TW202317736A - Compound, composition for anisotropic dye film comprising said compound, anisotropic dye film, and optical element - Google Patents

Compound, composition for anisotropic dye film comprising said compound, anisotropic dye film, and optical element Download PDF

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TW202317736A
TW202317736A TW111138285A TW111138285A TW202317736A TW 202317736 A TW202317736 A TW 202317736A TW 111138285 A TW111138285 A TW 111138285A TW 111138285 A TW111138285 A TW 111138285A TW 202317736 A TW202317736 A TW 202317736A
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ring
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liquid crystal
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髙見芳恵
志賀靖
秋山誠治
大澤輝恒
小島奏也
大泉淳一
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日商三菱化學股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B43/00—Preparation of azo dyes from other azo compounds
    • C09B43/08—Preparation of azo dyes from other azo compounds by reduction
    • C09B43/10—Preparation of azo dyes from other azo compounds by reduction with formation of a new azo or an azoxy bridge
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors

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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optics & Photonics (AREA)
  • Polymers & Plastics (AREA)
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  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Liquid Crystal Substances (AREA)
  • Polarising Elements (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A compound which is represented by formula (1). (1): X-A1-(N=N-A2)n-N=N-A3-Y (-A1- and -A2- are a divalent group from a possibly substituted polycyclic aromatic heterocycle that contains at least one S atom, or a divalent group from a possibly substituted aromatic hydrocarbon ring. -A3- is a divalent group from a possibly substituted aromatic hydrocarbon ring. -X is a monovalent organic group. -Y is -N(-Ry)-Rx, -OC(=O)-Rx, or -C(=O)-O-Rx. -Rx is a branched C3-C15 alkyl group. -Ry is a hydrogen atom or a possibly branched C1-C15 alkyl group. n is 1 to 3. -A1- and -A2- are not both a divalent group from a possibly substituted aromatic hydrocarbon ring.).

Description

化合物、含有該化合物的各向異性色素膜用組成物、各向異性色素膜和光學元件Compound, composition for anisotropic dye film containing same, anisotropic dye film and optical element

本發明是有關於一種化合物，其有效用於調光元件、液晶元件（液晶顯示器（liquid crystal display，LCD））、及有機電致發光元件（有機發光二極體（organic light-emitting diode，OLED））的顯示元件所包括的偏光膜等。並且本發明是有關於一種含有該化合物的各向異性色素膜形成用組成物、各向異性色素膜和光學元件。The present invention relates to a compound, which is effectively used in a light-adjusting element, a liquid crystal element (liquid crystal display (liquid crystal display, LCD)), and an organic electroluminescence element (organic light-emitting diode (organic light-emitting diode, OLED) )) The display element includes polarizing film, etc. Furthermore, the present invention relates to a composition for forming an anisotropic dye film containing the compound, an anisotropic dye film, and an optical element.

在LCD中，使用直線偏光膜及圓偏光膜以控制顯示時的旋光性或雙折射性。在OLED中，亦使用圓偏光膜以防止亮處的外界光的反射。In LCDs, linear polarizing films and circular polarizing films are used to control optical rotation or birefringence during display. In OLEDs, circular polarizing films are also used to prevent reflection of ambient light in bright places.

先前，作為此種偏光膜，例如已知有包括藉由低濃度的碘對聚乙烯醇（poly vinyl alcohol，PVA）進行染色而得的偏光膜（碘-PVA偏光膜）者（專利文獻1）。然而，使PVA為低濃度的碘-PVA偏光板根據使用環境不同，存在碘昇華或變質導致色澤發生變化等問題、或者因PVA的延伸被緩和而產生翹曲等問題。Conventionally, as such a polarizing film, for example, one including a polarizing film obtained by dyeing polyvinyl alcohol (PVA) with a low concentration of iodine (iodine-PVA polarizing film) is known (Patent Document 1). . However, iodine-PVA polarizing plates with low PVA concentrations have problems such as color changes due to iodine sublimation or deterioration, or warping due to relaxation of PVA stretching, depending on the usage environment.

亦已知塗佈含有色素的液晶組成物而形成的各向異性色素膜作為偏光膜發揮功能（專利文獻2）。然而，關於在波長560 nm～800 nm的範圍具有極大吸收且兼顧充分的二色比與溶解性的二色性色素，並未進行揭示。It is also known that an anisotropic dye film formed by coating a liquid crystal composition containing a dye functions as a polarizing film (Patent Document 2). However, there is no disclosure regarding a dichroic dye that has a maximum absorption in a wavelength range of 560 nm to 800 nm and that satisfies a sufficient dichroic ratio and solubility.

關於在波長550 nm～800 nm的範圍具有極大吸收的二色性色素，已知有將具有苯並噻唑或噻吩並噻唑骨架的色素與聚合性液晶組合而得的各向異性色素膜（專利文獻3）。然而，關於具有苯並噻唑或噻吩並噻唑骨架的色素，有於要求溶解性的各向異性色素膜形成用組成物中產生色素析出之虞。An anisotropic dye film obtained by combining a dye having a benzothiazole or thienothiazole skeleton with a polymerizable liquid crystal is known as a dichroic dye having maximum absorption in a wavelength range of 550 nm to 800 nm (Patent Document 3). However, with respect to a dye having a benzothiazole or thienothiazole skeleton, there is a possibility that the dye may precipitate in an anisotropic dye film-forming composition requiring solubility.

專利文獻1：日本專利特開平1-105204號公報 專利文獻2：日本專利特開2013-210624號公報 專利文獻3：日本專利特開2016-170368號公報 Patent Document 1: Japanese Patent Laid-Open No. 1-105204 Patent Document 2: Japanese Patent Laid-Open No. 2013-210624 Patent Document 3: Japanese Patent Laid-Open No. 2016-170368

於塗佈含有色素的液晶組成物而形成的偏光膜中，期望即便為薄膜亦具有高的光吸收選擇性能，於350 nm～800 nm的波長區域中不會發生漏光。因此，需要以如下方式進行調節，即，使用多種二色性高的色素來全面地吸收350 nm～800 nm的波長區域。然而，在所述情況下，由於包含多種色素，故組成物中的色素濃度變高，在以薄膜條件進行塗佈的情況下，相對於液晶的色素濃度變濃，而導致色素容易析出，從而會使塗佈性能下降。In a polarizing film formed by coating a liquid crystal composition containing a pigment, it is desired to have high light absorption selectivity even as a thin film, and to prevent light leakage in the wavelength region of 350 nm to 800 nm. Therefore, it is necessary to adjust such that the entire wavelength range of 350 nm to 800 nm is absorbed using a plurality of dyes with high dichroism. However, in the above case, since a plurality of dyes are contained, the concentration of the dye in the composition becomes high, and in the case of coating under thin film conditions, the concentration of the dye relative to the liquid crystal becomes thicker, and the dye is easily precipitated, thereby Coating performance will be reduced.

本發明的目的在於提供一種色素化合物，其溶解性高而無需擔心在組成物中析出等，因此塗佈性能良好，所獲得的各向異性色素膜表現出高二色性。 本發明的目的還在於提供一種含有該化合物的各向異性色素膜形成用組成物、各向異性色素膜和光學元件。 [解決課題之手段] An object of the present invention is to provide a pigment compound which has high solubility without fear of precipitation in a composition, etc., and therefore has good coating performance, and the obtained anisotropic pigment film exhibits high dichroism. Another object of the present invention is to provide a composition for forming an anisotropic dye film containing the compound, an anisotropic dye film, and an optical element. [Means to solve the problem]

本發明人發現具有特定結構的化合物可解決所述課題。 本發明具有以下形態。 The present inventors found that a compound having a specific structure can solve the above-mentioned problems. The present invention has the following aspects.

[1] 一種化合物，由下述式（1）表示。 X-A 1-(N=N-A 2) n-N=N-A 3-Y      …（1） （式（1）中， -A 1-及-A 2-分別獨立地表示可具有取代基的含有一個以上S原子的多環式芳香族雜環的二價基、或者可具有取代基的芳香族烴環的二價基， -A 3-表示可具有取代基的芳香族烴環的二價基， -X表示一價有機基， -Y表示-N(-R y)-R x、-OC(=O)-R x、或者-C(=O)-O-R x， -R x表示可具有取代基的、具有分支的碳數3～15的烷基， -R y表示氫原子、或者可具有分支的碳數1～15的烷基，所述可具有分支的碳數1～15的烷基可具有取代基， 所述具有分支的碳數3～15的烷基及所述可具有分支的碳數1～15的烷基中所含的一個或者一個以上的亞甲基可為由-O-、-S-、-NH-、-N(-R z)-、-C(=O)-、-C(=O)-O-、-C(=O)-NH-、-CHF-、-CF 2-、-CHCl-、-CCl 2-、或者聚合性基取代的結構，-R z表示氫原子、或者可具有分支的碳數1～15的烷基， n表示1、2或者3， 在n為2或者3的情況下，多個-A 2-彼此可相同亦可不同， 其中，不存在-A 1-及-A 2-均為可具有取代基的芳香族烴環的二價基的情況） [1] A compound represented by the following formula (1). XA 1 -(N=NA 2 ) n -N=NA 3 -Y...(1) (In the formula (1), -A 1 - and -A 2 - each independently represent a substituent containing one or more S Atomic polycyclic aromatic heterocyclic divalent group, or a divalent group of an aromatic hydrocarbon ring that may have a substituent, -A 3 -represents a divalent group of an aromatic hydrocarbon ring that may have a substituent, -X Represents a monovalent organic group, -Y represents -N(-R y )-R x , -OC(=O)-R x , or -C(=O)-OR x , -R x represents a substituent , an alkyl group with a branched carbon number of 3 to 15, -R y represents a hydrogen atom, or an alkyl group with a branched carbon number of 1 to 15, and the branched alkyl group with a carbon number of 1 to 15 may have As a substituent, one or more methylene groups contained in the branched alkyl group with 3 to 15 carbons and the branched alkyl group with 1 to 15 carbons may be composed of -O-, -S-, -NH-, -N(-R z )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, - CF 2 -, -CHCl-, -CCl 2 -, or a structure substituted with a polymerizable group, -R z represents a hydrogen atom, or an alkyl group with 1 to 15 carbons that may have branches, n represents 1, 2 or 3, When n is 2 or 3, a plurality of -A 2 - may be the same as or different from each other, wherein none of -A 1 - and -A 2 - are divalent aromatic hydrocarbon rings which may have substituents base case)

[2] 如[1]所述的化合物，其中，在所述式（1）中，含有一個以上S原子的多環式芳香族雜環為苯並噻吩環、噻吩並吡咯環、噻吩並噻吩環、呋喃並噻唑環、噻吩並呋喃環、噻吩並噻唑環、苯並異噻唑環、或者苯並噻唑環。[2] The compound according to [1], wherein, in the formula (1), the polycyclic aromatic heterocycle containing one or more S atoms is a benzothiophene ring, a thienopyrrole ring, a thienothiophene ring ring, furothiazole ring, thienofuran ring, thienothiazole ring, benzisothiazole ring, or benzothiazole ring.

[3] 如[1]或[2]所述的化合物，其中，在所述式（1）中，-A 2-的至少一個為可具有取代基的含有一個以上S原子的多環式芳香族雜環的二價基。 [3] The compound according to [1] or [2], wherein, in the formula (1), at least one of -A 2 - is a polycyclic aromatic compound containing one or more S atoms which may have a substituent. Divalent group of heterocyclic rings.

[4] 如[1]至[3]中任一項所述的化合物，其中，在所述式（1）中，-Y為-N(-R y)-R x，-R x為可具有取代基的、具有分支的碳數3～15的烷基，-R y為氫原子、或者可具有分支的碳數1～15的烷基，-R x及-R y的烷基中的碳數的合計為15以下。 [4] The compound as described in any one of [1] to [3], wherein, in the formula (1), -Y is -N(-R y )-R x , and -R x is optional A substituent, branched alkyl group with 3 to 15 carbon atoms, -R y is a hydrogen atom, or a branched alkyl group with 1 to 15 carbon atoms, among the alkyl groups of -R x and -R y The sum of the carbon numbers is 15 or less.

[5] 如[1]至[4]中任一項所述的化合物，其中，在所述式（1）中，-Y為-N(-R y)-R x，-R x為可具有取代基的、具有分支的碳數3～15的烷基，-R y為氫原子、或者不具有分支的碳數1～15的烷基，所述不具有分支的碳數1～15的烷基可具有取代基。 [5] The compound as described in any one of [1] to [4], wherein, in the formula (1), -Y is -N(-R y )-R x , and -R x is optional A substituent, branched alkyl group with 3 to 15 carbons, -R y is a hydrogen atom, or an alkyl group with 1 to 15 carbons without branches, and the branched alkyl group with 1 to 15 carbons An alkyl group may have a substituent.

[6] 如[1]至[5]中任一項所述的化合物，其中，在所述式（1）中，-A 3-為可具有取代基的伸苯基。 [6] The compound according to any one of [1] to [5], wherein, in the formula (1), -A 3 - is an optionally substituted phenylene group.

[7] 如[1]至[6]中任一項所述的化合物，其中，在所述式（1）中，-A 1-為可具有取代基的伸苯基。 [7] The compound according to any one of [1] to [6], wherein, in the formula (1), -A 1 - is an optionally substituted phenylene group.

[8] 如[1]至[7]中任一項所述的化合物，其中，在所述式（1）中，-X為不具有分支的碳數3以上的烷基、烷氧基、烷基酯基、烷氧基羰基或者烷基硫基。[8] The compound according to any one of [1] to [7], wherein, in the formula (1), -X is an unbranched alkyl group having 3 or more carbon atoms, an alkoxy group, Alkyl ester group, alkoxycarbonyl group or alkylthio group.

[9] 一種各向異性色素膜形成用組成物，含有如[1]至[8]中任一項所述的化合物以及聚合性液晶化合物。[9] A composition for forming an anisotropic dye film, comprising the compound according to any one of [1] to [8] and a polymerizable liquid crystal compound.

[10] 如[9]所述的各向異性色素膜形成用組成物，其中，所述聚合性液晶化合物是具有碳-碳三鍵的化合物。[10] The anisotropic dye film-forming composition according to [9], wherein the polymerizable liquid crystal compound is a compound having a carbon-carbon triple bond.

[11] 如[9]或[10]所述的各向異性色素膜形成用組成物，其中，所述聚合性液晶化合物的質量濃度為所述式（1）所表示的化合物的質量濃度的一倍以上。[11] The anisotropic dye film-forming composition according to [9] or [10], wherein the mass concentration of the polymerizable liquid crystal compound is equal to the mass concentration of the compound represented by the formula (1). more than double.

[12] 如[9]至[11]中任一項所述的各向異性色素膜形成用組成物，更含有如下色素，所述色素在350 nm～800 nm的波長區域的吸收曲線中顯示出最大值的波長較所述式（1）所表示的化合物在350 nm～800 nm的波長區域的吸收曲線中顯示出最大值的波長更短。[12] The composition for forming an anisotropic pigment film according to any one of [9] to [11], further comprising a pigment having an absorption curve in the wavelength range of 350 nm to 800 nm: The wavelength showing the maximum value is shorter than the wavelength showing the maximum value in the absorption curve of the compound represented by the formula (1) in the wavelength region of 350 nm to 800 nm.

[13] 如[12]所述的各向異性色素膜形成用組成物，其中，所述色素為偶氮色素。[13] The anisotropic dye film-forming composition according to [12], wherein the dye is an azo dye.

[14] 一種各向異性色素膜，使用如[9]至[13]中任一項所述的各向異性色素膜形成用組成物而形成。[14] An anisotropic dye film formed using the anisotropic dye film-forming composition according to any one of [9] to [13].

[15] 一種光學元件，包括如[14]所述的各向異性色素膜。[15] An optical element comprising the anisotropic pigment film as described in [14].

[16] 一種各向異性色素膜的製造方法，具有將如[9]至[13]中任一項所述的各向異性色素膜形成用組成物塗佈於基板的步驟。 [發明的效果] [16] A method for producing an anisotropic dye film, comprising the step of applying the composition for forming an anisotropic dye film according to any one of [9] to [13] on a substrate. [Effect of the invention]

本發明的化合物是具有適度大體積的取代基且兼顧高二色性與溶解度者。 本發明的各向異性色素膜形成用組成物由於包含此種本發明的化合物，故而可抑制化合物的析出，謀求塗佈性能的提昇，並且達成高二色比。 藉由使用本發明的各向異性色素膜形成用組成物的各向異性色素膜和光學元件，可達成優異的光學性能、特別是充分的二色比。 The compounds of the present invention have moderately bulky substituents and have both high dichroism and solubility. Since the anisotropic dye film-forming composition of the present invention contains such a compound of the present invention, precipitation of the compound can be suppressed, coating performance can be improved, and a high dichromatic ratio can be achieved. Excellent optical performance, especially sufficient dichromatic ratio can be achieved by the anisotropic dye film and optical element using the composition for anisotropic dye film formation of this invention.

以下，對本發明的實施方式進行具體說明。本發明並不限定於以下的實施方式，可在其主旨範圍內進行各種變更而實施。Hereinafter, embodiments of the present invention will be specifically described. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist.

本發明中所謂各向異性色素膜，是指任意兩個方向上的電磁性質具有各向異性的色素膜，所述任意兩個方向選自各向異性色素膜的厚度方向及任意正交的面內兩個方向的立體座標系統中的合計三個方向中。作為電磁性質，例如可列舉吸收、折射等光學性質、電阻、電容等電性質。 作為具有吸收、折射等光學各向異性的膜，例如可列舉直線偏光膜、圓偏光膜等偏光膜、相位差膜、導電各向異性色素膜。 本發明的各向異性色素膜較佳為用作偏光膜或導電各向異性色素膜，更佳為用於偏光膜。 The so-called anisotropic pigment film in the present invention refers to a pigment film with anisotropic electromagnetic properties in any two directions, and the arbitrary two directions are selected from the thickness direction of the anisotropic pigment film and any orthogonal plane. The sum of the three directions in the three-dimensional coordinate system in the two directions. Examples of electromagnetic properties include optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance. Examples of the film having optical anisotropy such as absorption and refraction include polarizing films such as linear polarizing films and circular polarizing films, retardation films, and conductive anisotropic dye films. The anisotropic dye film of the present invention is preferably used as a polarizing film or a conductive anisotropic dye film, more preferably used as a polarizing film.

[化合物] 本發明的化合物是下述式（1）所表示的新穎化合物。 [compound] The compound of the present invention is a novel compound represented by the following formula (1).

X-A 1-(N=N-A 2) n-N=N-A 3-Y      …（1） （式（1）中， -A 1-及-A 2-分別獨立地表示可具有取代基的含有一個以上S原子的多環式芳香族雜環的二價基、或者可具有取代基的芳香族烴環的二價基， -A 3-表示可具有取代基的芳香族烴環的二價基， -X表示一價有機基， -Y表示-N(-R y)-R x、-OC(=O)-R x、或者-C(=O)-O-R x， -R x表示可具有取代基的、具有分支的碳數3～15的烷基， -R y表示氫原子、或者可具有分支的碳數1～15的烷基，所述可具有分支的碳數1～15的烷基可具有取代基， 所述具有分支的碳數3～15的烷基及所述可具有分支的碳數1～15的烷基中所含的一個或者一個以上的亞甲基可為由-O-、-S-、-NH-、-N(-R z)-、-C(=O)-、-C(=O)-O-、-C(=O)-NH-、-CHF-、-CF 2-、-CHCl-、-CCl 2-、或者聚合性基取代的結構，-R z表示氫原子、或者可具有分支的碳數1～15的烷基， n表示1、2或者3， 在n為2或者3的情況下，多個-A 2-彼此可相同亦可不同， 其中，不存在-A 1-及-A 2-均為可具有取代基的芳香族烴環的二價基的情況） XA 1 -(N=NA 2 ) n -N=NA 3 -Y...(1) (In the formula (1), -A 1 - and -A 2 - each independently represent a substituent containing one or more S Atomic polycyclic aromatic heterocyclic divalent group, or a divalent group of an aromatic hydrocarbon ring that may have a substituent, -A 3 -represents a divalent group of an aromatic hydrocarbon ring that may have a substituent, -X Represents a monovalent organic group, -Y represents -N(-R y )-R x , -OC(=O)-R x , or -C(=O)-OR x , -R x represents a substituent , an alkyl group with a branched carbon number of 3 to 15, -R y represents a hydrogen atom, or an alkyl group with a branched carbon number of 1 to 15, and the branched alkyl group with a carbon number of 1 to 15 may have As a substituent, one or more methylene groups contained in the branched alkyl group with 3 to 15 carbons and the branched alkyl group with 1 to 15 carbons may be composed of -O-, -S-, -NH-, -N(-R z )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, - CF 2 -, -CHCl-, -CCl 2 -, or a structure substituted with a polymerizable group, -R z represents a hydrogen atom, or an alkyl group with 1 to 15 carbons that may have branches, n represents 1, 2 or 3, When n is 2 or 3, a plurality of -A 2 - may be the same as or different from each other, wherein none of -A 1 - and -A 2 - are divalent aromatic hydrocarbon rings which may have substituents base case)

（-X） -X表示一價有機基。 (-X) -X represents a monovalent organic group.

作為-X中的一價有機基，可列舉：氫原子、羥基、胺基、氰基、胺甲醯基、硝基、鹵素原子、-R a、-O-R a、-NH-R a、-C(=O)-R a、-C(=O)-O-R a、-C(=O)-NH-R a、-C(=O)-N(-R b)-R a、-O-C(=O)-R a、-NH-C(=O)-R a、-N(-R b)-C(=O)-R a等。 Examples of the monovalent organic group in -X include hydrogen atom, hydroxyl group, amino group, cyano group, carbamoyl group, nitro group, halogen atom, -R a , -OR a , -NH-R a , - C(=O)-R a , -C(=O)-OR a , -C(=O)-NH-R a , -C(=O)-N(-R b )-R a , -OC (=O)-R a , -NH-C(=O)-R a , -N(-R b )-C(=O)-R a and the like.

-R a及-R b分別獨立地表示可具有分支的碳數為1～15、較佳為1～10、更佳為1～6的烷基，構成環的原子數為5～14、較佳為5～10的環烷基，或者構成環的原子數為5～14、較佳為5～10的芳基。 所述烷基、環烷基及芳基可分別具有取代基。 -R a及-R b可一體地形成碳數為2～15、較佳為2～10的環，該環可具有取代基。 -R a and -R b each independently represent an alkyl group having a branched carbon number of 1 to 15, preferably 1 to 10, more preferably 1 to 6, and the number of atoms constituting the ring is 5 to 14, preferably Preferably, it is a cycloalkyl group with 5-10 atoms, or an aryl group with 5-14, preferably 5-10 atoms constituting the ring. Each of the alkyl group, cycloalkyl group and aryl group may have a substituent. -R a and -R b may integrally form a ring having 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms, and this ring may have a substituent.

所述可具有分支的碳數1～15的烷基、構成環的原子數為5～14的環烷基、或者-R a及-R b一體地形成的環中所含的一個或者一個以上的亞甲基可為由-O-、-S-、-NH-、-C(=O)-、-C(=O)-O-、-C(=O)-NH-、-CHF-、-CF 2-、-CHCl-、-CCl 2-取代（displace）的結構，亦可為由丙烯醯氧基、甲基丙烯醯氧基、縮水甘油氧基的聚合性基取代的結構。 One or more of the above-mentioned alkyl group having 1 to 15 carbon atoms which may have a branch, a cycloalkyl group having 5 to 14 atoms constituting the ring, or a ring integrally formed by -R a and -R b The methylene group can be composed of -O-, -S-, -NH-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF- , -CF 2 -, -CHCl-, -CCl 2 - may be a displaced structure, or a structure substituted with a polymerizable group such as acryloxy, methacryloxy, or glycidyloxy.

作為-R a及-R b中的可具有分支的碳數1～15的烷基中容許的取代基，例如可列舉：-OH、-O-R f、-O-C(=O)-R f、-NH 2、-NH-R f、-N(-R g)-R f、-C(=O)-R f、-C(=O)-O-R f、-C(=O)-NH 2、-C(=O)-NH-R f、-C(=O)-N(-R g)-R f、-SH、-S-R f、胺磺醯基、羧基、氰基、硝基、鹵素、丙烯醯氧基、甲基丙烯醯氧基、縮水甘油氧基等聚合性基等。-R f及-R g分別獨立地表示碳數為1～15、較佳為1～10的直鏈狀或分支狀的烷基。 所述碳數1～15的直鏈狀或分支狀的烷基中所含的一個或者一個以上的亞甲基可為由-O-、-S-、-NH-、-N(R h)-、-C(=O)-、-C(=O)-O-、-C(=O)-NH-、-CHF-、-CF 2-、-CHCl-、-CCl 2-取代（displace）的結構，亦可為由丙烯醯氧基、甲基丙烯醯氧基、縮水甘油氧基的聚合性基取代的結構。此處，R h表示碳數1～6的直鏈狀或者分支狀的烷基。 Examples of acceptable substituents for C1-C15 alkyl groups in -R a and -R b include -OH, -OR f , -OC(=O)-R f , - NH 2 , -NH-R f , -N(-R g )-R f , -C(=O)-R f , -C(=O)-OR f , -C(=O)-NH 2 , -C(=O)-NH-R f , -C(=O)-N(-R g )-R f , -SH, -SR f , sulfamoyl, carboxyl, cyano, nitro, halogen , acryloxy, methacryloxy, glycidyloxy and other polymeric groups. -R f and -R g each independently represent a linear or branched alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms. One or more methylene groups contained in the linear or branched alkyl group having 1 to 15 carbons may be formed from -O-, -S-, -NH-, -N(R h ) -, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF 2 -, -CHCl-, -CCl 2 -substituted (displace ) or a structure substituted with polymerizable groups such as acryloxy, methacryloxy, or glycidyloxy. Here, Rh represents a linear or branched alkyl group having 1 to 6 carbon atoms.

其中，作為-R a及-R b中的可具有分支的碳數1～15的烷基中容許的取代基，較佳為-O-R f，例如可列舉：甲氧基、乙氧基、正丙氧基、正丁氧基、正戊氧基、正己氧基、正庚氧基、正辛氧基、丙烯醯氧基、甲基丙烯醯氧基、縮水甘油氧基等。 Among them, the acceptable substituents of -R a and -R b in C 1 to 15 alkyl groups which may have branching are preferably -OR f , for example, methoxy, ethoxy, n- Propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, acryloxy, methacryloxy, glycidyloxy, etc.

作為-R a及-R b中的構成環的原子數為5～14的環烷基或芳基中容許的取代基，例如可列舉：-R i、-OH、-O-R i、-O-C(=O)-R i、-NH 2、-NH-R i、-N(-R j)-R i、-C(=O)-R i、-C(=O)-O-R i、-C(=O)-NH 2、-C(=O)-NH-R i、-C(=O)-N(-R j)-R i、-SH、-S-R i、三氟甲基、胺磺醯基、羧基、氰基、硝基、鹵素。此處，-R i及-R j分別獨立地表示碳數為1～10、較佳為1～5的直鏈狀或分支狀的烷基。 Examples of acceptable substituents for cycloalkyl groups or aryl groups having 5 to 14 atoms constituting the ring in -R a and -R b include -R i , -OH, -OR i , -OC( =O)-R i , -NH 2 , -NH-R i , -N(-R j )-R i , -C(=O)-R i , -C(=O)-OR i , -C (=O)-NH 2 , -C(=O)-NH-R i , -C(=O)-N(-R j )-R i , -SH, -SR i , trifluoromethyl, amine Sulfonyl, carboxyl, cyano, nitro, halogen. Here, -R i and -R j each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.

其中，作為-R a及-R b中的構成環的原子數為5～14的環烷基或芳基中容許的取代基，較佳為-R i、-O-R i，例如可列舉：甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、2-乙基己基、甲氧基、乙氧基、正丙氧基、正丁氧基、正戊氧基、正己氧基、正庚氧基、正辛氧基、2-乙基己基氧基、5,5-二甲基-3-甲基己基氧基等。 Among them, -R i and -OR i are preferable as substituents allowed in the cycloalkyl group or aryl group having 5 to 14 atoms constituting the ring in -R a and -R b , for example, forma Base, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, methoxy, ethoxy, n-propoxy, n-butoxy , n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, 5,5-dimethyl-3-methylhexyloxy, etc.

作為-R a及-R b的構成環的原子數為5～14的環烷基的環烷烴環，例如可列舉：環丙烷環、環丁烷環、環戊烷環、環己烷環、環庚烷環、環辛烷環、環己烯環、降莰烷環、莰烷環、金剛烷環、四氫萘環、雙環[2.2.2]辛烷環等。 As the cycloalkane ring of a cycloalkyl group having 5 to 14 atoms constituting the ring of -R a and -R b , for example, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, Cycloheptane ring, cyclooctane ring, cyclohexene ring, norbornane ring, camphane ring, adamantane ring, tetrahydronaphthalene ring, bicyclo[2.2.2]octane ring, etc.

作為-R a及-R b的構成環的原子數為5～14的芳基，可列舉芳香族雜環的一價基、或作為-A 3-中的芳香族烴環而在後面例示的環的一價基。 Examples of the aryl group having 5 to 14 atoms constituting the ring of -R a and -R b include a monovalent group of an aromatic heterocyclic ring, or an aromatic hydrocarbon ring in -A 3 - exemplified later. The monovalent base of the ring.

作為-R a及-R b，較佳為可具有分支的碳數1～15的烷基、或者-R a及-R b一體地形成可具有取代基的碳數2～15的環。進而，更佳為可具有分支的碳數1～6的烷基、或者-R a及-R b一體地形成環；進而佳為可具有分支的碳數1～3的烷基、或者-R a及-R b一體地形成環。藉由如上所述，本發明的化合物的分子配向呈變良好的趨勢。 -R a and -R b are preferably an alkyl group having 1 to 15 carbons which may have a branch, or -R a and -R b integrally form a ring having 2 to 15 carbons which may have a substituent. Furthermore, an alkyl group having 1 to 6 carbon atoms that may have branches, or -R a and -R b integrally forming a ring is more preferable; an alkyl group having 1 to 3 carbon atoms that may have branches, or -R a and -R b integrally form a ring. As described above, the molecular alignment of the compound of the present invention tends to become better.

作為-X中的一價有機基，就兼顧高二色比與高溶解度的觀點而言，較佳為不具有分支的碳數3以上的烷基（-R）、烷氧基（-O-R）、烷基酯基（-O-C(=O)-R）、烷氧基羰基（-C(=O)-O-R）、或者烷基硫基（-S-R）。此處，就與本發明中使用的聚合性液晶化合物的分子配向變良好的觀點而言，-X的碳數較佳為3以上且15以下，更佳為3以上且10以下。As the monovalent organic group in -X, from the viewpoint of achieving both a high dichroic ratio and high solubility, an alkyl group (-R) having 3 or more carbon atoms without branching, an alkoxy group (-O-R), Alkyl ester (-O-C(=O)-R), alkoxycarbonyl (-C(=O)-O-R), or alkylthio (-S-R). Here, the carbon number of -X is preferably from 3 to 15, more preferably from 3 to 10, from the viewpoint of favorable molecular alignment with the polymerizable liquid crystal compound used in the present invention.

作為-R，例如可列舉：正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基。就與本發明中使用的聚合性液晶化合物的分子配向變良好的觀點而言，作為-R，較佳為正丁基、正戊基、正己基、正庚基、正辛基。Examples of -R include n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and n-nonyl. -R is preferably n-butyl, n-pentyl, n-hexyl, n-heptyl, or n-octyl from the viewpoint of better molecular alignment with the polymerizable liquid crystal compound used in the present invention.

作為-X中的一價有機基，就使與聚合性液晶化合物的分子配向良好的觀點而言，較佳為不具有聚合性基。另一方面，作為-X中的一價有機基，就提高各向異性色素膜的機械強度的觀點而言，較佳為具有聚合性基。The monovalent organic group in -X preferably does not have a polymerizable group from the viewpoint of making molecular alignment with the polymerizable liquid crystal compound favorable. On the other hand, as a monovalent organic group in -X, it is preferable to have a polymeric group from a viewpoint of improving the mechanical strength of an anisotropic dye film.

（-Y） Y表示-N(-R y)-R x、-OC(=O)-R x或者-C(=O)-O-R x。 (-Y) Y represents -N(-R y )-R x , -OC(=O)-R x or -C(=O)-OR x .

上述中，就本發明的化合物的分子配向性變良好的觀點而言，Y較佳為-N(-R y)-R x。 Among the above, Y is preferably -N(-R y )-R x from the viewpoint of improving the molecular alignment of the compound of the present invention.

此處，-R x表示可具有取代基的、具有分支的碳數3～15的烷基，就與聚合性液晶化合物的分子配向變良好的觀點而言，所述烷基的碳數較佳為3～10，更佳為3～8，進而佳為3～6。 Here, -R x represents a branched alkyl group having 3 to 15 carbon atoms which may have a substituent, and the carbon number of the alkyl group is preferably from the viewpoint of better molecular alignment with the polymerizable liquid crystal compound 3-10, more preferably 3-8, still more preferably 3-6.

作為-R x，具體而言，例如可列舉：1-甲基乙基、1,1-二甲基乙基、1-甲基丙基、2-甲基丙基、1,2-二甲基丙基、2,2-二甲基丙基、1,2,2-三甲基丙基、1-甲基丁基、2-甲基丁基、3-甲基丁基、3,3-二甲基丁基、2,3-二甲基丁基、1,3-二甲基丁基、1,3,3-三甲基丁基、2,3,3-三甲基丁基、2,2,3-三甲基丁基、1,2,2-三甲基丁基、4-甲基戊基、3-甲基戊基、2-甲基戊基、1-甲基戊基、4,4-二甲基戊基、3,3-二甲基戊基、2,2-二甲基戊基、3,4-二甲基戊基、2,4-二甲基戊基、1,4-二甲基戊基、3,4,4-三甲基戊基、2,4,4-三甲基戊基、1,4,4-三甲基戊基、3,3,4-三甲基戊基、2,3,3-三甲基戊基、1,3,3-三甲基戊基、2,2,4-三甲基戊基、2,2,3-三甲基戊基、1,2,2-三甲基戊基、2,3,4-三甲基戊基、5-甲基己基、4-甲基己基、3-甲基己基、2-甲基己基、1-甲基己基、5,5-二甲基己基、4,4-二甲基己基、3,3-二甲基己基、2,2-二甲基己基、4,5-二甲基己基、3,5-二甲基己基、2,5-二甲基己基、1,5-二甲基己基、1,4-二甲基己基、4,5,5-三甲基己基、3,5,5-三甲基己基、2,5,5-三甲基己基、1,5,5-三甲基己基、6-甲基庚基、5-甲基庚基、6,6-二甲基庚基、5,6-二甲基庚基、4,6-二甲基庚基、3,6-二甲基庚基、2,6-二甲基庚基、1,6-二甲基庚基、6-甲基辛基、3-甲基辛基、1-甲基辛基，1-甲基壬基、環己基、4-甲基環己基、4-乙基環己基、4-丙基環己基、4-丁基環己基等。 Specific examples of -R x include 1-methylethyl, 1,1-dimethylethyl, 1-methylpropyl, 2-methylpropyl, 1,2-dimethyl propyl, 2,2-dimethylpropyl, 1,2,2-trimethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 3,3 -Dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 1,3,3-trimethylbutyl, 2,3,3-trimethylbutyl , 2,2,3-trimethylbutyl, 1,2,2-trimethylbutyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methyl Pentyl, 4,4-dimethylpentyl, 3,3-dimethylpentyl, 2,2-dimethylpentyl, 3,4-dimethylpentyl, 2,4-dimethylpentyl Pentyl, 1,4-dimethylpentyl, 3,4,4-trimethylpentyl, 2,4,4-trimethylpentyl, 1,4,4-trimethylpentyl, 3 ,3,4-trimethylpentyl, 2,3,3-trimethylpentyl, 1,3,3-trimethylpentyl, 2,2,4-trimethylpentyl, 2,2 ,3-trimethylpentyl, 1,2,2-trimethylpentyl, 2,3,4-trimethylpentyl, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl , 2-methylhexyl, 1-methylhexyl, 5,5-dimethylhexyl, 4,4-dimethylhexyl, 3,3-dimethylhexyl, 2,2-dimethylhexyl, 4 ,5-dimethylhexyl, 3,5-dimethylhexyl, 2,5-dimethylhexyl, 1,5-dimethylhexyl, 1,4-dimethylhexyl, 4,5,5- Trimethylhexyl, 3,5,5-trimethylhexyl, 2,5,5-trimethylhexyl, 1,5,5-trimethylhexyl, 6-methylheptyl, 5-methylheptyl base, 6,6-dimethylheptyl, 5,6-dimethylheptyl, 4,6-dimethylheptyl, 3,6-dimethylheptyl, 2,6-dimethylheptyl Base, 1,6-dimethylheptyl, 6-methyloctyl, 3-methyloctyl, 1-methyloctyl, 1-methylnonyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, 4-butylcyclohexyl and the like.

