1,3-二噁烷-2-基、嘧啶-2-基、或吡啶-2-基,該些環中,至少一個氫可經氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、或至少一個氫經氟或氯取代的碳數1至12的烷基所取代;環K為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、萘-1,2-二基、萘-1,3-二基、萘-1,4-二基、萘-1,5-二基、 萘-1,6-二基、萘-1,7-二基、萘-1,8-二基、萘-2,3-二基、萘-2,6-二基、萘-2,7-二基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、或吡啶-2,5-二基,該些環中,至少一個氫可經氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、或至少一個氫經氟或氯取代的碳數1至12的烷基所取代;Z5及Z6獨立地為單鍵或碳數1至10的伸烷基,所述Z5及Z6中,至少一個-CH2-可經-O-、-CO-、-COO-或-OCO-取代,而且至少一個-CH2CH2-可經-CH=CH-、-C(CH3)=CH-、-CH=C(CH3)-、或-C(CH3)=C(CH3)-取代,至少一個氫可經氟或氯取代;P1、P2、及P3為聚合性基;Sp3、Sp4、及Sp5獨立地為單鍵或碳數1至10的伸烷基,所述Sp3、Sp4、及Sp5中,至少一個-CH2-可經-O-、-COO-、-OCO-、或-OCOO-取代,而且至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,至少一個氫可經氟或氯取代;q為0、1、或2;j、k、及p獨立地為0、1、2、3、或4,而且j、k、及p之和為1以上。 In formula (4), ring J and ring P are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxyl Alk-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in these rings, at least one hydrogen can be fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons Group, or at least one hydrogen is substituted by fluorine or chlorine substituted alkyl group with carbon number of 1 to 12; ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene Base, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1 ,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5 -Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen may be fluorine, Chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or at least one hydrogen is substituted with an alkyl group having 1 to 12 carbons substituted by fluorine or chlorine; Z 5 and Z 6 are independently A single bond or an alkylene having 1 to 10 carbon atoms, in the Z 5 and Z 6 , at least one -CH 2 -may be substituted with -O-, -CO-, -COO- or -OCO-, and at least one -CH 2 CH 2 -can be replaced by -CH=CH-, -C(CH 3 )=CH-, -CH=C(CH 3 )-, or -C(CH 3 )=C(CH 3 )-, At least one hydrogen may be replaced by fluorine or chlorine; P 1 , P 2 , and P 3 are polymerizable groups; Sp 3 , Sp 4 , and Sp 5 are independently single bonds or alkylene groups with 1 to 10 carbon atoms, so Among the Sp 3 , Sp 4 , and Sp 5 , at least one -CH 2 -may be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH 2 CH 2 -may be- CH=CH- or -C≡C- substituted, at least one hydrogen can be replaced by fluorine or chlorine; q is 0, 1, or 2; j, k, and p are independently 0, 1, 2, 3, or 4 , And the sum of j, k, and p is 1 or more.
項12.如項11所述的液晶組成物,其中式(4)中,P1、P2、及P3獨立地為選自式(P-1)至式(P-5)所表示的基團的群組中的聚合性基,
式(P-1)至式(P-5)中,M1、M2、及M3獨立地為氫、氟、碳數1至5的烷基、或至少一個氫經氟或氯取代的碳數1至5的烷基。 In formulas (P-1) to (P-5), M 1 , M 2 , and M 3 are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or at least one hydrogen substituted by fluorine or chlorine An alkyl group having 1 to 5 carbon atoms.
項13.如項1至項12中任一項所述的液晶組成物,其中第二添加物為選自式(4-1)至式(4-29)所表示的化合物的群組中的至少一種聚合性化合物,
式(4-1)至式(4-29)中,P1、P2、及P3獨立地為選自式(P-1)至式(P-3)所表示的基團的群組中的聚合性基,此處,M1、M2、及M3獨立地為氫、氟、碳數1至5的烷基、或至少一個氫經氟或
氯取代的碳數1至5的烷基;
Sp3、Sp4、及Sp5獨立地為單鍵或碳數1至10的伸烷基,所述Sp3、Sp4、及Sp5中,至少一個-CH2-可經-O-、-COO-、-OCO-、或-OCOO-取代,而且至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,至少一個氫可經氟或氯取代。 Sp 3 , Sp 4 , and Sp 5 are independently a single bond or an alkylene group having 1 to 10 carbon atoms. Among the Sp 3 , Sp 4 , and Sp 5 , at least one -CH 2 -may be through -O-, -COO-, -OCO-, or -OCOO- substituted, and at least one -CH 2 CH 2 -may be substituted with -CH=CH- or -C≡C-, and at least one hydrogen may be substituted with fluorine or chlorine.
項14.如項11至項13中任一項所述的液晶組成物,其中基於液晶組成物的重量,第二添加物的比例為0.03重量%至10重量%的範圍。 Item 14. The liquid crystal composition according to any one of Items 11 to 13, wherein the ratio of the second additive is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition.
項15.如項1至項14中任一項所述的液晶組成物,其含有選自式(5)所表示的化合物的群組中的至少一種聚合性化合物作為第三添加物,
式(5)中,R50為氫、鹵素、碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、至少一個氫經氟或氯取代的碳數1至12的烷基、或至少一個氫經氟或氯取代的碳數2至12 的烯基;R51為-OH、-NH2、-OR53、-N(R53)2、或-Si(R53)3所表示的基團,此處,R53為氫或碳數1至5的烷基,所述烷基中,至少一個-CH2-可經-O-取代,至少一個-(CH2)2-可經-CH=CH-取代,該些基團中,至少一個氫可經氟取代;環A50及環B50獨立地為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、萘-1,2-二基、萘-1,3-二基、萘-1,4-二基、萘-1,5-二基、萘-1,6-二基、萘-1,7-二基、萘-1,8-二基、萘-2,3-二基、萘-2,6-二基、萘-2,7-二基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、吡啶-2,5-二基、茀-2,7-二基、菲-2,7-二基、蒽-2,6-二基、全氫環戊并[a]菲-3,17-二基、或2,3,4,7,8,9,10,11,12,13,14,15,16,17-十四氫環戊并[a]菲-3,17-二基,該些環中,至少一個氫可經氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、或至少一個氫經氟或氯取代的碳數1至12的烷基所取代;Z50為單鍵、-(CH2)2-、-CH=CH-、-C≡C-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2O-、-OCH2-、或-CF=CF-;Sp51及Sp52獨立地為單鍵或碳數1至7的伸烷基,所述伸烷基中,至少一個-CH2-可經-O-、-COO-、或-OCO-取代,至少一個-CH2CH2-可經-CH=CH-取代,該些基團中,至少一個氫可經氟取代;a50為0、1、2、3、或4。 In formula (5), R 50 is hydrogen, halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, at least one hydrogen substituted by fluorine or chlorine An alkyl group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; R 51 is -OH, -NH 2 , -OR 53 , -N(R 53 ) 2 , Or a group represented by -Si(R 53 ) 3 , where R 53 is hydrogen or an alkyl group having 1 to 5 carbons, in which at least one -CH 2 -may be substituted by -O-, At least one -(CH 2 ) 2 -may be substituted by -CH=CH-, in these groups, at least one hydrogen may be substituted by fluorine; ring A 50 and ring B 50 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5 -Diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene -2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5- Diyl, phenanthrene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl, or 2, 3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, among these rings, at least One hydrogen may be replaced by fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; Z 50 It is a single bond, -(CH 2 ) 2 -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -CH 2 O-,- OCH 2 -or -CF=CF-; Sp 51 and Sp 52 are independently a single bond or an alkylene group having 1 to 7 carbon atoms. In the alkylene group, at least one -CH 2 -may be controlled by -O- , -COO-, or -OCO- substitution, at least one -CH 2 CH 2 -can be substituted by -CH=CH-, in these groups, at least one hydrogen can be substituted by fluorine; a 50 is 0, 1, 2 , 3, or 4.
項16.如項15所述的液晶組成物,其中基於液晶組成物的重量,第三添加物的比例為0.3重量%至10重量%的範圍。 Item 16. The liquid crystal composition according to Item 15, wherein the ratio of the third additive is in the range of 0.3% by weight to 10% by weight based on the weight of the liquid crystal composition.
項17.一種液晶顯示元件,其含有如項1至項16中任一項所述的液晶組成物。 Item 17. A liquid crystal display element comprising the liquid crystal composition according to any one of Items 1 to 16.
項18.如項17所述的液晶顯示元件,其中液晶顯示元件的運作模式為IPS模式、VA模式、FFS模式、或FPA模式,液晶顯示元件的驅動方式為主動矩陣方式。 Item 18. The liquid crystal display element according to Item 17, wherein the operation mode of the liquid crystal display element is IPS mode, VA mode, FFS mode, or FPA mode, and the driving mode of the liquid crystal display element is an active matrix mode.
項19.一種聚合物穩定配向型的液晶顯示元件,其含有如項1至項16中任一項所述的液晶組成物,且所述液晶組成物中的聚合性化合物進行聚合。 Item 19. A polymer stable alignment type liquid crystal display element, comprising the liquid crystal composition according to any one of items 1 to 16, and the polymerizable compound in the liquid crystal composition is polymerized.
項20.一種不具有配向膜的液晶顯示元件,其含有如項1至項16中任一項所述的液晶組成物,且所述液晶組成物中的聚合性化合物進行聚合。 Item 20. A liquid crystal display element without an alignment film, comprising the liquid crystal composition according to any one of Items 1 to 16, and the polymerizable compound in the liquid crystal composition is polymerized.
項21.一種液晶組成物的用途,所述液晶組成物為如項1至項16中任一項所述的液晶組成物,其用於液晶顯示元件中。 Item 21. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of Items 1 to 16, which is used in a liquid crystal display element.
項22.一種液晶組成物的用途,所述液晶組成物為如項1至項16中任一項所述的液晶組成物,其用於聚合物穩定配向型的液晶顯示元件中。 Item 22. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of Items 1 to 16, which is used in a polymer stable alignment type liquid crystal display device.
項23.一種液晶組成物的用途,所述液晶組成物為如項1至項16中任一項所述的液晶組成物,其用於不具有配向膜的液晶顯示元件中。 Item 23. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of Items 1 to 16, which is used in a liquid crystal display device that does not have an alignment film.
藉由利用本發明的包含具有極性基的聚合性極性化合物的液晶組成物,而不需要配向膜的形成步驟,因此可獲得使製造成本減少的液晶顯示元件。而且,可獲得與聚合性極性化合物的相容性良好的、具有負的介電各向異性的液晶組成物。 By using the liquid crystal composition containing a polymerizable polar compound having a polar group of the present invention, the step of forming an alignment film is not required, and therefore, a liquid crystal display element with reduced manufacturing cost can be obtained. Furthermore, a liquid crystal composition having good compatibility with the polymerizable polar compound and having negative dielectric anisotropy can be obtained.
該說明書中的用語的使用方法為如下所述。有時將「液晶組成物」及「液晶顯示元件」的用語分別簡稱為「組成物」及「元件」。「液晶顯示元件」為液晶顯示面板及液晶顯示模組的總稱。「液晶性化合物」是具有向列相、層列相等液晶相的化合物,以及雖不具有液晶相,但出於調節向列相的溫度範圍、黏度、介電各向異性之類的特性的目的而混合於組成物中的化合物的總稱。該化合物具有例如1,4-伸環己基或1,4-伸苯基之類的六員環,且其分子結構為棒狀(rod like)。「聚合性化合物」是出於使組成物中生成聚合物的目的而添加的化合物。 The usage of the terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" are sometimes abbreviated as "composition" and "device", respectively. "Liquid crystal display element" is the general term for liquid crystal display panels and liquid crystal display modules. A "liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and although it does not have a liquid crystal phase, it is for the purpose of adjusting the temperature range, viscosity, and dielectric anisotropy of the nematic phase. The general term for the compounds mixed in the composition. The compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition.
液晶組成物是藉由將多種液晶性化合物混合來製備。於該液晶組成物中視需要來添加光學活性化合物、抗氧化劑、紫外線吸收劑、色素、消泡劑、聚合性化合物、聚合起始劑、聚合抑制劑、極性化合物之類的添加物。液晶性化合物或添加物以此種順序混合。即便於添加有添加物的情況下,液晶性化合物的比例(含量)亦是由基於不含添加物的液晶組成物的重量的重量百分率(重量%)來表示。添加物的比例(添加量)是由基於不含添加物的液晶組成物的重量的重量百分率(重量%)來表示。有時亦使用重量百萬分率(ppm)。聚合起始劑及聚合抑制劑的比例例外地基於聚合性化合物的重量來表示。 The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to the liquid crystal composition as necessary. Liquid crystal compounds or additives are mixed in this order. Even when an additive is added, the ratio (content) of the liquid crystal compound is represented by the weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive. The ratio (addition amount) of the additives is represented by the weight percentage (weight %) based on the weight of the liquid crystal composition containing no additives. Sometimes parts per million by weight (ppm) are also used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.
有時將「向列相的上限溫度」簡稱為「上限溫度」。有時將「向列相的下限溫度」簡稱為「下限溫度」。「比電阻大」是指組成物在初始階段中不僅在室溫下,而且在接近於上限溫度的溫度下亦具有大的比電阻,而且在長時間使用後不僅在室溫下,而且在接近於上限溫度的溫度下亦具有大的比電阻。「電壓保持率大」是指元件在初始階段中不僅在室溫下,而且在接近於上限溫度的溫度下亦具有大的電壓保持率,而且在長時間使用後不僅在室溫下,而且在接近於上限溫度的溫度下亦具有大的電壓保持率。組成物或元件中,有時於經時變化試驗(包含加速劣化試驗)前後研究特性。「提高介電各向異性」的表述於介電各向異性為正的組成物時,是指其值正向地增加,於介電各向異性為負的組成物時,是指其值負向地增加。 The "upper limit temperature of the nematic phase" is sometimes simply referred to as the "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes referred to simply as the "lower limit temperature". "High specific resistance" means that the composition has a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and after long-term use, not only at room temperature, but also close to It also has a large specific resistance at the upper limit temperature. "High voltage holding rate" means that the device has a large voltage holding rate not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and after long-term use, not only at room temperature, but also at It also has a large voltage holding rate at a temperature close to the upper limit temperature. In a composition or element, characteristics may be studied before and after a time-dependent change test (including an accelerated deterioration test). The expression "increasing dielectric anisotropy" refers to a positive increase in the value of a composition with positive dielectric anisotropy, and a negative value in the case of a composition with negative dielectric anisotropy Increase to the ground.
有時將式(2)所表示的化合物簡稱為「化合物(2)」。 有時將選自式(2)所表示的化合物的群組中的至少一種化合物簡稱為「化合物(2)」。「化合物(2)」是指式(2)所表示的一種化合物、兩種化合物的混合物、或三種以上化合物的混合物。對於其他式所表示的化合物亦相同。「至少一個‘A’」的表述是指‘A’的數量為任意。「至少一個‘A’可經‘B’取代」的表述是指於‘A’的數量為一個時,‘A’的位置為任意,於‘A’的數量為兩個以上時,它們的位置亦可無限制地選擇。該規則亦適用於「至少一個‘A’經‘B’取代」的表述。而且,本說明書中,有時將式(1-1)所表示的化合物及作為其下位式的式(1-2)至式(1-60)所表示的化合物總稱為化 合物(1)。 The compound represented by formula (2) may be abbreviated as "compound (2)". At least one compound selected from the group of compounds represented by formula (2) may be simply referred to as "compound (2)". "Compound (2)" refers to one compound, a mixture of two compounds, or a mixture of three or more compounds represented by formula (2). The same is true for compounds represented by other formulas. The expression "at least one ‘A’" means that the number of ‘A’ is arbitrary. The expression "at least one'A' can be replaced by'B'" means that when the number of'A' is one, the position of'A' is arbitrary, and when the number of'A' is more than two, their positions Can also choose unlimitedly. This rule also applies to the expression "at least one ‘A’ is replaced by a ‘B’". In addition, in this specification, the compound represented by formula (1-1) and the compounds represented by formula (1-2) to formula (1-60) as its subordinate formula may be collectively referred to as Compound (1).
成分化合物的化學式中,將末端基R1的記號用於多種化合物。該些化合物中,任意的兩個R1所表示的兩個基可相同,或者亦可不同。例如,有化合物(1-1)的R1為乙基,且化合物(1-2)的R1為乙基的情況。亦有化合物(1-1)的R1為乙基,而化合物(1-2)的R1為丙基的情況。該規則亦適用於其他末端基等的記號。式(1-1)中,於a為2時,存在兩個環A。該化合物中,兩個環A所表示的兩個環可相同,或者亦可不同。於a大於2時,該規則亦適用於任意的兩個環A。該規則亦適用於其他記號。該規則亦適用於化合物(4-27)中的兩個-Sp4-P2之類的情況。 In the chemical formula of the component compound, the symbol of the terminal group R 1 is used for various compounds. In these compounds, two groups represented by any two R 1 may be the same or different. For example, there is a case where R 1 of compound (1-1) is ethyl, and R 1 of compound (1-2) is ethyl. There are also cases where R 1 of compound (1-1) is ethyl, and R 1 of compound (1-2) is propyl. This rule also applies to the markings of other end groups. In formula (1-1), when a is 2, two rings A exist. In this compound, the two rings represented by the two rings A may be the same or different. When a is greater than 2, this rule also applies to any two rings A. This rule also applies to other marks. This rule also applies to situations such as two -Sp 4 -P 2 in compound (4-27).
由六邊形包圍的A、C、D、E等記號分別與環A、環C、環D、環E等環相對應,且表示六員環、縮合環等環。將該六邊形橫切的斜線表示環上的任意氫可經-Sp3-P1等基團取代。‘j’等下標表示經取代的基團的數量。於下標‘j’為0時,不存在此種取代。 於下標‘j’為2以上時,於環J上存在多個-Sp3-P1。-Sp3-P1所表示的多個基可相同,或者亦可不同。 Symbols such as A, C, D, E surrounded by hexagons respectively correspond to rings such as ring A, ring C, ring D, and ring E, and indicate rings such as six-membered rings and condensed rings. The oblique line crossing the hexagon indicates that any hydrogen on the ring can be replaced by a group such as -Sp 3 -P 1 . Subscripts such as'j' indicate the number of substituted groups. When the subscript'j' is 0, there is no such substitution. When the subscript'j' is 2 or more, there are multiple -Sp 3 -P 1 on the ring J. The plural groups represented by -Sp 3 -P 1 may be the same or different.
2-氟-1,4-伸苯基是指下述兩種二價基。化學式中,氟可為朝左(L),亦可為朝右(R)。該規則亦適用於四氫吡喃-2,5-二基之類的藉由自環中去除兩個氫而生成的非對稱的二價基。該規則亦適用於羰氧基(-COO-或-OCO-)之類的二價鍵結基。 2-Fluoro-1,4-phenylene refers to the following two divalent groups. In the chemical formula, fluorine can be leftward (L) or rightward (R). This rule also applies to asymmetric divalent groups such as tetrahydropyran-2,5-diyl which are formed by removing two hydrogens from the ring. This rule also applies to divalent bonding groups such as carbonyloxy (-COO- or -OCO-).
於該說明書中使用「至少一個-CH2-可經-O-取代」之類的表述。該情況下,-CH2-CH2-CH2-可藉由不鄰接的-CH2-經-O-取代而轉換為-O-CH2-O-。然而,鄰接的-CH2-不會經-O-取代。這是因為該取代中生成-O-O-CH2-(過氧化物)。即,該表述是指「一個-CH2-可經-O-取代」與「至少兩個不鄰接的-CH2-可經-O-取代」兩者。該規則不僅適用於取代為-O-的情況,亦適用於取代為如-CH=CH-或-COO-之類的二價基的情況。式(1)中,R1為碳數1至25的烷基等。存在該烷基的碳數藉由此種取代而增加的情況。 此時,最大的碳數為30。該規則不僅適用於R1之類的一價基,亦適用於伸烷基之類的二價基。 Expressions such as "at least one -CH 2 -may be substituted by -O-" are used in this specification. In this case, -CH 2 -CH 2 -CH 2 -can be converted to -O-CH 2 -O- by replacing non-adjacent -CH 2 -with -O-. However, the adjacent -CH 2 -will not be substituted by -O-. This is because -OO-CH 2- (peroxide) is generated in the substitution. That is, the expression means both "one -CH 2 -can be substituted by -O-" and "at least two non-adjacent -CH 2 -can be substituted by -O-". This rule applies not only to the case of substitution with -O-, but also to the case of substitution with a divalent group such as -CH=CH- or -COO-. In the formula (1), R 1 is an alkyl group having 1 to 25 carbon atoms or the like. The carbon number of the alkyl group may increase by such substitution. At this time, the maximum carbon number is 30. This rule applies not only to such R 1 is a monovalent radical, is also applicable to a divalent alkyl extending like.
液晶性化合物的烷基為直鏈狀或分支狀,不包含環狀烷基。直鏈狀烷基優於分支狀烷基。該些情況對於烷氧基、烯基等末端基亦相同。與1,4-伸環己基相關的立體構型通常是反式構型優於順式構型。鹵素是指氟、氯、溴、碘。較佳的鹵素為氟或氯。 尤佳的鹵素為氟。 The alkyl group of the liquid crystal compound is linear or branched, and does not include a cyclic alkyl group. Straight-chain alkyl is better than branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. The three-dimensional configuration related to 1,4-cyclohexylene is usually the trans configuration better than the cis configuration. Halogen refers to fluorine, chlorine, bromine, and iodine. The preferred halogen is fluorine or chlorine. A particularly preferred halogen is fluorine.
本發明亦包括以下項。(a)液晶顯示元件的製造方法,其藉由將所述液晶組成物配置於兩塊基板之間,在對該組成物施加電壓的狀態下照射光,使該組成物中所含有的在分子末端的分 支結構中具有聚合性基與極性基的化合物進行聚合,來製造所述液晶顯示元件。(b)所述液晶組成物,其向列相的上限溫度為70℃以上,波長589nm下的光學各向異性(於25℃下測定)為0.08以上,而且頻率1kHz下的介電各向異性(於25℃下測定)為-2以下。 The present invention also includes the following items. (a) A method for manufacturing a liquid crystal display element, which comprises disposing the liquid crystal composition between two substrates, and irradiating light with a voltage applied to the composition, so that the in-molecule contained in the composition End points A compound having a polymerizable group and a polar group in the branch structure is polymerized to produce the liquid crystal display element. (b) The liquid crystal composition, wherein the upper limit temperature of the nematic phase is 70°C or higher, the optical anisotropy (measured at 25°C) at a wavelength of 589nm is 0.08 or higher, and the dielectric anisotropy at a frequency of 1kHz (Measured at 25°C) is -2 or less.
本發明亦包括以下項。(c)所述組成物,雖然日本專利特開2006-199941號公報中記載的化合物(5)至化合物(7)是介電各向異性為正的液晶性化合物,但所述組成物含有選自該些化合物的群組中的至少一種化合物。(d)所述組成物,其含有至少兩個所述在分子末端的分支結構中具有聚合性基與極性基的化合物(1-1)。(e)所述組成物,其更含有與在分子末端的分支結構中具有聚合性基與極性基的化合物(1-1)不同的極性化合物。(f)所述組成物,其含有一種、兩種、或至少三種光學活性化合物、抗氧化劑、紫外線吸收劑、色素、消泡劑、聚合性化合物、聚合起始劑、聚合抑制劑、極性化合物之類的添加物。(g)AM元件,其含有所述組成物。(h)元件,其含有所述組成物,而且具有TN模式、ECB模式、OCB模式、IPS模式、FFS模式、VA模式、或FPA模式。(i)透過型元件,其含有所述組成物。(j)將所述組成物用作具有向列相的組成物。(k)藉由在所述組成物中添加光學活性化合物而作為光學活性組成物的用途。 The present invention also includes the following items. (c) The composition, although the compounds (5) to (7) described in Japanese Patent Laid-Open No. 2006-199941 are liquid crystal compounds with positive dielectric anisotropy, the composition contains selected At least one compound from the group of these compounds. (d) The composition containing at least two compounds (1-1) having a polymerizable group and a polar group in the branched structure at the molecular terminal. (e) The composition further contains a polar compound different from the compound (1-1) having a polymerizable group and a polar group in the branched structure of the molecule terminal. (f) The composition, which contains one, two, or at least three optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds And other additives. (g) An AM device containing the composition. (h) A device containing the composition and having a TN mode, ECB mode, OCB mode, IPS mode, FFS mode, VA mode, or FPA mode. (i) A transmissive element containing the composition. (j) Use the composition as a composition having a nematic phase. (k) Use as an optically active composition by adding an optically active compound to the composition.
以如下順序對本發明的組成物進行說明。第一,對組成物的構成進行說明。第二,對成分化合物的主要特性、及該化合 物給組成物帶來的主要效果進行說明。第三,對組成物中的成分的組合、成分的較佳的比例及其根據進行說明。第四,對成分化合物的較佳的形態進行說明。第五,示出較佳的成分化合物。第六,對可添加於組成物中的添加物進行說明。第七,對成分化合物的合成方法進行說明。最後,對組成物的用途進行說明。 The composition of the present invention will be described in the following order. First, the composition of the composition will be explained. Second, the main characteristics of the component compounds and the compound The main effects of the composition on the composition will be explained. Thirdly, the combination of the components in the composition, the preferable ratio of the components, and the basis will be described. Fourth, the preferred form of the component compounds will be described. Fifth, the preferred component compounds are shown. Sixth, additives that can be added to the composition will be described. Seventh, the synthesis method of the component compounds will be described. Finally, the use of the composition will be explained.
第一,對組成物的構成進行說明。本發明的組成物被分類為組成物A及組成物B。組成物A除了含有選自化合物(2)及化合物(3)中的液晶性化合物以外,亦可更含有其他的液晶性化合物、添加物等。「其他的液晶性化合物」是與化合物(2)及化合物(3)不同的液晶性化合物。此種化合物是出於進一步調整特性的目的而混合於組成物中。添加物為光學活性化合物、抗氧化劑、紫外線吸收劑、色素、消泡劑、聚合性化合物、聚合起始劑、聚合抑制劑、極性化合物等。 First, the composition of the composition will be explained. The composition of the present invention is classified into composition A and composition B. In addition to the liquid crystal compound selected from the compound (2) and the compound (3), the composition A may further contain other liquid crystal compounds, additives, and the like. The "other liquid crystal compound" is a liquid crystal compound different from the compound (2) and the compound (3). Such compounds are mixed in the composition for the purpose of further adjusting the characteristics. The additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like.
組成物B實質上僅包含選自化合物(2)及化合物(3)中的液晶性化合物。「實質上」是指組成物雖可含有添加物,但不含其他的液晶性化合物。與組成物A相比較,組成物B的成分的數量少。自降低成本的觀點而言,組成物B優於組成物A。自可藉由混合其他液晶性化合物來進一步調整特性的觀點而言,組成物A優於組成物B。 The composition B essentially contains only the liquid crystal compound selected from the compound (2) and the compound (3). "Substantially" means that although the composition may contain additives, it does not contain other liquid crystal compounds. Compared with composition A, the number of components of composition B is small. From the viewpoint of cost reduction, composition B is superior to composition A. From the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds, the composition A is superior to the composition B.
