TWI795538B - Composition for preparing anisotropic dye film, anisotropic dye film, and optical device - Google Patents

Composition for preparing anisotropic dye film, anisotropic dye film, and optical device Download PDF

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TWI795538B
TWI795538B TW108109137A TW108109137A TWI795538B TW I795538 B TWI795538 B TW I795538B TW 108109137 A TW108109137 A TW 108109137A TW 108109137 A TW108109137 A TW 108109137A TW I795538 B TWI795538 B TW I795538B
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group
ring
liquid crystal
anisotropic dye
dye film
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TW108109137A
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TW201940672A (en
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大澤輝恒
藤田理惠子
西村政昭
秋山誠治
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日商三菱化學股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
    • C09K19/2007—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups
    • C09K19/2014—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers the chain containing -COO- or -OCO- groups containing additionally a linking group other than -COO- or -OCO-, e.g. -CH2-CH2-, -CH=CH-, -C=C-; containing at least one additional carbon atom in the chain containing -COO- or -OCO- groups, e.g. -(CH2)m-COO-(CH2)n-
    • 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
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/02—Disazo dyes
    • C09B35/037—Disazo dyes characterised by two coupling components of different types
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/08—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of polarising materials
    • 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
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal 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
    • 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

Abstract

The composition for preparing anisotropic dye film of the first embodiment of the present invention comprises a dye and a liquid crystal compound having a partial chemical structure represented by the formula (1).
-Cy-X2-C≡C-X- (1)
(In the formula, Cy represents a hydrocarbon ring group or a hetero ring group; -X- represents -C(=O)O-, -O(C=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-; -X2- represents a single bond, -C(=O)O-, -O(C=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-.)

Description

異向性色素膜形成用組成物、異向性色素膜及光學元件 Composition for forming anisotropic dye film, anisotropic dye film, and optical element

本發明係關於一種藉由塗佈液晶組成物而形成之異向性色素膜，尤其關於可用於調光元件、液晶元件(LCD)、及有機電致發光元件(OLED)之顯示元件所具備之偏光膜等的顯示高二色性的異向性色素膜形成用組成物及異向性色素膜暨光學元件。 The present invention relates to an anisotropic pigment film formed by coating a liquid crystal composition, in particular to the display elements that can be used in light-adjusting elements, liquid crystal elements (LCD), and organic electroluminescent elements (OLED) A composition for forming an anisotropic dye film exhibiting high dichroism, such as a polarizing film, and an anisotropic dye film and an optical element.

於LCD，為了控制顯示時之旋光性或雙折射性，而使用直線偏光膜及圓偏光膜。於OLED，亦為了防止亮處之外光之反射而使用圓偏光膜。 In LCD, linear polarizing film and circular polarizing film are used in order to control optical rotation or birefringence during display. In OLED, circular polarizing film is also used to prevent the reflection of light outside the bright place.

習知，作為此種偏光膜，已知有例如包含將聚乙烯醇(PVA)藉低濃度碘進行了染色的偏光膜(碘-PVA偏光膜)者(專利文獻1)。 Conventionally, such a polarizing film includes, for example, a polarizing film in which polyvinyl alcohol (PVA) is dyed with a low concentration of iodine (iodine-PVA polarizing film) (Patent Document 1).

又，塗佈含有色素之液晶組成物所形成之異向性色素膜亦已知具有作為偏光膜之機能(專利文獻2)。 Furthermore, it is also known that an anisotropic dye film formed by coating a liquid crystal composition containing a dye has a function as a polarizing film (Patent Document 2).

[先前技術文獻] [Prior Art Literature] [專利文獻] [Patent Document]

[專利文獻1]日本專利特開平1-105204號公報 [Patent Document 1] Japanese Patent Laid-Open No. 1-105204

[專利文獻2]日本專利特表2004-535483號公報 [Patent Document 2] Japanese Patent Application Publication No. 2004-535483

然而，如此作成低濃度之碘-PVA偏光板係視使用環境，而有碘昇華、或變質，造成色調改變的問題，或有發生因PVA之延伸被緩和而造成之翹曲等問題。 However, the iodine-PVA polarizing plate made in such a low concentration depends on the use environment, iodine sublimates or deteriorates, resulting in a change in color tone, or warping caused by the relaxation of the extension of PVA.

又，在塗佈含有色素之液晶組成物而形成之偏光膜方面，有無法得到較高之光吸收選擇性能、或若欲獲得較高之光吸收選擇性能則發生製程上之困難等問題。 In addition, in the aspect of the polarizing film formed by coating the liquid crystal composition containing the pigment, there are problems such as that it is impossible to obtain high light absorption selectivity, or if it is desired to obtain high light absorption selectivity, it will cause difficulties in the process.

於此種情況下，期望即使為薄膜仍具有較高之光吸收選擇性能的偏光膜。 In such a case, a polarizing film having high light absorption selectivity even if it is a thin film is desired.

然而，於異向性色素膜之製造過程中，在異向性色素膜形成用組成物對基板之塗佈、乾燥後視需要所進行之配向製程中，係在加熱至異向性色素膜形成用組成物之等向相表觀溫度以上後，進行冷卻而再次成為液晶相。又，在加熱至表現高流動性之液晶相(例如向列相等)的溫度後，進行冷卻。因此，等向相表觀溫度較高之異向性色素膜形成用組成物係於上述配向製程中，必須為更高溫，由色素或液晶化合物之穩定性、製程之處理容易度、能量消耗之觀點等而言不利。再者，於液晶化合物具有聚合性基的情況，由於上述再配向製程之高溫下的加熱，可能發生非刻意之熱聚合。又，視基材之耐熱溫度，有可使用之基材之選定自由度降低的情形。 However, in the manufacturing process of the anisotropic dye film, in the alignment process performed after coating and drying the substrate with the composition for forming the anisotropic dye film, heating until the anisotropic dye film is formed After the apparent temperature of the isotropic phase of the composition exceeds the apparent temperature, it is cooled to become a liquid crystal phase again. Moreover, it cools after heating to the temperature which expresses the liquid crystal phase (for example, nematic equivalence) of high fluidity. Therefore, the composition for forming an anisotropic pigment film with a higher apparent temperature of the isotropic phase must be at a higher temperature in the above-mentioned alignment process, due to the stability of the pigment or liquid crystal compound, the ease of handling of the process, and the energy consumption Viewpoints etc. are not good. Furthermore, when the liquid crystal compound has a polymerizable group, unintentional thermal polymerization may occur due to the heating at high temperature in the above-mentioned re-alignment process. Also, depending on the heat-resistant temperature of the base material, the degree of freedom in selecting the usable base material may decrease.

另一方面，為了提高由異向性色素膜形成用組成物所形成之異向性色素膜之二色性，可考慮使異向性色素膜形成用組成物所含有之液晶化合物分子之核的長軸與短軸的比率增大。 On the other hand, in order to improve the dichroism of the anisotropic dye film formed by the anisotropic dye film-forming composition, it may be considered to make the nucleus of the liquid crystal compound molecule contained in the anisotropic dye film-forming composition The ratio of the major axis to the minor axis increases.

然而，若增大液晶化合物分子之核，則液晶化合物之融點(固體及液體間之相轉移點)、或等向相表觀溫度(液晶及液體間之相轉 移點)有變高的傾向。 However, if the molecular nucleus of the liquid crystal compound is increased, the melting point (phase transition point between solid and liquid) or isotropic apparent temperature (phase transition point between liquid crystal and liquid) of the liquid crystal compound tends to increase .

亦即，若欲減低等向相表觀溫度，可考慮減小液晶化合物分子之核，但另一方面，由於減小液晶化合物分子之核，液晶化合物分子之核的長軸與短軸之比率變小，其結果，由異向性色素膜形成用組成物所形成之異向性色素膜之二色性減低。 That is, if you want to reduce the apparent temperature of the isotropic phase, you can consider reducing the nucleus of the liquid crystal compound molecule, but on the other hand, due to the reduction of the nucleus of the liquid crystal compound molecule, the ratio of the long axis to the short axis of the nucleus of the liquid crystal compound molecule As a result, the dichroism of the anisotropic dye film formed from the anisotropic dye film-forming composition decreases.

於此種狀況下，期望在較高地維持由異向性色素膜形成用組成物所形成之異向性色素膜之二色性之下，減低異向性色素膜形成用組成物之等向相表觀溫度。 Under such circumstances, it is desired to reduce the isotropic phase of the anisotropic dye film forming composition while maintaining high the dichroism of the anisotropic dye film formed from the anisotropic dye film forming composition. apparent temperature.

本發明之態樣(第一態樣)的目的在於提供一種異向性色素膜形成用組成物，其可在維持優越之光學性能、尤其是充分之二色比之下，實現較低之等向相表觀溫度。 The aspect (the first aspect) of the present invention aims to provide a composition for forming an anisotropic dye film which can achieve a lower etc. phase apparent temperature.

又，本發明之態樣(第一態樣)的目的在於提供一種異向性色素膜，其可在維持優越之光學性能、尤其是充分之二色比之下，依更低溫度形成。 Also, the aspect (first aspect) of the present invention aims to provide an anisotropic dye film which can be formed at a lower temperature while maintaining excellent optical properties, especially a sufficient dichromatic ratio.

又，本發明之態樣(第一態樣)的目的在於提供一種光學元件，其含有可在維持優越之光學性能、尤其是充分之二色比之下，依更低溫度形成的異向性色素膜。 Also, the aspect (first aspect) of the present invention aims to provide an optical element including anisotropy that can be formed at a lower temperature while maintaining superior optical performance, especially a sufficient dichromatic ratio. Pigment film.

再者，另一方面，為了使由異向性色素膜形成用組成物所形成之異向性色素膜之二色性提高，可考慮將異向性色素膜形成用組成物所含有之液晶化合物分子之核的長軸與短軸的比率增大，使液晶分子朝單軸方向配向。 Furthermore, on the other hand, in order to improve the dichroism of the anisotropic dye film formed from the anisotropic dye film-forming composition, it is conceivable to add the liquid crystal compound contained in the anisotropic dye film-forming composition to The ratio of the long axis to the short axis of the nucleus of the molecule increases, so that the liquid crystal molecules are aligned in a uniaxial direction.

然而，若增大液晶化合物分子之核，由於核係由苯環等芳香族環或環己烷環等之脂環式環所構成，故有因分子間相互作用而分子相對於由配向膜等所得之配向限制力之方向呈傾斜配向的傾向。 However, if the nucleus of the liquid crystal compound molecule is enlarged, since the nucleus is composed of an aromatic ring such as a benzene ring or an alicyclic ring such as a cyclohexane ring, there is a problem that the molecule is relatively different from an alignment film due to intermolecular interactions. The direction of the obtained alignment restricting force has a tendency of oblique alignment.

亦即，為了使液晶化合物分子朝單軸方向配向，可考慮減小液晶化合物分子之核，以減小分子間相互作用，而減小分子傾斜；另一方面，由於減小液晶化合物分子之核，液晶化合物分子之核之長軸與短軸的比率變小，其結果，使由異向性色素膜形成用組成物所形成之異向性色素膜之二色性減低。 That is, in order to align the molecules of the liquid crystal compound toward the uniaxial direction, it may be considered to reduce the nucleus of the molecule of the liquid crystal compound to reduce the intermolecular interaction and reduce the molecular tilt; on the other hand, due to the reduction of the nucleus of the molecule of the liquid crystal compound As a result, the ratio of the major axis to the minor axis of the nucleus of the liquid crystal compound molecule decreases, and as a result, the dichroism of the anisotropic dye film formed from the composition for forming an anisotropic dye film decreases.

於此種狀況下，期望開發出使異向性色素膜表現較高二色性的液晶化合物分子、與含有其之異向性色素膜形成用組成物。 Under such circumstances, it is desired to develop a liquid crystal compound molecule that expresses high dichroism in an anisotropic dye film, and a composition for forming an anisotropic dye film containing the same.

本發明之另一態樣(第二態樣)的目的在於提供一種異向性色素膜形成用組成物，其可實現優越之光學性能、尤其是充分之二色比。 Another aspect (second aspect) of the present invention aims to provide a composition for forming an anisotropic dye film capable of achieving superior optical performance, particularly a sufficient dichromatic ratio.

又，本發明之另一態樣(第二態樣)的目的在於提供一種異向性色素膜，其可實現優越之光學性能、尤其是充分之二色比。 Moreover, another aspect (2nd aspect) of this invention aims at providing the anisotropic dye film which can realize the outstanding optical performance, especially sufficient dichromatic ratio.

又，本發明之另一態樣(第二態樣)的目的在於提供一種光學元件，其含有可實現優越之光學性能、尤其是充分之二色比的異向性色素膜。 Moreover, another aspect (2nd aspect) of this invention aims at providing the optical element containing the anisotropic dye film which can realize excellent optical performance, especially sufficient dichromatic ratio.

本案發明人等發現，於含有色素及液晶化合物的異向性色素膜形成用組成物中，藉由使用具有特定構造之液晶化合物，可解決上述課題。 The present inventors found that the above-mentioned problems can be solved by using a liquid crystal compound having a specific structure in a composition for forming an anisotropic dye film containing a dye and a liquid crystal compound.

亦即，本發明之第一態樣係以以下為要旨。 That is, the first aspect of the present invention makes the following gist.

[1]一種異向性色素膜形成用組成物，係含有色素及液晶化合物者， 上述液晶化合物係含有具式(1)所示部分構造之液晶化合物；-Cy-X2-C≡C-X-‧‧‧(1)(式中，Cy表示烴環基或雜環基；-X-表示-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、-CH2O-、-OCH2-、-CH2S-或-SCH2-；-X2-表示單鍵、-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、-CH2O-、-OCH2-、-CH2S-或-SCH2-)。 [1] A composition for forming an anisotropic pigment film, which contains a pigment and a liquid crystal compound, and the above liquid crystal compound contains a liquid crystal compound with a partial structure shown in formula (1); -Cy-X2-C≡CX-‧ ‧‧(1) (In the formula, Cy represents hydrocarbon ring group or heterocyclic group; -X- 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 -; -X2- represents 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)-, -CH2O- , -OCH2- , -CH2S- or -SCH2- ).

[2]如[1]之異向性色素膜形成用組成物，其中，-X-為-C(=O)O-、-OC(=O)-、-CH2CH2-、-CH2O-或-OCH2-。 [2] The anisotropic dye film-forming composition according to [1], wherein -X- is -C(=O)O-, -OC(=O)-, -CH 2 CH 2 -, -CH 2 O- or -OCH 2 -.

[3]如[1]或[2]之異向性色素膜形成用組成物，其中，Cy為烴環基，-X2-為單鍵。 [3] The anisotropic dye film-forming composition according to [1] or [2], wherein Cy is a hydrocarbon ring group, and -X2- is a single bond.

[4]如[1]至[3]中任一項之異向性色素膜形成用組成物，其中，上述液晶化合物為式(2)所示液晶化合物。R1-A1-Y1-A2-Y2-A3-R2‧‧‧(2)(式中，R1及R2分別獨立表示鏈狀有機基；A1及A3分別獨立表示上述式(1)所示部分構造、2價有機基或單鍵；A2表示上述式(1)所示部分構造或2價有機基；-Y1-及-Y2-分別獨立表示單鍵、-C(=O)O-、-OC(=O)-、 -C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、-CH2O-、-OCH2-、-CH2S-或-SCH2-；A1及A3之一者為上述式(1)所示部分構造或2價有機基；A1、A2及A3中之至少一者為上述式(1)所示部分構造)。 [4] The anisotropic dye film-forming composition according to any one of [1] to [3], wherein the liquid crystal compound is a liquid crystal compound represented by formula (2). R1-A1-Y1-A2-Y2-A3-R2‧‧‧(2) (In the formula, R1 and R2 independently represent a chain organic group; A1 and A3 independently represent the partial structure shown in the above formula (1), A divalent organic group or a single bond; A2 represents a partial structure or a divalent organic group shown in the above formula (1); -Y1- and -Y2- 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(=O)NH-, -NHC(=O)-, -CH 2 O-, -OCH 2 -, -CH 2 S- or -SCH 2 -; one of A1 and A3 is the above formula (1) the partial structure or divalent organic group; at least one of A1, A2 and A3 is the partial structure shown in the above formula (1)).

[5]如[4]之異向性色素膜形成用組成物，其中，A1、A2及A3中之一者為上述式(1)所示部分構造，Cy為烴環基，-X2-為單鍵；其以外之二者分別獨立為2價有機基，上述2價有機基為烴環基。 [5] The anisotropic pigment film-forming composition according to [4], wherein one of A1, A2, and A3 has a partial structure represented by the above formula (1), Cy is a hydrocarbon ring group, and -X2- is a single bond; the other two are independently divalent organic groups, and the above-mentioned divalent organic groups are hydrocarbon ring groups.

[6]如[5]之異向性色素膜形成用組成物，其中，上述烴環基為1,4-伸苯基或環己烷-1,4-二基。 [6] The anisotropic dye film-forming composition according to [5], wherein the hydrocarbon ring group is a 1,4-phenylene group or a cyclohexane-1,4-diyl group.

[7]如[4]至[6]中任一項之異向性色素膜形成用組成物，其中，-Y1-及-Y2-分別獨立為單鍵、-C(=O)O-、-OC(=O)-、-CH2CH2-、-CH2O-或-OCH2-；-X-為-C(=O)O-、-OC(=O)-、-CH2CH2-、-CH2O-或-OCH2-。 [7] The anisotropic dye film-forming composition according to any one of [4] to [6], wherein -Y1- and -Y2- are each independently a single bond, -C(=O)O-, -OC(=O)-, -CH 2 CH 2 -, -CH 2 O- or -OCH 2 -; -X- is -C(=O)O-, -OC(=O)-, -CH 2 CH2- , -CH2O- or -OCH2- .

[8]如[4]至[7]中任一項之異向性色素膜形成用組成物，其中，Cy為1,4-伸苯基。 [8] The composition for forming an anisotropic dye film according to any one of [4] to [7], wherein Cy is a 1,4-phenylene group.

[9]如[4]至[8]中任一項之異向性色素膜形成用組成物，其中，A1及A3之一者為環己烷-1,4-二基。 [9] The anisotropic dye film-forming composition according to any one of [4] to [8], wherein one of A1 and A3 is cyclohexane-1,4-diyl.

[10]如[4]至[9]中任一項之異向性色素膜形成用組成物，其中，A1及A3之一者為上述式(1)所示部分構造；另一者為環己烷-1,4-二基。 [10] The composition for forming an anisotropic dye film according to any one of [4] to [9], wherein one of A1 and A3 has a partial structure represented by the above formula (1); the other is a ring Hexane-1,4-diyl.

[11]一種異向性色素膜，係使用[1]至[10]中任一項之異向性色素膜形成用組成物所形成。 [11] An anisotropic dye film formed using the composition for forming an anisotropic dye film according to any one of [1] to [10].

[12]一種光學元件，係含有[11]之異向性色素膜。 [12] An optical element comprising the anisotropic pigment film of [11].

又，本發明之第二態樣係以以下為要旨。 Moreover, the 2nd aspect of this invention makes the following summary.

<1>一種異向性色素膜形成用組成物，係含有色素及液晶化合物者，上述液晶化合物係含有具式(B1)所示部分構造之液晶化合物；-CyH-Z1-E1-C≡C-E2-‧‧‧(B1)(式中，CyH表示經取代或無取代之非芳香族烴環基；E1及E2分別獨立表示烴環基或雜環基；-Z1-表示-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH=CH-、-C≡C-、-C(=O)NH-、-NHC(=O)-、-CH2O-、-OCH2-、-CH2S-或-SCH2-)。 <1> A composition for forming an anisotropic pigment film, which contains a pigment and a liquid crystal compound, and the above liquid crystal compound contains a liquid crystal compound with a partial structure shown in formula (B1); -CyH-Z1-E1-C≡C -E2-‧‧‧(B1)(In the formula, CyH represents a substituted or unsubstituted non-aromatic hydrocarbon ring group; E1 and E2 independently represent a hydrocarbon ring group or a heterocyclic group; -Z1- represents -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 -).

<2>如<1>之異向性色素膜形成用組成物，其中，上述液晶化合物為式(B2)所示液晶化合物；T1-CyH-Z1-E1-C≡C-E2-Z2-E3-T2‧‧‧(B2)(式中，CyH、E1、E2及-Z1-係分別與上述式(B1)中之定義相同；T1及T2分別獨立表示鏈狀有機基；E3表示2價有機基或單鍵；-Z2-表示單鍵、-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH=CH-、-C≡C-、-C(=O)NH-、-NHC(=O)-、-CH2O-、-OCH2-、-CH2S-或-SCH2-)。 <2> The anisotropic dye film-forming composition according to <1>, wherein the liquid crystal compound is a liquid crystal compound represented by the formula (B2); T1-CyH-Z1-E1-C≡C-E2-Z2-E3 -T2‧‧‧(B2) (In the formula, CyH, E1, E2 and -Z1- are respectively the same as the definitions in the above formula (B1); T1 and T2 independently represent a chain organic group; E3 represents a divalent organic group or single bond; -Z2- means 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- ).

<3>如<1>或<2>之異向性色素膜形成用組成物，其中，-Z1-為-C(=O)O-、-OC(=O)-、-CH2CH2-、-CH2O-或-OCH2-。 <3> The anisotropic dye film-forming composition according to <1> or <2>, wherein -Z1- is -C(=O)O-, -OC(=O)-, -CH 2 CH 2 -, -CH2O- or -OCH2- .

<4>如<1>至<3>中任一項之異向性色素膜形成用組成物，其中，E1或E2為烴環基。 <4> The anisotropic dye film-forming composition according to any one of <1> to <3>, wherein E1 or E2 is a hydrocarbon ring group.

<5>如<4>之異向性色素膜形成用組成物，其中，上述烴環基為伸苯基或環己烷二基。 <5> The anisotropic dye film-forming composition according to <4>, wherein the hydrocarbon ring group is a phenylene group or a cyclohexanediyl group.

<6>如<2>至<5>中任一項之異向性色素膜形成用組成物，其中，E3為烴環基、雜環基或單鍵。 <6> The anisotropic dye film-forming composition according to any one of <2> to <5>, wherein E3 is a hydrocarbon ring group, a heterocyclic group, or a single bond.

<7>如<6>之異向性色素膜形成用組成物，其中，E3為伸苯基、環己烷二基或單鍵。 <7> The anisotropic dye film-forming composition according to <6>, wherein E3 is a phenylene group, a cyclohexanediyl group, or a single bond.

<8>如<2>至<7>中任一項之異向性色素膜形成用組成物，其中，-Z2-為單鍵、-C(=O)O-、-OC(=O)-、-CH2CH2-、-CH2O-或-OCH2-。 <8> The anisotropic dye film-forming composition according to any one of <2> to <7>, wherein -Z2- is a single bond, -C(=O)O-, -OC(=O) - , -CH2CH2- , -CH2O- or -OCH2- .

<9>一種異向性色素膜，係使用<1>至<8>中任一項之異向性色素膜形成用組成物所形成。 <9> An anisotropic dye film formed using the composition for forming an anisotropic dye film according to any one of <1> to <8>.

<10>一種光學元件，係含有<9>之異向性色素膜。 <10> An optical element comprising the anisotropic pigment film of <9>.

本發明之第一態樣之異向性色素膜形成用組成物可在維持優越之光學性能、尤其是充分之二色比之下，實現較低之等向相表觀溫度。 The composition for forming an anisotropic dye film according to the first aspect of the present invention can realize a lower apparent temperature of the isotropic phase while maintaining excellent optical properties, especially a sufficient dichroic ratio.

本發明之第一態樣之異向性色素膜由於使用本發明之異向性色素膜形成用組成物所形成，故可在維持優越之光學性能、尤其是充分之二色比之下，依更低溫度形成。 The anisotropic dye film of the first aspect of the present invention is formed by using the composition for forming an anisotropic dye film of the present invention, so it can maintain excellent optical performance, especially a sufficient dichromatic ratio, according to formed at lower temperatures.

本發明之第一態樣之光學元件由於含有本發明之異向性色素膜，故可含有可在維持優越之光學性能、尤其是充分之二色比之下，依更低溫度形成的異向性色素膜。 The optical element of the first aspect of the present invention contains the anisotropic pigment film of the present invention, so it can contain the anisotropy that can be formed at a lower temperature while maintaining excellent optical performance, especially a sufficient dichromatic ratio. Sexual pigment film.

本發明之第二態樣之異向性色素膜形成用組成物可實現優越之光學性能、尤其是充分之二色比。 The composition for forming an anisotropic dye film according to the second aspect of the present invention can realize excellent optical performance, especially sufficient dichromatic ratio.

本發明之第二態樣之異向性色素膜由於使用本發明之異向性色素膜形成用組成物所形成，故可實現優越之光學性能、尤其是充分之二色比。 Since the anisotropic dye film of the second aspect of the present invention is formed using the composition for forming an anisotropic dye film of the present invention, excellent optical performance, particularly sufficient dichromatic ratio can be realized.

本發明之第二態樣之光學元件由於含有本發明之異向性色素膜，故可實現優越之光學性能、尤其是充分之二色比。 The optical element of the second aspect of the present invention can realize superior optical performance, especially sufficient dichromatic ratio, because it contains the anisotropic dye film of the present invention.

以下，具體說明本發明之實施形態，但本發明並不限定於以下之實施形態，可於其主旨之範圍內進行各種變更並實施。 Hereinafter, although the embodiment of this invention is demonstrated concretely, this invention is not limited to the following embodiment, Various changes can be made and implemented within the range of the summary.

本發明中所謂異向性色素膜，係指於選自異向性色素膜之厚度方向及任意之正交之面內2個方向之立體座標系統的合計3個方向中，任意2個方向上之電磁學性質具有異向性的色素膜。作為電磁學性質，可舉例如吸收、折射等光學性質、電阻、電容等電性質。 The so-called anisotropic pigment film in the present invention refers to any two directions in the total three directions of the three-dimensional coordinate system selected from the thickness direction of the anisotropic pigment film and any two directions in the plane perpendicular to the plane. The electromagnetic property has anisotropic pigment film. Examples of electromagnetic properties include optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance.

作為具有吸收、折射等光學異向性之膜，可舉例如直線偏光膜、圓偏光膜等偏光膜、相位差膜、導電異向性色素膜。本發明之異向性色素膜較佳係使用作為偏光膜、或導電異向性色素膜，更佳為用於偏光膜。 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 in a polarizing film.

[異向性色素膜形成用組成物] [Composition for forming anisotropic pigment film]

本發明之異向性色素膜形成用組成物係含有色素及液晶化合 物。 The anisotropic dye film-forming composition of the present invention contains a dye and a liquid crystal compound.

本發明之異向性色素膜形成用組成物若為不引起相分離之狀態，則可為溶液、液晶、或分散狀態，作為異向性色素膜形成用組成物，由容易塗佈至基材的觀點而言，較佳為溶液。另一方面，由異向性色素膜形成用組成物去除了溶劑的固形份成分，如後述般由在基板上使其配向的觀點而言，較佳係任意溫度下呈液晶相之狀態。 The anisotropic dye film-forming composition of the present invention may be in a solution, liquid crystal, or dispersed state as long as it is in a state where no phase separation occurs. From the point of view, it is preferably a solution. On the other hand, the solid content of the composition for forming an anisotropic dye film from which the solvent has been removed is preferably in a liquid crystal phase state at any temperature from the viewpoint of alignment on the substrate as described later.

尚且，本發明中，所謂液晶相之狀態，具體而言係如「液晶之基礎與應用」(松本正一、角田市良著；1991年)之1~16頁所記載般，為顯示液體與結晶之雙方或中間之性質的液晶狀態，有如向列相、層列相、膽固醇相、或盤狀相。 Moreover, in the present invention, the state of the so-called liquid crystal phase is specifically as described in pages 1 to 16 of "Basics and Applications of Liquid Crystals" (Shoichi Matsumoto, Yoshikazu Kakuda; 1991), which is used to display liquid and liquid crystal phases. The liquid crystal state of the two sides or the middle of the crystal, such as nematic phase, smectic phase, cholesteric phase, or discotic phase.

(色素) (pigment)

本發明中所謂色素，係指吸收可見光區域(380nm~780nm)之波長之至少一部分的物質或化合物。 The term "pigment" in the present invention refers to a substance or compound that absorbs at least a part of the wavelength in the visible light region (380nm~780nm).

作為可使用於本發明之色素，可舉例如二色性色素。尚且，所謂二色性色素，係指分子之長軸方向之吸光度、與短軸方向之吸光度具有相異性質的色素。又，色素可為具有液晶性之色素，亦可不具有液晶性。又，所謂具有液晶性，係指於任意溫度下表現液晶相。 As a dye which can be used in this invention, a dichroic dye is mentioned, for example. Furthermore, the so-called dichroic pigment refers to a pigment whose absorbance in the long-axis direction of the molecule is different from that in the short-axis direction. In addition, the dye may have liquid crystallinity or may not have liquid crystallinity. In addition, "having liquid crystallinity" means expressing a liquid crystal phase at any temperature.

作為本發明之異向性色素膜形成用組成物所含有的色素，可舉例如偶氮系色素、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、酞青素系色素、靛藍系色素、縮合多環系色素(包括苝系色素、

Figure 108109137-A0101-12-0010-57
系色素、吖啶系色素等)等。此等色素中，偶氮系色素由於分子長短軸比較大、於異向性色 素膜中可獲得較高之分子配列，故較佳。 Examples of the dye contained in the anisotropic dye film-forming composition of the present invention include azo-based dyes, quinone-based dyes (including naphthoquinone-based dyes, anthraquinone-based dyes, etc.), stilbene-based dyes, floral dyes, etc. Cyan pigments, phthalocyanine pigments, indigo pigments, condensed polycyclic pigments (including perylene pigments,
Figure 108109137-A0101-12-0010-57
pigments, acridine pigments, etc.), etc. Among these pigments, azo-based pigments are preferred due to their large ratio of molecular length and short axis, and higher molecular arrangement in the anisotropic pigment film.

所謂偶氮系色素，係指具有至少1個以上之偶氮基(-N=N-)的色素，由對溶劑之溶解性、與液晶化合物之相溶性、色調及製造容易性的觀點而言，其一分子中之偶氮基之數量較佳為1以上、更佳為2以上，且較佳為6以下、更佳為4以下、再更佳為3以下。 The so-called azo-based pigments refer to pigments 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, still more preferably 3 or less.

作為偶氮系色素，可舉例如式(A)所示化合物。 As an azo dye, the compound represented by formula (A) is mentioned, for example.

R11-D1-N=N-(D2-N=N)p-D3-R12‧‧‧(A) R11-D1-N=N-(D2-N=N) p -D3-R12‧‧‧(A)

式(A)中，D1、D2及D3分別獨立表示亦可具有取代基之伸苯基、亦可具有取代基之伸萘基、或亦可具有取代基之2價雜環基；p表示0~4之整數；在p為2以上之整數時，複數之D2彼此可為相同或相異；R11及R12表示相同或分別相異之1價有機基。 In formula (A), D1, D2, and D3 independently represent a phenylene group that may also have a substituent, a naphthylenyl group that may also have a substituent, or a divalent heterocyclic group that may also have a substituent; p represents 0 An integer of ~4; when p is an integer of 2 or more, the plural D2 may be the same or different from each other; R11 and R12 represent the same or different monovalent organic groups.

D1、D2及D3分別獨立表示亦可具有取代基之伸苯基、亦可具有取代基之伸萘基、或亦可具有取代基之2價雜環基。 D1, D2, and D3 each independently represent a phenylene group which may also have a substituent, a naphthylene group which may also have a substituent, or a divalent heterocyclic group which may also have a substituent.

作為伸苯基之取代位置，1,4-伸苯基由於分子之直線性高，故較佳。 As the substitution position of the phenylene group, a 1,4-phenylene group is preferable because the linearity of the molecule is high.

作為伸萘基之取代位置，1,4-伸萘基或2,6-伸萘基由於分子之直線性高，故較佳。 As the substitution position of naphthylene, 1,4-naphthylene or 2,6-naphthylene is preferable because the linearity of the molecule is high.

作為2價雜環基，形成環之碳數較佳為3以上且14以下、更佳為10以下。特佳係單環或2環式之雜環基。 As a divalent heterocyclic group, the number of carbon atoms forming the ring is preferably 3 or more and 14 or less, more preferably 10 or less. Particularly preferred is a monocyclic or bicyclic heterocyclic group.

作為構成2價雜環基之碳以外的原子，可舉例如選自氮原子、硫原子及氧原子之至少一者。在雜環基具有複數個碳以外之構成環的原子時，其等可為相同或相異。 As atoms other than carbon constituting the divalent heterocyclic group, at least one member selected from a nitrogen atom, a sulfur atom, and an oxygen atom may be mentioned, for example. When the heterocyclic group has atoms constituting a ring other than a plurality of carbons, they may be the same or different.

具體而言可舉例如吡啶二基、喹啉二基、異喹啉二基、噻唑二基、苯并噻唑二基、噻吩并噻唑二基、噻吩并噻吩二基、苯并咪唑啶酮二基、苯并呋喃二基、酞醯亞胺二基、

Figure 108109137-A0101-12-0012-58
唑二基、苯并
Figure 108109137-A0101-12-0012-59
唑二基等。 Specifically, for example, pyridinediyl, quinolinediyl, isoquinolinediyl, thiazolyldiyl, benzothiazolediyl, thienothiazolyldiyl, thienothiophenediyl, benzimidazolidinonediyl , benzofuran diyl, phthalimide diyl,
Figure 108109137-A0101-12-0012-58
Azodiyl, benzo
Figure 108109137-A0101-12-0012-59
Azodiyl, etc.

作為D1、D2及D3中之伸苯基、伸萘基及2價雜環基所任意具有的取代基，可舉例如：碳數1~4之烷基；甲氧基、乙氧基及丁氧基等之碳數1~4之烷氧基；三氟甲基等碳數1~4之氟化烷基；氰基；硝基。羥基；鹵原子；胺基、二乙基胺基及吡咯啶基等取代或無取代胺基(所謂取代胺基，係指具有1個或2個碳數1~4之烷基的胺基，或2個取代烷基彼此鍵結形成碳數2~8之烷二基的胺基。無取代胺基為-NH2。又，作為碳數1~4之烷基，可舉例如甲基、乙基及丁基等。作為碳數2~8之烷二基，可舉例如伸乙基、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)。 As the optional substituents of phenylene, naphthylene, and divalent heterocyclic groups in D1, D2, and D3, examples include: alkyl groups with 1 to 4 carbon atoms; methoxy groups, ethoxy groups, and butyl groups. Alkoxy with 1 to 4 carbons such as oxy; fluorinated alkyl with 1 to 4 carbons such as trifluoromethyl; cyano; nitro. Hydroxyl; halogen atom; substituted or unsubstituted amine groups such as amine group, diethylamino group and pyrrolidinyl group (the so-called substituted amine group refers to the amine group having 1 or 2 alkyl groups with 1 to 4 carbon numbers, Or two substituted alkyl groups are bonded to each other to form an amino group of an alkanediyl group having 2 to 8 carbon atoms. The unsubstituted amino group is -NH 2 . Also, as an alkyl group having 1 to 4 carbon atoms, for example, methyl, Ethyl, butyl, etc. Examples of alkanediyl having 2 to 8 carbon atoms include ethylidene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4 -diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc.).

由分子直線性較高的觀點而言，較佳為無取代，或在取代時，係由甲基、甲氧基、羥基、氟原子、氯原子、二甲基胺基、吡咯啶基、哌啶基所取代者。 From the point of view of high molecular linearity, it is preferably unsubstituted, or when substituted, it is composed of methyl, methoxy, hydroxyl, fluorine atom, chlorine atom, dimethylamino, pyrrolidinyl, piperidine Substituted by pyridyl.

p表示0~4之整數。由對溶劑之溶解性、與液晶化合物間之相溶性、色調及製造容易性的觀點而言，較佳為1以上，且較佳為4以下、更佳為3以下。 p represents an integer from 0 to 4. From the viewpoints of solubility in solvents, compatibility with liquid crystal compounds, color tone, and ease of production, it is preferably 1 or more, and is preferably 4 or less, more preferably 3 or less.

R11及R12表示相同或分別相異之1價有機基。 R11 and R12 represent the same or respectively different monovalent organic groups.