所述基中，就本發明的化合物的分子配向變良好的觀點而言，作為-R x，較佳為1-甲基乙基、1,1-二甲基乙基、1-甲基丙基、2-甲基丙基、1,2-二甲基丙基、2,2-二甲基丙基、1,2,2-三甲基丙基、1-甲基丁基、2-甲基丁基、3-甲基丁基、3,3-二甲基丁基、2,3-二甲基丁基、1,3-二甲基丁基、1,3,3-三甲基丁基、2,3,3-三甲基丁基、1,2,2-三甲基丁基、4-甲基戊基、3-甲基戊基、2-甲基戊基、1-甲基戊基、4,4-二甲基戊基、3,4,4-三甲基戊基、2,4,4-三甲基戊基、1,4,4-三甲基戊基、5-甲基己基、4-甲基己基、3-甲基己基、2-甲基己基、1-甲基己基、5,5-二甲基己基、3,5,5-三甲基己基。 Among the above-mentioned groups, from the viewpoint of improving the molecular alignment of the compound of the present invention, -Rx is preferably 1-methylethyl, 1,1-dimethylethyl, 1-methylpropane Base, 2-methylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1,2,2-trimethylpropyl, 1-methylbutyl, 2- Methylbutyl, 3-methylbutyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 1,3,3-trimethylbutyl butylbutyl, 2,3,3-trimethylbutyl, 1,2,2-trimethylbutyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1 -Methylpentyl, 4,4-dimethylpentyl, 3,4,4-trimethylpentyl, 2,4,4-trimethylpentyl, 1,4,4-trimethylpentyl base, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl, 5,5-dimethylhexyl, 3,5,5-trimethyl Hexyl.

就良好地兼顧本發明的化合物的分子配向與溶解度的觀點而言，較佳為在-R x的根部側具有分支的結構，更佳為1-甲基乙基、1-甲基丙基、1-甲基丁基、1,2-二甲基丁基、1-甲基戊基、1,2-二甲基戊基、1,3-二甲基戊基、1,2,3-三甲基戊基、1-甲基己基、1,2-二甲基己基、1,3-二甲基己基、1,4-二甲基己基、1,2,3-三甲基己基、1,3,4-三甲基己基、1-甲基庚基、1,2-二甲基庚基、1,3-二甲基庚基、1,4-二甲基庚基、1,5-二甲基庚基。 From the viewpoint of a good balance between molecular alignment and solubility of the compound of the present invention, it is preferable to have a branched structure at the root side of -Rx , more preferably 1-methylethyl, 1-methylpropyl, 1-methylbutyl, 1,2-dimethylbutyl, 1-methylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,2,3- Trimethylpentyl, 1-methylhexyl, 1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,2,3-trimethylhexyl, 1,3,4-Trimethylhexyl, 1-methylheptyl, 1,2-dimethylheptyl, 1,3-dimethylheptyl, 1,4-dimethylheptyl, 1, 5-Dimethylheptyl.

所述具有分支的碳數3～15的烷基中所含的一個或者一個以上的亞甲基可為由-O-、-S-、-NH-、-N(R z)-、-C(=O)-、-C(=O)-O-、-C(=O)-NH-、-CHF-、-CF 2-、-CHCl-、-CCl 2-、或者丙烯醯氧基、甲基丙烯醯氧基、縮水甘油氧基等聚合性基取代的結構。在所述亞甲基被取代的結構中，就分子配向性及溶解度的觀點而言，較佳為-O-、-S-、-NH-、-N(-R z)-、-C(=O)-、-C(=O)-O-、-C(=O)-NH-，更佳為-O-、-C(=O)-、-C(=O)-O-，進而佳為-O-。 此處，-R z表示氫原子、或者可具有分支的碳數1～15的烷基。作為可具有分支的碳數1～15的烷基的具體例，可列舉作為所述-X的一價有機基中的可具有分支的碳數1～15的烷基而例示者。 One or more methylene groups contained in the branched alkyl group having 3 to 15 carbons may be composed of -O-, -S-, -NH-, -N(R z )-, -C (=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF 2 -, -CHCl-, -CCl 2 -, or acryloxy, A structure substituted with a polymerizable group such as methacryloxy group or glycidyloxy group. In the structure in which the methylene group is substituted, -O-, -S-, -NH-, -N(-R z )-, -C( =O)-, -C(=O)-O-, -C(=O)-NH-, more preferably -O-, -C(=O)-, -C(=O)-O-, More preferably, it is -O-. Here, -R z represents a hydrogen atom or an alkyl group having 1 to 15 carbons which may have a branch. Specific examples of the alkyl group having 1 to 15 carbons which may have a branch include those exemplified as the alkyl group having 1 to 15 carbons which may have a branch among the monovalent organic groups of -X described above.

作為-R x中具有分支的碳數3～15的烷基中容許的取代基，例如可列舉-OH、-O-R z1、-O-C(=O)-R z1、-NH 2、-NH-R z1、-N(-R z2)-R z1、-C(=O)-R z1、-C(=O)-O-R z1、-C(=O)-NH 2、-C(=O)-NH-R z1、-C(=O)-N(-R z2)-R z1、-SH、-S-R z1、胺磺醯基、羧基、氰基、硝基、鹵素、丙烯醯氧基、甲基丙烯醯氧基、縮水甘油氧基等聚合性基等。-R z1及-R z2分別獨立地表示碳數為1～15、較佳為碳數1～10的直鏈狀或分支狀的烷基。 所述碳數1～15的直鏈狀或分支狀的烷基中所含的一個或者一個以上的亞甲基可為由-O-、-S-、-NH-、-N(R z3)-、-C(=O)-、-C(=O)-O-、-C(=O)-NH-、-CHF-、-CF 2-、-CHCl-、-CCl 2-取代（displace）的結構，亦可為由丙烯醯氧基、甲基丙烯醯氧基、縮水甘油氧基的聚合性基取代的結構。此處，R z3表示碳數1～6的直鏈狀或者分支狀的烷基。 Examples of acceptable substituents for C3-C15 alkyl groups having branches in -R x include -OH, -OR z1 , -OC(=O)-R z1 , -NH 2 , -NH-R z1 , -N(-R z2 )-R z1 , -C(=O)-R z1 , -C(=O)-OR z1 , -C(=O)-NH 2 , -C(=O)- NH-R z1 , -C(=O)-N(-R z2 )-R z1 , -SH, -SR z1 , sulfamoyl, carboxyl, cyano, nitro, halogen, acryloxy, methyl Polymerizable groups such as acryloxy, glycidyloxy and the like. -R z1 and -R z2 each independently represent a linear or branched alkyl group having 1 to 15 carbons, preferably 1 to 10 carbons. One or more methylene groups contained in the linear or branched alkyl group having 1 to 15 carbons may be represented by -O-, -S-, -NH-, -N(R z3 ) -, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF 2 -, -CHCl-, -CCl 2 -substituted (displace ) or a structure substituted with polymerizable groups such as acryloxy, methacryloxy, or glycidyloxy. Here, R z3 represents a linear or branched alkyl group having 1 to 6 carbon atoms.

其中，作為-R x中具有分支的碳數3～15的烷基中容許的取代基，較佳為-O-R z1，具體而言例如可列舉：甲氧基、乙氧基、正丙氧基、正丁氧基、正戊氧基、正己氧基、正庚氧基、正辛氧基、丙烯醯氧基、甲基丙烯醯氧基、縮水甘油氧基。 就使與聚合性液晶化合物的分子配向良好的觀點而言，-R x中的具有分支的碳數3～15的烷基較佳為不具有環烷基結構。 作為-R x中的具有分支的碳數3～15的烷基，就使與聚合性液晶化合物的分子配向良好的觀點而言，較佳為不具有聚合性基。另一方面，作為所述具有分支的碳數3～15的烷基，就提高各向異性色素膜的機械強度的觀點而言，較佳為具有聚合性基。 Among them, the acceptable substituents of -R x in a branched C 3-15 alkyl group are preferably -OR z1 , and specific examples thereof include methoxy, ethoxy, and n-propoxy. , n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, acryloxy, methacryloxy, glycidyloxy. The branched C3-C15 alkyl group in -Rx preferably does not have a cycloalkyl structure from the viewpoint of making molecular alignment with the polymerizable liquid crystal compound favorable. The branched C3-15 alkyl group in -R x preferably does not have a polymerizable group from the viewpoint of making molecular alignment with the polymerizable liquid crystal compound favorable. On the other hand, as the alkyl group having 3 to 15 carbon atoms having a branch, it is preferable to have a polymerizable group from the viewpoint of improving the mechanical strength of the anisotropic dye film.

-R y表示氫原子、或者可具有分支的碳數1～15的烷基，所述可具有分支的碳數1～15的烷基可具有取代基。 作為可具有分支的碳數1～15的烷基的具體例，可列舉作為所述-X的一價有機基中的可具有分支的碳數1～15的烷基而例示者。 -R y represents a hydrogen atom or an optionally branched alkyl group having 1 to 15 carbons, and the optionally branched alkyl group having 1 to 15 carbons may have a substituent. Specific examples of the alkyl group having 1 to 15 carbons which may have a branch include those exemplified as the alkyl group having 1 to 15 carbons which may have a branch among the monovalent organic groups of -X described above.

所述可具有分支的碳數1～15的烷基中所含的一個或者一個以上的亞甲基可為由-O-、-S-、-NH-、-N(R z)-、-C(=O)-、-C(=O)-O-、-C(=O)-NH-、-CHF-、-CF 2-、-CHCl-、-CCl 2-、或者丙烯醯氧基、甲基丙烯醯氧基、縮水甘油氧基等聚合性基取代的結構。在所述亞甲基被取代的結構中，就分子配向性及溶解度的觀點而言，較佳為-O-、-S-、-NH-、-N(-R z)-、-C(=O)-、-C(=O)-O-、-C(=O)-NH-，更佳為-O-、-C(=O)-、-C(=O)-O-，進而佳為-O-。 此處，-R z表示氫原子、或者可具有分支的碳數1～15的烷基。作為可具有分支的碳數1～15的烷基的具體例，可列舉作為所述-X的一價有機基中的可具有分支的碳數1～15的烷基而例示者。 One or more methylene groups contained in the branched alkyl group having 1 to 15 carbons may be represented by -O-, -S-, -NH-, -N(R z )-, - C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF 2 -, -CHCl-, -CCl 2 -, or acryloxy , methacryloxy, glycidyloxy and other polymeric groups substituted structure. In the structure in which the methylene group is substituted, -O-, -S-, -NH-, -N(-R z )-, -C( =O)-, -C(=O)-O-, -C(=O)-NH-, more preferably -O-, -C(=O)-, -C(=O)-O-, More preferably, it is -O-. Here, -R z represents a hydrogen atom or an alkyl group having 1 to 15 carbons which may have a branch. Specific examples of the alkyl group having 1 to 15 carbons which may have a branch include those exemplified as the alkyl group having 1 to 15 carbons which may have a branch among the monovalent organic groups of -X described above.

作為-R y中可具有分支的碳數1～15的烷基中容許的取代基，例如可列舉-OH、-O-R z1、-O-C(=O)-R z1、-NH 2、-NH-R z1、-N(-R z2)-R z1、-C(=O)-R z1、-C(=O)-O-R z1、-C(=O)-NH 2、-C(=O)-NH-R z1、-C(=O)-N(-R z2)-R z1、-SH、-S-R z1、胺磺醯基、羧基、氰基、硝基、鹵素、丙烯醯氧基、甲基丙烯醯氧基、縮水甘油氧基的聚合性基等。-R z1及-R z2分別獨立地表示碳數為1～15、較佳為1～10的直鏈狀或分支狀的烷基。 所述碳數1～15的直鏈狀或分支狀的烷基中所含的一個或者一個以上的亞甲基可為由-O-、-S-、-NH-、-N(R z3)-、-C(=O)-、-C(=O)-O-、-C(=O)-NH-、-CHF-、-CF 2-、-CHCl-、-CCl 2-取代（displace）的結構，亦可為由丙烯醯氧基、甲基丙烯醯氧基、縮水甘油氧基等聚合性基取代的結構。此處，R z3表示碳數1～6的直鏈狀或者分支狀的烷基。 Examples of acceptable substituents for an alkyl group having 1 to 15 carbon atoms that may have a branch in -R y include -OH, -OR z1 , -OC(=O)-R z1 , -NH 2 , -NH- R z1 , -N(-R z2 )-R z1 , -C(=O)-R z1 , -C(=O)-OR z1 , -C(=O)-NH 2 , -C(=O) -NH-R z1 , -C(=O)-N(-R z2 )-R z1 , -SH, -SR z1 , sulfamoyl, carboxyl, cyano, nitro, halogen, acryloxy, Polymerizable groups such as methacryloxy group and glycidyloxy group. -R z1 and -R z2 each independently represent a linear or branched alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms. One or more methylene groups contained in the linear or branched alkyl group having 1 to 15 carbons may be represented by -O-, -S-, -NH-, -N(R z3 ) -, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF 2 -, -CHCl-, -CCl 2 -substituted (displace ) structure, or a structure substituted with polymerizable groups such as acryloxy, methacryloxy, and glycidyloxy. Here, R z3 represents a linear or branched alkyl group having 1 to 6 carbon atoms.

其中，作為-R y中可具有分支的碳數1～15的烷基中容許的取代基，較佳為-O-R z1，具體而言例如可列舉：甲氧基、乙氧基、正丙氧基、正丁氧基、正戊氧基、正己氧基、正庚氧基、正辛氧基、丙烯醯氧基、甲基丙烯醯氧基、縮水甘油氧基。 就使與聚合性液晶化合物的分子配向良好的觀點而言，-R y中的可具有分支的碳數1～15的烷基較佳為不具有環烷基結構。 Among them, the acceptable substituent in -R y in an alkyl group having 1 to 15 carbon atoms which may have a branch is preferably -OR z1 , and specific examples thereof include methoxy, ethoxy, and n-propoxy. n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, acryloxy, methacryloxy, glycidyloxy. The alkyl group having 1 to 15 carbon atoms which may have a branch in -R y preferably does not have a cycloalkyl structure from the viewpoint of making molecular alignment with the polymerizable liquid crystal compound favorable.

就分子配向性及溶解度的觀點而言，-R y較佳為氫原子、或者可具有分支的碳數1～15的烷基，更佳為氫原子、或者可具有分支的碳數1～10的烷基，進而佳為氫原子、或者可具有分支的碳數1～4的烷基。 From the viewpoint of molecular alignment and solubility, -Ry is preferably a hydrogen atom, or an alkyl group having 1 to 15 carbons which may have branches, more preferably a hydrogen atom, or an alkyl group having 1 to 10 carbons which may have branches An alkyl group, more preferably a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms which may have branches.

就本發明的化合物由於採取非對稱結構而分子配向可變得更良好的觀點而言，較佳為-R x與-R y不同。具體而言，-R y較佳為氫原子或者不具有分支的碳數1～15的烷基，更佳為氫原子或者不具有分支的碳數1～10的烷基，進而佳為氫原子或者不具有分支的碳數1～4的烷基。 -Y所具有的分支數並無特別規定，就使分子配向良好的觀點而言，較佳為6以下，更佳為3以下，進而佳為2以下，特佳為1。 It is preferable that -R x and -R y are different from the viewpoint that molecular alignment can be improved by adopting an asymmetric structure of the compound of the present invention. Specifically, -Ry is preferably a hydrogen atom or an unbranched alkyl group with 1 to 15 carbons, more preferably a hydrogen atom or an unbranched alkyl group with 1 to 10 carbons, and even more preferably a hydrogen atom Or an alkyl group having 1 to 4 carbon atoms having no branch. The number of branches of -Y is not particularly limited, but is preferably 6 or less, more preferably 3 or less, still more preferably 2 or less, particularly preferably 1, from the viewpoint of making molecular alignment favorable.

就良好地兼顧本發明的化合物的分子配向與溶解度的觀點而言，在所述式（1）中，-Y為-N(-R y)-R x，-R x及-R y中的碳數的合計較佳為15以下，更佳為13以下，進而佳為11以下，更進而佳為9以下，特佳為7以下。 From the viewpoint of a good balance between molecular alignment and solubility of the compounds of the present invention, in the formula (1), -Y is -N(-R y )-R x , -R x and -R y The total number of carbon atoms is preferably 15 or less, more preferably 13 or less, still more preferably 11 or less, still more preferably 9 or less, particularly preferably 7 or less.

就良好地兼顧本發明的化合物的分子配向與溶解度的觀點而言，亦較佳為在所述式（1）中，-Y為-N(-R y)-R x，-R x為可具有取代基的、具有分支的碳數3～15的烷基，-R y為氫原子或者可具有分支的碳數1～15的烷基，所述可具有分支的碳數1～15的烷基可具有取代基，-R x及-R y的烷基中的碳數合計為15以下。 From the viewpoint of a good balance between molecular alignment and solubility of the compounds of the present invention, it is also preferred that in the formula (1), -Y is -N(-R y )-R x , and -R x is optional A substituent, branched alkyl group with 3 to 15 carbons, -R y is a hydrogen atom or a branched alkyl group with 1 to 15 carbons, and the branched alkyl group with 1 to 15 carbons The group may have a substituent, and the total number of carbon atoms in the alkyl groups of -R x and -R y is 15 or less.

另外，就良好地兼顧本發明的化合物的分子配向與溶解度的觀點而言，亦較佳為在所述式（1）中，-Y為-N(-R y)-R x，-R x為可具有取代基的、具有分支的碳數3～15的烷基，-R y為氫原子或者不具有分支的碳數1～15的烷基，所述不具有分支的碳數1～15的烷基可具有取代基。 In addition, from the viewpoint of a good balance between molecular alignment and solubility of the compound of the present invention, it is also preferable that in the formula (1), -Y is -N(-R y )-R x , -R x It is an alkyl group with a branched carbon number of 3 to 15 that may have a substituent, and -R y is a hydrogen atom or an alkyl group with a carbon number of 1 to 15 without branches, and the branched carbon number of 1 to 15 is The alkyl group of may have a substituent.

就使本發明的化合物的溶解度良好的觀點而言，較佳為在所述式（1）的-Y中，在距-A 3-的Y側末端近的位置具有多個分支結構。 認為藉由在距-A 3-末端近的位置存在多個分支結構，呈抑制化合物的締合及凝聚的趨勢，從而本發明的化合物的溶解度變良好。 具體而言，在-Y中，較佳為在自-A 3-的Y側末端起的共價鍵數為5以下的位置存在兩個以上分支結構，更佳為在自-A 3-的Y側末端起的共價鍵數為3以下的位置存在兩個以上分支結構。 所述共價鍵數是指自-A 3-的Y側末端原子至成為分支起點的原子的共價鍵數。在-Y為-N(-R y)-R x，-R y為可具有分支的碳數1～15的烷基的情況下，-R x、-R y所鍵結的N成為分支起點，在自-A 3-的Y側末端起的共價鍵數為1的位置存在分支結構。 From the viewpoint of improving the solubility of the compound of the present invention, in -Y of the formula (1), it is preferable to have a plurality of branched structures at a position close to the Y-side terminal of -A 3 -. It is considered that the presence of a plurality of branched structures near the -A 3 -terminus tends to inhibit the association and aggregation of the compounds, thereby improving the solubility of the compound of the present invention. Specifically, in -Y, there are preferably two or more branched structures at positions where the number of covalent bonds from the Y-side end of -A 3 - is 5 or less, and more preferably at the positions from -A 3 - There are two or more branched structures at positions where the number of covalent bonds from the end on the Y side is 3 or less. The number of covalent bonds refers to the number of covalent bonds from the terminal atom on the Y side of -A 3 - to the atom serving as the starting point of the branch. When -Y is -N(-R y )-R x , and -R y is an alkyl group having 1 to 15 carbon atoms that may have a branch, the N to which -R x and -R y are bonded becomes the starting point of the branch , a branched structure exists at a position where the number of covalent bonds from the Y-side terminal of -A 3 - is 1.

（-A 3-） -A 3-表示可具有取代基的芳香族烴環的二價基。 (-A 3 -) -A 3 - represents a divalent group of an aromatic hydrocarbon ring which may have a substituent.

作為-A 3-的芳香族烴環，可列舉：苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯並芘環、䓛環、三伸苯環、乙烷合萘（acenaphthene）環、螢蒽環、芴環等。 就本發明的化合物的吸收躍遷矩呈與色素的長軸方向一致的趨勢從而可提高二色比而言，作為-A 3-的芳香族烴環的二價基，較佳為可具有取代基的、苯環的二價基（伸苯基）、萘環的二價基（伸萘基），更佳為苯環的二價基（伸苯基）。尤其是，更佳為1,4-伸苯基、1,4-伸萘基、2,6-伸萘基，進而佳為1,4-伸苯基，尤佳為不具有取代基的1,4-伸苯基。藉由如上所述，本發明的化合物的吸收的躍遷矩呈與化合物的長軸方向一致的趨勢，從而可提高二色比。 Examples of the aromatic hydrocarbon ring of -A 3 - include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, fused tetraphenyl ring, pyrene ring, benzopyrene ring, fenene ring, triphenylene ring, Ethane and naphthalene (acenaphthene) ring, fluoranthene ring, fluorene ring, etc. Since the absorption transition moment of the compound of the present invention tends to be aligned with the long axis direction of the pigment so that the dichromatic ratio can be improved, the divalent group of the aromatic hydrocarbon ring as -A 3 - may preferably have a substituent A divalent group of a benzene ring (phenylene), a divalent group of a naphthalene ring (naphthyl), more preferably a divalent group of a benzene ring (phenylene). In particular, 1,4-phenylene, 1,4-naphthyl, and 2,6-naphthyl are more preferable, 1,4-phenylene is more preferable, and 1,4-phenylene without substituent is especially preferable. ,4-phenylene. As described above, the absorption transition moment of the compound of the present invention tends to coincide with the long axis direction of the compound, thereby improving the dichroic ratio.

作為-A 3-的芳香族烴環的二價基中容許的取代基，例如可列舉：-R A、-OH、-O-R A、-O-C(=O)-R A、-NH 2、-NH-R A、-N(-R B)-R A、-C(=O)-R A、-C(=O)-O-R A、-C(=O)-NH 2、-C(=O)-NH-R A、-C(=O)-N(-R B)-R A、-SH、-S-R A、三氟甲基、氟基、胺磺醯基、羧基、氰基、硝基、鹵素。此處，-R A及-R B分別獨立地表示碳數1～15的直鏈狀或分支狀的烷基。就與本發明中所使用的聚合性液晶化合物的分子配向變良好的觀點而言，-R A及-R B的碳數較佳為1以上且12以下，進而佳為1以上且9以下。 Examples of permissible substituents in the divalent group of the aromatic hydrocarbon ring of -A 3 - include -RA , -OH, -OR A , -OC(=O) -RA , -NH 2 , - NH-R A , -N(-R B )-R A , -C(=O)-R A , -C(=O)-OR A , -C(=O)-NH 2 , -C(= O)-NH- RA , -C(=O)-N(-R B )-RA , -SH , -SR A , trifluoromethyl, fluoro, sulfamoyl, carboxyl, cyano, Nitro, halogen. Here, -RA and -RB each independently represent a linear or branched alkyl group having 1 to 15 carbons. The carbon numbers of -RA and -RB are preferably from 1 to 12, more preferably from 1 to 9, from the viewpoint of favorable molecular alignment with the polymerizable liquid crystal compound used in the present invention.

所述直鏈狀或分支狀的烷基中所含的一個或一個以上的亞甲基可設為由醚性氧原子、硫醚性硫原子、胺性氮原子（-NH-、-N(R z)-：此處，R z表示碳數為1～6、較佳為1～4的直鏈狀或分支狀的烷基）、羰基、酯鍵、醯胺鍵、-CHF-、-CF 2-、-CHCl-、-CCl 2-取代的結構，亦可由丙烯醯氧基、甲基丙烯醯氧基、縮水甘油氧基的聚合性基取代。 One or more methylene groups contained in the straight-chain or branched alkyl groups may be formed from an etheric oxygen atom, a thioether sulfur atom, an amine nitrogen atom (-NH-, -N( R z )-: Here, R z represents a linear or branched alkyl group with 1 to 6 carbons, preferably 1 to 4), carbonyl, ester bond, amide bond, -CHF-, - CF 2 -, -CHCl-, -CCl 2 - substituted structures may also be substituted with polymerizable groups such as acryloxy, methacryloxy, and glycidyloxy.

其中，作為-A 3-中的芳香族烴環的二價基中容許的取代基，較佳為-R A、-O-R A、三氟甲基、氟基。作為-R A，例如可列舉：正丙基、正丁基、正戊基、正己基、正庚基、正辛基、5,5-二甲基-3-甲基己基等。藉由具有所述取代基，本發明的化合物的色素的分子配向呈變良好的趨勢。 Among them, as substituents permissible in the divalent group of the aromatic hydrocarbon ring in -A 3 -, -RA , -OR A , trifluoromethyl, and fluorine are preferable. Examples of -RA include n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 5,5-dimethyl-3-methylhexyl and the like. By having such a substituent, the molecular alignment of the dye of the compound of the present invention tends to be improved.

（-A 1-及-A 2-） -A 1-及-A 2-分別獨立地為可具有取代基的含有一個以上S原子的多環式芳香族雜環的二價基、或者可具有取代基的芳香族烴環的二價基。其中，不存在-A 1-及-A 2-均為可具有取代基的芳香族烴環的二價基的情況。 (-A 1 - and -A 2 -) -A 1 - and -A 2 - are each independently a divalent group of a polycyclic aromatic heterocycle containing one or more S atoms that may have a substituent, or may have A divalent group of an aromatic hydrocarbon ring as a substituent. However, there is no case where both -A 1 - and -A 2 - are divalent groups of an aromatic hydrocarbon ring which may have a substituent.

作為-A 1-及-A 2-的可具有取代基的芳香族烴環的二價基，可列舉作為-A 3-的可具有取代基的芳香族烴環的二價基而例示者，可具有的取代基的種類、較佳者亦相同。 As the divalent group of the aromatic hydrocarbon ring which may have a substituent of -A1- and -A2- , the divalent group of the aromatic hydrocarbon ring which may have a substituent of -A3- is mentioned as an example, The kind and preferable ones of the substituent which may have are also the same.

-A 1-及-A 2-的可具有取代基的含有一個以上S原子的多環式芳香族雜環的二價基是縮合的芳香族雜環基。所述芳香族雜環的碳數並無特別限定，較佳為4以上且20以下。 The divalent group of the polycyclic aromatic heterocyclic ring containing one or more S atoms which may have a substituent in -A 1 - and -A 2 - is a condensed aromatic heterocyclic group. The carbon number of the aromatic heterocyclic ring is not particularly limited, but is preferably 4 or more and 20 or less.

作為-A 1-及-A 2-的芳香族雜環，例如可列舉：苯並噻吩環、噻吩並吡咯環、噻吩並噻吩環、呋喃並噻唑環、噻吩並呋喃環、噻吩並噻唑環、苯並異噻唑環、苯並噻唑環等。其中，就本發明的化合物的分子配向變良好的觀點而言，較佳為苯並噻吩環、噻吩並噻吩環、呋喃並噻唑環、噻吩並呋喃環、噻吩並噻唑環、苯並異噻唑環、苯並噻唑環，基於本發明的化合物的吸收躍遷矩呈與色素的長軸方向一致的趨勢從而可提高二色比的理由，更佳為以下所示的結構。（下述結構中的*1與*2表示式（1）中的鍵） Examples of the aromatic heterocycles of -A 1 - and -A 2 - include: benzothiophene ring, thienopyrrole ring, thienothiophene ring, furothiazole ring, thienofuran ring, thienothiazole ring, Benzisothiazole ring, benzothiazole ring, etc. Among these, preferred are benzothiophene rings, thienothiophene rings, furothiazole rings, thienofuran rings, thienothiazole rings, and benzisothiazole rings from the viewpoint that the molecular alignment of the compound of the present invention becomes favorable. , The benzothiazole ring is more preferably the structure shown below because the absorption transition moment of the compound of the present invention tends to coincide with the long-axis direction of the pigment, thereby improving the dichromatic ratio. (*1 and *2 in the following structures represent the keys in formula (1))

[化1]

Figure 02_image001
[chemical 1]
Figure 02_image001

就與本發明中使用的聚合性液晶化合物的分子配向變良好的觀點而言，較佳為在式（1）中，-A 2-的至少一個為可具有取代基的含有一個以上S原子的多環式芳香族雜環的二價基。作為該二價基的含有一個以上S原子的多環式芳香族雜環較佳為苯並噻吩環、噻吩並噻吩環、呋喃並噻唑環、噻吩並呋喃環、噻吩並噻唑環、苯並異噻唑環、苯並噻唑環。 From the viewpoint of better molecular alignment with the polymerizable liquid crystal compound used in the present invention, in formula (1), at least one of -A 2 - is preferably a substituent containing one or more S atoms. A divalent group of a polycyclic aromatic heterocycle. The polycyclic aromatic heterocycle containing one or more S atoms as the divalent group is preferably a benzothiophene ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, a thienothiazole ring, a benziso Thiazole ring, benzothiazole ring.

就與本發明中使用的聚合性液晶化合物的分子配向變良好的觀點而言，較佳為在式（1）中，-A 1-為可具有取代基的芳香族烴環的二價基。尤其是就本發明的化合物的吸收躍遷矩呈與色素的長軸方向一致的趨勢從而可提高二色比而言，較佳為可具有取代基的、苯環的二價基（伸苯基）、萘環的二價基（伸萘基），更佳為苯環的二價基（伸苯基）。尤其是，更佳為1,4-伸苯基、1,4-伸萘基、2,6-伸萘基，進而佳為1,4-伸苯基，尤佳為不具有取代基的1,4-伸苯基。藉由如上所述，本發明的化合物的吸收的躍遷矩呈與化合物的長軸方向一致的趨勢，從而可提高二色比。 In formula (1), -A 1 - is preferably a divalent group of an aromatic hydrocarbon ring which may have a substituent, from the viewpoint of better molecular alignment with the polymerizable liquid crystal compound used in the present invention. In particular, in terms of the absorption transition moment of the compound of the present invention tending to be in line with the long axis direction of the pigment so that the dichromatic ratio can be improved, it is preferably a divalent group of a benzene ring (phenylene group) that may have a substituent , a divalent group (naphthylene) of a naphthalene ring, more preferably a divalent group (phenylene) of a benzene ring. In particular, 1,4-phenylene, 1,4-naphthyl, and 2,6-naphthyl are more preferable, 1,4-phenylene is more preferable, and 1,4-phenylene without substituent is especially preferable. ,4-phenylene. As described above, the absorption transition moment of the compound of the present invention tends to coincide with the long axis direction of the compound, thereby improving the dichroic ratio.

（n） n表示1、2或者3。 n較佳為1或者2，更佳為1。藉由如上所述，本發明的化合物的分子配向呈變良好的趨勢。 在n為2或者3的情況下，各-A 2-可相同亦可不同。 (n) n means 1, 2 or 3. n is preferably 1 or 2, more preferably 1. As described above, the molecular alignment of the compound of the present invention tends to become better. When n is 2 or 3, each -A 2 - may be the same or different.

基於提高本發明的化合物的直線性的觀點，式（1）中的-N=N-較佳為反式。From the viewpoint of improving the linearity of the compound of the present invention, -N=N- in formula (1) is preferably trans.

（本發明的化合物的具體例） 作為本發明的化合物的具體例，可列舉以下的化合物，但並不限定於該些。 (Specific examples of compounds of the present invention) Specific examples of the compound of the present invention include the following compounds, but are not limited thereto.

[化2]

Figure 02_image002
[Chem 2]
Figure 02_image002

[化3]

Figure 02_image004
[Chem 3]
Figure 02_image004

[化4]

Figure 02_image006
[chemical 4]
Figure 02_image006

[化5]

Figure 02_image008
[chemical 5]
Figure 02_image008

[化6]

Figure 02_image010
[chemical 6]
Figure 02_image010

[化7]

Figure 02_image012
[chemical 7]
Figure 02_image012

（吸收特性） 本發明的化合物在藉由後述方法製成的各向異性色素膜中，可在350 nm～800 nm的波長範圍具有極大吸收（λmax1），較佳為在450 nm～800 nm的波長範圍具有極大吸收，更佳為在510 nm～750 nm的波長範圍具有極大吸收，進而佳為在510 nm～700 nm的波長範圍具有極大吸收。藉由在所述波長範圍具有極大吸收（λmax1），在與在更短波長側具有極大吸收的色素組合的情況下，呈能夠全面地吸收350 nm～800 nm的波長範圍的趨勢。 (Absorptive properties) The compound of the present invention can have maximum absorption (λmax1) in the wavelength range of 350 nm to 800 nm in the anisotropic pigment film produced by the method described later, preferably has maximum absorption in the wavelength range of 450 nm to 800 nm. The absorption is more preferably has maximum absorption in the wavelength range of 510 nm to 750 nm, and more preferably has maximum absorption in the wavelength range of 510 nm to 700 nm. By having a maximum absorption (λmax1) in the above-mentioned wavelength range, when combined with a dye having a maximum absorption on the shorter wavelength side, it tends to be able to fully absorb the wavelength range of 350 nm to 800 nm.

本發明的化合物較佳為，相較於溶解於溶媒進行測定而得的極大吸收（λmax2），各向異性色素膜中的極大吸收（所述λmax1）存在於長波長中。該長波長偏移是因式（1）所表示的化合物分散於聚合性液晶化合物及/或具有基於聚合性液晶化合物的單元的聚合物中而表現出的現象，且表示式（1）所表示的化合物與聚合性液晶化合物及/或具有基於聚合性液晶化合物的單元的聚合物強烈地發生分子間相互作用。長波長偏移是指吸收最大值的差值（λmax1-λmax2）為正值，其差較佳為10 nm以上，更佳為20 nm以上，進而佳為30 nm以上。In the compound of the present invention, the maximum absorption (λmax1) in the anisotropic dye film is preferably present at a longer wavelength than the maximum absorption (λmax2) measured when dissolved in a solvent. This long wavelength shift is a phenomenon exhibited by the compound represented by formula (1) being dispersed in a polymerizable liquid crystal compound and/or a polymer having a unit based on a polymerizable liquid crystal compound, and represents the The compound strongly interacts with the polymerizable liquid crystal compound and/or the polymer having a unit based on the polymerizable liquid crystal compound. The long wavelength shift means that the difference (λmax1-λmax2) of the absorption maximum value is a positive value, and the difference is preferably at least 10 nm, more preferably at least 20 nm, and more preferably at least 30 nm.

（溶解度） 本發明的化合物的溶解度並無特別限定，在環戊酮中的溶解度較佳為0.4質量%以上，更佳為0.6質量%以上，進而佳為0.8質量%以上。藉由溶解度為所述下限以上，呈可獲得良好的塗膜性能的趨勢。 (solubility) The solubility of the compound of the present invention is not particularly limited, but the solubility in cyclopentanone is preferably at least 0.4% by mass, more preferably at least 0.6% by mass, and still more preferably at least 0.8% by mass. When solubility is more than the said minimum, it exists in the tendency for favorable coating-film performance to be acquired.

[各向異性色素膜形成用組成物] 本發明的各向異性色素膜形成用組成物含有色素以及聚合性液晶化合物，作為該色素，至少含有所述式（1）所表示的本發明的化合物。 本發明的各向異性色素膜形成用組成物可含有僅一種本發明的化合物，亦可含有兩種以上本發明的化合物。 就呈在組成物中抑制析出的趨勢的觀點而言，本發明的各向異性色素膜形成用組成物較佳為含有僅一種式（1）中的A 1、A 2、A 3及n相同的本發明的化合物，更佳為含有僅一種本發明的化合物。 [Anisotropic Dye Film Forming Composition] The anisotropic dye film forming composition of the present invention contains a dye and a polymerizable liquid crystal compound, and the dye contains at least the compound of the present invention represented by the above-mentioned formula (1) . The composition for anisotropic dye film formation of this invention may contain only 1 type of compound of this invention, and may contain 2 or more types of compounds of this invention. From the viewpoint of suppressing the tendency of precipitation in the composition, the anisotropic pigment film-forming composition of the present invention preferably contains only one of A 1 , A 2 , A 3 and n in the formula (1) are the same. compounds of the invention, more preferably contain only one compound of the invention.

