TWI636973B - Manufacturing method of substrate with liquid crystal alignment film for lateral electric field drive type liquid crystal display element - Google Patents

Manufacturing method of substrate with liquid crystal alignment film for lateral electric field drive type liquid crystal display element Download PDF

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TWI636973B
TWI636973B TW102136027A TW102136027A TWI636973B TW I636973 B TWI636973 B TW I636973B TW 102136027 A TW102136027 A TW 102136027A TW 102136027 A TW102136027 A TW 102136027A TW I636973 B TWI636973 B TW I636973B
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Taiwan
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group
ring
liquid crystal
compound
carbon atoms
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TW102136027A
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Chinese (zh)
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TW201427936A (en
Inventor
後藤耕平
Kohei Goto
山之內洋一
Hirokazu Yamanouchi
南悟志
Satoshi Minami
名木達哉
Tatsuya NAGI
萬代淳彦
Atsuhiko MANDAI
芦澤亮一
Ryoichi Ashizawa
之
Takayuki Negi
櫻葉汀丹尼爾
Daniel Antonio Sahade
森內正人
Masato Moriuchi
川野勇太
Yuta Kawano
川月喜弘
Nobuhiro Kawatsuki
近藤瑞穂
Mizuho KONDO
Original Assignee
日商日產化學工業股份有限公司
Nissan Chemical Industries, Ltd.
公立大學法人兵庫縣立大學
University Of Hyogo
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/58—One oxygen atom, e.g. butenolide
    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
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    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
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    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
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    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
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    • C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
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    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G—PHYSICS
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    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
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    • G—PHYSICS
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    • 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
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    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
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Abstract

本發明係提供一種以高效率賦予配向控制功能，且烙印(burn-in)特性優異之橫向電場驅動型液晶顯示元件。本發明係提供一種基板的製造方法，其特徵為藉由具有[I]~[III]之步驟，而得到賦予配向控制功能之橫向電場驅動型液晶顯示元件用液晶配向膜，而具有前述液晶配向膜，[I]：將含有(A)於特定之溫度範圍表現液晶性之感光性側鏈型高分子、及(B)有機溶劑之聚合物組成物，塗佈於具有橫向電場驅動用之導電膜之基板上而形成塗膜之步驟；[II]：於[I]所得到之塗膜照射經偏光之紫外線之步驟；及[III]：加熱[II]所得到之塗膜之步驟。 The present invention provides a lateral electric field drive type liquid crystal display element that provides an alignment control function with high efficiency and has excellent burn-in characteristics. The present invention provides a method for manufacturing a substrate, which is characterized by having a step of [I] to [III] to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element that provides an alignment control function, and has the aforementioned liquid crystal alignment. Film, [I]: A polymer composition containing (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range, and (B) an organic solvent is applied to a conductive material having a lateral electric field drive A step of forming a coating film on the substrate of the film; [II]: a step of irradiating polarized ultraviolet rays on the coating film obtained in [I]; and [III]: a step of heating the coating film obtained in [II].

Description

具有橫向電場驅動型液晶顯示元件用液晶配向膜之基板的製造方法 Manufacturing method of substrate with liquid crystal alignment film for lateral electric field drive type liquid crystal display element

本發明係關於具有橫向電場驅動型液晶顯示元件用液晶配向膜之基板的製造方法。更詳細而言，係關於用以製造烙印(burn-in)特性優異之液晶顯示元件之新穎方法。 The present invention relates to a method for manufacturing a substrate having a liquid crystal alignment film for a liquid crystal display element driven by a lateral electric field. More specifically, it relates to a novel method for manufacturing a liquid crystal display element having excellent burn-in characteristics.

液晶顯示元件已知作為輕量、薄型且低消費電力之顯示裝置，於近年來被用在大型電視用途等，取得顯著的發展。液晶顯示元件例如係藉由具備電極之一對透明基板挾持液晶層而構成。因此，於液晶顯示元件，液晶於基板間以成為如所期望之配向狀態，由有機材料所構成之有機膜係被作為液晶配向膜使用。 Liquid crystal display elements are known as light-weight, thin, and low power consumption display devices. In recent years, they have been used in large-scale television applications, and have achieved remarkable development. The liquid crystal display element is configured, for example, by holding a liquid crystal layer on a transparent substrate with one of the electrodes. Therefore, in the liquid crystal display element, the liquid crystal is in a desired alignment state between the substrates, and an organic film system composed of an organic material is used as the liquid crystal alignment film.

亦即，液晶配向膜為液晶顯示元件之構成構件，形成於與挾持液晶之基板的液晶接觸之面，於其基板間擔負將液晶配向為一定方向之類的功能。而且，於液晶配向膜，例如以相對於基板之平行方向等，除了將液晶配向為一定方向的功能之外，亦有追求控制液晶之預傾角的 功能。在如此液晶配向膜，控制液晶配向之能力(以下稱為配向控制功能)，係藉由對於構成液晶配向膜之有機膜進行配向處理而給予。 That is, the liquid crystal alignment film is a constituent member of a liquid crystal display element, and is formed on a surface in contact with the liquid crystal of a substrate holding a liquid crystal, and functions to orient the liquid crystal in a certain direction between the substrates. In addition, in the liquid crystal alignment film, for example, in a direction parallel to the substrate, etc., in addition to the function of aligning the liquid crystal in a certain direction, there are also pursuits to control the pretilt angle of the liquid crystal. Features. In such a liquid crystal alignment film, the ability to control the liquid crystal alignment (hereinafter referred to as an alignment control function) is given by performing an alignment treatment on an organic film constituting the liquid crystal alignment film.

作為用以賦予配向控制功能之液晶配向膜的配向處理方法，從以往已知有有摩擦法。所謂摩擦法係指對於基板上之聚乙烯醇或聚醯胺或聚醯亞胺等有機膜，將其表面以綿、尼龍、聚酯等布以一定方向擦拭(Rubbing)，使液晶配向於擦拭方向(Rubbing direction)之方法。此摩擦法因為可簡便地實現比較安定之液晶的配向狀態，可被利用在以往之液晶顯示元件的製造製程。而且，作為液晶配向膜所使用之有機膜，主要是選擇耐熱性等信賴性或電氣特性優異之聚醯亞胺系的有機膜。 As a method for aligning a liquid crystal alignment film for providing an alignment control function, a rubbing method has been known from the past. The so-called rubbing method refers to rubbing the surface of an organic film such as polyvinyl alcohol, polyimide, or polyimide on a substrate with a cloth such as cotton, nylon, polyester, etc., so that the liquid crystal is aligned to wipe. Direction (Rubbing direction) method. Since this rubbing method can easily achieve a relatively stable alignment state of liquid crystals, it can be used in the manufacturing process of conventional liquid crystal display elements. In addition, as the organic film used for the liquid crystal alignment film, a polyimide-based organic film having excellent reliability such as heat resistance or excellent electrical characteristics is mainly selected.

然而，擦拭由聚醯亞胺等所成之液晶配向膜的表面之摩擦法，有因發塵或靜電產生而造成問題。又，近年來之液晶顯示元件的高精細化、或由於所對應基板上之電極或液晶驅動用之切換主動元件導致的凹凸，會有無法將液晶配向膜之表面以布均勻地擦拭，而無法實現均勻液晶之配向。 However, the rubbing method of wiping the surface of a liquid crystal alignment film made of polyimide or the like causes problems due to dust generation or generation of static electricity. In addition, in recent years, the high definition of liquid crystal display elements or unevenness caused by electrodes on corresponding substrates or switching active elements for liquid crystal driving may make it impossible to wipe the surface of the liquid crystal alignment film uniformly with a cloth, making it impossible to To achieve uniform liquid crystal alignment.

因此，作為不進行摩擦之液晶配向膜其他配向處理方法，正積極地研究光配向法。 Therefore, as another alignment processing method of the liquid crystal alignment film without rubbing, an optical alignment method is being actively studied.

在光配向法雖有各種方法，藉由直線偏光或經視準之光，於構成液晶配向膜之有機膜內形成各向異性，遵循其各向異性使液晶配向。 Although there are various methods in the light alignment method, an anisotropy is formed in an organic film constituting a liquid crystal alignment film by linearly polarized light or collimated light, and the liquid crystal is aligned according to the anisotropy.

作為主要之光配向法，已知有分解型之光配 向法。例如照射偏光紫外線於聚醯亞胺膜，利用分子構造之紫外線吸收的偏光方向依存性使其產生各向異性的分解。而且進行藉由未分解而殘留的聚醯亞胺而使液晶配向之方式(例如參照專利文獻1)。 As the main photo-alignment method, a decomposition-type photo-alignment is known To the law. For example, the polarized ultraviolet light is irradiated to the polyimide film, and the polarization direction dependence of the ultraviolet absorption of the molecular structure is used to cause anisotropic decomposition. Furthermore, a method of aligning the liquid crystal with polyfluorene imide remaining without being decomposed is performed (for example, refer to Patent Document 1).

又，亦已知有光交聯型或光異構化型之光配向法。例如使用聚乙烯基桂皮酸酯，照射偏光紫外線，以與偏光平行之2個側鏈之雙鍵部分使其產生二聚化反應(交聯反應)。而且，使液晶配向於與偏光方向正交之方向(例如參照非專利文獻1)。又，使用偶氮苯之側鏈具有側鏈型高分子時，照射偏光紫外線，以與偏光平行之側鏈的偶氮苯部使其產生異構化反應，使液晶配向於與偏光方向正交之方向(例如參照非專利文獻2)。 Moreover, a photo-alignment method of a photo-crosslinking type or a photo-isomerization type is also known. For example, polyvinyl cinnamate is used, and polarized ultraviolet light is irradiated to cause a dimerization reaction (crosslinking reaction) of the double bond portion of the two side chains parallel to the polarized light. Then, the liquid crystal is aligned in a direction orthogonal to the polarization direction (for example, refer to Non-Patent Document 1). In the case of using a side chain type polymer having an azobenzene side chain, the polarized ultraviolet light is irradiated to cause an isomerization reaction with the azobenzene portion of the side chain parallel to the polarized light, so that the liquid crystal is aligned orthogonal to the polarization direction Direction (for example, refer to Non-Patent Document 2).

如以上之例，於藉由光配向法之液晶配向膜的配向處理方法，不需要摩擦，無發塵或靜電發生之懸念。而且，即使對於表面有凹凸之液晶顯示元件的基板亦可實施配向處理，成為適合在工業上生產製程之液晶配向膜的配向處理方法。 As in the above example, the alignment processing method of the liquid crystal alignment film by the photo-alignment method does not require friction, and there is no suspense of dust generation or static electricity generation. In addition, alignment processing can be performed even on a substrate of a liquid crystal display element having an uneven surface, and it becomes an alignment processing method suitable for a liquid crystal alignment film in an industrial production process.

[先前技術文獻] [Prior technical literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利第3893659號公報 [Patent Document 1] Japanese Patent No. 3893659

[非專利文獻] [Non-patent literature]

[非專利文獻1]M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155(1992)。 [Non-Patent Document 1] M. Shadt et al., Jpn. J. Appl. Phys. 31, 2155 (1992).

[非專利文獻2]K. Ichimura et al., Chem. Rev. 100, 1847(2000)。 [Non-Patent Document 2] K. Ichimura et al., Chem. Rev. 100, 1847 (2000).

如以上，光配向法作為液晶顯示元件的配向處理方法，與從以往工業上一直利用之摩擦法相比較不需要摩擦步驟，因此而具備一大優勢。而且，與藉由摩擦使配向控制功能幾乎成為一定之摩擦法相比較，於光配向法，可使經偏光之光的照射量變化來控制配向控制功能。然而，於光配向法，藉由摩擦法時與欲實現同程度之配向控制功能時，不是有必要大量經偏光之光的照射量，就是有無法實現安定液晶之配向的情況。 As described above, the photo-alignment method, as an alignment processing method for liquid crystal display elements, does not require a rubbing step as compared with the rubbing method that has been used in the past in the industry, and therefore has a great advantage. In addition, compared with the friction method in which the alignment control function becomes almost constant by friction, the light alignment method can control the alignment control function by changing the irradiation amount of polarized light. However, in the photo-alignment method, when the same degree of alignment control function is to be achieved by the rubbing method, it is not necessary to irradiate a large amount of polarized light, or there may be cases where stable liquid crystal alignment cannot be achieved.

