TW202144878A - Liquid crystal element and method for producing same - Google Patents
Liquid crystal element and method for producing same Download PDFInfo
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Abstract
Description
[關聯申請的相互參照] 本申請案基於2020年5月21日提出申請的日本專利申請編號2020-89042號,將其記載內容引用於本申請案中。[Cross-reference to related applications] This application is based on Japanese Patent Application No. 2020-89042 for which it applied on May 21, 2020, and the description is incorporated herein by reference.
本揭示是有關於一種液晶元件及其製造方法。The present disclosure relates to a liquid crystal element and a manufacturing method thereof.
作為液晶元件,已知有於表面形成有透明電極的一對膜基材之間配置有包含液晶與高分子的複合材料的液晶層的高分子分散型液晶元件。近年來,提出了將高分子分散型液晶元件用作調光元件(例如,參照專利文獻1或專利文獻2)。專利文獻1及專利文獻2的調光元件藉由透明電極的電壓施加/未施加電壓的切換,透明性發生變化,從而顯現出調光功能。另外,正在研究利用高分子分散型液晶元件的調光功能,賦予展示窗或智慧型手機、電視、監視器、建築物、家具等新的功能。作為高分子分散型液晶,已知有聚合物分散液晶(Polymer Dispersed Liquid Cristal,PDLC)或聚合物網絡液晶(Polymer Network Liquid Cristal,PNLC)等。As a liquid crystal element, a polymer-dispersed liquid crystal element in which a liquid crystal layer containing a composite material of liquid crystal and a polymer is arranged between a pair of film substrates on which transparent electrodes are formed is known. In recent years, it has been proposed to use a polymer-dispersed liquid crystal element as a light control element (for example, refer to
作為高分子分散型液晶元件,先前提出了藉由將高分子/液晶複合膜的構成材料與矽烷偶合劑一起注入至單元中並進行光照射,於一對基板的表面不形成液晶配向膜而獲得均勻且穩定的液晶配向狀態(例如,參照專利文獻3)。根據該專利文獻3的技術,可不形成控制液晶的配向的液晶配向膜,因此可實現製造步驟的簡化。 [現有技術文獻] [專利文獻]As a polymer-dispersed liquid crystal element, it has previously been proposed to inject a constituent material of a polymer/liquid crystal composite film into a cell together with a silane coupling agent and irradiate it with light, without forming a liquid crystal alignment film on the surfaces of a pair of substrates. Uniform and stable liquid crystal alignment state (for example, see Patent Document 3). According to the technique of this patent document 3, since the liquid crystal alignment film which controls the alignment of a liquid crystal can not be formed, the simplification of a manufacturing process can be achieved. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本專利特開2013-3319號公報 [專利文獻2]日本專利特開2013-148744號公報 [專利文獻3]日本專利特開2000-321562號公報[Patent Document 1] Japanese Patent Laid-Open No. 2013-3319 [Patent Document 2] Japanese Patent Laid-Open No. 2013-148744 [Patent Document 3] Japanese Patent Laid-Open No. 2000-321562
[發明所欲解決之課題] 藉由不使用液晶配向膜來控制液晶分子的配向的無配向膜技術製造的液晶元件由於不進行利用配向膜進行的液晶的初期配向的控制,因此難以決定液晶的初期配向,有時無法形成充分透明的狀態。另外,設想高分子分散型液晶元件於室外或高溫環境下使用。因此,高分子分散型液晶元件要求耐熱性或重覆驅動耐性、彎曲後的光學特性高。[The problem to be solved by the invention] Since the liquid crystal element manufactured by the non-alignment film technique that controls the alignment of liquid crystal molecules without using a liquid crystal alignment film does not control the initial alignment of the liquid crystal by using the alignment film, it is difficult to determine the initial alignment of the liquid crystal, and it may not be possible to form a sufficient liquid crystal element. transparent state. In addition, it is assumed that the polymer-dispersed liquid crystal element is used outdoors or in a high-temperature environment. Therefore, the polymer-dispersed liquid crystal element is required to have high heat resistance, repeated driving resistance, and high optical properties after bending.
本揭示是鑑於所述課題而成者,其主要目的在於提供一種即使不具有液晶配向膜,透明性及光散射性亦高且耐熱性、重覆驅動耐性及彎曲後的光學特性亦良好的液晶元件。 [解決課題之手段]The present disclosure has been made in view of the above-mentioned problems, and its main object is to provide a liquid crystal that has high transparency and light scattering properties, and also has good heat resistance, repetitive driving resistance, and optical properties after bending without having a liquid crystal alignment film. element. [Means of Solving Problems]
本揭示為了解決所述課題而採用以下方法。The present disclosure employs the following methods in order to solve the above-mentioned problems.
<1>一種液晶元件,包括:第一基材,設置有第一電極;第二基材,設置有第二電極且與所述第一基材相向配置;以及液晶層,與所述第一基材及所述第二基材鄰接配置且使含有液晶及聚合性化合物的液晶組成物硬化而形成,所述液晶元件不具有液晶配向膜,自所述第一基材及所述第二基材中的至少一者剝離所述液晶層,將剝離了所述液晶層的基材於己烷中於23℃下浸漬30秒並進行乾燥,對乾燥後的剝離面側的基材表面藉由X射線光電子分光法進行測定時的矽原子相對於碳原子、氧原子與矽原子的合計量的比例為0.05%以上且10%以下。 <2>一種液晶元件的製造方法,包括:將設置有第一電極的第一基材與設置有第二電極的第二基材經由包含含有液晶及聚合性化合物的液晶組成物的層相向配置來構築液晶單元的步驟;以及藉由對所述液晶單元進行光照射,使所述液晶組成物硬化而形成液晶層的步驟, 所述液晶元件不具有液晶配向膜,自所述第一基材及所述第二基材中的至少一者剝離所述液晶層,將剝離了所述液晶層的基材於己烷中於23℃下浸漬30秒並進行乾燥,對乾燥後的剝離面側的基材表面藉由X射線光電子分光法進行測定時的矽原子相對於碳原子、氧原子與矽原子的合計量的比例為0.05%以上且10%以下。 <3>一種液晶元件的製造方法,包括:將設置有第一電極的第一基材與設置有第二電極的第二基材經由包含含有液晶及聚合性化合物的液晶組成物的層相向配置來構築液晶單元的步驟;以及藉由對所述液晶單元進行光照射,使所述液晶組成物硬化的步驟, 所述液晶元件不具有液晶配向膜,藉由以50 mW/cm2 以上的照射量照射150秒以下波長313 nm的光或以150 mW/cm2 以上的照射量照射150秒以下波長365 nm的光來進行所述液晶組成物的硬化。 [發明的效果]<1> A liquid crystal element, comprising: a first base material provided with a first electrode; a second base material provided with a second electrode and disposed opposite to the first base material; and a liquid crystal layer provided with the first base material The base material and the second base material are arranged adjacent to each other and formed by curing a liquid crystal composition containing a liquid crystal and a polymerizable compound. The liquid crystal element does not have a liquid crystal alignment film and is formed from the first base material and the second base material. At least one of the materials peeled off the liquid crystal layer, the substrate from which the liquid crystal layer was peeled was immersed in hexane at 23° C. for 30 seconds and dried, and the surface of the substrate on the side of the peeled surface after drying was treated with The ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms, and silicon atoms when measured by X-ray photoelectron spectroscopy is 0.05% or more and 10% or less. <2> A method for producing a liquid crystal element, comprising: arranging a first substrate provided with a first electrode and a second substrate provided with a second electrode to face each other through a layer containing a liquid crystal composition containing a liquid crystal and a polymerizable compound a step of constructing a liquid crystal cell; and a step of forming a liquid crystal layer by irradiating the liquid crystal cell with light to harden the liquid crystal composition, wherein the liquid crystal element does not have a liquid crystal alignment film, and is formed from the first substrate and at least one of the second substrates to peel off the liquid crystal layer, immerse the substrate from which the liquid crystal layer was peeled at 23° C. in hexane for 30 seconds, and then dry it. The ratio of silicon atoms to the total amount of carbon atoms, oxygen atoms, and silicon atoms when the surface of the substrate is measured by X-ray photoelectron spectroscopy is 0.05% or more and 10% or less. <3> A method for producing a liquid crystal element, comprising: arranging a first substrate provided with a first electrode and a second substrate provided with a second electrode to face each other through a layer containing a liquid crystal composition containing a liquid crystal and a polymerizable compound The step of constructing a liquid crystal cell; and the step of curing the liquid crystal composition by irradiating the liquid crystal cell with light, the liquid crystal cell does not have a liquid crystal alignment film, and by irradiating the liquid crystal cell with more than 50 mW/cm 2 The liquid crystal composition is cured by irradiating light with a wavelength of 313 nm for 150 seconds or less or irradiating light with a wavelength of 365 nm for 150 seconds or less at an irradiation amount of 150 mW/cm 2 or more. [Effect of invention]
根據所述結構,可獲得一種即使於基材上不具有液晶配向膜,透明性及光散射性亦高且耐熱性、重覆驅動耐性及彎曲後的光學特性亦良好的液晶元件。According to such a structure, even if a liquid crystal alignment film is not provided on a base material, transparency and light-scattering property are high, and a liquid crystal element with good heat resistance, repeated driving resistance, and optical characteristics after bending can be obtained.
以下,對與本揭示的態樣相關的事項進行詳細說明。
(第一實施方式)
<液晶元件>
本實施方式的液晶元件為高分子分散型液晶元件。如圖1所示,液晶元件10包括:包含第一基材11及第二基材12的一對基材、以及配置於第一基材11與第二基材12之間的液晶層13。液晶元件10為如下調光元件:利用電場來控制液晶層13中所形成的聚合物網絡13a中存在的液晶分子13b的配向,藉此切換透過光的透過狀態與散射光的不透過狀態。Hereinafter, matters related to the aspect of the present disclosure will be described in detail.
(first embodiment)
<Liquid crystal element>
The liquid crystal element of the present embodiment is a polymer-dispersed liquid crystal element. As shown in FIG. 1 , the
第一基材11及第二基材12為包含玻璃或樹脂材料的透明基材。作為構成基材的樹脂材料,例如可列舉:矽、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚醚碸、聚碳酸酯、聚丙烯、聚氯乙烯、芳香族聚醯胺、聚醯胺醯亞胺、聚醯亞胺、三乙醯基纖維素(Triacetyl Cellulose,TAC)、聚甲基丙烯酸甲酯等材料。第一基材11及第二基材12可為玻璃基板,就可實現液晶元件10的薄型化及輕量化的方面而言,較佳為塑膠基板。The
於第一基材11及第二基材12中,透明電極16、透明電極17分別配置於彼此相向的面,電極對由該些透明電極16、透明電極17構築。透明電極16、透明電極17為透明導電膜,例如為包含氧化錫(SnO2
)的奈塞(NESA)膜(美國PPG公司註冊商標)、包含氧化銦-氧化錫(In2
O3
-SnO2
)的氧化銦錫(Indium Tin Oxide,ITO)膜、或包含碳材料的膜。透明電極16、透明電極17亦可具有梳齒狀等的規定的圖案。In the
液晶層13藉由對含有液晶與聚合性化合物的液晶組成物進行硬化而形成。液晶層13為聚合物與液晶分子13b混合存在的高分子/液晶複合材料層,液晶層13中,構築有使聚合性化合物進行聚合而形成的聚合物網絡13a。液晶元件10中,於第一基材11及第二基材12未形成用於使液晶層13中的液晶分子13b配向的液晶配向膜。再者,液晶元件10於第一基材11及第二基材12的外側表面不包括偏光板。因此,就光的吸收損失少、光的利用效率高的方面而言優異。The
圖2(a)、圖2(b)是用於說明液晶元件10的功能的圖,圖2(a)表示於在透明電極16、透明電極17之間未施加電壓的狀態,圖2(b)表示於在透明電極16、透明電極17之間施加電壓的狀態。液晶元件10是反向型高分子分散型液晶元件。FIGS. 2( a ) and 2 ( b ) are diagrams for explaining the function of the
液晶元件10中,於在透明電極16、透明電極17之間未施加電壓的狀態下,液晶分子13b的長軸方向成為與基板面垂直的方向,藉此,入射光自一對基材的其中一者向另一者透過而成為透明狀態。另一方面,於在透明電極16、透明電極17之間施加電壓的狀態下,液晶分子13b的配向狀態發生變化,液晶分子13b朝向與基板面平行的方向旋轉。藉此,入射光散射而成為非透明的狀態。藉由此種電壓的施加/未施加的切換,液晶元件10顯現出調光功能。液晶元件10例如為膜狀或板狀。再者,液晶元件10亦可根據施加電壓使光透過率可變。In the
液晶元件10中,自第一基材11及第二基材12中的至少一者剝離液晶層13,將剝離了液晶層13的基材於己烷中於23℃下浸漬30秒並進行乾燥,對乾燥後的剝離面側的基材表面藉由X射線光電子分光法(X-ray Photoelectron Spectroscopy,XPS)進行測定時的矽原子相對於碳原子、氧原子與矽原子的合計量的比例(以下,亦稱為「矽表面被覆率」)為0.05%以上且10%以下。若矽表面被覆率未滿0.05%,則存在無法確定液晶的初期配向,無法充分確保透明性,或者無法充分獲得耐熱性、重覆驅動耐性、彎曲耐性及彎曲後的光學特性的改善效果的傾向。就此種觀點而言,矽表面被覆率較佳為0.06%以上,更佳為0.08%以上,進而佳為0.10%以上。另外,若矽表面被覆率多於10%,則存在液晶元件10的重覆驅動耐性、彎曲耐性及彎曲後的光學特性降低的傾向。因此,矽表面被覆率較佳為8.0%以下,更佳為7.5%以下,進而佳為5.0%以下。In the
再者,矽表面被覆率可藉由液晶組成物中的含矽化合物的含量、含矽化合物所具有的矽原子的比率、含矽化合物所具有的含矽基(例如烷氧基矽烷基)的結構等進行調整。藉由基於XPS的表面分析,可獲得關於存在於距離表面數nm深度的元素的資訊。因此,根據所述矽表面被覆率,可掌握液晶元件10中存在於基材與液晶層13的邊界部分的矽原子的量(更具體而言為含矽化合物的量)。Furthermore, the silicon surface coverage can be determined by the content of the silicon-containing compound in the liquid crystal composition, the ratio of silicon atoms contained in the silicon-containing compound, and the amount of silicon-containing groups (such as alkoxysilyl groups) contained in the silicon-containing compound. structure, etc. By XPS-based surface analysis, information about elements present at a depth of several nm from the surface can be obtained. Therefore, the amount of silicon atoms (more specifically, the amount of the silicon-containing compound) present in the boundary portion between the substrate and the
<液晶組成物>
其次,對用於形成液晶元件10的液晶層13的液晶組成物進行說明。液晶組成物含有液晶與聚合性化合物。另外,液晶組成物含有含矽化合物。<Liquid crystal composition>
Next, the liquid crystal composition for forming the
(液晶) 作為液晶,可列舉向列型液晶或層列型液晶等具有液晶相的低分子化合物。使用的液晶較佳為低分子液晶,更佳為向列型液晶。再者,本說明書中,所謂「低分子液晶」,是指不具有分子量分佈且分子量為2000以下的液晶性化合物。低分子液晶較佳為具有合計為2個~10個如下環結構的液晶性化合物:經取代或未經取代的苯環及環己烷環中的至少任一種環結構。低分子液晶具有的環的數量更佳為2個~8個,進而佳為2個~5個。(liquid crystal) Examples of the liquid crystal include low molecular weight compounds having a liquid crystal phase, such as nematic liquid crystals and smectic liquid crystals. The liquid crystal used is preferably a low molecular liquid crystal, more preferably a nematic liquid crystal. In addition, in this specification, the "low molecular weight liquid crystal" means a liquid crystal compound which does not have a molecular weight distribution and a molecular weight is 2000 or less. The low-molecular-weight liquid crystal is preferably a liquid crystal compound having a total of 2 to 10 ring structures including at least any one of a substituted or unsubstituted benzene ring and a cyclohexane ring. The number of rings which the low-molecular-weight liquid crystal has is more preferably 2 to 8, further preferably 2 to 5.