作為R11及R12中之1價有機基，可舉例如：氫原子、亦可具有分枝之碳數1~20之烷基；脂環式之碳數1~20之烷基；甲氧基、乙氧基及丁氧基等亦可具有分枝之碳數1~20之烷氧基；三氟甲基 等亦可具有分枝之碳數1~20之氟化烷基；氰基；硝基、羥基、鹵原子；胺基、二乙基胺基及吡咯啶基等取代或無取代胺基(所謂取代胺基，係指具有1個或2個亦可具有分枝之碳數1~20之烷基的胺基，或2個取代烷基彼此鍵結形成碳數2~20之烷二基的胺基。無取代胺基為-NH2。又，作為碳數1~20之烷基，可舉例如甲基、乙基及丁基等。作為碳數2~20之烷二基，可舉例如伸乙基、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)；羧基；丁氧基羧基等亦可具有分枝之碳數1~20之烷基氧基羰基；乙烯基等亦可具有分枝之碳數1~20之烯基；2-(4-丁基苯基)乙烯基等烷基苯基烯基；胺甲醯基；丁基胺甲醯基等亦可具有分枝之碳數1~20之烷基胺甲醯基；胺磺醯基；丁基胺磺醯基等亦可具有分枝之碳數1~20之烷基胺磺醯基；丁基羰基胺基等亦可具有分枝之碳數1~20之醯基胺基；丁基羰基氧基等亦可具有分枝之碳數1~20之醯基氧基；氫硫基；丁基氫硫基等碳數1~20之烷基氫硫基；具有後述之液晶化合物中之R1及R2之聚合性基的鏈狀有機基。 As the monovalent organic group in R11 and R12, for example: a hydrogen atom, an alkyl group with 1 to 20 carbon atoms that may also have branches; an alicyclic alkyl group with 1 to 20 carbon atoms; a methoxy group, Ethoxy and butoxy can also have branched alkoxy groups with 1-20 carbons; trifluoromethyl can also have branched fluorinated alkyl groups with 1-20 carbons; cyano; nitro substituted or unsubstituted amino groups such as amino groups, diethylamino groups, and pyrrolidinyl groups (the so-called substituted amino groups refer to those with 1 or 2 carbon atoms that can also have branches. The amino group of an alkyl group of 20, or the amino group of an alkanediyl group with 2 to 20 carbon atoms bonded by two substituted alkyl groups. The unsubstituted amino group is -NH 2 . Also, as an alkane group with a carbon number of 1 to 20 For example, methyl group, ethyl group and butyl group, etc. As the alkanediyl group with 2 to 20 carbon atoms, for example, ethylidene group, propane-1,3-diyl group, butane-1,3-diyl group, etc. base, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl group, etc.); carboxyl group; butoxycarboxyl group, etc. may also have a branched alkyloxycarbonyl group with 1 to 20 carbon atoms; vinyl group, etc. may also have a branched alkenyl group with 1 to 20 carbon atoms; 2-( 4-butylphenyl)vinyl and other alkylphenylalkenyl groups; aminoformyl; butylaminoformyl, etc. may also have branched alkylaminoformyl groups with 1 to 20 carbon atoms; sulfamic acid Acyl group; butyl sulfamoyl group, etc. can also have branched alkyl sulfamoyl group with 1-20 carbons; butylcarbonylamine group, etc. can also have branched acylamine with 1-20 carbons butyl carbonyloxy, etc. may also have branched acyloxy groups with 1 to 20 carbons; mercapto; butyl mercapto and other alkyl mercaptos with 1 to 20 carbons; A chain organic group of a polymerizable group of R1 and R2 in a liquid crystal compound.

作為R11及R12，可舉例如氫原子、鏈狀基、脂肪族有機基(「脂肪族有機基」係包括鏈狀者及環狀者)、碳之一部分經氮及/或氧取代之脂肪族有機基(「碳之一部分經氮及/或氧取代之脂肪族有機基」係包括鏈狀者及環狀者，包括脂肪族有機基之一部分甲基分別被取代為羥基、側氧基(=O)、胺基、亞胺基等者)等，作為某態樣，較佳為氫原子、鏈狀基，作為其他態樣，較佳為氫原子、脂肪族有機基，進而作為其他態樣較佳為氫原子、碳之一部分經氮及/或氧取代的脂肪族有機基。 Examples of R11 and R12 include a hydrogen atom, a chain group, an aliphatic organic group ("aliphatic organic group" includes a chain and a ring), and an aliphatic group in which a part of the carbon is substituted with nitrogen and/or oxygen. Organic groups ("aliphatic organic groups with a part of carbon substituted by nitrogen and/or oxygen" include chains and rings, including aliphatic organic groups in which a part of the methyl group is substituted with hydroxyl, pendant oxygen (= (O), amine group, imino group, etc.), etc., as a certain aspect, preferably a hydrogen atom, a chain group, as another aspect, preferably a hydrogen atom, an aliphatic organic group, and then as another aspect Preferably, it is an aliphatic organic group in which a hydrogen atom or a part of carbon is substituted with nitrogen and/or oxygen.

作為鏈狀基，可舉例如上述亦可具有分枝之碳數1~20之烷基；亦可具有分枝之碳數1~20之烷氧基；亦可具有分枝之碳數1~20之氟化烷基；取代或無取代胺基(所謂取代胺基，係指具有1個或2個亦可具有分枝之碳數1~20之烷基的胺基。無取代胺基為-NH2。)；羧基；亦可具有分枝之碳數1~20之烷基氧基羰基；胺甲醯基；亦可具有分枝之碳數1~20之烷基胺甲醯基；胺磺醯基；亦可具有分枝之碳數1~20之烷基胺磺醯基；亦可具有分枝之碳數1~20之醯基胺基；亦可具有分枝之碳數1~20之醯基氧基；氫硫基；碳數1~20之烷基氫硫基等。 As the chain group, for example, the above-mentioned alkyl group with 1 to 20 carbon atoms may be branched; an alkoxy group with 1 to 20 carbon atoms may be branched; 20 fluorinated alkyl group; substituted or unsubstituted amino group (the so-called substituted amino group refers to an amino group that has one or two alkyl groups with 1 to 20 carbon atoms that may also have branches. The unsubstituted amino group is -NH 2 .); carboxyl; may also have a branched alkyloxycarbonyl group with 1 to 20 carbons; carbamoyl group; may also have a branched alkylcarbamoyl group with 1 to 20 carbons; Aminosulfonyl; may also have a branched alkylaminosulfonyl group with 1-20 carbons; may also have a branched acylamino group with 1-20 carbons; may also have a branched carbon number 1 ~20 acyloxy; mercapto; alkyl mercapto with 1~20 carbons, etc.

作為脂肪族有機基，可舉例如上述亦可具有分枝之碳數1~20之烷基、脂環式之碳數1~20之烷基等。 Examples of the aliphatic organic group include the above-mentioned alkyl group having 1 to 20 carbon atoms which may have a branch, the alicyclic alkyl group having 1 to 20 carbon atoms, and the like.

作為碳之一部分經氮及/或氧取代之脂肪族有機基，可舉例如上述亦可具有分枝之碳數1~20之烷氧基；取代或無取代胺基(所謂取代胺基，係指具有1個或2個亦可具有分枝之碳數1~20之烷基的胺基，或2個取代烷基彼此鍵結形成碳數2~20之烷二基的胺基。無取代胺基為-NH2。又，作為碳數1~20之烷基，可舉例如甲基、乙基及丁基等。作為碳數2~20之烷二基，可舉例如伸乙基、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)；羧基；亦可具有分枝之碳數1~20之烷基氧基羰基；胺甲醯基；亦可具有分枝之碳數1~20之烷基胺甲醯基；亦可具有分枝之碳數1~20之醯基胺基；亦可具有分枝之碳數1~20之醯基氧基等。 As an aliphatic organic group with a part of carbon substituted by nitrogen and/or oxygen, there may be, for example, an alkoxy group with 1 to 20 carbons which may have branches; substituted or unsubstituted amino groups (so-called substituted amino groups are Refers to an amino group with one or two alkyl groups with 1 to 20 carbon atoms that may also have branches, or an amino group with two substituted alkyl groups bonded to each other to form an alkanediyl group with 2 to 20 carbon atoms. Unsubstituted The amino group is -NH 2 . In addition, examples of alkyl groups having 1 to 20 carbons include methyl, ethyl, and butyl groups. Examples of alkanediyl groups having 2 to 20 carbons include ethylidene, Propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane alkane-1,7-diyl, octane-1,8-diyl, etc.); carboxyl; may also have a branched alkyloxycarbonyl group with 1 to 20 carbon atoms; carbamoyl; may also have branched Alkylcarbamoyl groups with 1-20 carbon atoms in the branches; acylamino groups with 1-20 carbon atoms in the branches; acyloxy groups with 1-20 carbon atoms in the branches, etc.

作為R11及R12，由分子直線性較高的觀點而言，較佳係分別獨立的氫原子、或由丁基、戊基、己基、庚基、辛基等碳 數1~10之烷基；丁氧基、戊基氧基、己基氧基、庚基氧基、辛基氧基等碳數1~10之烷氧基、二乙基胺基、吡咯啶基及哌啶基所取代。又，後述之具有第一態樣之液晶化合物中之R1及R2之聚合性基的鏈狀有機基中的較佳者、具有第二態樣之液晶化合物中之T1及T2之聚合性基的鏈狀有機基中的較佳者亦為較佳。 As R11 and R12, from the viewpoint of higher molecular linearity, they are preferably independent hydrogen atoms, or alkyl groups with 1 to 10 carbons such as butyl, pentyl, hexyl, heptyl, and octyl; Butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and other alkoxy groups with 1 to 10 carbon atoms, diethylamino, pyrrolidinyl and piperidinyl. In addition, among the chain organic groups having the polymerizable groups of R1 and R2 in the liquid crystal compound of the first aspect described later, the preferred one having the polymerizable groups of T1 and T2 in the liquid crystal compound of the second aspect Preferable ones among chain organic groups are also preferable.

作為本發明之異向性色素膜形成用組成物所含有的色素並無特別限定，亦可使用公知色素。 The dye contained in the anisotropic dye film-forming composition of the present invention is not particularly limited, and known dyes can also be used.

作為公知色素，可舉例如上述專利文獻1、日本專利第5982762號公報、日本專利公開第2017-025317號公報、日本專利公開第2014-095899號公報記載的色素(二色性色素、二色性染料)。 Examples of known dyes include dyes (dichroic dyes, dichroic dye).

具體而言，可舉例如以下記載之色素，但並不限定於此等。 Specifically, dyes such as those described below may be mentioned, but are not limited thereto.

[化1]

Figure 108109137-A0101-12-0016-1
[chemical 1]
Figure 108109137-A0101-12-0016-1

Figure 108109137-A0101-12-0016-2
Figure 108109137-A0101-12-0016-2

Figure 108109137-A0101-12-0017-3
Figure 108109137-A0101-12-0017-3

[化4]

Figure 108109137-A0101-12-0018-4
[chemical 4]
Figure 108109137-A0101-12-0018-4

作為本發明之異向性色素膜形成用組成物所含有之色素的分子量，較佳為300以上、更佳為350以上、再更佳為380以上，且較佳為1500以下、更佳為1200以下、再更佳為1000以下。具體而言，作為本發明之異向性色素膜形成用組成物所含有之色素的分子量，較佳為300~1500、更佳為350~1200、更佳為380~1000。 The molecular weight of the dye contained in the anisotropic dye film-forming composition of the present invention is preferably at least 300, more preferably at least 350, still more preferably at least 380, and is preferably at most 1500, more preferably at least 1200. Below, more preferably below 1000. Specifically, the molecular weight of the dye contained in the anisotropic dye film-forming composition of the present invention is preferably from 300 to 1500, more preferably from 350 to 1200, and more preferably from 380 to 1000.

異向性色素膜形成用組成物中色素(二色性色素)所佔的含量，例如相對於異向性色素膜形成用組成物之固形份(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10質量份以下。具體而言，異向性色素膜形成用組成物中色素(二色性色素)所佔的含量，例如相對於異向性色素膜形成用組成物之固形份(100質量份)，較佳為0.01~30質量份、更佳為0.05~10質量份。 The content of the dye (dichroic dye) in the composition for forming an anisotropic dye film is, for example, preferably 0.01 parts by mass or more relative to the solid content (100 parts by mass) of the composition for forming an anisotropic dye film , more preferably at least 0.05 parts by mass, and preferably at most 30 parts by mass, more preferably at most 10 parts by mass. Specifically, the content of the dye (dichroic dye) in the composition for forming an anisotropic dye film is preferably, for example, relative to the solid content (100 parts by mass) of the composition for forming an anisotropic dye film. 0.01 to 30 parts by mass, more preferably 0.05 to 10 parts by mass.

若色素(二色性色素)所佔的含量為上述範圍內，則有不擾亂本發明之異向性色素膜形成用組成物所含之液晶化合物之配向、可使本發明之異向性色素膜形成用組成物所含之化合物聚合的傾向。又，若色素(二色性色素)所佔之含量為上述下限值以上，則有可獲 得充分之光吸收、可獲得充分之偏光性能的傾向。又，若色素(二色性色素)所佔之含量為上述上限值以下，則有容易抑制液晶分子之配向阻礙的傾向。 If the content of the dye (dichroic dye) is within the above range, the anisotropic dye of the present invention can be made without disturbing the alignment of the liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention. The tendency of the compound contained in the film-forming composition to polymerize. Also, when the content of the dye (dichroic dye) is more than the above lower limit, sufficient light absorption and sufficient polarizing performance tend to be obtained. Moreover, when the content of a dye (dichroic dye) is below the said upper limit, it exists in the tendency for the inhibition of alignment of a liquid crystal molecule to be suppressed easily.

色素(二色性色素)係配合目的，可使用1種，亦可併用複數種。 The dye (dichroic dye) may be used alone or in combination according to the purpose.

(液晶化合物) (liquid crystal compound)

本發明中所謂液晶化合物，係指顯示液晶狀態之物質，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)之第1~28頁記載般，由結晶不直接轉移為液體，經過顯示結晶與液體雙方性質之中間狀態而成為液體的化合物。 The so-called liquid crystal compound in the present invention refers to a substance that exhibits a liquid crystal state. Specifically, as described on pages 1 to 28 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., issued on October 30, 2000), the crystallization A compound that transfers directly to a liquid and then becomes a liquid through an intermediate state that exhibits both the properties of crystals and liquids.

本發明第一態樣之異向性色素膜形成用組成物所含有之第一態樣之液晶化合物，係包括具有下述式(1)所示部分構造之液晶化合物。 The liquid crystal compound of the first aspect contained in the anisotropic dye film-forming composition of the first aspect of the present invention includes a liquid crystal compound having a partial structure represented by the following formula (1).

-Cy-X2-C≡C-X-‧‧‧(1) -Cy-X2-C≡C-X-‧‧‧(1)

式(1)中，Cy表示烴環基或雜環基；-X-表示-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、-CH2O-、-OCH2-、-CH2S-或-SCH2-；-X2-表示單鍵、-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、-CH2O-、-OCH2-、-CH2S-或-SCH2-。 In the formula (1), Cy represents a hydrocarbon ring group or a heterocyclic group; -X- 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 -; -X2- represents 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)-, -CH2O- , -OCH2- , -CH2S- or -SCH2- .

Cy中之烴環基包括芳香族烴環基與非芳香族烴環 基。 The hydrocarbon ring group in Cy includes aromatic hydrocarbon ring group and non-aromatic hydrocarbon ring group.

芳香族烴環基包括非連結芳香族烴環基與連結芳香族烴環基。 The aromatic hydrocarbon ring group includes non-linkage aromatic hydrocarbon ring group and linking aromatic hydrocarbon ring group.

非連結芳香族烴環基為單環或縮合之芳香族烴環之2價基，碳數較佳為6~20。作為芳香族烴環，可舉例如苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、

Figure 108109137-A0101-12-0020-60
環、聯伸三苯環、苊萘環、苯并苊環、茀環等。 The non-linked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and the number of carbon atoms is preferably 6-20. Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,
Figure 108109137-A0101-12-0020-60
ring, triphenyl ring, acenaphthylene ring, benzoacenaphthene ring, fennel ring, etc.

連結芳香族烴環係單環或經縮合之芳香族烴環之複數個藉由單鍵鍵結，於構成環之原子上具有鍵結基的2價基。單環或縮合環之碳數較佳為6~20。例如，第1之碳數6~20之單環或經縮合之芳香族烴環與第2之碳數6~20之單環或經縮合之芳香族烴環藉由單鍵鍵結，於第1之碳數6~20之單環或經縮合之芳香族烴環的構成環之原子上具有第1鍵結基，於第2之碳數6~20之單環或經縮合之芳香族烴環的構成環之原子上具有第2鍵結基的2價基。作為連結芳香族烴環基，可舉例如聯苯基-4,4’-二基。 A divalent group having a bonding group on an atom constituting the ring is a single bond between a single aromatic hydrocarbon ring system or a plurality of condensed aromatic hydrocarbon rings. The carbon number of the monocyclic or condensed ring is preferably 6-20. For example, the first monocyclic or condensed aromatic hydrocarbon ring with 6 to 20 carbon atoms and the second monocyclic or condensed aromatic hydrocarbon ring with 6 to 20 carbon atoms are bonded by a single bond. A monocyclic or condensed aromatic hydrocarbon ring with a carbon number of 6 to 20 in 1 has a first bonding group on the atoms constituting the ring, and a monocyclic or condensed aromatic hydrocarbon with a carbon number of 6 to 20 in the second A divalent group having a second bonding group on an atom constituting the ring. The linking aromatic hydrocarbon ring group may, for example, be biphenyl-4,4'-diyl.

作為芳香族烴環基，較佳為非連結芳香族烴環基。 The aromatic hydrocarbon ring group is preferably a non-linked aromatic hydrocarbon ring group.

此等之中，作為芳香族烴環基，較佳為苯環之2價基、萘環之2價基，更佳為苯環之2價基(伸苯基)。作為伸苯基，較佳為1,4-伸苯基。 Among them, as the aromatic hydrocarbon ring group, a divalent group of a benzene ring and a divalent group of a naphthalene ring are preferable, and a divalent group of a benzene ring (phenylene group) is more preferable. The phenylene group is preferably a 1,4-phenylene group.

非芳香族烴環基包括非連結非芳香族烴環基與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係單環或經縮合之非芳香族烴環的2價基，碳數較佳為3~20。作為非芳香族烴環，可舉例如環丙烷環、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

Figure 108109137-A0101-12-0021-61
烷環、
Figure 108109137-A0101-12-0021-63
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, and the carbon number is preferably 3-20. Examples of the non-aromatic hydrocarbon ring include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, nor
Figure 108109137-A0101-12-0021-61
alkane ring,
Figure 108109137-A0101-12-0021-63
Alkane ring, adamantane ring, tetrahydronaphthalene ring, bicyclo[2.2.2]octane ring, etc.

非連結非芳香族烴環基係包括：在非芳香族烴環之構成環之原子間鍵結不具有不飽和鍵的脂環式烴環基；與在非芳香族烴環之構成環之原子間鍵結具有不飽和鍵的不飽和非芳香族烴環基。作為非連結非芳香族烴環基，較佳為脂環式烴環基。 The non-linking non-aromatic hydrocarbon ring group includes: an alicyclic hydrocarbon ring group with no unsaturated bond bonded between the atoms constituting the non-aromatic hydrocarbon ring; An unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond between bonds. The non-linkage non-aromatic hydrocarbon ring group is preferably an alicyclic hydrocarbon ring group.

連結非芳香族烴環基係單環或經縮合之非芳香族烴環之複數個藉由單鍵鍵結，於構成環之原子上具有鍵結基的2價基；或者，選自由單環之芳香族烴環、經縮合之芳香族烴環、單環之非芳香族烴環、及經縮合之非芳香族烴環所構成之群的1種以上之環，與單環或經縮合之非芳香族烴環藉由單鍵鍵結，並於構成環之原子上具有鍵結基的2價基。單環或縮合環之碳數較佳為3~20。例如，第1之碳數3~20之單環或經縮合之非芳香族烴環與第2之碳數3~20之單環或經縮合之非芳香族烴環藉由單鍵鍵結，於第1之碳數3~20之單環或經縮合之非芳香族烴環的構成環之原子上具有第1鍵結基，於第2之碳數3~20之單環或經縮合之非芳香族烴環的構成環之原子上具有第2鍵結基的2價基；例如，碳數3~20之單環或經縮合之芳香族烴環與碳數3~20之單環或經縮合之非芳香族烴環藉由單鍵鍵結，於碳數3~20之單環或經縮合之芳香族烴環的構成環之原子上具有第1鍵結基，於碳數3~20之單環或經縮合之非芳香族烴環的構成環之原子上具有第2鍵結基的2價基。作為連結非芳香族烴環基，可舉例如雙(環己烷)-4,4’-二基、1-環己基苯-4,4’-二基。 The non-aromatic hydrocarbon ring group is a single ring or a plurality of condensed non-aromatic hydrocarbon rings are bonded by a single bond, and a divalent group having a bonding group on the atoms constituting the ring; or, selected from a single ring Aromatic hydrocarbon rings, condensed aromatic hydrocarbon rings, monocyclic non-aromatic hydrocarbon rings, and condensed non-aromatic hydrocarbon rings, and monocyclic or condensed The non-aromatic hydrocarbon ring is bonded by a single bond, and has a divalent group of a bonded group on the atoms constituting the ring. The carbon number of the monocyclic or condensed ring is preferably 3-20. For example, the first monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbons and the second monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbons are bonded by a single bond, There is a first bonding group on the atoms of the first monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbon atoms, and the second monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbon atoms A divalent group with a second bonding group on the atom constituting the non-aromatic hydrocarbon ring; for example, a monocyclic ring with 3 to 20 carbons or a condensed aromatic hydrocarbon ring and a monocyclic or condensed aromatic hydrocarbon ring with 3 to 20 carbons The condensed non-aromatic hydrocarbon ring is bonded by a single bond, and has a first bonding group on the atoms of the monocyclic ring with 3 to 20 carbons or the atoms constituting the ring of the condensed aromatic hydrocarbon ring. A divalent group having a second bonding group on an atom constituting the ring of a monocyclic or condensed non-aromatic hydrocarbon ring of 20. 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，較佳為非連結非芳香族烴環基。 As the non-aromatic hydrocarbon ring group, a non-linkage non-aromatic hydrocarbon ring group is preferred.

此等之中，作為非芳香族烴環基，較佳為環己烷之2價基(環己烷二基)。作為環己烷二基，較佳為環己烷-1,4-二基。 Among them, a divalent group of cyclohexane (cyclohexanediyl) is preferable as the non-aromatic hydrocarbon ring group. The cyclohexanediyl group is preferably cyclohexane-1,4-diyl group.

Cy中之雜環基，係包括芳香族雜環基與非芳香族雜環基。 The heterocyclic group in Cy includes aromatic heterocyclic group and non-aromatic heterocyclic group.

芳香族雜環基係包括非連結芳香族雜環基與連結芳香族雜環基。 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為單環或經縮合之芳香族雜環的2價基，碳數較佳為4~20。作為芳香族雜環，可舉例如呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、

Figure 108109137-A0101-12-0022-64
二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、噻吩并噻唑環、苯并異
Figure 108109137-A0101-12-0022-65
唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡
Figure 108109137-A0101-12-0022-66
環、嗒
Figure 108109137-A0101-12-0022-67
環、嘧啶環、三
Figure 108109137-A0101-12-0022-68
環、喹啉環、異喹啉環、
Figure 108109137-A0101-12-0022-69
啉環、喹
Figure 108109137-A0101-12-0022-70
啉環、啡啶環、苯并咪唑環、嘧啶環、喹唑啉環、喹唑啉酮環、薁環等。 The non-connecting aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocyclic ring, and the number of carbon atoms is preferably 4-20. Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring,
Figure 108109137-A0101-12-0022-64
Oxadiazole ring, indole ring, carbazole ring, pyrrolopyrrole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thieno Furan ring, thienothiazole ring, benziso
Figure 108109137-A0101-12-0022-65
Azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine
Figure 108109137-A0101-12-0022-66
Ring, click
Figure 108109137-A0101-12-0022-67
ring, pyrimidine ring, three
Figure 108109137-A0101-12-0022-68
ring, quinoline ring, isoquinoline ring,
Figure 108109137-A0101-12-0022-69
Phenyl ring, quinoline
Figure 108109137-A0101-12-0022-70
Line ring, phenanthridine ring, benzimidazole ring, pyrimidine ring, quinazoline ring, quinazolinone ring, azulene ring, etc.

連結芳香族雜環基係單環或經縮合之芳香族雜環之複數個藉由單鍵鍵結，於構成環之原子上具有鍵結基的2價基。單環或縮合環之碳數較佳為4~20。例如，第1之碳數4~20之單環或經縮合之芳香族雜環與第2之碳數4~20之單環或經縮合之芳香族雜環藉由單鍵鍵結，於第1之碳數4~20之單環或經縮合之芳香族雜環的構成環之原子上具有第1鍵結基，於第2之碳數4~20之單環或經縮合之芳香族雜環的構成環之原子上具有第2鍵結基的2價基。 The linking aromatic heterocyclic group is a divalent group in which a plurality of single rings or condensed aromatic heterocyclic rings are bonded by a single bond and have a bonding group on the atom constituting the ring. The carbon number of the monocyclic or condensed ring is preferably 4-20. For example, the first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms and the second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded by a single bond. A monocyclic or condensed aromatic heterocyclic ring with 4 to 20 carbon atoms in 1 has a first bonding group on the atoms constituting the ring, and a monocyclic or condensed aromatic heterocyclic ring with 4 to 20 carbon atoms in the second A divalent group having a second bonding group on an atom constituting the ring.

非芳香族雜環基係包括非連結非芳香族雜環基與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係單環或經縮合之非芳香族雜環的2價基，碳數較佳為4~20。為碳數4~20之單環或經縮合之非芳香族雜 環基的2價基，作為非芳香族雜環，可舉例如四氫呋喃環、四氫吡喃環、二

Figure 108109137-A0101-12-0023-71
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
Figure 108109137-A0101-12-0023-72
環、四氫噻唑環、四氫
Figure 108109137-A0101-12-0023-74
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、四氫苯并咪唑環、
Figure 108109137-A0101-12-0023-75
啶環等。 The non-linking non-aromatic heterocyclic group is a divalent group of a monocyclic or condensed non-aromatic heterocyclic ring, and the number of carbon atoms is preferably 4-20. A divalent group that is a monocyclic ring with 4 to 20 carbons or a condensed non-aromatic heterocyclic group. As a non-aromatic heterocyclic ring, examples include tetrahydrofuran ring, tetrahydropyran ring, bis
Figure 108109137-A0101-12-0023-71
Alkane ring, tetrahydrothiophene ring, tetrahydrothiopyran ring, pyrrolidine ring, piperidine ring, dihydropyridine ring, piperidine ring
Figure 108109137-A0101-12-0023-72
ring, tetrahydrothiazole ring, tetrahydro
Figure 108109137-A0101-12-0023-74
Azole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzimidazole ring,
Figure 108109137-A0101-12-0023-75
Pyridine ring etc.

連結非芳香族雜環基係單環或經縮合之非芳香族雜環之複數個藉由單鍵鍵結，於構成環之原子上具有鍵結基的2價基。單環或縮合環之碳數較佳為4~20。例如，第1之碳數4~20之單環或經縮合之非芳香族雜環與第2之碳數4~20之單環或經縮合之非芳香族雜環藉由單鍵鍵結，於第1之碳數4~20之單環或經縮合之非芳香族雜環的構成環之原子上具有第1鍵結基，於第2之碳數4~20之單環或經縮合之非芳香族雜環的構成環之原子上具有第2鍵結基的2價基。 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 has a bonding group on the atom constituting the ring. The carbon number of the monocyclic or condensed ring is preferably 4-20. For example, the first monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded to the second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms via a single bond, There is a first bonding group on the atoms of the first monocyclic or condensed non-aromatic heterocyclic ring with 4 to 20 carbon atoms, and the second monocyclic or condensed non-aromatic heterocyclic ring with 4 to 20 carbon atoms A divalent group having a second bonding group on an atom constituting the ring of a non-aromatic heterocyclic ring.

Cy中之芳香族烴環基、非芳香族烴環基、芳香族雜環基、非芳香族雜環基，係分別可藉由選自由RA、-OH、-O-RA、-O-C(=O)-RA、-NH2、-NH-RA、-N(RB)-RA、-C(=O)-RA、-C(=O)-O-RA、-C(=O)-NH2、-C(=O)-NH-RA、-C(=O)-N(RB)-RA、-SH、-S-RA、三氟甲基、胺磺醯基、羧基、磺酸基、氰基、硝基及鹵素所構成之群的1種以上基所取代。於此，RA及RB分別獨立表示碳數1~6之直鏈狀或分枝狀之烷基。 The aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, non-aromatic heterocyclic group in Cy can be selected from RA, -OH, -O-RA, -OC (= O)-RA, -NH 2 , -NH-RA, -N(RB)-RA, -C(=O)-RA, -C(=O)-O-RA, -C(=O)-NH 2. -C(=O)-NH-RA, -C(=O)-N(RB)-RA, -SH, -S-RA, trifluoromethyl, sulfamoyl, carboxyl, sulfonic acid , cyano, nitro and halogen are substituted by one or more of the group. Here, RA and RB each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms.

Cy中之芳香族烴環基、非芳香族烴環基、芳香族雜環基、非芳香族雜環基，由分子構造之直線性高、具有式(1)所示部分構造之液晶化合物彼此容易會合而容易表現液晶狀態的觀點而言，較佳係分別獨立為無取代，或經甲基、甲氧基、氟原子、氯原子、溴原子 所取代，更佳為無取代。 The aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Cy are composed of liquid crystal compounds with high linearity in molecular structure and a partial structure shown in formula (1). From the viewpoint of being easy to join and easily expressing a liquid crystal state, it is preferably independently unsubstituted, or substituted with methyl, methoxy, fluorine atom, chlorine atom, or bromine atom, and more preferably unsubstituted.

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之取代基可為相同或相異，又，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，亦可全部為無取代，亦可為部分取代而部分無取代。 The substituents of the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be the same or different, and the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group The group, the aromatic heterocyclic group, and the non-aromatic heterocyclic group may all be substituted, all may be unsubstituted, or may be partially substituted and partially unsubstituted.

作為Cy，較佳為烴環基，更佳為伸苯基、環己烷二基。又，由可提高液晶化合物之分子構造的直線性而言，作為Cy更佳為1,4-伸苯基、環己烷-1,4-二基，特佳為1,4-伸苯基。 Cy is preferably a hydrocarbon ring group, more preferably a phenylene group or a cyclohexanediyl group. In addition, since the linearity of the molecular structure of the liquid crystal compound can be improved, Cy is more preferably 1,4-phenylene, cyclohexane-1,4-diyl, particularly preferably 1,4-phenylene .

由液晶化合物之直線性或有於分子短軸周圍之旋轉運動容易的傾向而言，作為-X-，較佳係π鍵結性較小的-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH2O-、-OCH2-、-CH2S-、-SCH2-，更佳係-C(=O)O-、-OC(=O)-、-CH2CH2-、-CH2O-、-OCH2-。作為某態樣，-X-為-C(=O)O-或-OC(=O)-，作為其他態樣，-X-為-CH2CH2-、-CH2O-或-OCH2-。 From the linearity of the liquid crystal compound or the tendency to easily rotate around the short axis of the molecule, -X- is preferably -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 -, more preferably -C(=O)O-, -OC(=O)-, -CH 2 CH 2 -, -CH 2 O-, -OCH 2 -. In a certain aspect, -X- is -C(=O)O- or -OC(=O)-, and in another aspect, -X- is -CH 2 CH 2 -, -CH 2 O-, or -OCH 2 -.

由增大液晶化合物之核、以增加由異向性色素膜形成用組成物所形成之異向性色素膜之二色性的觀點而言，較佳係將直線性高之基的-Cy-與-C≡C-連結。具體而言，作為-X2-，較佳為單鍵、或具有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)-，由直線性更高而言更佳為單鍵。 From the viewpoint of increasing the nucleus of the liquid crystal compound and increasing the dichroism of the anisotropic dye film formed from the composition for forming an anisotropic dye film, it is preferable to use -Cy- Linked with -C≡C-. Specifically, -X2- is preferably a single bond, or -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC having π bonding (=S)-, -C(=O)S-, -SC(=O)-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, more linear In terms of height, it is more preferably a single bond.

本發明之異向性色素膜形成用組成物所含的具有上述式(1)所示部分構造的液晶化合物，可舉例如下述式(2)所示液晶化合物。 The liquid crystal compound having the partial structure represented by the above formula (1) contained in the anisotropic dye film forming composition of the present invention includes, for example, a liquid crystal compound represented by the following formula (2).

R1-A1-Y1-A2-Y2-A3-R2‧‧‧(2) R1-A1-Y1-A2-Y2-A3-R2‧‧‧(2)

式(2)中，R1及R2分別獨立表示鏈狀有機基；A1及A3分別獨立表示上述式(1)所示部分構造、2價有機基、或單鍵；A2表示上述式(1)所示部分構造或2價有機基；-Y1-及-Y2-分別獨立表示單鍵、-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、-CH2O-、-OCH2-、-CH2S-或-SCH2-；A1及A3之一者為上述式(1)所示部分構造或2價有機基；A1、A2及A3中之至少一者為上述式(1)所示部分構造。 In formula (2), R1 and R2 independently represent a chain organic group; A1 and A3 independently represent a part of the structure shown in the above formula (1), a divalent organic group, or a single bond; A2 represents the above-mentioned formula (1) Represents a partial structure or a divalent organic group; -Y1- and -Y2- 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(=O)NH-, -NHC(=O )-, -CH 2 O-, -OCH 2 -, -CH 2 S- or -SCH 2 -; one of A1 and A3 is a part of the structure shown in the above formula (1) or a divalent organic group; A1, A2 and at least one of A3 is a partial structure shown in the above formula (1).

尚且，A1為式(1)所示部分構造時，式(2)可為R1-Cy-X2-C≡C-X-Y1-A2-Y2-A3-R2‧‧‧(2A)，亦可為R1-X-C≡C-X2-Cy-Y1-A2-Y2-A3-R2‧‧‧(2B)。 Moreover, when A1 is a partial structure shown in formula (1), formula (2) can be R1-Cy-X2-C≡C-X-Y1-A2-Y2-A3-R2‧‧‧(2A), or R1 -X-C≡C-X2-Cy-Y1-A2-Y2-A3-R2‧‧‧(2B).

又，A2為式(1)所示部分構造時，式(2)可為R1-A1-Y1-Cy-X2-C≡C-X-Y2-A3-R2‧‧‧(2C)，亦可為R1-A1-Y1-X-C≡C-X2-Cy-Y2-A3-R2‧‧‧(2D)。 Also, when A2 is a partial structure shown in formula (1), formula (2) can be R1-A1-Y1-Cy-X2-C≡C-X-Y2-A3-R2‧‧‧(2C), or R1 -A1-Y1-X-C≡C-X2-Cy-Y2-A3-R2‧‧‧(2D).

A3為式(1)所示部分構造時，式(2)可為R1-A1-Y1-A2-Y2-Cy-X2-C≡C-X-R2‧‧‧(2E)，亦可為R1-A1-Y1-A2-Y2-X-C≡C-X2-Cy-R2‧‧‧(2F)。 When A3 is a partial structure shown in formula (1), formula (2) can be R1-A1-Y1-A2-Y2-Cy-X2-C≡C-X-R2‧‧‧(2E), or R1-A1 -Y1-A2-Y2-X-C≡C-X2-Cy-R2‧‧‧(2F).

同樣地，A1、A2及A3中，在二個以上為式(1)所示部分構造時，亦可分別獨立使式(1)所示部分構造之方向反轉。 Similarly, in A1, A2, and A3, when two or more partial structures are represented by the formula (1), the direction of the partial structures represented by the formula (1) can also be independently reversed.

又，如上述，A1、A2及A3分別獨立為式(1)所示部分構造或2價有機基；此外，A1及A3亦可為單鍵，但A1及A3 不同時為單鍵；A1、A2及A3中，至少一者表示上述式(1)所示部分構造。 Also, as mentioned above, A1, A2 and A3 are independently part of the structure shown in formula (1) or a divalent organic group; in addition, A1 and A3 can also be single bonds, but A1 and A3 are not single bonds at the same time; A1, A3 At least one of A2 and A3 represents a partial structure represented by the above formula (1).

R1及R2中之鏈狀有機基，係不含上述芳香族烴環、非芳香族烴環、芳香族雜環、非芳香族雜環等環狀構造(其中，在R1及R2中之鏈狀有機基具有環氧乙烷環、氧還丁烷環、乙烯基苯環等後述環狀之聚合性基時，聚合性基之外的部分不含上述環狀構造。)的1價有機基。 The chain organic groups in R1 and R2 do not contain the above-mentioned ring structures such as aromatic hydrocarbon rings, non-aromatic hydrocarbon rings, aromatic heterocycles, and non-aromatic heterocycles (among them, the chain organic groups in R1 and R2 When the organic group has a cyclic polymerizable group described later such as an oxirane ring, an oxirane ring, or a vinylbenzene ring, the part other than the polymerizable group does not contain the above-mentioned cyclic structure.) Monovalent organic group.

作為此種鏈狀有機基，可舉例如-(烷基)、-O-(烷基)、-S-(烷基)、-NH-(烷基)、-N(烷基)-(烷基)、-O(C=O)-(烷基)、-C(=O)O-(烷基)。作為此種鏈狀有機基，較佳為-(烷基)、-O-(烷基)。作為某態樣，此種鏈狀有機基為-(烷基)，作為其他態樣，此種鏈狀有機基為-O-(烷基)。 Examples of such chain organic groups include -(alkyl), -O-(alkyl), -S-(alkyl), -NH-(alkyl), -N(alkyl)-(alk group), -O(C=O)-(alkyl), -C(=O)O-(alkyl). As such a chain organic group, -(alkyl group) and -O-(alkyl group) are preferable. In a certain aspect, such a chain organic group is -(alkyl), and in another aspect, such a chain organic group is -O-(alkyl).

作為此等鏈狀有機基中之烷基，可舉例如碳數1~25之直鏈狀或分枝狀之烷基，烷基之碳-碳鍵可部分為不飽和鍵，或者亦可為使烷基所含之一個或一個以上之亞甲基藉由醚性氧原子、硫醚素硫原子、胺性氮原子(-NH-、-N(RA)-；於此，RA表示碳數1~6之直鏈狀或分枝狀之烷基。)、羰基、酯鍵、醯胺鍵、-CHF-、-CF2-、-CHCl-、-CCl2-所取代(displace)的構造。 As the alkyl group in these chain organic groups, for example, a straight chain or branched alkyl group with 1 to 25 carbons, the carbon-carbon bond of the alkyl group may be partially unsaturated bond, or may be One or more methylene groups contained in the alkyl group are passed through etheric oxygen atoms, thioether sulfur atoms, and amine nitrogen atoms (-NH-, -N(RA)-; here, RA represents the number of carbons 1~6 linear or branched alkyl.), carbonyl, ester bond, amide bond, -CHF-, -CF 2 -, -CHCl-, -CCl 2 -substituted (displace) structure .