本發明的各向異性色素膜形成用組成物只要為不引起相分離的狀態，則可為溶液，亦可為液晶，還可為分散狀態。 就作為各向異性色素膜形成用組成物而容易塗佈於基材的觀點而言，本發明的各向異性色素膜形成用組成物較佳為溶液。 就如後所述使自各向異性色素膜形成用組成物中除去溶劑後的固形物成分在基板上配向的觀點而言，本發明的各向異性色素膜形成用組成物較佳為在任意溫度下為液晶相的狀態。 The anisotropic dye film-forming composition of the present invention may be a solution, a liquid crystal, or a dispersed state as long as it is in a state that does not cause phase separation. The anisotropic dye film-forming composition of the present invention is preferably a solution from the viewpoint of ease of coating on a substrate as the anisotropic dye film-forming composition. From the viewpoint of aligning the solid content on the substrate after removing the solvent from the anisotropic dye film-forming composition as described later, the anisotropic dye film-forming composition of the present invention is preferably at any temperature The state of the liquid crystal phase is shown below.

在本發明中，所謂液晶相的狀態，具體而言，如「液晶的基礎與應用」（松本正一、角田市良著；1991年）第1～16頁所記載般，是指顯示出液體與結晶兩者或中間的性質的液晶狀態，且為向列相、層列相、膽固醇相、或者圓盤狀相。In the present invention, the state of the liquid crystal phase, specifically, as described on pages 1 to 16 of "Basics and Applications of Liquid Crystals" (Shoichi Matsumoto, Yoshikazu Kakuda, 1991), refers to a phase that exhibits a liquid crystal phase. A liquid crystal state that is both or intermediate in nature, and is a nematic phase, a smectic phase, a cholesteric phase, or a discotic phase.

＜色素＞ 在本發明中，所謂色素，是吸收可見光區域（350 nm～800 nm）的波長的至少一部分的物質或化合物。 作為本發明中可使用的色素，可列舉二色性色素。 所謂二色性色素，是指具有分子的長軸方向上的吸光度與短軸方向上的吸光度不同的性質的色素。另外，色素可為具有液晶性的色素，亦可不具有液晶性。再者，所謂具有液晶性，是指在任意溫度下均表現出液晶相。 ＜Pigment＞ In the present invention, a pigment is a substance or compound that absorbs at least a part of wavelengths in the visible light region (350 nm to 800 nm). Examples of dyes usable in the present invention include dichroic dyes. The dichroic dye refers to a dye having a property in which the absorbance in the long axis direction and the absorbance in the short axis direction of the molecule are different. In addition, the dye may have liquid crystallinity or may not have liquid crystallinity. In addition, the term "having liquid crystallinity" means that a liquid crystal phase is exhibited at any temperature.

本發明的各向異性色素膜形成用組成物含有所述式（1）所表示的本發明的化合物作為色素，但亦可含有本發明的化合物以外的色素。作為本發明的各向異性色素膜形成用組成物中所含的除所述式（1）所表示的本發明的化合物以外的色素，可列舉：偶氮系色素、醌系色素（包括萘醌系色素、蒽醌系色素等）、二苯乙烯系色素、花青系色素、酞菁系色素、靛藍系色素、縮合多環系色素（包括苝系色素、噁嗪系色素、吖啶系色素等）等。 本發明的各向異性色素膜用組成物中，可單獨含有僅一種除本發明的化合物以外的色素，亦可以任意組合及比率含有兩種以上除本發明的化合物以外的色素。 The anisotropic dye film-forming composition of the present invention contains the compound of the present invention represented by the formula (1) as a dye, but may contain dyes other than the compound of the present invention. Examples of dyes other than the compound of the present invention represented by the formula (1) contained in the anisotropic dye film-forming composition of the present invention include: azo-based dyes, quinone-based dyes (including naphthoquinone pigments, anthraquinone pigments, etc.), stilbene pigments, cyanine pigments, phthalocyanine pigments, indigo pigments, condensed polycyclic pigments (including perylene pigments, oxazine pigments, acridine pigments etc. The composition for anisotropic dye film of the present invention may contain only one kind of dye other than the compound of the present invention alone, or may contain two or more dyes other than the compound of the present invention in any combination and ratio.

上述所例示的色素中，偶氮系色素由於可在各向異性色素膜中獲得高的分子排列故而較佳。Among the dyes exemplified above, azo dyes are preferable because they can obtain high molecular alignment in the anisotropic dye film.

所謂偶氮系色素，是指具有至少一個以上偶氮基(-N=N-)的色素，就在溶劑中的溶解性、與液晶化合物的相容性、色調及製造容易性的觀點而言，其一分子中的偶氮基的數量較佳為1以上，更佳為2以上，且較佳為6以下，更佳為4以下，進而佳為3以下。The so-called azo dyes refer to dyes having at least one azo group (-N=N-), from the viewpoints of solubility in solvents, compatibility with liquid crystal compounds, color tone, and ease of manufacture , the number of azo groups in one molecule is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, more preferably 4 or less, further preferably 3 or less.

作為偶氮系色素，例如可列舉下述式（A）所表示的化合物。 R 11-E 1-N=N-(E 2-N=N) p-E 3-R 12･･･（A） （式（A）中， -E 1-、-E 2-及-E 3-分別獨立地表示可具有取代基的伸苯基、可具有取代基的伸萘基、或者可具有取代基的二價雜環基； p表示0～4的整數； 在p為2以上的整數的情況下，多個-E 2-彼此可相同亦可不同； R 11及R 12分別獨立地表示一價有機基） As an azo dye, the compound represented by following formula (A) is mentioned, for example. R 11 -E 1 -N=N-(E 2 -N=N) p -E 3 -R 12 ･･･(A) (In formula (A), -E 1 -, -E 2 - and -E 3 -represent independently a phenylene group that may have a substituent, a naphthylene group that may have a substituent, or a divalent heterocyclic group that may have a substituent; p represents an integer of 0 to 4; when p is 2 or more In the case of an integer, a plurality of -E 2 - may be the same or different from each other; R 11 and R 12 each independently represent a monovalent organic group)

-E 1-、-E 2-及-E 3-分別獨立地表示可具有取代基的伸苯基、可具有取代基的伸萘基、或者可具有取代基的二價雜環基。 關於伸苯基的取代位置，1,4-伸苯基由於分子的直線性高故而較佳。 關於伸萘基的取代位置，1,4-伸萘基或者2,6-伸萘基由於分子的直線性高故而較佳。 -E 1 -, -E 2 -, and -E 3 - each independently represent an optionally substituted phenylene group, an optionally substituted naphthylene group, or an optionally substituted divalent heterocyclic group. Regarding the substitution position of the phenylene group, a 1,4-phenylene group is preferable because the linearity of the molecule is high. Regarding the substitution position of naphthyl, 1,4-naphthyl or 2,6-naphthyl is preferable because the linearity of the molecule is high.

作為二價雜環基，較佳為形成環的碳數為3以上且14以下的雜環基，進而佳為形成環的碳數為10以下的雜環基。尤佳為單環或者雙環式雜環基。 作為構成二價雜環基的碳以外的原子，可列舉選自氮原子、硫原子及氧原子中的至少一種。在雜環基具有多個碳以外的構成環的原子的情況下，該些可相同亦可不同。 作為二價雜環基，具體而言可列舉：吡啶二基、喹啉二基、異喹啉二基、噻唑二基、苯並噻唑二基、噻吩並噻唑二基、噻吩並噻吩二基、苯並咪唑啶酮二基、苯並呋喃二基、鄰苯二甲醯亞胺二基、噁唑二基、苯並噁唑二基等。 The divalent heterocyclic group is preferably a heterocyclic group having 3 to 14 carbon atoms forming the ring, more preferably a heterocyclic group having 10 or less carbon atoms forming the ring. Especially preferred is a monocyclic or bicyclic heterocyclic group. As atoms other than carbon constituting the divalent heterocyclic group, at least one selected from a nitrogen atom, a sulfur atom, and an oxygen atom is exemplified. When the heterocyclic group has a plurality of atoms constituting the ring other than carbon, these may be the same or different. Specific examples of the divalent heterocyclic group include pyridinediyl, quinolinediyl, isoquinolinediyl, thiazolediyl, benzothiazolediyl, thienothiazolyl, thienothiophenediyl, Benzimidazolidinone diyl, benzofuran diyl, phthalimide diyl, oxazole diyl, benzoxazole diyl, etc.

作為-E 1-、-E 2-及-E 3-中的伸苯基、伸萘基及二價雜環基任意具有的取代基，可列舉：碳數1～4的烷基；甲氧基、乙氧基及丁氧基等碳數1～4的烷氧基；三氟甲基等碳數1～4的氟化烷基；氰基；硝基；羥基；鹵素原子；胺基、二乙基胺基及吡咯啶基等經取代或未經取代的胺基（經取代的胺基是指具有一個或兩個碳數1～4的烷基的胺基、或者兩個經取代的烷基相互鍵結而形成碳數2～8的烷二基的胺基；未經取代的胺基為-NH 2； 作為碳數1～4的烷基，可列舉甲基、乙基及丁基等；作為碳數2～8的烷二基，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、辛烷-1,8-二基等）。 就分子直線性高的方面而言，-E 1-、-E 2-及-E 3-中的伸苯基、伸萘基及二價雜環基較佳為：未經取代，或者在經取代的情況下，由甲基、甲氧基、羥基、氟原子、氯原子、二甲基胺基、吡咯啶基（pyrrolidinyl）、哌啶基取代。 Examples of optional substituents for phenylene, naphthylene, and divalent heterocyclic groups in -E 1 -, -E 2 -, and -E 3 - include alkyl groups having 1 to 4 carbon atoms; methoxy groups; alkoxy groups with 1 to 4 carbons such as trifluoromethyl group, ethoxy group and butoxy group; fluorinated alkyl groups with 1 to 4 carbons such as trifluoromethyl group; cyano group; nitro group; hydroxyl group; halogen atom; amino group, Substituted or unsubstituted amino groups such as diethylamino and pyrrolidinyl (substituted amino groups refer to amino groups having one or two alkyl groups with 1 to 4 carbons, or two substituted Alkyl groups are bonded to each other to form an amino group of an alkanediyl group having 2 to 8 carbons; the unsubstituted amino group is -NH 2 ; the alkyl group having 1 to 4 carbons includes methyl, ethyl and butyl and the like; as the alkanediyl group having 2 to 8 carbon atoms, ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane alkane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc.). In terms of high molecular linearity, the phenylene, naphthylene and divalent heterocyclic groups in -E 1 -, -E 2 - and -E 3 - are preferably: unsubstituted, or In the case of substitution, it is substituted with methyl group, methoxy group, hydroxyl group, fluorine atom, chlorine atom, dimethylamino group, pyrrolidinyl group (pyrrolidinyl), piperidinyl group.

p表示0～4的整數。就在溶劑中的溶解性、與液晶化合物的相容性、色調及製造容易性的觀點而言，p較佳為1以上，且較佳為4以下，更佳為3以下。p represents an integer of 0-4. From the viewpoints of solubility in solvents, compatibility with liquid crystal compounds, color tone, and ease of production, p is preferably 1 or more, and is preferably 4 or less, more preferably 3 or less.

R 11及R 12表示同一或者各不相同的一價有機基。 作為R 11及R 12中的一價有機基，可列舉：氫原子、可具有分支的碳數1～15的烷基；脂環式的碳數1～15的烷基；甲氧基、乙氧基及丁氧基等可具有分支的碳數1～15的烷氧基；三氟甲基等可具有分支的碳數1～15的氟化烷基；氰基；硝基；羥基；鹵素原子；胺基、二乙基胺基及吡咯啶基等經取代或未經取代的胺基；羧基；丁氧基羰基等可具有分支的碳數1～15的烷氧基羰基；2-(4-丁基苯基)乙烯基等烷基苯基烯基；胺甲醯基；丁基胺甲醯基等可具有分支的碳數1～15的烷基胺甲醯基；胺磺醯基；丁基胺磺醯基等可具有分支的碳數1～15的烷基胺磺醯基；丁基羰基胺基等可具有分支的碳數1～15的醯基胺基；丁基羰氧基等可具有分支的碳數1～15的醯氧基；硫基；丁基硫基等碳數1～15的烷基硫基；後述的液晶化合物中的-R 1及-R 2。 所述經取代的胺基是指具有一個或兩個碳數1～4的烷基的胺基、或者兩個經取代的烷基相互鍵結而形成碳數2～8的烷二基的胺基。未經取代的胺基為-NH 2。作為碳數1～4的烷基，可列舉：甲基、乙基及丁基等。作為碳數2～8的烷二基，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、辛烷-1,8-二基等。 R 11 and R 12 represent the same or different monovalent organic groups. As the monovalent organic group in R 11 and R 12 , there may be mentioned: a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have branches; an alicyclic alkyl group having 1 to 15 carbon atoms; Alkoxy groups with 1 to 15 carbon atoms that may have branches such as oxy and butoxy groups; fluorinated alkyl groups with 1 to 15 carbon atoms that may have branches such as trifluoromethyl; cyano groups; nitro groups; hydroxyl groups; halogens Atoms; substituted or unsubstituted amino groups such as amino groups, diethylamino groups, and pyrrolidinyl groups; carboxyl groups; butoxycarbonyl groups that may have branched alkoxycarbonyl groups with 1 to 15 carbon atoms; 2-( Alkyl phenyl alkenyl groups such as 4-butylphenyl) vinyl; aminoformyl; butylaminoformyl, etc., which may have branched alkylaminoformyl groups with 1 to 15 carbon atoms; aminosulfonyl ; Butyl sulfamoyl and the like can have branched alkyl sulfamoyl groups with 1 to 15 carbons; butyl carbonylamine and the like can have branched acylamino groups with 1 to 15 carbons; acyloxy group having 1 to 15 carbons; thio group; alkylthio group such as butylthio group having 1 to 15 carbons; -R 1 and -R 2 in liquid crystal compounds described later. The substituted amine group refers to an amine group having one or two alkyl groups with 1 to 4 carbons, or an amine with two substituted alkyl groups bonded to each other to form an alkanediyl group with 2 to 8 carbons base. An unsubstituted amine group is -NH 2 . As a C1-C4 alkyl group, a methyl group, an ethyl group, a butyl group, etc. are mentioned. Examples of the alkanediyl group having 2 to 8 carbon atoms include ethylidene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,3-diyl, and pentane-1,3-diyl. 1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc.

作為R 11及R 12，可列舉：氫原子、鏈狀基、脂肪族有機基（「脂肪族有機基」包含鏈狀者及環狀者）、碳原子的一部分由氮原子及/或氧原子取代的脂肪族有機基（「碳原子的一部分由氮原子及/或氧原子取代的脂肪族有機基」包括鏈狀者及環狀者，且包括脂肪族有機基的一部分甲基分別由羥基、側氧基（=O）、胺基、亞胺基等取代者）等，在某一形態中，較佳為氫原子、鏈狀基，在另一形態中，較佳為氫原子、脂肪族有機基，在又一形態中，較佳為氫原子、碳原子的一部分由氮原子及/或氧原子取代的脂肪族有機基。 Examples of R 11 and R 12 include: a hydrogen atom, a chain group, an aliphatic organic group ("aliphatic organic group" includes chains and rings), nitrogen atoms and/or oxygen atoms in part of carbon atoms Substituted aliphatic organic groups (“aliphatic organic groups in which part of the carbon atoms are replaced by nitrogen atoms and/or oxygen atoms” include chain-shaped and cyclic ones, and include aliphatic organic groups in which a part of the methyl group is replaced by hydroxyl, Substituents such as pendant oxygen group (=O), amino group, imino group), etc., in one form, preferably hydrogen atom, chain group, in another form, preferably hydrogen atom, aliphatic In yet another aspect, the organic group is preferably an aliphatic organic group in which a hydrogen atom or a part of carbon atoms is substituted with a nitrogen atom and/or an oxygen atom.

作為鏈狀基，可列舉：所述可具有分支的碳數1～15的烷基；可具有分支的碳數1～15的烷氧基；可具有分支的碳數1～15的氟化烷基；經取代或者未經取代的胺基（所謂經取代的胺基是指具有一個或兩個可具有分支的碳數1～15的烷基的胺基，未經取代的胺基為-NH 2）；羧基；可具有分支的碳數1～15的烷氧基羰基；胺甲醯基；可具有分支的碳數1～15的烷基胺甲醯基；胺磺醯基；可具有分支的碳數1～15的烷基胺磺醯基；可具有分支的碳數1～15的醯基胺基；可具有分支的碳數1～15的醯氧基；硫基；碳數1～15的烷基硫基等。所述鏈狀基與脂肪族有機基有一部分重覆。 Examples of the chain group include: the alkyl group having 1 to 15 carbons that may have branches; the alkoxy group having 1 to 15 carbons that may have branches; the fluorinated alkyl group having 1 to 15 carbons that may have branches Substituted or unsubstituted amino group (the so-called substituted amino group refers to an amino group with one or two branched carbon numbers of 1 to 15 alkyl groups, and the unsubstituted amino group is -NH 2 ); carboxyl group; alkoxycarbonyl group with branched carbon number of 1 to 15; carboxyl group; alkylcarbamoyl group with branched carbon number of 1 to 15; sulfamoyl group; branched Alkylsulfamoyl group with 1 to 15 carbons; acylamino group with branched carbons 1 to 15; acyloxy group with branched carbons 1 to 15; sulfur group; 15's alkylthio group etc. The chain group partially overlaps with the aliphatic organic group.

作為脂肪族有機基，可列舉所述可具有分支的碳數1～15的烷基、脂環式的碳數1～15的烷基等。 作為碳原子的一部分由氮原子及/或氧原子取代的脂肪族有機基，可列舉：所述可具有分支的碳數1～15的烷氧基；經取代或未經取代的胺基；羧基；可具有分支的碳數1～15的烷氧基羰基；胺甲醯基；可具有分支的碳數1～15的烷基胺甲醯基；可具有分支的碳數1～15的醯基胺基；可具有分支的碳數1～15的醯氧基等。 所述經取代的胺基是指具有一個或兩個可具有分支的碳數1～15的烷基的胺基、或者兩個經取代的烷基相互鍵結而形成碳數2～15的烷二基的胺基。未經取代的胺基為-NH 2。作為碳數1～15的烷基，可列舉：甲基、乙基及丁基等。作為碳數2～15的烷二基，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、辛烷-1,8-二基等。 Examples of the aliphatic organic group include the above-mentioned optionally branched alkyl group having 1 to 15 carbons, alicyclic alkyl group having 1 to 15 carbons, and the like. Examples of the aliphatic organic group in which a part of the carbon atoms are substituted with a nitrogen atom and/or an oxygen atom include: the above-mentioned alkoxy group having 1 to 15 carbon atoms which may have a branch; a substituted or unsubstituted amino group; a carboxyl group ; Alkoxycarbonyl with branched carbon number 1 to 15; Aminoformyl group; Alkylcarbamoyl group with branched carbon number 1 to 15; Acyl group with branched carbon number 1 to 15 Amino group; acyloxy group with 1 to 15 carbon atoms that may have branches, etc. The substituted amine group refers to an amine group having one or two branched alkyl groups with 1 to 15 carbons, or two substituted alkyl groups bonded to each other to form an alkane with 2 to 15 carbons. Diyl amine group. An unsubstituted amine group is -NH 2 . Examples of the alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, and a butyl group. Examples of the alkanediyl group having 2 to 15 carbon atoms include ethylidene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,3-diyl, 1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc.

就分子直線性高的方面而言，作為R 11及R 12，分別獨立地較佳為：氫原子，或者由丁基、戊基、己基、庚基、辛基等碳數1～10的烷基；丁氧基、戊基氧基、己基氧基、庚基氧基、辛基氧基等碳數1～10的烷氧基、二乙基胺基、吡咯啶基及哌啶基取代。作為R 11及R 12，後述的液晶化合物中的-R 1及-R 2亦較佳。 In terms of high linearity of the molecule, R 11 and R 12 are each independently preferably a hydrogen atom, or an alkyl group having 1 to 10 carbons such as butyl, pentyl, hexyl, heptyl, or octyl. butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and other alkoxy groups with 1 to 10 carbon atoms, diethylamino, pyrrolidinyl and piperidinyl. As R 11 and R 12 , -R 1 and -R 2 in liquid crystal compounds described later are also preferable.

作為本發明的各向異性色素膜形成用組成物中所含的除本發明的化合物以外的偶氮系色素，並無特別限定，亦可使用公知的偶氮系色素。 作為公知的偶氮系色素，例如可列舉：所述專利文獻1、日本專利第5982762號公報、日本專利特開2017-025317號公報、日本專利特開2014-095899號公報所記載的色素（二色性色素、二色性染料）。 The azo-based dyes other than the compound of the present invention contained in the anisotropic dye film-forming composition of the present invention are not particularly limited, and known azo-based dyes can also be used. As known azo-based dyes, for example, the dyes described in Patent Document 1, Japanese Patent No. 5982762, Japanese Patent Laid-Open No. 2017-025317, and Japanese Patent Laid-Open No. 2014-095899 (two Chromatic pigments, dichroic dyes).

具體而言，可列舉以下所記載的偶氮系色素，但並不限定於該些。Specifically, although the azo dyes described below are mentioned, it is not limited to these.

[化8]

Figure 02_image014
[chemical 8]
Figure 02_image014

[化9]

Figure 02_image016
[chemical 9]
Figure 02_image016

[化10]

Figure 02_image018
[chemical 10]
Figure 02_image018

[化11]

Figure 02_image020
[chemical 11]
Figure 02_image020

作為本發明的各向異性色素膜形成用組成物中所含的除式（1）所表示的本發明的化合物以外的色素，較佳為如下色素：相較於各向異性色素膜形成用組成物中所含的式（1）所表示的本發明的化合物在350 nm～800 nm的波長區域的吸收曲線中顯示出最大值的波長，所述色素在350 nm～800 nm的波長區域的吸收曲線中顯示出極大值的波長更短，且較佳為偶氮色素。另外，所述波長之差較佳為5 nm以上，更佳為10 nm以上。藉由如上所述，在將使用本發明的各向異性色素膜形成用組成物形成的各向異性色素膜應用於顯示器等的偏光元件的情況下，可在可見光區域的廣範圍內表現出偏光特性。The dyes other than the compound of the present invention represented by the formula (1) contained in the anisotropic dye film-forming composition of the present invention are preferably the following dyes: The compound of the present invention represented by formula (1) contained in the product shows the wavelength of the maximum value in the absorption curve of the wavelength region of 350 nm to 800 nm, and the absorption of the pigment in the wavelength region of 350 nm to 800 nm is The wavelength showing the maximum value in the curve is shorter, and is preferably an azo dye. In addition, the wavelength difference is preferably at least 5 nm, more preferably at least 10 nm. As described above, when the anisotropic dye film formed using the anisotropic dye film-forming composition of the present invention is applied to a polarizing element such as a display, it is possible to express polarization in a wide range of the visible light region. characteristic.

（色素的分子量） 本發明的各向異性色素膜形成用組成物中所含的色素的分子量（在併用兩種以上色素的情況下為各者的分子量）較佳為300以上，更佳為350以上，進而佳為380以上，且較佳為1500以下，更佳為1200以下，進而佳為1000以下。具體而言，本發明的各向異性色素膜形成用組成物中所含的色素的分子量較佳為300～1500，更佳為350～1200，進而佳為380～1000。藉由處於所述範圍，會變成適當的分子長度、大體積，故而色素的分子配向呈變良好的趨勢。 色素的分子量是色素中所含的原子量的總和。 (molecular weight of pigment) The molecular weight of the dye contained in the anisotropic dye film-forming composition of the present invention (the molecular weight of each when two or more dyes are used in combination) is preferably 300 or more, more preferably 350 or more, and still more preferably 380 or more, and preferably 1500 or less, more preferably 1200 or less, still more preferably 1000 or less. Specifically, the molecular weight of the dye contained in the composition for anisotropic dye film formation of this invention becomes like this. Preferably it is 300-1500, More preferably, it is 350-1200, More preferably, it is 380-1000. By being in the above-mentioned range, the molecular alignment of the dye tends to become favorable because the molecular length becomes appropriate and the volume becomes large. The molecular weight of a pigment is the sum of the atomic weights contained in the pigment.

（色素的含量） 關於本發明的各向異性色素膜形成用組成物中二色性色素等色素所佔的含量（在併用兩種以上色素的情況下為各者的含量的總和），例如相對於各向異性色素膜形成用組成物的固體成分（100質量份）較佳為0.01質量份以上，更佳為0.05質量份以上，且較佳為30質量份以下，更佳為25質量份以下，進而佳為20質量份以下，尤佳為10質量份以下。具體而言，關於各向異性色素膜形成用組成物中色素（二色性色素）所佔的含量，例如相對於各向異性色素膜形成用組成物的固體成分（100質量份）為0.01質量份～30質量份，較佳為0.05質量份～20質量份，更佳為0.05質量份～10質量份。 (content of pigment) Regarding the content of dyes such as dichroic dyes in the anisotropic dye film-forming composition of the present invention (the sum of the respective contents when two or more dyes are used in combination), for example, relative to the anisotropic dye The solid content (100 parts by mass) of the composition for film formation is preferably at least 0.01 parts by mass, more preferably at least 0.05 parts by mass, and is preferably at most 30 parts by mass, more preferably at most 25 parts by mass, still more preferably at most 20 parts by mass. It is not more than 10 parts by mass, preferably not more than 10 parts by mass. Specifically, the content of the dye (dichroic dye) in the composition for forming an anisotropic dye film is, for example, 0.01 mass with respect to the solid content (100 parts by mass) of the composition for forming an anisotropic dye film 30 parts by mass, preferably 0.05 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass.

只要色素所佔的含量為所述範圍內，則呈如下趨勢，即，在不擾亂本發明的各向異性色素膜形成用組成物中所含的液晶化合物的配向的情況下，可使本發明的各向異性色素膜形成用組成物中所含的聚合性液晶化合物聚合。只要色素所佔的含量為所述下限值以上，則呈獲得充分的光吸收，從而獲得充分的偏光性能的趨勢。只要色素所佔的含量為所述上限值以下，則呈容易抑制液晶分子的配向阻礙的趨勢。 此處，各向異性色素膜用組成物的固體成分相當於各向異性色素膜用組成物中的除溶劑以外的所有成分的合計。 As long as the content of the dye is within the above range, there is a tendency that the present invention can be used without disturbing the alignment of the liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention. The polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition is polymerized. As long as the content occupied by the dye is more than the above lower limit value, sufficient light absorption and sufficient polarization performance tend to be obtained. As long as the content of the dye is not more than the above upper limit, it tends to be easy to suppress the inhibition of alignment of liquid crystal molecules. Here, the solid content of the composition for anisotropic dye films corresponds to the total of all the components in the composition for anisotropic dye films except the solvent.

本發明的各向異性色素膜用組成物只要含有作為色素的本發明的化合物以作為必須成分即可，亦可在含有本發明的化合物的同時含有所述其他色素。 在本發明的各向異性色素膜用組成物含有其他色素的情況下，就更有效地獲得使用本發明的化合物所產生的本發明的效果的觀點而言，在本發明的各向異性色素膜用組成物中的色素的總量100質量%中，本發明的化合物的比例較佳為5質量%以上，更佳為10質量%以上，進而佳為15質量%以上，尤佳為20質量%以上。就在可見光區域的廣範圍內表現出偏光特性的觀點而言，該比例較佳為80質量%以下，更佳為60質量%以下，進而佳為50質量%以下，特佳為40質量%以下。 The composition for anisotropic dye film of the present invention may contain the compound of the present invention as a dye as an essential component, and may contain the other dyes together with the compound of the present invention. When the composition for anisotropic dyed film of the present invention contains other dyes, from the viewpoint of more effectively obtaining the effect of the present invention produced by using the compound of the present invention, in the anisotropic dyed film of the present invention The ratio of the compound of the present invention is preferably at least 5% by mass, more preferably at least 10% by mass, further preferably at least 15% by mass, and most preferably at least 20% by mass, based on 100% by mass of the total amount of the pigment in the composition. above. From the viewpoint of exhibiting polarization characteristics in a wide range of the visible light region, the ratio is preferably at most 80% by mass, more preferably at most 60% by mass, still more preferably at most 50% by mass, and most preferably at most 40% by mass. .

（色素的製造方法） 本發明的各向異性色素膜形成用組成物所含有的本發明的化合物等色素可藉由將烷基化反應、酯化反應、醯胺化反應、醚化反應、本位（ipso）取代反應、重氮偶合反應、使用金屬觸媒的偶合反應等公知的化學反應加以組合而製造。 (Manufacturing method of pigment) The pigment such as the compound of the present invention contained in the composition for forming an anisotropic dye film of the present invention can be obtained by subjecting an alkylation reaction, an esterification reaction, an amidation reaction, an etherification reaction, an ipso substitution reaction, Manufactured by combining known chemical reactions such as diazo coupling reaction and coupling reaction using a metal catalyst.

例如，本發明的化合物可依照後述的實施例所記載的方法、或「新染料化學」（細田豐著，1973年12月21日，技報堂）、「總說合成染料」（堀口博著，1968年，三共出版）、「理論製造 染料化學」（細田豐著，1957年，技報堂）所記載的方法合成。For example, the compound of the present invention can be obtained according to the method described in the Examples described later, or "New Dye Chemistry" (by Toyo Hosoda, December 21, 1973, Gihodo), "General Synthetic Dyes" (by Hiroshi Horiguchi, 1968 Sankyo Publishing, 1957) and "Theoretical Fabrication of Dye Chemistry" (Toyoto Hosoda, 1957, Gihodo) for synthesis.

＜聚合性液晶化合物＞ 在本發明中，液晶化合物是指顯示出液晶狀態的物質，具體而言，如「液晶便覽」（丸善股份有限公司，2000年10月30日發行）的第1～28頁所記載般，是指不自結晶直接轉變為液體而經過顯示出結晶與液體兩者的性質的中間狀態而變成液體的化合物。 ＜Polymerizable Liquid Crystal Compound＞ In the present invention, a liquid crystal compound refers to a substance exhibiting a liquid crystal state. Specifically, as described on pages 1 to 28 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2000), it is Refers to a compound that does not directly change from crystal to liquid, but becomes liquid through an intermediate state showing the properties of both crystal and liquid.

本發明的各向異性色素膜形成用組成物中所含的聚合性液晶化合物是後述的具有聚合性基的液晶化合物。The polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention is a liquid crystal compound having a polymerizable group described later.

在聚合性液晶化合物中，聚合性基可配置於液晶化合物分子內的任意位置，但就容易進行聚合的觀點而言，聚合性基較佳為在液晶化合物分子的末端進行取代。 在聚合性液晶化合物中，聚合性基可在液晶化合物分子內存在一個以上，在存在兩個以上的情況下，就容易進行聚合的觀點而言，較佳為分別存在於液晶化合物分子的兩末端。 In the polymerizable liquid crystal compound, the polymerizable group can be arranged at any position in the molecule of the liquid crystal compound, but from the viewpoint of ease of polymerization, the polymerizable group is preferably substituted at the terminal of the liquid crystal compound molecule. In the polymerizable liquid crystal compound, one or more polymerizable groups may exist in the liquid crystal compound molecule, and in the case where there are two or more, it is preferable to exist at both ends of the liquid crystal compound molecule from the viewpoint of easy polymerization. .

聚合性液晶化合物較佳為在液晶化合物分子內具有碳-碳三鍵的化合物。若為具有碳-碳三鍵的化合物，則該碳-碳三鍵能夠進行旋轉運動並且能夠成為液晶分子的核，從而分子的運動性高且液晶分子彼此或與色素分子等具有π共軛系的化合物的分子間相互作用強，從而分子配向呈變高的趨勢。The polymerizable liquid crystal compound is preferably a compound having a carbon-carbon triple bond in the liquid crystal compound molecule. If it is a compound having a carbon-carbon triple bond, the carbon-carbon triple bond can perform rotational motion and can become the nucleus of a liquid crystal molecule, so that the mobility of the molecule is high and the liquid crystal molecules have a π-conjugated system with each other or with the pigment molecule. The intermolecular interactions of the compounds are strong, and the molecular alignment tends to be high.

作為本發明的各向異性色素膜形成用組成物中所含的聚合性液晶化合物，並無特別限定，可使用具有聚合性基的液晶化合物。The polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention is not particularly limited, and a liquid crystal compound having a polymerizable group can be used.

例如，作為本發明的各向異性色素膜形成用組成物中所含的聚合性液晶化合物，可列舉下述式（2）所表示的化合物（以下，有時稱為「聚合性液晶化合物（2）」）。For example, as the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention, compounds represented by the following formula (2) (hereinafter sometimes referred to as "polymerizable liquid crystal compound (2 )").

Q 1-R 1-A 11-Y 1-A 12-(Y 2-A 13) k-R 2-Q 2･･･（2） Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 ･･･（2）

（式（2）中， -Q 1表示氫原子或者聚合性基； -Q 2表示聚合性基； -R 1-及-R 2-分別獨立地表示鏈狀有機基； -A 11-及-A 13-分別獨立地表示下述式（3）所表示的部分結構、二價有機基、或者單鍵； -A 12-表示下述式（3）所表示的部分結構或者二價有機基； -Y 1-及-Y 2-分別獨立地表示單鍵、-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH 2CH 2-、-CH=CH-、-C≡C-、-C(=O)NH-、-NHC(=O)-、-CH 2O-、-OCH 2-、-CH 2S-、或者-SCH 2-； -A 11-及-A 13-中的一者為下述式（3）所表示的部分結構或者二價有機基； k為1或2， 在k為2的情況下，兩個-Y 2-A 13-彼此可相同亦可不同） (In formula (2), -Q 1 represents a hydrogen atom or a polymerizable group; -Q 2 represents a polymerizable group; -R 1 - and -R 2 - independently represent a chain organic group; -A 11 -and- A 13 - each independently represents a partial structure represented by the following formula (3), a divalent organic group, or a single bond; -A 12 - represents a partial structure or a divalent organic group represented by the following formula (3); -Y 1 - and -Y 2 - independently represent a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH 2 CH 2 -, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O )-, -CH 2 O-, -OCH 2 -, -CH 2 S-, or -SCH 2 -; one of -A 11 - and -A 13 - is a moiety represented by the following formula (3) structure or divalent organic group; k is 1 or 2, when k is 2, two -Y 2 -A 13 - can be the same or different from each other)

-C y-X 2-C≡C-X 1-   ･･･（3） （式（3）中， -C y-表示烴環基或者雜環基； -X 1-表示-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH 2CH 2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、-CH 2O-、-OCH 2-、-CH 2S-、或者-SCH 2-； -X 2-表示單鍵、-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH 2CH 2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、-CH 2O-、-OCH 2-、-CH 2S-、或者-SCH 2-） -C y -X 2 -C≡CX 1 - ･･･(3) (In formula (3), -C y -represents hydrocarbon ring or heterocyclic group; -X 1 -represents -C(=O)O -, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH 2 CH 2 - , -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH 2 O-, -OCH 2 -, -CH 2 S-, or -SCH 2 -; -X 2 -Indicates a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC (=O)-, -CH 2 CH 2 -, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH 2 O-, -OCH 2 -, -CH 2 S-, or -SCH 2 -)

再者，在-A 11-為式（3）所表示的部分結構的情況下，式（2）可為下述式（2A），亦可為下述式（2B）。 Q 1-R 1-C y-X 2-C≡C-X 1-Y 1-A 12-(Y 2-A 13) k-R 2-Q 2･･･（2A） Q 1-R 1-X 1-C≡C-X 2-C y-Y 1-A 12-(Y 2-A 13) k-R 2-Q 2･･･（2B） Furthermore, when -A 11 - is a partial structure represented by formula (3), formula (2) may be the following formula (2A), or may be the following formula (2B). Q 1 -R 1 -C y -X 2 -C≡CX 1 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 ･･･（2A） Q 1 -R 1 -X 1 -C≡CX 2 -C y -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 ･･･（2B）

另外，在-A 12-為式（3）所表示的部分結構的情況下，式（2）可為下述式（2C），亦可為下述式（2D）。 Q 1-R 1-A 11-Y 1-C y-X 2-C≡C-X 1-(Y 2-A 13) k-R 2-Q 2･･･（2C） Q 1-R 1-A 11-Y 1-X 1-C≡C-X 2-C y-(Y 2-A 13) k-R 2-Q 2･･･（2D） In addition, when -A 12 - is a partial structure represented by formula (3), formula (2) may be the following formula (2C), or may be the following formula (2D). Q 1 -R 1 -A 11 -Y 1 -C y -X 2 -C≡CX 1 -(Y 2 -A 13 ) k -R 2 -Q 2 ･･･（2C） Q 1 -R 1 -A 11 -Y 1 -X 1 -C≡CX 2 -C y -(Y 2 -A 13 ) k -R 2 -Q 2 ･･･（2D）

另外，在-A 13-為式（3）所表示的部分結構的情況下，式（2）可為下述式（2E），亦可為下述式（2F）。 Q 1-R 1-A 11-Y 1-A 12-(Y 2-C y-X 2-C≡C-X 1) k-R 2-Q 2･･･（2E） Q 1-R 1-A 11-Y 1-A 12-(Y 2-X 1-C≡C-X 2-C y) k-R 2-Q 2･･･（2F） In addition, when -A 13 - is a partial structure represented by formula (3), formula (2) may be the following formula (2E), or may be the following formula (2F). Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -C y -X 2 -C≡CX 1 ) k -R 2 -Q 2 ･･･（2E） Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -X 1 -C≡CX 2 -C y ) k -R 2 -Q 2 ･･･（2F）

同樣地，在-A 11-、-A 12-及-A 13-中的兩者以上為式（3）所表示的部分結構的情況下，可分別獨立地使式（3）所表示的部分結構的朝向反轉。 Similarly, when two or more of -A 11 -, -A 12 -, and -A 13 - are partial structures represented by formula (3), each of the moieties represented by formula (3) can be independently The orientation of the structure is reversed.