第二,對成分化合物的主要特性、及該化合物給組成物的特性帶來的主要效果進行說明。基於本發明的效果,將成分化合物的主要特性歸納於表2中。表2的記號中,L是指大或高,M 是指中等程度的,S是指小或低。記號L、M、S是基於成分化合物之間的定性比較的分類,記號0是指值為零,或接近於零。 Second, the main characteristics of the component compounds and the main effects of the compounds on the characteristics of the composition will be explained. Based on the effects of the present invention, the main characteristics of the component compounds are summarized in Table 2. In the notation in Table 2, L means large or high, M Means moderate, S means small or low. The symbols L, M, and S are classifications based on the qualitative comparison between component compounds, and the symbol 0 means that the value is zero or close to zero.
於將成分化合物混合於組成物中時,成分化合物給組成物的特性帶來的主要效果為如下所述。化合物(1)藉由極性基的作用而吸附於基板表面,並控制液晶分子的配向。為了獲得所期望的效果,化合物(1)必須具有與液晶性化合物的高的相容性。 可認為化合物(1)具有1,4-伸環己基或1,4-伸苯基之類的六員環且具有棒狀的分子結構,而且於分子結構的單末端具有分支狀的結構而可提高相容性,因此最適於該目的。化合物(1)藉由聚合而形成聚合物。該聚合物由於使液晶分子的配向穩定化,因此縮短元件的響應時間,而且改善圖像的殘像。化合物(2)提高介電各向異性,而且降低下限溫度。化合物(3)降低黏度。化合物(4)藉由聚合而形成聚合物。該聚合物由於使液晶分子的配向穩定化,因此縮短元件的響應時間,而且改善圖像的殘像。自液晶分子的配向的觀點而言,化合物(1)的聚合物由於具有與基板表面 的相互作用,因此推斷相較於化合物(4)的聚合物而更有效果。 化合物(5)在分子結構的末端以直鏈狀具有極性基與聚合性基,與化合物(1)同樣地控制、促進液晶分子的配向。 When the component compounds are mixed in the composition, the main effects of the component compounds on the characteristics of the composition are as follows. The compound (1) is adsorbed on the surface of the substrate by the action of the polar group and controls the alignment of the liquid crystal molecules. In order to obtain the desired effect, the compound (1) must have high compatibility with the liquid crystal compound. It can be considered that compound (1) has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene and has a rod-shaped molecular structure, and has a branched structure at one end of the molecular structure. It improves compatibility and is therefore most suitable for this purpose. The compound (1) forms a polymer by polymerization. Since the polymer stabilizes the alignment of liquid crystal molecules, the response time of the device is shortened, and the afterimage of the image is improved. The compound (2) increases the dielectric anisotropy and lowers the minimum temperature. Compound (3) reduces viscosity. Compound (4) forms a polymer by polymerization. Since the polymer stabilizes the alignment of liquid crystal molecules, the response time of the device is shortened, and the afterimage of the image is improved. From the viewpoint of the alignment of liquid crystal molecules, the polymer of compound (1) has Therefore, it is inferred that it is more effective than the polymer of compound (4). The compound (5) has a polar group and a polymerizable group in a linear form at the end of the molecular structure, and controls and promotes the alignment of liquid crystal molecules in the same manner as the compound (1).
第三,對組成物中的成分的組合、成分的較佳的比例及其根據進行說明。組成物中的成分的較佳組合為化合物(1)+化合物(2)+化合物(3)、或化合物(1)+化合物(2)+化合物(3)+化合物(4)。亦可於該些組合中進一步組合化合物(5)。 Thirdly, the combination of the components in the composition, the preferable ratio of the components, and the basis will be described. A preferable combination of the components in the composition is compound (1) + compound (2) + compound (3), or compound (1) + compound (2) + compound (3) + compound (4). Compound (5) can also be further combined in these combinations.
化合物(1)是出於控制液晶分子的配向的目的而添加於組成物中。為了使液晶分子進行配向,化合物(1)的較佳的比例為約0.05重量%以上,為了防止元件的顯示不良,化合物(1)的較佳的比例為約10重量%以下。尤佳的比例為約0.1重量%至約7重量%的範圍。特佳的比例為約0.5重量%至約5重量%的範圍。 The compound (1) is added to the composition for the purpose of controlling the alignment of liquid crystal molecules. In order to align the liquid crystal molecules, the preferable ratio of the compound (1) is about 0.05% by weight or more, and in order to prevent poor display of the device, the preferable ratio of the compound (1) is about 10% by weight or less. A particularly preferable ratio is in the range of about 0.1% by weight to about 7% by weight. A particularly preferable ratio is in the range of about 0.5% by weight to about 5% by weight.
為了提高介電各向異性,化合物(2)的較佳的比例為約10重量%以上,為了降低下限溫度,化合物(2)的較佳的比例為約90重量%以下。尤佳的比例為約20重量%至約85重量%的範圍。特佳的比例為約30重量%至約85重量%的範圍。 In order to increase the dielectric anisotropy, the preferred proportion of the compound (2) is about 10% by weight or more, and in order to reduce the minimum temperature, the preferred proportion of the compound (2) is about 90% by weight or less. A particularly preferable ratio is in the range of about 20% by weight to about 85% by weight. A particularly preferable ratio is in the range of about 30% by weight to about 85% by weight.
為了提高上限溫度或為了降低下限溫度,化合物(3)的較佳的比例為約10重量%以上,為了提高介電各向異性,化合物(3)的較佳的比例為約90重量%以下。尤佳的比例為約15重量%至約75重量%的範圍。特佳的比例為約15重量%至約60重量%的範圍。 In order to increase the upper limit temperature or lower the lower limit temperature, the preferred proportion of compound (3) is about 10% by weight or more, and in order to increase the dielectric anisotropy, the preferred proportion of compound (3) is about 90% by weight or less. A particularly preferable ratio is in the range of about 15% by weight to about 75% by weight. A particularly preferable ratio is in the range of about 15% by weight to about 60% by weight.
化合物(4)是出於適合於聚合物穩定配向型的元件的目的而添加於組成物中。為了使元件的長期可靠性提高,化合物(4)的較佳的比例為約0.03重量%以上,為了防止元件的顯示不良,化合物(4)的較佳的比例為約10重量%以下。尤佳的比例為約0.1重量%至約2重量%的範圍。特佳的比例為約0.2重量%至約1.0重量%的範圍。 The compound (4) is added to the composition for the purpose of being suitable for a polymer stable alignment type element. In order to improve the long-term reliability of the device, the preferred ratio of the compound (4) is about 0.03% by weight or more. To prevent poor display of the device, the preferred ratio of the compound (4) is about 10% by weight or less. A particularly preferable ratio is in the range of about 0.1% by weight to about 2% by weight. A particularly preferred ratio is in the range of about 0.2% by weight to about 1.0% by weight.
化合物(5)是出於控制、促進液晶分子的配向的目的而添加於組成物中。為了使液晶分子進行配向,化合物(5)的較佳的比例為約0.05重量%以上,為了防止元件的顯示不良,化合物(5)的較佳的比例為約10重量%以下。尤佳的比例為約0.1重量%至約7重量%的範圍。特佳的比例為約0.3重量%至約5重量%的範圍。 The compound (5) is added to the composition for the purpose of controlling and promoting the alignment of liquid crystal molecules. In order to align the liquid crystal molecules, the preferred ratio of the compound (5) is about 0.05% by weight or more, and in order to prevent poor display of the device, the preferred ratio of the compound (5) is about 10% by weight or less. A particularly preferable ratio is in the range of about 0.1% by weight to about 7% by weight. A particularly preferable ratio is in the range of about 0.3% by weight to about 5% by weight.
第四,對成分化合物的較佳的形態進行說明。式(1-1)中,式(1f)、式(1g)、式(1h)、及式(1i)的X1為極性基。化合物(1-1)因添加於組成物中,因此較佳為穩定。於將化合物(1-1)添加於組成物中時,較佳為該化合物不會降低元件的電壓保持率。化合物(1-1)較佳為具有低的揮發性。較佳的莫耳質量為130g/mol以上。尤佳的莫耳質量為150g/mol至800g/mol的範圍。 較佳的化合物(1-1)具有丙烯醯氧基(-OCO-CH=CH2)、甲基丙烯醯氧基(-OCO-(CH3)C=CH2)、丙烯酸α-羥基烷基酯之類的聚合性基。 Fourth, the preferred form of the component compounds will be described. In formula (1-1), X 1 in formula (1f), formula (1g), formula (1h), and formula (1i) is a polar group. Since the compound (1-1) is added to the composition, it is preferably stable. When the compound (1-1) is added to the composition, it is preferable that the compound does not reduce the voltage holding ratio of the device. The compound (1-1) preferably has low volatility. The preferred molar mass is 130 g/mol or more. A particularly preferred molar mass is in the range of 150 g/mol to 800 g/mol. The preferred compound (1-1) has acryloxy group (-OCO-CH=CH 2 ), methacryloxy group (-OCO-(CH 3 )C=CH 2 ), acrylic acid α-hydroxyalkyl Polymeric groups such as esters.
式(1f)、式(1g)、式(1h)、及式(1i)中,X1為-OH、 -NH2、-OR15、-N(R15)2、-COOH、-SH、-B(OH)2或-Si(R15)3所表示的基團,此處,R15為氫或碳數1至5的烷基,所述烷基中,至少一個-CH2-可經-O-取代,至少一個-CH2CH2-可經-CH=CH-取代,該些基團中,至少一個氫可經氟取代。就於液晶組成物中的高的溶解度的觀點而言,X1特佳為-OH或-NH2。-OH因具有高的錨固力,因此優於-O-、-CO-、或-COO-。特佳為具有多個雜原子(氮、氧)的基。具有此種極性基的化合物即便為低濃度,亦有效。 In formula (1f), formula (1g), formula (1h), and formula (1i), X 1 is -OH, -NH 2 , -OR 15 , -N(R 15 ) 2 , -COOH, -SH, A group represented by -B(OH) 2 or -Si(R 15 ) 3 , where R 15 is hydrogen or an alkyl group having 1 to 5 carbon atoms, in which at least one -CH 2 -may be Substituting -O-, at least one -CH 2 CH 2 -may be substituted with -CH=CH-, and in these groups, at least one hydrogen may be substituted with fluorine. From the viewpoint of high solubility in the liquid crystal composition, X 1 is particularly preferably -OH or -NH 2 . -OH is superior to -O-, -CO-, or -COO- because of its high anchoring force. Particularly preferred is a group having multiple heteroatoms (nitrogen, oxygen). The compound having such a polar group is effective even at a low concentration.
式(1-1)中,R1為碳數1至15的烷基,所述R1中,至少一個-CH2-可經-O-或-S-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,至少一個氫可經鹵素取代。 In the formula (1-1), R 1 is an alkyl group having 1 to 15 carbons. In the R 1 , at least one -CH 2 -may be substituted with -O- or -S-, and at least one -CH 2 CH 2 -May be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by halogen.
環A1及環A2獨立地為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、萘-2,6-二基、十氫萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、吡啶-2,5-二基、茀-2,7-二基、菲-2,7-二基、蒽-2,6-二基、全氫環戊并[a]菲-3,17-二基、或2,3,4,7,8,9,10,11,12,13,14,15,16,17-十四氫環戊并[a]菲-3,17-二基,該些環中,至少一個氫可經氟、氯、碳數1至12的烷基、碳數2至12的烯基、碳數1至11的烷氧基、或碳數2至11的烯氧基取代,該些基團中,至少一個氫可經氟或氯取代。 較佳的環A1或環A2為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、萘-2,6-二基、或3-乙基-1,4-伸苯基。 Ring A 1 and Ring A 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decalin-2 ,6-Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-di Base, pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyridine-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydro ring Pentano[a]phenanthrene-3,17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[ a] Phenanthrene-3,17-diyl, in these rings, at least one hydrogen may be fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkane having 1 to 11 carbons. An oxy group or an alkenyloxy group having a carbon number of 2 to 11 is substituted. In these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferred ring A 1 or ring A 2 is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, naphthalene-2,6-diyl, or 3 -Ethyl-1,4-phenylene.
式(1-1)中,Z1為單鍵或碳數1至6的伸烷基,所述Z1中,至少一個-CH2-可經-O-、-CO-、-COO-、-OCO-、或-OCOO- 取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,至少一個氫可經氟或氯取代。較佳的Z1為單鍵、-CH2CH2-、-CH2O-、-OCH2-、-COO-、或-OCO-。尤佳的Z1為單鍵。 In the formula (1-1), Z 1 is a single bond or an alkylene group having 1 to 6 carbons, and in the Z 1 at least one -CH 2 -can pass through -O-, -CO-, -COO-, -OCO- or -OCOO- substitution, at least one -CH 2 CH 2 -can be replaced by -CH=CH- or -C≡C-, at least one hydrogen can be replaced by fluorine or chlorine. Preferably Z 1 is a single bond, -CH 2 CH 2 -, -CH 2 O-, -OCH 2 -, -COO-, or -OCO-. Z 1 is particularly preferably a single bond.
式(1-1)中,a為0、1、2、3、或4。較佳的a為0、1、2、或3。尤佳的a為0、1、或2。特佳的a為1或2。 In formula (1-1), a is 0, 1, 2, 3, or 4. Preferably a is 0, 1, 2, or 3. More preferably, a is 0, 1, or 2. Particularly preferred a is 1 or 2.
式(1-1)中,Sp1為單鍵或碳數1至10的伸烷基,所述Sp1中,至少一個-CH2-可經-O-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,至少一個氫可經鹵素取代,該些基團中,至少一個氫經選自式(1a)所表示的基團中的基團取代;
式(1a)中, Sp12為單鍵或碳數1至10的伸烷基,所述Sp12中,至少一個-CH2-可經-O-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,至少一個氫可經鹵素取代。較佳的Sp12為單鍵、碳數1至5的伸烷基、或一個-CH2-經-O-取代的碳數1至5的伸烷基。尤佳的Sp12為單鍵、碳數1至3的 伸烷基、或一個-CH2-經-O-取代的碳數1至3的伸烷基。 In the formula (1a), Sp 12 is a single bond or an alkylene group having 1 to 10 carbon atoms, and in the Sp 12 , at least one -CH 2 -can pass through -O-, -CO-, -COO-, -OCO -Or -OCOO- substitution, at least one -CH 2 CH 2 -can be substituted by -CH=CH- or -C≡C-, at least one hydrogen can be substituted by halogen. Preferred Sp 12 is a single bond, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms substituted by -CH 2 --O-. Particularly preferred Sp 12 is a single bond, an alkylene group having 1 to 3 carbon atoms, or an alkylene group having 1 to 3 carbon atoms substituted with -CH 2 --O-.
M11及M12獨立地為氫、鹵素、碳數1至5的烷基、或至少一個氫經鹵素取代的碳數1至5的烷基。為了提高反應性,較佳的M11或M12為氫或甲基。尤佳的M11或M12為氫。 M 11 and M 12 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is substituted with halogen. In order to improve the reactivity, preferred M 11 or M 12 is hydrogen or methyl. More preferably, M 11 or M 12 is hydrogen.
R12為碳數1至15的烷基,所述R12中,至少一個-CH2-可經-O-或-S-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,至少一個氫可經鹵素取代。較佳的R12為氫、或碳數1至5的伸烷基、或一個-CH2-經-O-取代的碳數1至5的伸烷基。尤佳的R12為氫、或碳數1至3的伸烷基、或一個-CH2-經-O-取代的碳數1至3的伸烷基。特佳的R12為氫或甲基。於R12為-CH2-OH的情況下,由於在分子內存在兩個羥基的效果而可期待低濃度添加的垂直配向。 R 12 is an alkyl group having 1 to 15 carbons. In the R 12 , at least one -CH 2 -may be substituted by -O- or -S-, and at least one -CH 2 CH 2 -may be substituted by -CH=CH- Or -C≡C- substitution, at least one hydrogen may be substituted by halogen. Preferably, R 12 is hydrogen, or an alkylene group having 1 to 5 carbons, or a -CH 2 -alkylene group having 1 to 5 carbons substituted by -O-. Particularly preferred R 12 is hydrogen, or an alkylene group having 1 to 3 carbons, or an alkylene group having 1 to 3 carbons substituted by -CH 2 -with -O-. Particularly preferred R 12 is hydrogen or methyl. In the case where R 12 is -CH 2 -OH, the effect of the presence of two hydroxyl groups in the molecule makes it possible to expect vertical alignment added at a low concentration.
式(1-1)中,較佳的Sp1為碳數1至5的伸烷基、或一個-CH2-經-O-取代的碳數1至5的伸烷基。尤佳的Sp1為碳數1至3的伸烷基、或一個-CH2-經-O-取代的碳數1至3的伸烷基,該些基團中,至少一個氫可經式(1a)所表示的聚合性基取代。 In formula (1-1), preferred Sp 1 is an alkylene group having 1 to 5 carbons, or an alkylene group having 1 to 5 carbons substituted by -CH 2 --O-. Particularly preferred Sp 1 is an alkylene group having 1 to 3 carbons, or a -CH 2 -alkylene group having 1 to 3 carbons substituted by -O-. In these groups, at least one hydrogen may be The polymerizable group represented by (1a) is substituted.
P11為選自式(1e)及式(1f)所表示的基團中的基團,
式(1e)中,R13為選自式(1g)、式(1h)、及式(1i)所表示的基團中的基團。 In formula (1e), R 13 is a group selected from the groups represented by formula (1g), formula (1h), and formula (1i).
式(1e)及式(1f)中, Sp13為單鍵或碳數1至10的伸烷基,所述Sp13中,至少一個-CH2-可經-O-、-NH-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,該些基團中,至少一個氫可經鹵素取代。較佳的Sp13為碳數1至7的伸烷基、或一個-CH2-經-O-取代的碳數1至5的伸烷基。尤佳的Sp13為碳數1至5的伸烷基、或一個-CH2-經-O-取代的碳數1至5的伸烷基。特佳的Sp13為-CH2-。 In formula (1e) and formula (1f), Sp 13 is a single bond or an alkylene group having 1 to 10 carbon atoms, and in the Sp 13 , at least one -CH 2 -can be controlled by -O-, -NH-,- CO-, -COO-, -OCO-, or -OCOO- substituted, at least one -CH 2 CH 2 -may be substituted with -CH=CH- or -C≡C-, in these groups, at least one hydrogen may Replaced by halogen. Preferably, Sp 13 is an alkylene group having 1 to 7 carbon atoms, or an alkylene group having 1 to 5 carbon atoms substituted by -CH 2 --O-. Particularly preferred Sp 13 is an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms substituted by -CH 2 -with -O-. Particularly preferred Sp 13 is -CH 2 -.
式(1e)中,M13及M14獨立地為氫、鹵素、碳數1至5的烷基、或至少一個氫經鹵素取代的碳數1至5的烷基,為了提高反應性,較佳的M13或M14為氫或甲基。尤佳的M13或M14為氫。 In the formula (1e), M 13 and M 14 are independently hydrogen, halogen, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is substituted by halogen. In order to improve the reactivity, it is more Preferably M 13 or M 14 is hydrogen or methyl. Particularly preferred M 13 or M 14 is hydrogen.
式(1e)中,R13為選自式(1g)、式(1h)、及式(1i)所表示的極性基的群組中的基團,較佳的R13為式(1g)或式(1h)所表示的極性基。尤佳的R13為式(1g)所表示的極性基。 In formula (1e), R 13 is a group selected from the group of polar groups represented by formula (1g), formula (1h), and formula (1i), preferably R 13 is formula (1g) or The polar group represented by formula (1h). Particularly preferred R 13 is a polar group represented by formula (1g).
式(1g)、式(1h)、及式(1i)中,Sp14及Sp15獨立地為單鍵或碳數1至10的伸烷基,所述Sp14及Sp15中,至少一個-CH2-可經-O-、-NH-、-CO-、-COO-、-OCO-、或-OCOO-取代,至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,該些基團中,至少一個氫可經鹵素取代。較佳的Sp14或Sp15為碳數1至7的伸烷基、或一個-CH2-經-O-取代的碳數1至5的伸烷基。尤佳的Sp14或Sp15為碳數1至5的伸烷基、或一個-CH2-經-O-取代的碳數1至5的伸烷基。特佳的Sp14或Sp15為-CH2-。 In formula (1g), formula (1h), and formula (1i), Sp 14 and Sp 15 are independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of Sp 14 and Sp 15 is- CH 2 -can be substituted by -O-, -NH-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -CH 2 CH 2 -can be -CH=CH- or -C≡ C-substituted, in these groups, at least one hydrogen may be substituted by halogen. Preferred Sp 14 Sp 15 carbon atoms or alkylene of 1 to 7, or a -CH 2 - replaced by -O- alkylene group having a carbon number of 1 to 5. Particularly preferred Sp 14 or Sp 15 is an alkylene group having 1 to 5 carbon atoms, or a -CH 2 -alkylene group having 1 to 5 carbon atoms substituted by -O-. Particularly preferred Sp 14 or Sp 15 is -CH 2 -.
式(1h)及式(1i)中,S1為>CH-或>N-,而且S2為>C<或>Si<。較佳的S1為>CH-,較佳的S2為>C<。 In formula (1h) and formula (1i), S 1 is >CH- or >N-, and S 2 is >C< or >Si<. The preferred S 1 is >CH-, and the preferred S 2 is >C<.
式(1f)、式(1g)、及式(1i)中,X1為-OH、-NH2、-OR5、-N(R15)2、-COOH、-SH、-B(OH)2、或-Si(R15)3,此處,R15為氫或碳數1至10的烷基,所述烷基中,至少一個-CH2-可經-O-取代,至少一個-CH2-CH2-可經-CH=CH-取代,該些基團中,至少一個氫可經氟或氯取代。較佳的X1為-OH、-NH2、或-N(R15)2,此處,R15為氫或碳數1至10的烷基,所述R15中,至少一個-CH2-可經-O-取代,至少一個-CH2CH2-可經-CH=CH-取代,至少一個氫可經鹵素取代。較佳的X1為碳數1至5的烷基或碳數1至4的烷氧基。 尤佳的X1為-OH、-NH2、或-N(R15)2。特佳的X1為-OH。 In formula (1f), formula (1g), and formula (1i), X 1 is -OH, -NH 2 , -OR 5 , -N(R 15 ) 2 , -COOH, -SH, -B(OH) 2 , or -Si(R 15 ) 3 , where R 15 is hydrogen or an alkyl group having 1 to 10 carbons. In the alkyl group, at least one -CH 2 -may be substituted by -O-, and at least one- CH 2 -CH 2 -may be substituted by -CH=CH-, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine. Preferably X 1 is -OH, -NH 2 , or -N(R 15 ) 2 , where R 15 is hydrogen or an alkyl group having 1 to 10 carbons, and at least one of -CH 2 in R 15 -May be substituted by -O-, at least one -CH 2 CH 2 -may be substituted by -CH=CH-, at least one hydrogen may be substituted by halogen. Preferably X 1 is an alkyl group having 1 to 5 carbons or an alkoxy group having 1 to 4 carbons. Particularly preferred X 1 is -OH, -NH 2 , or -N(R 15 ) 2 . Particularly preferred X 1 is -OH.
式(1-4)至式(1-60)中, R1為碳數1至10的烷基; Z1、Z12、及Z13獨立地為單鍵、-CH2CH2-、或-(CH2)4-; Sp12、Sp13、及Sp14獨立地為單鍵或碳數1至5的伸烷基,所述伸烷基中,至少一個-CH2-可經-O-取代; L1、L2、L3、L4、L5、L6、L7、L8、L9、L10、L11、及L12獨立地為氫、氟、甲基、或乙基。 In formulas (1-4) to (1-60), R 1 is an alkyl group having 1 to 10 carbons; Z 1 , Z 12 , and Z 13 are independently a single bond, -CH 2 CH 2 -, or -(CH 2 ) 4 -; Sp 12 , Sp 13 , and Sp 14 are independently a single bond or an alkylene group having 1 to 5 carbon atoms, in which at least one -CH 2 -may be -O -Substitution; L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 , L 8 , L 9 , L 10 , L 11 , and L 12 are independently hydrogen, fluorine, methyl, or Ethyl.
式(2)及式(3)中,R3及R4獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、或碳數2至12的烯氧基。為了提高穩定性,較佳的R3或R4為碳數1至12的烷基,為了提高介電各向異性,較佳的R3或R4為碳數1至12的烷氧基。R5及R6獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、至少一個氫經氟或氯取代的碳數1至12的烷基、或至少一個氫經氟或氯取代的碳數2至12的烯基。為了降低黏度,較佳的R5或R6為碳數2至12的烯基,為了提高穩定性,較佳的R5或R6為碳數1至12的烷基。液晶性化合物的烷基為直鏈狀或分支狀,不含環狀烷基。直鏈狀烷基優於分支狀烷基。該些情況對於烷氧基、烯基等末端基亦相同。 In formula (2) and formula (3), R 3 and R 4 are independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or a carbon number 2 to 12 alkenyloxy. In order to improve the stability, preferably R 3 or R 4 is an alkyl group having 1 to 12 carbons. In order to increase the dielectric anisotropy, preferably R 3 or R 4 is an alkoxy group having 1 to 12 carbons. R 5 and R 6 are independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or a carbon number of 1 to 12 in which at least one hydrogen is substituted by fluorine or chlorine The alkyl group or the alkenyl group having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. In order to reduce the viscosity, preferably R 5 or R 6 is an alkenyl group having 2 to 12 carbons, and in order to improve stability, preferably R 5 or R 6 is an alkyl group having 1 to 12 carbons. The alkyl group of the liquid crystal compound is linear or branched, and does not contain a cyclic alkyl group. Straight-chain alkyl is better than branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl.
較佳的烷基為甲基、乙基、丙基、丁基、戊基、己基、庚基、或辛基。為了降低黏度,尤佳的烷基為乙基、丙基、丁基、戊基、或庚基。 Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. In order to reduce the viscosity, particularly preferred alkyl groups are ethyl, propyl, butyl, pentyl, or heptyl.
較佳的烷氧基為甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、或庚氧基。為了降低黏度,尤佳的烷氧基為甲氧基或乙氧基。 Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, or heptoxy. In order to reduce the viscosity, particularly preferred alkoxy groups are methoxy or ethoxy.
較佳的烯基為乙烯基、1-丙烯基、2-丙烯基、1-丁烯基、 2-丁烯基、3-丁烯基、1-戊烯基、2-戊烯基、3-戊烯基、4-戊烯基、1-己烯基、2-己烯基、3-己烯基、4-己烯基、或5-己烯基。為了降低黏度,尤佳的烯基為乙烯基、1-丙烯基、3-丁烯基、或3-戊烯基。 該些烯基中的-CH=CH-的較佳的立體構型依存於雙鍵的位置。為了降低黏度等原因,於1-丙烯基、1-丁烯基、1-戊烯基、1-己烯基、3-戊烯基、3-己烯基之類的烯基中較佳為反式構型。於2-丁烯基、2-戊烯基、2-己烯基之類的烯基中較佳為順式構型。該些烯基中,直鏈烯基優於分支烯基。 Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3- Hexenyl, 4-hexenyl, or 5-hexenyl. In order to reduce the viscosity, particularly preferred alkenyl groups are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl. The preferred configuration of -CH=CH- in these alkenyl groups depends on the position of the double bond. In order to reduce viscosity and other reasons, preferred among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl Trans configuration. Among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl, the cis configuration is preferred. Among these alkenyl groups, linear alkenyl groups are preferred to branched alkenyl groups.