作為此等鏈狀有機基中之烷基，由分子直線性高而言，較佳係可使烷基之一部分碳為不飽和鍵，或係可使烷基所含之一個或一個以上之亞甲基藉上述基所取代(displace)的構造，且碳數1~25之直鏈狀烷基。 As the alkyl group in these chain organic groups, in terms of high linearity of the molecule, it is preferable to make a part of the carbon of the alkyl group an unsaturated bond, or to make one or more subunits contained in the alkyl group A straight-chain alkyl group with 1 to 25 carbon atoms, in which the methyl group is substituted (displaced) by the above group.

鏈狀有機基中之主鏈(意指鏈狀有機基中的最長鏈狀部分，在鏈狀有機基藉後述聚合性基所取代時，意指聚合性基以外之部分中 的最長鏈狀部分。)的原子數，較佳為3~25、更佳為5~20、再更佳為6~20。 The main chain in the chain organic group (means the longest chain part in the chain organic group, when the chain organic group is replaced by the polymerizable group described later, it means the longest chain part in the part other than the polymerizable group .) The number of atoms is preferably 3-25, more preferably 5-20, and more preferably 6-20.

又，此等烷基中，亦可取代1~3個聚合性基。聚合性基係具有可藉由光、熱及/或放射線進行聚合之部分構造的基，係用於保持聚合機能所必要的官能基或原子團。聚合性基係由異向性色素膜之製造的觀點而言較佳為光聚合性基。 In addition, among these alkyl groups, 1 to 3 polymerizable groups may be substituted. The polymerizable group is a group having a partial structure that can be polymerized by light, heat and/or radiation, and is a functional group or an atomic group necessary for maintaining the polymerization function. The polymerizable group is preferably a photopolymerizable group from the viewpoint of production of the anisotropic dye film.

作為聚合性基，可舉例如丙烯醯基、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、環氧乙烷基、氧環丁烷基、環氧丙基、環氧丙氧基、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、環氧乙烷基、環氧丙基、環氧丙氧基，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、環氧丙基、環氧丙氧基，再更佳為丙烯醯氧基、甲基丙烯醯氧基、環氧丙氧基。 Examples of polymerizable groups include acryl, methacryl, acryloxy, methacryloxy, acrylamine, methacrylamine, vinyl, vinyloxy , ethynyl, ethynyloxy, 1,3-butadienyl, 1,3-butadienyloxy, oxirane, oxetane, glycidyl, glycidoxy, Styryl, styryloxy, etc., preferably acryl, methacryl, acryloxy, methacryloxy, acrylamine, methacrylamine, cyclic Oxyethyl, epoxypropyl, glycidoxy, more preferably acryl, methacryl, acryloxy, methacryloxy, acrylamine, methacryl Acylamino group, glycidyl group, glycidoxy group, more preferably acryloxy group, methacryloxy group, glycidoxy group.

在此等烷基經聚合性基取代的情況，較佳係經1個聚合性基取代，更佳係於烷基末端經1個聚合性基取代。 When such an alkyl group is substituted with a polymerizable group, it is preferably substituted with one polymerizable group, and more preferably substituted with one polymerizable group at the terminal of the alkyl group.

作為鏈狀有機基，較佳為-(CH2)n-CH3、-(CH2)n-CH2-聚合性基、-O-(CH2)n-CH3、-O-(CH2)n-CH2-聚合性基、-(O)n1-(CH2CH2O)n2-(CH2)n3-CH3、-(O)n1-(CH2CH2O)n2-(CH2)n3-聚合性基、-(O)n1-(CH2)n2-(CH2CH2O)n3-CH3、-(O)n1-(CH2)n2-(CH2CH2O)n3-聚合性基。又，此等式中之n為1~24之整數、較佳為2~24之整數、更佳為4~19之整數、再更佳為5~19之整數。又，此等式中之n1、n2、n3分別獨立表示整數，鏈狀有機基中之主鏈(意指鏈狀有機基中 的最長鏈狀部分，在鏈狀有機基藉取代性基所取代時，意指聚合性基以外之部分中的最長鏈狀部分。)的原子數係依較佳為3~25、更佳為5~20、再更佳為6~20的方式適當調整。 The chain organic group is preferably -(CH 2 ) n -CH 3 , -(CH 2 ) n -CH 2 -polymerizable group, -O-(CH 2 ) n -CH 3 , -O-(CH 2 ) n -CH 2 -polymerizable group, -(O) n1 -(CH 2 CH 2 O)n 2 -(CH 2 ) n3 -CH 3 , -(O) n1 -(CH 2 CH 2 O)n 2 -(CH 2 ) n3 -polymerizable group, -(O) n1 -(CH 2 ) n2 -(CH 2 CH 2 O)n 3 -CH 3 , -(O) n1 -(CH 2 ) n2 -( CH 2 CH 2 O)n 3 - polymerizable group. Also, n in this equation is an integer of 1-24, preferably an integer of 2-24, more preferably an integer of 4-19, and more preferably an integer of 5-19. Also, n1, n2, and n3 in this equation independently represent an integer, and the main chain in the chain organic group (meaning the longest chain part in the chain organic group is replaced by a substituent group in the chain organic group) , means the longest chain-like part among the parts other than the polymerizable group.) The number of atoms is appropriately adjusted in such a manner that it is preferably 3-25, more preferably 5-20, and even more preferably 6-20.

R1及R2分別獨立，較佳為亦可經聚合性基取代的-(烷基)、烷基亦可經聚合性基取代的-O-(烷基)，更佳為經聚合性基取代的-(烷基)、烷基經聚合性基取代的-O-(烷基)。 R1 and R2 are independent, preferably -(alkyl) which may also be substituted by a polymerizable group, -O-(alkyl) which may also be substituted by a polymerizable group, more preferably -(alkyl) which may be substituted by a polymerizable group -(alkyl), -O-(alkyl) in which the alkyl is substituted with a polymerizable group.

如式(2B)、式(2E)般，在X與R1或X與R2鍵結時，或例如在式(2B)中A3為單鍵時，或式(2E)中A1為單鍵時，R1或R2與Y1或Y2鍵結時，與X或Y1或Y2鍵結之R1或R2較佳係亦可經聚合性基取代的-(烷基)，更佳係經聚合性基取代的-(烷基)。 As in formula (2B), formula (2E), when X and R1 or X and R2 are bonded, or for example, when A3 is a single bond in formula (2B), or when A1 is a single bond in formula (2E), When R1 or R2 is bonded to Y1 or Y2, R1 or R2 bonded to X or Y1 or Y2 is preferably -(alkyl) that may also be substituted by a polymerizable group, more preferably - that is substituted by a polymerizable group (alkyl).

或者，如上述以外般，未與X或Y1或Y2鍵結之R1或R2，較佳係亦可經聚合性基取代的-O-(烷基)，更佳係經聚合性基取代的-O-(烷基)。 Alternatively, as other than the above, R1 or R2 that is not bonded to X or Y1 or Y2 is preferably -O-(alkyl) that may also be substituted by a polymerizable group, more preferably - that is substituted by a polymerizable group O-(alkyl).

A1、A2及A3中之2價有機基較佳係下述式(3)所示基。 The divalent organic group in A1, A2 and A3 is preferably a group represented by the following formula (3).

-Q1-‧‧‧(3) -Q1-‧‧‧(3)

式(3)中，Q1表示烴環基或雜環基。 In formula (3), Q1 represents a hydrocarbon ring group or a heterocyclic group.

Q1中之經環基係包括芳香族烴環基與非芳香族烴環基。 The ring group in Q1 includes aromatic hydrocarbon ring group and non-aromatic hydrocarbon ring group.

芳香族烴環基係包括非連結芳香族烴環基與連結芳香族烴環基。 The aromatic hydrocarbon ring group includes a non-linkage aromatic hydrocarbon ring group and a linking aromatic hydrocarbon ring group.

非連結芳香族烴環基為單環或縮合之芳香族烴環之2價基，碳 數較佳為6~20。作為芳香族烴環，可舉例如苯環、萘環、蒽環、菲環、苝環、稠四苯環、芘環、苯并芘環、

Figure 108109137-A0101-12-0029-76
環、聯伸三苯環、苊環、苯并苊環、茀環等。 The non-linked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and the number of carbon atoms is preferably 6-20. Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring,
Figure 108109137-A0101-12-0029-76
ring, triphenyl ring, acenaphthene ring, benzoacenaphthene ring, fennel ring, etc.

連結芳香族烴環基係單環或經縮合之芳香族烴環之複數個藉由單鍵鍵結，於構成環之原子上具有鍵結基的2價基。單環或縮合環之碳數較佳為6~20。例如，第1之碳數6~20之單環或經縮合之芳香族烴環與第2之碳數6~20之單環或經縮合之芳香族烴環藉由單鍵鍵結，於第1之碳數6~20之單環或經縮合之芳香族烴環的構成環之原子上具有第1鍵結基，於第2之碳數6~20之單環或經縮合之芳香族烴環的構成環之原子上具有第2鍵結基的2價基。作為連結芳香族烴環基，可舉例如聯苯基-4,4’-二基。 A linking aromatic hydrocarbon ring group is a divalent group in which a single ring or a plurality of condensed aromatic hydrocarbon rings are bonded by a single bond and has a linking group on an atom constituting the ring. The carbon number of the monocyclic or condensed ring is preferably 6-20. For example, the first monocyclic or condensed aromatic hydrocarbon ring with 6 to 20 carbon atoms and the second monocyclic or condensed aromatic hydrocarbon ring with 6 to 20 carbon atoms are bonded by a single bond. A monocyclic or condensed aromatic hydrocarbon ring with a carbon number of 6 to 20 in 1 has a first bonding group on the atoms constituting the ring, and a monocyclic or condensed aromatic hydrocarbon with a carbon number of 6 to 20 in the second A divalent group having a second bonding group on an atom constituting the ring. The linking aromatic hydrocarbon ring group may, for example, be biphenyl-4,4'-diyl.

作為芳香族烴環基，較佳為非連結芳香族烴環基。 The aromatic hydrocarbon ring group is preferably a non-linked aromatic hydrocarbon ring group.

此等之中，作為芳香族烴環基，較佳為苯環之2價基、萘環之2價基，更佳為苯環之2價基(伸苯基)。作為伸苯基，較佳為1,4-伸苯基。 Among them, as the aromatic hydrocarbon ring group, a divalent group of a benzene ring and a divalent group of a naphthalene ring are preferable, and a divalent group of a benzene ring (phenylene group) is more preferable. The phenylene group is preferably a 1,4-phenylene group.

非芳香族烴環基包括非連結非芳香族烴環基與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係單環或經縮合之非芳香族烴環的2價基，碳數較佳為3~20。作為非芳香族烴環，可舉例如環丙烷環、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

Figure 108109137-A0101-12-0029-77
烷環、
Figure 108109137-A0101-12-0029-78
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, and the carbon number is preferably 3-20. As the non-aromatic hydrocarbon ring, for example, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, nor
Figure 108109137-A0101-12-0029-77
alkane ring,
Figure 108109137-A0101-12-0029-78
Alkane ring, adamantane ring, tetrahydronaphthalene ring, bicyclo[2.2.2]octane ring, etc.

非連結非芳香族烴環基係包括：在非芳香族烴環之構成環之原子間鍵結不具有不飽和鍵的脂環式烴環基；與在非芳香族烴環之構成環之原子間鍵結具有不飽和鍵的不飽和非芳香族烴環基。作為非 連結非芳香族烴環基，較佳為脂環式烴環基。 The non-linking non-aromatic hydrocarbon ring group includes: an alicyclic hydrocarbon ring group with no unsaturated bond bonded between the atoms constituting the non-aromatic hydrocarbon ring; An unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond between bonds. The non-linked non-aromatic hydrocarbon ring group is preferably an alicyclic hydrocarbon ring group.

連結非芳香族烴環基係單環或經縮合之非芳香族烴環之複數個藉由單鍵鍵結，於構成環之原子上具有鍵結基的2價基；或者，選自由單環之芳香族烴環、經縮合之芳香族烴環、單環之非芳香族烴環、及經縮合之非芳香族烴環所構成之群的1種以上之環，與單環或經縮合之非芳香族烴環藉由單鍵鍵結，並於構成環之原子上具有鍵結基的2價基。單環或縮合環之碳數較佳為3~20。例如，第1之碳數3~20之單環或經縮合之非芳香族烴環與第2之碳數3~20之單環或經縮合之非芳香族烴環藉由單鍵鍵結，於第1之碳數3~20之單環或經縮合之非芳香族烴環的構成環之原子上具有第1鍵結基，於第2之碳數3~20之單環或經縮合之非芳香族烴環的構成環之原子上具有第2鍵結基的2價基；例如，碳數3~20之單環或經縮合之芳香族烴環與碳數3~20之單環或經縮合之非芳香族烴環藉由單鍵鍵結，於碳數3~20之單環或經縮合之芳香族烴環的構成環之原子上具有第1鍵結基，於碳數3~20之單環或經縮合之非芳香族烴環的構成環之原子上具有第2鍵結基的2價基。作為連結非芳香族烴環基，可舉例如雙(環己烷)-4,4’-二基、1-環己基苯-4,4’-二基。 The non-aromatic hydrocarbon ring group is a single ring or a plurality of condensed non-aromatic hydrocarbon rings are bonded by a single bond, and a divalent group having a bonding group on the atoms constituting the ring; or, selected from a single ring Aromatic hydrocarbon rings, condensed aromatic hydrocarbon rings, monocyclic non-aromatic hydrocarbon rings, and condensed non-aromatic hydrocarbon rings, and monocyclic or condensed The non-aromatic hydrocarbon ring is bonded by a single bond, and has a divalent group of a bonded group on the atoms constituting the ring. The carbon number of the monocyclic or condensed ring is preferably 3-20. For example, the first monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbons and the second monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbons are bonded by a single bond, There is a first bonding group on the atoms of the first monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbon atoms, and the second monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbon atoms A divalent group with a second bonding group on the atom constituting the non-aromatic hydrocarbon ring; for example, a monocyclic ring with 3 to 20 carbons or a condensed aromatic hydrocarbon ring and a monocyclic or condensed aromatic hydrocarbon ring with 3 to 20 carbons The condensed non-aromatic hydrocarbon ring is bonded by a single bond, and has a first bonding group on the atoms of the monocyclic ring with 3 to 20 carbons or the atoms constituting the ring of the condensed aromatic hydrocarbon ring. A divalent group having a second bonding group on an atom constituting the ring of a monocyclic or condensed non-aromatic hydrocarbon ring of 20. 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，較佳為非連結非芳香族烴環基。 As the non-aromatic hydrocarbon ring group, a non-linkage non-aromatic hydrocarbon ring group is preferred.

此等之中，作為非芳香族烴環基，較佳為環己烷之2價基(環己烷二基)。作為環己烷二基，較佳為環己烷-1,4-二基。 Among them, a divalent group of cyclohexane (cyclohexanediyl) is preferable as the non-aromatic hydrocarbon ring group. The cyclohexanediyl group is preferably cyclohexane-1,4-diyl group.

Q1中之雜環基，係包括芳香族雜環基與非芳香族雜環基。 The heterocyclic group in Q1 includes aromatic heterocyclic groups and non-aromatic heterocyclic groups.

芳香族雜環基係包括非連結芳香族雜環基與連結芳香族雜環基。 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為單環或經縮合之芳香族雜環的2價基，碳數較佳為4~20。作為芳香族雜環，可舉例如呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、

Figure 108109137-A0101-12-0031-79
二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、噻吩并噻唑環、苯并異
Figure 108109137-A0101-12-0031-80
唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡
Figure 108109137-A0101-12-0031-81
環、嗒
Figure 108109137-A0101-12-0031-82
環、嘧啶環、三
Figure 108109137-A0101-12-0031-83
環、喹啉環、異喹啉環、
Figure 108109137-A0101-12-0031-85
啉環、喹
Figure 108109137-A0101-12-0031-86
啉環、啡啶環、苯并咪唑環、嘧啶環、喹唑啉環、喹唑啉酮環、薁環等。 The non-connecting aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocyclic ring, and the number of carbon atoms is preferably 4-20. Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring,
Figure 108109137-A0101-12-0031-79
Oxadiazole ring, indole ring, carbazole ring, pyrrolopyrrole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thieno Furan ring, thienothiazole ring, benziso
Figure 108109137-A0101-12-0031-80
Azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine
Figure 108109137-A0101-12-0031-81
Ring, click
Figure 108109137-A0101-12-0031-82
ring, pyrimidine ring, three
Figure 108109137-A0101-12-0031-83
ring, quinoline ring, isoquinoline ring,
Figure 108109137-A0101-12-0031-85
Phenyl ring, quinoline
Figure 108109137-A0101-12-0031-86
Line ring, phenanthridine ring, benzimidazole ring, pyrimidine ring, quinazoline ring, quinazolinone ring, azulene ring, etc.

連結芳香族雜環基係單環或經縮合之芳香族雜環之複數個藉由單鍵鍵結，於構成環之原子上具有鍵結基的2價基。單環或縮合環之碳數較佳為4~20。例如，第1之碳數4~20之單環或經縮合之芳香族雜環與第2之碳數4~20之單環或經縮合之芳香族雜環藉由單鍵鍵結，於第1之碳數4~20之單環或經縮合之芳香族雜環的構成環之原子上具有第1鍵結基，於第2之碳數4~20之單環或經縮合之芳香族雜環的構成環之原子上具有第2鍵結基的2價基。 The linking aromatic heterocyclic group is a divalent group in which a plurality of single rings or condensed aromatic heterocyclic rings are bonded by a single bond and have a bonding group on the atom constituting the ring. The carbon number of the monocyclic or condensed ring is preferably 4-20. For example, the first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms and the second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded by a single bond. A monocyclic or condensed aromatic heterocyclic ring with 4 to 20 carbon atoms in 1 has a first bonding group on the atoms constituting the ring, and a monocyclic or condensed aromatic heterocyclic ring with 4 to 20 carbon atoms in the second A divalent group having a second bonding group on an atom constituting the ring.

非芳香族雜環基係包括非連結非芳香族雜環基與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係單環或經縮合之非芳香族雜環的2價基，碳數較佳為4~20。為碳數4~20之單環或經縮合之非芳香族雜環基的2價基，作為非芳香族雜環，可舉例如四氫呋喃環、四氫吡喃環、二

Figure 108109137-A0101-12-0031-87
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
Figure 108109137-A0101-12-0031-88
環、四氫噻唑環、四氫
Figure 108109137-A0101-12-0031-89
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、四氫苯并 咪唑環、
Figure 108109137-A0101-12-0032-90
啶環等。 The non-linking non-aromatic heterocyclic group is a divalent group of a monocyclic or condensed non-aromatic heterocyclic ring, and the number of carbon atoms is preferably 4-20. A divalent group that is a monocyclic ring with 4 to 20 carbons or a condensed non-aromatic heterocyclic group. As a non-aromatic heterocyclic ring, examples include tetrahydrofuran ring, tetrahydropyran ring, bis
Figure 108109137-A0101-12-0031-87
Alkane ring, tetrahydrothiophene ring, tetrahydrothiopyran ring, pyrrolidine ring, piperidine ring, dihydropyridine ring, piperidine ring
Figure 108109137-A0101-12-0031-88
ring, tetrahydrothiazole ring, tetrahydro
Figure 108109137-A0101-12-0031-89
Azole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzimidazole ring,
Figure 108109137-A0101-12-0032-90
Pyridine ring etc.

連結非芳香族雜環基係單環或經縮合之非芳香族雜環之複數個藉由單鍵鍵結，於構成環之原子上具有鍵結基的2價基。單環或縮合環之碳數較佳為4~20。例如，第1之碳數4~20之單環或經縮合之非芳香族雜環與第2之碳數4~20之單環或經縮合之非芳香族雜環藉由單鍵鍵結，於第1之碳數4~20之單環或經縮合之非芳香族雜環的構成環之原子上具有第1鍵結基，於第2之碳數4~20之單環或經縮合之非芳香族雜環的構成環之原子上具有第2鍵結基的2價基。 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 has a bonding group on the atom constituting the ring. The carbon number of the monocyclic or condensed ring is preferably 4-20. For example, the first monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded to the second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms via a single bond, There is a first bonding group on the atoms of the first monocyclic or condensed non-aromatic heterocyclic ring with 4 to 20 carbon atoms, and the second monocyclic or condensed non-aromatic heterocyclic ring with 4 to 20 carbon atoms A divalent group having a second bonding group on an atom constituting the ring of a non-aromatic heterocyclic ring.

Q1中之芳香族烴環基、非芳香族烴環基、芳香族雜環基、非芳香族雜環基，係分別可藉由選自由RA、-OH、-O-RA、-O-C(=O)-RA、-NH2、-NH-RA、-N(RB)-RA、-C(=O)-RA、-C(=O)-O-RA、-C(=O)-NH2、-C(=O)-NH-RA、-C(=O)-N(RB)-RA、-SH、-S-RA、三氟甲基、胺磺醯基、羧基、磺酸基、氰基、硝基及鹵素所構成之群的1種以上基所取代。於此，RA及RB分別獨立表示碳數1~6之直鏈狀或分枝狀之烷基。 The aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Q1 can be selected from RA, -OH, -O-RA, -OC (= O)-RA, -NH 2 , -NH-RA, -N(RB)-RA, -C(=O)-RA, -C(=O)-O-RA, -C(=O)-NH 2. -C(=O)-NH-RA, -C(=O)-N(RB)-RA, -SH, -S-RA, trifluoromethyl, sulfamoyl, carboxyl, sulfonic acid , cyano, nitro and halogen are substituted by one or more of the group. Here, RA and RB each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms.

Q1中之芳香族烴環基、非芳香族烴環基、芳香族雜環基、非芳香族雜環基，由分子構造之直線性高、具有式(1)所示部分構造之液晶化合物彼此容易會合而容易表現液晶狀態的觀點而言，較佳係分別獨立為無取代，或經甲基、甲氧基、氟原子、氯原子、溴原子所取代，更佳為無取代。 The aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Q1 are composed of a liquid crystal compound with a highly linear molecular structure and a partial structure shown in formula (1). From the viewpoint of being easy to join and easily expressing a liquid crystal state, it is preferably independently unsubstituted, or substituted with methyl, methoxy, fluorine atom, chlorine atom, or bromine atom, and more preferably unsubstituted.

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之取代基可為相同或相異，又，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 部為無取代，亦可為部分取代而部分無取代。 The substituents of the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be the same or different, and the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group The group, the aromatic heterocyclic group, and the non-aromatic heterocyclic group may all be substituted, all may be unsubstituted, or may be partially substituted and partially unsubstituted.

又，A1、A2及A3中之2價有機基所具有的取代基，可為相同或相異，A1、A2及A3中之2價有機基可全部經取代，亦可全部為無取代，亦可為部分取代而部分無取代。 Also, the substituents of the divalent organic groups in A1, A2 and A3 may be the same or different, and the divalent organic groups in A1, A2 and A3 may be all substituted or unsubstituted, or Partial substitution and partial non-substitution are possible.

作為Q1，較佳為烴環基，更佳為伸苯基、環己烷二基。又，由可提高液晶化合物之分子構造的直線性而言，作為Q1更佳為1,4-伸苯基、環己烷-1,4-二基。 Q1 is preferably a hydrocarbon ring group, more preferably a phenylene group or a cyclohexanediyl group. Moreover, since the linearity of the molecular structure of a liquid crystal compound can be improved, Q1 is more preferably a 1,4-phenylene group or a cyclohexane-1,4-diyl group.

作為2價有機基，較佳係Q1為烴環基、即以烴環基作為2價有機基。又，作為2價有機基，更佳為伸苯基、環己烷二基，由可提高液晶化合物之分子構造之直線性而言，更佳係1,4-伸苯基、環己烷-1,4-二基。 As the divalent organic group, Q1 is preferably a hydrocarbon ring group, that is, a hydrocarbon ring group is used as the divalent organic group. Also, as a divalent organic group, phenylene and cyclohexanediyl are more preferable, and 1,4-phenylene, cyclohexane- 1,4-diradical.

作為式(2)，較佳係A1、A2及A3中，一者為式(1)所示部分構造，其以外之二者分別獨立為2價有機基；A1、A2及A3中，式(1)所示部分構造之Cy較佳係烴環基，特佳係2價有機基為烴環基。再者，烴環基較佳為1,4-伸苯基或環己烷-1,4-二基。又，較佳係A1及A3之一者為環己烷-1,4-二基。 As formula (2), preferably among A1, A2 and A3, one is a partial structure shown in formula (1), and the other two are independently divalent organic groups; among A1, A2 and A3, formula ( 1) Cy in the partial structure shown is preferably a hydrocarbon ring group, and particularly preferably a divalent organic group is a hydrocarbon ring group. Furthermore, the hydrocarbon ring group is preferably 1,4-phenylene or cyclohexane-1,4-diyl. Also, one of A1 and A3 is preferably cyclohexane-1,4-diyl.

又，更佳係A1及A3中，一者為式(1)所示部分構造，其以外之一者及A2為2價有機基。此時，A1及A3中，屬於2價有機基之一者較佳為環己烷-1,4-二基，A2特佳為1,4-伸苯基。 Moreover, among A1 and A3, one is more preferably a partial structure represented by formula (1), and the other one and A2 are divalent organic groups. In this case, among A1 and A3, one of the divalent organic groups is preferably a cyclohexane-1,4-diyl group, and A2 is particularly preferably a 1,4-phenylene group.

由液晶化合物之直線性或有於分子短軸周圍之旋轉運動容易的傾向而言，作為-Y1-及-Y2-，較佳係分別獨立為π鍵結性較小的單鍵、-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、-CH2O-、-OCH2-、-CH2S-或-SCH2-，更佳為單鍵、-C(=O)O-、 -OC(=O)-、-CH2CH2-、-CH2O-、-OCH2-。 From the linearity of the liquid crystal compound or the tendency to easily rotate around the short axis of the molecule, as -Y1- and -Y2-, it is preferable to independently be a single bond with a small π bonding property, -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 preferred are single bond, -C(=O)O-, -OC(=O)-, -CH 2 CH 2 -, -CH 2 O-, -OCH 2 -.

如式(2A)、式(2C)、式(2D)、式(2F)般，在X與Y1或X與Y2鍵結的情況，與X鍵結之Y1或與X鍵結之Y2較佳為單鍵；-X-與-Y1-及-Y2-之另一者較佳為-C(=O)O-或-OC(=O)-。 As in formula (2A), formula (2C), formula (2D), and formula (2F), in the case where X is bonded to Y1 or X to Y2, Y1 bonded to X or Y2 bonded to X is preferable is a single bond; the other of -X- and -Y1- and -Y2- is preferably -C(=O)O- or -OC(=O)-.

又，如式(2B)、式(2E)般，在X均未與Y1及Y2之任一者鍵結的情況，-X-較佳為-CH2CH2-、-CH2O-或-OCH2-；-Y1-及-Y2-均較佳為-C(=O)O-或-OC(=O)-。 Also, as in formula (2B) and formula (2E), when none of X is bonded to any of Y1 and Y2, -X- is preferably -CH 2 CH 2 -, -CH 2 O- or -OCH 2 -; -Y1- and -Y2- are preferably -C(=O)O- or -OC(=O)-.

作為式(2)，較佳為上述式(2A)、上述式(2B)、上述式(2E)、上述式(2F)。 The formula (2) is preferably the above formula (2A), the above formula (2B), the above formula (2E), or the above formula (2F).

具體而言，作為式(2)可舉例如以下化合物，但並不限定於此等。 Specifically, the following compounds are exemplified as formula (2), but are not limited thereto.

[化5]

Figure 108109137-A0101-12-0035-5
[chemical 5]
Figure 108109137-A0101-12-0035-5

[化6]

Figure 108109137-A0101-12-0036-6
[chemical 6]
Figure 108109137-A0101-12-0036-6

[化7]

Figure 108109137-A0101-12-0037-7
[chemical 7]
Figure 108109137-A0101-12-0037-7

[化8]

Figure 108109137-A0101-12-0038-8
[chemical 8]
Figure 108109137-A0101-12-0038-8

[化9]

Figure 108109137-A0101-12-0039-9
[chemical 9]
Figure 108109137-A0101-12-0039-9

[化10]

Figure 108109137-A0101-12-0040-10
[chemical 10]
Figure 108109137-A0101-12-0040-10

[化11]

Figure 108109137-A0101-12-0041-11
[chemical 11]
Figure 108109137-A0101-12-0041-11

[化12]

Figure 108109137-A0101-12-0042-12
[chemical 12]
Figure 108109137-A0101-12-0042-12

[化13]

Figure 108109137-A0101-12-0043-13
[chemical 13]
Figure 108109137-A0101-12-0043-13

[化14]

Figure 108109137-A0101-12-0044-14
[chemical 14]
Figure 108109137-A0101-12-0044-14

[化15]

Figure 108109137-A0101-12-0045-15
[chemical 15]
Figure 108109137-A0101-12-0045-15

[化16]

Figure 108109137-A0101-12-0046-16
[chemical 16]
Figure 108109137-A0101-12-0046-16

本發明第一態樣之異向性色素膜形成用組成物所含有的第一態樣之液晶化合物，較佳係由具有上述式(1)所示部分構造的液晶化合物所構成。於此，本發明第一態樣之異向性色素膜形成用組成物所含有之第一態樣之液晶化合物，可為具有上述式(1)所示部分構造之液晶化合物的1種，亦可併用2種以上。又，亦可併用具有上述式(1)所示部分構造之液晶化合物以外的液晶化合物。 The liquid crystal compound of the first aspect contained in the anisotropic dye film-forming composition of the first aspect of the present invention is preferably composed of a liquid crystal compound having a partial structure represented by the above formula (1). Here, the liquid crystal compound of the first aspect contained in the anisotropic dye film-forming composition of the first aspect of the present invention may be one of the liquid crystal compounds having a partial structure represented by the above formula (1), or Two or more kinds can be used together. In addition, a liquid crystal compound other than the liquid crystal compound having the partial structure represented by the above formula (1) may be used in combination.

本發明第二態樣之異向性色素膜形成用組成物所含有之第二態樣之液晶化合物，係包含具有下述式(B1)所示部分構造 的液晶化合物。 The liquid crystal compound of the second aspect contained in the anisotropic dye film-forming composition of the second aspect of the present invention includes a liquid crystal compound having a partial structure represented by the following formula (B1).

-CyH-Z1-E1-C≡C-E2-‧‧‧(B1) -CyH-Z1-E1-C≡C-E2-‧‧‧(B1)

式(1)中，CyH表示經取代或無取代之非芳香族烴環基；E1及E2分別獨立表示烴環基或雜環基；-Z1-表示-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH=CH-、-C≡C-、-C(=O)NH-、-NHC(=O)-、-CH2O-、-OCH2-、-CH2S-或-SCH2-。 In formula (1), CyH represents a substituted or unsubstituted non-aromatic hydrocarbon ring group; E1 and E2 independently represent a hydrocarbon ring group or a heterocyclic group; -Z1- represents -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- .

CyH中之非芳香族烴環基係包括非連結非芳香族烴環基與連結非芳香族烴環基，其與本發明第一態樣之異向性色素膜形成用組成物之第一態樣之液晶化合物中，式(1)中之Cy的非芳香族烴環基同義。 The non-aromatic hydrocarbon ring group in CyH includes a non-linkage non-aromatic hydrocarbon ring group and a linking non-aromatic hydrocarbon ring group, which is consistent with the first aspect of the anisotropic pigment film-forming composition of the first aspect of the present invention In such liquid crystal compounds, the non-aromatic hydrocarbon ring group of Cy in formula (1) is synonymous.

又，CyH中之非芳香族烴環基中所容許的取代基，亦與本發明第一態樣之異向性色素膜形成用組成物之第一態樣之液晶化合物中，式(1)中之Cy的非芳香族烴環基中所容許的取代基相同。 In addition, the substituents allowed in the non-aromatic hydrocarbon ring group in CyH are also the same as in the liquid crystal compound of the first aspect of the anisotropic dye film-forming composition of the first aspect of the present invention, the formula (1) Among them, the permissible substituents of the non-aromatic hydrocarbon ring group of Cy are the same.

作為CyH中之非芳香族烴環基，較佳係環己烷之2價基(環己烷二基)。作為環己烷二基，由可提高液晶化合物之分子構造之直線性而言，較佳係經取代或無取代之環己烷-1,4-二基。 The non-aromatic hydrocarbon ring group in CyH is preferably a divalent group of cyclohexane (cyclohexanediyl). As the cyclohexanediyl group, a substituted or unsubstituted cyclohexane-1,4-diyl group is preferable because the linearity of the molecular structure of the liquid crystal compound can be improved.

又，CyH中經取代或無取代之非芳香族烴環基，由分子構造之直線性高、具有式(B1)所示部分構造之液晶化合物彼此容易會合而容易表現液晶狀態的觀點而言，較佳為無取代，或經甲基、甲氧基、氟原子、氯原子、溴原子取代，更佳為無取代。 In addition, the substituted or unsubstituted non-aromatic hydrocarbon ring group in CyH is highly linear in molecular structure, and the liquid crystal compounds having the partial structure shown in formula (B1) are easy to combine with each other and easily express the liquid crystal state. It is preferably unsubstituted, or substituted with a methyl group, methoxy group, a fluorine atom, a chlorine atom, or a bromine atom, more preferably unsubstituted.

E1及E2中之烴環基及雜環基，分別獨立與本發明第 一態樣之異向性色素膜形成用組成物之第一態樣之液晶化合物中，式(1)中之Cy的烴環基及雜環基同義。 The hydrocarbon cyclic group and heterocyclic group in E1 and E2 are respectively independently related to Cy in formula (1) in the liquid crystal compound of the first aspect of the anisotropic dye film-forming composition of the first aspect of the present invention. Hydrocarbyl and heterocyclyl are synonymous.

又，E1及E2中之烴環基及雜環基中所容許的取代基，亦分別獨立與本發明第一態樣之異向性色素膜形成用組成物之第一態樣之液晶化合物中，式(1)中之Cy的烴環基及雜環基中所容許的取代基相同。 In addition, the permissible substituents in the hydrocarbon ring group and heterocyclic group in E1 and E2 are also independently compatible with those in the liquid crystal compound of the first aspect of the composition for forming an anisotropic dye film according to the first aspect of the present invention. , the permissible substituents in the hydrocarbon ring group and heterocyclic group of Cy in formula (1) are the same.

又，E1及E2中之烴環基及雜環基中的較佳態樣，亦分別獨立與本發明第一態樣之異向性色素膜形成用組成物之第一態樣之液晶化合物中，式(1)中之Cy的烴環基及雜環基中的較佳態樣相同。 In addition, the preferred aspects of the hydrocarbon ring group and heterocyclic group in E1 and E2 are also independently related to the liquid crystal compound of the first aspect of the composition for forming an anisotropic dye film of the first aspect of the present invention. , the preferred aspects of Cy in the formula (1) are the same as the hydrocarbon ring group and the heterocyclyl group.

由液晶化合物之直線性或有於分子短軸周圍之旋轉運動容易的傾向而言，作為-Z1-，較佳係-C≡C-，或π鍵結性較小的-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH2O-、-OCH2-、-CH2S-、-SCH2-，更佳係-C(=O)O-、-OC(=O)-、-CH2CH2-、-CH2O-、-OCH2-。作為某態樣，-Z1-為-C(=O)O-或-OC(=O)-，作為其他態樣，-Z1-為-CH2CH2-、-CH2O-或-OCH2-。 From the linearity of the liquid crystal compound or the tendency to easily rotate around the short axis of the molecule, -Z1- is preferably -C≡C-, or -C(=O) with less π bonding 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 -, more preferably -C(=O)O-, -OC(=O)-, -CH 2 CH 2 - , -CH 2 O-, -OCH 2 -. In a certain aspect, -Z1- is -C(=O)O- or -OC(=O)-, and in another aspect, -Z1- is -CH 2 CH 2 -, -CH 2 O-, or -OCH 2 -.

本發明之異向性色素膜形成用組成物所含有之具有上述式(B1)所示部分構造之液晶化合物，可舉例如下述式(B2)所示液晶化合物。 The liquid crystal compound having the partial structure represented by the above formula (B1) contained in the anisotropic dye film forming composition of the present invention includes, for example, a liquid crystal compound represented by the following formula (B2).

T1-CyH-Z1-E1-C≡C-E2-Z2-E3-T2‧‧‧(B2) T1-CyH-Z1-E1-C≡C-E2-Z2-E3-T2‧‧‧(B2)

式(B2)中，CyH、E1及E2及-Z1-分別與上述式(B1)中之定義相同。 In formula (B2), CyH, E1 and E2, and -Z1- are respectively as defined in the above formula (B1).

T1及T2分別獨立表示鏈狀有機基。 T1 and T2 each independently represent a chain organic group.

E3表示2價有機基或單鍵； -Z2-表示單鍵、-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH=CH-、-C≡C-、-C(=O)NH-、-NHC(=O)-、-CH2O-、-OCH2-、-CH2S-或-SCH2-。 E3 represents a divalent organic group or a single bond; -Z2- represents 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- .

T1及T2中之鏈狀有機基係分別獨立與本發明第一態樣之異向性色素膜形成用組成物之第一態樣之液晶化合物中，式(2)中之R1及R2中之鏈狀有機基同義。 The chain organic groups in T1 and T2 are respectively independent from the liquid crystal compound of the first aspect of the anisotropic pigment film forming composition of the first aspect of the present invention, the R1 and R2 in the formula (2) Chain organic group is synonymous.