如上所述，-A 11-、-A 12-及-A 13-分別獨立地為式（3）所表示的部分結構或者二價有機基，此外，-A 11-及-A 13-亦可為單鍵，但不存在-A 11-及-A 13-均為單鍵的情況。 As mentioned above, -A 11 -, -A 12 - and -A 13 - are each independently a partial structure represented by formula (3) or a divalent organic group, and -A 11 - and -A 13 - may also be is a single bond, but there is no case where both -A 11 - and -A 13 - are single bonds.

（-C y-） -C y-中的烴環基包含芳香族烴環基及非芳香族烴環基。 芳香族烴環基包含非連結芳香族烴環基及連結芳香族烴環基。 (-C y -) The hydrocarbon ring group in -C y - includes an aromatic hydrocarbon ring group and a non-aromatic hydrocarbon ring group. The aromatic hydrocarbon ring group includes a non-connected aromatic hydrocarbon ring group and a linked aromatic hydrocarbon ring group.

非連結芳香族烴環基是單環或縮合的芳香族烴環的二價基，其碳數為6～20時，藉由適當的核的大小使分子配向性變良好，故而較佳。非連結芳香族烴環基的碳數更佳為6～15。作為芳香族烴環，例如可列舉：苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯並芘環、䓛環、三伸苯環、乙烷合萘環、螢蒽環、芴環等。The non-connecting aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring. When the carbon number is 6 to 20, molecular alignment becomes good due to an appropriate nucleus size, so it is preferable. The number of carbon atoms in the non-connected aromatic hydrocarbon ring group is more preferably 6-15. Examples of the aromatic hydrocarbon ring include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, fused tetraphenyl ring, pyrene ring, benzopyrene ring, pyrene ring, triphenylene ring, ethane-naphthalene ring ring, fluoranthene ring, fluorene ring, etc.

連結芳香族烴環基是多個單環或縮合的芳香族烴環以單鍵鍵結而在構成環的原子上具有鍵結鍵的二價基。單環或縮合環的碳數為6～20時，藉由適當的核的大小使分子配向性變良好，故而較佳。單環或縮合環的碳數更佳為6～15。作為連結芳香族烴環基，例如可列舉如下二價基，即，第一碳數6～20的單環或縮合的芳香族烴環與第二碳數6～20的單環或縮合的芳香族烴環以單鍵鍵結，在第一碳數6～20的單環或縮合的芳香族烴環的構成環的原子上具有第一鍵結鍵，在第二碳數6～20的單環或縮合的芳香族烴環的構成環的原子上具有第二鍵結鍵的二價基。作為連結芳香族烴環基，具體而言可列舉聯苯-4,4'-二基。The linking aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed aromatic hydrocarbon rings are bonded by a single bond and has bonding bonds on atoms constituting the rings. When the carbon number of a single ring or a condensed ring is 6-20, since molecular alignment becomes favorable by the size of an appropriate nucleus, it is preferable. The carbon number of a monocyclic or condensed ring is more preferably 6-15. As the linking aromatic hydrocarbon ring group, for example, the following bivalent group can be cited, that is, a first monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms and a second monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms. The aromatic hydrocarbon ring is bonded by a single bond, and has a first bond on the atom constituting the ring of the first carbon number of 6 to 20 single ring or condensed aromatic hydrocarbon ring, and the second carbon number of 6 to 20 single A ring or a condensed aromatic hydrocarbon ring has a divalent group having a second bond on an atom constituting the ring. As the linking aromatic hydrocarbon ring group, biphenyl-4,4'-diyl group is specifically mentioned.

作為芳香族烴環基，非連結芳香族烴環基會使作用於液晶化合物之間的分子間相互作用最佳藉此使分子配向性變良好，故而較佳。 其中，作為芳香族烴環基，較佳為苯環的二價基、萘環的二價基，更佳為苯環的二價基（伸苯基）。作為伸苯基，較佳為1,4-伸苯基。藉由-C y-為該些基，呈液晶分子的直線性提高而獲得分子配向性提昇的效果的趨勢。 As the aromatic hydrocarbon ring group, a non-connecting aromatic hydrocarbon ring group is preferable because it acts on the intermolecular interaction between liquid crystal compounds to make molecular alignment better. Among them, the aromatic hydrocarbon ring group is preferably a divalent group of a benzene ring or a divalent group of a naphthalene ring, more preferably a divalent group of a benzene ring (phenylene). The phenylene group is preferably a 1,4-phenylene group. When -C y - is these groups, the linearity of liquid crystal molecules tends to be improved to obtain an effect of improving molecular alignment.

非芳香族烴環基包含非連結非芳香族烴環基及連結非芳香族烴環基。The non-aromatic hydrocarbon ring group includes non-linkage non-aromatic hydrocarbon ring group and linking non-aromatic hydrocarbon ring group.

非連結非芳香族烴環基是單環或縮合的非芳香族烴環的二價基，其碳數為3～20時，藉由適當的核的大小使分子配向性變良好，故而較佳。非連結非芳香族烴環基的碳數更佳為3～15。作為非芳香族烴環，例如可列舉：環丙烷環、環丁烷環、環戊烷環、環己烷環、環庚烷環、環辛烷環、環己烯環、降莰烷環、莰烷環、金剛烷環、四氫萘環、雙環[2.2.2]辛烷環等。The non-linking non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring. When the carbon number is 3 to 20, the molecular alignment becomes good due to the appropriate size of the nucleus, so it is preferable . The carbon number of the non-linkage non-aromatic hydrocarbon ring group is more preferably 3-15. Examples of the non-aromatic hydrocarbon ring include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norbornane ring, Camphene ring, adamantane ring, tetrahydronaphthalene ring, bicyclo[2.2.2]octane ring, etc.

非連結非芳香族烴環基包含不具有不飽和鍵作為非芳香族烴環的構成環的原子間鍵的脂環式烴環基、及具有不飽和鍵作為非芳香族烴環的構成環的原子間鍵的不飽和非芳香族烴環基。作為非連結非芳香族烴環基，就生產性的觀點而言，較佳為脂環式烴環基。The non-connecting non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group not having an unsaturated bond as a bond between atoms constituting the non-aromatic hydrocarbon ring, and an alicyclic hydrocarbon ring group having an unsaturated bond as a constituting ring of the non-aromatic hydrocarbon ring. An unsaturated non-aromatic hydrocarbon ring group with an interatomic bond. The non-linkage non-aromatic hydrocarbon ring group is preferably an alicyclic hydrocarbon ring group from the viewpoint of productivity.

連結非芳香族烴環基是多個單環或縮合的非芳香族烴環以單鍵鍵結而在構成環的原子上具有鍵結鍵的二價基；或者選自由單環的芳香族烴環、縮合的芳香族烴環、單環的非芳香族烴環、及縮合的非芳香族烴環所組成的群組中的一種以上的環與單環或縮合的非芳香族烴環以單鍵鍵結而在構成環的原子上具有鍵結鍵的二價基。 基於藉由適當的核的大小使分子配向性變良好的理由，單環或縮合環的碳數較佳為3～20。 The linking non-aromatic hydrocarbon ring group is a divalent group with a plurality of monocyclic or condensed non-aromatic hydrocarbon rings bonded by a single bond and having a bonding bond on the atoms constituting the ring; or selected from a monocyclic aromatic hydrocarbon Ring, condensed aromatic hydrocarbon ring, monocyclic non-aromatic hydrocarbon ring, and condensed non-aromatic hydrocarbon ring in the group consisting of more than one ring and monocyclic or condensed non-aromatic hydrocarbon ring A divalent group that is bonded to have bonds on the atoms that make up the ring. The number of carbon atoms of a single ring or a condensed ring is preferably 3-20 for the reason that the molecular alignment becomes good due to an appropriate core size.

作為連結非芳香族烴環基，例如可列舉如下二價基，即，第一碳數3～20的單環或縮合的非芳香族烴環與第二碳數3～20的單環或縮合的非芳香族烴環以單鍵鍵結，在第一碳數3～20的單環或縮合的非芳香族烴環的構成環的原子上具有第一鍵結鍵，在第二碳數3～20的單環或縮合的非芳香族烴環的構成環的原子上具有第二鍵結鍵的二價基。進而，例如可列舉如下二價基，即，碳數3～20的單環或縮合的芳香族烴環與碳數3～20的單環或縮合的非芳香族烴環以單鍵鍵結，在碳數3～20的單環或縮合的芳香族烴環的構成環的原子上具有第一鍵結鍵，在碳數3～20的單環或縮合的非芳香族烴環的構成環的原子上具有第二鍵結鍵的二價基。As the linking non-aromatic hydrocarbon ring group, for example, the following bivalent group can be cited, that is, a monocyclic or condensed non-aromatic hydrocarbon ring having a first carbon number of 3 to 20 and a second monocyclic or condensed non-aromatic hydrocarbon ring having a second carbon number of 3 to 20 The non-aromatic hydrocarbon ring is bonded by a single bond, and has the first bond on the atoms constituting the ring of the monocyclic or condensed non-aromatic hydrocarbon ring with the first carbon number of 3 to 20, and the second carbon number is 3 A divalent group having a second bond on an atom constituting the ring of a monocyclic or condensed non-aromatic hydrocarbon ring of ~20. Further, for example, a divalent group in which a monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbons and a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbons is bonded with a single bond, There is a first bond on the atoms constituting the ring of a monocyclic or condensed aromatic hydrocarbon ring with 3 to 20 carbons; A divalent group with a second bond on the atom.

作為連結非芳香族烴環基，具體而言例如可列舉：雙(環己烷)-4,4'-二基、1-環己基苯-4,4'-二基。As a linking non-aromatic hydrocarbon ring group, a bis(cyclohexane)-4,4'-diyl group and a 1-cyclohexylbenzene-4,4'-diyl group are mentioned specifically,, for example.

作為非芳香族烴環基，非連結非芳香族烴環基會使作用於液晶化合物之間的分子間相互作用最佳藉此使分子配向性變良好，故而較佳。As the non-aromatic hydrocarbon ring group, a non-connecting non-aromatic hydrocarbon ring group is preferable because it can best act on intermolecular interaction between liquid crystal compounds and thereby improve molecular alignment.

作為非連結非芳香族烴環基，較佳為環己烷的二價基（環己烷二基），作為環己烷二基，較佳為環己烷-1,4-二基。藉由-C y-為該些基，呈液晶分子的直線性提高而獲得分子配向性提昇的效果的趨勢。 The non-linkage non-aromatic hydrocarbon ring group is preferably a divalent group of cyclohexane (cyclohexanediyl), and the cyclohexanediyl group is preferably cyclohexane-1,4-diyl. When -C y - is these groups, the linearity of liquid crystal molecules tends to be improved to obtain an effect of improving molecular alignment.

-C y-中的雜環基包含芳香族雜環基及非芳香族雜環基。 The heterocyclic group in -C y - includes aromatic heterocyclic groups and non-aromatic heterocyclic groups.

芳香族雜環基包含非連結芳香族雜環基及連結芳香族雜環基。The aromatic heterocyclic group includes a non-linked aromatic heterocyclic group and a linked aromatic heterocyclic group.

非連結芳香族雜環基是單環或縮合的芳香族雜環的二價基，其碳數為4～20時，藉由適當的核的大小使分子配向性變良好，故而較佳。非連結芳香族雜環基的碳數更佳為4～15。The non-connecting aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocyclic ring, and when the number of carbon atoms is 4 to 20, molecular alignment becomes good due to an appropriate nucleus size, so it is preferable. The number of carbon atoms in the non-connecting aromatic heterocyclic group is more preferably 4-15.

作為芳香族雜環，例如可列舉：呋喃環、苯並呋喃環、噻吩環、苯並噻吩環、吡咯環、吡唑環、咪唑環、噻唑環、異噻唑環、噁二唑環、噻二唑環、***環、吲哚環、咔唑環、吡咯並咪唑環、吡咯並吡唑環、吡咯並吡咯環、噻吩並吡咯環、噻吩並噻吩環、呋喃並吡咯環、呋喃並呋喃環、噻吩並呋喃環、噻吩並噻唑環、苯並異噁唑環、苯並異噻唑環、苯並咪唑環、吡啶環、吡嗪環、噠嗪環、嘧啶環、三嗪環、喹啉環、異喹啉環、噌啉環、喹噁啉環、啡啶環、喹唑啉環、喹唑啉酮環、薁環等。Examples of the aromatic heterocycle include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, oxadiazole ring, thiadiazole ring, Azole ring, triazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring , thienofuran ring, thienothiazole ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring , isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, quinazoline ring, quinazolinone ring, azulene ring, etc.

連結芳香族雜環基是多個單環或縮合的芳香族雜環以單鍵鍵結而在構成環的原子上具有鍵結鍵的二價基。單環或縮合環的碳數為4～20時，藉由適當的核的大小使分子配向性變良好，故而較佳。連結芳香族雜環基的碳數更佳為4～15。The linking aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocyclic rings are bonded by a single bond and have a bonding bond on atoms constituting the ring. When the carbon number of a single ring or a condensed ring is 4-20, since molecular alignment becomes favorable by the size of an appropriate core, it is preferable. The number of carbon atoms linked to the aromatic heterocyclic group is more preferably 4-15.

作為連結芳香族雜環基，例如可列舉如下的二價基，即，第一碳數4～20的單環或縮合的芳香族雜環與第二碳數4～20的單環或縮合的芳香族雜環以單鍵鍵結，在第一碳數4～20的單環或縮合的芳香族雜環的構成環的原子上具有第一鍵結鍵，在第二碳數4～20的單環或縮合的芳香族雜環的構成環的原子上具有第二鍵結鍵的二價基。The linking aromatic heterocyclic group includes, for example, a divalent group in which a first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms The aromatic heterocyclic ring is bonded by a single bond, and has a first bond on the atoms constituting the ring of the monocyclic or condensed aromatic heterocyclic ring with the first carbon number of 4 to 20, and the second carbon number of the 4 to 20 A monocyclic or condensed aromatic heterocyclic ring has a divalent group having a second bond on an atom constituting the ring.

非芳香族雜環基包含非連結非芳香族雜環基及連結非芳香族雜環基。The non-aromatic heterocyclic group includes non-linkage non-aromatic heterocyclic group and linking non-aromatic heterocyclic group.

非連結非芳香族雜環基是單環或縮合的非芳香族雜環的二價基，其碳數為4～20時，藉由適當的核的大小使分子配向性變良好，故而較佳。非連結非芳香族雜環基的碳數更佳為4～15。The non-linking non-aromatic heterocyclic group is a monocyclic or condensed non-aromatic heterocyclic divalent group. When the carbon number is 4 to 20, the molecular alignment becomes good due to the appropriate size of the nucleus, so it is preferable . The carbon number of the non-linkage non-aromatic heterocyclic group is more preferably 4-15.

作為碳數4～20的單環或縮合的非芳香族雜環的二價基的非芳香族雜環可列舉：四氫呋喃環、四氫吡喃環、二噁烷環、四氫噻吩環、四氫噻喃環、吡咯啶環、哌啶環、二氫吡啶環、哌嗪環、四氫噻唑環、四氫噁唑環、八氫喹啉環、四氫喹啉環、八氫喹唑啉環、四氫喹唑啉環、四氫咪唑環、四氫苯並咪唑環、奎寧環等。Examples of non-aromatic heterocycles that are divalent groups of monocyclic or condensed non-aromatic heterocycles having 4 to 20 carbon atoms include tetrahydrofuran rings, tetrahydropyran rings, dioxane rings, tetrahydrothiophene rings, and tetrahydrofuran rings. Hydrothiopyran ring, pyrrolidine ring, piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydrooxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzimidazole ring, quinuclidine, etc.

連結非芳香族雜環基是多個單環或縮合的非芳香族雜環以單鍵鍵結而在構成環的原子上具有鍵結鍵的二價基。單環或縮合環的碳數為4～20時，藉由適當的核的大小使分子配向性變良好，故而較佳。連結非芳香族雜環基的碳數更佳為4～15。The linking non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocyclic rings are bonded by a single bond and have a bonding bond on atoms constituting the ring. When the carbon number of a single ring or a condensed ring is 4-20, since molecular alignment becomes favorable by the size of an appropriate core, it is preferable. The number of carbon atoms connecting the non-aromatic heterocyclic group is more preferably 4-15.

作為連結芳香族雜環基，例如可列舉如下的二價基，即，第一碳數4～20的單環或縮合的非芳香族雜環與第二碳數4～20的單環或縮合的非芳香族雜環以單鍵鍵結，在第一碳數4～20的單環或縮合的非芳香族雜環的構成環的原子上具有第一鍵結鍵，在第二碳數4～20的單環或縮合的非芳香族雜環的構成環的原子上具有第二鍵結鍵的二價基。As the linking aromatic heterocyclic group, for example, a divalent group including a monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms in the first and a monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms in the second The non-aromatic heterocyclic ring is bonded with a single bond, and has a first bond on the atoms constituting the ring of the monocyclic or condensed non-aromatic heterocyclic ring with the first carbon number of 4 to 20, and the second carbon number is 4 A divalent group having a second bond on an atom constituting the ring of a monocyclic or condensed non-aromatic heterocyclic ring of ~20.

-C y-中的芳香族烴環基、非芳香族烴環基、芳香族雜環基、非芳香族雜環基分別可由選自由-R k、-OH、-O-R k、-O-C(=O)-R k、-NH 2、-NH-R k、-N(R k')-R k、-C(=O)-R k、-C(=O)-O-R k、-C(=O)-NH 2、-C(=O)-NH-R k、-C(=O)-N(R k')-R k、-SH、-S-R k、三氟甲基、胺磺醯基、羧基、磺基、氰基、硝基、及鹵素所組成的群組中的一種以上的基取代。-R k及-R k'分別獨立地表示碳數1～6的直鏈狀或分支狀的烷基。 The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -C y - can be selected from -R k , -OH, -OR k , -OC(= O)-R k , -NH 2 , -NH-R k , -N(R k' )-R k , -C(=O)-R k , -C(=O)-OR k , -C( =O)-NH 2 , -C(=O)-NH-R k , -C(=O)-N(R k' )-R k , -SH, -SR k , trifluoromethyl, sulfamic acid Substituted by one or more of the group consisting of acyl, carboxyl, sulfo, cyano, nitro, and halogen. -R k and -R k' each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms.

就分子結構的直線性高、聚合性液晶化合物（2）彼此容易締合而容易表現出液晶狀態的方面而言，-C y-中的芳香族烴環基、非芳香族烴環基、芳香族雜環基、非芳香族雜環基分別獨立地較佳為未經取代、或由甲基、甲氧基、氟原子、氯原子、溴原子取代，更佳為未經取代。 The linearity of the molecular structure is high, and the polymerizable liquid crystal compounds (2) are easy to associate with each other to easily express a liquid crystal state. The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic hydrocarbon ring group in -C y - The aromatic heterocyclic group and the non-aromatic heterocyclic group are each independently preferably unsubstituted, or substituted by methyl, methoxy, fluorine atom, chlorine atom, bromine atom, more preferably unsubstituted.

-C y-中的芳香族烴環基、非芳香族烴環基、芳香族雜環基、非芳香族雜環基所具有的取代基可相同亦可不同，另外，芳香族烴環基、非芳香族烴環基、芳香族雜環基、非芳香族雜環基可全部經取代，亦可全部未經取代，還可一部分經取代且一部分未經取代。 The substituents of the aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -C y - may be the same or different. In addition, the aromatic hydrocarbon cyclic group, All of the non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be substituted or may be unsubstituted, or some may be substituted and some may be unsubstituted.

作為-C y-，就聚合性液晶化合物（2）的分子配向性變良好而言，較佳為烴環基，更佳為伸苯基、環己烷二基。就可提高聚合性液晶化合物（2）的分子結構的直線性而言，作為-C y-，進而佳為1,4-伸苯基、環己烷-1,4-二基，特佳為1,4-伸苯基。 -C y - is preferably a hydrocarbon ring group, more preferably a phenylene group or a cyclohexanediyl group, since the molecular alignment of the polymerizable liquid crystal compound (2) becomes favorable. In terms of improving the linearity of the molecular structure of the polymerizable liquid crystal compound (2), -C y - is further preferably 1,4-phenylene, cyclohexane-1,4-diyl, particularly preferably 1,4-phenylene.

（-X 1-） -X 1-表示-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH 2CH 2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、-CH 2O-、-OCH 2-、-CH 2S-或者-SCH 2-，其中，就聚合性液晶化合物（2）的直線性或繞分子短軸的旋轉運動呈容易進行的趨勢而言，作為-X 1-，可列舉π鍵結性小的-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH 2CH 2-、-CH 2O-、-OCH 2-、-CH 2S-、-SCH 2-等為較佳者。該些中，更佳為-C(=O)O-、-OC(=O)-、-CH 2CH 2-、-CH 2O-、-OCH 2-，-X 1-進而佳為-C(=O)O-或者-OC(=O)-。在另一形態中，-X 1-較佳為-CH 2CH 2-、-CH 2O-或者-OCH 2-。 (-X 1 -) -X 1 - means -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O )S-, -SC(=O)-, -CH 2 CH 2 -, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH 2 O-, -OCH 2 -, -CH 2 S-, or -SCH 2 -, in which the linearity of the polymerizable liquid crystal compound (2) or the tendency of the rotational movement around the minor axis of the molecule to be easily performed, as -X 1 -, may be List -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH 2 CH 2 -, -CH 2 O-, -OCH 2 -, -CH 2 S-, -SCH 2 -, etc. are preferred. Among these, -C(=O)O-, -OC(=O)-, -CH 2 CH 2 -, -CH 2 O-, -OCH 2 -, -X 1 - are more preferably - C(=O)O- or -OC(=O)-. In another embodiment, -X 1 - is preferably -CH 2 CH 2 -, -CH 2 O- or -OCH 2 -.

（-X 2-） -X 2-表示單鍵、-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH 2CH 2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、-CH 2O-、-OCH 2-、-CH 2S-或者-SCH 2-。 (-X 2 -) -X 2 - indicates a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C (=O)S-, -SC(=O)-, -CH 2 CH 2 -, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH 2 O- , -OCH 2 -, -CH 2 S- or -SCH 2 -.

就使聚合性液晶化合物（2）的核變大、使由各向異性色素膜形成用組成物形成的各向異性色素膜的二色性變大的觀點而言，較佳為以直線性高的基將-C y-與-C≡C-連結。具體而言，作為-X 2-，較佳為單鍵、或者具有π鍵結性的-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH=CH-、-C(=O)NH-、-NHC(=O)-，就直線性更高而言，進而佳為單鍵。 From the viewpoint of increasing the size of the nucleus of the polymerizable liquid crystal compound (2) and increasing the dichroism of the anisotropic dye film formed from the composition for forming an anisotropic dye film, it is preferable to have a high linearity. The group that connects -C y - to -C≡C-. Specifically, -X 2 - is preferably a single bond, or -C(=O)O-, -OC(=O)-, -C(=S)O-, - having π bonding property. OC(=S)-, -C(=O)S-, -SC(=O)-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, in terms of linearity Higher, and more preferably a single bond.

（-Q 1及-Q 2） -Q 1及-Q 2中的聚合性基是具有能夠藉由光、熱及/或放射線而進行聚合的部分結構的基，且是為了確保聚合功能而必需的官能基或原子團。就各向異性色素膜的製造的觀點而言，該聚合性基較佳為光聚合性基。 (-Q 1 and -Q 2 ) The polymerizable group in -Q 1 and -Q 2 is a group having a partial structure capable of polymerizing by light, heat and/or radiation, and is necessary to ensure the polymerization function functional groups or atomic groups. From the viewpoint of production of an anisotropic dye film, the polymerizable group is preferably a photopolymerizable group.

作為該聚合性基，具體而言，例如可列舉：丙烯醯基、甲基丙烯醯基、丙烯醯氧基、甲基丙烯醯氧基、丙烯醯基胺基、甲基丙烯醯基胺基、乙烯基、乙烯氧基、乙炔基、乙炔氧基、1,3-丁二烯基、1,3-丁二烯氧基、氧雜環丙基、氧雜環丁基、縮水甘油基、縮水甘油氧基、苯乙烯基、苯乙烯氧基等；較佳為丙烯醯基、甲基丙烯醯基、丙烯醯氧基、甲基丙烯醯氧基、丙烯醯基胺基、甲基丙烯醯基胺基、氧雜環丙基、縮水甘油基、縮水甘油氧基，更佳為丙烯醯基、甲基丙烯醯基、丙烯醯氧基、甲基丙烯醯氧基、丙烯醯基胺基、甲基丙烯醯基胺基、縮水甘油基、縮水甘油氧基，進而佳為丙烯醯氧基、甲基丙烯醯氧基、縮水甘油氧基。Specific examples of the polymerizable group include: acryl group, methacryl group, acryloxy group, methacryloxy group, acrylamine group, methacrylamine group, Vinyl, vinyloxy, ethynyl, ethynyloxy, 1,3-butadienyl, 1,3-butadienyloxy, oxirane, oxetanyl, glycidyl, glycidyl Glyceryloxy, styryl, styryloxy, etc.; preferably acryl, methacryl, acryloxy, methacryloxy, acrylamino, methacryl Amino, oxirane, glycidyl, glycidyloxy, more preferably acryl, methacryl, acryloxy, methacryloxy, acrylamino, formazan Acrylamino group, glycidyl group, glycidyloxy group, more preferably acryloxyl group, methacryloxyl group, glycidyloxyl group.

（-R 1-及-R 2-） -R 1-及-R 2-中的鏈狀有機基是不包含所述芳香族烴環、非芳香族烴環、芳香族雜環、非芳香族雜環等環狀結構的二價有機基。 作為此種鏈狀有機基，可列舉：-(伸烷基)-、-O-(伸烷基)-、-S-(伸烷基)-、-NH-(伸烷基)-、-N(烷基)-(伸烷基)-、-OC(=O)-(伸烷基)-、-C(=O)O-(伸烷基)-。 (-R 1 - and -R 2 -) The chain organic groups in -R 1 - and -R 2 - do not include the aromatic hydrocarbon ring, non-aromatic hydrocarbon ring, aromatic heterocycle, non-aromatic A divalent organic group with a ring structure such as a heterocycle. Examples of such chain organic groups include: -(alkylene)-, -O-(alkylene)-, -S-(alkylene)-, -NH-(alkylene)-, - N(alkyl)-(alkylene)-, -OC(=O)-(alkylene)-, -C(=O)O-(alkylene)-.

作為該些鏈狀有機基中的伸烷基，可列舉碳數1～25的直鏈狀或分支狀的伸烷基。伸烷基的碳-碳鍵可一部分成為不飽和鍵。伸烷基中所含的一個或一個以上的亞甲基可設為由-O-、-S-、-NH-、-N(R m)-、-C(=O)-、-C(=O)-O-、-C(=O)-NH-、-CHF-、-CF 2-、-CHCl-、-CCl 2-取代（displace）的結構。R m表示碳數1～6的直鏈狀或分支狀的烷基。 Examples of the alkylene group in these chain organic groups include linear or branched alkylene groups having 1 to 25 carbon atoms. A part of the carbon-carbon bond of the alkylene group may be an unsaturated bond. One or more methylene groups contained in the alkylene group can be set as -O-, -S-, -NH-, -N(R m )-, -C(=O)-, -C( =O)-O-, -C(=O)-NH-, -CHF-, -CF 2 -, -CHCl-, -CCl 2 -displaced structures. R m represents a linear or branched alkyl group having 1 to 6 carbon atoms.

作為該些鏈狀有機基中的伸烷基，就分子直線性高而言，較佳為伸烷基的碳的一部分可為不飽和鍵、並且伸烷基中所含的一個或者一個以上的亞甲基可設為由所述基取代（displace）的結構的碳數1～25的直鏈狀的伸烷基。As the alkylene group in these chain organic groups, in terms of high linearity of the molecule, it is preferable that a part of the carbon of the alkylene group can be an unsaturated bond, and one or more of the alkylene groups contained in the alkylene group The methylene group may be a straight-chain alkylene group having 1 to 25 carbon atoms of a structure substituted (displaced) by the above group.

鏈狀有機基中的主鏈（指鏈狀有機基中的最長的鏈狀部分）的原子數較佳為3～25，更佳為5～20，進而佳為6～20。The number of atoms in the main chain (the longest chain part in the chain organic group) in the chain organic group is preferably from 3 to 25, more preferably from 5 to 20, and still more preferably from 6 to 20.

作為鏈狀有機基，較佳為-(CH 2) r-CH 2-、-O-(CH 2) r-CH 2-、-(O) r1-(CH 2CH 2O) r2-(CH 2) r3-、-(O) r1-(CH 2) r2-(CH 2CH 2O) r3-。該些式中的r為1～24的整數，較佳為2～24的整數，更佳為4～19的整數，進而佳為5～19的整數。該些式中的r1、r2、r3分別獨立地表示整數，且以鏈狀有機基中的主鏈（指鏈狀有機基中的最長的鏈狀部分）的原子數較佳成為3～25、更佳成為5～20、進而佳成為6～20的方式適當調整。 As the chain organic group, -(CH 2 ) r -CH 2 -, -O-(CH 2 ) r -CH 2 -, -(O) r1 -(CH 2 CH 2 O) r2 -(CH 2 ) r3 -, -(O) r1 -(CH 2 ) r2 -(CH 2 CH 2 O) r3 -. r in these formulas is an integer of 1-24, Preferably it is an integer of 2-24, More preferably, it is an integer of 4-19, More preferably, it is an integer of 5-19. r1, r2, and r3 in these formulas represent integers independently, and the number of atoms in the main chain (referring to the longest chain part in the chain organic group) in the chain organic group is preferably 3 to 25, More preferably 5-20, and more preferably 6-20, adjust appropriately.

-R 1-及-R 2-分別獨立地較佳為-(伸烷基)-、-O-(伸烷基)-，更佳為-(伸烷基)-、-O-(伸烷基)-。在某一形態中，-R 1-及-R 2-中的鏈狀有機基為-(伸烷基)-，在另一形態中，-R 1-及-R 2-中的鏈狀有機基為-O-(伸烷基)-。 -R 1 - and -R 2 - are independently preferably -(alkylene)-, -O-(alkylene)-, more preferably -(alkylene)-, -O-(alkylene) base)-. In a certain form, the chain organic group in -R 1 - and -R 2 - is -(alkylene)-, in another form, the chain organic group in -R 1 - and -R 2 - The group is -O-(alkylene)-.

在如所述式（2B）、式（2E）般，-X 1-與-R 1-或者-X 1-與-R 2-鍵結的情況下；或者在所述式（2B）中-A 13-為單鍵、或在所述式（2E）中-A 11-為單鍵，且-R 1-或-R 2-與-Y 1-或-Y 2-鍵結的情況下，與-X 1-、-Y 1-或-Y 2-直接鍵結的-R 1-或者-R 2-較佳為-(伸烷基)-。 In the case of a bond between -X 1 - and -R 1 - or -X 1 - and -R 2 - as in the formula (2B) and formula (2E); or in the formula (2B) - When A 13 - is a single bond, or -A 11 - is a single bond in the formula (2E), and -R 1 - or -R 2 - is bonded to -Y 1 - or -Y 2 -, -R 1 - or -R 2 - directly bonded to -X 1 -, -Y 1 - or -Y 2 - is preferably -(alkylene)-.

除上述以外，不與-X 1-、-Y 1-或-Y 2-直接鍵結的-R 1-或者-R 2-較佳為-O-(伸烷基)-。 In addition to the above, -R 1 - or -R 2 - not directly bonded to -X 1 -, -Y 1 - or -Y 2 - is preferably -O-(alkylene)-.

（-A 11-、-A 12-及-A 13-中的二價有機基） -A 11-、-A 12-及-A 13-中的二價有機基較佳為下述式（4）所表示的基。 (Divalent organic groups in -A 11 -, -A 12 - and -A 13 -) The divalent organic groups in -A 11 -, -A 12 - and -A 13 - are preferably the following formula (4 ) represents the basis.

-Q 3-   ･･･（4） （式（4）中，Q 3表示烴環基或者雜環基） -Q 3 - ･･･(4) (In the formula (4), Q 3 represents a hydrocarbon ring group or a heterocyclic group)

-Q 3-中的烴環基包含芳香族烴環基以及非芳香族烴環基。 芳香族烴環基包含非連結芳香族烴環基以及連結芳香族烴環基。 The hydrocarbon ring group in -Q 3 - includes an aromatic hydrocarbon ring group and a non-aromatic hydrocarbon ring group. The aromatic hydrocarbon ring group includes a non-linked aromatic hydrocarbon ring group and a linked aromatic hydrocarbon ring group.

非連結芳香族烴環基是單環或縮合的芳香族烴環的二價基，其碳數為6～20時，藉由適當的核的大小使分子配向性變良好，故而較佳。非連結芳香族烴環基的碳數更佳為6～15。作為芳香族烴環，可列舉：苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯並芘環、䓛環、三伸苯環、乙烷合萘環、螢蒽環、芴環等。The non-connecting aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring. When the carbon number is 6 to 20, molecular alignment becomes good due to an appropriate nucleus size, so it is preferable. The number of carbon atoms in the non-connected aromatic hydrocarbon ring group is more preferably 6-15. Examples of the aromatic hydrocarbon ring include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring, pyrene ring, triphenylene ring, ethane-naphthalene ring , Fluoranthene ring, fluorene ring, etc.

連結芳香族烴環基是多個單環或縮合的芳香族烴環以單鍵鍵結而在構成環的原子上具有鍵結鍵的二價基。單環或縮合環的碳數為6～20時，藉由適當的核的大小使配向性變良好，故而較佳。連結芳香族烴環基的碳數更佳為6～15。作為連結芳香族烴環基，例如可列舉如下的二價基，即，第一碳數6～20的單環或縮合的芳香族烴環與第二碳數6～20的單環或縮合的芳香族烴環以單鍵鍵結，在第一碳數6～20的單環或縮合的芳香族烴環的構成環的原子上具有第一鍵結鍵，在第二碳數6～20的單環或縮合的芳香族烴環的構成環的原子上具有第二鍵結鍵的二價基。作為連結芳香族烴環基，具體而言可列舉聯苯-4,4'-二基。The linking aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed aromatic hydrocarbon rings are bonded by a single bond and has bonding bonds on atoms constituting the rings. When the carbon number of a single ring or a condensed ring is 6-20, since alignment becomes favorable by the size of an appropriate core, it is preferable. The number of carbon atoms linked to the aromatic hydrocarbon ring group is more preferably 6-15. As the linking aromatic hydrocarbon ring group, for example, a divalent group including a first monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms and a second monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms can be cited. The aromatic hydrocarbon ring is bonded by a single bond, and has a first bond on the atoms constituting the ring of the monocyclic or condensed aromatic hydrocarbon ring with the first carbon number of 6 to 20, and the second carbon number of 6 to 20 A monocyclic or condensed aromatic hydrocarbon ring has a divalent group having a second bond on an atom constituting the ring. As the linking aromatic hydrocarbon ring group, biphenyl-4,4'-diyl group is specifically mentioned.

作為芳香族烴環基，非連結芳香族烴環基會使作用於液晶化合物之間的分子間相互作用最佳藉此使分子配向性變良好，故而較佳。 該些中，作為芳香族烴環基，較佳為苯環的二價基、萘環的二價基，更佳為苯環的二價基（伸苯基）。作為伸苯基，較佳為1,4-伸苯基。藉由-Q 3-為該些基，呈液晶分子的直線性提高而獲得分子配向性提昇的效果的趨勢。 As the aromatic hydrocarbon ring group, a non-connecting aromatic hydrocarbon ring group is preferable because it acts on the intermolecular interaction between liquid crystal compounds to make molecular alignment better. Among these, the aromatic hydrocarbon ring group is preferably a divalent group of a benzene ring or a divalent group of a naphthalene ring, more preferably a divalent group of a benzene ring (phenylene group). The phenylene group is preferably a 1,4-phenylene group. When -Q 3 - is these groups, the linearity of the liquid crystal molecules tends to be improved to obtain the effect of improving the molecular alignment.

