TWI721763B - Liquid crystal composition and liquid crystal display element - Google Patents
Liquid crystal composition and liquid crystal display element Download PDFInfo
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Abstract
本發明提供一種液晶組成物及液晶顯示元件。本發明所欲解決之課題在於:提供一種含有聚合性化合物的液晶組成物、及使用其之液晶顯示元件,其聚合性化合物的聚合速度足夠快,並且最適合於沒有或極少有由於預傾角的變化而產生的殘影等顯示不良、VHR高、可靠性優異的PSA型或PSVA型的液晶顯示元件。 提供一種液晶組成物,其含有一種或兩種以上通式(i)所示的化合物作為第一成分,含有一種或兩種以上通式(L)所示的化合物作為第二成分,含有選自通式(N-1d)及/或(N-1)所示的化合物群中的一種或兩種以上的化合物作為第三成分,且含有通式(II)所示的聚合性化合物作為第四成分。又,提供使用該等的液晶顯示元件。 The invention provides a liquid crystal composition and a liquid crystal display element. The problem to be solved by the present invention is to provide a liquid crystal composition containing a polymerizable compound and a liquid crystal display element using the same. The polymerizable compound has a sufficiently fast polymerization rate and is most suitable for those with no or little pretilt angle. PSA-type or PSVA-type liquid crystal display elements with poor display such as afterimages caused by changes, high VHR, and excellent reliability. Provided is a liquid crystal composition which contains one or more compounds represented by the general formula (i) as the first component, contains one or more compounds represented by the general formula (L) as the second component, and contains One or two or more compounds in the compound group represented by the general formula (N-1d) and/or (N-1) are used as the third component, and the polymerizable compound represented by the general formula (II) is contained as the fourth component ingredient. In addition, liquid crystal display elements using these are provided.
Description
本發明係關於一種含有聚合性化合物的液晶組成物及使用其之液晶顯示元件。The present invention relates to a liquid crystal composition containing a polymerizable compound and a liquid crystal display element using the liquid crystal composition.
液晶顯示元件被用於以鐘錶、計算器為代表的家庭用各種電氣設備、工業用測定設備、汽車用面板、手機、智慧手機、筆記型電腦、平板電腦、電視機等。作為液晶顯示方式,其代表性者可列舉TN(扭曲向列)型、STN(超扭曲向列)型、GH(賓主)型、IPS(平面轉換)型、FFS(邊緣場轉換)型、OCB(光學補償雙折射)型、ECB(電壓控制雙折射)型、VA(垂直配向)型、CSH(彩色超垂直配向)型、FLC(鐵電性液晶)等。又,作為驅動方式,亦可列舉靜態驅動、多工驅動、單純矩陣方式、利用TFT(薄膜電晶體)或TFD(薄膜二極體)等進行驅動的主動矩陣(AM)方式。已知在該等顯示方式中,IPS型、FFS型、ECB型、VA型、CSH型等在使用介電常數各向異性(Δε)顯示負值的液晶組成物(n型液晶組成物)時顯示有利的特性。Liquid crystal display elements are used in various household electrical equipment such as clocks and calculators, industrial measuring equipment, automotive panels, mobile phones, smartphones, notebook computers, tablet computers, and televisions. As a liquid crystal display method, representative ones include TN (twisted nematic) type, STN (super twisted nematic) type, GH (guest-host) type, IPS (in-plane switching) type, FFS (fringe field switching) type, OCB (Optical Compensation Birefringence) type, ECB (Voltage Controlled Birefringence) type, VA (Vertical Alignment) type, CSH (Color Super Vertical Alignment) type, FLC (Ferroelectric Liquid Crystal), etc. In addition, as the driving method, static driving, multiplex driving, simple matrix method, and active matrix (AM) method using TFT (thin film transistor) or TFD (thin film diode) for driving can also be cited. It is known that among these display methods, IPS type, FFS type, ECB type, VA type, CSH type, etc. are used when a liquid crystal composition (n-type liquid crystal composition) exhibiting a negative dielectric anisotropy (Δε) is used. Shows favorable characteristics.
在使用n型液晶組成物的顯示方式中,有以VA型、進一步使聚合性化合物在液晶相中聚合並控制了配向的PSA(聚合物持續配向)型或PSVA(聚合物穩定垂直配向)型為代表的垂直配向方式,以及以IPS型、FFS型為代表的水平配向方式。垂直配向方式具有視野角寬、穿透率高、對比度高、應答速度快的特徵,主要用於TV、監視器等大型顯示元件中。另一方面,從視野角寬、穿透率高、耗電低以及與觸控面板的最適性的觀點而言,例如在智慧手機、平板電腦等行動設備中採用水平配向方式,進而亦在推進在液晶電視機中的採用。Among the display methods using n-type liquid crystal composition, there are VA type, PSA (polymer continuous alignment) type or PSVA (polymer stable vertical alignment) type in which a polymerizable compound is further polymerized in the liquid crystal phase and the alignment is controlled. The vertical alignment method represented by the IPS type and the horizontal alignment method represented by the IPS type and the FFS type. The vertical alignment method has the characteristics of wide viewing angle, high transmittance, high contrast, and fast response speed, and is mainly used in large display elements such as TVs and monitors. On the other hand, from the viewpoint of wide viewing angle, high penetration rate, low power consumption, and optimum compatibility with touch panels, for example, the horizontal alignment method is adopted in mobile devices such as smartphones and tablets, which are also advancing Use in LCD TVs.
關於PSA型或PSVA型的液晶顯示裝置,為了控制液晶分子的預傾角,而在單元內形成聚合物結構物,在垂直配向方式的特徵中,特別是高速應答、高對比是眾所周知的。Regarding PSA-type or PSVA-type liquid crystal display devices, in order to control the pretilt angle of liquid crystal molecules, a polymer structure is formed in the cell. Among the characteristics of the vertical alignment method, high-speed response and high contrast are particularly well known.
PSA型或PSVA型的液晶顯示元件的製造藉由以下方式進行:將含有聚合性化合物的液晶組成物注入至基板間,在施加電壓而使液晶分子配向的狀態下照射紫外線,從而使聚合性化合物聚合並且將液晶分子的配向固定。因此,在使液晶組成物中的聚合性化合物聚合的步驟中,上述聚合性化合物的聚合速度非常重要。若聚合速度快,則在較短的紫外線照射時間內聚合性化合物的殘留量減少,因此不易發生紫外線導致的液晶組成物劣化等。又,亦具有能夠以較少的能量而製造如此之高生產率的優點。The production of PSA-type or PSVA-type liquid crystal display elements is carried out by injecting a liquid crystal composition containing a polymerizable compound between the substrates, and irradiating ultraviolet rays while applying a voltage to align the liquid crystal molecules, thereby making the polymerizable compound Polymerize and fix the alignment of liquid crystal molecules. Therefore, in the step of polymerizing the polymerizable compound in the liquid crystal composition, the polymerization rate of the above-mentioned polymerizable compound is very important. If the polymerization rate is high, the residual amount of the polymerizable compound is reduced in a short ultraviolet irradiation time, and therefore, deterioration of the liquid crystal composition caused by ultraviolet rays is less likely to occur. In addition, it also has the advantage of being able to produce such high productivity with less energy.
另一方面,聚合性化合物的聚合速度慢時,為了減少聚合性化合物的殘留量,需要較長的紫外線照射時間。如此,在聚合步驟中長時間照射強紫外線的情況下,會導致製造裝置大型化、製造效率下降並且發生紫外線導致的液晶組成物劣化等。然而,若使紫外線的照射時間變短,則聚合性化合物的殘留量變多,殘存的聚合性化合物會導致發生被稱為殘影的顯示不良。On the other hand, when the polymerization rate of the polymerizable compound is slow, in order to reduce the residual amount of the polymerizable compound, a longer UV irradiation time is required. In this way, when strong ultraviolet rays are irradiated for a long period of time in the polymerization step, the size of the manufacturing apparatus will be increased, the manufacturing efficiency will decrease, and degradation of the liquid crystal composition due to ultraviolet rays will occur. However, if the irradiation time of ultraviolet rays is shortened, the residual amount of the polymerizable compound will increase, and the remaining polymerizable compound will cause display failure called residual image to occur.
綜上所述,期望改善了聚合性化合物的聚合速度的液晶組成物。In summary, a liquid crystal composition having an improved polymerization rate of a polymerizable compound is desired.
作為用於改善聚合性化合物的聚合速度的方案,如專利文獻1的實施例所示,提出了使用如式(A)般的化合物而使所使用的液晶材料的吸收波長延伸到長波長側從而改善聚合性化合物的聚合速度的方法,然而,關於以預傾角的變化、電壓保持率為代表的可靠性,並不充分。As a solution for improving the polymerization rate of a polymerizable compound, as shown in the examples of Patent Document 1, it is proposed to use a compound such as formula (A) to extend the absorption wavelength of the liquid crystal material used to the long wavelength side. The method of improving the polymerization rate of the polymerizable compound, however, is not sufficient regarding the reliability represented by the change in the pretilt angle and the voltage retention rate.
先前技術文獻 專利文獻 Prior Art Document Patent Document
專利文獻1:日本特表2013-503952號公報Patent Document 1: Japanese Special Form No. 2013-503952
發明所欲解決之課題The problem to be solved by the invention
本發明要解決之課題在於:提供一種含有聚合性化合物的液晶組成物,其聚合性化合物的聚合速度足夠快,並且最適合於沒有或極少有由於預傾角的變化而產生的殘影(IS:Image Sticking)等顯示不良、VHR高、可靠性優異的PSA型或PSVA型的液晶顯示元件;並且,提供一種使用其之液晶顯示元件。 解決課題之技術手段 The problem to be solved by the present invention is to provide a liquid crystal composition containing a polymerizable compound whose polymerization rate of the polymerizable compound is sufficiently fast, and which is most suitable for having no or very little residual image due to the change of the pretilt angle (IS: Image Sticking) and other PSA-type or PSVA-type liquid crystal display elements with poor display, high VHR, and excellent reliability; and provide a liquid crystal display element using the same. Technical means to solve the problem
本發明者進行了努力研究,結果發現:利用含有具有特定化學結構的化合物及聚合性化合物的液晶組成物,能夠解決上述課題,從而完成了本發明。 發明之效果 The inventors of the present invention conducted diligent studies, and as a result, discovered that the above-mentioned problems can be solved by using a liquid crystal composition containing a compound having a specific chemical structure and a polymerizable compound, thereby completing the present invention. The effect of the invention
本發明的液晶組成物是介電常數各向異性(Δε)為負,顯示大的折射率各向異性(Δn)、高的向列相-各向同性液體相轉移溫度(T ni)、低的旋轉黏性(γ 1),且聚合性化合物的聚合速度足夠快的液晶組成物。使用了本發明的液晶組成物的液晶顯示元件由於聚合性化合物的殘留量少,因此驅動前後的預傾角的變化小,顯示出高的電壓保持率(VHR),不存在或抑制了殘影等顯示不良,顯示出優異的顯示品質。 The liquid crystal composition of the present invention has negative dielectric anisotropy (Δε), large refractive index anisotropy (Δn), high nematic-isotropic liquid phase transition temperature (T ni ), and low A liquid crystal composition with high rotational viscosity (γ 1 ) and a sufficiently fast polymerization rate of the polymerizable compound. Since the liquid crystal display element using the liquid crystal composition of the present invention has a small residual amount of polymerizable compounds, the change in pretilt angle before and after driving is small, exhibits a high voltage holding ratio (VHR), and does not exist or suppresses image sticking, etc. Poor display, showing excellent display quality.
本發明的液晶組成物中,含有一種或兩種以上通式(i)所示的化合物作為第一成分, (式中,R i1及R i2分別獨立地表示碳原子數1至8的烷基,該烷基中的1個或不相鄰的2個以上的-CH 2-可分別獨立地被-CH=CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代,A i1表示1,4-伸環己基(存在於該基團中的1個-CH 2-或不相鄰的2個以上的-CH 2-可被取代為-O-),n i1表示0、1或2);含有一種或兩種以上通式(L)所示的化合物作為第二成分, (式中,R L1及R L2分別獨立地表示碳原子數1至8的烷基,該烷基中的1個或不相鄰的2個以上的-CH 2-可分別獨立地被-CH=CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代, A L1、A L2及A L3分別獨立地表示選自由以下基團(a)~(c)組成的群中的基團, (a)1,4-伸環己基(存在於該基團中的1個-CH 2-或不相鄰的2個以上的-CH 2-可被取代為-O-)、 (b)1,4-伸苯基(存在於該基團中的1個-CH=或不相鄰的2個以上的-CH=可被取代為-N=)、及 (c)萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基或十氫萘-2,6-二基(存在於萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基中的1個-CH=或不相鄰的2個以上的-CH=可被取代為-N=), 上述基團(a)、基團(b)及基團(c)可分別獨立地被烷基(存在於該基團中的1個-CH 2-或不相鄰的2個以上的-CH 2-可被取代為-O-)、烯基(存在於該基團中的1個-CH 2-或不相鄰的2個以上的-CH 2-可被取代為-O-)、氰基、氟原子或氯原子取代, Z L1及Z L2分別獨立地表示單鍵、-CH 2CH 2-、-(CH 2) 4-、-OCH 2-、-CH 2O-、-COO-、-OCO-、-OCF 2-、-CF 2O-、-CH=N-N=CH-、-CH=CH-、-CF=CF-或-C≡C-, n L1表示0、1、2或3, 當A L2存在複數個時,該等可相同亦可不同,當Z L2存在複數個時,該等可相同亦可不同,但上述通式(i)、及通式(N-1d)或(N-1)所示的化合物除外);含有選自通式(N-1d)及/或通式(N-1)所示的化合物群中的一種或兩種以上的化合物作為第三成分, (式中,R Nd11及R Nd12分別獨立地表示碳原子數1至8的烷基,該烷基中的1個或不相鄰的2個以上的-CH 2-可分別獨立地被-CH=CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代,n Nd11表示1、2或3), (式中,R N11及R N12分別獨立地表示碳原子數1至8的烷基,該烷基中的1個或不相鄰的2個以上的-CH 2-可分別獨立地被-CH=CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代,n N11及n N12分別獨立地表示0、1、2或3,n N11+n N12表示1、2或3,A N11及A N12分別獨立地表示選自由以下基團(a)~(c)組成的群中的基團, (a)1,4-伸環己基(存在於該基團中的1個-CH 2-或不相鄰的2個以上的-CH 2-可被取代為-O-)、 (b)1,4-伸苯基(存在於該基團中的1個-CH=或不相鄰的2個以上的-CH=可被取代為-N=)、及 (c)萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基或十氫萘-2,6-二基(存在於萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基中的1個-CH=或不相鄰的2個以上的-CH=可被取代為-N=), 上述基團(a)、基團(b)及基團(c)可分別獨立地被烷基(存在於該基團中的1個-CH 2-或不相鄰的2個以上的-CH 2-可被取代為-O-)、烯基(存在於該基團中的1個-CH 2-或不相鄰的2個以上的-CH 2-可被取代為-O-)、氰基、氟原子或氯原子取代,Z N11及Z N12分別獨立地表示單鍵、-CH 2CH 2-、-(CH 2) 4-、-OCH 2-、-CH 2O-、-COO-、-OCO-、-OCF 2-、-CF 2O-、-CH=N-N=CH-、-CH=CH-、-CF=CF-或-C≡C-,當A N11及/或A N12存在複數個時,該等可相同亦可不同,當Z N11及/或Z N12存在複數個時,該等可相同亦可不同,但通式(N-1d)所示的化合物除外);且含有通式(II)所示的聚合性化合物作為第四成分, (式中,R 201、R 202、R 203、R 204、R 205、R 206、R 207、R 208、R 209及R 210分別獨立地表示P 21-S 21-、可被氟原子取代的碳原子數1至18的烷基、可被氟原子取代的碳原子數1至18的烷氧基、氟原子或氫原子中的任一者,P 21分別獨立地表示選自式(R-1)至式(R-7)中的聚合性基團, (式中,R 11、R 12、R 13、R 14及R 15分別獨立地表示碳原子數1至5的烷基、氟原子或氫原子中的任一者,m r5、m r7、n r5及n r7分別獨立地表示0、1、或2),S 21表示單鍵或碳數1至15的伸烷基,該伸烷基中的1個或2個以上的-CH 2-能夠以氧原子不直接相鄰的方式被-O-、-OCO-或-COO-取代,n 21表示0、1或2,A 21表示選自由以下基團(a)~(c)組成的群中的基團, (a)1,4-伸環己基(存在於該基團中的1個-CH 2-或不相鄰的2個以上的-CH 2-可被取代為-O-)、 (b)1,4-伸苯基(存在於該基團中的1個-CH=或不相鄰的2個以上的-CH=可被取代為-N=)、及 (c)萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基或十氫萘-2,6-二基(存在於萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基中的1個-CH=或不相鄰的2個以上的-CH=可被取代為-N=), 上述基團(a)、基團(b)及基團(c)可分別獨立地被碳原子數1至12的烷基、碳原子數1至12的烷氧基、鹵素、氰基、硝基或P 21-S 21-取代,在上述通式(II)的1分子中具有至少1個以上的P 21-S 21-,L 21表示單鍵、-OCH 2-、-CH 2O-、-C 2H 4-、-OC 2H 4O-、-COO-、-OCO-、-CH=CR a-COO-、-CH=CR a-OCO-、-COO-CR a=CH-、-OCO-CR a=CH-、-(CH 2) z-COO-、-(CH 2) z-OCO-、-OCO-(CH 2) z-、-COO-(CH 2) z-、-CH=CH-、-CF 2O-、-OCF 2-或-C≡C-(式中,R a分別獨立地表示氫原子或碳原子數1至3的烷基,上述式中,z分別獨立地表示1至4的整數),當P 21、S 21及A 21存在複數個時,分別可相同亦可不同)。 The liquid crystal composition of the present invention contains one or two or more compounds represented by the general formula (i) as the first component, (In the formula, R i1 and R i2 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH 2 -s in the alkyl group may be independently replaced by -CH =CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substituted, A i1 represents 1,4-cyclohexylene (one -CH 2 in the group -Or two or more non-adjacent -CH 2 -can be substituted with -O-), n i1 represents 0, 1 or 2); containing one or more compounds represented by the general formula (L) as the first Two components, (In the formula, R L1 and R L2 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH 2 -s in the alkyl group may be independently replaced by -CH =CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substituted, A L1 , A L2 and A L3 each independently represent selected from the following groups (a) to (c ) Groups in the group consisting of (a) 1,4-cyclohexylene (1 -CH 2 -or 2 or more non-adjacent -CH 2 -in the group can be substituted with -O-), (b) 1,4-phenylene (1 -CH= or 2 or more non-adjacent -CH= in the group can be substituted with -N=), and (c) Naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (present in naphthalene-2,6-diyl) One -CH= in diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl or two or more non-adjacent -CH= can be substituted with -N=), the above Group (a), group (b) and group (c) can each be independently substituted by an alkyl group (one -CH 2 -existing in the group-or two or more non-adjacent -CH 2 - may be substituted with -O-), an alkenyl group (present in the group in which one -CH 2 - or non-adjacent two or more -CH 2 - may be substituted with -O-), a cyano group , Fluorine atom or chlorine atom substitution, Z L1 and Z L2 each independently represent a single bond, -CH 2 CH 2 -, -(CH 2 ) 4 -, -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -OCF 2 -, -CF 2 O-, -CH=NN=CH-, -CH=CH-, -CF=CF- or -C≡C-, n L1 means 0, 1, 2 or 3. When there are plural A L2 , they may be the same or different. When Z L2 exists, they may be the same or different, but the above general formula (i) and general formula (N-1d) Or the compound represented by (N-1)); containing one or two or more compounds selected from the group of compounds represented by general formula (N-1d) and/or general formula (N-1) as the third ingredient, (In the formula, R Nd11 and R Nd12 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH 2 -s in the alkyl group may be independently replaced by -CH =CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substitution, n Nd11 represents 1, 2 or 3), (In the formula, R N11 and R N12 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH 2 -s in the alkyl group may be independently replaced by -CH =CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substitution, n N11 and n N12 respectively independently represent 0, 1, 2 or 3, n N11 + n N12 represents 1, 2 or 3, A N11 and A N12 each independently represent a group selected from the group consisting of the following groups (a) to (c): (a) 1,4-cyclohexylene (present in this group) One -CH 2 -or two or more non-adjacent -CH 2 -in the group can be substituted with -O-), (b) 1,4-phenylene (the 1 in the group One -CH= or two or more non-adjacent -CH= can be substituted with -N=), and (c) naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene- 2,6-diyl or decahydronaphthalene-2,6-diyl (1 in naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl One -CH= or two or more non-adjacent -CH= can be substituted with -N=), the above group (a), group (b) and group (c) can be each independently by an alkyl group (1 -CH 2 -or 2 or more non-adjacent -CH 2 -in the group can be substituted with -O-), alkenyl (1 -CH in the group 2 -or two or more non-adjacent -CH 2 -may be substituted with -O-), cyano, fluorine atom or chlorine atom, Z N11 and Z N12 each independently represent a single bond, -CH 2 CH 2 -, -(CH 2 ) 4 -, -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -OCF 2 -, -CF 2 O-, -CH=NN=CH-,- CH=CH-, -CF=CF- or -C≡C-, when there are plural A N11 and/or A N12 , these may be the same or different, when Z N11 and/or Z N12 exist plural , These may be the same or different, except for the compound represented by the general formula (N-1d)); and containing the polymerizable compound represented by the general formula (II) as the fourth component, (In the formula, R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 , R 209 and R 210 each independently represent P 21 -S 21 -, which may be substituted by a fluorine atom Any one of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms that may be substituted with a fluorine atom, a fluorine atom, or a hydrogen atom, and P 21 each independently represents selected from the formula (R- 1) to the polymerizable group in formula (R-7), (In the formula, R 11 , R 12 , R 13 , R 14 and R 15 each independently represent any of an alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a hydrogen atom, m r5 , m r7 , n r5 and n r7 each independently represent 0, 1, or 2), S 21 represents a single bond or an alkylene having 1 to 15 carbon atoms, and one or more of -CH 2 -in the alkylene can be It is substituted by -O-, -OCO- or -COO- in such a way that the oxygen atom is not directly adjacent, n 21 represents 0, 1 or 2, and A 21 represents the group selected from the following groups (a) to (c) the group, (a) 1,4- cyclohexylene (present in the group in which one -CH 2 - or non-adjacent two or more -CH 2 - may be substituted with -O-) , (B) 1,4-phenylene (1 -CH= or 2 or more non-adjacent -CH= in the group can be substituted with -N=), and (c) naphthalene -2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (present in naphthalene-2,6-diyl or 1 ,2,3,4-Tetrahydronaphthalene-2,6-diyl, one -CH= or two or more non-adjacent -CH= can be substituted with -N=), the above group (a ), group (b) and group (c) can be each independently covered by an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, halogen, cyano, nitro or P 21- S 21 -substituted, having at least one P 21 -S 21 -in one molecule of the general formula (II), and L 21 represents a single bond, -OCH 2 -, -CH 2 O-, -C 2 H 4 -, -OC 2 H 4 O-, -COO-, -OCO-, -CH=CR a -COO-, -CH=CR a -OCO-, -COO-CR a =CH-, -OCO-CR a =CH-, -(CH 2 ) z -COO-, -(CH 2 ) z -OCO-, -OCO-(CH 2 ) z -, -COO-(CH 2 ) z -, -CH=CH- , -CF 2 O-, -OCF 2 -or -C≡C- (wherein R a independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and in the above formula, z each independently represents 1 To 4), when there are plural P 21 , S 21 and A 21 , they may be the same or different respectively).