T1及T2分別獨立較佳係亦可經聚合性基取代的-(烷基)、烷基亦可經聚合性基取代的-O-(烷基)，更佳係經聚合性基取代的-(烷基)、烷基經聚合性基取代的-O-(烷基)。 T1 and T2 are independently preferably -(alkyl) that may also be substituted by a polymerizable group, -O-(alkyl) that may also be substituted by a polymerizable group, and more preferably - that is substituted by a polymerizable group (Alkyl), -O-(Alkyl) in which an alkyl group is substituted with a polymerizable group.

T1較佳係烷基亦可經聚合性基取代的-O-(烷基)，更佳係烷基經聚合性基取代的-O-(烷基)。 T1 is preferably -O-(alkyl) in which an alkyl group may be substituted with a polymerizable group, more preferably -O-(alkyl) in which an alkyl group is substituted with a polymerizable group.

在-Z2-為單鍵、E3為單鍵時，或E3為2價有機基時，T2較佳係烷基亦可經聚合性基取代的-O-(烷基)，更佳係烷基經聚合性基取代的-O-(烷基)。 When -Z2- is a single bond, E3 is a single bond, or E3 is a divalent organic group, T2 is preferably an alkyl group that may also be substituted by a polymerizable group -O-(alkyl group), more preferably an alkyl group -O-(alkyl) substituted with a polymerizable group.

在-Z2-為單鍵以外、E3為單鍵的情況，T2較佳係亦可經聚合性基取代的-(烷基)，更佳係經聚合性基取代的-(烷基)。 When -Z2- is a single bond and E3 is a single bond, T2 is preferably a -(alkyl group) which may be substituted with a polymerizable group, more preferably a -(alkyl group) which is substituted with a polymerizable group.

E3中之2價有機基，較佳係下述式(B3)所示基或單鍵。 The divalent organic group in E3 is preferably a group represented by the following formula (B3) or a single bond.

-Q1-‧‧‧(B3) -Q1-‧‧‧(B3)

上述式(B3)所示基，係與本發明第一態樣之異向性色素膜形成用組成物之第一態樣之液晶化合物中，屬於式(2)中之A1、A2及A3之2價有機基的式(3)所示基同義。 The group represented by the above formula (B3) belongs to A1, A2 and A3 in formula (2) in the liquid crystal compound of the first aspect of the anisotropic dye film forming composition of the first aspect of the present invention. The group represented by the formula (3) of the divalent organic group has the same meaning.

作為E3，較佳為伸苯基、環己烷二基或單鍵，更佳係1,4-伸苯基、環己烷-1,4-二基或單鍵。 E3 is preferably a phenylene group, a cyclohexanediyl group or a single bond, more preferably a 1,4-phenylene group, a cyclohexane-1,4-diyl group or a single bond.

由液晶化合物之直線性或有於分子短軸周圍之旋轉運動容易的傾向而言，作為-Z2-，較佳係-C≡C-，或π鍵結性較小的單鍵、-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、-CH2O-、-OCH2-、-CH2S-或-SCH2-，更佳係單鍵、-C(=O)O-、-OC(=O)-、-CH2CH2-、-CH2O-、-OCH2-。 From the linearity of the liquid crystal compound or the tendency to easily rotate around the short axis of the molecule, -Z2- is preferably -C≡C-, or a single bond with less π bonding, -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, it is a single bond, -C(=O)O-, -OC(=O)-, -CH 2 CH 2 -, -CH 2 O-, -OCH 2 -.

具體而言，作為式(B2)可舉例如以下化合物，但並不限定於此等。 Concretely, although the following compounds are mentioned as Formula (B2), it is not limited to these.

[化17]

Figure 108109137-A0101-12-0051-17
[chemical 17]
Figure 108109137-A0101-12-0051-17

[化18]

Figure 108109137-A0101-12-0052-18
[chemical 18]
Figure 108109137-A0101-12-0052-18

[化19]

Figure 108109137-A0101-12-0053-19
[chemical 19]
Figure 108109137-A0101-12-0053-19

[化20]

Figure 108109137-A0101-12-0054-20
[chemical 20]
Figure 108109137-A0101-12-0054-20

本發明第二態樣之異向性色素膜形成用組成物所含有之第二態樣之液晶化合物，較佳係由具有上述式(B1)所示部分構造的液晶化合物所構成。於此，本發明第二態樣之異向性色素膜形成用組成物所含有之第二態樣之液晶化合物可為具有上述式(B1)所示部分構造之液晶化合物的1種，亦可併用2種以上。又，亦可併用具有上述式(B1)所示部分構造之液晶化合物以外的液晶化合物。 The liquid crystal compound of the second aspect contained in the anisotropic dye film-forming composition of the second aspect of the present invention is preferably composed of a liquid crystal compound having a partial structure represented by the above formula (B1). Here, the liquid crystal compound of the second aspect contained in the composition for forming an anisotropic dye film of the second aspect of the present invention may be one of the liquid crystal compounds having the partial structure represented by the above formula (B1), or may be Use 2 or more kinds together. Moreover, a liquid crystal compound other than the liquid crystal compound which has the partial structure represented by said formula (B1) can also be used together.

本發明之異向性色素膜形成用組成物所含有的液晶化合物，由製程之觀點而言，其等向相表觀溫度一般為未滿200℃，較佳為未滿160℃、更佳為未滿140℃、再更佳為未滿115℃、又更佳為未滿110℃、特佳為未滿105℃。 The apparent temperature of the isotropic phase of the liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention is generally less than 200°C, preferably less than 160°C, more preferably It is less than 140°C, more preferably less than 115°C, still more preferably less than 110°C, and most preferably less than 105°C.

尚且，於此所謂等向相表觀溫度，意指由液晶至液體的相轉移溫度及由液體至液晶的相轉移溫度。本發明中，較佳係此等相轉移溫度之至少一者為上述範圍，更佳係此等相轉移溫度之兩者為上述範圍。 Furthermore, the apparent temperature of the isotropic phase here 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 these phase transition temperatures is in the above-mentioned range, and it is more preferable that both of these phase-transition temperatures are in the above-mentioned range.

本發明之異向性色素膜形成用組成物所含有的液晶化合物，可藉由組合烷基化反應、酯化反應、醯胺化反應、醚化反應、本位取代反應、使用金屬觸媒之偶合反應等公知化學反應而製造。 The liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention can be coupled by a combination of alkylation reaction, esterification reaction, amidation reaction, etherification reaction, native substitution reaction, and coupling using a metal catalyst. reaction and other known chemical reactions.

例如，本發明之異向性色素膜形成用組成物所含有的液晶化合物，可依照實施例記載之方法、或「液晶便覽」(丸善股份有限公司，2000年10月30日發行)之449~468頁記載的方法進行合成。 For example, the liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention can be obtained according to the method described in the examples, or 449-449 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., issued on October 30, 2000). The method described on page 468 was used for synthesis.

(溶劑) (solvent)

本發明之異向性色素膜形成用組成物視需要亦可含有溶劑。 The composition for anisotropic dye film formation of this invention may contain a solvent as needed.

作為可使用之溶劑，若為可使色素或其他添加劑充分分散或溶解於液晶化合物中者則無特別限定，可舉例如甲醇、乙醇、乙二醇、異丙醇、丙二醇、乙二醇甲基醚、乙二醇丁基醚、丙二醇單甲醚等醇溶劑；醋酸乙酯、醋酸丁酯、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。 Usable solvents are not particularly limited as long as they can sufficiently disperse or dissolve pigments or other additives in liquid crystal compounds, and examples include methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl Ether, ethylene glycol butyl ether, propylene glycol monomethyl ether and other alcohol solvents; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate Ester solvents; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone and other ketone solvents; pentane, hexane, heptane and other aliphatic hydrocarbon solvents; toluene , xylene and other aromatic hydrocarbon solvents; acetonitrile and other nitrile solvents; tetrahydrofuran, dimethoxyethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and other ether solvents; perfluorobenzene, perfluorotoluene, perfluorodeca Fluorine-containing solvents such as hydronaphthalene, perfluoromethylcyclohexane, and hexafluoro-2-propanol; and chlorinated solvents such as chloroform, methylene chloride, chlorobenzene, and dichlorobenzene.

此等溶劑可僅使用一種，亦可組合使用2種以上。 These solvents may be used alone or in combination of two or more.

溶劑較佳係可溶解液晶化合物及色素的溶劑，更佳係使液晶化合物及色素完全溶解的溶劑。又，在液晶化合物為聚合性化合物時，較佳係對聚合反應呈惰性的溶劑。又，由後述之塗佈本 發明之異向性色素膜形成用組成物的觀點而言，較佳係沸點為50~200℃之範圍的溶劑。 The solvent is preferably a solvent capable of dissolving the liquid crystal compound and the pigment, more preferably a solvent capable of completely dissolving the liquid crystal compound and the pigment. Also, when the liquid crystal compound is a polymerizable compound, it is preferably a solvent inert to the polymerization reaction. Also, from the viewpoint of coating the anisotropic dye film-forming composition of the present invention described later, it is preferably a solvent having a boiling point in the range of 50 to 200°C.

在本發明之異向性色素膜形成用組成物含有溶劑的情況，異向性色素膜形成用組成物中溶劑所佔的含有比例，係相對於本發明之組成物之總量(100質量%)，較佳為50~98質量%。換言之，本發明之異向性色素膜形成用組成物中之固形份較佳為2~50質量%。 In the case where 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 relative to the total amount of the composition of the present invention (100 mass % ), preferably 50 to 98% by mass. In other words, the solid content in the anisotropic dye film-forming composition of the present invention is preferably 2 to 50% by mass.

異向性色素膜形成用組成物中之固形份含量若為上述上限值以下，則有異向性色素膜形成用組成物之黏度不致變得過高，所得偏光膜之厚度均勻，有偏光膜不易發生不均的傾向。 If the solid content in the composition for forming an anisotropic dye film is below the above upper limit, the viscosity of the composition for forming an anisotropic dye film will not become too high, and the obtained polarizing film will have uniform thickness and polarized light. The film tends to be less prone to unevenness.

此種固形份含量可考慮所欲製造之偏光膜之厚度而決定。 Such solid content can be determined in consideration of the thickness of the polarizing film to be manufactured.

本發明之異向性色素膜形成用組成物之黏度係藉由後述塗佈方法，若可製造無厚度不均之均勻膜則無特別限制，但由可得到大面積時之厚度均勻性、塗佈速度等生產性、光學特性之面內均勻性的觀點而言，較佳為0.1mPa‧s以上，且較佳為500mPa‧s以下、更佳為100mPa‧s以下、再更佳為50mPa‧s以下。 The viscosity of the anisotropic pigment film-forming composition of the present invention is not particularly limited if a uniform film without thickness unevenness can be produced by the coating method described later. From the standpoint of productivity such as cloth speed and in-plane uniformity of optical properties, it is preferably at least 0.1mPa‧s, preferably at most 500mPa‧s, more preferably at most 100mPa‧s, and still more preferably at least 50mPa‧ below s.

(其他添加劑) (other additives)

本發明之異向性色素膜形成用組成物進一步視需要，亦可含有具有上述式(1)所示部分構造之液晶化合物以外的聚合性液晶化合物、具有上述式(1)所示部分構造之液晶化合物以外的非聚合性液晶化合物、聚合起始劑、聚合停止劑、聚合助劑、聚合性非液晶化合物、界面活性劑、均染劑、偶合劑、pH調整劑、分散劑、抗氧化劑、有機‧無機填充材、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。藉由含有添加劑，有可提升異向性色素膜形成用組成物之塗佈性或穩定性等，或提升由異向性色素膜形成用組成物所形成之異向性色素膜之穩定性的情形。 The anisotropic dye film-forming composition of the present invention may further contain a polymerizable liquid crystal compound other than a liquid crystal compound having a partial structure represented by the above formula (1), or a liquid crystal compound having a partial structure represented by the above formula (1), if necessary. Non-polymerizable liquid crystal compounds other than liquid crystal compounds, polymerization initiators, polymerization stoppers, polymerization assistants, polymerizable non-liquid crystal compounds, surfactants, leveling agents, coupling agents, pH adjusters, dispersants, antioxidants, Organic‧inorganic fillers, organic‧inorganic nanosheets, organic‧inorganic nanofibers, metal oxides and other additives. By containing additives, it is possible to improve the applicability or stability of the composition for forming an anisotropic dye film, or to improve the stability of the anisotropic dye film formed from the composition for forming an anisotropic dye film. situation.

[異向性色素膜形成用組成物之製造方法] [Manufacturing Method of Composition for Forming Anisotropic Dye Film]

製造本發明之異向性色素膜形成用組成物的方法並無特別限定。例如將色素、液晶化合物、視需要之溶劑、其他添加劑等混合，依0~80℃進行攪拌、振盪而溶解色素。在難溶性的情況，亦可使用均質機、球磨分散機等。 The method of manufacturing the composition for anisotropic dye film formation of this invention is not specifically limited. For example, mix pigment, liquid crystal compound, solvent if necessary, other additives, etc., stir and vibrate at 0~80°C to dissolve the pigment. In the case of poor solubility, a homogenizer, ball mill disperser, etc. can also be used.

作為製造本發明之異向性色素膜形成用組成物的方法，依去除組成物中之異物等的目的，亦可具有過濾步驟。 As a method of producing the anisotropic dye film-forming composition of the present invention, a filtration step may be included for the purpose of removing foreign substances in the composition.

本發明之異向性色素膜形成用組成物中，由異向性色素膜形成用組成物去除了溶劑的組成物可於任意溫度下為液晶或不為液晶，但較佳係於任意溫度下顯示液晶性。由異向性色素膜形成用組成物去除了溶劑的組成物，由下述記載之塗佈製程的觀點而言，其等向相表觀溫度一般為未滿200℃、較佳為未滿160℃、更佳為未滿140℃、再更佳為未滿115℃、又更佳為未滿110℃、特佳為未滿105℃。 In the anisotropic dye film-forming composition of the present invention, the composition from which the solvent is removed from the anisotropic dye film-forming composition may be liquid crystal or not at any temperature, but is preferably at any temperature Shows liquid crystallinity. From the composition for forming an anisotropic dye film from which the solvent has been removed, the apparent temperature of the isotropic phase is generally less than 200°C, preferably less than 160°C from the viewpoint of the coating process described below. °C, more preferably less than 140°C, still more preferably less than 115°C, still more preferably less than 110°C, most preferably less than 105°C.

[異向性色素膜] [Anisotropic pigment film]

本發明之異向性色素膜係含有色素及具有上述式(1)所示部分構造之液晶化合物(其中，在具有上述式(1)所示部分構造之液晶化合物為聚合性化合物時，係含有色素、與具有上述式(1)所示部分構造之液晶化合物及具有基於具有上述式(1)所示部分構造之液晶化 合物之單元的聚合物的一者或兩者)。 The anisotropic pigment film of the present invention contains a pigment and a liquid crystal compound having a partial structure represented by the above formula (1) (wherein, when the liquid crystal compound having a partial structure represented by the above formula (1) is a polymerizable compound, it contains One or both of a pigment, a liquid crystal compound having a partial structure represented by the above formula (1), and a polymer having a unit based on a liquid crystal compound having a partial structure represented by the above formula (1).

本發明之異向性色素膜亦可含有具有上述式(1)所示部分構造之液晶化合物以外的聚合性液晶化合物、非聚合性液晶化合物、聚合起始劑、聚合停止劑、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、均染劑、偶合劑、pH調整劑、分散劑、抗氧化劑、有機‧無機填充材、有機‧無機奈米片材、有機‧無機奈米纖維、金屬氧化物等。 The anisotropic dye film of the present invention may also contain polymerizable liquid crystal compounds, non-polymerizable liquid crystal compounds, polymerization initiators, polymerization stoppers, polymerization assistants, Polymeric non-liquid crystal compounds, non-polymerizable non-liquid crystal compounds, surfactants, leveling agents, coupling agents, pH regulators, dispersants, antioxidants, organic‧inorganic fillers, organic‧inorganic nanosheets, organic‧ Inorganic nanofibers, metal oxides, etc.

本發明之異向性色素膜可使用本發明之異向性色素膜形成用組成物而形成。 The anisotropic dye film of the present invention can be formed using the anisotropic dye film-forming composition of the present invention.

本發明之異向性色素膜係利用光吸收之異向性，而發揮可得到直線偏光、圓偏光、楕圓偏光等之偏光膜的機能，此外，藉由選擇膜形成製程與基板或含有有機化合物(色素或透明材料)之組成物，可機能化為折射異向性或傳導異向性等各種異向性色素膜。 The anisotropic pigment film of the present invention utilizes the anisotropy of light absorption to exert the function of polarizing films that can obtain linearly polarized light, circularly polarized light, and elliptically polarized light. In addition, by selecting the film forming process and substrate or containing organic The composition of compounds (pigments or transparent materials) can be functionalized into various anisotropic pigment films such as refractive anisotropy or conduction anisotropy.

在將本發明之異向性色素膜使用作為液晶顯示器用、或OLED用抗反射膜之偏光元件時，異向性色素膜之配向特性可使用二色比而表示。若二色比為8以上，則具有作為偏光元件之機能，較佳為15以上、更佳為20以上、再更佳為25以上、特佳為30以上、又更佳為40以上。又，二色比越高越佳。藉由二色比為上述下限值以上，可用於作為後述光學元件、尤其是偏光元件。 When the anisotropic dye film of the present invention is used as a polarizing element for a liquid crystal display or an antireflection film for an OLED, the alignment characteristics of the anisotropic dye film can be expressed using a dichroic ratio. If the dichroic ratio is 8 or more, it can function as a polarizing element. It is preferably 15 or more, more preferably 20 or more, still more preferably 25 or more, particularly preferably 30 or more, and more preferably 40 or more. Also, the higher the dichromatic ratio, the better. When the dichromatic ratio is more than the above-mentioned lower limit, it can be used as an optical element described later, especially a polarizing element.

在使用作為OLED用抗反射膜之偏光元件時，即使相位差膜等周邊材料之性能較低，若偏光元件之性能較高，作為抗反射膜之特性仍提升。因此，若偏光元件之性能高，則容易使層構成簡單化，即使為薄膜構成仍容易表現充分機能，亦可適合使用於使其凹折、 彎曲之變形而使用的用途中。又，亦可抑低成本。 When using a polarizing element as an antireflection film for OLED, even if the performance of peripheral materials such as a retardation film is low, if the performance of the polarizing element is high, the characteristics as an antireflection film are still improved. Therefore, if the performance of the polarizing element is high, it is easy to simplify the layer structure, and it is easy to exhibit sufficient functions even if it is a thin film structure, and it is also suitable for use in applications where it is deformed by concave folding or bending. In addition, the cost can also be kept down.

本發明所謂二色比(D)，於色素配向一致時，由下式表示。 In the present invention, the dichromatic ratio (D) is represented by the following formula when the dyes are aligned uniformly.

D=Az/Ay D=Az/Ay

於此，Az係入射至異向性色素膜之光之偏光方向與異向性色素之配向方向平行時所觀測到之吸光度，Ay係入射至異向性色素膜之光之偏光方向垂直時所觀測到之吸光度。 Here, Az is the absorbance observed when the polarization direction of the light incident on the anisotropic pigment film is parallel to the alignment direction of the anisotropic pigment, and Ay is the absorbance observed when the polarization direction of the light incident on the anisotropic pigment film is vertical. The observed absorbance.

各吸光度只要使用相同波長者則無特別限制，可視目的選擇任意波長，但於表示異向性色素膜之配向程度時，較佳係使用於異向性色素膜之380nm~780nm之特定波長區域藉視感度經修正的值，或可見區域之極大吸收波長時之值。 As long as the same wavelength is used for each absorbance, there is no special limitation. Any wavelength can be selected according to the purpose. However, when expressing the degree of alignment of the anisotropic pigment film, it is better to use the specific wavelength region of 380nm~780nm of the anisotropic pigment film. The corrected value of visual sensitivity, or the value at the wavelength of maximum absorption in the visible region.

進而，本發明之異向性色素膜於可見光波長區域之穿透率，較佳為25%以上、更佳為35%以上，特佳為40%以上。又，穿透率之上限係配合用途即可。例如，於提高偏光度時，穿透率較佳為50%以下。藉由穿透率為上述範圍，可用作為後述光學元件，尤其可用作為用於彩色顯示之液晶顯示器用、或組合了異向性色素膜與相位差膜的抗反射膜用的光學元件。 Furthermore, the transmittance of the anisotropic pigment film of the present invention in the visible light wavelength region is preferably at least 25%, more preferably at least 35%, and most preferably at least 40%. Also, the upper limit of the transmittance can be adjusted according to the application. For example, when the degree of polarization is increased, the transmittance is preferably below 50%. With the transmittance in the above range, it can be used as an optical element described later, especially as an optical element for a liquid crystal display for color display or an antireflection film combining an anisotropic dye film and a retardation film.

異向性色素膜之膜厚係以乾燥膜厚計，較佳為10nm以上、更佳為100nm以上、再更佳為500nm以上。另一方面，較佳為30μm以下、更佳為10μm以下、再更佳為5μm以下、特佳為3μm以下。藉由異向性色素膜之膜厚為上述範圍，有可於膜內得到色素之均勻配向及均勻膜厚的傾向。 The film thickness of the anisotropic pigment film is based on the dry film thickness, and is preferably at least 10 nm, more preferably at least 100 nm, and even more preferably at least 500 nm. On the other hand, it is preferably 30 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, particularly preferably 3 μm or less. When the film thickness of the anisotropic dye film is within the above-mentioned range, there is a tendency that uniform alignment of the dye and a uniform film thickness can be obtained in the film.

[異向性色素膜之製造方法] [Manufacturing method of anisotropic pigment film]

本發明之異向性色素膜較佳係使用本發明之異向性色素膜形成用組成物，藉由濕式成膜法所製造。 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.

本發明中之所謂濕式成膜法，係指利用任意手法於基板上塗佈異向性色素膜形成用組成物並使其配向的方法。因此，異向性色素膜形成用組成物若具有流動性即可，可含有或不含溶劑。由塗佈時之黏度或膜均勻性的觀點而言，更佳係含有溶劑。 The wet film-forming method in the present invention refers to a method of applying and aligning the anisotropic dye film-forming composition on a substrate by any method. Therefore, the anisotropic dye film-forming composition may contain or may not contain a solvent as long as it has fluidity. From the viewpoint of viscosity at the time of coating or film uniformity, it is more preferable to contain a solvent.

異向性色素膜中之液晶或色素的配向，可於塗佈過程藉由剪切等而進行配向，亦可於溶劑乾燥之過程中進行配向。又，亦可於塗佈、乾燥後進行加熱，經過使液晶或色素等再配向的製程，使液晶或色素等於基板上配向、積層。於濕式成膜法中，若於基板上賦予異向性色素膜形成用組成物，則立即於異向性色素膜形成用組成物中、或在溶劑乾燥的過程中、或溶媒被完全去除後，色素或液晶化合物藉由進行自己會合(液晶狀態等之分子會合狀態)而產生微小面積之配向。藉由對此狀態賦予外場而於宏觀區域朝固定方向配向，可獲得具有所需性能之異向性色素膜。此點係與以將聚乙烯醇(PVA)膜等利用包含色素之溶液進行染色並延伸、並僅利用延伸步驟使色素配向為原理的方法相異。尚且，於此所謂外場，可舉例如預先對基板上所施加之配向處理層之影響、剪切力、磁場、電場、熱等，其等可單獨使用，亦可組合複數種而使用。視需要亦可經過加熱步驟。 The alignment of liquid crystals or pigments in the anisotropic pigment film can be carried out by shearing or the like during the coating process, and can also be carried out during the solvent drying process. In addition, it can also be heated after coating and drying, and through a process of realigning liquid crystals or pigments, etc., the liquid crystals or pigments can be aligned and laminated on the substrate. In the wet film-forming method, if the composition for forming an anisotropic dye film is applied to the substrate, it is immediately in the composition for forming an anisotropic dye film, or in the process of drying the solvent, or the solvent is completely removed Afterwards, the pigment or liquid crystal compound undergoes self-assembly (molecular assembly state such as liquid crystal state) to produce alignment in a small area. By applying an external field to this state to align in a fixed direction in the macroscopic region, an anisotropic pigment film with desired properties can be obtained. This point is different from a method in which a polyvinyl alcohol (PVA) film or the like is dyed with a solution containing a dye, stretched, and the dye is aligned only by the stretching step. Furthermore, the term "external field" here includes, for example, the influence of an alignment treatment layer previously applied on the substrate, shear force, magnetic field, electric field, heat, etc., and these may be used alone or in combination. A heating step may also be performed if desired.

將異向性色素膜形成用組成物賦予至基板上進行成膜的過程、賦予外場使其配向的過程、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 forming an 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.

作為濕式成膜法中對基板上賦予異向性色素膜形成 用組成物之方法，可舉例如塗佈法、浸漬塗佈法、LB膜形成法、公知之印刷法等。又，亦有將如此獲得之異向性色素膜轉印至另一基板之方法。 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, an LB film forming method, and a known printing method. Moreover, there is also a method of transferring the anisotropic dye film thus obtained to another substrate.

於該等中，較佳係使用塗佈法將異向性色素膜形成用組成物賦予至基板上。 Among them, it is preferable to apply the composition for anisotropic dye film formation on a board|substrate using the coating method.

異向性色素膜之配向方向亦可與塗佈方向不同。尚且，於本發明中，所謂異向性色素膜之配向方向，例如若為偏光膜，則為偏光之穿透軸(偏光軸)或吸收軸，若為相位差膜，則為進相軸或遲相軸。 The alignment direction of the anisotropic pigment film may also be different from the coating direction. Moreover, in the present invention, the alignment direction of the so-called anisotropic pigment film is, for example, if it is a polarizing film, then it is the transmission axis (polarization axis) or absorption axis of polarized light, and if it is a retardation film, it is the phase advancement axis or lagging axis.

作為塗佈異向性色素膜形成用組成物而獲得異向性色素膜之方法，並無特別限定，可舉例如原崎勇次著「塗佈工學」(朝倉書店股份有限公司，1971年3月20日發行)之253~277頁所記載之方法、市村國宏監修「分子協調材料之創製與應用」(CMC股份有限公司出版，1998年3月3日發行)之118~149頁所記載之方法、於具有段差構造之基板(亦可預先實施配向處理)上利用狹縫式模塗法、旋轉塗佈法、噴塗法、棒塗法、輥塗法、刮刀塗佈法、淋幕式塗佈法、噴注法、浸漬法等進行塗佈之方法。其中，若採用狹縫式模塗法或棒塗法，可獲得均勻性較高之異向性色素膜故而較佳。 The method for obtaining the anisotropic dye film by applying the composition for forming the anisotropic dye film is not particularly limited, and examples thereof include "Coating Engineering" by Yuji Harasaki (Asakura Shoten Co., Ltd., March 1971) The method recorded on pages 253~277, issued on the 20th), and the method recorded on pages 118~149 of "Creation and Application of Molecular Coordination Materials" supervised by Kunihiro Ichimura (published by CMC Co., Ltd., released on March 3, 1998) Method, use slot die coating method, spin coating method, spray coating method, rod coating method, roller coating method, doctor blade coating method, curtain coating method on the substrate with step difference structure (orientation treatment can also be implemented in advance) Coating methods such as cloth method, jet injection method, dipping method, etc. Among them, it is preferable to use the slot die coating method or the bar coating method because a highly uniform anisotropic pigment film can be obtained.

狹縫式模塗法所使用之模塗機，係一般吐出塗佈液之塗佈機，具備所謂的狹縫式模。狹縫式模揭示於例如日本專利特開平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‧乾燥之基礎與應用」(2014年，Techno System股份有限公司，ISBN9784924728707 C 305)、「顯示器‧光學構件之濕式塗佈技術」(2007年，資訊機構，ISBN9784901677752)、「電子領域之精密塗佈‧乾燥技術」(2007 年，技術資訊協會，ISBN9784861041389)等。此等公知之狹縫式模即使係薄膜或帶等具可撓性之構件或如玻璃基板般之硬構件亦可實施塗佈。 The die coater used in the slot die coating method is a coater that generally discharges a coating liquid and has a so-called slot die. Slot dies are disclosed in, for example, 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" ( In 2014, Techno System Co., Ltd., ISBN9784924728707 C 305), "Wet Coating Technology of Display‧Optical Components" (2007, Information Agency, ISBN9784901677752), "Precision Coating‧Drying Technology in the Electronic Field" (2007 , Technical Information Association, ISBN9784861041389), etc. These well-known slot dies can be coated even on flexible members such as films or tapes, or hard members such as glass substrates.

作為本發明之異向性色素膜形成中所使用之基板，可舉例如玻璃或三乙酸酯、丙烯酸、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、三乙醯基纖維素或胺基甲酸乙酯系之薄膜等。又，於該基板表面，為了控制色素之配向方向，亦可藉由「液晶便覽」(丸善股份有限公司，2000年10月30日發行)之226~239頁等記載之公知之方法(摩擦定向法、於配向膜表面上形成溝(細微之溝構造)之方法、使用偏光紫外光‧偏光雷射之方法(光配向法)、由形成LB膜所進行之配向方法，由無機物之斜向蒸鍍所進行之配向方法等)施行配向處理(配向膜)。特佳可舉例如摩擦定向法、由光配向法所進行之配向處理。作為摩擦定向法所使用之材料，可舉例如聚乙烯醇(PVA)、聚醯亞胺(PI)、環氧樹脂、丙烯酸樹脂等。作為光配向法所使用之材料，可舉例如聚桂皮酸酯系、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，可認為藉由配向處理層之配向處理的影響、與塗佈時對異向性色素膜形成用組成物施加之剪切力，液晶化合物或色素進行配向。 As the substrate used in the formation of 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 films, etc. Also, on the surface of the substrate, in order to control the alignment direction of the pigment, it is also possible to use a known method (rubbing alignment) described on pages 226 to 239 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., issued on October 30, 2000). Method, method of forming grooves (fine groove structure) on the surface of alignment film, method of using polarized ultraviolet light‧polarized laser (photoalignment method), alignment method by forming LB film, oblique evaporation of inorganic substances The alignment method performed by plating, etc.) performs alignment treatment (alignment film). Particularly preferred examples include rubbing alignment and alignment treatment by photo-alignment. Examples of materials used in the rubbing alignment method include polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, and acrylic resin. Examples of materials used in the photo-alignment method include polycinnamate-based, polyamic acid-polyimide-based, azobenzene-based, and the like. 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 anisotropic dye film-forming composition during coating.

於塗佈異向性色素膜形成用組成物時，異向性色素膜形成用組成物之供給方法、供給間隔並無特別限定。由於有塗佈液之供給操作變得繁雜、或於塗佈液之開始時與停止時發生塗佈膜厚變動的情形，故在異向性色素膜之膜厚較薄時，較理想係連續地供給異向性色素膜形成用組成物而進行塗佈。 When applying the composition for anisotropic dye film formation, the supply method and supply interval of the composition for anisotropic dye film formation are not specifically limited. Since the supply operation of the coating liquid becomes complicated, or the coating film thickness varies between the start and stop of the coating liquid, when the film thickness of the anisotropic pigment film is thin, it is preferable to use continuous The composition for forming an anisotropic dye film is supplied and coated.

作為塗佈異向性色素膜形成用組成物之速度，通常為0.001m/分鐘以上、較佳為0.01m/分鐘以上、更佳為0.1m/分鐘以上、再更佳為1.0m/分鐘以上、特佳為5.0m/分鐘以上。又，通常為400m/分鐘以下、較佳為200m/分鐘以下、更佳為100m/分鐘以下、再更佳為50m/分鐘以下。藉由塗佈速度為上述範圍，可得到異向性色素膜之異向性，有可均勻塗佈的傾向。 The speed at which the composition for forming an anisotropic dye film is applied is usually at least 0.001 m/min, preferably at least 0.01 m/min, more preferably at least 0.1 m/min, still more preferably at least 1.0 m/min , especially preferably more than 5.0m/min. Moreover, it 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. When the coating speed is within the above range, the anisotropy of the anisotropic dye film can be obtained, and there is a tendency that uniform coating can be achieved.

作為異向性色素膜形成用為組成物之塗佈溫度，通常為0℃以上且100℃以下、較佳為80℃以下、更佳為60℃以下。 The coating temperature of the composition for forming an anisotropic dye film is usually not less than 0°C and not more than 100°C, preferably not more than 80°C, more preferably not more than 60°C.

異向性色素膜形成用組成物之塗佈時之濕度，較佳為10%RH以上，且較佳為80RH%以下。 The humidity at the time of application of the composition for forming an anisotropic dye film is preferably 10%RH or more and preferably 80RH% or less.

對於異向性色素膜亦可進行不溶化處理。所謂不溶化，意指藉由使異向性色素膜中之化合物之溶解性降低，控制化合物由異向性色素膜之溶出，提高膜之穩定性的處理。 Insolubilization treatment can also be carried out for anisotropic pigment film. The so-called insolubilization refers to the treatment of improving the stability of the film by reducing the solubility of the compound in the anisotropic dye film to control the dissolution of the compound from the anisotropic dye film.

具體而言，由後步驟之容易度、異向性色素膜之耐久性等觀點而言，較佳係膜之聚合或保護層塗佈等。 Specifically, from the viewpoints of easiness of subsequent steps and durability of the anisotropic dye film, polymerization of a system film, coating of a protective layer, and the like are preferable.

於進行膜之聚合時，對液晶分子與色素分子經配向的膜，使用光、熱、及/或放射線進行聚合。 When polymerizing the film, 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時，較佳係照射波長190~450nm範圍內的活性能量射線。 When polymerization is performed using light or radiation, it is preferable to irradiate active energy rays within a wavelength range of 190 to 450 nm.

波長190~450nm之活性能量射線的光源並無特別限定，可舉例如氙氣燈、鹵素燈、鎢燈、高壓水銀燈、超高壓水銀燈、金屬鹵素燈、中壓水銀燈、低壓水銀燈、碳弧、螢光燈等燈光源；氬離子雷射、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。在照射使用特定波長光時，亦可利用光學濾波器。活性 能量射線之曝光量較佳為1~100,000J/m2、更佳為10~10,000J/m2。 The source of active energy rays with a wavelength of 190-450nm is not particularly limited, and examples include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps. Lamp and other light sources; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, etc. When using light of a specific wavelength for irradiation, an optical filter can also be used. The exposure dose of active energy rays is preferably 1 to 100,000 J/m 2 , more preferably 10 to 10,000 J/m 2 .

於使用熱進行聚合時，較佳係依50~200℃之範圍進行、更佳係依60~150℃之範圍進行。 When polymerizing with heat, it is preferably carried out in the range of 50~200°C, more preferably in the range of 60~150°C.

亦可使用光、熱及/或放射線進行聚合，但使用光聚合、或併用光聚合與熱聚合時之膜形成製程的時間較短、裝置亦簡便，故較佳。 Polymerization can also be performed using light, heat and/or radiation, but it is preferable to use photopolymerization or a combination of photopolymerization and thermal polymerization because the film formation process takes a short time and the equipment is simple.

[光學元件] [Optical element]

本發明之光學元件係含有本發明之異向性色素膜。 The optical element of the present invention contains the anisotropic dye film of the present invention.

本發明之光學元件係表示利用光吸收之異向性而獲得直線偏光、圓偏光、橢圓偏光等之偏光元件、相位差元件、具有折射異向性或傳導異向性等機能之元件。此等機能可藉由異向性色素膜形成製程、與基板或含有有機化合物(色素或透明材料)之組成物的選擇而適當調整。 The optical element of the present invention refers to a polarizing element, a phase difference element, an element having functions such as refraction 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 through the formation process of the anisotropic pigment film, and the selection of the substrate or the composition containing organic compounds (pigment or transparent material).

本發明之光學元件最佳係使用作為偏光元件。 The optical element of the present invention is preferably used as a polarizing element.

本發明之光學元件由藉由塗佈於基板上等而形成異向性色素膜可得到偏光元件的觀點而言，亦可適合使用於可撓性顯示器等用途。 The optical element of the present invention can also be suitably used for applications such as flexible displays from the viewpoint that a polarizing element can be obtained by forming an anisotropic dye film on a substrate or the like.

為了維持、提升異向性色素膜之機能，光學元件亦可設置其他層。可舉例如：用於提升耐光性、耐熱性、耐水性等耐久性所使用的具有阻斷特定波長之機能的層或具有阻斷特定物質之機能的層(氧阻斷薄膜、水蒸氣阻斷薄膜等遮蔽薄膜等)；用於改變色域、或提升光學特性所使用的波長濾阻器或含有吸收特定波長之材料的層等。 In order to maintain and improve the performance of the anisotropic pigment film, the optical element can also be provided with 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 vapor blocking film) used to improve durability such as light resistance, heat resistance, and water resistance Films and other shielding films, etc.); wavelength filters used to change the color gamut, or to improve optical characteristics, or layers containing materials that absorb specific wavelengths, etc.

[偏光元件] [Polarizer]

本發明之偏光元件若為具有本發明之異向性色素膜者，則可為具有其他任何膜(層)者。例如，可藉由於基板上設置配向膜，並於該配向膜之表面形成本發明之異向性色素膜而製造。 As long as the polarizing element of the present invention has the anisotropic dye film of the present invention, it may have any other film (layer). 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.