就於不具有液晶配向膜的液晶元件中可實現光學特性提高的方面而言,液晶較佳為含有選自由含環己基氰基的液晶及含二苯乙炔結構的液晶所組成的群組中的至少一種化合物(以下,亦稱為「特定液晶」)。特定液晶較佳為具有負的介電常數各向異性。The liquid crystal preferably contains a liquid crystal selected from the group consisting of a cyclohexyl cyano group-containing liquid crystal and a diphenylacetylene structure-containing liquid crystal, in terms of realizing the improvement of optical properties in a liquid crystal element without a liquid crystal alignment film. At least one compound (hereinafter, also referred to as "specific liquid crystal"). The specific liquid crystal preferably has a negative dielectric constant anisotropy.
作為特定液晶的具體例,含環己基氰基的液晶可列舉下述式(1)所表示的化合物等;含二苯乙炔結構的液晶可列舉下述式(2)所表示的化合物等。 [化1] (式(1)及式(2)中,R1 ~R3 及Y1 ~Y4 分別獨立地為鹵素原子、氰基或碳數1~10的一價有機基,R4 為碳數1~10的一價有機基。a1、a2、b1及b2分別獨立地為0~4的整數)As a specific example of a specific liquid crystal, the compound etc. which are represented by following formula (1) are mentioned as a cyclohexylcyano group containing liquid crystal, and the compound etc. which are represented by following formula (2) are mentioned as a diphenylacetylene structure-containing liquid crystal. [hua 1] (In formula (1) and formula (2), R 1 to R 3 and Y 1 to Y 4 are each independently a halogen atom, a cyano group or a monovalent organic group having 1 to 10 carbon atoms, and R 4 is a carbon number of 1 A monovalent organic group of ~10. a1, a2, b1 and b2 are each independently an integer of 0 to 4)
所述式(1)及式(2)中,R1 ~R4 的一價有機基較佳為碳數1~12的一價烴基、碳數1~12的烴基與氧原子鍵結而成的一價基、或者碳數1~12的烴基的至少一個氫原子經氟原子或氰基取代而成的基。作為鹵素原子,可列舉氟原子、氯原子、溴原子、碘原子等,較佳為氟原子。 作為R1 ~R4 ,就進一步增大折射率各向異性的觀點而言,該些中,較佳為碳數1~10的烷基、碳數1~10的烷氧基、碳數1~10的氟烷基、碳數1~10的氟烷氧基、碳數2~11的含氰基的烷基、或碳數2~11的含氰基的烷氧基。 Y1 ~Y4 的一價有機基較佳為碳數1~3的烷基或烷氧基。作為Y1 ~Y4 ,較佳為氟原子、氰基、碳數1~3的烷基或碳數1~3的烷氧基。In the above formulas (1) and (2), the monovalent organic groups of R 1 to R 4 are preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms, a hydrocarbon group having 1 to 12 carbon atoms, and an oxygen atom bonded to each other. The monovalent group of , or a group in which at least one hydrogen atom of a hydrocarbon group having 1 to 12 carbon atoms is substituted with a fluorine atom or a cyano group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, Preferably it is a fluorine atom. From the viewpoint of further increasing the refractive index anisotropy as R 1 to R 4 , among them, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms are preferred. A fluoroalkyl group having ∼10 carbon atoms, a fluoroalkoxy group having 1 to 10 carbon atoms, a cyano group-containing alkyl group having 2 to 11 carbon atoms, or a cyano group-containing alkoxy group having 2 to 11 carbon atoms. The monovalent organic group of Y 1 to Y 4 is preferably an alkyl group or an alkoxy group having 1 to 3 carbon atoms. As Y 1 to Y 4 , a fluorine atom, a cyano group, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms is preferable.
更詳細而言,所述式(1)所表示的化合物是具有1,2-二苯基乙炔骨架的化合物。所述式(1)中,R1 及R2 更佳為碳數1~10的烷基或烷氧基,進而佳為碳數1~8的烷基或烷氧基。該些中,R1 較佳為碳數1~8的烷基,R2 較佳為碳數2~8的烷氧基。 Y1 及Y2 較佳為鹵素原子或甲基,更佳為氟原子。 a1及b1較佳為0~2,更佳為0或1。所述式(1)所表示的化合物較佳為介電常數各向異性幾乎為零的中性液晶、或者具有負的介電常數各向異性。More specifically, the compound represented by the formula (1) is a compound having a 1,2-diphenylacetylene skeleton. In the above formula (1), R 1 and R 2 are more preferably an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and still more preferably an alkyl group or an alkoxy group having 1 to 8 carbon atoms. Among these, R 1 is preferably an alkyl group having 1 to 8 carbon atoms, and R 2 is preferably an alkoxy group having 2 to 8 carbon atoms. Y 1 and Y 2 are preferably a halogen atom or a methyl group, more preferably a fluorine atom. a1 and b1 are preferably 0 to 2, and more preferably 0 or 1. It is preferable that the compound represented by the said formula (1) is a neutral liquid crystal whose dielectric constant anisotropy is almost zero, or has a negative dielectric constant anisotropy.
所述式(2)所表示的化合物是具有雙環己基氰基骨架的化合物。所述式(2)中,R3 及R4 更佳為碳數2~10的烷基或烷氧基。R3 及R4 的合計碳數較佳為4~15,更佳為6~12。 Y3 及Y4 較佳為鹵素原子或甲基,更佳為氟原子或甲基。a2及b2較佳為0~2,更佳為0或1。所述式(2)所表示的化合物較佳為具有負的介電常數各向異性。The compound represented by the formula (2) is a compound having a bicyclohexylcyano skeleton. In the above formula (2), R 3 and R 4 are more preferably an alkyl group or an alkoxy group having 2 to 10 carbon atoms. The total carbon number of R 3 and R 4 is preferably 4-15, more preferably 6-12. Y 3 and Y 4 are preferably a halogen atom or a methyl group, more preferably a fluorine atom or a methyl group. a2 and b2 are preferably 0 to 2, more preferably 0 or 1. It is preferable that the compound represented by the said formula (2) has negative dielectric constant anisotropy.
作為特定液晶的具體例,所述式(1)所表示的化合物例如可列舉下述式(1-1)~式(1-11)分別所表示的化合物等;所述式(2)所表示的化合物例如可列舉下述式(2-1)~式(2-10)分別所表示的化合物等。作為特定液晶,可單獨使用一種,亦可將兩種以上組合使用。 [化2] [化3] As a specific example of the specific liquid crystal, the compound represented by the formula (1) includes, for example, compounds represented by the following formulae (1-1) to (1-11), and the like; the compound represented by the formula (2) Examples of the compound include compounds represented by the following formulae (2-1) to (2-10), for example. As the specific liquid crystal, one type may be used alone, or two or more types may be used in combination. [hua 2] [hua 3]
液晶組成物亦可進而含有與特定液晶不同的液晶(以下,亦稱為「其他液晶」)。作為其他液晶,可列舉向列型液晶、層列型液晶等,該些中,亦較佳為向列型液晶。The liquid crystal composition may further contain liquid crystals (hereinafter, also referred to as "other liquid crystals") different from the specific liquid crystals. Examples of other liquid crystals include nematic liquid crystals, smectic liquid crystals, and the like, and among these, nematic liquid crystals are also preferred.
作為其他液晶的具體例,具有正的介電各向異性的液晶性化合物例如可列舉:聯苯系液晶、苯基環己烷系液晶、酯系液晶、三聯苯系液晶、聯苯環己烷系液晶、嘧啶系液晶、二噁烷系液晶、雙環辛烷系液晶、立方烷(cubane)系液晶等;具有負的介電各向異性的液晶性化合物例如可列舉:二氰基苯系液晶、噠嗪系液晶、席夫鹼(Schiff base)系液晶、氧化偶氮(azoxy)系液晶、聯苯系液晶、苯基環己烷系液晶、三聯苯系液晶、二氰基苯基酯系液晶、烯基系液晶等。另外,於向列型液晶中,作為液晶,亦可添加氯化膽甾醇(cholesteryl chloride)、膽甾醇壬酸酯(cholesteryl nonanoate)、膽甾醇碳酸酯等膽甾相液晶;對癸氧基苯亞甲基-對胺基-2-甲基丁基桂皮酸酯(p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate)等鐵電性液晶來使用。作為其他液晶,根據介電常數各向異性或雙折射率等各物性值,可單獨使用一種或將兩種以上的液晶混合使用。其他液晶較佳為具有負的介電常數各向異性,更佳為具有負的介電常數各向異性的負型液晶。Specific examples of other liquid crystals include liquid crystal compounds having positive dielectric anisotropy, for example, biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, ester-based liquid crystals, terphenyl-based liquid crystals, and biphenylcyclohexane-based liquid crystals. liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, cubane-based liquid crystals, etc.; liquid crystal compounds having negative dielectric anisotropy include, for example, dicyanobenzene-based liquid crystals , Pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, terphenyl liquid crystal, dicyanophenyl ester liquid crystal Liquid crystal, alkenyl liquid crystal, etc. In addition, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, and cholesteryl carbonate can also be added as liquid crystals to nematic liquid crystals; Ferroelectric liquid crystals such as methyl-p-amino-2-methylbutylcinnamate (p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate) are used. As other liquid crystals, one type of liquid crystal may be used alone or two or more types of liquid crystals may be used in combination according to various physical property values such as dielectric anisotropy and birefringence. The other liquid crystals are preferably negative-type liquid crystals having negative dielectric constant anisotropy, more preferably negative-type liquid crystals having negative dielectric constant anisotropy.
相對於液晶組成物中的特定液晶與其他液晶的合計量,特定液晶的含有比例較佳為1質量%以上,更佳為5質量%以上,進而佳為10質量%以上。另外,相對於液晶組成物中的特定液晶與其他液晶的合計量,特定液晶的含有比例較佳為80質量%以下,更佳為70質量%以下,進而佳為60質量%以下。藉由使特定液晶的含有比例為所述範圍內,可使液晶元件10的未施加電壓時的霧度值更低且使施加電壓時的霧度值更高,可使對比度特性良好,就該方面而言較佳。The content ratio of the specific liquid crystal is preferably 1 mass % or more, more preferably 5 mass % or more, and still more preferably 10 mass % or more with respect to the total amount of the specific liquid crystal and other liquid crystals in the liquid crystal composition. In addition, the content ratio of the specific liquid crystal is preferably 80 mass % or less, more preferably 70 mass % or less, and still more preferably 60 mass % or less with respect to the total amount of the specific liquid crystal and other liquid crystals in the liquid crystal composition. By making the content ratio of the specific liquid crystal within the above-mentioned range, the haze value of the
再者,根據特定液晶,認為由於特定液晶所具有的主骨架(1,2-二苯基乙炔骨架、雙環己基氰基骨架),液晶層中的液晶分子的折射率各向異性變大,藉此,可使未施加電壓時的霧度值更低且可使施加電壓時的霧度值更高,從而可獲得顯示出良好的光學特性的液晶元件。Furthermore, according to the specific liquid crystal, it is considered that the refractive index anisotropy of the liquid crystal molecules in the liquid crystal layer increases due to the main skeleton (1,2-diphenylacetylene skeleton, bicyclohexyl cyano skeleton) possessed by the specific liquid crystal, thereby increasing the refractive index anisotropy of the liquid crystal molecules in the liquid crystal layer. In this way, the haze value when no voltage is applied can be made lower, and the haze value when voltage is applied can be made higher, and a liquid crystal element showing favorable optical characteristics can be obtained.
(聚合性化合物) 聚合性化合物是藉由光及熱中的至少任一者可形成聚合物的低分子化合物。聚合性化合物若可溶解於液晶中,則並無特別限定,較佳為顯示出自由基聚合性的化合物。就光引起的自由基聚合性高的方面而言,自由基聚合性基較佳為選自由(甲基)丙烯醯基、乙烯基、乙烯基氧基、乙烯基苯基(-C6 H5 -CH=CH2 )、烯丙基、馬來醯亞胺基及衣康酸酐基所組成的群組中的至少一種,尤佳為(甲基)丙烯醯基。再者,本說明書中,「(甲基)丙烯酸酯」是指包含丙烯酸酯及甲基丙烯酸酯。「低分子化合物」是不具有分子量分佈的化合物,其分子量較佳為1000以下,更佳為800以下。(Polymerizable compound) A polymerizable compound is a low molecular weight compound which can form a polymer by at least any one of light and heat. The polymerizable compound is not particularly limited as long as it is soluble in a liquid crystal, but a compound showing radical polymerizability is preferred. The radical polymerizable group is preferably selected from the group consisting of a (meth)acryloyl group, a vinyl group, a vinyloxy group, a vinylphenyl group (—C 6 H 5 -CH=CH 2 ), allyl group, maleimide group and at least one of the group consisting of itaconic anhydride group, particularly preferably (meth)acryloyl group. In addition, in this specification, "(meth)acrylate" means that an acrylate and a methacrylate are included. The "low molecular weight compound" is a compound having no molecular weight distribution, and its molecular weight is preferably 1,000 or less, more preferably 800 or less.
作為聚合性化合物,例如可列舉單官能(甲基)丙烯酸酯化合物、多官能(甲基)丙烯酸酯化合物、苯乙烯系化合物。作為聚合性化合物,可較佳地使用具有一個或兩個以上的自由基聚合性基的液晶性化合物(以下,亦稱為「聚合性液晶化合物」)。藉由使用聚合性液晶化合物,可進一步提高液晶元件10的液晶配向性,就該方面而言較佳。As a polymerizable compound, a monofunctional (meth)acrylate compound, a polyfunctional (meth)acrylate compound, and a styrene-type compound are mentioned, for example. As the polymerizable compound, a liquid crystal compound having one or two or more radically polymerizable groups (hereinafter, also referred to as a "polymerizable liquid crystal compound") can be preferably used. By using the polymerizable liquid crystal compound, the liquid crystal alignment of the
聚合性液晶化合物較佳為具有合計兩個以上的經取代或未經取代的芳香環及脂肪族環中的至少任一者的化合物。再者,芳香環包含芳香族烴環及芳香族雜環。聚合性液晶化合物所具有的芳香環較佳為芳香族烴環,可列舉苯環、萘環、蒽環等。該些中,尤佳為苯環。作為聚合性液晶化合物所具有的脂肪族環,可列舉環己烷環、十二烷基環己烷環等,較佳為環己烷環。芳香環或脂肪族環可具有的取代基較佳為氟原子、氰基、羥基或碳數1~4的烷基、烷氧基、氟烷基或含氰基的烷基。The polymerizable liquid crystal compound is preferably a compound having at least one of a total of two or more substituted or unsubstituted aromatic rings and aliphatic rings. In addition, the aromatic ring includes an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The aromatic ring which the polymerizable liquid crystal compound has is preferably an aromatic hydrocarbon ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and the like. Among these, a benzene ring is particularly preferable. As an aliphatic ring which a polymerizable liquid crystal compound has, a cyclohexane ring, a dodecylcyclohexane ring, etc. are mentioned, Preferably it is a cyclohexane ring. The substituent which the aromatic ring or aliphatic ring may have is preferably a fluorine atom, a cyano group, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a fluoroalkyl group, or a cyano group-containing alkyl group.