較佳的烯氧基為乙烯氧基、烯丙氧基、3-丁烯氧基、3-戊烯氧基、或4-戊烯氧基。為了降低黏度,尤佳的烯氧基為烯丙氧基或3-丁烯氧基。 Preferred alkenyloxy groups are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. In order to reduce the viscosity, particularly preferred alkenyloxy groups are allyloxy or 3-butenyloxy.
至少一個氫經氟或氯取代的烷基的較佳的例子為氟甲基、2-氟乙基、3-氟丙基、4-氟丁基、5-氟戊基、6-氟己基、7-氟庚基、或8-氟辛基。為了提高介電各向異性,尤佳的例子為2-氟乙基、3-氟丙基、4-氟丁基、或5-氟戊基。 Preferred examples of alkyl groups in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl, or 8-fluorooctyl. In order to increase the dielectric anisotropy, particularly preferable examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl.
至少一個氫經氟或氯取代的烯基的較佳的例子為2,2-二氟乙烯基、3,3-二氟-2-丙烯基、4,4-二氟-3-丁烯基、5,5-二氟-4-戊烯基、或6,6-二氟-5-己烯基。為了降低黏度,尤佳的例子為2,2-二氟乙烯基或4,4-二氟-3-丁烯基。 Preferred examples of alkenyl groups in which at least one hydrogen is replaced by fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl , 5,5-difluoro-4-pentenyl, or 6,6-difluoro-5-hexenyl. In order to reduce the viscosity, particularly preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.
環C及環E獨立地為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、至少一個氫經氟或氯取代的1,4-伸苯基、或四氫吡喃-2,5-二基。「至少一個氫經氟或氯取代的1,4-伸苯基」的較佳的例
子為2-氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基、或2-氯-3-氟-1,4-伸苯基。為了降低黏度,較佳的環C或環E為1,4-伸環己基,為了提高介電各向異性,較佳的環C或環E為四氫吡喃-2,5-二基,為了提高光學各向異性,較佳的環C或環E為1,4-伸苯基。為了提高上限溫度,與1,4-伸環己基相關的立體構型是反式構型優於順式構型。四氫吡喃-2,5-二基為
或
,較佳為
環D為2,3-二氟-1,4-伸苯基、2-氯-3-氟-1,4-伸苯基、2,3-二氟-5-甲基-1,4-伸苯基、3,4,5-三氟萘-2,6-二基、或7,8-二氟色原烷-2,6-二基。為了降低黏度,較佳的環D為2,3-二氟-1,4-伸苯基,為了降低光學各向異性,較佳的環D為2-氯-3-氟-1,4-伸苯基,為了提高介電各向異性,較佳的環D為7,8-二氟色原烷-2,6-二基。 Ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4- Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl. In order to reduce the viscosity, the preferred ring D is 2,3-difluoro-1,4-phenylene. In order to reduce the optical anisotropy, the preferred ring D is 2-chloro-3-fluoro-1,4- In order to improve the dielectric anisotropy, the preferred ring D is 7,8-difluorochroman-2,6-diyl.
環F及環G獨立地為1,4-伸環己基、1,4-伸苯基、2-氟 -1,4-伸苯基、或2,5-二氟-1,4-伸苯基。為了降低黏度或為了提高上限溫度,較佳的環F或環G為1,4-伸環己基,為了降低下限溫度,較佳的環F或環G為1,4-伸苯基。為了提高上限溫度,與1,4-伸環己基相關的立體構型是反式構型優於順式構型。 Ring F and ring G are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro -1,4-phenylene, or 2,5-difluoro-1,4-phenylene. In order to reduce the viscosity or to increase the upper limit temperature, the preferred ring F or ring G is 1,4-cyclohexylene, and in order to reduce the lower limit temperature, the preferred ring F or ring G is 1,4-phenylene. In order to increase the maximum temperature, the three-dimensional configuration related to 1,4-cyclohexylene is the trans configuration better than the cis configuration.
Z2及Z3獨立地為單鍵、-CH2CH2-、-CH2O-、-OCH2-、-COO-、或-OCO-。為了降低黏度,較佳的Z2或Z3為單鍵,為了降低下限溫度,較佳的Z2或Z3為-CH2CH2-,為了提高介電各向異性,較佳的Z2或Z3為-CH2O-或-OCH2-。Z4為單鍵、-CH2CH2-、-CH2O-、-OCH2-、-COO-、或-OCO-。為了降低黏度,較佳的Z4為單鍵,為了降低下限溫度,較佳的Z4為-CH2CH2-,為了提高上限溫度,較佳的Z4為-COO-或-OCO-。 Z 2 and Z 3 are independently a single bond, -CH 2 CH 2 -, -CH 2 O-, -OCH 2 -, -COO-, or -OCO-. In order to reduce the viscosity, the preferred Z 2 or Z 3 is a single bond, in order to reduce the lower limit temperature, the preferred Z 2 or Z 3 is -CH 2 CH 2 -, in order to increase the dielectric anisotropy, the preferred Z 2 Or Z 3 is -CH 2 O- or -OCH 2 -. Z 4 is a single bond, -CH 2 CH 2 -, -CH 2 O-, -OCH 2 -, -COO-, or -OCO-. In order to reduce the viscosity, the preferred Z 4 is a single bond, in order to reduce the lower limit temperature, the preferred Z 4 is -CH 2 CH 2 -, and in order to increase the upper limit temperature, the preferred Z 4 is -COO- or -OCO-.
b為1、2、或3,c為0或1,而且b與c之和為3以下。 為了降低黏度,較佳的b為1,為了提高上限溫度,較佳的b為2或3。為了降低黏度,較佳的c為0,為了降低下限溫度,較佳的c為1。d為1、2、或3。為了降低黏度,較佳的d為1,為了提高上限溫度,較佳的d為2或3。 b is 1, 2, or 3, c is 0 or 1, and the sum of b and c is 3 or less. In order to reduce the viscosity, the preferred b is 1, and in order to increase the upper limit temperature, the preferred b is 2 or 3. In order to reduce the viscosity, the preferred c is 0, and in order to reduce the minimum temperature, the preferred c is 1. d is 1, 2, or 3. In order to reduce the viscosity, the preferable d is 1, and in order to increase the upper limit temperature, the preferable d is 2 or 3.
式(4)中,P1、P2、及P3獨立地為聚合性基。較佳的P1、P2、或P3為選自式(P-1)至式(P-5)所表示的基團的群組中的聚合性基。尤佳的P1、P2、或P3為式(P-1)、式(P-2)、或式(P-3)所表示的基團。特佳的P1、P2、或P3為式(P-1)或式(P-2)所表示的基團。最佳的P1、P2、或P3為式(P-1)所表示的基團。式(P-1)所表示的較佳的基團為-OCO-CH=CH2或 -OCO-C(CH3)=CH2。式(P-1)至式(P-5)的波形線表示鍵結的部位。 In formula (4), P 1 , P 2 , and P 3 are independently polymerizable groups. Preferably P 1 , P 2 , or P 3 is a polymerizable group selected from the group of groups represented by formula (P-1) to formula (P-5). More preferably, P 1 , P 2 , or P 3 is a group represented by formula (P-1), formula (P-2), or formula (P-3). Particularly preferred P 1 , P 2 , or P 3 are groups represented by formula (P-1) or formula (P-2). The most preferable P 1 , P 2 , or P 3 is a group represented by formula (P-1). The preferred group represented by formula (P-1) is -OCO-CH=CH 2 or -OCO-C(CH 3 )=CH 2 . The wavy lines of formula (P-1) to formula (P-5) indicate the bonding position.
式(P-1)至式(P-5)中,M1、M2、及M3獨立地為氫、氟、碳數1至5的烷基、或至少一個氫經氟或氯取代的碳數1至5的烷基。為了提高反應性,較佳的M1、M2或M3為氫或甲基。尤佳的M1為氫或甲基,尤佳的M2或M3為氫。 In formulas (P-1) to (P-5), M 1 , M 2 , and M 3 are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or at least one hydrogen substituted by fluorine or chlorine An alkyl group having 1 to 5 carbon atoms. In order to improve the reactivity, preferred M 1 , M 2 or M 3 are hydrogen or methyl. More preferably, M 1 is hydrogen or methyl, and more preferably M 2 or M 3 is hydrogen.
Sp3、Sp4、及Sp3獨立地為單鍵或碳數1至10的伸烷基,所述伸烷基中,至少一個-CH2-可經-O-、-COO-、-OCO-、或-OCOO-取代,而且至少一個-CH2CH2-可經-CH=CH-或-C≡C-取代,該些基團中,至少一個氫可經氟或氯取代。較佳的Sp3、Sp4、或Sp5為單鍵、-CH2-CH2-、-CH2O-、-OCH2-、-COO-、-OCO-、-CO-CH=CH-、或-CH=CH-CO-。尤佳的Sp3、Sp4、或Sp5為單鍵。 Sp 3 , Sp 4 , and Sp 3 are independently a single bond or an alkylene group having 1 to 10 carbon atoms. In the alkylene group, at least one -CH 2 -can be controlled by -O-, -COO-, -OCO -Or -OCOO- substituted, and at least one -CH 2 CH 2 -may be substituted with -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferably Sp 3 , Sp 4 , or Sp 5 is a single bond, -CH 2 -CH 2 -, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CO-CH=CH- , Or -CH=CH-CO-. More preferably, Sp 3 , Sp 4 , or Sp 5 is a single bond.
環J及環P獨立地為環己基、環己烯基、苯基、1-萘基、2-萘基、四氫吡喃-2-基、1,3-二噁烷-2-基、嘧啶-2-基、或吡啶-2-基,該些環中,至少一個氫可經氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、或至少一個氫經氟或氯取代的碳數1至12的烷基取代。較佳的環J或環P為苯基。環K為1,4-伸環己基、 1,4-伸環己烯基、1,4-伸苯基、萘-1,2-二基、萘-1,3-二基、萘-1,4-二基、萘-1,5-二基、萘-1,6-二基、萘-1,7-二基、萘-1,8-二基、萘-2,3-二基、萘-2,6-二基、萘-2,7-二基、四氫吡喃-2,5-二基、1,3-二噁烷-2,5-二基、嘧啶-2,5-二基、或吡啶-2,5-二基,該些環中,至少一個氫可經氟、氯、碳數1至12的烷基、碳數1至12的烷氧基、或至少一個氫經氟或氯取代的碳數1至12的烷基取代。較佳的環K為1,4-伸苯基或2-氟-1,4-伸苯基。 Ring J and ring P are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, Pyrimidine-2-yl or pyridin-2-yl, in these rings, at least one hydrogen may be fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen It is substituted by a fluorine or chlorine substituted alkyl group having 1 to 12 carbons. The preferred ring J or ring P is phenyl. Ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5 -Diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene -2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5 -A diyl group, in these rings, at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or at least one hydrogen having a carbon number of 1 substituted by fluorine or chlorine To 12 alkyl substitution. Preferred ring K is 1,4-phenylene or 2-fluoro-1,4-phenylene.
Z5及Z6獨立地為單鍵或碳數1至10的伸烷基,所述伸烷基中,至少一個-CH2-可經-O-、-CO-、-COO-、或-OCO-取代,而且至少一個-CH2CH2-可經-CH=CH-、-C(CH3)=CH-、-CH=C(CH3)-、或-C(CH3)=C(CH3)-取代,該些基團中,至少一個氫可經氟或氯取代。 較佳的Z5或Z6為單鍵、-CH2CH2-、-CH2O-、-OCH2-、-COO-、或-OCO-。尤佳的Z5或Z6為單鍵。 Z 5 and Z 6 are independently a single bond or an alkylene group having 1 to 10 carbon atoms. In the alkylene group, at least one -CH 2 -may be -O- , -CO- , -COO- , or- OCO- substitution, and at least one -CH 2 CH 2 -can be replaced by -CH=CH-, -C(CH 3 )=CH- , -CH=C(CH 3 )- , or -C(CH 3 )=C (CH 3 )-substitution, in these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferably Z 5 or Z 6 is a single bond, -CH 2 CH 2 -, -CH 2 O-, -OCH 2 -, -COO-, or -OCO-. Preferably, Z 5 or Z 6 is a single bond.
q為0、1、或2。較佳的q為0或1。j、k、及p獨立地為0、1、2、3、或4,而且,j、k、及p之和為1以上。較佳的j、k、或p為1或2。 q is 0, 1, or 2. Preferably q is 0 or 1. j, k, and p are independently 0, 1, 2, 3, or 4, and the sum of j, k, and p is 1 or more. Preferably j, k, or p is 1 or 2.
第五,示出較佳的成分化合物。較佳的化合物(1-1)為項2所述的化合物(1-2)及化合物(1-3)。尤佳的化合物(1-1)為項3所述的化合物(1-4)至化合物(1-60)。該些化合物中,較佳為第一添加物的至少一種為化合物(1-4)、化合物(1-5)、化合物(1-6)、化合物(1-12)、化合物(1-20)、化合物(1-22)、化合物(1-23)、化合物(1-24)、化合物(1-25)、化合物(1-42)、 化合物(1-43)、化合物(1-44)。較佳為第一添加物的至少兩種為化合物(1-4)及化合物(1-5)、或化合物(1-5)及化合物(1-6)的組合。 Fifth, the preferred component compounds are shown. Preferred compound (1-1) is the compound (1-2) and the compound (1-3) described in Item 2. Particularly desirable compound (1-1) is the compound (1-4) to the compound (1-60) described in Item 3. Among these compounds, preferably at least one of the first additives is compound (1-4), compound (1-5), compound (1-6), compound (1-12), compound (1-20) , Compound (1-22), compound (1-23), compound (1-24), compound (1-25), compound (1-42), Compound (1-43), Compound (1-44). Preferably, at least two of the first additives are compound (1-4) and compound (1-5), or a combination of compound (1-5) and compound (1-6).
較佳的化合物(2)為項6所述的化合物(2-1)至化合物(2-22)。該些化合物中,較佳為第一成分的至少一種為化合物(2-1)、化合物(2-3)、化合物(2-4)、化合物(2-6)、化合物(2-8)、或化合物(2-10)。較佳為第一成分的至少兩種為化合物(2-1)及化合物(2-6)、化合物(2-1)及化合物(2-10)、化合物(2-3)及化合物(2-6)、化合物(2-3)及化合物(2-10)、化合物(2-4)及化合物(2-6)、或化合物(2-4)及化合物(2-8)的組合。 Preferred compound (2) includes compound (2-1) to compound (2-22) described in Item 6. Among these compounds, at least one of the first components is preferably compound (2-1), compound (2-3), compound (2-4), compound (2-6), compound (2-8), Or compound (2-10). Preferably at least two of the first components are compound (2-1) and compound (2-6), compound (2-1) and compound (2-10), compound (2-3) and compound (2- 6) Compound (2-3) and compound (2-10), compound (2-4) and compound (2-6), or a combination of compound (2-4) and compound (2-8).
較佳的化合物(3)為項9所述的化合物(3-1)至化合物(3-13)。該些化合物中,較佳為第二成分的至少一種為化合物(3-1)、化合物(3-3)、化合物(3-5)、化合物(3-6)、化合物(3-8)、或化合物(3-9)。較佳為第二成分的至少兩種為化合物(3-1)及化合物(3-3)、化合物(3-1)及化合物(3-5)、或化合物(3-1)及化合物(3-6)的組合。 Preferred compound (3) includes compound (3-1) to compound (3-13) described in Item 9. Among these compounds, at least one of the second components is preferably compound (3-1), compound (3-3), compound (3-5), compound (3-6), compound (3-8), Or compound (3-9). Preferably at least two of the second components are compound (3-1) and compound (3-3), compound (3-1) and compound (3-5), or compound (3-1) and compound (3) -6) combination.
較佳的化合物(4)為項13所述的化合物(4-1)至化合物(4-29)。該些化合物中,較佳為第二添加物的至少一種為化合物(4-1)、化合物(4-2)、化合物(4-24)、化合物(4-25)、化合物(4-26)、化合物(4-27)或化合物(4-29)。較佳為第二添加物的至少兩種為化合物(4-1)及化合物(4-2)、化合物(4-1)及化合物(4-18)、化合物(4-2)及化合物(4-24)、化合物(4-2) 及化合物(4-25)、化合物(4-2)及化合物(4-26)、化合物(4-25)及化合物(4-26)、或化合物(4-18)及化合物(4-24)的組合。 Preferred compound (4) includes compound (4-1) to compound (4-29) described in Item 13. Among these compounds, preferably at least one of the second additives is compound (4-1), compound (4-2), compound (4-24), compound (4-25), compound (4-26) , Compound (4-27) or Compound (4-29). Preferably at least two of the second additives are compound (4-1) and compound (4-2), compound (4-1) and compound (4-18), compound (4-2) and compound (4 -24), compound (4-2) And compound (4-25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26), or compound (4-18) and compound (4-24) The combination.
較佳的化合物(5)的例子為化合物(5-1)至化合物(5-10)。化合物(5)的較佳的比例為約0.3重量%至約10重量%的範圍。 Examples of preferable compound (5) are compound (5-1) to compound (5-10). The preferable ratio of the compound (5) is in the range of about 0.3% by weight to about 10% by weight.
第六,對可添加於組成物中的第一添加物以外的添加物 進行說明。此種添加物為光學活性化合物、抗氧化劑、紫外線吸收劑、色素、消泡劑、聚合性化合物、聚合起始劑、聚合抑制劑、極性化合物等。出於引起液晶分子的螺旋結構來賦予扭轉角(torsion angle)的目的,而將光學活性化合物添加於組成物中。 此種化合物的例子為化合物(6-1)至化合物(6-5)。光學活性化合物的較佳的比例為約5重量%以下。尤佳的比例為約0.01重量%至約2重量%的範圍。 Sixth, for additives other than the first additive that can be added to the composition Be explained. Such additives include optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. For the purpose of causing a helical structure of liquid crystal molecules to impart a torsion angle, an optically active compound is added to the composition. Examples of such compounds are compound (6-1) to compound (6-5). A preferable ratio of the optically active compound is about 5 wt% or less. A particularly preferable ratio is in the range of about 0.01% by weight to about 2% by weight.
為了防止由大氣中的加熱所引起的比電阻下降,或者為了在長時間使用元件後,不僅在室溫下,而且在接近於上限溫度的溫度下亦維持大的電壓保持率,而將抗氧化劑添加於組成物中。抗氧化劑的較佳的例子是n為1至9的整數的化合物(7)等。 In order to prevent the decrease in specific resistance caused by heating in the atmosphere, or to maintain a large voltage retention rate not only at room temperature but also at a temperature close to the upper limit temperature after using the element for a long time, the antioxidant Add to the composition. Preferred examples of antioxidants are compound (7) in which n is an integer from 1 to 9, and the like.
化合物(7)中,較佳的n為1、3、5、7、或9。尤佳的n為7。n為7的化合物(7)由於揮發性小,因此對於在長時間使用元件後,不僅在室溫下,而且在接近於上限溫度的溫度下亦維持大的電壓保持率而言有效。為了獲得所述效果,抗氧化劑的較佳的比例為約50ppm以上,為了不降低上限溫度,或者為了不提高下限溫度,抗氧化劑的較佳的比例為約600ppm以下。尤佳的比例為約100ppm至約300ppm的範圍。 In compound (7), preferred n is 1, 3, 5, 7, or 9. A particularly good n is 7. The compound (7) with n of 7 has low volatility and is therefore effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time. In order to obtain the effect, the preferable ratio of the antioxidant is about 50 ppm or more. In order not to lower the upper limit temperature or to increase the lower limit temperature, the preferable ratio of the antioxidant is about 600 ppm or less. A particularly preferred ratio is in the range of about 100 ppm to about 300 ppm.
紫外線吸收劑的較佳的例子為二苯甲酮衍生物、苯甲酸酯衍生物、三唑衍生物等。而且,具有立體阻礙的胺之類的光穩定劑亦較佳。為了獲得所述效果,該些吸收劑或穩定劑的較佳的比例為約50ppm以上,為了不降低上限溫度,或者為了不提高下限溫度,該些吸收劑或穩定劑的較佳的比例為約10000ppm以下。 尤佳的比例為約100ppm至約10000ppm的範圍。 Preferred examples of ultraviolet absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like. Furthermore, light stabilizers such as amines with steric hindrance are also preferable. In order to obtain the effect, the preferred ratio of these absorbents or stabilizers is about 50 ppm or more. In order not to lower the upper limit temperature or increase the lower limit temperature, the preferred ratio of these absorbents or stabilizers is about Below 10000ppm. A particularly preferred ratio is in the range of about 100 ppm to about 10000 ppm.
為了適合於賓主(guest host,GH)模式的元件,而將 偶氮系色素、蒽醌系色素等之類的二色性色素(dichroic dye)添加於組成物中。色素的較佳的比例為約0.01重量%至約10重量%的範圍。為了防止起泡,而將二甲基矽酮油、甲基苯基矽酮油等消泡劑添加於組成物中。為了獲得所述效果,消泡劑的較佳的比例為約1ppm以上,為了防止顯示不良,消泡劑的較佳的比例為約1000ppm以下。尤佳的比例為約1ppm至約500ppm的範圍。 In order to be suitable for components in the guest host (GH) mode, the Dichroic dyes such as azo dyes and anthraquinone dyes are added to the composition. The preferred ratio of the pigment is in the range of about 0.01% by weight to about 10% by weight. To prevent foaming, antifoaming agents such as dimethyl silicone oil and methyl phenyl silicone oil are added to the composition. In order to obtain the effect, the preferred ratio of the defoaming agent is about 1 ppm or more, and in order to prevent display failure, the preferred ratio of the defoaming agent is about 1000 ppm or less. A particularly preferred ratio is in the range of about 1 ppm to about 500 ppm.
為了適合於聚合物穩定配向(PSA)型的元件,而使用聚合性化合物。化合物(1)及化合物(4)適合於該目的。可將化合物(5)與化合物(1)及化合物(4)一起添加於組成物中。 而且,亦可將與化合物(1)、化合物(4)及化合物(5)不同的其他的聚合性化合物與化合物(1)及化合物(4)一起添加於組成物中。其他的聚合性化合物的較佳的例子為丙烯酸酯、甲基丙烯酸酯、乙烯基化合物、乙烯氧基化合物、丙烯基醚、環氧化合物(氧雜環丙烷、氧雜環丁烷)、乙烯基酮等化合物。尤佳的例子為丙烯酸酯或甲基丙烯酸酯。基於聚合性化合物的總重量,化合物(1)、化合物(4)及化合物(5)的較佳的比例為約10重量%以上。尤佳的比例為約50重量%以上。更佳的比例為約80重量%以上。特佳的比例亦為100重量%。藉由改變化合物(1)、化合物(4)及化合物(5)的種類,或者藉由以適當的比使其他的聚合性化合物與化合物(1)、化合物(4)及化合物(5)組合,可調整聚合性化合物的反應性或液晶分子的預傾角。藉由將預傾角最佳化,可達成元件的短的響應時間。液晶分子的配向穩定化,因 此可達成大的對比度比或長壽命。 In order to be suitable for polymer stable alignment (PSA) type elements, polymerizable compounds are used. Compound (1) and compound (4) are suitable for this purpose. The compound (5) can be added to the composition together with the compound (1) and the compound (4). Furthermore, another polymerizable compound different from the compound (1), the compound (4), and the compound (5) may be added to the composition together with the compound (1) and the compound (4). Preferred examples of other polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxetane, oxetane), vinyl Ketones and other compounds. A particularly preferred example is acrylate or methacrylate. Based on the total weight of the polymerizable compound, the preferred ratio of the compound (1), the compound (4), and the compound (5) is about 10% by weight or more. A particularly preferable ratio is about 50% by weight or more. A more preferable ratio is about 80% by weight or more. A particularly preferred ratio is also 100% by weight. By changing the types of compound (1), compound (4), and compound (5), or by combining other polymerizable compounds with compound (1), compound (4), and compound (5) in an appropriate ratio, The reactivity of the polymerizable compound or the pretilt angle of the liquid crystal molecules can be adjusted. By optimizing the pretilt angle, a short response time of the device can be achieved. The alignment of the liquid crystal molecules is stabilized due to This can achieve a large contrast ratio or a long life.
化合物(1)、化合物(4)及化合物(5)之類的聚合性化合物藉由紫外線照射而聚合。亦可於光聚合起始劑等適當的起始劑存在下進行聚合。用以進行聚合的適當條件、起始劑的適當類型、及適當的量已為本領域技術人員所知,且記載於文獻中。 例如作為光聚合起始劑的豔佳固(Irgacure)651(註冊商標;巴斯夫(BASF))、豔佳固(Irgacure)184(註冊商標;巴斯夫(BASF))、或德牢固(Darocur)1173(註冊商標;巴斯夫(BASF))適合於自由基聚合。基於聚合性化合物的總重量,光聚合起始劑的較佳的比例為約0.1重量%至約5重量%的範圍。尤佳的比例為約1重量%至約3重量%的範圍。 Polymerizable compounds such as compound (1), compound (4), and compound (5) are polymerized by ultraviolet irradiation. It is also possible to perform polymerization in the presence of an appropriate initiator such as a photopolymerization initiator. The appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those skilled in the art and are described in the literature. For example, as a photopolymerization initiator, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 ( Registered trademark; BASF) is suitable for free radical polymerization. Based on the total weight of the polymerizable compound, the preferred ratio of the photopolymerization initiator is in the range of about 0.1% by weight to about 5% by weight. A particularly preferable ratio is in the range of about 1% by weight to about 3% by weight.
於保管化合物(1)、化合物(4)及化合物(5)之類的聚合性化合物時,為了防止聚合,亦可添加聚合抑制劑。聚合性化合物通常是以未去除聚合抑制劑的狀態添加於組成物中。聚合抑制劑的例子為對苯二酚、如甲基對苯二酚之類的對苯二酚衍生物、4-第三丁基兒茶酚、4-甲氧基苯酚、啡噻嗪等。 When storing polymerizable compounds such as compound (1), compound (4), and compound (5), in order to prevent polymerization, a polymerization inhibitor may be added. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine, and the like.