通式(i)中,R i1表示碳原子數1至8的烷基、碳原子數1至8的烷氧基、碳原子數2至8的烯基或碳原子數2至8的烯氧基,較佳為碳原子數1至5的烷基、碳原子數1至5的烷氧基、碳原子數2至5的烯基或碳原子數2至5的烯氧基,進而較佳為碳原子數2至5的烷基或碳原子數2至5的烯基。R i2較佳為碳原子數1至8的烷基、碳原子數2至8的烯基,較佳為碳原子數1至5的烷基或碳原子數2至5的烯基,進而較佳為碳原子數1至3的烷基或碳原子數2至5的烯基,尤佳為碳原子數1的烷基。A i1表示1,4-伸環己基(存在於該基團中的1個-CH 2-或不相鄰的2個以上的-CH 2-可被取代為-O-),較佳為非取代的1,4-伸環己基。n i1表示0、1或2,較佳為1或2,尤佳為1。 In the general formula (i), R i1 represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkylene oxide having 2 to 8 carbon atoms. The group is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms, and more preferably It is an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. R i2 is preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and more It is preferably an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and particularly preferably an alkyl group having 1 carbon atom. A i1 represents 1,4-cyclohexylene group (in the presence of a group -CH 2 - or non-adjacent two or more -CH 2 - may be substituted with -O-), a non-preferred Substituted 1,4-cyclohexylene. n i1 represents 0, 1, or 2, preferably 1 or 2, and particularly preferably 1.
通式(i)所示的化合物較佳為選自式(i-0.1)至式(i-0.7)、式(i-1.1)至式(i-1.7)及式(i-2.1)至式(i-2.7)所示的化合物群中的化合物。The compound represented by general formula (i) is preferably selected from formula (i-0.1) to formula (i-0.7), formula (i-1.1) to formula (i-1.7) and formula (i-2.1) to formula Compounds in the compound group shown in (i-2.7).
在式(i-0.1)至式(i-0.7)所示的化合物群中,進而較佳為式(i-0.3)、式(i-0.5)、式(i-0.7),尤佳為式(i-0.7)。Among the group of compounds represented by formula (i-0.1) to formula (i-0.7), formula (i-0.3), formula (i-0.5), and formula (i-0.7) are more preferred, and formula (i-0.7) is particularly preferred (i-0.7).
在式(i-1.1)至式(i-1.7)所示的化合物群中,進而較佳為式(i-1.3)、式(i-1.6)、式(i-1.7)所示的化合物,尤佳為式(i-1.3)所示的化合物。Among the group of compounds represented by formula (i-1.1) to formula (i-1.7), compounds represented by formula (i-1.3), formula (i-1.6), and formula (i-1.7) are more preferred, Particularly preferred is a compound represented by formula (i-1.3).
在式(i-2.1)至式(i-2.7)所示的化合物群中,進而較佳為式(i-2.3)、式(i-2.6)、式(i-2.7)所示的化合物,尤佳為式(i-2.3)所示的化合物。Among the group of compounds represented by formula (i-2.1) to formula (i-2.7), compounds represented by formula (i-2.3), formula (i-2.6), and formula (i-2.7) are more preferred, Particularly preferred is a compound represented by formula (i-2.3).
相對於本發明的組成物的總量,式(i)所示的化合物的較佳含量的下限值為1%、2%、3%、5%、7%。較佳含量的上限值為20%、15%、13%、10%、9%。以下,只要沒有特別記載,%即是指質量%。The lower limit of the preferable content of the compound represented by formula (i) is 1%, 2%, 3%, 5%, 7% relative to the total amount of the composition of the present invention. The upper limit of the preferred content is 20%, 15%, 13%, 10%, 9%. Hereinafter, as long as there is no special description,% means mass %.
式(i)所示的化合物可單獨使用一種,亦可將兩種以上組合使用。藉由將兩種以上的式(i)所示的化合物組合使用,可顯著地得到本發明的效果。在使用兩種以上的式(i)所示的化合物時,較佳為式(i-0.1)~(i-0.7)所示的化合物與式(i-1.1)~(i-1.7)所示的化合物的組合,亦較佳為將式(i-1.1)~(i-1.7)所示的化合物中的兩種組合。The compound represented by formula (i) may be used singly or in combination of two or more kinds. By combining two or more compounds represented by formula (i), the effects of the present invention can be remarkably obtained. When two or more compounds represented by formula (i) are used, the compounds represented by formulas (i-0.1) to (i-0.7) and those represented by formulas (i-1.1) to (i-1.7) are preferred The combination of the compounds of is also preferably a combination of two of the compounds represented by formulas (i-1.1) to (i-1.7).
本發明的液晶組成物較佳為含有一種或兩種以上通式(L)所示的化合物。通式(L)所示的化合物屬於在介電性方面為大致中性的化合物(Δε的值為-2至2)。其中,通式(i)所示的化合物除外。The liquid crystal composition of the present invention preferably contains one or two or more compounds represented by the general formula (L). The compound represented by the general formula (L) is a compound that is substantially neutral in terms of dielectric properties (the value of Δε is -2 to 2). Among them, the compound represented by the general formula (i) is excluded.
通式(L)所示的化合物可單獨使用,亦可組合使用。對於可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等期望性能適當組合使用。例如,作為本發明的一個實施方式,所使用的化合物的種類為一種。或者,在本發明的其他實施方式中,為2種、3種、4種、5種、6種、7種、8種、9種、10種以上。The compound represented by the general formula (L) may be used alone or in combination. There are no particular restrictions on the types of compounds that can be combined, and they are used in appropriate combinations according to desired properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. For example, as one embodiment of the present invention, there is one kind of compound used. Or, in other embodiments of the present invention, they are 2, 3, 4, 5, 6, 7, 8, 9, or 10 or more types.
通式(L)所示的化合物是Δε為0左右的所謂非極性化合物。因此,分子內的鹵素原子等極性基團的數量較佳為2個以下,較佳為1個以下,為了改善與其他液晶化合物的溶解性,較佳為1個,在著眼於黏性時較佳為未發生取代。The compound represented by the general formula (L) is a so-called non-polar compound in which Δε is about zero. Therefore, the number of polar groups such as halogen atoms in the molecule is preferably 2 or less, preferably 1 or less. In order to improve the solubility with other liquid crystal compounds, it is preferably one. Preferably, no substitution has occurred.
相對於本發明的組成物的總量,通式(L)所示的化合物的較佳含量的下限值為1%、10%、20%、30%、40%、50%、55%、60%、65%、70%、75%、80%。較佳含量的上限值為95%、85%、75%、65%、55%、45%、35%、25%。Relative to the total amount of the composition of the present invention, the lower limit of the preferred content of the compound represented by the general formula (L) is 1%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%.
相對於本發明的組成物的總量,通式(i)、通式(L)、通式(N-1d)、通式(N-1)及通式(II)所示的化合物的較佳含量的下限值為50%、55%、60%、65%、70%、75%、80%、85%、90%、95%、99%、100%。較佳含量的上限值為100%、95%、85%、75%、65%。Relative to the total amount of the composition of the present invention, the comparison of compounds represented by general formula (i), general formula (L), general formula (N-1d), general formula (N-1) and general formula (II) The lower limit of the optimum content is 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 99%, 100%. The upper limit of the preferred content is 100%, 95%, 85%, 75%, 65%.
為了解決本發明的課題,較佳為上述的下限值高且上限值高。In order to solve the problem of the present invention, it is preferable that the above-mentioned lower limit value is high and the upper limit value is high.
在重視可靠性時,較佳為R L1及R L2均為烷基,在重視黏性的下降時,較佳為至少一者為烯基。 When reliability is important, both R L1 and R L2 are preferably alkyl groups, and when viscosity reduction is important, at least one of them is preferably an alkenyl group.
存在於分子內的鹵素原子較佳為氟原子,其數量較佳為0、1、2或3個,較佳為0或1。The halogen atoms present in the molecule are preferably fluorine atoms, and the number thereof is preferably 0, 1, 2, or 3, preferably 0 or 1.
R L1及R L2在其所鍵合的環結構為苯基(芳香族)時,較佳為直鏈狀的碳原子數1至5的烷基、直鏈狀的碳原子數1至4的烷氧基及碳原子數4至5的烯基,在其所鍵合的環結構為環己烷、哌喃及二㗁烷等飽和的環結構時,較佳為直鏈狀的碳原子數1至5的烷基、直鏈狀的碳原子數1至4的烷氧基及直鏈狀的碳原子數2至5的烯基。為了使向列相穩定化,碳原子及存在氧原子時的氧原子的合計較佳為5以下,較佳為直鏈狀。 When the ring structure to which R L1 and R L2 are bonded is a phenyl group (aromatic), it is preferably a linear alkyl group having 1 to 5 carbon atoms, or a linear alkyl group having 1 to 4 carbon atoms. When the alkoxy group and the alkenyl group having 4 to 5 carbon atoms are bonded to a saturated ring structure such as cyclohexane, piperan, or dioxane, the number of carbon atoms is preferably linear An alkyl group of 1 to 5, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms in the presence of oxygen atoms is preferably 5 or less, and is preferably linear.
作為烯基,較佳為選自由式(R1)至式(R5)中的任一者所示的基團(各式中的黑點表示環結構中的碳原子)。The alkenyl group is preferably a group selected from any one of formula (R1) to formula (R5) (black dots in each formula represent carbon atoms in the ring structure).
關於n L1,在重視應答速度時較佳為0,為了改善向列相的上限溫度則較佳為2或3,為了取得該等的平衡則較佳為1。又,為了滿足作為液晶組成物所要求的特性,較佳為將不同值的化合物組合。 Regarding n L1 , 0 is preferable when the response speed is important, 2 or 3 is preferable in order to improve the upper limit temperature of the nematic phase, and 1 is preferable in order to balance these. Moreover, in order to satisfy the characteristics required as a liquid crystal composition, it is preferable to combine compounds of different values.
關於A L1、A L2及A L3,在需要增大Δn時較佳為芳香族,為了改善應答速度則較佳為脂肪族,較佳為分別獨立地表示反-1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、3-氟-1,4-伸苯基、3,5-二氟-1,4-伸苯基、1,4-伸環己烯基、1,4-雙環[2.2.2]伸辛基、哌啶-1,4-二基、萘-2,6-二基、十氫萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基,更佳為表示下述的結構, Regarding A L1 , A L2 and A L3 , when it is necessary to increase Δn, they are preferably aromatic, in order to improve the response speed, they are preferably aliphatic, and each independently represents trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, 1,4 -Cyclohexenyl, 1,4-bicyclo[2.2.2]octyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl Or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, more preferably the following structure,
更佳為表示反-1,4-伸環己基或1,4-伸苯基。More preferably, it represents trans-1,4-cyclohexylene or 1,4-phenylene.
關於Z L1及Z L2,在重視應答速度時,較佳為單鍵。 Regarding Z L1 and Z L2 , when the response speed is important, a single key is preferable.
通式(L)所示的化合物較佳分子內的鹵原子數量為0個或1個。The compound represented by the general formula (L) preferably has 0 or 1 halogen atoms in the molecule.
通式(L)所示的化合物較佳為選自通式(L-1)至(L-7)所示的化合物群中的化合物。The compound represented by general formula (L) is preferably a compound selected from the group of compounds represented by general formulas (L-1) to (L-7).
通式(L-1)所示的化合物為下述的化合物。The compound represented by the general formula (L-1) is the following compound.
(式中,R L11及R L12分別獨立地表示與通式(L)中的R L1及R L2相同意義)。 (In the formula, R L11 and R L12 each independently represent the same meaning as R L1 and R L2 in the general formula (L)).
R L11及R L12較佳為直鏈狀的碳原子數1至5的烷基、直鏈狀的碳原子數1至4的烷氧基及直鏈狀的碳原子數2至5的烯基。 R L11 and R L12 are preferably linear alkyl having 1 to 5 carbon atoms, linear alkoxy having 1 to 4 carbon atoms, and linear alkenyl having 2 to 5 carbon atoms .
通式(L-1)所示的化合物可單獨使用,亦可將兩種以上的化合物組合使用。可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能適當組合使用。關於所使用的化合物的種類,例如,作為本發明的一個實施方式,為1種、2種、3種、4種、5種以上。The compound represented by the general formula (L-1) may be used alone, or two or more compounds may be used in combination. The types of compounds that can be combined are not particularly limited, and are used in appropriate combinations according to required properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. Regarding the kind of compound used, for example, as an embodiment of the present invention, there are one kind, two kinds, three kinds, four kinds, and five or more kinds.
較佳含量的下限值相對於本發明的組成物的總量為1%、2%、3%、5%、7%、10%。較佳含量的上限值相對於本發明的組成物的總量為40%、35%、33%、30%、25%。The lower limit of the preferable content is 1%, 2%, 3%, 5%, 7%, 10% relative to the total amount of the composition of the present invention. The upper limit of the preferable content is 40%, 35%, 33%, 30%, 25% relative to the total amount of the composition of the present invention.
在需要使本發明的組成物的黏度保持較低、需要應答速度快的組成物時,較佳為上述的下限值高且上限值高。進而,在需要使本發明的組成物的Tni保持較高、需要溫度穩定性良好的組成物時,較佳為上述的下限值為中等且上限值為中等。又,在為了將驅動電壓保持較低而欲增大介電常數各向異性時,較佳為上述的下限值低且上限值低。對於提高視野角特性而言,較不佳為使上限值增大。When it is necessary to keep the viscosity of the composition of the present invention low and a composition with a fast response speed is required, it is preferable that the above-mentioned lower limit is high and the upper limit is high. Furthermore, when it is necessary to keep the Tni of the composition of the present invention high and a composition with good temperature stability is required, it is preferable that the above-mentioned lower limit is medium and the upper limit is medium. Moreover, when it is desired to increase the dielectric constant anisotropy in order to keep the driving voltage low, it is preferable that the above-mentioned lower limit value is low and the upper limit value is low. In terms of improving the viewing angle characteristics, it is not preferable to increase the upper limit value.
通式(L-1)所示的化合物較佳為選自通式(L-1-1)所示的化合物群中的化合物。The compound represented by general formula (L-1) is preferably a compound selected from the group of compounds represented by general formula (L-1-1).
(式中,R L12表示與通式(L-1)中的R L2相同意義)。 (In the formula, R L12 has the same meaning as R L2 in the general formula (L-1)).
通式(L-1-1)所示的化合物較佳為選自式(L-1-1.1)至式(L-1-1.3)所示的化合物群中的化合物,較佳為式(L-1-1.2)或式(L-1-1.3)所示的化合物,尤佳為式(L-1-1.3)所示的化合物。The compound represented by general formula (L-1-1) is preferably a compound selected from the group of compounds represented by formula (L-1-1.1) to formula (L-1-1.3), and is preferably a compound represented by formula (L-1-1.1) to (L-1-1.3). The compound represented by -1-1.2) or formula (L-1-1.3) is particularly preferably a compound represented by formula (L-1-1.3).
相對於本發明的組成物的總量,式(L-1-1.3)所示的化合物的較佳含量的下限值為1%、2%、3%、5%、7%、10%。較佳含量的上限值相對於本發明的組成物的總量為20%、15%、13%、10%、8%、7%、6%、5%、3%。The lower limit of the preferable content of the compound represented by formula (L-1-1.3) is 1%, 2%, 3%, 5%, 7%, 10% relative to the total amount of the composition of the present invention. The upper limit of the preferred content is 20%, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3% relative to the total amount of the composition of the present invention.
通式(L-1)所示的化合物較佳為選自通式(L-1-2)所示的化合物群中的化合物。The compound represented by general formula (L-1) is preferably a compound selected from the group of compounds represented by general formula (L-1-2).
(式中,R L12表示與通式(L-1)中的R L2相同意義)。 (In the formula, R L12 has the same meaning as R L2 in the general formula (L-1)).
相對於本發明的組成物的總量,式(L-1-2)所示的化合物的較佳含量的下限值為1%、5%、10%、15%、17%、20%、23%、25%、27%、30%、35%。較佳含量的上限值相對於本發明的組成物的總量為60%、55%、50%、45%、42%、40%、38%、35%、33%、30%。Relative to the total amount of the composition of the present invention, the lower limit of the preferable content of the compound represented by formula (L-1-2) is 1%, 5%, 10%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 35%. The upper limit of the preferable content is 60%, 55%, 50%, 45%, 42%, 40%, 38%, 35%, 33%, 30% relative to the total amount of the composition of the present invention.
進而,通式(L-1-2)所示的化合物較佳為選自式(L-1-2.1)至式(L-1-2.4)所示的化合物群中的化合物,較佳為式(L-1-2.2)至式(L-1-2.4)所示的化合物。特別是式(L-1-2.2)所示的化合物,由於特別改善本發明的組成物的應答速度而較佳。又,在與應答速度相比更要求高Tni時,較佳為使用式(L-1-2.3)或式(L-1-2.4)所示的化合物。關於式(L-1-2.3)及式(L-1-2.4)所示的化合物的含量,為了使低溫時的溶解度良好,較不佳為設為30%以上。Furthermore, the compound represented by general formula (L-1-2) is preferably a compound selected from the group of compounds represented by formula (L-1-2.1) to formula (L-1-2.4), preferably (L-1-2.2) to the compound represented by formula (L-1-2.4). In particular, the compound represented by the formula (L-1-2.2) is preferable because it particularly improves the response speed of the composition of the present invention. In addition, when Tni is required to be higher than the response speed, it is preferable to use a compound represented by formula (L-1-2.3) or formula (L-1-2.4). Regarding the content of the compound represented by the formula (L-1-2.3) and the formula (L-1-2.4), in order to improve the solubility at low temperatures, it is less preferable to be 30% or more.
相對於本發明的組成物的總量,式(L-1-2.2)所示的化合物的較佳含量的下限值為10%、15%、18%、20%、23%、25%、27%、30%、33%、35%、38%、40%。較佳含量的上限值相對於本發明的組成物的總量為60%、55%、50%、45%、43%、40%、38%、35%、32%、30%、27%、25%、22%。Relative to the total amount of the composition of the present invention, the lower limit of the preferred content of the compound represented by formula (L-1-2.2) is 10%, 15%, 18%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 38%, 40%. The upper limit of the preferred content relative to the total amount of the composition of the present invention is 60%, 55%, 50%, 45%, 43%, 40%, 38%, 35%, 32%, 30%, 27% , 25%, 22%.
相對於本發明的組成物的總量,式(L-1-1.3)所示的化合物與式(L-1-2.2)所示的化合物的合計較佳含量的下限值為10%、15%、20%、25%、27%、30%、35%、40%。較佳含量的上限值相對於本發明的組成物的總量為60%、55%、50%、45%、43%、40%、38%、35%、32%、30%、27%、25%、22%。The lower limit of the total content of the compound represented by formula (L-1-1.3) and the compound represented by formula (L-1-2.2) is preferably 10%, 15% relative to the total amount of the composition of the present invention. %, 20%, 25%, 27%, 30%, 35%, 40%. The upper limit of the preferred content relative to the total amount of the composition of the present invention is 60%, 55%, 50%, 45%, 43%, 40%, 38%, 35%, 32%, 30%, 27% , 25%, 22%.
通式(L-1)所示的化合物較佳為選自通式(L-1-3)所示的化合物群中的化合物。The compound represented by general formula (L-1) is preferably a compound selected from the group of compounds represented by general formula (L-1-3).
(式中,R L13及R L14分別獨立地表示碳原子數1至8的烷基或碳原子數1至8的烷氧基)。 (In the formula, R L13 and R L14 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms).
R L13及R L14較佳為直鏈狀的碳原子數1至5的烷基、直鏈狀的碳原子數1至4的烷氧基及直鏈狀的碳原子數2至5的烯基。 R L13 and R L14 are preferably linear alkyl having 1 to 5 carbon atoms, linear alkoxy having 1 to 4 carbon atoms, and linear alkenyl having 2 to 5 carbon atoms .
相對於本發明的組成物的總量,式(L-1-3)所示的化合物的較佳含量的下限值為1%、5%、10%、13%、15%、17%、20%、23%、25%、30%。較佳含量的上限值相對於本發明的組成物的總量為60%、55%、50%、45%、40%、37%、35%、33%、30%、27%、25%、23%、20%、17%、15%、13%、10%。Relative to the total amount of the composition of the present invention, the lower limit of the preferable content of the compound represented by formula (L-1-3) is 1%, 5%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 30%. The upper limit of the preferred content relative to the total amount of the composition of the present invention is 60%, 55%, 50%, 45%, 40%, 37%, 35%, 33%, 30%, 27%, 25% , 23%, 20%, 17%, 15%, 13%, 10%.
進而,通式(L-1-3)所示的化合物較佳為選自式(L-1-3.1)至式(L-1-3.12)所示的化合物群中的化合物,較佳為式(L-1-3.1)、式(L-1-3.3)或式(L-1-3.4)所示的化合物。特別是式(L-1-3.1)所示的化合物,由於特別改善本發明的組成物的應答速度而較佳。又,在與應答速度相比更要求高Tni時,較佳為使用式(L-1-3.3)、式(L-1-3.4)、式(L-1-3.11)及式(L-1-3.12)所示的化合物。關於式(L-1-3.3)、式(L-1-3.4)、式(L-1-3.11)及式(L-1-3.12)所示的化合物的合計含量,為了使低溫時的溶解度良好,較不佳為設為20%以上。Furthermore, the compound represented by general formula (L-1-3) is preferably a compound selected from the group of compounds represented by formula (L-1-3.1) to formula (L-1-3.12), preferably (L-1-3.1), a compound represented by formula (L-1-3.3) or formula (L-1-3.4). In particular, the compound represented by the formula (L-1-3.1) is preferable because it particularly improves the response speed of the composition of the present invention. In addition, when a higher Tni is required than the response speed, it is better to use the formula (L-1-3.3), formula (L-1-3.4), formula (L-1-3.11) and formula (L-1 -3.12) The compound shown in. Regarding the total content of the compounds represented by formula (L-1-3.3), formula (L-1-3.4), formula (L-1-3.11) and formula (L-1-3.12), in order to make the solubility at low temperature It is good, and less preferable is set to 20% or more.