非芳香族烴環基包含非連結非芳香族烴環基以及連結非芳香族烴環基。The non-aromatic hydrocarbon ring group includes non-linkage non-aromatic hydrocarbon ring group and linking non-aromatic hydrocarbon ring group.

非連結非芳香族烴環基是單環或縮合的非芳香族烴環的二價基，其碳數為3～20時，藉由適當的核的大小使分子配向性變良好，故而較佳。非連結非芳香族烴環基的碳數更佳為3～15。作為非芳香族烴環，可列舉：環丙烷環、環丁烷環、環戊烷環、環己烷環、環庚烷環、環辛烷環、環己烯環、降莰烷環、莰烷環、金剛烷環、四氫萘環、雙環[2.2.2]辛烷環等。The non-linking non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring. When the carbon number is 3 to 20, the molecular alignment becomes good due to the appropriate size of the nucleus, so it is preferable . The carbon number of the non-linkage non-aromatic hydrocarbon ring group is more preferably 3-15. Examples of the non-aromatic hydrocarbon ring include: cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norbornane ring, camphene ring, Alkane ring, adamantane ring, tetrahydronaphthalene ring, bicyclo[2.2.2]octane ring, etc.

非連結非芳香族烴環基包含不具有不飽和鍵作為非芳香族烴環的構成環的原子間鍵的脂環式烴環基、以及具有不飽和鍵作為非芳香族烴環的構成環的原子間鍵的不飽和非芳香族烴環基。就生產性的觀點而言，非連結非芳香族烴環基較佳為脂環式烴環基。The non-connecting non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group not having an unsaturated bond as a bond between atoms constituting the non-aromatic hydrocarbon ring, and an alicyclic hydrocarbon ring group having an unsaturated bond as a constituting ring of the non-aromatic hydrocarbon ring. An unsaturated non-aromatic hydrocarbon ring group with an interatomic bond. From the viewpoint of productivity, the non-linkage non-aromatic hydrocarbon ring group is preferably an alicyclic hydrocarbon ring group.

連結非芳香族烴環基是多個單環或縮合的非芳香族烴環以單鍵鍵結而在構成環的原子上具有鍵結鍵的二價基；或者選自由單環的芳香族烴環、縮合的芳香族烴環、單環的非芳香族烴環、及縮合的非芳香族烴環所組成的群組中的一種以上的環與單環或縮合的非芳香族烴環以單鍵鍵結而在構成環的原子上具有鍵結鍵的二價基。 基於藉由適當的核的大小使分子配向性變良好的理由，單環或縮合環的碳數較佳為3～20。 The linking non-aromatic hydrocarbon ring group is a divalent group with a plurality of monocyclic or condensed non-aromatic hydrocarbon rings bonded by a single bond and having a bonding bond on the atoms constituting the ring; or selected from a monocyclic aromatic hydrocarbon Ring, condensed aromatic hydrocarbon ring, monocyclic non-aromatic hydrocarbon ring, and condensed non-aromatic hydrocarbon ring in the group consisting of more than one ring and monocyclic or condensed non-aromatic hydrocarbon ring A divalent group that is bonded to have bonds on the atoms that make up the ring. The number of carbon atoms of a single ring or a condensed ring is preferably 3-20 for the reason that the molecular alignment becomes good due to an appropriate core size.

作為連結非芳香族烴環基，例如可列舉如下的二價基，即，第一碳數3～20的單環或縮合的非芳香族烴環與第二碳數3～20的單環或縮合的非芳香族烴環以單鍵鍵結，在第一碳數3～20的單環或縮合的非芳香族烴環的構成環的原子上具有第一鍵結鍵，在第二碳數3～20的單環或縮合的非芳香族烴環的構成環的原子上具有第二鍵結鍵的二價基。進而，例如可列舉如下的二價基，即，碳數3～20的單環或縮合的芳香族烴環與碳數3～20的單環或縮合的非芳香族烴環以單鍵鍵結，在碳數3～20的單環或縮合的芳香族烴環的構成環的原子上具有第一鍵結鍵，在碳數3～20的單環或縮合的非芳香族烴環的構成環的原子上具有第二鍵結鍵的二價基。As the linking non-aromatic hydrocarbon ring group, for example, the following divalent group can be cited, that is, a monocyclic or condensed non-aromatic hydrocarbon ring having a first carbon number of 3 to 20 and a second monocyclic or condensed non-aromatic hydrocarbon ring having a second carbon number of 3 to 20 The condensed non-aromatic hydrocarbon ring is bonded with a single bond, and has a first bond on the atoms constituting the ring of the monocyclic or condensed non-aromatic hydrocarbon ring with the first carbon number of 3 to 20, and the second carbon number A divalent group having a second bond on an atom constituting the ring of a monocyclic or condensed non-aromatic hydrocarbon ring of 3 to 20. Furthermore, for example, a divalent group in which a monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbons and a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbons is bonded with a single bond can be cited. , having a first bond on the atoms constituting the ring of a monocyclic or condensed aromatic hydrocarbon ring with a carbon number of 3 to 20, and having a first bond on the constituent ring of a monocyclic or condensed non-aromatic hydrocarbon ring with a carbon number of 3 to 20 A divalent group with a second bond on its atom.

作為連結非芳香族烴環基，具體而言可列舉：雙(環己烷)-4,4'-二基、1-環己基苯-4,4'-二基。Specific examples of the linking non-aromatic hydrocarbon ring group include bis(cyclohexane)-4,4'-diyl and 1-cyclohexylbenzene-4,4'-diyl.

作為非芳香族烴環基，非連結非芳香族烴環基會使作用於液晶化合物之間的分子間相互作用最佳藉此使分子配向性變良好，故而較佳。As the non-aromatic hydrocarbon ring group, a non-connecting non-aromatic hydrocarbon ring group is preferable because it can best act on intermolecular interaction between liquid crystal compounds and thereby improve molecular alignment.

作為非連結非芳香族烴環基，較佳為環己烷的二價基（環己烷二基），作為環己烷二基，較佳為環己烷-1,4-二基。The non-linkage non-aromatic hydrocarbon ring group is preferably a divalent group of cyclohexane (cyclohexanediyl), and the cyclohexanediyl group is preferably cyclohexane-1,4-diyl.

-Q 3-中的雜環基包含芳香族雜環基以及非芳香族雜環基。 The heterocyclic group in -Q 3 - includes aromatic heterocyclic groups and non-aromatic heterocyclic groups.

芳香族雜環基包含非連結芳香族雜環基以及連結芳香族雜環基。The aromatic heterocyclic group includes a non-linked aromatic heterocyclic group and a linked aromatic heterocyclic group.

非連結芳香族雜環基是單環或縮合的芳香族雜環的二價基，其碳數為4～20時，藉由適當的核的大小使分子配向性變良好，故而較佳。非連結芳香族雜環基的碳數更佳為4～15。The non-connecting aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocyclic ring, and when the number of carbon atoms is 4 to 20, molecular alignment becomes good due to an appropriate nucleus size, so it is preferable. The number of carbon atoms in the non-connecting aromatic heterocyclic group is more preferably 4-15.

作為芳香族雜環，可列舉：呋喃環、苯並呋喃環、噻吩環、苯並噻吩環、吡咯環、吡唑環、咪唑環、噻唑環、噁二唑環、吲哚環、咔唑環、吡咯並咪唑環、吡咯並吡唑環、吡咯並吡咯環、噻吩並吡咯環、噻吩並噻吩環、呋喃並吡咯環、呋喃並呋喃環、噻吩並呋喃環、噻吩並噻唑環、苯並異噁唑環、苯並異噻唑環、苯並咪唑環、吡啶環、吡嗪環、噠嗪環、嘧啶環、三嗪環、喹啉環、異喹啉環、噌啉環、喹噁啉環、啡啶環、喹唑啉環、喹唑啉酮環、薁環等。Examples of the aromatic heterocycle include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, thiazole ring, oxadiazole ring, indole ring, and carbazole ring. , pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, thienothiazole ring, benziso Oxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring , phenanthridine ring, quinazoline ring, quinazolinone ring, azulene ring, etc.

連結芳香族雜環基是多個單環或縮合的芳香族雜環以單鍵鍵結而在構成環的原子上具有鍵結鍵的二價基。單環或縮合環的碳數為4～20時，藉由適當的核的大小使分子配向性變良好，故而較佳。連結芳香族雜環基的碳數更佳為4～15。The linking aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocyclic rings are bonded by a single bond and have a bonding bond on atoms constituting the ring. When the carbon number of a single ring or a condensed ring is 4-20, since molecular alignment becomes favorable by the size of an appropriate core, it is preferable. The number of carbon atoms linked to the aromatic heterocyclic group is more preferably 4-15.

作為連結芳香族雜環基，例如可列舉如下的二價基，即，第一碳數4～20的單環或縮合的芳香族雜環與第二碳數4～20的單環或縮合的芳香族雜環以單鍵鍵結，在第一碳數4～20的單環或縮合的芳香族雜環的構成環的原子上具有第一鍵結鍵，在第二碳數4～20的單環或縮合的芳香族雜環的構成環的原子上具有第二鍵結鍵的二價基。The linking aromatic heterocyclic group includes, for example, a divalent group in which a first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms The aromatic heterocyclic ring is bonded by a single bond, and has a first bond on the atoms constituting the ring of the monocyclic or condensed aromatic heterocyclic ring with the first carbon number of 4 to 20, and the second carbon number of the 4 to 20 A monocyclic or condensed aromatic heterocyclic ring has a divalent group having a second bond on an atom constituting the ring.

非芳香族雜環基包含非連結非芳香族雜環基以及連結非芳香族雜環基。The non-aromatic heterocyclic group includes non-linkage non-aromatic heterocyclic group and linking non-aromatic heterocyclic group.

非連結非芳香族雜環基是單環或縮合的非芳香族雜環的二價基，其碳數為4～20時，藉由適當的核的大小使分子配向性變良好，故而較佳。非連結非芳香族雜環基的碳數更佳為4～15。The non-linking non-aromatic heterocyclic group is a monocyclic or condensed non-aromatic heterocyclic divalent group. When the carbon number is 4 to 20, the molecular alignment becomes good due to the appropriate size of the nucleus, so it is preferable . The carbon number of the non-linkage non-aromatic heterocyclic group is more preferably 4-15.

作為碳數4～20的單環或縮合的非芳香族雜環的二價基的非芳香族雜環可列舉：四氫呋喃環、四氫吡喃環、二噁烷環、四氫噻吩環、四氫噻喃環、吡咯啶環、哌啶環、二氫吡啶環、哌嗪環、四氫噻唑環、四氫噁唑環、八氫喹啉環、四氫喹啉環、八氫喹唑啉環、四氫喹唑啉環、四氫咪唑環、四氫苯並咪唑環、奎寧環等。Examples of non-aromatic heterocycles that are divalent groups of monocyclic or condensed non-aromatic heterocycles having 4 to 20 carbon atoms include tetrahydrofuran rings, tetrahydropyran rings, dioxane rings, tetrahydrothiophene rings, and tetrahydrofuran rings. Hydrothiopyran ring, pyrrolidine ring, piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydrooxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzimidazole ring, quinuclidine, etc.

連結非芳香族雜環基是多個單環或縮合的非芳香族雜環以單鍵鍵結而在構成環的原子上具有鍵結鍵的二價基。單環或縮合環的碳數為4～20時，藉由適當的核的大小使分子配向性變良好，故而較佳。連結非芳香族雜環基的碳數更佳為4～15。The linking non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocyclic rings are bonded by a single bond and have a bonding bond on atoms constituting the ring. When the carbon number of a single ring or a condensed ring is 4-20, since molecular alignment becomes favorable by the size of an appropriate core, it is preferable. The number of carbon atoms connecting the non-aromatic heterocyclic group is more preferably 4-15.

作為連結芳香族雜環基，例如可列舉如下的二價基，即，第一碳數4～20的單環或縮合的非芳香族雜環與第二碳數4～20的單環或縮合的非芳香族雜環以單鍵鍵結，在第一碳數4～20的單環或縮合的非芳香族雜環的構成環的原子上具有第一鍵結鍵，在第二碳數4～20的單環或縮合的非芳香族雜環的構成環的原子上具有第二鍵結鍵的二價基。As the linking aromatic heterocyclic group, for example, a divalent group including a monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms in the first and a monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms in the second The non-aromatic heterocyclic ring is bonded with a single bond, and has a first bond on the atoms constituting the ring of the monocyclic or condensed non-aromatic heterocyclic ring with the first carbon number of 4 to 20, and the second carbon number is 4 A divalent group having a second bond on an atom constituting the ring of a monocyclic or condensed non-aromatic heterocyclic ring of ~20.

-Q 3-中的芳香族烴環基、非芳香族烴環基、芳香族雜環基、非芳香族雜環基分別可由選自由-R n、-OH、-O-R n、-O-C(=O)-R n、-NH 2、-NH-R n、-N(R n')-R n、-C(=O)-R n、-C(=O)-O-R n、-C(=O)-NH 2、-C(=O)-NH-R n、-C(=O)-N(R n')-R n、-SH、-S-R n、三氟甲基、胺磺醯基、羧基、磺基、氰基、硝基及鹵素所組成的群組中的一種以上的基取代。-R n及-R n'分別獨立地表示碳數1～6的直鏈狀或分支狀的烷基。 The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -Q 3 - can be selected from the group consisting of -R n , -OH, -OR n , -OC(= O)-R n , -NH 2 , -NH-R n , -N(R n' )-R n , -C(=O)-R n , -C(=O)-OR n , -C( =O)-NH 2 , -C(=O)-NH-R n , -C(=O)-N(R n' )-R n , -SH, -SR n , trifluoromethyl, sulfamic acid Substituted by one or more of the group consisting of acyl, carboxyl, sulfo, cyano, nitro and halogen. -R n and -R n' each independently represent a linear or branched alkyl group having 1 to 6 carbons.

就分子結構的直線性高、聚合性液晶化合物（2）彼此容易締合而容易表現出液晶狀態的方面而言，-Q 3-中的芳香族烴環基、非芳香族烴環基、芳香族雜環基、非芳香族雜環基分別獨立地較佳為未經取代，或由甲基、甲氧基、氟原子、氯原子、溴原子取代，更佳為未經取代。 The linearity of the molecular structure is high, and the polymerizable liquid crystal compounds ( 2 ) are easily associated with each other to easily express a liquid crystal state. The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic The aromatic heterocyclic group and the non-aromatic heterocyclic group are independently preferably unsubstituted, or substituted by methyl, methoxy, fluorine atom, chlorine atom, bromine atom, more preferably unsubstituted.

-Q 3-中的芳香族烴環基、非芳香族烴環基、芳香族雜環基、非芳香族雜環基所具有的取代基可相同亦可不同，另外，芳香族烴環基、非芳香族烴環基、芳香族雜環基、非芳香族雜環基可全部經取代，亦可全部未經取代，還可一部分經取代且一部分未經取代。 The substituents of the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -Q 3 - may be the same or different. In addition, the aromatic hydrocarbon ring group, All of the non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be substituted or may be unsubstituted, or some may be substituted and some may be unsubstituted.

-A 11-、-A 12-及-A 13-中的二價有機基所具有的取代基可相同亦可不同，-A 11-、-A 12-及-A 13-中的二價有機基可全部經取代，亦可全部未經取代，還可一部分經取代且一部分未經取代。 The substituents of the divalent organic groups in -A 11 -, -A 12 - and -A 13 - may be the same or different, and the divalent organic groups in -A 11 -, -A 12 - and -A 13 - The groups may be all substituted, all may be unsubstituted, or some may be substituted and some may be unsubstituted.

作為-Q 3-，較佳為烴環基，更佳為伸苯基、環己烷二基。就可提高聚合性液晶化合物（2）的分子結構的直線性而言，-Q 3-進而佳為1,4-伸苯基、環己烷-1,4-二基。 -Q 3 - is preferably a hydrocarbon ring group, more preferably a phenylene group or a cyclohexanediyl group. -Q 3 - is more preferably a 1,4-phenylene group or a cyclohexane-1,4-diyl group since the linearity of the molecular structure of the polymerizable liquid crystal compound (2) can be improved.

作為-A 11-、-A 12-及-A 13-的二價有機基，較佳為-Q 3-為烴環基，即，較佳為二價有機基為烴環基。作為二價有機基，更佳為伸苯基、環己烷二基，就可提高聚合性液晶化合物（2）的分子結構的直線性而言，進而佳為1,4-伸苯基、環己烷-1,4-二基。 As the divalent organic groups of -A 11 -, -A 12 - and -A 13 -, -Q 3 - is preferably a hydrocarbon ring group, that is, the divalent organic group is preferably a hydrocarbon ring group. The divalent organic group is more preferably a phenylene group and a cyclohexanediyl group, and in terms of improving the linearity of the molecular structure of the polymerizable liquid crystal compound (2), further preferably a 1,4-phenylene group, a cyclohexanediyl group, Hexane-1,4-diyl.

作為聚合性液晶化合物（2），較佳為-A 11-、-A 12-及-A 13-中的一者為式（3）所表示的部分結構且另外兩者分別獨立地為二價有機基，且較佳為-A 11-、-A 12-及-A 13-中的式（3）所表示的部分結構的-C y-為烴環基，尤佳為二價有機基為烴環基。進而，較佳為該烴環基為1,4-伸苯基或者環己烷-1,4-二基。另外，較佳為-A 11-及-A 13-中的一者為環己烷-1,4-二基。 另外，更佳為-A 11-及-A 13-中的一者為式（3）所表示的部分結構，另外一者及-A 12-為二價有機基。在所述情況下，較佳為-A 11-及-A 13-中的為二價有機基的一者為環己烷-1,4-二基，尤佳為-A 12-為1,4-伸苯基。 As the polymerizable liquid crystal compound (2), preferably one of -A 11 -, -A 12 - and -A 13 - has a partial structure represented by formula (3) and the other two are independently divalent An organic group, and preferably -C y - of the partial structure represented by the formula (3) in -A 11 -, -A 12 - and -A 13 - is a hydrocarbon ring group, especially a divalent organic group is hydrocarbon ring. Furthermore, it is preferable that the hydrocarbon ring group is 1,4-phenylene or cyclohexane-1,4-diyl. In addition, one of -A 11 - and -A 13 - is preferably cyclohexane-1,4-diyl. In addition, it is more preferable that one of -A 11 - and -A 13 - is a partial structure represented by formula (3), and the other one and -A 12 - are divalent organic groups. In such a case, one of the divalent organic groups among -A 11 - and -A 13 - is preferably cyclohexane-1,4-diyl, especially -A 12 - is 1, 4-phenylene.

（-Y 1-及-Y 2-） -Y 1-及-Y 2-分別獨立地表示單鍵、-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH 2CH 2-、-CH=CH-、-C≡C-、-C(=O)NH-、-NHC(=O)-、-CH 2O-、-OCH 2-、-CH 2S-或者-SCH 2-。就聚合性液晶化合物（2）的直線性或繞分子短軸的旋轉運動呈容易進行的趨勢而言，作為-Y 1-及-Y 2-，分別獨立地較佳為π鍵結性小的單鍵、-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH 2CH 2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、-CH 2O-、-OCH 2-、-CH 2S-或者-SCH 2-，更佳為單鍵、-C(=O)O-、-OC(=O)-、-CH 2CH 2-、-CH 2O-、-OCH 2-。 (-Y 1 - and -Y 2 -) -Y 1 - and -Y 2 - each independently represent a single bond, -C(=O)O-, -OC(=O)-, -C(=S) O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH 2 CH 2 -, -CH=CH-, -C≡C-, -C( =O)NH-, -NHC(=O)-, -CH2O- , -OCH2- , -CH2S- or -SCH2- . Since the linearity of the polymerizable liquid crystal compound (2) or the rotational movement around the minor axis of the molecule tends to be easily performed, -Y 1 - and -Y 2 - are each independently preferably one having a small π-bonding property. Single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(= O)-, -CH 2 CH 2 -, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH 2 O-, -OCH 2 -, -CH 2 S- Or -SCH 2 -, more preferably a single bond, -C(=O)O-, -OC(=O)-, -CH 2 CH 2 -, -CH 2 O-, -OCH 2 -.

在如所述式（2A）、式（2C）、式（2D）、式（2F）般，-X 1-與-Y 1-或者-X 1-與-Y 2-鍵結的情況下，與-X 1-鍵結的-Y 1-或者與-X 1-鍵結的-Y 2-較佳為單鍵。-X 1-與-Y 1-及-Y 2-中的另一者較佳為-C(=O)O-或者-OC(=O)-。 In the case where -X 1 - and -Y 1 - or -X 1 - and -Y 2 - are bonded as in the formula (2A), formula (2C), formula (2D), and formula ( 2F ), -Y 1 - bonded to -X 1 - or -Y 2 - bonded to -X 1 - is preferably a single bond. The other of -X 1 - and -Y 1 - and -Y 2 - is preferably -C(=O)O- or -OC(=O)-.

在如所述式（2B）、式（2E）般，-X 1-與-Y 1-及-Y 2-中的任一者均未鍵結的情況下，-X 1-較佳為-CH 2CH 2-、-CH 2O-、或者-OCH 2-，-Y 1-及-Y 2-均較佳為-C(=O)O-或者-OC(=O)-。 When none of -X 1 - and -Y 1 - and -Y 2 - is bonded like the formula (2B) and formula (2E), -X 1 - is preferably - CH 2 CH 2 -, -CH 2 O-, or -OCH 2 -, -Y 1 - and -Y 2 - are all preferably -C(=O)O- or -OC(=O)-.

（k） k為1或者2。在某一形態中，k較佳為1。在另一形態中，k較佳為2。 在k為2的情況下，各-Y 2-彼此可相同亦可不同，各-A 13-彼此可相同亦可不同。 (k) k is 1 or 2. In a certain form, k is preferably 1. In another form, k is preferably 2. When k is 2, each -Y 2 - may be the same or different from each other, and each -A 13 - may be the same or different from each other.

（適宜結構） 作為聚合性液晶化合物（2），為所述式（2A）、式（2B）、式（2E）或者式（2F）所表示的化合物時會使作用於液晶化合物之間的分子間相互作用最佳，且成為適當的核的大小而使分子配向性變良好，故而較佳。 (suitable structure) As the polymerizable liquid crystal compound (2), when it is a compound represented by the formula (2A), formula (2B), formula (2E) or formula (2F), the intermolecular interaction acting on the liquid crystal compound will be maximized. It is preferable because the size of the nucleus is appropriate and the molecular alignment becomes good.

另外，就呈獲得良好的分子配向性的趨勢的觀點而言，本發明中使用的聚合性液晶化合物較佳為低分子聚合性液晶化合物，尤佳為不具有共聚結構的低分子聚合性液晶化合物。 作為低分子聚合性液晶化合物的分子量，較佳為2000以下，更佳為1500以下，進而佳為1000以下。下限並無特別限定，較佳為400以上，更佳為500以上。作為分子量範圍，較佳為400～2000，更佳為400～1500，尤佳為500～1000。 聚合性液晶化合物的分子量是聚合性液晶化合物中所含的原子量的總和。 In addition, the polymerizable liquid crystal compound used in the present invention is preferably a low-molecular-weight polymerizable liquid crystal compound, and particularly preferably a low-molecular-weight polymerizable liquid crystal compound that does not have a copolymer structure, from the viewpoint of a tendency to obtain good molecular alignment. . The molecular weight of the low-molecular polymerizable liquid crystal compound is preferably at most 2,000, more preferably at most 1,500, still more preferably at most 1,000. The lower limit is not particularly limited, but is preferably 400 or more, more preferably 500 or more. The molecular weight range is preferably from 400 to 2000, more preferably from 400 to 1500, and especially preferably from 500 to 1000. The molecular weight of the polymerizable liquid crystal compound is the sum of the atomic weights contained in the polymerizable liquid crystal compound.

（聚合性液晶化合物的具體例） 作為本發明的各向異性色素膜形成用組成物中所含的聚合性液晶化合物，具體而言可列舉以下所記載的聚合性液晶化合物，但並不限定於該些。以下的例示式中，C 6H 13是指正己基。 (Specific examples of polymerizable liquid crystal compounds) Examples of the polymerizable liquid crystal compounds contained in the anisotropic dye film-forming composition of the present invention specifically include the polymerizable liquid crystal compounds described below, but are not limited to Should some. In the following exemplary formulas, C 6 H 13 means n-hexyl.

[化12]

Figure 02_image022
[chemical 12]
Figure 02_image022

[化13]

Figure 02_image024
[chemical 13]
Figure 02_image024

[化14]

Figure 02_image026
[chemical 14]
Figure 02_image026

[化15]

Figure 02_image028
[chemical 15]
Figure 02_image028

[化16]

Figure 02_image030
[chemical 16]
Figure 02_image030

[化17]

Figure 02_image032
[chemical 17]
Figure 02_image032

[化18]

Figure 02_image034
[chemical 18]
Figure 02_image034

[化19]

Figure 02_image036
[chemical 19]
Figure 02_image036

[化20]

Figure 02_image038
[chemical 20]
Figure 02_image038

[化21]

Figure 02_image040
[chem 21]
Figure 02_image040

[化22]

Figure 02_image042
[chem 22]
Figure 02_image042

[化23]

Figure 02_image044
[chem 23]
Figure 02_image044

[化24]

Figure 02_image046
[chem 24]
Figure 02_image046

（液晶化合物的含量） 本發明的各向異性色素膜形成用組成物所含有的液晶化合物較佳為包含聚合性液晶化合物（2）。本發明的各向異性色素膜形成用組成物中，可單獨包含僅一種聚合性液晶化合物，亦可以任意組合及比率包含兩種以上聚合性液晶化合物。 (content of liquid crystal compound) The liquid crystal compound contained in the anisotropic dye film forming composition of the present invention preferably includes a polymerizable liquid crystal compound (2). The anisotropic dye film-forming composition of the present invention may contain only one polymerizable liquid crystal compound alone, or may contain two or more polymerizable liquid crystal compounds in any combination and ratio.

本發明的各向異性色素膜用組成物中的液晶化合物的含量（在併用兩種以上液晶化合物的情況下，為各者的含量的總和）相對於各向異性色素膜用組成物的固體成分（100質量份）較佳為35質量份以上，更佳為50質量份以上，進而佳為55質量份以上，且較佳為99質量份以下，更佳為98質量份以下。只要各向異性色素膜用組成物的液晶化合物的含量為所述下限以上且為上限以下，則液晶分子的配向性呈提高的趨勢。The content of the liquid crystal compound in the composition for anisotropic dye film of the present invention (when two or more liquid crystal compounds are used in combination, the sum of the respective contents) relative to the solid content of the composition for anisotropic dye film (100 parts by mass) is preferably at least 35 parts by mass, more preferably at least 50 parts by mass, still more preferably at least 55 parts by mass, and is preferably at most 99 parts by mass, more preferably at most 98 parts by mass. When content of the liquid crystal compound of the composition for anisotropic dye films is more than the said minimum and below the upper limit, the orientation of a liquid crystal molecule will tend to improve.

本發明的各向異性色素膜用組成物亦可包含一種或者兩種以上除聚合性液晶化合物（2）以外的其他聚合性液晶化合物或者非聚合性液晶化合物，就更進一步有效地獲得使用聚合性液晶化合物（2）所產生的本發明的效果的觀點而言，在本發明的各向異性色素膜用組成物中所含的液晶化合物的總量100質量%中，聚合性液晶化合物（2）的比例較佳為5質量%以上，更佳為10質量%以上，尤佳為15質量%～100質量%。The composition for the anisotropic pigment film of the present invention may also contain one or two or more other polymerizable liquid crystal compounds or non-polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (2), so that the use of polymerizable liquid crystal compounds can be obtained more effectively. From the viewpoint of the effects of the present invention produced by the liquid crystal compound (2), the polymerizable liquid crystal compound (2) is The proportion of is preferably at least 5% by mass, more preferably at least 10% by mass, particularly preferably at least 15% by mass to 100% by mass.

另外，本發明的各向異性色素膜用組成物較佳為以如下方式含有聚合性液晶化合物，即，所述聚合性液晶化合物在各向異性色素膜用組成物中的質量濃度相對於所述式（1）所表示的本發明的化合物的濃度而成為後述的質量濃度。In addition, the composition for anisotropic dye film of the present invention preferably contains a polymerizable liquid crystal compound in such a manner that the mass concentration of the polymerizable liquid crystal compound in the composition for anisotropic dye film is relative to the The concentration of the compound of the present invention represented by the formula (1) becomes the mass concentration described later.

（各向同性相出現溫度） 就製程的觀點而言，本發明的各向異性色素膜形成用組成物所含有的聚合性液晶化合物的各向同性相出現溫度較佳為160℃以下，更佳為140℃以下，進而佳為115℃以下，進而更佳為110℃以下，尤佳為105℃以下。 此處，各向同性相出現溫度是指自液晶向液體的相轉變溫度及自液體向液晶的相轉變溫度。在本發明中，較佳為該些相轉變溫度的至少一者為所述上限以下，更佳為該些相轉變溫度兩者均為所述上限以下。 (Temperature at which the isotropic phase appears) From the viewpoint of the production process, the temperature at which the isotropic phase of the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention is preferably 160°C or lower, more preferably 140°C or lower, and still more preferably 140°C or lower. 115°C or lower, more preferably 110°C or lower, especially preferably 105°C or lower. Here, the isotropic phase appearance temperature refers to the phase transition temperature from liquid crystal to liquid and the phase transition temperature from liquid to liquid crystal. In the present invention, it is preferable that at least one of the phase transition temperatures is below the upper limit, more preferably both of the phase transition temperatures are below the upper limit.

（聚合性液晶化合物的製造方法） 本發明的各向異性色素膜形成用組成物所含有的聚合性液晶化合物可藉由將烷基化反應、酯化反應、醯胺化反應、醚化反應、本位取代反應、使用金屬觸媒的偶合反應等公知的化學反應加以組合而製造。 例如，本發明的各向異性色素膜形成用組成物所含有的聚合性液晶化合物可依照後述的實施例所記載的方法、或「液晶便覽」（丸善股份有限公司，2000年10月30日發行）第449～468頁所記載的方法而合成。 (Method for producing polymerizable liquid crystal compound) The polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention can be obtained by alkylation reaction, esterification reaction, amidation reaction, etherification reaction, native substitution reaction, metal catalyst Manufactured by combining known chemical reactions such as coupling reactions. For example, the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention can be obtained according to the method described in the examples described later, or "Liquid Crystal Handbook" (Maruzen Co., Ltd., issued on October 30, 2000) ) and synthesized by the method described on pages 449-468.

（聚合性液晶化合物與本發明的化合物的關係） 基於容易提昇使用各向異性色素膜形成用組成物形成的各向異性色素膜的配向性的觀點，在各向異性色素膜形成用組成物中，聚合性液晶化合物的分子長度與色素的分子長度之差較小時，液晶分子與色素分子的分子間相互作用強，色素分子不易阻礙液晶分子彼此的締合，故而較佳。 (Relationship between the polymerizable liquid crystal compound and the compound of the present invention) From the viewpoint of improving the alignment of the anisotropic dye film formed using the composition for forming anisotropic dye film, in the composition for forming anisotropic dye film, the molecular length of the polymerizable liquid crystal compound and the molecular length of the dye When the difference is small, the intermolecular interaction between the liquid crystal molecules and the pigment molecules is strong, and the pigment molecules are less likely to hinder the association of the liquid crystal molecules, which is preferable.

因此，在本發明的各向異性色素膜形成用組成物中，各向異性色素膜形成用組成物中所含的聚合性液晶化合物所具有的環結構的數量（r n1）與各向異性色素膜形成用組成物中所含的式（1）所表示的本發明的化合物所具有的環結構的數量（r n2）之比（r n1/r n2）較佳為0.7～1.5。 再者，兩個以上的環縮合的縮合環以環結構計，計為1個。 Therefore, in the anisotropic dye film-forming composition of the present invention, the number (r n1 ) of ring structures contained in the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition is related to the anisotropic dye The ratio (r n1 /r n2 ) of the number of ring structures (r n2 ) that the compound of the present invention represented by the formula (1) contained in the film-forming composition has is preferably 0.7 to 1.5. In addition, the condensed ring in which two or more rings are condensed is counted as one in terms of the ring structure.

此處，式（1）所表示的本發明的化合物所具有的環結構的數量（r n2）是式中的A 1、A 2及A 3的總和，具體而言，在n為1的情況下，r n2為3；在n為2的情況下，r n2為4；在n為3的情況下，r n2為5。 再者，即便-Y為如吡咯啶基或哌啶基般的環狀的官能基，-Y中所含的環結構亦不包含於式（1）所表示的本發明的化合物所具有的環結構的數量（r n2）中。 Here, the number (r n2 ) of ring structures possessed by the compound of the present invention represented by formula (1) is the sum of A 1 , A 2 and A 3 in the formula, specifically, when n is 1 Under the condition, r n2 is 3; when n is 2, r n2 is 4; when n is 3, r n2 is 5. Furthermore, even if -Y is a cyclic functional group such as pyrrolidinyl or piperidinyl, the ring structure contained in -Y is not included in the ring structure of the compound of the present invention represented by formula (1). The number of structures (r n2 ).

更具體而言如下所述。 在n為1的情況下，r n2為3，故而r n1為3或者4。 在n為2的情況下，r n2為4，故而r n1為3、4、5或者6。 在n為3的情況下，r n2為5，故而r n1為4、5、6或者7。 若為如上所述的值，則各向異性色素膜形成用組成物中所含的聚合性液晶化合物所具有的環結構的數量（r n1）與各向異性色素膜形成用組成物中所含的式（1）所表示的色素所具有的環結構的數量（r n2）之比（r n1/r n2）成為0.7～1.5，故而較佳。 More specifically, it is as follows. When n is 1, r n2 is 3, so r n1 is 3 or 4. When n is 2, r n2 is 4, so r n1 is 3, 4, 5 or 6. When n is 3, r n2 is 5, so r n1 is 4, 5, 6 or 7. If it is the above-mentioned value, the number (r n1 ) of the ring structure contained in the polymerizable liquid crystal compound contained in the composition for forming anisotropic dye film is the same as that contained in the composition for forming anisotropic dye film. The ratio (r n1 /r n2 ) of the number of ring structures (r n2 ) of the dye represented by the formula ( 1 ) is preferably 0.7 to 1.5.

各向異性色素膜形成用組成物中所含的聚合性液晶化合物所具有的環結構的數量（rn1）不包含聚合性液晶化合物中的聚合性基所包含的環結構（例如氧雜環丙烷環或氧雜環丁烷環等）。The number of ring structures (rn1) contained in the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film does not include the ring structure contained in the polymerizable group in the polymerizable liquid crystal compound (such as oxirane ring or oxetane ring, etc.).

本發明的各向異性色素膜用組成物較佳為以聚合性液晶化合物的質量濃度成為式（1）所表示的本發明的化合物的質量濃度的1倍以上的方式含有聚合性液晶化合物。若聚合性液晶化合物的質量濃度為式（1）所表示的本發明的化合物的質量濃度的1倍以上，則呈獲得高的二色性比的趨勢，可提高各向異性色素膜的機械強度，就上述觀點而言較佳。本發明的各向異性色素膜用組成物的聚合性液晶化合物的質量濃度更佳為式（1）所表示的本發明的化合物的質量濃度的1.5倍以上，進而佳為2倍以上，尤佳為3倍以上。另一方面，聚合性液晶化合物相對於式（1）所表示的本發明的化合物過多時，呈作為各向異性色素膜的吸光度變小的趨勢。因此，本發明的各向異性色素膜用組成物中的聚合性液晶化合物的質量濃度較佳為式（1）所表示的本發明的化合物的質量濃度的1000倍以下，更佳為700倍以下，進而佳為500倍以下。The composition for anisotropic dye films of the present invention preferably contains a polymerizable liquid crystal compound such that the mass concentration of the polymerizable liquid crystal compound is at least one time the mass concentration of the compound of the present invention represented by formula (1). When the mass concentration of the polymerizable liquid crystal compound is at least one time the mass concentration of the compound of the present invention represented by the formula (1), a high dichroic ratio tends to be obtained, and the mechanical strength of the anisotropic dye film can be improved. , which is preferable from the above point of view. The mass concentration of the polymerizable liquid crystal compound in the composition for anisotropic pigment film of the present invention is more preferably 1.5 times or more than the mass concentration of the compound of the present invention represented by formula (1), more preferably 2 times or more, especially preferably more than 3 times. On the other hand, when there are too many polymerizable liquid crystal compounds with respect to the compound of this invention represented by formula (1), it exists in the tendency for the absorbance as an anisotropic dye film to become small. Therefore, the mass concentration of the polymerizable liquid crystal compound in the composition for anisotropic pigment film of the present invention is preferably 1000 times or less, more preferably 700 times or less, the mass concentration of the compound of the present invention represented by formula (1). , and more preferably 500 times or less.

