TWI839166B - Composition, vertical alignment liquid crystal cured film, laminate, elliptical polarizing plate and organic EL display device - Google Patents

Composition, vertical alignment liquid crystal cured film, laminate, elliptical polarizing plate and organic EL display device Download PDF

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TWI839166B
TWI839166B TW112110838A TW112110838A TWI839166B TW I839166 B TWI839166 B TW I839166B TW 112110838 A TW112110838 A TW 112110838A TW 112110838 A TW112110838 A TW 112110838A TW I839166 B TWI839166 B TW I839166B
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liquid crystal
film
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cured film
crystal cured
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TW202325825A (en
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葛西辰昌
幡中伸行
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日商住友化學股份有限公司
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Abstract

本發明之組合物包含:具有下述式(I)-1: [式(I)-1中,Ar表示具有2個以上之環結構之2價基,該2個以上之環結構中之1個為6員環,於該6員環之1位及4位與L 1及L 2鍵結, L 1及L 2分別獨立表示單鍵或二價連結基, G 1及G 2分別獨立表示二價芳香族基或二價脂環式烴基, *表示鍵結鍵] 所表示之結構之1種以上之液晶化合物、以及選自由非離子性矽烷化合物及離子性化合物所組成之群中之至少一者。 The composition of the present invention comprises: having the following formula (I)-1: [In formula (I)-1, Ar represents a divalent group having two or more ring structures, one of the two or more ring structures is a 6-membered ring, and is bonded to L1 and L2 at the 1-position and 4-position of the 6-membered ring, L1 and L2 each independently represent a single bond or a divalent linking group, G1 and G2 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, and * represents a bond] at least one liquid crystal compound having a structure represented by, and at least one selected from the group consisting of a non-ionic silane compound and an ionic compound.

Description

組合物、垂直配向液晶硬化膜、積層體、橢圓偏光板及有機EL顯示裝置Composition, vertical alignment liquid crystal cured film, laminate, elliptical polarizing plate and organic EL display device

本發明係關於一種組合物、垂直配向液晶硬化膜、積層體、橢圓偏光板、及有機EL(Electroluminescence,電致發光)顯示裝置。The present invention relates to a composition, a vertically aligned liquid crystal cured film, a laminate, an elliptical polarizer, and an organic EL (Electroluminescence) display device.

橢圓偏光板係偏光板與相位差板積層而成之光學構件,例如在以平面狀態顯示圖像之裝置(例如有機EL顯示裝置)中,用於防止構成裝置之電極上之光反射。於該橢圓偏光板中,作為相位差板,使用所謂之λ/4板。 作為該用於橢圓偏光板之相位差板,顯示逆波長分散性者就在可見光之較廣之波長範圍內發揮同等之相位差性能之方面而言較佳。作為顯示逆波長分散性之相位差板,已知有如下相位差板,其包含使顯示逆波長分散性之聚合性液晶化合物在朝水平方向配向之狀態下聚合並硬化而成之水平配向液晶硬化膜。 又,亦要求附光學補償功能之偏光板,其具有以即便在自斜向觀察之情形時,亦發揮與自正面方向觀察時相同之光學性能之方式進行補償的功能。作為此種附光學補償功能之偏光板,可列舉具備逆波長分散性之水平配向液晶硬化膜,且進而具備使聚合性液晶化合物於垂直配向之狀態下聚合硬化而成之垂直配向液晶硬化膜者。進而,於該垂直配向液晶硬化膜之中,於專利文獻1中亦提出使用顯示逆波長分散性之聚合性液晶化合物的垂直配向液晶硬化膜。 [先前技術文獻] [專利文獻] An elliptical polarizing plate is an optical component formed by laminating a polarizing plate and a phase difference plate, and is used, for example, in a device that displays an image in a planar state (such as an organic EL display device) to prevent light reflection on the electrode constituting the device. In the elliptical polarizing plate, a so-called λ/4 plate is used as a phase difference plate. As a phase difference plate used in the elliptical polarizing plate, one that exhibits reverse wavelength dispersion is better in terms of exerting the same phase difference performance in a wider wavelength range of visible light. As a phase difference plate that exhibits reverse wavelength dispersion, the following phase difference plate is known, which includes a horizontally aligned liquid crystal cured film formed by polymerizing and curing a polymerizable liquid crystal compound that exhibits reverse wavelength dispersion in a horizontally aligned state. In addition, a polarizing plate with an optical compensation function is also required, which has the function of compensating in a manner that the same optical performance as when observed from the front direction is exhibited even when observed from an oblique direction. As such a polarizing plate with an optical compensation function, there can be cited a horizontally aligned liquid crystal cured film having reverse wavelength dispersion, and further a vertically aligned liquid crystal cured film formed by polymerizing and curing a polymerizable liquid crystal compound in a vertically aligned state. Furthermore, among the vertically aligned liquid crystal cured films, a vertically aligned liquid crystal cured film using a polymerizable liquid crystal compound showing reverse wavelength dispersion is also proposed in Patent Document 1. [Prior Technical Document] [Patent Document]

[專利文獻1]日本專利特開2015-57646號公報[Patent Document 1] Japanese Patent Publication No. 2015-57646

[發明所欲解決之問題][The problem the invention is trying to solve]

然而,由於顯示逆波長分散性之液晶化合物之分子重心不穩定,故而僅液晶化合物則會產生大量配向缺陷而不易垂直配向。因此,於製作垂直配向液晶硬化膜時,需要垂直配向用之配向膜。然而,於該情形時,必需形成垂直配向用之配向膜之步驟,因此有生產性降低之問題。However, since the molecular center of gravity of the liquid crystal compound showing reverse wavelength dispersion is unstable, the liquid crystal compound alone will produce a large number of alignment defects and is not easy to align vertically. Therefore, when making a vertically aligned liquid crystal cured film, an alignment film for vertical alignment is required. However, in this case, a step of forming an alignment film for vertical alignment is required, so there is a problem of reduced productivity.

本發明係鑒於上述課題而完成者,其目的在於提供一種能夠形成即便無配向膜亦抑制配向缺陷之產生之垂直配向液晶硬化膜的組合物。 [解決問題之技術手段] The present invention was completed in view of the above-mentioned subject, and its purpose is to provide a composition capable of forming a vertically aligned liquid crystal cured film that suppresses the generation of alignment defects even without an alignment film. [Technical means for solving the problem]

本發明者為了解決上述課題而進行了銳意研究,結果完成了本發明。即,本發明中包含以下態樣。 [1]一種組合物,其包含:具有下述式(I)-1: [化1] [式(I)-1中,Ar表示具有2個以上之環結構之2價基,該2個以上之環結構中之1個為6員環,於該6員環之1位及4位與L 1及L 2鍵結, L 1及L 2分別獨立表示單鍵或二價連結基, G 1及G 2分別獨立表示二價芳香族基或二價脂環式烴基,該二價芳香族基及該二價脂環式烴基所包含之氫原子可分別獨立被取代為鹵素原子、碳數1~4之烷基、碳數1~4之氟烷基、碳數1~4之烷氧基、氰基、或硝基,該二價芳香族基及該二價脂環式烴基所包含之碳原子可分別獨立被取代為氧原子、硫原子、或氮原子, *表示鍵結鍵] 所表示之結構之1種以上之液晶化合物、以及選自由非離子性矽烷化合物及離子性化合物所組成之群中之至少一者。 [2]如[1]所記載之組合物,其中上述具有式(I)-1所表示之結構之1種以上之液晶化合物於波長260 nm以上400 nm以下之區域具有極大吸收。 [3]如[1]或[2]所記載之組合物,其中上述具有式(I)-1所表示之結構之液晶化合物為具有下述式(I)-2: [化2] [式(I)-2中,Ar表示具有2個以上之環結構之2價基,該2個以上之環結構中之1個為6員環,於該6員環之1位及4位與L 1及L 2鍵結, L 1、L 2、及B 1分別獨立表示單鍵或二價連結基, G 1、G 2、及G 3分別獨立表示二價芳香族基或二價脂環式烴基,該二價芳香族基及該二價脂環式烴基所包含之氫原子可分別獨立被取代為鹵素原子、碳數1~4之烷基、碳數1~4之氟烷基、碳數1~4之烷氧基、氰基、或硝基,該二價芳香族基及該二價脂環式烴基所包含之碳原子可分別獨立被取代為氧原子、硫原子、或氮原子, *表示鍵結鍵] 所表示之結構之液晶化合物。 [4]如[1]至[3]中任一項所記載之組合物,其中上述具有式(I)-1所表示之結構之液晶化合物為下述式(I)-3: [化3] [式(I)-3中,Ar表示具有2個以上之環結構之2價基,該2個以上之環結構中之1個為6員環,於該6員環之1位及4位與L 1及L 2鍵結, L 1、L 2、B 1、及B 2分別獨立表示單鍵或二價連結基, G 1、G 2、G 3、及G 4分別獨立表示二價芳香族基或二價脂環式烴基,該二價芳香族基及該二價脂環式烴基所包含之氫原子可分別獨立被取代為鹵素原子、碳數1~4之烷基、碳數1~4之氟烷基、碳數1~4之烷氧基、氰基、或硝基,該二價芳香族基及該二價脂環式烴基所包含之碳原子可分別獨立被取代為氧原子、硫原子、或氮原子, *表示鍵結鍵] 所表示之液晶化合物。 [5]如[1]至[4]中任一項所記載之組合物,其中上述液晶化合物具有1個以上之聚合性基。 [6]如[1]至[5]中任一項所記載之組合物,其中上述非離子性矽烷化合物為矽烷偶合劑。 [7]如[1]至[6]中任一項所記載之組合物,其中上述非離子性矽烷化合物為具有烷氧基矽烷基與極性基之矽烷偶合劑。 [8]如[1]至[7]中任一項所記載之組合物,其中上述離子性化合物整體由非金屬元素構成。 [9]如[1]至[8]中任一項所記載之組合物,其中上述離子性化合物之分子量為100以上10,000以下。 [10]一種垂直配向液晶硬化膜,其係如[1]至[9]中任一項所記載之組合物之硬化物,且上述組合物所包含之液晶化合物相對於液晶硬化膜之面內方向朝垂直方向配向。 [11]如[10]所記載之垂直配向液晶硬化膜,其滿足下述關係式(1): -150 nm≦RthC(550)≦-30 nm      (1) [關係式(1)中,RthC(550)表示垂直配向液晶硬化膜於波長550 nm下之厚度方向之相位差值]。 [12]如[10]或[11]所記載之垂直配向液晶硬化膜,其滿足下述關係式(2): RthC(450)/RthC(550)≦1        (2) [關係式(2)中,RthC(450)表示垂直配向液晶硬化膜於波長450 nm下之厚度方向之相位差值,RthC(550)表示垂直配向液晶硬化膜於波長550 nm下之厚度方向之相位差值]。 [13]一種積層體,其具備基材、及如[10]至[12]中任一項所記載之垂直配向液晶硬化膜,且 上述垂直配向液晶硬化膜與上述基材鄰接。 [14]一種積層體,其具備如[10]至[12]中任一項所記載之垂直配向液晶硬化膜、及相對於上述垂直配向液晶硬化膜之面內方向朝水平方向配向之膜。 [15]如[14]所記載之積層體,其滿足下述關係式(3): ReA(450)/ReA(550)≦1     (3) [關係式(3)中,ReA(450)表示上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜於波長450 nm下之面內相位差值,ReA(550)表示上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜於波長550 nm下之面內相位差值]。 [16]如[14]或[15]所記載之積層體,其滿足下述關係式(4): |R0(550)-R40(550)|≦10 nm       (4) [關係式(4)中,R0(550)表示波長550 nm下之積層體之面內相位差值,R40(550)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時於波長550 nm下之相位差值]。 [17]如技術方案14至16中任一項所記載之積層體,其滿足下述關係式(5): |R0(450)-R40(450)|≦10 nm       (5) [關係式(5)中,R0(450)表示波長450 nm下之積層體之面內相位差值,R40(450)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時於波長450 nm下之相位差值]。 [18]如[14]至[17]中任一項所記載之積層體,其滿足下述關係式(6): |{R0(450)-R40(450)}-{R0(550)-R40(550)}|≦3 nm       (6) [關係式(6)中,R0(450)表示波長450 nm下之積層體之面內相位差值,R0(550)表示波長550 nm下之積層體之面內相位差值,R40(450)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時波長450 nm下之相位差值,R40(550)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時波長550 nm下之相位差值]。 [19]如[14]至[18]中任一項所記載之積層體,其中上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜為水平配向液晶硬化膜。 [20]一種橢圓偏光板,其包含如[14]至[19]中任一項所記載之積層體、及偏光膜。 [21]如[20]所記載之橢圓偏光板,其中上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜為水平配向液晶硬化膜。 [22]如[20]或[21]所記載之橢圓偏光板,其中上述朝水平方向配向之膜之遲相軸與偏光膜之吸收軸所成之角為45±5°。 [23]如[20]至[22]中任一項所記載之橢圓偏光板,其中上述偏光膜包含液晶化合物相對於偏光膜之膜面內朝水平方向配向之水平配向液晶硬化膜,且該水平配向液晶硬化膜包含二色性色素。 [24]如[23]所記載之橢圓偏光板,其中上述二色性色素具有偶氮基。 [25]如[23]或[24]所記載之橢圓偏光板,其中上述構成偏光膜之水平配向液晶硬化膜係液晶化合物於相對於膜之面內方向朝水平方向配向之層列相之狀態下硬化而成的硬化膜。 [26]一種有機EL顯示裝置,其包含如[20]至[25]中任一項所記載之橢圓偏光板。 [發明之效果] The inventors of the present invention have conducted intensive research to solve the above problems and have completed the present invention. That is, the present invention includes the following aspects. [1] A composition comprising: having the following formula (I)-1: [Chemical 1] [In formula (I)-1, Ar represents a divalent group having two or more ring structures, one of the two or more ring structures is a 6-membered ring, and is bonded to L1 and L2 at the 1-position and 4-position of the 6-membered ring, L1 and L2 each independently represent a single bond or a divalent linking group, G1 and G2 each independently represent a divalent aromatic group or a divalent alicyclic alkyl group, the hydrogen atom contained in the divalent aromatic group and the divalent alicyclic alkyl group may be independently substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, the carbon atom contained in the divalent aromatic group and the divalent alicyclic alkyl group may be independently substituted by an oxygen atom, a sulfur atom, or a nitrogen atom, and * represents a bond] [2] The composition described in [1], wherein the above-mentioned one or more liquid crystal compounds having a structure represented by formula (I)-1 have a maximum absorption in the wavelength region of not less than 260 nm and not more than 400 nm. [3] The composition described in [1] or [2], wherein the above-mentioned liquid crystal compound having a structure represented by formula (I)-1 is a compound having the following formula (I)-2: [Chemical 2] [In formula (I)-2, Ar represents a divalent group having two or more ring structures, one of the two or more ring structures is a 6-membered ring, and is bonded to L1 and L2 at the 1-position and 4-position of the 6-membered ring, L1 , L2 , and B1 each independently represent a single bond or a divalent linking group, G1 , G2 , and G 3 independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, the hydrogen atoms contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group can be independently substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, the carbon atoms contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group can be independently substituted by an oxygen atom, a sulfur atom, or a nitrogen atom, * represents a bond] A liquid crystal compound having a structure represented by. [4] A composition as described in any one of [1] to [3], wherein the liquid crystal compound having a structure represented by formula (I)-1 is the following formula (I)-3: [Chemical 3] [In formula (I)-3, Ar represents a divalent group having two or more ring structures, one of the two or more ring structures is a 6-membered ring, and is bonded to L1 and L2 at the 1-position and 4-position of the 6-membered ring, L1 , L2 , B1 , and B2 each independently represent a single bond or a divalent linking group, G1 , G2 , G3 , and G 4 independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, the hydrogen atoms contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group can be independently substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, the carbon atoms contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group can be independently substituted by an oxygen atom, a sulfur atom, or a nitrogen atom, * represents a bonding bond] A liquid crystal compound represented by. [5] A composition as described in any one of [1] to [4], wherein the liquid crystal compound has one or more polymerizable groups. [6] A composition as described in any one of [1] to [5], wherein the non-ionic silane compound is a silane coupling agent. [7] A composition as described in any one of [1] to [6], wherein the non-ionic silane compound is a silane coupling agent having an alkoxysilane group and a polar group. [8] A composition as described in any one of [1] to [7], wherein the ionic compound is entirely composed of non-metallic elements. [9] A composition as described in any one of [1] to [8], wherein the molecular weight of the ionic compound is greater than 100 and less than 10,000. [10] A vertically aligned liquid crystal cured film, which is a cured product of the composition as described in any one of [1] to [9], wherein the liquid crystal compound contained in the composition is aligned in a vertical direction relative to the in-plane direction of the liquid crystal cured film. [11] The vertically aligned liquid crystal cured film as described in [10] satisfies the following relationship (1): -150 nm ≦ RthC(550) ≦ -30 nm (1) [In the relationship (1), RthC(550) represents the phase difference value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 550 nm]. [12] The vertically aligned liquid crystal cured film as described in [10] or [11] satisfies the following relationship (2): RthC(450)/RthC(550) ≦ 1 (2) [In the relationship (2), RthC(450) represents the phase difference value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 450 nm, and RthC(550) represents the phase difference value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 550 nm]. [13] A laminate comprising a substrate and a vertically aligned liquid crystal cured film as described in any one of [10] to [12], wherein the vertically aligned liquid crystal cured film is adjacent to the substrate. [14] A laminate comprising a vertically aligned liquid crystal cured film as described in any one of [10] to [12], and a film aligned in a horizontal direction relative to the in-plane direction of the vertically aligned liquid crystal cured film. [15] The laminate described in [14] satisfies the following relationship (3): ReA(450)/ReA(550)≦1 (3) [In the relationship (3), ReA(450) represents the in-plane phase difference of the film oriented horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and ReA(550) represents the in-plane phase difference of the film oriented horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm]. [16] The laminate as described in [14] or [15] satisfies the following relationship (4): |R0(550)-R40(550)|≦10 nm (4) [In the relationship (4), R0(550) represents the in-plane phase difference of the laminate at a wavelength of 550 nm, and R40(550) represents the phase difference at a wavelength of 550 nm when the phase axis of the film aligned horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film is rotated 40°]. [17] The multilayer body described in any one of technical solutions 14 to 16 satisfies the following relationship (5): |R0(450)-R40(450)|≦10 nm (5) [In the relationship (5), R0(450) represents the in-plane phase difference of the multilayer body at a wavelength of 450 nm, and R40(450) represents the phase difference at a wavelength of 450 nm when the phase advance axis of the film oriented horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film is rotated 40° at a wavelength of 450 nm]. [18] The laminate described in any one of [14] to [17] satisfies the following relational expression (6): |{R0(450)-R40(450)}-{R0(550)-R40(550)}|≦3 nm (6) [In relational expression (6), R0(450) represents the in-plane phase difference value of the laminate at a wavelength of 450 nm, R0(550) represents the in-plane phase difference value of the laminate at a wavelength of 550 nm, and R40(450) represents the in-plane phase difference value of the laminate at a wavelength of 450 nm when the phase axis of the film aligned horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film is rotated 40°. [19] A laminate as described in any one of [14] to [18], wherein the film which is oriented in the in-plane direction relative to the vertically aligned liquid crystal cured film toward the horizontal direction is a horizontally aligned liquid crystal cured film. [20] An elliptical polarizing plate comprising a laminate as described in any one of [14] to [19], and a polarizing film. [21] An elliptical polarizing plate as described in [20], wherein the film which is oriented in the in-plane direction relative to the vertically aligned liquid crystal cured film toward the horizontal direction is a horizontally aligned liquid crystal cured film. [22] An elliptical polarizing plate as described in [20] or [21], wherein the angle between the retardation axis of the horizontally aligned film and the absorption axis of the polarizing film is 45±5°. [23] An elliptical polarizing plate as described in any one of [20] to [22], wherein the polarizing film comprises a horizontally aligned liquid crystal cured film in which the liquid crystal compound is aligned horizontally relative to the film surface of the polarizing film, and the horizontally aligned liquid crystal cured film comprises a dichroic dye. [24] An elliptical polarizing plate as described in [23], wherein the dichroic dye has an azo group. [25] An elliptical polarizing plate as described in [23] or [24], wherein the horizontally aligned liquid crystal cured film constituting the polarizing film is a cured film formed by curing the liquid crystal compound in a lamellar phase state in which the liquid crystal compound is aligned horizontally relative to the film surface. [26] An organic EL display device comprising an elliptical polarizing plate as described in any one of [20] to [25]. [Effects of the Invention]

根據本發明,可提供一種能夠形成即便無配向膜亦抑制配向缺陷之產生之垂直配向液晶硬化膜的組合物。According to the present invention, a composition capable of forming a vertically aligned liquid crystal cured film which suppresses the generation of alignment defects even without an alignment film can be provided.

以下,對本發明之實施形態詳細地進行說明。再者,於本說明書中,有時將丙烯酸及甲基丙烯酸稱為「(甲基)丙烯酸」。又,有時於化合物名之後加上「系」,對化合物及其衍生物進行統稱。於在化合物名之後加上「系」來表示聚合物名之情形時,意指聚合物之重複單元源自化合物或其衍生物、或者對源自化合物或其衍生物之重複單元於聚合後實施化學修飾等而成之聚合物。The following is a detailed description of the embodiments of the present invention. In addition, in this specification, acrylic acid and methacrylic acid are sometimes referred to as "(meth)acrylic acid". In addition, "system" is sometimes added after the compound name to collectively refer to the compound and its derivatives. When "system" is added after the compound name to indicate the name of a polymer, it means that the repeating units of the polymer are derived from the compound or its derivatives, or the repeating units derived from the compound or its derivatives are chemically modified after polymerization.

<組合物> 本發明之組合物(以下,有時記載為垂直配向液晶硬化膜形成用組合物)包含:具有下述式(I)-1: [化4] [式(I)-1中,Ar表示具有2個以上之環結構之2價基,該2個以上之環結構中之1個為6員環,於該6員環之1位及4位與L 1及L 2鍵結, L 1及L 2分別獨立表示單鍵或二價連結基, G 1及G 2分別獨立表示二價芳香族基或二價脂環式烴基,該二價芳香族基及該二價脂環式烴基所包含之氫原子可分別獨立被取代為鹵素原子、碳數1~4之烷基、碳數1~4之氟烷基、碳數1~4之烷氧基、氰基、或硝基,該二價芳香族基及該二價脂環式烴基所包含之碳原子可分別獨立被取代為氧原子、硫原子、或氮原子, *表示鍵結鍵] 所表示之結構之1種以上之液晶化合物、以及選自由非離子性矽烷化合物及離子性化合物所組成之群中之至少一者,較佳為同時包含非離子性矽烷化合物及離子性化合物。 <Composition> The composition of the present invention (hereinafter, sometimes referred to as a composition for forming a vertically aligned liquid crystal cured film) comprises: a composition having the following formula (I)-1: [Chemical 4] [In formula (I)-1, Ar represents a divalent group having two or more ring structures, one of the two or more ring structures is a 6-membered ring, and is bonded to L1 and L2 at the 1-position and 4-position of the 6-membered ring, L1 and L2 each independently represent a single bond or a divalent linking group, G1 and G2 each independently represent a divalent aromatic group or a divalent alicyclic alkyl group, the hydrogen atom contained in the divalent aromatic group and the divalent alicyclic alkyl group may be independently substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, the carbon atom contained in the divalent aromatic group and the divalent alicyclic alkyl group may be independently substituted by an oxygen atom, a sulfur atom, or a nitrogen atom, and * represents a bond] One or more liquid crystal compounds having the structure represented and at least one selected from the group consisting of non-ionic silane compounds and ionic compounds, preferably contain both non-ionic silane compounds and ionic compounds.

組合物除了上述式(I)-1所表示之1種以上之液晶化合物、以及非離子性矽烷化合物及/或離子性化合物以外,亦可視需要進而包含其他成分。The composition may further include other components as needed in addition to one or more liquid crystal compounds represented by the above formula (I)-1 and the non-ionic silane compound and/or the ionic compound.

本發明之組合物能夠形成即便無配向膜亦抑制配向缺陷之產生之垂直配向液晶硬化膜。其理由推測如下。具有式(I)-1所表示之結構之1種以上之液晶化合物(以下,有時記載為液晶化合物(I)-1)於式(I)-1中,Ar表示具有2個以上之環結構之2價基,該2個以上之環結構中之1個為6員環,於該6員環之1、4位與L 1及L 2鍵結,故而有形成T字型之結構之傾向。具有此種結構之化合物一般有顯示逆波長分散性之傾向,液晶化合物(I)-1通常表現逆波長分散性。另一方面,液晶化合物(I)-1由於具有T字型結構,故而通常單獨時不易進行垂直配向。本發明之組合物包含液晶化合物(I)-1、以及選自由非離子性矽烷化合物及離子性化合物所組成之群中之至少一者。於液晶硬化膜之製造中,若將組合物塗佈於基材而形成塗佈膜,且將塗佈膜加熱使之乾燥而形成乾燥覆膜,則於乾燥覆膜中,由於非離子性矽烷化合物與液晶化合物(I)-1之親和性及/或離子性化合物與液晶化合物(I)-1之親和性,產生離子性化合物存在於基材表面側,且/或非離子性矽烷化合物存在於乾燥覆膜之與基材為相反側之表面側的分佈。此種分佈由於提高垂直配向限制力,故而有液晶化合物(I)-1於乾燥覆膜內相對於基材表面朝垂直方向配向之傾向。因此,能夠保持液晶化合物(I)-1垂直配向之狀態而形成硬化膜。因此,認為本實施形態之組合物即便不於基材上形成配向膜,亦能夠形成垂直配向液晶硬化膜。作為選自由非離子性矽烷化合物及離子性化合物所組成之群中之至少一者,可列舉僅包含非離子性矽烷化合物、僅包含離子性化合物、以及包含非離子性矽烷化合物及離子性化合物兩者之3種態樣。雖然僅非離子性矽烷化合物及離子性化合物任一者亦具有提高垂直配向限制力之效果,但就進一步提高垂直配向限制力之觀點而言,較佳為同時包含非離子性矽烷化合物及離子性化合物。 The composition of the present invention can form a vertically aligned liquid crystal cured film that suppresses the generation of alignment defects even without an alignment film. The reason is presumed to be as follows. One or more liquid crystal compounds having a structure represented by formula (I)-1 (hereinafter, sometimes recorded as liquid crystal compound (I)-1) In formula (I)-1, Ar represents a divalent group having two or more ring structures, one of the two or more ring structures is a six-membered ring, and is bonded to L1 and L2 at the 1 and 4 positions of the six-membered ring, so there is a tendency to form a T-shaped structure. Compounds having such a structure generally tend to show reverse wavelength dispersion, and liquid crystal compound (I)-1 usually shows reverse wavelength dispersion. On the other hand, since liquid crystal compound (I)-1 has a T-shaped structure, it is generally difficult to perform vertical alignment when alone. The composition of the present invention comprises a liquid crystal compound (I)-1 and at least one selected from the group consisting of a non-ionic silane compound and an ionic compound. In the production of a liquid crystal cured film, if the composition is applied to a substrate to form a coated film, and the coated film is heated and dried to form a dry film, then in the dry film, due to the affinity between the non-ionic silane compound and the liquid crystal compound (I)-1 and/or the affinity between the ionic compound and the liquid crystal compound (I)-1, the ionic compound is present on the surface side of the substrate, and/or the non-ionic silane compound is present on the surface side of the dry film opposite to the substrate. This distribution increases the vertical alignment restraining force, so there is a tendency for the liquid crystal compound (I)-1 to be aligned vertically relative to the substrate surface in the dried film. Therefore, the liquid crystal compound (I)-1 can be maintained in a vertically aligned state to form a cured film. Therefore, it is believed that the composition of this embodiment can form a vertically aligned liquid crystal cured film even if an alignment film is not formed on the substrate. As at least one selected from the group consisting of non-ionic silane compounds and ionic compounds, three aspects can be listed, including only non-ionic silane compounds, only ionic compounds, and both non-ionic silane compounds and ionic compounds. Although either the non-ionic silane compound or the ionic compound alone has the effect of improving the vertical alignment limiting force, from the viewpoint of further improving the vertical alignment limiting force, it is preferred to include both the non-ionic silane compound and the ionic compound.

[1.液晶化合物] 液晶化合物(I)-1係具有下述式(I)-1: [化5] 所表示之結構之1種以上之液晶化合物。 [1. Liquid crystal compound] The liquid crystal compound (I)-1 has the following formula (I)-1: [Chemical 5] One or more liquid crystal compounds having the structures represented.

式(I)-1中,Ar表示具有2個以上之環結構之2價基,該2個以上之環結構中之1個為6員環,於該6員環之1位及4位與L 1及L 2鍵結, L 1及L 2分別獨立表示單鍵或二價連結基, G 1及G 2分別獨立表示二價芳香族基或二價脂環式烴基,該二價芳香族基及該二價脂環式烴基所包含之氫原子可分別獨立被取代為鹵素原子、碳數1~4之烷基、碳數1~4之氟烷基、碳數1~4之烷氧基、氰基、或硝基,該二價芳香族基及該二價脂環式烴基所包含之碳原子可分別獨立被取代為氧原子、硫原子、或氮原子, *表示鍵結鍵。 In formula (I)-1, Ar represents a divalent group having two or more ring structures, one of the two or more ring structures is a 6-membered ring, and is bonded to L1 and L2 at the 1-position and 4-position of the 6-membered ring, L1 and L2 each independently represent a single bond or a divalent linking group, G1 and G2 each independently represent a divalent aromatic group or a divalent alicyclic alkyl group, the hydrogen atom contained in the divalent aromatic group and the divalent alicyclic alkyl group can be independently substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, the carbon atom contained in the divalent aromatic group and the divalent alicyclic alkyl group can be independently substituted by an oxygen atom, a sulfur atom, or a nitrogen atom, and * represents a bond.

Ar表示具有2個以上之環結構之2價基。於本說明書中,Ar所具有之環結構之單位為單環。例如,於下述液晶化合物A、(A)-2、及(A)-3中,Ar分別具有4個、2個、及3個環結構。2個以上之環結構可2個以上之單環縮合而相互相鄰,亦可2個以上之單環經由化學鍵而相互鍵結,亦可2個以上之單環不縮合且不經由化學鍵地相鄰。又,可單環經由化學鍵而與單環縮合而成之縮合環(多環)相互鍵結,亦可多環與多環經由化學鍵而相互鍵結。將2個以上之環鍵結之化學鍵例如可包含如共軛雙鍵(更具體而言為-C=C-及-C=N-等)及羰基般擴展共軛系之空間上之擴散的鍵或基。Ar represents a divalent group having two or more ring structures. In this specification, the unit of the ring structure possessed by Ar is a monocyclic ring. For example, in the following liquid crystal compounds A, (A)-2, and (A)-3, Ar has 4, 2, and 3 ring structures, respectively. The two or more ring structures may be adjacent to each other by condensation of two or more monocyclic rings, or may be bonded to each other via chemical bonds, or may be adjacent to each other without condensation and without chemical bonds. In addition, a monocyclic ring may be bonded to a condensed ring (polycyclic ring) formed by condensation of a monocyclic ring via chemical bonds, or polycyclic rings may be bonded to each other via chemical bonds. The chemical bonds that link two or more rings may include, for example, conjugated double bonds (more specifically, -C=C- and -C=N-, etc.) and bonds or groups that spatially expand the conjugated system such as a carbonyl group.

作為單環,例如可列舉單環式之烴環(更具體而言為環烷烴環及苯環等)、及單環式之雜環。作為單環式之雜環,例如可列舉5員環之雜環(更具體而言為吡咯環、呋喃環、噻吩環、㗁唑環、咪唑環、吡唑環、噻唑環、三唑環、吡咯啶環、四氫呋喃環、及四氫噻吩環等)、及6員環之雜環(更具體而言為吡啶環、吡𠯤環、嘧啶環、噻𠯤環、及哌啶環等)。多環為具有2環以上之環結構之結構,該環結構可為芳香環,亦可為烴環。作為多環,例如可列舉包含縮合環及單環式之雜環者。縮合環例如為該等單環中同一種類之單環縮合2個以上而成之環、及不同種類之單環縮合2個以上而成之環。作為縮合環,例如可列舉多環式之烴環(更具體而言為萘環、蒽環、及菲環等)、及多環式之雜環(更具體而言為喹啉環、喹㗁啉環、苯并呋喃環、苯并噻吩環、茀環、吲哚環、咔唑環、苯并咪唑環、苯并噻唑環、噻吩并噻唑環、苯并㗁唑環、1,3-苯二硫酚環、及啡啉環等)。該等縮合環中,就表現逆波長分散特性之觀點而言,較佳為多環結構,更佳為多環式之雜環結構。Examples of the monocyclic ring include monocyclic hydrocarbon rings (more specifically, cycloalkane rings and benzene rings) and monocyclic heterocyclic rings. Examples of the monocyclic heterocyclic ring include 5-membered heterocyclic rings (more specifically, pyrrole ring, furan ring, thiophene ring, oxadiazole ring, imidazole ring, pyrazole ring, thiazole ring, triazole ring, pyrrolidinyl ring, tetrahydrofuran ring, and tetrahydrothiophene ring) and 6-membered heterocyclic rings (more specifically, pyridine ring, pyrrolidine ring, pyrimidine ring, thiazole ring, and piperidine ring). A polycyclic ring is a ring structure having two or more rings, and the ring structure may be an aromatic ring or a hydrocarbon ring. Examples of polycyclic rings include heterocyclic rings including condensed rings and monocyclic rings. Condensed rings include, for example, rings formed by condensing two or more single rings of the same type among the monocyclic rings, and rings formed by condensing two or more single rings of different types. Examples of the condensed ring include polycyclic hydrocarbon rings (more specifically, naphthalene ring, anthracene ring, and phenanthrene ring), and polycyclic heterocyclic rings (more specifically, quinoline ring, quinoline ring, benzofuran ring, benzothiophene ring, fluorene ring, indole ring, carbazole ring, benzimidazole ring, benzothiazole ring, thienothiazole ring, benzoxazole ring, 1,3-benzenedithiophenol ring, and phenanthroline ring). Among these condensed rings, a polycyclic structure is preferred, and a polycyclic heterocyclic structure is more preferred from the viewpoint of expressing the reverse wavelength dispersion property.

單環及多環可具有取代基。作為單環及多環可具有之取代基,例如可列舉氫原子、碳數1~20之烷基、及碳數1~20之烷氧基,該等取代基可進而具有氰基、亞胺基、烷多烯基、氰基、或胺基,該取代基中之碳原子可進而被取代為氧原子、氮原子、或硫原子(於該情形時,鍵結於碳原子上之氫原子可根據取代之原子之價數而增減)。該等取代基之中,可如亞胺基、烷多烯基、氰基、羥基、及胺基般擴展共軛系之空間上之擴散。該等取代基可進而經取代。The monocyclic and polycyclic rings may have substituents. Examples of substituents that the monocyclic and polycyclic rings may have include hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, and alkoxy groups having 1 to 20 carbon atoms. These substituents may further include cyano groups, imino groups, alkoxy groups, cyano groups, or amino groups. The carbon atoms in the substituents may further be replaced by oxygen atoms, nitrogen atoms, or sulfur atoms (in this case, the hydrogen atoms bonded to the carbon atoms may increase or decrease depending on the valence of the replaced atoms). Among these substituents, the spatial diffusion of the conjugated system may be expanded like imino groups, alkoxy groups, cyano groups, hydroxyl groups, and amino groups. These substituents may further be substituted.

作為Ar所具有之6員環,例如可列舉苯環及環己烷環。6員環可包含雜原子作為環員原子。作為包含6員環之縮合環,例如可列舉喹啉環、喹㗁啉環、苯并呋喃環、苯并噻吩環、茀環、吲哚環、咔唑環、苯并咪唑環、苯并噻唑環、噻吩并噻唑環、苯并㗁唑環、1,3-苯二硫酚環、及啡啉環。Examples of the 6-membered ring possessed by Ar include a benzene ring and a cyclohexane ring. The 6-membered ring may include a heteroatom as a ring member atom. Examples of the condensed ring including the 6-membered ring include a quinoline ring, a quinoline ring, a benzofuran ring, a benzothiophene ring, a fluorene ring, an indole ring, a carbazole ring, a benzimidazole ring, a benzothiazole ring, a thienothiazole ring, a benzoxazole ring, a 1,3-benzenedithiol ring, and a phenanthroline ring.

就進一步提高偏光板之逆波長分散性之觀點而言,Ar較佳為表示包含具有1個以上之硫原子作為環員原子之環結構的2價基。就進一步提高逆波長分散性之觀點而言,Ar較佳為表示下述式所表示之2價基。*表示鍵結鍵。 [化6] 上述式中,X 1、X 2、及X 3分別獨立選自CR 1X、R 2X、NR 3X、硫原子、及氧原子之任一者。R 1X、R 2X、及R 3X分別獨立表示氫原子或碳數1~4之烷基。 U包含至少1個環結構,作為該環結構,可列舉包含上述段落0016~0018所記載之單環及/或多環之結構, Y可為任意之取代基,就提高逆波長分散性之觀點而言,較佳為包含至少1個以上之環結構,作為該環結構,可列舉包含上述段落0016~0018所記載之單環及/或多環之結構。 L 10為二價連結基,表示單鍵、-O-CO-O-、-N=N-、-C≡C-、-CR a=CR b-、-CH=N-N=CH-、或-CR c=N-。 L 11為二價連結基,表示單鍵、-CO-、-COO-、-O-CO-O-、-CO-NH-、-CH=CH-COO-、-CH=CH-OCO-、-CH 2CH 2-COO-、-CH 2CH 2-OCO-、-CH 2-COO-、-CH 2-OCO-、-N=N-、-C≡C-、-CR d=CR e-、-CH=N-N=CH-、-CR f=N-、-CR g=N-NR h-、-N=N-CR iR j-、-N=CR k-CR lR m-、-N=CR n-NR o-、-CR p=CR q-NR r-、或-CR sR t-N=CR u-。此處,R c~R u分別獨立表示氫原子或碳數1~10之烷基,該烷基中之碳原子可被取代為氮原子、氧原子、硫原子(於該情形時,可根據原子價數適當地增減氫原子數)。 Z表示可鍵結氫原子或取代基之第14~16族之非金屬原子。就提高逆波長分散性之觀點而言,Z較佳為具有選自由:擴張共軛系之空間上之擴散之結構(更具體而言為雙鍵部位、三鍵部位、以及滿足休克爾定律之芳香環及雜環等),及選自氮原子及硫原子之原子所組成之群中之至少一種以上。 From the viewpoint of further improving the reverse wavelength dispersion of the polarizing plate, Ar is preferably a divalent group including a ring structure having one or more sulfur atoms as ring member atoms. From the viewpoint of further improving the reverse wavelength dispersion, Ar is preferably a divalent group represented by the following formula. * represents a bond. [Chem. 6] In the above formula, X 1 , X 2 , and X 3 are independently selected from any one of CR 1X , R 2X , NR 3X , a sulfur atom, and an oxygen atom. R 1X , R 2X , and R 3X are independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms. U contains at least one ring structure, and as the ring structure, the monocyclic and/or polycyclic structures described in the above paragraphs 0016 to 0018 can be listed. Y can be any substituent, and from the viewpoint of improving reverse wavelength dispersion, it is preferably a ring structure containing at least one or more ring structures, and as the ring structure, the monocyclic and/or polycyclic structures described in the above paragraphs 0016 to 0018 can be listed. L10 is a divalent linking group and represents a single bond, -O-CO-O-, -N=N-, -C≡C-, -CRa = CRb- , -CH=NN=CH-, or -CRc =N-. L11 is a divalent linking group and represents a single bond, -CO-, -COO-, -O-CO-O-, -CO-NH-, -CH=CH-COO-, -CH=CH - OCO-, -CH2CH2-COO-, -CH2CH2-OCO-, -CH2 - COO-, -CH2 -OCO-, -N= N- , -C≡C-, -CRd = CRe-, -CH=NN = CH-, -CRf = N- , -CRg = N - NRh- , -N =N- CRiRj- , -N=CRk- CRlRm- , -N=CRn - NRo- , -CRp = CRq - NRr- , or -CRsRt - N = CRu- . Here, R c to Ru each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, wherein the carbon atoms in the alkyl group may be substituted with nitrogen atoms, oxygen atoms, or sulfur atoms (in this case, the number of hydrogen atoms may be appropriately increased or decreased according to the atomic valence). Z represents a non-metal atom of Groups 14 to 16 that can bond to a hydrogen atom or a substituent. From the viewpoint of improving reverse wavelength dispersion, Z preferably has at least one selected from the group consisting of: a spatially diffuse structure of an extended conjugated system (more specifically, a double-bonding site, a triple-bonding site, and an aromatic ring and a heterocyclic ring that satisfy Huckel's law), and nitrogen atoms and sulfur atoms.