相對於本發明的組成物的總量,式(L-1-3.1)所示的化合物的較佳含量的下限值為1%、2%、3%、5%、7%、10%、13%、15%、18%、20%。較佳含量的上限值相對於本發明的組成物的總量為20%、18%、17%、15%、13%、10%、8%、7%、6%。Relative to the total amount of the composition of the present invention, the lower limit of the preferable content of the compound represented by formula (L-1-3.1) is 1%, 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18%, 20%. The upper limit of the preferable content is 20%, 18%, 17%, 15%, 13%, 10%, 8%, 7%, 6% relative to the total amount of the composition of the present invention.
為了解決本發明的課題,較佳為將選自式(L-1-3.1)、式(L-1-3.3)、式(L-1-3.4)、式(L-1-3.11)及式(L-1-3.12)所示的化合物群中的兩種以上的化合物組合。在重視應答速度時,亦較佳為使用式(L-1-1.3)所示的化合物。In order to solve the problem of the present invention, it is preferable to select from formula (L-1-3.1), formula (L-1-3.3), formula (L-1-3.4), formula (L-1-3.11) and formula A combination of two or more compounds in the compound group shown in (L-1-3.12). When attaching importance to response speed, it is also preferable to use the compound represented by formula (L-1-1.3).
通式(L-2)所示的化合物為下述的化合物。The compound represented by the general formula (L-2) is the following compound.
(式中,R L21及R L22分別獨立地表示與通式(L)中的R L1及R L2相同意義)。 (In the formula, R L21 and R L22 each independently represent the same meaning as R L1 and R L2 in the general formula (L)).
R L21較佳為碳原子數1至5的烷基或碳原子數2至5的烯基,R L22較佳為碳原子數1至5的烷基、碳原子數4至5的烯基或碳原子數1至4的烷氧基。 R L21 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R L22 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or An alkoxy group having 1 to 4 carbon atoms.
通式(L-2)所示的化合物可單獨使用,亦可將兩種以上的化合物組合使用。可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能適當組合使用。關於所使用的化合物的種類,例如,作為本發明的一個實施方式,為1種、2種、3種、4種、5種以上。The compound represented by the general formula (L-2) may be used alone, or two or more compounds may be used in combination. The types of compounds that can be combined are not particularly limited, and are used in appropriate combinations according to required properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. Regarding the kind of compound used, for example, as an embodiment of the present invention, there are one kind, two kinds, three kinds, four kinds, and five or more kinds.
在重視低溫時的溶解性時,將含量設定得多一些則效果高,相對地,在重視應答速度時,將含量設定得少一些則效果高。進而,在改良滴痕、殘影特性的情況下,較佳為將含量的範圍設定為中等。When focusing on the solubility at low temperatures, setting the content to a larger amount will result in a higher effect, whereas when focusing on the response speed, setting the content to a lower amount will result in a higher effect. Furthermore, in the case of improving drip marks and residual image characteristics, it is preferable to set the range of the content to a medium level.
相對於藉由本發明的製造方法得到的液晶組成物(或液晶混合物)的總量,式(L-2)所示的化合物的較佳含量的下限值為1%、2%、3%、5%、7%、10%。較佳含量的上限值相對於藉由本發明的製造方法得到的液晶組成物(或液晶混合物)的總量為20%、18%、15%、13%、10%、8%、7%、6%、5%、3%。With respect to the total amount of the liquid crystal composition (or liquid crystal mixture) obtained by the production method of the present invention, the lower limit of the preferable content of the compound represented by formula (L-2) is 1%, 2%, 3%, 5%, 7%, 10%. The upper limit of the preferred content is 20%, 18%, 15%, 13%, 10%, 8%, 7%, relative to the total amount of the liquid crystal composition (or liquid crystal mixture) obtained by the manufacturing method of the present invention. 6%, 5%, 3%.
進而,通式(L-2)所示的化合物較佳為選自式(L-2.1)至式(L-2.6)所示的化合物群中的化合物,較佳為式(L-2.1)、式(L-2.3)、式(L-2.4)及式(L-2.6)所示的化合物。Furthermore, the compound represented by general formula (L-2) is preferably a compound selected from the group of compounds represented by formula (L-2.1) to formula (L-2.6), preferably formula (L-2.1), Compounds represented by formula (L-2.3), formula (L-2.4) and formula (L-2.6).
通式(L-3)所示的化合物為下述的化合物。The compound represented by general formula (L-3) is the following compound.
(式中,R L31及R L32分別獨立地表示與通式(L)中的R L1及R L2相同意義,但R L32不表示烷氧基或烯氧基。其中,R L31及R L32分別獨立地較佳為碳原子數1至5的烷基或碳原子數4至5的烯基)。 (In the formula, R L31 and R L32 each independently represent the same meaning as R L1 and R L2 in the general formula (L) , but R L32 does not represent an alkoxy group or an alkenyloxy group. Wherein, R L31 and R L32 respectively It is independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 to 5 carbon atoms).
通式(L-3)所示的化合物可單獨使用,亦可將兩種以上的化合物組合使用。可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能適當組合使用。關於所使用的化合物的種類,例如,作為本發明的一個實施方式,為1種、2種、3種、4種、5種以上。The compound represented by the general formula (L-3) may be used alone, or two or more compounds may be used in combination. The types of compounds that can be combined are not particularly limited, and are used in appropriate combinations according to required properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. Regarding the kind of compound used, for example, as an embodiment of the present invention, there are one kind, two kinds, three kinds, four kinds, and five or more kinds.
相對於藉由本發明的製造方法得到的液晶組成物(或液晶混合物)的總量,式(L-3)所示的化合物的較佳含量的下限值為1%、2%、3%、5%、7%、10%。較佳含量的上限值相對於藉由本發明的製造方法得到的液晶組成物(或液晶混合物)的總量為20%、15%、13%、10%、8%、7%、6%、5%、3%。With respect to the total amount of the liquid crystal composition (or liquid crystal mixture) obtained by the production method of the present invention, the lower limit of the preferable content of the compound represented by formula (L-3) is 1%, 2%, 3%, 5%, 7%, 10%. The upper limit of the preferred content is 20%, 15%, 13%, 10%, 8%, 7%, 6%, relative to the total amount of the liquid crystal composition (or liquid crystal mixture) obtained by the manufacturing method of the present invention. 5%, 3%.
在得到高的雙折射率的情況下,將含量設定得多一些則效果高,相對地,在重視高的Tni的情況下,將含量設定得少一些則效果高。進而,在改良滴痕、殘影特性的情況下,較佳為將含量的範圍設定為中等。In the case of obtaining a high birefringence, the effect is high if the content is set larger, while the effect is relatively high if the content is set smaller if the high Tni is emphasized. Furthermore, in the case of improving drip marks and residual image characteristics, it is preferable to set the range of the content to a medium level.
進而,通式(L-3)所示的化合物較佳為選自式(L-3.1)至式(L-3.4)所示的化合物群中的化合物,進而較佳為式(L-3.1)或式(L-3.4)所示的化合物。Furthermore, the compound represented by general formula (L-3) is preferably a compound selected from the group of compounds represented by formula (L-3.1) to formula (L-3.4), and more preferably formula (L-3.1) Or the compound represented by formula (L-3.4).
通式(L-4)所示的化合物為下述的化合物。The compound represented by general formula (L-4) is the following compound.
(式中,R L41及R L42分別獨立地表示與通式(L)中的R L1及R L2相同意義)。 (In the formula, R L41 and R L42 each independently represent the same meaning as R L1 and R L2 in the general formula (L)).
R L41較佳為碳原子數1至5的烷基或碳原子數2至5的烯基,R L42較佳為碳原子數1至5的烷基、碳原子數4至5的烯基或碳原子數1至4的烷氧基)。 R L41 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R L42 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or Alkoxy having 1 to 4 carbon atoms).
通式(L-4)所示的化合物可單獨使用,亦可將兩種以上的化合物組合使用。可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能適當組合使用。關於所使用的化合物的種類,例如,作為本發明的一個實施方式,為1種、2種、3種、4種、5種以上。The compound represented by the general formula (L-4) may be used alone, or two or more compounds may be used in combination. The types of compounds that can be combined are not particularly limited, and are used in appropriate combinations according to required properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. Regarding the kind of compound used, for example, as an embodiment of the present invention, there are one kind, two kinds, three kinds, four kinds, and five or more kinds.
在本發明的組成物中,通式(L-4)所示的化合物的含量需要根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率、製程適應性、滴痕、殘影、介電常數各向異性等所要求的性能來適當調整。In the composition of the present invention, the content of the compound represented by the general formula (L-4) needs to be based on solubility at low temperature, transition temperature, electrical reliability, birefringence, process adaptability, drip marks, residual image, The required performance such as dielectric anisotropy can be adjusted appropriately.
相對於本發明的組成物的總量,式(L-4)所示的化合物的較佳含量的下限值為1%、2%、3%、5%、7%、10%、14%、16%、20%、23%、26%、30%、35%、40%。相對於本發明的組成物的總量,式(L-4)所示的化合物的較佳含量的上限值為50%、40%、35%、30%、20%、15%、10%、5%。Relative to the total amount of the composition of the present invention, the lower limit of the preferred content of the compound represented by formula (L-4) is 1%, 2%, 3%, 5%, 7%, 10%, 14% , 16%, 20%, 23%, 26%, 30%, 35%, 40%. Relative to the total amount of the composition of the present invention, the upper limit of the preferred content of the compound represented by formula (L-4) is 50%, 40%, 35%, 30%, 20%, 15%, 10% , 5%.
通式(L-4)所示的化合物較佳為例如式(L-4.1)至式(L-4.3)所示的化合物。The compound represented by general formula (L-4) is preferably, for example, a compound represented by formula (L-4.1) to formula (L-4.3).
根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能,可含有式(L-4.1)所示的化合物,亦可含有式(L-4.2)所示的化合物,亦可含有式(L-4.1)所示的化合物及式(L-4.2)所示的化合物此兩者,亦可含有式(L-4.1)至式(L-4.3)所示的全部化合物。相對於本發明的組成物的總量,式(L-4.1)或式(L-4.2)所示的化合物的較佳含量的下限值為3%、5%、7%、9%、11%、12%、13%、18%、21%,較佳的上限值為45%、40%、35%、30%、25%、23%、20%、18%、15%、13%、10%、8%。According to the required properties such as solubility at low temperature, transition temperature, electrical reliability, birefringence, etc., it may contain the compound represented by formula (L-4.1) or the compound represented by formula (L-4.2), It may contain both the compound represented by formula (L-4.1) and the compound represented by formula (L-4.2), and may contain all the compounds represented by formula (L-4.1) to formula (L-4.3). The lower limit of the preferable content of the compound represented by formula (L-4.1) or formula (L-4.2) is 3%, 5%, 7%, 9%, 11 relative to the total amount of the composition of the present invention. %, 12%, 13%, 18%, 21%, the preferred upper limit value is 45%, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13% , 10%, 8%.
在含有式(L-4.1)所示的化合物及式(L-4.2)所示的化合物此兩者的情況下,相對於本發明的組成物的總量,兩化合物的較佳含量的下限值為15%、19%、24%、30%,較佳的上限值為45%、40%、35%、30%、25%、23%、20%、18%、15%、13%。In the case of containing both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2), the lower limit of the preferable content of the two compounds relative to the total amount of the composition of the present invention Values are 15%, 19%, 24%, 30%, and the preferred upper limit values are 45%, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13% .
通式(L-4)所示的化合物較佳為例如式(L-4.4)至式(L-4.6)所示的化合物,較佳為式(L-4.4)所示的化合物。The compound represented by general formula (L-4) is preferably, for example, a compound represented by formula (L-4.4) to formula (L-4.6), and is preferably a compound represented by formula (L-4.4).
根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能,可含有式(L-4.4)所示的化合物,亦可含有式(L-4.5)所示的化合物,亦可含有式(L-4.4)所示的化合物及式(L-4.5)所示的化合物此兩者。According to the required properties such as solubility at low temperature, transition temperature, electrical reliability, birefringence, etc., it may contain the compound represented by formula (L-4.4) or the compound represented by formula (L-4.5), It may contain both the compound represented by formula (L-4.4) and the compound represented by formula (L-4.5).
相對於本發明的組成物的總量,式(L-4.4)或式(L-4.5)所示的化合物的較佳含量的下限值為3%、5%、7%、9%、11%、12%、13%、18%、21%。較佳的上限值為45%、40%、35%、30%、25%、23%、20%、18%、15%、13%、10%、8%。The lower limit of the preferable content of the compound represented by formula (L-4.4) or formula (L-4.5) is 3%, 5%, 7%, 9%, 11 relative to the total amount of the composition of the present invention. %, 12%, 13%, 18%, 21%. The preferred upper limit value is 45%, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%.
含有式(L-4.4)所示的化合物及式(L-4.5)所示的化合物此兩者的情況下,相對於本發明的組成物的總量,兩化合物的較佳含量的下限值為15%、19%、24%、30%,較佳的上限值為45%、40%、35%、30%、25%、23%、20%、18%、15%、13%。In the case of containing both the compound represented by the formula (L-4.4) and the compound represented by the formula (L-4.5), the lower limit of the preferable content of the two compounds relative to the total amount of the composition of the present invention It is 15%, 19%, 24%, 30%, and the preferable upper limit value is 45%, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%.
通式(L-4)所示的化合物較佳為式(L-4.7)至式(L-4.10)所示的化合物,尤佳為式(L-4.9)所示的化合物。The compound represented by general formula (L-4) is preferably a compound represented by formula (L-4.7) to formula (L-4.10), and is particularly preferably a compound represented by formula (L-4.9).
通式(L-5)所示的化合物為下述的化合物。The compound represented by general formula (L-5) is the following compound.
(式中,R L51及R L52分別獨立地表示與通式(L)中的R L1及R L2相同意義,但R L52不表示烷氧基或烯氧基。其中,R L51及R L52分別獨立地較佳為碳原子數1至5的烷基或碳原子數2至5的烯基。 (In the formula, R L51 and R L52 each independently represent the same meaning as R L1 and R L2 in the general formula (L) , but R L52 does not represent an alkoxy group or an alkenyloxy group. Wherein, R L51 and R L52 respectively It is independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.
通式(L-5)所示的化合物可單獨使用,亦可將兩種以上的化合物組合使用。可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能適當組合使用。關於所使用的化合物的種類,例如,作為本發明的一個實施方式,為1種、2種、3種、4種、5種以上。The compound represented by the general formula (L-5) may be used alone, or two or more compounds may be used in combination. The types of compounds that can be combined are not particularly limited, and are used in appropriate combinations according to required properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. Regarding the kind of compound used, for example, as an embodiment of the present invention, there are one kind, two kinds, three kinds, four kinds, and five or more kinds.
在本發明的組成物中,通式(L-5)所示的化合物的含量需要根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率、製程適應性、滴痕、殘影、介電常數各向異性等所要求的性能適當調整。In the composition of the present invention, the content of the compound represented by the general formula (L-5) needs to be based on solubility at low temperature, transition temperature, electrical reliability, birefringence, process adaptability, drip marks, residual image, The required performance such as dielectric anisotropy is adjusted appropriately.
相對於本發明的組成物的總量,式(L-5)所示的化合物的較佳含量的下限值為1%、2%、3%、5%、7%、10%、14%、16%、20%、23%、26%、30%、35%、40%。相對於本發明的組成物的總量,式(L-5)所示的化合物的較佳含量的上限值為50%、40%、35%、30%、20%、15%、10%、5%。Relative to the total amount of the composition of the present invention, the lower limit of the preferred content of the compound represented by formula (L-5) is 1%, 2%, 3%, 5%, 7%, 10%, 14% , 16%, 20%, 23%, 26%, 30%, 35%, 40%. Relative to the total amount of the composition of the present invention, the upper limit of the preferred content of the compound represented by formula (L-5) is 50%, 40%, 35%, 30%, 20%, 15%, 10% , 5%.
通式(L-5)所示的化合物較佳為式(L-5.1)、式(L-5.2)或式(L-5.3)所示的化合物,尤佳為式(L-5.1)或式(L-5.2)所示的化合物。The compound represented by the general formula (L-5) is preferably the compound represented by the formula (L-5.1), the formula (L-5.2) or the formula (L-5.3), and particularly preferably the formula (L-5.1) or the formula The compound shown in (L-5.2).
相對於本發明的組成物的總量,該等化合物的較佳含量的下限值為1%、2%、3%、5%、7%。該等化合物的較佳含量的上限值為20%、15%、13%、10%、9%。Relative to the total amount of the composition of the present invention, the lower limit of the preferable content of these compounds is 1%, 2%, 3%, 5%, 7%. The upper limit of the preferred content of these compounds is 20%, 15%, 13%, 10%, 9%.
通式(L-5)所示的化合物較佳為式(L-5.4)或式(L-5.5)所示的化合物。The compound represented by general formula (L-5) is preferably a compound represented by formula (L-5.4) or formula (L-5.5).
相對於本發明的組成物的總量,該等化合物的較佳含量的下限值為1%、2%、3%、5%、7%。該等化合物的較佳含量的上限值為20%、15%、13%、10%、9%。Relative to the total amount of the composition of the present invention, the lower limit of the preferable content of these compounds is 1%, 2%, 3%, 5%, 7%. The upper limit of the preferred content of these compounds is 20%, 15%, 13%, 10%, 9%.
通式(L-6)所示的化合物為下述的化合物。The compound represented by general formula (L-6) is the following compound.
(式中,R L61及R L62分別獨立地表示與通式(L)中的R L1及R L2相同意義,X L61、X L62、X L63及X L64分別獨立地表示氫原子或氟原子,但X L61~X L64中的2個以上不同時表示氟原子)。 (In the formula, R L61 and R L62 each independently represent the same meaning as R L1 and R L2 in the general formula (L), and X L61 , X L62 , X L63 and X L64 each independently represent a hydrogen atom or a fluorine atom, However , two or more of X L61 to X L64 do not simultaneously represent a fluorine atom).
通式(L-6)所示的化合物可單獨使用,亦可將兩種以上的化合物組合使用。可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能適當組合使用。關於所使用的化合物的種類,例如,作為本發明的一個實施方式,為1種、2種、3種、4種、5種以上。The compound represented by the general formula (L-6) may be used alone, or two or more compounds may be used in combination. The types of compounds that can be combined are not particularly limited, and are used in appropriate combinations according to required properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. Regarding the kind of compound used, for example, as an embodiment of the present invention, there are one kind, two kinds, three kinds, four kinds, and five or more kinds.
相對於本發明的組成物的總量,式(L-6)所示的化合物的較佳含量的下限值為1%、2%、3%、5%、7%、10%、14%、16%、20%、23%、26%、30%、35%、40%。相對於本發明的組成物的總量,式(L-6)所示的化合物的較佳含量的上限值為50%、40%、35%、30%、20%、15%、10%、5%。當重點在於增大Δn時,較佳為將含量設為較多,當重點在於低溫時的析出時,較佳為含量少。Relative to the total amount of the composition of the present invention, the lower limit of the preferred content of the compound represented by formula (L-6) is 1%, 2%, 3%, 5%, 7%, 10%, 14% , 16%, 20%, 23%, 26%, 30%, 35%, 40%. Relative to the total amount of the composition of the present invention, the upper limit of the preferred content of the compound represented by formula (L-6) is 50%, 40%, 35%, 30%, 20%, 15%, 10% , 5%. When the emphasis is on increasing Δn, it is preferable to set the content to be larger, and when the emphasis is on precipitation at low temperature, it is preferable to set the content to be small.
通式(L-6)所示的化合物較佳為式(L-6.1)至式(L-6.6)所示的化合物。The compound represented by general formula (L-6) is preferably a compound represented by formula (L-6.1) to formula (L-6.6).
可組合的化合物的種類沒有特別限制,較佳為含有該等化合物中的1種至3種,進而較佳為含有1種至4種。There are no particular restrictions on the types of compounds that can be combined, but it is preferable to contain one to three of these compounds, and it is more preferable to contain one to four.
相對於本發明的組成物的總量,該等化合物的較佳含量的下限值為1%、2%、3%、5%、7%。該等化合物的較佳含量的上限值為20%、15%、13%、10%、9%。Relative to the total amount of the composition of the present invention, the lower limit of the preferable content of these compounds is 1%, 2%, 3%, 5%, 7%. The upper limit of the preferred content of these compounds is 20%, 15%, 13%, 10%, 9%.
通式(L-7)所示的化合物為下述的化合物。The compound represented by general formula (L-7) is the following compound.
(式中,R L71及R L72分別獨立地表示與通式(L)中的R L1及R L2相同意義,A L71及A L72分別獨立地表示與通式(L)中的A L2及A L3相同意義,A L71及A L72上的氫原子可分別獨立地被氟原子取代,Z L71表示與通式(L)中的Z L2相同意義,X L71及X L72分別獨立地表示氟原子或氫原子,但不同時表示氟原子)。 (In the formula, R L71 and R L72 independently represent the same meaning as R L1 and R L2 in general formula (L), and A L71 and A L72 independently represent the same meaning as A L2 and A in general formula (L). L3 has the same meaning, the hydrogen atoms on A L71 and A L72 can be independently replaced by fluorine atoms, Z L71 has the same meaning as Z L2 in the general formula (L), and X L71 and X L72 each independently represent a fluorine atom or Hydrogen atom, but does not mean fluorine atom at the same time).
式中,R L71及R L72分別獨立地較佳為碳原子數1至5的烷基、碳原子數2至5的烯基或碳原子數1至4的烷氧基,A L71及A L72分別獨立地較佳為1,4-伸環己基或1,4-伸苯基,A L71及A L72上的氫原子可分別獨立地被氟原子取代,Z L71較佳為單鍵或COO-,較佳為單鍵,X L71及X L72較佳為氫原子。 In the formula, R L71 and R L72 are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, A L71 and A L72 Each independently is preferably 1,4-cyclohexylene or 1,4-phenylene . The hydrogen atoms on A L71 and A L72 may be independently substituted by fluorine atoms. Z L71 is preferably a single bond or COO- , Preferably a single bond, and X L71 and X L72 are preferably hydrogen atoms.
可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能進行組合。關於所使用的化合物的種類,例如,作為本發明的一個實施方式,為1種、2種、3種、4種。The types of compounds that can be combined are not particularly limited, and they are combined according to required properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. Regarding the kind of compound used, for example, as an embodiment of the present invention, there are one kind, two kinds, three kinds, and four kinds.
在本發明的組成物中,通式(L-7)所示的化合物的含量需要根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率、製程適應性、滴痕、殘影、介電常數各向異性等所要求的性能適當調整。In the composition of the present invention, the content of the compound represented by the general formula (L-7) needs to be based on solubility at low temperature, transition temperature, electrical reliability, birefringence, process adaptability, drip marks, residual image, The required performance such as dielectric anisotropy is adjusted appropriately.
相對於本發明的組成物的總量,式(L-7)所示的化合物的較佳含量的下限值為1%、2%、3%、5%、7%、10%、14%、16%、20%。相對於本發明的組成物的總量,式(L-7)所示的化合物的較佳含量的上限值為30%、25%、23%、20%、18%、15%、10%、5%。Relative to the total amount of the composition of the present invention, the lower limit of the preferred content of the compound represented by formula (L-7) is 1%, 2%, 3%, 5%, 7%, 10%, 14% , 16%, 20%. Relative to the total amount of the composition of the present invention, the upper limit of the preferred content of the compound represented by formula (L-7) is 30%, 25%, 23%, 20%, 18%, 15%, 10% , 5%.