又，偏光元件並不侷限於異向性色素膜，亦可組合使用具有提升偏光性能、提升機械強度等機能的保護塗層；黏著層或抗反射層；配向膜；具有作為相位差薄膜之機能、作為亮度提高薄膜之機能、作為反射或抗反射薄膜之機能、作為半穿透反射薄膜之機能、作為擴散薄膜之機能等光學機能之層等。具體而言，可將上述具有各種機能之層藉由塗佈或貼合等進行積層形成，作成積層體而使用。 In addition, the polarizing element is not limited to the anisotropic pigment film, and can also be used in combination with a protective coating that has the functions of improving polarizing performance and mechanical strength; an adhesive layer or an anti-reflection layer; an alignment film; and has the function of a retardation film. , A layer with optical functions such as a function of a brightness-enhancing film, a function of a reflective or anti-reflective film, a function of a semi-transmissive reflective film, a function of a diffusion film, etc. Specifically, the above-mentioned layers having various functions can be laminated and formed by coating, bonding, etc., and can be used as a laminate.

此等層可配合製造製程、特性及機能而適當設置，其積層之位置、順序並無特別限定。例如，形成各層之位置可形成於異向性色素膜上，亦可形成於設置有異向性色素膜之基板的相反面。又，形成各層之順序可為形成異向性色素膜之前或之後。 These layers can be appropriately arranged in accordance with the manufacturing process, characteristics and functions, and the position and sequence of the stacked layers are not particularly limited. For example, the position where each layer is formed may be formed on the anisotropic dye film, or may be formed on the opposite side of the substrate on which the anisotropic dye film is provided. Moreover, the order of forming each layer may be before or after forming an anisotropic dye film.

此等具有光學機能之層可藉由以下方法形成。 These optically functional layers can be formed by the following methods.

具有作為相位差薄膜之機能之層，可藉由於構成偏光元件之其他層上將相位差薄膜進行塗佈或貼合等而形成。相位差薄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號公報等記載之延伸處理、或實施日本專利特開平7-230007號公報等記載之處理而形成。 A layer having a function as a retardation film can be formed by coating or laminating a retardation film on another layer constituting a polarizing element. The retardation film can be formed, for example, by carrying out the stretching treatment described in Japanese Patent Laid-Open No. 2-59703, Japanese Patent Laid-Open No. 4-230704, etc., or implementing the treatment described in Japanese Patent Laid-Open No. 7-230007 .

具有作為亮度提高薄膜之機能之層，可藉由於構成偏光元件之其他層上將亮度提升薄膜進行塗佈或貼合等而形成。亮度提升薄膜例如可藉由利用日本專利特開2002-169025號公報及日本 專利特開2003-29030號公報記載般之方法形成微細孔、或將選擇反射之中心波長不同之2層以上之膽固醇液晶層重疊而形成。 The layer that functions as a brightness-improving film can be formed by coating or laminating the brightness-improving film on other layers constituting the polarizing element. Brightness-enhancing films can be formed, for example, by using methods described in Japanese Patent Laid-Open No. 2002-169025 and Japanese Patent Laid-Open No. 2003-29030 to form micropores, or cholesteric liquid crystals having two or more layers with different central wavelengths of selective reflection. formed by overlapping layers.

具有作為反射薄膜或半穿透反射薄膜之機能之層，例如可藉由於構成偏光元件之其他層上將藉由蒸鍍或濺鍍等獲得之金屬薄膜進行塗佈或貼合等而形成。 A 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.

具有作為擴散薄膜之機能之層，例如可藉由於構成偏光元件之其他層上塗佈含有微粒子之樹脂溶液而形成。 The layer that functions as a diffusion film can be formed, for example, by coating a resin solution containing fine particles on other layers constituting the polarizing element.

具有作為相位差薄膜或光學補償薄膜之機能之層，可藉由於構成偏光元件之其他層上塗佈盤狀液晶性化合物、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並使其配向而形成。此時，亦可於基板上設置配向膜，於配向膜表面形成相位差薄膜或光學補償薄膜。 A layer that functions as a retardation film or an optical compensation film can be coated with liquid crystals such as discotic liquid crystal compounds, nematic liquid crystal compounds, smectic liquid crystal compounds, and cholesteric liquid crystal compounds on other layers constituting a polarizing element. sexual compounds and align them to form. At this time, an alignment film may also be provided on the substrate, and a retardation film or an optical compensation film may be formed on the surface of the alignment film.

在將本發明之異向性色素膜於LCD或OLED等各種顯示元件中使用作為異向性色素膜等時，可於構成此等顯示元件之電極基板等之表面直接形成本發明之異向性色素膜，亦可將形成有本發明之異向性色素膜之基板使用作為此等顯示元件之構成構件。 When the anisotropic dye film of the present invention is used as an anisotropic dye film in various display elements such as LCDs and OLEDs, the anisotropic dye film of the present invention can be directly formed on the surface of electrode substrates constituting these display elements. As a dye film, 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.

[實施例] [Example]

藉由實施例更具體地說明本發明，但本發明在不超出其要旨之前提下，並不限定於以下之實施例。 The present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples unless the gist thereof is exceeded.

以下記載中，「份」表示「重量份」。 In the following description, "part" means "part by weight".

[液晶相之同定方法] [How to determine the liquid crystal phase]

所得異向性色素膜形成用組成物之液晶性，係藉由示差掃描熱量測定(Seiko Instruments公司「DSC220CU」)、X射線構造分析 (RIGAKU股份有限公司「NANO-Viewer」)、加熱台(東陽股份有限公司「HCS302-LN190」)所附屬之偏光顯微鏡(Nikon Instech股份有限公司「ECLIPSE LV100N POL」)進行觀察，依照「液晶便覽」(丸善股份有限公司，2000年10月30日發行)之第9~50頁、第117~176頁等記載之方法，進行液晶之同定。 The liquid crystallinity of the obtained composition for anisotropic pigment film formation was measured by differential scanning calorimetry (Seiko Instruments company "DSC220CU"), X-ray structure analysis (RIGAKU Co., Ltd. Co., Ltd. "HCS302-LN190") attached to the polarizing microscope (Nikon Instech Co., Ltd. "ECLIPSE LV100N POL"), according to "Liquid Crystal Handbook" (Maruzen Co., Ltd., issued on October 30, 2000) 9~50 pages, 117~176 pages, etc., to identify liquid crystals.

[異向性色素膜之對於吸收軸/偏光軸方向之偏光的穿透率的測定及二色比] [Measurement of transmittance and dichroic ratio of polarized light in the direction of absorption axis/polarization axis of anisotropic pigment film]

所得異向性色素膜之對於吸收軸/偏光軸方向之偏光的穿透率，係使用具備格蘭湯姆森偏光片的分光光度計(大塚電子(股)製，製品名「RETS-100」)進行測定。 The transmittance of the obtained anisotropic dye film with respect to the polarized light in the direction of the absorption axis/polarization axis was measured using a spectrophotometer equipped with a Glan Thomson polarizer (manufactured by Otsuka Electronics Co., Ltd., product name "RETS-100") To measure.

對異向性色素膜射入直線偏光之測定光，測定異向性色素膜之對吸收軸方向之偏光的穿透率及異向性色素膜之對偏光軸方向之偏光的穿透率，藉下式算出二色比(D)。 The measurement light of linear polarized light is injected into the anisotropic pigment film, and the transmittance of the anisotropic pigment film to the polarized light in the direction of the absorption axis and the transmittance of the anisotropic pigment film to the polarized light in the direction of the polarization axis are measured. The dichroic ratio (D) was calculated by the following formula.

D=Az/Ay D=Az/Ay

(式中，Ay=-log(Ty) (where, Ay=-log(Ty)

Az=-log(Tz) Az=-log(Tz)

Tz係異向性色素膜之對於吸收軸方向之偏光的透過率；Ty係異向性色素膜之對於偏光軸方向之偏光的透過率。 Tz is the transmittance of the anisotropic pigment film to the polarized light in the direction of the absorption axis; Ty is the transmittance of the anisotropic pigment film to the polarized light in the direction of the polarization axis.

具體而言，於作為基材之玻璃上形成有聚醯亞胺之配向膜(LX1400，日立化成杜邦MicroSystems公司製)之夾層單元(單元間隙：8.0μm、10.0μm、12.0μm，對已成膜之聚醯亞胺事先藉由布施行了摩擦處理者)上，依等向相注入異向性色素膜形成用組成 物，依5℃/min冷卻至80℃，藉此得到異向性色素膜，進而一邊依5℃/min冷卻至0℃、一邊於各溫度測定二色比。其中，將顯示最大二色比之溫度及波長下的二色比決定為此異向性色素膜之二色比。 Specifically, a sandwich cell (cell gap: 8.0 μm, 10.0 μm, 12.0 μm) with an alignment film of polyimide (LX1400, manufactured by Hitachi Chemical DuPont MicroSystems Co., Ltd.) was formed on glass as a base material. On the polyimide that has been subjected to rubbing treatment by cloth in advance), the composition for forming an anisotropic pigment film is injected into the isotropic phase, and cooled to 80 °C at 5 °C/min, thereby obtaining an anisotropic pigment film. Furthermore, the dichromatic ratio was measured at each temperature, cooling to 0 degreeC at 5 degreeC/min. Among them, 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.

又，異向性色素膜之二色比為40以上者評價為A，20以上且未滿40者評價為B，8以上且未滿20者評價為C，未滿8者評價為D；又，異向性色素膜之二色比為30以上者評價為「++」，20以上且未滿30者評價為「+」，8以上且未滿20者評價為「-」，未滿8者評價為「--」。 In addition, the dichroic ratio of the anisotropic dye film was evaluated as A when it was 40 or more, as B when it was 20 or more and less than 40, as C when it was 8 or more and less than 20, and as D when it was less than 8; , The dichroic ratio of the anisotropic pigment film is rated as "++" if it is 30 or more, "+" if it is 20 or more and less than 30, "-" if it is 8 or more and less than 20, and less than 8 rated as "--".

以下使用具體例說明本發明第一態樣。 The first aspect of the present invention will be described below using specific examples.

[液晶化合物之合成A] [Synthesis A of liquid crystal compound] <液晶化合物(I-1)> <Liquid Crystal Compound (I-1)>

依以下記載之合成法，合成液晶化合物(I-1)。 The liquid crystal compound (I-1) was synthesized according to the synthesis method described below.

[化21]

Figure 108109137-A0101-12-0069-21
[chem 21]
Figure 108109137-A0101-12-0069-21

(I-1-a)之合成： Synthesis of (I-1-a):

於對碘苯酚(11.0g，50mmol)之N,N-二甲基甲醯胺溶液(150mL) 中，添加丙酸乙酯(9.7g，99mmol)、氧化銅(I)(7.5g，94mmol)，於110℃攪拌9小時，放冷至室溫。濾取沉澱後添加醋酸乙酯，以水、接著飽和食鹽水洗淨。藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到褐色結晶(I-1-a)7.3g。 In p-iodophenol (11.0g, 50mmol) in N,N-dimethylformamide solution (150mL), add ethyl propionate (9.7g, 99mmol), copper oxide (I) (7.5g, 94mmol) , stirred at 110°C for 9 hours, and allowed to cool to room temperature. After the precipitate was collected by filtration, ethyl acetate was added, followed by washing with water and then with saturated brine. Purification by silica gel column chromatography (hexane/ethyl acetate) gave 7.3 g of brown crystals (I-1-a).

(I-1-b)之合成： Synthesis of (I-1-b):

將(I-1-a)(4.20g，22.1mmol)、11-溴-1-十一醇(5.55g，22.1mmol)、碳酸鉀(6.10g，44.2mmol)、N,N-二甲基甲醯胺(30mL)混合，於80℃攪拌4小時。濾取沉澱後，添加二乙基醚，以水、接著飽和食鹽水洗淨。藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到橙色固體(I-1-b)5.5g。 (I-1-a) (4.20g, 22.1mmol), 11-bromo-1-undecanol (5.55g, 22.1mmol), potassium carbonate (6.10g, 44.2mmol), N,N-dimethyl Formamide (30 mL) was mixed and stirred at 80°C for 4 hours. After the precipitate was collected by filtration, diethyl ether was added, followed by washing with water and then with saturated brine. Purification was carried out by silica gel column chromatography (hexane/ethyl acetate) to obtain 5.5 g of an orange solid (I-1-b).

(I-1-c)之合成： Synthesis of (I-1-c):

將(I-1-b)(3.6g，10mmol)、氫氧化鉀(1.7g，30mmol)、水(20mL)混合，於100℃攪拌2小時。加入水(20mL)，藉濃鹽酸使其成為酸性後，濾取析出之沉澱。將所得沉澱藉乙腈進行懸浮洗淨，得到乳白色固體(I-1-c)3.2g。 (I-1-b) (3.6 g, 10 mmol), potassium hydroxide (1.7 g, 30 mmol), and water (20 mL) were mixed and stirred at 100° C. for 2 hours. Water (20 mL) was added to make it acidic with concentrated hydrochloric acid, and the precipitate was collected by filtration. The obtained precipitate was suspended and washed with acetonitrile to obtain 3.2 g of milky white solid (I-1-c).

(I-1-d)之合成： Synthesis of (I-1-d):

將(I-1-c)(2.33g，7.0mmol)、四氫呋喃(20mL)混合，接著添加N,N-二甲基苯胺(1.02g，8.4mmol)、2,5-二第三丁基酚(54mg)。藉冰浴冷卻後，緩慢添加丙烯醯氯(0.76g，8.4mmol)。於冰浴下攪拌6小時後，添加二氯甲烷，依序以1mol/L鹽酸、飽和碳酸氫鈉水、飽和食鹽水進行洗淨。藉由矽膠管柱層析法(氯仿/甲醇)進行精製， 得到白色固體(I-1-d)2.0g。 (I-1-c) (2.33 g, 7.0 mmol), tetrahydrofuran (20 mL) were mixed, followed by addition of N,N-dimethylaniline (1.02 g, 8.4 mmol), 2,5-di-tert-butylphenol (54 mg). After cooling in an ice bath, acryloyl chloride (0.76 g, 8.4 mmol) was added slowly. After stirring in an ice bath for 6 hours, dichloromethane was added, followed by washing with 1 mol/L hydrochloric acid, saturated sodium bicarbonate water, and saturated brine in this order. Purification was carried out by silica gel column chromatography (chloroform/methanol) to obtain 2.0 g of white solid (I-1-d).

(I-1-e)之合成： Synthesis of (I-1-e):

藉由日本專利特開2014-262884號公報記載之合成法，合成(I-1-e)。 (I-1-e) was synthesized by the synthesis method described in Japanese Patent Laid-Open No. 2014-262884.

(I-1-f)之合成： Synthesis of (I-1-f):

將(I-1-d)(2.00g，5.17mmol)、(I-1-e)(1.01g，5.17mmol)、N,N-二甲基胺基-4-吡啶(0.13g，1.03mmol)、2,5-二第三丁基酚(58mg)、二氯甲烷(30mL)混合，藉冰浴冷卻後，添加1-乙基-3-(3-二甲基胺基丙基)碳二亞胺鹽酸鹽(1.09g，5.69mmol)。放置一晚後，以氯化銨飽和水溶液、接著飽和食鹽水洗淨。藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到白色固體(I-1-f)1.9g。 (I-1-d) (2.00g, 5.17mmol), (I-1-e) (1.01g, 5.17mmol), N,N-dimethylamino-4-pyridine (0.13g, 1.03mmol ), 2,5-di-tert-butylphenol (58mg), and dichloromethane (30mL) were mixed, cooled in an ice bath, and 1-ethyl-3-(3-dimethylaminopropyl) carbon was added Diimine hydrochloride (1.09 g, 5.69 mmol). After being left to stand overnight, it was washed with a saturated aqueous solution of ammonium chloride and then with saturated saline. Purification was carried out by silica gel column chromatography (hexane/ethyl acetate) to obtain 1.9 g of white solid (I-1-f).

(I-1-g)之合成： Synthesis of (I-1-g):

將(I-1-f)(2.6g，4.62mmol)、對甲苯磺酸吡啶鎓鹽(0.23g，0.92mmol)、2,5-二第三丁基酚(44mg)、乙醇(20mL)混合，於50℃攪拌2小時。將反應溶液釋出至水中，濾取析出之沉澱，使其乾燥，得到白色固體(I-1-g)2.0g。 Mix (I-1-f) (2.6g, 4.62mmol), pyridinium p-toluenesulfonate (0.23g, 0.92mmol), 2,5-di-tert-butylphenol (44mg), ethanol (20mL) , and stirred at 50°C for 2 hours. The reaction solution was released into water, and the precipitated precipitate was collected by filtration and dried to obtain 2.0 g of a white solid (I-1-g).

(I-1-h)之合成： Synthesis of (I-1-h):

依下述記載之合成法，合成化合物(I-1-h)。 Compound (I-1-h) was synthesized according to the synthesis method described below.

[化22]

Figure 108109137-A0101-12-0072-22
[chem 22]
Figure 108109137-A0101-12-0072-22

根據Lub et al.,Recl.Trav.ChIm.Pays-Bas,115,321-328(1996)記載之化合物的方法合成(I-1-i)。 (I-1-i) was synthesized according to the method of the compound described in Lub et al., Recl. Trav. ChIm. Pays-Bas, 115, 321-328 (1996).

接著，將(I-1-i)(僅反式物)(42.9g，107.6mmol)、對甲苯磺酸吡啶鎓鹽(2.6g，10.8mmol)、乙醇(430mL)混合，於78℃攪拌2小時。餾除溶媒，溶解於醋酸乙酯(150mL)，加入己烷(750mL)進行冷卻。濾取析出之沉澱物，藉己烷洗淨後，使其乾燥而得到白色固體(I-1-j)29.2g。 Next, (I-1-i) (only the trans form) (42.9 g, 107.6 mmol), pyridinium p-toluenesulfonate (2.6 g, 10.8 mmol), and ethanol (430 mL) were mixed and stirred at 78° C. for 2 Hour. The solvent was distilled off, dissolved in ethyl acetate (150 mL), and cooled by adding hexane (750 mL). The deposited precipitate was collected by filtration, washed with hexane, and dried to obtain 29.2 g of a white solid (I-1-j).

將(I-1-j)(37.2g，118.3mmol)、N,N-二甲基苯胺(21.5g，177.5mmol)、2,5-二第三丁基酚(0.24g)、四氫呋喃(380mL)混合。藉冰浴冷卻後，緩慢添加丙烯醯氯(16.1g，177.5mmol)。滴下後於50℃攪拌2小時後，餾除溶媒直到液量成為190mL為止，釋出至冰冷下之1mol/L鹽酸。濾取析出之沉澱，以水、己烷洗淨。藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到白色固體(I-1-h)39.4g。 (I-1-j) (37.2g, 118.3mmol), N,N-dimethylaniline (21.5g, 177.5mmol), 2,5-di-tert-butylphenol (0.24g), tetrahydrofuran (380mL )mix. After cooling in an ice bath, acryloyl chloride (16.1 g, 177.5 mmol) was added slowly. After dropping and stirring at 50° C. for 2 hours, the solvent was distilled off until the liquid volume became 190 mL, and 1 mol/L hydrochloric acid was released under ice cooling. The precipitated precipitate was collected by filtration and washed with water and hexane. Purification was carried out by silica gel column chromatography (hexane/ethyl acetate) to obtain 39.4 g of white solid (I-1-h).

(I-1)之合成： Synthesis of (I-1):

將(I-1-g)(494mg，1.03mmol)、(I-1-h)(400mg，1.09mmol)、N,N-二甲基胺基-4-吡啶(27mg，0.22mmol)、2,5-二第三丁基酚(2mg)、二氯甲烷(10mL)混合，藉冰浴冷卻後，添加1-乙基-3-(3-二甲基胺基丙基)碳二亞胺鹽酸鹽(230mg，1.19mmol)。於冰浴下攪拌4小時後，以氯化銨飽和水溶液、接著飽和食鹽水洗淨。藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到白色固體之液晶化合物(I-1)530mg。 (I-1-g) (494mg, 1.03mmol), (I-1-h) (400mg, 1.09mmol), N,N-dimethylamino-4-pyridine (27mg, 0.22mmol), 2 , Mix 5-di-tert-butylphenol (2mg) and dichloromethane (10mL), cool in an ice bath, add 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide Hydrochloride (230 mg, 1.19 mmol). After stirring in an ice bath for 4 hours, it was washed with a saturated aqueous solution of ammonium chloride and then with saturated brine. It was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 530 mg of liquid crystal compound (I-1) as a white solid.

將此化合物之液體層析質量分析的結果表示如下。 The results of liquid chromatography mass analysis of this compound are shown below.

LC-MS(APCI)m/z 851.5(M+Na+) LC-MS (APCI) m/z 851.5 (M+Na + )

又，藉由NMR進行構造確認。結果表示如下。 Also, the structure was confirmed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ`1.20-1.70(m,38H),1.74-1.85(m,2H),2.05-2.25(m,4H),2.49-2.57(m,1H),3.21-3.29(m,1H),3.46(t,2H,J=6.8Hz),3.99(t,2H,J=6.8Hz),4.15(t,4H,J=6.8Hz),5.80(d,2H,J=10.4Hz),6.12(dd,2H,J=17.2,10.4Hz),6.39(d,2H,J=17.2Hz),6.89(d,2H,J=6.8Hz),7.10(d,2H,J=6.8Hz),7.19(d,2H,J=6.8Hz),7.55(d,2H,J=6.8Hz) 1 H NMR(CDCl 3 ,400MHz)δ`1.20-1.70(m,38H),1.74-1.85(m,2H),2.05-2.25(m,4H),2.49-2.57(m,1H),3.21-3.29 (m,1H),3.46(t,2H,J=6.8Hz),3.99(t,2H,J=6.8Hz),4.15(t,4H,J=6.8Hz),5.80(d,2H,J=6.8Hz) 10.4Hz),6.12(dd,2H,J=17.2,10.4Hz),6.39(d,2H,J=17.2Hz),6.89(d,2H,J=6.8Hz),7.10(d,2H,J= 6.8Hz),7.19(d,2H,J=6.8Hz),7.55(d,2H,J=6.8Hz)

<液晶化合物(I-2)> <Liquid Crystal Compound (I-2)>

依照下述記載之合成法，合成液晶化合物(I-2)。 According to the synthesis method described below, the liquid crystal compound (I-2) was synthesized.

[化23]

Figure 108109137-A0101-12-0074-23
[chem 23]
Figure 108109137-A0101-12-0074-23

(I-2-a)之合成： Synthesis of (I-2-a):

將4-碘苯甲酸乙酯(8.20g，29.7mmol)、二氯雙(三苯基膦)鈀(II)(626mg，0.89mmol)、碘化銅(I)(170mg，0.89mmol)、三乙基胺(200mL)混合，添加10-十一炔-1-醇(5.0g，29.7mmol)。於室溫放置4小時、進而於40℃加熱1小時後，放冷至室溫。以水-醚萃取後，進而以1mol/L鹽酸洗淨，進行分液、濃縮而得到粗精製之茶色油狀化合物(I-2-a)。 Ethyl 4-iodobenzoate (8.20g, 29.7mmol), dichlorobis(triphenylphosphine) palladium (II) (626mg, 0.89mmol), copper (I) iodide (170mg, 0.89mmol), tri Ethylamine (200 mL) was mixed and 10-undecyn-1-ol (5.0 g, 29.7 mmol) was added. After standing at room temperature for 4 hours and further heating at 40° C. for 1 hour, it was left to cool to room temperature. After extraction with water-ether, it was further washed with 1 mol/L hydrochloric acid, liquid-separated, and concentrated to obtain a crudely refined brown oily compound (I-2-a).

(I-2-b)之合成： Synthesis of (I-2-b):

將上述操作所得之粗精製之(I-2-a)、氫氧化鉀(5.0g，90mmol)之50mL水溶液混合，於100℃加熱5小時。放冷至室溫後，於冰浴下添加水20mL後，添加濃鹽酸直到成為pH=1。濾取析出之白色固體，藉熱乙腈進行再結晶，得到乳白色固體(I-2-b)7.5g。 The crudely purified (I-2-a) obtained in the above operations and 50 mL of aqueous solution of potassium hydroxide (5.0 g, 90 mmol) were mixed, and heated at 100° C. for 5 hours. After standing to cool to room temperature, 20 mL of water was added under an ice bath, and then concentrated hydrochloric acid was added until pH=1. The precipitated white solid was collected by filtration and recrystallized with hot acetonitrile to obtain 7.5 g of milky white solid (I-2-b).

(I-2-c)之合成： Synthesis of (I-2-c):

將(I-2-b)(7.4g，25.7mmol)、四氫呋喃(50mL)、N,N-二甲基苯胺(3.78g，31.2mmol)、對甲氧基酚(89mg)混合，於水浴下確認內溫成為15℃以下後，緩慢添加丙烯醯氯(2.82g，31.2mmol)。經過30分鐘後，移取水浴，進而攪拌2小時。將反應液釋出至100mL之水中，加入濃鹽酸(0.8mL)後，藉醋酸乙酯萃取。對藉由濃縮所得之褐色粉末之半量藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到乳白色粉末(I-2-c)3.0g。 Mix (I-2-b) (7.4g, 25.7mmol), tetrahydrofuran (50mL), N,N-dimethylaniline (3.78g, 31.2mmol), p-methoxyphenol (89mg), and place in a water bath After confirming that the internal temperature was 15° C. or lower, acryloyl chloride (2.82 g, 31.2 mmol) was gradually added. After 30 minutes had elapsed, the water bath was removed, and the mixture was further stirred for 2 hours. The reaction solution was released into 100 mL of water, concentrated hydrochloric acid (0.8 mL) was added, and extracted with ethyl acetate. Half of the brown powder obtained by concentration was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 3.0 g of milky white powder (I-2-c).

(I-2-d)之合成： Synthesis of (I-2-d):

將(I-2-c)(2.95g，8.6mmol)、(I-1-e)(1.70g，8.8mmol)、N,N-二甲基胺基吡啶(0.21g，1.75mmol)、二氯甲烷(13mL)混合，於冰浴下，添加1-乙基-3-(3-甲基胺基丙基)碳二亞胺鹽酸鹽(1.84g，9.6mmol)。於冰浴下攪拌30分鐘後，再於室溫攪拌1小時。將反應液以氯化銨飽和水溶液、再接著以飽和食鹽水萃取後，藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到白色固體(I-2-d)4.4g。 (I-2-c) (2.95g, 8.6mmol), (I-1-e) (1.70g, 8.8mmol), N,N-dimethylaminopyridine (0.21g, 1.75mmol), di Chloromethane (13 mL) was mixed, and 1-ethyl-3-(3-methylaminopropyl)carbodiimide hydrochloride (1.84 g, 9.6 mmol) was added under ice cooling. After stirring in an ice bath for 30 minutes, it was stirred at room temperature for 1 hour. The reaction solution was extracted with a saturated aqueous ammonium chloride solution, followed by saturated brine, and purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 4.4 g of a white solid (I-2-d) .

(I-2-e)之合成： Synthesis of (I-2-e):

將(I-2-d)(4.1g，7.9mmol)、乙醇(20mL)、對甲苯磺酸吡啶鎓鹽(0.40g，1.58mmol)混合，於60℃加熱1小時。放冷至室溫後，釋出於水(100mL)中，濾取所得固體。將所得固體進行再結晶(乙醇-水)，濾取而得到固體之(I-2-e)3.3g。 Mix (I-2-d) (4.1 g, 7.9 mmol), ethanol (20 mL), pyridinium p-toluenesulfonate (0.40 g, 1.58 mmol), and heat at 60° C. for 1 hour. After cooling to room temperature, it was released in water (100 mL), and the resulting solid was collected by filtration. The obtained solid was recrystallized (ethanol-water), and it was collected by filtration to obtain 3.3 g of (I-2-e) as a solid.

(I-2-f)之合成： Synthesis of (I-2-f):

加入(I-2-e)(435mg，1.0mmol)、(I-1-i)(反/順=67：33之混合物)(438mg，1.1mmol)、N,N-二甲基胺基吡啶(24mg，0.2mmol)、二氯甲烷(10mL)，於冰浴下，添加1-乙基-3-(3-二甲基胺基丙基)碳二亞胺鹽酸鹽(211mg，1.1mmol)。於冰浴下攪拌30分鐘後，於室溫下再攪拌2小時。將反應液以氯化銨飽和水溶液、再接著以飽和食鹽水洗淨後，藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到反式物之(I-2-f)0.46g。 Add (I-2-e) (435mg, 1.0mmol), (I-1-i) (trans/cis=67:33 mixture) (438mg, 1.1mmol), N,N-dimethylaminopyridine (24mg, 0.2mmol), dichloromethane (10mL), under ice-cooling, add 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (211mg, 1.1mmol ). After stirring in an ice bath for 30 minutes, it was further stirred at room temperature for 2 hours. The reaction solution was washed with a saturated aqueous solution of ammonium chloride, and then washed with saturated brine, and purified by silica gel column chromatography (hexane/ethyl acetate) to obtain the trans product (I-2-f ) 0.46g.

(I-2-g)之合成： Synthesis of (I-2-g):

將(I-2-f)(0.46g，0.56mmol)、乙醇(10mL)、對甲苯磺酸吡啶鎓鹽(28mg，0.11mmol)混合，於60℃加熱2小時。放冷至室溫後，添加水(20mL)，濾取所得固體。將所得固體進行再結晶(乙醇-水)，得到固體之(I-2-g)0.36g。 (I-2-f) (0.46 g, 0.56 mmol), ethanol (10 mL), pyridinium p-toluenesulfonate (28 mg, 0.11 mmol) were mixed, and heated at 60°C for 2 hours. After cooling to room temperature, water (20 mL) was added, and the obtained solid was collected by filtration. The obtained solid was recrystallized (ethanol-water) to obtain 0.36 g of (I-2-g) as a solid.

(I-2)之合成： Synthesis of (I-2):

將(I-2-g)(0.36g，0.49mmol)、四氫呋喃(10mL)、N,N-二甲基苯胺(72mg，0.59mmol)、對甲氧基酚(3.6mg)混合，於水浴下，緩慢添加丙烯醯氯(53mg，0.59mmol)。於水浴下攪拌30分鐘後，再攪拌2小時。將反應液釋出於水(20mL)中，加入濃鹽酸(0.2mL)後，以醋酸乙酯萃取。將藉濃縮所得之褐色粉末之半量藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到白色粉末之液晶化合物(I-2)183mg。 Mix (I-2-g) (0.36g, 0.49mmol), tetrahydrofuran (10mL), N,N-dimethylaniline (72mg, 0.59mmol), p-methoxyphenol (3.6mg), and place in a water bath , acryloyl chloride (53 mg, 0.59 mmol) was added slowly. After stirring in a water bath for 30 minutes, it was stirred for another 2 hours. The reaction solution was dissolved in water (20 mL), concentrated hydrochloric acid (0.2 mL) was added, and extracted with ethyl acetate. Half of the brown powder obtained by concentration was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 183 mg of liquid crystal compound (I-2) as a white powder.

<液晶化合物(I-3)> <Liquid Crystal Compound (I-3)>

依照以下記載之合成法，合成液晶化合物(I-3)。 According to the synthesis method described below, the liquid crystal compound (I-3) was synthesized.

[化24]

Figure 108109137-A0101-12-0078-24
[chem 24]
Figure 108109137-A0101-12-0078-24

(I-3-a)之合成： Synthesis of (I-3-a):

將對乙醯氧基苯甲酸(3.60g，20.0mmol)、(I-1-e)(3.88g，20.0mmol)、N,N-二甲基胺基吡啶(489mg，4.0mmol)、二氯甲烷(50mL)混合，於2℃添加1-乙基-3-(3-二甲基胺基丙基)碳二亞胺鹽酸鹽(4.22g，22.0mmol)。於2℃攪拌30分鐘後，再於室溫攪拌17小時。 將反應液以氯化銨飽和水溶液、再接著以飽和食鹽水洗淨後，藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到白色固體之(I-3-a)3.63g。 P-Acetoxybenzoic acid (3.60g, 20.0mmol), (I-1-e) (3.88g, 20.0mmol), N,N-dimethylaminopyridine (489mg, 4.0mmol), dichloro Methane (50 mL) was mixed, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (4.22 g, 22.0 mmol) was added at 2°C. After stirring at 2°C for 30 minutes, it was stirred at room temperature for 17 hours. The reaction solution was washed with a saturated aqueous solution of ammonium chloride and then with saturated brine, and purified by silica gel column chromatography (hexane/ethyl acetate) to obtain (I-3-a) as a white solid 3.63g.

(I-3-b)之合成： Synthesis of (I-3-b):

將(I-3-a)(0.95g，2.7mmol)、乙醇(20mL)、對甲苯磺酸吡啶鎓鹽(134mg，0.53mmol)混合，於78℃加熱3小時。放冷至室溫後，添加水(60mL)，濾取所得固體，於減壓下依50℃進行乾燥，得到白色固體(I-3-b)0.31g。 (I-3-a) (0.95 g, 2.7 mmol), ethanol (20 mL), pyridinium p-toluenesulfonate (134 mg, 0.53 mmol) were mixed, and heated at 78°C for 3 hours. After cooling to room temperature, water (60 mL) was added, and the obtained solid was collected by filtration and dried at 50° C. under reduced pressure to obtain 0.31 g of a white solid (I-3-b).

(I-3-c)之合成： Synthesis of (I-3-c):

將(I-3-b)(230mg，1.0mmol)、(I-1-i)(僅反式物)(810mg，2.0mmol)、N,N-二甲基胺基吡啶(58g，0.48mmol)、二氯甲烷(6mL)混合，於2℃添加1-乙基-3-(3-二甲基胺基丙基)碳二亞胺鹽酸鹽(428mg，2.2mmol)。於2℃攪拌30分鐘後，再於室溫攪拌20小時。將反應液以氯化銨飽和水溶液、再接著以飽和食鹽水洗淨後，藉由矽膠管柱層析法(二氯甲烷/醋酸乙酯)進行精製，得到白色固體之(I-3-c)662mg。 (I-3-b) (230mg, 1.0mmol), (I-1-i) (trans only) (810mg, 2.0mmol), N,N-dimethylaminopyridine (58g, 0.48mmol ), dichloromethane (6 mL), and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (428 mg, 2.2 mmol) was added at 2°C. After stirring at 2°C for 30 minutes, it was stirred at room temperature for 20 hours. The reaction solution was washed with a saturated aqueous solution of ammonium chloride, and then washed with saturated brine, and purified by silica gel column chromatography (dichloromethane/ethyl acetate) to obtain (I-3-c ) 662 mg.

(I-3-d)之合成： Synthesis of (I-3-d):

將(I-3-c)(662mg，0.67mmol)、乙醇(15mL)、對甲苯磺酸吡啶鎓鹽(69mg，0.27mmol)混合，於78℃加熱1小時。放冷至室溫後，添加水(70mL)，濾取所得固體，於減壓下依50℃乾燥，得到白色固體(I-3-d)555mg。 (I-3-c) (662mg, 0.67mmol), ethanol (15mL), pyridinium p-toluenesulfonate (69mg, 0.27mmol) were mixed, and heated at 78°C for 1 hour. After cooling to room temperature, water (70 mL) was added, and the resulting solid was collected by filtration and dried at 50°C under reduced pressure to obtain 555 mg of white solid (I-3-d).

(I-3)之合成： Synthesis of (I-3):

將(I-3-d)(555mg，0.67mmol)、二氯甲烷(12mL)、N,N-二甲基苯胺(225mg，1.85mmol)混合，於2℃緩慢添加丙烯醯氯(169mg，1.87mmol)。於2℃攪拌30分鐘後，再於室溫攪拌18小時。將反應液以氯化銨飽和水溶液、再接著以飽和食鹽水洗淨後，藉由矽膠管柱層析法(甲苯/醋酸乙酯)進行精製，得到白色固體之液晶化合物(I-3)424mg。 Mix (I-3-d) (555mg, 0.67mmol), dichloromethane (12mL), N,N-dimethylaniline (225mg, 1.85mmol), and slowly add acryloyl chloride (169mg, 1.87mmol) at 2°C mmol). After stirring at 2°C for 30 minutes, it was stirred at room temperature for 18 hours. The reaction solution was washed with a saturated aqueous solution of ammonium chloride and then with saturated brine, and purified by silica gel column chromatography (toluene/ethyl acetate) to obtain 424 mg of liquid crystal compound (I-3) as a white solid .

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ8.21(d,2H,J=9.2Hz),7.21(d,4H,J=9.2Hz),7.12(d,2H,J=9.2Hz),6.40(dd,2H,J=17.2,1.6Hz),6.12(dd,2H,J=17.2,10.4Hz),5.81(dd,2H,J=10.4,1.6Hz),4.15(t,4H,J=7.2Hz),3.47(t,4H,J=6.8Hz),3.32-3.21(m,2H),2.62-2.49(m,2H),2.25-2.10(m,8H),1.71-1.52(m,16H),1.42-1.25(m,28H) 1 H NMR(CDCl 3 ,400MHz)δ8.21(d,2H,J=9.2Hz),7.21(d,4H,J=9.2Hz),7.12(d,2H,J=9.2Hz),6.40(dd ,2H,J=17.2,1.6Hz),6.12(dd,2H,J=17.2,10.4Hz),5.81(dd,2H,J=10.4,1.6Hz),4.15(t,4H,J=7.2Hz) ,3.47(t,4H,J=6.8Hz),3.32-3.21(m,2H),2.62-2.49(m,2H),2.25-2.10(m,8H),1.71-1.52(m,16H),1.42 -1.25(m,28H)

<液晶化合物(I-4)> <Liquid Crystal Compound (I-4)>

依照以下記載之合成法，合成液晶化合物(I-4)。 According to the synthesis method described below, the liquid crystal compound (I-4) was synthesized.

[化25]

Figure 108109137-A0101-12-0081-25
[chem 25]
Figure 108109137-A0101-12-0081-25

(I-4-b)之合成： Synthesis of (I-4-b):

藉由日本專利特開2015-896號公報記載之合成法，合成 (I-4-b)。 (I-4-b) was synthesized by the synthesis method described in Japanese Patent Laid-Open No. 2015-896.