＜聚合起始劑＞ 本發明的各向異性色素膜形成用組成物亦可視需要包含聚合起始劑。 ＜Polymerization initiator＞ The composition for anisotropic dye film formation of this invention may contain a polymerization initiator as needed.

聚合起始劑是可使聚合性液晶化合物的聚合反應開始的化合物。作為聚合起始劑，較佳為藉由光的作用產生活性自由基的光聚合起始劑。The polymerization initiator is a compound capable of starting the polymerization reaction of the polymerizable liquid crystal compound. The polymerization initiator is preferably a photopolymerization initiator that generates active radicals by the action of light.

作為可使用的聚合起始劑，例如可列舉：二茂鈦衍生物類；聯咪唑衍生物類；鹵甲基化噁二唑衍生物類；鹵甲基-均三嗪衍生物類；苯烷基酮衍生物類；肟酯系衍生物類；安息香類；二苯甲酮衍生物類；醯基氧化膦衍生物類；錪鹽類；鋶鹽類；蒽醌衍生物類；苯乙酮衍生物類；噻噸酮衍生物類；苯甲酸酯衍生物類；吖啶衍生物類；吩嗪衍生物類；蒽酮衍生物類等。 該些光聚合起始劑中，更佳為苯烷基酮衍生物類、肟酯系衍生物類、聯咪唑衍生物類、苯乙酮衍生物類、及噻噸酮衍生物類。 Examples of usable polymerization initiators include: titanocene derivatives; biimidazole derivatives; halomethylated oxadiazole derivatives; halomethyl-s-triazine derivatives; Ketone derivatives; oxime ester derivatives; benzoin; benzophenone derivatives; acyl phosphine oxide derivatives; Species; thioxanthone derivatives; benzoate derivatives; acridine derivatives; phenazine derivatives; anthrone derivatives, etc. Among these photopolymerization initiators, phenalkone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.

具體而言，作為二茂鈦衍生物類，例如可列舉：二環戊二烯基二氯化鈦、二環戊二烯基二苯基鈦、二環戊二烯基雙(2,3,4,5,6-五氟苯-1-基)鈦、二環戊二烯基雙(2,3,5,6-四氟苯-1-基)鈦、二環戊二烯基雙(2,4,6-三氟苯-1-基)鈦、二環戊二烯基二(2,6-二氟苯-1-基)鈦、二環戊二烯基二(2,4-二氟苯-1-基)鈦、二(甲基環戊二烯基)雙(2,3,4,5,6-五氟苯-1-基)鈦、二(甲基環戊二烯基)雙(2,6-二氟苯-1-基)鈦、二環戊二烯基〔2,6-二-氟-3-(吡咯-1-基)-苯-1-基〕鈦等。Specifically, examples of titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyl titanium, dicyclopentadienyl bis(2,3, 4,5,6-pentafluorophen-1-yl)titanium, dicyclopentadienylbis(2,3,5,6-tetrafluorophen-1-yl)titanium, dicyclopentadienylbis( 2,4,6-trifluorophen-1-yl)titanium, dicyclopentadienylbis(2,6-difluorophen-1-yl)titanium, dicyclopentadienylbis(2,4- Difluorophen-1-yl)titanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophen-1-yl)titanium, bis(methylcyclopentadiene base) bis(2,6-difluorophen-1-yl)titanium, dicyclopentadienyl[2,6-di-fluoro-3-(pyrrol-1-yl)-benzene-1-yl]titanium wait.

作為聯咪唑衍生物類，例如可列舉：2-(2'-氯苯基)-4,5-二苯基咪唑二聚物、2-(2'-氯苯基)-4,5-雙(3'-甲氧基苯基)咪唑二聚物、2-(2'-氟苯基)-4,5-二苯基咪唑二聚物、2-(2'-甲氧基苯基)-4,5-二苯基咪唑二聚物、(4'-甲氧基苯基)-4,5-二苯基咪唑二聚物等。Examples of biimidazole derivatives include: 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis (3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl)-4,5-diphenylimidazole dimer, etc.

作為鹵甲基化噁二唑衍生物類，例如可列舉：2-三氯甲基-5-(2'-苯並呋喃基)-1,3,4-噁二唑、2-三氯甲基-5-〔β-(2'-苯並呋喃基)乙烯基〕-1,3,4-噁二唑、2-三氯甲基-5-〔β-(2'-(6''-苯並呋喃基)乙烯基)〕-1,3,4-噁二唑、2-三氯甲基-5-呋喃基-1,3,4-噁二唑等。Examples of halomethylated oxadiazole derivatives include: 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethane Base-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6'' -benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole, etc.

作為鹵甲基-均三嗪衍生物類，例如可列舉：2-(4-甲氧基苯基)-4,6-雙(三氯甲基)-均三嗪、2-(4-甲氧基萘基)-4,6-雙(三氯甲基)-均三嗪、2-(4-乙氧基萘基)-4,6-雙(三氯甲基)-均三嗪、2-(4-乙氧基羰基萘基)-4,6-雙(三氯甲基)-均三嗪等。Examples of halomethyl-s-triazine derivatives include: 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl) Oxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine, etc.

作為苯烷基酮衍生物類，例如可列舉：二乙氧基苯乙酮、2-甲基-1-〔4-(甲硫基)苯基〕-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮-1、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)丁烷-1-酮、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、4-二乙基胺基苯乙酮、4-二甲基胺基苯丙酮、1,4-二甲基胺基苯甲酸2-乙基己酯、2,5-雙(4-二乙基胺基亞苄基)環己酮、7-二乙基胺基-3-(4-二乙基胺基苯甲醯基)香豆素、4-(二乙基胺基)查耳酮等。Examples of phenylalkyl ketone derivatives include diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholino Linylphenyl)butan-1-one, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4- Dimethylaminopropiophenone, 2-ethylhexyl 1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-bis Ethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone, etc.

作為肟酯系衍生物類，例如可列舉：2-(苯甲醯氧基亞胺基)-1-[4-(苯硫基)苯基]-1-辛酮、O-乙醯基-1-[6-(2-甲基苯甲醯基)-9-乙基-9H-咔唑-3-基]乙酮肟、日本專利特開2000-80068號公報、日本專利特開2006-36750號公報、國際公開第2009/131189號等所記載的肟酯衍生物等。Examples of oxime ester derivatives include: 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, O-acetyl- 1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open 2006- Oxime ester derivatives described in Publication No. 36750, International Publication No. 2009/131189, etc.

作為安息香類，例如可列舉：安息香、安息香甲醚、安息香苯醚、安息香異丁醚、安息香異丙醚等。Examples of benzoins include benzoin, benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether.

作為二苯甲酮衍生物類，例如可列舉：二苯甲酮、米氏酮、2-甲基二苯甲酮、3-甲基二苯甲酮、4-甲基二苯甲酮、2-氯二苯甲酮、4-溴二苯甲酮、2-羧基二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4'-甲基二苯硫醚、3,3',4,4'-四(第三丁基過氧基羰基)二苯甲酮、及2,4,6-三甲基二苯甲酮等。Examples of benzophenone derivatives include: benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2 -Chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 '-Methyl diphenyl sulfide, 3,3',4,4'-tetra(tertiary butylperoxycarbonyl) benzophenone, and 2,4,6-trimethylbenzophenone, etc. .

作為醯基氧化膦衍生物類，例如可列舉：2,4,6-三甲基苯甲醯基二苯基氧化膦、雙-(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦及雙(2,4,6-三甲基苯甲醯基)苯基氧化膦等。Examples of acylphosphine oxide derivatives include: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2 , 4,4-trimethylpentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, etc.

作為錪鹽類，例如可列舉：二苯基錪-四(五氟苯基)硼酸鹽、二苯基錪-六氟磷酸鹽、二苯基錪-六氟銻酸鹽、二(4-壬基苯基)錪-六氟磷酸鹽等。Examples of iodonium salts include: diphenyliodonium-tetrakis(pentafluorophenyl) borate, diphenyliodonium-hexafluorophosphate, diphenyliodonium-hexafluoroantimonate, bis(4-nonan Base phenyl) iodine-hexafluorophosphate, etc.

作為鋶鹽類，例如可列舉：三苯基鋶-六氟磷酸鹽、三苯基鋶-六氟銻酸鹽、三苯基鋶-四(五氟苯基)硼酸鹽、二苯基〔4-(苯硫基)苯基〕鋶-六氟磷酸鹽、4,4'-雙〔二苯基鋶基〕二苯硫醚-雙六氟磷酸鹽、4,4'-雙〔二(β-羥基乙氧基)苯基鋶基〕二苯硫醚-雙六氟銻酸鹽、4,4'-雙〔二(β-羥基乙氧基)苯基鋶基〕二苯硫醚-雙六氟磷酸鹽、7-〔二(對甲苯甲醯基)鋶基〕-2-異丙基噻噸酮-六氟銻酸鹽、7-〔二(對甲苯甲醯基)鋶基〕-2-異丙基噻噸酮-四(五氟苯基)硼酸鹽、4-苯基羰基-4'-二苯基鋶基-二苯硫醚-六氟磷酸鹽、4-(對第三丁基苯基羰基)-4'-二苯基鋶基-二苯硫醚-六氟銻酸鹽、4-(對第三丁基苯基羰基)-4'-二(對甲苯甲醯基)鋶基-二苯硫醚-四(五氟苯基)硼酸鹽等。Examples of cobaltium salts include: triphenylcolumbite-hexafluorophosphate, triphenylcolumbite-hexafluoroantimonate, triphenylcolumbite-tetrakis(pentafluorophenyl)borate, diphenyl[4 -(Phenylsulfanyl)phenyl]percolium-hexafluorophosphate, 4,4'-bis[diphenylpervilyl]diphenylsulfide-bishexafluorophosphate, 4,4'-bis[bis(β -Hydroxyethoxy)phenylperidyl]diphenylsulfide-bishexafluoroantimonate, 4,4'-bis[bis(β-hydroxyethoxy)phenylperidyl]diphenylsulfide-bis Hexafluorophosphate, 7-[bis(p-tolylyl)persidyl]-2-isopropylthioxanthone-hexafluoroantimonate, 7-[bis(p-tolylyl)persidyl]- 2-isopropylthioxanthone-tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylpermyl-diphenylsulfide-hexafluorophosphate, 4-(to the third Butylphenylcarbonyl)-4'-diphenylperidyl-diphenylsulfide-hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-bis(p-toluyl ) percolium-diphenyl sulfide-tetrakis(pentafluorophenyl) borate, etc.

作為蒽醌衍生物類，可列舉：2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、1-氯蒽醌等。Examples of the anthraquinone derivatives include 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, and the like.

作為苯乙酮衍生物類，例如可列舉：2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、1-羥基環己基苯基酮、α-羥基-2-甲基苯基丙酮、1-羥基-1-甲基乙基-(對異丙基苯基)酮、1-羥基-1-(對十二烷基苯基)酮、2-甲基-(4'-甲硫基苯基)-2-嗎啉基-1-丙酮、1,1,1-三氯甲基-(對丁基苯基)酮等。Examples of acetophenone derivatives include 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-Hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-(4'-methylthiophenyl)-2-morpholinyl-1-propanone, 1,1,1-trichloromethyl-(p-butylphenyl)ketone, etc.

作為噻噸酮衍生物類，例如可列舉：噻噸酮、2-乙基噻噸酮、2-異丙基噻噸酮、2-氯噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等。Examples of thioxanthone derivatives include thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, and 2,4-dimethylthioxanthone , 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc.

作為苯甲酸酯衍生物類，例如可列舉：對二甲基胺基苯甲酸乙酯、對二乙基胺基苯甲酸乙酯等。Examples of benzoate derivatives include ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, and the like.

作為吖啶衍生物類，例如可列舉：9-苯基吖啶、9-(對甲氧基苯基)吖啶等。Examples of acridine derivatives include 9-phenylacridine, 9-(p-methoxyphenyl)acridine, and the like.

作為吩嗪衍生物類，例如可列舉：9,10-二甲基苯並吩嗪等。As phenazine derivatives, 9,10- dimethylbenzophenazine etc. are mentioned, for example.

作為蒽酮衍生物類，例如可列舉：苯並蒽酮等。Examples of anthrone derivatives include benzanthrone and the like.

聚合起始劑可單獨使用一種，亦可併用兩種以上。A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

作為聚合起始劑，亦可使用市售品。 作為市售品，例如可列舉：豔佳固（IRGACURE）（註冊商標，下同）250、豔佳固（IRGACURE）651、豔佳固（IRGACURE）184、德牢固（DAROCURE）1173、豔佳固（IRGACURE）2959、豔佳固（IRGACURE）127、豔佳固（IRGACURE）907、豔佳固（IRGACURE）369、豔佳固（IRGACURE）379EG、路西林（LUCIRIN）TPO、豔佳固（IRGACURE）819、豔佳固（IRGACURE）784、OXE-01、OXE-02（均為巴斯夫（BASF）公司製造）；賽庫奧路（SEIKUOL）（註冊商標）BZ、Z及BEE（精工化學股份有限公司製造）；卡亞庫（kayacure）（註冊商標）BP100及UVI-6992（陶氏化學（Dow·Chemical）股份有限公司製造）；艾迪科歐普托瑪（Adeka Optomer）SP-152及SP-170（艾迪科（ADEKA）股份有限公司製造）；TAZ-A及TAZ-PP（日本華嘉（Siber Hegner）股份有限公司製造）；以及TAZ-104（三和化學股份有限公司製造）；強力特（TRONLYTR）-PBG-304、強力特（TRONLYTR）-PBG-309、強力特（TRONLYTR）-PBG-305、強力特（TRONLYTR）-PBG-314（常州強力電子新材料有限公司（CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD）製造）。 As a polymerization initiator, a commercial item can also be used. Examples of commercially available products include: Irgacure (registered trademark, the same below) 250, Irgacure 651, Irgacure 184, DAROCURE 1173, and Irgacure (IRGACURE) 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRIN TPO, IRGACURE 819, IRGACURE 784, OXE-01, OXE-02 (all manufactured by BASF); SEIKUOL (registered trademark) BZ, Z and BEE (Seiko Chemical Co., Ltd. manufactured); kayacure (registered trademark) BP100 and UVI-6992 (manufactured by Dow Chemical Co., Ltd.); Adeka Optomer (Adeka Optomer) SP-152 and SP-170 (manufactured by ADEKA Co., Ltd.); TAZ-A and TAZ-PP (manufactured by Siber Hegner Co., Ltd.); and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.); (TRONLYTR)-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-314 (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD)).

在本發明的各向異性色素膜形成用組成物包含聚合起始劑的情況下，就不易擾亂聚合性液晶化合物的配向的觀點而言，本發明的各向異性色素膜形成用組成物中的聚合起始劑的含量相對於聚合性液晶化合物100質量份，通常為0.1質量份～30質量份，較佳為0.5質量份～10質量份，更佳為0.5質量份～8質量份。When the anisotropic dye film-forming composition of the present invention contains a polymerization initiator, from the viewpoint of being less likely to disturb the alignment of the polymerizable liquid crystal compound, the anisotropic dye film-forming composition of the present invention The content of the polymerization initiator is usually 0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal compound.

亦可視需要在聚合起始劑中併用聚合加速劑。作為所使用的聚合加速劑，例如可列舉：N,N-二甲基胺基苯甲酸乙酯等N,N-二烷基胺基苯甲酸烷基酯類；2-巰基苯並噻唑、2-巰基苯並噁唑2-巰基苯並咪唑等具有雜環的巰基化合物；脂肪族多官能巰基化合物等巰基化合物類等。 另外，聚合加速劑可單獨使用一種，亦可併用兩種以上。 A polymerization accelerator can also be used together with a polymerization initiator as needed. As the polymerization accelerator to be used, for example, N,N-dialkylaminobenzoic acid alkyl esters such as N,N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2 - mercapto compounds having a heterocycle such as mercaptobenzoxazole 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds, and the like. Moreover, a polymerization accelerator may be used individually by 1 type, and may use 2 or more types together.

亦可視需要以提高感應感度為目的而併用增感色素。增感色素可根據曝光光源的波長使用適當者。例如可列舉：日本專利特開平4-221958號公報、日本專利特開平4-219756號公報等所記載的呫噸酮系色素；日本專利特開平3-239703號公報、日本專利特開平5-289335號公報等所記載的具有雜環的香豆素系色素；日本專利特開平3-239703號公報、日本專利特開平5-289335號公報等所記載的3-酮基香豆素系色素；日本專利特開平6-19240號公報等所記載的吡咯亞甲基系色素；日本專利特開昭47-2528號公報、日本專利特開昭54-155292號公報、日本專利特公昭45-37377號公報、日本專利特開昭48-84183號公報、日本專利特開昭52-112681號公報、日本專利特開昭58-15503號公報、日本專利特開昭60-88005號公報、日本專利特開昭59-56403號公報、日本專利特開平2-69號公報、日本專利特開昭57-168088號公報、日本專利特開平5-107761號公報、日本專利特開平5-210240號公報、日本專利特開平4-288818號公報等所記載的具有二烷基胺基苯骨架的色素等。 另外，增感色素可單獨使用一種，亦可併用兩種以上。 A sensitizing dye may be used in combination for the purpose of improving the sensitivity if necessary. As the sensitizing dye, an appropriate one can be used according to the wavelength of the exposure light source. Examples include xanthone-based dyes described in Japanese Patent Laid-Open No. 4-221958, Japanese Patent Laid-Open No. 4-219756, etc.; Japanese Patent Laid-Open No. 3-239703 and Japanese Patent Laid-Open No. 5-289335 No. 3-ketocoumarin-based pigments described in Japanese Patent Laid-Open Publication No. 3-239703, Japanese Patent Laid-Open Publication No. 5-289335, etc.; Japan Pyrromethene pigments described in Japanese Patent Laid-Open Publication No. 6-19240, etc.; Japanese Patent Laid-Open Publication No. 47-2528, Japanese Patent Laid-Open Publication No. 54-155292, and Japanese Patent Publication No. 45-37377 , Japanese Patent Laid-Open No. 48-84183, Japanese Patent Laid-Open No. 52-112681, Japanese Patent Laid-Open No. 58-15503, Japanese Patent Laid-Open No. 60-88005, Japanese Patent Laid-Open No. 59-56403 communique, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent Laid-Open No. 5-107761, Japanese Patent Laid-Open No. 5-210240, Japanese Patent Laid-Open No. A dye having a dialkylaminobenzene skeleton described in KOKAI Publication No. 4-288818 and the like. In addition, one kind of sensitizing dye may be used alone, or two or more kinds may be used in combination.

＜溶劑＞ 本發明的各向異性色素膜形成用組成物亦可視需要含有溶劑。 <Solvent> The composition for anisotropic dye film formation of this invention may contain a solvent as needed.

作為本發明的各向異性色素膜形成用組成物可使用的溶劑，只要為可使色素或其他添加劑充分地分散或溶解於聚合性液晶化合物中者，則並無特別限定。例如可列舉：甲醇、乙醇、乙二醇、異丙醇、丙二醇、乙二醇甲醚、乙二醇丁醚、丙二醇單甲醚等醇溶劑；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、乳酸乙酯等酯溶劑；丙酮、甲基乙基酮、環戊酮、環己酮、2-庚酮、甲基異丁基酮等酮溶劑；戊烷、己烷、庚烷等脂肪族烴溶劑；甲苯、二甲苯等芳香族烴溶劑；乙腈等腈溶劑；四氫呋喃、二甲氧基乙烷、乙二醇二甲醚、乙二醇二***等醚溶劑；全氟苯、全氟甲苯、全氟十氫萘、全氟甲基環己烷、六氟-2-丙醇等含氟溶劑；及氯仿、二氯甲烷、氯苯、二氯苯等含氯溶劑。 該些溶劑可僅使用一種，亦可組合使用兩種以上。 The solvent that can be used in the anisotropic dye film-forming composition of the present invention is not particularly limited as long as it can sufficiently disperse or dissolve a dye or other additives in a polymerizable liquid crystal compound. For example, alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether, etc.; Ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate and other ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl Ketone solvents such as ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; tetrahydrofuran, dimethoxyethane, and ethylene glycol dimethyl ether , ethylene glycol diethyl ether and other ether solvents; perfluorobenzene, perfluorotoluene, perfluorodecalin, perfluoromethylcyclohexane, hexafluoro-2-propanol and other fluorinated solvents; and chloroform, dichloromethane , chlorobenzene, dichlorobenzene and other chlorinated solvents. These solvents may be used alone or in combination of two or more.

溶劑較佳為可使聚合性液晶化合物及色素溶解的溶劑，進而佳為使聚合性液晶化合物及色素完全溶解的溶劑。溶劑較佳為對聚合性液晶化合物的聚合反應為惰性的溶劑。就塗佈後述的本發明的各向異性色素膜形成用組成物的觀點而言，溶劑較佳為沸點為50℃～200℃的範圍的溶劑。The solvent is preferably a solvent capable of dissolving the polymerizable liquid crystal compound and the pigment, more preferably a solvent capable of completely dissolving the polymerizable liquid crystal compound and the pigment. The solvent is preferably a solvent inert to the polymerization reaction of the polymerizable liquid crystal compound. The solvent is preferably a solvent having a boiling point in the range of 50°C to 200°C from the viewpoint of coating the composition for forming an anisotropic dye film of the present invention described later.

在本發明的各向異性色素膜形成用組成物含有溶劑的情況下，溶劑在各向異性色素膜形成用組成物中所佔的含有比例較佳為相對於本發明的組成物的總量（100質量%）為50質量%～98質量%。換言之，本發明的各向異性色素膜形成用組成物中的固體成分較佳為2質量%～50質量%。When the composition for forming an anisotropic dye film of the present invention contains a solvent, the content ratio of the solvent in the composition for forming an anisotropic dye film is preferably relative to the total amount of the composition of the present invention ( 100% by mass) is 50% by mass to 98% by mass. In other words, the solid content in the anisotropic dye film-forming composition of the present invention is preferably 2% by mass to 50% by mass.

只要各向異性色素膜形成用組成物中的固體成分含量為所述上限值以下，則呈各向異性色素膜形成用組成物的黏度不會變得過高，所獲得的偏光膜的厚度變均勻從而偏光膜中不易產生不均的趨勢。As long as the solid content in the anisotropic dye film-forming composition is below the upper limit, the viscosity of the anisotropic dye film-forming composition does not become too high, and the thickness of the obtained polarizing film It becomes uniform so that unevenness is less likely to occur in the polarizing film.

本發明的各向異性色素膜形成用組成物的固體成分含量可考慮所欲製造的偏光膜的厚度來決定。The solid content of the anisotropic dye film-forming composition of the present invention can be determined in consideration of the thickness of the polarizing film to be produced.

只要可藉由後述的塗佈方法製作不存在厚度不均而均勻的膜，則本發明的各向異性色素膜用組成物的黏度並無特別限定。就獲得大面積下的厚度均勻性、塗佈速度等生產性、光學特性的面內均勻性的觀點而言，本發明的各向異性色素膜形成用組成物的黏度較佳為0.1 mPa·s以上，且較佳為500 mPa·s以下，更佳為100 mPa·s以下，進而佳為50 mPa·s以下。The viscosity of the composition for anisotropic dye films of the present invention is not particularly limited as long as a uniform film without uneven thickness can be produced by the coating method described later. The viscosity of the anisotropic dye film-forming composition of the present invention is preferably 0.1 mPa·s from the viewpoint of obtaining productivity such as thickness uniformity over a large area, coating speed, and in-plane uniformity of optical properties. Above, and preferably 500 mPa·s or less, more preferably 100 mPa·s or less, still more preferably 50 mPa·s or less.

＜其他添加劑＞ 本發明之各向異性色素膜形成用組成物亦可除所述聚合起始劑等以外，視需要進而含有聚合抑制劑、聚合助劑、聚合性非液晶化合物、界面活性劑、調平劑、偶合劑、pH調整劑、分散劑、抗氧化劑、有機/無機填料、有機/無機奈米片材、有機/無機奈米纖維、金屬氧化物等其他添加劑作為色素及聚合性液晶化合物以外的成分。藉由含有該些添加劑，而存在可提昇本發明的各向異性色素膜形成用組成物的塗佈性或穩定性等、或提昇由本發明的各向異性色素膜形成用組成物形成的各向異性色素膜的穩定性的情況。 ＜Other additives＞ The anisotropic dye film-forming composition of the present invention may further contain a polymerization inhibitor, a polymerization assistant, a polymerizable non-liquid crystal compound, a surfactant, a leveling agent, a Coupling agents, pH adjusters, dispersants, antioxidants, organic/inorganic fillers, organic/inorganic nanosheets, organic/inorganic nanofibers, metal oxides and other additives are used as components other than pigments and polymerizable liquid crystal compounds. By containing these additives, it is possible to improve the applicability or stability of the composition for forming anisotropic dye film of the present invention, or to improve the anisotropy formed by the composition for forming anisotropic dye film of the present invention. The stability of heterochromatic membranes.

＜各向異性色素膜形成用組成物的製造方法＞ 製造本發明的各向異性色素膜用組成物的方法並無特別限定。例如，將包含本發明的化合物的色素、聚合性液晶化合物、視需要添加的溶劑、其他添加劑等混合，在0℃～80℃下進行攪拌、振盪而使色素溶解。在難溶性的情況下，亦可使用均質機、珠磨機分散機等。 <Manufacturing method of composition for forming anisotropic dye film> The method of manufacturing the composition for anisotropic dye films of this invention is not specifically limited. For example, a dye containing the compound of the present invention, a polymerizable liquid crystal compound, an optional solvent, other additives, etc. are mixed, stirred and shaken at 0°C to 80°C to dissolve the dye. In the case of poor solubility, a homogenizer, a bead mill disperser, etc. can also be used.

作為製造本發明的各向異性色素膜用組成物的方法，出於去除組成物中的異物等的目的，亦可具有過濾步驟。As a method of manufacturing the composition for anisotropic dye films of this invention, for the purpose of removing foreign matter etc. in a composition, you may have a filtration process.

關於本發明的各向異性色素膜形成用組成物，自各向異性色素膜形成用組成物中去除溶劑後的組成物在任意溫度下可為液晶亦可並非液晶，但較佳為在任意溫度下均顯示出液晶性。Regarding the anisotropic dye film-forming composition of the present invention, the composition obtained by removing the solvent from the anisotropic dye film-forming composition may or may not be liquid crystal at any temperature, but is preferably at any temperature. All showed liquid crystallinity.

就下述所記載的塗敷製程的觀點而言，自本發明的各向異性色素膜形成用組成物中去除溶劑後的組成物的各向同性相出現溫度較佳為小於160℃，更佳為小於140℃，進而佳為小於115℃，進而更佳為小於110℃，尤佳為小於105℃。From the viewpoint of the coating process described below, the isotropic phase appearance temperature of the composition after removing the solvent from the anisotropic dye film-forming composition of the present invention is preferably less than 160°C, more preferably It is less than 140°C, more preferably less than 115°C, even more preferably less than 110°C, and most preferably less than 105°C.

[各向異性色素膜] 本發明的各向異性色素膜是使用本發明的各向異性色素膜形成用組成物而形成。因此，本發明的各向異性色素膜包含色素、以及聚合性液晶化合物及具有基於聚合性液晶化合物的單元的聚合物中的一者或兩者，色素包含本發明的化合物。 [Anisotropic Pigment Film] The anisotropic dye film of the present invention is formed using the composition for forming anisotropic dye film of the present invention. Therefore, the anisotropic dye film of the present invention includes a dye, and one or both of a polymerizable liquid crystal compound and a polymer having a unit derived from a polymerizable liquid crystal compound, and the dye includes the compound of the present invention.

關於使用本發明的各向異性色素膜用組成物形成的本發明的各向異性色素膜，較佳為以如下方式包含如下化合物，即，聚合性液晶化合物及具有基於聚合性液晶化合物的單元的聚合物的合計質量濃度成為式（1）所表示的本發明的化合物的質量濃度的1倍以上，更佳成為1.5倍以上，進而佳成為2倍以上，尤佳成為3倍以上，並且較佳成為1000倍以下，更佳成為700倍以下，進而佳成為500倍以下。The anisotropic dye film of the present invention formed using the composition for anisotropic dye film of the present invention preferably contains a polymerizable liquid crystal compound and a compound having a unit based on the polymerizable liquid crystal compound. The total mass concentration of the polymer is 1 time or more, more preferably 1.5 times or more, further preferably 2 times or more, especially preferably 3 times or more, and preferably 1 time or more the mass concentration of the compound of the present invention represented by formula (1). It is less than 1000 times, more preferably less than 700 times, and more preferably less than 500 times.

本發明的各向異性色素膜亦可包含非聚合性液晶化合物、聚合起始劑、聚合抑制劑、聚合助劑、聚合性非液晶化合物、非聚合性非液晶化合物、界面活性劑、調平劑、偶合劑、pH調整劑、分散劑、抗氧化劑、有機/無機填料、有機/無機奈米片材、有機/無機奈米纖維、金屬氧化物等作為其他成分。The anisotropic dye film of the present invention may also contain a non-polymerizable liquid crystal compound, a polymerization initiator, a polymerization inhibitor, a polymerization assistant, a polymerizable non-liquid crystal compound, a non-polymerizable non-liquid crystal compound, a surfactant, and a leveling agent , coupling agent, pH adjuster, dispersant, antioxidant, organic/inorganic filler, organic/inorganic nanosheet, organic/inorganic nanofiber, metal oxide, etc. as other components.

本發明的各向異性色素膜除可作為利用光吸收的各向異性而獲得直線偏光、圓偏光、橢圓偏光等的偏光膜發揮功能以外，亦能夠藉由膜形成製程及基板或含有有機化合物（色素或透明材料）的組成物的選擇，而作為折射各向異性或傳導各向異性等各種各向異性色素膜加以功能化。The anisotropic pigment film of the present invention can function as a polarizing film that utilizes the anisotropy of light absorption to obtain linear polarization, circular polarization, elliptical polarization, etc. Pigment or transparent material) composition selection, and functionalized as various anisotropic pigment films such as refractive anisotropy or conduction anisotropy.

在使用本發明的各向異性色素膜作為液晶顯示器用或OLED用抗反射膜的偏光元件的情況下，各向異性色素膜的配向特性可使用二色比來表示。只要二色比為8以上，則作為偏光元件發揮功能，較佳為15以上，更佳為20以上，進而佳為25以上，尤佳為30以上，特佳為40以上。各向異性色素膜的二色比越高越佳。藉由二色比為所述下限值以上，有效用作後述的光學元件、尤其是偏光元件。When the anisotropic dye film of the present invention is used as a polarizing element of an antireflection film for liquid crystal displays or OLEDs, the alignment characteristics of the anisotropic dye film can be expressed using a dichroic ratio. As long as the dichroic ratio is 8 or more, it functions as a polarizing element. It is preferably 15 or more, more preferably 20 or more, still more preferably 25 or more, especially preferably 30 or more, and particularly preferably 40 or more. The higher the dichroic ratio of the anisotropic dye film, the better. When a dichromatic ratio is more than the said lower limit, it can be used effectively as an optical element mentioned later, especially a polarizing element.

在用作OLED用抗反射膜的偏光元件的情況下，即便相位差膜等周邊材料的性能低，只要偏光元件的性能高，則作為抗反射膜的特性亦會提昇。因此，只要偏光元件的性能高，則容易簡化層構成，且即便為薄膜結構亦容易表現出充分的功能，從而亦可適宜地用於進行包含彎折、彎曲在內的變形後使用的用途。另外，亦可將成本抑制得低。When used as a polarizer for an antireflection film for OLEDs, even if peripheral materials such as a retardation film have low performance, as long as the performance of the polarizer is high, the characteristics as an antireflection film will be improved. Therefore, as long as the performance of the polarizing element is high, it is easy to simplify the layer configuration, and it is easy to exhibit sufficient functions even if it is a thin film structure, so it can be suitably used for use after deformation including bending and bending. In addition, the cost can also be kept low.

本發明中提及的二色比（D）在色素同樣地配向的情況下，以如下的式表示。 D＝Az/Ay 此處，Az是入射至各向異性色素膜的光的偏光方向平行於各向異性色素的配向方向的情況下所觀測到的吸光度。Ay是入射至各向異性色素膜的光的偏光方向垂直的情況下所觀測到的吸光度。 The dichroic ratio (D) mentioned in the present invention is represented by the following formula when the dyes are aligned in the same way. D=Az/Ay Here, Az is the absorbance observed when the polarization direction of the light incident on the anisotropic dye film is parallel to the alignment direction of the anisotropic dye. Ay is the absorbance observed when the polarization direction of the light incident on the anisotropic dye film is vertical.

各吸光度（Az、Ay）只要使用相同波長者，則並無特別限制，可根據目的選擇任一波長。在表示各向異性色素膜的配向程度的情況下，較佳為使用各向異性色素膜的在350 nm～800 nm的特定波長區域中以視感度修正後所得的值、或可見光區域的極大吸收波長下的值。Absorbance (Az, Ay) is not particularly limited as long as the same wavelength is used, and any wavelength can be selected according to the purpose. When expressing the degree of alignment of the anisotropic dye film, it is preferable to use the value obtained by correcting the visual sensitivity in the specific wavelength region of 350 nm to 800 nm, or the maximum absorption in the visible light region of the anisotropic dye film value at the wavelength.

本發明的各向異性色素膜的透過率在所使用的目標波長下，較佳為25%以上，進而佳為35%以上，尤佳為40%以上。在將本發明的各向異性色素膜用作在整個可見光波長區域中具有各向異性的色素膜的情況下，各向異性色素膜在可見光波長區域中的透過率較佳為25%以上，進而佳為35%以上，尤佳為40%以上。本發明的各向異性色素膜的透過率的上限只要與用途相應即可。例如，在提高偏光度的情況下，透過率較佳為50%以下。藉由透過率為所述範圍，有效用作後述的光學元件，尤其是有效用作用於彩色顯示的液晶顯示器用、或將各向異性色素膜與相位差膜組合而得的抗反射膜用的光學元件。The transmittance of the anisotropic pigment film of the present invention is preferably at least 25%, more preferably at least 35%, and most preferably at least 40% at the target wavelength used. When the anisotropic pigment film of the present invention is used as a pigment film having anisotropy in the entire visible light wavelength region, the transmittance of the anisotropic pigment film in the visible light wavelength region is preferably 25% or more, and further The best is more than 35%, and the most preferred is more than 40%. The upper limit of the transmittance of the anisotropic dye film of this invention should just correspond to a use. For example, when the degree of polarization is increased, the transmittance is preferably 50% or less. Since the transmittance is in the above-mentioned range, it can be effectively used as an optical element described later, especially for a liquid crystal display for color display, or an antireflection film obtained by combining an anisotropic pigment film and a retardation film. Optical element.

各向異性色素膜的膜厚以乾燥膜厚計，較佳為10 nm以上，更佳為100 nm以上，進而佳為500 nm以上。各向異性色素膜的膜厚較佳為30 μm以下，更佳為10 μm以下，進而佳為5 μm以下，特佳為3 μm以下。藉由各向異性色素膜的膜厚處於所述範圍，呈獲得在膜內色素均勻的配向及均勻的膜厚的趨勢。The film thickness of the anisotropic dye film is preferably at least 10 nm, more preferably at least 100 nm, and still more preferably at least 500 nm, in terms of dry film thickness. The film thickness of the anisotropic dye film is preferably at most 30 μm, more preferably at most 10 μm, still more preferably at most 5 μm, particularly preferably at most 3 μm. When the film thickness of the anisotropic dye film is within the above range, uniform alignment of the dye within the film and a uniform film thickness tend to be obtained.

[各向異性色素膜的製造方法] 本發明的各向異性色素膜較佳為使用本發明的各向異性色素膜形成用組成物，並藉由濕式成膜法而製作。 [Manufacturing method of anisotropic dye film] The anisotropic dye film of the present invention is preferably produced by a wet film-forming method using the anisotropic dye film-forming composition of the present invention.

本發明中所謂濕式成膜法是藉由某些方法將各向異性色素膜用組成物塗佈於基板上並使其配向的方法。因此，各向異性色素膜用組成物只要具有流動性即可，可含有溶劑，亦可不含有溶劑。就塗佈時的黏度或膜均勻性的觀點而言，更佳為含有溶劑。The so-called wet film-forming method in the present invention is a method of coating and aligning the composition for anisotropic dye film on a substrate by some method. Therefore, as long as the composition for anisotropic dye films has fluidity, it may contain a solvent, and may not contain a solvent. From the viewpoint of viscosity and film uniformity at the time of coating, it is more preferable to contain a solvent.