就本發明的組成物而言,在期望為高T ni的實施方式時,較佳為將式(L-7)所示的化合物的含量設定得多一些,在期望為低黏度的實施方式時,較佳為將含量設定得少一些。 With regard to the composition of the present invention, when a high T ni embodiment is desired, it is preferable to set the content of the compound represented by formula (L-7) to be larger, and when a low viscosity embodiment is desired , It is better to set the content less.
進而,通式(L-7)所示的化合物較佳為式(L-7.11)至式(L-7.13)所示的化合物,較佳為式(L-7.11)所示的化合物。Furthermore, the compound represented by general formula (L-7) is preferably a compound represented by formula (L-7.11) to formula (L-7.13), and is preferably a compound represented by formula (L-7.11).
進而,通式(L-7)所示的化合物為式(L-7.21)至式(L-7.23)所示的化合物。較佳為式(L-7.21)所示的化合物。Furthermore, the compound represented by general formula (L-7) is a compound represented by formula (L-7.21) to formula (L-7.23). Preferably, it is a compound represented by formula (L-7.21).
進而,通式(L-7)所示的化合物較佳為式(L-7.31)至式(L-7.34)所示的化合物,較佳為式(L-7.31)或/及式(L-7.32)所示的化合物。Furthermore, the compound represented by general formula (L-7) is preferably a compound represented by formula (L-7.31) to formula (L-7.34), preferably formula (L-7.31) or/and formula (L-7.31) 7.32) The compound shown in.
進而,通式(L-7)所示的化合物較佳為式(L-7.41)至式(L-7.44)所示的化合物,較佳為式(L-7.41)或/及式(L-7.42)所示的化合物。Furthermore, the compound represented by general formula (L-7) is preferably a compound represented by formula (L-7.41) to formula (L-7.44), preferably formula (L-7.41) or/and formula (L-7.41) 7.42) The compound shown in.
進而,通式(L-7)所示的化合物較佳為式(L-7.51)至式(L-7.53)所示的化合物。Furthermore, the compound represented by general formula (L-7) is preferably a compound represented by formula (L-7.51) to formula (L-7.53).
本發明的液晶組成物中,含有選自後述的通式(N-1d)及/或通式(N-1)所示的化合物群中的一種或兩種以上的化合物作為第三成分。The liquid crystal composition of the present invention contains one or two or more compounds selected from the group of compounds represented by the general formula (N-1d) and/or the general formula (N-1) described later as the third component.
通式(N-1d)所示的化合物屬於在介電性方面為負的化合物(Δε的符號為負且其絕對值大於2)。通式(N-1d)所示的化合物可僅使用一種,亦可使用兩種以上。The compound represented by the general formula (N-1d) is a compound that is negative in terms of dielectric properties (the sign of Δε is negative and its absolute value is greater than 2). Only one kind of the compound represented by general formula (N-1d) may be used, or two or more kinds may be used.
(式中,R Nd11及R Nd12分別獨立地表示碳原子數1至8的烷基,該烷基中的1個或不相鄰的2個以上的-CH 2-可分別獨立地被-CH=CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代,n Nd11表示1、2或3)。 (In the formula, R Nd11 and R Nd12 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH 2 -s in the alkyl group may be independently replaced by -CH =CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substitution, n Nd11 represents 1, 2 or 3).
通式(N-1d)中,R Nd11較佳為碳原子數1至8的烷基、碳原子數1至8的烷氧基、碳原子數2至8的烯基或碳原子數2至8的烯氧基,較佳為碳原子數1至5的烷基、碳原子數1至5的烷氧基、碳原子數2至5的烯基或碳原子數2至5的烯氧基,進而較佳為碳原子數1至5的烷基或碳原子數2至5的烯基,進而較佳為碳原子數2至5的烷基或碳原子數2至3的烯基,尤佳為碳原子數3的烯基(丙烯基)。較佳為直鏈狀的碳原子數1至5的烷基、直鏈狀的碳原子數1至4的烷氧基及直鏈狀的碳原子數2至5的烯基。為了使向列相穩定化,碳原子及存在氧原子時的氧原子的合計較佳為5以下,較佳為直鏈狀。尤佳為丙基。R Nd12較佳為碳原子數1至8的烷基、碳原子數1至8的烷氧基、碳原子數2至8的烯基或碳原子數2至8的烯氧基,較佳為碳原子數1至5的烷基、碳原子數1至5的烷氧基、碳原子數2至5的烯基或碳原子數2至5的烯氧基,進而較佳為碳原子數1至5的烷基或碳原子數2至5的烯基,進而較佳為碳原子數2至5的烷基或碳原子數2至3的烯基,尤佳為碳原子數3的烯基(丙烯基)。較佳為直鏈狀的碳原子數1至5的烷基、直鏈狀的碳原子數1至4的烷氧基及直鏈狀的碳原子數2至5的烯基。為了使向列相穩定化,碳原子及存在氧原子時的氧原子的合計較佳為5以下,較佳為直鏈狀。尤佳為甲氧基及乙氧基。 In the general formula (N-1d), R Nd11 is preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms. The alkenyloxy group of 8 is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms , More preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and still more preferably an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, especially Preferably, it is an alkenyl group having 3 carbon atoms (propenyl group). Preferably, it is a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms in the presence of oxygen atoms is preferably 5 or less, and is preferably linear. Especially preferred is propyl. R Nd12 is preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, preferably An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms, and more preferably a carbon atom number of 1 Alkyl group having to 5 or alkenyl group having 2 to 5 carbon atoms, more preferably alkyl group having 2 to 5 carbon atoms or alkenyl group having 2 to 3 carbon atoms, particularly preferably alkenyl group having 3 carbon atoms (Allyl). Preferably, it is a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms in the presence of oxygen atoms is preferably 5 or less, and is preferably linear. Particularly preferred are methoxy and ethoxy.
通式(N-1d)中,n Nd11較佳為1或2,較佳為同時含有n Nd11為1的化合物及n Nd11為2的化合物,又,亦較佳為僅含有n Nd11為2的化合物。 In the general formula (N-1d), n Nd11 is preferably 1 or 2, and preferably contains both a compound in which n Nd11 is 1 and a compound in which n Nd11 is 2, and also preferably contains only n Nd11 in 2. Compound.
通式(N-1d)所示的化合物較佳為通式(N-1-10)所示的化合物及通式(N-1-11)所示的化合物。The compound represented by general formula (N-1d) is preferably a compound represented by general formula (N-1-10) and a compound represented by general formula (N-1-11).
通式(N-1-10)所示的化合物為下述的化合物。The compound represented by general formula (N-1-10) is the following compound.
(式中,R N1101及R N1102分別獨立地表示與通式(N-1d)中的R Nd11及R Nd12相同意義)。 (In the formula, R N1101 and R N1102 each independently represent the same meaning as R Nd11 and R Nd12 in the general formula (N-1d)).
R N1101較佳為碳原子數1至5的烷基或碳原子數2至5的烯基,較佳為乙基、丙基、丁基、乙烯基或1-丙烯基。R N1102較佳為碳原子數1至5的烷基、碳原子數4至5的烯基或碳原子數1至4的烷氧基,較佳為乙氧基、丙氧基或丁氧基。 R N1101 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl, propyl, butyl, vinyl, or 1-propenyl group. R N1102 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, preferably ethoxy, propoxy or butoxy .
通式(N-1-10)所示的化合物可單獨使用,亦可將兩種以上的化合物組合使用。可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能適當組合使用。關於所使用的化合物的種類,例如,作為本發明的一個實施方式,為1種、2種、3種、4種、5種以上。The compound represented by the general formula (N-1-10) may be used alone, or two or more compounds may be used in combination. The types of compounds that can be combined are not particularly limited, and are used in appropriate combinations according to required properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. Regarding the kind of compound used, for example, as an embodiment of the present invention, there are one kind, two kinds, three kinds, four kinds, and five or more kinds.
在重視Δε的改善時,較佳為將含量設定得高一些,在重視低溫時的溶解性時,將含量設定得高一些則效果高,在重視T NI時,將含量設定得高一些則效果高。進而,在改良滴痕、殘影特性的情況下,較佳為將含量的範圍設定為中等。 When the improvement of Δε is important, it is better to set the content higher. When the solubility at low temperature is important, the effect is higher if the content is higher, and when T NI is important, the content is higher if the content is set higher. high. Furthermore, in the case of improving drip marks and residual image characteristics, it is preferable to set the range of the content to a medium level.
相對於本發明的組成物的總量,式(N-1-10)所示的化合物的較佳含量的下限值為5%、10%、13%、15%、17%、20%。較佳含量的上限值相對於本發明的組成物的總量為35%、30%、28%、25%、23%、20%、18%、15%、13%。The lower limit of the preferable content of the compound represented by formula (N-1-10) is 5%, 10%, 13%, 15%, 17%, 20% relative to the total amount of the composition of the present invention. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% relative to the total amount of the composition of the present invention.
進而,通式(N-1-10)所示的化合物較佳為選自式(N-1-10.1)至式(N-1-10.14)所示的化合物群中的化合物,更佳為選自式(N-1-10.1)至(N-1-10.5)所示的化合物,進而較佳為式(N-1-10.1)或式(N-1-10.2)所示的化合物,尤佳為式(N-1-10.2)所示的化合物。Furthermore, the compound represented by general formula (N-1-10) is preferably a compound selected from the group of compounds represented by formula (N-1-10.1) to formula (N-1-10.14), more preferably Compounds represented by formula (N-1-10.1) to (N-1-10.5) are more preferably compounds represented by formula (N-1-10.1) or formula (N-1-10.2), especially It is a compound represented by formula (N-1-10.2).
通式(N-1-11)所示的化合物為下述的化合物。The compound represented by general formula (N-1-11) is the following compound.
(式中,R N1111及R N1112分別獨立地表示與通式(N-1d)中的R Nd11及R Nd12相同意義)。 (In the formula, R N1111 and R N1112 each independently represent the same meaning as R Nd11 and R Nd12 in the general formula (N-1d)).
R N1111較佳為碳原子數1至5的烷基或碳原子數2至5的烯基,較佳為乙基、丙基、丁基、乙烯基或1-丙烯基。R N1112較佳為碳原子數1至5的烷基、碳原子數4至5的烯基或碳原子數1至4的烷氧基,較佳為乙氧基、丙氧基或丁氧基。 R N1111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl, propyl, butyl, vinyl, or 1-propenyl group. R N1112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, preferably ethoxy, propoxy or butoxy .
通式(N-1-11)所示的化合物可單獨使用,亦可將兩種以上的化合物組合使用。可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能適當組合使用。關於所使用的化合物的種類,例如,作為本發明的一個實施方式,為1種、2種、3種、4種、5種以上。The compound represented by the general formula (N-1-11) may be used alone, or two or more compounds may be used in combination. The types of compounds that can be combined are not particularly limited, and are used in appropriate combinations according to required properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. Regarding the kind of compound used, for example, as an embodiment of the present invention, there are one kind, two kinds, three kinds, four kinds, and five or more kinds.
在重視Δε的改善時,較佳為將含量設定得高一些,在重視低溫時的溶解性時,將含量設定得低一些則效果高,在重視T NI時,將含量設定得高一些則效果高。進而,在改良滴痕、殘影特性的情況下,較佳為將含量的範圍設定為中等。 When the improvement of Δε is important, it is better to set the content higher. When the solubility at low temperature is important, the effect is higher if the content is set lower, and when the T NI is important, the content is set higher for the effect. high. Furthermore, in the case of improving drip marks and residual image characteristics, it is preferable to set the range of the content to a medium level.
相對於本發明的組成物的總量,式(N-1-11)所示的化合物的較佳含量的下限值為5%、10%、13%、15%、17%、20%。較佳含量的上限值相對於本發明的組成物的總量為35%、30%、28%、25%、23%、20%、18%、15%、13%。The lower limit of the preferable content of the compound represented by formula (N-1-11) is 5%, 10%, 13%, 15%, 17%, 20% relative to the total amount of the composition of the present invention. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% relative to the total amount of the composition of the present invention.
進而,通式(N-1-11)所示的化合物較佳為選自式(N-1-11.1)至式(N-1-11.14)所示的化合物群中的化合物,更佳為式(N-1-11.1)至(N-1-11.4)所示的化合物,進而較佳為式(N-1-11.2)及式(N-1-11.4)所示的化合物。Furthermore, the compound represented by general formula (N-1-11) is preferably a compound selected from the group of compounds represented by formula (N-1-11.1) to formula (N-1-11.14), more preferably The compounds represented by (N-1-11.1) to (N-1-11.4) are more preferably compounds represented by formula (N-1-11.2) and formula (N-1-11.4).
作為式(N-1d)所示的化合物,較佳為使用一種或兩種以上的選自式(N-1-10.1)、式(N-1-10.2)、式(N-1-11.2)、式(N-1-11.4)及式(N-1-11.14)所示的化合物群中的化合物。As the compound represented by formula (N-1d), it is preferable to use one or two or more selected from formula (N-1-10.1), formula (N-1-10.2), and formula (N-1-11.2) , A compound in the group of compounds represented by formula (N-1-11.4) and formula (N-1-11.14).
通式(N-1)所示的化合物屬於在介電性方面為負的化合物(Δε的符號為負且其絕對值大於2)。通式(N-1)所示的化合物較佳為Δε為負且其絕對值大於3的化合物。又,通式(N-1)所示的化合物可僅使用一種,亦可使用兩種以上。The compound represented by the general formula (N-1) is a compound that is negative in terms of dielectric properties (the sign of Δε is negative and its absolute value is greater than 2). The compound represented by the general formula (N-1) is preferably a compound in which Δε is negative and its absolute value is greater than 3. Moreover, the compound represented by general formula (N-1) may use only 1 type, and may use 2 or more types.
(式中,R N11及R N12分別獨立地表示碳原子數1至8的烷基,該烷基中的1個或不相鄰的2個以上的-CH 2-可分別獨立地被-CH=CH-、-C≡C-、-O-、-CO-、-COO-或-OCO-取代,n N11及n N12分別獨立地表示0、1、2或3,n N11+n N12表示1、2或3,A N11及A N12分別獨立地表示選自由以下基團(a)~(c)組成的群中的基團, (a)1,4-伸環己基(存在於該基團中的1個-CH 2-或不相鄰的2個以上的-CH 2-可被取代為-O-)、 (b)1,4-伸苯基(存在於該基團中的1個-CH=或不相鄰的2個以上的-CH=可被取代為-N=)、及 (c)萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基或十氫萘-2,6-二基(存在於萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基中的1個-CH=或不相鄰的2個以上的-CH=可被取代為-N=), 上述基團(a)、基團(b)及基團(c)可分別獨立地被烷基(存在於該基團中的1個-CH 2-或不相鄰的2個以上的-CH 2-可被取代為-O-)、烯基(存在於該基團中的1個-CH 2-或不相鄰的2個以上的-CH 2-可被取代為-O-)、氰基、氟原子或氯原子取代,Z N11及Z N12分別獨立地表示單鍵、-CH 2CH 2-、-(CH 2) 4-、-OCH 2-、-CH 2O-、-COO-、-OCO-、-OCF 2-、-CF 2O-、-CH=N-N=CH-、-CH=CH-、-CF=CF-或-C≡C-,當A N11及/或A N12存在複數個時,該等可相同亦可不同,當Z N11及/或Z N12存在複數個時,該等可相同亦可不同,但通式(N-1d)所示的化合物除外)。 (In the formula, R N11 and R N12 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH 2 -s in the alkyl group may be independently replaced by -CH =CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substitution, n N11 and n N12 respectively independently represent 0, 1, 2 or 3, n N11 + n N12 represents 1, 2 or 3, A N11 and A N12 each independently represent a group selected from the group consisting of the following groups (a) to (c): (a) 1,4-cyclohexylene (present in this group) One -CH 2 -or two or more non-adjacent -CH 2 -in the group can be substituted with -O-), (b) 1,4-phenylene (the 1 in the group One -CH= or two or more non-adjacent -CH= can be substituted with -N=), and (c) naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene- 2,6-diyl or decahydronaphthalene-2,6-diyl (1 in naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl One -CH= or two or more non-adjacent -CH= can be substituted with -N=), the above group (a), group (b) and group (c) can be each independently by an alkyl group (1 -CH 2 -or 2 or more non-adjacent -CH 2 -in the group can be substituted with -O-), alkenyl (1 -CH in the group 2 -or two or more non-adjacent -CH 2 -may be substituted with -O-), cyano, fluorine atom or chlorine atom, Z N11 and Z N12 each independently represent a single bond, -CH 2 CH 2 -, -(CH 2 ) 4 -, -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -OCF 2 -, -CF 2 O-, -CH=NN=CH-,- CH=CH-, -CF=CF- or -C≡C-, when there are plural A N11 and/or A N12 , these may be the same or different, when Z N11 and/or Z N12 exist plural , These may be the same or different, except for the compound represented by the general formula (N-1d)).
通式(N-1)中,R N11及R N12分別獨立地較佳為碳原子數1至8的烷基、碳原子數1至8的烷氧基、碳原子數2至8的烯基或碳原子數2至8的烯氧基,較佳為碳原子數1至5的烷基、碳原子數1至5的烷氧基、碳原子數2至5的烯基或碳原子數2至5的烯氧基,進而較佳為碳原子數1至5的烷基或碳原子數2至5的烯基,進而較佳為碳原子數2至5的烷基或碳原子數2至3的烯基,尤佳為碳原子數3的烷基或丙烯基。 In the general formula (N-1), R N11 and R N12 are each independently preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkenyl group having 2 to 8 carbon atoms. Or an alkenyloxy group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 2 Alkenyloxy group up to 5 is more preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and still more preferably an alkyl group having 2 to 5 carbon atoms or an alkyl group having 2 to 5 carbon atoms. The alkenyl group of 3 is particularly preferably an alkyl group having 3 carbon atoms or a propenyl group.
又,在其所鍵合的環結構為苯基(芳香族)時,較佳為直鏈狀的碳原子數1至5的烷基、直鏈狀的碳原子數1至4的烷氧基及碳原子數4至5的烯基,在其所鍵合的環結構為環己烷、哌喃及二㗁烷等飽和的環結構時,較佳為直鏈狀的碳原子數1至5的烷基、直鏈狀的碳原子數1至4的烷氧基及直鏈狀的碳原子數2至5的烯基。為了使向列相穩定化,碳原子及存在氧原子時的氧原子的合計較佳為5以下,較佳為直鏈狀。Moreover, when the ring structure to which it is bonded is a phenyl group (aromatic), it is preferably a linear alkyl group having 1 to 5 carbon atoms, or a linear alkoxy group having 1 to 4 carbon atoms. And an alkenyl group having 4 to 5 carbon atoms, when the ring structure to which it is bonded is a saturated ring structure such as cyclohexane, piperan, or dioxane, it is preferably a linear chain having 1 to 5 carbon atoms Alkyl group, linear alkoxy group having 1 to 4 carbon atoms, and linear alkenyl group having 2 to 5 carbon atoms. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms in the presence of oxygen atoms is preferably 5 or less, and is preferably linear.
作為烯基,較佳為選自式(R1)至式(R5)中的任一者所示的基團(各式中的黑點表示環結構中的碳原子)。The alkenyl group is preferably a group selected from any one of formula (R1) to formula (R5) (black dots in each formula represent carbon atoms in the ring structure).
較佳為碳原子數1至5的烷基及碳原子數1至5的烷氧基,較佳為甲基、乙基、丙基、甲氧基、乙氧基及丙氧基。Preferred are alkyl groups having 1 to 5 carbon atoms and alkoxy groups having 1 to 5 carbon atoms, and preferred are methyl, ethyl, propyl, methoxy, ethoxy and propoxy.
關於A N11及A N12,在需要增大Δn時分別獨立地較佳為芳香族,為了改善應答速度則分別獨立地較佳為脂肪族,較佳為表示反-1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、3-氟-1,4-伸苯基、3,5-二氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基、1,4-伸環己烯基、1,4-雙環[2.2.2]伸辛基、哌啶-1,4-二基、萘-2,6-二基、十氫萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基,更佳為表示下述的結構, 較佳為反-1,4-伸環己基、1,4-伸環己烯基或1,4-伸苯基,更佳為反-1,4-伸環己基或1,4-伸苯基。 Regarding A N11 and A N12 , when it is necessary to increase Δn, they are each independently preferably aromatic, and in order to improve the response speed, they are each independently preferably aliphatic, preferably representing trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, 2,3 -Difluoro-1,4-phenylene, 1,4-cyclohexenylene, 1,4-bicyclo[2.2.2]octyl, piperidine-1,4-diyl, naphthalene-2, 6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, more preferably represents the following structure, Preferably it is trans-1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene, and more preferably is trans-1,4-cyclohexenylene or 1,4-phenylene base.
Z N11及Z N12分別獨立地較佳為表示-CH 2O-、-CF 2O-、-CH 2CH 2-、-CF 2CF 2-或單鍵,進而較佳為-CH 2O-、-CH 2CH 2-或單鍵,尤佳為-CH 2O-或單鍵。 Z N11 and Z N12 each independently preferably represent -CH 2 O-, -CF 2 O-, -CH 2 CH 2 -, -CF 2 CF 2 -or a single bond, and more preferably -CH 2 O- , -CH 2 CH 2 -or a single bond, particularly preferably -CH 2 O- or a single bond.
n N11+n N12較佳為1或2,較佳為n N11為1且n N12為0的組合、n N11為2且n N12為0的組合、n N11為1且n N12為1的組合、n N11為2且n N12為1的組合。其中,通式(N-1d)所示的化合物除外。又,具有聯三苯骨架的介電常數各向異性為負的液晶化合物除外。 n N11 +n N12 is preferably 1 or 2, preferably a combination where n N11 is 1 and n N12 is 0, n N11 is 2 and n N12 is 0, and n N11 is 1 and n N12 is 1 , N N11 is 2 and n N12 is a combination of 1. Among them, the compound represented by the general formula (N-1d) is excluded. In addition, liquid crystal compounds having a terphenyl skeleton with negative dielectric anisotropy are excluded.
相對於本發明的組成物的總量,通式(N-1)所示的化合物的較佳含量的下限值為1%、10%、20%、30%、40%、50%、55%、60%、65%、70%、75%、80%。較佳含量的上限值為95%、85%、75%、65%、55%、45%、35%、25%、20%。Relative to the total amount of the composition of the present invention, the lower limit of the preferable content of the compound represented by the general formula (N-1) is 1%, 10%, 20%, 30%, 40%, 50%, 55 %, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%.
相對於本發明的組成物的總量,通式(N-1d)所示的化合物及通式(N-1)所示的化合物的合計的較佳含量的下限值為1%、10%、20%、30%、40%、50%、55%、60%、65%、70%、75%、80%。較佳含量的上限值為95%、85%、75%、65%、55%、45%、35%、25%、20%。The lower limit of the preferable total content of the compound represented by the general formula (N-1d) and the compound represented by the general formula (N-1) is 1% and 10% relative to the total amount of the composition of the present invention , 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%.