(I-4-c)之合成： Synthesis of (I-4-c):

將(I-4-b)(50.3g，162mmol)、四氫呋喃(320mL)、N,N-二甲基苯胺(23.6mg，195mmol)、4-甲氧基酚(307mg)混合，於15℃歷時40分鐘添加丙烯醯氯(17.6g，195mmol)。於室溫攪拌18小時後，將反應液釋出至水(940mL)中，藉濃鹽酸使pH成為1.2後，濾取析出之固體。將所得固體以水洗淨，於50℃且減壓下進行乾燥，得到白色固體之(I-4-c)58.5g。 Mix (I-4-b) (50.3g, 162mmol), tetrahydrofuran (320mL), N,N-dimethylaniline (23.6mg, 195mmol), 4-methoxyphenol (307mg), and Acryloyl chloride (17.6 g, 195 mmol) was added over 40 minutes. After stirring at room temperature for 18 hours, the reaction solution was released into water (940 mL), and the pH was adjusted to 1.2 with concentrated hydrochloric acid, and the precipitated solid was collected by filtration. The obtained solid was washed with water, and dried at 50° C. under reduced pressure to obtain 58.5 g of (I-4-c) as a white solid.

(I-4-d)之合成： Synthesis of (I-4-d):

將(I-4-c)(35.8g，98.7mmol)、(I-1-e)(19.2g，98.7mmol)、N,N-二甲基胺基吡啶(2.41g，19.7mmol)、4-甲氧基酚(47mg)、二氯甲烷(150mL)混合，於3℃添加1-乙基-3-(3-二甲基胺基丙基)碳二亞胺(16.9g，109mmol)。於冰浴下攪拌30分鐘後，再於室溫攪拌21小時。將反應液以氯化銨飽和水溶液、再接著以飽和食鹽水洗淨，藉硫酸鎂進行乾燥後，餾除溶媒，得到淡褐色固體。將此淡褐色固體依60℃溶解於乙醇(220mL)後，於0℃靜置15小時，濾取產生之固體，於50℃減壓下進行乾燥，得到白色固體之(I-4-d)39.1g。 (I-4-c) (35.8g, 98.7mmol), (I-1-e) (19.2g, 98.7mmol), N,N-dimethylaminopyridine (2.41g, 19.7mmol), 4 -Methoxyphenol (47mg) and dichloromethane (150mL) were mixed, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (16.9g, 109mmol) was added at 3°C. After stirring in an ice bath for 30 minutes, it was stirred at room temperature for 21 hours. The reaction solution was washed with a saturated aqueous solution of ammonium chloride and then with saturated brine, dried over magnesium sulfate, and the solvent was distilled off to obtain a light brown solid. Dissolve the light brown solid in ethanol (220mL) at 60°C and let it stand at 0°C for 15 hours. The resulting solid was collected by filtration and dried under reduced pressure at 50°C to obtain (I-4-d) as a white solid 39.1 g.

(I-4-e)之合成： Synthesis of (I-4-e):

將(I-4-d)(39.0g，72.4mmol)、乙醇(180mL)、對甲苯磺酸吡啶鎓鹽(3.71g，14.8mmol)混合，於60℃加熱1小時。放冷至室溫後，釋出至水(490mL)中，濾取所得固體，於減壓下以50℃進行乾燥， 得到白色固體(I-4-e)32.8g。 (I-4-d) (39.0 g, 72.4 mmol), ethanol (180 mL), pyridinium p-toluenesulfonate (3.71 g, 14.8 mmol) were mixed, and heated at 60° C. for 1 hour. After standing to cool to room temperature, it was released into water (490 mL), and the obtained solid was collected by filtration and dried at 50° C. under reduced pressure to obtain 32.8 g of a white solid (I-4-e).

(I-4-f)之合成： Synthesis of (I-4-f):

依照以下記載之合成法，合成化合物(I-4-f)。 Compound (I-4-f) was synthesized according to the synthesis method described below.

Figure 108109137-A0101-12-0083-26
Figure 108109137-A0101-12-0083-26

將反-4-羥基環己烷羧酸(4.33g，30.0mmol)、二氯甲烷(100mL)、對甲苯磺酸吡啶鎓鹽(1.51g，6.0mmol)混合，於15℃歷時10分鐘滴下3,4-二氫-2H-吡喃(5.05g，60mmol)。於室溫攪拌15小時後，將反應液以7.5wt%碳酸氫鈉水溶液、水、飽和食鹽水洗淨，藉無水硫酸鎂乾燥後，餾除溶媒，得到透明液體之(I-4-i)8.47g。 Mix trans-4-hydroxycyclohexanecarboxylic acid (4.33g, 30.0mmol), dichloromethane (100mL), and pyridinium p-toluenesulfonate (1.51g, 6.0mmol), drop 3 , 4-Dihydro-2H-pyran (5.05 g, 60 mmol). After stirring at room temperature for 15 hours, the reaction solution was washed with 7.5wt% sodium bicarbonate aqueous solution, water, and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain (I-4-i) as a transparent liquid. 8.47g.

將上述所得(I-4-i)(8.14g，26.0mmol)與10wt%氫氧化鉀水溶液(73g)混合，於100℃攪拌5小時。放冷至室溫後，添加33wt%檸檬酸水溶液(75g)，攪拌後，藉二氯甲烷(200mL)萃取，以水、飽和食鹽水洗淨。藉無水硫酸鎂乾燥後，餾除溶媒，將所得固體藉由矽膠管柱層析法(氯仿/醋酸乙酯)進行精製，得到白色固體(I-4-f)4.35g。 The above-obtained (I-4-i) (8.14 g, 26.0 mmol) was mixed with 10 wt % potassium hydroxide aqueous solution (73 g), and stirred at 100° C. for 5 hours. After cooling to room temperature, 33 wt% citric acid aqueous solution (75 g) was added, stirred, extracted with dichloromethane (200 mL), washed with water and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off, and the obtained solid was purified by silica gel column chromatography (chloroform/ethyl acetate) to obtain 4.35 g of a white solid (I-4-f).

(I-4-g)之合成： Synthesis of (I-4-g):

將(I-4-e)(1.39g，3.1mmol)、(I-4-f)(700mg，3.1mmol)、N,N-二甲基胺基吡啶(75mg，0.61mmol)、二氯甲烷(7.5mL)混合，於2℃添加1-乙基-3-(3-二甲基胺基丙基)碳二亞胺鹽酸鹽(647mg，3.4mmol)。於2℃攪拌30分鐘後，再於室溫攪拌16小時。將反應液以氯化銨飽和水溶液、再接著以飽和食鹽水洗淨後，藉由矽膠管柱層析法(甲苯/醋酸乙酯)進行精製，得到白色固體之(I-4-g)1.68g。 (I-4-e) (1.39g, 3.1mmol), (I-4-f) (700mg, 3.1mmol), N,N-dimethylaminopyridine (75mg, 0.61mmol), dichloromethane (7.5 mL) were mixed, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (647 mg, 3.4 mmol) was added at 2°C. After stirring at 2°C for 30 minutes, it was stirred at room temperature for 16 hours. The reaction solution was washed with a saturated aqueous solution of ammonium chloride and then with saturated brine, and purified by silica gel column chromatography (toluene/ethyl acetate) to obtain (I-4-g) 1.68 g.

(I-4-h)之合成： Synthesis of (I-4-h):

將(I-4-g)(1.68g，2.53mmol)、乙醇(20mL)、對甲苯磺酸吡啶鎓鹽(64mg，0.25mmol)混合，於60℃加熱1小時。放冷至室溫後，添加水(40mL)，濾取所得固體，於減壓下以50℃進行乾燥，得到白色固體(I-4-h)1.42g。 (I-4-g) (1.68g, 2.53mmol), ethanol (20mL), pyridinium p-toluenesulfonate (64mg, 0.25mmol) were mixed, and heated at 60°C for 1 hour. After standing to cool to room temperature, water (40 mL) was added, and the obtained solid was collected by filtration and dried at 50° C. under reduced pressure to obtain 1.42 g of a white solid (I-4-h).

(I-4)之合成： Synthesis of (I-4):

將(I-4-h)(1.39g，2.4mmol)、(I-1-h)(888mg，2.4mmol)、N,N-二甲基胺基吡啶(58mg，0.48mmol)、二氯甲烷(7.5mL)混合，於2℃添加1-乙基-3-(3-二甲基胺基丙基)碳二亞胺鹽酸鹽(523mg，2.7mmol)。於2℃攪拌1小時後，再於室溫攪拌6小時。將反應液以氯化銨飽和水溶液、再接著以飽和食鹽水洗淨後，藉由矽膠管柱層析法(甲苯/醋酸乙酯)進行精製，得到白色固體之液晶化合物(I-4)1.13g。 (I-4-h) (1.39g, 2.4mmol), (I-1-h) (888mg, 2.4mmol), N,N-dimethylaminopyridine (58mg, 0.48mmol), dichloromethane (7.5 mL) were mixed, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (523 mg, 2.7 mmol) was added at 2°C. After stirring at 2°C for 1 hour, it was stirred at room temperature for 6 hours. The reaction solution was washed with a saturated aqueous solution of ammonium chloride and then with saturated brine, and purified by silica gel column chromatography (toluene/ethyl acetate) to obtain liquid crystal compound (I-4) 1.13 as a white solid g.

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ8.12(d,2H,J=8.8Hz),7.21(d,2H,J=8.8Hz),7.11(d,2H,J=8.8Hz),6.96(d,2H,J=9.2Hz),6.40(dd,2H,J=17.2,1.2Hz),6.12(dd,2H,J=17.2,10.4Hz),5.81(dd,2H,J=10.4,1.2Hz),4.81-4.68(m,1H),4.15(t,4H,J=6.8Hz),4.04(t,2H,J=6.8Hz),3.44(t,2H,J=6.8Hz),3.25-3.25(m,1H),2.62-2.48(m,1H),2.30-1.96(m,9H),1.86-1.20(m,44H) 1 H NMR(CDCl 3 ,400MHz)δ8.12(d,2H,J=8.8Hz),7.21(d,2H,J=8.8Hz),7.11(d,2H,J=8.8Hz),6.96(d ,2H,J=9.2Hz),6.40(dd,2H,J=17.2,1.2Hz),6.12(dd,2H,J=17.2,10.4Hz),5.81(dd,2H,J=10.4,1.2Hz) ,4.81-4.68(m,1H),4.15(t,4H,J=6.8Hz),4.04(t,2H,J=6.8Hz),3.44(t,2H,J=6.8Hz),3.25-3.25( m,1H),2.62-2.48(m,1H),2.30-1.96(m,9H),1.86-1.20(m,44H)

<液晶化合物(I-5)> <Liquid Crystal Compound (I-5)>

液晶化合物(I-5)係使用根據Lub et al.,Recl.Trav.Chim.Pays-Bas,115,321-328(1996)記載之化合物的方法所合成。 Liquid crystal compound (I-5) was synthesized using the method described in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ1.23-1.72(m,38H),1.76-1.86(m,2H),2.11-2.23(m,4H),2.48-2.60(m,1H),3.20-3.30(m,1H),3.47(t,2H,J=6.8Hz),4.04(t,2H,J=6.8Hz),4.15(t,2H,J=6.8Hz)5.82(d,2H,J=10.4Hz),6.12(dd,2H,J=10.4,17.4Hz),6.40(d,2H,J=17.4Hz),6.97(d,2H,J=9.2Hz),7.11(d,2H,J=9.2Hz),7.21(d,2H,J=9.0Hz),8.13(d,2H,J=9.0Hz) 1 H NMR(CDCl 3 ,400MHz)δ1.23-1.72(m,38H),1.76-1.86(m,2H),2.11-2.23(m,4H),2.48-2.60(m,1H),3.20-3.30 (m,1H),3.47(t,2H,J=6.8Hz),4.04(t,2H,J=6.8Hz),4.15(t,2H,J=6.8Hz)5.82(d,2H,J=10.4 Hz),6.12(dd,2H,J=10.4,17.4Hz),6.40(d,2H,J=17.4Hz),6.97(d,2H,J=9.2Hz),7.11(d,2H,J=9.2 Hz),7.21(d,2H,J=9.0Hz),8.13(d,2H,J=9.0Hz)

<液晶化合物(I-6)> <Liquid Crystal Compound (I-6)>

依照以下記載之合成法，合成液晶化合物(I-6)。 According to the synthesis method described below, the liquid crystal compound (I-6) was synthesized.

Figure 108109137-A0101-12-0086-27
Figure 108109137-A0101-12-0086-27

(I-6-a)之合成： Synthesis of (I-6-a):

將4-碘苯酚(25g，114mmol)、4-二氫-2H-吡喃(13.4g，160mmol)、二氯甲烷溶液(125mL)混合，加入對甲苯磺酸吡啶鎓鹽 (PPTS)(2.85g，11.4mmol)並於室溫攪拌5小時後，加入飽和碳酸氫鈉水溶液(200mL)，藉二氯甲烷進行萃取。將所得有機層以飽和碳酸氫鈉水溶液洗淨及飽和食鹽水洗淨後，加入硫酸鈉進行乾燥後，進行過濾濃縮，藉此得到粗製物。將所得粗製物藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到白色固體(I-6-a)32.7g。 4-iodophenol (25g, 114mmol), 4-dihydro-2H-pyran (13.4g, 160mmol), dichloromethane solution (125mL) were mixed, and pyridinium p-toluenesulfonate (PPTS) (2.85g , 11.4mmol) and stirred at room temperature for 5 hours, added saturated aqueous sodium bicarbonate solution (200mL), and extracted with dichloromethane. The obtained organic layer was washed with saturated aqueous sodium bicarbonate solution and saturated brine, dried over sodium sulfate, and concentrated by filtration to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 32.7 g of a white solid (I-6-a).

(I-6-b)之合成： Synthesis of (I-6-b):

於(I-6-a)(32.7g，107.5mmol)、四氫呋喃(370mL)中加入三甲基矽基乙炔(11.6g，118.3mmol)、三乙基胺(31.6mL，225.8mmol)、碘化銅(I)(2.03g，10.7mmol)，並攪拌。其後，加入二氯雙(三苯基膦)鈀(II)(3.8g，5.38mmol)。於室溫攪拌12小時後，以水-醋酸乙酯進行萃取。將有機層藉飽和食鹽水洗淨後，加入硫酸鈉進行乾燥後，進行過濾濃縮，得到粗製物。將所得粗製物藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到白色固體(I-6-b)30.6g。 Add trimethylsilylacetylene (11.6g, 118.3mmol), triethylamine (31.6mL, 225.8mmol), iodide Copper (I) (2.03 g, 10.7 mmol), and stir. Thereafter, dichlorobis(triphenylphosphine)palladium(II) (3.8 g, 5.38 mmol) was added. After stirring at room temperature for 12 hours, extraction was performed with water-ethyl acetate. The organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated by filtration to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 30.6 g of a white solid (I-6-b).

(I-6-c)之合成： Synthesis of (I-6-c):

將(I-6-b)(30.6g，111.5mmol)、四氫呋喃(250mL)混合，藉冰浴冷卻。添加氟化四正丁基銨四氫呋喃溶液(1mol/L，133.8mL)，於室溫攪拌1小時。藉水-醋酸乙酯萃取，將有機層以飽和食鹽水洗淨後，加入硫酸鈉進行乾燥，進行過濾濃縮而得到(I-6-c)22.1g。 Mix (I-6-b) (30.6g, 111.5mmol) and tetrahydrofuran (250mL) and cool in an ice bath. Tetra-n-butylammonium fluoride tetrahydrofuran solution (1 mol/L, 133.8 mL) was added, and stirred at room temperature for 1 hour. After extracting with water-ethyl acetate, the organic layer was washed with saturated brine, dried by adding sodium sulfate, and concentrated by filtration to obtain 22.1 g of (I-6-c).

(I-6-d)之合成： Synthesis of (I-6-d):

將藉上述操作所得之(I-6-c)(22.1g，109.3mmol)、4-碘苯酚(26.4g，102.2mmol)、四氫呋喃(300mL)混合，加入三乙基胺(23mL， 229.5mmol)。於反應溶液加入碘化銅(I)(2.1g，10.9mmol)、肆三苯基膦鈀(0)(3.8g，5.5mmol)，於室溫進行攪拌4小時。將反應溶液進行矽藻土過濾後，將濾液減壓濃縮。將所得粗製物使用二氯甲烷進行懸浮洗淨，藉此得到(I-6-d)22.1g。 Mix (I-6-c) (22.1g, 109.3mmol), 4-iodophenol (26.4g, 102.2mmol) and tetrahydrofuran (300mL) obtained by the above operation, and add triethylamine (23mL, 229.5mmol) . Copper (I) iodide (2.1 g, 10.9 mmol) and tetraphenylphosphine palladium (0) (3.8 g, 5.5 mmol) were added to the reaction solution, and stirred at room temperature for 4 hours. After filtering the reaction solution through celite, the filtrate was concentrated under reduced pressure. The obtained crude product was suspended and washed with dichloromethane to obtain 22.1 g of (I-6-d).

(I-6-e)之合成： Synthesis of (I-6-e):

將(I-6-d)(11.0g，37.4mmol)、N,N-二甲基甲醯胺(22mL)混合，加入11-溴-1-十一醇(9.39g，37.4mmol)、碳酸鉀(25.8g，187mmol)於90℃攪拌1小時。放冷後加入至冰水中，濾取析出之固體，藉由己烷洗淨得到粗製物。將所得粗製物溶解於醋酸乙酯後，加入硫酸鈉進行乾燥，進行矽藻土過濾，進行溶媒餾除，藉此得到(I-6-e)17.0g。 Mix (I-6-d) (11.0g, 37.4mmol), N,N-dimethylformamide (22mL), add 11-bromo-1-undecanol (9.39g, 37.4mmol), carbonic acid Potassium (25.8 g, 187 mmol) was stirred at 90°C for 1 hour. After cooling, it was added to ice water, and the precipitated solid was collected by filtration and washed with hexane to obtain a crude product. After dissolving the obtained crude product in ethyl acetate, sodium sulfate was added and dried, Celite filtration was performed, and the solvent was distilled off to obtain 17.0 g of (I-6-e).

(I-6-f)之合成： Synthesis of (I-6-f):

將(I-6-e)(4.0g，8.61mmol)、四氫呋喃(40mL)、三乙基胺(2.4mL，17.2mmol)混合，藉冰浴冷卻後，加入丙烯醯氯(1.04mL，12.9mmol)，攪拌10分鐘。將反應液加入至冰水中後，藉醋酸乙酯進行萃取，將有機層以飽和碳酸氫鈉水溶液與飽和食鹽水洗淨。於所得有機層中加入硫酸鈉進行乾燥後，進行過濾濃縮，得到(I-6-f)4.44g。 (I-6-e) (4.0g, 8.61mmol), tetrahydrofuran (40mL), triethylamine (2.4mL, 17.2mmol) were mixed, after cooling in an ice bath, acryloyl chloride (1.04mL, 12.9mmol) was added ), and stirred for 10 minutes. The reaction solution was added to ice water, extracted with ethyl acetate, and the organic layer was washed with saturated aqueous sodium bicarbonate and saturated brine. Sodium sulfate was added to the obtained organic layer, dried, and then concentrated by filtration to obtain 4.44 g of (I-6-f).

(I-6-g)之合成： Synthesis of (I-6-g):

將(I-6-f)(4.44g，8.56mmol)、乙醇(45mL)混合，加入PPTS(215mg，0.856mmol)於50℃攪拌1小時。放冷後，進行減壓濃縮後， 將粗製物藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到(I-6-g)3.36g。 Mix (I-6-f) (4.44g, 8.56mmol) and ethanol (45mL), add PPTS (215mg, 0.856mmol) and stir at 50°C for 1 hour. After standing to cool and concentrating under reduced pressure, the crude product was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 3.36 g of (I-6-g).

(I-6)之合成： Synthesis of (I-6):

將(I-6-g)(1.0g，2.3mmol)、(I-1-i)(0.85g，2.3mmol)、N,N-二甲基胺基-4-吡啶(56mg，0.46mmol)、二氯甲烷(10mL)混合，於0℃加入1-(3-二甲基胺基丙基)-3-乙基碳二亞胺鹽酸鹽(EDC)(0.57g，3.0mmol)，於室溫攪拌2小時。將所得反應溶液注入至冰水(20mL)後，藉二氯甲烷進行萃取。將所得有機層以飽和食鹽水洗淨，加入硫酸鈉進行乾燥後，進行過濾濃縮藉此得到粗製物。將所得粗製物藉由矽膠管柱層析法(己烷/二氯甲烷/醋酸乙酯)進行精製，得到(I-6)0.98g。 (I-6-g) (1.0g, 2.3mmol), (I-1-i) (0.85g, 2.3mmol), N,N-dimethylamino-4-pyridine (56mg, 0.46mmol) , dichloromethane (10mL) were mixed, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) (0.57g, 3.0mmol) was added at 0°C. Stir at room temperature for 2 hours. The obtained reaction solution was poured into ice water (20 mL), and extracted with dichloromethane. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated by filtration to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (hexane/dichloromethane/ethyl acetate) to obtain 0.98 g of (I-6).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.50(d,2H,J=6.8Hz),7.44(d,2H,J=6.8Hz),7.04(d,2H,J=6.8Hz),6.86(d,2H,J=6.8Hz),6.39(d,2H,J=17.2Hz),6.12(dd,2H,J=17.2,10.4Hz),5.82(d,2H,J=10.4Hz),4.15(t,4H,J=6.8Hz),3.99(t,2H,J=6.8Hz),3.47(t,2H,J=6.8Hz),3.29-3.21(m,1H),2.57-2.49(m,1H),2.25-2.10(m,4H),1.88-1.70(m,2H),1.70-1.24(m,38H) 1 H NMR(CDCl 3 ,400MHz)δ7.50(d,2H,J=6.8Hz),7.44(d,2H,J=6.8Hz),7.04(d,2H,J=6.8Hz),6.86(d ,2H,J=6.8Hz),6.39(d,2H,J=17.2Hz),6.12(dd,2H,J=17.2,10.4Hz),5.82(d,2H,J=10.4Hz),4.15(t ,4H,J=6.8Hz),3.99(t,2H,J=6.8Hz),3.47(t,2H,J=6.8Hz),3.29-3.21(m,1H),2.57-2.49(m,1H) ,2.25-2.10(m,4H),1.88-1.70(m,2H),1.70-1.24(m,38H)

<液晶化合物(I-7)> <Liquid Crystal Compound (I-7)>

依以下記載之合成法，合成液晶化合物(I-7)。 The liquid crystal compound (I-7) was synthesized according to the synthesis method described below.

Figure 108109137-A0101-12-0090-28
Figure 108109137-A0101-12-0090-28

(I-7)之合成： Synthesis of (I-7):

將除了使用12-溴-1-十二醇作為起始原料以外其餘依與(I-1-g)相同之方法所合成的(I-7-a)(2g，4.0mmol)、除了使用12-溴-1-十二醇作為起始原料以外其餘依與(I-1-h)相同之方法所合成的(I-7-b)(1.68g，4.4mmol)、N,N-二甲基-4-胺基吡啶(97.7mg，0.8mmol)與二氯甲烷(30mL)混合，於0℃加入EDC(0.92g，4.8mmol)，於室溫攪拌12小時。於反應溶液中加入飽和碳酸氫鈉水溶液後，藉由二氯甲烷進行萃取，將所得有機層以飽和食鹽水洗淨，加入硫酸鎂進行乾燥後，進行過濾濃縮。將所得粗製生成物藉由矽膠管柱層析法(己烷/二氯甲烷/醋酸乙酯)進行精製，得到(I-7)2.17g。 (I-7-a) (2g, 4.0mmol) synthesized by the same method as (I-1-g) except using 12-bromo-1-dodecanol as the starting material, except using 12 (I-7-b) (1.68g, 4.4mmol), N,N-dimethyl Dichloromethane (30 mL) was mixed with 4-aminopyridine (97.7 mg, 0.8 mmol), EDC (0.92 g, 4.8 mmol) was added at 0°C, and stirred at room temperature for 12 hours. After adding saturated aqueous sodium bicarbonate solution to the reaction solution, extraction was performed with dichloromethane, and the obtained organic layer was washed with saturated brine, dried by adding magnesium sulfate, and concentrated by filtration. The obtained crude product was purified by silica gel column chromatography (hexane/dichloromethane/ethyl acetate) to obtain 2.17 g of (I-7).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.55(d,2H),7.19(d,2H),7.11(d,2H),6.89(d,2H),6.39(dd,2H),6.12(dd,2H),5.81(dd,2H),4.15(t,4H),3.99(t,2H),3.46(t,2H),3.21- 3.29(m,1H),2.49-2.57(m,1H),2.15(m4H),1.79(m,2H),1.52-1.72(m,12H),1.24-1.49(m,42H) 1 H NMR(CDCl 3 ,400MHz)δ7.55(d,2H),7.19(d,2H),7.11(d,2H),6.89(d,2H),6.39(dd,2H),6.12(dd, 2H),5.81(dd,2H),4.15(t,4H),3.99(t,2H),3.46(t,2H),3.21-3.29(m,1H),2.49-2.57(m,1H),2.15 (m4H),1.79(m,2H),1.52-1.72(m,12H),1.24-1.49(m,42H)

<液晶化合物(I-8)> <Liquid Crystal Compound (I-8)>

依照以下記載之合成法，合成液晶化合物(I-8)。 According to the synthesis method described below, the liquid crystal compound (I-8) was synthesized.

Figure 108109137-A0101-12-0091-29
Figure 108109137-A0101-12-0091-29

(I-8-a)之合成： Synthesis of (I-8-a):

於反-4-羥基環己基酚(10.0g，52.0mmol)、碳酸鉀(28.8g，208mmol)之DMF溶液(100mL)中加入氯甲基甲基醚(6.30g，78.0mmol)攪拌6小時。於反應溶液中加入水(100mL)後，藉二異丙 基醚(100mL)進行萃取3次。將所得有機層以飽和食鹽水洗淨後，加入硫酸鎂並攪拌。進行過濾濃縮後，藉由進行矽膠管柱層析法(二氯甲烷/醋酸乙酯)，得到(I-8-a)5.79g。 Chloromethyl methyl ether (6.30 g, 78.0 mmol) was added to a DMF solution (100 mL) of trans-4-hydroxycyclohexylphenol (10.0 g, 52.0 mmol), potassium carbonate (28.8 g, 208 mmol) and stirred for 6 hours. After adding water (100 mL) to the reaction solution, extraction was performed 3 times with diisopropyl ether (100 mL). After washing the obtained organic layer with saturated brine, magnesium sulfate was added and stirred. After filtration and concentration, 5.79 g of (I-8-a) was obtained by silica gel column chromatography (dichloromethane/ethyl acetate).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.12(d,2H),6.96(d,2H),5.15(s,2H),3.6-3.7(m,1H),3.47(d,3H),2.6-2.7(m,1H),2.0-2.1(m,2H),1.85-1.95(m,2H),1.3-1.6(m,6H) 1 H NMR(CDCl 3 ,400MHz)δ7.12(d,2H),6.96(d,2H),5.15(s,2H),3.6-3.7(m,1H),3.47(d,3H),2.6- 2.7(m,1H),2.0-2.1(m,2H),1.85-1.95(m,2H),1.3-1.6(m,6H)

(I-8-b)之合成： Synthesis of (I-8-b):

將(I-8-a)(5.30g，22.0mmol)溶解於DMF(30mL)，加入碘化十二烷(13.0g，44.0mmol)、氫化鈉(油性50-70%，2.0g)於室溫攪拌8小時。於反應溶液中加入水並使用二異丙基醚萃取後，將有機層以飽和食鹽水洗淨。進而加入硫酸鎂進行乾燥後，進行過濾濃縮，得到粗製生成物。藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到(I-8-b)4.58g。 Dissolve (I-8-a) (5.30g, 22.0mmol) in DMF (30mL), add dodecane iodide (13.0g, 44.0mmol), sodium hydride (oily 50-70%, 2.0g) in room Warm stirring for 8 hours. Water was added to the reaction solution, followed by extraction with diisopropyl ether, and the organic layer was washed with saturated brine. Furthermore, magnesium sulfate was added and dried, and then concentrated by filtration to obtain a crude product. Purification was carried out by silica gel column chromatography (hexane/ethyl acetate) to obtain 4.58 g of (I-8-b).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.11(d,2H),6.96(d,2H),5.14(s,2H),3.47(m,5H),3.2-3.3(m,1H),2.4-2.5(m,1H),2.1-2.2(m,2H),1.9-2.0(m,2H),1.2-1.6(m,20H),0.88(t,3H) 1 H NMR(CDCl 3 ,400MHz)δ7.11(d,2H),6.96(d,2H),5.14(s,2H),3.47(m,5H),3.2-3.3(m,1H),2.4- 2.5(m,1H),2.1-2.2(m,2H),1.9-2.0(m,2H),1.2-1.6(m,20H),0.88(t,3H)

(I-8-c)之合成： Synthesis of (I-8-c):

將(I-8-b)(4.58g，11.7mmol)溶解於甲醇(60mL)，加入濃鹽酸(18mL)於40℃攪拌2小時，於室溫攪拌24小時。將生成之沉澱過濾後，以水洗淨，得到(I-8-c)3.93g。 Dissolve (I-8-b) (4.58 g, 11.7 mmol) in methanol (60 mL), add concentrated hydrochloric acid (18 mL) and stir at 40° C. for 2 hours, then at room temperature for 24 hours. The generated precipitate was filtered and washed with water to obtain 3.93 g of (I-8-c).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.07(d,2H),6.75(d,2H),3.49(t,2H),3.2-3.3(m,1H),2.4-2.5(m,1H),2.1-2.2(m,2H),1.9-2.0(m,2H),1.2-1.6(m,20H),0.88(t,3H) 1 H NMR(CDCl 3 ,400MHz)δ7.07(d,2H),6.75(d,2H),3.49(t,2H),3.2-3.3(m,1H),2.4-2.5(m,1H), 2.1-2.2(m,2H),1.9-2.0(m,2H),1.2-1.6(m,20H),0.88(t,3H)

(I-8)之合成： Synthesis of (I-8):

將(I-8-c)(438mg，1.26mmol)、(I-1-d)(465mg，1.20mmol)、N,N-二甲基-4-胺基吡啶(29.3mg，0.24mmol)溶解於二氯甲烷(30mL)，於0℃加入EDC(276mg，1.44mmol)，於室溫攪拌4小時。於反應溶液中加入碳酸氫鈉飽和水溶液後，藉二氯甲烷進行萃取，將所得有機層以飽和食鹽水洗淨，加入硫酸鎂進行乾燥後，進行過濾濃縮。將所得粗製生成物藉由矽膠管柱層析法(己烷/醋酸乙酯)進行管柱精製，得到(I-8)447mg。 Dissolve (I-8-c) (438 mg, 1.26 mmol), (I-1-d) (465 mg, 1.20 mmol), N,N-dimethyl-4-aminopyridine (29.3 mg, 0.24 mmol) To dichloromethane (30 mL), EDC (276 mg, 1.44 mmol) was added at 0°C, and stirred at room temperature for 4 hours. After adding a saturated aqueous solution of sodium bicarbonate to the reaction solution, extraction was carried out with dichloromethane, and the obtained organic layer was washed with saturated brine, dried by adding magnesium sulfate, and concentrated by filtration. The obtained crude product was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 447 mg of (I-8).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.6(d,2H),6.95(d,2H),3.47(t,2H),3.2-3.3(m,1H),2.4-2.5(m,1H),2.1-2.2(m,2H),1.8-1.9(m,1H),1.2-1.6(m,20H),0.88(t,3H) 1 H NMR(CDCl 3 ,400MHz)δ7.6(d,2H),6.95(d,2H),3.47(t,2H),3.2-3.3(m,1H),2.4-2.5(m,1H), 2.1-2.2(m,2H),1.8-1.9(m,1H),1.2-1.6(m,20H),0.88(t,3H)

<液晶化合物(I-9)> <Liquid Crystal Compound (I-9)> 依照以下記載之合成法，合成液晶化合物(I-9)。 According to the synthesis method described below, the liquid crystal compound (I-9) was synthesized.

Figure 108109137-A0101-12-0094-30
Figure 108109137-A0101-12-0094-30

(I-9-a)之合成： Synthesis of (I-9-a):

於下述合成之(I-10-b)(3.25g，10.7mmol)之DMF溶液(20mL)中加入氫化鈉(油性50-70%，1.03g)攪拌1小時。其後，加入1-溴十一烷(7.80g，31.4mmol)，再於室溫攪拌4小時。於反應溶液中加入飽和氯化銨水溶液(50mL)與水(50mL)並使用二異丙基醚進行萃取。將有機層以飽和食鹽水洗淨，加入硫酸鎂進行乾燥後，進行過濾於減壓下濃縮。將所得粗製生成物藉由矽膠管柱層析法(洗提液：己烷)進行精製後，藉由甲醇進行懸浮洗淨，得到(I-9-a)3.61g。 Sodium hydride (oily 50-70%, 1.03 g) was added to a DMF solution (20 mL) of (I-10-b) (3.25 g, 10.7 mmol) synthesized below and stirred for 1 hour. Thereafter, 1-bromoundecane (7.80 g, 31.4 mmol) was added, followed by stirring at room temperature for 4 hours. Saturated aqueous ammonium chloride solution (50 mL) and water (50 mL) were added to the reaction solution, followed by extraction with diisopropyl ether. The organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: hexane), and then suspended and washed with methanol to obtain 3.61 g of (I-9-a).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.6(d,2H),6.9 5(d,2H),3.47(t,2H),3.2-3.3(m,1H),2.4-2.5(m,1H),2.1-2.2(m,2H),1.8-1.9(m,1H),1.2-1.6(m,20H),0.88(t,3H) 1 H NMR(CDCl 3 ,400MHz)δ7.6(d,2H),6.95(d,2H),3.47(t,2H),3.2-3.3(m,1H),2.4-2.5(m,1H) ,2.1-2.2(m,2H),1.8-1.9(m,1H),1.2-1.6(m,20H),0.88(t,3H)

(I-9-b)之合成： Synthesis of (I-9-b):

將(I-9-a)(1.88g，4.0mmol)、氧化銅(I)(858mg，6.0mmol)、DMF(10mL)混合，加入丙酸(785mg，8.0mmol)，於氮氣流下，以110℃加熱攪拌10.5小時。冷卻至室溫後，加入水(100mL)，藉二異丙基醚進行萃取。於有機層中加入硫酸鎂進行乾燥後，進行過濾，於減壓下濃縮。將所得粗製生成物藉由矽膠管柱層析法(洗提液：己烷/醋酸乙酯)進行精製，得到(I-9-b)791mg。 (I-9-a) (1.88g, 4.0mmol), copper (I) oxide (858mg, 6.0mmol), DMF (10mL) were mixed, and propionic acid (785mg, 8.0mmol) was added. It was heated and stirred at ℃ for 10.5 hours. After cooling to room temperature, water (100 mL) was added and extracted with diisopropyl ether. Magnesium sulfate was added to the organic layer to dry, filtered, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate) to obtain 791 mg of (I-9-b).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.5(d,2H),7.2(d,2H),4.28(q,2H),3.47(t,2H),3.2-3.3(m,1H),2.4-2.5(m,1H),2.1-2.2(m,2H),1.8-1.9(m,1H),1.2-1.6(m,20H),0.88(t,3H) 1 H NMR (CDCl 3 , 400MHz)δ7.5(d,2H),7.2(d,2H),4.28(q,2H),3.47(t,2H),3.2-3.3(m,1H),2.4- 2.5(m,1H),2.1-2.2(m,2H),1.8-1.9(m,1H),1.2-1.6(m,20H),0.88(t,3H)

(I-9-c)之合成： Synthesis of (I-9-c):

加入(I-9-b)(420mg，0.95mmol)、氫氧化鉀(104mg，2.0mmol)、二氯甲烷(4mL)與水(10mL)於100℃加熱攪拌1小時後，冷卻至室溫，加入2mol/L之鹽酸，藉乙醇洗淨生成之沉澱物，得到(I-9-c)237mg。 Add (I-9-b) (420mg, 0.95mmol), potassium hydroxide (104mg, 2.0mmol), dichloromethane (4mL) and water (10mL), heat and stir at 100°C for 1 hour, then cool to room temperature, 2 mol/L hydrochloric acid was added, and the resulting precipitate was washed with ethanol to obtain 237 mg of (I-9-c).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.5(d,2H),7.2(d,2H),3.47(t,2H),3.2-3.3(m,1H),2.4-2.5(m,1H),2.1-2.2(m,2H),1.8-1.9(m,1H),1.2-1.6(m,20H),0.88(t,3H) 1 H NMR(CDCl 3 ,400MHz)δ7.5(d,2H),7.2(d,2H),3.47(t,2H),3.2-3.3(m,1H),2.4-2.5(m,1H), 2.1-2.2(m,2H),1.8-1.9(m,1H),1.2-1.6(m,20H),0.88(t,3H)

(I-9)之合成： Synthesis of (I-9):

將(I-9-c)(697mg，1.6mmol)、(I-10-g)(602mg，1.8mmol)、N,N-二甲基-4-胺基吡啶(39.0mg，0.32mmol)、二氯甲烷(30mL)混合，於氮氣流下、0℃加入EDC(364mg，1.9mmol)後，升溫至室溫，攪拌6小時。加入飽和碳酸氫鈉水溶液，以二氯甲烷溶液萃取，將所得有機層以飽和食鹽水洗淨。其後，加入硫酸鎂進行乾燥後，進行過濾，並於減壓下濃縮。將所得粗製生成物藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到(I-9)774mg。 (I-9-c) (697mg, 1.6mmol), (I-10-g) (602mg, 1.8mmol), N,N-dimethyl-4-aminopyridine (39.0mg, 0.32mmol), Dichloromethane (30 mL) was mixed, and EDC (364 mg, 1.9 mmol) was added at 0° C. under a nitrogen stream, then warmed up to room temperature, and stirred for 6 hours. Saturated aqueous sodium bicarbonate solution was added, extracted with dichloromethane solution, and the obtained organic layer was washed with saturated brine. Thereafter, magnesium sulfate was added to dry, filtered, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 774 mg of (I-9).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.54(d,2H),7.23(d,2H),7.08(d,2H),6.89(d,2H),6.39(d,1H),6.12(dd,1H),5.8(d,1H),4.15(t,2H),3.94(t,2H),3.48(t,2H),3.2-3.3(m,1H),2.4-2.5(m,1H),2.1-2.2(m,2H),1.9-2.0(m,1H),1.7-1.8(m,2H),1.6-1.7(m,2H),1.2-1.6(m,34H),0.88(t,3H) 1 H NMR(CDCl 3 ,400MHz)δ7.54(d,2H),7.23(d,2H),7.08(d,2H),6.89(d,2H),6.39(d,1H),6.12(dd, 1H),5.8(d,1H),4.15(t,2H),3.94(t,2H),3.48(t,2H),3.2-3.3(m,1H),2.4-2.5(m,1H),2.1 -2.2(m,2H),1.9-2.0(m,1H),1.7-1.8(m,2H),1.6-1.7(m,2H),1.2-1.6(m,34H),0.88(t,3H)

<液晶化合物(I-10)> <Liquid Crystal Compound (I-10)>

依照以下記載之合成法，合成液晶化合物(I-10)。 According to the synthesis method described below, the liquid crystal compound (I-10) was synthesized.