作為L 1及L 2所表示之二價連結基,例如可列舉碳數1~4之伸烷基、-O-、-S-、-R a1OR a2-、-R a3COOR a4-、-R a5OCOR a6-、R a7OC=OOR a8-、-N=N-、-CR c=CR d-、及-C≡C-。此處,R a1~R a8分別獨立表示單鍵或碳數1~4之伸烷基(更具體而言為亞甲基、伸乙基、伸丙基、及伸丁基等),R c及R d分別獨立表示碳數1~4之烷基(更具體而言為甲基、乙基、丙基、及丁基等)或氫原子。 Examples of the divalent linking group represented by L1 and L2 include an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -Ra1OR2- , -Ra3COOR4-, -Ra5OCOR6-, Ra7OC= OOR8- , -N=N- , -CRc = CRd- , and -C≡C-. Here, Ra1 to Ra8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms (more specifically, a methylene group, an ethyl group, a propyl group, and a butyl group), and Rc and Rd each independently represent an alkyl group having 1 to 4 carbon atoms (more specifically, a methyl group, an ethyl group, a propyl group, and a butyl group) or a hydrogen atom.

L 1及L 2較佳為分別獨立表示單鍵、碳數1~4之伸烷基、-O-、-S-、-R a1OR a2-、-R a3COOR a4-、-R a5OCOR a6-、R a7OC=OOR a8-、-N=N-、-CR c=CR d-、或-C≡C-。L 1及L 2更佳為分別獨立表示單鍵、-OR a2-1-、-CH 2-、-CH 2CH 2-、-COOR a4-1-、或OCOR a6-1-。此處,R a2-1、R a4-1、及R a6-1分別獨立表示單鍵、-CH 2-、或-CH 2CH 2-。L 1及L 2進而較佳為分別獨立表示單鍵、-O-、-CH 2CH 2-、-COO-、-COOCH 2CH 2-、或-OCO-。 L1 and L2 are preferably independently a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S- , -Ra1OR2-, -Ra3COOR4-, -Ra5OCOR6-, Ra7OC = OOR8- , -N=N-, -CRc = CRd- , or -C≡C-. L1 and L2 are more preferably independently a single bond , -OR2-1- , -CH2- , -CH2CH2-, -COOR4-1-, or OCOR6-1-. Here, Ra2-1, Ra4-1 , and Ra6-1 are independently a single bond , -CH2- , or -CH2CH2- . Further, L1 and L2 preferably independently represent a single bond, -O-, -CH2CH2- , -COO-, -COOCH2CH2- , or -OCO-.

作為G 1及G 2所表示之二價芳香族基,例如可列舉伸苯二基及伸萘二基(naphthylylenediyl)。二價芳香族基可經鹵素原子(更具體而言為氟原子、氯原子、及溴原子等)或碳數1~4之烷基之類之取代基取代。二價芳香族基可具有雜原子(更具體而言為氧原子、硫原子、及氮原子等)作為環員原子。作為G 1及G 2所表示之二價脂環式烴基,例如可列舉環戊二基、環己二基、及環庚二基。二價脂環式烴基可經鹵素原子及碳數1~4之烷基之類之取代基取代。 Examples of the divalent aromatic group represented by G1 and G2 include phenylenediyl and naphthylylenediyl. The divalent aromatic group may be substituted by a substituent such as a halogen atom (more specifically, a fluorine atom, a chlorine atom, and a bromine atom) or an alkyl group having 1 to 4 carbon atoms. The divalent aromatic group may have a heteroatom (more specifically, an oxygen atom, a sulfur atom, and a nitrogen atom) as a ring member atom. Examples of the divalent alicyclic alkyl group represented by G1 and G2 include cyclopentanediyl, cyclohexanediyl, and cycloheptanediyl. The divalent alicyclic alkyl group may be substituted by a substituent such as a halogen atom and an alkyl group having 1 to 4 carbon atoms.

本說明書中,芳香族基係指具有平面性之環狀結構之基,該環狀結構所具有之π電子數依據休克爾定律為[4n+2]個(n表示1以上之正整數)。於包含-N=及S-之類之雜原子作為環員原子而形成環狀結構之情形時,亦包括包含該等雜原子上之非共價鍵電子對在內滿足休克爾定律,具有芳香族性之情形。In this specification, an aromatic group refers to a group having a planar cyclic structure, and the number of π electrons in the cyclic structure is [4n+2] (n represents a positive integer greater than 1) according to Huckel's law. When a cyclic structure is formed by including heteroatoms such as -N= and S- as ring member atoms, it also includes the case where the non-covalent bond electron pairs on such heteroatoms satisfy Huckel's law and have aromaticity.

G 1及G 2較佳為分別獨立為可經選自由鹵素原子及碳數1~4之烷基所組成之群中之至少1個取代基取代的1,4-伸苯二基、可經選自由鹵素原子及碳數1~4之烷基所組成之群中之至少1個取代基取代的1,4-環己二基,更佳為經甲基取代之1,4-伸苯二基、未經取代之1,4-伸苯二基、或未經取代之1,4-反式環己二基,尤佳為未經取代之1,4-伸苯二基、或未經取代之1,4-反式環己二基。又,較佳為存在複數個之G 1及G 2中之至少1個為二價脂環式烴基,又,更佳為鍵結於L 1或L 2之G 1及G 2中之至少1個為二價脂環式烴基。 G1 and G2 are preferably 1,4-phenylenediyl which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, or 1,4-cyclohexanediyl which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1,4-phenylenediyl substituted with methyl, unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4-trans-cyclohexanediyl, and particularly preferably unsubstituted 1,4-phenylenediyl or unsubstituted 1,4-trans-cyclohexanediyl. Furthermore, it is preferred that at least one of the plural G1 and G2 is a divalent alicyclic hydrocarbon group, and it is more preferred that at least one of the G1 and G2 bonded to L1 or L2 is a divalent alicyclic hydrocarbon group.

液晶化合物(I)-1較佳為於波長260~400 nm之區域具有極大吸收。於液晶化合物(I)-1具備具有雜原子之芳香族基或使共軛系擴張之結構之情形時,與苯環相比,近紫外區域之吸收向長波長側偏移,因此多數情況下於260 nm以上之波長區域具有極大吸收,若如此於260 nm以上之波長區域具有極大吸收,則就提高逆波長分散性之觀點而言較佳。又,於在大於波長400 nm之波長區域具有極大吸收之情形時,有產生著色之情況,故而液晶化合物(I)-1較佳為於波長400 nm以下之區域具有極大吸收。進而,就進一步提高波長分散性之觀點而言,更佳為於波長280 nm以上400 nm以下之區域具有極大吸收,進而較佳為於波長300 nm以上400 nm以下之區域具有極大吸收。Liquid crystal compound (I)-1 preferably has a maximum absorption in the wavelength region of 260 to 400 nm. When liquid crystal compound (I)-1 has an aromatic group having a heteroatom or a structure that expands the conjugate system, the absorption in the near-ultraviolet region shifts to the long-wavelength side compared to the benzene ring, and therefore has a maximum absorption in the wavelength region above 260 nm in most cases. If it has a maximum absorption in the wavelength region above 260 nm, it is better from the perspective of improving the reverse wavelength dispersion. In addition, when it has a maximum absorption in the wavelength region greater than 400 nm, coloring may occur, so liquid crystal compound (I)-1 preferably has a maximum absorption in the wavelength region below 400 nm. Furthermore, from the viewpoint of further improving the wavelength dispersion, it is more preferable to have a maximum absorption in the wavelength region of 280 nm to 400 nm, and it is further more preferable to have a maximum absorption in the wavelength region of 300 nm to 400 nm.

液晶化合物(I)-1較佳為具有下述式(I)-2: [化7] 所表示之結構之液晶化合物(以下,有時記載為液晶化合物(I)-2)。 The liquid crystal compound (I)-1 preferably has the following formula (I)-2: [Chemical 7] A liquid crystal compound having a structure represented by (hereinafter, sometimes referred to as liquid crystal compound (I)-2).

式(I)-2中,Ar表示具有2個以上之環結構之2價基,該2個以上之環結構中之1個為6員環,於該6員環之1位及4位與L 1及L 2鍵結, L 1、L 2、及B 1分別獨立表示單鍵或二價連結基, G 1、G 2、及G 3分別獨立表示二價芳香族基或二價脂環式烴基,該二價芳香族基及該二價脂環式烴基所包含之氫原子可分別獨立被取代為鹵素原子、碳數1~4之烷基、碳數1~4之氟烷基、碳數1~4之烷氧基、氰基、或硝基,該二價芳香族基及該二價脂環式烴基所包含之碳原子可分別獨立被取代為氧原子、硫原子、或氮原子, *表示鍵結鍵。 In formula (I)-2, Ar represents a divalent group having two or more ring structures, one of the two or more ring structures is a 6-membered ring, and is bonded to L1 and L2 at the 1-position and 4-position of the 6-membered ring, L1 , L2 , and B1 each independently represent a single bond or a divalent linking group, G1 , G2 , and G 3 independently represent a divalent aromatic group or a divalent alicyclic alkyl group, the hydrogen atom contained in the divalent aromatic group and the divalent alicyclic alkyl group can be independently substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, the carbon atom contained in the divalent aromatic group and the divalent alicyclic alkyl group can be independently substituted by an oxygen atom, a sulfur atom, or a nitrogen atom, and * represents a bond.

式(I)-2中之Ar、L 1、L 2、G 1、及G 2分別與式(I)-1中之Ar、L 1、L 2、G 1、及G 2含義相同。 Ar, L 1 , L 2 , G 1 , and G 2 in formula (I)-2 have the same meanings as Ar, L 1 , L 2 , G 1 , and G 2 in formula (I)-1, respectively.

B 1較佳為表示單鍵、碳數1~4之伸烷基、-O-、-S-、-R a1OR a2-、-R a3COOR a4-、-R a5OCOR a6-、R a7OC=OOR a8-、-N=N-、-CR c=CR d-、或-C≡C-。L 1及L 2更佳為分別獨立表示單鍵、-OR a2-1-、-CH 2-、-CH 2CH 2-、-COOR a4-1-、或-OCOR a6-1-。此處,R a2-1、R a4-1、R a6-1分別獨立表示單鍵、-CH 2-、或-CH 2CH 2-。L 1及L 2進而較佳為分別獨立表示單鍵、-O-、-CH 2CH 2-、-COO-、-COOCH 2CH 2-、或-OCO-。 B1 preferably represents a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -Ra1OR2-, -Ra3COOR4- , -Ra5OCOR6-, Ra7OC = OOR8- , -N = N-, -CRc = CRd- , or -C≡C-. L1 and L2 more preferably each independently represent a single bond, -OR2-1- , -CH2-, -CH2CH2-, -COOR4-1-, or -OCOR6-1-. Here, Ra2-1, Ra4-1 , and Ra6-1 each independently represent a single bond , -CH2- , or -CH2CH2- . Further, L1 and L2 preferably independently represent a single bond, -O-, -CH2CH2- , -COO-, -COOCH2CH2- , or -OCO-.

作為G 3所表示之二價芳香族基,例如可列舉伸苯二基及伸萘二基。二價芳香族基可經鹵素原子(更具體而言為氟原子、氯原子、及溴原子等)或碳數1~4之烷基之類之取代基取代。作為G 3所表示之二價脂環式烴基,例如可列舉環戊二基、環己二基、及環庚二基。二價脂環式烴基可經鹵素原子或碳數1~4之烷基之類之取代基取代。 Examples of the divalent aromatic group represented by G 3 include phenylenediyl and naphthylenediyl. The divalent aromatic group may be substituted by a substituent such as a halogen atom (more specifically, a fluorine atom, a chlorine atom, and a bromine atom) or an alkyl group having 1 to 4 carbon atoms. Examples of the divalent alicyclic alkyl group represented by G 3 include cyclopentanediyl, cyclohexanediyl, and cycloheptanediyl. The divalent alicyclic alkyl group may be substituted by a substituent such as a halogen atom or an alkyl group having 1 to 4 carbon atoms.

G 3較佳為分別獨立為可經選自由鹵素原子及碳數1~4之烷基所組成之群中之至少1個取代基取代的1,4-伸苯二基、可經選自由鹵素原子及碳數1~4之烷基所組成之群中之至少1個取代基取代的1,4-環己二基,更佳為經甲基取代之1,4-伸苯二基、未經取代之1,4-伸苯二基、或未經取代之1,4-反式環己二基,尤佳為未經取代之1,4-伸苯二基、或未經取代之1,4-反式環己二基。 G3 is preferably 1,4-phenylenediyl which may be substituted by at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, or 1,4-cyclohexanediyl which may be substituted by at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1,4-phenylenediyl substituted by methyl, unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4-trans-cyclohexanediyl, and particularly preferably unsubstituted 1,4-phenylenediyl or unsubstituted 1,4-trans-cyclohexanediyl.

液晶化合物(I)-1更佳為具有下述式(I)-3: [化8] 所表示之結構之液晶化合物(以下,有時記載為液晶化合物(I)-3)。 The liquid crystal compound (I)-1 is more preferably a compound having the following formula (I)-3: [Chemical 8] A liquid crystal compound having a structure represented by (hereinafter, sometimes referred to as liquid crystal compound (I)-3).

式(I)-3中,Ar表示具有2個以上之環結構之2價基,該2個以上之環結構中之1個為6員環,於該6員環之1位及4位與L 1及L 2鍵結, L 1、L 2、B 1、及B 2分別獨立表示單鍵或二價連結基, G 1、G 2、G 3、及G 4分別獨立表示二價芳香族基或二價脂環式烴基,該二價芳香族基或該二價脂環式烴基所包含之氫原子可被取代為鹵素原子、碳數1~4之烷基、碳數1~4之氟烷基、碳數1~4之烷氧基、氰基、或硝基,該二價芳香族基或該二價脂環式烴基所包含之碳原子可被取代為氧原子、硫原子、或氮原子, *表示鍵結鍵。 In formula (I)-3, Ar represents a divalent group having two or more ring structures, one of the two or more ring structures is a 6-membered ring, and is bonded to L1 and L2 at the 1-position and 4-position of the 6-membered ring, L1 , L2 , B1 , and B2 each independently represent a single bond or a divalent linking group, G1 , G2 , G3 , and G 4 independently represent a divalent aromatic group or a divalent alicyclic alkyl group, the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic alkyl group may be substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, the carbon atom contained in the divalent aromatic group or the divalent alicyclic alkyl group may be substituted by an oxygen atom, a sulfur atom, or a nitrogen atom, and * represents a bond.

式(I)-3中之Ar、L 1、L 2、G 1、及G 2分別與式(I)-1中之Ar、L 1、L 2、G 1、及G 2含義相同。式(I)-3中之B 1及G 3分別與式(I)-2中之B 1及G 3含義相同。 Ar, L1 , L2 , G1 , and G2 in formula (I)-3 have the same meanings as Ar, L1 , L2 , G1 , and G2 in formula (I)-1. B1 and G3 in formula (I)-3 have the same meanings as B1 and G3 in formula (I)-2.

B 2較佳為表示單鍵、碳數1~4之伸烷基、-O-、-S-、-R a1OR a2-、-R a3COOR a4-、-R a5OCOR a6-、R a7OC=OOR a8-、-N=N-、-CR c=CR d-、或-C≡C-。L 1及L 2更佳為分別獨立表示單鍵、-OR a2-1-、-CH 2-、-CH 2CH 2-、-COOR a4-1-、或-OCOR a6-1-。此處,R a2-1、R a4-1、R a6-1分別獨立表示單鍵、-CH 2-、或-CH 2CH 2-。L 1及L 2進而較佳為分別獨立表示單鍵、-O-、-CH 2CH 2-、-COO-、-COOCH 2CH 2-、或-OCO-。 B2 preferably represents a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -Ra1OR2-, -Ra3COOR4- , -Ra5OCOR6-, Ra7OC = OOR8- , -N = N-, -CRc = CRd- , or -C≡C-. L1 and L2 more preferably each independently represent a single bond, -OR2-1- , -CH2-, -CH2CH2-, -COOR4-1-, or -OCOR6-1-. Here, Ra2-1, Ra4-1 , and Ra6-1 each independently represent a single bond , -CH2- , or -CH2CH2- . Further, L1 and L2 preferably independently represent a single bond, -O-, -CH2CH2- , -COO-, -COOCH2CH2- , or -OCO-.

作為G 4所表示之二價芳香族基,例如可列舉伸苯二基或伸萘二基。二價芳香族基可經鹵素原子(更具體而言為氟原子、氯原子、及溴原子等)或碳數1~4之烷基之類之取代基取代。作為G 3所表示之二價脂環式烴基,例如可列舉環戊二基、環己二基、及環庚二基。二價脂環式烴基可經鹵素原子或碳數1~4之烷基之類之取代基取代。 Examples of the divalent aromatic group represented by G4 include phenylenediyl and naphthylenediyl. The divalent aromatic group may be substituted by a substituent such as a halogen atom (more specifically, a fluorine atom, a chlorine atom, and a bromine atom) or an alkyl group having 1 to 4 carbon atoms. Examples of the divalent alicyclic alkyl group represented by G3 include cyclopentanediyl, cyclohexanediyl, and cycloheptanediyl. The divalent alicyclic alkyl group may be substituted by a substituent such as a halogen atom or an alkyl group having 1 to 4 carbon atoms.

G 4較佳為可經選自由鹵素原子及碳數1~4之烷基所組成之群中之至少1個取代基取代的1,4-伸苯二基、可經選自由鹵素原子及碳數1~4之烷基所組成之群中之至少1個取代基取代的1,4-環己二基,更佳為經甲基取代之1,4-伸苯二基、未經取代之1,4-伸苯二基、或未經取代之1,4-反式環己二基,尤佳為未經取代之1,4-伸苯二基、或未經取代之1,4-反式環己二基。 G4 is preferably 1,4-phenylenediyl which may be substituted by at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, 1,4-cyclohexanediyl which may be substituted by at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1,4-phenylenediyl substituted by methyl, unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4-trans-cyclohexanediyl, and particularly preferably unsubstituted 1,4-phenylenediyl or unsubstituted 1,4-trans-cyclohexanediyl.

液晶化合物(I)-1可具有1個以上之聚合性基。於本說明書中,聚合性基係指能夠藉由自光聚合起始劑產生之活性自由基或酸之類之活性種而參與聚合之基。作為聚合性基,例如可列舉環氧基、乙烯基、乙烯氧基、1-氯乙烯基、異丙烯基、4-乙烯基苯基、丙烯醯氧基、甲基丙烯醯氧基、環氧乙烷基、及氧雜環丁基。該等聚合性基之中,較佳為丙烯醯氧基及甲基丙烯醯氧基。於本說明書中,具有聚合性基之液晶化合物(I)-1可藉由聚合反應形成聚合物。Liquid crystal compound (I)-1 may have one or more polymerizable groups. In the present specification, a polymerizable group refers to a group that can participate in polymerization by an active free radical or an active species such as an acid generated from a photopolymerization initiator. Examples of polymerizable groups include epoxy, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, ethylene oxide, and cyclobutylene. Among the polymerizable groups, acryloxy and methacryloxy are preferred. In the present specification, a liquid crystal compound (I)-1 having a polymerizable group can form a polymer by a polymerization reaction.

作為液晶化合物(I)-1,例如可列舉具有式(A)-1~式(A)-5所表示之結構之液晶化合物。Examples of the liquid crystal compound (I)-1 include liquid crystal compounds having structures represented by formula (A)-1 to formula (A)-5.

(液晶化合物A) [化9] (液晶化合物(A)-2) [化10] (液晶化合物(A)-3) [化11] (液晶化合物(A)-4) [化12] (液晶化合物(A)-5) [化13] (Liquid crystal compound A) [Chemical 9] (Liquid crystal compound (A)-2) [Chemical 10] (Liquid crystal compound (A)-3) [Chemical 11] (Liquid crystal compound (A)-4) [Chemical 12] (Liquid crystal compound (A)-5) [Chemical 13]

液晶化合物(I)-1之含量(於包含複數種液晶化合物之情形時為其含量之合計)較佳為相對於組合物之固形物成分100質量份為50~99.5質量份,更佳為60~99質量份,進而較佳為70~99質量份。於本說明書中,組合物之固形物成分之質量係指自該組合物去除溶劑後之成分之合計質量。The content of the liquid crystal compound (I)-1 (the total content of the liquid crystal compounds when the liquid crystal compound is included) is preferably 50 to 99.5 parts by mass, more preferably 60 to 99 parts by mass, and further preferably 70 to 99 parts by mass, relative to 100 parts by mass of the solid content of the composition. In this specification, the mass of the solid content of the composition refers to the total mass of the components after removing the solvent from the composition.

[2.非離子性矽烷化合物] 於本說明書中,非離子性矽烷化合物係非離子性且包含Si元素之化合物。非離子性矽烷化合物於垂直配向液晶硬化膜之製作中,能夠充分地提高液晶化合物(I)-1之垂直配向性,且藉由與離子性化合物之組合而進一步提高液晶化合物(I)-1之垂直配向性。又,非離子性矽烷化合物容易降低組合物之表面張力,能夠提昇組合物對基材之潤濕性。作為非離子性矽烷化合物,例如可列舉聚矽烷之類之矽聚合物、聚矽氧油及聚矽氧樹脂之類之聚矽氧樹脂、以及聚矽氧低聚物、倍半矽氧烷、及烷氧基矽烷之類之有機無機矽烷化合物(更具體而言為矽烷偶合劑等)。 [2. Non-ionic silane compound] In this specification, a non-ionic silane compound is a non-ionic compound containing Si element. In the preparation of vertically aligned liquid crystal cured film, the non-ionic silane compound can fully improve the vertical alignment of the liquid crystal compound (I)-1, and further improve the vertical alignment of the liquid crystal compound (I)-1 by combining with an ionic compound. In addition, the non-ionic silane compound can easily reduce the surface tension of the composition and can improve the wettability of the composition to the substrate. Examples of non-ionic silane compounds include silicone polymers such as polysilane, silicone oils and silicone resins, and organic and inorganic silane compounds such as polysiloxane oligomers, silsesquioxanes, and alkoxysilanes (more specifically, silane coupling agents, etc.).

非離子性矽烷化合物可為聚矽氧單體型,亦可為聚矽氧低聚物(聚合物)型。若以(單體)-(單體)共聚物之形式表示聚矽氧低聚物,則可列舉:3-巰基丙基三甲氧基矽烷-四甲氧基矽烷共聚物、3-巰基丙基三甲氧基矽烷-四乙氧基矽烷共聚物、3-巰基丙基三乙氧基矽烷-四甲氧基矽烷共聚物、及3-巰基丙基三乙氧基矽烷-四乙氧基矽烷共聚物之類之含巰基丙基之共聚物;巰基甲基三甲氧基矽烷-四甲氧基矽烷共聚物、巰基甲基三甲氧基矽烷-四乙氧基矽烷共聚物、巰基甲基三乙氧基矽烷-四甲氧基矽烷共聚物、及巰基甲基三乙氧基矽烷-四乙氧基矽烷共聚物之類之含巰基甲基之共聚物;3-甲基丙烯醯氧基丙基三甲氧基矽烷-四甲氧基矽烷共聚物、3-甲基丙烯醯氧基丙基三甲氧基矽烷-四乙氧基矽烷共聚物、3-甲基丙烯醯氧基丙基三乙氧基矽烷-四甲氧基矽烷共聚物、3-甲基丙烯醯氧基丙基三乙氧基矽烷-四乙氧基矽烷共聚物、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、及3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物之類之含甲基丙烯醯氧基丙基之共聚物;3-丙烯醯氧基丙基三甲氧基矽烷-四甲氧基矽烷共聚物、3-丙烯醯氧基丙基三甲氧基矽烷-四乙氧基矽烷共聚物、3-丙烯醯氧基丙基三乙氧基矽烷-四甲氧基矽烷共聚物、3-丙烯醯氧基丙基三乙氧基矽烷-四乙氧基矽烷共聚物、3-丙烯醯氧基丙基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、3-丙烯醯氧基丙基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、3-丙烯醯氧基丙基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、及3-丙烯醯氧基丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物之類之含丙烯醯氧基丙基之共聚物;乙烯基三甲氧基矽烷-四甲氧基矽烷共聚物、乙烯基三甲氧基矽烷-四乙氧基矽烷共聚物、乙烯基三乙氧基矽烷-四甲氧基矽烷共聚物、乙烯基三乙氧基矽烷-四乙氧基矽烷共聚物、乙烯基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、乙烯基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、乙烯基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、及乙烯基甲基二乙氧基矽烷-四乙氧基矽烷共聚物之類之含乙烯基之共聚物;3-胺基丙基三甲氧基矽烷-四甲氧基矽烷共聚物、3-胺基丙基三甲氧基矽烷-四乙氧基矽烷共聚物、3-胺基丙基三乙氧基矽烷-四甲氧基矽烷共聚物、3-胺基丙基三乙氧基矽烷-四乙氧基矽烷共聚物、3-胺基丙基甲基二甲氧基矽烷-四甲氧基矽烷共聚物、3-胺基丙基甲基二甲氧基矽烷-四乙氧基矽烷共聚物、3-胺基丙基甲基二乙氧基矽烷-四甲氧基矽烷共聚物、及3-胺基丙基甲基二乙氧基矽烷-四乙氧基矽烷共聚物之類之含胺基之共聚物等。該等非離子性矽烷化合物可單獨使用1種,或者亦可組合2種以上使用。又,亦可使用調平劑之項所例示之含矽烷之化合物。該等非離子性矽烷化合物之中,就進一步提高密接性之觀點而言,較佳為矽烷偶合劑。The non-ionic silane compound may be a polysiloxane monomer type or a polysiloxane oligomer (polymer) type. If the polysiloxane oligomer is represented by a (monomer)-(monomer) copolymer, it may include copolymers containing butylene propyl groups such as 3-butylene propyltrimethoxysilane-tetramethoxysilane copolymer, 3-butylene propyltrimethoxysilane-tetraethoxysilane copolymer, 3-butylene propyltriethoxysilane-tetramethoxysilane copolymer, and 3-butylene propyltriethoxysilane-tetraethoxysilane copolymer; methyl trimethoxysilane-tetramethoxysilane copolymer, methyl trimethoxysilane-tetraethoxysilane copolymer, methyl triethoxysilane-tetramethoxysilane copolymer, and methyl triethoxysilane-tetraethoxysilane copolymer; 3-methacryloyloxypropyl trimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyl trimethoxysilane-tetramethoxysilane copolymer; 3-Methacryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-Methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-Methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-Methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-Methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer Methacryloyloxypropyl copolymers such as acryloyloxypropyl methyldiethoxysilane-tetramethoxysilane copolymers and 3-methacryloyloxypropyl methyldiethoxysilane-tetraethoxysilane copolymers; 3-acryloyloxypropyl trimethoxysilane-tetramethoxysilane copolymers, 3-acryloyloxypropyl trimethoxysilane-tetraethoxysilane copolymers, 3-acryloyloxypropyl triethoxysilane 3-acryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-acryloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer. acryloxypropyl copolymers such as vinyltrimethoxysilane-tetramethoxysilane copolymers, vinyltrimethoxysilane-tetraethoxysilane copolymers, vinyltriethoxysilane-tetramethoxysilane copolymers, vinyltriethoxysilane-tetraethoxysilane copolymers, vinylmethyldimethoxysilane-tetramethoxysilane copolymers, vinylmethyldimethoxysilane-tetramethoxysilane copolymers, vinylmethyldimethoxysilane-tetramethoxysilane copolymers, vinyltrimethoxysilane-tetraethoxysilane copolymers, vinyltri ... vinyl-containing copolymers such as 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymers, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymers, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymers, and 3-aminopropyltriethoxysilane-tetramethoxysilane copolymers. The present invention can be used to prepare the non-ionic silane compound. The non-ionic silane compound can be a copolymer containing amino groups, such as a copolymer of 3-aminopropyltriethoxysilane-tetraethoxysilane, a copolymer of 3-aminopropylmethyldimethoxysilane-tetramethoxysilane, a copolymer of 3-aminopropylmethyldimethoxysilane-tetraethoxysilane, a copolymer of 3-aminopropylmethyldiethoxysilane-tetramethoxysilane, and a copolymer of 3-aminopropylmethyldiethoxysilane-tetraethoxysilane. The non-ionic silane compound can be used alone or in combination of two or more. In addition, the silane-containing compounds exemplified in the leveling agent can also be used. Among the non-ionic silane compounds, a silane coupling agent is preferred from the viewpoint of further improving the adhesion.

矽烷偶合劑係於末端具有選自由乙烯基、環氧基、苯乙烯基、甲基丙烯醯基、丙烯醯基、胺基、異氰尿酸酯基、脲基、巰基、異氰酸酯基、羧基、及羥基所組成之群中之至少1種之類之官能基、及至少一個烷氧基矽烷基或矽烷醇基的包含Si元素之化合物。藉由適當選定該等官能基,能夠賦予垂直配向液晶硬化膜之機械強度之提高、垂直配向液晶硬化膜之表面改質、與鄰接於垂直配向液晶硬化膜之層(例如基材)之密接性提高等特殊之效果。就進一步提高密接性之觀點而言,矽烷偶合劑較佳為具有烷氧基矽烷基及另一不同之反應基(例如上述官能基)的矽烷偶合劑。矽烷偶合劑進而較佳為具有烷氧基矽烷基與極性基之矽烷偶合劑。若矽烷偶合劑於其分子內具有至少一個烷氧基矽烷基及至少一個極性基,則液晶化合物之垂直配向性進一步提昇,可明顯獲得垂直配向促進效果。作為極性基,例如可列舉環氧基、胺基、異氰尿酸酯基、巰基、羧基、及羥基。再者,極性基為了控制矽烷偶合劑之反應性,亦可適當具有取代基或保護基。The silane coupling agent is a compound containing Si element and having at least one functional group selected from the group consisting of vinyl, epoxy, styryl, methacryl, acryl, amino, isocyanurate, urea, hydroxyl, isocyanate, carboxyl, and hydroxyl groups at the terminal, and at least one alkoxysilyl group or silanol group. By appropriately selecting these functional groups, special effects such as improving the mechanical strength of the vertical alignment liquid crystal curing film, modifying the surface of the vertical alignment liquid crystal curing film, and improving the adhesion with the layer adjacent to the vertical alignment liquid crystal curing film (such as a substrate) can be imparted. From the viewpoint of further improving the adhesion, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and another different reactive group (such as the above-mentioned functional group). The silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and a polar group. If the silane coupling agent has at least one alkoxysilyl group and at least one polar group in its molecule, the vertical alignment of the liquid crystal compound is further improved, and a vertical alignment promotion effect can be significantly obtained. Examples of the polar group include an epoxy group, an amine group, an isocyanurate group, a hydroxyl group, a carboxyl group, and a hydroxyl group. Furthermore, the polar group may also have a substituent or a protecting group to control the reactivity of the silane coupling agent.

作為矽烷偶合劑,例如可列舉:乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺、3-縮水甘油氧基丙基三甲氧基矽烷、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、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、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-縮水甘油氧基丙基二甲氧基甲基矽烷、及3-縮水甘油氧基丙基乙氧基二甲基矽烷。Examples of the silane coupling agent include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, Oleyloxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-butyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropyldimethoxymethylsilane, and 3-glycidyloxypropylethoxydimethylsilane.

又,作為市售之矽烷偶合劑,例如可列舉KP321、KP323、KP324、KP326、KP340、KP341、X22-161A、KF6001、KBM-1003、KBE-1003、KBM-303、KBM-402、KBM-403、KBE-402、KBE-403、KBM-1403、KBM-502、KBM-503、KBE-502、KBE-503、KBM-5103、KBM-602、KBM-603、KBM-903、KBE-903、KBE-9103、KBM-573、KBM-575、KBM-9659、KBE-585、KBM-802、KBM-803、KBE-846、及KBE-9007之類之信越化學工業(股)製造之矽烷偶合劑。Moreover, as commercially available silane coupling agents, for example, KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, Silane coupling agents such as KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.

非離子性矽烷化合物之含有率通常相對於組合物之固形物成分,較佳為0.01~5質量%,更佳為0.05~4質量%,進而較佳為0.1~3質量%。若非離子性矽烷化合物之含有率相對於組合物之固形物成分為0.01質量%以上,則液晶化合物之垂直配向性進一步提高,若非離子性矽烷化合物之含有率相對於組合物之固形物成分,以5質量%以下含有,則組合物之塗佈性不易降低。The content of the non-ionic silane compound is usually preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, and further preferably 0.1 to 3% by mass relative to the solid content of the composition. If the content of the non-ionic silane compound is 0.01% by mass or more relative to the solid content of the composition, the vertical alignment of the liquid crystal compound is further improved. If the content of the non-ionic silane compound is 5% by mass or less relative to the solid content of the composition, the coating property of the composition is not easily reduced.

[3.離子性化合物] 離子性化合物於垂直配向液晶硬化膜之製作中,能夠充分地提高液晶化合物(I)-1之垂直配向性,且藉由與非離子性矽烷化合物之組合而進一步提高液晶化合物(I)-1之垂直配向性。 [3. Ionic compounds] Ionic compounds can fully improve the vertical alignment of liquid crystal compound (I)-1 in the preparation of vertical alignment liquid crystal cured film, and further improve the vertical alignment of liquid crystal compound (I)-1 by combining with non-ionic silane compounds.

作為離子性化合物,例如可列舉鎓鹽(更具體而言為氮原子具有正電荷之四級銨鹽、三級鋶鹽、及磷原子具有正電荷之四級鏻鹽等)。該等鎓鹽之中,就進一步提高液晶化合物(I)-1之垂直配向性之觀點而言,較佳為四級鎓鹽,就提高獲取性及量產性之觀點而言,進而較佳為四級鏻鹽或四級銨鹽。鎓鹽亦可於分子內具有2個以上四級鎓鹽部位,亦可為低聚物或聚合物。As the ionic compound, for example, an onium salt (more specifically, a quaternary ammonium salt whose nitrogen atom has a positive charge, a tertiary cobalt salt, and a quaternary phosphonium salt whose phosphorus atom has a positive charge, etc.) can be listed. Among these onium salts, a quaternary onium salt is preferred from the viewpoint of further improving the vertical alignment of the liquid crystal compound (I)-1, and a quaternary phosphonium salt or a quaternary ammonium salt is further preferred from the viewpoint of improving the availability and mass productivity. The onium salt may have two or more quaternary onium salt sites in the molecule, and may be an oligomer or a polymer.

就進一步提高液晶化合物(I)-1之垂直配向性之觀點而言,離子性化合物之分子量較佳為100以上。又,就進一步提高組合物之塗佈性之觀點而言,離子性化合物之分子量較佳為10000以下,更佳為5000以下,進而較佳為3000以下。就進一步提高液晶化合物(I)-1之垂直配向性且進一步提高組合物之塗佈性之觀點而言,離子性化合物之分子量更佳為100以上10000以下。From the viewpoint of further improving the vertical alignment of the liquid crystal compound (I)-1, the molecular weight of the ionic compound is preferably 100 or more. Furthermore, from the viewpoint of further improving the coating property of the composition, the molecular weight of the ionic compound is preferably 10,000 or less, more preferably 5,000 or less, and further preferably 3,000 or less. From the viewpoint of further improving the vertical alignment of the liquid crystal compound (I)-1 and further improving the coating property of the composition, the molecular weight of the ionic compound is more preferably 100 or more and 10,000 or less.

作為離子性化合物之陽離子成分,例如可列舉無機之陽離子及有機之陽離子。該等離子性化合物之陽離子成分之中,就抑制液晶化合物之配向缺陷產生之觀點而言,較佳為有機之陽離子。作為有機之陽離子,例如可列舉咪唑鎓陽離子、吡啶鎓陽離子、銨陽離子、鋶陽離子、及鏻陽離子。Examples of cationic components of the ionic compound include inorganic cations and organic cations. Among the cationic components of the ionic compound, organic cations are preferred from the viewpoint of suppressing the generation of alignment defects of the liquid crystal compound. Examples of organic cations include imidazolium cations, pyridinium cations, ammonium cations, galvanium cations, and phosphonium cations.