例如，於上述專利文獻1所記載之分解型的光配向法，有必要將從輸出500W之高壓水銀燈之紫外光照射60分鐘於聚醯亞胺膜等，長時間且大量之紫外線照射成為必要。又，即使在二聚化型或光異構化型的光配向法時，有數J(焦耳)~數十J程度之多量之紫外線照射成為必須的情況。進而，於光交聯型或光異構化型的光配向法時，因為液晶之配向的熱安定性或光安定性劣化，於作為液晶顯示元件時，有導致產生配向不良或烙印顯示之類的問題。尤其是於橫向電場驅動型之液晶顯示元件因為是將液晶分子於面內進行切換，容易產生液晶驅動後液晶 之配向移位，起因於AC驅動之烙印顯示成為一重大課題。 For example, in the decomposition-type photo-alignment method described in the above-mentioned Patent Document 1, it is necessary to irradiate ultraviolet light from a 500 W high-pressure mercury lamp for 60 minutes to a polyimide film or the like, and it is necessary to irradiate a large amount of ultraviolet rays for a long time. In addition, even in a dimerization-type or photo-isomerization-type photo-alignment method, it is necessary to irradiate a large amount of ultraviolet rays in the range of several J (Joules) to several tens J. Furthermore, in the photo-alignment method of the photo-crosslinking type or the photo-isomerization type, the thermal stability or the photo-stability of the alignment of the liquid crystal is deteriorated. When used as a liquid crystal display element, it may cause misalignment or imprinting. The problem. In particular, the liquid crystal display element driven by the lateral electric field is easy to generate liquid crystal after liquid crystal driving because the liquid crystal molecules are switched in-plane. The alignment shift caused by the AC-driven imprint display has become a major issue.

據此，於光配向法，已正追求配向處理的高效率化或安定之液晶配向的實現，正追求可高效率進行對液晶配向膜之高配向控制功能的賦予之液晶配向膜或液晶配向劑。 Accordingly, in the photo-alignment method, a liquid crystal alignment film or a liquid crystal alignment agent that is pursuing high efficiency or stable liquid crystal alignment of the alignment treatment is being pursued, and a high alignment control function for the liquid crystal alignment film is being pursued. .

本發明目的係提供一種以高效率賦予配向控制功能，烙印特性優異、具有橫向電場驅動型液晶顯示元件用液晶配向膜之基板及具有該基板之橫向電場驅動型液晶顯示元件。 An object of the present invention is to provide a substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element and a substrate with a lateral electric field drive type liquid crystal display element, which are provided with an alignment control function with high efficiency, have excellent imprinting characteristics.

本發明者們為了達成上述課題進行銳意研究之結果，發現以下之發明。 As a result of earnest research to achieve the above-mentioned subject, the present inventors have found the following inventions.

<1>一種基板的製造方法，其特徵為藉由具有[I]~[III]之步驟，而得到賦予配向控制功能之橫向電場驅動型液晶顯示元件用液晶配向膜，而具有前述液晶配向膜，[I]：將含有(A)於特定之溫度範圍表現液晶性之感光性側鏈型高分子、及(B)有機溶劑之聚合物組成物，塗佈於具有橫向電場驅動用之導電膜之基板上而形成塗膜之步驟；[II]：於[I]所得到之塗膜照射經偏光之紫外線之步驟；及[III]：加熱[II]所得到之塗膜之步驟。 <1> A method for manufacturing a substrate, comprising the steps of [I] to [III] to obtain a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element that provides an alignment control function, and has the liquid crystal alignment film described above. , [I]: A polymer composition containing (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range, and (B) an organic solvent is applied to a conductive film having a lateral electric field drive A step of forming a coating film on a substrate; [II]: a step of irradiating polarized ultraviolet rays on the coating film obtained in [I]; and [III]: a step of heating the coating film obtained in [II].

<2>在上述<1>中，(A)成分係以具有引起光交聯、光異構化、或光弗賴斯重排(Photo Fries Rearrangement)之感光性側鏈為宜。 <2> In the above-mentioned <1>, the component (A) preferably has a photosensitive side chain that causes photocrosslinking, photoisomerization, or Photo Fries Rearrangement.

<3>在上述<1>或<2>中，(A)成分係以具有由下述式(1)~(6)所成之群中選出之任1種感光性側鏈為宜； <3> In the above <1> or <2>, the component (A) is preferably one having a photosensitive side chain selected from the group consisting of the following formulae (1) to (6);

式中，A、B、D分別獨立表示單鍵、-O-、 -CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、或-O-CO-CH=CH-；S為碳數1~12之伸烷基、鍵結於該等之氫原子可被取代為鹵素基；T為單鍵或碳數1~12之伸烷基、鍵結於該等之氫原子可被取代為鹵素基；Y1表示選自1價之苯環、萘環、聯苯環、呋喃環、吡咯環及碳數5~8之脂環式烴之環、或選自該等之取代基相同或相異之2~6之環為透過鍵結基B鍵結而成之基，鍵結於該等之氫原子分別獨立可被-COOR0(式中，R0表示氫原子或碳數1~5之烷基)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；Y2為2價之苯環、萘環、聯苯環、呋喃環、吡咯環、碳數5~8之脂環式烴、及選自由該等之組合所成之群中之基、鍵結於該等之氫原子分別獨立可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；R表示羥基、碳數1~6之烷氧基、或表示與Y1相同定義；X表示單鍵、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、或-O-CO-CH=CH-，X之數成為2時，X彼此可為相同或相異；Cou表示香豆素-6-基或香豆素-7-基，鍵結於該等之 氫原子分別獨立可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；q1與q2一方為1另一方為0；q3為0或1；P及Q分別獨立為2價之苯環、萘環、聯苯環、呋喃環、吡咯環、碳數5~8之脂環式烴、及選自由該等之組合所成之群中之基；惟，X為-CH=CH-CO-O-、-O-CO-CH=CH-時，於-CH=CH-鍵結側之P或Q為芳香環，P之數成為2以上時，P彼此可為相同或相異、Q之數成為2以上時，Q彼此可為相同或相異；l1為0或1；l2為0~2之整數；l1與l2皆為0時，T為單鍵時A亦表示單鍵；l1為1時，且T為單鍵時B亦表示單鍵；H及I分別獨立為2價之苯環、萘環、聯苯環、呋喃環、吡咯環、及選自該等組合之基。 In the formula, A, B, and D each independently represent a single bond, -O-, -CH 2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O- Or -O-CO-CH = CH-; S is an alkyl group having 1 to 12 carbon atoms, and a hydrogen atom bonded to these may be substituted with a halogen group; T is a single bond or 1 to 12 carbon atoms The alkyl groups and hydrogen atoms bonded to these may be substituted with halogen groups; Y 1 represents a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and a lipid having 5 to 8 carbon atoms. Rings of cyclic hydrocarbons, or rings of 2 to 6 with the same or different substituents selected from these are the groups bonded through the bonding group B, and the hydrogen atoms bonded to these can be independently- COOR 0 (where R 0 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen group, carbon number Substituted by alkyl groups of 1 to 5 or alkyloxy groups of 1 to 5 carbons; Y 2 is a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and 5 to 8 carbon lipids Cyclic hydrocarbons, and groups selected from the group consisting of these, and hydrogen atoms bonded to these can be independently -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halo, 1 to 5 carbons, or carbon The alkyl group substituted with 1 to 5; R & lt represents a hydroxyl group, an alkoxy group having a carbon number of 1 to 6, or the same meanings as Y 1; X represents a single bond, -COO -, - OCO -, - N = N -, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, and when the number of X becomes 2, X may be the same or different from each other ; Cou means coumarin-6-yl or coumarin-7-yl, hydrogen atoms bonded to these can be independently -NO 2 , -CN, -CH = C (CN) 2 , -CH = Substituted by CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or alkyloxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q They are independently a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of these; When X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the -CH = CH- bonding side is an aromatic ring, and when the number of P is 2 or more, P It can be the same or different, when the number of Q becomes 2 or more, Q can be the same or different from each other; l1 is 0 or 1; l2 is an integer from 0 to 2; when both l1 and l2 are 0, T is a single bond A also indicates a single bond; when l1 is 1, and T is a single bond, B also indicates a single bond; H and I are independent A divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and a group selected from these combinations.

<4>在上述<1>或<2>中，(A)成分係以具有由下述式(7)~(10)所成之群中選出之任1種感光性側鏈為宜，式中，A、B、D、Y1、X、Y2、及R具有與上述相同之定義；l表示1~12之整數；m表示0~2之整數，m1、m2表示1~3之整數； n表示0~12之整數(惟，n=0時B為單鍵)。 <4> In the above <1> or <2>, the component (A) is preferably one having a photosensitive side chain selected from the group consisting of the following formulae (7) to (10). Among them, A, B, D, Y 1 , X, Y 2 , and R have the same definitions as above; l represents an integer from 1 to 12; m represents an integer from 0 to 2; m1 and m2 represent integers from 1 to 3 ; N represents an integer from 0 to 12 (however, B is a single bond when n = 0).

<5>在上述<1>或<2>中，(A)成分係以具有由下述式(11)~(13)所成之群中選出之任1種感光性側鏈為宜，式中，A、X、l、m、m1及R具有與上述相同之定義。 <5> In the above <1> or <2>, the component (A) is preferably one having a photosensitive side chain selected from the group consisting of the following formulae (11) to (13). Here, A, X, 1, m, m1, and R have the same definitions as above.

<6>在上述<1>或<2>中，(A)成分係以具有下述式(14)或(15)所示之感光性側鏈為宜，式中，A、Y1、l、m1及m2具有與上述相同之定義。 <6> In the above <1> or <2>, the (A) component preferably has a photosensitive side chain represented by the following formula (14) or (15). In the formula, A, Y 1 , l , M1 and m2 have the same definitions as above.

<7>在上述<1>或<2>中，(A)成分係以具有下述式(16)或(17)所示之感光性側鏈為宜，式中，A、X、l及m具有與上述相同之定義。 <7> In the above <1> or <2>, the (A) component preferably has a photosensitive side chain represented by the following formula (16) or (17), where A, X, l, and m has the same definition as above.

<8>在上述<1>或<2>中，(A)成分係以具 有下述式(18)或(19)所示之感光性側鏈為宜，式中，A、B、Y1、q1、q2、m1、及m2具有與上述相同之定義。 <8> In the above <1> or <2>, the (A) component preferably has a photosensitive side chain represented by the following formula (18) or (19), where A, B, and Y 1 , Q1, q2, m1, and m2 have the same definitions as above.

R1表示氫原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基。 R 1 represents a hydrogen atom, -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms Oxygen.

<9>在上述<1>或<2>中，(A)成分係以具有下述式(20)所示之感光性側鏈為宜，式中，A、Y1、X、l及m具有與上述相同之定義。 <9> In the above <1> or <2>, the (A) component preferably has a photosensitive side chain represented by the following formula (20), where A, Y 1 , X, l, and m Has the same definition as above.

<10>在上述<1>~<9>之任一項，(A)成分係以具有由下述式(21)~(31)所成之群中選出之任1種液晶性側鏈為宜，式中，A、B、q1及q2具有與上述相同之定義；Y3為1價之苯環、萘環、聯苯環、呋喃環、含有氮 之雜環、及碳數5~8之脂環式烴、及選自由該等之組合所成之群中之基、鍵結於該等之氫原子分別獨立可被-NO2、-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；R3表示氫原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、1價之苯環、萘環、聯苯環、呋喃環、含有氮之雜環、碳數5~8之脂環式烴、碳數1~12之烷基、或碳數1~12之烷氧基；l表示1~12之整數，m表示0~2之整數，惟，在式(23)~(24)，全部m之合計為2以上，在式(25)~(26)，全部m之合計為1以上，m1、m2及m3分別獨立表示1~3之整數；R2表示氫原子、-NO2、-CN、鹵素基、1價之苯環、萘環、聯苯環、呋喃環、含有氮之雜環、及碳數5~8之脂環式烴、及烷基、或烷基氧基；Z1、Z2表示單鍵、-CO-、-CH2O-、-CH=N-、-CF2-。 <10> In any one of the above <1> to <9>, the component (A) is one having a liquid crystal side chain selected from the group consisting of the following formulae (21) to (31): Preferably, in the formula, A, B, q1 and q2 have the same definitions as above; Y 3 is a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, nitrogen-containing heterocyclic ring, and carbon number 5-8 Alicyclic hydrocarbons, and groups selected from the group consisting of these groups, and hydrogen atoms bonded to these groups can be independently -NO 2 , -CN, halogen group, and alkane having 1 to 5 carbon atoms Group, or an alkyloxy group having 1 to 5 carbon atoms; R 3 represents a hydrogen atom, -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen group, monovalent Benzene ring, naphthalene ring, biphenyl ring, furan ring, heterocyclic ring containing nitrogen, alicyclic hydrocarbon having 5 to 8 carbons, alkyl having 1 to 12 carbons, or alkoxy having 1 to 12 carbons ; L represents an integer from 1 to 12, and m represents an integer from 0 to 2. However, in formulas (23) to (24), the total of all m is 2 or more, and in formulas (25) to (26), all of m The total number is 1 or more, m1, m2, and m3 each independently represent an integer of 1 to 3; R 2 represents a hydrogen atom, -NO 2 , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, and a furan ring Containing nitrogen Ring, and the carbon number of 5 to 8 aliphatic cyclic hydrocarbon, and an alkyl group, or an alkyl group; Z 1, Z 2 represents a single bond, -CO -, - CH 2 O -, - CH = N -, - CF 2- .