作為聚合性液晶化合物,就對光的反應性高的方面而言,該些中,尤佳為具有一個或多個(甲基)丙烯醯基且分子量為1000以下的含(甲基)丙烯酸基的化合物(以下,亦稱為「化合物(RM)」)。就於不具有液晶配向膜的液晶元件中進一步提高液晶配向性的觀點而言,化合物(RM)所具有的(甲基)丙烯醯基的數量較佳為2個~6個,更佳為2個~4個。Among the polymerizable liquid crystal compounds, those having one or more (meth)acryloyl groups and having a molecular weight of 1,000 or less are particularly preferred in terms of their high reactivity to light. compound (hereinafter, also referred to as "compound (RM)"). From the viewpoint of further improving the liquid crystal alignment in a liquid crystal element without a liquid crystal alignment film, the number of (meth)acryloyl groups contained in the compound (RM) is preferably 2 to 6, more preferably 2 to 4.
化合物(RM)較佳為具有二價芳香環基。化合物(RM)所具有的芳香環基為自經取代或未經取代的芳香環的環部分中去除兩個氫原子而成的基,較佳為經取代或未經取代的1,4-伸苯基。就賦予良好的液晶配向性的觀點而言,化合物(RM)所具有的芳香環的數量較佳為2個~6個,更佳為2個~4個,尤佳為2個或3個。多個芳香環較佳為經由單鍵或二價連結基而鍵結。就利用剛直的結構提高液晶配向性的觀點而言,二價連結基較佳為-COO-。The compound (RM) preferably has a divalent aromatic ring group. The aromatic ring group possessed by the compound (RM) is a group obtained by removing two hydrogen atoms from the ring moiety of a substituted or unsubstituted aromatic ring, preferably a substituted or unsubstituted 1,4-extended phenyl. From the viewpoint of imparting favorable liquid crystal alignment, the number of the aromatic rings contained in the compound (RM) is preferably 2 to 6, more preferably 2 to 4, and particularly preferably 2 or 3. A plurality of aromatic rings are preferably bonded via a single bond or a divalent linking group. The divalent linking group is preferably -COO- from the viewpoint of improving the alignment of the liquid crystal with a rigid structure.
作為化合物(RM)的具體例,例如可列舉下述式(r-1)~式(r-6)分別所表示的化合物等。另外,作為化合物(RM)的市售品,可列舉LC242(巴斯夫(BASF)公司製造)、RM257(默克(Merck)公司製造)等聚合性液晶。其中,化合物(RM)並不限定於該些化合物。 [化4] (式(r-1)~式(r-6)中,RA 為氫原子或甲基。式中的多個RA 相同或不同)Specific examples of the compound (RM) include compounds represented by the following formulae (r-1) to (r-6), for example. Moreover, as a commercial item of a compound (RM), polymerizable liquid crystals, such as LC242 (made by BASF) and RM257 (made by Merck), are mentioned. However, the compound (RM) is not limited to these compounds. [hua 4] (In formula (r-1) to formula (r-6), R A is a hydrogen atom or a methyl group. A plurality of R A in the formula are the same or different)
於液晶組成物中,聚合性化合物的調配比例可根據應用的液晶元件的種類適宜選擇。於應用於高分子分散型液晶元件的情況下,相對於液晶組成物的全部構成成分的合計量,聚合性化合物的調配比例較佳為設為0.05質量%以上,更佳為設為0.1質量%以上,進而佳為設為0.5質量%以上。另外,相對於液晶組成物的全部構成成分的合計量,聚合性化合物的調配比例較佳為設為30質量%以下,更佳為設為20質量%以下,進而佳為設為15質量%以下。作為聚合性化合物,可單獨使用一種,亦可將兩種以上組合使用。In the liquid crystal composition, the compounding ratio of the polymerizable compound can be appropriately selected according to the type of the liquid crystal element to be applied. When applied to a polymer-dispersed liquid crystal element, the blending ratio of the polymerizable compound is preferably 0.05 mass % or more, more preferably 0.1 mass % with respect to the total amount of all constituent components of the liquid crystal composition. As mentioned above, it is more preferable to set it as 0.5 mass % or more. In addition, the blending ratio of the polymerizable compound is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less with respect to the total amount of all the constituent components of the liquid crystal composition. . As the polymerizable compound, one type may be used alone, or two or more types may be used in combination.
相對於聚合性化合物的總量,聚合性液晶化合物的調配比例較佳為20質量%以上,更佳為30質量%以上,進而佳為50質量%以上。再者,聚合性液晶化合物具有液晶性,但於本說明書中被分類為聚合性化合物。於製備液晶組成物時,就獲得透明性高的液晶元件10的觀點、以及獲得重覆驅動耐性及彎曲後的光學特性良好的液晶元件的觀點而言,尤其是較佳為將聚合性液晶化合物與特定液晶組合使用。The compounding ratio of the polymerizable liquid crystal compound is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 50% by mass or more with respect to the total amount of the polymerizable compound. In addition, although a polymerizable liquid crystal compound has liquid crystallinity, it is classified as a polymerizable compound in this specification. When preparing the liquid crystal composition, from the viewpoint of obtaining a
(含矽化合物)
含矽化合物較佳為含矽聚合物,更佳為聚有機矽氧烷。液晶組成物所含有的聚有機矽氧烷較佳為於側鏈含有具有使液晶分子垂直配向的功能的基(以下,亦稱為「液晶配向性基」)、聚合性基等功能性基的聚有機矽氧烷(以下,亦稱為「功能性聚有機矽氧烷」)。再者,功能性聚有機矽氧烷所具有的功能性基可僅為一種,亦可為兩種以上。功能性聚有機矽氧烷較佳為至少具有液晶配向性基。藉由使用含有具有液晶配向性基的聚有機矽氧烷的液晶組成物形成液晶層13,耐熱性高,且即使不設置液晶配向膜,亦可獲得透明性、重覆驅動耐性、彎曲耐性及彎曲後的光學特性高的液晶元件,就該方面而言較佳。(silicon-containing compound)
The silicon-containing compound is preferably a silicon-containing polymer, more preferably a polyorganosiloxane. The polyorganosiloxane contained in the liquid crystal composition preferably contains functional groups such as a group having a function of vertically aligning liquid crystal molecules (hereinafter, also referred to as a "liquid crystal alignment group") and a polymerizable group in a side chain. Polyorganosiloxane (hereinafter, also referred to as "functional polyorganosiloxane"). Furthermore, the functional group which the functional polyorganosiloxane has may be only one kind, or two or more kinds may be sufficient. The functional polyorganosiloxane preferably has at least a liquid crystal alignment group. By forming the
(液晶配向性基)
作為液晶配向性基,例如可列舉碳數4~20的烷基、碳數4~20的烷氧基、碳數4~20的氟烷基、碳數4~20的氟烷氧基、具有一個環與碳數1~20的鏈狀結構鍵結而成的結構的基、具有兩個以上的環直接或經由二價連結基鍵結而成的結構的基、具有類固醇骨架的基等。該些中,液晶配向性基亦較佳為下述式(3)所表示的基。
*-L1
-R11
-R12
-R13
-R14
…(3)
(式(3)中,L1
為單鍵、-O-、-CO-、-COO-*1
、-OCO-*1
、-NR15
-、-NR15
-CO-*1
、-CO-NR15
-*1
、碳數1~6的烷二基、碳數2~6的烷二基所具有的氫原子經羥基取代而成的二價基、-O-R16
-*1
或-R16
-O-*1
(其中,R15
為氫原子或碳數1~10的一價烴基,R16
為碳數1~3的烷二基。「*1
」表示與R11
的鍵結鍵)。R11
及R13
分別獨立地為單鍵、經取代或未經取代的伸苯基、或者經取代或未經取代的伸環烷基,R12
為單鍵、經取代或未經取代的伸苯基、經取代或未經取代的伸環烷基、或-R17
-B1
-R18
-(其中,R17
及R18
分別獨立地為經取代或未經取代的伸苯基或伸環烷基,B1
為單鍵、-O-、-COO-*2
、-OCO-*2
、-OCH2
-*2
、-CH2
O-*2
或碳數1~3的烷二基。「*2
」表示與R18
的鍵結鍵)。R14
為氫原子、氟原子、氰基、CH3
COO-*3
(「*3
」表示與R13
的鍵結鍵)、碳數1~18的烷基、碳數1~18的氟烷基、碳數1~18的烷氧基、碳數1~18的氟烷氧基、具有類固醇骨架的碳數17~51的烴基、或者碳數1~18的烷基或氟烷基所具有的氫原子經氰基取代而成的一價基。其中,於R11
、R12
及R13
全部為單鍵、或者R11
、R12
及R13
所具有的經取代或未經取代的伸苯基及伸環烷基的合計為一個的情況下,R14
為碳數4~18的烷基、碳數4~18的氟烷基、碳數4~18的烷氧基、碳數4~18的氟烷氧基或具有類固醇骨架的碳數17~51的烴基。「*」表示鍵結鍵)(Liquid Crystal Alignment Group) Examples of the liquid crystal alignment group include an alkyl group having 4 to 20 carbon atoms, an alkoxy group having 4 to 20 carbon atoms, a fluoroalkyl group having 4 to 20 carbon atoms, and an alkyl group having 4 to 20 carbon atoms. Fluoroalkoxy, a group having a structure in which one ring is bonded to a chain structure having 1 to 20 carbon atoms, a group having a structure in which two or more rings are bonded directly or via a divalent linking group, a group having The base of the steroid backbone, etc. Among these, the liquid crystal alignment group is also preferably a group represented by the following formula (3). *-L 1 -R 11 -R 12 -R 13 -R 14 ... (3) (In formula (3), L 1 is a single bond, -O-, -CO-, -COO-* 1 , -OCO- * 1 , -NR 15 -, -NR 15 -CO-* 1 , -CO-NR 15 -* 1 , a hydrogen atom contained in an alkanediyl group having 1 to 6 carbon atoms and an alkanediyl group having 2 to 6 carbon atoms A divalent group substituted by a hydroxyl group, -OR 16 -* 1 or -R 16 -O-* 1 (wherein, R 15 is a hydrogen atom or a monovalent hydrocarbon group with 1 to 10 carbon atoms, and R 16 is a carbon number of 1 ~3 alkanediyl. "* 1 " represents a bond with R 11 ). R 11 and R 13 are each independently a single bond, a substituted or unsubstituted phenylene, or a substituted or unsubstituted phenylene Substituted cycloextended alkyl, R 12 is a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted cycloextended alkyl, or -R 17 -B 1 -R 18 - (wherein, R 17 and R 18 are each independently a substituted or unsubstituted phenylene or cycloalkylene, and B 1 is a single bond, -O-, -COO-* 2 , -OCO-* 2 , -OCH 2 -* 2 , -CH 2 O-* 2 or an alkanediyl group having 1 to 3 carbon atoms. "* 2 " represents a bond with R 18 ). R 14 is a hydrogen atom, a fluorine atom, a cyano group, and a CH 3 group. COO-* 3 (“* 3 ” represents a bond with R 13 ), an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms A 1-18 fluoroalkoxy group, a C17-51 hydrocarbon group having a steroid skeleton, or a C1-18 alkyl group or a monovalent group in which a fluoroalkyl group has a hydrogen atom substituted with a cyano group. However, in the case where all of R 11 , R 12 and R 13 are single bonds, or the total of substituted or unsubstituted phenylene and cycloalkyl groups possessed by R 11 , R 12 and R 13 is one , R 14 is an alkyl group of carbon number 4-18, a fluoroalkyl group of carbon number 4-18, an alkoxy group of carbon number 4-18, a fluoroalkoxy group of carbon number 4-18 or a carbon number having a
所述式(3)中,L1 的烷二基較佳為直鏈狀。作為R15 的碳數1~10的一價烴基,可列舉鏈狀烴基、脂環式烴基及芳香族烴基,較佳為碳數1~3的烷基。 關於R14 ,碳數1~18的烷基、碳數1~18的氟烷基、碳數1~18的烷氧基、碳數1~18的氟烷氧基、或者碳數1~18的烷基或氟烷基所具有的氫原子經氰基取代而成的一價基較佳為直鏈狀。於將液晶元件設為垂直配向系的情況下,該些基較佳為碳數2~18,更佳為碳數3~18,進而佳為碳數4~18。作為R14 的具有類固醇骨架的碳數17~51的烴基,例如可列舉膽甾烷基、膽甾醇基、羊毛甾烷基等。In the above formula (3), the alkanediyl group of L 1 is preferably linear. Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms in R 15 include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and an alkyl group having 1 to 3 carbon atoms is preferred. R 14 is an alkyl group having 1 to 18 carbon atoms, a fluoroalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a fluoroalkoxy group having 1 to 18 carbon atoms, or a fluoroalkoxy group having 1 to 18 carbon atoms. The monovalent group obtained by substituting the hydrogen atom of the alkyl group or the fluoroalkyl group with a cyano group is preferably a straight chain. When the liquid crystal element is a vertical alignment system, the groups preferably have 2 to 18 carbon atoms, more preferably 3 to 18 carbon atoms, and still more preferably 4 to 18 carbon atoms. As a C17-C51 hydrocarbon group which has a steroid skeleton of R14 , a cholestyl group, a cholesteryl group, a lanostane group, etc. are mentioned, for example.
就獲得於不具有液晶配向膜的情況下亦顯示出良好的液晶配向性的液晶元件的觀點而言,液晶配向性基較佳為R11 、R12 及R13 具有合計兩個以上的選自由經取代或未經取代的伸苯基及經取代或未經取代的伸環烷基所組成的群組中的至少一種,更佳為具有2個~4個。再者,具有液晶配向性基的聚有機矽氧烷可於側鏈上與液晶配向性基一起具有聚合性基。再者,具有聚合性基的聚有機矽氧烷是與所述聚合性化合物不同的成分。From the viewpoint of obtaining a liquid crystal element exhibiting good liquid crystal alignment even without a liquid crystal alignment film, the liquid crystal alignment group preferably has a total of two or more selected from R 11 , R 12 and R 13 . At least one of the group consisting of substituted or unsubstituted phenylene and substituted or unsubstituted cycloalkylene, more preferably 2 to 4 pieces. Furthermore, the polyorganosiloxane having a liquid crystal alignment group may have a polymerizable group on the side chain together with the liquid crystal alignment group. In addition, the polyorganosiloxane having a polymerizable group is a different component from the polymerizable compound.
於液晶組成物中所含的聚有機矽氧烷具有液晶配向性基的情況下,相對於聚有機矽氧烷所具有的全部單體單元,液晶配向性基的含有比例較佳為1莫耳%以上,更佳為2莫耳%以上,進而佳為5莫耳%以上。另外,相對於聚有機矽氧烷所具有的全部單體單元,液晶配向性基的含有比例較佳為70莫耳%以下,更佳為50莫耳%以下,進而佳為40莫耳%以下。再者,聚有機矽氧烷可僅具有一種液晶配向性基,亦可具有兩種以上。When the polyorganosiloxane contained in the liquid crystal composition has a liquid crystal alignment group, the content ratio of the liquid crystal alignment group is preferably 1 mol with respect to all the monomer units contained in the polyorganosiloxane % or more, more preferably 2 mol % or more, still more preferably 5 mol % or more. In addition, the content ratio of the liquid crystal aligning group is preferably 70 mol % or less, more preferably 50 mol % or less, and further preferably 40 mol % or less with respect to all the monomer units contained in the polyorganosiloxane. . Furthermore, the polyorganosiloxane may have only one type of liquid crystal alignment group, or may have two or more types.