關於各向異性色素膜中的液晶或色素的配向，可在塗佈過程中藉由剪切等進行配向，亦可在溶劑乾燥的過程中進行配向。另外，亦可經由在塗佈、乾燥後進行加熱以使液晶或色素等再配向的製程，而使液晶或色素等在基板上配向、積層。在濕式成膜法中，若向基板上賦予各向異性色素膜用組成物，則已在各向異性色素膜用組成物中、或在溶劑乾燥的過程中、或在溶劑完全去除後，色素或液晶化合物獲得自締合（液晶狀態等分子締合狀態），藉此引起微小面積下的配向。藉由在該狀態下施加外場，可在大區域中沿一定方向配向，而獲得具有所需性能的各向異性色素膜。在此方面，與如下原理的方法有所不同，該原理是藉由包含色素的溶液對聚乙烯醇（PVA）膜等進行染色並延伸，且僅藉由延伸步驟使色素配向。此處，所謂外場，可列舉：預先向基板上施加的配向處理層的影響、剪切力、磁場、電場、熱等，該些可單獨使用，亦可組合使用多種。若有必要，亦可經由加熱步驟。The alignment of the liquid crystal or the dye in the anisotropic dye film may be performed by shearing or the like during the coating process, or may be performed during the solvent drying process. In addition, liquid crystals, dyes, etc. may be aligned and laminated on a substrate through a process of realigning liquid crystals, dyes, etc. by heating after coating and drying. In the wet film-forming method, if the composition for anisotropic dye film is applied to the substrate, the Pigment or liquid crystal compound acquires self-association (molecular association state such as liquid crystal state), thereby causing alignment in a small area. By applying an external field in this state, it is possible to align in a certain direction in a large area and obtain an anisotropic pigment film with desired properties. In this respect, it is different from the method of the principle of dyeing and extending a polyvinyl alcohol (PVA) film or the like with a solution containing a dye, and aligning the dye only by the extending step. Here, the term "external field" includes the influence of an alignment treatment layer previously applied to the substrate, shear force, magnetic field, electric field, heat, etc., and these may be used alone or in combination. A heating step can also be performed if necessary.

向基板上賦予各向異性色素膜用組成物並使之成膜的過程、施加外場以使之配向的過程、使溶劑乾燥的過程可逐次進行，亦可同時進行。The process of applying the composition for anisotropic dye film on the substrate to form a film, the process of applying an external field to align it, and the process of drying the solvent may be performed sequentially or simultaneously.

作為濕式成膜法中的向基板上賦予各向異性色素膜形成用組成物的方法，例如可列舉：塗佈法、浸漬塗佈法、朗謬-布洛傑（Langmuir-Blodgett，LB）膜形成法、公知的印刷法等。另外，亦有將以此方式獲得的各向異性色素膜轉印至另一基板的方法。Examples of the method of applying the anisotropic dye film-forming composition to the substrate in the wet film-forming method include a coating method, a dip coating method, and Langmuir-Blodgett (LB). A film forming method, a known printing method, and the like. In addition, there is also a method of transferring the anisotropic dye film obtained in this manner to another substrate.

該些中，較佳為使用塗佈法向基板上賦予各向異性色素膜形成用組成物。Among these, it is preferable to provide the composition for anisotropic dye film formation on a board|substrate by the coating method.

各向異性色素膜的配向方向可與塗佈方向不同。在本發明中，所謂各向異性色素膜的配向方向，例如若為偏光膜，則是指偏光的透過軸（偏光軸）或者吸收軸，若為相位差膜，則是指進相軸或者遲相軸。The alignment direction of the anisotropic dye film may be different from the coating direction. In the present invention, the alignment direction of the so-called anisotropic pigment film refers to the transmission axis (polarization axis) or absorption axis of polarized light if it is a polarizing film, and the phase advance axis or retardation axis if it is a retardation film. phase axis.

作為塗佈各向異性色素膜用組成物而獲得各向異性色素膜的方法，並無特別限定，例如可列舉：原崎勇次著「塗佈工學」（朝倉書店股份有限公司，1971年3月20日發行）的第253～277頁所記載的方法；市村國宏主編「分子協調材料的創製與應用」（CMC股份有限公司出版，1998年3月3日發行）的第118～149頁所記載的方法；在具有階差結構的基板（亦可預先實施配向處理）上藉由狹縫式模嘴塗佈法、旋轉塗佈法、噴塗法、棒式塗佈法、輥式塗佈法、刮刀塗佈法、簾幕式塗佈法、噴注法、浸漬法等塗佈的方法。其中，若採用狹縫式模嘴塗佈法或棒式塗佈法，則可獲得均勻性高的各向異性色素膜故而適宜。The method for obtaining an anisotropic dye film by applying the composition for the anisotropic dye film is not particularly limited, for example, "Coating Engineering" by Yuji Harasaki (Asakura Shoten Co., Ltd., March 1971) The method described on pages 253 to 277, published on the 20th; and the method described on pages 118 to 149 of "Creation and Application of Molecularly Coordinated Materials" edited by Kunihiro Ichimura (published by CMC Co., Ltd., released on March 3, 1998) The method described; on a substrate with a stepped structure (orientation treatment can also be performed in advance) by slit die coating method, spin coating method, spray coating method, rod coating method, roll coating method , knife coating method, curtain coating method, jet injection method, dipping method and other coating methods. Among them, a slit die coating method or a bar coating method is suitable because a highly uniform anisotropic dye film can be obtained.

狹縫式模嘴塗佈法所使用的模嘴塗佈機通常包括噴出塗佈液的塗佈機、所謂的狹縫口模。狹縫口模例如揭示於日本專利特開平2-164480號公報、日本專利特開平6-154687號公報、日本專利特開平9-131559號公報、「分散、塗佈、乾燥的基礎及應用」（2014年，科技體系（Techno System）股份有限公司，國際標準書號（International Standard Book Number，ISBN）9784924728707 C 305）、「顯示器、光學構件中的濕式塗佈技術」（2007年，資訊機構，ISBN9784901677752）、「電子學領域中的精密塗佈、乾燥技術」（2007年，技術資訊協會，ISBN9784861041389）等中。關於該些公知的狹縫口模，即便為膜或帶等具有可撓性的構件或如玻璃基板般硬的構件，亦可實施塗佈。A die coater used in the slot die coating method generally includes a coater that discharges a coating liquid, a so-called slit die. Slot dies are disclosed, for example, in Japanese Patent Laid-Open No. 2-164480, Japanese Patent Laid-Open No. 6-154687, Japanese Patent Laid-Open No. 9-131559, "Basis and Application of Dispersion, Coating, and Drying" ( 2014, Techno System Co., Ltd., International Standard Book Number (ISBN) 9784924728707 C 305), "Wet Coating Technology in Displays and Optical Components" (2007, Information Agency, ISBN9784901677752 ), "Precision coating and drying technology in the field of electronics" (2007, Technical Information Association, ISBN9784861041389), etc. With regard to these known slit dies, coating can also be performed on flexible members such as films and tapes, or hard members such as glass substrates.

作為本發明的各向異性色素膜形成所使用的基板，例如可列舉：玻璃、或者三乙酸酯、壓克力、聚酯、聚醯亞胺、聚醚醯亞胺、聚醚醚酮、聚碳酸酯、環烯烴聚合物、聚烯烴、聚氯乙烯、三乙醯纖維素或胺基甲酸酯系的膜等。As the substrate used for forming the anisotropic dye film of the present invention, for example, glass, or triacetate, acrylic, polyester, polyimide, polyetherimide, polyetheretherketone, Polycarbonate, cycloolefin polymer, polyolefin, polyvinyl chloride, triacetyl cellulose, or urethane-based film, etc.

為了控制色素的配向方向，亦可在基板表面，藉由「液晶便覽」（丸善股份有限公司，2000年10月30日發行）的第226～239頁等所記載的公知的方法（摩擦法、在配向膜表面上形成溝槽（groove）（微細的槽構造）的方法、使用偏光紫外光/偏光雷射的方法（光配向法）、藉由LB膜形成的配向方法、藉由無機物的斜向蒸鍍的配向方法等）實施配向處理（配向膜）。尤佳可列舉藉由摩擦法、光配向法的配向處理。作為用於摩擦法的材料，可列舉：聚乙烯醇（PVA）、聚醯亞胺（PI）、環氧樹脂、丙烯酸樹脂等。作為用於光配向法的材料，例如可列舉：聚肉桂酸酯系、聚醯胺酸-聚醯亞胺系、偶氮苯系等。在設置有配向處理層的情況下，認為藉由配向處理層的配向處理的影響、及塗佈時施加於各向異性色素膜用組成物的剪切力，使液晶化合物或色素配向。In order to control the alignment direction of the pigment, it is also possible to use known methods (rubbing method, rubbing method, etc.) A method of forming a groove (fine groove structure) on the surface of an alignment film, a method of using polarized ultraviolet light/polarized laser (photoalignment method), an alignment method formed by LB film, an oblique Alignment treatment (alignment film) is carried out to the alignment method of vapor deposition, etc.). Particularly preferable examples include alignment treatment by a rubbing method and a photo-alignment method. Examples of materials used in the rubbing method include polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, acrylic resin, and the like. Examples of materials used in the photo-alignment method include polycinnamate-based materials, polyamide-polyimide-based materials, and azobenzene-based materials. When an alignment treatment layer is provided, it is considered that the liquid crystal compound or dye is aligned due to the influence of the alignment treatment of the alignment treatment layer and the shear force applied to the composition for anisotropic dye film during coating.

塗佈各向異性色素膜用組成物時的各向異性色素膜用組成物的供給方法、供給間隔並無特別限定。在各向異性色素膜為薄的膜厚時，由於存在塗佈液的供給操作變繁雜、或塗佈液的供給開始時及停止時塗佈膜厚發生變動的情況，故而理想的是一面連續地供給各向異性色素膜用組成物一面進行塗佈。The supply method and supply interval of the composition for anisotropic dye film when coating the composition for anisotropic dye film are not specifically limited. When the anisotropic dye film has a thin film thickness, the supply operation of the coating liquid may become complicated, or the coating film thickness may fluctuate when the supply of the coating liquid is started and stopped, so it is desirable to be continuous on one side. Coating was carried out while supplying the composition for anisotropic dye film.

塗佈各向異性色素膜用組成物的速度通常為0.001 m/分鐘以上，較佳為0.01 m/分鐘以上，更佳為0.1 m/分鐘以上，進而佳為1.0 m/分鐘以上，尤佳為5.0 m/分鐘以上。塗佈各向異性色素膜用組成物的速度通常為400 m/分鐘以下，較佳為200 m/分鐘以下，更佳為100 m/分鐘以下，進而佳為50 m/分鐘以下。藉由塗佈速度為所述範圍，呈獲得各向異性色素膜的各向異性、可均勻地塗佈的趨勢。The speed of coating the composition for anisotropic pigment film is usually 0.001 m/min or more, preferably 0.01 m/min or more, more preferably 0.1 m/min or more, still more preferably 1.0 m/min or more, especially preferably 5.0 m/min or more. The speed of coating the composition for anisotropic pigment film is usually 400 m/min or less, preferably 200 m/min or less, more preferably 100 m/min or less, still more preferably 50 m/min or less. The anisotropy of an anisotropic dye film tends to be acquired and it can apply|coat uniformly when a coating speed is the said range.

各向異性色素膜用組成物的塗佈溫度通常為0℃以上且100℃以下，較佳為80℃以下，進而佳為60℃以下。The coating temperature of the composition for an anisotropic dye film is 0 degreeC or more and 100 degreeC or less normally, Preferably it is 80 degreeC or less, More preferably, it is 60 degreeC or less.

塗佈各向異性色素膜用組成物時的濕度較佳為10%RH以上，且較佳為80RH%以下。The humidity at the time of coating the composition for anisotropic dye film is preferably 10%RH or more, and preferably 80RH% or less.

亦可對各向異性色素膜進行不溶化處理。不溶化是指藉由使各向異性色素膜中的化合物的溶解性降低，控制化合物自各向異性色素膜溶出從而提高膜的穩定性的處理。 具體而言，就後續步驟的容易性、各向異性色素膜的耐久性等方面而言，較佳為膜的聚合或外敷等。 Insolubilization treatment can also be performed on the anisotropic pigment film. Insolubilization refers to a process of improving the stability of the film by reducing the solubility of the compound in the anisotropic dye film to control the compound's elution from the anisotropic dye film. Specifically, in terms of ease of subsequent steps, durability of the anisotropic dye film, and the like, polymerization or external application of the film is preferable.

在進行膜的聚合的情況下，對液晶分子與色素分子進行了配向的膜，使用光、熱及/或放射線進行聚合。In the case of film polymerization, the film in which liquid crystal molecules and dye molecules are aligned is polymerized using light, heat and/or radiation.

在使用光或放射線進行聚合的情況下，較佳為照射波長處於190 nm～450 nm的範圍的活性能量線。 波長190 nm～450 nm的活性能量線的光源並無特別限定，例如可列舉：氙氣燈、鹵素燈、鎢絲燈、高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、中壓水銀燈、低壓水銀燈、碳弧、螢光燈等燈光源；氬離子雷射、釔鋁石榴石（Yttrium Aluminum Garnet，YAG）雷射、準分子雷射、氮雷射、氦-鎘雷射、半導體雷射等雷射光源等。在照射特定波長的光而使用的情況下，亦可利用光學濾光片。活性能量線的曝光量較佳為10 J/m 2～10,000 J/m 2。 When performing polymerization using light or radiation, it is preferable to irradiate active energy rays having a wavelength in the range of 190 nm to 450 nm. The light source of active energy rays with a wavelength of 190 nm to 450 nm is not particularly limited, and examples thereof include xenon lamps, halogen lamps, tungsten filament lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, Light sources such as carbon arc and fluorescent lamps; argon ion lasers, Yttrium Aluminum Garnet (YAG) lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, semiconductor lasers and other lasers light source etc. When irradiating light of a specific wavelength and using it, an optical filter can also be utilized. The exposure amount of active energy rays is preferably 10 J/m 2 to 10,000 J/m 2 .

在使用熱進行聚合的情況下，較佳為在50℃～200℃的範圍進行，進而佳為在60℃～150℃的範圍進行。When superposing|polymerizing using heat, it is preferable to carry out in the range of 50 degreeC - 200 degreeC, and it is more preferable to carry out in the range of 60 degreeC - 150 degreeC.

聚合可使用光、熱及/或放射線進行，但使用光聚合或併用光聚合與熱聚合時，膜形成製程的時間短且裝置亦簡易，故而較佳。Polymerization can be performed using light, heat, and/or radiation, but when photopolymerization or photopolymerization and thermal polymerization are used in combination, the time for the film formation process is short and the equipment is simple, so it is preferable.

[光學元件] 本發明的光學元件包括本發明的各向異性色素膜。 [Optical element] The optical element of the present invention includes the anisotropic dye film of the present invention.

本發明中的光學元件表示利用光吸收的各向異性而獲得直線偏光、圓偏光、橢圓偏光等的偏光元件、相位差元件、具有折射各向異性或傳導各向異性等功能的元件。該些功能可藉由各向異性色素膜形成製程、及基板或含有有機化合物（色素或透明材料）的組成物的選擇而適當調整。The optical element in the present invention refers to a polarizing element, a phase difference element, an element having functions such as refractive anisotropy or conduction anisotropy, which utilize the anisotropy of light absorption to obtain linear polarization, circular polarization, and elliptical polarization. These functions can be properly adjusted by the anisotropic pigment film forming process and the selection of the substrate or the composition containing organic compounds (pigment or transparent material).

本發明的光學元件最佳為用作偏光元件。 就可藉由塗佈等在基板上形成各向異性色素膜而獲得偏光元件的方面而言，本發明的光學元件亦可適宜地用於柔性顯示器等用途。 The optical elements of the present invention are optimally used as polarizing elements. The optical element of the present invention can also be suitably used for applications such as flexible displays in terms of forming an anisotropic dye film on a substrate by coating or the like to obtain a polarizing element.

為了維持、提昇各向異性色素膜的功能，光學元件亦可設置有其他層。作為其他層，例如可列舉：為了提昇耐光性、耐熱性、耐水性等耐久性而使用的具有阻斷特定波長的功能的層或具有阻斷特定物質的功能的層（氧阻斷膜、水蒸氣阻斷膜等障壁膜等）；為了變更色域或提昇光學特性而使用的波長截止濾光片或含有吸收特定波長的材料的層等。In order to maintain and enhance the function of the anisotropic pigment film, the optical element can also be provided with other layers. As other layers, for example, a layer having a function of blocking a specific wavelength or a layer having a function of blocking a specific substance (oxygen blocking film, water Barrier films such as vapor barrier films, etc.); wavelength cut filters used to change the color gamut or improve optical characteristics, or layers containing materials that absorb specific wavelengths, etc.

[偏光元件] 可使用本發明的各向異性色素膜製造偏光元件（以下，有時稱為「本發明的偏光元件」）。 [Polarizer] A polarizing element (hereinafter, sometimes referred to as "the polarizing element of the present invention") can be produced using the anisotropic dye film of the present invention.

本發明的偏光元件只要具有本發明的各向異性色素膜則亦可具有其他任意膜（層）。例如，可藉由在基板上設置配向膜，並在配向膜的表面形成本發明的各向異性色素膜而製造。The polarizing element of the present invention may have other arbitrary films (layers) as long as it has the anisotropic dye film of the present invention. For example, it can be manufactured by disposing an alignment film on a substrate and forming the anisotropic dye film of the present invention on the surface of the alignment film.

偏光元件並不僅限於各向異性色素膜，亦可與如下的層等組合使用：具有提昇偏光性能、提昇機械強度等功能的外敷層；黏著層或抗反射層；配向膜；具有作為相位差膜的功能、作為亮度提昇膜的功能、作為反射膜或抗反射膜的功能、作為半透過反射膜的功能、作為擴散膜的功能等光學功能的層。具體而言，亦可藉由塗佈或貼合等而積層形成具有所述各種功能的層，並以積層體的形式使用。The polarizing element is not limited to the anisotropic pigment film, and can also be used in combination with the following layers: an overcoat layer with the functions of improving polarizing performance and mechanical strength; an adhesive layer or an anti-reflection layer; an alignment film; A layer with optical functions such as the function of a brightness enhancement film, a function of a reflective film or an antireflection film, a function of a semi-transparent reflective film, and a function of a diffusion film. Specifically, layers having the various functions described above may be laminated by coating, bonding, or the like, and used as a laminate.

該些層可配合製造製程、特性及功能適當設置，其積層位置、順序等並無特別限定。例如，形成各層的位置可為各向異性色素膜之上，亦可為設置有各向異性色素膜的基板的相反面。另外，形成各層的順序可為形成各向異性色素膜之前，亦可為形成各向異性色素膜之後。These layers can be appropriately arranged in accordance with the manufacturing process, characteristics and functions, and there are no special limitations on the lamination position and sequence. For example, the position where each layer is formed may be on the anisotropic dye film, or may be the opposite surface of the substrate on which the anisotropic dye film is provided. In addition, the order of forming each layer may be before forming an anisotropic dye film, and may be after forming an anisotropic dye film.

該些具有光學功能的層可藉由如下方法形成。These optically functional layers can be formed by the following methods.

具有作為相位差膜的功能的層可藉由在構成偏光元件的其他層進行相位差膜的塗佈或貼合等而形成。相位差膜例如可藉由實施日本專利特開平2-59703號公報、日本專利特開平4-230704號公報等所記載的延伸處理，或實施日本專利特開平7-230007號公報等所記載的處理而形成。A layer having a function as a retardation film can be formed by applying or bonding a retardation film to another layer constituting a polarizing element. The retardation film can be processed, for example, by implementing the stretching treatment described in Japanese Patent Laid-Open No. 2-59703, Japanese Patent Laid-Open No. 4-230704, etc., or by implementing the treatment described in Japanese Patent Laid-Open No. 7-230007. And formed.

具有作為亮度提昇膜的功能的層可藉由在構成偏光元件的其他層進行亮度提昇膜的塗佈或貼合等而形成。亮度提昇膜例如可藉由利用如日本專利特開2002-169025號公報及日本專利特開2003-29030號公報所記載的方法形成微細孔、或藉由將選擇反射的中心波長不同的兩層以上的膽固醇液晶層重疊而形成。A layer having a function as a brightness enhancement film can be formed by coating or laminating a brightness enhancement film on another layer constituting the polarizing element. The brightness enhancement film can be formed, for example, by using the methods described in Japanese Patent Application Laid-Open No. 2002-169025 and Japanese Patent Laid-Open No. 2003-29030 to form micropores, or by making two or more layers with different central wavelengths of selective reflection Layers of cholesteric liquid crystals are formed by overlapping.

具有作為反射膜或半透過反射膜的功能的層例如可藉由在構成偏光元件的其他層進行利用蒸鍍或濺鍍等獲得的金屬薄膜的塗佈或貼合等而形成。The layer that functions as a reflective film or a semi-transmissive reflective film can be formed, for example, by coating or laminating a metal thin film obtained by vapor deposition or sputtering on other layers constituting the polarizing element.

具有作為擴散膜的功能的層例如可藉由將包含微粒子的樹脂溶液塗佈於構成偏光元件的其他層而形成。The layer that functions as a diffusion film can be formed, for example, by applying a resin solution containing fine particles to other layers constituting the polarizing element.

具有作為相位差膜或光學補償膜的功能的層可藉由將圓盤狀液晶性化合物、向列液晶性化合物、層列液晶性化合物、膽固醇液晶性化合物等液晶性化合物塗佈於構成偏光元件的其他層並使其配向而形成。此時，亦可在基板上設置配向膜，並在配向膜的表面形成相位差膜或光學補償膜。A layer having a function as a retardation film or an optical compensation film can be formed by applying a liquid crystal compound such as a discotic liquid crystal compound, a nematic liquid crystal compound, a smectic liquid crystal compound, or a cholesterol liquid crystal compound to form a polarizing element. other layers and align them to form. At this time, an alignment film may be provided on the substrate, and a retardation film or an optical compensation film may be formed on the surface of the alignment film.

在將本發明的各向異性色素膜作為各向異性色素膜等而用於液晶元件（LCD）或有機電致發光元件（OLED）等各種顯示元件的情況下，可在構成該些顯示元件的電極基板等的表面直接形成本發明的各向異性色素膜，亦可將形成有本發明的各向異性色素膜的基板用作該些顯示元件的構成構件。 [實施例] When the anisotropic dye film of the present invention is used as an anisotropic dye film or the like in various display elements such as a liquid crystal element (LCD) or an organic electroluminescent element (OLED), it can be used in the components constituting these display elements The anisotropic dye film of the present invention is directly formed on the surface of an electrode substrate or the like, and a substrate on which the anisotropic dye film of the present invention is formed can also be used as a constituent member of these display elements. [Example]

以下，藉由實施例對本發明更具體地進行說明。本發明只要不超出其主旨，便不限定於以下實施例。 在以下的記載中，「份」是指「質量份」。 Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples unless the gist is exceeded. In the following description, "part" means "part by mass".

[液晶相的鑑定方法] 所獲得的各向異性色素膜形成用組成物的液晶性是藉由示差掃描熱量測定（精工電子（Seiko Instruments）公司「DSC220CU」）、X射線結構分析（理學（RIGAKU）股份有限公司「奈米觀察器（NANO-Viewer）」）、附帶高溫載台（東陽特克尼卡股份有限公司「HCS302-LN190」）的偏光顯微鏡（尼康因斯特克（NIKON INSTECH）股份有限公司「日蝕（ECLIPSE） LV100N POL」）進行觀察，並依照「液晶便覽」（丸善股份有限公司，2000年10月30日發行）的第9～50頁、第117～176頁等所記載的方法，對為液晶的情況進行鑑定。 [Identification method of liquid crystal phase] The liquid crystallinity of the obtained composition for anisotropic pigment film formation was measured by differential scanning calorimetry (Seiko Instruments "DSC220CU"), X-ray structural analysis (RIGAKU Co., Ltd. "Nano Viewer (NANO-Viewer)"), Polarizing Microscope (NIKON INSTECH Co., Ltd. LV100N POL"), and according to the methods described on pages 9-50, 117-176, etc. for identification.

[各向異性色素膜對於吸收軸/偏光軸方向的偏光的透過率的測定及二色比] 所獲得的各向異性色素膜對於吸收軸/偏光軸方向的偏光的透過率是使用包括葛蘭-湯普生（Glan-Thompson）偏光鏡的分光光度計（大塚電子（股）製造，製品名「RETS-100」）進行測定。 向各向異性色素膜入射直線偏光的測定光，測定各向異性色素膜對於吸收軸方向的偏光的透過率及各向異性色素膜對於偏光軸方向的偏光的透過率，並根據下式計算出二色比（D）。 D＝Az/Ay （式中， Ay＝-log（Ty）； Az＝-log（Tz）； Tz是各向異性色素膜對於吸收軸方向的偏光的透過率； Ty是各向異性色素膜對於偏光軸方向的偏光的透過率） [Measurement of transmittance of anisotropic dye film with respect to polarized light in the direction of absorption axis/polarization axis and dichroic ratio] The transmittance of the obtained anisotropic dye film with respect to the polarized light in the absorption axis/polarization axis direction was measured using a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., product name "RETS") including a Glan-Thompson polarizer. -100") for measurement. The measurement light of linear polarization is incident on the anisotropic dye film, and the transmittance of the anisotropic dye film with respect to the polarized light in the direction of the absorption axis and the transmittance of the anisotropic dye film with respect to the polarized light in the direction of the polarization axis are measured, and calculated according to the following formula Dichroic ratio (D). D=Az/Ay (where, Ay=-log(Ty); Az=-log(Tz); Tz is the transmittance of the anisotropic pigment film for the polarized light in the absorption axis direction; Ty is the transmittance of the anisotropic pigment film for polarized light in the direction of the polarization axis)

具體而言，向在作為基材的玻璃上形成有聚醯亞胺的配向膜（LX1400，日立化成杜邦微系統（Hitachi Chemical DuPont Microsystems）公司製造）的夾層單元（單元間隙：8.0 μm、10.0 μm，預先用布對已成膜的聚醯亞胺實施了摩擦處理者）中，以各向同性相注入各向異性色素膜用組成物，並以5℃/min冷卻至80℃，藉此獲得各向異性色素膜，進而以5℃/min冷卻至0℃，並且在各溫度下測定二色比。其中，將顯示出最大二色比的溫度及波長下的二色比確定為該各向異性色素膜的二色比。Specifically, to a sandwich cell (cell gap: 8.0 µm, 10.0 µm , which has been rubbed with a cloth on the film-formed polyimide in advance), inject the composition for anisotropic pigment film in the isotropic phase, and cool it to 80°C at 5°C/min, thereby obtaining The anisotropic dye film was further cooled to 0° C. at 5° C./min, and the dichroic ratio was measured at each temperature. Here, the dichromatic ratio at the temperature and wavelength at which the maximum dichromatic ratio is exhibited is determined as the dichromatic ratio of the anisotropic dye film.

作為所述測定的各向異性色素膜的二色比，只要為20以上，則實用上充分而較佳，更佳為30以上，進而佳為40以上。As the dichromatic ratio of the anisotropic dye film measured above, if it is 20 or more, it is practically enough and it is preferable, It is more preferable that it is 30 or more, It is more preferable that it is 40 or more.

[聚合性液晶化合物的合成] ＜聚合性液晶化合物（I-1）＞ 依照日本專利特開2020-042305號公報的記載合成下述結構式所表示的聚合性液晶化合物（I-1）。下述式中，C 11H 22是指呈直鏈狀鍵結有11個亞甲基鏈。 [Synthesis of Polymerizable Liquid Crystal Compound] <Polymerizable Liquid Crystal Compound (I-1)> A polymerizable liquid crystal compound (I-1) represented by the following structural formula was synthesized according to the description in JP-A-2020-042305. In the following formulae, C 11 H 22 means that 11 methylene chains are bonded in a straight chain.

[化25]

Figure 02_image048
[chem 25]
Figure 02_image048

對於聚合性液晶化合物（I-1），藉由示差掃描熱量測定求出各向同性相出現溫度（自液晶向液體的相轉變溫度及自液體向液晶的相轉變溫度）。在示差掃描熱量測定中，使用相對於聚合性液晶化合物（I-1）100質量份添加作為聚合抑制劑的4-甲氧基苯酚0.2質量份所得者。 聚合性液晶化合物（I-1）的自液晶向液體的相轉變溫度為111.0℃，自液體向液晶的相轉變溫度為109.4℃。 藉由偏光顯微鏡觀察及X射線結構分析來確認該溫度為各向同性相出現溫度。 For the polymerizable liquid crystal compound (I-1), the isotropic phase emergence temperature (phase transition temperature from liquid crystal to liquid and phase transition temperature from liquid to liquid crystal) was determined by differential scanning calorimetry. In differential scanning calorimetry, what added 0.2 mass parts of 4-methoxyphenol as a polymerization inhibitor with respect to 100 mass parts of polymerizable liquid crystal compounds (I-1) was used. The phase transition temperature from liquid crystal to liquid of the polymerizable liquid crystal compound (I-1) was 111.0°C, and the phase transition temperature from liquid to liquid crystal was 109.4°C. This temperature was confirmed to be the temperature at which the isotropic phase appeared by polarizing microscope observation and X-ray structure analysis.

[色素的合成] ＜色素（II-1）＞ 依照下述所記載的合成法，合成色素（II-1）。 [synthesis of pigment] ＜Pigment (II-1)＞ The dye (II-1) was synthesized according to the synthesis method described below.

[化26]

Figure 02_image050
[chem 26]
Figure 02_image050

（II-1-a）的合成： 將2-噻吩羧酸（2.00 g，15.6 mmol）、疊氮磷酸二苯酯（4.30 g，15.6 mmol）、三乙基胺（2.2 ml，15.6 mmol）、第三丁基醇（20 mL）混合，並在回流狀態下加熱攪拌5小時。冷卻至25℃後，向其中添加水（300 mL），並藉由二***進行萃取。將有機層濃縮後，利用矽膠層析法（己烷/二氯甲烷）進行精製，獲得1.9 g（II-1-a）。 Synthesis of (II-1-a): Mix 2-thiophenecarboxylic acid (2.00 g, 15.6 mmol), diphenylphosphoryl azide (4.30 g, 15.6 mmol), triethylamine (2.2 ml, 15.6 mmol), tert-butyl alcohol (20 mL) , and heated and stirred under reflux for 5 hours. After cooling to 25°C, water (300 mL) was added thereto, and extraction was performed by diethyl ether. After concentrating the organic layer, it purified by silica gel chromatography (hexane/dichloromethane) to obtain 1.9 g of (II-1-a).

（II-1-b）的合成： 將（II-1-a）（2.00 g，10.0 mmol）、12 N鹽酸（36 mL）、二***（85 mL）混合，並於25℃下攪拌30分鐘後，蒸餾去除溶媒，獲得1.36 g（II-1-b）。 Synthesis of (II-1-b): (II-1-a) (2.00 g, 10.0 mmol), 12 N hydrochloric acid (36 mL), diethyl ether (85 mL) were mixed, and stirred at 25°C for 30 minutes, then the solvent was distilled off to obtain 1.36 g ( II-1-b).

（II-1-c）的合成： 在氮氣流下，將4-丁基苯胺（44.35 g，369 mmol）、12 N鹽酸（410 mL）混合，並冷卻至0℃攪拌1小時。向其中添加將亞硝酸鈉（32.0 g，461 mmol）與水（220 mL）混合所得的水溶液，並在5℃下攪拌1小時，製備重氮溶液。 將（II-1-b）（62.5 g，461 mmol）與甲醇（625 mL）混合，冷卻至0℃後，花費40分鐘滴加所述重氮溶液。在0℃～5℃下攪拌1小時後，昇溫至25℃並攪拌3小時。濾取所析出的固體，並利用離子交換水對所獲得的粗製體進行洗淨，藉此獲得72.66 g（II-1-c）。 Synthesis of (II-1-c): Under nitrogen flow, 4-butylaniline (44.35 g, 369 mmol) and 12 N hydrochloric acid (410 mL) were mixed, cooled to 0°C and stirred for 1 hour. An aqueous solution obtained by mixing sodium nitrite (32.0 g, 461 mmol) and water (220 mL) was added thereto, and stirred at 5° C. for 1 hour to prepare a diazonium solution. (II-1-b) (62.5 g, 461 mmol) was mixed with methanol (625 mL), and after cooling to 0° C., the diazo solution was added dropwise over 40 minutes. After stirring at 0°C to 5°C for 1 hour, the mixture was heated up to 25°C and stirred for 3 hours. The precipitated solid was collected by filtration, and the obtained crude product was washed with ion-exchanged water to obtain 72.66 g of (II-1-c).

（II-1-d）的合成： 在氮氣流下，將（II-1-c）（72.6 g，245 mmol）、硫氰酸鈉（39.4 g，490 mmol）、乙酸（1100 mL）混合後，滴加溴（13.2 ml，257 mmol），並在25℃下攪拌3小時。添加水（1000 mL）加以混合後進行過濾分離，其後，對所獲得的固體成分進行減壓乾燥，獲得粗製體。利用甲醇（150 mL）對粗製體進行懸洗，並進行減壓乾燥，藉此獲得59.4 g（II-1-d）。 Synthesis of (II-1-d): Under nitrogen flow, after mixing (II-1-c) (72.6 g, 245 mmol), sodium thiocyanate (39.4 g, 490 mmol), and acetic acid (1100 mL), bromine (13.2 ml, 257 mmol) was added dropwise , and stirred at 25 °C for 3 hours. Water (1000 mL) was added and mixed, followed by separation by filtration, and the obtained solid was dried under reduced pressure to obtain a crude product. The crude product was suspended washed with methanol (150 mL) and dried under reduced pressure to obtain 59.4 g of (II-1-d).

[化27]

Figure 02_image052
[chem 27]
Figure 02_image052

（II-1-e）的合成： 將3,5,5-三乙基-1-己醇（38.4 g，266 mmol）、47%HBr水溶液（50.4 g，293 mmol）、濃硫酸（8.3 g，82.5 mmol）混合，在120℃下攪拌5小時。冷卻至25℃後，添加至己烷（600 mL）中，並利用水（1200 mL×3次）進行清洗。將有機層濃縮後，利用矽膠層析法（己烷）進行精製，獲得35.5 g（II-1-e）。 Synthesis of (II-1-e): Mix 3,5,5-triethyl-1-hexanol (38.4 g, 266 mmol), 47% HBr aqueous solution (50.4 g, 293 mmol), concentrated sulfuric acid (8.3 g, 82.5 mmol), and Stir for 5 hours. After cooling to 25° C., it was added to hexane (600 mL), and washed with water (1200 mL×3 times). After concentrating the organic layer, it purified by silica gel chromatography (hexane), and obtained 35.5 g of (II-1-e).

（II-1-f）的合成： 將N-乙基苯胺（20.0 g，165 mmol）、（II-1-e）（47.9 g，231 mmol）、碳酸鉀（59.4 g，330 mmol）、乙腈（80 mL）混合，並在回流狀態下加熱攪拌26小時。冷卻至25℃後，對反應液進行過濾，將濾液濃縮。利用矽膠層析法（己烷/二氯甲烷）對所獲得的黃色油狀的粗製體進行精製，獲得25.4 g（II-1-f）。 Synthesis of (II-1-f): Mix N-ethylaniline (20.0 g, 165 mmol), (II-1-e) (47.9 g, 231 mmol), potassium carbonate (59.4 g, 330 mmol), acetonitrile (80 mL), and Stirring under heating for 26 hours. After cooling to 25°C, the reaction solution was filtered, and the filtrate was concentrated. The obtained yellow oily crude product was purified by silica gel chromatography (hexane/dichloromethane) to obtain 25.4 g of (II-1-f).

（II-1）的合成： 將（II-1-d）（0.75 g，2.37 mmol）、乙酸（20 mL）、丙酸（10 mL）混合，並冷卻至3℃。向冷卻的溶液中滴加亞硝酸鈉（0.21 g，3.08 mmol）與濃硫酸的混合物，在3℃下攪拌1小時，製備重氮溶液。 將（II-1-f）（0.58 g，3.56 mmol）、四氫呋喃（6 mL）、甲醇（6 mL）、乙酸鈉（5.4 g）混合，冷卻至3℃後，花費1小時滴加所述重氮溶液，在3℃下攪拌3小時。昇溫至25℃並攪拌12小時後，加入水（10 mL）並進行攪拌。濾取析出的固體，利用矽膠層析法（己烷/二氯甲烷）對所獲得的粗製體進行精製，藉此獲得0.16 g色素（II-1）。 Synthesis of (II-1): Mix (II-1-d) (0.75 g, 2.37 mmol), acetic acid (20 mL), propionic acid (10 mL) and cool to 3°C. A mixture of sodium nitrite (0.21 g, 3.08 mmol) and concentrated sulfuric acid was added dropwise to the cooled solution, and stirred at 3°C for 1 hour to prepare a diazonium solution. (II-1-f) (0.58 g, 3.56 mmol), tetrahydrofuran (6 mL), methanol (6 mL), sodium acetate (5.4 g) were mixed, cooled to 3°C, and the weight was added dropwise over 1 hour. Nitrogen solution, stirred at 3°C for 3 hours. After raising the temperature to 25°C and stirring for 12 hours, water (10 mL) was added and stirred. The precipitated solid was collected by filtration, and the obtained crude product was purified by silica gel chromatography (hexane/dichloromethane) to obtain 0.16 g of a pigment (II-1).