<11>一種基板，其係具有藉由上述<1>~<10>中任一項記載之方法所製造之橫向電場驅動型液晶顯示元件用液晶配向膜。 <11> A substrate comprising a liquid crystal alignment film for a lateral electric field-driven liquid crystal display element manufactured by the method described in any one of <1> to <10>.

<12>一種橫向電場驅動型液晶顯示元件，其係具有上述<11>之基板。 <12> A lateral electric field drive type liquid crystal display device having the substrate of the above <11>.

<13>一種液晶顯示元件之製造方法，該液晶顯示元件係藉由具有：準備上述<11>所記載之基板(第1基板)之步驟、得到具有液晶配向膜之第2基板之步驟、 及得到液晶顯示元件之步驟，而得到橫向電場驅動型液晶顯示元件；該得到具有液晶配向膜之第2基板之步驟為藉由具有下述[I’]~[III’]步驟，而得到賦予配向控制功能之液晶配向膜，[I’]：於第2基板上塗佈含有(A)於特定之溫度範圍表現出液晶性之感光性側鏈型高分子、及(B)有機溶劑之聚合物組成物而形成塗膜之步驟，[II’]：於[I’]所得到之塗膜照射經偏光之紫外線之步驟，及[III’]：加熱[II’]所得到之塗膜之步驟；得到液晶顯示元件之步驟為下述[IV]步驟，[IV]：透過液晶並使第1及第2基板之液晶配向膜以相對之方式，使第1及第2基板為對向配置。 <13> A method for manufacturing a liquid crystal display element, comprising: a step of preparing the substrate (first substrate) described in the above <11>; a step of obtaining a second substrate having a liquid crystal alignment film; And a step of obtaining a liquid crystal display element to obtain a lateral electric field drive type liquid crystal display element; the step of obtaining a second substrate having a liquid crystal alignment film is obtained by having the following steps [I '] to [III'] [I ']: A liquid crystal alignment film with an alignment control function is coated on the second substrate with (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range, and (B) an organic solvent polymerization. [II ']: a step of irradiating the coating film obtained by [I'] with polarized ultraviolet light, and [III ']: a step of heating the coating film obtained by [II'] Step; The step of obtaining a liquid crystal display element is the following [IV] step, [IV]: transmitting the liquid crystal and causing the liquid crystal alignment film of the first and second substrates to face each other so that the first and second substrates are oppositely arranged .

<14>一種橫向電場驅動型液晶顯示元件，其係藉由上述<13>記載之方法來製造。 <14> A lateral electric field-driven liquid crystal display device manufactured by the method described in the above <13>.

<15>一種橫向電場驅動型液晶顯示元件用液晶配向膜製造用組成物，其係含有(A)於特定之溫度範圍表現液晶性之感光性側鏈型高分子及(B)有機溶劑。 <15> A composition for manufacturing a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element, which contains (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range and (B) an organic solvent.

<16>一種化合物，其係如下述式(1)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)； <16> A compound which is a compound represented by the following formula (1) (where R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);

<17>一種化合物，其係如下述式(2)所示之化合物，(式中，R表示氫原子或甲基；R10表示Br或CN；S表示碳數2~10之伸烷基)； <17> A compound which is a compound represented by the following formula (2) (wherein R represents a hydrogen atom or a methyl group; R 10 represents Br or CN; S represents an alkylene group having 2 to 10 carbon atoms) ;

<18>一種化合物，其係如下述式(3)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)； <18> A compound, which is a compound represented by the following formula (3) (where R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);

<19>一種化合物，其係如下述式(4)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之 伸烷基；u表示0或1)； <19> A compound, which is a compound represented by the following formula (4) (where R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; u represents 0 or 1);

<20>一種化合物，其係如下述式(5)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基；u表示0或1)； <20> A compound, which is a compound represented by the following formula (5) (where R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; u represents 0 or 1);

<21>一種化合物，其係如下述式(6)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)； <21> A compound, which is a compound represented by the following formula (6) (where R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);

<22>一種化合物，其係如下述式(7)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)； <22> A compound, which is a compound represented by the following formula (7) (where R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);

<23>一種化合物，其係如下述式(8)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)； <23> A compound, which is a compound represented by the following formula (8) (where R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);

<24>一種化合物，其係如下述式(9)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)； <24> A compound, which is a compound represented by the following formula (9) (where R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);

<25>一種化合物，其係如下述式(10)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)； <25> A compound, which is a compound represented by the following formula (10) (where R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);

<26>一種化合物，其係如下述式(11)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基；Py表示2-吡啶基、3-吡啶基或4-吡啶基；u表示0或1)； <26> A compound which is a compound represented by the following formula (11) (where R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; Py represents a 2-pyridyl group, 3-pyridyl or 4-pyridyl; u represents 0 or 1);

<27>一種化合物，其係如下述式(12)所示 之化合物，(式中，S表示碳數2~9之伸烷基；v表示1或2)； <27> A compound, which is a compound represented by the following formula (12) (wherein S represents an alkylene group having 2 to 9 carbon atoms; v represents 1 or 2);

<28>一種化合物，其係如下述式(13)所示之化合物，(式中，S表示碳數2~10之伸烷基；u表示0或1)； <28> A compound which is a compound represented by the following formula (13) (wherein, S represents an alkylene group having 2 to 10 carbon atoms; u represents 0 or 1);

<29>一種化合物，其係如下述式(14)所示之化合物，(式中，S表示碳數1~10之伸烷基；u表示0或1)； <29> A compound, which is a compound represented by the following formula (14) (wherein S represents an alkylene group having 1 to 10 carbon atoms; u represents 0 or 1);

<30>一種化合物，其係如下述式(15)所示之化合物，(式中，S表示碳數2~10之伸烷基)； <30> A compound, which is a compound represented by the following formula (15) (wherein, S represents an alkylene group having 2 to 10 carbon atoms);

<31>一種化合物，其係如下述式(16)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)； <31> A compound, which is a compound represented by the following formula (16) (where R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);

<32>一種化合物，其係如下述式(17)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之 伸烷基)； <32> A compound, which is a compound represented by the following formula (17) (where R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);

1.一種橫向電場驅動型液晶顯示元件的製造方法，其係於具有橫向電場驅動用之導電膜之基板上，塗佈含有(A)於特定之溫度範圍表現液晶性之感光性側鏈型高分子、以及(B)有機溶劑之聚合物組成物而形成塗膜，其特徵為經過藉由將紫外線之照射與其後之加熱而賦予配向控制功能之一對塗膜附基板，透過液晶分子之層使前述塗膜以成為相對之方式進行對向配置而形成液晶晶胞之步驟。 1. A method for manufacturing a lateral electric field-driven liquid crystal display device, which is coated on a substrate having a conductive film for lateral electric field drive, and has a photosensitive side chain type containing (A) a liquid crystallinity exhibiting a specific temperature range. Molecules, and (B) a polymer composition of an organic solvent to form a coating film, which is characterized in that the coating film has a substrate attached to the coating film through one of the alignment control functions by irradiating ultraviolet rays and subsequent heating, and the layer of liquid crystal molecules is transmitted A step of causing the aforementioned coating films to face each other so as to form a liquid crystal cell.

2.如1之方法，其中，(A)成分係具有引起光交聯、光異構化、或光弗賴斯重排之側鏈。 2. The method according to 1, wherein the component (A) has a side chain which causes photocrosslinking, photoisomerization, or photofries rearrangement.

3.如1或2之方法，其中，(A)成分係具有下述式(1)~(8)之感光性側鏈。 3. The method according to 1 or 2, wherein the component (A) is a photosensitive side chain having the following formulae (1) to (8).

惟，A、B、D分別獨立表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-；Y1為1價之苯環、萘環、聯苯環、呋喃環、吡咯環、碳數5~8之環狀烴、及由該等之組合中選出之基，鍵結於該等之氫原子分別獨立可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、烷基、或烷基氧基所取代；X表示單鍵、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-；l表示1~12之整數；m表示0~2之整數；m1、m2表示1~3之整數；n表示0~12之整數(惟n=0時B為單鍵)； Y2為2價之苯環、萘環、聯苯環、呋喃環、吡咯環、碳數5~8之環狀烴、及由該等之組合中選出之基，鍵結於該等之氫原子分別獨立可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、烷基、或烷基氧基所取代；R表示氫原子、及碳數1~6之烷基；R1表示氫原子-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、烷基、或烷基氧基。 However, A, B, and D each independently represent a single bond, -O-, -CH 2- , -COO-, -OCO-, -CONH-, -NH-CO-; Y 1 is a monovalent benzene ring, naphthalene Rings, biphenyl rings, furan rings, pyrrole rings, cyclic hydrocarbons having 5 to 8 carbons, and groups selected from these combinations. The hydrogen atoms bonded to these can be independently -NO 2 ,- CN, -CH = C (CN) 2 , -CH = CH-CN, halo, alkyl, or alkyloxy; X represents a single bond, -COO-, -OCO-, -N = N- , -CH = CH-, -C≡C-; l represents an integer from 1 to 12; m represents an integer from 0 to 2; m1, m2 represents an integer from 1 to 3; n represents an integer from 0 to 12 (but n = B is a single bond at 0); Y 2 is a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, a cyclic hydrocarbon having 5 to 8 carbon atoms, and a base selected from a combination of these The hydrogen atoms bonded to these can be independently substituted by -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halo, alkyl, or alkyloxy; R represents a hydrogen atom and an alkyl group having 1 to 6 carbon atoms; R 1 represents a hydrogen atom -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, a halogen group, an alkyl group, or Alkyloxy.

4.如1~3中任一項之方法，其中，(A)成分係具有下述式(5)~(13)液晶性之側鏈。 4. The method according to any one of 1 to 3, wherein the component (A) is a side chain having liquid crystallinity of the following formulae (5) to (13).

惟，A、B、Y1、R、l、m、m1、m2、及R1具有與上述相同之定義；Z1、Z2表示-CO-、-CH2O-、-C=N-、-CF2-。 However, A, B, Y 1 , R, 1, m, m1, m2, and R 1 have the same definitions as above; Z 1 , Z 2 represent -CO-, -CH 2 O-, -C = N- , -CF 2- .

5.一種前述聚合物組成物，其係含有如1~4中任一項記載之(A)於特定之溫度範圍表現液晶性之感光性側鏈型高分子、以及(B)有機溶劑之聚合物組成物，其係在於具有橫向電場驅動用之導電膜之基板上形成塗膜，並將紫外線之照射與其後之加熱而賦予配向控制功能之一對塗膜附基板，透過液晶分子之層使前述塗膜以成為相對之方式進行對向配置而形成液晶晶胞之步驟之橫向電場驅動型液晶顯示元件的製造方法，其特徵為為了形成前述塗膜而使用前述聚合物組成物。 5. The aforementioned polymer composition comprising (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range as described in any one of 1 to 4 and (B) polymerization of an organic solvent The composition is formed by forming a coating film on a substrate having a conductive film for driving a transverse electric field, and irradiating ultraviolet rays and subsequent heating to impart an alignment control function to the coating film with a substrate, and passing through a layer of liquid crystal molecules. The method for manufacturing a lateral electric field-driven liquid crystal display element in which the coating film is oppositely disposed to form a liquid crystal cell is a method of forming the coating film, wherein the polymer composition is used to form the coating film.

6.一種液晶顯示元件，其特徵為藉由如1~4中任一項之液晶顯示元件的製造方法而製造。 6. A liquid crystal display element characterized by being manufactured by the method for manufacturing a liquid crystal display element according to any one of 1 to 4.

7.一種下述式(1)所示之液晶性化合物， 式中，R表示氫原子或甲基，S表示碳原子數2~10之伸烷基。 7. A liquid crystalline compound represented by the following formula (1), In the formula, R represents a hydrogen atom or a methyl group, and S represents an alkylene group having 2 to 10 carbon atoms.