(聚有機矽氧烷的合成) 液晶組成物中調配的聚有機矽氧烷例如可列舉如下方法等:(I)使具有功能性基(聚合性基或液晶配向性基等)的水解性矽烷化合物水解、縮合的方法;(II)使用具有環氧基的水解性矽烷化合物(以下,亦稱為「含有環氧基的矽烷化合物」)作為單體並進行水解、縮合反應,藉此獲得具有環氧基的聚有機矽氧烷,繼而,使所得的含有環氧基的聚有機矽氧烷、與具有功能性基的羧酸進行反應,藉此對聚有機矽氧烷的側鏈導入功能性基的方法;(III)藉由將所述(I)的方法與所述(II)的方法組合來進行而獲得目標聚合物的方法。(Synthesis of polyorganosiloxane) Examples of the polyorganosiloxane to be prepared in the liquid crystal composition include the following methods: (I) a method of hydrolyzing and condensing a hydrolyzable silane compound having a functional group (polymerizable group, liquid crystal alignment group, etc.); (II) ) using a hydrolyzable silane compound having an epoxy group (hereinafter, also referred to as an "epoxy-group-containing silane compound") as a monomer and performing a hydrolysis and condensation reaction to obtain a polyorganosiloxane having an epoxy group , and then, the obtained epoxy group-containing polyorganosiloxane is reacted with a carboxylic acid having a functional group, thereby introducing a functional group to the side chain of the polyorganosiloxane; (III) by A method for obtaining a target polymer by combining the method of (I) and the method of (II).
作為聚有機矽氧烷的合成中使用的矽烷化合物,例如可列舉:四甲氧基矽烷、四乙氧基矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、二甲基二甲氧基矽烷、二甲基二乙氧基矽烷等烷氧基矽烷化合物;3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、巰基甲基三甲氧基矽烷、巰基甲基三乙氧基矽烷、3-脲基丙基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-(3-環己基胺基)丙基三甲氧基矽烷等含有氮、硫的烷氧基矽烷化合物; 3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷等含有環氧基的矽烷化合物; 3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、3-(甲基)丙烯醯氧基丙基甲基二乙氧基矽烷、8-(甲基)丙烯醯氧基辛基三甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷等含有不飽和鍵的烷氧基矽烷化合物;三甲氧基矽烷基丙基琥珀酸酐等。水解性矽烷化合物可單獨使用該些中的一種或者將兩種以上組合使用。再者,「(甲基)丙烯醯氧基」為包含「丙烯醯氧基」及「甲基丙烯醯氧基」的含義。Examples of the silane compound used for the synthesis of polyorganosiloxane include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and phenyltrimethoxysilane. Silane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane and other alkoxysilane compounds; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Ethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, N-(3-cyclohexylamino)propyltrimethoxysilane and other alkoxysilane compounds containing nitrogen and sulfur; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4- Epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane and other epoxy-containing silane compounds; 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropylmethyldi Methoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, 8-(meth)acrylooxyoctyltrimethoxysilane, vinyltrimethoxysilane, ethylene alkoxysilane compounds containing unsaturated bonds such as triethoxysilane and p-styryltrimethoxysilane; trimethoxysilylpropyl succinic anhydride, etc. The hydrolyzable silane compound may be used alone or in combination of two or more. In addition, "(meth)acryloyloxy" means a meaning including "acryloyloxy" and "methacryloyloxy".
所述水解、縮合反應可藉由使如所述般的矽烷化合物的一種或兩種以上與水較佳為於適當的觸媒及有機溶媒的存在下反應來進行。於水解、縮合反應時,相對於矽烷化合物(合計量)1莫耳,水的使用比例較佳為0.5莫耳~100莫耳,更佳為1莫耳~30莫耳。The hydrolysis and condensation reactions can be carried out by reacting one or two or more of the above-mentioned silane compounds with water, preferably in the presence of a suitable catalyst and an organic solvent. In the hydrolysis and condensation reactions, the use ratio of water is preferably 0.5 mol to 100 mol, more preferably 1 mol to 30 mol, relative to 1 mol of the silane compound (total amount).
作為水解、縮合反應時使用的觸媒,例如可列舉酸、鹼金屬化合物、有機鹼、鈦化合物、鋯化合物等。觸媒的使用量根據觸媒的種類、溫度等反應條件等而不同,應該適宜設定,例如相對於矽烷化合物的合計量,較佳為0.01倍莫耳~3倍莫耳,更佳為0.05倍莫耳~1倍莫耳。 作為所述水解、縮合反應時使用的有機溶媒,例如可列舉:烴、酮、酯、醚、醇等。該些中,較佳為使用非水溶性或難水溶性的有機溶媒。相對於反應中使用的矽烷化合物的合計100質量份,有機溶媒的使用比例較佳為10質量份~10,000質量份,更佳為50質量份~1,000質量份。Examples of catalysts used in the hydrolysis and condensation reactions include acids, alkali metal compounds, organic bases, titanium compounds, and zirconium compounds. The amount of the catalyst used varies depending on the type of catalyst, reaction conditions such as temperature, etc., and should be appropriately set. For example, relative to the total amount of the silane compound, it is preferably 0.01 to 3 moles, more preferably 0.05 moles. Molar to 1 times Molar. Examples of the organic solvent used in the hydrolysis and condensation reactions include hydrocarbons, ketones, esters, ethers, alcohols, and the like. Among these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent. The use ratio of the organic solvent is preferably from 10 parts by mass to 10,000 parts by mass, more preferably from 50 parts by mass to 1,000 parts by mass, with respect to 100 parts by mass of the total silane compound used in the reaction.
所述水解、縮合反應較佳為利用油浴等進行加熱來實施。於水解、縮合反應時,較佳為將加熱溫度設為130℃以下,更佳為設為40℃~100℃。加熱時間較佳為設為0.5小時~12小時,更佳為設為1小時~8小時。加熱過程中,可對混合液進行攪拌,亦可置於回流下。另外,於反應結束後,較佳為利用水對自反應液分取出的有機溶媒層進行清洗。於所述清洗時,使用包含少量鹽的水(例如,0.2質量%左右的硝酸銨水溶液等)進行清洗,藉此清洗操作變得容易,就該方面而言較佳。清洗進行至清洗後的水層變為中性為止,之後,於視需要利用無水硫酸鈣、分子篩(molecular sieve)等乾燥劑對有機溶媒層進行乾燥後,去除溶媒,藉此可獲得目標聚有機矽氧烷。再者,聚有機矽氧烷的合成方法並不限於所述水解、縮合反應,例如亦可藉由如下方法等進行:使水解性矽烷化合物於草酸及醇的存在下反應。The hydrolysis and condensation reactions are preferably carried out by heating with an oil bath or the like. In the case of hydrolysis and condensation reaction, the heating temperature is preferably 130°C or lower, and more preferably 40°C to 100°C. The heating time is preferably 0.5 hours to 12 hours, and more preferably 1 hour to 8 hours. During the heating process, the mixed solution can be stirred or placed under reflux. Moreover, after completion|finish of reaction, it is preferable to wash|clean the organic solvent layer extracted from the reaction liquid with water. At the time of said washing, it is preferable in this respect that washing operation is facilitated by washing with water containing a small amount of salt (for example, an aqueous ammonium nitrate solution of about 0.2 mass %, etc.). Washing is performed until the water layer after washing becomes neutral, after that, after drying the organic solvent layer with a desiccant such as anhydrous calcium sulfate, molecular sieve, etc. as necessary, the solvent is removed, whereby the target polyorganic organic solvent can be obtained. Siloxane. In addition, the synthesis method of the polyorganosiloxane is not limited to the above-mentioned hydrolysis and condensation reaction, and may be carried out by, for example, a method such as the following: reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol.
於所述縮合反應時,藉由於原料的至少一部分中使用含有環氧基的矽烷化合物,可獲得於側鏈具有環氧基的聚有機矽氧烷。另外,藉由使所得的含有環氧基的聚有機矽氧烷與具有功能性基的羧酸反應,可獲得於側鏈具有功能性基的聚有機矽氧烷。In the condensation reaction, a polyorganosiloxane having an epoxy group in a side chain can be obtained by using an epoxy group-containing silane compound for at least a part of the raw material. In addition, a polyorganosiloxane having a functional group in a side chain can be obtained by reacting the obtained epoxy group-containing polyorganosiloxane with a functional group-containing carboxylic acid.
含有環氧基的聚有機矽氧烷與羧酸的反應較佳為於有機溶媒中視需要於觸媒的存在下進行。作為使用的有機溶媒,例如可列舉:醇、醚、酮、醯胺、酯、烴化合物等。作為觸媒,可使用三級有機胺或四級有機胺等有機鹼、四級銨鹽等。所述反應的反應溫度較佳為設為30℃~120℃,反應時間較佳為設為1小時~24小時。關於溶解目標聚合物而成的反應溶液,可使用公知的分離方法將反應溶液中所含的聚合物分離後供於液晶配向劑的製備。The reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid is preferably carried out in an organic solvent in the presence of a catalyst if necessary. As an organic solvent to be used, alcohol, ether, ketone, amide, ester, hydrocarbon compound etc. are mentioned, for example. As the catalyst, organic bases such as tertiary organic amines and quaternary organic amines, quaternary ammonium salts, and the like can be used. The reaction temperature of the reaction is preferably 30°C to 120°C, and the reaction time is preferably 1 hour to 24 hours. About the reaction solution which melt|dissolved the target polymer, the polymer contained in a reaction solution can be isolate|separated using a well-known isolation|separation method, and it can be used for preparation of a liquid crystal aligning agent.
關於聚有機矽氧烷,利用凝膠滲透層析法(Gel Permeation Chromatography,GPC)測定的聚苯乙烯換算的重量平均分子量(Mw)較佳為處於100~50,000的範圍內,更佳為處於500~20,000的範圍內,進而佳為處於1000~10,000的範圍內,進而更佳為處於1200~10,000的範圍內。The polyorganosiloxane has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC), preferably in the range of 100 to 50,000, more preferably in the range of 500 In the range of -20,000, it is more preferable to exist in the range of 1000-10,000, and it is still more preferable to exist in the range of 1200-10,000.
於液晶組成物中,含矽化合物的調配比例根據含矽化合物的種類適宜設定。於含矽化合物為聚有機矽氧烷的情況下,相對於液晶組成物的總量,聚有機矽氧烷的含有比例較佳為0.0001質量%以上。若聚有機矽氧烷的含有比例為0.0001質量%以上,則可充分增加液晶層13與基材的邊界部分的矽含量,可充分獲得液晶層13與基材的密接性、以及液晶元件10的耐熱性、重覆驅動耐性、彎曲耐性及彎曲後的光學特性的改善效果,就該方面而言較佳。就此種觀點而言,相對於液晶組成物的總量,聚有機矽氧烷的含有比例更佳為0.0005質量%以上,進而佳為0.001質量%以上。另外,就良好地維持液晶元件10的品質的觀點而言,相對於液晶組成物的總量,聚有機矽氧烷的含有比例較佳為20質量%以下,更佳為15質量%以下。In the liquid crystal composition, the compounding ratio of the silicon-containing compound is appropriately set according to the type of the silicon-containing compound. When the silicon-containing compound is a polyorganosiloxane, the content of the polyorganosiloxane is preferably 0.0001 mass % or more with respect to the total amount of the liquid crystal composition. When the content ratio of the polyorganosiloxane is 0.0001 mass % or more, the silicon content in the boundary portion between the
本實施方式的液晶組成物除了所述成分以外亦可視需要進而含有其他成分。The liquid crystal composition of the present embodiment may contain other components in addition to the above-mentioned components as necessary.
<聚合起始劑> 液晶組成物亦可進而含有聚合起始劑。作為聚合起始劑,可較佳地使用藉由光來產生自由基的光自由基聚合起始劑。作為光自由基聚合起始劑,例如可列舉:O-醯基肟化合物、苯乙酮化合物、聯咪唑化合物等。<Polymerization initiator> The liquid crystal composition may further contain a polymerization initiator. As the polymerization initiator, a photoradical polymerization initiator that generates radicals by light can be preferably used. As a photoradical polymerization initiator, an O-acyl oxime compound, an acetophenone compound, a biimidazole compound, etc. are mentioned, for example.
作為該些的具體例,O-醯基肟化合物例如可列舉:1,2-辛二酮1-[4-(苯硫基)-2-(O-苯甲醯基肟)]、乙酮-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-1-(O-乙醯基肟)、乙酮-1-[9-乙基-6-(2-甲基-4-四氫呋喃基甲氧基苯甲醯基)-9.H.-咔唑-3-基]-1-(O-乙醯基肟)或乙酮-1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二氧雜環戊基)甲氧基苯甲醯基}-9.H.-咔唑-3-基]-1-(O-乙醯基肟)等;As specific examples of these, the O-acyl oxime compound includes, for example, 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzyl oxime)], ethyl ketone -1-[9-Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9 -Ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzyl)-9.H.-carbazol-3-yl]-1-(O-acetyloxime) or ethyl Keto-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolane)methoxybenzyl}-9 .H.-carbazol-3-yl]-1-(O-acetyl oxime), etc.;
苯乙酮化合物例如較佳為α-胺基酮化合物,尤其是可列舉:2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮、2-二甲基胺基-2-(4-甲基苄基)-1-(4-嗎啉-4-基-苯基)-丁烷-1-酮、2-甲基-1-(4-甲硫基苯基)-2-嗎啉基丙烷-1-酮等; 聯咪唑化合物例如可列舉2,2'-雙(2,4-二氯苯基)-4,4',5,5'-四苯基-1,2'-聯咪唑等。For example, the acetophenone compound is preferably an α-amino ketone compound, and in particular, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1- Ketone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1 -(4-Methylthiophenyl)-2-morpholinopropan-1-one, etc.; As a biimidazole compound, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole etc. are mentioned, for example.
作為本揭示的液晶組成物中所含的聚合起始劑,可自現有公知的化合物中適宜選擇使用,就硬化進行至液晶層13的內部為止且可提高耐久性的方面、以及使液晶元件彎曲後的基材與液晶層的密接性良好的觀點而言,較佳為使用選自由醯基氧化膦系聚合起始劑、α-胺基苯烷基酮系聚合起始劑、α-羥基苯乙酮系聚合起始劑及肟酯系聚合起始劑所組成的群組中的至少一種聚合起始劑(以下,亦稱為「特定起始劑」)。再者,所使用的特定起始劑可僅為一種,亦可混合兩種以上。進而,亦可將特定起始劑及與特定起始劑不同的光聚合起始劑混合使用。The polymerization initiator contained in the liquid crystal composition of the present disclosure can be appropriately selected from conventionally known compounds and used in terms of curing progresses to the inside of the
作為醯基氧化膦系聚合起始劑,例如可列舉:雙(2,4,6-三甲基苯甲醯基)-苯基-氧化膦(例如,商品名:豔佳固(Irgacure)819,巴斯夫(BASF)公司製造)、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基苯基氧化膦、2,4,6-三甲基苯甲醯基-二苯基-氧化膦(商品名:魯西林(Lucirin)TPO:巴斯夫(BASF)公司製造等)等。 作為α-胺基苯烷基酮系聚合起始劑,可列舉:2-甲基-2-嗎啉基-1-(4-甲硫基苯基)丙烷-1-酮、2-二甲基胺基-2-苄基-1-(4-嗎啉基苯基)丁烷-1-酮等。 作為α-羥基苯乙酮系聚合起始劑,可列舉:1-羥基環己基苯基酮、2-羥基-2-甲基-1-苯基丙烷-1-酮等。 作為肟酯系聚合起始劑,可列舉:1,2-辛二酮,1-[4-(苯硫基)苯基]-,2-(O-苯甲醯基肟)、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)等。Examples of the acylphosphine oxide-based polymerization initiator include: bis(2,4,6-trimethylbenzyl)-phenyl-phosphine oxide (eg, trade name: Irgacure 819 , BASF (BASF) company), bis(2,6-dimethoxybenzyl)-2,4,4-trimethyl-pentylphenylphosphine oxide, 2,4,6-trimethyl benzalyl-diphenyl-phosphine oxide (trade name: Lucirin, TPO: manufactured by BASF, etc.) and the like. Examples of the α-aminophenalkyl ketone-based polymerization initiator include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-dimethylene amino-2-benzyl-1-(4-morpholinylphenyl)butan-1-one and the like. As an α-hydroxyacetophenone-based polymerization initiator, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc. are mentioned. As the oxime ester-based polymerization initiator, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) and the like.