另一方面,離子性化合物一般具有抗衡陰離子。作為成為上述陽離子成分之抗衡離子的陰離子成分,例如可列舉無機之陰離子或有機之陰離子。該等陰離子成分之中,就抑制液晶化合物之配向缺陷產生之觀點而言,較佳為有機之陰離子。又,陽離子與陰離子並非必須一對一地對應。作為陰離子成分,例如可列舉如下者。 氯化物陰離子[Cl -]、 溴化物陰離子[Br -]、 碘化物陰離子[I -]、 四氯鋁酸根陰離子[AlCl 4 -]、 七氯二鋁酸根陰離子[Al 2Cl 7 -]、 四氟硼酸根陰離子[BF 4 -]、 六氟磷酸根陰離子[PF 6 -]、 過氯酸根陰離子[ClO 4 -]、 硝酸根陰離子[NO 3 -]、 乙酸根陰離子[CH 3COO -]、 三氟乙酸根陰離子[CF 3COO -]、 氟磺酸根陰離子[FSO 3 -]、 甲磺酸根陰離子[CH 3SO 3 -]、 三氟甲磺酸根陰離子[CF 3SO 3 -]、 對甲苯磺酸根陰離子[p-CH 3C 6H 4SO 3 -]、 雙(氟磺醯)亞胺陰離子[(FSO 2) 2N -]、 雙(三氟甲磺醯)亞胺陰離子[(CF 3SO 2) 2N -]、 三(三氟甲磺醯)甲烷陰離子[(CF 3SO 2) 3C -]、 六氟砷酸根陰離子[AsF 6 -]、 六氟銻酸根陰離子[SbF 6 -]、 六氟鈮酸根陰離子[NbF 6 -]、 六氟鉭酸根陰離子[TaF 6 -]、 二甲基次膦酸根陰離子[(CH 3) 2POO -]、 (聚)氫氟氟化物陰離子[F(HF) n -](例如,n表示1~3之整數)、 二氰亞胺陰離子[(CN) 2N -]、 硫氰化物陰離子[SCN -]、 全氟丁磺酸根陰離子[C 4F 9SO 3 -]、 雙(五氟乙磺醯)亞胺陰離子[(C 2F 5SO 2) 2N -]、 全氟丁酸根陰離子[C 3F 7COO -]、及 (三氟甲磺醯基)(三氟甲烷羰基)醯亞胺陰離子[(CF 3SO 2)(CF 3CO)N -]。 On the other hand, ionic compounds generally have counter anions. As anionic components that serve as counter ions for the above-mentioned cationic components, for example, inorganic anions or organic anions can be listed. Among these anionic components, organic anions are preferred from the perspective of suppressing the generation of alignment defects of liquid crystal compounds. In addition, cations and anions do not necessarily correspond one to one. As anionic components, for example, the following can be listed. Chloride anion [Cl - ], bromide anion [Br - ], iodide anion [I - ], tetrachloroaluminate anion [AlCl 4 - ], heptachlorodialuminate anion [Al 2 Cl 7 - ], tetrafluoroborate anion [BF 4 - ], hexafluorophosphate anion [PF 6 - ], perchlorate anion [ClO 4 - ], nitrate anion [NO 3 - ], acetate anion [CH 3 COO - ], trifluoroacetate anion [CF 3 COO - ], fluorosulfonate anion [FSO 3 - ], methanesulfonate anion [CH 3 SO 3 - ], Trifluoromethanesulfonate anion [CF 3 SO 3 - ], p-toluenesulfonate anion [p-CH 3 C 6 H 4 SO 3 - ], bis(fluorosulfonyl)imide anion [(FSO 2 ) 2 N - ], bis(trifluoromethanesulfonyl)imide anion [(CF 3 SO 2 ) 2 N - ], tris(trifluoromethanesulfonyl)methane anion [(CF 3 SO 2 ) 3 C - ], hexafluoroarsenate anion [AsF 6 - ], hexafluoroantimonate anion [SbF 6 - ], hexafluoroniobate anion [NbF 6 - ], hexafluorotibrate anion [TaF 6 - ], dimethylphosphinate anion [(CH 3 ) 2 POO - ], (poly)hydrofluorofluoride anion [F(HF) n - ] (for example, n represents an integer of 1 to 3), dicyanimide anion [(CN) 2 N - ], thiocyanate anion [SCN - ], perfluorobutanesulfonate anion [C 4 F 9 SO 3 - ], bis(pentafluoroethanesulfonyl)imide anion [(C 2 F 5 SO 2 ) 2 N - ], perfluorobutyrate anion [C 3 F 7 COO - ], and (trifluoromethanesulfonyl)(trifluoromethanecarbonyl)imide anion [(CF 3 SO 2 )(CF 3 CO)N - ].

作為離子性化合物之具體例,可自上述陽離子成分與陰離子成分之組合適當選擇。作為具體之陽離子成分與陰離子成分組合之化合物,可列舉如下者。Specific examples of ionic compounds can be appropriately selected from the above-mentioned combinations of cationic components and anionic components. Specific examples of compounds of the combination of cationic components and anionic components include the following.

(吡啶鎓鹽) 六氟磷酸N-己基吡啶鎓、 六氟磷酸N-辛基吡啶鎓、 六氟磷酸N-甲基-4-己基吡啶鎓、 六氟磷酸N-丁基-4-甲基吡啶鎓、 六氟磷酸N-辛基-4-甲基吡啶鎓、 雙(氟磺醯)亞胺N-己基吡啶鎓、 雙(氟磺醯)亞胺N-辛基吡啶鎓、 雙(氟磺醯)亞胺N-甲基-4-己基吡啶鎓、 雙(氟磺醯)亞胺N-丁基-4-甲基吡啶鎓、 雙(氟磺醯)亞胺N-辛基-4-甲基吡啶鎓、 雙(三氟甲磺醯)亞胺N-己基吡啶鎓、 雙(三氟甲磺醯)亞胺N-辛基吡啶鎓、 雙(三氟甲磺醯)亞胺N-甲基-4-己基吡啶鎓、 雙(三氟甲磺醯)亞胺N-丁基-4-甲基吡啶鎓、 雙(三氟甲磺醯)亞胺N-辛基-4-甲基吡啶鎓、 對甲苯磺酸N-己基吡啶鎓、 對甲苯磺酸N-辛基吡啶鎓、 對甲苯磺酸N-甲基-4-己基吡啶鎓、 對甲苯磺酸N-丁基-4-甲基吡啶鎓、及 對甲苯磺酸N-辛基-4-甲基吡啶鎓。 (Pyridinium salts) N-hexylpyridinium hexafluorophosphate, N-octylpyridinium hexafluorophosphate, N-methyl-4-hexylpyridinium hexafluorophosphate, N-butyl-4-methylpyridinium hexafluorophosphate, N-octyl-4-methylpyridinium hexafluorophosphate, N-hexylpyridinium bis(fluorosulfonyl)imide, N-octylpyridinium bis(fluorosulfonyl)imide, N-methyl-4-hexylpyridinium bis(fluorosulfonyl)imide, N-butyl-4-methylpyridinium bis(fluorosulfonyl)imide, N-octyl-4-methylpyridinium bis(fluorosulfonyl)imide, Bis(trifluoromethanesulfonyl)imide N-hexylpyridinium, Bis(trifluoromethanesulfonyl)imide N-octylpyridinium, Bis(trifluoromethanesulfonyl)imide N-methyl-4-hexylpyridinium, Bis(trifluoromethanesulfonyl)imide N-butyl-4-methylpyridinium, Bis(trifluoromethanesulfonyl)imide N-octyl-4-methylpyridinium, N-hexylpyridinium p-toluenesulfonate, N-octylpyridinium p-toluenesulfonate, N-methyl-4-hexylpyridinium p-toluenesulfonate, N-butyl-4-methylpyridinium p-toluenesulfonate, and N-octyl-4-methylpyridinium p-toluenesulfonate.

(咪唑鎓鹽) 六氟磷酸1-乙基-3-甲基咪唑鎓、 雙(氟磺醯)亞胺1-乙基-3-甲基咪唑鎓、 雙(三氟甲磺醯)亞胺1-乙基-3-甲基咪唑鎓、 對甲苯磺酸1-乙基-3-甲基咪唑鎓、 甲磺酸1-丁基-3-甲基咪唑鎓等。 (Imidazolium salts) 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium p-toluenesulfonate, 1-butyl-3-methylimidazolium methanesulfonate, etc.

(吡咯啶鎓鹽) 六氟磷酸N-丁基-N-甲基吡咯啶鎓、 雙(氟磺醯)亞胺N-丁基-N-甲基吡咯啶鎓、 雙(三氟甲磺醯)亞胺N-丁基-N-甲基吡咯啶鎓、 對甲苯磺酸N-丁基-N-甲基吡咯啶鎓等。 (Pyrrolidinium salts) N-butyl-N-methylpyrrolidinium hexafluorophosphate, N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide, N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, N-butyl-N-methylpyrrolidinium p-toluenesulfonate, etc.

(銨鹽) 六氟磷酸四丁基銨、 雙(氟磺醯)亞胺四丁基銨、 雙(氟磺醯)亞胺四己基銨、 雙(氟磺醯)亞胺三辛基甲基銨、 雙(氟磺醯)亞胺(2-羥基乙基)三甲基銨、 雙(三氟甲磺醯)亞胺四丁基銨、 雙(三氟甲磺醯)亞胺四己基銨、 雙(三氟甲磺醯)亞胺三辛基甲基銨、 雙(三氟甲磺醯)亞胺(2-羥基乙基)三甲基銨、 對甲苯磺酸四丁基銨、 對甲苯磺酸四己基銨、 對甲苯磺酸三辛基甲基銨、 對甲苯磺酸(2-羥基乙基)三甲基銨、 二甲基亞膦酸(2-羥基乙基)三甲基銨、 雙(三氟甲磺醯)亞胺1-(3-三甲氧基矽烷基丙基)-1,1,1-三丁基銨、 雙(三氟甲磺醯)亞胺1-(3-三甲氧基矽烷基丙基)-1,1,1-三甲基銨、 雙(三氟甲磺醯)亞胺1-(3-三甲氧基矽烷基丁基)-1,1,1-三丁基銨、 雙(三氟甲磺醯)亞胺1-(3-三甲氧基矽烷基丁基)-1,1,1-三甲基銨、 雙(三氟甲磺醯)亞胺N-{(3-三乙氧基矽烷基丙基)胺甲醯氧基乙基)}-N,N,N-三甲基銨、及 雙(三氟甲磺醯)亞胺N-[2-{3-(3-三甲氧基矽烷基丙基胺基)-1-側氧基丙氧基}乙基]-N,N,N-三甲基銨。 (Ammonium salts) Tetrabutylammonium hexafluorophosphate, Tetrabutylammonium bis(fluorosulfonyl)imide, Tetrahexylammonium bis(fluorosulfonyl)imide, Trioctylmethylammonium bis(fluorosulfonyl)imide, (2-hydroxyethyl)trimethylammonium bis(fluorosulfonyl)imide, Tetrabutylammonium bis(trifluoromethanesulfonyl)imide, Tetrahexylammonium bis(trifluoromethanesulfonyl)imide, Trioctylmethylammonium bis(trifluoromethanesulfonyl)imide, (2-hydroxyethyl)trimethylammonium bis(trifluoromethanesulfonyl)imide, Tetrabutylammonium p-toluenesulfonate, Tetrahexylammonium p-toluenesulfonate, Trioctylmethylammonium p-toluenesulfonate, (2-hydroxyethyl) trimethylammonium p-toluenesulfonate, (2-hydroxyethyl) trimethylammonium dimethylphosphinate, 1-(3-trimethoxysilylpropyl)-1,1,1-tributylammonium bis(trifluoromethanesulfonyl)imide, 1-(3-trimethoxysilylpropyl)-1,1,1-trimethylammonium bis(trifluoromethanesulfonyl)imide, 1-(3-trimethoxysilylbutyl)-1,1,1-tributylammonium bis(trifluoromethanesulfonyl)imide, Bis(trifluoromethanesulfonyl)imide N-{(3-triethoxysilylpropyl)aminomethyloxyethyl)}-N,N,N-trimethylammonium, and Bis(trifluoromethanesulfonyl)imide N-[2-{3-(3-trimethoxysilylpropylamino)-1-oxopropyloxy}ethyl]-N,N,N-trimethylammonium.

(鏻鹽) 雙(三氟甲磺醯)亞胺三丁基(2-甲氧基乙基)鏻、 雙(三氟甲磺醯)亞胺三丁基甲基鏻、 雙(三氟甲磺醯)亞胺1,1,1-三甲基-1-[(三甲氧基矽烷基)甲基]鏻、 雙(三氟甲磺醯)亞胺1,1,1-三甲基-1-[2-(三甲氧基矽烷基)乙基]鏻、 雙(三氟甲磺醯)亞胺1,1,1-三甲基-1-[3-(三甲氧基矽烷基)丙基]鏻、 雙(三氟甲磺醯)亞胺1,1,1-三甲基-1-[4-(三甲氧基矽烷基)丁基]鏻、 雙(三氟甲磺醯)亞胺1,1,1-三丁基-1-[(三甲氧基矽烷基)甲基]鏻、 雙(三氟甲磺醯)亞胺1,1,1-三丁基-1-[2-(三甲氧基矽烷基)乙基]鏻、及 雙(三氟甲磺醯)亞胺1,1,1-三丁基-1-[3-(三甲氧基矽烷基)丙基]鏻。 (Phosphonium salts) Bis(trifluoromethanesulfonyl)imide tributyl(2-methoxyethyl)phosphonium, Bis(trifluoromethanesulfonyl)imide tributylmethylphosphonium, Bis(trifluoromethanesulfonyl)imide 1,1,1-trimethyl-1-[(trimethoxysilyl)methyl]phosphonium, Bis(trifluoromethanesulfonyl)imide 1,1,1-trimethyl-1-[2-(trimethoxysilyl)ethyl]phosphonium, Bis(trifluoromethanesulfonyl)imide 1,1,1-trimethyl-1-[3-(trimethoxysilyl)propyl]phosphonium, Bis(trifluoromethanesulfonyl)imide 1,1,1-trimethyl-1-[4-(trimethoxysilyl)butyl]phosphonium, Bis(trifluoromethanesulfonyl)imide 1,1,1-tributyl-1-[(trimethoxysilyl)methyl]phosphonium, Bis(trifluoromethanesulfonyl)imide 1,1,1-tributyl-1-[2-(trimethoxysilyl)ethyl]phosphonium, and Bis(trifluoromethanesulfonyl)imide 1,1,1-tributyl-1-[3-(trimethoxysilyl)propyl]phosphonium.

該等離子性化合物可分別單獨使用,或者亦可組合2種以上使用。又,就進一步提高液晶化合物之垂直配向性之觀點而言,離子性化合物較佳為於陽離子部位之分子結構中具有Si元素及/或F元素。其原因在於,若離子性化合物於陽離子部位之分子結構中具有Si元素及/或F元素,則能夠使離子性化合物偏析至垂直配向液晶硬化膜之表面。該等離子性化合物之中,較佳為整體由非金屬元素構成之離子性化合物(更具體而言為下述離子性化合物(1)~(3)等)。The ionic compounds can be used alone or in combination of two or more. In order to further improve the vertical alignment of the liquid crystal compound, the ionic compound preferably has Si and/or F elements in the molecular structure of the cationic part. The reason is that if the ionic compound has Si and/or F elements in the molecular structure of the cationic part, the ionic compound can be segregated to the surface of the vertically aligned liquid crystal cured film. Among the ionic compounds, the ionic compound composed entirely of non-metallic elements is preferred (more specifically, the following ionic compounds (1) to (3)).

(離子性化合物(1)) [化14] (離子性化合物(2)) [化15] (離子性化合物(3)) [化16] (Ionic compound (1)) [Chemical 14] (Ionic compound (2)) [Chemical 15] (Ionic compound (3)) [Chemical 16]

作為提高液晶化合物之垂直配向性之方法,例如可列舉使用具有鏈長一定程度較長之烷基之界面活性劑對基材表面進行處理之方法。該方法例如記載於「液晶便覽」之第2章 液晶之配向與物性(丸善股份有限公司發行)等。如此藉由界面活性劑而提高液晶化合物之垂直配向性之方法可應用於離子性化合物。即,作為提高液晶化合物之垂直配向性之方法,例如可列舉使用具有鏈長一定程度較長之烷基之離子性化合物對基材表面進行處理之方法。更具體而言,就提高液晶化合物之垂直配向性之觀點而言,離子性化合物較佳為滿足下述式(10)。 5<M<16         (10) 式(10)中,M由下述式(11)表示。 M=(直接鍵結於具有正電荷之原子上之取代基中,至分子鏈末端之共價鍵數最多之取代基的自具有正電荷之原子起至分子鏈末端之共價鍵數)÷(具有正電荷之原子之數)        (11) As a method for improving the vertical alignment of a liquid crystal compound, for example, a method of treating the surface of a substrate with a surfactant having an alkyl group with a relatively long chain length can be cited. This method is described, for example, in Chapter 2 of "Liquid Crystal Handbook" - Alignment and Physical Properties of Liquid Crystals (published by Maruzen Co., Ltd.). Such a method of improving the vertical alignment of a liquid crystal compound by a surfactant can be applied to an ionic compound. That is, as a method for improving the vertical alignment of a liquid crystal compound, for example, a method of treating the surface of a substrate with an ionic compound having an alkyl group with a relatively long chain length can be cited. More specifically, from the viewpoint of improving the vertical alignment of a liquid crystal compound, the ionic compound preferably satisfies the following formula (10). 5<M<16         (10) In formula (10), M is represented by the following formula (11). M = (the number of covalent bonds from the atom with positive charge to the end of the molecular chain of the substituent with the largest number of covalent bonds to the end of the molecular chain among the substituents directly bonded to the atom with positive charge) ÷ (the number of atoms with positive charge)        (11)

再者,於在離子性化合物之分子中存在2個以上具有正電荷之原子之情形時,關於具有2個以上具有正電荷之原子之取代基,將自視作基點之具有正電荷之原子開始算起,至最近之另一具有正電荷之原子的共價鍵數作為上述M之定義中所記載之「自具有正電荷之原子起至分子鏈末端之共價鍵數」。又,於離子性化合物為具有2個以上重複單元之低聚物或聚合物之情形時,將結構單元視作一分子,算出上述M。於具有正電荷之原子組入至環結構之情形時,將經由環結構至該具有正電荷之原子之共價鍵數、或至環結構上鍵結之取代基之末端之共價鍵數中共價鍵數較多者作為上述M之定義中所記載之「自具有正電荷之原子起至分子鏈末端之共價鍵數」。Furthermore, when there are two or more atoms with positive charge in the molecule of the ionic compound, the number of covalent bonds from the positively charged atom regarded as the base point to the nearest other positively charged atom is regarded as the "number of covalent bonds from the positively charged atom to the molecular chain terminal" in the definition of the above M. Furthermore, when the ionic compound is an oligomer or polymer having two or more repeating units, the structural unit is regarded as one molecule and the above M is calculated. When an atom having a positive charge is incorporated into a ring structure, the number of covalent bonds from the ring structure to the atom having a positive charge or to the terminal of a substituent bonded to the ring structure, whichever number is greater, is regarded as the "number of covalent bonds from the atom having a positive charge to the terminal of the molecular chain" described in the above definition of M.

離子性化合物之含有率通常相對於組合物之固形物成分,較佳為0.01~5質量%,更佳為0.05~4質量%,進而較佳為0.1~3質量%。若離子性化合物之含有率於組合物之固形物成分中為0.01質量%以上,則液晶化合物之垂直配向性進一步提高,若離子性化合物之含有率相對於組合物之固形物成分為5質量%以下,則組合物之塗佈性不易降低。The content of the ionic compound is usually preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, and further preferably 0.1 to 3% by mass relative to the solid content of the composition. If the content of the ionic compound is 0.01% by mass or more in the solid content of the composition, the vertical alignment of the liquid crystal compound is further improved. If the content of the ionic compound is 5% by mass or less relative to the solid content of the composition, the coating property of the composition is not easily reduced.

[4.其他成分] 本發明之組合物亦可視需要進而包含例如溶劑、光聚合起始劑、聚合抑制劑、光增感劑、調平劑、密接性改善劑之類之添加劑作為其他成分。該等添加劑可單獨使用1種,或者亦可組合2種以上使用。 [4. Other components] The composition of the present invention may further contain additives such as solvents, photopolymerization initiators, polymerization inhibitors, photosensitizers, leveling agents, and adhesion improvers as other components as needed. These additives may be used alone or in combination of two or more.

(溶劑) 本發明之組合物由於通常以溶解於溶劑中之狀態塗佈於基材等,故而較佳為包含溶劑。作為溶劑,例如可列舉水、甲醇、乙醇、乙二醇、異丙醇、丙二醇、乙二醇甲醚、乙二醇丁醚、1-甲氧基-2-丙醇、2-丁氧基乙醇、及丙二醇單甲醚之類之醇溶劑;乙酸乙酯、乙酸丁酯、乙二醇甲醚乙酸酯、γ-丁內酯、丙二醇甲醚乙酸酯及乳酸乙酯之類之酯溶劑;丙酮、甲基乙基酮、環戊酮、環己酮、2-庚酮、及甲基異丁基酮之類之酮溶劑;戊烷、己烷、及庚烷之類之脂肪族烴溶劑;乙基環己烷之類之脂環式烴溶劑;甲苯及二甲苯之類之芳香族烴溶劑;乙腈之類之腈溶劑;四氫呋喃及二甲氧基乙烷之類之醚溶劑;氯仿及氯苯之類之含氯溶劑;二甲基乙醯胺、二甲基甲醯胺、N-甲基-2-吡咯啶酮(NMP)、及1,3-二甲基-2-咪唑啶酮之類之醯胺系溶劑。該等溶劑可單獨使用1種,亦可組合2種以上使用。該等溶劑之中,較佳為醇溶劑、酯溶劑、酮溶劑、含氯溶劑、醯胺系溶劑、及芳香族烴溶劑。該等溶劑可單獨使用1種,或者亦可組合2種以上使用。 (Solvent) Since the composition of the present invention is usually applied to a substrate in a state of being dissolved in a solvent, it is preferred to contain a solvent. Examples of the solvent include alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; Ketone solvents such as pentane, hexane, and heptane; aliphatic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone. These solvents may be used alone or in combination of two or more. Among these solvents, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents, and aromatic hydrocarbon solvents are preferred. These solvents can be used alone or in combination of two or more.

溶劑之含量相對於組合物100質量份,較佳為50~98質量份,更佳為70~95質量份。因此,組合物100質量份中固形物成分所占之含量較佳為2~50質量份。若組合物之固形物成分為50質量份以下,則組合物之黏度變低,故而有垂直配向液晶硬化膜之厚度大致變均一,不易於垂直配向液晶硬化膜產生不均之傾向。上述固形物成分可考慮欲製造之垂直配向液晶硬化膜之厚度而適當決定。The content of the solvent is preferably 50 to 98 parts by mass, more preferably 70 to 95 parts by mass, relative to 100 parts by mass of the composition. Therefore, the content of the solid component in 100 parts by mass of the composition is preferably 2 to 50 parts by mass. If the solid component of the composition is less than 50 parts by mass, the viscosity of the composition becomes low, so the thickness of the vertically aligned liquid crystal cured film becomes roughly uniform, and it is not easy to produce unevenness in the vertically aligned liquid crystal cured film. The above-mentioned solid component can be appropriately determined in consideration of the thickness of the vertically aligned liquid crystal cured film to be manufactured.

(光聚合起始劑) 本發明之組合物亦可以使聚合反應進行為目的而包含光聚合起始劑。於本說明書中,光聚合起始劑提供吸收活性能量線而使聚合反應開始之活性種。關於光聚合起始劑,於將利用自由基聚合而硬化之硬化性組合物、例如(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯用作硬化性材料之情形時,可使用光自由基聚合起始劑,於將利用陽離子聚合而硬化之硬化性組合物、例如環氧化合物、氧雜環丁烷化合物用作硬化性組合物之情形時,可使用光陽離子聚合起始劑。 (Photopolymerization initiator) The composition of the present invention may also contain a photopolymerization initiator for the purpose of causing the polymerization reaction to proceed. In this specification, the photopolymerization initiator provides an active species that absorbs active energy rays to start the polymerization reaction. Regarding the photopolymerization initiator, when a curable composition that is cured by free radical polymerization, such as (meth)acrylate, (meth)acrylate urethane, is used as a curable material, a photoradical polymerization initiator can be used, and when a curable composition that is cured by cationic polymerization, such as epoxy compounds, cyclohexane compounds, can be used as a curable composition, a photocationic polymerization initiator can be used.

作為光聚合起始劑,可列舉光自由基聚合起始劑、及光陽離子聚合起始劑。作為光自由基聚合起始劑,例如可列舉安息香化合物、二苯甲酮化合物、苯偶醯縮酮化合物、α-羥基酮化合物、α-胺基酮化合物、三𠯤化合物等。作為光陽離子聚合起始劑,例如可列舉芳香族重氮鎓鹽、芳香族錪鹽或芳香族鋶鹽等鎓鹽、及鐵-芳烴錯合物。作為光聚合起始劑,例如可列舉Irgacure(註冊商標)907、Irgacure 184、Irgacure 651、Irgacure 819、Irgacure 250、Irgacure 369、Irgacure 379、Irgacure 127、Irgacure 2959、Irgacure 754、及Irgacure 379EG之類之BASF Japan股份有限公司製造之光聚合起始劑;SEIKUOL BZ、SEIKUOL Z、及SEIKUOL BEE之類之精工化學股份有限公司製造之光聚合起始劑;Kayacure BP100(日本化藥股份有限公司製造)、及Kayacure UVI-6992之類之Dow公司製造之光聚合起始劑;Adeka Optomer SP-152、Adeka Optomer SP-170、Adeka Optomer N-1717、Adeka Optomer N-1919、Adeka Arkls NCI-831、Adeka Arkls NCI-930之類之ADEKA股份有限公司製造之光聚合起始劑;TAZ-A、及TAZ-PP之類之Nihon Siber Hegner公司製造之光聚合起始劑;TAZ-104之類之Sanwa Chemical公司製造之光聚合起始劑;Kayarad(註冊商標)系列之類之日本化藥股份有限公司製造之光聚合起始劑;Cyracure UVI系列之類之Dow Chemical公司製造之光聚合起始劑;CPI系列之類之San-Apro股份有限公司製造之光聚合起始劑;TAZ、BBI、及DTS之類之Midori Kagaku股份有限公司製造之光聚合起始劑;RHODORSIL(註冊商標)之類之Rhodia股份有限公司製造之光聚合起始劑。該等光聚合起始劑可單獨使用1種,或者亦可組合2種以上使用。光聚合起始劑可根據使用之材料適當選擇使用。As the photopolymerization initiator, there can be listed a photoradical polymerization initiator and a photocationic polymerization initiator. As the photoradical polymerization initiator, for example, there can be listed benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, tris(iodine) compounds, etc. As the photocationic polymerization initiator, for example, there can be listed onium salts such as aromatic diazonium salts, aromatic iodonium salts or aromatic stibnium salts, and iron-arene complexes. Examples of the photopolymerization initiator include Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, and Irgacure 379EG, manufactured by BASF Japan Co., Ltd.; SEIKUOL BZ, SEIKUOL Z, and SEIKUOL BEE, manufactured by Seiko Chemical Co., Ltd.; Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.) and Kayacure UVI-6992, manufactured by Dow Chemical Co., Ltd.; Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer N-1919, Adeka Arkls NCI-831, Adeka Arkls NCI-930 and the like, manufactured by ADEKA Co., Ltd.; TAZ-A, TAZ-PP and the like, manufactured by Nihon Siber Hegner Co., Ltd.; TAZ-104 and the like, manufactured by Sanwa Chemical Co., Ltd.; Kayarad (registered trademark) series and the like, manufactured by Nippon Kayaku Co., Ltd.; Cyracure UVI series and the like, manufactured by Dow Chemical Co., Ltd.; CPI series and the like, manufactured by San-Apro Co., Ltd.; TAZ, BBI, and DTS and the like, manufactured by Midori Photopolymerization initiators manufactured by Kagaku Co., Ltd.; photopolymerization initiators manufactured by Rhodia Co., Ltd. such as RHODORSIL (registered trademark). These photopolymerization initiators may be used alone or in combination of two or more. The photopolymerization initiator may be appropriately selected and used according to the material used.

光聚合起始劑就能夠充分地利用自光源發出之能量而生產性優異而言,光聚合起始劑之極大吸收波長較佳為300 nm~400 nm,更佳為300 nm~380 nm,該等光聚合起始劑之中,較佳為α-苯乙酮系聚合起始劑及肟系光聚合起始劑。In order for the photopolymerization initiator to fully utilize the energy emitted from the light source and have excellent productivity, the maximum absorption wavelength of the photopolymerization initiator is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm. Among the photopolymerization initiators, α-acetophenone-based polymerization initiators and oxime-based photopolymerization initiators are preferred.

作為α-苯乙酮系聚合起始劑,例如可列舉2-甲基-2-𠰌啉基-1-(4-甲基硫基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-𠰌啉基苯基)-2-苄基丁烷-1-酮(2-二甲基胺基-2-苄基-1-(4-𠰌啉基苯基)丁烷-1-酮)、及2-二甲基胺基-1-(4-𠰌啉基苯基)-2-(4-甲基苯基甲基)丁烷-1-酮。α-苯乙酮系聚合起始劑較佳為2-甲基-2-𠰌啉基-1-(4-甲基硫基苯基)丙烷-1-酮、及2-二甲基胺基-1-(4-𠰌啉基苯基)-2-苄基丁烷-1-酮。作為α-苯乙酮化合物之市售品,可列舉Irgacure 369、379EG、及907之類之BASF Japan(股)製造之α-苯乙酮系聚合起始劑、及SEIKUOL BEE之類之精工化學公司製造之α-苯乙酮系聚合起始劑等。Examples of the α-acetophenone-based polymerization initiator include 2-methyl-2-oxanthyl-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-oxanthylphenyl)-2-benzylbutane-1-one (2-dimethylamino-2-benzyl-1-(4-oxanthylphenyl)butane-1-one), and 2-dimethylamino-1-(4-oxanthylphenyl)-2-(4-methylphenylmethyl)butane-1-one. The α-acetophenone-based polymerization initiator is preferably 2-methyl-2-oxanthyl-1-(4-methylthiophenyl)propane-1-one and 2-dimethylamino-1-(4-oxanthylphenyl)-2-benzylbutane-1-one. Examples of commercially available α-acetophenone compounds include α-acetophenone-based polymerization initiators such as Irgacure 369, 379EG, and 907 manufactured by BASF Japan Co., Ltd. and α-acetophenone-based polymerization initiators such as SEIKUOL BEE manufactured by Seiko Chemical Industries, Ltd.

肟系光聚合起始劑可藉由照射光而生成自由基。藉由該自由基,塗佈膜之深部之組合物良好地進行聚合。又,就更有效率地進行塗佈膜之深部之聚合反應之觀點而言,較佳為使用能夠有效率地利用波長350 nm以上之紫外線之肟系光聚合起始劑。作為能夠有效率地利用波長350 nm以上之紫外線之肟系光聚合起始劑,例如較佳為列舉三𠯤化合物及肟酯型咔唑化合物,就感度之觀點而言,例如更佳為列舉肟酯型咔唑化合物。作為肟酯型咔唑化合物,例如可列舉1,2-辛二酮、1-[4-(苯硫基)-2-(O-苯甲醯基肟)]、及1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮-1-(O-乙醯基肟)。作為肟酯型咔唑化合物之市售品,例如可列舉Irgacure OXE-01、Irgacure OXE-02、Irgacure OXE-03之類之BASF Japan股份有限公司製造之肟酯型咔唑化合物、及Adeka Optomer N-1919、Adeka Arkls NCI-831之類之ADEKA股份有限公司製造之肟酯型咔唑化合物。Oxime-based photopolymerization initiators can generate free radicals by irradiation with light. The free radicals allow the composition in the deep part of the coating to be well polymerized. In addition, from the perspective of more efficiently performing the polymerization reaction in the deep part of the coating, it is preferred to use an oxime-based photopolymerization initiator that can efficiently utilize ultraviolet rays with a wavelength of more than 350 nm. As oxime-based photopolymerization initiators that can efficiently utilize ultraviolet rays with a wavelength of more than 350 nm, for example, trioxime compounds and oxime ester-type carbazole compounds are preferred. From the perspective of sensitivity, for example, oxime ester-type carbazole compounds are more preferred. Examples of the oxime ester carbazole compound include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl oxime). Examples of commercially available oxime ester carbazole compounds include oxime ester carbazole compounds manufactured by BASF Japan Co., Ltd. such as Irgacure OXE-01, Irgacure OXE-02, and Irgacure OXE-03, and oxime ester carbazole compounds manufactured by ADEKA Co., Ltd. such as Adeka Optomer N-1919 and Adeka Arkls NCI-831.

於將本發明之組合物中所包含之固形物成分(自組合物中去除溶劑之含量後)設為100質量份時,光聚合起始劑之含量通常較佳為0.1~20質量份,更佳為0.5~10質量份,進而較佳為1~7質量份。若光聚合起始劑相對於組合物100質量份為0.1~20質量份,則聚合反應容易充分進行。When the solid content (after removing the solvent from the composition) contained in the composition of the present invention is 100 parts by mass, the content of the photopolymerization initiator is usually preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and further preferably 1 to 7 parts by mass. If the photopolymerization initiator is 0.1 to 20 parts by mass relative to 100 parts by mass of the composition, the polymerization reaction is easy to proceed sufficiently.

(調平劑) 調平劑亦可以調製本發明之組合物之塗佈性為目的、即以調整用於塗佈之組合物之流動性而使塗佈該組合物所獲得之層表面更平坦為目的而添加於組合物中。作為調平劑,例如可列舉矽烷偶合劑等聚矽氧系之調平劑、聚丙烯酸酯系之調平劑、及氟烷基系之調平劑。該等調平劑之中,就進一步提高液晶化合物之垂直配向性之觀點而言,較佳為聚矽氧系之調平劑及氟烷基系之調平劑。 (Leveling agent) The leveling agent can also be added to the composition for the purpose of adjusting the coating properties of the composition of the present invention, that is, for the purpose of adjusting the fluidity of the composition used for coating so that the surface of the layer obtained by coating the composition is flatter. As leveling agents, for example, polysiloxane-based leveling agents such as silane coupling agents, polyacrylate-based leveling agents, and fluoroalkyl-based leveling agents can be listed. Among these leveling agents, polysiloxane-based leveling agents and fluoroalkyl-based leveling agents are preferred from the viewpoint of further improving the vertical alignment of liquid crystal compounds.

作為市售之調平劑,例如可列舉DC3PA、SH7PA、DC11PA、SH28PA、SH29PA、SH30PA、ST80PA、ST86PA、SH8400、SH8700、及FZ2123之類之東麗道康寧(股)製造之調平劑;KP321、KP323、KP324、KP326、KP340、KP341、X22-161A、KF6001、KBM-1003、KBE-1003、KBM-303、KBM-402、KBM-403、KBE-402、KBE-403、KBM-1403、KBM-502、KBM-503、KBE-502、KBE-503、KBM-5103、KBM-602、KBM-603、KBM-903、KBE-903、KBE-9103、KBM-573、KBM-575、KBE-585、KBM-802、KBM-802、KBM-803、KBE-846、及KBE-9007之類之信越化學工業(股)製造之調平劑;TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF-4446、TSF4452、及TSF4460之類之Momentive Performance Materials Japan有限責任公司製造之調平劑;Fluorinert(註冊商標)FC-72、Fluorinert FC-40、Fluorinert FC-43、及Fluorinert FC-3283之類之住友3M(股)製造之調平劑;MEGAFAC(註冊商標)R-08、MEGAFAC R-30、MEGAFAC R-90、MEGAFAC F-410、MEGAFAC F-411、MEGAFAC F-443、MEGAFAC F-445、MEGAFAC F-470、MEGAFAC F-477、MEGAFAC F-479、MEGAFAC F-482、MEGAFAC F-483、MEGAFAC F-556之類之DIC(股)製造之調平劑;Eftop(商品名)EF301、Eftop EF303、Eftop EF351、及Eftop EF352之類之Mitsubishi Materials Electronic Chemicals(股)製造之調平劑;Surflon(註冊商標)S-381、Surflon S-382、Surflon S-383、Surflon S-393、Surflon SC-101、Surflon SC-105、KH-40、及SA-100之類之AGC SEIMI CHEMICAL(股)製造之調平劑;商品名E1830、商品名E5844之類之(股)大金精密化學研究所製造之調平劑;BM-1000、BM-1100、BYK-352、BYK-353、及BYK-361N之類之Chemie公司製造之調平劑(商品名均為BM)。該等調平劑可單獨使用1種,或者亦可組合2種以上使用。Examples of commercially available leveling agents include DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, and FZ2123, which are leveling agents manufactured by Toray Dow Corning Co., Ltd.; KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM -503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBE-585, KBM-802, KBM-802, KBM-803, KBE-846, and KBE-9007, etc.; TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460, etc., manufactured by Shin-Etsu Chemical Co., Ltd. Leveling agents manufactured by Performance Materials Japan Co., Ltd.; Fluorinert (registered trademark) FC-72, Fluorinert FC-40, Fluorinert FC-43, and Fluorinert FC-3283, etc., leveling agents manufactured by Sumitomo 3M Co., Ltd.; MEGAFAC (registered trademark) R-08, MEGAFAC R-30, MEGAFAC R-90, MEGAFAC F-410, MEGAFAC F-411, MEGAFAC F-443, MEGAFAC F-445, MEGAFAC F-470, MEGAFAC F-477, MEGAFAC F-479, MEGAFAC F-482, MEGAFAC F-483, MEGAFAC F-556 and other leveling agents manufactured by DIC Corporation; Eftop (trade name) EF301, Eftop EF303, Eftop EF351, and Eftop EF352 and other leveling agents manufactured by Mitsubishi Materials Electronic Chemicals Corporation; Surflon (registered trademark) S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-105, KH-40, and SA-100 and other leveling agents manufactured by AGC SEIMI Leveling agents manufactured by CHEMICAL Co., Ltd.; leveling agents manufactured by Daikin Fine Chemicals Laboratories Co., Ltd. with trade names such as E1830 and E5844; leveling agents manufactured by Chemie Co., Ltd. with trade names such as BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N (all with trade names of BM). These leveling agents may be used alone or in combination of two or more.

調平劑之含有率通常相對於本發明之組合物之固形物成分,較佳為0.001~3質量%,更佳為0.01~3質量%,進而較佳為0.1~3質量%。若調平劑之含有率相對於組合物之固形物成分為0.001~3質量%,則組合物之塗佈性進一步提高。The content of the leveling agent is generally preferably 0.001 to 3 mass %, more preferably 0.01 to 3 mass %, and further preferably 0.1 to 3 mass % relative to the solid content of the composition of the present invention. If the content of the leveling agent is 0.001 to 3 mass % relative to the solid content of the composition, the coating properties of the composition are further improved.

(垂直配向液晶硬化膜形成用組合物之製備方法) 本發明之組合物例如可藉由將液晶化合物(I)-1、非離子性矽烷化合物或離子性化合物之任一者或兩者、及視需要添加之添加劑於特定之溫度下攪拌等,從而使該等成分大致均勻地分散或溶解而獲得。 (Preparation method of a composition for forming a vertically aligned liquid crystal cured film) The composition of the present invention can be obtained by, for example, stirring the liquid crystal compound (I)-1, any one or both of a non-ionic silane compound or an ionic compound, and an additive added as needed at a specific temperature, thereby dispersing or dissolving the components roughly uniformly.

<垂直配向液晶硬化膜> 垂直配向液晶硬化膜為本發明之組合物之硬化物,且液晶化合物相對於面內方向朝垂直方向配向。即,垂直配向液晶硬化膜包含相對於垂直配向液晶硬化膜之面內方向朝垂直方向配向之狀態的液晶化合物。又,垂直配向液晶硬化膜亦可包含相對於垂直配向液晶硬化膜之面內方向朝垂直方向配向之狀態的液晶化合物之聚合物。垂直配向液晶硬化膜所形成之三維折射率橢球可具有雙軸性,但較佳為具有單軸性。 <Vertical alignment liquid crystal cured film> The vertical alignment liquid crystal cured film is a cured product of the composition of the present invention, and the liquid crystal compound is aligned in a vertical direction relative to the in-plane direction. That is, the vertical alignment liquid crystal cured film includes a liquid crystal compound that is aligned in a vertical direction relative to the in-plane direction of the vertical alignment liquid crystal cured film. In addition, the vertical alignment liquid crystal cured film may also include a polymer of a liquid crystal compound that is aligned in a vertical direction relative to the in-plane direction of the vertical alignment liquid crystal cured film. The three-dimensional refractive index ellipsoid formed by the vertical alignment liquid crystal cured film may have biaxiality, but preferably has uniaxiality.