由本發明，係提供一種以高效率賦予配向控制功能，且烙印特性優異之具有橫向電場驅動型液晶顯示元件用液晶配向膜之基板及具有該基板之橫向電場驅動型液晶顯示元件。 According to the present invention, a substrate having a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element which is provided with an alignment control function with high efficiency and excellent in imprinting characteristics, and a lateral electric field drive type liquid crystal display element having the substrate.

藉由本發明之方法而製造之橫向電場驅動型液晶顯示元件，因為賦予高效率之配向控制功能即使連續長時間驅動亦不會損及顯示特性。 The lateral electric field drive type liquid crystal display element manufactured by the method of the present invention does not impair the display characteristics even if it is driven for a long period of time because of its highly efficient alignment control function.

1‧‧‧側鏈型高分子膜 1‧‧‧ side chain polymer film

2、2a‧‧‧側鏈 2, 2a‧‧‧ side chain

3‧‧‧側鏈型高分子膜 3‧‧‧ side chain polymer film

4、4a‧‧‧側鏈 4, 4a‧‧‧ side chain

5‧‧‧側鏈型高分子膜 5‧‧‧ side chain polymer film

6、6a‧‧‧側鏈 6, 6a‧‧‧ side chain

7‧‧‧側鏈型高分子膜 7‧‧‧ side chain polymer film

8、8a‧‧‧側鏈 8, 8a‧‧‧ side chain

[圖1]為模式說明在本發明所使用之液晶配向膜的製造方法之各向異性導入處理之一個例圖，為於感光性之側鏈使用交聯性之有機基，所導入之各向異性為小時的圖。 [Fig. 1] An example of an anisotropic introduction process for schematically explaining a method for manufacturing a liquid crystal alignment film used in the present invention, and for the use of a crosslinkable organic group in a photosensitive side chain, the introduced orientation The figure of the opposite sex is small.

[圖2]為模式說明在本發明所使用之液晶配向膜的製造方法之各向異性導入處理之一個例圖，為於感光性之側 鏈使用交聯性之有機基，所導入之各向異性為大時的圖。 [Fig. 2] An example diagram for explaining anisotropic introduction processing of a method for manufacturing a liquid crystal alignment film used in the present invention, which is on the side of photosensitivity. The cross-linked organic group is used, and the anisotropy introduced is large.

[圖3]為模式說明在本發明所使用之液晶配向膜的製造方法之各向異性導入處理之一個例圖，使用於感光性之側鏈引起弗賴斯重排(Fries rearrangement)或異構化之有機基，所導入之各向異性為小時的圖。 [Fig. 3] An example of a pattern for explaining anisotropic introduction processing in a method for manufacturing a liquid crystal alignment film used in the present invention. Fries rearrangement or isomerization caused by photosensitive side chains is used. The figure shows the anisotropy introduced for the organic group which is converted into a small group.

[圖4]為模式說明在本發明所使用之液晶配向膜的製造方法之各向異性導入處理之一個例圖，使用於感光性之側鏈引起弗賴斯重排(Fries rearrangement)或異構化之有機基，所導入之各向異性為大時的圖。 [Fig. 4] An example of a pattern for explaining anisotropic introduction processing in a method for manufacturing a liquid crystal alignment film used in the present invention. Fries rearrangement or isomerization caused by photosensitive side chains is used. The figure shows when the anisotropy introduced into the organic group is large.

本發明者進行銳意研究之結果，得到以下之知見而終至完成本發明。 As a result of earnest research, the inventors obtained the following knowledge and finally completed the present invention.

在本發明的製造方法所使用之聚合物組成物，係具有可表現液晶性之感光性之側鏈型高分子(以下亦單稱為側鏈型高分子)，使用前述聚合物組成物而得到之塗膜，係具有可表現液晶性之感光性之側鏈型高分子之膜。於此塗膜不進行摩擦處理，藉由偏光照射進行配向處理。而且，偏光照射之後，經由加熱其側鏈型高分子膜之步驟，成為賦予配向控制功能之塗膜(以下亦稱為液晶配向膜)。此時，藉由偏光照射而表現之些微各向異性成為驅動力，液晶性之側鏈型高分子本身由自我組織化有效率地進行再配向。其結果，作為液晶配向膜實現高效率之配向處理，可得到賦予高度配向控制功能之液晶配向膜。 The polymer composition used in the production method of the present invention is a side-chain polymer (hereinafter also simply referred to as a side-chain polymer) having photosensitivity capable of expressing liquid crystal properties, and is obtained by using the polymer composition described above. The coating film is a film having a photosensitive side chain polymer which can express liquid crystallinity. Here, the coating film was not subjected to rubbing treatment, and alignment treatment was performed by polarized light irradiation. In addition, after the polarized light is irradiated, it becomes a coating film (hereinafter also referred to as a liquid crystal alignment film) that imparts an alignment control function through a step of heating the side chain polymer film. At this time, the slight anisotropy exhibited by polarized light irradiation becomes a driving force, and the liquid crystal side chain polymer itself is efficiently realigned by self-organization. As a result, a highly efficient alignment process can be realized as a liquid crystal alignment film, and a liquid crystal alignment film provided with a high alignment control function can be obtained.

以下對於本發明之實施形態進行詳細說明。 Hereinafter, embodiments of the present invention will be described in detail.

<具有液晶配向膜之基板的製造方法>及<液晶顯示元件的製造方法> <Manufacturing method of substrate with liquid crystal alignment film> and <Manufacturing method of liquid crystal display element>

具有本發明之液晶配向膜之基板的製造方法係具有：[I]將含有(A)於特定之溫度範圍表現液晶性之感光性側鏈型高分子、及(B)有機溶劑之聚合物組成物，塗佈於具有橫向電場驅動用之導電膜之基板上而形成塗膜之步驟；[II]於[I]所得到之塗膜照射經偏光之紫外線之步驟；及[III]加熱[II]所得到之塗膜之步驟。 The manufacturing method of the substrate having the liquid crystal alignment film of the present invention includes: [I] a polymer composition containing (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range, and (B) an organic solvent Step of forming a coating film on a substrate having a conductive film for driving a transverse electric field; [II] a step of irradiating polarized ultraviolet rays on the coating film obtained in [I]; and [III] heating [II] ] The obtained coating film step.

由上述步驟，可得到賦予配向控制功能之橫向電場驅動型液晶顯示元件用液晶配向膜，可得到具有該液晶配向膜之基板。 According to the above steps, a liquid crystal alignment film for a lateral electric field drive type liquid crystal display element having an alignment control function can be obtained, and a substrate having the liquid crystal alignment film can be obtained.

又，除了上述所得到基板(第1基板)之外，藉由準備第2基板，可得到橫向電場驅動型液晶顯示元件。 In addition to the substrate (first substrate) obtained as described above, by preparing a second substrate, a lateral electric field drive type liquid crystal display element can be obtained.

第2基板取代具有橫向電場驅動用之導電膜之基板，除了使用不具有橫向電場驅動用之導電膜之基板以外，藉由使用上述步驟[I]~[III](因為使用不具有橫向電場驅動用之導電膜之基板，基本上本案中，有簡稱為步驟[I’]~[III’]的情況)，可得到具有賦予配向控制功能之液晶配 向膜之第2基板。 The second substrate replaces the substrate with a conductive film for lateral electric field driving, and in addition to using a substrate without a conductive film for lateral electric field driving, the above steps [I] to [III] are used (because the driving without lateral electric field is used) The substrate of the conductive film used is basically referred to in this case as steps [I '] to [III']), and a liquid crystal alignment having a function for imparting alignment control can be obtained. To the second substrate of the film.

橫向電場驅動型液晶顯示元件的製造方法為具有：[IV]將上述所得到之第1及第2基板，透過液晶之第1及第2基板之液晶配向膜以成為相對之方式，得到經對向配置之液晶顯示元件之步驟。藉由此可得到橫向電場驅動型液晶顯示元件。 A method for manufacturing a lateral electric field-driven liquid crystal display device includes: [IV] passing the first and second substrates obtained above through the liquid crystal alignment film of the first and second substrates of the liquid crystal in a relative manner to obtain Steps to arrange the liquid crystal display element. Thereby, a lateral electric field drive type liquid crystal display element can be obtained.

以下，對於本發明之製造方法所具有之[I]~[III]、及[IV]之各步驟進行說明。 Hereinafter, each step of [I] to [III] and [IV] included in the manufacturing method of the present invention will be described.

<步驟[I]> <Step [I]>

於步驟[I]，於具有橫向電場驅動用之導電膜之基板上，塗佈於特定之溫度範圍表現液晶性之感光性側鏈型高分子及含有有機溶劑之聚合物組成物而形成塗膜。 In step [I], a substrate having a conductive film for driving a lateral electric field is coated with a photosensitive side chain polymer exhibiting liquid crystallinity and a polymer composition containing an organic solvent in a specific temperature range to form a coating film. .

<基板> <Substrate>

對於基板，雖並未特別限定，但所製造之液晶顯示元件為透過型時，以透明性高之基板為佳。此時，並未特別限定，可使用玻璃基板、或丙烯酸基板或聚碳酸酯基板等之塑膠基板等。 The substrate is not particularly limited, but when the manufactured liquid crystal display element is a transmissive type, a substrate with high transparency is preferred. In this case, it is not particularly limited, and a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or the like can be used.

又，考慮對反射型之液晶顯示元件的適用，亦可使用矽晶圓等不透明之基板。 In addition, considering the application to a reflective liquid crystal display element, an opaque substrate such as a silicon wafer may be used.

<橫向電場驅動用之導電膜> <Conductive film for lateral electric field drive>

基板係具有橫向電場驅動用之導電膜。 The substrate has a conductive film for driving a lateral electric field.

作為該導電膜，液晶顯示元件為透過型時，雖可列舉ITO(Indium Tin Oxide：氧化銦錫)、IZO(Indium Zinc Oxide：氧化銦鋅)等，但並非被限定於此等。 When the liquid crystal display element is a transmissive type as the conductive film, ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and the like are mentioned, but it is not limited to these.

又，反射型之液晶顯示元件時，作為導電膜，雖可列舉反射鋁等光之材料等，但並非被限定於此等。 In the case of a reflective liquid crystal display element, the conductive film may be a material that reflects light such as aluminum, but is not limited thereto.

形成導電膜於基板之方法，可使用以往公知之手法。 As a method for forming a conductive film on a substrate, a conventionally known method can be used.

<聚合物組成物> <Polymer composition>

具有橫向電場驅動用之導電膜之基板上，尤其是導電膜上，塗佈聚合物組成物。 A polymer composition is coated on a substrate having a conductive film for driving a lateral electric field, especially a conductive film.

使用於本發明之製造方法，該聚合物組成物係含有(A)於特定之溫度範圍表現液晶性之感光性側鏈型高分子；及(B)有機溶劑。 The polymer composition used in the production method of the present invention contains (A) a photosensitive side chain polymer that exhibits liquid crystallinity in a specific temperature range; and (B) an organic solvent.

<<(A)側鏈型高分子>> << (A) side chain polymer >>

(A)成分係於特定之溫度範圍表現液晶性之感光性側鏈型高分子。 (A) The component is a photosensitive side chain polymer which shows liquid crystallinity in a specific temperature range.

(A)側鏈型高分子係於250nm~400nm波長範圍之光進行反應，且於100℃~300℃之溫度範圍顯示液晶性為宜。 (A) The side chain polymer reacts with light in a wavelength range of 250 nm to 400 nm, and preferably displays liquid crystallinity in a temperature range of 100 ° C to 300 ° C.

(A)側鏈型高分子以於250nm~400nm波長範圍之光具有反應之感光性側鏈為佳。 (A) The side chain polymer is preferably a photosensitive side chain that reacts with light in a wavelength range of 250 nm to 400 nm.

(A)側鏈型高分子以於100℃~300℃之溫度範圍具 有用以顯示液晶性之液晶基為佳。 (A) The side chain polymer has a temperature range of 100 ° C to 300 ° C. A liquid crystal base for displaying liquid crystal properties is preferred.

(A)側鏈型高分子係於主鏈鍵結具有感光性之側鏈，感應光可引起交聯反應、異構化反應、或光弗賴斯重排(Photo Fries rearrangement)。具有感光性之側鏈的構造雖並未特別限定，期望為感應光而引起交聯反應、或光弗賴斯重排之構造，更期望為引起交聯反應者。此時，即使曝露於熱等之外部壓力，亦可長期間安定保持經實現之配向控制功能。可表現液晶性之感光性之側鏈型高分子膜的構造，若為滿足如此特性者雖未有特別限定，但以於側鏈構造具有剛直之液晶基成分為佳。此時，於進行液晶配向膜該側鏈型高分子之際，可得到安定之液晶配向。 (A) The side chain polymer is a side chain having a photosensitive main chain bond, and the induced light can cause a crosslinking reaction, an isomerization reaction, or a photo Fries rearrangement. Although the structure of the photosensitive side chain is not particularly limited, a structure that induces a cross-linking reaction or a photo-Fries rearrangement by sensing light is more desirable, and a cross-linking reaction is more desirable. At this time, even if exposed to external pressure such as heat, the realized orientation control function can be stably maintained for a long period of time. The structure of the photosensitive side chain polymer film that can express liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable that the side chain structure has a rigid liquid crystal-based component. At this time, when the side chain polymer of the liquid crystal alignment film is carried out, stable liquid crystal alignment can be obtained.