第七,對成分化合物的合成方法進行說明。該些化合物可利用已知的方法來合成。例示合成方法。化合物(1)的合成方法是記載於實施例的項中。化合物(2-1)是利用日本專利特表平2-503441號公報中記載的方法來合成。化合物(3-5)是利用日本專利特開昭57-165328號公報中記載的方法來合成。化合物(5)是利用國際公開第2016/015803號手冊中記載的方法來合成。化合 物(4-18)是利用日本專利特開平7-101900號公報中記載的方法來合成。化合物(7)的一部分被市售。式(7)的n為1的化合物可自西格瑪奧德里奇公司(Sigma-Aldrich Corporation)獲取。n為7的化合物(7)等是利用美國專利3660505號說明書中記載的方法來合成。 Seventh, the synthesis method of the component compounds will be described. These compounds can be synthesized by known methods. Illustrate the synthesis method. The synthesis method of compound (1) is described in the section of Examples. Compound (2-1) was synthesized by the method described in JP 2-503441 A. Compound (3-5) was synthesized by the method described in Japanese Patent Laid-Open No. 57-165328. Compound (5) was synthesized by the method described in the manual of International Publication No. 2016/015803. Compound The compound (4-18) was synthesized by the method described in Japanese Patent Laid-Open No. 7-101900. A part of compound (7) is commercially available. The compound of formula (7) where n is 1 can be obtained from Sigma-Aldrich Corporation. Compound (7) in which n is 7 is synthesized by the method described in the specification of U.S. Patent No. 3660505.
未記載合成方法的化合物可利用以下成書中記載的方法來合成:「有機合成(Organic Syntheses)」(約翰威立父子出版公司(John Wiley & Sons,Inc.))、「有機反應(Organic Reactions)」(約翰威立父子出版公司(John Wiley & Sons,Inc.))、「綜合有機合成(Comprehensive Organic Synthesis)」(培格曼出版公司(Pergamon Press))、「新實驗化學講座」(丸善)等。組成物是利用公知的方法,由以所述方式獲得的化合物來製備。例如,將成分化合物混合,然後藉由加熱而使其相互溶解。 Compounds without a description of the synthesis method can be synthesized by the method described in the following book: "Organic Syntheses" (John Wiley & Sons, Inc.), "Organic Reactions (Organic Reactions) )'' (John Wiley & Sons, Inc.), ``Comprehensive Organic Synthesis'' (Pergamon Press), ``New Experimental Chemistry Lecture'' (Maruzen )Wait. The composition is prepared from the compound obtained in the manner described above using a known method. For example, the component compounds are mixed and then heated to dissolve each other.
最後,對組成物的用途進行說明。大部分的組成物具有約-10℃以下的下限溫度、約70℃以上的上限溫度、及約0.07至約0.20的範圍的光學各向異性。亦可藉由控制成分化合物的比例、或藉由混合其他的液晶性化合物,來製備具有約0.08至約0.25的範圍的光學各向異性的組成物。進而亦可藉由嘗試錯誤,來製備具有約0.10至約0.30的範圍的光學各向異性的組成物。含有該組成物的元件具有大的電壓保持率。該組成物適合於AM元件。 該組成物特別適合於透過型的AM元件。該組成物可用作具有向列相的組成物,且可藉由添加光學活性化合物而用作光學活性組 成物。 Finally, the use of the composition will be explained. Most of the compositions have a lower limit temperature of about -10°C or lower, an upper limit temperature of about 70°C or higher, and an optical anisotropy in the range of about 0.07 to about 0.20. It is also possible to prepare a composition having an optical anisotropy in the range of about 0.08 to about 0.25 by controlling the ratio of component compounds or by mixing other liquid crystal compounds. Furthermore, it is also possible to prepare a composition having an optical anisotropy in the range of about 0.10 to about 0.30 through trial and error. The device containing this composition has a large voltage holding ratio. This composition is suitable for AM devices. The composition is particularly suitable for transmission type AM devices. The composition can be used as a composition having a nematic phase, and can be used as an optically active group by adding an optically active compound Into things.
該組成物可用於AM元件。進而亦可用於PM元件。該組成物可用於具有PC、TN、STN、ECB、OCB、IPS、FFS、VA、FPA等模式的AM元件及PM元件。特佳為用於具有TN模式、OCB模式、IPS模式或FFS模式的AM元件。具有IPS模式或FFS模式的AM元件中,於不施加電壓時,液晶分子的配向可與玻璃基板平行,或者亦可為垂直。該些元件可為反射型、透過型、或半透過型。較佳為用於透過型元件。亦可用於非晶矽-TFT元件或多晶矽-TFT元件。亦可用於將該組成物進行微膠囊化而製作的向列曲線排列相(nematic curvilinear aligned phase,NCAP)型元件、或使組成物中形成有三維網狀高分子的聚合物分散(polymer dispersed,PD)型元件。 This composition can be used for AM devices. It can also be used for PM devices. The composition can be used for AM devices and PM devices with PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA and other modes. It is particularly preferred for AM devices with TN mode, OCB mode, IPS mode or FFS mode. In an AM device with an IPS mode or an FFS mode, when no voltage is applied, the alignment of the liquid crystal molecules may be parallel to the glass substrate, or may be vertical. These elements can be reflective, transmissive, or semi-transmissive. It is preferably used for transmissive elements. It can also be used for amorphous silicon-TFT devices or polysilicon-TFT devices. It can also be used for nematic curvilinear aligned phase (NCAP) type devices produced by microencapsulating the composition, or for polymer dispersed, polymer dispersed, in which three-dimensional network polymers are formed in the composition. PD) type element.
製造現有的聚合物穩定配向型的元件的方法的一例為如下所述。組裝包括兩塊基板的元件,該兩塊基板被稱為陣列基板及彩色濾光片基板。該基板具有配向膜。該基板的至少一塊具有電極層。將液晶性化合物進行混合來製備液晶組成物。於該組成物中添加聚合性化合物。視需要可進而添加添加物。將該組成物注入至元件中。在對該元件施加電壓的狀態下進行光照射。較佳為紫外線。藉由光照射而使聚合性化合物進行聚合。藉由該聚合而生成含有聚合物的組成物。聚合物穩定配向型的元件是以此種順序來製造。 An example of a method of manufacturing a conventional polymer stable alignment type element is as follows. Assemble an element including two substrates, which are called an array substrate and a color filter substrate. The substrate has an alignment film. At least one of the substrates has an electrode layer. The liquid crystal compounds are mixed to prepare a liquid crystal composition. A polymerizable compound is added to this composition. If necessary, additives can be further added. The composition is injected into the device. Light irradiation is performed in a state where a voltage is applied to the element. Preferably it is ultraviolet light. The polymerizable compound is polymerized by light irradiation. This polymerization produces a polymer-containing composition. The polymer stabilized alignment type components are manufactured in this order.
該順序中,於施加電壓時,液晶分子藉由電場的作用而 配向。依據該配向,聚合性化合物的分子亦進行配向。由於聚合性化合物是在該狀態下藉由紫外線來進行聚合,因此生成維持該配向的聚合物。藉由該聚合物的效果,元件的響應時間縮短。由於圖像的殘像為液晶分子的運作不良,因此藉由該聚合物的效果,殘像亦同時得到改善。此外,亦可使組成物中的聚合性化合物預先進行聚合,將該組成物配置於液晶顯示元件的基板之間。 In this sequence, when a voltage is applied, the liquid crystal molecules are Alignment. According to this alignment, the molecules of the polymerizable compound are also aligned. Since the polymerizable compound is polymerized by ultraviolet rays in this state, a polymer that maintains the alignment is produced. With the effect of the polymer, the response time of the device is shortened. Since the afterimage of the image is the poor operation of the liquid crystal molecules, the afterimage is also improved by the effect of the polymer. In addition, the polymerizable compound in the composition may be polymerized in advance, and the composition may be arranged between the substrates of the liquid crystal display element.
於使用化合物(1)、即在分子末端的分支結構中具有聚合性基與極性基的化合物的情況下,於元件的基板上不需要配向膜。不具有配向膜的元件除了使用不具有配向膜的基板以外,依據兩段落前的段落中記載的順序來製造。 In the case of using compound (1), that is, a compound having a polymerizable group and a polar group in the branch structure at the molecular end, an alignment film is not required on the substrate of the element. The device without the alignment film is manufactured in accordance with the procedure described in the paragraph two paragraphs before, except that the substrate without the alignment film is used.
該順序中,化合物(1)因極性基與基板表面發生相互作用,因此於基板上進行排列。依據該排列,液晶分子進行配向。 於施加電壓時,進一步促進液晶分子的配向。由於聚合性基是在該狀態下藉由紫外線來進行聚合,因此生成維持該配向的聚合物。藉由該聚合物的效果,液晶分子的配向追加地穩定化,元件的響應時間縮短。由於圖像的殘像為液晶分子的運作不良,因此藉由該聚合物的效果,殘像亦同時得到改善。 In this sequence, the compound (1) is arranged on the substrate due to the interaction of the polar group with the surface of the substrate. According to this arrangement, the liquid crystal molecules are aligned. When voltage is applied, the alignment of liquid crystal molecules is further promoted. Since the polymerizable group is polymerized by ultraviolet rays in this state, a polymer that maintains the alignment is produced. Due to the effect of the polymer, the alignment of the liquid crystal molecules is additionally stabilized, and the response time of the device is shortened. Since the afterimage of the image is the poor operation of the liquid crystal molecules, the afterimage is also improved by the effect of the polymer.
[實施例] [Example]
藉由實施例來對本發明進一步進行詳細說明。本發明不受該些實施例的限制。本發明包含組成物M1與組成物M2的混合物。本發明亦包含將實施例的組成物的至少兩種混合而成的混合物。所合成的化合物是藉由核磁共振(nuclear magnetic resonance, NMR)分析等方法來鑑定。化合物、組成物及元件的特性是藉由下述方法進行測定。 The present invention will be further described in detail through examples. The present invention is not limited by these embodiments. The present invention includes a mixture of composition M1 and composition M2. The present invention also includes a mixture obtained by mixing at least two of the compositions of the examples. The synthesized compound is based on nuclear magnetic resonance (nuclear magnetic resonance, NMR) analysis and other methods to identify. The characteristics of the compound, composition, and device were measured by the following methods.
NMR分析:於測定中使用布魯克拜厄斯賓(Bruker BioSpin)公司製造的DRX-500。1H-NMR的測定中,使試樣溶解於CDCl3等氘化溶媒中,於室溫下、500MHz、累計次數16次的條件進行測定。使用四甲基矽烷作為內部標準。19F-NMR的測定中,使用CFCl3作為內部標準,以累計次數24次來進行。核磁共振光譜的說明中,s是指單峰(singlet),d是指雙重峰(doublet),t是指三重峰(triplet),q是指四重峰(quartet),quin是指五重峰(quintet),sex是指六重峰(sextet),m是指多重峰(multiplet),br是指寬峰(broad)。 NMR analysis: DRX-500 manufactured by Bruker BioSpin was used in the measurement. In the 1 H-NMR measurement, the sample is dissolved in a deuterated solvent such as CDCl 3 and the measurement is performed under the conditions of room temperature, 500 MHz, and 16 cumulative times. Use tetramethylsilane as the internal standard. In the 19 F-NMR measurement, CFCl 3 was used as an internal standard, and the measurement was carried out at 24 times of accumulation. In the description of NMR spectroscopy, s refers to singlet, d refers to doublet, t refers to triplet, q refers to quartet, and quin refers to quintet. (quintet), sex refers to sextet, m refers to multiplet, and br refers to broad.
氣相層析分析:於測定中使用島津製作所製造的GC-14B型氣相層析儀。載體氣體為氦氣(2mL/min)。將試樣氣化室設定為280℃,將檢測器(火焰離子化檢測器(flame ionization detector,FID))設定為300℃。當進行成分化合物的分離時,使用安捷倫科技有限公司(Agilent Technologies Inc.)製造的毛細管柱DB-1(長度30m、內徑0.32mm、膜厚0.25μm;固定液相為二甲基聚矽氧烷;無極性)。該管柱於200℃下保持2分鐘後,以5℃/min的比例升溫至280℃。將試樣製備成丙酮溶液(0.1重量%)後,將其1μL注入至試樣氣化室中。記錄計為島津製作所製造的C-R5A型層析儀組件(Chromatopac)或其同等品。所得的氣相層析圖顯示出與成分化合物相對應的峰值的保持時間及峰值的面 積。 Gas chromatographic analysis: GC-14B gas chromatograph manufactured by Shimadzu Corporation was used in the measurement. The carrier gas is helium (2mL/min). The sample vaporization chamber was set to 280°C, and the detector (flame ionization detector (FID)) was set to 300°C. When separating the component compounds, use the capillary column DB-1 manufactured by Agilent Technologies Inc. (length 30m, inner diameter 0.32mm, film thickness 0.25μm; the fixed liquid phase is dimethyl polysiloxane Alkane; non-polar). After the column was kept at 200°C for 2 minutes, the temperature was increased to 280°C at a rate of 5°C/min. After preparing the sample into an acetone solution (0.1% by weight), 1 μL of it was injected into the sample vaporization chamber. The recorder is a C-R5A Chromatopac manufactured by Shimadzu Corporation or its equivalent. The resulting gas chromatogram shows the peak retention time and peak surface area corresponding to the component compounds. product.
用以稀釋試樣的溶媒可使用氯仿、己烷等。為了將成分化合物分離,可使用如下的毛細管柱。安捷倫科技有限公司製造的HP-1(長度30m、內徑0.32mm、膜厚0.25μm)、瑞斯泰克公司(Restek Corporation)製造的Rtx-1(長度30m、內徑0.32mm、膜厚0.25μm)、澳大利亞SGE國際公司(SGE International Pty.Ltd)製造的BP-1(長度30m、內徑0.32mm、膜厚0.25μm)。 出於防止化合物峰值的重疊的目的,可使用島津製作所製造的毛細管柱CBP1-M50-025(長度50m、內徑0.25mm、膜厚0.25μm)。 The solvent used to dilute the sample can be chloroform, hexane, etc. In order to separate the component compounds, the following capillary column can be used. HP-1 (length 30m, inner diameter 0.32mm, film thickness 0.25μm) manufactured by Agilent Technologies, Rtx-1 (length 30m, inner diameter 0.32mm, film thickness 0.25μm) manufactured by Restek Corporation ), BP-1 (length 30m, inner diameter 0.32mm, film thickness 0.25μm) manufactured by SGE International Pty. Ltd. in Australia. For the purpose of preventing overlapping of compound peaks, a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation can be used.
組成物中所含有的液晶性化合物的比例可利用如下所述的方法來算出。利用氣相層析法(FID)來對液晶性化合物的混合物進行分析。氣相層析圖中的峰值的面積比相當於液晶性化合物的比例。於使用上文記載的毛細管柱時,可將各種液晶性化合物的修正係數視為1。因此,液晶性化合物的比例(重量%)可根據峰值的面積比來算出。 The ratio of the liquid crystal compound contained in the composition can be calculated by the method described below. Gas chromatography (FID) was used to analyze the mixture of liquid crystal compounds. The peak area ratio in the gas chromatogram corresponds to the ratio of liquid crystal compounds. When using the capillary column described above, the correction factor of various liquid crystal compounds can be regarded as 1. Therefore, the ratio (weight %) of the liquid crystal compound can be calculated from the area ratio of the peak.
測定試樣:於測定組成物及元件的特性時,將組成物直接用作試樣。於測定化合物的特性時,藉由將該化合物(15重量%)混合於母液晶(85重量%)中來製備測定用試樣。根據藉由測定而獲得的值,利用外推法來算出化合物的特性值。(外推值)={(試樣的測定值)-0.85×(母液晶的測定值)}/0.15。於在該比例下,層列相(或結晶)於25℃下析出時,將化合物與母液晶的比例以10重量%:90重量%、5重量%:95重量%、1重量%:99重 量%的順序變更。利用該外推法來求出與化合物相關的上限溫度、光學各向異性、黏度、及介電各向異性的值。 Measurement sample: When measuring the characteristics of the composition and the device, the composition is directly used as the sample. When measuring the characteristics of the compound, a sample for measurement was prepared by mixing the compound (15% by weight) in the mother liquid crystal (85% by weight). Based on the value obtained by the measurement, the property value of the compound is calculated by extrapolation. (Extrapolated value)={(Measured value of sample)-0.85×(Measured value of mother liquid crystal)}/0.15. At this ratio, when the smectic phase (or crystal) is precipitated at 25°C, the ratio of the compound to the mother liquid crystal is 10wt%: 90wt%, 5wt%: 95wt%, 1wt%: 99wt Change the order of the amount %. This extrapolation method is used to obtain the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy values related to the compound.
使用下述母液晶。成分化合物的比例是以重量%表示。 The following mother liquid crystals are used. The ratio of component compounds is expressed in% by weight.
測定方法:利用下述方法來進行特性的測定。該些方法大多是社團法人電子資訊技術產業協會(Japan Electronics and Information Technology Industries Association;稱為JEITA)所審議製定的JEITA標準(JEITA.ED-2521B)中記載的方法或者將其加以修飾而成的方法。用於測定的TN元件中,未安裝薄膜電晶體(TFT)。 Measurement method: Use the following method to measure the characteristics. Most of these methods are the methods described in the JEITA standard (JEITA.ED-2521B) reviewed and established by the Japan Electronics and Information Technology Industries Association (JEITA) or modified method. In the TN device used for the measurement, no thin film transistor (TFT) was installed.
(1)向列相的上限溫度(NI;℃):於具備偏光顯微鏡的熔點測定裝置的加熱板上放置試樣,以1℃/min的速度進行加熱。對試樣的一部分自向列相變化為各向同性液體時的溫度進行測定。有時將向列相的上限溫度簡稱為「上限溫度」。 (1) The upper limit temperature of the nematic phase (NI; °C): Place the sample on a hot plate of a melting point measuring device equipped with a polarizing microscope, and heat it at a rate of 1 °C/min. The temperature at which a part of the sample changes from a nematic phase to an isotropic liquid is measured. The upper limit temperature of the nematic phase is sometimes referred to simply as the "upper limit temperature".
(2)向列相的下限溫度(TC;℃):將具有向列相的試樣放入玻璃瓶中,於0℃、-10℃、-20℃、-30℃、及-40℃的冷凍器中保管10天後,觀察液晶相。例如,於試樣在-20℃下為向列相的狀態,而在-30℃下變化為結晶或者層列相時,將TC記載為<-20℃。有時將向列相的下限溫度簡稱為「下限溫度」。 (2) Lower limit temperature of nematic phase (T C ;°C): Put the sample with nematic phase into a glass bottle at 0°C, -10°C, -20°C, -30°C, and -40°C After storage in the refrigerator for 10 days, the liquid crystal phase was observed. For example, when the sample is in a nematic state at -20°C and changes to a crystalline or smectic phase at -30°C, T C is described as <-20°C. The lower limit temperature of the nematic phase is sometimes referred to simply as the "lower limit temperature".
(3)黏度(體積黏度;η;於20℃下測定;mPa.s):於測定中使用東京計器股份有限公司製造的E型旋轉黏度計。 (3) Viscosity (bulk viscosity; η; measured at 20°C; mPa·s): In the measurement, an E-type rotary viscometer manufactured by Tokyo Keiki Co., Ltd. was used.
(4)黏度(旋轉黏度;γ1;於25℃下測定;mPa.s):依據M.今井(M.Imai)等人的「分子晶體與液晶(Molecular Crystals and Liquid Crystals)」第259期第37頁(1995)中記載的方法來進行測定。於兩塊玻璃基板的間隔(單元間隙)為20μm的VA元件中注入試樣。對該元件於39伏特至50伏特的範圍內,以1伏特為單位來階段性地施加電壓。不施加電壓0.2秒後,以僅施加1個矩形波(矩形脈衝;0.2秒)與不施加電壓(2秒)的條件反覆施加。測定藉由該施加而產生的暫態電流(transient current)的峰值電流(peak current)及峰值時間(peak time)。根據該些測定值與M.今井等人的論文第40頁的計算式(8)來獲得旋轉黏度的值。該計算所需要的介電各向異性是利用測定(6)中記載的方法進行測定。 (4) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s): According to M. Imai et al. "Molecular Crystals and Liquid Crystals" No. 259 The measurement was performed by the method described on page 37 (1995). A sample was injected into a VA device with a distance (cell gap) of 20 μm between two glass substrates. The voltage was applied stepwise in units of 1 volt in the range of 39 volts to 50 volts to the device. After the voltage was not applied for 0.2 seconds, it was repeatedly applied with only one rectangular wave (rectangular pulse; 0.2 second) and no voltage (2 seconds) applied. The peak current and peak time of the transient current generated by the application are measured. The value of rotational viscosity is obtained based on these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al. The dielectric anisotropy required for this calculation is measured by the method described in Measurement (6).
(5)光學各向異性(折射率各向異性;△n;於25℃下測定):使用波長為589nm的光,利用在接目鏡上安裝有偏光板的阿貝折射計來進行測定。將主稜鏡的表面向一個方向摩擦後, 將試樣滴加於主稜鏡上。折射率n∥是於偏光的方向與摩擦的方向平行時進行測定。折射率n⊥是於偏光的方向與摩擦的方向垂直時進行測定。光學各向異性的值是根據△n=n∥-n⊥的式子來計算。 (5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25°C): Using light with a wavelength of 589 nm, it was measured with an Abbe refractometer with a polarizing plate attached to an eyepiece. After rubbing the surface of the main shaft in one direction, Drop the sample onto the main stalk. The refractive index n∥ is measured when the direction of polarized light is parallel to the direction of rubbing. The refractive index n⊥ is measured when the direction of polarized light is perpendicular to the direction of rubbing. The value of optical anisotropy is calculated according to the formula of △n=n∥-n⊥.
(6)介電各向異性(△ε;於25℃下測定):介電各向異性的值是根據△ε=ε∥-ε⊥的式子來計算。介電常數(ε∥及ε⊥)是以如下方式測定。 (6) Dielectric anisotropy (△ε; measured at 25°C): The value of dielectric anisotropy is calculated according to the formula of △ε=ε∥-ε⊥. The dielectric constant (ε∥ and ε⊥) is measured in the following manner.
1)介電常數(ε∥)的測定:於經充分洗滌的玻璃基板上塗佈十八烷基三乙氧基矽烷(0.16mL)的乙醇(20mL)溶液。利用旋轉器使玻璃基板旋轉後,於150℃下加熱1小時。於兩塊玻璃基板的間隔(單元間隙)為4μm的VA元件中放入試樣,利用以紫外線進行硬化的黏接劑將該元件密封。對該元件施加正弦波(0.5V、1kHz),2秒後測定液晶分子的長軸方向的介電常數(ε∥)。 1) Measurement of dielectric constant (ε∥): a solution of octadecyltriethoxysilane (0.16mL) in ethanol (20mL) is coated on a fully washed glass substrate. After rotating the glass substrate with a spinner, it was heated at 150°C for 1 hour. A sample was placed in a VA device with a distance (cell gap) of 4 μm between two glass substrates, and the device was sealed with an adhesive cured by ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to the device, and after 2 seconds, the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured.
2)介電常數(ε⊥)的測定:於經充分洗滌的玻璃基板上塗佈聚醯亞胺溶液。將該玻璃基板煅燒後,對所得的配向膜進行摩擦處理。於兩塊玻璃基板的間隔(單元間隙)為9μm、扭轉角為80度的TN元件中注入試樣。對該元件施加正弦波(0.5V,1kHz),2秒後測定液晶分子的短軸方向的介電常數(ε⊥)。 2) Measurement of dielectric constant (ε⊥): Coat a polyimide solution on a sufficiently washed glass substrate. After firing the glass substrate, rubbing treatment is performed on the resulting alignment film. A sample was injected into a TN device with a gap (cell gap) of 9 μm between two glass substrates and a twist angle of 80 degrees. A sine wave (0.5V, 1kHz) was applied to the device, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured.
(7)臨限電壓(Vth;於25℃下測定;V):於測定中使用大塚電子股份有限公司製造的LCD5100型亮度計。光源為鹵素燈。於兩塊玻璃基板的間隔(單元間隙)為4μm且摩擦方向為反平行的正常顯黑模式(normally black mode)的VA元件中放入試樣,使用以紫外線進行硬化的黏接劑將該元件密封。對該元件 施加的電壓(60Hz、矩形波)是以0.02V為單位,自0V階段性地增加至20V。此時,自垂直方向對元件照射光,測定透過元件的光量。製成於該光量達到最大時透過率為100%,且於該光量為最小時透過率為0%的電壓-透過率曲線。臨限電壓是由透過率達到10%時的電壓來表示。 (7) Threshold voltage (Vth; measured at 25°C; V): LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used in the measurement. The light source is a halogen lamp. Place a sample in a VA device in a normally black mode (normally black mode) with a distance of 4 μm between two glass substrates (cell gap) and an anti-parallel rubbing direction, and use an adhesive cured by ultraviolet light to make the device seal. For this component The applied voltage (60 Hz, rectangular wave) is 0.02V as the unit, and it is gradually increased from 0V to 20V. At this time, the element was irradiated with light from the vertical direction, and the amount of light passing through the element was measured. A voltage-transmittance curve is made that has a transmittance of 100% when the amount of light reaches its maximum and a transmittance of 0% when the amount of light reaches its minimum. The threshold voltage is expressed by the voltage when the transmittance reaches 10%.
(8)電壓保持率(VHR-1;於25℃下測定;%):測定中使用的TN元件具有聚醯亞胺配向膜,而且兩塊玻璃基板的間隔(單元間隙)為5μm。該元件在注入試樣後,利用以紫外線進行硬化的黏接劑來密封。對該TN元件施加脈衝電壓(5V、60微秒)來充電。利用高速電壓計,於16.7毫秒期間測定所衰減的電壓,求出單位週期中的電壓曲線與橫軸之間的面積A。面積B為未衰減時的面積。電壓保持率是由面積A相對於面積B的百分率來表示。 (8) Voltage holding ratio (VHR-1; measured at 25°C; %): The TN device used in the measurement has a polyimide alignment film, and the interval (cell gap) between two glass substrates is 5 μm. After the device is injected with a sample, it is sealed with an adhesive that is cured by ultraviolet light. A pulse voltage (5V, 60 microseconds) was applied to the TN device to charge it. Using a high-speed voltmeter, the attenuated voltage was measured during 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit period was obtained. Area B is the area without attenuation. The voltage retention rate is expressed by the percentage of area A to area B.
(9)電壓保持率(VHR-2;於80℃下測定;%):除了代替25℃而於80℃下進行測定以外,以與所述相同的順序來測定電壓保持率。由VHR-2來表示所得的值。 (9) Voltage holding ratio (VHR-2; measured at 80°C; %): The voltage holding ratio was measured in the same procedure as described above except that the measurement was performed at 80°C instead of 25°C. The value obtained is represented by VHR-2.
(10)電壓保持率(VHR-3;於25℃下測定;%):照射紫外線後,測定電壓保持率,來評價對紫外線的穩定性。用於測定的TN元件具有聚醯亞胺配向膜,而且單元間隙為5μm。於該元件中注入試樣,照射光20分鐘。光源為超高壓水銀燈USH-500D(牛尾(USHIO)電機製造),元件與光源的間隔為20cm。VHR-3的測定中,於16.7毫秒期間測定所衰減的電壓。具有 大的VHR-3的組成物對紫外線具有大的穩定性。VHR-3較佳為90%以上,尤佳為95%以上。 (10) Voltage retention rate (VHR-3; measured at 25°C; %): After irradiating ultraviolet rays, the voltage retention rate is measured to evaluate the stability to ultraviolet rays. The TN device used for the measurement has a polyimide alignment film, and the cell gap is 5 μm. The sample was injected into the element, and light was irradiated for 20 minutes. The light source is an ultra-high pressure mercury lamp USH-500D (manufactured by USHIO Motor), and the distance between the element and the light source is 20cm. In the measurement of VHR-3, the attenuated voltage was measured during 16.7 milliseconds. have The composition of large VHR-3 has great stability to ultraviolet rays. VHR-3 is preferably 90% or more, and more preferably 95% or more.