就抑制具備包含垂直配向液晶硬化膜之橢圓偏光板的顯示器之斜向反射色相變差(例如於該顯示器之斜向之色相確認到紅及藍之類之著色的問題)之觀點而言,垂直配向液晶硬化膜較佳為滿足 下述關係式(1): -150 nm≦RthC(550)≦-30 nm      (1) [關係式(1)中,RthC(550)表示垂直配向液晶硬化膜於波長550 nm下之厚度方向之相位差值]。 垂直配向液晶硬化膜之厚度方向之相位差值RthC(550)就進一步抑制上述顯示器之斜向反射色相之變差之觀點而言,更佳為-100 nm以上-40 nm以下,進而較佳為-80 nm以上-40 nm以下。 From the perspective of suppressing the deterioration of the oblique reflection hue of a display having an elliptical polarizing plate including a vertical alignment liquid crystal cured film (for example, the problem of red and blue coloring being recognized in the oblique hue of the display), the vertical alignment liquid crystal cured film preferably satisfies the following relationship (1): -150 nm ≦ RthC (550) ≦ -30 nm      (1) [In the relationship (1), RthC (550) represents the phase difference value in the thickness direction of the vertical alignment liquid crystal cured film at a wavelength of 550 nm]. From the perspective of further suppressing the deterioration of the oblique reflection hue of the above-mentioned display, the phase difference value RthC (550) in the thickness direction of the vertical alignment liquid crystal cured film is more preferably -100 nm or more and -40 nm or less, and further preferably -80 nm or more and -40 nm or less.

垂直配向液晶硬化膜之厚度方向之相位差值RthC(550)可藉由垂直配向液晶硬化膜之厚度dC而調整。由於面內相位差值可由下述式(1-2): RthC(550)=[(nxC(550)+nyC(550))/2-nzC(550)]×dC       (1-2) [式(1-2)中,nxC(550)表示垂直配向液晶硬化膜於膜面內之波長550 nm之主折射率,nyC(550)表示與nxC(550)於同一面內正交之方向之波長550 nm之折射率,nzC(550)表示垂直配向液晶硬化膜之厚度方向之波長550 nm之折射率,dC表示垂直配向液晶硬化膜之膜厚] 決定,故而為了獲得所需之厚度方向之相位差值RthC(550),只要調整三維折射率與膜厚dC即可。再者,三維折射率取決於上述之液晶化合物之分子結構及配向性。又,於nxC(550)=nyC(550)之情形時,nxC(550)可設為膜面內任意之方向之折射率。 The retardation value RthC(550) in the thickness direction of the vertical alignment liquid crystal cured film can be adjusted by the thickness dC of the vertical alignment liquid crystal cured film. Since the in-plane phase difference value can be determined by the following formula (1-2): RthC(550)=[(nxC(550)+nyC(550))/2-nzC(550)]×dC      (1-2) [In formula (1-2), nxC(550) represents the principal refractive index of the vertically aligned liquid crystal cured film at a wavelength of 550 nm in the film plane, nyC(550) represents the refractive index of the wavelength of 550 nm in the direction orthogonal to nxC(550) in the same plane, nzC(550) represents the refractive index of the vertically aligned liquid crystal cured film at a wavelength of 550 nm in the thickness direction, and dC represents the film thickness of the vertically aligned liquid crystal cured film] , in order to obtain the desired phase difference value RthC(550) in the thickness direction, it is only necessary to adjust the three-dimensional refractive index and the film thickness dC. Furthermore, the three-dimensional refractive index depends on the molecular structure and orientation of the liquid crystal compound mentioned above. In addition, when nxC(550)=nyC(550), nxC(550) can be set as the refractive index of any direction within the film surface.

就薄膜化之觀點而言,垂直配向液晶硬化膜之膜厚之上限較佳為3 μm以下,更佳為2.5 μm以下,進而較佳為2.0 μm以下,尤佳為1.5 μm以下。又,垂直配向液晶硬化膜之膜厚之下限較佳為0.1 μm以上,更佳為0.3 μm以上,進而較佳為0.4 μm以上。垂直配向液晶硬化膜之膜厚可使用橢偏計或接觸式膜厚計測定。From the perspective of thin film, the upper limit of the thickness of the vertically aligned liquid crystal cured film is preferably 3 μm or less, more preferably 2.5 μm or less, further preferably 2.0 μm or less, and particularly preferably 1.5 μm or less. In addition, the lower limit of the thickness of the vertically aligned liquid crystal cured film is preferably 0.1 μm or more, more preferably 0.3 μm or more, and further preferably 0.4 μm or more. The thickness of the vertically aligned liquid crystal cured film can be measured using an elliptical meter or a contact-type film thickness meter.

又,就抑制包含垂直配向液晶硬化膜之橢圓偏光板於短波長側自斜向觀察之情形時橢圓率降低之觀點而言,垂直配向液晶硬化膜較佳為滿足 下述關係式(2): RthC(450)/RthC(550)≦1        (2) [關係式(2)中,RthC(450)表示垂直配向液晶硬化膜於波長450 nm下之厚度方向之相位差值,RthC(550)表示垂直配向液晶硬化膜於波長550 nm下之厚度方向之相位差值]。 就進一步抑制上述橢圓率之降低之觀點而言,垂直配向液晶硬化膜之RthC(450)/RthC(550)更佳為0.95以下,進而較佳為0.90以下。又,垂直配向液晶硬化膜之厚度方向之相位差值RthC(450)與RthC(550)同樣地可藉由垂直配向液晶硬化膜之厚度dC而調整。 Furthermore, from the viewpoint of suppressing the decrease in ellipticity of an elliptical polarizer including a vertically aligned liquid crystal cured film when observed from an oblique direction at a short wavelength, the vertically aligned liquid crystal cured film preferably satisfies the following relationship (2): RthC(450)/RthC(550)≦1        (2) [In the relationship (2), RthC(450) represents the phase difference value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 450 nm, and RthC(550) represents the phase difference value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 550 nm]. From the viewpoint of further suppressing the decrease in the above-mentioned ellipticity, RthC(450)/RthC(550) of the vertically aligned liquid crystal cured film is more preferably 0.95 or less, and further preferably 0.90 or less. In addition, the phase difference values RthC(450) and RthC(550) in the thickness direction of the vertical alignment liquid crystal cured film can also be adjusted by the thickness dC of the vertical alignment liquid crystal cured film.

[垂直配向液晶硬化膜之製造方法] 垂直配向液晶硬化膜之製造方法包括:塗佈膜形成步驟,其將垂直配向液晶硬化膜形成用組合物塗佈於基材而於基材上形成塗佈膜;乾燥覆膜形成步驟,其使塗佈膜乾燥而形成乾燥覆膜;及硬化膜形成步驟,其對乾燥覆膜照射活性能量線而形成垂直配向液晶硬化膜。本製造方法中製造之積層體由基材與垂直配向液晶硬化膜構成。以液晶化合物具有1個以上聚合性基且該組合物進而包含光聚合起始劑之情形為例進行說明。 [Manufacturing method of vertically aligned liquid crystal cured film] The manufacturing method of vertically aligned liquid crystal cured film includes: a coating film forming step, in which a composition for forming a vertically aligned liquid crystal cured film is coated on a substrate to form a coating film on the substrate; a dry film forming step, in which the coated film is dried to form a dry film; and a cured film forming step, in which the dry film is irradiated with active energy rays to form a vertically aligned liquid crystal cured film. The laminate manufactured in this manufacturing method is composed of a substrate and a vertically aligned liquid crystal cured film. The case where the liquid crystal compound has one or more polymerizable groups and the composition further contains a photopolymerization initiator is used as an example for explanation.

(塗佈膜形成步驟) 於塗佈膜形成步驟中,例如使用印刷裝置將上述組合物塗佈於基材而於基材上形成塗佈膜。作為塗佈之方法,例如可列舉凹版塗佈法、模嘴塗佈法、及軟版法之類之印刷方法。 (Coating film forming step) In the coating film forming step, the composition is applied to the substrate using a printing device to form a coating film on the substrate. Examples of coating methods include gravure coating, die nozzle coating, and flexographic printing.

(乾燥覆膜形成步驟) 於乾燥覆膜形成步驟中,例如使用加熱裝置使塗佈膜乾燥而形成乾燥覆膜。塗佈膜於經加熱而去除了塗佈膜中之溶劑後,液晶化合物垂直地配向,轉化成乾燥覆膜。加熱溫度較佳為能夠去除溶劑,且為液晶化合物之相轉移溫度以上。 (Dry coating formation step) In the dry coating formation step, for example, a heating device is used to dry the coating to form a dry coating. After the coating is heated to remove the solvent in the coating, the liquid crystal compound is vertically aligned and converted into a dry coating. The heating temperature is preferably capable of removing the solvent and is above the phase transition temperature of the liquid crystal compound.

(硬化膜形成步驟) 於硬化膜形成步驟中,例如使用光照射裝置對乾燥覆膜照射活性能量線(更具體而言為紫外線等)而形成垂直配向液晶硬化膜。於本發明中,垂直配向液晶硬化膜形成用組合物藉由包含非離子性矽烷化合物及/或離子性化合物而對液晶化合物表現垂直配向限制力,因此液晶化合物於乾燥覆膜中保持相對於基材平面垂直地配向之液晶狀態。藉由對乾燥覆膜照射活性能量線,液晶化合物保持垂直配向之液晶狀態進行光聚合。藉此,能夠於基材上直接形成垂直配向液晶硬化膜。 (Curing film forming step) In the curing film forming step, for example, a light irradiation device is used to irradiate the dry film with active energy rays (more specifically, ultraviolet rays, etc.) to form a vertically aligned liquid crystal curing film. In the present invention, the composition for forming a vertically aligned liquid crystal curing film exhibits a vertically aligned restrictive force on the liquid crystal compound by including a non-ionic silane compound and/or an ionic compound, so that the liquid crystal compound maintains a liquid crystal state vertically aligned relative to the substrate plane in the dry film. By irradiating the dry film with active energy rays, the liquid crystal compound maintains a vertically aligned liquid crystal state and performs photopolymerization. In this way, a vertically aligned liquid crystal curing film can be directly formed on the substrate.

(其他步驟:垂直配向膜形成步驟) 如上文說明,本發明之垂直配向液晶硬化膜能夠不形成配向膜而直接形成於基材上。另一方面,垂直配向液晶硬化膜之製造方法亦可以進一步提高垂直配向液晶硬化膜之配向性為目的,進而包括形成垂直配向膜之垂直配向膜形成步驟。於該情形時,垂直配向液晶硬化膜介隔垂直配向膜而間接地形成於基材上。 (Other steps: vertical alignment film forming step) As described above, the vertical alignment liquid crystal cured film of the present invention can be directly formed on the substrate without forming an alignment film. On the other hand, the manufacturing method of the vertical alignment liquid crystal cured film can also be aimed at further improving the alignment of the vertical alignment liquid crystal cured film, and further includes a vertical alignment film forming step of forming a vertical alignment film. In this case, the vertical alignment liquid crystal cured film is indirectly formed on the substrate via the vertical alignment film.

垂直配向膜形成步驟係於塗佈膜形成步驟之前執行之步驟,形成垂直配向膜。此處,對垂直配向膜之形成方法之例進行說明。配向膜形成步驟例如包括:形成垂直配向膜形成用組合物之塗佈膜之步驟、由上述塗佈膜形成乾燥覆膜之步驟、及視需要使上述乾燥覆膜硬化而形成配向膜之步驟。 於塗佈膜形成步驟中,例如使用印刷裝置於基材上塗佈垂直配向膜形成用組合物而形成塗佈膜。作為垂直配向膜形成用組合物,例如可使用包含如下文所述之配向性聚合物及溶劑之組合物。於乾燥覆膜形成步驟中,例如使用加熱裝置加熱上述塗佈膜使塗佈膜乾燥而形成乾燥覆膜。於進而需要藉由UV照射而硬化之步驟之情形時,使用UV照射裝置對第2乾燥覆膜照射UV進行硬化而形成垂直配向膜。於垂直配向液晶硬化膜之製造方法包括垂直配向膜形成步驟之情形時,於垂直配向膜上形成垂直配向液晶硬化膜。 The vertical alignment film forming step is a step performed before the coating film forming step to form a vertical alignment film. Here, an example of a method for forming a vertical alignment film is described. The alignment film forming step includes, for example, a step of forming a coating film of a composition for forming a vertical alignment film, a step of forming a dry coating from the coating film, and a step of hardening the dry coating as needed to form an alignment film. In the coating film forming step, for example, a coating film is formed by coating a composition for forming a vertical alignment film on a substrate using a printing device. As a composition for forming a vertical alignment film, for example, a composition comprising an alignment polymer and a solvent as described below can be used. In the dry coating formation step, for example, a heating device is used to heat the above-mentioned coating film to dry the coating film to form a dry coating. In the case where a step of curing by UV irradiation is further required, a UV irradiation device is used to irradiate UV on the second dry coating to cure it to form a vertical alignment film. In the case where the manufacturing method of the vertical alignment liquid crystal cured film includes the vertical alignment film formation step, a vertical alignment liquid crystal cured film is formed on the vertical alignment film.

<積層體> 本發明之積層體具備上述垂直配向液晶硬化膜。積層體可進而具備基材、垂直配向膜、水平配向用之配向膜(以下,有時記載為水平配向膜)、黏著層、及/或下述相對於上述垂直配向液晶硬化膜之面內方向朝水平方向配向之膜(以下,有時記載為水平配向薄膜)。作為積層體之構成,例如可列舉具備上述垂直配向液晶硬化膜、水平配向膜、及水平配向薄膜之積層體、具備上述垂直配向液晶硬化膜及基材之積層體、以及具備上述垂直配向液晶硬化膜、水平配向膜、水平配向薄膜、及基材之積層體。但於本發明中,由於即便無垂直配向膜亦能夠形成垂直配向液晶硬化膜,故而積層體亦可不具備垂直配向膜。例如,於積層體具備基材及垂直配向液晶硬化膜之情形時,垂直配向液晶硬化膜可與基材鄰接。又,利用上述方法製作之與基材鄰接之垂直配向液晶硬化膜亦可經由黏著層僅轉印垂直配向液晶硬化膜,去除基材而製造積層體。 <Laminate> The laminate of the present invention has the vertically aligned liquid crystal cured film. The laminate may further have a substrate, a vertically aligned film, an alignment film for horizontal alignment (hereinafter, sometimes described as a horizontally aligned film), an adhesive layer, and/or the following film that is aligned in a horizontal direction relative to the in-plane direction of the vertically aligned liquid crystal cured film (hereinafter, sometimes described as a horizontally aligned film). As the composition of the laminate, for example, there can be listed a laminate having the vertically aligned liquid crystal cured film, a horizontally aligned film, and a horizontally aligned film, a laminate having the vertically aligned liquid crystal cured film and a substrate, and a laminate having the vertically aligned liquid crystal cured film, a horizontally aligned film, a horizontally aligned film, and a substrate. However, in the present invention, since a vertical alignment liquid crystal curing film can be formed even without a vertical alignment film, the laminate may not have a vertical alignment film. For example, when the laminate has a substrate and a vertical alignment liquid crystal curing film, the vertical alignment liquid crystal curing film may be adjacent to the substrate. In addition, the vertical alignment liquid crystal curing film adjacent to the substrate produced by the above method may be transferred only to the vertical alignment liquid crystal curing film via an adhesive layer, and the substrate may be removed to produce a laminate.

[基材] 作為基材,可列舉玻璃基材及膜基材,就加工性之觀點而言,較佳為膜基材,就能夠連續製造之方面而言,更佳為長條之捲筒狀膜。作為構成膜基材之樹脂,例如可列舉聚乙烯、聚丙烯、及降𦯉烯系聚合物之類之聚烯烴;環狀烯烴系樹脂;聚乙烯醇;聚對苯二甲酸乙二酯;聚甲基丙烯酸酯;聚丙烯酸酯;三乙醯纖維素、二乙醯纖維素、及乙酸丙酸纖維素之類之纖維素酯;聚萘二甲酸乙二酯;聚碳酸酯;聚碸;聚醚碸;聚醚酮;聚苯硫醚及聚苯醚之類之塑膠。於該基材之與黏著層之接合面可實施聚矽氧處理之類之脫模處理。作為市售之纖維素酯基材,例如可列舉FUJITAC膜之類之富士膠片股份有限公司製造之纖維素酯基材;「KC8UX2M」、「KC8UY」、及「KC4UY」之類之Konica Minolta Opto股份有限公司製造之纖維素酯基材。可將此種樹脂藉由溶劑流延法、溶融擠出法等公知之方法製膜而製成基材。 [Substrate] As the substrate, a glass substrate and a film substrate can be cited. From the viewpoint of processability, a film substrate is preferred, and from the viewpoint of continuous production, a long roll film is more preferred. As the resin constituting the film substrate, for example, polyolefins such as polyethylene, polypropylene, and norolefin polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate; polyacrylate; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; plastics such as polyphenylene sulfide and polyphenylene ether can be cited. A mold release treatment such as silicone treatment can be applied to the bonding surface between the substrate and the adhesive layer. Examples of commercially available cellulose ester substrates include cellulose ester substrates such as FUJITAC films manufactured by Fuji Film Co., Ltd., and cellulose ester substrates such as "KC8UX2M", "KC8UY", and "KC4UY" manufactured by Konica Minolta Opto Co., Ltd. This resin can be made into a substrate by forming a film using a known method such as solvent casting or melt extrusion.

作為市售之環狀烯烴系樹脂,例如可列舉「Topas(註冊商標)」之類之Ticona公司(德)製造之環狀烯烴系樹脂;「ARTON(註冊商標)」之類之JSR股份有限公司製造之環狀烯烴系樹脂;「ZEONOR(註冊商標)」、及「ZEONEX(註冊商標)」之類之Zeon corporation股份有限公司製造之環狀烯烴系樹脂;「Apel」(註冊商標)之類之三井化學股份有限公司製造之環狀烯烴系樹脂。亦可使用市售之環狀烯烴系樹脂基材。作為市售之環狀烯烴系樹脂基材,可列舉「S-SINA(註冊商標)」及「SCA40(註冊商標)」之類之積水化學工業股份有限公司製造之環狀烯烴系樹脂基材;「ZeonorFilm(註冊商標)」之類之Optes股份有限公司製造之環狀烯烴系樹脂基材;「ARTON Film(註冊商標)」之類之JSR股份有限公司製造之環狀烯烴系樹脂基材。Examples of commercially available cyclic olefin resins include "Topas (registered trademark)" and the like manufactured by Ticona (Germany); "ARTON (registered trademark)" and the like manufactured by JSR Corporation; "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)" and the like manufactured by Zeon Corporation; and "Apel (registered trademark)" and the like manufactured by Mitsui Chemicals, Inc. A commercially available cyclic olefin resin substrate may also be used. Examples of commercially available cyclic olefin resin substrates include "S-SINA (registered trademark)" and "SCA40 (registered trademark)" manufactured by Sekisui Chemical Industries, Ltd.; "ZeonorFilm (registered trademark)" manufactured by Optes Co., Ltd.; and "ARTON Film (registered trademark)" manufactured by JSR Co., Ltd.

基材較佳為容易使各層積層且容易剝離之厚度。此種基材之厚度通常為5~300 μm,較佳為10~150 μm。The thickness of the substrate is preferably such that each layer can be easily stacked and easily peeled off. The thickness of such a substrate is usually 5 to 300 μm, preferably 10 to 150 μm.

[垂直配向膜] 配向膜係具有使液晶硬化膜之液晶化合物向特定方向配向之配向限制力的膜。關於配向膜之形成方法,可藉由配向膜材料之種類、摩擦條件或光照射條件實現垂直配向、水平配向、混合配向、及傾斜配向等各種配向之控制。將如此使配向限制力表現之處理稱為配向處理。其中,垂直配向膜為具有使液晶化合物朝垂直方向配向之配向限制力的配向膜。藉由使用垂直配向膜,能夠形成垂直配向液晶硬化膜。 [Vertical alignment film] The alignment film is a film that has an alignment limiting force that aligns the liquid crystal compound of the liquid crystal cured film in a specific direction. Regarding the formation method of the alignment film, various alignments such as vertical alignment, horizontal alignment, mixed alignment, and tilted alignment can be controlled by the type of alignment film material, friction conditions, or light irradiation conditions. The treatment that makes the alignment limiting force manifest in this way is called alignment treatment. Among them, the vertical alignment film is an alignment film that has an alignment limiting force that aligns the liquid crystal compound in the vertical direction. By using the vertical alignment film, a vertically aligned liquid crystal cured film can be formed.

垂直配向膜較佳為具有不因垂直配向液晶硬化膜形成用組合物之塗佈等而溶解之溶劑耐性,且具有對用於溶劑之去除或液晶化合物之配向之加熱處理的耐熱性。The vertical alignment film preferably has solvent resistance so as not to be dissolved by coating of the vertical alignment liquid crystal cured film-forming composition, and has heat resistance to heat treatment for removing the solvent or aligning the liquid crystal compound.

垂直配向膜較佳為應用降低基材等之表面之表面張力的材料。作為此種材料,可列舉配向性聚合物、例如聚醯亞胺、聚醯胺、作為其水解物之聚醯胺酸、及全氟烷基之氟系聚合物、矽烷化合物、以及藉由該等之縮合反應而獲得之聚矽氧烷化合物。垂直配向膜可藉由將包含此種材料與溶劑、例如垂直配向液晶硬化膜之項中例示之溶劑的組合物塗佈於基材等之上,去除溶劑後對塗佈膜實施加熱等而獲得。The vertical alignment film is preferably a material that reduces the surface tension of the surface of a substrate or the like. Examples of such materials include alignment polymers such as polyimide, polyamide, polyamide as a hydrolyzate thereof, and perfluoroalkyl fluorine polymers, silane compounds, and polysiloxane compounds obtained by condensation reactions thereof. The vertical alignment film can be obtained by applying a composition comprising such a material and a solvent, such as the solvent exemplified in the section of the vertical alignment liquid crystal curing film, on a substrate or the like, removing the solvent, and then applying heat to the coated film.

於垂直配向膜使用矽烷化合物之情形時,就容易降低表面張力且容易提高與鄰接於垂直配向膜之層之密接性的觀點而言,垂直配向膜較佳為具有構成元素包含Si元素與C元素之化合物的膜,可良好地使用矽烷化合物。作為矽烷化合物,可使用前述非離子性矽烷化合物、或離子性化合物之項所例示之含矽烷之離子性化合物等,藉由使用該等矽烷化合物,能夠提高垂直配向限制力。該等矽烷化合物可單獨使用1種,亦可組合2種以上使用,亦可與其他材料混合使用。於矽烷化合物為非離子性矽烷化合物之情形時,就容易提高垂直配向限制力之觀點而言,較佳為分子末端具有烷基之矽烷化合物,更佳為具有碳數3~30之烷基之矽烷化合物。When a silane compound is used in the vertical alignment film, the vertical alignment film is preferably a film having a compound containing Si and C as constituent elements, from the viewpoint of being easy to reduce surface tension and easy to improve adhesion with a layer adjacent to the vertical alignment film, and a silane compound can be used well. As the silane compound, the aforementioned non-ionic silane compound or the ionic compound containing silane exemplified in the ionic compound section can be used. By using such silane compounds, the vertical alignment limiting force can be improved. Such silane compounds can be used alone, or in combination of two or more, or mixed with other materials. When the silane compound is a non-ionic silane compound, from the viewpoint of easily improving the vertical alignment limiting force, a silane compound having an alkyl group at the molecular end is preferred, and a silane compound having an alkyl group having 3 to 30 carbon atoms is more preferred.

就表現配向限制力之觀點而言,垂直配向膜之膜厚較佳為5 μm以下,更佳為3 μm以下,進而較佳為2 μm以下,且較佳為1 nm以上,更佳為5 nm以上,進而較佳為10 nm以上,尤佳為30 nm以上。垂直配向膜之膜厚可使用橢偏計或接觸式膜厚計進行測定。From the perspective of expressing the alignment restriction force, the thickness of the vertical alignment film is preferably 5 μm or less, more preferably 3 μm or less, and further preferably 2 μm or less, and is preferably 1 nm or more, more preferably 5 nm or more, further preferably 10 nm or more, and particularly preferably 30 nm or more. The thickness of the vertical alignment film can be measured using an elliptometer or a contact film thickness meter.

[水平配向用之配向膜] 水平配向膜具有使液晶化合物朝水平方向配向之配向限制力。於將水平配向液晶硬化膜形成用組合物於水平配向膜上製膜時,水平配向膜能夠形成水平配向液晶硬化膜之水平配向狀態。配向限制力例如能夠藉由配向膜之種類、表面狀態、及摩擦條件而任意地調整,於由光配向性聚合物形成之情形時,可藉由偏光照射條件等任意地調整。將如此使配向限制力表現之處理稱為配向處理。 [Alignment film for horizontal alignment] The horizontal alignment film has an alignment restraining force that aligns the liquid crystal compound in the horizontal direction. When the composition for forming a horizontal alignment liquid crystal cured film is formed on the horizontal alignment film, the horizontal alignment film can form a horizontal alignment state of the horizontal alignment liquid crystal cured film. The alignment restraining force can be arbitrarily adjusted by, for example, the type of alignment film, the surface state, and the rubbing conditions. When formed by a photo-alignable polymer, it can be arbitrarily adjusted by polarized light irradiation conditions, etc. The treatment that makes the alignment restraining force manifest in this way is called alignment treatment.

水平配向膜較佳為具有不因液晶組合物之塗佈等而溶解之溶劑耐性,且具有對用於溶劑之去除或液晶化合物之配向之加熱處理的耐熱性。The horizontal alignment film preferably has solvent resistance so as not to be dissolved by coating of the liquid crystal composition, etc., and has heat resistance against heat treatment for removing the solvent or aligning the liquid crystal compound.

作為水平配向膜,例如可列舉摩擦配向膜、光配向膜、及表面具有凹凸圖案或複數之槽的溝槽配向膜。例如於應用於長條之捲筒狀膜之情形時,就能夠容易地控制配向方向之方面而言,較佳為光配向膜。As the horizontal alignment film, for example, there can be cited a rubbing alignment film, a photo alignment film, and a groove alignment film having a concave-convex pattern or a plurality of grooves on the surface. For example, when applied to a long roll film, the photo alignment film is preferred in terms of being able to easily control the alignment direction.

摩擦配向膜通常可藉由將包含配向性聚合物與溶劑之組合物(以下,有時記載為摩擦配向膜形成用組合物)塗佈於基材,去除溶劑而形成塗佈膜,並對該塗佈膜進行摩擦而賦予配向限制力。The rubbed alignment film can be generally prepared by applying a composition including an aligning polymer and a solvent (hereinafter sometimes referred to as a rubbed alignment film forming composition) to a substrate, removing the solvent to form a coating film, and rubbing the coating film to provide an alignment regulating force.

作為配向性聚合物,例如可列舉具有醯胺鍵之聚醯胺或明膠類、具有醯亞胺鍵之聚醯亞胺及作為其水解物之聚醯胺酸、聚乙烯醇、烷基改性聚乙烯醇、聚丙烯醯胺、聚㗁唑、聚伸乙基亞胺、聚苯乙烯、聚乙烯基吡咯啶酮、聚丙烯酸、以及聚丙烯酸酯類。該等配向性聚合物可單獨使用1種,或者亦可組合2種以上使用。As the alignment polymer, for example, polyamide or gelatin having an amide bond, polyimide having an imide bond and polyamide acid as a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyazole, polyethyleneimine, polystyrene, polyvinyl pyrrolidone, polyacrylic acid, and polyacrylates can be listed. These alignment polymers can be used alone or in combination of two or more.

關於摩擦配向膜形成用組合物中之配向性聚合物之濃度,只要為配向性聚合物完全溶解於溶劑中之範圍即可。配向性聚合物之含量相對於摩擦配向膜形成用組合物100質量份,較佳為0.1~20質量份,更佳為0.1~10質量份。The concentration of the alignment polymer in the rubbing alignment film forming composition can be within the range that the alignment polymer is completely dissolved in the solvent. The content of the alignment polymer is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the rubbing alignment film forming composition.

作為摩擦配向膜形成用組合物之市售品,例如可列舉Sunever(註冊商標)之類之日產化學工業(股)製造之摩擦配向膜形成用組合物、及Optomer(註冊商標)之類之JSR(股)製造之摩擦配向膜形成用組合物。Examples of commercially available compositions for forming a rubbed alignment film include Sunever (registered trademark) manufactured by Nissan Chemical Industries, Ltd. and Optomer (registered trademark) manufactured by JSR Corporation.

作為摩擦處理之方法,例如可列舉使上述塗佈膜接觸於捲繞有摩擦布且旋轉之摩擦輥的方法。於進行摩擦處理時,若進行遮蔽,則亦能夠於配向膜形成配向之方向不同之複數個區域(圖案)。As a method of rubbing treatment, for example, a method of bringing the above-mentioned coating film into contact with a rubbing roller wound with a rubbing cloth and rotating can be cited. During the rubbing treatment, if masking is performed, a plurality of regions (patterns) with different orientation directions can also be formed on the orientation film.

光配向膜通常可藉由將包含具有光反應性基之聚合物或單體及溶劑之組合物(以下,有時記載為光配向膜形成用組合物)塗佈於基材,去除溶劑後照射偏光(較佳為偏光UV)而獲得。光配向膜可藉由選擇照射之偏光之偏光方向而任意地控制配向限制力之方向。The photo-alignment film can be obtained by applying a composition including a polymer or monomer having a photoreactive group and a solvent (hereinafter, sometimes referred to as a photo-alignment film-forming composition) to a substrate, removing the solvent, and then irradiating the substrate with polarized light (preferably polarized UV light). The photo-alignment film can arbitrarily control the direction of the alignment restraining force by selecting the polarization direction of the irradiated polarized light.

光反應性基係指藉由光照射而產生配向能力之基。具體而言,可列舉參與藉由光照射而產生之分子之配向誘發反應、異構化反應、光二聚反應、光交聯反應、或光分解反應之類之成為配向能力之起源之光反應的基。作為光反應性基,較佳為具有不飽和鍵、尤其是雙鍵之基,尤佳為具有選自由碳-碳雙鍵(C=C鍵)、碳-氮雙鍵(C=N鍵)、氮-氮雙鍵(N=N鍵)、及碳-氧雙鍵(C=O鍵)所組成之群中之至少一個雙鍵的基。Photoreactive groups refer to groups that generate alignment ability by light irradiation. Specifically, groups that participate in photoreactions that become the origin of alignment ability, such as alignment induction reaction, isomerization reaction, photodimerization reaction, photocrosslinking reaction, or photodecomposition reaction of molecules generated by light irradiation can be listed. As photoreactive groups, groups having unsaturated bonds, especially double bonds are preferred, and groups having at least one double bond selected from the group consisting of carbon-carbon double bonds (C=C bonds), carbon-nitrogen double bonds (C=N bonds), nitrogen-nitrogen double bonds (N=N bonds), and carbon-oxygen double bonds (C=O bonds) are particularly preferred.

作為具有C=C鍵之光反應性基,例如可列舉乙烯基、多烯基、茋基、茋唑基、茋唑鎓基、查耳酮基、及桂皮醯基。作為具有C=N鍵之光反應性基,例如可列舉具有芳香族希夫鹼、芳香族腙等結構之基。作為具有N=N鍵之光反應性基,例如可列舉偶氮苯基、偶氮萘基、芳香族雜環偶氮基、雙偶氮基、甲臢基、及具有氧偶氮苯結構之基。作為具有C=O鍵之光反應性基,例如可列舉二苯甲酮基、香豆素基、蒽醌基、及順丁烯二醯亞胺基。該等基可具有烷基、烷氧基、芳基、烯丙氧基、氰基、烷氧基羰基、羥基、磺酸基、及鹵化烷基之類之取代基。Examples of photoreactive groups having a C=C bond include vinyl, polyene, stilbene, stilbazolyl, stilbazolinium, chalcone, and cinnamyl groups. Examples of photoreactive groups having a C=N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. Examples of photoreactive groups having an N=N bond include azophenyl, azonaphthyl, aromatic heterocyclic azo, bisazo, formazan, and groups having an oxyazobenzene structure. Examples of photoreactive groups having a C=O bond include benzophenone, coumarin, anthraquinone, and cis-butylenediimide groups. These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.

參與光二聚反應或光交聯反應之基就配向性優異之方面而言較佳。其中,較佳為參與光二聚反應之光反應性基,就配向所需之偏光照射量相對較少、且容易獲得熱穩定性或經時穩定性優異之光配向膜之方面而言,較佳為桂皮醯基及查耳酮基。作為具有光反應性基之聚合物,尤佳為該聚合物側鏈之末端部成為桂皮酸結構或桂皮酸酯結構之具有桂皮醯基者。The groups participating in the photodimerization reaction or the photocrosslinking reaction are preferred in terms of excellent alignment. Among them, the photoreactive groups participating in the photodimerization reaction are preferably cinnamyl groups and chalcone groups in terms of relatively less polarized light irradiation required for alignment and easy acquisition of a photoalignment film with excellent thermal stability or stability over time. As the polymer having the photoreactive group, the polymer having the cinnamyl group whose end portion of the side chain is a cinnamic acid structure or a cinnamic acid ester structure is particularly preferred.

具有光反應性基之聚合物或單體之含量可根據聚合物或單體之種類或目標之光配向膜之厚度而調節,相對於光配向膜形成用組合物100質量份,較佳為設為0.2質量份以上,更佳為0.3~10質量份。The content of the polymer or monomer having a photoreactive group can be adjusted according to the type of the polymer or monomer or the thickness of the target photoalignment film, and is preferably set to 0.2 parts by mass or more, and more preferably 0.3 to 10 parts by mass, relative to 100 parts by mass of the photoalignment film-forming composition.

於照射偏光時,例如可為自塗佈於基材上之光配向膜形成用組合物去除溶劑後直接照射偏光之形式。又,該偏光若實質上為平行光則較佳。照射之偏光之波長較佳為具有光反應性基之聚合物或單體之光反應性基能夠吸收光能之波長區域者。具體而言,尤佳為波長250~400 nm之區域之UV(紫外線)。作為照射該偏光之光源,例如可列舉氙氣燈、高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、以及KrF及ArF之類之紫外光雷射。該等光源之中,高壓水銀燈、超高壓水銀燈、及金屬鹵化物燈由於波長313 nm之紫外線之發光強度較大,故而較佳。藉由使來自上述光源之光通過適當之偏光元件進行照射,能夠照射偏光UV。作為偏光元件,例如可列舉偏光濾光片、格蘭-湯姆森、及格蘭-泰勒之類之偏光稜鏡、以及線柵。該等偏光元件之中,就大面積化及對熱之耐性之觀點而言,較佳為線柵。When irradiating polarized light, for example, the polarized light may be directly irradiated after removing the solvent from the photo-alignment film-forming composition coated on the substrate. In addition, it is preferred if the polarized light is substantially parallel light. The wavelength of the irradiated polarized light is preferably in the wavelength region where the photoreactive group of the polymer or monomer having the photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) in the wavelength region of 250 to 400 nm is particularly preferred. As the light source for irradiating the polarized light, for example, xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and ultraviolet lasers such as KrF and ArF can be listed. Among these light sources, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferred because they have a high intensity of ultraviolet light with a wavelength of 313 nm. Polarized UV can be irradiated by passing light from the above light sources through an appropriate polarizing element. Examples of polarizing elements include polarizing filters, polarizing prisms such as Glen-Thomson and Glen-Taylor, and wire grids. Among these polarizing elements, wire grids are preferred from the perspective of large area and heat resistance.

再者,於進行摩擦或偏光照射時,若進行遮蔽,則亦能夠形成液晶配向之方向不同之複數個區域(圖案)。Furthermore, if shielding is performed during rubbing or polarized light irradiation, a plurality of regions (patterns) with different liquid crystal alignment directions can be formed.

溝槽(groove)配向膜係於膜表面具有凹凸圖案或複數個溝槽(槽)之膜。於將組合物塗佈於具有等間隔地排列之複數之直線狀之溝槽的膜之情形時,液晶化合物朝沿著該槽之方向配向。A groove alignment film is a film having a concave-convex pattern or a plurality of grooves on the film surface. When the composition is applied to a film having a plurality of straight grooves arranged at equal intervals, the liquid crystal compound is aligned in the direction along the grooves.

作為獲得溝槽配向膜之方法,可列舉:於感光性聚醯亞胺膜表面經由具有圖案形狀之狹縫之曝光用遮罩進行曝光後,進行顯影及沖洗處理而形成凹凸圖案的方法;於在表面具有槽之板狀之母盤形成硬化前之UV硬化樹脂之層,將形成之樹脂層轉移至基材後進行硬化的方法;及於形成於基材上之硬化前之UV硬化樹脂之膜按壓具有複數個槽之輥狀之母盤而形成凹凸,其後進行硬化之方法等。As methods for obtaining a groove alignment film, there are the following methods: a method of exposing the surface of a photosensitive polyimide film through an exposure mask having narrow slits in the shape of a pattern, and then performing development and rinsing treatment to form a concave-convex pattern; a method of forming a layer of a pre-cured UV-curable resin on a plate-shaped master having grooves on the surface, transferring the formed resin layer to a substrate and then curing it; and a method of pressing a film of a pre-cured UV-curable resin formed on a substrate against a roller-shaped master having a plurality of grooves to form concave-convex and concave, and then curing it.

就實現薄膜化及表現配向限制力之觀點而言,水平配向膜之膜厚較佳為1 μm以下,更佳為0.5 μm以下,進而較佳為0.3 μm以下。又,水平配向膜之膜厚較佳為1 nm以上,更佳為5 nm以上,進而較佳為10 nm以上,尤佳為30 nm以上。水平配向膜之膜厚可使用橢偏計或接觸式膜厚計進行測定。From the perspective of achieving thin film and showing alignment restriction force, the thickness of the horizontal alignment film is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.3 μm or less. In addition, the thickness of the horizontal alignment film is preferably 1 nm or more, more preferably 5 nm or more, further preferably 10 nm or more, and particularly preferably 30 nm or more. The thickness of the horizontal alignment film can be measured using an elliptical meter or a contact film thickness meter.

[相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜] 構成本發明之積層體的相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜為相位差膜。作為水平配向薄膜,例如可列舉延伸膜及水平配向液晶硬化膜(以下亦稱為水平配向液晶硬化膜A)。水平配向薄膜之光學特性可藉由聚合性液晶化合物之配向狀態或延伸方法而調整。就水平配向薄膜之薄膜化之觀點而言,較佳為水平配向液晶硬化膜A。 [Film oriented horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film] The film oriented horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film constituting the laminate of the present invention is a phase difference film. As horizontally aligned thin films, for example, stretch films and horizontally aligned liquid crystal cured films (hereinafter also referred to as horizontally aligned liquid crystal cured films A) can be listed. The optical properties of the horizontally aligned thin films can be adjusted by the alignment state or stretching method of the polymerizable liquid crystal compound. From the perspective of thinning the horizontally aligned thin films, the horizontally aligned liquid crystal cured film A is preferred.

(水平配向液晶硬化膜A) 本說明書中,水平配向液晶硬化膜A係聚合性液晶化合物於相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之狀態下硬化而成的液晶硬化膜。水平配向液晶硬化膜A中,聚合性液晶化合物之光軸相對於垂直配向液晶硬化膜之面內方向朝水平方向配向。作為聚合性液晶化合物,例如可列舉具有至少1個聚合性基之液晶化合物(I)-1。再者,於本說明書中,將本發明之積層體所包含之水平配向液晶硬化膜稱為水平配向液晶硬化膜A,將下述偏光板之偏光膜所包含之水平配向液晶硬化膜稱為水平配向液晶硬化膜B而區分各者。 (Horizontally aligned liquid crystal cured film A) In this specification, the horizontally aligned liquid crystal cured film A is a liquid crystal cured film formed by curing a polymerizable liquid crystal compound in a state where the polymerizable liquid crystal compound is aligned in a horizontal direction relative to the in-plane direction of the vertically aligned liquid crystal cured film. In the horizontally aligned liquid crystal cured film A, the optical axis of the polymerizable liquid crystal compound is aligned in a horizontal direction relative to the in-plane direction of the vertically aligned liquid crystal cured film. As the polymerizable liquid crystal compound, for example, a liquid crystal compound (I)-1 having at least one polymerizable group can be listed. Furthermore, in this specification, the horizontally aligned liquid crystal cured film included in the laminate of the present invention is referred to as a horizontally aligned liquid crystal cured film A, and the horizontally aligned liquid crystal cured film included in the polarizing film of the polarizing plate described below is referred to as a horizontally aligned liquid crystal cured film B to distinguish between them.