具體而言,通式(N-1)所示的化合物為選自通式(N-1-1)至(N-1-18)所示的化合物群中的化合物。Specifically, the compound represented by general formula (N-1) is a compound selected from the group of compounds represented by general formulas (N-1-1) to (N-1-18).
通式(N-1-1)所示的化合物為下述的化合物。The compound represented by general formula (N-1-1) is the following compound.
(式中,R N111表示碳原子數1至5的烷基或碳原子數2至5的烯基,R N112表示碳原子數1至5的烷基或碳原子數1至4的烷氧基)。 (In the formula, R N111 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R N112 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. ).
R N111較佳為碳原子數1至5的烷基或碳原子數2至5的烯基,較佳為丙基、戊基或乙烯基。R N112較佳為碳原子數1至5的烷基、碳原子數4至5的烯基或碳原子數1至4的烷氧基,較佳為乙氧基或丁氧基。 R N111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably a propyl group, a pentyl group or a vinyl group. R N112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and is preferably an ethoxy group or a butoxy group.
通式(N-1-1)所示的化合物可單獨使用,亦可將兩種以上的化合物組合使用。可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能適當組合使用。關於所使用的化合物的種類,例如,作為本發明的一個實施方式,為1種、2種、3種、4種、5種以上。The compound represented by the general formula (N-1-1) may be used alone, or two or more compounds may be used in combination. The types of compounds that can be combined are not particularly limited, and are used in appropriate combinations according to required properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. Regarding the kind of compound used, for example, as an embodiment of the present invention, there are one kind, two kinds, three kinds, four kinds, and five or more kinds.
在重視Δε的改善時,較佳為將含量設定得高一些,在重視低溫時的溶解性時,將含量設定得多一些則效果高,在重視T NI時,將含量設定得少一些則效果高。進而,在改良滴痕、殘影特性的情況下,較佳為將含量的範圍設定為中等。 When the improvement of Δε is important, it is better to set the content higher. When the solubility at low temperature is important, the effect will be higher if the content is set higher. When the T NI is important, the content will be set lower to achieve the effect. high. Furthermore, in the case of improving drip marks and residual image characteristics, it is preferable to set the range of the content to a medium level.
相對於本發明的組成物的總量,式(N-1-1)所示的化合物的較佳含量的下限值為5%、10%、13%、15%、17%、20%、23%、25%、27%、30%、33%、35%。較佳含量的上限值相對於本發明的組成物的總量為50%、40%、38%、35%、33%、30%、28%、25%、23%、20%、18%、15%、13%、10%、8%、7%、6%、5%、3%。Relative to the total amount of the composition of the present invention, the lower limit of the preferable content of the compound represented by formula (N-1-1) is 5%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%. The upper limit of the preferred content relative to the total amount of the composition of the present invention is 50%, 40%, 38%, 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18% , 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3%.
進而,通式(N-1-1)所示的化合物較佳為選自式(N-1-1.1)至式(N-1-1.23)所示的化合物群中的化合物,較佳為式(N-1-1.1)至(N-1-1.4)所示的化合物,較佳為式(N-1-1.1)及式(N-1-1.3)所示的化合物。Furthermore, the compound represented by general formula (N-1-1) is preferably a compound selected from the group of compounds represented by formula (N-1-1.1) to formula (N-1-1.23), preferably The compounds represented by (N-1-1.1) to (N-1-1.4) are preferably compounds represented by formula (N-1-1.1) and formula (N-1-1.3).
式(N-1-1.1)至(N-1-1.22)所示的化合物可單獨使用,亦可組合使用,相對於本發明的組成物的總量,單獨或該等化合物的較佳含量的下限值為5%、10%、13%、15%、17%、20%、23%、25%、27%、30%、33%、35%。較佳含量的上限值相對於本發明的組成物的總量為50%、40%、38%、35%、33%、30%、28%、25%、23%、20%、18%、15%、13%、10%、8%、7%、6%、5%、3%。The compounds represented by formulas (N-1-1.1) to (N-1-1.22) can be used alone or in combination, relative to the total amount of the composition of the present invention, alone or in a preferred content of these compounds The lower limit is 5%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%. The upper limit of the preferred content relative to the total amount of the composition of the present invention is 50%, 40%, 38%, 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18% , 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3%.
通式(N-1-2)所示的化合物為下述的化合物。The compound represented by general formula (N-1-2) is the following compound.
(式中,R N121表示碳原子數1至5的烷基或碳原子數2至5的烯基,R N122表示碳原子數1至5的烷基或碳原子數1至4的烷氧基)。 (In the formula, R N121 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R N122 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. ).
R N121較佳為碳原子數1至5的烷基或碳原子數2至5的烯基,較佳為乙基、丙基、丁基或戊基。R N122較佳為碳原子數1至5的烷基、碳原子數4至5的烯基或碳原子數1至4的烷氧基,較佳為甲基、丙基、甲氧基、乙氧基或丙氧基。 R N121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl, propyl, butyl or pentyl group. R N122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, preferably methyl, propyl, methoxy, ethyl Oxy or propoxy.
通式(N-1-2)所示的化合物可單獨使用,亦可將兩種以上的化合物組合使用。可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能適當組合使用。關於所使用的化合物的種類,例如,作為本發明的一個實施方式,為1種、2種、3種、4種、5種以上。The compound represented by the general formula (N-1-2) may be used alone, or two or more compounds may be used in combination. The types of compounds that can be combined are not particularly limited, and are used in appropriate combinations according to required properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. Regarding the kind of compound used, for example, as an embodiment of the present invention, there are one kind, two kinds, three kinds, four kinds, and five or more kinds.
在重視Δε的改善時,較佳為將含量設定得高一些,在重視低溫時的溶解性時,將含量設定得少一些則效果高,在重視T NI時,將含量設定得多一些則效果高。進而,在改良滴痕、殘影特性的情況下,較佳為將含量的範圍設定為中等。 When the improvement of Δε is important, it is better to set the content higher. When the solubility at low temperature is important, the effect is higher if the content is set less, and when T NI is important, the content is set higher if the effect is higher. high. Furthermore, in the case of improving drip marks and residual image characteristics, it is preferable to set the range of the content to a medium level.
相對於本發明的組成物的總量,式(N-1-2)所示的化合物的較佳含量的下限值為5%、7%、10%、13%、15%、17%、20%、23%、25%、27%、30%、33%、35%、37%、40%、42%。較佳含量的上限值相對於本發明的組成物的總量為50%、48%、45%、43%、40%、38%、35%、33%、30%、28%、25%、23%、20%、18%、15%、13%、10%、8%、7%、6%、5%。Relative to the total amount of the composition of the present invention, the lower limit of the preferred content of the compound represented by formula (N-1-2) is 5%, 7%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 37%, 40%, 42%. The upper limit of the preferred content relative to the total amount of the composition of the present invention is 50%, 48%, 45%, 43%, 40%, 38%, 35%, 33%, 30%, 28%, 25% , 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6%, 5%.
進而,通式(N-1-2)所示的化合物較佳為選自式(N-1-2.1)至式(N-1-2.22)所示的化合物群中的化合物,較佳為式(N-1-2.3)至式(N-1-2.7)、式(N-1-2.10)、式(N-1-2.11)、式(N-1-2.13)及式(N-1-2.20)所示的化合物,在重視Δε的改良時,較佳為式(N-1-2.3)至式(N-1-2.7)所示的化合物,在重視T NI的改良時,較佳為式(N-1-2.10)、式(N-1-2.11)及式(N-1-2.13)所示的化合物,在重視應答速度的改良時,較佳為式(N-1-2.20)所示的化合物。 Furthermore, the compound represented by general formula (N-1-2) is preferably a compound selected from the group of compounds represented by formula (N-1-2.1) to formula (N-1-2.22), preferably (N-1-2.3) to formula (N-1-2.7), formula (N-1-2.10), formula (N-1-2.11), formula (N-1-2.13) and formula (N-1- The compound shown in 2.20) is preferably the compound represented by formula (N-1-2.3) to formula (N-1-2.7) when the improvement of Δε is important, and when the improvement of T NI is important, it is preferably The compound represented by formula (N-1-2.10), formula (N-1-2.11) and formula (N-1-2.13), when the improvement of response speed is important, the formula (N-1-2.20) is preferred The compound shown.
式(N-1-2.1)至式(N-1-2.22)所示的化合物可單獨使用,亦可組合使用,相對於本發明的組成物的總量,單獨或該等化合物的較佳含量的下限值為5%、10%、13%、15%、17%、20%、23%、25%、27%、30%、33%、35%。較佳含量的上限值相對於本發明的組成物的總量為50%、40%、38%、35%、33%、30%、28%、25%、23%、20%、18%、15%、13%、10%、8%、7%、6%、5%、3%。The compounds represented by formula (N-1-2.1) to formula (N-1-2.22) can be used alone or in combination, relative to the total amount of the composition of the present invention, alone or the preferred content of these compounds The lower limit is 5%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%. The upper limit of the preferred content relative to the total amount of the composition of the present invention is 50%, 40%, 38%, 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18% , 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3%.
通式(N-1-3)所示的化合物為下述的化合物。The compound represented by general formula (N-1-3) is the following compound.
(式中,R N131表示碳原子數1至5的烷基或碳原子數2至5的烯基,R N132表示碳原子數1至5的烷基或碳原子數1至4的烷氧基)。 (In the formula, R N131 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R N132 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. ).
R N131較佳為碳原子數1至5的烷基或碳原子數2至5的烯基,較佳為乙基、丙基或丁基。R N132較佳為碳原子數1至5的烷基、碳原子數3至5的烯基或碳原子數1至4的烷氧基,較佳為1-丙烯基、乙氧基、丙氧基或丁氧基。 R N131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably ethyl, propyl or butyl. R N132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, preferably 1-propenyl, ethoxy, or propoxy基 or butoxy.
通式(N-1-3)所示的化合物可單獨使用,亦可將兩種以上的化合物組合使用。可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能適當組合使用。關於所使用的化合物的種類,例如,作為本發明的一個實施方式,為1種、2種、3種、4種、5種以上。The compound represented by the general formula (N-1-3) may be used alone, or two or more compounds may be used in combination. The types of compounds that can be combined are not particularly limited, and are used in appropriate combinations according to required properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. Regarding the kind of compound used, for example, as an embodiment of the present invention, there are one kind, two kinds, three kinds, four kinds, and five or more kinds.
在重視Δε的改善時,較佳為將含量設定得高一些,在重視低溫時的溶解性時,將含量設定得多一些則效果高,在重視T NI時,將含量設定得多一些則效果高。進而,在改良滴痕、殘影特性的情況下,較佳為將含量的範圍設定為中等。 When the improvement of Δε is important, it is better to set the content higher. When the solubility at low temperature is important, the effect is higher if the content is set higher, and when T NI is important, the content is set higher if the effect is higher. high. Furthermore, in the case of improving drip marks and residual image characteristics, it is preferable to set the range of the content to a medium level.
相對於本發明的組成物的總量,式(N-1-3)所示的化合物的較佳含量的下限值為5%、10%、13%、15%、17%、20%。較佳含量的上限值相對於本發明的組成物的總量為35%、30%、28%、25%、23%、20%、18%、15%、13%。The lower limit of the preferable content of the compound represented by formula (N-1-3) is 5%, 10%, 13%, 15%, 17%, 20% relative to the total amount of the composition of the present invention. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% relative to the total amount of the composition of the present invention.
進而,通式(N-1-3)所示的化合物較佳為選自式(N-1-3.1)至式(N-1-3.21)所示的化合物群中的化合物,較佳為式(N-1-3.1)至(N-1-3.7)及式(N-1-3.21)所示的化合物,較佳為式(N-1-3.1)、式(N-1-3.2)、式(N-1-3.3)、式(N-1-3.4)及式(N-1-3.6)所示的化合物。Furthermore, the compound represented by general formula (N-1-3) is preferably a compound selected from the group of compounds represented by formula (N-1-3.1) to formula (N-1-3.21), preferably The compounds represented by (N-1-3.1) to (N-1-3.7) and formula (N-1-3.21) are preferably formula (N-1-3.1), formula (N-1-3.2), Compounds represented by formula (N-1-3.3), formula (N-1-3.4), and formula (N-1-3.6).
式(N-1-3.1)至式(N-1-3.4)、式(N-1-3.6)及式(N-1-3.21)所示的化合物可單獨使用,亦可組合使用,但較佳為式(N-1-3.1)與式(N-1-3.2)的組合;選自式(N-1-3.3)、式(N-1-3.4)及式(N-1-3.6)中的2種或3種的組合。相對於本發明的組成物的總量,單獨或該等化合物的較佳含量的下限值為5%、10%、13%、15%、17%、20%。較佳含量的上限值相對於本發明的組成物的總量為35%、30%、28%、25%、23%、20%、18%、15%、13%。The compounds represented by formula (N-1-3.1) to formula (N-1-3.4), formula (N-1-3.6) and formula (N-1-3.21) can be used alone or in combination, but more It is preferably a combination of formula (N-1-3.1) and formula (N-1-3.2); selected from formula (N-1-3.3), formula (N-1-3.4) and formula (N-1-3.6) A combination of 2 or 3 in. Relative to the total amount of the composition of the present invention, the lower limit of the preferred content of the compound alone or in the compound is 5%, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% relative to the total amount of the composition of the present invention.
通式(N-1-4)所示的化合物為下述的化合物。The compound represented by general formula (N-1-4) is the following compound.
(式中,R N141表示碳原子數1至5的烷基或碳原子數2至5的烯基,R N142表示碳原子數1至5的烷基或碳原子數1至4的烷氧基)。 (In the formula, R N141 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R N142 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. ).
R N141及R N142分別獨立地較佳為碳原子數1至5的烷基、碳原子數4至5的烯基或碳原子數1至4的烷氧基,較佳為甲基、丙基、乙氧基或丁氧基。 R N141 and R N142 are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, preferably methyl or propyl. , Ethoxy or butoxy.
通式(N-1-4)所示的化合物可單獨使用,亦可將兩種以上的化合物組合使用。可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能適當組合使用。關於所使用的化合物的種類,例如,作為本發明的一個實施方式,為1種、2種、3種、4種、5種以上。The compound represented by the general formula (N-1-4) may be used alone, or two or more compounds may be used in combination. The types of compounds that can be combined are not particularly limited, and are used in appropriate combinations according to required properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. Regarding the kind of compound used, for example, as an embodiment of the present invention, there are one kind, two kinds, three kinds, four kinds, and five or more kinds.
在重視Δε的改善時,較佳為將含量設定得高一些,在重視低溫時的溶解性時,將含量設定得多一些則效果高,在重視T NI時,將含量設定得少一些則效果高。進而,在改良滴痕、殘影特性的情況下,較佳為將含量的範圍設定為中等。 When the improvement of Δε is important, it is better to set the content higher. When the solubility at low temperature is important, the effect will be higher if the content is set higher. When the T NI is important, the content will be set lower to achieve the effect. high. Furthermore, in the case of improving drip marks and residual image characteristics, it is preferable to set the range of the content to a medium level.
相對於本發明的組成物的總量,式(N-1-4)所示的化合物的較佳含量的下限值為3%、5%、7%、10%、13%、15%、17%、20%。較佳含量的上限值相對於本發明的組成物的總量為35%、30%、28%、25%、23%、20%、18%、15%、13%、11%、10%、8%。Relative to the total amount of the composition of the present invention, the lower limit of the preferred content of the compound represented by formula (N-1-4) is 3%, 5%, 7%, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferred content relative to the total amount of the composition of the present invention is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 11%, 10% ,8%.
進而,通式(N-1-4)所示的化合物較佳為選自式(N-1-4.1)至式(N-1-4.14)所示的化合物群中的化合物,較佳為式(N-1-4.1)至(N-1-4.4)所示的化合物,較佳為式(N-1-4.1)、式(N-1-4.2)及式(N-1-4.4)所示的化合物。Furthermore, the compound represented by general formula (N-1-4) is preferably a compound selected from the group of compounds represented by formula (N-1-4.1) to formula (N-1-4.14), preferably The compounds represented by (N-1-4.1) to (N-1-4.4) are preferably those represented by formula (N-1-4.1), formula (N-1-4.2) and formula (N-1-4.4) The compound shown.
式(N-1-4.1)至(N-1-4.14)所示的化合物可單獨使用,亦可組合使用,相對於本發明的組成物的總量,單獨或該等化合物的較佳含量的下限值為3%、5%、7%、10%、13%、15%、17%、20%。較佳含量的上限值相對於本發明的組成物的總量為35%、30%、28%、25%、23%、20%、18%、15%、13%、11%、10%、8%。The compounds represented by formulas (N-1-4.1) to (N-1-4.14) can be used alone or in combination, and relative to the total amount of the composition of the present invention, alone or in a preferred content of these compounds The lower limit is 3%, 5%, 7%, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferred content relative to the total amount of the composition of the present invention is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 11%, 10% ,8%.
通式(N-1-16)所示的化合物為下述的化合物。The compound represented by general formula (N-1-16) is the following compound.
(式中,R N1161表示碳原子數1至5的烷基或碳原子數2至5的烯基,R N1162表示碳原子數1至5的烷基或碳原子數1至4的烷氧基)。 (In the formula, R N1161 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R N1162 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. ).
R N1161較佳為碳原子數1至5的烷基或碳原子數2至5的烯基,較佳為乙基、丙基或丁基。R N1162較佳為碳原子數1至5的烷基、碳原子數4至5的烯基或碳原子數1至4的烷氧基,較佳為乙氧基、丙氧基或丁氧基。 R N1161 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and is preferably an ethyl group, a propyl group, or a butyl group. R N1162 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, preferably ethoxy, propoxy or butoxy .
通式(N-1-16)所示的化合物可單獨使用,亦可將兩種以上的化合物組合使用。可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能適當組合使用。關於所使用的化合物的種類,例如,作為本發明的一個實施方式,為1種、2種、3種、4種、5種以上。The compound represented by the general formula (N-1-16) may be used alone, or two or more compounds may be used in combination. The types of compounds that can be combined are not particularly limited, and are used in appropriate combinations according to required properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. Regarding the kind of compound used, for example, as an embodiment of the present invention, there are one kind, two kinds, three kinds, four kinds, and five or more kinds.
在重視Δε的改善時,較佳為將含量設定得高一些,在重視低溫時的溶解性時,將含量設定得多一些則效果高,在重視T NI時,將含量設定得多一些則效果高。進而,在改良滴痕、殘影特性的情況下,較佳為將含量的範圍設定為中等。 When the improvement of Δε is important, it is better to set the content higher. When the solubility at low temperature is important, the effect is higher if the content is set higher, and when T NI is important, the content is set higher if the effect is higher. high. Furthermore, in the case of improving drip marks and residual image characteristics, it is preferable to set the range of the content to a medium level.
相對於本發明的組成物的總量,式(N-1-16)所示的化合物的較佳含量的下限值為5%、10%、13%、15%、17%、20%。較佳含量的上限值相對於本發明的組成物的總量為35%、30%、28%、25%、23%、20%、18%、15%、13%。The lower limit of the preferable content of the compound represented by formula (N-1-16) is 5%, 10%, 13%, 15%, 17%, 20% relative to the total amount of the composition of the present invention. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% relative to the total amount of the composition of the present invention.
通式(N-1-18)所示的化合物為下述的化合物。The compound represented by general formula (N-1-18) is the following compound.
(式中,R N1181表示碳原子數1至5的烷基或碳原子數2至5的烯基,R N1182表示碳原子數1至5的烷基或碳原子數1至4的烷氧基)。 (In the formula, R N1181 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R N1182 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. ).
R N1181較佳為碳原子數1至5的烷基或碳原子數2至5的烯基,較佳為甲基、乙基、丙基或丁基。R N1182較佳為碳原子數1至5的烷基、碳原子數4至5的烯基或碳原子數1至4的烷氧基,較佳為乙氧基、丙氧基或丁氧基。 R N1181 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably a methyl group, an ethyl group, a propyl group or a butyl group. R N1182 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, preferably ethoxy, propoxy or butoxy .
通式(N-1-18)所示的化合物可單獨使用,亦可將兩種以上的化合物組合使用。可組合的化合物的種類沒有特別限制,根據低溫時的溶解性、轉移溫度、電可靠性、雙折射率等所要求的性能適當組合使用。關於所使用的化合物的種類,例如,作為本發明的一個實施方式,為1種、2種、3種、4種、5種以上。The compound represented by the general formula (N-1-18) may be used alone, or two or more compounds may be used in combination. The types of compounds that can be combined are not particularly limited, and are used in appropriate combinations according to required properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. Regarding the kind of compound used, for example, as an embodiment of the present invention, there are one kind, two kinds, three kinds, four kinds, and five or more kinds.
在重視Δε的改善時,較佳為將含量設定得高一些,在重視低溫時的溶解性時,將含量設定得多一些則效果高,在重視T NI時,將含量設定得多一些則效果高。進而,在改良滴痕、殘影特性的情況下,較佳為將含量的範圍設定為中等。 When the improvement of Δε is important, it is better to set the content higher. When the solubility at low temperature is important, the effect is higher if the content is set higher, and when T NI is important, the content is set higher if the effect is higher. high. Furthermore, in the case of improving drip marks and residual image characteristics, it is preferable to set the range of the content to a medium level.
相對於本發明的組成物的總量,式(N-1-18)所示的化合物的較佳含量的下限值為5%、10%、13%、15%、17%、20%。較佳含量的上限值相對於本發明的組成物的總量為35%、30%、28%、25%、23%、20%、18%、15%、13%。The lower limit of the preferable content of the compound represented by formula (N-1-18) is 5%, 10%, 13%, 15%, 17%, 20% relative to the total amount of the composition of the present invention. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13% relative to the total amount of the composition of the present invention.
進而,通式(N-1-18)所示的化合物較佳為選自式(N-1-18.1)至式(N-1-18.5)所示的化合物群中的化合物,較佳為式(N-1-18.1)至(N-1-18.3)所示的化合物,較佳為式(N-1-18.2)及式(N-1-18.3)所示的化合物。Furthermore, the compound represented by general formula (N-1-18) is preferably a compound selected from the group of compounds represented by formula (N-1-18.1) to formula (N-1-18.5), preferably The compounds represented by (N-1-18.1) to (N-1-18.3) are preferably compounds represented by formula (N-1-18.2) and formula (N-1-18.3).
本發明的液晶組成物中含有通式(II)所示的聚合性化合物作為第四成分。The liquid crystal composition of the present invention contains a polymerizable compound represented by the general formula (II) as the fourth component.