(11)電壓保持率(VHR-4;於25℃下測定;%):將注入有試樣的TN元件於80℃的恆溫槽內加熱500小時後,測定電壓保持率,來評價對熱的穩定性。VHR-4的測定中,於16.7毫秒期間測定所衰減的電壓。具有大的VHR-4的組成物對熱具有大的穩定性。 (11) Voltage retention rate (VHR-4; measured at 25°C; %): After heating the sample-infused TN element in a constant temperature bath at 80°C for 500 hours, measure the voltage retention rate to evaluate the resistance to heat stability. In the measurement of VHR-4, the attenuated voltage was measured during 16.7 milliseconds. A composition with a large VHR-4 has a large stability to heat.
(12)響應時間(τ;於25℃下測定;ms):於測定中使用大塚電子股份有限公司製造的LCD5100型亮度計。光源為鹵素燈。低通濾波器(Low-pass filter)設定為5kHz。於兩塊玻璃基板的間隔(單元間隙)為3.5μm且不具有配向膜的VA元件中放入試樣。利用以紫外線進行硬化的黏接劑將該元件密封。對該元件一邊施加30V的電壓,一邊照射78mW/cm2(405nm)的紫外線449秒(35J)。於紫外線的照射中使用岩崎(EYE GRAPHICS)股份有限公司製造的紫外硬化用多金屬燈M04-L41。對該元件施加矩形波(120Hz)。此時,自垂直方向對元件照射光,測定透過元件的光量。於該光量達到最大時視為透過率為100%,於該光量為最小時視為透過率為0%。矩形波的最大電壓是以透過率成為90%的方式進行設定。矩形波的最低電壓是設定為透過率成為0%的2.5V。響應時間是由透過率自10%變化至90%所需要的時間(上升時間;rise time;毫秒)表示。 (12) Response time (τ; measured at 25°C; ms): LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used in the measurement. The light source is a halogen lamp. The low-pass filter is set to 5kHz. A sample was placed in a VA device with a distance (cell gap) of 3.5 μm between two glass substrates and no alignment film. The device is sealed with an adhesive that is cured by ultraviolet light. While applying a voltage of 30 V to the device, ultraviolet light of 78 mW/cm 2 (405 nm) was irradiated for 449 seconds (35 J). For the irradiation of ultraviolet rays, a multimetallic lamp M04-L41 for ultraviolet curing manufactured by EYE GRAPHICS Co., Ltd. was used. A rectangular wave (120 Hz) was applied to this element. At this time, the element was irradiated with light from the vertical direction, and the amount of light passing through the element was measured. When the light amount reaches the maximum, the transmittance is regarded as 100%, and when the light amount is the minimum, the transmittance is regarded as 0%. The maximum voltage of the rectangular wave is set so that the transmittance becomes 90%. The minimum voltage of the rectangular wave is set to 2.5V at which the transmittance becomes 0%. The response time is represented by the time (rise time; rise time; milliseconds) required for the transmittance to change from 10% to 90%.
(13)彈性常數(K11:展曲(splay)彈性常數、K33: 彎曲(bend)彈性常數;於25℃下測定;pN):於測定中使用東陽技術(TOYO Corporation)股份有限公司製造的EC-1型彈性常數測定器。於兩塊玻璃基板的間隔(單元間隙)為20μm的垂直配向元件中注入試樣。對該元件施加20伏特至0伏特的電荷,測定靜電電容及施加電壓。使用「液晶裝置手冊」(日刊工業新聞社)第75頁中的式(2.98)、式(2.101)對所測定的靜電電容(C)及施加電壓(V)的值進行擬合(fitting),根據式(2.100)獲得彈性常數的值。 (13) Elastic constant (K11: splay elastic constant, K33: Bend elastic constant; measured at 25°C; pN): An EC-1 elastic constant tester manufactured by TOYO Corporation Co., Ltd. was used in the measurement. A sample was injected into a vertical alignment element with a distance between two glass substrates (cell gap) of 20 μm. A charge of 20V to 0V was applied to the device, and the capacitance and applied voltage were measured. Fitting (fitting) the measured capacitance (C) and applied voltage (V) using the formula (2.98) and formula (2.101) on page 75 of "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), According to formula (2.100), the value of elastic constant is obtained.
(14)比電阻(ρ;於25℃下測定;Ωcm):於具備電極的容器中放入試樣1.0mL。對該容器施加直流電壓(10V),測定10秒後的直流電流。比電阻是根據下式而算出。(比電阻)={(電壓)×(容器的電容)}/{(直流電流)×(真空的介電常數)}。 (14) Specific resistance (ρ; measured at 25°C; Ωcm): Put 1.0 mL of the sample in a container equipped with electrodes. A DC voltage (10V) was applied to the container, and the DC current after 10 seconds was measured. The specific resistance is calculated according to the following formula. (Specific resistance)={(voltage)×(capacitance of container)}/{(DC current)×(dielectric constant of vacuum)}.
(15)預傾角(度):於預傾角的測定中使用分光橢圓儀M-2000U(J.A.沃蘭股份有限公司(J.A.Woollam Co.,Inc.)製造)。 (15) Pretilt angle (degrees): A spectroscopic ellipsometer M-2000U (manufactured by J.A. Woollam Co., Inc.) was used for the measurement of the pretilt angle.
(16)配向穩定性(液晶配向軸穩定性):評價液晶顯示元件的電極側的液晶配向軸的變化。測定施加應力前的電極側的液晶配向角度Φ(before),然後,對元件施加矩形波4.5V、60Hz 20分鐘後,緩衝1秒鐘,於1秒後及5分鐘後再次測定電極側的液晶配向角度Φ(after)。由該些值並使用下述式來算出1秒後及5分鐘後的液晶配向角度的變化△Φ(deg.)。 (16) Alignment stability (liquid crystal alignment axis stability): The change of the liquid crystal alignment axis on the electrode side of the liquid crystal display element was evaluated. Measure the alignment angle Φ (before) of the liquid crystal on the electrode side before stress is applied, then apply a rectangular wave of 4.5V, 60Hz to the device for 20 minutes, buffer for 1 second, and measure the liquid crystal on the electrode side again after 1 second and 5 minutes later Alignment angle Φ(after). From these values, the following formula was used to calculate the change ΔΦ (deg.) of the liquid crystal alignment angle after 1 second and 5 minutes later.
△Φ(deg.)=Φ(after)-Φ(before) (式2) △Φ(deg.)=Φ(after)-Φ(before) (Equation 2)
該些測定是以J.希爾菲克(J.Hilfiker)、B.喬司(B.Johs)、C.赫辛格(C.Herzinger)、J.F.埃爾曼(J.F.Elman)、E.蒙巴齊(E.Montbach)、D.布賴恩特(D.Bryant)及P.J.博斯(P.J.Bos)的「薄固體膜(Thin Solid Films)」455-456(2004)596-600為參考來進行。可以說△Φ越小液晶配向軸的變化率越小,液晶配向軸的穩定性越好。 These measurements are based on J. Hilfiker, B. Johs, C. Herzinger, JF Elman (JFElman), E. Momba E. Montbach, D. Bryant, and PJ Bos's "Thin Solid Films" 455-456 (2004) 596-600 are used as reference . It can be said that the smaller the ΔΦ, the smaller the rate of change of the liquid crystal alignment axis, and the better the stability of the liquid crystal alignment axis.
合成例1 Synthesis example 1
利用下述方法來合成化合物(1-23-1)。 The compound (1-23-1) was synthesized by the following method.
第1步驟 Step 1
將化合物(T-1)(40.0g)、膦醯基乙酸三乙酯(40.7g)及甲苯(800ml)放入至反應器中,冷卻至0℃。向其中緩慢地滴加乙 醇鈉(20%乙醇溶液)(61.8g),恢復至室溫並且攪拌12小時。 將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=4:1)將殘渣純化,而獲得化合物(T-2)(42.0g;83%)。 The compound (T-1) (40.0 g), triethyl phosphinyl acetate (40.7 g) and toluene (800 ml) were put into the reactor and cooled to 0°C. Add B slowly to it Sodium alkoxide (20% ethanol solution) (61.8 g), return to room temperature and stir for 12 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1) to obtain compound (T-2) (42.0 g; 83%).
第2步驟 Step 2
將化合物(T-2)(42.0g)及甲苯(400ml)、異丙醇(400ml)放入至反應器中,於加入Pd/C(0.7g)的氫氣環境下、室溫下攪拌24小時。將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用食鹽水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=4:1)將殘渣純化,而獲得化合物(T-3)(40.1g;95%)。 Put compound (T-2) (42.0g), toluene (400ml), and isopropanol (400ml) into the reactor, and stir at room temperature for 24 hours under a hydrogen environment with Pd/C (0.7g) . The reaction mixture was poured into water, and the water layer was extracted with toluene. The mixed organic layer was washed with salt water, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1) to obtain compound (T-3) (40.1 g; 95%).
第3步驟 Step 3
將化合物(T-3)(40.1g)、及四氫呋喃(tetrahydrofuran,THF)(400ml)放入至反應器中,冷卻至-60℃。緩慢地滴加二異丙胺鋰(Lithium diisopropylamide,LDA)(1.13M;THF溶液;142ml),並攪拌1小時。向其中緩慢地滴加氯甲酸甲酯(11.0ml),恢復至室溫並且攪拌5小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃 縮,利用矽膠層析法(容積比,甲苯:庚烷=4:1)將殘渣純化,而獲得化合物(T-4)(30.5g;65%)。 The compound (T-3) (40.1 g) and tetrahydrofuran (THF) (400 ml) were put into the reactor and cooled to -60°C. Lithium diisopropylamide (LDA) (1.13M; THF solution; 142 ml) was slowly added dropwise and stirred for 1 hour. Methyl chloroformate (11.0 ml) was slowly added dropwise thereto, returned to room temperature and stirred for 5 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. Concentrate the solution under reduced pressure After shrinking, the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1) to obtain compound (T-4) (30.5 g; 65%).
第4步驟 Step 4
將氫化鋁鋰(1.7g)及THF(300ml)放入至反應器中,並進行冰浴冷卻。緩慢地加入化合物(T-4)(30.5g)的THF(600ml)溶液,恢復至室溫並且攪拌3小時。將反應混合物注入至水中,並利用乙酸乙酯對水層進行萃取。利用食鹽水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=1:1)將殘渣純化。進而藉由自庚烷的再結晶來進行純化,而獲得化合物(T-5)(20.1g,80%)。 Lithium aluminum hydride (1.7g) and THF (300ml) were put into the reactor and cooled in an ice bath. A solution of compound (T-4) (30.5 g) in THF (600 ml) was slowly added, returned to room temperature and stirred for 3 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with salt water, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=1:1). Further, purification was performed by recrystallization from heptane to obtain compound (T-5) (20.1 g, 80%).
第5步驟 Step 5
將化合物(T-5)(20.1g)、三乙基胺(10.3ml)及THF(200ml)放入至反應器中,冷卻至0℃。向其中緩慢地滴加甲基丙烯醯氯(6.0ml),恢復至室溫並且攪拌4小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用乙酸乙酯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=9:1)將殘渣純化,而獲得化合物(1-23-1)(7.7g;32%)。 The compound (T-5) (20.1 g), triethylamine (10.3 ml) and THF (200 ml) were put into the reactor and cooled to 0°C. Methacrylic chloride (6.0 ml) was slowly added dropwise thereto, returned to room temperature and stirred for 4 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1) to obtain compound (1-23-1) (7.7 g; 32%).
所得的化合物(1-23-1)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-23-1) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):6.11(s,1H)、5.58(s,1H)、4.29-4.26(m,1H)、4.14-4.11(m,1H)、3.60-3.57(m,1H)、 3.50-3.47(m,1H)、1.98-1.95(m,5H)、1.78-1.67(m,8H)、1.32-1.11(m,12H)、0.99-0.81(m,13H) 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 6.11 (s, 1H), 5.58 (s, 1H), 4.29-4.26 (m, 1H), 4.14-4.11 (m, 1H), 3.60-3.57 (m,1H), 3.50-3.47(m,1H), 1.98-1.95(m,5H), 1.78-1.67(m,8H), 1.32-1.11(m,12H), 0.99-0.81(m,13H)
化合物(1-23-1)的物性為如下所述。 The physical properties of compound (1-23-1) are as follows.
轉變溫度:C 65.0 I. Transition temperature: C 65.0 I.
[合成例2] [Synthesis Example 2]
化合物(1-4-1)的合成
第1步驟 Step 1
將聚甲醛(paraformaldehyde)(30.0g)、1,4-二氮雜雙環[2.2.2]辛烷(1,4-diazabicyclo[2.2.2]octane,DABCO)(56.0g)、及水(600ml)放入至反應器中,於室溫下攪拌15分鐘。向其中滴加化合物(T-6)(50.0g)的THF(1200ml)溶液,於室溫下攪拌72小時。 將反應混合物注入至水中,並利用乙酸乙酯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=4:1)將殘渣純化,而獲得化合物(T-7)(43.2g;65%)。 Combine paraformaldehyde (30.0g), 1,4-diazabicyclo[2.2.2]octane (1,4-diazabicyclo[2.2.2]octane, DABCO) (56.0g), and water (600ml ) Put it into the reactor and stir for 15 minutes at room temperature. A THF (1200 ml) solution of compound (T-6) (50.0 g) was added dropwise thereto, and the mixture was stirred at room temperature for 72 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=4:1) to obtain compound (T-7) (43.2 g; 65%).
第2步驟 Step 2
將化合物(T-7)(42.2g)用作原料,並將咪唑(26.3g)、及二氯甲烷(800ml)放入至反應器中,冷卻至0℃。向其中緩慢地滴加第三丁基二苯基氯矽烷(tert-Butyl diphenyl chlorosilane,TBDPSCl)(106.4g)的二氯甲烷(100ml)溶液,恢復至室溫並且攪拌12小時。將反應混合物注入至水中,藉由二氯甲烷對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,庚烷:乙酸乙酯=10:1)將殘渣純化,而獲得化合物(T-8)(107.0g;90%)。 The compound (T-7) (42.2 g) was used as a raw material, and imidazole (26.3 g) and dichloromethane (800 ml) were put into the reactor and cooled to 0°C. A solution of tert-Butyl diphenyl chlorosilane (TBDPSCl) (106.4 g) in dichloromethane (100 ml) was slowly added dropwise thereto, returned to room temperature and stirred for 12 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=10:1) to obtain compound (T-8) (107.0 g; 90%).
第3步驟 Step 3
將化合物(T-8)(107.0g)、THF(800ml)、甲醇(200ml)、及水(100ml)放入至反應器中,冷卻至0℃。向其中加入氫氧化 鋰一水合物(24.3g),恢復至室溫並且攪拌12小時。將反應混合物注入至水中,並緩慢地加入6N鹽酸(100ml)而成為酸性後,利用乙酸乙酯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,藉由自庚烷的再結晶來進行純化,而獲得化合物(T-9)(47.4g;48%)。 The compound (T-8) (107.0 g), THF (800 ml), methanol (200 ml), and water (100 ml) were put into the reactor and cooled to 0°C. Add hydrogen to it Lithium monohydrate (24.3 g), returned to room temperature and stirred for 12 hours. The reaction mixture was poured into water, 6N hydrochloric acid (100 ml) was slowly added to make it acidic, and then the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and purified by recrystallization from heptane to obtain compound (T-9) (47.4 g; 48%).
第4步驟 Step 4
將化合物(1-23-1)(7.7g)、化合物(T-9)(8.0g)、N,N-二甲基-4-胺基吡啶(N,N-dimethyl-4-aminopyridine,DMAP)(1.0g)、及二氯甲烷(200ml)放入至反應器中,冷卻至0℃。向其中緩慢地滴加N,N'-二環己基碳二醯亞胺(N,N'-dicyclohexylcarbodiimide,DCC)(4.8g)的二氯甲烷(60ml)溶液,恢復至室溫並且攪拌12小時。將不溶物過濾分離後,將反應混合物注入至水中,利用二氯甲烷對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。 將該溶液於減壓下濃縮,利用矽膠層析法(容積比,庚烷:乙酸乙酯=19:1)將殘渣純化,而獲得化合物(T-10)(9.8g;70%)。 Compound (1-23-1) (7.7g), compound (T-9) (8.0g), N,N-dimethyl-4-aminopyridine (DMAP) ) (1.0g) and dichloromethane (200ml) were put into the reactor and cooled to 0°C. A solution of N,N'-dicyclohexylcarbodiimide (N,N'-dicyclohexylcarbodiimide, DCC) (4.8g) in dichloromethane (60ml) was slowly added dropwise, returned to room temperature and stirred for 12 hours . After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=19:1) to obtain compound (T-10) (9.8 g; 70%).
第5步驟 Step 5
將化合物(T-10)(9.8g)及THF(100ml)放入至反應器中,冷卻至0℃。向其中緩慢地加入四正丁基氟化銨(Tetra-n-butyl ammonium fluoride,TBAF)(1.00M;THF溶液;16.5ml),恢復至室溫並且攪拌1小時。將反應混合物注入至水中,利用乙酸乙酯對水層進行萃取。利用食鹽水對混在一起的有機層進行洗滌, 並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=9:1)將殘渣純化。進而藉由自庚烷的再結晶來進行純化,而獲得化合物(1-4-1)(3.1g;47%)。 The compound (T-10) (9.8 g) and THF (100 ml) were put into the reactor and cooled to 0°C. Tetra-n-butyl ammonium fluoride (TBAF) (1.00M; THF solution; 16.5 ml) was slowly added thereto, returned to room temperature and stirred for 1 hour. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. Wash the mixed organic layer with salt water, And use anhydrous magnesium sulfate for drying. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1). Further purification was performed by recrystallization from heptane to obtain compound (1-4-1) (3.1 g; 47%).
所得的化合物(1-4-1)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-4-1) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):6.25(s,1H)、6.10(s,1H)、5.85(s,1H)、5.57(s,1H)、4.33(d,J=4.5Hz,2H)、4.27-4.16(m,2H)、4.13-4.08(m,2H)、2.31(s,1H)、2.26-2.22(m,1H)、1.94(s,3H)、1.81-1.61(m,8H)、1.32-1.08(m,12H)、1.00-0.79(m,13H). 1 H-NMR: Chemical shift δ(ppm; CDCl 3 ): 6.25(s,1H), 6.10(s,1H), 5.85(s,1H), 5.57(s,1H), 4.33(d,J=4.5 Hz, 2H), 4.27-4.16 (m, 2H), 4.13-4.08 (m, 2H), 2.31 (s, 1H), 2.26-2.22 (m, 1H), 1.94 (s, 3H), 1.81-1.61 ( m,8H), 1.32-1.08(m,12H), 1.00-0.79(m,13H).
化合物(1-4-1)的物性為如下所述。 The physical properties of compound (1-4-1) are as follows.
轉變溫度:C 49.6 I. Transition temperature: C 49.6 I.
[合成例3] [Synthesis Example 3]
化合物(1-4-2)的合成
第1步驟 Step 1
將化合物(T-11)(15.0g)、N,N-二甲基-4-胺基吡啶(DMAP)(9.33g)、米氏酸(9.54g)及二氯甲烷(250ml)放入至反應器中,冷卻至0℃。向其中緩慢地加入N,N'-二環己基碳二醯亞胺(DCC)(15.7g),恢復至室溫並且攪拌12小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用二氯甲烷對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮。將殘渣、乙醇(250ml)放入至反應器中,於70℃下進行攪拌。將不溶物過濾分離後,將反應混合物注入至食鹽水中,並利用乙酸乙酯對水層進行萃取。利用無水硫酸鎂對混在一起的有機層進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,庚烷:甲苯=1:1)將殘渣純化,而獲得化合物(T-12)(10.2g;55%)。 Put compound (T-11) (15.0g), N,N-dimethyl-4-aminopyridine (DMAP) (9.33g), Michler's acid (9.54g) and methylene chloride (250ml) into In the reactor, cool to 0°C. N,N'-Dicyclohexylcarbodiimide (DCC) (15.7 g) was slowly added thereto, returned to room temperature and stirred for 12 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure. The residue and ethanol (250 ml) were put into the reactor and stirred at 70°C. After the insoluble matter was separated by filtration, the reaction mixture was poured into brine, and the aqueous layer was extracted with ethyl acetate. Dry the mixed organic layers with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:toluene=1:1) to obtain compound (T-12) (10.2 g; 55%).
第2步驟 Step 2
將氫化鋁鋰(0.6g)及THF(100ml)放入至反應器中,並進行冰浴冷卻。緩慢地加入化合物(T-12)(10.2g)的THF(100ml)溶液,恢復至室溫並且攪拌3小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用乙酸乙酯對水層進行萃取。利用食鹽水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=1:1)將殘渣純化,而獲得化合物(T-13)(7.35g;81%)。 Lithium aluminum hydride (0.6 g) and THF (100 ml) were put into the reactor and cooled in an ice bath. A solution of compound (T-12) (10.2 g) in THF (100 ml) was slowly added, returned to room temperature and stirred for 3 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with salt water, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=1:1) to obtain compound (T-13) (7.35 g; 81%).
第3步驟 Step 3
將化合物(T-13)(7.35g)、三乙基胺(3.75ml)、N,N-二甲基-4-胺基吡啶(DMAP)(0.27g)、二氯甲烷(200ml)放入至反應器中,冷卻至0℃。緩慢地滴加三異丙基氯矽烷(Triisopropylsilyl chloride,TIPSCl)(5.05ml),恢復至室溫並且攪拌24小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用乙酸乙酯對水層進行萃取。利用食鹽水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=19:1)將殘渣純化,而獲得化合物(T-14)(6.50g;60%)。 Put compound (T-13) (7.35g), triethylamine (3.75ml), N,N-dimethyl-4-aminopyridine (DMAP) (0.27g), methylene chloride (200ml) into Into the reactor, cool to 0°C. Triisopropylsilyl chloride (TIPSCl) (5.05ml) was slowly added dropwise, returned to room temperature and stirred for 24 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with salt water, and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=19:1) to obtain compound (T-14) (6.50 g; 60%).
第4步驟 Step 4
將化合物(T-14)(6.50g)、三乙基胺(3.77ml)、THF(200ml)放入至反應器中,冷卻至0℃。向其中緩慢地滴加甲基丙烯醯氯(2.00ml),恢復至室溫並且攪拌4小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=1:1)將殘渣純化,而獲得化合物(T-15)(4.70g;63%)。 The compound (T-14) (6.50 g), triethylamine (3.77 ml), and THF (200 ml) were put into the reactor and cooled to 0°C. Methacrylic chloride (2.00 ml) was slowly added dropwise thereto, returned to room temperature and stirred for 4 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:1) to obtain compound (T-15) (4.70 g; 63%).
第5步驟 Step 5
將化合物(T-15)(4.70g)、THF(100ml)放入至反應器中,冷卻至0℃。向其中緩慢地加入TBAF(1.00M;THF溶液;10.3ml),恢復至室溫並且攪拌1小時。將反應混合物注入至水中,並利用乙酸乙酯對水層進行萃取。利用食鹽水對混在一起的有機層 進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=9:1)將殘渣純化,而獲得化合物(T-16)(1.50g;45%)。 The compound (T-15) (4.70 g) and THF (100 ml) were put into the reactor and cooled to 0°C. TBAF (1.00M; THF solution; 10.3 ml) was slowly added thereto, returned to room temperature and stirred for 1 hour. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. Use salt water to mix the organic layer It is washed and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1) to obtain compound (T-16) (1.50 g; 45%).
第6步驟 Step 6
使用化合物(T-16)(1.50g)作為原料,藉由與合成例2的第4步驟相同的方法而獲得化合物(T-17)(1.51g;55%)。 Using compound (T-16) (1.50 g) as a raw material, the compound (T-17) (1.51 g; 55%) was obtained by the same method as in the fourth step of Synthesis Example 2.
第7步驟 Step 7
使用化合物(T-17)(1.51g)作為原料,藉由與合成例2的第5步驟相同的方法而獲得化合物(1-4-2)(0.45g;45%)。 Using compound (T-17) (1.51 g) as a raw material, the compound (1-4-2) (0.45 g; 45%) was obtained by the same method as in the fifth step of Synthesis Example 2.
所得的化合物(1-4-2)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-4-2) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):6.25(s,1H)、6.09(s,1H)、5.82(d,J=1.1Hz,1H)、5.55(s,1H)、5.22-5.17(m,1H)、4.32-4.26(m,3H)、4.17-4.12(m,3H)、2.50(s,1H)、2.03-1.89(m,5H)、1.83-1.58(m,9H)、1.41-1.08(m,11H)、0.96-0.78(m,13H).化合物(1-4-2)的物性為如下所述。 1 H-NMR: Chemical shift δ(ppm; CDCl 3 ): 6.25(s,1H), 6.09(s,1H), 5.82(d,J=1.1Hz,1H), 5.55(s,1H), 5.22- 5.17(m,1H), 4.32-4.26(m,3H), 4.17-4.12(m,3H), 2.50(s,1H), 2.03-1.89(m,5H), 1.83-1.58(m,9H), 1.41-1.08 (m, 11H), 0.96-0.78 (m, 13H). The physical properties of compound (1-4-2) are as follows.
轉變溫度:C 61.2 I. Transition temperature: C 61.2 I.
[合成例4] [Synthesis Example 4]
化合物(1-23-2)的合成
第1步驟 Step 1
將化合物(T-18)(20.0g)及THF(200ml)放入至反應器中,冷卻至-70℃,緩慢地滴加二異丙胺鋰(LDA)(1.10M;THF溶液;68.0ml),並攪拌1小時。向其中緩慢地加入氯甲酸甲酯(7.00g),恢復至室溫並且攪拌4小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=9:1)將殘渣純化,而獲得化合物(T-19)(19.4g;82%)。 Put compound (T-18) (20.0g) and THF (200ml) into the reactor, cool to -70°C, slowly add lithium diisopropylamine (LDA) (1.10M; THF solution; 68.0ml) dropwise , And stir for 1 hour. Methyl chloroformate (7.00 g) was slowly added thereto, returned to room temperature and stirred for 4 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=9:1) to obtain compound (T-19) (19.4 g; 82%).
第2步驟 Step 2
將氫化鋰鋁(1.93g)及THF(200ml)放入至反應器中,冷卻至0℃。向其中緩慢地加入化合物(T-19)(19.4g)的THF(100ml)溶液,恢復至室溫並且攪拌3小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用乙酸乙酯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=1:1)將殘渣純化,而獲得化合物(T-20)(6.0g;38%)。 Put lithium aluminum hydride (1.93 g) and THF (200 ml) into the reactor, and cool to 0°C. A THF (100 ml) solution of compound (T-19) (19.4 g) was slowly added thereto, returned to room temperature and stirred for 3 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=1:1) to obtain compound (T-20) (6.0 g; 38%).