(水平配向液晶硬化膜A之製造方法) 水平配向液晶硬化膜A係組合物(以下,有時記載為水平配向液晶硬化膜A形成用組合物)之硬化物。作為水平配向液晶硬化膜A之製造方法之一例,包括:塗佈步驟,其於預先製作之水平配向膜上塗佈水平配向液晶硬化膜A形成用組合物而形成塗佈膜;乾燥覆膜形成步驟,其使塗佈膜乾燥而形成乾燥覆膜;及硬化膜形成步驟,其對乾燥覆膜照射活性能量線而形成水平配向液晶硬化膜。 (Manufacturing method of horizontal alignment liquid crystal cured film A) The horizontal alignment liquid crystal cured film A is a cured product of a composition (hereinafter, sometimes described as a composition for forming a horizontal alignment liquid crystal cured film A). As an example of the manufacturing method of the horizontal alignment liquid crystal cured film A, it includes: a coating step, which forms a coating film by coating the composition for forming a horizontal alignment liquid crystal cured film A on a pre-made horizontal alignment film; a dry film forming step, which dries the coated film to form a dry film; and a cured film forming step, which irradiates the dry film with active energy rays to form a horizontal alignment liquid crystal cured film.

(延伸膜) 作為延伸膜,例如可列舉包含聚碳酸酯系樹脂之延伸膜。作為市售之延伸膜,例如可列舉「PURE-ACE(註冊商標)WR」之類之帝人股份有限公司製造之延伸膜。延伸膜通常可藉由對基材膜進行延伸而獲得。作為對基材膜進行延伸之方法,例如準備將基材膜捲繞成捲筒而得之捲繞體,自捲繞體連續地捲出基材膜,將捲出之基材膜搬送至加熱爐。加熱爐之設定溫度較佳為基材膜之玻璃轉移溫度附近~玻璃轉移溫度+50℃之範圍。於加熱爐中,向基材膜之搬送方向、或與搬送方向正交之方向進行延伸。延伸時,調整搬送方向或張力,向任意之角度加以傾斜地進行單軸延伸、雙軸延伸、或斜向延伸之熱延伸處理。延伸膜之遲相軸方向根據延伸方法而不同,根據延伸方法而決定遲相軸或光軸。延伸膜與本發明之積層體可經由黏著層而接著。 (Stretched film) As a stretched film, for example, a stretched film containing a polycarbonate resin can be listed. As a commercially available stretched film, for example, a stretched film manufactured by Teijin Co., Ltd. such as "PURE-ACE (registered trademark) WR" can be listed. A stretched film can generally be obtained by stretching a substrate film. As a method for stretching a substrate film, for example, a roll obtained by winding a substrate film into a roll is prepared, the substrate film is continuously unrolled from the roll, and the unrolled substrate film is conveyed to a heating furnace. The setting temperature of the heating furnace is preferably in the range of near the glass transition temperature of the substrate film to the glass transition temperature + 50°C. In the heating furnace, the substrate film is stretched in the conveying direction of the substrate film or in a direction orthogonal to the conveying direction. During stretching, the conveying direction or tension is adjusted, and the film is tilted at any angle to perform single-axis stretching, double-axis stretching, or oblique stretching heat stretching treatment. The direction of the retardation axis of the stretched film varies depending on the stretching method, and the retardation axis or optical axis is determined according to the stretching method. The stretched film and the laminate of the present invention can be connected via an adhesive layer.

本發明之積層體就降低具備積層體之橢圓偏光板於短波長側之橢圓率之觀點而言,構成積層體之水平配向薄膜較佳為滿足下述關係式(3): ReA(450)/ReA(550)≦1     (3) [關係式(3)中,ReA(450)表示上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜於波長450 nm下之面內相位差值,ReA(550)表示上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜於波長550 nm下之面內相位差值]。 就進一步抑制橢圓率降低之觀點而言,ReA(450)/ReA(550)更佳為0.95以下,進而較佳為0.90以下。 又,同樣地就提高具備積層體之橢圓偏光板之橢圓率之觀點而言,較佳為滿足以下(3)-2: 120 nm≦ReA(550)≦170 nm・・・(3)-2。 就提高具備積層體之橢圓偏光板之橢圓率之觀點而言,較佳為130 nm≦ReA(550)≦160 nm。 From the perspective of reducing the ellipticity of the elliptical polarizer having the laminate on the short wavelength side, the horizontal alignment film constituting the laminate preferably satisfies the following relation (3): ReA(450)/ReA(550)≦1     (3) [In relation (3), ReA(450) represents the in-plane phase difference of the film oriented horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and ReA(550) represents the in-plane phase difference of the film oriented horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm]. From the perspective of further suppressing the decrease in ellipticity, ReA(450)/ReA(550) is preferably 0.95 or less, and further preferably 0.90 or less. Similarly, from the perspective of improving the ellipticity of an elliptical polarizer having a laminate, it is preferably satisfied by the following (3)-2: 120 nm≦ReA(550)≦170 nm...(3)-2. From the perspective of improving the ellipticity of an elliptical polarizer having a laminate, it is preferably 130 nm≦ReA(550)≦160 nm.

本發明所記載之積層體之中,包含垂直配向液晶硬化膜及相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的積層體就縮小正面方向之相位差值與自斜向之相位差值之差之觀點而言,即就抑制具備包含該積層體之橢圓偏光板之顯示器之斜向反射色相變差的觀點而言,較佳為滿足下述關係式(4): |R0(550)-R40(550)|≦10 nm       (4) [關係式(4)中,R0(550)表示波長550 nm下之積層體之面內相位差值,R40(550)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時波長550 nm下之相位差值]。 就進一步抑制斜向反射色相變差之觀點而言,更佳為8 nm以下,進而較佳為4 nm以下。 Among the laminates described in the present invention, the laminate comprising a vertically aligned liquid crystal cured film and a film aligned in the horizontal direction relative to the in-plane direction of the vertically aligned liquid crystal cured film preferably satisfies the following relational expression (4) from the viewpoint of reducing the difference between the phase difference in the front direction and the phase difference in the oblique direction, that is, from the viewpoint of suppressing the oblique reflection hue degradation of a display having an elliptical polarizing plate including the laminate: |R0(550)-R40(550)|≦10 nm       (4) [In relational expression (4), R0(550) represents the wavelength 550 nm, R40(550) represents the phase difference at a wavelength of 550 nm when the phase advance axis of the film oriented horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film is rotated 40°]. From the perspective of further suppressing the hue change of oblique reflection, it is more preferably less than 8 nm, and more preferably less than 4 nm.

本發明所記載之積層體之中,包含垂直配向液晶硬化膜與相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的積層體就抑制具備包含該積層體之橢圓偏光板之顯示器之斜向反射色相變差的觀點而言,較佳為滿足下述關係式(5): |R0(450)-R40(450)|≦10 nm       (5) [關係式(5)中,R0(450)表示波長450 nm下之積層體之面內相位差值,R40(450)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時波長450 nm下之相位差值]。 就進一步抑制斜向反射色相變差之觀點而言,更佳為8 nm以下,進而較佳為4 nm以下。 Among the laminates described in the present invention, a laminate comprising a vertically aligned liquid crystal cured film and a film oriented in a horizontal direction relative to the in-plane direction of the vertically aligned liquid crystal cured film preferably satisfies the following relational expression (5) from the viewpoint of suppressing the oblique reflection chromatic aberration of a display having an elliptical polarizing plate including the laminate: |R0(450)-R40(450)|≦10 nm       (5) [In relational expression (5), R0(450) represents the in-plane phase difference value of the laminate at a wavelength of 450 nm, and R40(450) represents the phase difference value at a wavelength of 450 nm when the film oriented in a horizontal direction relative to the in-plane direction of the vertically aligned liquid crystal cured film is rotated 40° about the advance axis direction of the film oriented in a horizontal direction relative to the in-plane direction of the vertically aligned liquid crystal cured film]. From the perspective of further suppressing the deterioration of the oblique reflection hue, it is more preferably less than 8 nm, and even more preferably less than 4 nm.

本發明所記載之積層體之中,包含垂直配向液晶硬化膜及相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的積層體就抑制具備包含該積層體之橢圓偏光板之顯示器之斜向反射色相變差的觀點而言,較佳為滿足下述關係式(6): |{R0(450)-R40(450)}-{R0(550)-R40(550)}|≦3 nm       (6) [關係式(6)中,R0(450)表示波長450 nm下之積層體之面內相位差值,R0(550)表示波長550 nm下之積層體之面內相位差值,R40(450)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時波長450 nm下之相位差值,R40(550)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時波長550 nm下之相位差值]。 就進一步抑制斜向反射色相變差之觀點而言,更佳為2 nm以下,進而較佳為1 nm以下。 Among the laminates described in the present invention, a laminate comprising a vertically aligned liquid crystal cured film and a film aligned in a horizontal direction relative to the in-plane direction of the vertically aligned liquid crystal cured film preferably satisfies the following relational expression (6) from the viewpoint of suppressing the oblique reflection hue degradation of a display having an elliptical polarizing plate including the laminate: |{R0(450)-R40(450)}-{R0(550)-R40(550)}|≦3 nm       (6) [In relational expression (6), R0(450) represents the in-plane phase difference value of the laminate at a wavelength of 450 nm, and R0(550) represents the in-plane phase difference value of the laminate at a wavelength of 550 nm. nm, R40(450) represents the phase difference at a wavelength of 450 nm when the advance axis of the film oriented horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film is rotated 40°, and R40(550) represents the phase difference at a wavelength of 550 nm when the advance axis of the film oriented horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film is rotated 40°]. From the perspective of further suppressing the hue change of oblique reflection, it is more preferably less than 2 nm, and more preferably less than 1 nm.

[積層體之製造方法] 本發明之積層體之製造方法包括垂直配向液晶硬化膜形成步驟。垂直配向液晶硬化膜形成步驟可為上述垂直配向液晶硬化膜之製造方法。藉由已說明之垂直配向液晶硬化膜之製造方法,能夠製造由基材及垂直配向液晶硬化膜構成之積層體、以及由基材、配向膜、及垂直配向液晶硬化膜構成之積層體。 於積層體具備相對於垂直配向液晶硬化膜之面內方向朝水平配向進行配向之膜之情形時,積層體之製造方法進而包括延伸膜貼合步驟或水平配向液晶硬化膜A形成步驟。延伸膜貼合步驟係使用黏接著劑將延伸膜貼合於例如垂直配向液晶硬化膜。具備水平配向液晶硬化膜A之積層體之製造方法例如可經由黏著層將垂直配向液晶硬化膜與水平配向液晶硬化膜貼合而進行製造,亦可將水平配向膜及水平配向液晶硬化膜A形成於垂直配向液晶硬化膜上。又,亦可於延伸膜上或水平配向液晶硬化膜A形成垂直配向液晶硬化膜。 [Manufacturing method of laminate] The manufacturing method of the laminate of the present invention includes a step of forming a vertically aligned liquid crystal curing film. The step of forming a vertically aligned liquid crystal curing film may be the manufacturing method of the vertically aligned liquid crystal curing film described above. By the manufacturing method of the vertically aligned liquid crystal curing film described above, a laminate consisting of a substrate and a vertically aligned liquid crystal curing film, and a laminate consisting of a substrate, an alignment film, and a vertically aligned liquid crystal curing film can be manufactured. In the case where the laminate has a film that is oriented horizontally relative to the in-plane direction of the vertically aligned liquid crystal curing film, the manufacturing method of the laminate further includes a stretch film bonding step or a step of forming a horizontally aligned liquid crystal curing film A. The stretch film bonding step is to bond the stretch film to, for example, a vertically aligned liquid crystal curing film using an adhesive. The manufacturing method of the laminate having the horizontal alignment liquid crystal curing film A can be manufactured by laminating the vertical alignment liquid crystal curing film and the horizontal alignment liquid crystal curing film through an adhesive layer, or the horizontal alignment film and the horizontal alignment liquid crystal curing film A can be formed on the vertical alignment liquid crystal curing film. In addition, the vertical alignment liquid crystal curing film can also be formed on the stretching film or the horizontal alignment liquid crystal curing film A.

[黏接著劑] 作為黏接著劑,例如可列舉感壓式黏著劑、乾燥固化型接著劑、及化學反應型接著劑。作為化學反應型接著劑,例如可列舉活性能量線硬化型接著劑。 [Adhesive] Examples of adhesives include pressure-sensitive adhesives, dry-curing adhesives, and chemical-reaction adhesives. Examples of chemical-reaction adhesives include active energy ray-curing adhesives.

感壓式黏著劑通常包含聚合物,亦可包含溶劑。作為聚合物,例如可列舉丙烯酸系聚合物、聚矽氧系聚合物、聚酯、聚胺基甲酸酯、及聚醚。該等感壓式黏著劑之中,包含丙烯酸系聚合物之感壓式黏著劑由於光學透明性優異,具有適度之潤濕性或凝集力,接著性優異,進而耐候性或耐熱性等較高,且加熱或加濕之條件下不易產生鼓起或剝離等,故而較佳。Pressure-sensitive adhesives usually contain polymers and may also contain solvents. Examples of polymers include acrylic polymers, silicone polymers, polyesters, polyurethanes, and polyethers. Among these pressure-sensitive adhesives, pressure-sensitive adhesives containing acrylic polymers are preferred because they have excellent optical transparency, moderate wettability or cohesiveness, excellent adhesion, and higher weather resistance or heat resistance, and are less likely to bulge or peel off under heating or humidification conditions.

作為丙烯酸系聚合物,例如較佳為酯部分之烷基為甲基、乙基或丁基之類之碳數1~20之烷基之(甲基)丙烯酸酯與(甲基)丙烯酸或(甲基)丙烯酸羥基乙酯等具有官能基之(甲基)丙烯酸系單體的共聚物。The acrylic polymer is preferably a copolymer of a (meth)acrylate in which the alkyl group of the ester portion is an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl or butyl, and a (meth)acrylic acid or a (meth)acrylic acid monomer having a functional group such as hydroxyethyl (meth)acrylate.

包含此種共聚物之感壓式黏著劑由於黏著性優異,即便於貼合於被轉印體後移除,亦能夠不於被轉印體產生糊劑殘留等而相對容易地移除,故而較佳。丙烯酸系聚合物之玻璃轉移溫度較佳為25℃以下,更佳為0℃以下。此種丙烯酸系聚合物之質量平均分子量較佳為10萬以上。The pressure-sensitive adhesive containing such a copolymer is preferably used because of its excellent adhesiveness. Even if it is removed after being attached to the transfer body, it can be removed relatively easily without leaving any adhesive residue on the transfer body. The glass transition temperature of the acrylic polymer is preferably below 25°C, more preferably below 0°C. The mass average molecular weight of such an acrylic polymer is preferably above 100,000.

作為溶劑,例如可列舉作為上述溶劑而列舉之溶劑。感壓式黏著劑亦可含有光擴散劑。光擴散劑係對感壓式黏著劑賦予光擴散性之添加劑,只要為具有與感壓式黏著劑所包含之聚合物之折射率不同之折射率的微粒子即可。作為光擴散劑,可列舉包含無機化合物之微粒子、及包含有機化合物(聚合物)之微粒子。包括丙烯酸系聚合物在內,感壓式黏著劑作為有效成分所包含之聚合物大多具有1.4~1.6左右之折射率,因此較佳為自其折射率為1.2~1.8之光擴散劑適當選擇。感壓式黏著劑作為有效成分所包含之聚合物與光擴散劑之折射率差通常為0.01以上,就顯示裝置之亮度與顯示性之觀點而言,較佳為0.01~0.2。用作光擴散劑之微粒子較佳為球形之微粒子、尤其是接近單分散之微粒子,更佳為平均粒徑為2~6 μm之微粒子。折射率係藉由一般之最小偏角法或阿貝折射計進行測定。As the solvent, for example, the solvents listed as the above-mentioned solvents can be cited. The pressure-sensitive adhesive may also contain a light diffuser. The light diffuser is an additive that imparts light diffusion to the pressure-sensitive adhesive, and it only needs to be microparticles having a refractive index different from the refractive index of the polymer contained in the pressure-sensitive adhesive. As the light diffuser, microparticles containing inorganic compounds and microparticles containing organic compounds (polymers) can be cited. Most polymers contained in the pressure-sensitive adhesive as an active ingredient, including acrylic polymers, have a refractive index of about 1.4 to 1.6, so it is preferably appropriately selected from light diffusers whose refractive index is 1.2 to 1.8. The refractive index difference between the polymer and the light diffuser contained as the active ingredient of the pressure-sensitive adhesive is usually 0.01 or more, and preferably 0.01 to 0.2 from the perspective of the brightness and display of the display device. The microparticles used as the light diffuser are preferably spherical microparticles, especially microparticles close to monodisperse, and more preferably microparticles with an average particle size of 2 to 6 μm. The refractive index is measured by the general minimum deflection angle method or Abbe refractometer.

作為包含無機化合物之微粒子,例如可列舉氧化鋁(折射率1.76)及氧化矽(折射率1.45)。作為包含有機化合物(聚合物)之微粒子,例如可列舉三聚氰胺顆粒(折射率1.57)、聚甲基丙烯酸甲酯顆粒(折射率1.49)、甲基丙烯酸甲酯/苯乙烯共聚物樹脂顆粒(折射率1.50~1.59)、聚碳酸酯顆粒(折射率1.55)、聚乙烯顆粒(折射率1.53)、聚苯乙烯顆粒(折射率1.6)、聚氯乙烯顆粒(折射率1.46)、及聚矽氧樹脂顆粒(折射率1.46)。光擴散劑之含量通常相對於聚合物100質量份為3~30質量份。Examples of microparticles containing inorganic compounds include aluminum oxide (refractive index 1.76) and silicon oxide (refractive index 1.45). Examples of microparticles containing organic compounds (polymers) include melamine particles (refractive index 1.57), polymethyl methacrylate particles (refractive index 1.49), methyl methacrylate/styrene copolymer resin particles (refractive index 1.50 to 1.59), polycarbonate particles (refractive index 1.55), polyethylene particles (refractive index 1.53), polystyrene particles (refractive index 1.6), polyvinyl chloride particles (refractive index 1.46), and silicone resin particles (refractive index 1.46). The content of the light diffuser is usually 3 to 30 parts by mass relative to 100 parts by mass of the polymer.

感壓式黏著劑之厚度係根據其密接力等而決定,故而並無特別限制,通常為1 μm~40 μm。就加工性或耐久性等方面而言,該厚度較佳為3 μm~25 μm,更佳為5 μm~20 μm。藉由將由感壓式黏著劑形成之黏著層之厚度設為5 μm~20 μm,能夠保持自正面觀察顯示裝置之情形或自斜向觀察之情形之亮度,不易產生顯示圖像之暈染或模糊。The thickness of the pressure-sensitive adhesive is determined by its adhesion, etc., so there is no special restriction, and it is usually 1 μm to 40 μm. In terms of processability and durability, the thickness is preferably 3 μm to 25 μm, and more preferably 5 μm to 20 μm. By setting the thickness of the adhesive layer formed by the pressure-sensitive adhesive to 5 μm to 20 μm, the brightness of the display device when viewed from the front or from an oblique angle can be maintained, and it is not easy to produce smearing or blurring of the displayed image.

乾燥固化型接著劑亦可包含溶劑。作為乾燥固化型接著劑,例如可列舉如下組合物,其含有具有羥基、羧基、或胺基之類之質子性官能基與乙烯性不飽和基之單體之聚合物、或胺基甲酸酯聚合物作為主成分,且進而含有多元醛、環氧化合物、環氧樹脂、三聚氰胺化合物、氧化鋯化合物、及鋅化合物之類之交聯劑或硬化性化合物。作為具有羥基、羧基或胺基等質子性官能基與乙烯性不飽和基之單體之聚合物,例如可列舉乙烯-順丁烯二酸共聚物、伊康酸共聚物、丙烯酸共聚物、丙烯醯胺共聚物、聚乙酸乙烯酯之皂化物、及聚乙烯醇系樹脂。The dry curing adhesive may also contain a solvent. As dry curing adhesives, for example, the following compositions can be cited, which contain a polymer of a monomer having a protic functional group such as a hydroxyl group, a carboxyl group, or an amine group and an ethylenically unsaturated group, or a urethane polymer as a main component, and further contain a crosslinking agent or curing compound such as a polyaldehyde, an epoxy compound, an epoxy resin, a melamine compound, a zirconium oxide compound, and a zinc compound. As polymers of monomers having a protic functional group such as a hydroxyl group, a carboxyl group, or an amine group and an ethylenically unsaturated group, for example, ethylene-maleic acid copolymers, itaconic acid copolymers, acrylic acid copolymers, acrylamide copolymers, saponified products of polyvinyl acetate, and polyvinyl alcohol resins can be cited.

作為聚乙烯醇系樹脂,例如可列舉聚乙烯醇、部分皂化聚乙烯醇、完全皂化聚乙烯醇、羧基改性聚乙烯醇、乙醯乙醯基改性聚乙烯醇、羥甲基改性聚乙烯醇、及胺基改性聚乙烯醇。水系之黏接著劑中之聚乙烯醇系樹脂之含量相對於水100質量份,通常為1~10質量份,較佳為1~5質量份。Examples of polyvinyl alcohol resins include polyvinyl alcohol, partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, acetylacetyl-modified polyvinyl alcohol, hydroxymethyl-modified polyvinyl alcohol, and amino-modified polyvinyl alcohol. The content of the polyvinyl alcohol resin in the water-based adhesive is usually 1 to 10 parts by mass, preferably 1 to 5 parts by mass, relative to 100 parts by mass of water.

作為胺基甲酸酯樹脂,例如可列舉聚酯系離子聚合物型胺基甲酸酯樹脂。此處所謂聚酯系離子聚合物型胺基甲酸酯樹脂,係具有聚酯骨架之胺基甲酸酯樹脂,且係於其中導入有少量之離子性成分(親水成分)之樹脂。該離子聚合物型胺基甲酸酯樹脂由於不使用乳化劑,於水中乳化而成為乳液,故而可製成水系之黏接著劑。於使用聚酯系離子聚合物型胺基甲酸酯樹脂之情形時,有效的是調配水溶性之環氧化合物作為交聯劑。As urethane resins, for example, polyester-based ionic polymer urethane resins can be cited. The polyester-based ionic polymer urethane resins referred to herein are urethane resins having a polyester skeleton and into which a small amount of ionic components (hydrophilic components) are introduced. Since the ionic polymer urethane resins are emulsified in water to form an emulsion without using an emulsifier, they can be made into water-based adhesives. When using polyester-based ionic polymer urethane resins, it is effective to formulate a water-soluble epoxy compound as a crosslinking agent.

作為環氧樹脂,可列舉使表氯醇與藉由二伸乙基三胺或三伸乙基四胺等聚伸烷基聚胺與己二酸等二羧酸之反應而獲得之聚醯胺聚胺進行反應而獲得的聚醯胺環氧樹脂等。作為該聚醯胺環氧樹脂之市售品,例如可列舉Sumika Chemtex股份有限公司製造之「Sumirez Resin(註冊商標)650」及「Sumirez Resin 675」、以及日本PMC股份有限公司製造之「WS-525」。於調配環氧樹脂之情形時,其含量相對於聚乙烯醇系樹脂100質量份,通常為1~100質量份,較佳為1~50質量份。Examples of epoxy resins include polyamide epoxy resins obtained by reacting epichlorohydrin with polyamide polyamines obtained by reacting polyalkylene polyamines such as diethylenetriamine or triethylenetetramine with dicarboxylic acids such as adipic acid. Examples of commercially available polyamide epoxy resins include "Sumirez Resin (registered trademark) 650" and "Sumirez Resin 675" manufactured by Sumika Chemtex Co., Ltd., and "WS-525" manufactured by Japan PMC Co., Ltd. When epoxy resins are formulated, the content thereof is generally 1 to 100 parts by mass, preferably 1 to 50 parts by mass, relative to 100 parts by mass of the polyvinyl alcohol-based resin.

就抑制外觀不良之產生之觀點而言,由乾燥固化型接著劑形成之黏接著劑層之厚度通常為0.001~5 μm,較佳為0.01~2 μm,進而較佳為0.01~0.5 μm。From the viewpoint of suppressing the occurrence of poor appearance, the thickness of the adhesive layer formed by the dry curing adhesive is generally 0.001 to 5 μm, preferably 0.01 to 2 μm, and more preferably 0.01 to 0.5 μm.

活性能量線硬化型接著劑亦可包含溶劑。活性能量線硬化型接著劑係指受到活性能量線之照射而硬化之黏接著劑。作為活性能量線硬化型接著劑,例如可列舉含有環氧化合物與陽離子聚合起始劑之陽離子聚合性之接著劑、含有丙烯酸系硬化成分與自由基聚合起始劑之自由基聚合性之接著劑、含有環氧化合物之類之陽離子聚合性之硬化成分與丙烯酸系化合物等自由基聚合性之硬化成分兩者且進而含有陽離子聚合起始劑與自由基聚合起始劑之接著劑、及不含該等聚合起始劑而藉由照射電子束而硬化之接著劑。Active energy ray-curing adhesives may also contain solvents. Active energy ray-curing adhesives refer to adhesives that are cured by exposure to active energy rays. Examples of active energy ray-curing adhesives include cationic polymerizable adhesives containing epoxy compounds and cationic polymerization initiators, free radical polymerizable adhesives containing acrylic curing components and free radical polymerization initiators, adhesives containing both cationic polymerizable curing components such as epoxy compounds and free radical polymerizable curing components such as acrylic compounds and further containing cationic polymerization initiators and free radical polymerization initiators, and adhesives that do not contain these polymerization initiators but are cured by irradiation with electron beams.

該等活性能量線硬化型接著劑之中,較佳為含有丙烯酸系硬化成分與光自由基聚合起始劑之自由基聚合性之活性能量線硬化型接著劑、及含有環氧化合物與光陽離子聚合起始劑之陽離子聚合性之活性能量線硬化型接著劑。作為丙烯酸系硬化成分,例如可列舉(甲基)丙烯酸甲酯及(甲基)丙烯酸羥基乙酯之類之(甲基)丙烯酸酯、以及(甲基)丙烯酸。含有環氧化合物之活性能量線硬化型接著劑亦可進而含有環氧化合物以外之化合物。作為環氧化合物以外之化合物,例如可列舉氧雜環丁烷化合物及丙烯酸系化合物。Among the active energy ray-curing adhesives, preferred are free radical polymerizable active energy ray-curing adhesives containing acrylic curing components and photo-free radical polymerization initiators, and cationic polymerizable active energy ray-curing adhesives containing epoxy compounds and photo-cationic polymerization initiators. Examples of acrylic curing components include (meth)acrylates such as methyl (meth)acrylate and hydroxyethyl (meth)acrylate, and (meth)acrylic acid. Active energy ray-curing adhesives containing epoxy compounds may further contain compounds other than epoxy compounds. Examples of compounds other than epoxy compounds include cyclohexane compounds and acrylic compounds.

作為光自由基聚合起始劑及光陽離子聚合起始劑,例如可列舉上述光自由基聚合起始劑及光陽離子聚合起始劑。自由基聚合起始劑及陽離子聚合起始劑之含量相對於活性能量線硬化型接著劑100質量份,通常為0.5~20質量份,較佳為1~15質量份。As the photo-radical polymerization initiator and the photo-cationic polymerization initiator, for example, the above-mentioned photo-radical polymerization initiator and the photo-cationic polymerization initiator can be cited. The content of the radical polymerization initiator and the cationic polymerization initiator is usually 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass, relative to 100 parts by mass of the active energy ray-curable adhesive.

於活性能量線硬化型接著劑中亦可進而含有離子捕捉劑、抗氧化劑、鏈轉移劑、黏著賦予劑、熱塑性樹脂、填充劑、流動調整劑、塑化劑、及消泡劑。The active energy ray-curable adhesive may further contain an ion scavenger, an antioxidant, a chain transfer agent, a tackifier, a thermoplastic resin, a filler, a flow regulator, a plasticizer, and a defoaming agent.

<橢圓偏光板> 橢圓偏光板包含上述積層體與偏光膜。橢圓偏光板亦可視需要進而包含任意之層(更具體而言為保護層及黏接著劑等)。積層體及偏光膜例如係經由黏接著劑而接著。 <Elliptical polarizing plate> The elliptical polarizing plate includes the above-mentioned laminate and polarizing film. The elliptical polarizing plate may further include any layer (more specifically, a protective layer and an adhesive, etc.) as needed. The laminate and the polarizing film are bonded together, for example, via an adhesive.

圖1係表示橢圓偏光板之層構成之一例的概略剖視圖。圖1所示之橢圓偏光板20由積層體15、黏接著劑7、偏光膜11、及保護層13構成。積層體15由基材1、水平配向膜3、水平配向液晶硬化膜A 5、黏接著劑7、及垂直配向液晶硬化膜9構成。水平配向液晶硬化膜A 5之遲相軸與偏光膜11之吸收軸所成之角較佳為45±5°。FIG1 is a schematic cross-sectional view showing an example of the layer structure of an elliptical polarizer. The elliptical polarizer 20 shown in FIG1 is composed of a laminate 15, an adhesive 7, a polarizing film 11, and a protective layer 13. The laminate 15 is composed of a substrate 1, a horizontal alignment film 3, a horizontal alignment liquid crystal curing film A5, an adhesive 7, and a vertical alignment liquid crystal curing film 9. The angle between the retardation axis of the horizontal alignment liquid crystal curing film A5 and the absorption axis of the polarizing film 11 is preferably 45±5°.

(偏光膜) 偏光膜係具有偏光功能之膜。作為偏光膜,例如可列舉包含二色性色素且相對於偏光膜之膜表面朝水平方向配向之膜(更具體而言為吸附有二色性色素之延伸膜(以下,有時記載為偏光膜A)、及包含二色性色素之水平配向液晶硬化膜(以下,有時將構成偏光膜之上述水平配向液晶硬化膜記載為水平配向液晶硬化膜B、將由水平配向液晶硬化膜B構成之偏光膜記載為偏光膜B)等)。就橢圓偏光板之薄膜化之觀點而言,較佳為包含二色性色素之水平配向液晶硬化膜B。二色性色素意指顯示吸收各向異性,具有二色性色素之分子之長軸方向上之吸光度與短軸方向上之吸光度不同之性質的色素。 (Polarizing film) Polarizing film is a film with polarizing function. As polarizing film, for example, there can be listed films containing dichroic dye and oriented in the horizontal direction relative to the film surface of the polarizing film (more specifically, a stretched film adsorbed with dichroic dye (hereinafter, sometimes described as polarizing film A), and a horizontally aligned liquid crystal cured film containing dichroic dye (hereinafter, sometimes the above-mentioned horizontally aligned liquid crystal cured film constituting the polarizing film is described as horizontally aligned liquid crystal cured film B, and the polarizing film constituted by the horizontally aligned liquid crystal cured film B is described as polarizing film B)). From the perspective of thin filmization of elliptical polarizing plates, horizontally aligned liquid crystal cured film B containing dichroic dye is preferred. Dichroic dye means a dye that shows absorption anisotropy and has the property that the absorbance of the dichroic dye molecule in the long axis direction is different from the absorbance in the short axis direction.

(水平配向液晶硬化膜B) 水平配向液晶硬化膜B係含有二色性色素與聚合性液晶化合物(以下,有時將形成水平配向液晶硬化膜B之聚合性液晶化合物記載為聚合性液晶化合物(B))之組合物(以下,有時記載為偏光膜B形成用組合物)之硬化物。水平配向液晶硬化膜B包含二色性色素,且係聚合性液晶化合物(B)於相對於面內方向朝水平方向配向之狀態下硬化而成的液晶硬化膜。 (Horizontally aligned liquid crystal cured film B) The horizontally aligned liquid crystal cured film B is a cured product of a composition (hereinafter, sometimes described as a composition for forming a polarizing film B) containing a dichroic dye and a polymerizable liquid crystal compound (hereinafter, the polymerizable liquid crystal compound forming the horizontally aligned liquid crystal cured film B is sometimes described as a polymerizable liquid crystal compound (B)). The horizontally aligned liquid crystal cured film B contains a dichroic dye and is a liquid crystal cured film formed by curing the polymerizable liquid crystal compound (B) in a state of being aligned in a horizontal direction relative to the in-plane direction.

水平配向液晶硬化膜B較佳為聚合性液晶化合物(B)於相對於膜之面內方向朝水平方向配向之層列相之狀態下硬化而成的硬化膜。即,於聚合性液晶化合物(B)為熱致液晶之情形時,可為顯示向列液晶相之熱致性液晶化合物,亦可為顯示層列液晶相之熱致性液晶化合物。於藉由聚合反應而作為硬化膜表現偏光功能時,聚合性液晶化合物所顯示之液晶狀態較佳為層列相,若為高次層列相則就高性能化之觀點而言更佳。其中,更佳為形成層列B相、層列D相、層列E相、層列F相、層列G相、層列H相、層列I相、層列J相、層列K相或層列L相之高次層列液晶化合物,進而較佳為形成層列B相、層列F相或層列I相之高次層列液晶化合物。若聚合性液晶化合物(B)所形成之液晶相為該等高次層列相,則能夠製造偏光性能更高之偏光膜。又,偏光性能如上所述較高之偏光膜於X射線繞射測定中,可獲得源自六相或結晶相等高次結構之布勒格波峰。該布勒格波峰係源自分子配向之週期結構之波峰,可獲得其週期間隔為3~6 Å之膜。就獲得更高之偏光特性之觀點而言,水平配向液晶硬化膜B較佳為包含於層列相之狀態下聚合之聚合性液晶化合物(B)之聚合物。再者,聚合性液晶化合物(B)所具有之下述聚合性基於水平配向液晶硬化膜B中可為未聚合之狀態,亦可為已聚合之狀態。即,水平配向液晶硬化膜B可於聚合性液晶化合物(B)(單體)、聚合性液晶化合物(B)之低聚物、聚合性液晶化合物(B)之聚合物、及該等之組合之任一狀態下含有。聚合性液晶化合物(B)所具有之聚合性基於水平配向液晶硬化膜B中較佳為未聚合之狀態。The horizontally aligned liquid crystal cured film B is preferably a cured film formed by curing the polymerizable liquid crystal compound (B) in a smectic phase oriented in a horizontal direction relative to the in-plane direction of the film. That is, when the polymerizable liquid crystal compound (B) is a thermotropic liquid crystal, it may be a thermotropic liquid crystal compound showing a nematic liquid crystal phase, or it may be a thermotropic liquid crystal compound showing a smectic liquid crystal phase. When the cured film exhibits a polarizing function through a polymerization reaction, the liquid crystal state shown by the polymerizable liquid crystal compound is preferably a smectic phase, and a higher-order smectic phase is more preferable from the perspective of high performance. Among them, it is more preferred to form a higher order stratified liquid crystal compound that forms a stratified B phase, a stratified D phase, a stratified E phase, a stratified F phase, a stratified G phase, a stratified H phase, a stratified I phase, a stratified J phase, a stratified K phase or a stratified L phase, and furthermore, it is more preferred to form a higher order stratified liquid crystal compound that forms a stratified B phase, a stratified F phase or a stratified I phase. If the liquid crystal phase formed by the polymerizable liquid crystal compound (B) is such a higher order stratified phase, a polarizing film with higher polarization performance can be manufactured. In addition, the polarizing film with higher polarization performance as described above can obtain a Bragg peak derived from a higher order structure such as a hexagonal phase or a crystalline phase in the X-ray diffraction measurement. The Bragg peak is a peak of the periodic structure derived from the molecular alignment, and a film with a period interval of 3 to 6 Å can be obtained. From the viewpoint of obtaining higher polarization characteristics, the horizontal alignment liquid crystal cured film B is preferably a polymer of a polymerizable liquid crystal compound (B) polymerized in a laminar phase state. Furthermore, the following polymerizability of the polymerizable liquid crystal compound (B) can be in an unpolymerized state or a polymerized state based on the horizontal alignment liquid crystal cured film B. That is, the horizontal alignment liquid crystal cured film B can contain any state of a polymerizable liquid crystal compound (B) (monomer), an oligomer of a polymerizable liquid crystal compound (B), a polymer of a polymerizable liquid crystal compound (B), and a combination thereof. The polymerizability of the polymerizable liquid crystal compound (B) is preferably in an unpolymerized state based on the horizontal alignment liquid crystal cured film B.

作為聚合性液晶化合物(B),具體而言,可列舉下述式(B1)所表示之化合物(以下,亦稱為聚合性液晶化合物(B1))等。該聚合性液晶可單獨使用,亦可組合2種以上使用。Specific examples of the polymerizable liquid crystal compound (B) include compounds represented by the following formula (B1) (hereinafter, also referred to as polymerizable liquid crystal compound (B1)). The polymerizable liquid crystal may be used alone or in combination of two or more.

U 1-V 1-W 1-X 1-Y 1-X 2-Y 2-X 3-W 2-V 2-U 2(B1) [式(B1)中, X 1、X 2、及X 3分別獨立表示2價芳香族基或2價脂環式烴基,此處,該2價芳香族基或該2價脂環式烴基所包含之氫原子可被取代為鹵素原子、碳數1~4之烷基、碳數1~4之氟烷基、碳數1~4之烷氧基、氰基、或硝基,構成該2價芳香族基或該2價脂環式烴基之碳原子可被取代為氧原子、硫原子、或氮原子。其中,X 1、X 2、及X 3中之至少1個表示可具有取代基之1,4-伸苯基、或可具有取代基之環己烷-1,4-二基。 Y 1、Y 2、W 1、及W 2分別獨立表示單鍵或二價連結基。 V 1及V 2分別獨立表示可具有取代基之碳數1~20之烷二基,構成該烷二基之-CH 2-可被取代為-O-、-CO-、-S-或NH-。 U 1及U 2分別獨立表示聚合性基或氫原子,U 1及U 2中之至少1個表示聚合性基。 U 1 -V 1 -W 1 -X 1 -Y 1 -X 2 -Y 2 -X 3 -W 2 -V 2 -U 2 (B1) [In formula (B1), X 1 , X 2 , and X 3 each independently represent a divalent aromatic group or a divalent alicyclic alkyl group, wherein the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic alkyl group may be substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, and the carbon atom constituting the divalent aromatic group or the divalent alicyclic alkyl group may be substituted by an oxygen atom, a sulfur atom, or a nitrogen atom. Among them, at least one of X 1 , X 2 , and X 3 represents a 1,4-phenylene group which may have a substituent, or a cyclohexane-1,4-diyl group which may have a substituent. Y 1 , Y 2 , W 1 , and W 2 each independently represent a single bond or a divalent linking group. V 1 and V 2 each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH 2 - constituting the alkanediyl group may be substituted with -O-, -CO-, -S-, or NH-. U 1 and U 2 each independently represent a polymerizable group or a hydrogen atom, and at least one of U 1 and U 2 represents a polymerizable group.