Figure 108109137-A0101-12-0097-31
Figure 108109137-A0101-12-0097-31

(I-10-a)之合成： Synthesis of (I-10-a):

將4-環己基苯基(36.8g，211mmol)、1-氯甲基-4-氟-1,4-重氮化雙環[2.2.2]辛烷雙(四氟硼酸鹽)(30.0g，84.0mmol)、乙腈(800mL) 混合，加入碘(21.3g，84.0mmol)並以60℃加熱攪拌3小時。冷卻至室溫後，加入飽和碳酸氫鈉水溶液(400mL)後，藉二異丙基醚(200mL)進行萃取3次。將所得有機層以飽和食鹽水(200mL)洗淨後，加入硫酸鎂進行乾燥後，於減壓下進行濃縮。將所得粗製生成物藉由矽膠管柱層析法(洗提液：己烷/醋酸乙酯)進行精製，得到(I-10-a)28.0g。 4-Cyclohexylphenyl (36.8g, 211mmol), 1-chloromethyl-4-fluoro-1,4-diazobicyclo[2.2.2]octanebis(tetrafluoroborate) (30.0g, 84.0mmol), acetonitrile (800mL) were mixed, iodine (21.3g, 84.0mmol) was added and heated and stirred at 60°C for 3 hours. After cooling to room temperature, saturated aqueous sodium bicarbonate solution (400 mL) was added, followed by extraction with diisopropyl ether (200 mL) three times. The obtained organic layer was washed with saturated brine (200 mL), dried by adding magnesium sulfate, and then concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate) to obtain 28.0 g of (I-10-a).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.64(d,2H),6.99(d,2H),2.94-3.01(m,1H),2.48-2.51(m,4H),2.04-2.16(m,2H),1.56-1.85(m,2H) 1 H NMR(CDCl 3 ,400MHz)δ7.64(d,2H),6.99(d,2H),2.94-3.01(m,1H),2.48-2.51(m,4H),2.04-2.16(m,2H ),1.56-1.85(m,2H)

(I-10-b)之合成： Synthesis of (I-10-b):

將(I-10-a)(17.6g，58.6mmol)、碳酸氫鈉(1.62g，11.7mmol)與乙腈(330mL)混合，將氫化硼鈉(4.40g，107mmol)於40℃下加入，升溫至74℃，進行加熱攪拌1小時。冷卻至室溫，加入飽和氯化銨水溶液(20mL)並攪拌。其後，加入水(200mL)後，使用二異丙基醚(200mL)進行萃取，將有機層以飽和食鹽水洗淨。於所得有機層中加入硫酸鎂進行乾燥後進行過濾，於減壓下進行濃縮。將所得粗製生成物藉由丙酮洗淨，得到(I-10-b)8.93g。 (I-10-a) (17.6g, 58.6mmol), sodium bicarbonate (1.62g, 11.7mmol) and acetonitrile (330mL) were mixed, sodium borohydride (4.40g, 107mmol) was added at 40°C, and the temperature was raised Heat and stir at 74° C. for 1 hour. After cooling to room temperature, saturated aqueous ammonium chloride solution (20 mL) was added and stirred. Then, after adding water (200 mL), it extracted using diisopropyl ether (200 mL), and the organic layer was washed with saturated brine. Magnesium sulfate was added to the obtained organic layer, dried, filtered, and concentrated under reduced pressure. The obtained crude product was washed with acetone to obtain 8.93 g of (I-10-b).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.6(d,2H),6.95(d,2H),3.6-3.7(m,2H),2.4-2.5(m,1H),2.1-2.2(m,2H),1.9-2.0(m,2H),1.39-1.51(m,4H) 1 H NMR(CDCl 3 ,400MHz)δ7.6(d,2H),6.95(d,2H),3.6-3.7(m,2H),2.4-2.5(m,1H),2.1-2.2(m,2H ),1.9-2.0(m,2H),1.39-1.51(m,4H)

(I-10-c)之合成： Synthesis of (I-10-c):

將(I-10-b)(8.93g，29.6mmol)與DMF(60mL)混合，加入氫化鈉(油性50%，3.40g)，於氮氣流下，攪拌直到不再發生氣泡。其後，加入2-(11-溴十一烷氧基)

Figure 108109137-A0101-12-0099-91
烷(29.5g，88.0mmol)並於60℃攪拌5小時。冷卻至室溫後，加入水(100mL)，加入二異丙基醚(200mL)進行萃取。重複2次後，以飽和食鹽水洗淨後，加入硫酸鎂進行乾燥，過濾後於減壓下進行濃縮。將所得粗製生成物藉由矽膠管柱層析法(洗提液：己烷/醋酸乙酯)進行精製，得到(I-10-c)13.8g。 (I-10-b) (8.93g, 29.6mmol) was mixed with DMF (60mL), sodium hydride (50% oily, 3.40g) was added, and stirred under nitrogen flow until no more bubbles occurred. Thereafter, 2-(11-bromoundecyloxy) was added
Figure 108109137-A0101-12-0099-91
Alkane (29.5 g, 88.0 mmol) and stirred at 60°C for 5 hours. After cooling to room temperature, water (100 mL) was added, and diisopropyl ether (200 mL) was added for extraction. After repeating twice, the mixture was washed with saturated brine, dried by adding magnesium sulfate, filtered, and then concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate) to obtain 13.8 g of (I-10-c).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.59(d,2H),6.95(d,2H),4.5-4.6(m,1H),3.83-3.9(m,1H),3.69-3.74(m,1H),3.2-3.5(m,5H),2.4-2.5(m,1H),2.13-2.18(m,2H),1.2-1.92(m,22H) 1 H NMR(CDCl 3 ,400MHz)δ7.59(d,2H),6.95(d,2H),4.5-4.6(m,1H),3.83-3.9(m,1H),3.69-3.74(m,1H ),3.2-3.5(m,5H),2.4-2.5(m,1H),2.13-2.18(m,2H),1.2-1.92(m,22H)

(I-10-d)之合成： Synthesis of (I-10-d):

將(I-10-c)(2.22g，4.0mmol)、雙(三苯基膦)二氯化鈀(II)(84.0mg，0.12mmol)、碘化銅(I)(44.0mg，0.24mmol)、碳酸鈉(1.66g，12.0mmol)、DMF(20mL)混合，於氮氣流下加入丙酸乙酯(588mg，6.0mmol)，於70℃攪拌5小時。冷卻至室溫後，加入水(100mL)，藉二異丙基醚進行萃取。將所得有機層以飽和食鹽水洗淨，加入硫酸鎂進行乾燥後，進行過濾，於減壓下進行濃縮。將所得粗製生成物藉由矽膠管柱層析法(洗提液：己烷/醋酸乙酯)進行精製，得到(I-10-d)1.78g。 (I-10-c) (2.22g, 4.0mmol), bis(triphenylphosphine)palladium(II) chloride (84.0mg, 0.12mmol), copper(I) iodide (44.0mg, 0.24mmol ), sodium carbonate (1.66g, 12.0mmol), DMF (20mL) were mixed, ethyl propionate (588mg, 6.0mmol) was added under nitrogen flow, and stirred at 70°C for 5 hours. After cooling to room temperature, water (100 mL) was added and extracted with diisopropyl ether. The obtained organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate) to obtain 1.78 g of (I-10-d).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.59(d,2H),7.19(d,2H),4.5-4.6(m,1H),4.29(q,2H),3.83-3.9(m,1H),3.69-3.74(m,1H),3.2-3.5(m,5H),2.4-2.5(m,1H),2.13-2.18(m,2H),1.2-1.92(m,25H) 1 H NMR(CDCl 3 ,400MHz)δ7.59(d,2H),7.19(d,2H),4.5-4.6(m,1H),4.29(q,2H),3.83-3.9(m,1H), 3.69-3.74(m,1H),3.2-3.5(m,5H),2.4-2.5(m,1H),2.13-2.18(m,2H),1.2-1.92(m,25H)

(I-10-e)之合成： Synthesis of (I-10-e):

於(I-10-d)(602mg，1.1mmol)中加入THF(5mL)、乙醇(2.5mL)，使其完全溶解後，加入使氫氧化鉀(188mg，3.3mmol)溶解於水(5mL)的液體並於室溫攪拌1小時。加入2mol/L鹽酸(20mL)後，於室溫再攪拌10分鐘。對此溶液加入二異丙基醚進行萃取，將有機層以飽和食鹽水洗淨後，加入硫酸鎂進行乾燥，過濾後於減壓下進行濃縮。將所得粗製生成物與乙醇(20mL)、PPTS(30mg，0.12mmol)混合，於50℃攪拌1小時。將溶媒濃縮後，進行水洗，藉此得到(I-10-e)435mg。 Add THF (5mL) and ethanol (2.5mL) to (I-10-d) (602mg, 1.1mmol) to dissolve completely, then add potassium hydroxide (188mg, 3.3mmol) to dissolve in water (5mL) liquid and stirred at room temperature for 1 hour. After adding 2 mol/L hydrochloric acid (20 mL), the mixture was stirred at room temperature for 10 minutes. Diisopropyl ether was added to this solution for extraction, and the organic layer was washed with saturated brine, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained crude product was mixed with ethanol (20 mL) and PPTS (30 mg, 0.12 mmol), and stirred at 50° C. for 1 hour. The solvent was concentrated and washed with water to obtain 435 mg of (I-10-e).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CD3OD,400MHz)δ7.52(d,2H),7.30(d,2H),3.52-3.57(m,4H),3.32-3.36(m,1H),2.4-2.5(m,1H),2.13-2.18(m,2H),1.34-1.59(m,22H) 1 H NMR(CD 3 OD,400MHz)δ7.52(d,2H),7.30(d,2H),3.52-3.57(m,4H),3.32-3.36(m,1H),2.4-2.5(m, 1H),2.13-2.18(m,2H),1.34-1.59(m,22H)

(I-10-f)之合成： Synthesis of (I-10-f):

將(I-10-e)(1.20g，3.0mmol)、N,N-二甲基苯胺(909mg， 7.5mmol)、THF(30mL)混合，於0℃加入丙烯醯氯(452mg，5.0mmol)，於50℃攪拌2.5小時。其後，將冰冷之2mol/L鹽酸(50mL)加入至反應液並攪拌後，使用二異丙基醚進行萃取。將有機層以飽和食鹽水洗淨後，加入硫酸鎂進行乾燥後，過濾後於減壓下進行濃縮。於所得粗製生成物中加入己烷並過濾、懸浮洗淨，藉此得到(I-10-f)691mg。 Mix (I-10-e) (1.20g, 3.0mmol), N,N-dimethylaniline (909mg, 7.5mmol), THF (30mL), add acryloyl chloride (452mg, 5.0mmol) at 0°C , stirred at 50°C for 2.5 hours. Thereafter, ice-cold 2 mol/L hydrochloric acid (50 mL) was added to the reaction liquid, stirred, and extracted with diisopropyl ether. The organic layer was washed with saturated brine, dried by adding magnesium sulfate, filtered, and concentrated under reduced pressure. Hexane was added to the obtained crude product, followed by filtration, suspension washing, and 691 mg of (I-10-f) were obtained.

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.53(d,2H),7.23(d,2H),6.39(d,1H),6.11(dd,1H),5.81(d,1H),4.15(t,2H),3.48(t,2H),3.32-3.36(m,1H),2.45-2.5(m,1H),2.13-2.18(m,2H),1.28-1.69(m,22H) 1 H NMR(CDCl 3 ,400MHz)δ7.53(d,2H),7.23(d,2H),6.39(d,1H),6.11(dd,1H),5.81(d,1H),4.15(t, 2H),3.48(t,2H),3.32-3.36(m,1H),2.45-2.5(m,1H),2.13-2.18(m,2H),1.28-1.69(m,22H)

(I-10-g)之合成： Synthesis of (I-10-g):

依照以下記載之合成法，合成化合物(I-10-g)。 Compound (I-10-g) was synthesized according to the synthesis method described below.

Figure 108109137-A0101-12-0101-32
Figure 108109137-A0101-12-0101-32

(I-10-h)之合成： Synthesis of (I-10-h):

將(I-1-e)(31.1g，160mmol)、11-溴-1-十一醇(44.2g，176mmol)、 碳酸鉀(44.2g，320mmol)與DMF(125mL)混合，於100℃攪拌1.5小時。攪拌後，冷卻至室溫後，加入至水(2L)中，濾取固形物並以水洗淨。其後將固形物溶解於二氯甲烷中，以水、飽和食鹽水洗淨，加入硫酸鈉進行乾燥後，於減壓下進行濃縮。濃縮後，加入異丙醇使其懸浮，濾取固形物而得到(I-10-h)47.6g。 (I-1-e) (31.1g, 160mmol), 11-bromo-1-undecanol (44.2g, 176mmol), potassium carbonate (44.2g, 320mmol) and DMF (125mL) were mixed and stirred at 100°C 1.5 hours. After stirring and cooling to room temperature, it was added to water (2 L), and the solid was collected by filtration and washed with water. Thereafter, the solid was dissolved in dichloromethane, washed with water and saturated brine, dried by adding sodium sulfate, and then concentrated under reduced pressure. After concentrating, isopropanol was added and suspended, and the solid was collected by filtration to obtain 47.6 g of (I-10-h).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ6.96(d,2H),6.92(d,2H),5.28(m,1H),3.38-3.94(m,3H),3.3-3.6(m,3H),1.14-2.0(m,22H) 1 H NMR(CDCl 3 ,400MHz)δ6.96(d,2H),6.92(d,2H),5.28(m,1H),3.38-3.94(m,3H),3.3-3.6(m,3H), 1.14-2.0(m,22H)

(I-10-i)之合成： Synthesis of (I-10-i):

將(I-10-h)(47.6g，131mmol)與THF(480mL)混合，加入N,N-二甲基苯胺(31.6g，261mmol)與丙烯醯氯(17.7g，196mmol)，於室溫攪拌2小時。將反應液注入至水中，以醋酸乙酯萃取。將萃取液依序以1mol/L鹽酸、飽和食鹽水洗淨，加入硫酸鈉進行乾燥後，於減壓下進行濃縮。將所得粗製生成物藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到(I-10-i)48.6g。 Mix (I-10-h) (47.6g, 131mmol) with THF (480mL), add N,N-dimethylaniline (31.6g, 261mmol) and acryloyl chloride (17.7g, 196mmol), at room temperature Stir for 2 hours. The reaction liquid was poured into water, and extracted with ethyl acetate. The extract was washed sequentially with 1 mol/L hydrochloric acid and saturated brine, dried by adding sodium sulfate, and then concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 48.6 g of (I-10-i).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ6.96(d,2H),6.92(d,2H),6.3(d,1H),6.15(dd,1H),5.8(d,1H),5.28(m,1H),4.15(t,2H),3.8-4.0(m,3H),3.5-3.6(m,1H),1.2-2.1(m,24H) 1 H NMR(CDCl 3 ,400MHz)δ6.96(d,2H),6.92(d,2H),6.3(d,1H),6.15(dd,1H),5.8(d,1H),5.28(m, 1H),4.15(t,2H),3.8-4.0(m,3H),3.5-3.6(m,1H),1.2-2.1(m,24H)

(I-10-g)之合成： Synthesis of (I-10-g):

將(I-10-i)(48.6g，116mmol)與乙醇(260mL)混合，加入PPTS(2.9g，11.6mmol)，進行加熱迴流1小時。冷卻至室溫後，將反應液於減壓下進行濃縮。將所得粗製生成物藉由矽膠管柱層析法(己烷/二氯甲烷/醋酸乙酯)進行精製，得到(I-10-g)25.9g。 (I-10-i) (48.6 g, 116 mmol) was mixed with ethanol (260 mL), PPTS (2.9 g, 11.6 mmol) was added, and the mixture was heated under reflux for 1 hour. After cooling to room temperature, the reaction solution was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane/dichloromethane/ethyl acetate) to obtain 25.9 g of (I-10-g).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ6.7-6.8(m,4H),6.37(d,2H),6.14(d,1H),6.80(dd,1H),5.8(d,1H),4.15(t,2H),3.75(t,2H),1.2-2.1(m,18H) 1 H NMR (CDCl 3 , 400MHz) δ6.7-6.8 (m, 4H), 6.37 (d, 2H), 6.14 (d, 1H), 6.80 (dd, 1H), 5.8 (d, 1H), 4.15 ( t,2H),3.75(t,2H),1.2-2.1(m,18H)

(I-10)之合成 Synthesis of (I-10)

將(I-10-f)(829mg，1.77mmol)、(I-10-g)(669mg，2mmol)、N,N-二甲基-4-胺基吡啶(43mg，0.35mmol)與二氯甲烷(20mL)混合，於氮氣流下以0℃加入EDC(403mg，2.1mmol)後，升溫至室溫並攪拌3小時。加入飽和碳酸氫鈉水溶液並藉二氯甲烷溶液進行萃取，將所得有機層以飽和食鹽水洗淨。其後，加入硫酸鎂進行乾燥後，進行過濾，於減壓下進行濃縮。將所得粗製生成物藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到(1-10)740mg。 (I-10-f) (829mg, 1.77mmol), (I-10-g) (669mg, 2mmol), N,N-dimethyl-4-aminopyridine (43mg, 0.35mmol) and dichloro Methane (20 mL) was mixed, and EDC (403 mg, 2.1 mmol) was added at 0° C. under a nitrogen stream, then warmed to room temperature and stirred for 3 hours. Saturated aqueous sodium bicarbonate solution was added and extracted with dichloromethane solution, and the obtained organic layer was washed with saturated brine. Then, after adding magnesium sulfate and drying, it filtered and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 740 mg of (1-10).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.53(d,2H),7.23(d,2H),7.07(d,2H),6.90(d,2H),6.39(d,2H),6.11(dd,2H),5.81(d,4H),4.15(t,2H),3.94(t,2H),3.48(t,2H),3.24-3.27(m,1H),2.45-2.5(m,1H),2.13-2.18(m, 2H),1.92-1.95(m,2H),1.2-1.8(m,40H) 1 H NMR(CDCl 3 ,400MHz)δ7.53(d,2H),7.23(d,2H),7.07(d,2H),6.90(d,2H),6.39(d,2H),6.11(dd, 2H),5.81(d,4H),4.15(t,2H),3.94(t,2H),3.48(t,2H),3.24-3.27(m,1H),2.45-2.5(m,1H),2.13 -2.18(m, 2H),1.92-1.95(m,2H),1.2-1.8(m,40H)

<液晶化合物(I-11)> <Liquid Crystal Compound (I-11)>

依照以下記載之合成法，合成液晶化合物(I-11) According to the synthesis method described below, the liquid crystal compound (I-11) was synthesized

Figure 108109137-A0101-12-0104-33
Figure 108109137-A0101-12-0104-33

(I-11-a)之合成： Synthesis of (I-11-a):

將(I-8-a)(7.20g，30.5mmol)與DMF(35mL)混合，加入氫氧化鈉(油性：含量50%，3.6g，91.4mmol)，於氮氣流下，攪拌直到不再發生氣泡。其後，加入2-(11-溴十二烷氧基)

Figure 108109137-A0101-12-0105-92
烷(19.3g，54.5mmol)並加熱攪拌6小時。冷卻至室溫後，加入水(100mL)，使用醋酸乙酯進行萃取。重複3次後，以飽和食鹽水洗淨後，加入硫酸鈉進行乾燥，過濾後於減壓下進行濃縮。將所得粗製生成物藉由矽膠管柱層析法(洗提液：己烷/醋酸乙酯)進行精製，得到(I-11-a)12.4g。 Mix (I-8-a) (7.20g, 30.5mmol) with DMF (35mL), add sodium hydroxide (oily: content 50%, 3.6g, 91.4mmol), and stir under nitrogen flow until no more bubbles occur . Thereafter, 2-(11-bromododecyloxy) was added
Figure 108109137-A0101-12-0105-92
Alkane (19.3g, 54.5mmol) and stirred with heating for 6 hours. After cooling to room temperature, water (100 mL) was added, and extraction was performed with ethyl acetate. After repeating 3 times, the mixture was washed with saturated brine, dried over sodium sulfate, filtered, and then concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate) to obtain 12.4 g of (I-11-a).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.12(d,2H),6.97(d,2H),5.15(s,2H),4.56-4.58(m,1H),3.85-3.9(m,1H),3.7-3.75(m,1H),3.41-3.52(m,6H),3.35-3.39(m,1H),3.22-3.35(m,1H),2.4-2.5(m,1H),2.1-2.2(m,2H),1.8-1.93(m,3H),1.68-1.75(m,1H),1.2-1.6(m,29H) 1 H NMR(CDCl 3 ,400MHz)δ7.12(d,2H),6.97(d,2H),5.15(s,2H),4.56-4.58(m,1H),3.85-3.9(m,1H), 3.7-3.75(m,1H),3.41-3.52(m,6H),3.35-3.39(m,1H),3.22-3.35(m,1H),2.4-2.5(m,1H),2.1-2.2(m ,2H),1.8-1.93(m,3H),1.68-1.75(m,1H),1.2-1.6(m,29H)

(I-11-b)之合成： Synthesis of (I-11-b):

於氮氣流下，將(I-11-a)(18.6g，37.9mmol)、PPTS(1.0g，3.8mmol)與乙醇(200mL)混合，於40℃攪拌。將溶媒進行減壓蒸餾後，將所得粗製生成物藉由矽膠管柱層析法(洗提液：己烷/醋酸乙酯)進行精製，得到(I-11-b)10.5g。 Under nitrogen flow, (I-11-a) (18.6 g, 37.9 mmol), PPTS (1.0 g, 3.8 mmol) and ethanol (200 mL) were mixed and stirred at 40°C. After the solvent was distilled under reduced pressure, the obtained crude product was purified by silica gel column chromatography (eluent: hexane/ethyl acetate) to obtain 10.5 g of (I-11-b).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.12(d,2H),6. 96(d,2H),5.15(s,2H),3.65(t,2H),3.48(t,3H),3.23-3.28(m,1H),2.4-2.5(m,1H),2.1-2.2(m,2H),1.89-1.93(m,2H),1.2-1.6(m,19H) 1 H NMR (CDCl 3 , 400MHz) δ7.12(d,2H),6.96(d,2H),5.15(s,2H),3.65(t,2H),3.48(t,3H),3.23- 3.28(m,1H),2.4-2.5(m,1H),2.1-2.2(m,2H),1.89-1.93(m,2H),1.2-1.6(m,19H)

(I-11-c)之合成： Synthesis of (I-11-c):

於氮氣流下，將(I-11-b)(1.2g，3.0mmol)與THF(12mL)混合，加入N,N-二甲基苯胺(0.56mL，4.5mmol)，一邊冰冷、一邊加入丙烯醯氯(0.29mL，3.6mmol)，於室溫攪拌3小時。將反應溶液加入至混合有2mol/L鹽酸(2.3mL)與冰水(10mL)的溶液中使pH成為1後，藉醋酸乙酯進行萃取3次。將有機層以水、飽和食鹽水洗淨後，加入硫酸鈉進行乾燥，過濾後，於減壓下進行濃縮，藉此得到(I-11-c)1.36g。 Under nitrogen flow, (I-11-b) (1.2g, 3.0mmol) was mixed with THF (12mL), N,N-dimethylaniline (0.56mL, 4.5mmol) was added, and acrylamide was added while ice-cooling Chlorine (0.29 mL, 3.6 mmol), stirred at room temperature for 3 hours. The reaction solution was added to a solution mixed with 2 mol/L hydrochloric acid (2.3 mL) and ice water (10 mL) to adjust the pH to 1, and extracted three times with ethyl acetate. The organic layer was washed with water and saturated brine, dried by adding sodium sulfate, filtered, and concentrated under reduced pressure to obtain 1.36 g of (I-11-c).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.12(d,2H),6.96(d,2H),6.39(d,1H),6.12(dd,1H),5.81(d,1H),5.15(s,2H),4.12(t,2H),3.46(t,2H),3.23-3.28(m,1H),2.4-2.5(m,1H),2.1-2.2(m,2H),1.89-1.93(m,2H),1.2-1.6(m,19H) 1 H NMR(CDCl 3 ,400MHz)δ7.12(d,2H),6.96(d,2H),6.39(d,1H),6.12(dd,1H),5.81(d,1H),5.15(s, 2H),4.12(t,2H),3.46(t,2H),3.23-3.28(m,1H),2.4-2.5(m,1H),2.1-2.2(m,2H),1.89-1.93(m, 2H),1.2-1.6(m,19H)

(I-11-d)之合成： Synthesis of (I-11-d):

將(I-11-c)(0.05g，0.11mmol)與甲醇(1mL)混合，冰冷後，加入氯三甲基矽烷(19μL，0.11mmol)並於室溫攪拌4小時。減壓濃縮後， 藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到(I-11-d)35mg。 (I-11-c) (0.05g, 0.11mmol) was mixed with methanol (1mL). After ice-cooling, chlorotrimethylsilane (19μL, 0.11mmol) was added and stirred at room temperature for 4 hours. After concentration under reduced pressure, it was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 35 mg of (I-11-d).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.08(d,2H),6.77(d,2H),6.39(d,1H),6.12(dd,1H),5.81(d,1H),4.8(s,1H),4.15(t,2H),3.48(t,2H),3.22-3.3(m,1H),2.4-2.47(m,1H),2.1-2.2(m,2H),1.89-1.93(m,2H),1.2-1.6(m,19H) 1 H NMR(CDCl 3 ,400MHz)δ7.08(d,2H),6.77(d,2H),6.39(d,1H),6.12(dd,1H),5.81(d,1H),4.8(s, 1H),4.15(t,2H),3.48(t,2H),3.22-3.3(m,1H),2.4-2.47(m,1H),2.1-2.2(m,2H),1.89-1.93(m, 2H),1.2-1.6(m,19H)

(I-11)之合成： Synthesis of (I-11):

將(I-11-d)(3.55g，8.5mmol)、(I-1-d)(3.05g，7.7mmol)、N,N-二甲基-4-胺基吡啶(188mg，1.54mmol)與二氯甲烷(50mL)混合，於0℃加入EDC(1.77g，9.24mmol)，於室溫攪拌4小時。於反應溶液中加入碳酸氫鈉之飽和溶液後，藉二氯甲烷進行萃取，將所得有機層以飽和食鹽水洗淨，加入硫酸鎂進行乾燥後，進行過濾濃縮。將所得粗製生成物藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到(I-11)1.60g。 (I-11-d) (3.55g, 8.5mmol), (I-1-d) (3.05g, 7.7mmol), N,N-dimethyl-4-aminopyridine (188mg, 1.54mmol) Mix with dichloromethane (50 mL), add EDC (1.77 g, 9.24 mmol) at 0° C., and stir at room temperature for 4 hours. After adding a saturated solution of sodium bicarbonate to the reaction solution, extraction was performed with dichloromethane, and the obtained organic layer was washed with saturated brine, dried by adding magnesium sulfate, and concentrated by filtration. The obtained crude product was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 1.60 g of (I-11).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.54(d,2H),7.22(d,2H),7.09(d,2H),6.88(d,2H),6.39(d,2H),6.12(dd,2H),5.81(d,1H),4.15(t,4H),3.98(t,2H),3.48(t,2H),3.22-3.3(m,1H),2.4-2.47(m,1H),2.1-2.2(m,2H),1.89-1.93(m,2H),1.75-1.81(m,2H),1.2- 1.6(m,38H) 1 H NMR(CDCl 3 ,400MHz)δ7.54(d,2H),7.22(d,2H),7.09(d,2H),6.88(d,2H),6.39(d,2H),6.12(dd, 2H),5.81(d,1H),4.15(t,4H),3.98(t,2H),3.48(t,2H),3.22-3.3(m,1H),2.4-2.47(m,1H),2.1 -2.2(m,2H),1.89-1.93(m,2H),1.75-1.81(m,2H),1.2-1.6(m,38H)

<液晶化合物(I-12)> <Liquid Crystal Compound (I-12)>

依照下述記載之合成法，合成液晶化合物(I-12) According to the synthesis method described below, the liquid crystal compound (I-12) was synthesized

Figure 108109137-A0101-12-0108-34
Figure 108109137-A0101-12-0108-34

(I-12)之合成： Synthesis of (I-12):

將(I-1-g)(1.44g，3.0mmol)、(I-7-b)(1.26g，3.3mmol)、N,N-二甲基-4-胺基吡啶(80mg，0.60mmol)與二氯甲烷(30mL)混合，於0℃加入EDC(632mg，3.3mmol)，於室溫攪拌17小時。於反應溶液中加入飽和碳酸氫鈉水溶液後，以二氯甲烷進行萃取，將所得有機層以飽和食鹽水洗淨，加入硫酸鎂進行乾燥後，進行過濾濃縮。將所得粗製生成物藉由矽膠管柱層析法(己烷/二氯甲烷/醋酸乙酯)進行精製，得到(I-12)1.26g。 (I-1-g) (1.44g, 3.0mmol), (I-7-b) (1.26g, 3.3mmol), N,N-dimethyl-4-aminopyridine (80mg, 0.60mmol) Mix with dichloromethane (30 mL), add EDC (632 mg, 3.3 mmol) at 0°C, and stir at room temperature for 17 hours. After adding saturated aqueous sodium bicarbonate solution to the reaction solution, extraction was performed with dichloromethane, and the obtained organic layer was washed with saturated brine, dried by adding magnesium sulfate, and concentrated by filtration. The obtained crude product was purified by silica gel column chromatography (hexane/dichloromethane/ethyl acetate) to obtain 1.26 g of (I-12).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3,400MHz)δ7.55(d,2H),7.19(d,2H),7.11(d,2H),6.89(d,2H),6.39(dd,2H),6.12(dd,2H),5.81(dd,2H),4.1 5(t,4H),3.99(t,2H),3.46(t,2H),3.21-3.29(m,1H),2.49-2.57(m,1H),2.15(m4H),1.79(m,2H),1.52-1.72(m,12H),1.24-1.49(m,40H) 1 H NMR(CDCl 3 ,400MHz)δ7.55(d,2H),7.19(d,2H),7.11(d,2H),6.89(d,2H),6.39(dd,2H),6.12(dd, 2H),5.81(dd,2H),4.1 5(t,4H),3.99(t,2H),3.46(t,2H),3.21-3.29(m,1H),2.49-2.57(m,1H), 2.15(m4H),1.79(m,2H),1.52-1.72(m,12H),1.24-1.49(m,40H)

以下表示上述合成之液晶化合物、及以下述實施例或比較例所使用之色素的化學構造式。又，式中，C11H22意指11個亞甲基鏈依直鏈狀鍵結，C9H18意指9個亞甲基鏈依直鏈狀鍵結，C12H24意指12個亞甲基鏈依直鏈狀鍵結。 The chemical structural formulas of the liquid crystal compounds synthesized above and the pigments used in the following examples or comparative examples are shown below. Also, in the formula, C 11 H 22 means that 11 methylene chains are linked in a straight chain, C 9 H 18 means that 9 methylene chains are linked in a straight chain, and C 12 H 24 means that 12 The methylene chains are linked in a straight chain.

Figure 108109137-A0101-12-0109-35
Figure 108109137-A0101-12-0109-35

Figure 108109137-A0101-12-0109-36
Figure 108109137-A0101-12-0109-36

[化37]

Figure 108109137-A0101-12-0110-37
[chem 37]
Figure 108109137-A0101-12-0110-37

Figure 108109137-A0101-12-0110-38
Figure 108109137-A0101-12-0110-38

Figure 108109137-A0101-12-0110-39
Figure 108109137-A0101-12-0110-39

Figure 108109137-A0101-12-0110-40
Figure 108109137-A0101-12-0110-40

Figure 108109137-A0101-12-0110-41
Figure 108109137-A0101-12-0110-41

Figure 108109137-A0101-12-0111-42
Figure 108109137-A0101-12-0111-42

Figure 108109137-A0101-12-0111-43
Figure 108109137-A0101-12-0111-43

Figure 108109137-A0101-12-0111-44
Figure 108109137-A0101-12-0111-44

Figure 108109137-A0101-12-0111-45
Figure 108109137-A0101-12-0111-45

Figure 108109137-A0101-12-0111-46
Figure 108109137-A0101-12-0111-46

Figure 108109137-A0101-12-0112-47
Figure 108109137-A0101-12-0112-47

Figure 108109137-A0101-12-0112-48
Figure 108109137-A0101-12-0112-48

針對液晶化合物(I-1)~液晶化合物(I-12)，藉由示差掃描熱量測定求得等向相表觀溫度(由液晶至液體的相轉移溫度及由液體至液晶的相轉移溫度)。示差掃描熱量測定係樣本量為0.5mg~10mg，使用鋁盤，將升溫過程及冷卻過程設為5℃/分鐘或10℃/分鐘，對-50℃至任意溫度為止之加熱與冷卻重複測定3次，以第3次之測定值作為相轉移溫度。 For liquid crystal compound (I-1)~liquid crystal compound (I-12), the apparent temperature of the isotropic phase (phase transition temperature from liquid crystal to liquid and phase transition temperature from liquid to liquid crystal) was obtained by differential scanning calorimetry . The sample size of the differential scanning calorimetry system is 0.5mg~10mg, use an aluminum plate, set the heating process and cooling process to 5°C/min or 10°C/min, and repeat the heating and cooling from -50°C to any temperature 3 The second time, the third measured value was used as the phase transition temperature.

尚且，示差掃描熱量測定時，係於液晶化合物(I-1)~液晶化合物(I-8)及(I-12)，使用相對於液晶化合物100重量份添加了作為聚合停止劑之4-甲氧基酚0.2重量份者。於液晶化合物(I-9)，係使用後述異向性色素膜形成用組成物11。於液晶化合物(I-10)，係使用後述異向性色素膜形成用組成物12。於液晶化合物(I-11)，係使用後述異向性色素膜形成用組成物13。 Furthermore, in the differential scanning calorimetric measurement, liquid crystal compounds (I-1) to liquid crystal compounds (I-8) and (I-12) were used, with respect to 100 parts by weight of liquid crystal compounds, 4-formazan, which was added as a polymerization stopper, was used. 0.2 parts by weight of oxyphenol. The liquid crystal compound (I-9) used the composition 11 for anisotropic dye film formation mentioned later. The liquid crystal compound (I-10) used the composition 12 for anisotropic dye film formation mentioned later. The liquid crystal compound (I-11) used the composition 13 for anisotropic dye film formation mentioned later.

將其結果示於表1。 The results are shown in Table 1.

尚且，此溫度是否為等向相表觀溫度，係藉由偏光顯微鏡觀察及X射線構造分析所確認。 Moreover, whether this temperature is the apparent temperature of the isotropic phase was confirmed by polarizing microscope observation and X-ray structure analysis.

Figure 108109137-A0101-12-0113-49
Figure 108109137-A0101-12-0113-49

可明顯得知，相較於屬於不具有上述式(1)所示部分構造之液晶化合物的液晶化合物(I-3)、液晶化合物(I-4)及液晶化合物(I-5)，屬於具有上述式(1)所示部分構造之液晶化合物的液晶化合物(I-1)、液晶化合物(I-2)、液晶化合物(I-7)、液晶化合物(I-8)、液晶化合物(I-9)、液晶化合物(I-10)、液晶化合物(I-11)及液晶化合物(I-12)係等向相表觀溫度較低，在製程之操作容易度、能量消耗之觀點、加熱為等向相之再配向製程、或基材之選定自由度方面均優越。 It can be clearly seen that, compared with the liquid crystal compound (I-3), the liquid crystal compound (I-4) and the liquid crystal compound (I-5) that do not have the partial structure shown in the above formula (1), the liquid crystal compound (I-5) belongs to the Liquid crystal compound (I-1), liquid crystal compound (I-2), liquid crystal compound (I-7), liquid crystal compound (I-8), liquid crystal compound (I- 9), liquid crystal compound (I-10), liquid crystal compound (I-11) and liquid crystal compound (I-12) are isotropic phase apparent temperature is relatively low, in terms of ease of operation of the process, energy consumption, heating is It is superior in the rearrangement process of the isotropic phase, or in the freedom of selection of the substrate.