第3步驟 Step 3
將化合物(T-20)(6.0g)、三乙基胺(3.2ml)及THF(100ml)放入至反應器中,冷卻至0℃。向其中緩慢地加入甲基丙烯醯氯(1.8ml),恢復至室溫並且攪拌5小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用乙酸乙酯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=9:1)將殘渣純化,而獲得化合物(1-23-2)(2.5g;34%)。 The compound (T-20) (6.0 g), triethylamine (3.2 ml), and THF (100 ml) were put into the reactor and cooled to 0°C. Methacrylic chloride (1.8 ml) was slowly added thereto, returned to room temperature and stirred for 5 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1) to obtain compound (1-23-2) (2.5 g; 34%).
所得的化合物(1-23-2)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-23-2) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):6.10(s,1H)、5.57(d,J=1.1Hz,1H)、4.38(dd,J=11.4Hz,J=4.3Hz,1H)、4.23(dd,J=11.3Hz,J=6.7Hz,1H)、3.71-3.68(m,1H)、3.63-3.60(m,1H)、1.97(s,1H)、1.94(s,3H)、1.82-1.62(m,9H)、1.41-1.18(m,7H)、1.14-0.79(m,16H). 1 H-NMR: Chemical shift δ(ppm; CDCl 3 ): 6.10(s,1H), 5.57(d,J=1.1Hz,1H), 4.38(dd,J=11.4Hz,J=4.3Hz,1H) , 4.23(dd,J=11.3Hz,J=6.7Hz,1H), 3.71-3.68(m,1H), 3.63-3.60(m,1H), 1.97(s,1H), 1.94(s,3H), 1.82-1.62(m,9H), 1.41-1.18(m,7H), 1.14-0.79(m,16H).
化合物(1-23-2)的物性為如下所述。 The physical properties of compound (1-23-2) are as follows.
轉變溫度:C 68.4 SA 89.3 I Transition temperature: C 68.4 S A 89.3 I
[合成例5] [Synthesis Example 5]
化合物(1-4-3)的合成
第1步驟 Step 1
將化合物(T-7)、3,4-二氫-2H-吡喃(23.3g)、吡啶對甲苯磺酸鹽(Pyridinium p-Toluenesulfonate,PPTS)(5.80g)放入至反應器中並於50℃下攪拌10小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用二氯甲烷對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,庚烷:乙酸乙酯=2:1)將殘渣純化,而獲得化合物(T-21)(39.5g;80%)。 Put compound (T-7), 3,4-dihydro-2H-pyran (23.3g), pyridinium p-Toluenesulfonate (Pyridinium p-Toluenesulfonate, PPTS) (5.80g) into the reactor and add Stir at 50°C for 10 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=2:1) to obtain compound (T-21) (39.5 g; 80%).
第2步驟 Step 2
將化合物(T-21)(39.5g)、THF(400ml)、及水(400ml)放入至反應器中,冷卻至0℃。向其中加入氫氧化鋰一水合物(15.4g),恢復至室溫並且攪拌12小時。將反應混合物注入至水中,並緩慢地加入6N鹽酸(60ml)而成為酸性後,利用乙酸乙酯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,而獲得化合物(T-22)(32.6g;95%)。 The compound (T-21) (39.5 g), THF (400 ml), and water (400 ml) were put into the reactor and cooled to 0°C. Lithium hydroxide monohydrate (15.4 g) was added thereto, returned to room temperature and stirred for 12 hours. The reaction mixture was poured into water, 6N hydrochloric acid (60 ml) was slowly added to make it acidic, and then the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain compound (T-22) (32.6 g; 95%).
第3步驟 Step 3
將化合物(1-23-2)(2.0g)、化合物(T-22)(1.18g)、DMAP(0.32g)、及二氯甲烷(100ml)放入至反應器中,冷卻至0℃。 向其中緩慢地滴加DCC(1.30g)的二氯甲烷(60ml)溶液,恢復至室溫並且攪拌12小時。將不溶物過濾分離後,將反應混合物注入至水中,利用二氯甲烷對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=19:1)將殘渣純化,而獲得化合物(T-23)(2.37g;82%)。 The compound (1-23-2) (2.0 g), the compound (T-22) (1.18 g), DMAP (0.32 g), and dichloromethane (100 ml) were put into the reactor and cooled to 0°C. A solution of DCC (1.30 g) in dichloromethane (60 ml) was slowly added dropwise thereto, returned to room temperature and stirred for 12 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=19:1) to obtain compound (T-23) (2.37 g; 82%).
第4步驟 Step 4
將化合物(T-23)(2.37g)、吡啶對甲苯磺酸鹽(PPTS)(0.54g)、THF(50ml)及甲醇(50ml)放入至反應器中,於50℃下攪拌5小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用乙酸乙酯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=9:1)將殘渣純化,而獲得化合物(1-4-3)(1.50g;75%)。 The compound (T-23) (2.37g), pyridine p-toluenesulfonate (PPTS) (0.54g), THF (50ml) and methanol (50ml) were put into the reactor and stirred at 50°C for 5 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1) to obtain compound (1-4-3) (1.50 g; 75%).
所得的化合物(1-4-3)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-4-3) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):6.24(s,1H)、6.09(s,1H)、5.84(s,1H)、5.57(s,1H)、4.33-4.27(m,4H)、4.20-4.16(m,2H)、2.34-2.31(m,1H)、1.97-1.90(m,4H)、1.82-1.67(m,8H)、1.43-1.39(m,1H)、1.31-1.18(m,6H)、1.15-0.75(m,16H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 6.24 (s, 1H), 6.09 (s, 1H), 5.84 (s, 1H), 5.57 (s, 1H), 4.33-4.27 (m, 4H) ), 4.20-4.16(m,2H), 2.34-2.31(m,1H), 1.97-1.90(m,4H), 1.82-1.67(m,8H), 1.43-1.39(m,1H), 1.31-1.18 (m, 6H), 1.15-0.75 (m, 16H).
化合物(1-4-3)的物性為如下所述。 The physical properties of compound (1-4-3) are as follows.
轉變溫度:C 66.5 I Transition temperature: C 66.5 I
[合成例6] [Synthesis Example 6]
化合物(1-24-1)的合成
第1步驟 Step 1
將化合物(T-24)(30.0g)、乙醇(14.4ml)、磷酸鉀(53.6g)、碘化銅(1.60g)、乙醯乙酸乙酯(32.8g)及二甲基亞碸(dimethyl sulfoxide,DMSO)(500ml)放入至反應器中,於80℃下攪拌6小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=4:1)將殘渣純化,而獲得化合物(T-25)(19.5g;73%)。 Compound (T-24) (30.0g), ethanol (14.4ml), potassium phosphate (53.6g), copper iodide (1.60g), ethyl acetate (32.8g) and dimethyl sulfide (dimethyl sulfoxide, DMSO) (500ml) was put into the reactor and stirred at 80°C for 6 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1) to obtain compound (T-25) (19.5 g; 73%).
第2步驟 Step 2
使用化合物(T-25)(19.5g)作為原料,藉由與合成例4的第1步驟相同的方法而獲得化合物(T-26)(16.2g;70%)。 Using the compound (T-25) (19.5 g) as a raw material, the compound (T-26) (16.2 g; 70%) was obtained by the same method as in the first step of Synthesis Example 4.
第3步驟 Step 3
使用化合物(T-26)(16.2g)作為原料,藉由與合成例4的第2步驟相同的方法而獲得化合物(T-27)(6.0g;45%)。 Using the compound (T-26) (16.2 g) as a raw material, the compound (T-27) (6.0 g; 45%) was obtained by the same method as in the second step of Synthesis Example 4.
第4步驟 Step 4
使用化合物(T-27)(6.0g)作為原料,藉由與合成例4的第3步驟相同的方法而獲得化合物(1-24-1)(2.3g;31%)。 Using compound (T-27) (6.0 g) as a raw material, the compound (1-24-1) (2.3 g; 31%) was obtained by the same method as in the third step of Synthesis Example 4.
所得的化合物(1-24-1)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-24-1) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):7.18-7.17(m,4H)、6.09(s,1H)、5.57(s,1H)、4.47-4.38(m,2H)、3.91-3.85(m,2H)、3.19-3.14(m,1H)、2.44(tt,J=12.2Hz,J=3.0Hz,1H)、1.93-1.86(m,8H)、1.48-1.38(m,2H)、1.34-1.19(m,9H)、1.07-0.99(m,2H)、0.89(t,J=6.8Hz,3H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 7.18-7.17 (m, 4H), 6.09 (s, 1H), 5.57 (s, 1H), 4.47-4.38 (m, 2H), 3.91-3.85 (m,2H), 3.19-3.14(m,1H), 2.44(tt,J=12.2Hz,J=3.0Hz,1H), 1.93-1.86(m,8H), 1.48-1.38(m,2H), 1.34-1.19(m,9H), 1.07-0.99(m,2H), 0.89(t,J=6.8Hz,3H).
化合物(1-24-1)的物性為如下所述。 The physical properties of compound (1-24-1) are as follows.
轉變溫度:C 36.1 I. Transition temperature: C 36.1 I.
[合成例7] [Synthesis Example 7]
化合物(1-5-2)的合成 Synthesis of compound (1-5-2)
第1步驟 Step 1
使用化合物(1-24-1)(2.0g)作為原料,藉由與合成例5的第3步驟相同的方法而獲得化合物(T-28)(2.2g;76%)。 Using the compound (1-24-1) (2.0 g) as a raw material, the compound (T-28) (2.2 g; 76%) was obtained by the same method as in the third step of Synthesis Example 5.
第2步驟 Step 2
使用化合物(T-28)(2.2g)作為原料,藉由與合成例5的第4步驟相同的方法而獲得化合物(1-5-2)(1.3g;70%)。 Using compound (T-28) (2.2 g) as a raw material, the compound (1-5-2) (1.3 g; 70%) was obtained by the same method as in the fourth step of Synthesis Example 5.
所得的化合物(1-5-2)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-5-2) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):7.17-7.16(m,4H)、6.21(s,1H)、6.07(s,1H)、5.81(d,J=1.0Hz,1H)、5.55(s,1H)、4.46-4.39(m,4H)、4.27(d,J=6.2Hz,2H)、3.42-3.37(m,1H)、2.44(tt,J=12.2Hz,J=3.1Hz,1H)、2.22-2.21(m,1H)、1.95(s,3H)、1.87-1.85(m,4H)、1.46-1.38(m,2H)、1.34-1.19(m,9H)、1.07-0.99(m,2H)、0.89(t,J=7.0Hz,3H). 1 H-NMR: Chemical shift δ(ppm; CDCl 3 ): 7.17-7.16(m,4H), 6.21(s,1H), 6.07(s,1H), 5.81(d,J=1.0Hz,1H), 5.55(s,1H), 4.46-4.39(m,4H), 4.27(d,J=6.2Hz,2H), 3.42-3.37(m,1H), 2.44(tt,J=12.2Hz,J=3.1Hz ,1H), 2.22-2.21(m,1H), 1.95(s,3H), 1.87-1.85(m,4H), 1.46-1.38(m,2H), 1.34-1.19(m,9H), 1.07-0.99 (m,2H), 0.89(t,J=7.0Hz,3H).
化合物(1-5-2)的物性為如下所述。 The physical properties of compound (1-5-2) are as follows.
轉變溫度:C 52.3 I. Transition temperature: C 52.3 I.
[合成例8] [Synthesis Example 8]
化合物(1-25-2)的合成
第1步驟 Step 1
將化合物(T-29)(30.0g)、膦醯基乙酸三乙酯(33.0g)及甲苯(500ml)放入至反應器中,冷卻至0℃。向其中緩慢地滴加乙醇鈉(20%乙醇溶液)(50.1g),恢復至室溫並且攪拌6小時。 將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=4:1)將殘渣純化,而獲得化合物(T-30)(32.8g;85%)。 The compound (T-29) (30.0 g), triethyl phosphinyl acetate (33.0 g) and toluene (500 ml) were put into the reactor and cooled to 0°C. Sodium ethoxide (20% ethanol solution) (50.1 g) was slowly added dropwise thereto, returned to room temperature and stirred for 6 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1) to obtain compound (T-30) (32.8 g; 85%).
第2步驟 Step 2
將化合物(T-30)(32.8g)、甲苯(300ml)、異丙醇(Iso Propyl Alcohol,IPA)(300ml)及Pd/C(0.55g)放入至反應器中,於 氫氣環境下攪拌12小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=4:1)將殘渣純化。 進而藉由自庚烷的再結晶來進行純化,而獲得化合物(T-31)(16.8g;51%)。 Put compound (T-30) (32.8g), toluene (300ml), isopropanol (Iso Propyl Alcohol, IPA) (300ml) and Pd/C (0.55g) into the reactor, Stir for 12 hours under hydrogen atmosphere. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1). Further purification was carried out by recrystallization from heptane to obtain compound (T-31) (16.8 g; 51%).
第3步驟 Step 3
使用化合物(T-31)(16.8g)作為原料,藉由與合成例4的第1步驟相同的方法而獲得化合物(T-32)(14.1g;71%)。 Using the compound (T-31) (16.8 g) as a raw material, the compound (T-32) (14.1 g; 71%) was obtained by the same method as in the first step of Synthesis Example 4.
第4步驟 Step 4
使用化合物(T-32)(14.1g)作為原料,藉由與合成例4的第2步驟相同的方法而獲得化合物(T-33)(6.0g;52%)。 Using compound (T-32) (14.1 g) as a raw material, the compound (T-33) (6.0 g; 52%) was obtained by the same method as in the second step of Synthesis Example 4.
第5步驟 Step 5
使用化合物(T-33)(6.0g)作為原料,藉由與合成例4的第3步驟相同的方法而獲得化合物(1-25-2)(2.3g;32%)。 Using compound (T-33) (6.0 g) as a raw material, compound (1-25-2) (2.3 g; 32%) was obtained by the same method as in the third step of Synthesis Example 4.
所得的化合物(1-25-2)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-25-2) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):7.14-7.10(m,4H)、6.12(s,1H)、5.59(s,1H)、4.43-4.40(m,1H)、4.28-4.25(m,1H)、3.75-3.64(m,2H)、2.55(t,J=7.6Hz,2H)、2.47-2.42(m,1H)、2.14(s,1H)、1.96-1.91(m,7H)、1.74-1.69(m,1H)、1.62-1.22(m,11H)、0.88(t,J=6.8Hz,3H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 7.14-7.10 (m, 4H), 6.12 (s, 1H), 5.59 (s, 1H), 4.43-4.40 (m, 1H), 4.28-4.25 (m,1H), 3.75-3.64(m,2H), 2.55(t,J=7.6Hz,2H), 2.47-2.42(m,1H), 2.14(s,1H), 1.96-1.91(m,7H) ), 1.74-1.69(m,1H), 1.62-1.22(m,11H), 0.88(t,J=6.8Hz,3H).
化合物(1-25-2)的物性為如下所述。 The physical properties of compound (1-25-2) are as follows.
轉變溫度:C<-50.0 I. Transition temperature: C<-50.0 I.
[合成例9] [Synthesis Example 9]
化合物(1-6-1)的合成
第1步驟 Step 1
使用化合物(1-25-1)(2.0g)作為原料,藉由與合成例5的第3步驟相同的方法而獲得化合物(T-34)(1.9g;68%)。 Using compound (1-25-1) (2.0 g) as a raw material, compound (T-34) (1.9 g; 68%) was obtained by the same method as in the third step of Synthesis Example 5.
第2步驟 Step 2
使用化合物(T-34)(1.9g)作為原料,藉由與合成例5的第4步驟相同的方法而獲得化合物(1-6-1)(1.2g;75%)。 Using compound (T-34) (1.9 g) as a raw material, the compound (1-6-1) (1.2 g; 75%) was obtained by the same method as in the fourth step of Synthesis Example 5.
所得的化合物(1-6-1)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-6-1) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):7.13-7.10(m,4H)、6.27(s,1H)、6.11(s,1H)、5.86(s,1H)、5.58(s,1H)、4.40-4.32(m,4H)、4.25-4.20(m,2H)、2.56(t,J=7.6Hz,2H)、2.45(tt,J=12.1Hz,J=2.9Hz,1H)、2.35-2.32(m,1H)、2.04-1.91(m,7H)、1.62-1.26(m,12H)、0.88(t,J=6.8Hz,3H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 7.13-7.10 (m, 4H), 6.27 (s, 1H), 6.11 (s, 1H), 5.86 (s, 1H), 5.58 (s, 1H) ), 4.40-4.32(m,4H), 4.25-4.20(m,2H), 2.56(t,J=7.6Hz,2H), 2.45(tt,J=12.1Hz,J=2.9Hz,1H), 2.35 -2.32(m,1H), 2.04-1.91(m,7H), 1.62-1.26(m,12H), 0.88(t,J=6.8Hz,3H).
化合物(1-6-1)的物性為如下所述。 The physical properties of compound (1-6-1) are as follows.
轉變溫度:C 35.8 I. Transition temperature: C 35.8 I.
[合成例10] [Synthesis Example 10]
化合物(1-23-3)的合成
第1步驟 Step 1
將2-(1,3-二噁烷-2-基)乙基三苯基溴化鏻(103.7g)及THF(500ml)放入至反應器中,冷卻至-30℃,加入第三丁醇鉀(25.4g),並攪拌1小時。向其中緩慢地滴加化合物(T-35)(50.0g)的THF(300ml)溶液,恢復至室溫並且攪拌6小時。將不溶物 過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=1:1)將殘渣純化,而獲得化合物(T-36)(63.0g;92%)。 Put 2-(1,3-dioxan-2-yl)ethyltriphenylphosphonium bromide (103.7g) and THF (500ml) into the reactor, cool to -30°C, and add tertiary butyl Potassium alkoxide (25.4g) and stirred for 1 hour. A THF (300 ml) solution of compound (T-35) (50.0 g) was slowly added dropwise thereto, returned to room temperature and stirred for 6 hours. Insoluble matter After filtration and separation, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:1) to obtain compound (T-36) (63.0 g; 92%).
第2步驟 Step 2
將化合物(T-36)(63.0g)、甲苯(500ml)、IPA(500ml)及Pd/C(0.55g)放入至反應器中,並於氫氣環境下攪拌16小時。 將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=1:1)將殘渣純化,而獲得化合物(T-37)(60.1g;95%)。 The compound (T-36) (63.0 g), toluene (500 ml), IPA (500 ml) and Pd/C (0.55 g) were put into the reactor and stirred for 16 hours under a hydrogen atmosphere. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:1) to obtain compound (T-37) (60.1 g; 95%).
第3步驟 Step 3
將化合物(T-37)(60.1g)、甲酸(75.8g)、及甲苯(1000ml)放入至反應器中,並於100℃下攪拌6小時。將不溶物過濾分離後,利用碳酸氫鈉水溶液進行中和,並利用甲苯對水層進行萃取。 利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法並利用甲苯將殘渣純化,而獲得化合物(T-38)(45.0g;89%)。 The compound (T-37) (60.1 g), formic acid (75.8 g), and toluene (1000 ml) were put in the reactor and stirred at 100°C for 6 hours. After the insoluble matter was separated by filtration, it was neutralized with an aqueous sodium hydrogen carbonate solution, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-38) (45.0 g; 89%).
第4步驟 Step 4
將化合物(T-38)(45.0g)、過氧單硫酸鉀(OXONE)(108.3 g)及二甲基甲醯胺(Dimethyl Formamide,DMF)(1000ml)放入至反應器中,並於室溫下攪拌8小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用乙酸乙酯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,而獲得化合物(T-39)(28.5g;60%)。 Compound (T-38) (45.0g), potassium peroxymonosulfate (OXONE) (108.3 g) Put Dimethyl Formamide (DMF) (1000ml) into the reactor and stir at room temperature for 8 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain compound (T-39) (28.5 g; 60%).
第5步驟 Step 5
將化合物(T-39)(28.5g)、硫酸(0.5ml)及甲醇(500ml)放入至反應器中,並於60℃下攪拌5小時。將不溶物過濾分離後,進行濃縮,利用矽膠層析法並利用甲苯對殘渣進行純化,而獲得化合物(T-40)(22.3g;75%)。 The compound (T-39) (28.5 g), sulfuric acid (0.5 ml), and methanol (500 ml) were put into the reactor and stirred at 60°C for 5 hours. After filtering the insoluble matter, it was concentrated, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-40) (22.3 g; 75%).
第6步驟 Step 6
使用化合物(T-40)(22.3g)作為原料,藉由與合成例4的第1步驟相同的方法而獲得化合物(T-41)(18.3g;70%)。 Using the compound (T-40) (22.3 g) as a raw material, the compound (T-41) (18.3 g; 70%) was obtained by the same method as in the first step of Synthesis Example 4.
第7步驟 Step 7
使用化合物(T-41)(18.3g)作為原料,藉由與合成例4的第2步驟相同的方法而獲得化合物(T-42)(5.9g;38%)。 Using the compound (T-41) (18.3 g) as a raw material, the compound (T-42) (5.9 g; 38%) was obtained by the same method as in the second step of Synthesis Example 4.
第8步驟 Step 8
使用化合物(T-42)(5.9g)作為原料,藉由與合成例4的第3步驟相同的方法而獲得化合物(1-23-3)(2.4g;34%)。 Using the compound (T-42) (5.9 g) as a raw material, the compound (1-23-3) (2.4 g; 34%) was obtained by the same method as in the third step of Synthesis Example 4.
所得的化合物(1-23-3)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-23-3) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):6.11(s,1H)、5.81(s,1H)、4.31-4.28(m,1H)、4.17-4.14(m,1H)、3.63-3.58(m,1H)、 3.54-3.49(m,1H)、1.98-1.95(m,4H)、1.84-1.69(m,9H)、1.41-1.18(m,10H)、1.15-1.06(m,4H)、1.02-0.80(m,13H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 6.11 (s, 1H), 5.81 (s, 1H), 4.31-4.28 (m, 1H), 4.17-4.14 (m, 1H), 3.63-3.58 (m,1H), 3.54-3.49(m,1H), 1.98-1.95(m,4H), 1.84-1.69(m,9H), 1.41-1.18(m,10H), 1.15-1.06(m,4H) , 1.02-0.80 (m, 13H).
化合物(1-23-3)的物性為如下所述。 The physical properties of compound (1-23-3) are as follows.
轉變溫度:C 33.6 SA 101 I. Transition temperature: C 33.6 S A 101 I.
[合成例11] [Synthesis Example 11]
化合物(1-4-4)的合成
第1步驟 Step 1
使用化合物(1-23-3)(2.0g)作為原料,藉由與合成例5的第3步驟相同的方法而獲得化合物(T-43)(2.1g;74%)。 Using the compound (1-23-3) (2.0 g) as a raw material, the compound (T-43) (2.1 g; 74%) was obtained by the same method as in the third step of Synthesis Example 5.
第2步驟 Step 2
使用化合物(T-43)(2.1g)作為原料,藉由與合成例5的第4步驟相同的方法而獲得化合物(1-4-4)(1.3g;72%)。 Using compound (T-43) (2.1 g) as a raw material, the compound (1-4-4) (1.3 g; 72%) was obtained by the same method as in the fourth step of Synthesis Example 5.
所得的化合物(1-4-4)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-4-4) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):6.25(s,1H)、6.10(s,1H)、5.85(d,J=1.1Hz,1H)、5.57(s,1H)、4.33(d,J=6.5Hz,2H)、 4.24-4.11(m,4H)、2.28(t,J=6.6Hz,1H)、2.09-2.03(m,1H)、1.94(s,3H)、1.75-1.67(m,8H)、1.44-1.39(m,2H)、1.32-1.18(m,8H)、1.15-1.06(m,4H)、1.02-0.79(m,13H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 6.25 (s, 1H), 6.10 (s, 1H), 5.85 (d, J = 1.1 Hz, 1H), 5.57 (s, 1H), 4.33 ( d,J=6.5Hz,2H), 4.24-4.11(m,4H), 2.28(t,J=6.6Hz,1H), 2.09-2.03(m,1H), 1.94(s,3H), 1.75-1.67 (m,8H), 1.44-1.39(m,2H), 1.32-1.18(m,8H), 1.15-1.06(m,4H), 1.02-0.79(m,13H).
化合物(1-4-4)的物性為如下所述。 The physical properties of compound (1-4-4) are as follows.
轉變溫度:C 71.4 I. Transition temperature: C 71.4 I.
[合成例12] [Synthesis Example 12]
化合物(1-42-1)的合成
第1步驟 Step 1
將化合物(T-20)(2.0g)、化合物(T-22)(2.63g)、DMAP(0.78g)、及二氯甲烷(100ml)放入至反應器中,冷卻至0℃。 向其中緩慢地滴加DCC(2.92g)的二氯甲烷(60ml)溶液,恢復至室溫並且攪拌12小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用二氯甲烷對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於 減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=9:1)將殘渣純化,而獲得化合物(T-44)(2.83g;68%)。 The compound (T-20) (2.0 g), the compound (T-22) (2.63 g), DMAP (0.78 g), and dichloromethane (100 ml) were put into the reactor and cooled to 0°C. A dichloromethane (60 ml) solution of DCC (2.92 g) was slowly added dropwise thereto, returned to room temperature and stirred for 12 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. Put the solution in It was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1) to obtain compound (T-44) (2.83 g; 68%).
第2步驟 Step 2
將化合物(T-44)(2.83g)、吡啶對甲苯磺酸鹽(PPTS)(1.09g)、THF(50ml)及甲醇(50ml)放入至反應器中,於50℃下攪拌8小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用乙酸乙酯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=1:1)將殘渣純化,而獲得化合物(1-42-1)(1.47g;70%)。 The compound (T-44) (2.83 g), pyridine p-toluenesulfonate (PPTS) (1.09 g), THF (50 ml) and methanol (50 ml) were put into the reactor, and stirred at 50°C for 8 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=1:1) to obtain compound (1-42-1) (1.47 g; 70%).
所得的化合物(1-42-1)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-42-1) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):6.24(s,2H)、5.82(s,2H)、4.35-4.31(m,6H)、4.22-4.19(m,2H)、2.36(s,2H)、1.97-1.91(s,1H)、1.82-1.63(m,8H)、1.43-1.18(m,7H)、1.15-0.79(m,16H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 6.24 (s, 2H), 5.82 (s, 2H), 4.35-4.31 (m, 6H), 4.22-4.19 (m, 2H), 2.36 (s ,2H), 1.97-1.91(s,1H), 1.82-1.63(m,8H), 1.43-1.18(m,7H), 1.15-0.79(m,16H).
化合物(1-42-1)的物性為如下所述。 The physical properties of compound (1-42-1) are as follows.
轉變溫度:C 102 I. Transition temperature: C 102 I.
[合成例13] [Synthesis Example 13]
化合物(1-43-1)的合成
第1步驟 Step 1
使用化合物(T-27)(2.0g)作為原料,藉由與合成例12的第1步驟相同的方法而獲得化合物(T-45)(2.7g;64%)。 Using the compound (T-27) (2.0 g) as a raw material, the compound (T-45) (2.7 g; 64%) was obtained by the same method as the first step of Synthesis Example 12.