色素（II-1）在10 ppm氯仿溶液中的極大吸收波長（λmax）為593 nm，克吸光係數為131.9 Lg -1cm -1。 The maximum absorption wavelength (λmax) of the pigment (II-1) in 10 ppm chloroform solution is 593 nm, and the gram absorption coefficient is 131.9 Lg -1 cm -1 .

利用核磁共振（nuclear magnetic resonance，NMR）進行色素（II-1）的結構確認。將結果示於以下。 1H-NMR（CDCl 3,400 MHz）δ0.95-1.00 (m, 12H), δ1.06 (d, 3H, J=6.3 Hz), δ1.16-1.21 (m, 1H), δ1.27-1.32 (m, 4H), δ1.38-1.43 (m, 2H), δ1.63-1.71 (m, 3H), δ2.71 (t, 2H, J=7.5 Hz), δ3.40-3.55 (m, 4 Hz), δ6.74 (d, 2H, 9.4 Hz), δ7.32 (d, 2H, 8.5 Hz), δ7.82 (d, 2H, 8.5 Hz), δ7.92 (s ,1H), δ7.96 (d, 2H, 9.4 Hz) The structure of the pigment (II-1) was confirmed by nuclear magnetic resonance (NMR). The results are shown below. 1 H-NMR (CDCl 3 , 400 MHz) δ0.95-1.00 (m, 12H), δ1.06 (d, 3H, J=6.3 Hz), δ1.16-1.21 (m, 1H), δ1.27 -1.32 (m, 4H), δ1.38-1.43 (m, 2H), δ1.63-1.71 (m, 3H), δ2.71 (t, 2H, J=7.5 Hz), δ3.40-3.55 ( m, 4 Hz), δ6.74 (d, 2H, 9.4 Hz), δ7.32 (d, 2H, 8.5 Hz), δ7.82 (d, 2H, 8.5 Hz), δ7.92 (s ,1H) , δ7.96 (d, 2H, 9.4 Hz)

測定色素（II-1）在環戊酮中的溶解度。 向103 mg環戊酮中添加3 mg色素（II-1），並在80℃下攪拌5分鐘。其後，在室溫下靜置1小時，使用包括針筒過濾器（邁博瑞（Membrane Solutions）公司製造，PTFE13045，口徑0.45 μm）的針筒對所獲得的混合液進行過濾，藉此獲得色素（II-1）的環戊酮飽和溶液。利用746 mg四氫呋喃將該溶液稀釋，使用高效液相層析儀（high performance liquid chromatograph，HPLC）（日立高新技術（Hitachi High-Technologies）製造的L-2300系列）來確定濃度。製作在四氫呋喃中溶解有0.1質量%的色素（II-1）的溶液，並在吸收波長254 nm下繪製校準曲線。使用該校準曲線，測定環戊酮飽和溶液的濃度。將結果示於表1。 The solubility of the pigment (II-1) in cyclopentanone was determined. 3 mg of the pigment (II-1) was added to 103 mg of cyclopentanone, and stirred at 80° C. for 5 minutes. Thereafter, it was allowed to stand at room temperature for 1 hour, and the obtained mixture was filtered using a syringe filter (manufactured by Membrane Solutions, PTFE13045, diameter 0.45 μm) to obtain Cyclopentanone saturated solution of pigment (II-1). The solution was diluted with 746 mg of tetrahydrofuran, and the concentration was determined using a high performance liquid chromatograph (HPLC) (L-2300 series manufactured by Hitachi High-Technologies). A solution in which 0.1% by mass of the dye (II-1) was dissolved in tetrahydrofuran was prepared, and a calibration curve was drawn at an absorption wavelength of 254 nm. Using this calibration curve, the concentration of a saturated solution of cyclopentanone was determined. The results are shown in Table 1.

＜色素（II-2）＞ 依照下述所記載的合成法，合成色素（II-2）。 ＜Pigment (II-2)＞ The dye (II-2) was synthesized according to the synthesis method described below.

[化28]

Figure 02_image054
[chem 28]
Figure 02_image054

（II-2-a）的合成： 將N-乙基苯胺（130.0 g，1073 mmol）、2-碘丙烷（200 g，1080 mmol）、碳酸鉀（297 g，2146 mmol）、乙腈（520 mL）混合，在回流狀態下加熱攪拌16小時。冷卻至25℃後，對反應液進行過濾，將濾液濃縮。利用矽膠層析法（己烷/二氯甲烷）對所獲得的黃色油狀的粗製體進行精製，獲得100 g（II-2-a）。 Synthesis of (II-2-a): Mix N-ethylaniline (130.0 g, 1073 mmol), 2-iodopropane (200 g, 1080 mmol), potassium carbonate (297 g, 2146 mmol), and acetonitrile (520 mL), and heat and stir under reflux for 16 Hour. After cooling to 25°C, the reaction solution was filtered, and the filtrate was concentrated. The obtained yellow oily crude product was purified by silica gel chromatography (hexane/dichloromethane) to obtain 100 g of (II-2-a).

（II-2）的合成： 將（II-1-d）（0.75 g，2.37 mmol）、乙酸（20 mL）、丙酸（10 mL）混合，冷卻至3℃。向冷卻的溶液中滴加亞硝酸鈉（0.21 g，3.08 mmol）與濃硫酸的混合物，在3℃下攪拌1小時，製備重氮溶液。 將（II-2-a）（0.58 g，3.56 mmol）、四氫呋喃（6 mL）、甲醇（6 mL）、乙酸鈉（5.3 g）混合，冷卻至3℃後，花費1小時滴加所述重氮溶液，在3℃下攪拌3小時。昇溫至25℃並攪拌12小時後，加入水（10 mL）、甲醇（8 mL）並進行攪拌。向將析出物過濾分離後的濾液中添加50 ml水，對析出的固體成分進行過濾分離而獲得粗製體。利用矽膠層析法（己烷/二氯甲烷）對粗製體進行精製，獲得0.04 g色素（II-2）。 Synthesis of (II-2): Mix (II-1-d) (0.75 g, 2.37 mmol), acetic acid (20 mL), propionic acid (10 mL), and cool to 3°C. A mixture of sodium nitrite (0.21 g, 3.08 mmol) and concentrated sulfuric acid was added dropwise to the cooled solution, and stirred at 3°C for 1 hour to prepare a diazonium solution. (II-2-a) (0.58 g, 3.56 mmol), tetrahydrofuran (6 mL), methanol (6 mL) and sodium acetate (5.3 g) were mixed, cooled to 3°C, and the weight was added dropwise over 1 hour. Nitrogen solution, stirred at 3°C for 3 hours. After raising the temperature to 25°C and stirring for 12 hours, water (10 mL) and methanol (8 mL) were added and stirred. 50 ml of water was added to the filtrate obtained by filtering the precipitate, and the precipitated solid was filtered to obtain a crude product. The crude product was purified by silica gel chromatography (hexane/dichloromethane) to obtain 0.04 g of the pigment (II-2).

色素（II-2）在10 ppm氯仿溶液中的極大吸收波長（λmax）為596 nm，克吸光係數為153.2 Lg -1cm -1。 The maximum absorption wavelength (λmax) of the pigment (II-2) in 10 ppm chloroform solution is 596 nm, and the gram absorption coefficient is 153.2 Lg -1 cm -1 .

利用NMR進行色素（II-2）的結構確認。將結果示於以下。 1H-NMR（CDCl 3,400 MHz）δ0.97 (t, 3H, J=7.4 Hz), δ1.28-1.34 (m, 8H), δ1.38-1.44 (m, 2H), δ1.65-1.70 (m, 2H), δ2.71 (t, 2H, J=7.9 Hz), δ3.47 (q, 2H, J=7.3 Hz), δ4.32 (m, 1H), δ6.85 (d, 2H, 9.4 Hz), δ7.32 (d, 2H, 8.5 Hz), δ7.82 (d, 2H, 8.5 Hz), δ7.92 (s, 1H), δ7.97 (d, 2H, 9.4 Hz) The structure of the dye (II-2) was confirmed by NMR. The results are shown below. 1 H-NMR (CDCl 3 , 400 MHz) δ0.97 (t, 3H, J=7.4 Hz), δ1.28-1.34 (m, 8H), δ1.38-1.44 (m, 2H), δ1.65 -1.70 (m, 2H), δ2.71 (t, 2H, J=7.9 Hz), δ3.47 (q, 2H, J=7.3 Hz), δ4.32 (m, 1H), δ6.85 (d , 2H, 9.4 Hz), δ7.32 (d, 2H, 8.5 Hz), δ7.82 (d, 2H, 8.5 Hz), δ7.92 (s, 1H), δ7.97 (d, 2H, 9.4 Hz )

對於色素（II-2），亦與色素（II-1）同樣地測定環戊酮飽和溶液的濃度。將結果示於表1。Also for the dye (II-2), the concentration of the cyclopentanone saturated solution was measured in the same manner as the dye (II-1). The results are shown in Table 1.

＜色素（III-1）＞ 依照下述記載的合成法，合成色素（III-1）。 ＜Pigment (III-1)＞ The dye (III-1) was synthesized according to the synthesis method described below.

[化29]

Figure 02_image056
[chem 29]
Figure 02_image056

（III-1-a）的合成： 將3,5,5-三乙基-1-己醇（38.4 g，266 mmol）、47%HBr水溶液（50.4 g，293 mmol）、濃硫酸（8.3 g，82.5 mmol）混合，在120℃下攪拌5小時。冷卻至25℃後，添加至己烷（600 mL）中，並利用水（1200 mL×3次）進行清洗。將有機層濃縮後，利用矽膠層析法（己烷）進行精製，獲得35.5 g（III-1-a）。 Synthesis of (III-1-a): Mix 3,5,5-triethyl-1-hexanol (38.4 g, 266 mmol), 47% HBr aqueous solution (50.4 g, 293 mmol), concentrated sulfuric acid (8.3 g, 82.5 mmol), and Stir for 5 hours. After cooling to 25° C., it was added to hexane (600 mL), and washed with water (1200 mL×3 times). After concentrating the organic layer, it purified by silica gel chromatography (hexane), and obtained 35.5 g of (III-1-a).

（III-1-b）的合成： 在氮氣流下，將4-硝基苯酚（65.0 g，467 mmol）、（III-1-a）（116.2 g，560 mmol）、二甲基甲醯胺（520 mL）、碳酸鉀（129.1 g，934 mmol）混合，在90℃下攪拌6小時。向其中添加水（1000 mL），利用乙酸乙酯/己烷=1/4混合液進行萃取，將油層濃縮。利用矽膠層析法（乙酸乙酯/己烷）進行精製，獲得113.5 g（III-1-b）。 Synthesis of (III-1-b): Under nitrogen flow, 4-nitrophenol (65.0 g, 467 mmol), (III-1-a) (116.2 g, 560 mmol), dimethylformamide (520 mL), potassium carbonate (129.1 g, 934 mmol) and stirred at 90°C for 6 hours. Water (1000 mL) was added thereto, extracted with ethyl acetate/hexane=1/4 mixture, and the oil layer was concentrated. Purification by silica gel chromatography (ethyl acetate/hexane) gave 113.5 g of (III-1-b).

（III-1-c）的合成： 在氬氣流下，將（III-1-b）（113.5 g，427.7 mmol）、乙酸乙酯（1100 ml）混合後，添加鈀碳（5%Pd-C，含水量55質量%，11.4 g），並在氫環境下在25℃下攪拌60小時。對容器內進行氬置換後，將觸媒過濾分離。藉由二氯甲烷對觸媒進行萃取，合併有機層進行濃縮後，利用矽膠層析法（二氯甲烷）進行精製，獲得99.5 g（III-1-c）。 Synthesis of (III-1-c): After mixing (III-1-b) (113.5 g, 427.7 mmol) and ethyl acetate (1100 ml) under argon flow, palladium carbon (5% Pd-C, water content 55% by mass, 11.4 g) was added , and stirred at 25 °C for 60 h under a hydrogen atmosphere. After replacing the container with argon, the catalyst was separated by filtration. The catalyst was extracted with dichloromethane, the organic layers were combined and concentrated, and purified by silica gel chromatography (dichloromethane) to obtain 99.5 g of (III-1-c).

[化30]

Figure 02_image058
[chem 30]
Figure 02_image058

（III-1-d）的合成： 將2-噻吩羧酸（2.00 g，15.6 mmol）、疊氮磷酸二苯酯（4.30 g，15.6 mmol）、三乙基胺（2.2 mL，15.6 mmol）、第三丁基醇（20 mL）混合，並在回流狀態下加熱攪拌5小時。冷卻至25℃後，向其中添加水（300 mL），並藉由二***進行萃取。將有機層濃縮後，利用矽膠層析法（己烷/二氯甲烷）進行精製，獲得1.9 g（III-1-d）。 Synthesis of (III-1-d): Mix 2-thiophenecarboxylic acid (2.00 g, 15.6 mmol), diphenylphosphoryl azide (4.30 g, 15.6 mmol), triethylamine (2.2 mL, 15.6 mmol), tert-butyl alcohol (20 mL) , and heated and stirred under reflux for 5 hours. After cooling to 25°C, water (300 mL) was added thereto, and extraction was performed by diethyl ether. After concentrating the organic layer, it purified by silica gel chromatography (hexane/dichloromethane) to obtain 1.9 g of (III-1-d).

（III-1-e）的合成： 將（III-1-d）（2.00 g，10.0 mmol）、12 N鹽酸（36 mL）、二***（85 mL）混合，並在25℃下攪拌30分鐘後，蒸餾去除溶媒，獲得1.36 g（III-1-e）。 Synthesis of (III-1-e): (III-1-d) (2.00 g, 10.0 mmol), 12 N hydrochloric acid (36 mL), diethyl ether (85 mL) were mixed, and stirred at 25 °C for 30 minutes, and the solvent was distilled off to obtain 1.36 g ( III-1-e).

（III-1-f）的合成： 在氮氣流下，將（III-1-c）（47.3 g，201 mmol）、12 N鹽酸（375 mL）混合，並冷卻至0℃攪拌1小時。向其中添加將亞硝酸鈉（17.3 g，251 mmol）與水（130 mL）混合所得的水溶液，並在5℃下攪拌1小時，製備重氮溶液。 將（III-1-e）（37.2 g，241 mmol）與甲醇混合，冷卻至0℃後，花費40分鐘滴加所述重氮溶液。昇溫至25℃並攪拌3小時，濾取所析出的固體，並利用己烷對所獲得的粗製體進行清洗，藉此獲得48.1 g（III-1-f）。 Synthesis of (III-1-f): Under nitrogen flow, (III-1-c) (47.3 g, 201 mmol), 12 N hydrochloric acid (375 mL) were mixed, cooled to 0°C and stirred for 1 hour. An aqueous solution obtained by mixing sodium nitrite (17.3 g, 251 mmol) and water (130 mL) was added thereto, and stirred at 5° C. for 1 hour to prepare a diazo solution. (III-1-e) (37.2 g, 241 mmol) was mixed with methanol, and after cooling to 0° C., the diazo solution was added dropwise over 40 minutes. The temperature was raised to 25° C. and stirred for 3 hours, the precipitated solid was collected by filtration, and the obtained crude product was washed with hexane to obtain 48.1 g of (III-1-f).

（III-1-g）的合成： 在氮氣流下，將（III-1-f）（48.1 g，125.7 mmol）、硫氰酸鈉（20.4 g，251.4 mmol）、乙酸（720 mL）混合後，滴加N-溴丁二醯亞胺（24.6 g，138.3 mmol），並在25℃下攪拌3小時。向其中加入水（600 mL）加以混合後進行過濾分離，其後，對所獲得的固體成分進行減壓乾燥，獲得粗製體。利用矽膠層析法（二氯甲烷/甲醇）對粗製體進行精製，獲得31.4 g（III-1-g）。 Synthesis of (III-1-g): Under nitrogen flow, after mixing (III-1-f) (48.1 g, 125.7 mmol), sodium thiocyanate (20.4 g, 251.4 mmol), and acetic acid (720 mL), N-bromosuccinimide was added dropwise (24.6 g, 138.3 mmol), and stirred at 25°C for 3 hours. Water (600 mL) was added thereto, mixed, filtered and separated, and the obtained solid was dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography (dichloromethane/methanol) to obtain 31.4 g (III-1-g).

（III-1）的合成： 將（III-1-g）（0.75 g，1.86 mmol）、乙酸（3.8 mL）、鹽酸（3.8 mL）混合，並冷卻至3℃。加入亞硝酸鈉（0.17 g，2.42 mmol），並在3℃下攪拌1小時，製備重氮溶液。 將二乙基苯胺（0.56 g，3.73 mmol）、四氫呋喃（15 mL）、乙酸鈉（7.4 g）混合，冷卻至3℃後，花費1小時滴加所述重氮溶液，並在3℃下攪拌3小時。昇溫至25℃並攪拌12小時後，加入水（7.5 mL）、甲醇（15 mL）並進行攪拌。濾取所析出的固體，利用矽膠層析法（己烷/二氯甲烷）對所獲得的粗製體進行精製，藉此獲得0.14 g色素（III-1）。 Synthesis of (III-1): (III-1-g) (0.75 g, 1.86 mmol), acetic acid (3.8 mL), hydrochloric acid (3.8 mL) were mixed, and cooled to 3°C. Sodium nitrite (0.17 g, 2.42 mmol) was added and stirred at 3 °C for 1 h to prepare a diazonium solution. Mix diethylaniline (0.56 g, 3.73 mmol), tetrahydrofuran (15 mL), and sodium acetate (7.4 g), and after cooling to 3°C, add the diazo solution dropwise over 1 hour and stir at 3°C 3 hours. After heating up to 25°C and stirring for 12 hours, water (7.5 mL) and methanol (15 mL) were added and stirred. The precipitated solid was collected by filtration, and the obtained crude product was purified by silica gel chromatography (hexane/dichloromethane) to obtain 0.14 g of a pigment (III-1).

色素（III-1）在10 ppm氯仿溶液中的極大吸收波長（λmax）為563 nm，克吸光係數為134.8 Lg -1cm -1。 The maximum absorption wavelength (λmax) of the pigment (III-1) in 10 ppm chloroform solution is 563 nm, and the gram absorption coefficient is 134.8 Lg -1 cm -1 .

利用NMR進行色素（III-1）的結構確認。將結果示於以下。 1H-NMR（CDCl 3, 400 MHz）δ0.93 (s, 9H), δ1.03 (d, 3H, J=6.7 Hz), δ1.13-1.18 (m, 1H), δ1.28-1.37 (m, 7H), δ1.65-1.72 (m, 1H), δ1.76-1.91 (m, 2H), δ3.53 (q, 4H, J=7.2 Hz), δ4.09 (t, 2H, J=6.7 Hz), δ6.76 (d, 2H, 9.4 Hz), δ7.00 (d, 2H, 9.1 Hz), δ7.85 (s, 1H), δ7.88 (d, 2H, 9.1 Hz), δ7.95 (d, 2H, 9.4 Hz) The structure of the dye (III-1) was confirmed by NMR. The results are shown below. 1 H-NMR (CDCl 3 , 400 MHz) δ0.93 (s, 9H), δ1.03 (d, 3H, J=6.7 Hz), δ1.13-1.18 (m, 1H), δ1.28-1.37 (m, 7H), δ1.65-1.72 (m, 1H), δ1.76-1.91 (m, 2H), δ3.53 (q, 4H, J=7.2 Hz), δ4.09 (t, 2H, J=6.7 Hz), δ6.76 (d, 2H, 9.4 Hz), δ7.00 (d, 2H, 9.1 Hz), δ7.85 (s, 1H), δ7.88 (d, 2H, 9.1 Hz) , δ7.95 (d, 2H, 9.4 Hz)

對於色素（III-1），亦與色素（II-1）同樣地測定環戊酮飽和溶液的濃度。將結果示於表1。Also for the dye (III-1), the concentration of the cyclopentanone saturated solution was measured in the same manner as the dye (II-1). The results are shown in Table 1.

將上述中所合成的聚合性液晶化合物（I-1）及色素（II-1）、色素（II-2）、色素（III-1）的化學結構示於以下。The chemical structures of the polymerizable liquid crystal compound (I-1), dye (II-1), dye (II-2), and dye (III-1) synthesized above are shown below.

[化31]

Figure 02_image060
[chem 31]
Figure 02_image060

將比較例中使用的色素（III-2）的化學結構示於以下。The chemical structure of the dye (III-2) used in the comparative example is shown below.

[化32]

Figure 02_image062
[chem 32]
Figure 02_image062

[實施例1] 向2959.1份的氯仿中，加入20.00份的聚合性液晶化合物（I-1）、0.23份的色素（II-1），進行攪拌使其等相容後，去除溶媒，藉此獲得各向異性色素膜形成用組成物1。各向異性色素膜形成用組成物1的rn 1/rn 2為1。 各向異性色素膜形成用組成物1顯示出液晶性是根據藉由附帶高溫載台的偏光顯微鏡在40℃下觀察到雙折射來確認。 為了使用所獲得的各向異性色素膜形成用組成物1，並利用所述方法來確定二色比，使用單元間隙8.0 μm的夾層單元製作各向異性色素膜1。確定各向異性色素膜1的二色比。 將其結果示於表1。 [Example 1] Add 20.00 parts of polymerizable liquid crystal compound (I-1) and 0.23 parts of pigment (II-1) to 2959.1 parts of chloroform, stir to make them compatible, and then remove the solvent. Composition 1 for forming an anisotropic dye film was obtained. rn 1 /rn 2 of the anisotropic dye film-forming composition 1 was 1. The composition 1 for forming an anisotropic dye film confirmed liquid crystallinity by observing birefringence at 40° C. with a polarizing microscope equipped with a high-temperature stage. In order to use the obtained anisotropic dye film-forming composition 1 and determine the dichromatic ratio by the method described above, an anisotropic dye film 1 was fabricated using a sandwich cell with a cell gap of 8.0 μm. The dichroic ratio of the anisotropic pigment film 1 is determined. The results are shown in Table 1.

[實施例2] 加入0.20份的色素（II-2）代替0.23份的色素（II-1），除此以外，藉由與實施例1同樣的方式，獲得各向異性色素膜形成用組成物2及各向異性色素膜2。各向異性色素膜形成用組成物2的rn 1/rn 2為1。 各向異性色素膜形成用組成物2顯示出液晶性是根據藉由附帶高溫載台的偏光顯微鏡在40℃下觀察到雙折射來確認。 確定各向異性色素膜2的二色比。 將其結果示於表1。 [Example 2] Except adding 0.20 parts of pigment (II-2) instead of 0.23 parts of pigment (II-1), in the same manner as in Example 1, an anisotropic pigment film-forming composition was obtained 2 and anisotropic pigment film 2. rn 1 /rn 2 of the anisotropic dye film forming composition 2 was 1. The liquid crystallinity of the anisotropic dye film-forming composition 2 was confirmed by observing birefringence at 40° C. with a polarizing microscope equipped with a high-temperature stage. The dichroic ratio of the anisotropic pigment film 2 is determined. The results are shown in Table 1.

[比較例1] 使用0.22份的色素（III-1）代替0.23份的色素（II-1），除此以外，藉由與實施例1同樣的方式，獲得各向異性色素膜形成用組成物3及各向異性色素膜3。各向異性色素膜形成用組成物3的rn 1/rn 2為1。 各向異性色素膜形成用組成物3顯示出液晶性是根據藉由附帶高溫載台的偏光顯微鏡在40℃下觀察到雙折射來確認。 確定各向異性色素膜3的二色比。 將其結果示於表1。 [Comparative Example 1] In the same manner as in Example 1, except that 0.22 parts of the dye (III-1) was used instead of 0.23 parts of the dye (II-1), an anisotropic dye film-forming composition was obtained 3 and anisotropic pigment film 3. rn 1 /rn 2 of the anisotropic dye film forming composition 3 was 1. The liquid crystallinity of the anisotropic dye film-forming composition 3 was confirmed by observing birefringence at 40° C. with a polarizing microscope equipped with a high-temperature stage. The dichroic ratio of the anisotropic pigment film 3 is determined. The results are shown in Table 1.

[比較例2] 使用0.20份的色素（III-2）代替0.23份的色素（II-1），除此以外，藉由與實施例1同樣的方式，獲得各向異性色素膜形成用組成物4及各向異性色素膜4。各向異性色素膜形成用組成物4的rn 1/rn 2為1。 各向異性色素膜形成用組成物4顯示出液晶性是根據藉由附帶高溫載台的偏光顯微鏡在40℃下觀察到雙折射來確認。 確定各向異性色素膜4的二色比。 將其結果示於表1。 [Comparative Example 2] An anisotropic dye film-forming composition was obtained in the same manner as in Example 1 except that 0.20 parts of the dye (III-2) was used instead of 0.23 parts of the dye (II-1). 4 and anisotropic pigment film 4. The rn 1 /rn 2 of the anisotropic dye film forming composition 4 was 1. The composition 4 for forming an anisotropic dye film confirmed liquid crystallinity by observing birefringence at 40° C. with a polarizing microscope equipped with a high-temperature stage. The dichroic ratio of the anisotropic pigment film 4 is determined. The results are shown in Table 1.

[表1]    實施例1 實施例2 比較例1 比較例2 聚合性液晶化合物 I-1 I-1 I-1 I-1 色素 II-1 II-2 III-1 III-2 在350 nm～800 nm間顯示出 極大的二色比的波長（nm） 595 665 665 640 所述波長下的二色比 22 47 47 47 所使用的色素在環戊酮 中的溶解度（質量%） 2.9 2.0 0.3 0.2 [Table 1] Example 1 Example 2 Comparative example 1 Comparative example 2 polymerizable liquid crystal compound I-1 I-1 I-1 I-1 pigment II-1 II-2 III-1 III-2 Wavelength (nm) at which a large dichromatic ratio is exhibited between 350 nm and 800 nm 595 665 665 640 Dichroic ratio at stated wavelengths twenty two 47 47 47 Solubility of the pigment used in cyclopentanone (mass %) 2.9 2.0 0.3 0.2

根據表1，實施例1中使用的色素（II-1）、實施例2中使用的色素（II-2）在環戊酮中的溶解性高，且在所獲得的各向異性色素膜中顯示出良好的二色比。另一方面，在比較例1及比較例2中，示出雖然成為良好的二色比，但在環戊酮中的溶解性低的情況。According to Table 1, the pigment (II-1) used in Example 1 and the pigment (II-2) used in Example 2 have high solubility in cyclopentanone, and in the obtained anisotropic pigment film Shows a good two-color ratio. On the other hand, in Comparative Example 1 and Comparative Example 2, it was shown that the solubility in cyclopentanone was low although a good dichromatic ratio was obtained.

使用特定的形態對本發明進行了詳細說明，但對於本領域技術人員而言顯而易見的是，能夠在不脫離本發明的意圖與範圍的情況下進行各種變更。 本申請案基於2021年10月11日提出申請的日本專利申請案2021-166895，並藉由引用將其整體加以援用。 Although this invention was demonstrated in detail using the specific aspect, it is clear for those skilled in the art that various changes can be made without deviating from the intent and range of this invention. This application is based on Japanese Patent Application No. 2021-166895 filed on October 11, 2021, the entirety of which is incorporated by reference.

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Claims (16)

一種化合物，由下述式（1）表示， X-A 1-(N=N-A 2) n-N=N-A 3-Y      …（1） 式（1）中， -A 1-及-A 2-分別獨立地表示可具有取代基的含有一個以上S原子的多環式芳香族雜環的二價基、或者可具有取代基的芳香族烴環的二價基， -A 3-表示可具有取代基的芳香族烴環的二價基， -X表示一價有機基， -Y表示-N(-R y)-R x、-OC(=O)-R x、或者-C(=O)-O-R x， -R x表示可具有取代基的、具有分支的碳數3～15的烷基， -R y表示氫原子、或者可具有分支的碳數1～15的烷基，所述可具有分支的碳數1～15的烷基可具有取代基， 所述具有分支的碳數3～15的烷基及所述可具有分支的碳數1～15的烷基中所含的一個或者一個以上的亞甲基可為由-O-、-S-、-NH-、-N(-R z)-、-C(=O)-、-C(=O)-O-、-C(=O)-NH-、-CHF-、-CF 2-、-CHCl-、-CCl 2-、或者聚合性基取代的結構，-R z表示氫原子、或者可具有分支的碳數1～15的烷基， n表示1、2或者3， 在n為2或者3的情況下，多個-A 2-彼此可相同亦可不同， 其中，不存在-A 1-及-A 2-均為可具有取代基的芳香族烴環的二價基的情況。 A compound represented by the following formula (1), XA 1 -(N=NA 2 ) n -N=NA 3 -Y ... (1) In formula (1), -A 1 - and -A 2 - are independently represents a divalent group of a polycyclic aromatic heterocycle containing one or more S atoms that may have a substituent, or a divalent group of an aromatic hydrocarbon ring that may have a substituent, and -A 3 - represents a divalent group that may have a substituent A divalent group of an aromatic hydrocarbon ring, -X represents a monovalent organic group, -Y represents -N(-R y )-R x , -OC(=O)-R x , or -C(=O)-OR x , -R x represents an alkyl group with 3 to 15 carbons that may have a branch, and -R y represents a hydrogen atom, or an alkyl group with 1 to 15 carbons that may have a branch, and the alkyl group that may have a branch The alkyl group with 1 to 15 carbons may have a substituent, one or more of the branched alkyl group with 3 to 15 carbons and the branched alkyl group with 1 to 15 carbons may have substituents The methylene group can be composed of -O-, -S-, -NH-, -N(-R z )-, -C(=O)-, -C(=O)-O-, -C(= O) -NH-, -CHF-, -CF 2 -, -CHCl-, -CCl 2 -, or a structure substituted with a polymerizable group, -R z represents a hydrogen atom, or a carbon number of 1 to 15 that may have branches Alkyl group, n represents 1, 2 or 3, when n is 2 or 3, a plurality of -A 2 - may be the same or different from each other, wherein the absence of -A 1 - and -A 2 - are both optional In the case of a divalent group of an aromatic hydrocarbon ring having a substituent. 如請求項1所述的化合物，其中，在所述式（1）中，含有一個以上S原子的多環式芳香族雜環為苯並噻吩環、噻吩並吡咯環、噻吩並噻吩環、呋喃並噻唑環、噻吩並呋喃環、噻吩並噻唑環、苯並異噻唑環、或者苯並噻唑環。The compound as claimed in claim 1, wherein, in the formula (1), the polycyclic aromatic heterocycle containing more than one S atom is a benzothiophene ring, a thienopyrrole ring, a thienothiophene ring, a furan Thiazole ring, thienofuran ring, thienothiazole ring, benzisothiazole ring, or benzothiazole ring. 如請求項1或請求項2所述的化合物，其中，在所述式（1）中，-A 2-的至少一個為可具有取代基的含有一個以上S原子的多環式芳香族雜環的二價基。 The compound according to claim 1 or claim 2, wherein, in the formula (1), at least one of -A 2 - is a polycyclic aromatic heterocycle containing one or more S atoms that may have substituents of the divalent base. 如請求項1至請求項3中任一項所述的化合物，其中，在所述式（1）中，-Y為-N(-R y)-R x，-R x為可具有取代基的、具有分支的碳數3～15的烷基，-R y為氫原子、或者可具有分支的碳數1～15的烷基，所述可具有分支的碳數1～15的烷基可具有取代基，-R x及-R y的烷基中的碳數的合計為15以下。 The compound as described in any one of claim 1 to claim 3, wherein, in the formula (1), -Y is -N(-R y )-R x , and -R x may have a substituent An alkyl group with a branched carbon number of 3 to 15, -R y is a hydrogen atom, or an alkyl group with a branched carbon number of 1 to 15, and the branched alkyl group with a carbon number of 1 to 15 can be The total number of carbons in the alkyl groups having substituents -R x and -R y is 15 or less. 如請求項1至請求項4中任一項所述的化合物，其中，在所述式（1）中，-Y為-N(-R y)-R x，-R x為可具有取代基的、具有分支的碳數3～15的烷基，-R y為氫原子、或者不具有分支的碳數1～15的烷基，所述不具有分支的碳數1～15的烷基可具有取代基。 The compound as described in any one of claim 1 to claim 4, wherein, in the formula (1), -Y is -N(-R y )-R x , and -R x may have a substituent An alkyl group with a branched carbon number of 3 to 15, -R y is a hydrogen atom, or an alkyl group with a carbon number of 1 to 15 without branches, and the alkyl group with a carbon number of 1 to 15 without branches can be with substituents. 如請求項1至請求項5中任一項所述的化合物，其中，在所述式（1）中，-A 3-為可具有取代基的伸苯基。 The compound according to any one of claim 1 to claim 5, wherein, in the formula (1), -A 3 - is a phenylene group which may have a substituent. 如請求項1至請求項6中任一項所述的化合物，其中，在所述式（1）中，-A 1-為可具有取代基的伸苯基。 The compound according to any one of claim 1 to claim 6, wherein, in the formula (1), -A 1 - is a phenylene group which may have a substituent. 如請求項1至請求項7中任一項所述的化合物，其中，在所述式（1）中，-X為不具有分支的碳數3以上的烷基、烷氧基、烷基酯基、烷氧基羰基或者烷基硫基。The compound as described in any one of claim 1 to claim 7, wherein, in the formula (1), -X is an alkyl, alkoxy, or alkyl ester with no branching and more than 3 carbons group, alkoxycarbonyl or alkylthio group. 一種各向異性色素膜形成用組成物，含有如請求項1至請求項8中任一項所述的化合物以及聚合性液晶化合物。A composition for forming an anisotropic dye film, comprising the compound described in any one of claim 1 to claim 8 and a polymerizable liquid crystal compound. 如請求項9所述的各向異性色素膜形成用組成物，其中，所述聚合性液晶化合物是具有碳-碳三鍵的化合物。The anisotropic dye film-forming composition according to claim 9, wherein the polymerizable liquid crystal compound is a compound having a carbon-carbon triple bond. 如請求項9或請求項10所述的各向異性色素膜形成用組成物，其中，所述聚合性液晶化合物的質量濃度為所述式（1）所表示的化合物的質量濃度的一倍以上。The composition for forming anisotropic pigment film according to Claim 9 or Claim 10, wherein the mass concentration of the polymerizable liquid crystal compound is more than twice the mass concentration of the compound represented by the formula (1) . 如請求項9至請求項11中任一項所述的各向異性色素膜形成用組成物，更含有如下色素，所述色素在350 nm～800 nm的波長區域的吸收曲線中顯示出最大值的波長較所述式（1）所表示的化合物在350 nm～800 nm的波長區域的吸收曲線中顯示出最大值的波長更短。The composition for forming an anisotropic pigment film according to any one of claim 9 to claim 11, further comprising a pigment that exhibits a maximum value in an absorption curve in a wavelength region of 350 nm to 800 nm The wavelength is shorter than the wavelength at which the absorption curve of the compound represented by the formula (1) shows a maximum value in the wavelength region of 350 nm to 800 nm. 如請求項12所述的各向異性色素膜形成用組成物，其中，所述色素為偶氮色素。The composition for forming an anisotropic dye film according to claim 12, wherein the dye is an azo dye. 一種各向異性色素膜，使用如請求項9至請求項13中任一項所述的各向異性色素膜形成用組成物而形成。An anisotropic dye film formed using the composition for forming anisotropic dye film according to any one of claim 9 to claim 13. 一種光學元件，包括如請求項14所述的各向異性色素膜。An optical element comprising the anisotropic pigment film as claimed in claim 14. 一種各向異性色素膜的製造方法，具有將如請求項9至請求項13中任一項所述的各向異性色素膜形成用組成物塗佈於基板的步驟。A method for producing an anisotropic pigment film, comprising the step of applying the composition for forming an anisotropic pigment film according to any one of claim 9 to claim 13 on a substrate.
TW111138285A 2021-10-11 2022-10-07 Compound, composition for anisotropic dye film comprising said compound, anisotropic dye film, and optical element TW202317736A (en)

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