於聚合性液晶化合物(B1)中,X 1、X 2、及X 3中之至少1個表示可具有取代基之1,4-伸苯基、或可具有取代基之環己烷-1,4-二基。特別是X 1及X 3較佳為表示可具有取代基之環己烷-1,4-二基,該環己烷-1,4-二基進而較佳為反式環己烷-1,4-二基。作為可具有取代基之1,4-伸苯基、或可具有取代基之環己烷-1,4-二基任意地具有之取代基,例如可列舉甲基、乙基、及丁基之類之碳數1~4之烷基、氰基、以及氯原子及氟原子之類之鹵素原子。可具有取代基之1,4-伸苯基、或可具有取代基之環己烷-1,4-二基較佳為1,4-伸苯基及環己烷-1,4-二基。又,於Y 1及Y 2為同一結構之情形時,較佳為X 1、X 2及X 3中之至少1個為不同之結構。於X 1、X 2及X 3中之至少1個為不同之結構之情形時,有容易表現層列液晶性之傾向。 In the polymerizable liquid crystal compound (B1), at least one of X1 , X2 , and X3 represents a 1,4-phenylene group which may have a substituent, or a cyclohexane-1,4-diyl group which may have a substituent. In particular, X1 and X3 preferably represent a cyclohexane-1,4-diyl group which may have a substituent, and the cyclohexane-1,4-diyl group is further preferably a trans-cyclohexane-1,4-diyl group. Examples of the substituent that the 1,4-phenylene group which may have a substituent, or the cyclohexane-1,4-diyl group which may have a substituent include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a butyl group, a cyano group, and a halogen atom such as a chlorine atom and a fluorine atom. The 1,4-phenylene group which may have a substituent or the cyclohexane-1,4-diyl group which may have a substituent is preferably a 1,4-phenylene group and a cyclohexane-1,4-diyl group. When Y1 and Y2 have the same structure, it is preferred that at least one of X1 , X2 and X3 has a different structure. When at least one of X1 , X2 and X3 has a different structure, there is a tendency to easily express staggered liquid crystal properties.

Y 1及Y 2較佳為分別獨立表示單鍵、-CH 2CH 2-、-CH 2O-、-CH 2CH 2O-、-COO-、-OCO-、-N=N-、-CR a=CR b-、-C≡C-或CR a=N-,R a及R b分別獨立表示氫原子或碳數1~4之烷基。Y 1及Y 2更佳為分別獨立表示-CH 2CH 2-、-COO-、-OCO-、或單鍵。又,於X 1、X 2及X 3全部為同一結構之情形時,較佳為Y 1及Y 2為互不相同之鍵結方式。於Y 1及Y 2為互不相同之鍵結方式之情形時,有容易表現層列液晶性之傾向。 Y1 and Y2 are preferably independently single bonds, -CH2CH2- , -CH2O- , -CH2CH2O-, -COO-, -OCO-, -N=N-, -CRa = CRb- , -C≡C- or CRa =N-, and Ra and Rb are independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms. Y1 and Y2 are more preferably independently -CH2CH2- , -COO- , -OCO- , or single bonds. When X1 , X2 and X3 are all the same structure, it is preferred that Y1 and Y2 have different bonding modes. When Y1 and Y2 have different bonding modes, there is a tendency to easily express staggered liquid crystal properties.

W 1及W 2較佳為分別獨立表示單鍵、-O-、-S-、-COO-、或OCO-,更佳為分別獨立表示單鍵或-O-。 W1 and W2 preferably independently represent a single bond, -O-, -S-, -COO-, or OCO-, and more preferably independently represent a single bond or -O-.

作為V 1及V 2所表示之碳數1~20之烷二基,例如可列舉亞甲基、伸乙基、丙烷-1,3-二基、丁烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基、庚烷-1,7-二基、辛烷-1,8-二基、癸烷-1,10-二基、十四烷-1,14-二基、及二十烷-1,20-二基。V 1及V 2較佳為表示碳數2~12之烷二基,更佳為表示直鏈狀之碳數6~12之烷二基。於V 1及V 2表示直鏈狀之碳數6~12之烷二基之情形時,有聚合性液晶化合物(B1)之配向性提高,容易表現層列液晶性之傾向。 作為可具有取代基之碳數1~20之烷二基任意地具有之取代基,例如可列舉氰基、以及氯原子及氟原子之類之鹵素原子,但該烷二基較佳為未經取代,更佳為未經取代且直鏈狀之烷二基。 Examples of the alkanediyl group having 1 to 20 carbon atoms represented by V1 and V2 include methylene, ethylidene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,10-diyl, tetradecane-1,14-diyl, and eicosane-1,20-diyl. V1 and V2 are preferably alkanediyl groups having 2 to 12 carbon atoms, and more preferably linear alkanediyl groups having 6 to 12 carbon atoms. When V1 and V2 are linear alkanediyl groups having 6 to 12 carbon atoms, the alignment of the polymerizable liquid crystal compound (B1) is improved, and the polymerizable liquid crystal compound (B1) tends to exhibit lamellar liquid crystal properties. Examples of the substituent that the optionally substituted alkanediyl group having 1 to 20 carbon atoms may have include a cyano group, and a halogen atom such as a chlorine atom and a fluorine atom. The alkanediyl group is preferably unsubstituted, and more preferably an unsubstituted linear alkanediyl group.

U 1及U 2較佳為均表示聚合性基,更佳為均表示光聚合性基。具有光聚合性基之聚合性液晶化合物(B1)由於能夠於較熱聚合性基低溫之條件下進行聚合,故而能夠於液晶之秩序度更高之狀態下形成聚合物,就該方面而言有利。 U1 and U2 preferably both represent polymerizable groups, and more preferably both represent photopolymerizable groups. The polymerizable liquid crystal compound (B1) having a photopolymerizable group can be polymerized at a lower temperature than a thermal polymerizable group, and thus can form a polymer in a state where the liquid crystal has a higher degree of order, which is advantageous in this respect.

U 1及U 2所表示之聚合性基可相互相同亦可不同,較佳為相同。作為聚合性基,例如可列舉乙烯基、乙烯氧基、1-氯乙烯基、異丙烯基、4-乙烯基苯基、丙烯醯氧基、甲基丙烯醯氧基、環氧乙烷基、及氧雜環丁基。該等光聚合性基之中,較佳為丙烯醯氧基、甲基丙烯醯氧基、乙烯氧基、環氧乙烷基、及氧雜環丁基,更佳為甲基丙烯醯氧基、及丙烯醯氧基。 The polymerizable groups represented by U1 and U2 may be the same or different, but are preferably the same. Examples of the polymerizable groups include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, oxirane, and cyclobutyl. Among the photopolymerizable groups, acryloxy, methacryloxy, vinyloxy, oxirane, and cyclobutyl are preferred, and methacryloxy and acryloxy are more preferred.

作為此種聚合性液晶化合物(B1),例如可列舉以下之式(1-1)~(1-23)所表示之聚合性液晶化合物。 [化17] Examples of such polymerizable liquid crystal compounds (B1) include polymerizable liquid crystal compounds represented by the following formulae (1-1) to (1-23).

[化18] [Chemistry 18]

[化19] [Chemistry 19]

[化20] [Chemistry 20]

例示之上述聚合性液晶化合物(B1)之中,較佳為選自由式(1-2)、式(1-3)、式(1-4)、式(1-6)、式(1-7)、式(1-8)、式(1-13)、式(1-14)及式(1-15)所表示之化合物所組成之群中之至少1種。聚合性液晶化合物可單獨使用1種,亦可組合2種以上使用。Among the above-mentioned polymerizable liquid crystal compounds (B1), it is preferred that at least one selected from the group consisting of compounds represented by formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1-7), formula (1-8), formula (1-13), formula (1-14) and formula (1-15) be used. The polymerizable liquid crystal compound may be used alone or in combination of two or more.

聚合性液晶化合物(B1)例如可藉由Lub等、Recl. Trav. Chim. Pays-Bas、115、321-328(1996)、或日本專利第4719156號等所記載之公知之方法製造。The polymerizable liquid crystal compound (B1) can be produced by a known method described in, for example, Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996), or Japanese Patent No. 4719156.

偏光膜B形成用組合物只要無損本發明之效果,則亦可含有聚合性液晶化合物(B)以外之其他液晶化合物,就獲得配向秩序度較高之偏光膜之觀點而言,聚合性液晶化合物(B)相對於偏光膜B形成用組合物中所含之所有液晶化合物之總質量的比率較佳為51質量%以上,更佳為70質量%以上,進而較佳為90質量%以上。The composition for forming polarizing film B may contain other liquid crystal compounds besides the polymerizable liquid crystal compound (B) as long as it does not impair the effect of the present invention. From the viewpoint of obtaining a polarizing film with a higher degree of orientation order, the ratio of the polymerizable liquid crystal compound (B) to the total mass of all liquid crystal compounds contained in the composition for forming polarizing film B is preferably 51 mass % or more, more preferably 70 mass % or more, and further preferably 90 mass % or more.

又,於偏光膜B形成用組合物包含2種以上之聚合性液晶化合物(B)之情形時,可其中至少1種為聚合性液晶化合物(B1),亦可其全部為聚合性液晶化合物(B1)。藉由組合複數種聚合性液晶化合物,有於液晶-結晶相轉移溫度以下之溫度下亦能夠暫時地保持液晶性之情況。Furthermore, when the composition for forming the polarizing film B contains two or more polymerizable liquid crystal compounds (B), at least one of them may be the polymerizable liquid crystal compound (B1), or all of them may be the polymerizable liquid crystal compound (B1). By combining a plurality of polymerizable liquid crystal compounds, it is possible to temporarily maintain liquid crystallinity even at a temperature below the liquid crystal-crystalline phase transition temperature.

偏光膜B形成用組合物中之聚合性液晶化合物(B)之含量相對於偏光膜B形成用組合物之固形物成分,較佳為40~99.9質量%,更佳為60~99質量%,進而較佳為70~99質量%。若聚合性液晶化合物(B)之含量為上述範圍內,則有液晶化合物之配向性變高之傾向。再者,固形物成分係指自偏光膜B形成用組合物去除溶劑後之成分之合計量。The content of the polymerizable liquid crystal compound (B) in the composition for forming polarizing film B is preferably 40 to 99.9% by weight, more preferably 60 to 99% by weight, and further preferably 70 to 99% by weight relative to the solid content of the composition for forming polarizing film B. If the content of the polymerizable liquid crystal compound (B) is within the above range, the orientation of the liquid crystal compound tends to be higher. In addition, the solid content refers to the total amount of the components after removing the solvent from the composition for forming polarizing film B.

(二色性色素) 二色性色素係指具有分子之長軸方向上之吸光度與短軸方向上之吸光度不同之性質之色素。作為二色性色素,較佳為具有吸收可見光之特性,更佳為於380~680 nm之波長範圍具有吸收極大波長(λ MAX)。作為二色性色素,例如可列舉碘及二色性之有機染料。作為二色性之有機染料,例如可列舉吖啶色素、㗁𠯤色素、花青色素、萘色素、偶氮色素、及蒽醌色素。該等二色性之有機染料之中,較佳為偶氮色素。作為偶氮色素,例如可列舉單偶氮色素、雙偶氮色素、三偶氮色素、四偶氮色素、及茋偶氮色素。該等偶氮色素之中,較佳為雙偶氮色素及三偶氮色素。二色性之有機染料可單獨使用1種,亦可組合2種以上使用,為了於可見光全域獲得吸收,較佳為組合3種以上之二色性色素使用,更佳為組合3種以上之偶氮色素使用。聚乙烯醇系樹脂膜較佳為於染色處理前實施向水中之浸漬處理。 (Dichroic pigment) Dichroic pigment refers to a pigment having a property that the absorbance in the long axis direction of the molecule is different from the absorbance in the short axis direction. As a dichroic pigment, it is preferred to have the property of absorbing visible light, and it is more preferred to have an absorption maximum wavelength (λ MAX ) in the wavelength range of 380 to 680 nm. As dichroic pigments, for example, iodine and dichroic organic dyes can be listed. As dichroic organic dyes, for example, acridine pigments, thiocyanine pigments, naphthalene pigments, azo pigments, and anthraquinone pigments can be listed. Among these dichroic organic dyes, azo pigments are preferred. As azo pigments, for example, monoazo pigments, disazo pigments, trisazo pigments, tetrakis azo pigments, and stilbene azo pigments can be listed. Among the azo dyes, bis-azo dyes and tris-azo dyes are preferred. The dichroic organic dyes may be used alone or in combination of two or more. In order to obtain absorption in the entire visible light range, it is preferred to use a combination of three or more dichroic dyes, and more preferably a combination of three or more azo dyes. The polyvinyl alcohol resin film is preferably immersed in water before dyeing.

作為偶氮色素,例如可列舉式(I)所表示之化合物。 T 1-A 1(-N=N-A 2) p-N=N-A 3-T 2(I) [式(I)中, A 1、A 2、及A 3分別獨立表示可具有取代基之1,4-伸苯基、萘-1,4-二基、或可具有取代基之2價雜環基,T 1及T 2分別獨立表示拉電子基或推電子基,位於相對於偶氮鍵面內實質上為180°之位置;p表示0~4之整數;於p表示2以上之整數之情形時,複數個A 2相互可相同亦可不同。於偶氮色素在可見光區域顯示吸收之範圍內,-N=N-鍵可被取代為-C=C-鍵、-COO-鍵、-NHCO-鍵、或-N=CH-鍵] As the azo dye, for example, a compound represented by formula (I) can be cited. T 1 -A 1 (-N=NA 2 ) p -N=NA 3 -T 2 (I) [In formula (I), A 1 , A 2 , and A 3 each independently represent a 1,4-phenylene group which may have a substituent, a naphthalene-1,4-diyl group, or a divalent heterocyclic group which may have a substituent; T 1 and T 2 each independently represent an electron-withdrawing group or an electron-donating group, and are located at a position substantially 180° relative to the azo bond plane; p represents an integer of 0 to 4; when p represents an integer greater than 2, a plurality of A 2s may be the same or different from each other. In the range where azo dyes show absorption in the visible light region, the -N=N- bond can be replaced by a -C=C- bond, a -COO- bond, a -NHCO- bond, or a -N=CH- bond.]

作為A 1、A 2、及A 3所表示之1,4-伸苯基、萘-1,4-二基、及2價雜環基任意地具有之取代基,例如可列舉:甲基、乙基、及丁基之類之碳數1~4之烷基;甲氧基、乙氧基、及丁氧基之類之碳數1~4之烷氧基;三氟甲基之類之碳數1~4之氟烷基;氰基;硝基;氯原子及氟原子之類之鹵素原子;胺基、二乙胺基及吡咯啶基之類之經取代之胺基或未經取代之胺基(經取代之胺基係指具有1個或2個碳數1~6之烷基之胺基、或者2個取代烷基相互鍵結而形成碳數2~8之烷二基之胺基;未經取代之胺基為-NH 2)。再者,作為碳數1~6之烷基,例如可列舉甲基、乙基、及己基。作為碳數2~8之烷二基,例如可列舉伸乙基、丙烷-1,3-二基、丁烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基、庚烷-1,7-二基、及辛烷-1,8-二基。為了包含在層列液晶之類之高秩序液晶結構中,A 1、A 2及A 3較佳為表示未經取代或氫原子被取代為甲基或甲氧基之1,4-伸苯基、或2價雜環基,p較佳為表示0~2之整數。其中,p為1且A 1、A 2及A 3之3個結構中之至少2個為1,4-伸苯基就兼具分子合成之簡便性與較高之性能之方面而言更佳。 Examples of the substituents optionally possessed by the 1,4-phenylene group, naphthalene-1,4-diyl group, and divalent heterocyclic group represented by A 1 , A 2 , and A 3 include: alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, and butyl; alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, and butoxy; fluoroalkyl groups having 1 to 4 carbon atoms such as trifluoromethyl; cyano; nitro; halogen atoms such as chlorine and fluorine; substituted or unsubstituted amino groups such as amino, diethylamino, and pyrrolidinyl (the substituted amino group refers to an amino group having 1 or 2 alkyl groups having 1 to 6 carbon atoms, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms; the unsubstituted amino group is -NH 2 ). Furthermore, examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, and hexyl. Examples of the alkanediyl group having 2 to 8 carbon atoms include ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, and octane-1,8-diyl. In order to be included in a high-order liquid crystal structure such as a stratigraphic liquid crystal, A1 , A2 , and A3 preferably represent 1,4-phenylene, which is unsubstituted or in which the hydrogen atom is substituted with a methyl or methoxy group, or a divalent heterocyclic group, and p preferably represents an integer of 0 to 2. Among them, it is more preferable that p is 1 and at least two of the three structures of A 1 , A 2 and A 3 are 1,4-phenylene groups in terms of both simplicity of molecular synthesis and higher performance.

作為2價雜環基,例如可列舉自喹啉、噻唑、苯并噻唑、噻吩并噻唑、咪唑、苯并咪唑、㗁唑、及苯并㗁唑之類之雜環分別去除2個氫原子所得之基。於A 2表示2價雜環基之情形時,較佳為分子鍵角度實質上成為180°之結構,具體而言,更佳為兩個5員環縮合而成之苯并噻唑結構、苯并咪唑結構、及苯并㗁唑結構。 Examples of the divalent heterocyclic group include groups obtained by removing two hydrogen atoms from heterocyclic rings such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxadiazole, and benzoxadiazole. When A2 represents a divalent heterocyclic group, a structure in which the molecular bond angle is substantially 180° is preferred, and more specifically, a benzothiazole structure, a benzimidazole structure, and a benzoxadiazole structure in which two 5-membered rings are condensed are more preferred.

T 1及T 2分別獨立表示拉電子基或推電子基,較佳為表示互不相同之結構之拉電子基或推電子基,進而較佳為T 1表示拉電子基且T 2表示推電子基之情形、或T 1表示推電子基且T 2表示拉電子基之情形。具體而言,T 1及T 2較佳為分別獨立為碳數1~8之烷基、碳數1~8之烷氧基、氰基、硝基、具有1個或2個碳數1~6之烷基之經取代之胺基、2個該取代烷基相互鍵結而形成碳數2~8之烷二基之胺基、及三氟甲基。其中,為了包含在層列液晶之類之高秩序液晶結構中,必須為分子之排斥體積更小之結構體,故而較佳為碳數1~6之烷基、碳數1~6之烷氧基、氰基、具有1個或2個碳數1~6之烷基之經取代之胺基、2個該取代烷基相互鍵結而形成碳數2~8之烷二基之胺基。 T1 and T2 are each independently an electron-withdrawing group or an electron-pushing group, preferably an electron-withdrawing group or an electron-pushing group having different structures, and more preferably T1 is an electron-withdrawing group and T2 is an electron-pushing group, or T1 is an electron-pushing group and T2 is an electron-withdrawing group. Specifically, T1 and T2 are each independently preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, a nitro group, an amino group having 1 or 2 alkyl groups having 1 to 6 carbon atoms, an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms, and a trifluoromethyl group. Among them, in order to be included in a high-order liquid crystal structure such as a stratigraphic liquid crystal, a structure with a smaller molecular repulsion volume is required, and therefore preferably an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, a cyano group, an amino group substituted with 1 or 2 alkyl groups with 1 to 6 carbon atoms, and an amino group in which two of the substituted alkyl groups are bonded to each other to form an alkanediyl group with 2 to 8 carbon atoms.

作為此種偶氮色素,例如可列舉以下之式(2-1)~(2-8)所表示之偶氮色素。Examples of such azo dyes include azo dyes represented by the following formulas (2-1) to (2-8).

[化21] [Chemistry 21]

[化22] [化23] [Chemistry 22] [Chemistry 23]

式(2-1)~(2-8)中, B 1~B 30分別獨立表示氫原子、碳數1~6之烷基、碳數1~6之烷氧基、氰基、硝基、經取代或未經取代之胺基(經取代之胺基及未經取代之胺基之定義如上所述)、氯原子、或三氟甲基。又,就於與層列液晶組合之情形時獲得較高之偏光性能之觀點而言,B 2、B 6、B 9、B 14、B 18、B 19、B 22、B 23、B 24、B 27、B 28、及B 29較佳為分別獨立表示氫原子或甲基,進而較佳為表示氫原子。 n1~n4分別獨立表示0~2之整數。 於n1表示2之情形時,複數個B 2相互可相同亦可不同, 於n2表示2之情形時,複數個B 6相互可相同亦可不同, 於n3表示2之情形時,複數個B 9相互可相同亦可不同, 於n4表示2之情形時,複數個B 14相互可相同亦可不同。 In formulas (2-1) to (2-8), B1 to B30 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, a nitro group, a substituted or unsubstituted amino group (the definitions of the substituted amino group and the unsubstituted amino group are as described above), a chlorine atom, or a trifluoromethyl group. In addition, from the viewpoint of obtaining higher polarization performance when combined with a smectic liquid crystal, B2 , B6 , B9 , B14, B18 , B19 , B22 , B23 , B24 , B27 , B28 , and B29 each independently represent a hydrogen atom or a methyl group, and further preferably represent a hydrogen atom. n1 to n4 each independently represent an integer of 0 to 2. When n1 represents 2, multiple B2s may be the same as or different from each other, when n2 represents 2, multiple B6s may be the same as or different from each other, when n3 represents 2, multiple B9s may be the same as or different from each other, and when n4 represents 2, multiple B14s may be the same as or different from each other.

作為上述蒽醌色素,較佳為式(2-9)所表示之化合物。As the anthraquinone pigment, a compound represented by formula (2-9) is preferred.

[化24] [Chemistry 24]

[式(2-9)中, R 1~R 8分別獨立表示氫原子、-R x、-NH 2、-NHR x、-NR x 2、-SR x、或鹵素原子; R x表示碳數1~4之烷基或碳數6~12之芳基] [In formula (2-9), R 1 to R 8 each independently represent a hydrogen atom, -R x , -NH 2 , -NHR x , -NR x 2 , -SR x , or a halogen atom; R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms]

作為上述㗁𠯤色素,較佳為式(2-10)所表示之化合物。As the above-mentioned chromophore dye, a compound represented by formula (2-10) is preferred.

[化25] [Chemistry 25]

[式(2-10)中, R 9~R 15分別獨立表示氫原子、-R x、-NH 2、-NHR x、-NR x 2、-SR x、或鹵素原子; R x表示碳數1~4之烷基或碳數6~12之芳基] [In formula (2-10), R 9 to R 15 each independently represent a hydrogen atom, -R x , -NH 2 , -NHR x , -NR x 2 , -SR x , or a halogen atom; R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms]

作為上述吖啶色素,較佳為式(2-11)所表示之化合物。As the acridine dye, a compound represented by formula (2-11) is preferred.

[化26] [Chemistry 26]

[式(2-11)中, R 16~R 23分別獨立表示氫原子、-R x、-NH 2、-NHR x、-NR x 2、-SR x、或鹵素原子; R x表示碳數1~4之烷基或碳數6~12之芳基] [In formula (2-11), R 16 to R 23 each independently represent a hydrogen atom, -R x , -NH 2 , -NHR x , -NR x 2 , -SR x , or a halogen atom; R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms]

式(2-9)、式(2-10)及式(2-11)中,作為R x所表示之碳數1~4之烷基,例如可列舉甲基、乙基、丙基、丁基、戊基、及己基。式(2-9)、式(2-10)及式(2-11)中,作為R x所表示之碳數6~12之芳基,例如可列舉苯基、甲苯甲醯基、二甲苯基、及萘基。 In formula (2-9), formula (2-10) and formula (2-11), examples of the alkyl group having 1 to 4 carbon atoms represented by R x include methyl, ethyl, propyl, butyl, pentyl and hexyl. In formula (2-9), formula (2-10) and formula (2-11), examples of the aryl group having 6 to 12 carbon atoms represented by R x include phenyl, toluyl, xylyl and naphthyl.

作為上述花青色素,較佳為式(2-12)所表示之化合物及式(2-13)所表示之化合物。As the above-mentioned cyanine pigment, the compound represented by formula (2-12) and the compound represented by formula (2-13) are preferred.

[化27] [Chemistry 27]

[式(2-12)中, D 1及D 2分別獨立表示式(2-12a)~式(2-12d)之任一者所表示之基; [化28] n5表示1~3之整數] [In formula (2-12), D 1 and D 2 each independently represent a group represented by any one of formulas (2-12a) to (2-12d); [Chemical 28] n5 represents an integer from 1 to 3]

[化29] [Chemistry 29]

[式(2-13)中, D 3及D 4分別獨立表示式(2-13a)~式(2-13h)之任一者所表示之基; [化30] n6表示1~3之整數] [In formula (2-13), D 3 and D 4 each independently represent a group represented by any one of formulas (2-13a) to (2-13h); [Chemical 30] n6 represents an integer from 1 to 3]

就獲得良好之光吸收特性之觀點而言,二色性之有機染料之含量(於包含複數種之情形時為其合計量)相對於聚合性液晶化合物(B)100質量份,通常為0.1~30質量份,較佳為1~20質量份,更佳為3~15質量份。若二色性之有機染料之含量相對於聚合性液晶化合物(B)100質量份為0.1質量份以上,則有二色性之有機染料之光吸收變充分而獲得充分之偏光性能的傾向。若二色性之有機染料之含量相對於聚合性液晶化合物(B)100質量份為30質量份以下,則聚合性液晶化合物之配向不易被妨礙。From the viewpoint of obtaining good light absorption characteristics, the content of the dichroic organic dye (the total amount when multiple types are included) is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 3 to 15 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound (B). If the content of the dichroic organic dye is 0.1 parts by mass or more relative to 100 parts by mass of the polymerizable liquid crystal compound (B), the light absorption of the dichroic organic dye becomes sufficient and there is a tendency to obtain sufficient polarization performance. If the content of the dichroic organic dye is 30 parts by mass or less relative to 100 parts by mass of the polymerizable liquid crystal compound (B), the alignment of the polymerizable liquid crystal compound is not easily hindered.

(吸附有二色性色素之延伸膜) 於吸附有二色性色素之延伸膜之至少一側亦可具備透明保護膜。包含吸附有二色性色素之延伸膜作為偏光元件的膜通常係藉由在偏光元件之至少一面經由接著劑被透明保護膜夾入而製作,該偏光元件係經由如下步驟而製造:將聚乙烯醇系樹脂膜進行單軸延伸之步驟、藉由利用二色性色素對聚乙烯醇系樹脂膜進行染色而吸附該二色性色素之步驟、利用硼酸水溶液對吸附有二色性色素之聚乙烯醇系樹脂膜進行處理之步驟、及於利用硼酸水溶液進行處理後進行水洗之步驟。 (Stretched film adsorbed with dichroic dye) A transparent protective film may also be provided on at least one side of the stretched film adsorbed with dichroic dye. The film including the stretched film adsorbed with dichroic dye as a polarizing element is usually produced by sandwiching the transparent protective film through an adhesive on at least one side of the polarizing element. The polarizing element is produced by the following steps: a step of uniaxially stretching a polyvinyl alcohol resin film, a step of dyeing the polyvinyl alcohol resin film with a dichroic dye to adsorb the dichroic dye, a step of treating the polyvinyl alcohol resin film adsorbed with dichroic dye with a boric acid aqueous solution, and a step of washing with water after the treatment with the boric acid aqueous solution.

聚乙烯醇系樹脂係藉由使聚乙酸乙烯酯系樹脂皂化而獲得。作為聚乙酸乙烯酯系樹脂,例如除了可使用乙酸乙烯酯之均聚物即聚乙酸乙烯酯以外,亦可使用乙酸乙烯酯與能夠與其共聚之其他單體的共聚物。作為能夠與乙酸乙烯酯共聚之其他單體,例如可列舉不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類、及具有銨基之丙烯醯胺類。Polyvinyl alcohol resins are obtained by saponifying polyvinyl acetate resins. As polyvinyl acetate resins, for example, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, copolymers of vinyl acetate and other monomers copolymerizable therewith can also be used. Examples of other monomers copolymerizable therewith include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

聚乙烯醇系樹脂之皂化度通常為85~100莫耳%左右,較佳為98莫耳%以上。聚乙烯醇系樹脂可經改性,例如亦可使用經醛類改性之聚乙烯醇縮甲醛或聚乙烯醇縮乙醛。聚乙烯醇系樹脂之聚合度通常為1,000~10,000左右,較佳為1,500~5,000之範圍。The saponification degree of the polyvinyl alcohol resin is usually about 85-100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin can be modified, for example, polyvinyl formal or polyvinyl acetaldehyde modified with aldehydes can also be used. The polymerization degree of the polyvinyl alcohol resin is usually about 1,000-10,000, preferably in the range of 1,500-5,000.

將此種聚乙烯醇系樹脂製膜而成者係用作偏光膜之坯膜。將聚乙烯醇系樹脂製膜之方法並無特別限定,可使用公知之方法製膜。聚乙烯醇系坯膜之膜厚例如可設為10~150 μm左右。The film formed by forming such a polyvinyl alcohol resin is used as a raw film of a polarizing film. The method of forming the polyvinyl alcohol resin is not particularly limited, and a known method can be used. The film thickness of the raw film of the polyvinyl alcohol can be set to about 10 to 150 μm, for example.

聚乙烯醇系樹脂膜之單軸延伸可於利用二色性色素進行染色之前、與染色同時、或於染色之後進行。於染色之後進行單軸延伸之情形時,該單軸延伸可於硼酸處理之前進行,亦可於硼酸處理中進行。又,亦可於該等複數個階段中進行單軸延伸。於進行單軸延伸時,可於周速不同之輥間單軸地進行延伸,亦可使用熱輥單軸地進行延伸。又,單軸延伸可為於大氣中進行延伸之乾式延伸,亦可為使用溶劑而於使聚乙烯醇系樹脂膜膨潤之狀態下進行延伸之濕式延伸。延伸倍率通常為3~8倍左右。The uniaxial stretching of the polyvinyl alcohol resin film can be performed before dyeing with a dichroic dye, at the same time as dyeing, or after dyeing. When the uniaxial stretching is performed after dyeing, the uniaxial stretching can be performed before the boric acid treatment or during the boric acid treatment. Furthermore, the uniaxial stretching can be performed in these multiple stages. When performing the uniaxial stretching, the uniaxial stretching can be performed between rollers with different peripheral speeds, or the uniaxial stretching can be performed using a hot roller. Furthermore, the uniaxial stretching can be dry stretching performed in the atmosphere, or wet stretching performed using a solvent while the polyvinyl alcohol resin film is swollen. The stretching ratio is usually about 3 to 8 times.

聚乙烯醇系樹脂膜之利用二色性色素進行之染色例如係藉由將聚乙烯醇系樹脂膜浸漬於含有二色性色素之水溶液中之方法而進行。The polyvinyl alcohol-based resin film is dyed with a dichroic dye by, for example, immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye.

於將碘用作二色性色素之情形時,通常採用將聚乙烯醇系樹脂膜浸漬於含有碘及碘化鉀之水溶液中進行染色之方法。該水溶液中之碘之含量相對於水100質量份,通常為0.01~1質量份左右。又,碘化鉀之含量相對於水100質量份,通常為0.5~20質量份左右。用於染色之水溶液之溫度通常為20~40℃左右。又,向該水溶液之浸漬時間(染色時間)通常為20~1,800秒左右。When iodine is used as a dichroic dye, a method of dyeing is usually adopted in which a polyvinyl alcohol-based resin film is immersed in an aqueous solution containing iodine and potassium iodide. The content of iodine in the aqueous solution is usually about 0.01 to 1 mass part relative to 100 mass parts of water. In addition, the content of potassium iodide is usually about 0.5 to 20 mass parts relative to 100 mass parts of water. The temperature of the aqueous solution used for dyeing is usually about 20 to 40°C. In addition, the immersion time in the aqueous solution (dyeing time) is usually about 20 to 1,800 seconds.

另一方面,於使用二色性之有機染料作為二色性色素之情形時,通常採用將聚乙烯醇系樹脂膜浸漬於包含水溶性二色性染料之水溶液進行染色之方法。該水溶液中之二色性有機染料之含量相對於水100質量份,通常為1×10 -4~10質量份左右,較佳為1×10 -3~1質量份,進而較佳為1×10 -3~1×10 -2質量份。該水溶液亦可包含硫酸鈉等無機鹽作為染色助劑。用於染色之二色性染料水溶液之溫度通常為20~80℃左右。又,向該水溶液之浸漬時間(染色時間)通常為10~1,800秒左右。 On the other hand, when a dichroic organic dye is used as a dichroic pigment, a method of dyeing is usually adopted in which a polyvinyl alcohol-based resin film is immersed in an aqueous solution containing a water-soluble dichroic dye. The content of the dichroic organic dye in the aqueous solution is usually about 1× 10-4 to 10 parts by mass, preferably 1× 10-3 to 1 part by mass, and further preferably 1× 10-3 to 1× 10-2 parts by mass relative to 100 parts by mass of water. The aqueous solution may also contain an inorganic salt such as sodium sulfate as a dyeing auxiliary. The temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80°C. In addition, the immersion time (dyeing time) in the aqueous solution is usually about 10 to 1,800 seconds.

利用二色性色素進行染色後之硼酸處理通常可藉由將經染色之聚乙烯醇系樹脂膜浸漬於硼酸水溶液之方法而進行。該硼酸水溶液中之硼酸之含量相對於水100質量份,通常為2~15質量份左右,較佳為5~12質量份。於使用碘作為二色性色素之情形時,該硼酸水溶液較佳為含有碘化鉀,該情形時之碘化鉀之含量相對於水100質量份,通常為0.1~15質量份左右,較佳為5~12質量份。向硼酸水溶液之浸漬時間通常為60~1,200秒左右,較佳為150~600秒,進而較佳為200~400秒。硼酸處理之溫度通常為50℃以上,較佳為50~85℃,進而較佳為60~80℃。The boric acid treatment after dyeing with a dichroic dye can usually be performed by immersing the dyed polyvinyl alcohol-based resin film in an aqueous boric acid solution. The content of boric acid in the aqueous boric acid solution is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass, relative to 100 parts by mass of water. When iodine is used as the dichroic dye, the aqueous boric acid solution preferably contains potassium iodide, and the content of potassium iodide in this case is usually about 0.1 to 15 parts by mass, preferably 5 to 12 parts by mass, relative to 100 parts by mass of water. The immersion time in the aqueous boric acid solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and further preferably 200 to 400 seconds. The temperature of the boric acid treatment is usually above 50°C, preferably 50-85°C, and further preferably 60-80°C.

硼酸處理後之聚乙烯醇系樹脂膜通常進行水洗處理。水洗處理例如可藉由將經硼酸處理之聚乙烯醇系樹脂膜浸漬於水中之方法進行。水洗處理中之水之溫度通常為5~40℃左右。又,浸漬時間通常為1~120秒左右。The polyvinyl alcohol resin film treated with boric acid is usually washed with water. The washing treatment can be performed, for example, by immersing the polyvinyl alcohol resin film treated with boric acid in water. The temperature of the water in the washing treatment is usually about 5 to 40°C. The immersion time is usually about 1 to 120 seconds.

於水洗後實施乾燥處理而獲得偏光元件。乾燥處理例如可使用熱風乾燥機或遠紅外線加熱器進行。乾燥處理之溫度通常為30~100℃左右,較佳為50~80℃。乾燥處理之時間通常為60~600秒左右,較佳為120~600秒。藉由乾燥處理,偏光元件之水分率降低至實用程度。該水分率通常為5~20質量%左右,較佳為8~15質量%。若水分率低於5質量%,則有失去偏光元件之可撓性,偏光元件於其乾燥後損傷或破斷之情況。又,若水分率高於20質量%,則有偏光元件之熱穩定變差之可能性。After washing with water, drying treatment is performed to obtain a polarizing element. Drying treatment can be performed, for example, using a hot air dryer or a far infrared heater. The temperature of the drying treatment is usually about 30 to 100°C, preferably 50 to 80°C. The time of the drying treatment is usually about 60 to 600 seconds, preferably 120 to 600 seconds. Through the drying treatment, the moisture content of the polarizing element is reduced to a practical level. The moisture content is usually about 5 to 20 mass%, preferably 8 to 15 mass%. If the moisture content is lower than 5 mass%, the flexibility of the polarizing element may be lost, and the polarizing element may be damaged or broken after drying. In addition, if the moisture content is higher than 20 mass%, the thermal stability of the polarizing element may deteriorate.

如此對聚乙烯醇系樹脂膜進行單軸延伸、利用二色性色素之染色、硼酸處理、水洗及乾燥而獲得之偏光元件之厚度較佳為5~40 μm。The thickness of the polarizing element obtained by uniaxially stretching the polyvinyl alcohol resin film, dyeing with a dichroic pigment, treating with boric acid, washing with water and drying is preferably 5 to 40 μm.

<有機EL顯示裝置> 有機EL顯示裝置包含上述橢圓偏光板。作為有機EL顯示裝置之較佳之態樣,例如可列舉經由黏著劑將橢圓偏光板貼合於有機EL面板而成之裝置。 [實施例] <Organic EL display device> The organic EL display device includes the above-mentioned elliptical polarizing plate. As a preferred embodiment of the organic EL display device, for example, a device in which the elliptical polarizing plate is bonded to the organic EL panel via an adhesive can be cited. [Example]

以下,藉由實施例對本發明更具體地進行說明。再者,例中之「%」及「份」只要無特別記載,則分別意指質量%及質量份。Hereinafter, the present invention will be described in more detail by way of examples. In addition, "%" and "parts" in the examples mean mass % and mass parts, respectively, unless otherwise specified.

[液晶化合物之製備] 液晶化合物A係依據日本專利特開2010-31223號公報所記載之方法製造。又,液晶化合物B係依據日本專利特開2009-173893號公報所記載之方法製造。以下,分別表示液晶化合物A及液晶化合物B之分子結構。 [Preparation of Liquid Crystal Compounds] Liquid crystal compound A is prepared according to the method described in Japanese Patent Publication No. 2010-31223. Liquid crystal compound B is prepared according to the method described in Japanese Patent Publication No. 2009-173893. The molecular structures of liquid crystal compound A and liquid crystal compound B are shown below.

(液晶化合物A) [化31] (Liquid crystal compound A) [Chemical 31]

(液晶化合物B) [化32] (Liquid crystal compound B) [Chemical 32]

[測定方法] (極大吸收波長及最大吸光度之比之算出方法) 製備液晶化合物A之1 mg/50 mL四氫呋喃溶液,作為測定用試樣。將測定用試樣放入至光程長1 cm之測定用單元。將測定用試樣設置於紫外可見分光光度計(島津製作所股份有限公司製造之「UV-2450」),測定吸收光譜。再者,對照係設為僅測定用試樣之溶劑。自獲得之吸收光譜讀取成為極大吸收度之波長,將其設為極大吸收波長λ max。進而,自獲得之吸收光譜讀取波長260 nm以上400 nm以下之區域中之液晶化合物A之極大吸收波長。再者,於在波長260 nm以上400 nm以下之區域存在複數之極大吸收波長之情形時,將複數之極大吸收波長之中吸光度最高之波長設為λ max。將獲得之極大吸收波長示於表1。 [Measurement method] (Calculation method of the ratio of the maximum absorption wavelength and the maximum absorbance) Prepare a 1 mg/50 mL tetrahydrofuran solution of liquid crystal compound A as a measurement sample. Place the measurement sample in a measurement unit with an optical path length of 1 cm. Set the measurement sample in an ultraviolet-visible spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation) and measure the absorption spectrum. In addition, the control is set to the solvent of the measurement sample only. Read the wavelength of maximum absorbance from the obtained absorption spectrum, and set it as the maximum absorption wavelength λ max . Furthermore, read the maximum absorption wavelength of liquid crystal compound A in the wavelength region above 260 nm and below 400 nm from the obtained absorption spectrum. Furthermore, when there are multiple maximum absorption wavelengths in the wavelength region of 260 nm to 400 nm, the wavelength with the highest absorbance among the multiple maximum absorption wavelengths is set as λ max . The obtained maximum absorption wavelengths are shown in Table 1.