第2步驟 Step 2
使用化合物(T-45)(2.7g)作為原料,藉由與合成例12的第2步驟相同的方法而獲得化合物(1-43-1)(1.3g;65%)。 Using the compound (T-45) (2.7 g) as a raw material, the compound (1-43-1) (1.3 g; 65%) was obtained by the same method as in the second step of Synthesis Example 12.
所得的化合物(1-43-1)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-43-1) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):7.20-7.16(m,4H)、6.26(s,2H)、5.83(d,J=0.8Hz,2H)、4.46(d,J=6.6Hz,4H)、4.28(d,J=6.3Hz,4H)、3.44-3.39(m,1H)、2.44(tt,J=12.2Hz,J=3.1Hz,1H)、2.16-2.13(m,2H)、1.87-1.85(m,4H)、1.46-1.19(m,11H)、1.07-0.99(m,2H)、0.89(t,J=6.8Hz,3H). 1 H-NMR: Chemical shift δ(ppm; CDCl 3 ): 7.20-7.16(m,4H), 6.26(s,2H), 5.83(d,J=0.8Hz,2H), 4.46(d,J=6.6 Hz,4H), 4.28(d,J=6.3Hz,4H), 3.44-3.39(m,1H), 2.44(tt,J=12.2Hz,J=3.1Hz,1H), 2.16-2.13(m,2H ), 1.87-1.85(m,4H), 1.46-1.19(m,11H), 1.07-0.99(m,2H), 0.89(t,J=6.8Hz,3H).
化合物(1-43-1)的物性為如下所述。 The physical properties of compound (1-43-1) are as follows.
轉變溫度:C 65.8 I. Transition temperature: C 65.8 I.
[合成例14] [Synthesis Example 14]
化合物(1-44-1)的合成
第1步驟 Step 1
使用化合物(T-33)(2.0g)作為原料,藉由與合成例12的第1步驟相同的方法而獲得化合物(T-46)(2.5g;59%)。 Using the compound (T-33) (2.0 g) as a raw material, the compound (T-46) (2.5 g; 59%) was obtained by the same method as in the first step of Synthesis Example 12.
第2步驟 Step 2
使用化合物(T-46)(2.7g)作為原料,藉由與合成例12的第2步驟相同的方法而獲得化合物(1-44-1)(1.1g;60%)。 Using the compound (T-46) (2.7 g) as a raw material, the compound (1-44-1) (1.1 g; 60%) was obtained by the same method as in the second step of Synthesis Example 12.
所得的化合物(1-44-1)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-44-1) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):7.14-7.10(m,4H)、6.27(s,2H)、5.87(d,J=1.1Hz,2H)、4.39-4.33(m,6H)、4.27-4.20(m,2H)、2.57-2.54(m,2H)、2.45(tt,J=12.2Hz,J=3.1Hz,1H)、2.38-2.35(m,2H)、2.05-1.91(m,5H)、1.63-1.26(m,11H)、0.88(t,J=6.8Hz,3H). 1 H-NMR: Chemical shift δ(ppm; CDCl 3 ): 7.14-7.10(m,4H), 6.27(s,2H), 5.87(d,J=1.1Hz,2H), 4.39-4.33(m,6H) ), 4.27-4.20(m,2H), 2.57-2.54(m,2H), 2.45(tt,J=12.2Hz,J=3.1Hz,1H), 2.38-2.35(m,2H), 2.05-1.91( m,5H), 1.63-1.26(m,11H), 0.88(t,J=6.8Hz,3H).
化合物(1-44-1)的物性為如下所述。 The physical properties of compound (1-44-1) are as follows.
轉變溫度:C 65.6 I. Transition temperature: C 65.6 I.
[合成例15] [Synthesis Example 15]
化合物(1-42-2)的合成
第1步驟 Step 1
使用化合物(T-42)(2.0g)作為原料,藉由與合成例12的第1步驟相同的方法而獲得化合物(T-47)(2.7g;67%)。 Using the compound (T-42) (2.0 g) as a raw material, the compound (T-47) (2.7 g; 67%) was obtained by the same method as in the first step of Synthesis Example 12.
第2步驟 Step 2
使用化合物(T-47)(2.7g)作為原料,藉由與合成例12的第2步驟相同的方法而獲得化合物(1-42-2)(1.3g;64%)。 Using compound (T-47) (2.7 g) as a raw material, the compound (1-42-2) (1.3 g; 64%) was obtained by the same method as in the second step of Synthesis Example 12.
所得的化合物(1-42-2)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-42-2) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):6.25(s,2H)、5.85(d,J=1.1Hz,2H)、4.33(d,J=6.3Hz,4H)、4.25-4.22(m,2H)、4.18-4.14(m,2H)、2.30-2.28(m,2H)、2.11-2.06(m,1H)、1.75-1.67(m,8H)、1.44-1.39(m,2H)、1.32-0.79(m,25H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 6.25 (s, 2H), 5.85 (d, J = 1.1 Hz, 2H), 4.33 (d, J = 6.3 Hz, 4H), 4.25-4.22 ( m,2H), 4.18-4.14(m,2H), 2.30-2.28(m,2H), 2.11-2.06(m,1H), 1.75-1.67(m,8H), 1.44-1.39(m,2H), 1.32-0.79 (m, 25H).
化合物(1-42-2)的物性為如下所述。 The physical properties of compound (1-42-2) are as follows.
轉變溫度:C 85.7 SA 125 I. Transition temperature: C 85.7 S A 125 I.
[合成例16] [Synthesis Example 16]
化合物(1-24-2)的合成 Synthesis of compound (1-24-2)
第1步驟 Step 1
將化合物(T-24)(50.0g)、及THF(1000ml)放入至反應器中,冷卻至-70℃。緩慢地滴加氯化異丙基鎂-氯化鋰(1.3M;THF溶液;130.0ml),攪拌1小時。向其中滴加DMF(13.0ml),恢復至室溫並且攪拌4小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=4:1)將殘渣純化,而獲得化合物(T-48)(34.5g;95%)。 The compound (T-24) (50.0 g) and THF (1000 ml) were put into the reactor and cooled to -70°C. Isopropylmagnesium chloride-lithium chloride (1.3M; THF solution; 130.0ml) was slowly added dropwise and stirred for 1 hour. DMF (13.0 ml) was added dropwise thereto, returned to room temperature and stirred for 4 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1) to obtain compound (T-48) (34.5 g; 95%).
第2步驟 Step 2
將甲氧基甲基-三苯基氯化鏻(54.9g)、及THF(1000ml)放入至反應器中,冷卻至-30℃。加入第三丁醇鉀(18.0g),攪拌1小時。向其中滴加化合物(T-48)(34.5g)的THF(50ml)溶液,恢復至室溫並且攪拌5小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=1:4)將殘渣純化,而獲得化合物(T-49)(31.7g;83%)。 Put methoxymethyl-triphenylphosphonium chloride (54.9g) and THF (1000ml) into the reactor and cool to -30°C. Potassium tert-butoxide (18.0 g) was added and stirred for 1 hour. A THF (50 ml) solution of compound (T-48) (34.5 g) was added dropwise thereto, returned to room temperature and stirred for 5 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:4) to obtain compound (T-49) (31.7 g; 83%).
第3步驟 Step 3
將化合物(T-49)(31.7g)、甲酸(50.9g)、及甲苯(1000ml)放入至反應器中,並於100℃下攪拌6小時。將不溶物過濾分離後,將反應混合物注入至水中,利用碳酸氫鈉水進行中和,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=4:1)將殘渣純化,而獲得化合物(T-50)(26.5g;88%)。 The compound (T-49) (31.7 g), formic acid (50.9 g), and toluene (1000 ml) were put in the reactor and stirred at 100°C for 6 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, neutralized with sodium bicarbonate water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1) to obtain compound (T-50) (26.5 g; 88%).
第4步驟 Step 4
將化合物(T-50)(26.5g)、膦醯基乙酸三乙酯(26.2g)及甲苯(500ml)放入至反應器中,冷卻至0℃。向其中緩慢地滴加乙醇鈉(20%乙醇溶液)(39.7g),恢復至室溫並且攪拌6小時。 將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對 水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=9:1)將殘渣純化,而獲得化合物(T-51)(30.6g;92%)。 The compound (T-50) (26.5 g), triethyl phosphinyl acetate (26.2 g) and toluene (500 ml) were put into the reactor and cooled to 0°C. Sodium ethoxide (20% ethanol solution) (39.7 g) was slowly added dropwise thereto, returned to room temperature and stirred for 6 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and toluene was used to The aqueous layer is extracted. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=9:1) to obtain compound (T-51) (30.6 g; 92%).
第5步驟 Step 5
將化合物(T-51)(30.6g)、Pd/C(0.55g)、甲苯(250ml)、及IPA(250ml)放入至反應器中,於氫氣環境下攪拌12小時。 將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=9:1)將殘渣純化,而獲得化合物(T-52)(29.2g;95%)。 The compound (T-51) (30.6 g), Pd/C (0.55 g), toluene (250 ml), and IPA (250 ml) were put into the reactor and stirred for 12 hours under a hydrogen atmosphere. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=9:1) to obtain compound (T-52) (29.2 g; 95%).
第6步驟 Step 6
將化合物(T-52)(29.2g)、及THF(250ml)放入至反應器中,冷卻至-70℃。緩慢地滴加二異丙胺鋰(LDA)(1.1M;THF溶液;92.5ml)。攪拌1小時,向其中滴加苄基氯甲醚(16.0g),恢復至室溫並且攪拌12小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=9:1)將殘渣純化,而獲得化合物(T-53)(31.5g;80%)。 The compound (T-52) (29.2 g) and THF (250 ml) were put into the reactor and cooled to -70°C. Slowly add lithium diisopropylamine (LDA) (1.1M; THF solution; 92.5 ml) dropwise. After stirring for 1 hour, benzyl chloromethyl ether (16.0 g) was added dropwise thereto, returning to room temperature and stirring for 12 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=9:1) to obtain compound (T-53) (31.5 g; 80%).
第7步驟 Step 7
將化合物(T-53)(31.5g)、氫氧化鈀(0.28g)、甲苯(250ml)、及IPA(250ml)放入至反應器中,於氫氣環境下攪拌12小時。 將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=4:1)將殘渣純化,而獲得化合物(T-54)(23.3g;92%)。 The compound (T-53) (31.5 g), palladium hydroxide (0.28 g), toluene (250 ml), and IPA (250 ml) were put into the reactor and stirred for 12 hours under a hydrogen atmosphere. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=4:1) to obtain compound (T-54) (23.3 g; 92%).
第8步驟 Step 8
將化合物(T-54)(23.3g)、3,4-二氫-2H-吡喃(5.8g)、PPTS(對甲苯磺酸吡啶鎓)(1.5g)、及二氯甲烷(500ml)放入至反應器,於室溫下攪拌8小時。將反應混合物注入至水中,並利用二氯甲烷對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=9:1)將殘渣純化,而獲得化合物(T-55)(25.4g;89%)。 Put compound (T-54) (23.3g), 3,4-dihydro-2H-pyran (5.8g), PPTS (pyridinium p-toluenesulfonate) (1.5g), and dichloromethane (500ml) Put into the reactor and stir for 8 hours at room temperature. The reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1) to obtain compound (T-55) (25.4 g; 89%).
第9步驟 Step 9
將氫化鋰鋁(Lithium Aluminium Hydride,LAH)(1.2g)、及THF(300ml)放入至反應器中,冷卻至0℃。向其中緩慢地滴加化合物(T-55)(25.4g)的THF(100ml)溶液,恢復至室溫並且攪拌3小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用乙酸乙酯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃 縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=4:1)將殘渣純化,而獲得化合物(T-56)(19.2g;83%)。 Lithium Aluminium Hydride (LAH) (1.2 g) and THF (300 ml) were put into the reactor and cooled to 0°C. A THF (100 ml) solution of compound (T-55) (25.4 g) was slowly added dropwise thereto, returned to room temperature and stirred for 3 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. Concentrate the solution under reduced pressure After shrinking, the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=4:1) to obtain compound (T-56) (19.2 g; 83%).
第10步驟 Step 10
將化合物(T-56)(19.2g)、三乙基胺(7.6ml)及THF(200ml)放入至反應器中,冷卻至0℃。向其中緩慢地加入甲基丙烯醯氯(5.3ml),恢復至室溫並且攪拌5小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用乙酸乙酯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=19:1)將殘渣純化,而獲得化合物(T-57)(17.9g;80%)。 The compound (T-56) (19.2 g), triethylamine (7.6 ml) and THF (200 ml) were put into the reactor and cooled to 0°C. Methacrylic chloride (5.3 ml) was slowly added thereto, returned to room temperature and stirred for 5 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=19:1) to obtain compound (T-57) (17.9 g; 80%).
第11步驟 Step 11
將化合物(T-57)(17.9g)、吡啶對甲苯磺酸鹽(PPTS)(4.6g)、THF(200ml)及甲醇(200ml)放入至反應器中,於50℃下攪拌6小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用乙酸乙酯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:乙酸乙酯=9:1)將殘渣純化,而獲得化合物(1-24-2)(12.4g;84%)。 The compound (T-57) (17.9 g), pyridine p-toluenesulfonate (PPTS) (4.6 g), THF (200 ml) and methanol (200 ml) were put into the reactor, and stirred at 50°C for 6 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1) to obtain compound (1-24-2) (12.4 g; 84%).
所得的化合物(1-24-2)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-24-2) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):7.13-7.09(m,4H)、6.10(s,1H)、5.57(s,1H)、4.33-4.30(m,1H)、4.23-4.20(m,1H)、3.65-3.62 (m,1H)、3.58-3.54(m,1H)、2.66(t,J=8.0Hz,2H)、2.45-2.39(m,1H)、1.94-1.81(m,8H)、1.74-1.60(m,2H)、1.46-1.19(m,12H)、1.07-0.99(m,2H)、0.89(t,J=6.9Hz,3H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 7.13-7.09 (m, 4H), 6.10 (s, 1H), 5.57 (s, 1H), 4.33-4.30 (m, 1H), 4.23-4.20 (m, 1H), 3.65-3.62 (m, 1H), 3.58-3.54 (m, 1H), 2.66 (t, J=8.0Hz, 2H), 2.45-2.39 (m, 1H), 1.94-1.81 (m ,8H), 1.74-1.60(m,2H), 1.46-1.19(m,12H), 1.07-0.99(m,2H), 0.89(t,J=6.9Hz,3H).
化合物(1-24-2)的物性為如下所述。 The physical properties of compound (1-24-2) are as follows.
轉變溫度:C -24.7 I. Transition temperature: C -24.7 I.
[合成例17] [Synthesis Example 17]
化合物(1-5-2)的合成
第1步驟 Step 1
使用化合物(1-24-2)(2.0g)作為原料,藉由與合成例5的第3步驟相同的方法而獲得化合物(T-58)(2.1g;74%)。 Using compound (1-24-2) (2.0 g) as a raw material, compound (T-58) (2.1 g; 74%) was obtained by the same method as in the third step of Synthesis Example 5.
第2步驟 Step 2
使用化合物(T-58)(2.1g)作為原料,藉由與合成例5的第4步驟相同的方法而獲得化合物(1-5-2)(1.4g;78%)。 Using compound (T-58) (2.1 g) as a raw material, the compound (1-5-2) (1.4 g; 78%) was obtained by the same method as in the fourth step of Synthesis Example 5.
所得的化合物(1-5-2)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-5-2) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):7.14-7.08(m,4H)、6.24 (s,1H)、6.10(s,1H)、5.85(s,1H)、5.57(s,1H)、4.32(d,J=6.1Hz,2H)、4.27-4.18(m,4H)、2.67(t,J=7.4Hz,2H)、2.45-2.40(m,2H)、2.18-2.12(m,1H)、1.93(s,3H)、1.88-1.84(m,4H)、1.77-1.72(m,2H)、1.46-1.38(m,2H)、1.34-1.19(m,9H)、1.07-0.99(m,2H)、0.89(t,J=6.8Hz,3H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 7.14-7.08 (m, 4H), 6.24 (s, 1H), 6.10 (s, 1H), 5.85 (s, 1H), 5.57 (s, 1H) ), 4.32(d,J=6.1Hz,2H), 4.27-4.18(m,4H), 2.67(t,J=7.4Hz,2H), 2.45-2.40(m,2H), 2.18-2.12(m, 1H), 1.93 (s, 3H), 1.88-1.84 (m, 4H), 1.77-1.72 (m, 2H), 1.46-1.38 (m, 2H), 1.34-1.19 (m, 9H), 1.07-0.99 ( m,2H), 0.89(t,J=6.8Hz,3H).
化合物(1-5-2)的物性為如下所述。 The physical properties of compound (1-5-2) are as follows.
轉變溫度:C -30.2 SA -26.3 I. Transition temperature: C -30.2 S A -26.3 I.
[合成例18] [Synthesis Example 18]
化合物(1-25-2)的合成
第1步驟 Step 1
將甲氧基甲基-三苯基氯化鏻(84.2g)、及THF(1000ml)放入至反應器中,冷卻至-30℃。加入第三丁醇鉀(27.6g),攪拌1小時。向其中滴加化合物(T-29)(50.0g)的THF(500ml)溶 液,恢復至室溫並且攪拌5小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=1:4)將殘渣純化,而獲得化合物(T-59)(46.3g;83%)。 Put methoxymethyl-triphenylphosphonium chloride (84.2g) and THF (1000ml) into the reactor and cool to -30°C. Potassium tert-butoxide (27.6g) was added and stirred for 1 hour. Compound (T-29) (50.0g) in THF (500ml) was added dropwise Liquid, return to room temperature and stir for 5 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:4) to obtain compound (T-59) (46.3 g; 83%).
第2步驟 Step 2
將化合物(T-59)(46.3g)、對甲苯磺酸(p-toluenesulfonic acid,PTSA)(3.2g)、及甲苯(1000ml)放入至反應器中,於100℃下攪拌12小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=1:1)將殘渣純化,而獲得化合物(T-60)(49.2g;95%)。 The compound (T-59) (46.3 g), p-toluenesulfonic acid (PTSA) (3.2 g), and toluene (1000 ml) were put into the reactor and stirred at 100°C for 12 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:1) to obtain compound (T-60) (49.2 g; 95%).
第3步驟 Step 3
將化合物(T-60)(49.2g)、甲酸(74.4g)、及甲苯(1000ml)放入至反應器中,並於室溫下攪拌8小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用碳酸氫鈉水進行中和。利用甲苯對水層進行萃取,利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=1:1)將殘渣純化,而獲得化合物(T-61)(35.0g;84%)。 The compound (T-60) (49.2 g), formic acid (74.4 g), and toluene (1000 ml) were put in the reactor and stirred at room temperature for 8 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water and neutralized with sodium bicarbonate water. The aqueous layer was extracted with toluene, the mixed organic layer was washed with water, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:1) to obtain compound (T-61) (35.0 g; 84%).
第4步驟 Step 4
將甲氧基甲基-三苯基氯化鏻(55.7g)、及THF(1000ml)放入至反應器中,冷卻至-30℃。加入第三丁醇鉀(18.2g),攪拌1小時。向其中滴加化合物(T-61)(35.0g)的THF(500ml)溶液,恢復至室溫並且攪拌5小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=1:4)將殘渣純化,而獲得化合物(T-62)(36.5g;94%)。 Put methoxymethyl-triphenylphosphonium chloride (55.7g) and THF (1000ml) into the reactor and cool to -30°C. Potassium tert-butoxide (18.2 g) was added and stirred for 1 hour. A solution of compound (T-61) (35.0 g) in THF (500 ml) was added dropwise thereto, returned to room temperature and stirred for 5 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:4) to obtain compound (T-62) (36.5 g; 94%).
第5步驟 Step 5
將化合物(T-62)(36.5g)、甲酸(58.6g)、及甲苯(1000ml)放入至反應器中,並於100℃下攪拌4小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用碳酸氫鈉水進行中和。利用甲苯對水層進行萃取,利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=1:1)將殘渣純化,而獲得化合物(T-63)(33.0g;95%)。 The compound (T-62) (36.5 g), formic acid (58.6 g), and toluene (1000 ml) were put in the reactor, and stirred at 100°C for 4 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water and neutralized with sodium bicarbonate water. The aqueous layer was extracted with toluene, the mixed organic layer was washed with water, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:1) to obtain compound (T-63) (33.0 g; 95%).
第6步驟 Step 6
使用化合物(T-63)(33.0g)作為原料,藉由與合成例16的第4步驟相同的方法而獲得化合物(T-64)(38.2g;92%)。 Using the compound (T-63) (33.0 g) as a raw material, the compound (T-64) (38.2 g; 92%) was obtained by the same method as in the fourth step of Synthesis Example 16.
第7步驟 Step 7
使用化合物(T-64)(38.2g)作為原料,藉由與合成例16的第5步驟相同的方法而獲得化合物(T-65)(18.7g;48%)。 Using compound (T-64) (38.2 g) as a raw material, the compound (T-65) (18.7 g; 48%) was obtained by the same method as in the fifth step of Synthesis Example 16.
第8步驟 Step 8
使用化合物(T-65)(18.7g)作為原料,藉由與合成例16的第6步驟相同的方法而獲得化合物(T-66)(21.5g;85%)。 Using compound (T-65) (18.7 g) as a raw material, the compound (T-66) (21.5 g; 85%) was obtained by the same method as in the sixth step of Synthesis Example 16.
第9步驟 Step 9
使用化合物(T-66)(21.5g)作為原料,藉由與合成例16的第7步驟相同的方法而獲得化合物(T-67)(15.6g;90%)。 Using the compound (T-66) (21.5 g) as a raw material, the compound (T-67) (15.6 g; 90%) was obtained by the same method as in the seventh step of Synthesis Example 16.
第10步驟 Step 10
使用化合物(T-67)(15.6g)作為原料,藉由與合成例16的第8步驟相同的方法而獲得化合物(T-68)(16.8g;88%)。 Using compound (T-67) (15.6 g) as a raw material, the compound (T-68) (16.8 g; 88%) was obtained by the same method as in the eighth step of Synthesis Example 16.
第11步驟 Step 11
使用化合物(T-68)(16.8g)作為原料,藉由與合成例16的第9步驟相同的方法而獲得化合物(T-69)(13.0g;85%)。 Using compound (T-68) (16.8 g) as a raw material, the compound (T-69) (13.0 g; 85%) was obtained by the same method as in the ninth step of Synthesis Example 16.
第12步驟 Step 12
使用化合物(T-69)(13.0g)作為原料,藉由與合成例16的第10步驟相同的方法而獲得化合物(T-70)(11.6g;77%)。 Using the compound (T-69) (13.0 g) as a raw material, the compound (T-70) (11.6 g; 77%) was obtained by the same method as in the 10th step of Synthesis Example 16.
第13步驟 Step 13
使用化合物(T-70)(11.6g)作為原料,藉由與合成例16的第11步驟相同的方法而獲得化合物(1-25-2)(7.8g;82%)。 Using compound (T-70) (11.6 g) as a raw material, compound (1-25-2) (7.8 g; 82%) was obtained by the same method as in the 11th step of Synthesis Example 16.
所得的化合物(1-25-2)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-25-2) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):7.11-7.08(m,4H)、6.11(s,1H)、5.57(s,1H)、4.31-4.28(m,1H)、4.19-4.16(m,1H)、3.63-3.60(m,1H)、3.55-3.52(m,1H)、1.95(s,3H)、1.89-1.81(m,5H)、 1.62-1.56(m,2H)、1.47-1.28(m,12H)、1.09-1.01(m,2H)、0.88(t,J=6.7Hz,3H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 7.11-7.08 (m, 4H), 6.11 (s, 1H), 5.57 (s, 1H), 4.31-4.28 (m, 1H), 4.19-4.16 (m,1H), 3.63-3.60(m,1H), 3.55-3.52(m,1H), 1.95(s,3H), 1.89-1.81(m,5H), 1.62-1.56(m,2H), 1.47 -1.28(m,12H), 1.09-1.01(m,2H), 0.88(t,J=6.7Hz,3H).
化合物(1-25-2)的物性為如下所述。 The physical properties of compound (1-25-2) are as follows.
轉變溫度:C<-50 I. Transition temperature: C<-50 I.
[合成例19] [Synthesis Example 19]
化合物(1-6-2)的合成
第1步驟 Step 1
使用化合物(1-25-2)(3.0g)作為原料,藉由與合成例5的第3步驟相同的方法而獲得化合物(T-71)(3.2g;75%)。 Using compound (1-25-2) (3.0 g) as a raw material, compound (T-71) (3.2 g; 75%) was obtained by the same method as in the third step of Synthesis Example 5.
第2步驟 Step 2
使用化合物(T-71)(3.2g)作為原料,藉由與合成例5的第4步驟相同的方法而獲得化合物(1-6-2)(1.9g;70%)。 Using compound (T-71) (3.2 g) as a raw material, the compound (1-6-2) (1.9 g; 70%) was obtained by the same method as in the fourth step of Synthesis Example 5.
所得的化合物(1-6-2)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-6-2) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):7.12-7.08(m,4H)、6.26(s,1H)、6.11(s,1H)、5.86(s,1H)、5.58(s,1H)、4.34(d,J=6.5Hz,2H)、4.26-4.14(m,4H)、2.55(t,J=7.8Hz,2H)、2.45-2.40(m,1H)、2.34(s,1H)、2.13-2.08(m,1H)、1.95(s,3H)、1.90-1.84(m,4H)、1.63-1.56(m,2H)、1.48-1.39(m,4H)、1.35-1.27(m,7H)、1.09-1.01(m,2H)、0.88(t,J=6.8Hz,3H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 7.12-7.08 (m, 4H), 6.26 (s, 1H), 6.11 (s, 1H), 5.86 (s, 1H), 5.58 (s, 1H) ), 4.34(d,J=6.5Hz,2H), 4.26-4.14(m,4H), 2.55(t,J=7.8Hz,2H), 2.45-2.40(m,1H), 2.34(s,1H) , 2.13-2.08(m,1H), 1.95(s,3H), 1.90-1.84(m,4H), 1.63-1.56(m,2H), 1.48-1.39(m,4H), 1.35-1.27(m, 7H), 1.09-1.01 (m, 2H), 0.88 (t, J=6.8Hz, 3H).
化合物(1-6-2)的物性為如下所述。 The physical properties of compound (1-6-2) are as follows.
轉變溫度:C 35.9 I. Transition temperature: C 35.9 I.
[合成例20] [Synthesis Example 20]
化合物(1-28-1)的合成
第1步驟 Step 1
使用化合物(T-72)(50.0g)作為原料,藉由與合成例6的第1步驟相同的方法而獲得化合物(T-73)(31.8g;70%)。 Using the compound (T-72) (50.0 g) as a raw material, the compound (T-73) (31.8 g; 70%) was obtained by the same method as in the first step of Synthesis Example 6.
第2步驟 Step 2
使用化合物(T-73)(31.8g)作為原料,藉由與合成例6的第2步驟相同的方法而獲得化合物(T-74)(26.2g;72%)。 Using the compound (T-73) (31.8 g) as a raw material, the compound (T-74) (26.2 g; 72%) was obtained by the same method as in the second step of Synthesis Example 6.