(式中,R 201、R 202、R 203、R 204、R 205、R 206、R 207、R 208、R 209及R 210分別獨立地表示P 21-S 21-、可被氟原子取代的碳原子數1至18的烷基、可被氟原子取代的碳原子數1至18的烷氧基、氟原子或氫原子中的任一者,P 21分別獨立地表示選自式(R-1)至式(R-7)中的聚合性基團, (式中,R 11、R 12、R 13、R 14及R 15分別獨立地表示碳原子數1至5的烷基、氟原子或氫原子中的任一者,m r5、m r7、n r5及n r7分別獨立地表示0、1、或2,但氧原子不直接相鄰),S 21表示單鍵或碳數1至15的伸烷基,該伸烷基中的1個或2個以上的-CH 2-能夠以氧原子不直接相鄰的方式被-O-、-OCO-或-COO-取代,n 21表示0、1或2,A 21表示選自由以下(a)~(c)基團組成的群中的基團, (a)1,4-伸環己基(存在於該基團中的1個-CH 2-或不相鄰的2個以上的-CH 2-可被取代為-O-)、 (b)1,4-伸苯基(存在於該基團中的1個-CH=或不相鄰的2個以上的-CH=可被取代為-N=)、及 (c)萘-2,6-二基、1,2,3,4-四氫萘-2,6-二基或十氫萘-2,6-二基(存在於萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基中的1個-CH=或不相鄰的2個以上的-CH=可被取代為-N=), 上述基團(a)、基團(b)及基團(c)可分別獨立地被碳原子數1至12的烷基、碳原子數1至12的烷氧基、鹵素、氰基、硝基或P 21-S 21-取代,在上述通式(II)的1分子中具有至少1個以上的P 21-S 21-,L 21表示單鍵、-OCH 2-、-CH 2O-、-C 2H 4-、-OC 2H 4O-、-COO-、-OCO-、-CH=CR a-COO-、-CH=CR a-OCO-、-COO-CR a=CH-、-OCO-CR a=CH-、-(CH 2) z-COO-、-(CH 2) z-OCO-、-OCO-(CH 2) z-、-COO-(CH 2) z-、-CH=CH-、-CF 2O-、-OCF 2-或-C≡C-(式中,R a分別獨立地表示氫原子或碳原子數1至3的烷基,上述式中,z分別獨立地表示1至4的整數),當P 21、S 21、及A 21存在複數個時,分別可相同亦可不同)。 (In the formula, R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 , R 209 and R 210 each independently represent P 21 -S 21 -, which may be substituted by a fluorine atom Any one of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms that may be substituted with a fluorine atom, a fluorine atom, or a hydrogen atom, and P 21 each independently represents selected from the formula (R- 1) to the polymerizable group in formula (R-7), (In the formula, R 11 , R 12 , R 13 , R 14 and R 15 each independently represent any of an alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a hydrogen atom, m r5 , m r7 , n r5 and n r7 each independently represent 0, 1, or 2, but the oxygen atom is not directly adjacent), S 21 represents a single bond or an alkylene group having 1 to 15 carbon atoms, and 1 or 2 of the alkylene group More than one -CH 2 -can be substituted by -O-, -OCO- or -COO- in such a way that the oxygen atom is not directly adjacent, n 21 represents 0, 1 or 2, and A 21 represents selected from the following (a)~ (c) Groups in the group consisting of groups, (a) 1,4-cyclohexylene (1 -CH 2 -existing in the group or 2 or more non-adjacent -CH 2- Can be substituted with -O-), (b) 1,4-phenylene (1 -CH= or 2 or more non-adjacent -CH= in the group can be substituted with -N =), and (c) naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (present in naphthalene- One -CH= in 2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl or two or more non-adjacent -CH= can be substituted with -N =), the above-mentioned groups (a), group (b) and group (c) may be independently substituted by an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen, or a cyanide group. Group, nitro group or P 21 -S 21 -substitution, having at least one P 21 -S 21 -in one molecule of the general formula (II), L 21 represents a single bond, -OCH 2 -, -CH 2 O-, -C 2 H 4 -, -OC 2 H 4 O-, -COO-, -OCO-, -CH=CR a -COO-, -CH=CR a -OCO-, -COO-CR a =CH-, -OCO-CR a =CH-, -(CH 2 ) z -COO-, -(CH 2 ) z -OCO-, -OCO-(CH 2 ) z -, -COO-(CH 2 ) z -, -CH=CH-, -CF 2 O-, -OCF 2 -or -C≡C- (wherein R a independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, the above formula Where z independently represents an integer from 1 to 4), and when there are plural P 21 , S 21 , and A 21 , they may be the same or different).
通式(II)中,較佳在該通式(II)所示的化合物的1分子內具有1或2個以上的P 21-S 21-,較佳為具有4個以下的P 21-S 21-,存在於上述通式(II)的1分子內的P 21-S 21-的數量較佳為1以上且4以下,更佳為1以上且3以下,上述通式(II)所示的化合物的分子內的P 21-S 21-的數量尤佳為2或3。即,通式(II)所示的化合物為至少2個苯環與根據需要的環A 21連接而成的結構,該等複數個苯環及環A 21中具有至少一個P 21-S 21-,因此通式(II)所示的化合物發揮作為聚合性化合物的作用、效果。 In the general formula (II), the compound represented by the general formula (II) preferably has 1 or 2 or more P 21 -S 21 -in one molecule, and preferably has 4 or less P 21 -S 21 -, the number of P 21 -S 21 -present in 1 molecule of the above general formula (II) is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, as represented by the above general formula (II) The number of P 21 -S 21 -in the molecule of the compound is particularly preferably 2 or 3. That is, the compound represented by the general formula (II) has a structure in which at least two benzene rings and ring A 21 are connected as necessary, and the plural benzene rings and ring A 21 have at least one P 21 -S 21- Therefore, the compound represented by the general formula (II) exerts functions and effects as a polymerizable compound.
在上述通式(II)中,選自由R 201、R 202、R 203、R 204、R 205、R 206、R 207、R 208、R 209及R 210組成的群中的一種或兩種以上為P 21-S 21-時,較佳為R 201、R 202、R 204、R 207、R 209或R 210中的任一種或兩種以上為P 21-S 21-,更佳為R 201及R 210為P 21-S 21-。 In the above general formula (II), one or two or more selected from the group consisting of R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 , R 209 and R 210 When it is P 21 -S 21 -, preferably any one or more of R 201 , R 202 , R 204 , R 207 , R 209 or R 210 is P 21 -S 21 -, more preferably R 201 And R 210 is P 21 -S 21 -.
在上述通式(II)中,R 201及R 210分別獨立地較佳為P 21-S 21-,於此種情況下,R 201及R 210可為相同的P 21-S 21-,亦可為不同的P 21-S 21-。 In the above general formula (II), R 201 and R 210 are each independently preferably P 21 -S 21 -, in this case, R 201 and R 210 may be the same P 21 -S 21 -, also Can be different P 21 -S 21 -.
在上述通式(II)中,R 201、R 202、R 203、R 204、R 205、R 206、R 207、R 208、R 209及R 210分別獨立地表示P 21-S 21-、可被氟原子取代的碳原子數1至18的烷基、可被氟原子取代的碳原子數1至18的烷氧基、氟原子或氫原子中的任一者,於此種情況下,上述烷基及烷氧基的較佳的碳原子數為1至16,更佳為1至10,進而較佳為1至8,更而更佳為1至6,進而更佳為1至4,尤佳為1至3。又,上述烷基及烷氧基可為直鏈狀或支鏈狀,尤佳為直鏈狀。 In the above general formula (II), R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 , R 209 and R 210 each independently represent P 21 -S 21 -, Any one of an alkyl group having 1 to 18 carbon atoms substituted by a fluorine atom, an alkoxy group having 1 to 18 carbon atoms that may be substituted by a fluorine atom, a fluorine atom or a hydrogen atom, in this case, the above The preferable number of carbon atoms of the alkyl group and the alkoxy group is 1 to 16, more preferably 1 to 10, still more preferably 1 to 8, still more preferably 1 to 6, and still more preferably 1 to 4. Especially preferably, it is 1 to 3. In addition, the above-mentioned alkyl group and alkoxy group may be linear or branched, and are particularly preferably linear.
在上述通式(II)中,R 202、R 203、R 204、R 205、R 206、R 207、R 208及R 209分別獨立地較佳為P 21-S 21-、碳原子數1至3的烷基、碳原子數1至3的烷氧基、氟原子或氫原子,更佳為P 21-S 21-、甲基、甲氧基、氟原子或氫原子,進而較佳為甲基、甲氧基、氟原子或氫原子。 In the above general formula (II), R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 and R 209 are each independently preferably P 21 -S 21 -, and the number of carbon atoms is 1 to The alkyl group of 3, the alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a hydrogen atom, more preferably P 21 -S 21 -, a methyl group, a methoxy group, a fluorine atom or a hydrogen atom, and still more preferably a methyl group Group, methoxy group, fluorine atom or hydrogen atom.
P 21較佳為式(R-1),更佳為丙烯醯基或甲基丙烯醯基,進而較佳為甲基丙烯醯基。 P 21 is preferably the formula (R-1), more preferably an acryloyl group or a methacryloyl group, and still more preferably a methacryloyl group.
S 21較佳為單鍵或碳數1至3的伸烷基,進而較佳為單鍵。 S 21 is preferably a single bond or an alkylene group having 1 to 3 carbon atoms, and more preferably a single bond.
在上述通式(II)中,n 21較佳為0或1。 In the above general formula (II), n 21 is preferably 0 or 1.
在上述通式(II)中,A 21較佳為1,4-伸苯基或萘-2,6-二基,進而較佳為1,4-伸苯基。 In the above general formula (II), A 21 is preferably 1,4-phenylene or naphthalene-2,6-diyl, and more preferably 1,4-phenylene.
在上述通式(II)中,L 21較佳為單鍵、-OCH 2-、-CH 2O-、-C 2H 4-、-COO-、-OCO-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-C 2H 4-COO-、-C 2H 4-OCO-、-OCO-C 2H 4-、-COO-C 2H 4-、-CH=CH-、-CF 2O-、-OCF 2-或-C≡C-。 In the above general formula (II), L 21 is preferably a single bond, -OCH 2 -, -CH 2 O-, -C 2 H 4 -, -COO-, -OCO-, -CH=CH-COO- , -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -C 2 H 4 -COO-, -C 2 H 4 -OCO-, -OCO-C 2 H 4 -, -COO-C 2 H 4 -, -CH=CH-, -CF 2 O-, -OCF 2 -or -C≡C-.
關於通式(II)所示的聚合性化合物的合計含量,含有0.01至5質量%,含量的下限較佳為0.02質量%、較佳為0.03質量%、較佳為0.04質量%、較佳為0.05質量%、較佳為0.06質量%、較佳為0.07質量%、較佳為0.08質量%、較佳為0.09質量%、較佳為0.1質量%、較佳為0.15質量%、較佳為0.2質量%、較佳為0.25質量%、較佳為0.3質量%、較佳為0.35質量%、較佳為0.4質量%、較佳為0.5質量%、較佳為0.55質量%;且含量的上限較佳為4.5質量%、較佳為4質量%、較佳為3.5質量%、較佳為3質量%、較佳為2.5質量%、較佳為2質量%、較佳為1.5質量%、較佳為1質量%、較佳為0.95質量%、較佳為0.9質量%、較佳為0.85質量%、較佳為0.8質量%、較佳為0.75質量%、較佳為0.7質量%、較佳為0.65質量%、較佳為0.6質量%、較佳為0.55質量%。Regarding the total content of the polymerizable compound represented by the general formula (II), it contains 0.01 to 5% by mass, and the lower limit of the content is preferably 0.02% by mass, more preferably 0.03% by mass, more preferably 0.04% by mass, more preferably 0.05% by mass, preferably 0.06% by mass, preferably 0.07% by mass, preferably 0.08% by mass, preferably 0.09% by mass, preferably 0.1% by mass, preferably 0.15% by mass, preferably 0.2 % By mass, preferably 0.25% by mass, preferably 0.3% by mass, preferably 0.35% by mass, preferably 0.4% by mass, preferably 0.5% by mass, preferably 0.55% by mass; and the upper limit of the content is lower Preferably it is 4.5% by mass, preferably 4% by mass, more preferably 3.5% by mass, preferably 3% by mass, preferably 2.5% by mass, preferably 2% by mass, preferably 1.5% by mass, more preferably 1% by mass, preferably 0.95% by mass, preferably 0.9% by mass, preferably 0.85% by mass, preferably 0.8% by mass, preferably 0.75% by mass, preferably 0.7% by mass, preferably 0.65 mass%, preferably 0.6 mass%, more preferably 0.55 mass%.
本發明的通式(II)所示的化合物較佳為通式(IV)所示的聚合性化合物。The compound represented by general formula (II) of the present invention is preferably a polymerizable compound represented by general formula (IV).
在上述通式(IV)中,R 7及R 8分別獨立地表示上述的式(R-1)至式(R-7)中的任一者,X 1至X 8分別獨立地表示氟原子、氫原子、三氟甲基、三氟甲氧基、碳原子數1至3的烷基或碳原子數1至3的烷氧基。在上述通式(IV)中,R 7及R 8分別獨立地表示甲基丙烯醯基或丙烯醯基。 In the above general formula (IV), R 7 and R 8 each independently represent any one of the above formula (R-1) to formula (R-7), and X 1 to X 8 each independently represent a fluorine atom , A hydrogen atom, a trifluoromethyl group, a trifluoromethoxy group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. In the above general formula (IV), R 7 and R 8 each independently represent a methacryl group or an acryl group.
上述通式(IV)所示的化合物進而較佳為選自由通式(IV-11)至通式(IV-19)組成的群中的一種或兩種以上,尤佳為通式(IV-11)、通式(IV-12)、通式(IV-16)、通式(IV-17)。The compound represented by the above general formula (IV) is more preferably one or two or more selected from the group consisting of the general formula (IV-11) to the general formula (IV-19), and particularly preferably the general formula (IV- 11) General formula (IV-12), general formula (IV-16), general formula (IV-17).
上述通式中的1,4-伸苯基中的氫原子可進一步被-F、-CF 3、-CH 3或式(R-1)至式(R-7)中的任一者取代。 The hydrogen atom in the 1,4-phenylene group in the above general formula may be further substituted by -F, -CF 3 , -CH 3 or any of formula (R-1) to formula (R-7).
關於通式(IV)所示的聚合性化合物的合計含量,含有0.01至5質量%,含量的下限較佳為0.02質量%、較佳為0.03質量%、較佳為0.04質量%、較佳為0.05質量%、較佳為0.06質量%、較佳為0.07質量%、較佳為0.08質量%、較佳為0.09質量%、較佳為0.1質量%、較佳為0.15質量%、較佳為0.2質量%、較佳為0.25質量%、較佳為0.3質量%、較佳為0.35質量%、較佳為0.4質量%、較佳為0.5質量%、較佳為0.55質量%;且含量的上限較佳為4.5質量%、較佳為4質量%、較佳為3.5質量%、較佳為3質量%、較佳為2.5質量%、較佳為2質量%、較佳為1.5質量%、較佳為1質量%、較佳為0.95質量%、較佳為0.9質量%、較佳為0.85質量%、較佳為0.8質量%、較佳為0.75質量%、較佳為0.7質量%、較佳為0.65質量%、較佳為0.6質量%、較佳為0.55質量%。Regarding the total content of the polymerizable compound represented by the general formula (IV), it contains 0.01 to 5% by mass, and the lower limit of the content is preferably 0.02% by mass, more preferably 0.03% by mass, more preferably 0.04% by mass, more preferably 0.05% by mass, preferably 0.06% by mass, preferably 0.07% by mass, preferably 0.08% by mass, preferably 0.09% by mass, preferably 0.1% by mass, preferably 0.15% by mass, preferably 0.2 % By mass, preferably 0.25% by mass, preferably 0.3% by mass, preferably 0.35% by mass, preferably 0.4% by mass, preferably 0.5% by mass, preferably 0.55% by mass; and the upper limit of the content is lower Preferably it is 4.5% by mass, preferably 4% by mass, more preferably 3.5% by mass, preferably 3% by mass, preferably 2.5% by mass, preferably 2% by mass, preferably 1.5% by mass, more preferably 1% by mass, preferably 0.95% by mass, preferably 0.9% by mass, preferably 0.85% by mass, preferably 0.8% by mass, preferably 0.75% by mass, preferably 0.7% by mass, preferably 0.65 mass%, preferably 0.6 mass%, more preferably 0.55 mass%.
本發明的液晶組成物於20℃的介電常數各向異性(Δε)為-2.0至-8.0,較佳為-2.0至-6.0,更佳為-2.0至-5.0,尤佳為-2.5至-5.0。The dielectric anisotropy (Δε) of the liquid crystal composition of the present invention at 20°C is -2.0 to -8.0, preferably -2.0 to -6.0, more preferably -2.0 to -5.0, and particularly preferably -2.5 to -5.0.
本發明的液晶組成物於20℃的折射率各向異性(Δn)為0.08至0.14,更佳為0.09至0.13,尤佳為0.09至0.12。若進一步詳述,則在對應於薄的單元間隙時較佳為0.10至0.13,在對應於厚的單元間隙時較佳為0.08至0.10。The refractive index anisotropy (Δn) of the liquid crystal composition of the present invention at 20°C is 0.08 to 0.14, more preferably 0.09 to 0.13, and particularly preferably 0.09 to 0.12. In further detail, it is preferably 0.10 to 0.13 when corresponding to a thin cell gap, and preferably 0.08 to 0.10 when corresponding to a thick cell gap.
本發明的液晶組合物於20℃的黏度(η)為10至50mPa・s,較佳為10至45mPa・s、較佳為10至40mPa・s、較佳為10至35mPa・s、較佳為10至30mPa・s、進而較佳為10至25mPa・s、尤佳為10至22mPa・s。The viscosity (η) of the liquid crystal composition of the present invention at 20°C is 10 to 50 mPa·s, preferably 10 to 45 mPa·s, preferably 10 to 40 mPa·s, preferably 10 to 35 mPa·s, more preferably It is 10 to 30 mPa·s, more preferably 10 to 25 mPa·s, and particularly preferably 10 to 22 mPa·s.
本發明的液晶組成物於20℃的旋轉黏性(γ 1)為50至160mPa・s,較佳為55至160mPa・s、較佳為60至160mPa・s、較佳為60至150mPa・s、較佳為60至140mPa・s、較佳為60至130mPa・s、較佳為60至125mPa・s、更佳為60至120mPa・s、更佳為60至115mPa・s、更佳為60至110mPa・s、尤佳為60至100mPa・s。 The rotational viscosity (γ 1 ) of the liquid crystal composition of the present invention at 20°C is 50 to 160 mPa·s, preferably 55 to 160 mPa·s, preferably 60 to 160 mPa·s, preferably 60 to 150 mPa·s , Preferably 60 to 140mPa·s, preferably 60 to 130mPa·s, preferably 60 to 125mPa·s, more preferably 60 to 120mPa·s, more preferably 60 to 115mPa·s, more preferably 60 To 110mPa·s, particularly preferably 60 to 100mPa·s.
本發明的液晶組成物的向列相-各向同性液體相轉移溫度(T ni)為60℃至120℃,更佳為70℃至100℃,尤佳為70℃至85℃。 The nematic-isotropic liquid phase transition temperature (T ni ) of the liquid crystal composition of the present invention is 60°C to 120°C, more preferably 70°C to 100°C, and particularly preferably 70°C to 85°C.
相對於本發明的組成物的總量,通式(i)、通式(L)、通式(N-1d)、通式(N-1)及通式(II)所示的化合物的合計的較佳含量的下限值為80%、85%、88%、90%、92%、93%、94%、95%、96%、97%、98%、99%、100%。較佳含量的上限值為100%、99%、98%、95%。The total of the compounds represented by general formula (i), general formula (L), general formula (N-1d), general formula (N-1), and general formula (II) relative to the total amount of the composition of the present invention The lower limit of the preferred content is 80%, 85%, 88%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%. The upper limit of the preferred content is 100%, 99%, 98%, 95%.
中性的化合物(通式(i)所示的化合物及通式(L)所示的化合物)中的通式(i)所示的化合物的合計的較佳含量的下限值為0.5%、1%、3%、5%、7%、9%、12%、15%。較佳的上限值為20%、15%、12%、10%、8%、6%、5%。The lower limit of the total preferable content of the compound represented by the general formula (i) in the neutral compound (the compound represented by the general formula (i) and the compound represented by the general formula (L)) is 0.5%, 1%, 3%, 5%, 7%, 9%, 12%, 15%. The preferred upper limit value is 20%, 15%, 12%, 10%, 8%, 6%, 5%.
相對於本發明的液晶組成物的總量,通式(i)及通式(L)所示的化合物的合計的較佳含量的下限值為5%、10%、15%、20%、25%、30%。較佳含量的上限值為70%、60%、55%、50%、45%、40%。With respect to the total amount of the liquid crystal composition of the present invention, the lower limits of the total preferable content of the compounds represented by general formula (i) and general formula (L) are 5%, 10%, 15%, 20%, 25%, 30%. The upper limit of the preferred content is 70%, 60%, 55%, 50%, 45%, 40%.
在本發明的液晶組成物中,作為中性的化合物的組合,較佳為將通式(i)、(L-1)、(L-4)及/或(L-5)所示的化合物組合。In the liquid crystal composition of the present invention, as a combination of neutral compounds, it is preferable to combine compounds represented by general formulas (i), (L-1), (L-4) and/or (L-5) combination.
在本發明的液晶組成物中,作為中性的化合物的組合,較佳為將通式(i)、(L-1-3)及(L-2)所示的化合物組合。In the liquid crystal composition of the present invention, as a combination of neutral compounds, it is preferable to combine compounds represented by general formulas (i), (L-1-3), and (L-2).
在本發明的液晶組成物中,作為中性的化合物的組合,較佳為將通式(i)、(L-1-3)及(L-3)所示的化合物組合。In the liquid crystal composition of the present invention, as a combination of neutral compounds, it is preferable to combine compounds represented by general formulas (i), (L-1-3) and (L-3).
在本發明的液晶組成物中,為了加快聚合性化合物的聚合速度,較佳為將通式(i)及(L-3.6)或(L-3.7)所示的化合物組合。In the liquid crystal composition of the present invention, in order to increase the polymerization rate of the polymerizable compound, it is preferable to combine the compounds represented by the general formula (i) and (L-3.6) or (L-3.7).
在重視應答速度時,較佳為含有具有烯基的化合物。相對於本發明的組成物的總量,具有烯基的化合物的合計的較佳含量的上限值為95%、90%、85%、80%、75%、70%、65%、60%、55%、50%、45%、40%、35%、30%、25%、20%、15%、10%、5%。When attaching importance to response speed, it is preferable to contain a compound having an alkenyl group. With respect to the total amount of the composition of the present invention, the upper limit of the total preferable content of the compounds having alkenyl groups is 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60% , 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%.
在重視可靠性時,較佳為減少具有烯基的化合物。相對於本發明的組成物的總量,含有烯基的化合物的合計的較佳含量的上限值為30%、25%、20%、15%、13%、10%、8%、5%、3%、2%、1%,較佳為實質上不含。When reliability is important, it is preferable to reduce compounds having alkenyl groups. The upper limit value of the total preferable content of the alkenyl group-containing compound relative to the total amount of the composition of the present invention is 30%, 25%, 20%, 15%, 13%, 10%, 8%, 5% , 3%, 2%, 1%, preferably substantially free.