[離子性化合物之製備] 離子性化合物(1)係依據日本專利特願2016-514802號公報所記載之方法製造。又,離子性化合物(2)及離子性化合物(3)係依據日本專利特開2013-28586號公報或日本專利特開2013-199509號公報所記載之方法製造。以下,分別表示離子性化合物(1)~(3)之結構式。 [Preparation of ionic compounds] Ionic compound (1) is produced according to the method described in Japanese Patent Application No. 2016-514802. Ionic compound (2) and ionic compound (3) are produced according to the method described in Japanese Patent Application No. 2013-28586 or Japanese Patent Application No. 2013-199509. The structural formulas of ionic compounds (1) to (3) are shown below.

(離子性化合物(1)) [化33] (離子性化合物(2)) [化34] (離子性化合物(3)) [化35] (Ionic compound (1)) [Chemistry 33] (Ionic compound (2)) [Chemistry 34] (Ionic compound (3)) [Chemical 35]

<實施例1> [垂直配向液晶硬化膜形成用組合物(A-1)之製備] 以質量比90:10混合液晶化合物A及液晶化合物B,獲得混合物。相對於獲得之混合物100質量份,添加調平劑(DIC公司製造之「F-556」)1.5質量份、及作為光聚合起始劑之2-二甲基胺基-2-苄基-1-(4-𠰌啉基苯基)丁烷-1-酮(BASF Japan股份有限公司製造之「Irgacure(註冊商標)369(Irg369)」)6質量份。又,進而以成為0.5%之方式添加作為矽烷化合物之3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺(信越化學工業股份有限公司製造之「KBE-9103」),以成為2.0%之方式添加離子性化合物(1)。 <Example 1> [Preparation of a composition for forming a vertically aligned liquid crystal cured film (A-1)] A liquid crystal compound A and a liquid crystal compound B were mixed at a mass ratio of 90:10 to obtain a mixture. 1.5 parts by mass of a leveling agent ("F-556" manufactured by DIC Corporation) and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-oxo-1-phenyl)butane-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator were added to 100 parts by mass of the obtained mixture. Furthermore, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine ("KBE-9103" manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a silane compound in an amount of 0.5%, and an ionic compound (1) was added in an amount of 2.0%.

以固形物成分濃度成為13%之方式添加N-甲基-2-吡咯啶酮(NMP)。於80℃下攪拌1小時,藉此獲得垂直配向液晶硬化膜形成用組合物(A-1)(以下,有時記載為組合物(A-1))。再者,確認矽烷化合物(信越化學工業股份有限公司製造之「KBE-9103」)於組合物(A-1)中與溶劑或環境中之水分反應而進行水解,生成作為極性基之胺基。N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. The mixture was stirred at 80°C for 1 hour to obtain a composition (A-1) for forming a vertically aligned liquid crystal cured film (hereinafter, sometimes referred to as composition (A-1)). Furthermore, it was confirmed that the silane compound ("KBE-9103" manufactured by Shin-Etsu Chemical Co., Ltd.) reacted with the moisture in the solvent or the environment in the composition (A-1) and hydrolyzed to generate an amino group as a polar group.

[垂直配向液晶硬化膜(A-1)之製作方法] 使用電暈處理裝置(春日電機股份有限公司製造之「AGF-B10」)對作為基材之非晶質環烯烴聚合物膜(COP膜)(Zeon corporation股份有限公司「ZF-14-23」)於輸出0.3 kW及處理速度3 m/分鐘之條件下實施1次電暈處理。使用棒式塗佈機於實施過電暈處理之基材之表面塗佈組合物(A-1)而形成塗佈膜。將塗佈膜於120℃下乾燥1分鐘而形成乾燥覆膜。繼而,使用高壓水銀燈(牛尾電機股份有限公司製造之「UNICURE VB-15201BY-A」),於氮氣氛圍下及波長365 nm下之累計光量500 mJ/cm 2之條件下,對乾燥覆膜照射紫外線。其結果,形成垂直配向液晶硬化膜(A-1)(膜厚:1.0 μm)。 [Method for preparing vertically aligned liquid crystal cured film (A-1)] A corona treatment device ("AGF-B10" manufactured by Kasuga Electric Co., Ltd.) was used to perform a corona treatment once on an amorphous cycloolefin polymer film (COP film) ("Zeon Corporation" ZF-14-23) as a substrate at an output of 0.3 kW and a treatment speed of 3 m/min. The composition (A-1) was applied to the surface of the corona-treated substrate using a rod coater to form a coating film. The coating film was dried at 120°C for 1 minute to form a dry coating film. Then, the dried film was irradiated with ultraviolet light using a high-pressure mercury lamp ("UNICURE VB-15201BY-A" manufactured by Ushio Electric Co., Ltd.) in a nitrogen atmosphere at a wavelength of 365 nm with a cumulative light intensity of 500 mJ/ cm2 . As a result, a vertically aligned liquid crystal cured film (A-1) (film thickness: 1.0 μm) was formed.

[垂直配向液晶硬化膜(A-1)之光學特性] 將獲得之垂直配向液晶硬化膜(A-1)經由黏著劑(LINTEC公司製造之感壓式黏著劑 15 μm)與玻璃進行貼合,製作光學特性測定用樣品。 [Optical properties of vertically aligned liquid crystal cured film (A-1)] The obtained vertically aligned liquid crystal cured film (A-1) was bonded to glass via an adhesive (pressure-sensitive adhesive 15 μm manufactured by LINTEC) to prepare a sample for measuring optical properties.

(相位差值之測定) 確認作為基材之ZF-14-23係波長550 nm下之相位差值R F(550)為1 nm以下之光學各向同性膜,對光學特性測定用樣品之測定值不產生影響。繼而,使用測定機(王子計測公司製造之「KOBRA-WPR」),改變光對光學特性測定用樣品之入射角,測定相位差值。 (Measurement of phase difference) It was confirmed that the ZF-14-23 used as the substrate is an optically isotropic film with a phase difference value RF (550) of less than 1 nm at a wavelength of 550 nm, and that it has no effect on the measured value of the sample for optical property measurement. Then, using a measuring machine ("KOBRA-WPR" manufactured by Oji Instruments), the phase difference value was measured by changing the incident angle of light on the sample for optical property measurement.

(平均折射率之測定) 波長λ=450 nm及550 nm下之平均折射率係使用折射率計(Atago股份有限公司製造之「多波長阿貝折射計DR-M4」)進行測定。根據獲得之膜厚、平均折射率、及測定機(王子計測機器股份有限公司製造之「KOBRA-WPR」)之測定結果算出之Rth分別為Rth(450)=-60 nm、Rth(550)=-70 nm,Rth(450)/Rth(550)=0.85。 (Measurement of average refractive index) The average refractive index at wavelength λ = 450 nm and 550 nm was measured using a refractometer ("Multi-wavelength Abbe Refractometer DR-M4" manufactured by Atago Co., Ltd.). The Rth calculated based on the obtained film thickness, average refractive index, and the measurement results of the measuring machine ("KOBRA-WPR" manufactured by Oji Testing Instruments Co., Ltd.) was Rth(450) = -60 nm, Rth(550) = -70 nm, and Rth(450)/Rth(550) = 0.85.

(配向液晶硬化膜之配向性評價) 使用偏光顯微鏡(Olympus股份有限公司製造之「BX-51」),於倍率200倍之條件下進行觀察,對視野480 μm×320 μm下之配向缺陷數進行計數。此處,僅對起因於測定用樣品之配向缺陷數進行計數,起因於光學特性樣品以外之環境異物等之缺陷數被排除而不進行計數。根據利用偏光顯微鏡進行觀察之結果,基於以下之評價基準對垂直配向液晶硬化膜(A-1)之配向性進行評價。將A、B及C判斷為配向性優異。如表1所示,利用組合物(A-1)所製作之垂直配向液晶硬化膜(A-1)之配向性為A。 (評價基準) A(極為良好):配向缺陷數為0個以上3個以下。 B(非常良好):配向缺陷數為4個以上10個以下。 C(良好):配向缺陷數為11個以上50個以下。 D(差):配向缺陷數為51個以上或完全未配向。 (Evaluation of the alignment of the oriented liquid crystal cured film) Using a polarizing microscope ("BX-51" manufactured by Olympus Co., Ltd.), observation was performed at a magnification of 200 times, and the number of alignment defects under a field of view of 480 μm×320 μm was counted. Here, only the number of alignment defects caused by the sample for measurement was counted, and the number of defects caused by environmental foreign matter other than the optical characteristic sample was excluded and not counted. Based on the results of observation using a polarizing microscope, the alignment of the vertically aligned liquid crystal cured film (A-1) was evaluated based on the following evaluation criteria. A, B, and C were judged to have excellent alignment. As shown in Table 1, the alignment of the vertically aligned liquid crystal cured film (A-1) prepared using the composition (A-1) is A. (Evaluation criteria) A (extremely good): The number of alignment defects is 0 or more and 3 or less. B (very good): The number of alignment defects is 4 or more and 10 or less. C (good): The number of alignment defects is 11 or more and 50 or less. D (poor): The number of alignment defects is 51 or more or no alignment at all.

<實施例2~9、實施例20、實施例21、及比較例1> 將實施例1之基材、矽烷化合物0.5%、及離子性化合物(2)2%變更為表1所記載之基材之種類、矽烷化合物之種類及添加量、以及離子性化合物之種類及添加量,除此以外,以與實施例1之組合物(A-1)之製備方法相同之方式分別製備實施例2~9及實施例20、實施例21、比較例1之組合物(A-2)~(A-9)、(A-20)、(A-21)、及(B-1)。將組合物(A-1)變更為組合物(A-2)~(A-9)、(A-20)、(A-21)、及(B-1),進而變更塗佈膜之膜厚,以成為表1所示之相位差值之方式進行變更,除此以外,以與實施例1之垂直配向液晶硬化膜(A-1)之製作方法相同之方式,分別製作實施例2~9、實施例20、實施例21、及比較例1之垂直配向液晶硬化膜(A-2)~(A-9)、(A-20)、(A-21)、及(B-1)。又,以與實施例1相同之方法,製作光學特性測定用樣品,並評價相位差值、平均折射率及配向性。將結果示於表1。 <Examples 2 to 9, Example 20, Example 21, and Comparative Example 1> Examples 2 to 9, Example 20, Example 21, and Comparative Example 1 were prepared in the same manner as the preparation method of the composition (A-1) of Example 1, except that the substrate, 0.5% of the silane compound, and 2% of the ionic compound (2) of Example 1 were changed to the type of substrate, the type and amount of the silane compound, and the type and amount of the ionic compound recorded in Table 1. Compositions (A-2) to (A-9), (A-20), (A-21), and (B-1) of Examples 2 to 9, Example 20, Example 21, and Comparative Example 1 were prepared. Composition (A-1) was changed to compositions (A-2) to (A-9), (A-20), (A-21), and (B-1), and the film thickness of the coating film was changed to achieve the phase difference value shown in Table 1. In addition, in the same manner as the preparation method of the vertically aligned liquid crystal cured film (A-1) of Example 1, vertically aligned liquid crystal cured films (A-2) to (A-9), (A-20), (A-21), and (B-1) of Examples 2 to 9, Example 20, Example 21, and Comparative Example 1 were prepared. In addition, samples for measuring optical properties were prepared in the same manner as in Example 1, and the phase difference value, average refractive index, and orientation were evaluated. The results are shown in Table 1.

<實施例10> 將基材自COP膜(Zeon corporation股份有限公司製造之「ZF-14-23」)變更為附保護層之聚對苯二甲酸乙二酯(以下,有時記載為附保護層之PET),且於光學特性測定時剝離PET基材而製作樣品,除此以外,以與實施例1之垂直配向液晶硬化膜(A-1)之製備方法相同之方式,製備垂直配向液晶硬化膜(A-10)。又,以與實施例1相同之方法,製作光學特性測定用樣品,並評價相位差值、平均折射率及配向性。將結果示於表1。以下,對附保護層之PET之製備方法進行說明。 <Example 10> The substrate was changed from a COP film ("ZF-14-23" manufactured by Zeon Corporation) to a polyethylene terephthalate with a protective layer (hereinafter, sometimes described as PET with a protective layer), and the PET substrate was peeled off during the optical property measurement to prepare a sample. In addition, a vertically aligned liquid crystal cured film (A-10) was prepared in the same manner as the preparation method of the vertically aligned liquid crystal cured film (A-1) of Example 1. In addition, a sample for optical property measurement was prepared in the same manner as Example 1, and the phase difference value, average refractive index and orientation were evaluated. The results are shown in Table 1. The preparation method of PET with a protective layer is described below.

[保護層形成用組合物之製備] 將二季戊四醇六丙烯酸酯(東亞合成股份有限公司製造之「ARONIX(註冊商標)M-403」多官能丙烯酸酯)50份、丙烯酸酯樹脂(Daicel - UCB股份有限公司製造之「Ebecryl 4858」)50份、及2-甲基-1[4-(甲硫基)苯基]-2-𠰌啉基丙烷-1-酮(Ciba Specialty Chemicals公司製造之「Irgacure(註冊商標)907」)3份溶解於異丙醇250份中,製備溶液。將獲得之溶液設為保護層形成用組合物。 [Preparation of a composition for forming a protective layer] 50 parts of dipentaerythritol hexaacrylate ("ARONIX (registered trademark) M-403" multifunctional acrylate manufactured by Toagosei Co., Ltd.), 50 parts of an acrylate resin ("Ebecryl 4858" manufactured by Daicel-UCB Co., Ltd.), and 3 parts of 2-methyl-1[4-(methylthio)phenyl]-2-oxopropane-1-one ("Irgacure (registered trademark) 907" manufactured by Ciba Specialty Chemicals Co., Ltd.) were dissolved in 250 parts of isopropyl alcohol to prepare a solution. The obtained solution was used as a composition for forming a protective layer.

[附保護層之PET之製造] 使用棒式塗佈機,於PET膜(膜厚38 μm)上塗佈保護層形成用組合物而形成塗佈膜。將塗佈膜於50℃下乾燥1分鐘,形成乾燥覆膜。使用高壓水銀燈(牛尾電機股份有限公司製造之「UNICURE VB-15201BY-A」),於氮氣氛圍下及波長365 nm下之累計光量400 mJ/cm 2之條件下,對乾燥覆膜照射紫外線。其結果,形成包含丙烯酸系樹脂之附保護層之PET。再者,依據實施例1所記載之光學特性測定方法,經由黏著劑貼合於玻璃,剝離PET膜後,測定保護層於波長550 nm下之相位差值,結果為1 nm以下,確認為光學各向同性膜。又,利用橢偏計測定形成之保護層之膜厚,結果為2 μm。 [Manufacturing of PET with protective layer] A coating film was formed by coating a protective layer-forming composition on a PET film (film thickness 38 μm) using a bar coater. The coated film was dried at 50°C for 1 minute to form a dry coating film. A high-pressure mercury lamp ("UNICURE VB-15201BY-A" manufactured by Ushio Electric Co., Ltd.) was used to irradiate the dry coating film with ultraviolet light at a wavelength of 365 nm and a cumulative light amount of 400 mJ/ cm2 in a nitrogen atmosphere. As a result, a PET with a protective layer containing an acrylic resin was formed. Furthermore, according to the optical property measurement method described in Example 1, after being bonded to glass with an adhesive and the PET film peeled off, the phase difference value of the protective layer at a wavelength of 550 nm was measured, and the result was less than 1 nm, confirming that it was an optically isotropic film. In addition, the film thickness of the formed protective layer was measured using an elliptometer, and the result was 2 μm.

<實施例11> 將實施例1之液晶化合物之組成自液晶化合物A/液晶化合物B=90%/10%變更為液晶化合物(A)-2 100%,除此以外,以與實施例1之組合物(A-1)及垂直配向液晶硬化膜(A-1)之製備方法相同之方式,分別製作實施例11之組合物(A-11)及垂直配向液晶硬化膜(A-11)。液晶化合物(A)-2係參考日本專利特開2016-81035號公報而製備。液晶化合物(A)-2係由下述式(A)-2所表示。又,以與實施例1相同之方法,製作測定用樣品,並評價相位差值、平均折射率及配向性。進而,以與實施例1相同之方式亦算出液晶化合物(A)-2之極大吸收波長及最大吸光度之比。將結果示於表1。 [化36] <Example 11> The composition of the liquid crystal compound of Example 1 is changed from liquid crystal compound A/liquid crystal compound B=90%/10% to liquid crystal compound (A)-2 100%. In addition, the composition (A-11) and the vertically aligned liquid crystal cured film (A-1) of Example 1 are prepared in the same manner as the preparation method of the composition (A-1) and the vertically aligned liquid crystal cured film (A-1) of Example 1. Liquid crystal compound (A)-2 is prepared with reference to Japanese Patent Publication No. 2016-81035. Liquid crystal compound (A)-2 is represented by the following formula (A)-2. In addition, a sample for measurement is prepared in the same manner as in Example 1, and the phase difference value, average refractive index and alignment are evaluated. Furthermore, the ratio of the maximum absorption wavelength and the maximum absorbance of the liquid crystal compound (A)-2 is also calculated in the same manner as in Example 1. The results are shown in Table 1.

<實施例12> 將實施例1之液晶化合物之組成自液晶化合物A/液晶化合物B=90%/10%變更為液晶化合物(A)-3 100%,除此以外,以與實施例1之組合物(A-1)及垂直配向液晶硬化膜(A-1)之製備方法相同之方式,分別製作實施例12之組合物(A-12)及垂直配向液晶硬化膜(A-12)。液晶化合物(A)-3係參考國際專利公開2015/025793號公報進行製備。液晶化合物(A)-3係由下述式(A)-3所表示。又,利用與實施例1相同之方法,製作光學特性測定用樣品,並評價相位差值、平均折射率及配向性。進而,以與實施例1相同之方式亦算出液晶化合物(A)-3之極大吸收波長及最大吸光度之比。將結果示於表1。 [化37] <Example 12> The composition of the liquid crystal compound of Example 1 was changed from liquid crystal compound A/liquid crystal compound B=90%/10% to liquid crystal compound (A)-3 100%. In addition, the composition (A-12) and the vertically aligned liquid crystal cured film (A-12) of Example 12 were prepared in the same manner as the preparation method of the composition (A-1) and the vertically aligned liquid crystal cured film (A-1) of Example 1. Liquid crystal compound (A)-3 was prepared with reference to International Patent Publication No. 2015/025793. Liquid crystal compound (A)-3 is represented by the following formula (A)-3. In addition, samples for measuring optical properties were prepared using the same method as in Example 1, and the phase difference value, average refractive index and alignment were evaluated. Furthermore, the ratio of the maximum absorption wavelength and the maximum absorbance of the liquid crystal compound (A)-3 was calculated in the same manner as in Example 1. The results are shown in Table 1.

<實施例13> 將實施例1之液晶化合物之組成自液晶化合物A/液晶化合物B=90%/10%變更為液晶化合物(A)-4 100%,除此以外,以與實施例1之組合物(A-1)及垂直配向液晶硬化膜(A-1)之製備方法相同之方式,分別製作實施例11之組合物(A-13)及垂直配向液晶硬化膜(A-13)。液晶化合物(A)-4係參考日本專利特開2011-207765號公報進行製備。液晶化合物(A)-4係由下述式(A)-4所表示。又,以與實施例1相同之方法,製作光學特性測定用樣品,並評價相位差值、平均折射率及配向性。進而,以與實施例1相同之方式亦算出液晶化合物(A)-4之極大吸收波長及最大吸光度之比。將結果示於表1。 [化38] <Example 13> The composition of the liquid crystal compound of Example 1 was changed from liquid crystal compound A/liquid crystal compound B=90%/10% to liquid crystal compound (A)-4 100%. In addition, the composition (A-13) and the vertically aligned liquid crystal cured film (A-13) of Example 11 were prepared in the same manner as the preparation method of the composition (A-1) and the vertically aligned liquid crystal cured film (A-1) of Example 1. Liquid crystal compound (A)-4 was prepared with reference to Japanese Patent Publication No. 2011-207765. Liquid crystal compound (A)-4 is represented by the following formula (A)-4. In addition, a sample for measuring optical properties was prepared in the same manner as in Example 1, and the phase difference value, average refractive index and alignment were evaluated. Furthermore, the ratio of the maximum absorption wavelength and the maximum absorbance of the liquid crystal compound (A)-4 was calculated in the same manner as in Example 1. The results are shown in Table 1.

<實施例14> 將實施例1之液晶化合物之組成自液晶化合物A/液晶化合物B=90%/10%變更為液晶化合物(A)-5 100%,除此以外,以與實施例1之組合物(A-1)及垂直配向液晶硬化膜(A-1)之製備方法相同之方式,分別製作實施例14之組合物(A-14)及垂直配向液晶硬化膜(A-14)。液晶化合物(A)-5係參考日本專利特開2010-31223號公報進行製備。液晶化合物(A)-5係由下述式(A)-5所表示。又,以與實施例1相同之方法,製作光學特性測定用樣品,並評價相位差值、平均折射率及配向性。進而,以與實施例1相同之方式亦算出液晶化合物(A)-5之極大吸收波長及最大吸光度之比。將結果示於表1。 [化39] <Example 14> The composition of the liquid crystal compound of Example 1 was changed from liquid crystal compound A/liquid crystal compound B=90%/10% to liquid crystal compound (A)-5 100%. In addition, the composition (A-14) and the vertically aligned liquid crystal cured film (A-14) of Example 14 were prepared in the same manner as the preparation method of the composition (A-1) and the vertically aligned liquid crystal cured film (A-1) of Example 1. Liquid crystal compound (A)-5 was prepared with reference to Japanese Patent Publication No. 2010-31223. Liquid crystal compound (A)-5 is represented by the following formula (A)-5. In addition, a sample for measuring optical properties was prepared in the same manner as in Example 1, and the phase difference value, average refractive index and alignment were evaluated. Furthermore, the ratio of the maximum absorption wavelength and the maximum absorbance of the liquid crystal compound (A)-5 was calculated in the same manner as in Example 1. The results are shown in Table 1.

<實施例15> 將實施例1之矽烷化合物自3-三乙氧基矽烷基-N-(1,3-二甲基-亞丁基)丙基胺(信越化學工業股份有限公司製造之「KBE-9103」)變更為3-縮水甘油氧基丙基三乙氧基矽烷(信越化學工業股份有限公司製造之「KBE-403」),除此以外,以與實施例1之組合物(A-1)及垂直配向液晶硬化膜(A-1)之製備方法相同之方式,分別製作實施例15之組合物(A-15)及垂直配向液晶硬化膜(A-15)。又,以與實施例1相同之方法,製作光學特性測定用樣品,並評價相位差值、平均折射率及配向性。將結果示於表1。 <Example 15> The silane compound of Example 1 was changed from 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine ("KBE-9103" manufactured by Shin-Etsu Chemical Co., Ltd.) to 3-glycidyloxypropyltriethoxysilane ("KBE-403" manufactured by Shin-Etsu Chemical Co., Ltd.). In addition, the composition (A-15) and the vertical alignment liquid crystal cured film (A-15) of Example 15 were prepared in the same manner as the preparation method of the composition (A-1) and the vertical alignment liquid crystal cured film (A-1) of Example 1. In addition, the sample for measuring optical properties was prepared in the same manner as Example 1, and the phase difference value, average refractive index and alignment were evaluated. The results are shown in Table 1.

<實施例16> [偏光膜A之製造] 將聚乙烯醇膜(平均聚合度約2,400、皂化度99.9莫耳%以上、厚度75 μm)浸漬於30℃之純水後,於30℃下浸漬於碘/碘化鉀/水之質量比為0.02/2/100之水溶液進行碘染色(碘染色步驟)。將經過碘染色步驟之聚乙烯醇膜於56.5℃下浸漬於碘化鉀/硼酸/水之質量比為12/5/100之水溶液進行硼酸處理(硼酸處理步驟)。將經過硼酸處理步驟之聚乙烯醇膜利用8℃之純水洗淨後,於65℃下乾燥,獲得碘吸附配向於聚乙烯醇而成之偏光元件(延伸後之厚度27 μm)。此時,於碘染色步驟與硼酸處理步驟中進行延伸。該延伸中之總延伸倍率為5.3倍。將獲得之偏光元件與經皂化處理之三乙醯纖維素膜(Konica Minolta製造之「KC4UYTAC」40 μm)經由水系接著劑利用夾輥進行貼合。將所獲得之貼合物之張力保持於430 N/m,並於60℃下乾燥2分鐘,獲得單面具有三乙醯纖維素膜作為保護膜之偏光膜A。再者,上述水系接著劑係於水100份中添加羧基改性聚乙烯醇(Kuraray製造之「Kuraray Poval KL318」)3份、及水溶性聚醯胺環氧樹脂(Sumika Chemtex製造之「Sumirez Resin 650」、固形物成分濃度30%之水溶液)1.5份而製備。 <Example 16> [Manufacturing of polarizing film A] A polyvinyl alcohol film (average degree of polymerization of about 2,400, saponification degree of 99.9 mol% or more, thickness of 75 μm) was immersed in pure water at 30°C, and then immersed in an aqueous solution of iodine/potassium iodide/water with a mass ratio of 0.02/2/100 at 30°C for iodine dyeing (iodine dyeing step). The polyvinyl alcohol film that had undergone the iodine dyeing step was immersed in an aqueous solution of potassium iodide/boric acid/water with a mass ratio of 12/5/100 at 56.5°C for boric acid treatment (boric acid treatment step). The polyvinyl alcohol film that had undergone the boric acid treatment step was washed with pure water at 8°C, and then dried at 65°C to obtain a polarizing element formed by iodine adsorption and alignment on polyvinyl alcohol (thickness 27 μm after stretching). At this time, the film was stretched during the iodine dyeing step and the boric acid treatment step. The total stretching ratio in the stretching was 5.3 times. The obtained polarizing element was bonded to the saponified triacetyl cellulose film ("KC4UYTAC" 40 μm manufactured by Konica Minolta) using a water-based adhesive and a roller. The tension of the obtained bond was maintained at 430 N/m and dried at 60°C for 2 minutes to obtain a polarizing film A having a triacetyl cellulose film as a protective film on one side. Furthermore, the above-mentioned water-based adhesive is prepared by adding 3 parts of carboxyl-modified polyvinyl alcohol ("Kuraray Poval KL318" manufactured by Kuraray) and 1.5 parts of water-soluble polyamide epoxy resin ("Sumirez Resin 650" manufactured by Sumika Chemtex, an aqueous solution with a solid content concentration of 30%) to 100 parts of water.

[偏光膜A之光學特性之測定] 對獲得之偏光膜A進行光學特性之測定。測定係將上述所獲得之偏光膜A之偏光元件面作為入射面,利用分光光度計(日本分光製造之「V7100」)實施。偏光膜之吸收軸與聚乙烯醇之延伸方向一致,所獲得之偏光膜之視感度補正單體透過率為42.1%,視感度補正偏光度為99.996%,單體色相a為-1.1、單體色相b為3.7。 [Measurement of optical properties of polarizing film A] The optical properties of the obtained polarizing film A were measured. The measurement was carried out using a spectrophotometer ("V7100" manufactured by JASCO Corporation) with the polarizing element surface of the polarizing film A obtained as the incident surface. The absorption axis of the polarizing film was consistent with the stretching direction of polyvinyl alcohol. The obtained polarizing film had a sensitivity-corrected monomer transmittance of 42.1%, a sensitivity-corrected polarization degree of 99.996%, a monomer hue of -1.1, and a monomer hue of 3.7.

[水平配向膜形成用組合物之製備] 將下述結構之光配向性材料(重量平均分子量:30000)5份與作為溶劑之環戊酮95份混合,將獲得之混合物於80℃下攪拌1小時,藉此獲得水平配向膜形成用組合物。 [化40] [Preparation of a composition for forming a horizontal alignment film] 5 parts of a photoalignment material (weight average molecular weight: 30,000) having the following structure was mixed with 95 parts of cyclopentanone as a solvent, and the obtained mixture was stirred at 80° C. for 1 hour to obtain a composition for forming a horizontal alignment film. [Chemical 40]

[水平配向液晶硬化膜A形成用組合物之製備] 以質量比90:10混合液晶化合物A及液晶化合物B,獲得混合物。相對於獲得之混合物100質量份,添加調平劑(DIC公司製造之「F-556」)1.0份、及作為聚合起始劑之2-二甲基胺基-2-苄基-1-(4-𠰌啉基苯基)丁烷-1-酮(BASF Japan股份有限公司製造之「Irgacure(註冊商標)369(Irg369)」)6份。又,以固形物成分濃度成為13%之方式添加N-甲基-2-吡咯啶酮(NMP)。於80℃下攪拌1小時,藉此獲得水平配向液晶硬化膜A形成用組合物。 [Preparation of a composition for forming a horizontally aligned liquid crystal cured film A] Liquid crystal compound A and liquid crystal compound B were mixed at a mass ratio of 90:10 to obtain a mixture. 1.0 part of a leveling agent ("F-556" manufactured by DIC Corporation) and 6 parts of 2-dimethylamino-2-benzyl-1-(4-oxo-1-phenyl)butane-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Co., Ltd.) as a polymerization initiator were added to 100 parts by mass of the obtained mixture. In addition, N-methyl-2-pyrrolidone (NMP) was added in such a way that the solid content concentration became 13%. Stirring was carried out at 80°C for 1 hour to obtain a composition for forming a horizontally aligned liquid crystal cured film A.

[水平配向液晶硬化膜A之製造] 於COP膜(Zeon corporation股份有限公司製造之「ZF-14-50」)上實施電暈處理。其後,使用棒式塗佈機塗佈水平配向膜形成用組合物,形成塗佈膜。將塗佈膜於80℃下乾燥1分鐘,形成乾燥覆膜。使用偏光UV照射裝置(牛尾電機股份有限公司製造之「SPOT CURE SP-9」),於波長313 nm下之累計光量100 mJ/cm 2及軸角度45°之條件下實施偏光UV曝光而獲得水平配向膜。利用橢偏計測定獲得之水平配向膜之膜厚,結果為100 nm。 [Manufacturing of horizontally aligned liquid crystal cured film A] Corona treatment was performed on a COP film ("ZF-14-50" manufactured by Zeon Corporation). Subsequently, a rod coater was used to apply a composition for forming a horizontally aligned film to form a coated film. The coated film was dried at 80°C for 1 minute to form a dry coating. A polarized UV irradiation device ("SPOT CURE SP-9" manufactured by Ushio Electric Co., Ltd.) was used to perform polarized UV exposure at a wavelength of 313 nm, a cumulative light amount of 100 mJ/ cm2 , and an axial angle of 45° to obtain a horizontally aligned film. The film thickness of the obtained horizontally aligned film was measured using an elliptometer and the result was 100 nm.

繼而,使用棒式塗佈機,於水平配向膜塗佈水平配向液晶硬化膜A形成用組合物而形成塗佈膜。將塗佈膜於120℃下乾燥1分鐘,形成乾燥覆膜。使用高壓水銀燈(牛尾電機股份有限公司製造之「UNICURE VB-15201BY-A」),於氮氣氛圍下及波長365 nm下之累計光量500 mJ/cm 2之條件下,對乾燥覆膜照射紫外線,藉此形成水平配向液晶硬化膜A。獲得包含基材、水平配向膜及水平配向液晶硬化膜A之積層體。利用橢偏計測定水平配向液晶硬化膜A之膜厚,結果為2.3 μm。 Next, a rod coater was used to coat the horizontal alignment film with a composition for forming a horizontal alignment liquid crystal curing film A to form a coating film. The coating film was dried at 120°C for 1 minute to form a dry coating. A high-pressure mercury lamp ("UNICURE VB-15201BY-A" manufactured by Ushio Electric Co., Ltd.) was used to irradiate the dry coating with ultraviolet light under a nitrogen atmosphere and a wavelength of 365 nm with a cumulative light amount of 500 mJ/ cm2 to form a horizontal alignment liquid crystal curing film A. A laminate including a substrate, a horizontal alignment film, and a horizontal alignment liquid crystal curing film A was obtained. The film thickness of the horizontal alignment liquid crystal curing film A was measured using an ellipsometry, and the result was 2.3 μm.

[水平配向液晶硬化膜A之Re測定] 將包含基材、水平配向膜及水平配向液晶硬化膜A之積層體經由黏著劑貼合於玻璃之後,剝離作為基材之COP膜。藉此,獲得Re測定用之水平配向液晶硬化膜A。使用測定機(王子計測機器股份有限公司製造之「KOBRA-WPR」),測定水平配向液晶硬化膜A之面內相位差值ReA(λ)。測定各波長(450 nm、550 nm、及650 nm)下之相位差值ReA(λ)之結果為,ReA(450)=121 nm、ReA(550)=142 nm、ReA(650)=146 nm、及ReA(450)/ReA(550)=0.85。 [Re measurement of horizontal alignment liquid crystal cured film A] After the laminate including the substrate, horizontal alignment film and horizontal alignment liquid crystal cured film A was attached to glass via an adhesive, the COP film as the substrate was peeled off. In this way, the horizontal alignment liquid crystal cured film A for Re measurement was obtained. The in-plane phase difference value ReA(λ) of the horizontal alignment liquid crystal cured film A was measured using a measuring machine ("KOBRA-WPR" manufactured by Oji Testing Instruments Co., Ltd.). The phase difference value ReA(λ) at each wavelength (450 nm, 550 nm, and 650 nm) was measured as follows: ReA(450) = 121 nm, ReA(550) = 142 nm, ReA(650) = 146 nm, and ReA(450)/ReA(550) = 0.85.

[包含水平配向液晶硬化膜A與垂直配向液晶硬化膜之積層體之R0、及R40之測定] 將利用上述方法所製造之水平配向液晶硬化膜A、及利用實施例1之方法所製作之垂直配向液晶硬化膜(A-1)經由黏著劑(LINTEC公司製造之感壓式黏著劑 15 μm)貼合,製作包含水平配向液晶硬化膜A與垂直配向液晶硬化膜(A-1)之積層體。進而,自該積層體剝離1片用作基材之COP膜,經由黏著劑與玻璃貼合,獲得相位差值測定用之積層體。在確認COP膜及水平配向膜無相位差之基礎上,使用測定機(王子計測機器股份有限公司製造之「KOBRA-WPR」)測定相位差值測定用之積層體之正面方向之相位差值R0(λ)、及以水平配向液晶硬化膜A之進相軸為中心傾斜40°時之相位差值R40(λ)(λ=450 nm及550 nm)。將測定結果示於表2。根據所獲得之R0(λ)及R40(λ)(λ=450 nm及550 nm)之值,算出|R0(550)-R40(550)|、|R0(450)-R40(450)|、及|{R0(450)-R40(450)}-{R0(550)-R40(550)}|。將結果示於表3。 [Measurement of R0 and R40 of a laminate containing a horizontally aligned liquid crystal cured film A and a vertically aligned liquid crystal cured film] The horizontally aligned liquid crystal cured film A produced by the above method and the vertically aligned liquid crystal cured film (A-1) produced by the method of Example 1 were laminated by means of an adhesive (pressure-sensitive adhesive 15 μm manufactured by LINTEC) to produce a laminate containing a horizontally aligned liquid crystal cured film A and a vertically aligned liquid crystal cured film (A-1). Furthermore, a COP film used as a substrate was peeled off from the laminate, and the laminate was laminated to glass by means of an adhesive to obtain a laminate for phase difference measurement. After confirming that the COP film and the horizontal alignment film had no phase difference, the phase difference value R0(λ) in the front direction of the multilayer for phase difference measurement and the phase difference value R40(λ) (λ=450 nm and 550 nm) when tilted 40° around the advance axis of the horizontal alignment liquid crystal cured film A were measured using a measuring machine ("KOBRA-WPR" manufactured by Oji Testing Instruments Co., Ltd.). The measurement results are shown in Table 2. Based on the obtained values of R0(λ) and R40(λ) (λ=450 nm and 550 nm), |R0(550)-R40(550)|, |R0(450)-R40(450)|, and |{R0(450)-R40(450)}-{R0(550)-R40(550)}| were calculated. The results are shown in Table 3.

[斜向反射色相之評價] 將利用上述方法所製作之積層體(包含水平配向液晶硬化膜A與垂直配向液晶硬化膜(A-1)之積層體)與偏光膜A以偏光膜A之吸收軸與水平配向液晶硬化膜A之遲相軸所成之角度成為45°之方式經由黏著劑進行貼合,剝離基材,製作附光學補償功能之橢圓偏光板。其後,經由黏著劑貼合於鋁箔,自仰角45°、方位角0~360°方向利用目視觀察橢圓偏光板之斜向反射色相。根據利用目視觀察之結果,基於下述評價基準評價斜向反射色相。將結果示於表3。 (評價基準) A(良好):利用目視確認到黑色。 B(差):利用目視確認到明顯之著色。 [Evaluation of oblique reflection hue] The laminate (including a laminate of a horizontally aligned liquid crystal cured film A and a vertically aligned liquid crystal cured film (A-1)) prepared by the above method was bonded to the polarizing film A with an adhesive in such a way that the angle between the absorption axis of the polarizing film A and the retardation axis of the horizontally aligned liquid crystal cured film A was 45°, and the substrate was peeled off to prepare an elliptical polarizing plate with an optical compensation function. Thereafter, the elliptical polarizing plate was bonded to an aluminum foil with an adhesive, and the oblique reflection hue of the elliptical polarizing plate was visually observed from an elevation angle of 45° and an azimuth angle of 0 to 360°. Based on the results of visual observation, the oblique reflection hue was evaluated based on the following evaluation criteria. The results are shown in Table 3. (Evaluation criteria) A (good): Black is visually confirmed. B (poor): Clear coloration is visually confirmed.

<實施例17及18> 藉由變更垂直配向液晶硬化膜之膜厚,而如表2所記載般變更RthC(450)、及RthC(550)之值,除此以外,以與實施例16相同之方式實施相位差值測定、斜向反射色相確認。將結果示於表2及表3。 <Examples 17 and 18> By changing the thickness of the vertically aligned liquid crystal cured film, the values of RthC(450) and RthC(550) were changed as shown in Table 2. In addition, the phase difference value was measured and the oblique reflection color was confirmed in the same manner as in Example 16. The results are shown in Tables 2 and 3.

<實施例19> 將偏光膜A變更為利用以下所示之方法所製作之包含朝水平方向配向之水平配向液晶硬化膜B與二色性色素之偏光膜B,除此以外,與實施例16同樣地實施相位差值之測定、及斜向反射色相之評價。將結果示於表2及表3。 <Example 19> The polarizing film A was changed to a polarizing film B comprising a horizontally aligned liquid crystal cured film B and a dichroic pigment produced by the method shown below. The phase difference value was measured and the oblique reflection hue was evaluated in the same manner as in Example 16. The results are shown in Tables 2 and 3.