相對於液晶組成物的總量,液晶組成物中的聚合起始劑的比例較佳為0.001質量%以上,更佳為0.005質量%以上。另外,相對於液晶組成物的總量,聚合起始劑的比例較佳為7.0質量%以下,更佳為5.0質量%以下。藉由將聚合起始劑的比例設為所述範圍內,於對液晶元件進行光照射時,即使減少曝光量亦可促進聚合性化合物的聚合,可進一步提高液晶分子的配向控制性,就該方面而言較佳。再者,作為聚合起始劑,可單獨使用一種,亦可將兩種以上組合使用。The ratio of the polymerization initiator in the liquid crystal composition is preferably 0.001 mass % or more, more preferably 0.005 mass % or more, with respect to the total amount of the liquid crystal composition. In addition, the ratio of the polymerization initiator is preferably 7.0 mass % or less, more preferably 5.0 mass % or less, with respect to the total amount of the liquid crystal composition. By setting the ratio of the polymerization initiator to be within the above-mentioned range, the polymerization of the polymerizable compound can be accelerated even if the exposure amount is reduced when the liquid crystal element is irradiated with light, and the alignment controllability of the liquid crystal molecules can be further improved. In terms of better. In addition, as a polymerization initiator, 1 type may be used individually, and 2 or more types may be used in combination.
<聚合抑制劑> 液晶組成物亦可進而含有聚合抑制劑。聚合抑制劑例如可用於調節液晶組成物對於光的感度。作為使用的聚合抑制劑,例如可列舉:苯酚、對苯二酚、對甲氧基苯酚、苯醌、甲氧基苯醌、1,2-萘醌、甲酚、對第三丁基鄰苯二酚等鄰苯二酚類、烷基酚類、烷基雙酚類、啡噻嗪、2,5-二-第三丁基對苯二酚、2,6-二-第三丁基苯酚、十八烷基-3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯、N,N'-六亞甲基雙(3,5-二-第三丁基-4-羥基-氫化桂皮醯胺)、2,2'-亞甲基雙(4-甲基-6-第三丁基苯酚)、4,4'-亞甲基雙(2,6-二-第三丁基苯酚)、4,4'-亞丁基雙(3-甲基-6-第三丁基苯酚)、2,6-雙(2'-羥基-3'-第三丁基-5'-甲基苄基)4-甲基苯酚、1,1,3-三(2'-甲基-5'-第三丁基-4'-羥基苯基)丁烷、1,3,5-三甲基-2,4,6-三(3'-5'-二-第三丁基-4'-羥基苄基)苯、三乙二醇雙[3-(3-第三丁基-5-甲基-4-羥基苯基)丙酸酯]、季戊四醇四[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、2-第三丁基-6-(3-第三丁基-2-羥基-5-甲基苄基)-4-甲基苯基丙烯酸酯、2,4-二甲基-6-第三丁基苯酚、及2-第三丁基-4-甲氧基苯酚等酚類、6-第三丁基間甲酚、2,6-二-第三丁基對甲酚、2-第三丁基對苯二酚、亞甲藍、二甲基二硫代胺基甲酸銅鹽、二乙基二硫代胺基甲酸銅鹽、二丙基二硫代胺基甲酸銅鹽、二丁基二硫代胺基甲酸銅鹽、二丁基二硫代胺基甲酸銅、水楊酸銅、硫代二丙酸酯類、巰基苯並咪唑、及亞磷酸鹽(phosphite)類中的至少一種。另外,亦可併用含氧氣體(空氣等)。<Polymerization inhibitor> The liquid crystal composition may further contain a polymerization inhibitor. The polymerization inhibitor can be used to adjust the light sensitivity of the liquid crystal composition, for example. As the polymerization inhibitor to be used, for example, phenol, hydroquinone, p-methoxyphenol, benzoquinone, methoxybenzoquinone, 1,2-naphthoquinone, cresol, p-tert-butyl phthaloquinone can be mentioned. Catechols such as diphenols, alkylphenols, alkylbisphenols, phenothiazine, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butylphenol , octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N,N'-hexamethylene bis(3,5-di-tert-butyl) yl-4-hydroxy-hydrocinnamamide), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-methylenebis(2,6- Di-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 2,6-bis(2'-hydroxy-3'-tert-butyl) -5'-methylbenzyl)4-methylphenol, 1,1,3-tris(2'-methyl-5'-tert-butyl-4'-hydroxyphenyl)butane, 1,3 ,5-trimethyl-2,4,6-tris(3'-5'-di-tert-butyl-4'-hydroxybenzyl)benzene, triethylene glycol bis[3-(3-tertiary Butyl-5-methyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-th Tributyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2,4-dimethyl-6-tert-butylphenol , and phenols such as 2-tert-butyl-4-methoxyphenol, 6-tert-butyl-m-cresol, 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-p-cresol Hydroquinone, methylene blue, copper dimethyl dithiocarbamate, copper diethyl dithiocarbamate, copper dipropyl dithiocarbamate, dibutyl dithiocarbamate At least one of copper carbamate, copper dibutyldithiocarbamate, copper salicylate, thiodipropionate, mercaptobenzimidazole, and phosphite. Moreover, an oxygen-containing gas (air etc.) may be used together.
聚合抑制劑的使用比例並無特別限制,相對於液晶組成物的總量,較佳為0.001質量%以上,更佳為0.005質量%以上。另外,聚合抑制劑的使用比例較佳為7.0質量%以下,更佳為5.0質量%以下。聚合抑制劑可單獨使用一種或者將兩種以上組合使用。The usage ratio of the polymerization inhibitor is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, based on the total amount of the liquid crystal composition. In addition, the use ratio of the polymerization inhibitor is preferably 7.0% by mass or less, more preferably 5.0% by mass or less. A polymerization inhibitor can be used individually by 1 type or in combination of 2 or more types.
作為液晶組成物中所含的其他成分,除了所述成分以外,可列舉手性劑(例如,商品名「C-15」、「CB-15」(默克(Merck)公司製造)等)、抗氧化劑、紫外線吸收劑、色素、消泡劑、光增感劑、增容劑等。關於其他成分的調配比例,可於不損及本揭示的效果的範圍內,根據各成分而適宜選擇。Examples of other components contained in the liquid crystal composition include, in addition to the above-mentioned components, chiral agents (eg, trade names "C-15", "CB-15" (manufactured by Merck), etc.), Antioxidants, UV absorbers, pigments, defoaming agents, photosensitizers, compatibilizers, etc. The compounding ratio of other components can be suitably selected according to each component within the range which does not impair the effect of this disclosure.
所述液晶組成物藉由將液晶及聚合性化合物、以及視需要調配的成分混合來製備。將該些成分混合的處理可於常溫下進行,亦可一邊升溫一邊進行。另外,亦可將各成分溶解於有機溶媒(例如,丙酮、氯仿、甲醇等)中,之後,藉由例如蒸餾操作將溶媒去除。The liquid crystal composition is prepared by mixing a liquid crystal, a polymerizable compound, and optionally prepared components. The treatment of mixing these components may be performed at normal temperature, or may be performed while raising the temperature. In addition, each component may be dissolved in an organic solvent (for example, acetone, chloroform, methanol, etc.), and after that, the solvent may be removed by, for example, a distillation operation.
《液晶元件的製造方法》
其次,對液晶元件10的製造方法進行說明。液晶元件10可藉由包括如下步驟的方法來製造:步驟A,將包含第一基材11及第二基材12的一對基材經由包含液晶組成物的層相向配置來構築液晶單元;以及步驟B,於液晶單元的構築後進行光照射使液晶組成物硬化。再者,本製造方法不包括形成液晶配向膜的步驟。"Method for manufacturing a liquid crystal element"
Next, the manufacturing method of the
(步驟A:單元構築步驟)
步驟A中,準備兩片具有電極的基材,於以電極形成面相對的方式相向配置的兩片基材間配置液晶組成物的層來製造液晶單元。具體而言,可列舉如下方法等:藉由密封劑將第一基材11及第二基材12的周邊部貼合且於由基材表面及密封劑劃分的單元間隙內注入填充液晶組成物後,將注入孔密封的方法;於其中一個基材的液晶配向膜側的周邊部塗佈密封劑,進而於液晶配向膜面上的規定的數個部位滴加液晶組成物後,以液晶配向膜14、液晶配向膜15相向的方式貼合另一個基材且將液晶組成物於基材11、基材12的整個面上展開,之後將密封劑硬化的方法(液晶滴注(One Drop Filling,ODF)方式)等。作為密封劑,例如可使用含有硬化劑以及作為間隔物(spacer)的氧化鋁球的環氧樹脂等。(step A: unit construction step)
In step A, two substrates having electrodes are prepared, and a liquid crystal cell is produced by disposing a layer of a liquid crystal composition between the two substrates facing each other so that the electrode formation surfaces are opposed to each other. Specifically, the following methods can be mentioned. The peripheral parts of the
對於所得的液晶單元,較佳為藉由進而於加熱至所使用的液晶取得各向同性相的溫度後進行緩慢冷卻至室溫的退火處理,去除液晶填充時的流動配向(退火步驟)。用於退火處理的加熱的溫度根據所使用的液晶適宜設定。The obtained liquid crystal cell is preferably heated to a temperature at which the liquid crystal to be used acquires an isotropic phase and then slowly cooled to room temperature by annealing treatment to remove the flow alignment at the time of liquid crystal filling (annealing step). The heating temperature for the annealing treatment is appropriately set according to the liquid crystal to be used.
(步驟B:曝光步驟)
步驟B中,藉由實施選自加熱以及光照射中的一種以上的處理,來進行使液晶組成物硬化的處理。藉由所述硬化反應,可獲得於內部形成有聚合物網絡的液晶層13。於利用熱進行的硬化的情況下,加熱溫度例如為40℃~80℃的範圍內。加熱時間較佳為0.5分鐘~5分鐘。(Step B: Exposure Step)
In step B, the process of hardening the liquid crystal composition is performed by performing one or more processes selected from heating and light irradiation. By the hardening reaction, the
於利用光照射進行的硬化的情況下,作為照射光,可較佳地使用具有200 nm~500 nm的範圍的波長的非偏光紫外線。光的照射量較佳為設為50 mJ/cm2
以上,更佳為設為100 mJ/cm2
以上。另外,光的照射量較佳為設為10,000 mJ/cm2
以下,更佳為設為5,000 mJ/cm2
以下。藉由對液晶組成物的光照射,液晶組成物中所含的聚合性化合物的聚合反應進行。於使用含有聚有機矽氧烷的液晶組成物的情況下,於液晶元件10中,聚有機矽氧烷於液晶層13中至少存在於與基材11、基材12的界面附近。In the case of curing by light irradiation, as the irradiation light, non-polarized ultraviolet rays having a wavelength in the range of 200 nm to 500 nm can be preferably used. The irradiation amount of light is preferably 50 mJ/cm 2 or more, and more preferably 100 mJ/cm 2 or more. In addition, the irradiation amount of light is preferably 10,000 mJ/cm 2 or less, and more preferably 5,000 mJ/cm 2 or less. By irradiating the liquid crystal composition with light, the polymerization reaction of the polymerizable compound contained in the liquid crystal composition proceeds. When the liquid crystal composition containing polyorganosiloxane is used, in the
關於使液晶組成物硬化時的光照射,更具體而言,較佳為藉由以50 mW/cm2
以上的照射量照射150秒以下波長313 nm的光或以150 mW/cm2
以上的照射量照射150秒以下波長365 nm的光來進行。就獲得透明性及光散射性更高且耐熱性、重覆驅動特性及彎曲後的光學特性更良好的液晶元件10的觀點而言,照射波長313 nm的光時的照射量更佳為設為55 mW/cm2
以上。另外,照射波長313 nm的光時的照射量較佳為設為300 mW/cm2
以下,更佳為設為200 mW/cm2
以下,進而佳為設為100 mW/cm2
以下。Light irradiation at the time of curing the liquid crystal composition, more specifically, is preferably by irradiating light with a wavelength of 313 nm or less for 150 seconds or less at an irradiation amount of 50 mW/cm 2 or more, or by irradiating light with a wavelength of 150 mW/cm 2 or more It was performed by irradiating light with a wavelength of 365 nm for 150 seconds or less. From the viewpoint of obtaining a
照射波長365 nm的光時的照射量更佳為設為155 mW/cm2 以上。另外,就照射波長365 nm的光時的產量提高的觀點而言,照射量較佳為設為1000 mW/cm2 以下,更佳為設為500 mW/cm2 以下,進而佳為設為300 mW/cm2 以下。The irradiation amount when irradiating light with a wavelength of 365 nm is more preferably 155 mW/cm 2 or more. In addition, from the viewpoint of improving the yield when irradiated with light having a wavelength of 365 nm, the irradiation amount is preferably 1000 mW/cm 2 or less, more preferably 500 mW/cm 2 or less, and still more preferably 300 mW/cm 2 or less. mW/cm 2 or less.
照射波長313 nm或波長365 nm的光時的照射時間更佳為設為1秒以上,進而佳為設為2秒以上,尤佳為設為10秒以上。另外,照射時間更佳為設為120秒以下,進而佳為設為100秒以下,尤佳為設為60秒以下。於光的照射時,可進行對液晶單元進行加溫的處理及於液晶單元的電極間施加電壓的處理中的至少任一者。The irradiation time when irradiating light with a wavelength of 313 nm or a wavelength of 365 nm is more preferably 1 second or more, more preferably 2 seconds or more, and particularly preferably 10 seconds or more. Moreover, the irradiation time is more preferably 120 seconds or less, more preferably 100 seconds or less, and particularly preferably 60 seconds or less. At the time of light irradiation, at least any one of the process of heating a liquid crystal cell and the process of applying a voltage between electrodes of a liquid crystal cell can be performed.
所述步驟A及步驟B的一系列的處理亦可連續地進行。因此,例如於應用TAC膜或(甲基)丙烯酸膜、聚對苯二甲酸乙二酯(polyethylene terephthalate,PET)膜等樹脂膜基材作為液晶元件10的基材11、基材12的情況下,可藉由利用輥對輥的生產方式製造液晶元件10,就該方面而言較佳。作為一例,於將捲成卷狀的膜基材捲回的過程中,首先藉由所述步驟A,藉由ODF方式製作液晶單元,之後,藉由步驟B進行使配置於一對基材間的液晶組成物硬化的處理,將其作為捲繞體。根據此種生產方式,工業規模上的生產性高,可實現低成本化,製程優點大。A series of processing of the said step A and the step B may be performed continuously. Therefore, for example, in the case of applying resin film substrates such as TAC films, (meth)acrylic films, and polyethylene terephthalate (PET) films as the
液晶元件10可應用於各種用途,例如可於建築物的窗戶、或室內外的隔板(隔離物(partition))、展示窗、車輛(汽車、飛機、船舶、鐵路等)的窗戶、室內外的各種廣告、引導標識、家電設備、行動電話、智慧型手機、各種監視器、鐘錶、可攜式遊戲機、個人電腦、眼鏡、太陽鏡、醫療設備、家具等的各種用途中作為調光元件而有效地使用。液晶元件10根據元件的厚度或硬度、形狀、用途等可直接使用,亦可貼附於玻璃或透明樹脂等來使用。The
(第二實施方式) 其次,對第二實施方式進行說明。再者,本說明書中,為了簡化說明,以與第一實施方式的不同點為中心進行說明。(Second Embodiment) Next, the second embodiment will be described. In addition, in this specification, in order to simplify description, it demonstrates centering on the difference from 1st Embodiment.