[實施例A1] [Example A1]

於氯仿79.80份中加入液晶化合物(I-1)之20.00份、式(II-1)之偶氮色素(林原股份有限公司製)0.12份、式(II-2)之偶氮色素(昭和化工股份有限公司製)0.08份，攪拌使其相溶後，去除溶媒，藉此得到異向性色素膜形成用組成物A1。 In 79.80 parts of chloroform, add 20.00 parts of liquid crystal compound (I-1), 0.12 parts of azochrome (manufactured by Hayashibara Co., Ltd.) of formula (II-1), azochrome of formula (II-2) (Showa Chemical Industry Co., Ltd. Co., Ltd.) 0.08 part, stirred to make it compatible, and removed the solvent to obtain composition A1 for anisotropic dye film formation.

使用所得異向性色素膜形成用組成物A1，為了依上述方法決定二色比，製作異向性色素膜A1，決定異向性色素膜A1之二色比。 Using the obtained composition A1 for anisotropic dye film formation, in order to determine the dichromatic ratio by the method mentioned above, the anisotropic dye film A1 was produced, and the dichromatic ratio of the anisotropic dye film A1 was determined.

將其結果示於表2。又，異向性色素膜A1之二色比係於40.0℃、570nm下為46.34。 The results are shown in Table 2. Moreover, the dichromatic ratio of the anisotropic dye film A1 was 46.34 at 40.0 degreeC and 570 nm.

[實施例A2] [Example A2]

除了取代液晶化合物(I-1)、使用液晶化合物(I-2)之外，其餘依與實施例A1同樣的方式，得到異向性色素膜形成用組成物A2及異向性色素膜A2。針對異向性色素膜A2決定異向性色素膜A2之二色比。 Except having used the liquid crystal compound (I-2) instead of the liquid crystal compound (I-1), it carried out similarly to Example A1, and obtained the composition A2 for anisotropic dye film formation, and the anisotropic dye film A2. The dichroic ratio of the anisotropic dye film A2 is determined with respect to the anisotropic dye film A2.

其結果示於表2。 The results are shown in Table 2.

[實施例A3] [Example A3]

除了取代液晶化合物(I-1)、使用液晶化合物(I-7)之外，其餘依與實施例A1同樣的方式，得到異向性色素膜形成用組成物A9及異向性色素膜A9。針對異向性色素膜A9決定異向性色素膜A9之二色比。 Except having used the liquid crystal compound (I-7) instead of the liquid crystal compound (I-1), it carried out similarly to Example A1, and obtained the composition A9 for anisotropic dye film formation, and the anisotropic dye film A9. The dichroic ratio of the anisotropic dye film A9 is determined for the anisotropic dye film A9.

其結果示於表2。 The results are shown in Table 2.

[實施例A4] [Example A4]

除了取代液晶化合物(I-1)、使用液晶化合物(I-8)之外，其餘依與實施例A1同樣的方式，得到異向性色素膜形成用組成物A10及異向性色素膜A10。針對異向性色素膜A10決定異向性色素膜A10之二色比。 Except having used the liquid crystal compound (I-8) instead of the liquid crystal compound (I-1), it carried out similarly to Example A1, and obtained the composition A10 for anisotropic dye film formation, and the anisotropic dye film A10. The dichroic ratio of the anisotropic dye film A10 is determined with respect to the anisotropic dye film A10.

其結果示於表2。 The results are shown in Table 2.

[實施例A5] [Example A5]

於氯仿79.80份中加入液晶化合物(I-1)8.00份、液晶化合物(I-9)12.00份、式(II-1)之偶氮色素(林原股份有限公司製)0.12份、式(II-2)之偶氮色素(昭和化工股份有限公司製)0.08份，攪拌使其相溶後，去除溶媒，藉此得到異向性色素膜形成用組成物A11。 In 79.80 parts of chloroform, add 8.00 parts of liquid crystal compound (I-1), 12.00 parts of liquid crystal compound (I-9), 0.12 parts of azochrome (manufactured by Hayashibara Co., Ltd.) of formula (II-1), 0.12 parts of formula (II- 2) 0.08 parts of an azo dye (manufactured by Showa Chemical Industry Co., Ltd.), was stirred to make it compatible, and then the solvent was removed to obtain anisotropic dye film-forming composition A11.

使用所得異向性色素膜形成用組成物A11，為了依上述方法決定二色比，製作異向性色素膜A11，決定異向性色素膜A11之二色比。 Using the obtained composition A11 for anisotropic dye film formation, in order to determine the dichromatic ratio by the method mentioned above, the anisotropic dye film A11 was produced, and the dichromatic ratio of the anisotropic dye film A11 was determined.

將其結果示於表2。 The results are shown in Table 2.

[實施例A6] [Example A6]

除了取代液晶化合物(I-9)、使用液晶化合物(I-10)之外，其餘依與實施例A5同樣的方式，得到異向性色素膜形成用組成物A12及異向性色素膜A12。針對異向性色素膜A12決定異向性色素膜A12之二色比。 Except having used the liquid crystal compound (I-10) instead of the liquid crystal compound (I-9), it carried out similarly to Example A5, and obtained the composition A12 for anisotropic dye film formation, and the anisotropic dye film A12. The dichroic ratio of the anisotropic dye film A12 is determined for the anisotropic dye film A12.

其結果示於表2。 The results are shown in Table 2.

[實施例A7] [Example A7]

除了取代液晶化合物(I-9)、使用液晶化合物(I-11)之外，其餘依與實施例A5同樣的方式，得到異向性色素膜形成用組成物A13及異向性色素膜A13。針對異向性色素膜A13決定異向性色素膜A13之二色比。 Except having used the liquid crystal compound (I-11) instead of the liquid crystal compound (I-9), it carried out similarly to Example A5, and obtained the composition A13 for anisotropic dye film formation, and the anisotropic dye film A13. The dichroic ratio of the anisotropic dye film A13 is determined for the anisotropic dye film A13.

其結果示於表2。 The results are shown in Table 2.

[比較例A1] [Comparative Example A1]

除了取代液晶化合物(I-1)、使用液晶化合物(I-3)之外，其餘依與實施例A1同樣的方式，得到異向性色素膜形成用組成物A3及異向性色素膜A3。針對異向性色素膜A3決定異向性色素膜A3之二色比。 Except having used the liquid crystal compound (I-3) instead of the liquid crystal compound (I-1), it carried out similarly to Example A1, and obtained the composition A3 for anisotropic dye film formation, and the anisotropic dye film A3. The dichroic ratio of the anisotropic dye film A3 is determined with respect to the anisotropic dye film A3.

其結果示於表2。 The results are shown in Table 2.

[比較例A2] [Comparative example A2]

除了取代液晶化合物(I-1)、使用液晶化合物(I-4)之外，其餘依與實施例A1同樣的方式，得到異向性色素膜形成用組成物A4及異向性色素膜A4。針對異向性色素膜A4決定異向性色素膜A4之二色比。 Except having used the liquid crystal compound (I-1) instead of the liquid crystal compound (I-4), it carried out similarly to Example A1, and obtained the composition A4 for anisotropic dye film formation, and the anisotropic dye film A4. The dichroic ratio of the anisotropic dye film A4 is determined with respect to the anisotropic dye film A4.

其結果示於表2。 The results are shown in Table 2.

[比較例A3] [Comparative example A3]

除了取代液晶化合物(I-1)、使用液晶化合物(I-5)之外，其餘依 與實施例A1同樣的方式，得到異向性色素膜形成用組成物A5及異向性色素膜A5。針對異向性色素膜A5決定異向性色素膜A5之二色比。 Anisotropic dye film-forming composition A5 and anisotropic dye film A5 were obtained in the same manner as in Example A1 except that liquid crystal compound (I-1) was used instead of liquid crystal compound (I-5). The dichroic ratio of the anisotropic dye film A5 is determined with respect to the anisotropic dye film A5.

其結果示於表2。 The results are shown in Table 2.

[參考例A1] [Reference example A1]

除了取代液晶化合物(I-1)、使用液晶化合物(I-6)之外，其餘依與實施例A1同樣的方式，得到異向性色素膜形成用組成物A8及異向性色素膜A8。針對異向性色素膜A8決定異向性色素膜A8之二色比。 Except having used the liquid crystal compound (I-6) instead of the liquid crystal compound (I-1), it carried out similarly to Example A1, and obtained the composition A8 for anisotropic dye film formation, and the anisotropic dye film A8. The dichroic ratio of the anisotropic dye film A8 is determined with respect to the anisotropic dye film A8.

其結果示於表2。 The results are shown in Table 2.

Figure 108109137-A0101-12-0117-50
Figure 108109137-A0101-12-0117-50

[實施例A8] [Example A8]

於環戊酮69.99份中加入液晶化合物(I-1)28.57份、式(II-1)之偶氮色素0.43份、式(II-2)之偶氮色素0.29份、IRGACURE(註冊商標)369(BASF公司製品)0.29份、BYK-361N(BYK-Chemie公司製)0.43份，於80℃加熱攪拌後，使用具備針筒過濾器(Membrane Solutions公司製，PTFE13045，口徑0.45μm)之針筒進行過濾，得到異向性色素膜形成用組成物A6。 Add 28.57 parts of liquid crystal compound (I-1), 0.43 parts of azochrome of formula (II-1), 0.29 parts of azochrome of formula (II-2) and 369 parts of IRGACURE (registered trademark) into 69.99 parts of cyclopentanone. (BASF company) 0.29 part, BYK-361N (BYK-Chemie company) 0.43 part, after heating and stirring at 80°C, use a syringe equipped with a syringe filter (Membrane Solutions company, PTFE13045, diameter 0.45μm) It was filtered to obtain composition A6 for forming an anisotropic dye film.

將異向性色素膜形成用組成物A6藉由旋塗法，於在玻璃上形成有聚醯亞胺之配向膜(LX1400，日立化成杜邦MicroSystems公司製，依摩擦法製作配向膜)之基板上進行成膜，於120℃加熱乾燥2分鐘後，冷卻至液晶相並以曝光量500mj/cm2(365nm基準)進行聚合，得到異向性色素膜A6。將所得異向性色素膜A6遮蓋於市售之偏光板上並使其旋轉則發生明暗，可確認到其顯示可利用作為偏光膜的良好性能。 The anisotropic dye film-forming composition A6 was spin-coated on a glass substrate with an alignment film of polyimide (LX1400, manufactured by Hitachi Chemical DuPont MicroSystems Co., Ltd., and an alignment film was produced by rubbing method) After forming a film, heating and drying at 120° C. for 2 minutes, cooling to liquid crystal phase, and polymerizing at an exposure dose of 500 mj/cm 2 (based on 365 nm), an anisotropic dye film A6 was obtained. When the obtained anisotropic dye film A6 was covered and rotated on a commercially available polarizing plate, light and shade were generated, and it was confirmed that it showed good performance usable as a polarizing film.

[實施例A9] [Example A9]

除了於所使用之基板，使用在聚醯亞胺薄膜(膜厚100μm)上形成了聚醯亞胺之配向膜(LX1400，日立化成杜邦MicroSystems公司製，依摩擦法製作配向膜)的基板之外，其餘依與實施例A8同樣的方式，由異向性色素膜形成用組成物A6獲得異向性色素膜A7。將所得異向性色素膜A7遮蓋於市售之偏光板上並使其旋轉則發生明暗，可確認到其顯示可利用作為偏光膜的良好性能。 In addition to the substrate used, a polyimide alignment film (LX1400, manufactured by Hitachi Kasei DuPont MicroSystems Co., Ltd., manufactured by a rubbing method) was used on a polyimide thin film (film thickness 100 μm). , and the rest were in the same manner as in Example A8 to obtain anisotropic dye film A7 from composition A6 for forming anisotropic dye film. When the obtained anisotropic dye film A7 was covered on a commercially available polarizing plate and it was rotated, light and shade were generated, and it was confirmed that it showed good performance usable as a polarizing film.

由上述得知，使用屬於具有上述式(1)所示部分構造之 液晶化合物的液晶化合物(I-1)或液晶化合物(I-2)而作成的膜，具有作為偏光膜之充分機能。 From the above, it was found that a film prepared using liquid crystal compound (I-1) or liquid crystal compound (I-2) which is a liquid crystal compound having a partial structure represented by the above formula (1) has a sufficient function as a polarizing film.

以下使用具體例說明本發明第二態樣。 The second aspect of the present invention will be described below using specific examples.

[液晶化合物之合成B] [Synthesis B of liquid crystal compound] <液晶化合物(III-1)> <Liquid Crystal Compound (III-1)>

依照以下記載之合成法，合成液晶化合物(III-1)。 The liquid crystal compound (III-1) was synthesized according to the synthesis method described below.

[化49]

Figure 108109137-A0101-12-0120-51
[chem 49]
Figure 108109137-A0101-12-0120-51

(III-1-a)之合成： Synthesis of (III-1-a):

藉由根據Lub et al.,Recl.Trav.Chim.Pays-Bas,115,321-328(1996)記載之化合物的方法合成(III-1-a)。 (III-1-a) was synthesized by a method based on the compound described in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

(III-1-b)之合成： Synthesis of (III-1-b):

將4-碘苯酚(3.62g，16.5mmol)、(III-1-a)(6.43g，16.1mmol)、N,N-二甲基胺基-4-吡啶(0.39g，3.20mmol)、二氯甲烷(80mL)混合，以冰浴冷卻後，添加1-乙基-3-(3-二甲基胺基丙基)碳二亞胺鹽酸鹽(EDC)(3.39g，17.7mmol)，攪拌5分鐘。其後，於室溫攪拌2小時，藉氯化銨飽和水溶液、接著飽和食鹽水洗淨。將溶液濃縮，藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到白色固體(III-1-b)8.49g。 4-iodophenol (3.62g, 16.5mmol), (III-1-a) (6.43g, 16.1mmol), N,N-dimethylamino-4-pyridine (0.39g, 3.20mmol), di Chloromethane (80 mL) was mixed, and after cooling in an ice bath, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) (3.39 g, 17.7 mmol) was added, Stir for 5 minutes. Thereafter, the mixture was stirred at room temperature for 2 hours, and washed with a saturated aqueous solution of ammonium chloride and then with saturated brine. The solution was concentrated and purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 8.49 g of white solid (III-1-b).

(III-1-c)之合成： Synthesis of (III-1-c):

於二異丙基胺(70mL)中加入(III-1-b)(5.00g，8.33mmol)使其完全溶解後，混合二氯雙(三苯基膦)鈀(II)(58mg，0.08mmol)、碘化銅(I)(48mg，0.25mmol)，添加三甲基矽基乙炔(0.98g，9.99mmol)。於室溫攪拌30分鐘後，藉水-醋酸乙酯萃取後，以飽和食鹽水洗淨。將溶液濃縮，藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到白色固體(III-1-c)4.30g。 After adding (III-1-b) (5.00g, 8.33mmol) to diisopropylamine (70mL) to completely dissolve it, mix dichlorobis(triphenylphosphine) palladium (II) (58mg, 0.08mmol ), copper(I) iodide (48mg, 0.25mmol), and trimethylsilylacetylene (0.98g, 9.99mmol) was added. After stirring at room temperature for 30 minutes, it was extracted with water-ethyl acetate and washed with saturated brine. The solution was concentrated and purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 4.30 g of white solid (III-1-c).

(III-1-d)之合成： Synthesis of (III-1-d):

將(III-1-c)(4.30g，7.53mmol)、氯仿(100mL)混合，藉冰浴冷卻後，添加氟化四正丁基銨(TABF)四氫呋喃溶液(1mol/L，9mL)。攪拌20分鐘後，藉水-氯仿萃取後，以飽和食鹽水洗淨。將溶液濃縮，藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到白色固體(III-1-d)3.80g。 (III-1-c) (4.30g, 7.53mmol) and chloroform (100mL) were mixed, cooled in an ice bath, and tetra-n-butylammonium fluoride (TABF) tetrahydrofuran solution (1mol/L, 9mL) was added. After stirring for 20 minutes, it was extracted with water-chloroform, and washed with saturated brine. The solution was concentrated and purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 3.80 g of a white solid (III-1-d).

(III-1-e)之合成： Synthesis of (III-1-e):

將(III-1-b)(3.56g，5.93mmol)、肆三苯基膦鈀(0)(68mg， 0.06mmol)、碘化銅(I)(34mg，0.18mmol)、二異丙基胺(120mL)混合，藉冰浴冷卻後，添加(III-1-d)(2.96g，5.93mmol)之二異丙基胺(40mL)溶液。於室溫攪拌1小時後，藉水-氯仿萃取後，以飽和食鹽水洗淨。將溶液濃縮，藉由矽膠管柱層析法(氯仿)進行精製，得到白色固體(III-1-e)。 (III-1-b) (3.56g, 5.93mmol), tetraphenylphosphine palladium (0) (68mg, 0.06mmol), copper iodide (I) (34mg, 0.18mmol), diisopropylamine (120 mL) were mixed, and after cooling in an ice bath, a solution of (III-1-d) (2.96 g, 5.93 mmol) in diisopropylamine (40 mL) was added. After stirring at room temperature for 1 hour, the mixture was extracted with water-chloroform, and washed with saturated brine. The solution was concentrated and purified by silica gel column chromatography (chloroform) to obtain a white solid (III-1-e).

(III-1-f)之合成： Synthesis of (III-1-f):

將上述操作所得之(III-1-e)、四氫呋喃(60mL)混合，於50℃使其完全溶解後，添加乙醇(60mL)。於此漿料溶液中加入對甲苯磺酸吡啶鎓鹽(PPTS)(0.54g，2.13mmol)，於60℃加熱2小時後，放置一晚。翌日再加熱至60℃使其完全溶解後，將反應液加入至冰水中。藉氯仿萃取，將溶液濃縮後，對所得固體藉己烷進行懸浮清洗而得到白色固體(III-1-f)4.02g。 (III-1-e) obtained in the above operation and tetrahydrofuran (60 mL) were mixed and dissolved completely at 50°C, and then ethanol (60 mL) was added. Pyridinium p-toluenesulfonate (PPTS) (0.54 g, 2.13 mmol) was added to the slurry solution, heated at 60° C. for 2 hours, and left overnight. The next day, after reheating to 60° C. to dissolve completely, the reaction solution was added to ice water. After extracting with chloroform and concentrating the solution, the obtained solid was suspended and washed with hexane to obtain 4.02 g of a white solid (III-1-f).

(III-1)之合成： Synthesis of (III-1):

將(III-1-f)(4.00g，4.98mmol)、丙烯酸(0.72g，9.96mmol)、N,N-二甲基-4-胺基吡啶(0.12g，0.10mmol)、二氯甲烷(100mL)混合，藉冰浴冷卻後，添加1-(3-二甲基胺基丙基)-3-乙基碳二亞胺鹽酸鹽(EDC)(2.10g，11.0mmol)。攪拌2小時後，添加丙烯酸(0.36g，4.98mmol)、EDC(1.05g，5.5mmol)，於18小時後再添加丙烯酸(0.36g，4.98mmol)、EDC(1.05g，5.5mmol)，攪拌5小時。將反應液藉氯化銨飽和水溶液、接著飽和食鹽水洗淨，藉由矽膠管柱層析法(己烷/醋酸乙酯)進行精製，得到白色固體(III-1)2.30g。 (III-1-f) (4.00g, 4.98mmol), acrylic acid (0.72g, 9.96mmol), N,N-dimethyl-4-aminopyridine (0.12g, 0.10mmol), dichloromethane ( 100 mL) were mixed, and after cooling in an ice bath, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) (2.10 g, 11.0 mmol) was added. After stirring for 2 hours, add acrylic acid (0.36g, 4.98mmol), EDC (1.05g, 5.5mmol), add acrylic acid (0.36g, 4.98mmol), EDC (1.05g, 5.5mmol) after 18 hours, stir for 5 Hour. The reaction solution was washed with a saturated aqueous solution of ammonium chloride and then saturated brine, and purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 2.30 g of white solid (III-1).

藉由NMR進行構造確認。結果表示如下。 Structural confirmation was performed by NMR. The results are shown below.

1H NMR(CDCl3、400MHz)δ7.52(d,4H,J=8.8Hz),7.06(d,4H,J=8.8Hz),6.40(d,2H,J=17.2Hz),6.12(dd,2H,J=10.4,17.2Hz),5.81(d,2H,J=10.4Hz),4.15(t,4H,J=6.8Hz),3.46(t,4H,J=9.2Hz),3.30-3.20(m,2H),2.60-2.45(m,2H),2.22-2.10(m,8H),1.70-1.50(m,8H),1.45-1.25(m,36H) 1 H NMR (CDCl 3 , 400MHz) δ7.52(d, 4H, J=8.8Hz), 7.06(d, 4H, J=8.8Hz), 6.40(d, 2H, J=17.2Hz), 6.12(dd ,2H,J=10.4,17.2Hz),5.81(d,2H,J=10.4Hz),4.15(t,4H,J=6.8Hz),3.46(t,4H,J=9.2Hz),3.30-3.20 (m,2H),2.60-2.45(m,2H),2.22-2.10(m,8H),1.70-1.50(m,8H),1.45-1.25(m,36H)

有關化合物(III-1)之液晶性顯示，係使用相對於液晶化合物100重量份添加了作為聚合停止劑之4-甲氧基酚0.2重量份者，藉由加熱台所附屬之偏光顯微鏡，於70℃觀察複折射而進行確認。 The liquid crystal display of the relevant compound (III-1) was obtained by using 0.2 parts by weight of 4-methoxyphenol as a polymerization stopper relative to 100 parts by weight of the liquid crystal compound, and using a polarizing microscope attached to the heating stage at 70 It was confirmed by observing birefringence at °C.

<液晶化合物(III-2)> <Liquid Crystal Compound (III-2)>

依與上述<液晶化合物(I-6)>相同的合成法，合成與液晶化合物(I-6)相同化合物的液晶化合物(III-2)。 Liquid crystal compound (III-2) which is the same compound as liquid crystal compound (I-6) was synthesized by the same synthesis method as the above-mentioned <liquid crystal compound (I-6)>.

有關化合物(III-2)之液晶性顯示，係使用相對於液晶化合物100重量份添加了作為聚合停止劑之4-甲氧基酚0.2重量份者，藉由加熱台所附屬之偏光顯微鏡，於40℃觀察複折射而進行確認。 The liquid crystal display of the relevant compound (III-2) was obtained by using a polarizing microscope attached to the heating stage at 40 with respect to 100 parts by weight of the liquid crystal compound added with 0.2 parts by weight of 4-methoxyphenol as a polymerization stopper. It was confirmed by observing birefringence at °C.

以下表示上述合成之液晶化合物、及以下述實施例所使用之色素的化學構造式。又，式中，C11H22意指11個亞甲基鏈依直鏈狀鍵結。 The chemical structural formulas of the liquid crystal compounds synthesized above and the pigments used in the following examples are shown below. Also, in the formula, C 11 H 22 means that 11 methylene chains are linearly bonded.

[化50]

Figure 108109137-A0101-12-0124-52
Figure 108109137-A0101-12-0124-53
 [chemical 50]
Figure 108109137-A0101-12-0124-52
Figure 108109137-A0101-12-0124-53

Figure 108109137-A0101-12-0124-54
Figure 108109137-A0101-12-0124-54

Figure 108109137-A0101-12-0124-55
Figure 108109137-A0101-12-0124-55

[實施例B1] [Example B1]

於氯仿79.80份中加入液晶化合物(III-1)之20.00份、式(II-1)之偶氮色素(林原股份有限公司製)0.12份、式(II-2)之偶氮色素(昭 和化工股份有限公司製)0.08份，攪拌使其相溶後，去除溶媒，藉此得到異向性色素膜形成用組成物B1。 In 79.80 parts of chloroform, add 20.00 parts of liquid crystal compound (III-1), 0.12 parts of azochrome (manufactured by Hayashibara Co., Ltd.) of formula (II-1), azochrome of formula (II-2) (Showa Chemical Industry Co., Ltd. Co., Ltd.) 0.08 part, stirred to make it compatible, and removed the solvent to obtain composition B1 for anisotropic dye film formation.

有關異向性色素膜形成用組成物B1之液晶性顯示，係藉由加熱台所附屬之偏光顯微鏡，於70℃觀察複折射而進行確認。 The liquid crystal display of the anisotropic dye film-forming composition B1 was confirmed by observing birefringence at 70° C. with a polarizing microscope attached to the heating stage.

使用所得異向性色素膜形成用組成物B1，為了依上述方法決定二色比，製作異向性色素膜B1，決定異向性色素膜B1之二色比。 Using the obtained composition B1 for anisotropic dye film formation, in order to determine the dichromatic ratio by the method mentioned above, the anisotropic dye film B1 was produced, and the dichromatic ratio of the anisotropic dye film B1 was determined.

將其結果示於表3。 The results are shown in Table 3.

[實施例B2] [Example B2]

於環戊酮69.99份中加入液晶化合物(III-1)28.57份、式(II-1)之偶氮色素0.43份、式(II-2)之偶氮色素0.29份、IRGACURE(註冊商標)369(BASF公司製品)0.29份、BYK-361N(BYK-Chemie公司製)0.43份，於80℃加熱攪拌後，使用具備針筒過濾器(Membrane Solutions公司製，PTFE13045，口徑0.45μm)之針筒進行過濾，得到異向性色素膜形成用組成物B2。 Add 28.57 parts of liquid crystal compound (III-1), 0.43 parts of azochrome of formula (II-1), 0.29 part of azochrome of formula (II-2) and 369 parts of IRGACURE (registered trademark) into 69.99 parts of cyclopentanone. (BASF company) 0.29 part, BYK-361N (BYK-Chemie company) 0.43 part, after heating and stirring at 80°C, use a syringe equipped with a syringe filter (Membrane Solutions company, PTFE13045, diameter 0.45μm) Filtration was performed to obtain composition B2 for forming an anisotropic dye film.

將異向性色素膜形成用組成物B2藉由旋塗法，於在玻璃上形成了聚醯亞胺之配向膜(LX1400，日立化成杜邦MicroSystems公司製，藉摩擦法形成配向膜)之基板上進行成膜，於120℃加熱乾燥2分鐘後，冷卻至液晶相並以曝光量500mj/cm2(365nm基準)進行聚合，得到異向性色素膜B2。將所得異向性色素膜B2遮蓋於市售之偏光板上並使其旋轉則發生明暗，可確認到其顯示可利用作為偏光膜的良好性能。 Composition B2 for forming an anisotropic dye film was spin-coated on a glass substrate on which a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont MicroSystems Co., Ltd., formed by a rubbing method) was formed. After forming a film, heating and drying at 120°C for 2 minutes, cooling to liquid crystal phase and polymerizing at an exposure dose of 500mj/cm 2 (based on 365nm), the anisotropic dye film B2 was obtained. When the obtained anisotropic dye film B2 was covered on a commercially available polarizing plate and it was rotated, light and shade were generated, and it was confirmed that it showed good performance usable as a polarizing film.

由上述得知，使用屬於具有上述式(B1)所示部分構造之液晶化合物的液晶化合物(III-1)而作成的膜，具有作為偏光膜之 充分機能。 From the above, it was found that a film formed using the liquid crystal compound (III-1), which is a liquid crystal compound having a partial structure represented by the above formula (B1), has a sufficient function as a polarizing film.

[實施例B3] [Example B3]

除了取代液晶化合物(III-1)、使用液晶化合物(III-2)以外，其餘依與實施例B1同樣的方式，得到異向性色素膜形成用組成物B3及異向性色素膜B3。 Except having used the liquid crystal compound (III-2) instead of the liquid crystal compound (III-1), it carried out similarly to Example B1, and obtained the composition B3 for anisotropic dye film formation, and the anisotropic dye film B3.

有關異向性色素膜形成用組成物B3之液晶性顯示，係藉由加熱台所附屬之偏光顯微鏡，於40℃觀察複折射而進行確認。 The liquid crystal display of the anisotropic dye film-forming composition B3 was confirmed by observing birefringence at 40° C. with a polarizing microscope attached to the heating stage.

針對異向性色素膜B3，決定異向性色素膜B3之二色比。 Regarding the anisotropic dye film B3, the dichroic ratio of the anisotropic dye film B3 is determined.

其結果示於表3。 The results are shown in Table 3.

Figure 108109137-A0101-12-0126-56
Figure 108109137-A0101-12-0126-56

由上述得知，使用屬於具有上述式(B1)所示部分構造之液晶化合物的液晶化合物(III-1)或液晶化合物(III-2)而作成的膜，具有作為偏光膜之充分機能。 From the above, it can be seen that a film prepared using liquid crystal compound (III-1) or liquid crystal compound (III-2) which is a liquid crystal compound having a partial structure represented by the above formula (B1) has a sufficient function as a polarizing film.

本發明之異向性色素膜形成用組成物可實施優越之光學性能、尤其是充分的二色比。 The composition for forming an anisotropic dye film of the present invention can realize excellent optical performance, especially sufficient dichromatic ratio.

本發明之異向性色素膜由於使用本發明之異向性色素膜形成用組成物所形成，故可實現優越的光學性能、尤其是充分的二色比。 Since the anisotropic dye film of the present invention is formed using the anisotropic dye film-forming composition of the present invention, excellent optical performance, particularly sufficient dichromatic ratio can be realized.

本發明之光學元件由於包含本發明之異向性色素膜，故可實現優越的光學性能、尤其是充分的二色比。 Since the optical element of the present invention includes the anisotropic dye film of the present invention, it can realize excellent optical performance, especially sufficient dichromatic ratio.

(產業上之可利用性) (industrial availability)

本發明之異向性色素膜形成用組成物可於維持著優越的光學性能、尤其是充分的二色比之下，實現較低之等向相表觀溫度。 The anisotropic pigment film-forming composition of the present invention can achieve a lower apparent temperature of the isotropic phase while maintaining excellent optical properties, especially a sufficient dichroic ratio.

本發明之異向性色素膜由於使用本發明之異向性色素膜形成用組成物所形成，故可維持優越的光學性能、尤其是充分的二色比，可依較低溫度形成。 The anisotropic dye film of the present invention is formed by using the anisotropic dye film-forming composition of the present invention, so it can maintain excellent optical properties, especially a sufficient dichromatic ratio, and can be formed at a relatively low temperature.

本發明之光學元件由於包含本發明之異向性色素膜，故可含有能維持優越的光學性能、尤其是充分的二色比，並可依較低溫度形成的異向性色素膜。 Since the optical element of the present invention includes the anisotropic dye film of the present invention, it can contain an anisotropic dye film that can maintain excellent optical performance, especially sufficient dichromatic ratio, and can be formed at a relatively low temperature.

本發明之異向性色素膜形成用組成物可實施優越之光學性能、尤其是充分的二色比。 The composition for forming an anisotropic dye film of the present invention can realize excellent optical performance, especially sufficient dichromatic ratio.

本發明之異向性色素膜由於使用本發明之異向性色素膜形成用組成物所形成，故可實現優越的光學性能、尤其是充分的二色比。 Since the anisotropic dye film of the present invention is formed using the anisotropic dye film-forming composition of the present invention, excellent optical performance, particularly sufficient dichromatic ratio can be realized.

本發明之光學元件由於包含本發明之異向性色素膜，故可實現優越的光學性能、尤其是充分的二色比。 Since the optical element of the present invention includes the anisotropic dye film of the present invention, it can realize excellent optical performance, especially sufficient dichromatic ratio.

Claims (13)

一種異向性色素膜形成用組成物，係含有色素及液晶化合物者，上述液晶化合物係含有式(2)所示之液晶化合物；R1-A1-Y1-A2-Y2-A3-R2‧‧‧(2)(式中，R1及R2分別獨立表示鏈狀有機基；R1及R2所表示之上述鏈狀有機基中，至少一者為-(CH2)n-CH2-聚合性基或-O-(CH2)n-CH2-聚合性基，n為1~24之整數；A1及A3分別獨立表示式(1)所示部分構造、2價有機基或單鍵；A2表示式(1)所示部分構造或2價有機基；-Y1-及-Y2-分別獨立表示單鍵、-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、-CH2O-、-OCH2-、-CH2S-或-SCH2-；A1及A3之一者為式(1)所示部分構造或2價有機基；A1、A2及A3中之至少一者為式(1)所示部分構造；)-Cy-X2-C≡C-X-‧‧‧(1)(式中，Cy表示烴環基或雜環基；-X-表示-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、-CH2O-、-OCH2-、-CH2S-或-SCH2-；-X2-表示單鍵、-C(=O)O-、-OC(=O)-、-C(=S)O-、-OC(=S)-、-C(=O)S-、-SC(=O)-、-CH2CH2-、-CH=CH-、-C(=O)NH-、-NHC(=O)-、 -CH2O-、-OCH2-、-CH2S-或-SCH2-)。 A composition for forming an anisotropic pigment film, which contains a pigment and a liquid crystal compound, and the above liquid crystal compound contains a liquid crystal compound represented by formula (2); R1-A1-Y1-A2-Y2-A3-R2‧‧‧ (2) (In the formula, R1 and R2 independently represent a chain organic group; among the chain organic groups represented by R1 and R2, at least one of them is -(CH 2 ) n -CH 2 -polymerizable group or - O-(CH 2 ) n -CH 2 -polymerizable group, n is an integer from 1 to 24; A1 and A3 independently represent the partial structure shown in formula (1), a divalent organic group or a single bond; A2 represents the formula ( 1) Part of the structure shown or a divalent organic group; -Y1- and -Y2- 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(=O)NH-, -NHC (=O)-, -CH 2 O-, -OCH 2 -, -CH 2 S- or -SCH 2 -; one of A1 and A3 is a partial structure shown in formula (1) or a divalent organic group; A1 , at least one of A2 and A3 is a partial structure shown in formula (1);)-Cy-X2-C≡CX-‡‧‧(1) (wherein, Cy represents hydrocarbon ring group or heterocyclic group;- X- 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 -; -X2- means 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 -). 如請求項1之異向性色素膜形成用組成物，其中，-X-為-C(=O)O-、-OC(=O)-、-CH2CH2-、-CH2O-或-OCH2-。 The composition for forming an anisotropic dye film according to Claim 1, wherein -X- is -C(=O)O-, -OC(=O)-, -CH 2 CH 2 -, -CH 2 O- or -OCH 2 -. 如請求項1或2之異向性色素膜形成用組成物，其中，Cy為烴環基，-X2-為單鍵。 The anisotropic dye film-forming composition according to claim 1 or 2, wherein Cy is a hydrocarbon ring group, and -X2- is a single bond. 如請求項1或2之異向性色素膜形成用組成物，其中，A1、A2及A3中之一者為上述式(1)所示部分構造。 The composition for forming an anisotropic dye film according to claim 1 or 2, wherein one of A1, A2 and A3 has a partial structure represented by the above formula (1). 如請求項1或2之異向性色素膜形成用組成物，其中，Cy為烴環基，-X2-為單鍵；A1、A2及A3中之一者為上述式(1)所示部分構造，其以外之二者分別獨立為烴環基。 The composition for forming an anisotropic pigment film according to claim 1 or 2, wherein Cy is a hydrocarbon ring group, and -X2- is a single bond; one of A1, A2 and A3 is a part represented by the above formula (1) structure, and the other two are independently hydrocarbon ring groups. 如請求項3之異向性色素膜形成用組成物，其中，上述烴環基為1,4-伸苯基或環己烷-1,4-二基。 The anisotropic dye film-forming composition according to Claim 3, wherein the hydrocarbon ring group is 1,4-phenylene or cyclohexane-1,4-diyl. 如請求項5之異向性色素膜形成用組成物，其中，上述烴環基為1,4-伸苯基或環己烷-1,4-二基。 The anisotropic dye film-forming composition according to claim 5, wherein the hydrocarbon ring group is 1,4-phenylene or cyclohexane-1,4-diyl. 如請求項1或2之異向性色素膜形成用組成物，其中，-Y1-及-Y2-分別獨立為單鍵、-C(=O)O-、-OC(=O)-、-CH2CH2-、-CH2O-或-OCH2-；-X-為-C(=O)O-、-OC(=O)-、-CH2CH2-、-CH2O-或-OCH2-。 The composition for forming an anisotropic dye film according to Claim 1 or 2, wherein -Y1- and -Y2- are independently a single bond, -C(=O)O-, -OC(=O)-, - CH 2 CH 2 -, -CH 2 O- or -OCH 2 -; -X- is -C(=O)O-, -OC(=O)-, -CH 2 CH 2 -, -CH 2 O- or -OCH 2 -. 如請求項1或2之異向性色素膜形成用組成物，其中，Cy為1,4-伸苯基。 The anisotropic dye film-forming composition according to claim 1 or 2, wherein Cy is a 1,4-phenylene group. 如請求項1或2之異向性色素膜形成用組成物，其中，A1及A3之一者為環己烷-1,4-二基。 The composition for forming an anisotropic dye film according to claim 1 or 2, wherein one of A1 and A3 is cyclohexane-1,4-diyl. 如請求項1或2之異向性色素膜形成用組成物，其中，A1及A3之一者為上述式(1)所示部分構造； 另一者為環己烷-1,4-二基。 The composition for forming an anisotropic pigment film according to claim 1 or 2, wherein one of A1 and A3 has a partial structure shown in the above formula (1); The other is cyclohexane-1,4-diyl. 一種異向性色素膜，係使用請求項1至11中任一項之異向性色素膜形成用組成物所形成。 An anisotropic dye film formed using the composition for forming an anisotropic dye film according to any one of Claims 1 to 11. 一種光學元件，係包含請求項12之異向性色素膜。 An optical element comprising the anisotropic pigment film of claim 12.
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