該高分子之構造，例如可成為具有主鏈與鍵結於其之側鏈，該側鏈將具有聯苯基、三苯基、苯基環己基、苯甲酸苯酯基、偶氮苯基等之液晶基成分、與鍵結於先端部，感應光而進行交聯反應或異構化反應之感光性基的構造、或具有主鏈與鍵結於其之側鏈，該側鏈具有亦成為液晶基成分，且進行光弗賴斯重排反應之苯甲酸苯酯基的構造。 The structure of the polymer can be, for example, a main chain and a side chain bonded thereto, and the side chain will have biphenyl, triphenyl, phenylcyclohexyl, phenyl benzoate, azophenyl, etc. The structure of the liquid crystal-based component and the photosensitive group bonded to the apex and inducing light to perform a cross-linking reaction or an isomerization reaction, or has a main chain and a side chain bonded to the side chain. A liquid crystal-based component and a structure of a phenyl benzoate group that undergoes a photo-Fries rearrangement reaction.

作為可表現液晶性之感光性之側鏈型高分子膜的構造更具體之例，以由烴、(甲基)丙烯酸酯、衣康酸酯(Itaconate)、富馬酸酯、馬來酸酯、α-伸甲基-γ-丁內酯、苯乙烯、乙烯基、馬來醯亞胺、降莰烯等之自由基聚合性基及矽氧烷所成之群中選出至少1種經構成之主 鏈、與具有由下述式(1)至(6)中至少1種所成之側鏈的構造為佳。 As a more specific example of the structure of the photosensitive side chain polymer film capable of expressing liquid crystallinity, a hydrocarbon, (meth) acrylate, itaconate, fumarate, and maleate are used. At least one selected from the group consisting of radical polymerizable groups, such as α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxane Lord A chain and a structure having a side chain composed of at least one of the following formulae (1) to (6) are preferred.

式中，A、B、D分別獨立表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、或-O-CO-CH=CH-；S為碳數1~12之伸烷基、鍵結於該等之氫原子可被取代為鹵素基；T為單鍵或碳數1~12之伸烷基、鍵結於該等之氫原 子可被取代為鹵素基；Y1表示選自由1價之苯環、萘環、聯苯環、呋喃環、吡咯環及碳數5~8之脂環式烴中之環、或選自該等之取代基相同或相異之2~6之環透過鍵結基B鍵結而成之基，鍵結於該等之氫原子分別獨立可被-COOR0(式中，R0表示氫原子或碳數1~5之烷基)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；Y2為2價之苯環、萘環、聯苯環、呋喃環、吡咯環、碳數5~8之脂環式烴、及選自由該等之組合所成之群中之基、鍵結於該等之氫原子分別獨立可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；R表示羥基、碳數1~6之烷氧基、或表示與Y1相同定義；X表示單鍵、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、或-O-CO-CH=CH-，X之數成為2時，X彼此可為相同或相異；Cou表示香豆素-6-基或香豆素-7-基，鍵結於該等之氫原子分別獨立可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；q1與q2一方為1另一方為0；q3為0或1； P及Q分別獨立為2價之苯環、萘環、聯苯環、呋喃環、吡咯環、碳數5~8之脂環式烴、及、選自由該等之組合所成之群中之基；惟，X為-CH=CH-CO-O-、-O-CO-CH=CH-時，於-CH=CH-鍵結側之P或Q為芳香環，P之數成為2以上時，P彼此可為相同或相異、Q之數成為2以上時，Q彼此可為相同或相異；l1為0或1；l2為0~2之整數；l1與l2皆為0時，T為單鍵時A亦表示單鍵；l1為1時，且T為單鍵時B亦表示單鍵；H及I分別獨立為2價之苯環、萘環、聯苯環、呋喃環、吡咯環、及選自該等組合之基。 In the formula, A, B, and D respectively represent a single bond, -O-, -CH 2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O- Or -O-CO-CH = CH-; S is an alkyl group having 1 to 12 carbon atoms, and a hydrogen atom bonded to these may be substituted with a halogen group; T is a single bond or 1 to 12 carbon atoms The alkyl group and hydrogen atoms bonded to these groups may be substituted with halogen groups; Y 1 represents a group selected from monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, pyrrole rings, and lipids having 5 to 8 carbon atoms. Rings in cyclic hydrocarbons, or 2 to 6 rings with the same or different substituents selected from these, are bonded through a bonding group B, and the hydrogen atoms bonded to these can be independently- COOR 0 (where R 0 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen group, carbon number Substituted by alkyl groups of 1 to 5 or alkyloxy groups of 1 to 5 carbons; Y 2 is a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and 5 to 8 carbon lipids Cyclic hydrocarbons, and groups selected from the group consisting of these, and hydrogen atoms bonded to these can be independently -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or An alkyl group having 1 to 5 of the substituents; R & lt represents a hydroxyl group, an alkoxy group having a carbon number of 1 to 6, or represents the same as defined in Y 1; X represents a single bond, -COO -, - OCO -, - N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, and when the number of X becomes 2, X may be the same or the same as each other Iso; Cou means coumarin-6-yl or coumarin-7-yl, hydrogen atoms bonded to these can be independently -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or alkyloxy group having 1 to 5 carbon atoms; q1 and q2 are 1 and the other is 0; q3 is 0 or 1; P and Q is independently a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of these; However, when X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the -CH = CH- bonding side is an aromatic ring, and when the number of P is 2 or more, When P is the same or different from each other, and Q is 2 or more, Q may be the same or different from each other; l1 is 0 or 1; l2 is an integer from 0 to 2; when l1 and l2 are both 0, T is A is also a single bond when there is a single bond; B is also a single bond when l1 is 1, and T is a single bond; H and I points Don't independently be a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and a group selected from these combinations.

側鏈係以選自由下述式(7)~(10)所成之群中任1種之感光性側鏈為宜。 The side chain is preferably a photosensitive side chain selected from any one of the group consisting of the following formulae (7) to (10).

式中，A、B、D、Y1、X、Y2、及R具有與上述相同之定義；l表示1~12之整數；m表示0~2之整數，m1、m2表示1~3之整數；n表示0~12之整數(惟n=0時B為單鍵)。 In the formula, A, B, D, Y 1 , X, Y 2 , and R have the same definitions as above; l represents an integer of 1 to 12; m represents an integer of 0 to 2; m1 and m2 represent 1 to 3; Integer; n represents an integer from 0 to 12 (but B is a single bond when n = 0).

側鏈係以選自由下述式(11)~(13)所成之群中任1種之感光性側鏈為宜。 The side chain is preferably a photosensitive side chain selected from any one of the group consisting of the following formulae (11) to (13).

式中，A、X、l、m、m1及R具有與上述相同之定義。 In the formula, A, X, 1, m, m1, and R have the same definitions as described above.

側鏈以下述式(14)或(15)所示之感光性側鏈為宜。 The side chain is preferably a photosensitive side chain represented by the following formula (14) or (15).

式中，A、Y1、l、m1及m2具有與上述相同之定義。 In the formula, A, Y 1 , 1, m1 and m2 have the same definitions as above.

側鏈以下述式(16)或(17)所示之感光性側鏈為宜。 The side chain is preferably a photosensitive side chain represented by the following formula (16) or (17).

式中，A、X、l及m具有與上述相同之定義。 In the formula, A, X, l, and m have the same definitions as described above.

又，側鏈以下述式(18)或(19)所示之感光性側鏈為宜。 The side chain is preferably a photosensitive side chain represented by the following formula (18) or (19).

式中，A、B、Y1、q1、q2、m1、及m2具有與上述相同之定義。 In the formula, A, B, Y 1 , q1, q2, m1, and m2 have the same definitions as above.

R1表示氫原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基。 R 1 represents a hydrogen atom, -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms Oxygen.

側鏈以下述式(20)所示之感光性側鏈為宜。 The side chain is preferably a photosensitive side chain represented by the following formula (20).

式中，A、Y1、X、l及m具有與上述相同之定義。 In the formula, A, Y 1 , X, l, and m have the same definitions as above.

又，(A)側鏈型高分子係以具有選自由下述式(21)~(31)所成之群中任1種之液晶性側鏈為宜。 In addition, the (A) side chain type polymer preferably has a liquid crystal side chain selected from any one of the group consisting of the following formulae (21) to (31).

式中，A、B、q1及q2具有與上述相同之定義；Y3為1價之苯環、萘環、聯苯環、呋喃環、含有氮之雜環、及碳數5~8之脂環式烴、及選自由該等之組合所成之群中之基、鍵結於該等之氫原子分別獨立可被-NO2、-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；R3表示氫原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、1價之苯環、萘環、聯苯環、呋喃環、含有氮之雜環、碳數5~8之脂環式烴、碳數1~12之烷基、或碳數1~12之烷氧基；l表示1~12之整數，m表示0~2之整數，惟，在式 (23)~(24)中，全部m之合計為2以上，在式(25)~(26)中，全部m之合計為1以上，m1、m2及m3分別獨立表示1~3之整數；R2表示氫原子、-NO2、-CN、鹵素基、1價之苯環、萘環、聯苯環、呋喃環、含有氮之雜環、及碳數5~8之脂環式烴、及烷基、或烷基氧基；Z1、Z2表示單鍵、-CO-、-CH2O-、-CH=N-、-CF2-。 In the formula, A, B, q1, and q2 have the same definitions as above; Y 3 is a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, heterocyclic ring containing nitrogen, and lipid having 5 to 8 carbon atoms. A cyclic hydrocarbon, a group selected from the group consisting of these, and a hydrogen atom bonded to these groups can be independently -NO 2 , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, Or substituted by an alkyloxy group having 1 to 5 carbon atoms; R 3 represents a hydrogen atom, -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen group, monovalent benzene Ring, naphthalene ring, biphenyl ring, furan ring, heterocyclic ring containing nitrogen, alicyclic hydrocarbon with 5 to 8 carbons, alkyl with 1 to 12 carbons, or alkoxy with 1 to 12 carbons; l Represents an integer from 1 to 12, and m represents an integer from 0 to 2. However, in formulas (23) to (24), the total of all m is 2 or more. In formulas (25) to (26), all of m The total number is 1 or more, m1, m2, and m3 each independently represent an integer of 1 to 3; R 2 represents a hydrogen atom, -NO 2 , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, and a furan ring , A heterocyclic ring containing nitrogen, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, and an alkyl group or an alkyloxy group; Z 1 and Z 2 represent a single bond, -CO-, -CH 2 O-, -CH = N-, -CF 2 -.

<<感光性之側鏈型高分子的製法>> << Production method of photosensitive side chain polymer >>

上述可表現液晶性之感光性之側鏈型高分子可藉由聚合具有上述感光性側鏈之光反應性側鏈單體及液晶性側鏈單體而得到。 The above-mentioned photosensitive side chain polymer capable of expressing liquid crystallinity can be obtained by polymerizing a photoreactive side chain monomer and a liquid crystal side chain monomer having the above-mentioned photosensitive side chain.

[光反應性側鏈單體] [Photoreactive side chain monomer]

所謂光反應性側鏈單體，係指於形成高分子時，於高分子之側鏈部位可形成具有感光性側鏈之高分子之單體。 The photo-reactive side chain monomer refers to a monomer that can form a polymer having a photosensitive side chain at the side chain portion of the polymer when the polymer is formed.

作為側鏈具有光反應性基以下述之構造及其衍生物為佳。 The photoreactive group as the side chain is preferably the following structure and its derivative.