本發明的液晶組成物較佳為不含在分子內具有過酸(-CO-OO-)結構等由氧原子彼此鍵合而成的結構的化合物。The liquid crystal composition of the present invention preferably does not contain a compound having a structure in which oxygen atoms are bonded to each other such as a peracid (-CO-OO-) structure in the molecule.
就本發明的液晶組成物而言,在重視可靠性及長期穩定性時,較佳為將具有羰基的化合物的含量相對於上述組成物的總質量設為5%以下,更佳為設為3%以下,進而較佳為設為1%以下,最佳為實質上不含。In the liquid crystal composition of the present invention, when reliability and long-term stability are important, the content of the compound having a carbonyl group relative to the total mass of the composition is preferably 5% or less, more preferably 3 % Or less, more preferably 1% or less, and most preferably substantially no content.
在重視基於UV照射的穩定性時,較佳為將取代有氯原子的化合物的含量相對於上述組成物的總質量設為15%以下、較佳為設為10%以下、較佳為設為8%以下、更佳為設為5%以下、較佳為設為3%以下、進而較佳為實質上不含。When attaching importance to stability based on UV irradiation, it is preferable to set the content of the compound substituted with chlorine atoms to 15% or less, preferably 10% or less, and more preferably to the total mass of the above-mentioned composition. 8% or less, more preferably 5% or less, more preferably 3% or less, and still more preferably substantially free.
較佳為將分子內的環結構均為6員環的化合物的含量設為較多,較佳為將分子內的環結構均為6員環的化合物的含量相對於上述組成物的總質量設為80%以上、更佳為設為90%以上、進而較佳為設為95%以上、最佳為實質上僅由分子內的環結構均為6員環的化合物構成組成物。It is preferable to set the content of compounds whose intramolecular ring structures are all 6-membered rings to be large, and it is preferable to set the content of compounds whose intra-molecular ring structures are all 6-membered rings relative to the total mass of the above-mentioned composition. It is 80% or more, more preferably 90% or more, still more preferably 95% or more, and most preferably, the composition is substantially composed of compounds whose intramolecular ring structures are all 6-membered rings.
為了提高組成物的傾斜穩定性,較佳為將側鏈為烷基及烷氧基的化合物的含量設為較多,較佳為將側鏈為烷基及烷氧基的化合物的含量相對於上述組成物的總質量設為85%以上、較佳為設為87%以上、較佳為設為90%以上、較佳為設為93%以上、較佳為設為95%以上、較佳為設為98%以上、進而較佳為設為實質上100%。實質上100%意指,除了聚合性化合物、穩定劑及附帶混入的雜質以外為100%。In order to improve the tilt stability of the composition, it is preferable to increase the content of the compound whose side chain is an alkyl group and alkoxy group, and it is preferable to set the content of the compound whose side chain is an alkyl group and alkoxy group with respect to The total mass of the above composition is set to 85% or more, preferably 87% or more, preferably 90% or more, preferably 93% or more, preferably 95% or more, preferably It is set to 98% or more, and more preferably set to be substantially 100%. Substantially 100% means 100% except for the polymerizable compound, stabilizer, and incidental impurities.
為了抑制由組成物的氧化所致的劣化,較佳為將具有伸環己烯基作為環結構的化合物的含量設為較少,較佳為將具有伸環己烯基的化合物的含量相對於上述組成物的總質量設為10%以下、較佳為設為8%以下、更佳為設為5%以下、較佳為設為3%以下、進而較佳為實質上不含。In order to suppress deterioration due to oxidation of the composition, it is preferable to set the content of the compound having a cyclohexenylene group as a ring structure to be small, and it is preferable to set the content of the compound having a cyclohexenylene group to The total mass of the above composition is 10% or less, preferably 8% or less, more preferably 5% or less, more preferably 3% or less, and more preferably substantially free.
在重視黏度的改善及Tni的改善時,較佳為將分子內具有可使氫原子被取代為鹵素的2-甲基苯-1,4-二基的化合物的含量設為較少,較佳為將上述分子內具有2-甲基苯-1,4-二基的化合物的含量相對於上述組成物的總質量設為10%以下、較佳為設為8%以下、更佳為設為5%以下、較佳為設為3%以下、進而較佳為實質上不含。When focusing on improving the viscosity and improving the Tni, it is preferable to set the content of the compound having a 2-methylbenzene-1,4-diyl group capable of substituting a hydrogen atom with a halogen in the molecule to be small, and it is more preferable In order to set the content of the compound having 2-methylbenzene-1,4-diyl group in the molecule relative to the total mass of the composition to be 10% or less, preferably 8% or less, more preferably It is 5% or less, preferably 3% or less, and more preferably substantially not contained.
為了解決本發明的課題,需要將作為第一成分的通式(i)所示的化合物、作為第二成分的通式(L)所示的化合物、作為第三成分的通式(N-1d)及/或通式(N-1)所示的化合物、及作為第四成分的通式(II)所示的聚合性化合物組合。In order to solve the problem of the present invention, it is necessary to combine the compound represented by the general formula (i) as the first component, the compound represented by the general formula (L) as the second component, and the general formula (N-1d) as the third component. ) And/or a combination of a compound represented by general formula (N-1) and a polymerizable compound represented by general formula (II) as the fourth component.
在本發明中,實質上不含意指除了無意中含有的物質以外不含有。In the present invention, "substantially free" means not containing other than inadvertently contained substances.
向本發明的組成物添加單體時,即使不存在聚合起始劑,聚合亦進行,但為了促進聚合亦可含有聚合起始劑。作為聚合起始劑,可列舉苯偶姻醚類、二苯甲酮類、苯乙酮類、苯偶醯縮酮類、醯基氧化膦類等。When a monomer is added to the composition of the present invention, even if a polymerization initiator is not present, the polymerization proceeds, but in order to promote polymerization, a polymerization initiator may be contained. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzal ketals, and phosphine oxides.
本發明的液晶組成物除上述化合物以外,亦可含有常用之向列型液晶、層列型液晶、膽固醇型液晶、上述以外之聚合性化合物、抗氧化劑、紫外線吸收劑、光穩定劑或紅外線吸收劑等。In addition to the above-mentioned compounds, the liquid crystal composition of the present invention may also contain commonly used nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, polymerizable compounds other than the above, antioxidants, ultraviolet absorbers, light stabilizers, or infrared absorbers.剂 etc.
作為抗氧化劑,可列舉通式(Q-1)至通式(Q-4)所示的受阻酚(hindered phenol)。Examples of antioxidants include hindered phenols represented by general formula (Q-1) to general formula (Q-4).
上述式中,R Q1分別獨立地表示碳原子數1至30的烷基、碳原子數1至30的烷氧基、碳原子數2至30的烯基或碳原子數2至30的烯氧基,存在於基中的1個-CH 2-或不相鄰的2個以上的-CH 2-可分別獨立地被-O-、-COO-、-OCO-或-S-取代,又,存在於基中的1個或2個以上的氫原子可分別獨立地被氟原子或氯原子取代。 In the above formula, R Q1 each independently represents an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkylene oxide having 2 to 30 carbon atoms. The group, one -CH 2 -existing in the group or two or more non-adjacent -CH 2 -can be independently substituted by -O-, -COO-, -OCO- or -S-, and, One or two or more hydrogen atoms present in the group may be substituted with a fluorine atom or a chlorine atom, respectively.
M Q1表示碳原子數1至15的伸烷基(該伸烷基中的1個或2個以上的-CH 2-亦能夠以氧原子不直接相鄰的方式被-O-、-CO-、-COO-、-OCO-取代)、-OCH 2-、-CH 2O-、-COO-、-OCO-、-CF 2O-、-OCF 2-、-CF 2CF 2-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-CH=CH-、-C≡C-、單鍵、1,4-伸苯基(1,4-伸苯基中任意的氫原子亦可被氟原子取代)或反-1,4-伸環己基,較佳為碳原子數1至14的伸烷基。 M Q1 represents an alkylene group having 1 to 15 carbon atoms (one or more -CH 2 -in the alkylene group can also be -O-, -CO- in such a way that oxygen atoms are not directly adjacent to each other). , -COO-, -OCO- substituted), -OCH 2 -, -CH 2 O-, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -CF 2 CF 2 -, -CH =CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -C≡C-, single bond, 1,4-extension A phenyl group (any hydrogen atom in the 1,4-phenylene group may be substituted by a fluorine atom) or a trans-1,4-cyclohexylene group, preferably an alkylene group having 1 to 14 carbon atoms.
通式(Q-1)至通式(Q-4)中,1,4-伸苯基中的1個或非相鄰的2個以上的-CH=亦可被-N=取代。又,1,4-伸苯基中的氫原子各自獨立地亦可被氟原子或氯原子取代。In general formula (Q-1) to general formula (Q-4), one or two or more non-adjacent -CH= in the 1,4-phenylene group may be substituted with -N=. In addition, the hydrogen atoms in the 1,4-phenylene group may each independently be substituted with a fluorine atom or a chlorine atom.
通式(Q-2)及通式(Q-4)中,1,4-伸環己基中的1個或非相鄰的2個以上的-CH 2-亦可被-O-或-S-取代。又,1,4-伸環己基中的氫原子各自獨立地亦可被氟原子或氯原子取代。 In general formula (Q-2) and general formula (Q-4), one or more non-adjacent two or more -CH 2 -in 1,4-cyclohexylene may be -O- or -S -replace. In addition, the hydrogen atoms in the 1,4-cyclohexylene group may each independently be substituted with a fluorine atom or a chlorine atom.
作為抗氧化劑,更佳為可列舉下述式(Q-11)至(Q-41)所示的化合物。As the antioxidant, more preferably, compounds represented by the following formulas (Q-11) to (Q-41) can be cited.
上述式中,R Q11至R Q13分別獨立地表示碳原子數1至20的烷基,M Q11及M Q12分別獨立地表示碳原子數1至10的伸烷基。 In the above formula, R Q11 to R Q13 each independently represent an alkyl group having 1 to 20 carbon atoms, and M Q11 and M Q12 each independently represent an alkylene group having 1 to 10 carbon atoms.
本發明的液晶組成物亦可含有至少一種以上的通式(I-2)所示的化合物作為光穩定劑(HALS)。The liquid crystal composition of the present invention may contain at least one compound represented by the general formula (I-2) as a light stabilizer (HALS).
(式中,R H1及R H2分別獨立地表示氫原子或碳原子數1至10的烷基,M表示碳原子數1至15的伸烷基,存在於M中的1個以上的-CH 2-可被-O-、-CH=CH-、-C≡C-、-CO-、-OCO-、-COO-、反-1,4-伸環己基、1,4-伸苯基、萘-2,6-二基取代)。 (In the formula, R H1 and R H2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, M represents an alkylene group having 1 to 15 carbon atoms, and one or more -CH in M 2 -Can be -O-, -CH=CH-, -C≡C-, -CO-, -OCO-, -COO-, trans-1,4-cyclohexylene, 1,4-phenylene, Naphthalene-2,6-diyl substituted).
通式(I-2)中,R H1及R H2尤佳為氫原子。在為烷基的情況下,較佳為碳原子數為1至8、更佳為碳原子數為1至5、進而較佳為碳原子數為1至3、尤佳為碳原子數為1。 In the general formula (I-2), R H1 and R H2 are particularly preferably hydrogen atoms. In the case of an alkyl group, the number of carbon atoms is preferably 1 to 8, more preferably the number of carbon atoms is 1 to 5, still more preferably the number of carbon atoms is 1 to 3, and particularly preferably the number of carbon atoms is 1. .
通式(I-2)中,M表示碳原子數1至15的伸烷基,考慮對液晶組成物賦予的黏性、自身的揮發性,M較佳為碳原子數2至10的伸烷基、更佳為碳原子數4至8的伸烷基、進而較佳為碳原子數6或8的伸烷基。In the general formula (I-2), M represents an alkylene having 1 to 15 carbon atoms, and considering the viscosity imparted to the liquid crystal composition and its own volatility, M is preferably an alkylene having 2 to 10 carbon atoms The group is more preferably an alkylene group having 4 to 8 carbon atoms, and still more preferably an alkylene group having 6 or 8 carbon atoms.
具體而言,可列舉通式(I-24)、通式(I-26)及通式(I-28)所示的化合物。該等式中的R H1及R H2如前所述。 Specifically, compounds represented by general formula (I-24), general formula (I-26), and general formula (I-28) can be cited. R H1 and R H2 in the equation are as described above.
若進一步詳述,可列舉通式(I-24H)、通式(I-26H)及通式(I-28H)所示的化合物,最佳為通式(I-28H)所示的雙(2,2,6,6,-四甲基-4-哌啶基)癸二酸酯。In further detail, the compounds represented by general formula (I-24H), general formula (I-26H) and general formula (I-28H) can be cited, and the best is the double (I-28H) represented by general formula (I-28H). 2,2,6,6,-Tetramethyl-4-piperidinyl) sebacate.
又,亦較佳為通式(I-3)所示的化合物。通式(I-3)所示的化合物由於有效胺濃度高,故為更有效地作用的化合物。又,分子量小的光穩定劑吸附液晶顯示元件中的配向膜,從而誘發顯示不均的情況較多,但通式(I-3)所示的化合物的分子量大,因此能夠防止誘發顯示不均。 Moreover, the compound represented by general formula (I-3) is also preferable. Since the compound represented by the general formula (I-3) has a high effective amine concentration, it is a compound that acts more effectively. In addition, light stabilizers with a small molecular weight adsorb the alignment film in the liquid crystal display element to induce display unevenness in many cases, but the compound represented by the general formula (I-3) has a large molecular weight, so it can prevent the induction of display unevenness .
(式中,R H3、R H4及R H5分別獨立地表示氫原子或碳原子數1至10的烷基。n H1及n H2分別獨立地表示0至2。n H3表示1或2。當R H5存在複數個時,該等可相同亦可不同)。 (In the formula, R H3 , R H4 and R H5 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. n H1 and n H2 each independently represent 0 to 2. n H3 represents 1 or 2. When When there are plural R H5 , these may be the same or different).
通式(I-3)中,R H3、R H4及R H5尤佳為氫原子。在為烷基時,較佳為碳原子數為1至8、更佳為碳原子數為1至5、進而較佳為碳原子數為1至3、進而較佳為碳原子數為1。 In the general formula (I-3), R H3 , R H4 and R H5 are particularly preferably hydrogen atoms. In the case of an alkyl group, the number of carbon atoms is preferably 1 to 8, more preferably the number of carbon atoms is 1 to 5, still more preferably the number of carbon atoms is 1 to 3, and still more preferably the number of carbon atoms is 1.
具體而言,較佳為通式(I-31)、通式(I-32)及通式(I-33)所示的化合物。該等式中的R H3、R H4及R H5如前所述。 Specifically, compounds represented by general formula (I-31), general formula (I-32) and general formula (I-33) are preferred. R H3 , R H4 and R H5 in the equation are as described above.
更具體而言,較佳為式(I-31H)、式(I-31C)、式(I-32H)及式(I-33H)所示的化合物。More specifically, compounds represented by formula (I-31H), formula (I-31C), formula (I-32H), and formula (I-33H) are preferred.
本發明的液晶組成物較佳為在組成物中以下限值計含有光穩定劑(HALS)0.01%以上、較佳為含有0.02%以上、較佳為含有0.03%以上、較佳為含有0.05%以上、較佳為含有0.07%以上、較佳為含有0.1%以上、較佳為含有0.15%以上、較佳為含有0.2%以上、較佳為含有0.25%以上、較佳為含有0.3%以上、較佳為含有0.5%以上、較佳為含有1%以上。又,以上限值計較佳為含有5%以下、較佳為含有3%以下、較佳為含有1%以下、較佳為含有0.5%以下、較佳為含有0.45%以下、較佳為含有0.4%以下、較佳為含有0.35%以下、較佳為含有0.3%以下、較佳為含有0.25%以下、較佳為含有0.2%以下、較佳為含有0.15%以下、較佳為含有0.1%以下、較佳為含有0.07%以下、較佳為含有0.05%以下、較佳為含有0.03%以下。The liquid crystal composition of the present invention preferably contains a light stabilizer (HALS) in the composition below 0.01% or more, preferably 0.02% or more, preferably 0.03% or more, preferably 0.05% Above, preferably 0.07% or more, preferably 0.1% or more, preferably 0.15% or more, preferably 0.2% or more, preferably 0.25% or more, preferably 0.3% or more, Preferably it contains 0.5% or more, and more preferably contains 1% or more. In addition, the above limit is preferably 5% or less, preferably 3% or less, preferably 1% or less, preferably 0.5% or less, preferably 0.45% or less, and preferably 0.4 % Or less, preferably 0.35% or less, preferably 0.3% or less, preferably 0.25% or less, preferably 0.2% or less, preferably 0.15% or less, preferably 0.1% or less , The content is preferably 0.07% or less, preferably 0.05% or less, and more preferably 0.03% or less.
更具體而言,較佳為含有0.01至5質量%、較佳為0.01至0.3質量%、進而較佳為0.02至0.3質量%、尤佳為0.05至0.25質量%。若進一步詳述,在重視抑制低溫時的析出時,其含量較佳為0.01至0.1質量%。More specifically, the content is preferably 0.01 to 5% by mass, more preferably 0.01 to 0.3% by mass, more preferably 0.02 to 0.3% by mass, and particularly preferably 0.05 to 0.25% by mass. In further detail, when emphasis is placed on suppressing precipitation at low temperatures, the content is preferably 0.01 to 0.1% by mass.
關於本發明的含有聚合性化合物的組成物,其所含的聚合性化合物因紫外線照射而聚合,從而被賦予液晶配向能力,被用於利用組成物的雙折射來控制光的穿透光量的液晶顯示元件。Regarding the polymerizable compound-containing composition of the present invention, the polymerizable compound contained therein is polymerized by ultraviolet irradiation, thereby being endowed with liquid crystal alignment ability, and is used for a liquid crystal that uses the birefringence of the composition to control the amount of light transmitted Display components.
使用本發明的組成物的液晶顯示元件不存在或極少有殘影(IS:Image Sticking)等顯示不良、VHR高、可靠性優異,尤其可適用於主動矩陣驅動用液晶顯示元件的PSVA模式或PSA模式。又,亦可適用於以不具有配向膜為特徵的液晶顯示元件。The liquid crystal display element using the composition of the present invention does not have or has very little display failure such as image sticking (IS: Image Sticking), high VHR, and excellent reliability. It is especially suitable for the PSVA mode or PSA of liquid crystal display elements for active matrix driving. mode. In addition, it can also be applied to a liquid crystal display element characterized by not having an alignment film.
又,在基於ODF法的液晶顯示元件的製造步驟中,需要根據液晶顯示元件的尺寸來滴加最適當的液晶注入量,但本發明的液晶組成物例如對在液晶滴加時所產生的滴加裝置內的急遽壓力變化及衝擊的影響小、能夠長時間穩定地持續滴加液晶,因此亦能夠使液晶顯示元件的產率保持較高。特別是對於最近流行的智慧手機中常用的小型液晶顯示元件而言,由於最適當的液晶注入量少,因此難以將與最適值的偏差控制在一定範圍,但藉由使用本發明的液晶組成物,即使在小型液晶顯示元件中亦能夠實現穩定的液晶材料的吐出量。Furthermore, in the manufacturing process of the liquid crystal display element based on the ODF method, it is necessary to drop the most appropriate liquid crystal injection amount according to the size of the liquid crystal display element. The impact of sudden pressure changes and shocks in the application device is small, and liquid crystal can be continuously dropped for a long time and stably, so the yield of the liquid crystal display element can also be kept high. Especially for small liquid crystal display elements commonly used in smartphones that are popular recently, it is difficult to control the deviation from the optimal value within a certain range because the most appropriate liquid crystal injection amount is small, but by using the liquid crystal composition of the present invention , Even in a small liquid crystal display element, a stable discharge amount of liquid crystal material can be realized.
根據本發明的液晶組成物,聚合性化合物的聚合速度足夠快且能夠得到沒有或極少有由於預傾角的變化而產生的IS等顯示不良、VHR高、可靠性優異的液晶顯示元件。綜上所述,本發明的液晶組成物能夠顯著提高PSA型或PSVA型的液晶顯示元件的生產效率,產業上的利用價值非常高。According to the liquid crystal composition of the present invention, the polymerization rate of the polymerizable compound is sufficiently fast and it is possible to obtain a liquid crystal display element with no or very few display defects such as IS due to changes in the pretilt angle, high VHR, and excellent reliability. In summary, the liquid crystal composition of the present invention can significantly improve the production efficiency of PSA-type or PSVA-type liquid crystal display elements, and its industrial use value is very high.
本發明的液晶組成物適合於製作PSA型或PSVA型的液晶顯示元件的情形,亦適合於製作NPS型的液晶顯示元件的情形。又,亦適合於製作以不具有配向膜為特徵的PI-less型液晶顯示元件的情形。The liquid crystal composition of the present invention is suitable for the production of PSA type or PSVA type liquid crystal display elements, and is also suitable for the production of NPS type liquid crystal display elements. In addition, it is also suitable for the production of PI-less liquid crystal display elements characterized by not having an alignment film.
本發明的液晶組成物亦適合於不具有配向膜的液晶顯示元件,即通稱為PI-less的模式。例如,較佳為將日本特願2013-552125、日本特願2014-517515、日本特許06081361、日本特願2015-546888、日本特願2017-12710、WO2017041893A、日本特許06070973、WO17/047177等中記載的具有自發配向性的化合物與本發明的液晶組成物組合使用。The liquid crystal composition of the present invention is also suitable for liquid crystal display elements that do not have an alignment film, that is, a mode commonly referred to as PI-less. For example, it is preferable to record in Japanese Patent Application 2013-552125, Japanese Patent Application 2014-517515, Japanese Patent 06081361, Japanese Patent Application 2015-546888, Japanese Patent Application 2017-12710, WO2017041893A, Japanese Patent 06070973, WO17/047177, etc. The compound with spontaneous alignment is used in combination with the liquid crystal composition of the present invention.
本發明的液晶組成物在主動矩陣驅動用液晶顯示元件中有用,可用於PSA、PSVA、PS-IPS、PS-FFS、NPS等液晶顯示元件中。The liquid crystal composition of the present invention is useful in liquid crystal display elements for active matrix driving, and can be used in liquid crystal display elements such as PSA, PSVA, PS-IPS, PS-FFS, and NPS.