本實施方式的液晶元件是高分子分散型液晶元件,包括:包含第一基材11及第二基材12的一對基材、以及配置於第一基材11與第二基材12之間的液晶層13(參照圖1)。The liquid crystal element of this embodiment is a polymer-dispersed liquid crystal element, and includes a pair of substrates including a
用於形成液晶層13的液晶組成物含有液晶及聚合性化合物。作為液晶,除了所述第一實施方式中例示的液晶以外,例如可將作為垂直配向(Vertical Alignment,VA)模式用液晶組成物而市售的具有負的介電常數各向異性的液晶組成物(例如,默克(Merck)公司製造的MLC-6608、MLC-6609、MLC-6610、MLC-6882、MLC-6686、MLC-7026-000、MLC-7026-100、MLC-7029等)用作原料液晶。液晶較佳為具有負的介電常數各向異性。關於聚合性化合物,可應用所述第一實施方式的說明。另外,液晶組成物較佳為含有含矽化合物,更佳為含有聚有機矽氧烷作為含矽化合物,進而佳為含有功能性聚有機矽氧烷。含矽化合物及聚有機矽氧烷可應用所述第一實施方式的說明。The liquid crystal composition for forming the
於第二實施方式中,於製造液晶元件時,步驟B中,藉由以50 mW/cm2 以上的照射量照射150秒以下波長313 nm的光或以150 mW/cm2 以上的照射量照射150秒以下波長365 nm的光來進行使液晶組成物硬化時的光照射。藉由於此種條件下進行光照射,可獲得透明性及光散射性高且耐熱性、重覆驅動特性及彎曲後的光學特性良好的液晶元件。關於步驟B及其他步驟,可應用所述第一實施方式的說明。 [實施例]In the second embodiment, when manufacturing a liquid crystal element, in step B, by irradiating light with a wavelength of 313 nm or less for 150 seconds or less at an irradiation dose of 50 mW/cm 2 or more, or irradiating with an irradiation dose of 150 mW/cm 2 or more Light irradiation at the time of curing the liquid crystal composition was performed with light having a wavelength of 365 nm for 150 seconds or less. By irradiating light under such conditions, it is possible to obtain a liquid crystal element having high transparency and light scattering properties, and good heat resistance, repetitive driving properties, and optical properties after bending. Regarding step B and other steps, the description of the first embodiment can be applied. [Example]
以下,藉由實施例來更具體地進行說明,但本揭示並不受該些實施例的限定。Hereinafter, although an Example demonstrates more concretely, this disclosure is not limited to these Examples.
於以下的實施例及比較例中,藉由以下方法來測定聚合物的重量平均分子量及環氧當量。 [聚合物的重量平均分子量] 重量平均分子量是藉由以下條件下的凝膠滲透層析法來測定的聚苯乙烯換算值。 管柱:東曹(Tosoh)(股)製造,TSKgelGRCXLII 溶劑:四氫呋喃 溫度:40℃ 壓力:68 kgf/cm2 [環氧當量] 環氧當量是藉由日本工業標準(Japanese Industrial Standards,JIS)C 2105中記載的鹽酸-甲基乙基酮法而測定。In the following Examples and Comparative Examples, the weight average molecular weight and epoxy equivalent of the polymer were measured by the following methods. [Weight Average Molecular Weight of Polymer] The weight average molecular weight is a polystyrene conversion value measured by gel permeation chromatography under the following conditions. Column: Tosoh Co., Ltd., TSKgelGRCXLII Solvent: Tetrahydrofuran Temperature: 40°C Pressure: 68 kgf/cm 2 [Epoxy equivalent] The epoxy equivalent is determined by Japanese Industrial Standards (JIS) C Measured by the hydrochloric acid-methyl ethyl ketone method described in 2105.
以下示出本實施例中所使用的化合物的結構式。再者,以下為了方便,有時將「式(X)所表示的化合物」簡稱為「化合物(X)」。 [化5] The structural formula of the compound used in this Example is shown below. In addition, below, "the compound represented by formula (X)" may be abbreviated as "compound (X)" for convenience. [hua 5]
[化6] [hua 6]
[化7] [hua 7]
[化8] [hua 8]
<聚有機矽氧烷的合成> [合成例1] 於包括攪拌機、溫度計、滴加漏斗及回流冷卻管的反應容器中投入化合物(a-1)100 g、甲基異丁基酮500 g及三乙胺10 g,於室溫下進行混合。繼而,於歷時30分鐘自滴加漏斗滴加去離子水100 g後,一邊於回流下進行攪拌,一邊於80℃下進行6小時反應。於反應結束後,取出有機層,利用0.2質量%硝酸銨水溶液進行清洗,直至清洗後的水變為中性為止,之後於減壓下將溶媒及水蒸餾去除,藉此以黏稠的透明液體的形式獲得反應性聚有機矽氧烷(ESSQ-1)。對所述反應性聚有機矽氧烷(ESSQ-1)進行1 H-核磁共振(Nuclear Magnetic Resonance,NMR)分析,結果於化學位移(δ)=3.2 ppm附近可獲得基於環氧基的峰值。所得的反應性聚有機矽氧烷(ESSQ-1)的重量平均分子量Mw為3000,環氧當量為190 g/莫耳。<Synthesis of polyorganosiloxane> [Synthesis example 1] 100 g of compound (a-1), 500 g of methyl isobutyl ketone and 10 g of triethylamine were mixed at room temperature. Then, after 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, the reaction was performed at 80° C. for 6 hours while stirring under reflux. After the reaction was completed, the organic layer was taken out and washed with a 0.2 mass % ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a viscous transparent liquid. Form to obtain reactive polyorganosiloxane (ESSQ-1). The 1 H-NMR (Nuclear Magnetic Resonance, NMR) analysis of the reactive polyorganosiloxane (ESSQ-1) showed that a peak based on epoxy groups could be obtained around chemical shift (δ)=3.2 ppm. The weight average molecular weight Mw of the obtained reactive polyorganosiloxane (ESSQ-1) was 3000, and the epoxy equivalent weight was 190 g/mol.
[合成例2] 將使用的單體的種類及量如下述表1所記載般加以變更,除了該方面以外,與合成例1同樣地合成反應性聚有機矽氧烷(ESSQ-2)。再者,表1中,單體欄的數值表示相對於聚有機矽氧烷的合成中所使用的單體的合計量100莫耳份的、各化合物的比例(莫耳份)。表1中的「-」表示未使用相應欄的化合物(表2、表3、表5亦相同)。[Synthesis Example 2] A reactive polyorganosiloxane (ESSQ-2) was synthesized in the same manner as in Synthesis Example 1 except that the types and amounts of the monomers used were changed as described in Table 1 below. In addition, in Table 1, the numerical value of a monomer column shows the ratio (mol part) of each compound with respect to 100 mol parts of the total amount of monomers used for the synthesis|combination of polyorganosiloxane. "-" in Table 1 indicates that the compound in the corresponding column is not used (the same applies to Table 2, Table 3, and Table 5).
[表1]
[合成例3] 於500 mL的三口燒瓶中投入反應性聚有機矽氧烷(ESSQ-1)10.0 g、作為溶媒的甲基異丁基酮300 g、作為改質成分的化合物(b-1)3.10 g(相對於反應性聚有機矽氧烷所具有的單體單元數100莫耳份而為20莫耳份)、及化合物(b-2)3.24 g(相對於反應性聚有機矽氧烷所具有的單體單元數100莫耳份而為10莫耳份)、以及作為觸媒的優卡特(UCAT)18X(商品名,三亞普羅(San-Apro)(股)製造)0.10 g,於100℃、48小時攪拌下進行反應。於反應結束後,對在反應混合物中加入乙酸乙酯而獲得的溶液進行3次水洗,使用硫酸鎂對有機層進行乾燥,之後,將溶劑蒸餾去除,藉此獲得具有聚合性基及配向性基的聚有機矽氧烷(將其設為聚合物(PSQ-1))14.1 g。所得的聚合物的重量平均分子量Mw為8200。[Synthesis Example 3] Into a 500 mL three-necked flask were placed 10.0 g of reactive polyorganosiloxane (ESSQ-1), 300 g of methyl isobutyl ketone as a solvent, and 3.10 g of compound (b-1) as a modification component (relative to The number of monomer units contained in the reactive polyorganosiloxane is 20 mol parts from 100 mol parts), and 3.24 g of the compound (b-2) (relative to the monomer units contained in the reactive polyorganosiloxane) The number of body units is 100 mol parts instead of 10 mol parts), and UCAT 18X (trade name, manufactured by San-Apro Co., Ltd.) as a catalyst 0.10 g, at 100 ° C, 48 The reaction was carried out with stirring for hours. After the completion of the reaction, the solution obtained by adding ethyl acetate to the reaction mixture was washed three times with water, the organic layer was dried using magnesium sulfate, and then the solvent was distilled off to obtain a polymerizable group and an alignment group. of polyorganosiloxane (set it as polymer (PSQ-1)) 14.1 g. The weight average molecular weight Mw of the obtained polymer was 8200.
[合成例4] 將使用的反應性聚有機矽氧烷及改質成分的種類及量如下述表2所記載般加以變更,除了該方面以外,與合成例3同樣地合成具有配向性基的聚有機矽氧烷(PSQ-2)。再者,表2中,改質成分欄的數值表示相對於所使用的反應性聚有機矽氧烷所具有的單體單元數100莫耳份的、改質成分的各化合物的使用比例(莫耳份)。[Synthesis Example 4] A polyorganosiloxane having an alignment group was synthesized in the same manner as in Synthesis Example 3, except that the types and amounts of the reactive polyorganosiloxane and modified components used were changed as described in Table 2 below. (PSQ-2). In addition, in Table 2, the numerical value in the column of the modified component represents the usage ratio (mol ear portion).
[表2]
<高分子分散型液晶元件的評價方法> 藉由以下方法評價了以下的實施例及比較例中製造的高分子分散型液晶元件。 (1)透明性的評價 關於實施例及比較例中製造的高分子分散型液晶元件,藉由測定未施加電壓的狀態下的霧度(HAZE),評價未施加電壓時的透明性。測定是使用分光式霧度計(東京電色公司製造)來進行。關於評價,將霧度值未滿3%的情況設為「良好(○)」,將3%以上且未滿10%的情況設為「可(△)」,將10%以上的情況設為「不良(×)」。<Evaluation method of polymer-dispersed liquid crystal element> The polymer-dispersed liquid crystal cells produced in the following Examples and Comparative Examples were evaluated by the following methods. (1) Evaluation of transparency With respect to the polymer dispersion-type liquid crystal elements produced in the examples and comparative examples, the transparency when no voltage was applied was evaluated by measuring the haze (HAZE) in the state in which no voltage was applied. The measurement was performed using a spectroscopic haze meter (manufactured by Tokyo Denshoku Co., Ltd.). Regarding the evaluation, the case where the haze value was less than 3% was “good (○)”, the case where the haze value was not less than 3% and less than 10% was “acceptable (△)”, and the case where the haze value was not less than 10% was defined as “good (△)”. "Bad (×)".
(2)光散射性的評價 關於實施例及比較例中製造的高分子分散型液晶元件,藉由測定施加電壓的狀態下的霧度值,評價施加電壓時的光散射性。測定是以交流驅動對高分子分散型液晶元件施加40 V並與所述(1)同樣地使用分光式霧度計(東京電色公司製造)來進行。關於評價,將霧度值大於90%的情況設為「良好(○)」,將90%以下且大於85%的情況設為「可(△)」,將85%以下的情況設為「不良(×)」。(2) Evaluation of light scattering properties Regarding the polymer-dispersed liquid crystal elements produced in the Examples and Comparative Examples, the light scattering properties at the time of voltage application were evaluated by measuring the haze value in the state where the voltage was applied. The measurement was performed by applying 40 V to the polymer-dispersed liquid crystal element by AC driving and using a spectroscopic haze meter (manufactured by Tokyo Denshoku Co., Ltd.) in the same manner as in the above (1). Regarding the evaluation, the case where the haze value was more than 90% was set as "good (○)", the case where the haze value was less than 90% and more than 85% was set as "good (△)", and the case where the haze value was less than 85% was set as "defective" (×)”.
(3)密接性的評價 藉由對實施例及比較例中製造的高分子分散型液晶元件施加張力直至斷裂,而測定高分子分散型液晶元件的拉伸強度,並基於測定值評價密接性。測定藉由固定高分子分散型液晶元件的其中一個基板,並使用小型桌上試驗機(島津製作所公司製造)對另一個基板施加張力來進行。關於評價,將最大應力大於40 N的情況設為「良好(○)」,將40 N以下且大於20 N的情況設為「可(△)」,將20 N以下的情況設為「不良(×)」。(3) Evaluation of Adhesion The tensile strength of the polymer-dispersed liquid crystal cell was measured by applying tension to the polymer-dispersed liquid crystal cell produced in the Examples and Comparative Examples until it broke, and the adhesion was evaluated based on the measured value. The measurement was performed by immobilizing one of the substrates of the polymer-dispersed liquid crystal element and applying tension to the other substrate using a small desktop tester (manufactured by Shimadzu Corporation). Regarding the evaluation, the case where the maximum stress was larger than 40 N was regarded as "good (○)", the case of 40 N or less and more than 20 N was regarded as "acceptable (△)", and the case of 20 N or less was regarded as "poor ( ×)".