作為光反應性側鏈單體更具體之例，係選自 由烴、(甲基)丙烯酸酯、衣康酸酯、富馬酸酯、馬來酸酯、α-伸甲基-γ-丁內酯、苯乙烯、乙烯基、馬來醯亞胺、降莰烯等之自由基聚合性基及矽氧烷所成之群中至少1種所構成之聚合性基、與由上述式(1)~(6)中至少1種所成之感光性側鏈，較佳為例如以具有由上述式(7)~(10)中至少1種所成之感光性側鏈、由上述式(11)~(13)中至少1種所成之感光性側鏈、上述式(14)或(15)所示之感光性側鏈、上述式(16)或(17)所示之感光性側鏈、上述式(18)或(19)所示之感光性側鏈、上述式(20)所示之感光性側鏈的構造為佳。 As a more specific example of the photoreactive side chain monomer, it is selected from Composed of hydrocarbon, (meth) acrylate, itaconic acid ester, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, A polymerizable group composed of at least one of a radical polymerizable group such as pinene and a group of siloxanes, and a photosensitive side chain formed of at least one of the above formulae (1) to (6) Preferably, for example, it has a photosensitive side chain formed from at least one of the above formulae (7) to (10), and a photosensitive side chain formed from at least one of the above formulas (11) to (13). , The photosensitive side chain represented by the formula (14) or (15), the photosensitive side chain represented by the formula (16) or (17), the photosensitive side chain represented by the formula (18) or (19) The structure of the chain and the photosensitive side chain represented by the formula (20) is preferable.

本案作為光反應性及/或液晶性側鏈單體，係提供以下之新穎化合物。 This case provides the following novel compounds as photoreactive and / or liquid crystalline side chain monomers.

下述式(1)(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)所示之化合物。 A compound represented by the following formula (1) (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms).

下述式(2)(式中，R表示氫原子或甲基；R10表示Br或CN；S表示碳數2~10之伸烷基)所示之化合物。 A compound represented by the following formula (2) (wherein R represents a hydrogen atom or a methyl group; R 10 represents Br or CN; S represents an alkylene group having 2 to 10 carbon atoms).

下述式(3)(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)所示之化合物。 A compound represented by the following formula (3) (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms).

下述式(4)(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基；u表示0或1)所示之化合物。 The compound represented by the following formula (4) (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; u represents 0 or 1).

下述式(5)(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基；u表示0或1)所示之化合物。 The compound represented by the following formula (5) (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; and u represents 0 or 1).

下述式(6)(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)所示之化合物。 A compound represented by the following formula (6) (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms).

下述式(7)(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)所示之化合物。 A compound represented by the following formula (7) (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms).

下述式(8)(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)所示之化合物。 A compound represented by the following formula (8) (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms).

下述式(9)(式中，R表示氫原子或甲基； S表示碳數2~10之伸烷基)所示之化合物。 The following formula (9) (wherein R represents a hydrogen atom or a methyl group; S represents a compound represented by an alkylene group having 2 to 10 carbon atoms.

下述式(10)(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)所示之化合物。 A compound represented by the following formula (10) (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms).

下述式(11)(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基；Py表示2-吡啶基、3-吡啶基或4-吡啶基；u表示0或1)所示之化合物。 The following formula (11) (where R is a hydrogen atom or a methyl group; S is an alkylene group having 2 to 10 carbon atoms; Py is 2-pyridyl, 3-pyridyl, or 4-pyridyl; u is 0 Or 1).

下述式(12)(式中，S表示碳數2~9之伸烷基；v表示1或2)所示之化合物。 A compound represented by the following formula (12) (in the formula, S represents an alkylene group having 2 to 9 carbon atoms; v represents 1 or 2).

下述式(13)(式中，S表示碳數2~10之伸烷基；u表示0或1)所示之化合物。 The compound represented by the following formula (13) (in the formula, S represents an alkylene group having 2 to 10 carbon atoms; u represents 0 or 1).

下述式(14)(式中，S表示碳數1~10之伸烷基；u表示0或1)所示之化合物。 The compound represented by the following formula (14) (in the formula, S represents an alkylene group having 1 to 10 carbon atoms; u represents 0 or 1).

下述式(15)(式中，S表示碳數2~10之伸烷基)所示之化合物。 A compound represented by the following formula (15) (in the formula, S represents an alkylene group having 2 to 10 carbon atoms).

下述式(16)(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)所示之化合物。 A compound represented by the following formula (16) (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms).

下述式(17)(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)所示之化合物。 A compound represented by the following formula (17) (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms).

[液晶性側鏈單體] [Liquid crystal side chain monomer]

所謂液晶性側鏈單體，係指來自該單體之高分子表現液晶性，該高分子於側鏈部位可形成液晶基(Mesogen)之單體。 The so-called liquid crystalline side chain monomer refers to a monomer derived from a polymer exhibiting liquid crystallinity, and the polymer can form a liquid crystal group (Mesogen) at the side chain portion.

作為側鏈所具有之液晶基，可為以聯苯基或苯甲酸苯酯等單獨成為液晶基構造之基，可為藉由如安息香酸等使側鏈彼此進行氫鍵結而成為液晶基構造之基。作為側鏈所具有之液晶基以下述之構造為佳。 The liquid crystal group possessed by the side chain may be a base which becomes a liquid crystal group structure by using biphenyl or phenyl benzoate alone, or a liquid crystal group structure by hydrogen bonding the side chains to each other such as benzoic acid. The base. As a liquid crystal group which a side chain has, the following structure is preferable.

作為液晶性側鏈單更具體之例，以選自由烴、(甲基)丙烯酸酯、衣康酸酯、富馬酸酯、馬來酸酯、α-伸甲基-γ-丁內酯、苯乙烯、乙烯基、馬來醯亞胺、降莰烯等之自由基聚合性基及矽氧烷所成之群中至少1種所構成之聚合性基、與具有由上述式(21)~(31)中至少1種所成之側鏈之構造為佳。 As a more specific example of the liquid crystal side chain monomer, it is selected from the group consisting of hydrocarbons, (meth) acrylates, itaconic acid esters, fumaric acid esters, maleic acid esters, α-methylene-γ-butyrolactone, Free radically polymerizable groups such as styrene, vinyl, maleimine, norbornene, and at least one polymerizable group consisting of siloxane, and having a polymerizable group consisting of the above formula (21) ~ The structure of the side chain formed by at least one of (31) is preferable.

(A)側鏈型高分子可藉由表現上述液晶性之光反應性側鏈單體的聚合反應而得到。又，可藉由未表現液晶性之光反應性側鏈單體與液晶性側鏈單體的共聚合、或表現液晶性之光反應性側鏈單體與液晶性側鏈單體的共聚合而得到。進而，以不損及液晶性的表現能的範圍可與其他單體共聚合。 (A) A side chain polymer can be obtained by the polymerization reaction of the photoreactive side chain monomer which shows the said liquid crystallinity. In addition, copolymerization of a photoreactive side chain monomer and a liquid crystal side chain monomer that do not exhibit liquid crystallinity or copolymerization of a photoreactive side chain monomer and a liquid crystal side chain monomer that exhibit liquid crystallinity And get. Furthermore, it can copolymerize with other monomers in the range which does not impair the performance of liquid crystallinity.

作為其他單體，例如列舉工業上可取得之可進行自由基聚合反應之單體。 Examples of other monomers include monomers that are commercially available and can undergo radical polymerization.

作為其他單體之具體例，可列舉不飽和羧酸、丙烯酸酯化合物、甲基丙烯酸酯化合物、馬來醯亞胺化合物、丙烯腈、馬來酸酐、苯乙烯化合物及乙烯基化合物等。 Specific examples of other monomers include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

作為不飽和羧酸之具體例可列舉丙烯酸、甲基丙烯酸、衣康酸、馬來酸、富馬酸等。 Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.

作為丙烯酸酯化合物，例如可列舉甲基丙烯酸酯、乙基丙烯酸酯、異丙基丙烯酸酯、苄基丙烯酸酯、萘基丙烯酸酯、蒽基丙烯酸酯、蒽基甲基丙烯酸酯、苯基丙烯酸酯、2,2,2-三氟乙基丙烯酸酯、tert-丁基丙烯酸酯、環己基丙烯酸酯、異莰基丙烯酸酯、2-甲氧基乙基丙烯酸酯、甲氧基三乙二醇丙烯酸酯、2-乙氧基乙基丙烯酸酯、四氫糠基丙烯酸酯、3-甲氧基丁基丙烯酸酯、2-甲基-2-金剛烷基丙烯酸酯、2-丙基-2-金剛烷基丙烯酸酯、8-甲基-8-三環癸基丙烯酸酯、及8-乙基-8-三環癸基丙烯酸酯等。 Examples of the acrylate compound include methacrylate, ethacrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methacrylate, and phenyl acrylate , 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isofluorenyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylic acid Ester, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantine Alkyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

作為甲基丙烯酸酯化合物，例如可列舉甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸異丙酯、甲基丙烯酸苄酯、甲基丙烯酸萘酯、甲基丙烯酸蒽酯、蒽基甲基丙烯酸甲酯、甲基丙烯酸苯酯、2,2,2-三氟甲基丙烯酸乙酯、甲基丙烯酸第三丁酯、甲基丙烯酸環己酯、甲基丙烯酸異莰酯、2-甲氧基甲基丙烯酸乙酯、甲氧基三乙二醇甲基丙烯酸酯、2-乙氧基甲基丙烯酸乙酯、四氫糠基甲基丙烯酸酯、3-甲氧基丁基甲基丙烯酸酯、2-甲基-2-金剛烷基甲基丙烯酸酯、2-丙基-2-金剛烷基甲基丙烯酸酯、8-甲基-8-三環癸基甲基丙烯酸酯、及8-乙基-8-三環癸基甲基 丙烯酸酯等。亦可使用縮水甘油基(甲基)丙烯酸酯、(3-甲基-3-氧雜環丁基)甲基(甲基)丙烯酸酯、及具有(3-乙基-3-氧雜環丁基)甲基(甲基)丙烯酸酯等之環狀醚基之(甲基)丙烯酸酯化合物。 Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, and anthracene methyl Methyl acrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, third butyl methacrylate, cyclohexyl methacrylate, isoamyl methacrylate, 2-methyl Ethoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl Yl-8-tricyclodecylmethyl Acrylate, etc. Glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) meth (meth) acrylate, and (3-ethyl-3-oxetanyl) (Meth) acrylate compounds such as cyclic ether groups such as meth (meth) acrylate.

作為乙烯基化合物，例如可列舉乙烯基醚、甲基乙烯基醚、苄基乙烯基醚、2-羥基乙基乙烯基醚、苯基乙烯基醚、及、丙基乙烯基醚等。 Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

作為苯乙烯化合物，例如可列舉苯乙烯、甲基苯乙烯、氯苯乙烯、溴苯乙烯等。 Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, and bromostyrene.

作為馬來醯亞胺化合物，例如可列舉馬來醯亞胺、N-甲基馬來醯亞胺、N-苯基馬來醯亞胺、及N-環己基馬來醯亞胺等。 Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

對於本實施形態之側鏈型高分子的製造方法，並未特別限定，可利用工業上所取用的泛用方法。具體而言，可藉由利用液晶性側鏈單體或光反應性側鏈單體之乙烯基之陽離子聚合或自由基聚合、陰離子聚合來製造。此等之中從容易控制反應等觀點來看以自由基聚合為特佳。 The method for producing the side chain polymer of this embodiment is not particularly limited, and a general-purpose method used in industry can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization of a vinyl group of a liquid crystalline side chain monomer or a photoreactive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of easy control of the reaction and the like.

作為自由基聚合之聚合起始劑，可使用自由基聚合起始劑、或可逆加成-斷裂鏈轉移(RAFT)聚合試藥等公知之化合物。 As the polymerization initiator for radical polymerization, a known compound such as a radical polymerization initiator or a reversible addition-fragmentation chain transfer (RAFT) polymerization reagent can be used.

自由基熱聚合起始劑係藉由加熱至分解溫度以上，使其產生自由基之化合物。作為如此之自由基熱聚合起始劑，例如可列舉酮過氧化物類(甲基乙基酮過氧化 物、環己酮過氧化物等)、二醯基過氧化物類(乙醯基過氧化物、苯甲醯基過氧化物等)、氫過氧化物類(過氧化氫、tert-丁基氫過氧化物、異丙苯氫過氧化物等)、二烷基過氧化物類(二-tert-丁基過氧化物、二異苯丙基過氧化物、二過氧化月桂醯等)、過氧縮酮類(二丁基過氧環己烷等)、烷基全酯類(過氧新癸酸-tert-丁基酯、過氧三甲基乙酸-tert-丁基酯、過氧2-乙基環己烷酸-tert-戊酯等)、過硫酸鹽類(過硫酸鉀、過硫酸鈉、過硫酸銨等)、偶氮系化合物(偶氮雙異丁腈、及2,2'-二(2-羥基乙基)偶氮雙異丁腈等)。如此之自由基熱聚合起始劑亦可單獨1種使用，或亦可組合2種以上使用。 A radical thermal polymerization initiator is a compound that generates free radicals by heating it above a decomposition temperature. Examples of such a radical thermal polymerization initiator include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), and difluorenyl peroxides (acetamyl peroxide). Oxides, benzamyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides ( Di-tert-butyl peroxide, diisophenylpropyl peroxide, lauryl diperoxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.), alkyl all esters ( Peroxyneodecanoic acid-tert-butyl ester, peroxytrimethylacetate-tert-butyl ester, peroxy 2-ethylcyclohexane acid-tert-pentyl ester, etc.), persulfates (persulfate potassium, sodium persulfate, ammonium persulfate, etc.), azo compound (azobisisobutyronitrile, and 2,2 '- bis (2-hydroxyethyl) azobisisobutyronitrile, etc.). Such radical thermal polymerization initiators may be used singly or in combination of two or more kinds.