本發明的液晶顯示元件較佳為具有:對向配置的第一基板及第二基板;設於上述第一基板或上述第二基板的共用電極;設於上述第一基板或上述第二基板、並且具有薄膜電晶體的像素電極;以及設於上述第一基板與第二基板間的含有液晶組成物的液晶層。根據需要,可按照與上述液晶層接觸的方式在第一基板及/或第二基板的至少一個基板的對面側設置控制液晶分子的配向方向的配向膜。作為該配向膜,可結合液晶顯示元件的驅動模式而適當選擇垂直配向膜、水平配向膜等,且可使用摩擦配向膜(例如,聚醯亞胺)或光配向膜(分解型聚醯亞胺等)等公知的配向膜。進而,可將濾色器適當設置於第一基板或第二基板上,又,亦可在上述像素電極、共用電極上設置濾色器。The liquid crystal display element of the present invention preferably has: a first substrate and a second substrate arranged oppositely; a common electrode provided on the first substrate or the second substrate; And there is a pixel electrode of a thin film transistor; and a liquid crystal layer containing a liquid crystal composition provided between the first substrate and the second substrate. According to needs, an alignment film that controls the alignment direction of liquid crystal molecules may be provided on the opposite side of at least one of the first substrate and/or the second substrate in a manner in contact with the above-mentioned liquid crystal layer. As the alignment film, a vertical alignment film, a horizontal alignment film, etc. can be appropriately selected according to the driving mode of the liquid crystal display element, and a rubbing alignment film (for example, polyimide) or a photo-alignment film (decomposable polyimide) can be used. Etc.) and other well-known alignment films. Furthermore, the color filter can be appropriately provided on the first substrate or the second substrate, and the color filter can also be provided on the above-mentioned pixel electrode and the common electrode.
關於本發明的液晶顯示元件中所使用的液晶單元的2片基板,可使用玻璃或如塑膠般之具有柔軟性的透明材料,亦可一者為矽等不透明材料。具有透明電極層的透明基板例如可藉由在玻璃板等透明基板上濺鍍氧化銦錫(ITO)而得到。Regarding the two substrates of the liquid crystal cell used in the liquid crystal display element of the present invention, glass or a flexible transparent material such as plastic may be used, or one may be an opaque material such as silicon. The transparent substrate having a transparent electrode layer can be obtained by, for example, sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.
濾色器可藉由例如顏料分散法、印刷法、電沉積法或染色法等而製作。以利用顏料分散法的濾色器的製作方法為一例進行說明,將濾色器用的硬化性著色組成物塗布於該透明基板上,實施圖案化處理,繼而,利用加熱或光照射使之硬化。針對紅、綠、藍3種顏色分別進行該步驟,從而能夠製作濾色器用的像素部。又,亦可在該基板上設置設有TFT、薄膜二極體、金屬絕緣體金屬電阻率元件等主動元件的像素電極。The color filter can be produced by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. Taking a method of manufacturing a color filter by the pigment dispersion method as an example, a curable coloring composition for a color filter is coated on the transparent substrate, patterning is performed, and then the color filter is cured by heating or light irradiation. By performing this step for each of the three colors of red, green, and blue, it is possible to produce a pixel portion for a color filter. In addition, pixel electrodes provided with active elements such as TFTs, thin-film diodes, metal insulators and metal resistivity elements may also be provided on the substrate.
較佳為使上述第一基板及上述第二基板以共用電極、像素電極層成為內側的方式對向。Preferably, the first substrate and the second substrate are opposed to each other such that the common electrode and the pixel electrode layer are inside.
第一基板及第二基板之間的間隔可藉由間隔物進行調整。此時,較佳為以所得的調光層的厚度成為1~100μm的方式進行調整。進而較佳為1.5至10μm,在使用偏光板的情況下,較佳為以使對比度變為最大的方式調整液晶的折射率各向異性Δn與單元厚度d之積。又,在具有兩片偏光板的情況下,亦可調整各偏光板的偏光軸並以視野角、對比度變良好的方式進行調整。進而,亦可使用用於擴大視野角的相位差膜。作為間隔物,例如,可列舉玻璃粒子、塑膠粒子、氧化鋁粒子、光阻材料等。其後,根據需要,將環氧系熱硬化性組成物等密封劑以設有液晶注入口的形式網版印刷於該基板,將該基板彼此貼合,加熱使密封劑熱硬化。The interval between the first substrate and the second substrate can be adjusted by spacers. At this time, it is preferable to adjust so that the thickness of the obtained light control layer may become 1-100 micrometers. It is more preferably 1.5 to 10 μm. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so as to maximize the contrast. In addition, when there are two polarizing plates, the polarization axis of each polarizing plate may be adjusted and the viewing angle and contrast may be adjusted so that the viewing angle and contrast become good. Furthermore, a retardation film for expanding the viewing angle can also be used. As the spacer, for example, glass particles, plastic particles, alumina particles, photoresist materials, etc. can be cited. After that, if necessary, a sealant such as an epoxy-based thermosetting composition is screen-printed on the substrate in a form provided with a liquid crystal injection port, the substrates are bonded to each other, and the sealant is thermally cured by heating.
關於使液晶組成物夾持於2片基板間的方法,可使用通常的真空注入法或ODF法等。Regarding the method of sandwiching the liquid crystal composition between two substrates, a general vacuum injection method, ODF method, or the like can be used.
作為使本發明的液晶組成物所含的聚合性化合物進行聚合的方法,為了獲得液晶的良好配向性能,期望以適度的聚合速度進行聚合,因此較佳為藉由單獨或併用、或依次照射紫外線或電子束等活性能量射線進行聚合的方法。在使用紫外線的情況下,可使用偏光光源,亦可使用非偏光光源。又,在以使液晶組成物夾持於2片基板間的狀態進行聚合的情況下,至少照射面側的基板必須相對於活性能量射線被賦予適當的透明性。又,亦可使用以下方法:在光照射時使用遮罩而僅使特定的部分聚合後,藉由改變電場、磁場或溫度等條件而使未聚合部分的配向狀態變化,並且進一步照射活性能量射線使其聚合。特別是在進行紫外線曝光時,較佳為對液晶組成物施加直流電場或交流電場並同時進行紫外線曝光。再者,所施加的交流電場較佳為頻率1Hz至10kHz的交流,更佳為頻率60Hz至10kHz,電壓依據液晶顯示元件所期望的預傾角而選擇。即,可藉由施加的電壓來控制液晶顯示元件的預傾角。在PSA型或PSVA型的液晶顯示元件中,從配向穩定性及對比度的觀點而言,較佳為將預傾角控制在80度至89.9度。As a method of polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention, in order to obtain good alignment performance of the liquid crystal, it is desirable to perform the polymerization at a moderate polymerization rate. Therefore, it is preferable to use it alone or in combination or sequentially irradiating ultraviolet rays. Or electron beam and other active energy rays polymerization method. In the case of using ultraviolet light, either a polarized light source or a non-polarized light source can be used. In addition, when the liquid crystal composition is polymerized in a state in which the liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be provided with appropriate transparency with respect to active energy rays. In addition, the following method can also be used: after light irradiation uses a mask to polymerize only a specific part, change the alignment state of the unpolymerized part by changing conditions such as electric field, magnetic field, or temperature, and further irradiate active energy rays Make it aggregate. In particular, when performing ultraviolet exposure, it is preferable to apply a direct current electric field or an alternating current electric field to the liquid crystal composition while performing ultraviolet exposure. Furthermore, the applied AC electric field is preferably an AC with a frequency of 1 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage is selected according to the desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In the PSA type or PSVA type liquid crystal display element, from the viewpoint of alignment stability and contrast, it is preferable to control the pretilt angle to 80 degrees to 89.9 degrees.
在PSA型或PSVA型的液晶顯示元件中,當元件製造後聚合性化合物未聚合而原樣殘存時,會產生IS。該殘存的聚合性化合物的量較佳為20ppm以下、進而較佳為15ppm以下、尤佳為10ppm以下、尤佳為檢測下限以下或0。In a PSA-type or PSVA-type liquid crystal display element, when the polymerizable compound remains as it is without being polymerized after the element is manufactured, IS may occur. The amount of the remaining polymerizable compound is preferably 20 ppm or less, more preferably 15 ppm or less, particularly preferably 10 ppm or less, particularly preferably less than the lower detection limit or 0.
關於使本發明的液晶組成物所含的聚合性化合物聚合時所使用的紫外線或電子束等活性能量射線照射時的溫度,沒有特別限制。例如,在將本發明的液晶組成物應用於具備具有配向膜的基板的液晶顯示元件的情況下,較佳為可保持上述液晶組成物的液晶狀態的溫度範圍。即,較佳為以15~50℃聚合。There is no particular limitation on the temperature during irradiation of active energy rays such as ultraviolet rays or electron beams used when polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention. For example, when the liquid crystal composition of the present invention is applied to a liquid crystal display element provided with a substrate having an alignment film, it is preferably a temperature range in which the liquid crystal state of the liquid crystal composition can be maintained. That is, it is preferable to polymerize at 15 to 50°C.
作為產生紫外線的燈,可使用金屬鹵素燈、高壓水銀燈、超高壓水銀燈等。較佳為USHIO公司的超高壓UV燈、TOSHIBA公司的螢光型紫外線燈。又,作為所照射的紫外線的波長,較佳為照射波長區域不處於液晶組成物的吸收波長區域的紫外線,較佳為根據需要而截斷紫外線後使用。所照射的紫外線的強度較佳為0.1mW/cm 2~100W/cm 2、進而較佳為2mW/cm 2~50W/cm 2。所照射的紫外線的能量量可適當調整,較佳為10mJ/cm 2至500J/cm 2、進而較佳為100mJ/cm 2至200J/cm 2。 實施例 As a lamp that generates ultraviolet rays, metal halide lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and the like can be used. Preferably, it is an ultra-high pressure UV lamp of USHIO company, and a fluorescent type ultraviolet lamp of TOSHIBA company. In addition, as the wavelength of the ultraviolet rays to be irradiated, it is preferable to irradiate ultraviolet rays whose wavelength range is not in the absorption wavelength range of the liquid crystal composition, and it is preferable to cut off the ultraviolet rays as necessary and use. The intensity of the irradiated ultraviolet rays is preferably 0.1 mW/cm 2 to 100 W/cm 2 , and more preferably 2 mW/cm 2 to 50 W/cm 2 . The energy amount of the irradiated ultraviolet rays can be appropriately adjusted, and is preferably 10 mJ/cm 2 to 500 J/cm 2 , and more preferably 100 mJ/cm 2 to 200 J/cm 2 . Example
以下,列舉實施例來進一步詳述本發明,但本發明不受該等實施例限定。又,以下的實施例及比較例的組成物中的“%”表示“質量%”。Hereinafter, examples are listed to further describe the present invention, but the present invention is not limited by these examples. In addition, "%" in the composition of the following Examples and Comparative Examples means "mass %".
再者,在實施例中,關於化合物的記載,使用以下簡稱。 (環結構) In addition, in the examples, the following abbreviations are used for the description of the compounds. (Ring structure)
[表1]
[表2]
首先,對附ITO的基板塗布引發垂直配向的聚醯亞胺配向膜後,對上述聚醯亞胺配向膜進行摩擦處理,得到含有附ITO的基板的液晶單元。向該液晶單元以單元間隙3.5μm的方式使用真空注入法注入含有聚合性化合物的液晶組成物。作為垂直配向膜形成材料,使用JSR公司製的JALS2096。First, after coating a polyimide alignment film that initiates vertical alignment on a substrate with ITO, rubbing treatment is performed on the polyimide alignment film to obtain a liquid crystal cell containing a substrate with ITO. The liquid crystal composition containing a polymerizable compound was injected into the liquid crystal cell with a cell gap of 3.5 μm using a vacuum injection method. As a vertical alignment film forming material, JALS2096 manufactured by JSR Corporation was used.
其後,向注入含有聚合性化合物的液晶組成物後的液晶單元在以頻率100Hz施加10V電壓的狀態下使用高壓水銀燈照射紫外線。此時,以在中心波長365nm的條件下測定的照度成為100mW/cm 2的方式調整,並照射累積光量20J/cm 2的紫外線。將上述紫外線照射條件設為照射條件1。藉由該照射條件1對液晶單元中的液晶分子賦予預傾角。 Thereafter, the liquid crystal cell into which the liquid crystal composition containing the polymerizable compound was injected was irradiated with ultraviolet rays using a high-pressure mercury lamp in a state where a voltage of 10 V was applied at a frequency of 100 Hz. At this time, the illuminance measured under the condition of the center wavelength of 365 nm was adjusted so that the illuminance became 100 mW/cm 2 , and ultraviolet rays with a cumulative light amount of 20 J/cm 2 were irradiated. The above-mentioned ultraviolet irradiation condition was set to irradiation condition 1. With this irradiation condition 1, a pretilt angle is given to the liquid crystal molecules in the liquid crystal cell.
繼而,使用螢光UV燈且以在中心波長313nm的條件下測定的照度為3mW/cm 2的方式調整,且進一步照射累積光量10J/cm 2的紫外線,得到液晶顯示元件。將上述紫外線照射條件設為照射條件2。藉由照射條件2來減少在照射條件1下未反應的液晶單元中的聚合性化合物的殘留量。 Then, a fluorescent UV lamp was used and adjusted so that the illuminance measured under the condition of a center wavelength of 313 nm was 3 mW/cm 2 , and further irradiated with ultraviolet rays with a cumulative light amount of 10 J/cm 2 to obtain a liquid crystal display element. Let the above-mentioned ultraviolet irradiation condition be irradiation condition 2. Irradiation condition 2 reduces the residual amount of the polymerizable compound in the unreacted liquid crystal cell under irradiation condition 1.
在紫外線照射後,進行預傾角的變化所引起的顯示不良(殘影)評價。首先,測定液晶顯示元件的預傾角,作為預傾角(初期)。以頻率100Hz對該液晶顯示元件施加30V電壓,並同時照射背光24小時。其後,測定預傾角,作為預傾角(試驗後)。將所測定的預傾角(初期)減去預傾角(試驗後)而得的值作為預傾角變化量(=預傾角變化的絕對值)[°]。預傾角使用Shintec製OPTIPRO來測定。After the ultraviolet irradiation, the display failure (image sticking) caused by the change in the pretilt angle was evaluated. First, the pretilt angle of the liquid crystal display element is measured as the pretilt angle (initial stage). A voltage of 30V was applied to the liquid crystal display element at a frequency of 100 Hz, and the backlight was irradiated for 24 hours at the same time. Thereafter, the pretilt angle was measured and used as the pretilt angle (after the test). The value obtained by subtracting the pretilt angle (after the test) from the measured pretilt angle (initial stage) is used as the pretilt angle change amount (=absolute value of the pretilt angle change) [°]. The pretilt angle was measured using OPTIPRO manufactured by Shintec.
預傾角變化量越接近0[°],則發生預傾角變化所致的顯示不良的可能性越低,達到0.5[°]以上則發生預傾角變化所致的顯示不良的可能性變得更高。The closer the pretilt angle change amount is to 0[°], the lower the possibility of display failure due to the pretilt angle change, and the higher the possibility of display failure due to the pretilt angle change when it reaches 0.5[°] or more. .
測定在上述照射條件1及照射條件2的條件下分別照射紫外線後的液晶顯示元件中的聚合性化合物的殘留量[ppm]。對該聚合性化合物的殘留量的測定方法進行說明。首先,將液晶顯示元件分解,得到含有液晶組成物、聚合物、未反應的聚合性化合物的溶出成分的乙腈溶液。用高效液相層析法對其進行分析,測定各成分的峰面積。由作為指標的液晶化合物的峰面積與未反應的聚合性化合物的峰面積比確定殘存的聚合性化合物的量。由該值與最初添加的聚合性化合物的量確定聚合性化合物的殘留量。再者,聚合性化合物的殘留量的檢測極限為30ppm。在照射條件1及照射條件2的紫外線照射後殘存有聚合性化合物的情況下,發生殘存的聚合性化合物所致的顯示不良的可能性變大。The residual amount [ppm] of the polymerizable compound in the liquid crystal display element after irradiating ultraviolet rays under the conditions of the above-mentioned irradiation condition 1 and irradiation condition 2, respectively, was measured. The method for measuring the residual amount of the polymerizable compound will be described. First, the liquid crystal display element is decomposed to obtain an acetonitrile solution containing eluted components of the liquid crystal composition, the polymer, and the unreacted polymerizable compound. It was analyzed by high performance liquid chromatography to determine the peak area of each component. The amount of the remaining polymerizable compound is determined from the ratio of the peak area of the liquid crystal compound as an index to the peak area of the unreacted polymerizable compound. The residual amount of the polymerizable compound is determined from this value and the amount of the polymerizable compound initially added. In addition, the detection limit of the residual amount of the polymerizable compound is 30 ppm. When the polymerizable compound remains after the ultraviolet irradiation of the irradiation condition 1 and the irradiation condition 2, the possibility of occurrence of display failure due to the remaining polymerizable compound increases.
在頻率60Hz、電壓1V、溫度60℃的條件下測定以上述照射條件1及照射條件2的條件分別照射紫外線後的液晶顯示元件的電壓保持率(VHR)。The voltage holding ratio (VHR) of the liquid crystal display element after irradiating ultraviolet rays under the conditions of the above-mentioned irradiation condition 1 and irradiation condition 2 was measured under the conditions of a frequency of 60 Hz, a voltage of 1 V, and a temperature of 60°C.
(液晶組成物的製備及評價結果)(Preparation and evaluation results of liquid crystal composition)
製備LC-1至LC-4及LC-R1至LC-R3的液晶組成物,測定其物性值。液晶組成物的構成及其物性值的結果如下表所述。The liquid crystal compositions of LC-1 to LC-4 and LC-R1 to LC-R3 were prepared, and their physical properties were measured. The structure of the liquid crystal composition and the results of its physical properties are shown in the following table.
[表3] (實施例1至實施例4及比較例1至2) [table 3] (Example 1 to Example 4 and Comparative Examples 1 to 2)
對於所製備的液晶組成物LC-1至LC-4及LC-R1至LC-R2,以0.3%的摻合比率添加作為聚合性化合物的RM-4所示的聚合性化合物,從而製備含有聚合性化合物的液晶組成物。進行各種評價,作為實施例1至4及比較例1至2。To the prepared liquid crystal compositions LC-1 to LC-4 and LC-R1 to LC-R2, a polymerizable compound represented by RM-4 as a polymerizable compound was added at a blending ratio of 0.3% to prepare a polymer containing Liquid crystal composition of sexual compound. Various evaluations were performed as Examples 1 to 4 and Comparative Examples 1 to 2.
[表4]
可確認到:實施例1至4中,UV照射後的聚合性化合物的殘存量顯著地少,預傾角變化量亦非常小,VHR非常高。另一方面,比較例1中,聚合性化合物的殘存量非常多,暗示容易產生IS等顯示不良。實際評價預傾角變化量,結果比實施例差。可確認:比較例2中,預傾角變化量大,VHR低。It was confirmed that in Examples 1 to 4, the residual amount of the polymerizable compound after UV irradiation was remarkably small, the amount of change in the pretilt angle was also very small, and the VHR was very high. On the other hand, in Comparative Example 1, the residual amount of the polymerizable compound was very large, suggesting that display defects such as IS are likely to occur. The actual evaluation of the amount of change in the pretilt angle was inferior to the examples. It can be confirmed that in Comparative Example 2, the amount of change in the pretilt angle is large, and the VHR is low.
由以上結果確認到實施例1至4解決了本發明的課題。From the above results, it was confirmed that Examples 1 to 4 solved the problem of the present invention.
將實施例1至4中使用的聚合性化合物RM-4替換為RM-3並實施一系列的評價,結果確認到:該等亦是解決了本發明的課題的優異的液晶組成物,可得到優異的液晶顯示元件。The polymerizable compound RM-4 used in Examples 1 to 4 was replaced with RM-3 and a series of evaluations were performed. As a result, it was confirmed that these are also excellent liquid crystal compositions that solve the problems of the present invention, and can be obtained Excellent liquid crystal display element.
將實施例1至4中使用的聚合性化合物RM-4替換為RM-2並實施一系列評價,結果確認到:儘管為略差的結果,該等亦是解決了本發明的課題的優異的液晶組成物,可得到優異的液晶顯示元件。The polymerizable compound RM-4 used in Examples 1 to 4 was replaced with RM-2 and a series of evaluations were performed. As a result, it was confirmed that although the results were slightly worse, these were excellent for solving the problems of the present invention. The liquid crystal composition can provide an excellent liquid crystal display element.
將實施例1至4中使用的聚合性化合物RM-4替換為RM-1並實施一系列的評價,結果確認到:儘管為略差的結果,該等亦是解決了本發明的課題的優異的液晶組成物,可得到優異的液晶顯示元件。The polymerizable compound RM-4 used in Examples 1 to 4 was replaced with RM-1 and a series of evaluations were performed. As a result, it was confirmed that although the results were slightly worse, these were excellent in solving the problems of the present invention. The liquid crystal composition can obtain an excellent liquid crystal display element.
(實施例5至實施例10)(Example 5 to Example 10)
對於所製備的液晶組成物LC-5至LC-10,添加聚合性化合物RM-3,製備含有聚合性化合物的液晶組成物。進行各種評價,作為實施例5至10。To the prepared liquid crystal compositions LC-5 to LC-10, a polymerizable compound RM-3 is added to prepare a liquid crystal composition containing a polymerizable compound. Various evaluations were performed as Examples 5 to 10.
[表5] [table 5]
[表6]
可確認到:實施例5至10的聚合性化合物的殘存量顯著地少,預傾角變化量亦小,VHR亦高。It can be confirmed that the residual amount of the polymerizable compound of Examples 5 to 10 is remarkably small, the amount of pretilt angle change is also small, and the VHR is also high.
由以上結果確認到:本發明的液晶組成物的聚合性化合物的聚合速度充分快,且最適合於沒有由於預傾角的變化而產生的殘影等顯示不良、VHR高、可靠性優異的PSA型或PSVA型的液晶顯示元件。From the above results, it was confirmed that the polymerization rate of the polymerizable compound of the liquid crystal composition of the present invention is sufficiently fast, and it is most suitable for PSA type that has no display defects such as residual image due to changes in pretilt angle, high VHR, and excellent reliability. Or PSVA type liquid crystal display element.
(實施例11至實施例17)(Example 11 to Example 17)
對於所製備的液晶組成物LC-11至LC-13,添加下表所示的聚合性化合物,製備含有聚合性化合物的液晶組成物。進行各種評價,作為實施例11至17。To the prepared liquid crystal compositions LC-11 to LC-13, the polymerizable compound shown in the following table was added to prepare a liquid crystal composition containing the polymerizable compound. Various evaluations were performed as Examples 11-17.
[表7] [Table 7]
[表8]
可確認到:實施例11至17的聚合性化合物的殘存量顯著地少,預傾角變化量亦小,VHR亦高。It can be confirmed that the residual amount of the polymerizable compound of Examples 11 to 17 is remarkably small, the amount of pretilt angle change is also small, and the VHR is also high.
由以上結果確認到:本發明的液晶組成物的聚合性化合物的聚合速度充分快,且最適合於沒有由於預傾角的變化而產生的殘影等顯示不良、VHR高、可靠性優異的PSA型或PSVA型的液晶顯示元件。From the above results, it was confirmed that the polymerization rate of the polymerizable compound of the liquid crystal composition of the present invention is sufficiently fast, and it is most suitable for PSA type that has no display defects such as residual image due to changes in pretilt angle, high VHR, and excellent reliability. Or PSVA type liquid crystal display element.
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