[偏光膜B形成用組合物之製備] 混合下述之成分,於80℃下攪拌1小時,藉此獲得包含聚合性液晶化合物(B)與二色性色素之偏光膜B形成用組合物。二色性色素係使用日本專利特開2013-101328號公報之實施例所記載之偶氮系色素。作為聚合性液晶化合物(B)之式(1-6)及(1-7)所表示之聚合性液晶化合物係依據lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996)所記載之方法製造。 聚合性液晶化合物(B): [化41] 75份 [化42] 25份 二色性色素1: 聚偶氮色素:化合物(1-8)  2.5份 [化43] 化合物(1-5)         2.5份 [化44] 化合物(1-16)          2.5份 [化45] 聚合起始劑: 2-二甲基胺基-2-苄基-1-(4-𠰌啉基苯基)丁烷-1-酮(Irgacure 369;Ciba Specialty Chemicals公司製造)                                            6份 調平劑: 聚丙烯酸酯化合物(BYK-Chemie公司製造之「BYK-361N」) 1.2份 溶劑:鄰二甲苯                                                                 250份 [Preparation of a composition for forming a polarizing film B] The following ingredients are mixed and stirred at 80°C for 1 hour to obtain a composition for forming a polarizing film B comprising a polymerizable liquid crystal compound (B) and a dichroic dye. The dichroic dye is an azo dye described in the example of Japanese Patent Publication No. 2013-101328. The polymerizable liquid crystal compound (B) represented by formulas (1-6) and (1-7) is prepared according to the method described in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996). Polymerizable liquid crystal compound (B): [Chem. 41] 75 parts [42 parts] 25 parts of dichroic dye 1: Polyazo dye: Compound (1-8) 2.5 parts [Chemical 43] Compound (1-5) 2.5 parts [Chemical 44] Compound (1-16) 2.5 parts [Chemical 45] Polymerization initiator: 2-dimethylamino-2-benzyl-1-(4-oxo-1-phenyl)butane-1-one (Irgacure 369; manufactured by Ciba Specialty Chemicals) 6 parts Leveling agent: Polyacrylate compound ("BYK-361N" manufactured by BYK-Chemie) 1.2 parts Solvent: o-xylene 250 parts

[偏光膜B之製造] (水平配向膜之製作) 於三乙醯纖維素膜(TAC)(Konica Minolta公司製造之「KC4UY」)上實施電暈處理。繼而,使用棒式塗佈機,於實施過電暈處理之TAC表面塗佈水平配向膜形成用組合物而形成塗佈膜。使塗佈膜於80℃下乾燥1分鐘,形成乾燥覆膜。使用偏光UV照射裝置(牛尾電機股份有限公司製造之「SPOT CURE SP-7」),於累計光量100 mJ/cm 2及軸角度90°之條件下對乾燥覆膜實施偏光UV曝光而獲得水平配向膜。利用橢偏計對獲得之水平配向膜之膜厚進行測定,結果為150 nm。 [Manufacturing of polarizing film B] (Manufacturing of horizontal alignment film) A triacetyl cellulose film (TAC) ("KC4UY" manufactured by Konica Minolta) was subjected to a corona treatment. Subsequently, a rod-type coater was used to coat the surface of the TAC subjected to the corona treatment with a composition for forming a horizontal alignment film to form a coating film. The coated film was dried at 80°C for 1 minute to form a dry coating. A polarized UV irradiation device ("SPOT CURE SP-7" manufactured by Ushio Electric Co., Ltd.) was used to expose the dry coating to polarized UV at a cumulative light dose of 100 mJ/ cm2 and an axial angle of 90° to obtain a horizontal alignment film. The film thickness of the obtained horizontal alignment film was measured using an elliptometer and the result was 150 nm.

(水平配向液晶硬化膜B之製作) 進而,使用棒式塗佈機,將偏光膜B形成用組合物塗佈於水平配向膜而形成塗佈膜。其後,利用設定為120℃之乾燥烘箱使塗佈膜乾燥1分鐘。其結果,獲得聚合性液晶化合物(B)及二色性色素經配向之乾燥塗膜。將該乾燥塗膜自然冷卻至室溫(25℃)後,使用高壓水銀燈(牛尾電機股份有限公司製造之「UNICURE VB-15201BY-A」),於氮氣氛圍下、波長365 nm、及波長365 nm下之累計光量1000 mJ/cm 2之條件下照射紫外線,藉此使聚合性液晶化合物(B)聚合而製作具有包含二色性色素之水平配向液晶硬化膜B的偏光膜B。 (Preparation of horizontally aligned liquid crystal cured film B) Then, a rod-type coating machine was used to coat the composition for forming polarizing film B on the horizontally aligned film to form a coating film. Thereafter, the coating film was dried for 1 minute in a drying oven set at 120° C. As a result, a dry coating film in which the polymerizable liquid crystal compound (B) and the dichroic pigment were aligned was obtained. After the dried coating was naturally cooled to room temperature (25°C), it was irradiated with ultraviolet light using a high-pressure mercury lamp ("UNICURE VB-15201BY-A" manufactured by Ushio Electric Co., Ltd.) under a nitrogen atmosphere, a wavelength of 365 nm, and a cumulative light amount of 1000 mJ/ cm2 at a wavelength of 365 nm, thereby polymerizing the polymerizable liquid crystal compound (B) to produce a polarizing film B having a horizontally aligned liquid crystal cured film B containing a dichroic pigment.

[偏光膜B之偏光度、及單體透過率之測定] 所獲得之偏光膜B之偏光度及單體透過率係以如下方式測定。使用於分光光度計(島津製作所股份有限公司製造之「UV-3150」)中放置有附偏光元件之支座的裝置,藉由雙光束法以2 nm步進於380~680 nm之波長範圍內測定透過軸方向之透過率(T 1)及吸收軸方向之透過率(T 2)。使用下述式(p)及(q),算出各波長下之單體透過率及偏光度。進而,藉由日本工業標準JIS Z 8701之2度視野(C光源)進行視感度補正,算出視感度補正單體透過率(Ty)及視感度補正偏光度(Py),結果單體透過率為42%,偏光度為97%,確認係作為偏光膜有用之值。 單體透過率(%)=(T 1+T 2)/2              (p) 偏光度(%)={(T 1-T 2)/(T 1+T 2)}×100          (q) [Determination of polarization degree and monomer transmittance of polarizing film B] The polarization degree and monomer transmittance of the obtained polarizing film B were measured as follows. Using a spectrophotometer ("UV-3150" manufactured by Shimadzu Corporation) with a holder equipped with a polarizing element placed therein, the transmittance (T 1 ) in the transmission axis direction and the transmittance (T 2 ) in the absorption axis direction were measured in a wavelength range of 380 to 680 nm with a 2 nm step by using a double beam method. The monomer transmittance and polarization degree at each wavelength were calculated using the following formulas (p) and (q). Furthermore, the sensitivity correction was performed using the 2-degree field of view (C light source) of the Japanese Industrial Standard JIS Z 8701, and the sensitivity-corrected single transmittance (Ty) and sensitivity-corrected polarization (Py) were calculated. The results showed that the single transmittance was 42% and the polarization was 97%, which were confirmed to be useful values for polarizing films. Single transmittance (%) = (T 1 + T 2 )/2 (p) Polarization (%) = {(T 1 - T 2 )/(T 1 + T 2 )}×100 (q)

<比較例2> 製作以下所示之垂直配向膜及垂直配向液晶硬化膜,除此以外,以與實施例16相同之方式製作樣品,實施相位差值之測定及斜向反射色相之評價。將結果示於表2及表3。 <Comparative Example 2> The vertical alignment film and vertical alignment liquid crystal cured film shown below were prepared. In addition, samples were prepared in the same manner as in Example 16, and the phase difference value was measured and the oblique reflection hue was evaluated. The results are shown in Tables 2 and 3.

(垂直配向膜形成用組合物(B)之製作) 混合0.5%之聚醯亞胺(日產化學工業股份有限公司製造之「Sunever SE-610」)、72.3%之N-甲基-2-吡咯啶酮、18.1%之2-丁氧基乙醇、9.1%之乙基環己烷、及0.01%之DPHA(dipentaerythritol hexaacrylate,二季戊四醇六丙烯酸酯)(新中村化學製造),製作垂直配向膜形成用組合物(B)。 (Preparation of a composition for forming a vertical alignment film (B)) 0.5% of polyimide ("Sunever SE-610" manufactured by Nissan Chemical Industries, Ltd.), 72.3% of N-methyl-2-pyrrolidone, 18.1% of 2-butoxyethanol, 9.1% of ethylcyclohexane, and 0.01% of DPHA (dipentaerythritol hexaacrylate) (manufactured by Shin-Nakamura Chemical) were mixed to prepare a composition for forming a vertical alignment film (B).

(垂直配向液晶硬化膜形成用組合物(B)之製備) 相對於下述式(LC242)所示之液晶化合物LC242:PaliocolorLC242(BASF公司 註冊商標),添加調平劑(DIC公司製造之「F-556」)0.1份及聚合起始劑Irg369 3份,以固形物成分濃度成為13%之方式添加環戊酮,將該等混合而獲得垂直配向液晶硬化膜形成用組合物(B)。 液晶化合物LC242:PaliocolorLC242(BASF公司 註冊商標) [化46] (Preparation of a composition (B) for forming a vertically aligned liquid crystal cured film) To the liquid crystal compound LC242 represented by the following formula (LC242): Paliocolor LC242 (registered trademark of BASF), 0.1 parts of a leveling agent ("F-556" manufactured by DIC Corporation) and 3 parts of a polymerization initiator Irg369 were added, and cyclopentanone was added so that the solid content concentration became 13%, and the mixture was mixed to obtain a composition (B) for forming a vertically aligned liquid crystal cured film. Liquid crystal compound LC242: Paliocolor LC242 (registered trademark of BASF Corporation) [Chemical 46]

(垂直配向液晶硬化膜之製作) 對作為基材之COP膜(Zeon corporation股份有限公司「ZF-14-23」)實施電暈處理。使用棒式塗佈機,於實施過電暈處理之COP膜使用棒式塗佈機,塗佈垂直配向膜形成用組合物(B)而形成塗佈膜。將塗佈膜於80℃下乾燥1分鐘,獲得垂直配向膜。利用橢偏計測定獲得之垂直配向膜之膜厚,結果為0.2 μm。繼而,於製作之垂直配向膜上塗佈垂直配向液晶硬化膜形成用組合物(B)而形成塗佈膜。將塗佈膜於80℃下乾燥1分鐘,形成乾燥覆膜。其後,使用高壓水銀燈(牛尾電機股份有限公司製造之「UNICURE VB-15201BY-A」)於氮氣氛圍下、及波長365 nm下之累計光量500 mJ/cm 2之條件下對乾燥覆膜照射紫外線,形成垂直配向液晶硬化膜。獲得之垂直配向液晶硬化膜之膜厚為0.5 μm。 (Preparation of vertically aligned liquid crystal cured film) The COP film (Zeon Corporation "ZF-14-23") used as the substrate is subjected to a corona treatment. Using a rod coater, the COP film subjected to the corona treatment is coated with a composition (B) for forming a vertically aligned film to form a coated film. The coated film is dried at 80°C for 1 minute to obtain a vertically aligned film. The thickness of the obtained vertically aligned film is measured using an ellipsometry, and the result is 0.2 μm. Subsequently, a composition (B) for forming a vertically aligned liquid crystal cured film is coated on the prepared vertically aligned film to form a coated film. The coated film is dried at 80°C for 1 minute to form a dry coating. Afterwards, a high-pressure mercury lamp ("UNICURE VB-15201BY-A" manufactured by Ushio Electric Co., Ltd.) was used to irradiate the dried film with ultraviolet light at a wavelength of 365 nm and a cumulative light intensity of 500 mJ/ cm2 in a nitrogen atmosphere to form a vertical alignment liquid crystal cured film. The film thickness of the obtained vertical alignment liquid crystal cured film was 0.5 μm.

表1中,矽烷化合物之「添加量」及離子性化合物之「添加量」一欄分別表示相對於垂直配向液晶硬化膜形成用組合物之添加量(單位:重量%)。液晶化合物之比一欄之數字及括弧內之字母表示添加之液晶化合物之添加量之比率。例如,90/10(A/B)表示質量比(液晶化合物A/液晶化合物B)90/10。In Table 1, the "addition amount" of the silane compound and the "addition amount" of the ionic compound represent the addition amount relative to the composition for forming a vertically aligned liquid crystal cured film (unit: weight %). The numbers and letters in the brackets in the "ratio of liquid crystal compounds" column represent the ratio of the addition amount of the added liquid crystal compounds. For example, 90/10 (A/B) represents a mass ratio (liquid crystal compound A/liquid crystal compound B) of 90/10.

[表1]    基材 矽烷化合物 離子性化合物 液晶化合物 相位差測定結果 配向性 種類 添加量 [wt%] 種類 M 添加量 [wt%] 種類 λ max[nm] Rth (450) Rth (550) αth 實施例1 ZF14-23 KBE-9103 0.5 離子性化合物(1) 7 2 A、B 90/10(A/B) 350 -60 -70 0.85 A 實施例2 ZF14-23 KBE-9103 0.5 離子性化合物(1) 7 2 A、B 90/10(A/B) 350 -85 -100 0.85 A 實施例3 ZF14-23 KBE-9103 0.5 離子性化合物(1) 7 2 A、B 90/10(A/B) 350 -43 -50 0.85 A 實施例4 ZF14-23 KBE-9103 0.5 離子性化合物(1) 7 2 A、B 90/10(A/B) 350 -26 -30 0.85 A 實施例5 ZF14-23 KBE-9103 2 離子性化合物(1) 7 2 A、B 90/10(A/B) 350 -60 -70 0.85 A 實施例6 ZF14-23 KBE-9103 0.5 離子性化合物(1) 7 1 A、B 90/10(A/B) 350 -60 -70 0.85 A 實施例7 ZF14-23 KBE-9103 0.5 離子性化合物(1) 7 0.5 A、B 90/10(A/B) 350 -60 -70 0.85 A 實施例8 ZF14-23 KBE-9103 0.5 離子性化合物(2) 13 0.5 A、B 90/10(A/B) 350 -60 -70 0.85 A 實施例9 ZF14-23 KBE-9103 0.5 離子性化合物(3) 15 0.5 A、B 90/10(A/B) 350 -60 -70 0.85 B 實施例10 附保護層之PET KBE-9103 0.5 離子性化合物(1) 7 2 A、B 90/10(A/B) 350 -60 -70 0.85 A 實施例11 ZF14-23 KBE-9103 0.5 離子性化合物(1) 7 2 A-2 100(A-2) 352 -58 -70 0.83 A 實施例12 ZF14-23 KBE-9103 0.5 離子性化合物(1) 7 2 A-3 100(A-3) 352 -58 -70 0.83 A 實施例13 ZF14-23 KBE-9103 0.5 離子性化合物(1) 7 2 A-4 100(A-4) 354 -61 -70 0.87 A 實施例14 ZF14-23 KBE-9103 0.5 離子性化合物(1) 7 2 A-5 100(A-5) 324 -69 -70 0.98 A 實施例15 ZF14-23 KBE-403 0.5 離子性化合物(1) 7 2 A、B 90/10(A/B) 350 -60 -70 0.85 B 實施例20 ZF14-23 KBE-9103 0.5 - - - A、B 90/10(A/B) 350 - - - C 實施例21 ZF14-23 - - 離子性化合物(1) 7 2 A、B 90/10(A/B) 350 - - - C 比較例1 ZF14-23 - - - - - A、B 90/10(A/B) 350 - - - D [Table 1] Substrate Silane compounds Ionic compounds Liquid crystal compounds Phase difference measurement results Orientation Type Addition amount [wt%] Type M Addition amount [wt%] Type Compare λ max [nm] Rth (450) Rth (550) αth Embodiment 1 ZF14-23 KBE-9103 0.5 Ionic compounds (1) 7 2 A. B 90/10(A/B) 350 -60 -70 0.85 A Embodiment 2 ZF14-23 KBE-9103 0.5 Ionic compounds (1) 7 2 A. B 90/10(A/B) 350 -85 -100 0.85 A Embodiment 3 ZF14-23 KBE-9103 0.5 Ionic compounds (1) 7 2 A. B 90/10(A/B) 350 -43 -50 0.85 A Embodiment 4 ZF14-23 KBE-9103 0.5 Ionic compounds (1) 7 2 A. B 90/10(A/B) 350 -26 -30 0.85 A Embodiment 5 ZF14-23 KBE-9103 2 Ionic compounds (1) 7 2 A. B 90/10(A/B) 350 -60 -70 0.85 A Embodiment 6 ZF14-23 KBE-9103 0.5 Ionic compounds (1) 7 1 A. B 90/10(A/B) 350 -60 -70 0.85 A Embodiment 7 ZF14-23 KBE-9103 0.5 Ionic compounds (1) 7 0.5 A. B 90/10(A/B) 350 -60 -70 0.85 A Embodiment 8 ZF14-23 KBE-9103 0.5 Ionic compounds (2) 13 0.5 A. B 90/10(A/B) 350 -60 -70 0.85 A Embodiment 9 ZF14-23 KBE-9103 0.5 Ionic compounds (3) 15 0.5 A. B 90/10(A/B) 350 -60 -70 0.85 B Embodiment 10 PET with protective layer KBE-9103 0.5 Ionic compounds (1) 7 2 A. B 90/10(A/B) 350 -60 -70 0.85 A Embodiment 11 ZF14-23 KBE-9103 0.5 Ionic compounds (1) 7 2 A-2 100(A-2) 352 -58 -70 0.83 A Embodiment 12 ZF14-23 KBE-9103 0.5 Ionic compounds (1) 7 2 A-3 100(A-3) 352 -58 -70 0.83 A Embodiment 13 ZF14-23 KBE-9103 0.5 Ionic compounds (1) 7 2 A-4 100(A-4) 354 -61 -70 0.87 A Embodiment 14 ZF14-23 KBE-9103 0.5 Ionic compounds (1) 7 2 A-5 100(A-5) 324 -69 -70 0.98 A Embodiment 15 ZF14-23 KBE-403 0.5 Ionic compounds (1) 7 2 A. B 90/10(A/B) 350 -60 -70 0.85 B Embodiment 20 ZF14-23 KBE-9103 0.5 - - - A. B 90/10(A/B) 350 - - - C Embodiment 21 ZF14-23 - - Ionic compounds (1) 7 2 A. B 90/10(A/B) 350 - - - C Comparison Example 1 ZF14-23 - - - - - A. B 90/10(A/B) 350 - - - D

實施例1~15之組合物(A-1)~(A-15)含有液晶化合物A、(A)-2、(A)-3、(A)-4、及(A)-5中之至少1種、矽烷化合物KBE-9103或KBE-403、以及離子性化合物(1)~(3)中之任1種。液晶化合物A、(A)-2、(A)-3、(A)-4、及(A)-5係包含於式(I)-1所表示之液晶化合物中之液晶化合物。矽烷化合物KBE-9103及KBE-403係非離子性矽烷化合物。實施例1~15之垂直配向液晶硬化膜(A-1)~(A-15)之配向性評價為A及B之任一種。實施例20之組合物(A-20)包含液晶化合物A與離子性化合,實施例21之組合物(A-21)包含液晶化合物A與非離子性之矽烷性化合物。實施例(20)之垂直配向液晶硬化膜(A-20)、及實施例(21)之垂直配向液晶硬化膜(A-21)之配向性評價均為C。The compositions (A-1) to (A-15) of Examples 1 to 15 contain at least one of the liquid crystal compounds A, (A)-2, (A)-3, (A)-4, and (A)-5, the silane compound KBE-9103 or KBE-403, and any one of the ionic compounds (1) to (3). The liquid crystal compounds A, (A)-2, (A)-3, (A)-4, and (A)-5 are liquid crystal compounds included in the liquid crystal compound represented by formula (I)-1. The silane compounds KBE-9103 and KBE-403 are non-ionic silane compounds. The alignment of the vertically aligned liquid crystal cured films (A-1) to (A-15) of Examples 1 to 15 was evaluated as either A or B. The composition (A-20) of Example 20 includes a liquid crystal compound A and an ionic compound, and the composition (A-21) of Example 21 includes a liquid crystal compound A and a non-ionic silane compound. The alignment evaluation of the vertically aligned liquid crystal cured film (A-20) of Example (20) and the vertically aligned liquid crystal cured film (A-21) of Example (21) are both C.

比較例1之組合物(B-1)不含非離子性矽烷化合物及離子性化合物。比較例1之垂直配向液晶硬化膜(B-1)之配向性評價為D。The composition (B-1) of Comparative Example 1 does not contain non-ionic silane compounds and ionic compounds. The alignment evaluation of the vertically aligned liquid crystal cured film (B-1) of Comparative Example 1 is D.

根據以上,可知實施例1~15之垂直配向液晶硬化膜(A-1)~(A-15)、(A-20)、及(A-21)與比較例1之配向液晶硬化膜(B-1)相比,配向性優異。可知實施例1~15、實施例20、及實施例21之組合物(A-1)~(A-15)、(A-20)、及(A-21)與比較例1之組合物(B-1)相比,能夠形成即便無垂直配向膜,配向性亦優異之垂直配向液晶硬化膜。From the above, it can be seen that the vertically aligned liquid crystal cured films (A-1) to (A-15), (A-20), and (A-21) of Examples 1 to 15 have superior alignment properties compared to the aligned liquid crystal cured film (B-1) of Comparative Example 1. It can be seen that the compositions (A-1) to (A-15), (A-20), and (A-21) of Examples 1 to 15, Example 20, and Example 21 can form vertically aligned liquid crystal cured films having superior alignment properties even without a vertically aligned film, compared to the composition (B-1) of Comparative Example 1.

實施例16~19之橢圓偏光板包含使用組合物(A-1)所製作之垂直配向液晶硬化膜、水平配向膜、水平配向液晶硬化膜A、及偏光膜。實施例16~19之橢圓偏光板之斜向反射色相均為A。The elliptical polarizing plates of Examples 16 to 19 include a vertical alignment liquid crystal cured film, a horizontal alignment film, a horizontal alignment liquid crystal cured film A, and a polarizing film made using the composition (A-1). The oblique reflection hue of the elliptical polarizing plates of Examples 16 to 19 is all A.

比較例2之橢圓偏光板包含使用組合物(B-2)所製作之垂直配向液晶硬化膜、水平配向膜、水平配向液晶硬化膜A、及偏光膜。組合物(B-2)包含液晶化合物LC242。液晶化合物之Ar為具有1個環結構之2價基,不為包含於式(I)-1所表示之液晶化合物中之化合物。比較例2之橢圓偏光板之斜向反射色相為B。The elliptical polarizing plate of Comparative Example 2 includes a vertical alignment liquid crystal cured film, a horizontal alignment film, a horizontal alignment liquid crystal cured film A, and a polarizing film made using the composition (B-2). The composition (B-2) includes a liquid crystal compound LC242. Ar of the liquid crystal compound is a divalent group having a ring structure and is not a compound included in the liquid crystal compound represented by formula (I)-1. The oblique reflection hue of the elliptical polarizing plate of Comparative Example 2 is B.

根據以上,可知實施例16~19之橢圓偏光板與比較例2之橢圓偏光板相比,斜向反射色相優異。Based on the above, it can be seen that the elliptical polarizing plates of Examples 16 to 19 have superior oblique reflection hue compared to the elliptical polarizing plate of Comparative Example 2.

[表2]    ReA(450) [nm] ReA(550) [nm] RthA(550) [nm] RthA(550) [nm] ReA(450)/ ReA(550) ReC(450) ReC(550) RthC(450) [nm] RthC(550) [nm] RthC(450)/ RthC(550) 實施例16 121 142 60.5 70 0.85 0 0 -60 -70 0.85 實施例17 121 142 60.5 71 0.85 0 0 -46 -55 0.85 實施例18 121 142 60.5 71 0.85 0 0 -65 -77 0.85 實施例19 121 142 60.5 70 0.85 0 0 -60 -70 0.85 比較例2 121 142 60.5 71 0.85 0 0 -76 -68 1.11 [Table 2] ReA(450) [nm] ReA(550) [nm] RthA(550) [nm] RthA(550) [nm] ReA(450)/ ReA(550) ReC(450) ReC(550) RthC(450) [nm] RthC(550) [nm] RthC(450)/ RthC(550) Embodiment 16 121 142 60.5 70 0.85 0 0 -60 -70 0.85 Embodiment 17 121 142 60.5 71 0.85 0 0 -46 -55 0.85 Embodiment 18 121 142 60.5 71 0.85 0 0 -65 -77 0.85 Embodiment 19 121 142 60.5 70 0.85 0 0 -60 -70 0.85 Comparison Example 2 121 142 60.5 71 0.85 0 0 -76 -68 1.11

[表3]    |R0(550)-R40(550)| [nm] |R0(450)-R40(450)| [nm] |{R0(450)-R40(450)|-|R0(550)-R40(550)}| [nm] 斜向反射色相 實施例16 1 1 0 A 實施例17 4 3 1 A 實施例18 1 2 1 A 實施例19 1 1 0 A 比較例2 4 1 4 B [table 3] |R0(550)-R40(550)| [nm] |R0(450)-R40(450)| [nm] |{R0(450)-R40(450)|-|R0(550)-R40(550)}| [nm] Oblique reflection hue Embodiment 16 1 1 0 A Embodiment 17 4 3 1 A Embodiment 18 1 2 1 A Embodiment 19 1 1 0 A Comparison Example 2 4 1 4 B

1:基材 3:水平配向膜 5:水平配向液晶硬化膜A 7:黏著層 9:垂直配向液晶硬化膜 11:偏光膜 13:保護層 15:積層體 20:橢圓偏光板 1: Substrate 3: Horizontal alignment film 5: Horizontal alignment liquid crystal curing film A 7: Adhesive layer 9: Vertical alignment liquid crystal curing film 11: Polarizing film 13: Protective layer 15: Laminated body 20: Elliptical polarizing plate

圖1係表示本發明之橢圓偏光板之層構成之一例的概略剖視圖。FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the elliptical polarizing plate of the present invention.

Claims (24)

一種組合物,其包含:具有下述式(I)-1:*-G1-L1-Ar-L2-G2-*...(I)-1[式(I)-1中,Ar表示具有2個以上之環結構之2價基,該2個以上之環結構中之1個為6員環,於該6員環之1位及4位與L1及L2鍵結,L1及L2分別獨立表示單鍵或二價連結基,G1及G2分別獨立表示二價芳香族基或二價脂環式烴基,該二價芳香族基及該二價脂環式烴基所包含之氫原子可分別獨立被取代為鹵素原子、碳數1~4之烷基、碳數1~4之氟烷基、碳數1~4之烷氧基、氰基、或硝基,該二價芳香族基及該二價脂環式烴基所包含之碳原子可分別獨立被取代為氧原子、硫原子、或氮原子,*表示鍵結鍵]所表示之結構之1種以上之液晶化合物;及矽烷偶合劑或整體由非金屬元素構成之離子性化合物中任一者。 A composition comprising: a compound having the following formula (I)-1: * -G1 - L1 -Ar- L2 - G2- *. . . (I)-1 [In the formula (I)-1, Ar represents a divalent group having two or more ring structures, one of the two or more ring structures is a 6-membered ring, and is bonded to L1 and L2 at the 1-position and 4-position of the 6-membered ring, L1 and L2 each independently represent a single bond or a divalent linking group, G1 and G2 are 2 independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, the hydrogen atom contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group can be independently substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, the carbon atom contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group can be independently substituted by an oxygen atom, a sulfur atom, or a nitrogen atom, and * represents a bond] at least one liquid crystal compound having a structure represented by; and any one of a silane coupling agent or an ionic compound composed entirely of non-metallic elements. 如請求項1之組合物,其中上述具有式(I)-1所表示之結構之1種以上之液晶化合物於波長260nm以上400nm以下之區域具有極大吸收。 As in claim 1, the composition wherein one or more liquid crystal compounds having the structure represented by formula (I)-1 have a maximum absorption in the wavelength range of 260 nm to 400 nm. 如請求項1或2之組合物,其中上述具有式(I)-1所表示之結構之液晶化合物為具有下述式(I)-2: *-G3-B1-G1-L1-Ar-L2-G2-*...(I)-2[式(I)-2中,Ar表示具有2個以上之環結構之2價基,該2個以上之環結構中之1個為6員環,於該6員環之1位及4位與L1及L2鍵結,L1、L2、及B1分別獨立表示單鍵或二價連結基,G1、G2、及G3分別獨立表示二價芳香族基或二價脂環式烴基,該二價芳香族基及該二價脂環式烴基所包含之氫原子可分別獨立被取代為鹵素原子、碳數1~4之烷基、碳數1~4之氟烷基、碳數1~4之烷氧基、氰基、或硝基,該二價芳香族基及該二價脂環式烴基所包含之碳原子可分別獨立被取代為氧原子、硫原子、或氮原子,*表示鍵結鍵]所表示之結構之液晶化合物。 The composition of claim 1 or 2, wherein the liquid crystal compound having a structure represented by formula (I)-1 is a compound having the following formula (I)-2: *-G 3 -B 1 -G 1 -L 1 -Ar-L 2 -G 2 -*... (I)-2 [In formula (I)-2, Ar represents a divalent group having two or more ring structures, one of the two or more ring structures is a 6-membered ring, and is bonded to L 1 and L 2 at the 1-position and 4-position of the 6-membered ring, L 1 , L 2 , and B 1 each independently represent a single bond or a divalent linking group, G 1 , G 2 , and G 2 are each independently a divalent linking group . 3 independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, the hydrogen atom contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group can be independently substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group, the carbon atom contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group can be independently substituted by an oxygen atom, a sulfur atom, or a nitrogen atom, and * represents a bond] a liquid crystal compound having a structure represented by. 如請求項1或2之組合物,其中上述具有式(I)-1所表示之結構之液晶化合物為下述式(I)-3:[化49]*-G3-B1-G1-L1-Ar-L2-G2-B2-G4-*...(I)-3[式(I)-3中,Ar表示具有2個以上之環結構之2價基,該2個以上之環結構中之1個為6員環,於該6員環之1位及4位與L1及L2鍵結,L1、L2、B1、及B2分別獨立表示單鍵或二價連結基,G1、G2、G3、及G4分別獨立表示二價芳香族基或二價脂環式烴基,該二價芳香族基及該二價脂環式烴基所包含之氫原子可分別獨立被取代為鹵素原子、碳數1~4之烷基、碳數1~4之氟烷基、碳數1~4之烷氧基、 氰基、或硝基,該二價芳香族基及該二價脂環式烴基所包含之碳原子可分別獨立被取代為氧原子、硫原子、或氮原子,*表示鍵結鍵]所表示之液晶化合物。 The composition of claim 1 or 2, wherein the liquid crystal compound having a structure represented by formula (I)-1 is the following formula (I)-3: [Chemical 49]*-G 3 -B 1 -G 1 -L 1 -Ar-L 2 -G 2 -B 2 -G 4 -*... (I)-3 [In formula (I)-3, Ar represents a divalent group having two or more ring structures, one of the two or more ring structures is a 6-membered ring, and is bonded to L1 and L2 at the 1-position and 4-position of the 6-membered ring, L1 , L2 , B1 , and B2 each independently represent a single bond or a divalent linking group, G1 , G2 , G3 , and G4 each independently represent a divalent aromatic group or a divalent alicyclic alkyl group, and the hydrogen atom contained in the divalent aromatic group and the divalent alicyclic alkyl group may be independently substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, The liquid crystal compound represented by [a cyano group, a nitro group, a carbon atom contained in the divalent aromatic group and the divalent alicyclic hydrocarbon group can be independently substituted by an oxygen atom, a sulfur atom, or a nitrogen atom, and * represents a bond]. 如請求項1或2之組合物,其中上述液晶化合物具有1個以上之聚合性基。 As in claim 1 or 2, the liquid crystal compound has one or more polymerizable groups. 如請求項1或2之組合物,其中上述矽烷偶合劑為具有烷氧基矽烷基與極性基之矽烷偶合劑。 The composition of claim 1 or 2, wherein the silane coupling agent is a silane coupling agent having an alkoxysilyl group and a polar group. 如請求項1或2之組合物,其中上述離子性化合物之分子量為100以上10,000以下。 The composition of claim 1 or 2, wherein the molecular weight of the above-mentioned ionic compound is greater than 100 and less than 10,000. 一種垂直配向液晶硬化膜,其係如請求項1至7中任一項之組合物之硬化物,且上述組合物所包含之液晶化合物相對於液晶硬化膜之面內方向朝垂直方向配向。 A vertically aligned liquid crystal cured film, which is a cured product of a composition as described in any one of claims 1 to 7, and the liquid crystal compound contained in the above composition is aligned in a vertical direction relative to the in-plane direction of the liquid crystal cured film. 如請求項8之垂直配向液晶硬化膜,其滿足下述關係式(1):-150nm≦RthC(550)≦-30nm (1)[關係式(1)中,RthC(550)表示垂直配向液晶硬化膜於波長550nm下之厚度方向之相位差值]。 The vertically aligned liquid crystal cured film of claim 8 satisfies the following relational expression (1): -150nm≦RthC(550)≦-30nm (1) [In relational expression (1), RthC(550) represents the phase difference value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 550nm]. 如請求項8或9之垂直配向液晶硬化膜,其滿足下述關係式(2):RthC(450)/RthC(550)≦1 (2)[關係式(2)中,RthC(450)表示垂直配向液晶硬化膜於波長450nm下之厚度方向之相位差值,RthC(550)表示垂直配向液晶硬化膜於波長550nm下之厚度方向之相位差值]。 The vertical alignment liquid crystal cured film of claim 8 or 9 satisfies the following relational expression (2): RthC(450)/RthC(550)≦1 (2) [In relational expression (2), RthC(450) represents the phase difference value of the vertical alignment liquid crystal cured film in the thickness direction at a wavelength of 450nm, and RthC(550) represents the phase difference value of the vertical alignment liquid crystal cured film in the thickness direction at a wavelength of 550nm]. 一種積層體,其具備:基材、及如請求項8至10中任一項之垂直配向液晶硬化膜,且上述垂直配向液晶硬化膜與上述基材鄰接。 A laminated body comprising: a substrate, and a vertically aligned liquid crystal cured film as in any one of claims 8 to 10, wherein the vertically aligned liquid crystal cured film is adjacent to the substrate. 一種積層體,其具備如請求項8至10中任一項之垂直配向液晶硬化膜、及相對於上述垂直配向液晶硬化膜之面內方向朝水平方向配向之膜。 A laminate having a vertically aligned liquid crystal cured film as in any one of claims 8 to 10, and a film aligned in a horizontal direction relative to the in-plane direction of the vertically aligned liquid crystal cured film. 如請求項12之積層體,其滿足下述關係式(3):ReA(450)/ReA(550)≦1 (3)[關係式(3)中,ReA(450)表示上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜於波長450nm下之面內相位差值,ReA(550)表示上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜於波長550nm下之面內相位差值]。 The laminate of claim 12 satisfies the following relational expression (3): ReA(450)/ReA(550)≦1 (3) [In relational expression (3), ReA(450) represents the in-plane phase difference of the film oriented horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film at a wavelength of 450nm, and ReA(550) represents the in-plane phase difference of the film oriented horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film at a wavelength of 550nm]. 如請求項12或13之積層體,其滿足下述關係式(4):|R0(550)-R40(550)|≦10nm (4)[關係式(4)中,R0(550)表示波長550nm下之積層體之面內相位差 值,R40(550)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時波長550nm下之相位差值]。 The laminate of claim 12 or 13 satisfies the following relational expression (4): |R0(550)-R40(550)|≦10nm (4) [In relational expression (4), R0(550) represents the in-plane phase difference of the laminate at a wavelength of 550nm, and R40(550) represents the phase difference at a wavelength of 550nm when the phase advance axis of the film aligned horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film is rotated 40°]. 如請求項12或13之積層體,其滿足下述關係式(5):|R0(450)-R40(450)|≦10nm (5)[關係式(5)中,R0(450)表示波長450nm下之積層體之面內相位差值,R40(450)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時波長450nm下之相位差值]。 The laminate of claim 12 or 13 satisfies the following relational expression (5): |R0(450)-R40(450)|≦10nm (5) [In relational expression (5), R0(450) represents the in-plane phase difference value of the laminate at a wavelength of 450nm, and R40(450) represents the phase difference value at a wavelength of 450nm when the phase advance axis direction of the film aligned horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film is rotated 40°]. 如請求項12或13之積層體,其滿足下述關係式(6):|{R0(450)-R40(450)}-{R0(550)-R40(550)}|≦3nm (6)[關係式(6)中,R0(450)表示波長450nm下之積層體之面內相位差值,R0(550)表示波長550nm下之積層體之面內相位差值,R40(450)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時波長450nm下之相位差值,R40(550)表示繞上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜的進相軸方向旋轉40°時波長550nm下之相位差值]。 For example, the multilayer of claim 12 or 13 satisfies the following relation (6): |{R0(450)-R40(450)}-{R0(550)-R40(550)}|≦3nm (6) [In relational formula (6), R0(450) represents the in-plane phase difference of the laminate at a wavelength of 450nm, R0(550) represents the in-plane phase difference of the laminate at a wavelength of 550nm, R40(450) represents the phase difference at a wavelength of 450nm when the phase advance axis of the film oriented horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film is rotated 40°, and R40(550) represents the phase difference at a wavelength of 550nm when the phase advance axis of the film oriented horizontally relative to the in-plane direction of the vertically aligned liquid crystal cured film is rotated 40°]. 如請求項12或13之積層體,其中上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜為水平配向液晶硬化膜。 As in claim 12 or 13, the layered body, wherein the film aligned in the horizontal direction relative to the in-plane direction of the vertically aligned liquid crystal cured film is a horizontally aligned liquid crystal cured film. 一種橢圓偏光板,其包含如請求項12至17中任一項之積層體及偏光膜。 An elliptical polarizing plate comprising a laminate as described in any one of claims 12 to 17 and a polarizing film. 如請求項18之橢圓偏光板,其中上述相對於垂直配向液晶硬化膜之面內方向朝水平方向配向之膜為水平配向液晶硬化膜。 As in claim 18, the elliptical polarizing plate, wherein the film aligned in the horizontal direction relative to the in-plane direction of the vertically aligned liquid crystal cured film is a horizontally aligned liquid crystal cured film. 如請求項18或19之橢圓偏光板,其中上述朝水平方向配向之膜之遲相軸與偏光膜之吸收軸所成之角為45±5°。 For example, the elliptical polarizing plate of claim 18 or 19, wherein the angle between the retardation axis of the horizontally oriented film and the absorption axis of the polarizing film is 45±5°. 如請求項18或19之橢圓偏光板,其中上述偏光膜包含液晶化合物相對於偏光膜之膜面內朝水平方向配向之水平配向液晶硬化膜,且該水平配向液晶硬化膜包含二色性色素。 As in claim 18 or 19, the elliptical polarizing plate, wherein the polarizing film comprises a horizontally aligned liquid crystal cured film in which the liquid crystal compound is aligned in a horizontal direction relative to the film surface of the polarizing film, and the horizontally aligned liquid crystal cured film comprises a dichroic pigment. 如請求項21之橢圓偏光板,其中上述二色性色素具有偶氮基。 As in claim 21, the elliptical polarizing plate, wherein the dichroic dye has an azo group. 如請求項21之橢圓偏光板,其中上述構成偏光膜之水平配向液晶硬化膜係液晶化合物於相對於膜之面內方向朝水平方向配向之層列相之狀態下硬化而成的硬化膜。 As in claim 21, the horizontally aligned liquid crystal cured film constituting the polarizing film is a cured film formed by curing the liquid crystal compound in a lamellar phase state aligned in a horizontal direction relative to the in-plane direction of the film. 一種有機EL顯示裝置,其包含如請求項18至23中任一項之橢圓偏光板。 An organic EL display device comprising an elliptical polarizing plate as claimed in any one of claims 18 to 23.
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