自由基光聚合起始劑若為藉由光照射自由基聚合而開始之化合物則無特別限定。作為如此之自由基光聚合起始劑，可列舉二苯甲酮、米其勒酮、4,4’-雙(二乙基胺基)二苯甲酮、呫噸酮、噻噸酮、異丙基呫噸酮、2,4-二乙基噻噸酮、2-乙基蒽醌、苯乙酮、2-羥基-2-甲基丙酮、2-羥基-2-甲基-4’-異丙基丙酮、1-羥基環己基苯基酮、異丙基安息香醚、異丁基安息香醚、2,2-二乙氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、樟腦醌、苯并蒽酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮-1、4-二甲基胺基安息香酸乙酯、4-二甲基胺基安息香酸異戊酯、4,4’-二(t-丁基過氧羰基)二苯甲酮、3,4,4’-三(t-丁基過氧羰基)二苯甲酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、 2-(4’-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三嗪、2-(3’,4’-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三嗪、2-(2’,4’-二甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三嗪、2-(2’-甲氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三嗪、2-(4’-戊氧基苯乙烯基)-4,6-雙(三氯甲基)-s-三嗪、4-[p-N,N-二(乙氧基羰基甲基)]-2,6-二(三氯甲基)-s-三嗪、1,3-雙(三氯甲基)-5-(2’-氯苯基)-s-三嗪、1,3-雙(三氯甲基)-5-(4’-甲氧基苯基)-s-三嗪、2-(p-二甲基胺基苯乙烯基)苯并噁唑、2-(p-二甲基胺基苯乙烯基)苯并噻唑、2-巰基苯并噻唑、3,3’-羰基雙(7-二乙基胺基香豆素)、2-(o-氯苯基)-4,4’,5,5’-四苯基-1,2’-二咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-肆(4-乙氧基羰基苯基)-1,2’-二咪唑、2,2’-雙(2,4-二氯苯基)-4,4’,5,5’-四苯基-1,2’-二咪唑、2,2’雙(2,4-二溴苯基)-4,4’,5,5’-四苯基-1,2’-二咪唑、2,2’-雙(2,4,6-三氯苯基)-4,4’,5,5’-四苯基-1,2’-二咪唑、3-(2-甲基-2-二甲基胺基丙醯基)咔唑、3,6-雙(2-甲基-2-嗎啉基丙醯基)-9-n-十二基咔唑、1-羥基環己基苯基酮、雙(5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦、3,3’,4,4’-四(t-丁基過氧羰基)二苯甲酮、3,3’,4,4’-四(t-己基過氧羰基)二苯甲酮、3,3’-二(甲氧基羰基)-4,4’-二(t-丁基過氧羰基)二苯甲酮、3,4’-二(甲氧基羰基)-4,3’-二(t-丁基過氧羰基)二苯甲酮、4,4’-二(甲氧基羰基)-3,3’-二(t-丁基過氧羰基)二苯甲酮、2-(3-甲 基-3H-苯并噻唑-2-亞基)-1-萘-2-基-乙酮、或2-(3-甲基-1,3-苯并噻唑-2(3H)-亞基)-1-(2-苯甲醯基)乙酮等。此等之化合物可單獨使用，亦可混合2個以上使用。 The radical photopolymerization initiator is not particularly limited as long as it is a compound that starts by radical irradiation with light. Examples of such a radical photopolymerization initiator include benzophenone, Michelin, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl Propyl xanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylacetone, 2-hydroxy-2-methyl-4'- Isopropylacetone, 1-hydroxycyclohexylphenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-benzene Acetophenone, camphorquinone, benzoxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinylphenyl) -butanone-1, 4-dimethylamino benzoate ethyl ester, 4-dimethylamino benzoate isoamyl ester, 4, 4'-bis (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzene Formamidine diphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (2 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine , 2- (2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentoxystyryl) -4,6- Bis (trichloromethyl) -s-triazine, 4- [pN, N-bis (ethoxycarbonylmethyl)]-2,6-bis (trichloromethyl) -s-triazine, 1, 3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-di Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-((4-ethoxycarbonylphenyl) -1,2'-diimidazole, 2,2 ' -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-diimidazole, 2,2'bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-diimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-diimidazole, 3- (2-methyl-2-dimethylaminopropylamido) carbazole, 3,6-bis (2-methyl-2-morpholinylpropanyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis (5-2,4-cyclopentadiene-1- ) -Bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, 3,3 ', 4,4'-tetrakis (t-butylperoxycarbonyl) di Benzophenone, 3,3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-bis (methoxycarbonyl) -4,4'-bis (t- Butylperoxycarbonyl) benzophenone, 3,4'-bis (methoxycarbonyl) -4,3'-bis (t-butylperoxycarbonyl) benzophenone, 4,4'-di (Methoxycarbonyl) -3,3'-bis (t-butylperoxycarbonyl) benzophenone, 2- (3-methyl -3H-benzothiazol-2-ylidene) -1-naphthyl-2-yl-ethanone, or 2- (3-methyl-1,3-benzothiazole-2 (3H) -ylidene) -1- (2-benzylidene) ethanone and the like. These compounds may be used alone or in combination of two or more.

自由基聚合法並未特別限制，可使用乳化聚合法、懸濁聚合法、分散聚合法、沉澱聚合法、塊狀聚合法、溶液聚合法等。 The radical polymerization method is not particularly limited, and an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, a block polymerization method, a solution polymerization method, and the like can be used.

作為用於可表現液晶性之感光性之側鏈型高分子之聚合反應的有機溶劑，若為溶解經生成之高分子者則無特別限定。將其具體例列舉於以下。 The organic solvent used for the polymerization reaction of the photosensitive side chain polymer that can express liquid crystallinity is not particularly limited as long as it dissolves the polymer produced. Specific examples are listed below.

可列舉N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-甲基己內醯胺、二甲基亞碸、四甲基尿素、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、異丙基醇、甲氧基甲基戊醇、雙戊烯、乙基戊基酮、甲基壬基酮、甲基乙基酮、甲基異戊基酮、甲基異丙基酮、甲基賽珞蘇、乙基賽珞蘇、甲基賽珞蘇乙酸酯、乙基賽珞蘇乙酸酯、丁基卡必醇、乙基卡必醇、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-tert-丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙 基異丁基醚、二異丁烯、戊基乙酸酯、丁基丁酸酯、丁基醚、二異丁基酮、甲基環己烯、丙基醚、二己基醚、二噁烷、n-己烷、n-戊烷、n-辛烷、二乙基醚、環己酮、碳酸乙烯酯、碳酸丙烯酯、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲基、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、二甘二甲醚(Diglyme)、4-羥基-4-甲基-2-戊酮、3-甲氧基-N,N-二甲基丙醯胺、3-乙氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺等。 Examples include N, N-dimethylformamidine, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl Caprolactam, dimethyl sulfene, tetramethyl urea, pyridine, dimethyl fluorene, hexamethyl fluorene, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentyl Ene, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cyperidine, ethyl cyperidine, methyl cyperone Threoacetate, ethyl cyperthreate acetate, butylcarbitol, ethylcarbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol Monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol Glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, Dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutylacetic acid Ester, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl Isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n -Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid Butyl ester, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate Ester, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxyl 4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy -N, N-dimethylpropylamine and the like.

此等有機溶劑可單獨使用，可混合使用。進而，即使為不使其溶解經生成之高分子之溶劑，於不析出經生成之高分子範圍，可混合於上述之有機溶劑使用。 These organic solvents can be used alone or in combination. Furthermore, even if it is a solvent that does not dissolve the produced polymer, it can be mixed with the above-mentioned organic solvent and used in a range that does not precipitate the produced polymer.

又，在自由基聚合中，有機溶劑中之氧因為成為阻礙聚合反應之原因，以使用有機溶劑經可能程度脫氣者為佳。 In addition, in the radical polymerization, since the oxygen in the organic solvent hinders the polymerization reaction, it is preferable to use an organic solvent that can be deaerated to a certain degree.

自由基聚合之際的聚合溫度雖可選擇30℃~150℃之任意溫度，但較佳為50℃~100℃之範圍。又，反應雖可於任意之濃度進行，濃度過低時得到高分子量的聚合物變為困難，濃度過高時因為反應液之黏性變成過高使均勻攪拌變為困難，單體濃度較佳為1質量%~50質量%，更佳為5質量%~30質量%。反應初期以高濃度進行，然後可追加有機溶劑。 Although the polymerization temperature at the time of radical polymerization can be selected from any temperature of 30 ° C to 150 ° C, it is preferably in the range of 50 ° C to 100 ° C. In addition, although the reaction can be carried out at an arbitrary concentration, it becomes difficult to obtain a polymer having a high molecular weight when the concentration is too low. When the concentration is too high, uniform stirring becomes difficult because the viscosity of the reaction solution becomes too high, and the monomer concentration is better. It is 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction proceeds at a high concentration in the initial stage, and then an organic solvent can be added.

在上述之自由基聚合反應，因為自由基聚合起始劑之比率相對於單體為多時所得到之高分子的分子量變小，為少時所得到之高分子的分子量變大，自由基起始劑的比率相對於使其聚合之單體以0.1莫耳%~10莫耳%為佳。又聚合時亦可追加各種單體成分或溶劑、起始劑等。 In the above-mentioned radical polymerization reaction, the molecular weight of the polymer obtained when the ratio of the radical polymerization initiator is larger than that of the monomer becomes smaller, and the molecular weight of the polymer obtained when the monomer is smaller becomes larger, and the radical The ratio of the initiator is preferably 0.1 mol% to 10 mol% relative to the monomer to be polymerized. During the polymerization, various monomer components, solvents, and initiators may be added.

[聚合物之回收] [Recycling of polymers]

由上述反應所得到，從可表現液晶性之感光性之側鏈型高分子的反應溶液，回收經生成之高分子時，將反應溶液投入貧溶劑，使該等聚合物沉澱即可。作為用於沉澱之貧溶劑，可列舉甲醇、丙酮、己烷、庚烷、丁基賽珞蘇、庚烷、甲基乙基酮、甲基異丁基酮、乙醇、甲苯、苯、二乙基醚、甲基乙基醚、水等。投入貧溶劑使其沉澱之聚合物，過濾並回收之後，於常壓或減壓下，常溫或加熱可進行乾燥。又，將回收沉澱之聚合物使其再溶解於有機溶劑，重複回收再沉澱之操作2次~10次時，可將聚合物中的雜質變少。作為此時之貧溶劑，例如可列舉醇類、酮類、烴等，使用從此等之中選出3種以上貧溶劑時，因為更一層提高純化的效率故為佳。 Obtained from the above reaction, when the polymer produced is recovered from the reaction solution of the photosensitive side-chain polymer that can exhibit liquid crystallinity, the reaction solution can be put into a poor solvent to precipitate these polymers. Examples of the lean solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cyperidine, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and diethyl ether. Ether, methyl ethyl ether, water, etc. The polymer precipitated by adding a lean solvent, filtered and recovered, can be dried at room temperature or under normal pressure or reduced pressure. In addition, when the precipitated polymer is recovered and redissolved in an organic solvent, and the operation of recovering and reprecipitating is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the lean solvent at this time include alcohols, ketones, hydrocarbons, and the like. When three or more lean solvents are selected from these, it is preferable to further improve the purification efficiency.

本發明之(A)側鏈型高分子的分子量，考慮所得到塗膜之強度、塗膜形成時之作業性、及塗膜之均勻性時，以GPC(Gel Permeation Chromatography)法所測定之重量平均分子量較佳為2000~1000000，更佳為5000 ~100000。 The molecular weight of the (A) side chain polymer of the present invention is determined by GPC (Gel Permeation Chromatography) method when considering the strength of the obtained coating film, workability during coating film formation, and uniformity of the coating film. The average molecular weight is preferably 2,000 to 1,000,000, and more preferably 5,000 ~ 100000.