第3步驟 Step 3
使用化合物(T-74)(26.2g)作為原料,藉由與合成例6的第3步驟相同的方法而獲得化合物(T-75)(10.1g;46%)。 Using the compound (T-74) (26.2 g) as a raw material, the compound (T-75) (10.1 g; 46%) was obtained by the same method as in the third step of Synthesis Example 6.
第4步驟 Step 4
使用化合物(T-75)(10.1g)作為原料,藉由與合成例6的 第4步驟相同的方法而獲得化合物(1-28-1)(3.8g;32%)。 Using compound (T-75) (10.1g) as a raw material, by combining with the synthesis example 6 In the same manner as in the fourth step, compound (1-28-1) (3.8 g; 32%) was obtained.
所得的化合物(1-28-1)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-28-1) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):7.18-7.16(m,4H)、6.09(s,1H)、5.57(s,1H)、4.47-4.38(m,2H)、3.91-3.83(m,2H)、3.20-3.14(m,1H)、2.45-2.40(m,1H)、1.97-1.72(m,12H)、1.42-0.82(m,22H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 7.18-7.16 (m, 4H), 6.09 (s, 1H), 5.57 (s, 1H), 4.47-4.38 (m, 2H), 3.91-3.83 (m, 2H), 3.20-3.14 (m, 1H), 2.45-2.40 (m, 1H), 1.97-1.72 (m, 12H), 1.42-0.82 (m, 22H).
化合物(1-28-1)的物性為如下所述。 The physical properties of compound (1-28-1) are as follows.
轉變溫度:C 46.3 I. Transition temperature: C 46.3 I.
[合成例21] [Synthesis Example 21]
化合物(1-9-1)的合成
第1步驟 Step 1
使用化合物(1-28-1)(3.0g)作為原料,藉由與合成例5的第3步驟相同的方法而獲得化合物(T-76)(3.1g;75%)。 Using the compound (1-28-1) (3.0 g) as a raw material, the compound (T-76) (3.1 g; 75%) was obtained by the same method as in the third step of Synthesis Example 5.
第2步驟 Step 2
使用化合物(T-76)(3.1g)作為原料,藉由與合成例5的第4步驟相同的方法而獲得化合物(1-9-1)(1.9g;71%)。 Using compound (T-76) (3.1 g) as a raw material, the compound (1-9-1) (1.9 g; 71%) was obtained by the same method as in the fourth step of Synthesis Example 5.
所得的化合物(1-9-1)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-9-1) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):7.17(s,4H)、6.21(s,1H)、6.07(s,1H)、5.80(s,1H)、5.56(s,1H)、4.46-4.39(m,4H)、4.27(d,J=6.6Hz,2H)、3.42-3.37(m,1H)、2.45-2.39(m,1H)、2.12(t,J=6.6Hz,1H)、1.91-1.72(m,11H)、1.46-0.95(m,16H)、0.89-0.82(m,5H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 7.17 (s, 4H), 6.21 (s, 1H), 6.07 (s, 1H), 5.80 (s, 1H), 5.56 (s, 1H), 4.46-4.39(m,4H), 4.27(d,J=6.6Hz,2H), 3.42-3.37(m,1H), 2.45-2.39(m,1H), 2.12(t,J=6.6Hz,1H) , 1.91-1.72(m,11H), 1.46-0.95(m,16H), 0.89-0.82(m,5H).
化合物(1-9-1)的物性為如下所述。 The physical properties of compound (1-9-1) are as follows.
轉變溫度:C 80.0 I. Transition temperature: C 80.0 I.
[合成例22] [Synthesis Example 22]
化合物(1-23-4)的合成
第1步驟 Step 1
將化合物(T-77)(50.0g)、膦醯基乙酸三乙酯(48.3g)及甲苯(500ml)放入至反應器中,冷卻至0℃。向其中緩慢地滴加乙醇鈉(20%乙醇溶液)(73.3g),恢復至室溫並且攪拌6小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對 水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=9:1)將殘渣純化,而獲得化合物(T-78)(60.7g;97%)。 The compound (T-77) (50.0 g), triethyl phosphinyl acetate (48.3 g) and toluene (500 ml) were put into the reactor and cooled to 0°C. Sodium ethoxide (20% ethanol solution) (73.3 g) was slowly added dropwise thereto, returned to room temperature and stirred for 6 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and toluene was used to The aqueous layer is extracted. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=9:1) to obtain compound (T-78) (60.7 g; 97%).
第2步驟 Step 2
將化合物(T-78)(60.7g)、Pd/C(0.51g)、甲苯(500ml)、及IPA(50ml)放入至反應器中,於氫氣環境下攪拌12小時。將不溶物過濾分離後,將反應混合物注入至水中,並利用甲苯對水層進行萃取。利用水對混在一起的有機層進行洗滌,並利用無水硫酸鎂進行乾燥。將該溶液於減壓下濃縮,利用矽膠層析法(容積比,甲苯:庚烷=9:1)將殘渣純化,進而藉由自溶劑混合液(solmix)的再結晶來進行純化,而獲得化合物(T-79)(33.6g;55%)。 The compound (T-78) (60.7 g), Pd/C (0.51 g), toluene (500 ml), and IPA (50 ml) were put into the reactor and stirred for 12 hours under a hydrogen atmosphere. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=9:1), and then purified by recrystallization from a solvent mixture (solmix) to obtain Compound (T-79) (33.6 g; 55%).
第3步驟 Step 3
使用化合物(T-79)(33.6g)作為原料,藉由與合成例16的第6步驟相同的方法而獲得化合物(T-80)(38.8g;86%)。 Using compound (T-79) (33.6 g) as a raw material, compound (T-80) (38.8 g; 86%) was obtained by the same method as in the sixth step of Synthesis Example 16.
第4步驟 Step 4
使用化合物(T-80)(38.8g)作為原料,藉由與合成例16的第7步驟相同的方法而獲得化合物(T-81)(29.8g;95%)。 Using the compound (T-80) (38.8 g) as a raw material, the compound (T-81) (29.8 g; 95%) was obtained by the same method as in the seventh step of Synthesis Example 16.
第5步驟 Step 5
使用化合物(T-81)(29.8g)作為原料,藉由與合成例16的第8步驟相同的方法而獲得化合物(T-82)(34.6g;95%)。 Using the compound (T-81) (29.8 g) as a raw material, the compound (T-82) (34.6 g; 95%) was obtained by the same method as in the eighth step of Synthesis Example 16.
第6步驟 Step 6
使用化合物(T-82)(34.6g)作為原料,藉由與合成例16的第9步驟相同的方法而獲得化合物(T-83)(30.5g;97%)。 Using the compound (T-82) (34.6 g) as a raw material, the compound (T-83) (30.5 g; 97%) was obtained by the same method as in the ninth step of Synthesis Example 16.
第7步驟 Step 7
使用化合物(T-83)(30.5g)作為原料,藉由與合成例16的第10步驟相同的方法而獲得化合物(T-84)(26.6g;75%)。 Using the compound (T-83) (30.5 g) as a raw material, the compound (T-84) (26.6 g; 75%) was obtained by the same method as in the 10th step of Synthesis Example 16.
第8步驟 Step 8
使用化合物(T-84)(26.6g)作為原料,藉由與合成例16的第11步驟相同的方法而獲得化合物(1-23-4)(18.3g;83%)。 Using compound (T-84) (26.6 g) as a raw material, the compound (1-23-4) (18.3 g; 83%) was obtained by the same method as in the 11th step of Synthesis Example 16.
所得的化合物(1-23-4)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-23-4) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):6.10(s,1H)、5.57(s,1H)、4.40-4.37(m,1H)、4.24-4.20(m,1H)、3.69-3.61(m,2H)、1.9-1.94(m,4H)、1.78-1.58(m,9H)、1.43-1.37(m,1H)、1.32-1.02(m,17H)、0.90-0.79(m,9H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 6.10 (s, 1H), 5.57 (s, 1H), 4.40-4.37 (m, 1H), 4.24-4.20 (m, 1H), 3.69-3.61 (m,2H), 1.9-1.94(m,4H), 1.78-1.58(m,9H), 1.43-1.37(m,1H), 1.32-1.02(m,17H), 0.90-0.79(m,9H) .
化合物(1-23-4)的物性為如下所述。 The physical properties of compound (1-23-4) are as follows.
轉變溫度:C 54.5 SA 81.0 I. Transition temperature: C 54.5 S A 81.0 I.
[合成例23] [Synthesis Example 23]
化合物(1-4-5)的合成
第1步驟 Step 1
使用化合物(1-23-4)(3.0g)作為原料,藉由與合成例5的第3步驟相同的方法而獲得化合物(T-85)(3.3g;78%)。 Using compound (1-23-4) (3.0 g) as a raw material, compound (T-85) (3.3 g; 78%) was obtained by the same method as in the third step of Synthesis Example 5.
第2步驟 Step 2
使用化合物(T-85)(3.3g)作為原料,藉由與合成例5的第4步驟相同的方法而獲得化合物(1-4-5)(2.1g;75%)。 Using compound (T-85) (3.3 g) as a raw material, the compound (1-4-5) (2.1 g; 75%) was obtained by the same method as in the fourth step of Synthesis Example 5.
所得的化合物(1-4-5)的NMR分析值為如下所述。 The NMR analysis value of the obtained compound (1-4-5) is as follows.
1H-NMR:化學位移δ(ppm;CDCl3):6.24(s,1H)、6.09(s,1H)、5.84(s,1H)、5.56(s,1H)、4.33-4.28(m,4H)、4.20-4.16(m,2H)、2.28(t,J=6.6Hz,1H)、1.97-1.91(m,4H)、1.79-1.69(m,8H)、1.47-1.41(m,1H)、1.32-1.07(m,17H)、0.90-0.82(m,9H). 1 H-NMR: Chemical shift δ (ppm; CDCl 3 ): 6.24 (s, 1H), 6.09 (s, 1H), 5.84 (s, 1H), 5.56 (s, 1H), 4.33-4.28 (m, 4H) ), 4.20-4.16(m,2H), 2.28(t,J=6.6Hz,1H), 1.97-1.91(m,4H), 1.79-1.69(m,8H), 1.47-1.41(m,1H), 1.32-1.07(m,17H), 0.90-0.82(m,9H).
化合物(1-4-5)的物性為如下所述。 The physical properties of compound (1-4-5) are as follows.
轉變溫度:C 64.0 I. Transition temperature: C 64.0 I.
以下表示組成物的實施例。成分化合物基於下述表3的定義而以記號表示。表3中,與1,4-伸環己基相關的立體構型為反式構型。位於記號後的括弧內的編號表示化合物所屬的化學式。(-)的記號是指其他液晶性化合物。液晶性化合物的比例(百分率)是基於不含添加物的液晶組成物的重量的重量百分率(重量%)。最後歸納組成物的特性值。 The examples of the composition are shown below. The component compounds are represented by symbols based on the definition in Table 3 below. In Table 3, the three-dimensional configuration related to 1,4-cyclohexylene is the trans configuration. The number in parentheses after the symbol indicates the chemical formula to which the compound belongs. The symbol (-) refers to other liquid crystal compounds. The ratio (percentage) of the liquid crystalline compound is the weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additives. Finally, the characteristic values of the composition are summarized.
表3 使用記號的化合物的表述方法 Table 3 Representation method of compounds using symbols
R-(A1)-Z1-.....Zn-(An)-R' R-(A 1 )-Z 1 -. . . . . Z n -(A n )-R'
元件的實施例 Examples of components
1.原料 1. Raw materials
向不具有配向膜的元件中注入添加有在分子末端的分支結構中具有聚合性基與極性基的化合物的組成物。於照射紫外線後,研究該元件中的液晶分子的垂直配向。首先對原料進行說明。原料是組成物(M1)至組成物(M18)、在分子末端的分支結構中具有聚合性基與極性基的化合物(PC-1)至化合物(PC-28)、聚合性化合物(RM-1)至聚合性化合物(RM-8),並依序列出。 A composition in which a compound having a polymerizable group and a polar group in the branched structure of the molecular terminal is added to the element without the alignment film is injected. After irradiating ultraviolet rays, the vertical alignment of the liquid crystal molecules in the device was studied. First, the raw materials will be described. The raw materials are the composition (M1) to the composition (M18), the compound (PC-1) to the compound (PC-28), and the polymerizable compound (RM-1 ) To polymerizable compounds (RM-8), listed in order.
[組成物M1] [Composition M1]
NI=73.2℃;Tc<-20℃;△n=0.113;△ε=-4.0;Vth=2.18V;η=22.6mPa.s. NI=73.2℃; Tc<-20℃; △n=0.113; △ε=-4.0; Vth=2.18V; η=22.6mPa. s.
[組成物M2] [Composition M2]
NI=82.8℃;Tc<-30℃;△n=0.118;△ε=-4.4;Vth=2.13V;η=22.5mPa.s. NI=82.8℃; Tc<-30℃; △n=0.118; △ε=-4.4; Vth=2.13V; η=22.5mPa. s.
[組成物M3] [Composition M3]
NI=78.1℃;Tc<-30℃;△n=0.107;△ε=-3.2;Vth=2.02V;η=15.9mPa.s. NI=78.1℃; Tc<-30℃; △n=0.107; △ε=-3.2; Vth=2.02V; η=15.9mPa. s.
[組成物M4] [Composition M4]
NI=88.5℃;Tc<-30℃;△n=0.108;△ε=-3.8;Vth=2.25V;η=24.6mPa.s; NI=88.5℃; Tc<-30℃; △n=0.108; △ε=-3.8; Vth=2.25V; η=24.6mPa. s;
[組成物M5] [Composition M5]
NI=81.1℃;Tc<-30℃;△n=0.119;△ε=-4.5;Vth=1.69V;η=31.4mPa.s. NI=81.1℃; Tc<-30℃; △n=0.119; △ε=-4.5; Vth=1.69V; η=31.4mPa. s.
[組成物M6] [Composition M6]
NI=98.8℃;Tc<-30℃;△n=0.111;△ε=-3.2;Vth=2.47V;η=23.9mPa.s. NI=98.8℃; Tc<-30℃; △n=0.111; △ε=-3.2; Vth=2.47V; η=23.9mPa. s.
[組成物M7] [Composition M7]
NI=77.5℃;Tc<-30℃;△n=0.084;△ε=-2.6;Vth=2.43V;η=22.8mPa.s. NI=77.5℃; Tc<-30℃; △n=0.084; △ε=-2.6; Vth=2.43V; η=22.8mPa. s.
[組成物M8] [Composition M8]
NI=70.6℃;Tc<-20℃;△n=0.129;△ε=-4.3;Vth=1.69V;η=27.0mPa.s. NI=70.6℃; Tc<-20℃; △n=0.129; △ε=-4.3; Vth=1.69V; η=27.0mPa. s.
[組成物M9] [Composition M9]
NI=93.0℃;Tc<-30℃;△n=0.123;△ε=-4.0;Vth=2.27V;η=29.6mPa.s. NI=93.0℃; Tc<-30℃; △n=0.123; △ε=-4.0; Vth=2.27V; η=29.6mPa. s.
[組成物M10] [Composition M10]
NI=87.6℃;Tc<-30℃;△n=0.126;△ε=-4.5;Vth=2.21V;η=25.3 mPa.s. NI=87.6℃; Tc<-30℃; △n=0.126; △ε=-4.5; Vth=2.21V; η=25.3 mPa. s.
[組成物M11] [Composition M11]
NI=93.0℃;Tc<-20℃;△n=0.124;△ε=-4.5;Vth=2.22V;η=25.0mPa.s. NI=93.0℃; Tc<-20℃; △n=0.124; △ε=-4.5; Vth=2.22V; η=25.0mPa. s.
[組成物M12] [Composition M12]
3-HB(2F,3F)-O2 (2-1) 7% 3-HB(2F,3F)-O2 (2-1) 7%
NI=76.4℃;Tc<-30℃;△n=0.104;△ε=-3.2;Vth=2.06V;η=15.6mPa.s. NI=76.4℃; Tc<-30℃; △n=0.104; △ε=-3.2; Vth=2.06V; η=15.6mPa. s.
[組成物M13] [Composition M13]
NI=78.3℃;Tc<-20℃;△n=0.103;△ε=-3.2;Vth=2.17V;η=17.7mPa.s. NI=78.3℃; Tc<-20℃; △n=0.103; △ε=-3.2; Vth=2.17V; η=17.7mPa. s.
[組成物M14] [Composition M14]
NI=81.2℃;Tc<-20℃;△n=0.107;△ε=-3.2;Vth=2.11V;η=15.5mPa.s. NI=81.2℃; Tc<-20℃; △n=0.107; △ε=-3.2; Vth=2.11V; η=15.5mPa. s.
[組成物M15] [Composition M15]
NI=88.7℃;Tc<-30℃;△n=0.115;△ε=-1.9;Vth=2.82V;η=17.3mPa.s. NI=88.7℃; Tc<-30℃; △n=0.115; △ε=-1.9; Vth=2.82V; η=17.3mPa. s.
[組成物M16] [Composition M16]
NI=89.9℃;Tc<-20℃;△n=0.122;△ε=-4.2;Vth=2.16V;η=23.4mPa.s. NI=89.9℃; Tc<-20℃; △n=0.122; △ε=-4.2; Vth=2.16V; η=23.4mPa. s.
[組成物M17] [Composition M17]
NI=77.1℃;Tc<-20℃;△n=0.101;△ε=-3.0;Vth=2.04V;η=13.9mPa.s. NI=77.1℃; Tc<-20℃; △n=0.101; △ε=-3.0; Vth=2.04V; η=13.9mPa. s.
[組成物M18] [Composition M18]
NI=75.9℃;Tc<-20℃;△n=0.114;△ε=-3.9;Vth=2.20V;η=24.7mPa.s. NI=75.9℃; Tc<-20℃; △n=0.114; △ε=-3.9; Vth=2.20V; η=24.7mPa. s.
[組成物M19] [Composition M19]
NI=74.2℃;Tc<-20℃;△n=0.103;△ε=-2.5;Vth=2.36V;η=18.4mPa.s. NI=74.2℃; Tc<-20℃; △n=0.103; △ε=-2.5; Vth=2.36V; η=18.4mPa. s.
[組成物M20] [Composition M20]
NI=74.9℃;Tc<-20℃;△n=0.102;△ε=-2.8;Vth=2.30V;η=19.2mPa.s. NI=74.9℃; Tc<-20℃; △n=0.102; △ε=-2.8; Vth=2.30V; η=19.2mPa. s.
[組成物M21] [Composition M21]
NI=76.5℃;Tc<-20℃;△n=0.098;△ε=-3.0;Vth=2.15V;η=16.2mPa.s. NI=76.5℃; Tc<-20℃; △n=0.098; △ε=-3.0; Vth=2.15V; η=16.2mPa. s.
[組成物M22] [Composition M22]
NI=75.3℃;Tc<-20℃;△n=0.102;△ε=-2.6;Vth=2.41V;η=17.5mPa.s. NI=75.3℃; Tc<-20℃; △n=0.102; △ε=-2.6; Vth=2.41V; η=17.5mPa. s.
將以下的在分子末端的分支結構中具有聚合性基與極性基的化合物(PC-1)至化合物(PC-28)用作第一添加物。 The following compounds (PC-1) to (PC-28) having a polymerizable group and a polar group in the branched structure of the molecular terminal were used as the first additive.
將以下的聚合性化合物(RM-1)至聚合性化合物(RM-8) 用作第二添加物。 Change the following polymerizable compound (RM-1) to polymerizable compound (RM-8) Used as a second additive.
2.液晶分子的垂直配向 2. Vertical alignment of liquid crystal molecules
實施例1 Example 1
將在分子末端的分支結構中具有聚合性基與極性基的化合物(PC-1)以5重量%的比例添加於組成物(M1)中。於100℃的熱載台上將該混合物注入至2塊玻璃基板的間隔(單元間隙)為4.0μm且不具有配向膜的元件中。藉由使用超高壓水銀燈USH-250-BY(牛尾(Ushio)電機製造)對該元件照射紫外線(28J),來使在分子末端的分支結構中具有聚合性基與極性基的化合物(PC-1)進行聚合。將該元件配置於偏振器與檢偏器並行配置的偏光顯微鏡,自下方對元件照射光來觀察有無漏光。於液晶分子充分配向、光未透過元件時,判斷垂直配向為「良好」。於觀察到透過元件的光時,表示為「不良」。 A compound (PC-1) having a polymerizable group and a polar group in the branched structure of the molecular terminal was added to the composition (M1) at a ratio of 5% by weight. The mixture was injected on a hot stage at 100° C. into an element with a distance (cell gap) of 4.0 μm between two glass substrates and no alignment film. By using the ultra-high pressure mercury lamp USH-250-BY (manufactured by Ushio Motor) to irradiate the device with ultraviolet rays (28J), the compound having a polymerizable group and a polar group (PC-1 ) Perform polymerization. This element was placed in a polarizing microscope in which a polarizer and an analyzer were arranged in parallel, and light was irradiated to the element from below to observe whether there was light leakage. When the liquid crystal molecules are fully aligned and light does not pass through the device, the vertical alignment is judged to be "good". When the light passing through the element is observed, it is indicated as "bad".
實施例2至實施例55及比較例1~比較例2 Example 2 to Example 55 and Comparative Example 1 to Comparative Example 2
使用將組成物及在分子末端的分支結構中具有聚合性基與極性基的化合物組合而成的混合物來製作不具有配向膜的元件。以與實施例1相同的方法來觀察有無漏光。將結果歸納於表4及表5中。實施例18中,亦以0.5重量%的比例添加聚合性化合物(RM-1)。比較例1中,為了進行比較,選擇專利文獻5中記載的如下述之類的極性化合物(A-1)。該化合物由於在分子末端不具有分支結構,因此與化合物(1-1)不同。 A mixture of the composition and a compound having a polymerizable group and a polar group in the branch structure at the molecular terminal is used to produce an element without an alignment film. In the same manner as in Example 1, the presence or absence of light leakage was observed. The results are summarized in Table 4 and Table 5. In Example 18, the polymerizable compound (RM-1) was also added in a ratio of 0.5% by weight. In Comparative Example 1, for comparison, the following polar compound (A-1) described in Patent Document 5 was selected. Since this compound does not have a branched structure at the molecular end, it is different from the compound (1-1).
根據表4及表5可知般,實施例1至實施例55中,雖改變了組成物或第一添加物的種類及極性化合物的濃度,但未觀察到漏光。該結果表示,即便於元件中無配向膜,垂直配向亦良好,液晶分子穩定地進行配向。實施例18及實施例40中,進而添加了作為第二添加物的聚合性化合物(RM-1),但獲得同樣的結 果。另一方面,比較例1及比較例2中觀察到漏光。該結果表示垂直配向並非良好。 As can be seen from Tables 4 and 5, in Examples 1 to 55, although the type of the composition or the first additive and the concentration of the polar compound were changed, no light leakage was observed. This result shows that even if there is no alignment film in the device, the vertical alignment is good, and the liquid crystal molecules are aligned stably. In Example 18 and Example 40, a polymerizable compound (RM-1) was further added as a second additive, but the same structure was obtained. fruit. On the other hand, in Comparative Example 1 and Comparative Example 2, light leakage was observed. This result indicates that the vertical alignment is not good.
3.極性化合物的相容性 3. Compatibility of polar compounds
對所述實施例中所得的液晶組成物與第一添加物的混合物的室溫狀態下的穩定性進行評價。於混合後在100℃下進行各向同性化並放置冷卻至25℃。於室溫下經過半日後確認有無析出,結果實施例1~實施例55的混合物中未確認到析出,第一添加物的相容性良好。另一方面,比較例1~比較例2的混合物中確認到析出,極性化合物的相容性不良。 The stability at room temperature of the mixture of the liquid crystal composition and the first additive obtained in the example was evaluated. After mixing, it was isotropic at 100°C and left to cool to 25°C. The presence or absence of precipitation was confirmed after half a day at room temperature. As a result, precipitation was not confirmed in the mixture of Example 1 to Example 55, and the compatibility of the first additive was good. On the other hand, precipitation was confirmed in the mixture of Comparative Example 1 to Comparative Example 2, and the compatibility of the polar compound was poor.
根據所述結果可知:由在分子末端的分支結構中具有聚合性基與極性基的化合物生成的聚合物對液晶分子的垂直配向發揮重要的作用,亦使與液晶組成物的相容性提高。即便使用表4及表5所示的化合物(PC-1)至化合物(PC-28)以外的合成例1至合成例23所示的化合物,此種傾向亦相同。因此,若使用本發明的液晶組成物,則可獲得具有響應時間短、電壓保持率大、臨限電壓低、對比度比大、壽命長等特性的AM元件。進而,可獲得具有如下液晶組成物的液晶顯示元件,所述液晶組成物於向列相的上限溫度高、向列相的下限溫度低、黏度小、光學各向異性適當、負的介電各向異性大、比電阻大、對紫外線的穩定性高、對熱的穩定性高等特性中,滿足至少一種特性。 From the above results, it can be seen that a polymer produced from a compound having a polymerizable group and a polar group in the branched structure of the molecular terminal plays an important role in the vertical alignment of liquid crystal molecules, and also improves the compatibility with the liquid crystal composition. This tendency is the same even when the compounds shown in Synthesis Example 1 to Synthesis Example 23 other than the compound (PC-1) to the compound (PC-28) shown in Table 4 and Table 5 are used. Therefore, if the liquid crystal composition of the present invention is used, it is possible to obtain an AM device having characteristics such as a short response time, a large voltage retention rate, a low threshold voltage, a large contrast ratio, and a long life. Furthermore, a liquid crystal display element having a liquid crystal composition having a high upper limit temperature of the nematic phase, a low lower limit temperature of the nematic phase, low viscosity, appropriate optical anisotropy, and negative dielectric properties can be obtained. Among the characteristics of high anisotropy, high specific resistance, high stability to ultraviolet light, and high stability to heat, at least one characteristic is satisfied.
[產業上之可利用性] [Industrial availability]
本發明的液晶組成物於不具有配向膜的元件中可控制 液晶分子的配向,可用於液晶投影機、液晶監視器、液晶電視等中。 The liquid crystal composition of the present invention can be controlled in a device without an alignment film The alignment of liquid crystal molecules can be used in LCD projectors, LCD monitors, LCD TVs, etc.
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- 2017-07-27 TW TW106125279A patent/TWI710623B/en active
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- 2017-09-06 WO PCT/JP2017/032061 patent/WO2018047850A1/en active Application Filing
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WO2016129490A1 (en) * | 2015-02-09 | 2016-08-18 | Jnc株式会社 | Polymerizable polar compound, liquid crystal composition, and liquid crystal display element |
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JPWO2018047850A1 (en) | 2019-06-27 |
CN109312232B (en) | 2022-08-16 |
WO2018047850A1 (en) | 2018-03-15 |
JP6922921B2 (en) | 2021-08-18 |
CN109312232A (en) | 2019-02-05 |
TW201835309A (en) | 2018-10-01 |
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