(4)耐熱性的評價 將實施例及比較例中製造的高分子分散型液晶元件於100℃的烘箱中保管200小時。於經過200小時後取出高分子分散型液晶元件,測定未施加電壓的狀態下的霧度值HA1以及施加電壓的狀態下的霧度值HA2。關於評價,將藉由下述數式(1)獲得的ΔHZ1的值未滿5%的情況設為「優良(◎)」,將5%以上且未滿7.5%的情況設為「良好(○)」,將7.5%以上且未滿10%的情況設為「可(△)」,將10%以上的情況設為「不良(×)」。 ΔHZ1=(HB2-HB1)-(HA2-HA1) …(1) (數式(1)中,HB1是於賦予熱之前於未施加電壓的狀態下測定的霧度值,HB2是於賦予熱之前於施加電壓的狀態下測定的霧度值,HA1是於賦予熱之後於未施加電壓的狀態下測定的霧度值,HA2是於賦予熱之後於施加電壓的狀態下測定的霧度值)(4) Evaluation of heat resistance The polymer-dispersed liquid crystal cells produced in Examples and Comparative Examples were stored in an oven at 100° C. for 200 hours. After 200 hours, the polymer-dispersed liquid crystal element was taken out, and the haze value HA1 in the state in which the voltage was not applied and the haze value HA2 in the state in which the voltage was applied were measured. Regarding the evaluation, the case where the value of ΔHZ1 obtained by the following formula (1) was less than 5% was set as “excellent (⊚)”, and the case of 5% or more and less than 7.5% was set as “good (○)” )”, the case of 7.5% or more and less than 10% was designated as “OK (△)”, and the case of 10% or more was designated as “Bad (×)”. ΔHZ1=(HB2-HB1)-(HA2-HA1)…(1) (In the formula (1), HB1 is the haze value measured in a state where no voltage is applied before heat is applied, HB2 is the haze value measured in a state where a voltage is applied before heat is applied, and HA1 is the haze value measured before heat is applied. The haze value measured in the state where no voltage is applied after that, HA2 is the haze value measured in the state where voltage is applied after applying heat)
(5)重覆驅動性能的評價 於對實施例及比較例中製造的高分子分散型液晶元件以交流驅動施加1小時40 V的電壓後,將未施加電壓的狀態保持1小時。將該電壓施加-未施加的動作計數為1次,重覆進行100次。之後,測定未施加電壓的狀態下的霧度值HC1及施加電壓的狀態下的霧度值HC2。關於評價,將藉由下述數式(2)獲得的ΔHZ2未滿3%的情況設為「良好(○)」,將3%以上且未滿10%的情況設為「可(△)」,將10%以上的情況設為「不良(×)」。 ΔHZ2=(HB2-HB1)-(HC2-HC1) …(2) (數式(2)中,HB1是於重覆驅動之前於未施加電壓的狀態下測定的霧度值,HB2是於重覆驅動之前於施加電壓的狀態下測定的霧度值,HC1是於重覆驅動之後於未施加電壓的狀態下測定的霧度值,HC2是於重覆驅動之後於施加電壓的狀態下測定的霧度值)(5) Evaluation of repetitive driving performance After applying a voltage of 40 V to the polymer-dispersed liquid crystal elements produced in the Examples and Comparative Examples for 1 hour by AC driving, the state where no voltage was applied was maintained for 1 hour. This voltage application-non-application operation was counted as one, and repeated 100 times. After that, the haze value HC1 in the state in which the voltage was not applied and the haze value HC2 in the state in which the voltage was applied were measured. Regarding the evaluation, the case where the ΔHZ2 obtained by the following formula (2) was less than 3% was set as "good (○)", and the case where it was 3% or more and less than 10% was set as "acceptable (△)" , and 10% or more were set as "defective (×)". ΔHZ2=(HB2-HB1)-(HC2-HC1)…(2) (In Equation (2), HB1 is the haze value measured in the state where no voltage is applied before repeated driving, HB2 is the haze value measured in the state where voltage is applied before repeated driving, and HC1 is the haze value measured at The haze value measured in the state of no voltage application after repeated driving, HC2 is the haze value measured in the state of voltage application after repeated driving)
(6)彎曲耐性的評價 將實施例及比較例中製造的高分子分散型液晶元件捲繞於直徑2 cm的金屬棒上。之後,與所述(3)同樣地評價密接性。關於評價,將最大應力大於40 N的情況設為「優良(◎)」,將40 N以下且大於30 N的情況設為「良好(○)」,將30 N以下且大於20 N的情況設為「可(△)」,將20 N以下的情況設為「不良(×)」。(6) Evaluation of bending resistance The polymer-dispersed liquid crystal cells produced in Examples and Comparative Examples were wound around a metal rod having a diameter of 2 cm. After that, the adhesiveness was evaluated in the same manner as in the above (3). Regarding the evaluation, the case where the maximum stress was larger than 40 N was regarded as “excellent (⊚)”, the case of 40 N or less and more than 30 N was regarded as “good (○)”, and the case of 30 N or less and more than 20 N was regarded as “good (○)”. It is "acceptable (△)", and the case of 20 N or less is "defective (×)".
(7)彎曲耐性試驗後的光學特性 與所述(6)彎曲耐性的評價同樣地,將高分子分散型液晶元件捲繞於直徑2 cm的金屬棒上後,藉由與所述(1)、(2)同樣的操作測定透明性及光散射性。關於評價,將藉由下述數式(3)獲得的ΔHZ3未滿5%的情況設為「良好(○)」,將5%以上且未滿10%的情況設為「可(△)」,將10%以上的情況設為「不良(×)」。 ΔHZ3=(HB2-HB1)-(HD2-HD1) …(3) (數式(3)中,HB1是於彎曲耐性試驗前於未施加電壓的狀態下測定的霧度值,HB2是於彎曲耐性試驗前於施加電壓的狀態下測定的霧度值,HD1是於彎曲耐性試驗後於未施加電壓的狀態下測定的霧度值,HD2是於彎曲耐性試驗後於施加電壓的狀態下測定的霧度值)(7) Optical properties after bending resistance test In the same manner as in the evaluation of the bending resistance described in the above (6), after the polymer-dispersed liquid crystal element was wound on a metal rod having a diameter of 2 cm, the transparency was measured by the same operation as in the above (1) and (2). and light scattering. Regarding the evaluation, the case where the ΔHZ3 obtained by the following formula (3) was less than 5% was set as "good (○)", and the case where 5% or more and less than 10% was set as "acceptable (△)" , and 10% or more were set as "defective (×)". ΔHZ3=(HB2-HB1)-(HD2-HD1)…(3) (In Equation (3), HB1 is the haze value measured in the state where no voltage is applied before the bending resistance test, HB2 is the haze value measured in the state where the voltage is applied before the bending resistance test, HD1 is the Haze value measured in the state of no voltage applied after the bending resistance test, HD2 is the haze value measured in the state of applying voltage after the bending resistance test)
(8)對比度評價 關於實施例及比較例中製造的高分子分散型液晶元件中的於液晶層中調配了色素的液晶元件,使用分光光度計(日立製作所(股)製造的150-20型雙光束(Double Beam))進行了對比度評價。關於評價,首先於未施加電壓的狀態下測定光線透過率(%),分別算出波長450 nm、550 nm、650 nm下的光線透過率的平均值。其次,於以交流驅動施加40 V的電壓的狀態下測定光線透過率(%),算出波長450 nm、550 nm、650 nm下的光線透過率的平均值。繼而,根據下述數式(4)算出對比度(C值)。 C值=未施加電壓的狀態下的光線透過率/施加電壓的狀態下的光線透過率 …(4) 關於評價,將C值為15%以上的情況設為「良好(○)」,將未滿15%的情況設為「不良(×)」。可判斷為,未施加電壓的狀態下的光線透過率越高,光的透過性越高,電壓驅動時的光線透過率越低,光的遮斷性越高,對比度越良好。(8) Contrast evaluation A spectrophotometer (150-20 type Double Beam manufactured by Hitachi, Ltd.) was used for the liquid crystal element in which the dye was blended in the liquid crystal layer among the polymer-dispersed liquid crystal elements produced in the Examples and Comparative Examples. ) were evaluated for contrast. For evaluation, first, the light transmittance (%) was measured in a state where no voltage was applied, and the average value of the light transmittance at wavelengths of 450 nm, 550 nm, and 650 nm was calculated. Next, the light transmittance (%) was measured in a state where a voltage of 40 V was applied by AC driving, and the average value of the light transmittance at wavelengths of 450 nm, 550 nm, and 650 nm was calculated. Next, the contrast ratio (C value) was calculated according to the following formula (4). C value = light transmittance in the state where no voltage is applied / light transmittance in the state where voltage is applied ... (4) Regarding the evaluation, the case where the C value was 15% or more was set as "good (○)", and the case where it was less than 15% was set as "poor (x)". It can be judged that the higher the light transmittance in the state where no voltage is applied, the higher the light transmittance, and the lower the light transmittance during voltage driving, the higher the light blocking property, and the better the contrast.
(9)彎曲耐性試驗後的密接性 與所述(6)彎曲耐性的評價同樣地,將高分子分散型液晶元件捲繞於直徑2 cm的金屬棒上後,藉由與所述(3)同樣的操作測定拉伸強度,評價密接性。關於評價,將最大應力大於30 N的情況設為「良好(○)」,將30 N以下且大於20 N的情況設為「可(△)」,將20 N以下的情況設為「不良(×)」。(9) Adhesion after bending resistance test In the same manner as in the above (6) evaluation of bending resistance, after winding the polymer-dispersed liquid crystal element on a metal rod with a diameter of 2 cm, the tensile strength was measured by the same operation as in the above (3), and the adhesion was evaluated. sex. Regarding the evaluation, the case where the maximum stress was more than 30 N was set as "good (○)", the case where the maximum stress was 30 N or less and more than 20 N was set as "good (△)", and the case where the maximum stress was less than 20 N was set as "poor ( ×)".
[第一實施例] <高分子分散型液晶元件的製造及評價> [實施例1A] (1)液晶組成物的製備 藉由將化合物(d-1)、化合物(e-1)、化合物(f-1)、化合物(RM-2)及聚合物(PSQ-1)以相對於液晶組成物的全部構成成分的合計量而言各構成成分的含有比例分別為0.01質量%、3質量%、15質量%、3質量%、1質量%的方式添加於包含液晶化合物(L-1)5 g、液晶化合物(L-5)2 g、液晶化合物(L-8)1 g及液晶化合物(L-9)2 g的液晶化合物中並進行混合,而獲得液晶組成物(PLC-X1)(參照表3)。[First Embodiment] <Manufacture and evaluation of polymer-dispersed liquid crystal element> [Example 1A] (1) Preparation of liquid crystal composition By adding compound (d-1), compound (e-1), compound (f-1), compound (RM-2) and polymer (PSQ-1) to the total of all the constituent components of the liquid crystal composition Quantitatively, the content ratios of the constituent components were 0.01 mass %, 3 mass %, 15 mass %, 3 mass %, and 1 mass %, respectively. 5) 2 g, 1 g of the liquid crystal compound (L-8), and 2 g of the liquid crystal compound (L-9) were mixed in the liquid crystal compound to obtain a liquid crystal composition (PLC-X1) (see Table 3).
(2)高分子分散型液晶元件的製造 準備於表面具有ITO電極的一對PET膜基材(PET-ITO基材)10 cm見方。於兩基材上不形成液晶配向膜,於其中一基材的電極配置面塗佈18 μm的間隔物,之後,於塗佈有間隔物的面滴加所述製備的液晶組成物(PLC-X1)。繼而,以兩基材的電極配置面相面對的方式將兩片基材藉由密封劑貼合,獲得液晶單元。繼而,將所得的液晶單元於80℃的加熱板上加溫(退火步驟)。該退火步驟是加溫至液晶成為各向同性相的液晶轉移溫度以上的步驟。接著,於將液晶單元降低至室溫後,使用安裝有使波長313 nm附近的波長透過的帶通濾波器的、以高壓水銀燈為光源的紫外線照射裝置,於波長313 nm、紫外線強度60 mW/cm2 、照射時間30秒的條件下對液晶單元照射非偏光紫外線(曝光步驟),使液晶組成物(PLC-X1)硬化,而獲得高分子分散型液晶元件。於照射紫外線時,不對基材表面溫度進行加溫,且不對液晶單元施加電壓而照射紫外線。(2) Manufacture of polymer-dispersed liquid crystal element A pair of PET film substrates (PET-ITO substrates) having an ITO electrode on the surface was prepared in a 10 cm square. No liquid crystal alignment films were formed on the two substrates, a spacer of 18 μm was coated on the electrode configuration surface of one of the substrates, and then the prepared liquid crystal composition (PLC- X1). Next, the two base materials were bonded together through a sealant so that the electrode arrangement surfaces of the two base materials faced each other, and a liquid crystal cell was obtained. Next, the obtained liquid crystal cell was heated on a hot plate at 80° C. (annealing step). This annealing step is a step of heating to a temperature equal to or higher than the liquid crystal transition temperature at which the liquid crystal becomes an isotropic phase. Next, after cooling the liquid crystal cell to room temperature, using an ultraviolet irradiation device equipped with a bandpass filter that transmits wavelengths around 313 nm and using a high-pressure mercury lamp as a light source, at a wavelength of 313 nm and an ultraviolet intensity of 60 mW/ The liquid crystal cell was irradiated with non-polarized ultraviolet rays (exposure step) under the conditions of cm 2 and irradiation time of 30 seconds to harden the liquid crystal composition (PLC-X1) to obtain a polymer-dispersed liquid crystal cell. When irradiating the ultraviolet rays, the surface temperature of the substrate is not heated, and the ultraviolet rays are irradiated without applying a voltage to the liquid crystal cell.
(3)表面被覆率的測定 接著,關於所得的高分子分散型液晶元件,藉由利用手自兩片PET-ITO基材剝下液晶層,於液晶層與基材的邊界部分自基材剝離液晶層。於剝離了液晶層的基材的ITO電極面的整個表面,藉由目視確認了由於液晶層的殘存而引起的凹凸。接著,將剝離後的基材於己烷中於23℃下浸漬30秒,進行浸漬清洗,並進行風乾。使用XPS(日本真空(ULVAC-PHI)公司製造)對乾燥後的基材的ITO電極面的表面進行元素分析,算出矽原子相對於ITO電極上的碳原子、氧原子及矽原子的合計的比例(矽表面被覆率)。其結果,本實施例中的矽表面被覆率是於高分子分散型液晶元件的兩片基材中,滴加液晶組成物(PLC-X1)的基材(液晶滴加基材)側的值為1.02%,另一個基材(相向基材)側的值為0.96%。(3) Determination of surface coverage Next, regarding the obtained polymer-dispersed liquid crystal element, the liquid crystal layer was peeled off from the two PET-ITO substrates by hand, and the liquid crystal layer was peeled off from the substrate at the boundary portion between the liquid crystal layer and the substrate. On the entire surface of the ITO electrode surface of the substrate from which the liquid crystal layer was peeled off, unevenness due to the remaining of the liquid crystal layer was visually confirmed. Next, the peeled substrate was immersed in hexane at 23° C. for 30 seconds, immersed and washed, and air-dried. The surface of the ITO electrode surface of the dried substrate was subjected to elemental analysis using XPS (manufactured by Nippon Vacuum (ULVAC-PHI) Co., Ltd.), and the ratio of silicon atoms to the total of carbon atoms, oxygen atoms, and silicon atoms on the ITO electrode was calculated. (Silicon Surface Coverage). As a result, the silicon surface coverage in this example is the value on the side of the base material (liquid crystal dropping base material) on which the liquid crystal composition (PLC-X1) was dropped among the two base materials of the polymer-dispersed liquid crystal element. was 1.02%, and the value on the other substrate (opposing substrate) side was 0.96%.
(4)高分子分散型液晶元件的評價 使用所述(2)中製造的高分子分散型液晶元件,進行所述<高分子分散型液晶元件的評價方法>中的(1)~(7)及(9)的各評價。將評價結果示於下述表4中。(4) Evaluation of polymer-dispersed liquid crystal elements The respective evaluations of (1) to (7) and (9) in the above-mentioned <Evaluation Method of Polymer Dispersion Type Liquid Crystal Cell> were performed using the polymer-dispersed liquid crystal cell produced in the above (2). The evaluation results are shown in Table 4 below.
[實施例2A~實施例10A及比較例1A~比較例3A] 將液晶組成物的調配處方如下述表3般加以變更,除了該方面以外,與實施例1A同樣地分別製備液晶組成物(PLC-X2)~液晶組成物(PLC-X13)。再者,表3中的括號內的數值表示調配量。另外,使用所製備的各液晶組成物,與實施例1A同樣地製造高分子分散型液晶元件,並且與實施例1A同樣地進行各種評價。將該些評價的結果示於下述表4中。再者,關於實施例3A、實施例4A、實施例6A及實施例8A、以及比較例2A及比較例3A,使用以紫外線照射二極體為光源的紫外線照射裝置,除了該方面以外,於與實施例1A相同的條件下照射非偏光紫外線,使液晶組成物硬化,而獲得高分子分散型液晶元件。關於實施例7A,使用以紫外線照射二極體為光源的紫外線照射裝置,於波長365 nm、紫外線強度160 mW/cm2 、照射時間60秒的條件下照射非偏光紫外線,使液晶組成物硬化,而獲得高分子分散型液晶元件。(9)的評價是對實施例9A、實施例10A進行。[Example 2A to Example 10A and Comparative Example 1A to Comparative Example 3A] Liquid crystal compositions (PLC -X2) to liquid crystal composition (PLC-X13). In addition, the numerical value in the parenthesis in Table 3 shows the compounding amount. In addition, using each of the prepared liquid crystal compositions, a polymer-dispersed liquid crystal cell was produced in the same manner as in Example 1A, and various evaluations were performed in the same manner as in Example 1A. The results of these evaluations are shown in Table 4 below. Furthermore, with regard to Example 3A, Example 4A, Example 6A, and Example 8A, and Comparative Example 2A and Comparative Example 3A, an ultraviolet irradiation device using an ultraviolet irradiation diode as a light source was used. Unpolarized ultraviolet rays were irradiated under the same conditions as in Example 1A to cure the liquid crystal composition to obtain a polymer-dispersed liquid crystal element. Regarding Example 7A, the liquid crystal composition was cured by irradiating non-polarized ultraviolet rays under the conditions of a wavelength of 365 nm, an ultraviolet intensity of 160 mW/cm 2 and an irradiation time of 60 seconds using an ultraviolet irradiation device using an ultraviolet irradiation diode as a light source. Thus, a polymer-dispersed liquid crystal element was obtained. The evaluation of (9) was performed with respect to Example 9A and Example 10A.
[表3]
表3中的簡稱如下所述。 ACR-1:二季戊四醇六丙烯酸酯 TEOS:四乙氧基矽烷 ODTES:正十八烷基三乙氧基矽烷Abbreviations in Table 3 are as follows. ACR-1: dipentaerythritol hexaacrylate TEOS: Tetraethoxysilane ODTES: n-octadecyltriethoxysilane
[表4]
如表4所示,根據實施例1A~實施例10A,於不具有液晶配向膜的情況下,各種特性(透明性、光散射性、密接性、耐熱性、重覆驅動特性、彎曲耐性以及彎曲耐性試驗後的光學特性)亦為「◎」、「○」或「△」。相對於此,比較例1A~比較例3A中於兩個以上的評價項目中為「×」,相較於實施例1A~實施例10A而言差。As shown in Table 4, according to Examples 1A to 10A, when the liquid crystal alignment film is not provided, various properties (transparency, light scattering properties, adhesion, heat resistance, repetitive driving properties, bending resistance, and bending Optical properties after the resistance test) are also "◎", "○" or "△". On the other hand, in the comparative example 1A - the comparative example 3A, it is "x" in two or more evaluation items, and it is inferior to Example 1A - Example 10A.
即,於矽表面被覆率為0.04%以下的例子(比較例1A~比較例3A)中,彎曲耐性及彎曲耐性試驗後的光學特性均為「×」的評價,相對於此,於矽表面被覆率為0.06%以上的例子(實施例1A~實施例10A)中,彎曲耐性及彎曲耐性試驗後的光學特性為「◎」、「○」或「△」,相較於比較例而言優異。另外,於矽表面被覆率為0.06%以上的例子中,透明性及光散射性為「○」或「△」的評價,作為高分子型液晶元件的基本特性良好。另外,關於密接性、耐熱性及重覆驅動特性的評價亦為「◎」、「○」或「△」。尤其是於矽表面被覆率為0.10%以上且5.0%以下的範圍內的例子(實施例1A、實施例3A、實施例5A~實施例10A)中,任一評價項目均為「◎」或「○」,特別優異。That is, in the examples (Comparative Examples 1A to 3A) with a silicon surface coverage of 0.04% or less, the bending resistance and the optical properties after the bending resistance test were both evaluated as "X", whereas the silicon surface was covered with In the examples (Examples 1A to 10A) with a ratio of 0.06% or more, the bending resistance and the optical properties after the bending resistance test were "⊚", "○", or "△", which were superior to the comparative examples. In addition, in the case where the silicon surface coverage was 0.06% or more, the transparency and the light scattering property were evaluated as "○" or "△", which were good as the basic characteristics of the polymer-type liquid crystal element. In addition, the evaluations regarding adhesion, heat resistance, and repetitive driving characteristics are also "⊚", "○", or "△". In particular, in the examples (Example 1A, Example 3A, Example 5A to Example 10A) in which the silicon surface coverage was in the range of 0.10% or more and 5.0% or less, any evaluation item was "◎" or "" ○”, very excellent.
於使用含有特定液晶及聚合性液晶化合物的液晶組成物來形成不具有液晶配向膜的液晶元件中的液晶層的例子(實施例1A~實施例10A)中,彎曲耐性及彎曲耐性試驗後的光學特性為「◎」、「○」或「△」。該些例子中,透明性及光散射性的評價為「○」或「△」,作為高分子型液晶元件的基本特性亦良好。另外,該例子中,進而關於密接性、耐熱性及重覆驅動特性的評價亦為「◎」、「○」或「△」,相較於比較例1A~比較例3A而言優異。In an example (Example 1A to Example 10A) in which a liquid crystal layer in a liquid crystal cell without a liquid crystal alignment film was formed using a liquid crystal composition containing a specific liquid crystal and a polymerizable liquid crystal compound, the optical properties after bending resistance and bending resistance test The characteristic is "◎", "○", or "△". In these examples, the evaluation of transparency and light-scattering property was "○" or "△", and the basic characteristics as a polymer-type liquid crystal element were also favorable. In addition, in this example, the evaluations of adhesion, heat resistance, and repetitive driving characteristics were also "⊚", "○", or "△", which were superior to Comparative Examples 1A to 3A.
另外,根據實施例9A、實施例10A的結果可知,藉由使用α-羥基苯乙酮系聚合起始劑或醯基氧化膦系聚合起始劑,可保持透明性、光散射性、密接性、耐熱性、重覆驅動特性、彎曲耐性及彎曲耐性試驗後的光學特性,同時可改善彎曲耐性試驗後的密接性,從而可獲得優異的高分子分散型液晶元件。In addition, from the results of Example 9A and Example 10A, it was found that by using an α-hydroxyacetophenone-based polymerization initiator or an acylphosphine oxide-based polymerization initiator, transparency, light scattering properties, and adhesiveness were maintained. , heat resistance, repeated driving characteristics, bending tolerance and optical properties after bending tolerance test, and at the same time, the adhesiveness after bending tolerance test can be improved, so that an excellent polymer-dispersed liquid crystal element can be obtained.
[第二實施例] <高分子型液晶元件的製造及評價> 第二實施例中,對曝光條件與元件特性的關係進行了研究。 [實施例1B] (1)液晶組成物的製備 將化合物(d-1)、化合物(e-1)、化合物(f-1)、化合物(RM-1)及聚合物(PSQ-1)以相對於液晶組成物的全部構成成分的合計量而言各構成成分的含有比例分別為0.01質量%、3質量%、15質量%、5質量%、0.001質量%的方式添加於向列型液晶(默克(Merck)公司製造,MLC-6608)10 g中並進行混合,藉此獲得液晶組成物(PLC-1)(參照表5)。[Second Embodiment] <Manufacture and evaluation of polymer type liquid crystal element> In the second example, the relationship between exposure conditions and element characteristics was studied. [Example 1B] (1) Preparation of liquid crystal composition The compound (d-1), the compound (e-1), the compound (f-1), the compound (RM-1) and the polymer (PSQ-1) were calculated by the total amount with respect to all the constituent components of the liquid crystal composition. Said that the content ratio of each constituent component is 0.01 mass %, 3 mass %, 15 mass %, 5 mass %, 0.001 mass % and added to nematic liquid crystal (Merck (Merck), MLC-6608) 10 g and mixed to obtain a liquid crystal composition (PLC-1) (see Table 5).
(2)高分子分散型液晶元件的製造 準備於表面具有ITO電極的一對PET膜基材(PET-ITO基材)10 cm見方。於兩基材上不形成液晶配向膜,於其中一基材的電極配置面塗佈18 μm的間隔物,之後,於塗佈有間隔物的面滴加所述製備的液晶組成物(PLC-1)。繼而,以兩基材的電極配置面相面對的方式將兩片基材藉由密封劑貼合,獲得液晶單元。繼而,將所得的液晶單元於80℃的加熱板上加溫至液晶成為各向同性相的液晶轉移溫度以上(退火步驟)。接著,於將液晶單元降低至室溫後,使用以紫外線發光二極體為光源的紫外線照射裝置,於波長313 nm、紫外線強度60 mW/cm2 、照射時間30秒的條件下對液晶單元照射非偏光紫外線(曝光步驟),使液晶組成物(PLC-1)硬化,而獲得高分子分散型液晶元件。於照射紫外線時,不對基材表面溫度進行加溫,且不對液晶單元施加電壓而照射紫外線。(2) Manufacture of polymer-dispersed liquid crystal element A pair of PET film substrates (PET-ITO substrates) having an ITO electrode on the surface was prepared in a 10 cm square. No liquid crystal alignment films were formed on the two substrates, a spacer of 18 μm was coated on the electrode configuration surface of one of the substrates, and then the prepared liquid crystal composition (PLC- 1). Next, the two base materials were bonded together through a sealant so that the electrode arrangement surfaces of the two base materials faced each other, and a liquid crystal cell was obtained. Next, the obtained liquid crystal cell was heated on a hot plate at 80° C. to a temperature equal to or higher than the liquid crystal transition temperature at which the liquid crystal became an isotropic phase (annealing step). Next, after the liquid crystal cell was lowered to room temperature, the liquid crystal cell was irradiated under the conditions of a wavelength of 313 nm, an ultraviolet intensity of 60 mW/cm 2 , and an irradiation time of 30 seconds using an ultraviolet irradiation device using an ultraviolet light emitting diode as a light source. Unpolarized ultraviolet rays (exposure step) were used to harden the liquid crystal composition (PLC-1) to obtain a polymer-dispersed liquid crystal element. When irradiating the ultraviolet rays, the surface temperature of the substrate is not heated, and the ultraviolet rays are irradiated without applying a voltage to the liquid crystal cell.
(3)高分子分散型液晶元件的評價 使用所述(2)中製造的高分子分散型液晶元件,進行所述<高分子分散型液晶元件的評價方法>中記載的(1)~(7)及(9)的各評價。將評價結果示於下述表6中。(3) Evaluation of polymer-dispersed liquid crystal elements The respective evaluations of (1) to (7) and (9) described in the above-mentioned <Evaluation Method of Polymer Dispersion Type Liquid Crystal Cell> were performed using the polymer-dispersed liquid crystal cell produced in the above (2). The evaluation results are shown in Table 6 below.
[實施例2B~實施例13B及比較例1B~比較例3B] 將液晶組成物的調配處方如下述表5般加以變更,除了該方面以外,與實施例1B同樣地分別製備液晶組成物(PLC-2)~液晶組成物(PLC-6)。另外,使用所製備的各液晶組成物,與實施例1B同樣地製造高分子分散型液晶元件,並且與實施例1B同樣地進行各種評價。將該些評價的結果示於下述表6中。再者,實施例8B~實施例10B中,於退火步驟後的曝光步驟中,實施了於照射紫外線時加溫至60℃的處理及施加直流電壓10 V的處理中的至少一種處理(參照表6)。對實施例13B進行(9)的評價。[Example 2B to Example 13B and Comparative Example 1B to Comparative Example 3B] The liquid crystal composition (PLC-2) to the liquid crystal composition (PLC-6) were prepared in the same manner as in Example 1B except that the preparation recipe of the liquid crystal composition was changed as shown in Table 5 below. In addition, using each of the prepared liquid crystal compositions, a polymer-dispersed liquid crystal element was produced in the same manner as in Example 1B, and various evaluations were performed in the same manner as in Example 1B. The results of these evaluations are shown in Table 6 below. In addition, in Examples 8B to 10B, in the exposure step after the annealing step, at least one of the treatment of heating to 60° C. when irradiated with ultraviolet rays and the treatment of applying a DC voltage of 10 V were performed (see Table 1). 6). The evaluation of (9) was performed with respect to Example 13B.
另外,於使用液晶組成物(PLC-5)的實施例12B中,於所述<高分子分散型液晶元件的評價方法>中記載的評價項目中進行了「(3)密接性」及「(8)對比度評價」。其結果,實施例12B中,未施加電壓時的光線透過率為91%,施加交流驅動40 V時的光線透過率為5%,C值為18%,對比度為「良好(○)」的評價。同樣地,亦對比較例3B進行了對比度評價,但為「不良(×)」的評價。In addition, in Example 12B using the liquid crystal composition (PLC-5), in the evaluation items described in the above-mentioned <Evaluation method of polymer dispersion type liquid crystal element>, "(3) Adhesion" and "(( 8) Contrast evaluation". As a result, in Example 12B, the light transmittance when no voltage was applied was 91%, the light transmittance when AC driving at 40 V was applied was 5%, the C value was 18%, and the contrast was evaluated as "good (○)" . In the same manner, the comparative example 3B was evaluated for contrast, but it was evaluated as "defective (x)".
[表5]
[表6]
如表6所示,實施例1B~實施例11B、實施例13B中,於不具有液晶配向膜的情況下,各種特性(透明性、光散射性、密接性、耐熱性、重覆驅動特性及彎曲耐性試驗後的光學特性)亦為「◎」、「○」或「△」。相對於此,比較例1B及比較例2B中,4個或5個評價項目中為「×」,相較於實施例1B~實施例11B、實施例13B而言差。另外,調配了色素的實施例12B中,密接性及對比度的評價為「○」,相對於此,比較例3中均為「×」的評價。As shown in Table 6, in Example 1B to Example 11B and Example 13B, in the case of not having a liquid crystal alignment film, various properties (transparency, light scattering properties, adhesion, heat resistance, repetitive driving properties and Optical properties after bending resistance test) are also "◎", "○" or "△". On the other hand, in Comparative Example 1B and Comparative Example 2B, four or five evaluation items were "X", which were inferior to Examples 1B to 11B and Example 13B. In addition, in Example 12B which mix|blended the pigment|dye, the evaluation of the adhesiveness and contrast was "○", and the comparative example 3 was the evaluation of "X".
另外,根據實施例13B的結果可知,藉由使用醯基氧化膦系聚合起始劑,可保持透明性、光散射性、密接性、耐熱性、重覆驅動特性、彎曲耐性及彎曲耐性試驗後的光學特性,同時改善彎曲耐性試驗後的密接性,從而可獲得優異的高分子分散型液晶元件。In addition, according to the results of Example 13B, it was found that by using the acylphosphine oxide-based polymerization initiator, the transparency, light scattering properties, adhesion, heat resistance, repetitive driving characteristics, bending resistance, and bending resistance were maintained after the test. The optical properties are improved, and the adhesion after the bending resistance test is improved, so that an excellent polymer-dispersed liquid crystal element can be obtained.
10:液晶元件
11:第一基材
12:第二基材
13:液晶層
13a:聚合物網絡
13b:液晶分子
16、17:透明電極10: Liquid crystal element
11: The first substrate
12: Second substrate
13:
圖1為表示液晶元件的概略結構的圖。 圖2(a)、圖2(b)為說明液晶元件的功能的圖。FIG. 1 is a diagram showing a schematic configuration of a liquid crystal element. FIG. 2( a ) and FIG. 2( b ) are diagrams for explaining the function of the liquid crystal element.
無。none.
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