[聚合物組成物之調製] [Modulation of polymer composition]

本發明所使用之聚合物組成物，以調製成適合於液晶配向膜之形成的塗佈液為佳。亦即，本發明所使用之聚合物組成物，以調製成用以形成樹脂被膜之樹脂成分溶解於有機溶劑之溶液為佳。於此，所謂該樹脂成分係包含已經說明之可表現液晶性之感光性之側鏈型高分子之樹脂成分。此時，樹脂成分之含量，以1質量%~20質量%為佳，較佳為1質量%~15質量%，特佳為1質量%~10質量%。 The polymer composition used in the present invention is preferably prepared as a coating liquid suitable for the formation of a liquid crystal alignment film. That is, the polymer composition used in the present invention is preferably a solution prepared by dissolving a resin component for forming a resin film in an organic solvent. Here, the resin component is a resin component containing the above-mentioned photosensitive side chain polymer that can express liquid crystallinity. At this time, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and particularly preferably 1% by mass to 10% by mass.

在本實施形態之聚合物組成物，前述之樹脂成分雖可全部為上述可表現液晶性之感光性之側鏈型高分子，但在不損及液晶表現能及感光性能的範圍意亦可混合該等以外之其他聚合物。那時，在樹脂成分中之其他聚合物的含量為0.5質量%~80質量%，較佳為1質量%~50質量%。 In the polymer composition of this embodiment, although the aforementioned resin components may be all of the above-mentioned photosensitive side chain polymers capable of expressing liquid crystallinity, they may be mixed in a range that does not impair liquid crystal display performance and photosensitivity. Other polymers than these. At that time, the content of the other polymer in the resin component is 0.5% by mass to 80% by mass, and preferably 1% by mass to 50% by mass.

這般之其他聚合物，例如可列舉由聚(甲基)丙烯酸酯或聚醯胺酸或聚醯亞胺等所成，並非可表現液晶性之感光性之側鏈型高分子之聚合物等。 Such other polymers include, for example, polymers made of poly (meth) acrylate, polyamidic acid, or polyimide, which are not photosensitive side-chain polymers that exhibit liquid crystallinity. .

<有機溶劑> <Organic solvent>

用於本發明所使用之聚合物組成物之有機溶劑，若為使樹脂成分溶解之有機溶劑則並無特別限制。將其具體例 列舉於以下。 The organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves a resin component. Specific examples Listed below.

可列舉N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-甲基己內醯胺、2-吡咯啶酮、N-乙基吡咯啶酮、N-乙烯基吡咯啶酮、二甲基亞碸、四甲基尿素、吡啶、二甲基碸、六甲基亞碸、γ-丁內酯、3-甲氧基-N,N-二甲基丙醯胺、3-乙氧基-N,N-二甲基丙醯胺、3-丁氧基-N,N-二甲基丙醯胺、1,3-二甲基-四氫咪唑酮、乙基戊基酮、甲基壬基酮、甲基乙基酮、甲基異戊基酮、甲基異丙基酮、環己酮、碳酸乙烯酯、碳酸丙烯酯、二甘二甲醚(Diglyme)、4-羥基-4-甲基-2-戊酮、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-tert-丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚等。此等可單獨使用，可混合使用。 Examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl fluorene, tetramethyl urea, pyridine, dimethyl fluorene, hexamethyl fluorene, γ-butyrolactone, 3-methoxy -N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-tetrahydroimidazolone, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, vinyl carbonate, Propylene carbonate, Diglyme, 4-hydroxy-4-methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol mono Methyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxy Acetate, tripropylene glycol methyl ether. These can be used alone or in combination.

本發明所使用之聚合物組成物，可含有上述(A)及(B)成分以外之成分。作為其例，雖可列舉塗佈聚合物組成物之際提高膜厚均勻性或表面平滑性之溶劑或化合物、提高液晶配向膜與基板的密著性之化合物等，但並非被限定於此。 The polymer composition used in the present invention may contain components other than the components (A) and (B) described above. Examples thereof include solvents or compounds that improve film thickness uniformity or surface smoothness when coating a polymer composition, compounds that improve adhesion between a liquid crystal alignment film and a substrate, and the like, but are not limited thereto.

作為提高膜厚之均勻性或表面平滑性之溶劑(貧溶劑)的具體例，列舉以下者。 Specific examples of the solvent (lean solvent) for improving the uniformity of the film thickness or the surface smoothness include the following.

例如可列舉異丙基醇、甲氧基甲基戊醇、甲基賽珞蘇、乙基賽珞蘇、丁基賽珞蘇、甲基賽珞蘇乙酸酯、乙基賽珞蘇乙酸酯、丁基卡必醇、乙基卡必醇、乙基卡必醇乙酸酯、乙二醇、乙二醇單乙酸酯、乙二醇單異丙基醚、乙二醇單丁基醚、丙二醇、丙二醇單乙酸酯、丙二醇單甲基醚、丙二醇-tert-丁基醚、二丙二醇單甲基醚、二乙二醇、二乙二醇單乙酸酯、二乙二醇二甲基醚、二丙二醇單乙酸酯單甲基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單乙酸酯單乙基醚、二丙二醇單丙基醚、二丙二醇單乙酸酯單丙基醚、3-甲基-3-甲氧基丁基乙酸酯、三丙二醇甲基醚、3-甲基-3-甲氧基丁醇、二異丙基醚、乙基異丁基醚、二異丁烯、戊基乙酸酯、丁基丁酸酯、丁基醚、二異丁基酮、甲基環己烯、丙基醚、二己基醚、1-己醇、n-己烷、n-戊烷、n-辛烷、二乙基醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲基、丙酮酸乙酯、3-甲氧基丙酸甲基、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、1-甲氧基-2-丙醇、1-乙氧基-2-丙醇、1-丁氧基-2-丙醇、1-苯氧基-2-丙醇、丙二醇單乙酸酯、丙二醇二乙酸酯、丙二醇-1-單甲基醚-2-乙酸酯、丙二醇-1-單乙基醚-2-乙酸酯、二丙二醇、2-(2-乙氧基丙氧基)丙醇、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯、乳酸異戊酯等具有低表面張力之溶劑等。 Examples include isopropyl alcohol, methoxymethylpentyl alcohol, methyl cyperidine, ethyl cyperidine, butyl cyperidine, methyl cyperidine acetate, ethyl cyperidine acetate Ester, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl Ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol diethylene glycol Methyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol mono Acetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl Isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl Ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate , Methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl, 3 -Butyl methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2- Propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-propanediol (2-ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate and other solvents having low surface tension.

此等之貧溶劑可1種或混合多數種使用。使用如上述之溶劑時，使聚合物組成物所包含之溶劑整體之溶解性如一般顯著降低，以溶劑整體之5質量%~80質量%為佳，更佳為20質量%~60質量%。 These poor solvents can be used singly or in combination. When the solvent is used as described above, the solubility of the solvent contained in the polymer composition as a whole is generally significantly reduced, and the total solvent is preferably 5 to 80% by mass, and more preferably 20 to 60% by mass.

作為提高膜厚之均勻性或表面平滑性之化合物，可列舉氟系界面活性劑、矽氧系界面活性劑及非離子系界面活性劑等。 Examples of the compound that improves the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.

更具體而言，例如可列舉EFTOP(註冊商標)301、EF303、EF352(JEMCO公司製)、Mega fac(註冊商標)F171、F173、R-30(DIC公司製)、Florad FC430、FC431(住友3M公司製)、Asahi Guard(註冊商標)AG710(旭硝子公司製)、Surflon(註冊商標)S-382、SC101、SC102、SC103、SC104、SC105、SC106(AGC清美化學公司製)等。此等之界面活性劑的使用比例，相對於聚合物組成物所含有之樹脂成分之100質量份，較佳為0.01質量份~2質量份，更佳為0.01質量份~1質量份。 More specifically, for example, EFTOP (registered trademark) 301, EF303, EF352 (made by JEMCO), Mega fac (registered trademark) F171, F173, R-30 (made by DIC), Florad FC430, FC431 (Sumitomo 3M) Company), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Kiyomi Chemical Co., Ltd.), and the like. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, and more preferably 0.01 to 1 part by mass relative to 100 parts by mass of the resin component contained in the polymer composition.

作為提高液晶配向膜與基板的密著性之化合物的具體例，可列舉以下所示之含有官能性矽烷之化合物等。 Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and the like shown below.

例如可列舉3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、2-胺基丙基三甲氧基矽烷、2-胺基丙基三乙氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、3-脲基丙 基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、N-乙氧基羰基-3-胺基丙基三甲氧基矽烷、N-乙氧基羰基-3-胺基丙基三乙氧基矽烷、N-三乙氧基矽烷基丙基三伸乙基三胺、N-三甲氧基矽烷基丙基三伸乙基三胺、10-三甲氧基矽烷基-1,4,7-三氮雜癸烷(Triazadecane)、10-三乙氧基矽烷基-1,4,7-三氮雜癸烷、9-三甲氧基矽烷基-3,6-二氮雜壬基乙酸酯、9-三乙氧基矽烷基-3,6-二氮雜壬基乙酸酯、N-苄基-3-胺基丙基三甲氧基矽烷、N-苄基-3-胺基丙基三乙氧基矽烷、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷、N-雙(環氧乙烷)-3-胺基丙基三甲氧基矽烷、N-雙(環氧乙烷)-3-胺基丙基三乙氧基矽烷等。 Examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureido C Trimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrisilane Ethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4, 7-Triazadecane, 10-Triethoxysilyl-1,4,7-triazadecane, 9-Trimethoxysilyl-3,6-diazanonylethyl Acid ester, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-amino Propyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (ethylene oxide) 3-aminopropyltrimethoxysilane, N-bis (ethylene oxide) -3-aminopropyltriethoxysilane, and the like.

進而，除了基板與液晶配向膜的密著性的提高外，以防止藉由構成液晶顯示元件時之背光電氣特性的降低等為目的，可使如以下之酚醛樹脂(Phenoplast)系或環氧基含有化合物之添加劑含有於聚合物組成物中。具體而言雖將酚醛樹脂(Phenoplast)系添加劑展示於以下，但並未被限定於此構造。 Furthermore, in addition to improving the adhesion between the substrate and the liquid crystal alignment film, and for the purpose of preventing a reduction in the electrical characteristics of the backlight when constituting a liquid crystal display element, the following phenol resins (Phenoplast) or epoxy groups can be used. Compound-containing additives are contained in the polymer composition. Although the phenol resin (Phenoplast) type additive is shown below specifically, it is not limited to this structure.

作為具體之環氧基含有化合物，可例示乙二醇二環氧丙基醚、聚乙二醇二環氧丙基醚、丙二醇二環氧丙基醚、三丙二醇二環氧丙基醚、聚丙二醇二環氧丙基醚、新戊二醇二環氧丙基醚、1,6-己烷二醇二環氧丙基醚、甘油二環氧丙基醚、2,2-二溴新戊二醇二環氧丙基醚、1,3,5,6-四縮水甘油基-2,4-己烷二醇、N,N,N’,N’,-四縮水甘油基-m-二甲苯二胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、N,N,N’,N’,-四縮水甘油基-4、4’-二胺基二苯基甲烷等。 Specific examples of the epoxy-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and poly (ethylene glycol). Propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl Glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N',-tetraglycidyl-m-di Toluenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N',-tetraglycidyl-4, 4'-diamine Diphenylmethane and the like.

使用提高與基板之密著性之化合物時，其使用量相對於聚合物組成物所含有之樹脂成分100質量份以0.1質量份~30質量份為佳，更佳為1質量份~20質量份。使用量未滿0.1質量份時無法期望密著性提昇效果，多於30質量份時則有液晶之配向性惡化的情況。 When using a compound that improves adhesion to a substrate, the amount used is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass relative to 100 parts by mass of the resin component contained in the polymer composition. . When the usage amount is less than 0.1 parts by mass, the adhesion improving effect cannot be expected, and when it is more than 30 parts by mass, the alignment of the liquid crystal may be deteriorated.

作為添加劑亦可使用光增敏劑。較佳為無色增敏劑及三聯增敏劑。 A photosensitizer can also be used as an additive. Colorless sensitizers and triple sensitizers are preferred.

作為光增敏劑，係芳香族硝基化合物、香豆素(7-二乙基胺基-4-甲基香豆素、7-羥基4-甲基香豆素)、香豆素酮、羰基雙香豆素、芳香族2-羥基酮、及被胺基取代、芳香族2-羥基酮(2-羥基二苯甲酮、單-或是二-p-(二甲基胺基)-2-羥基二苯甲酮)、苯乙酮、蒽醌、呫噸酮、噻噸酮、苯并蒽酮、噻唑啉(2-苯甲醯基伸甲基-3-甲基-β-萘并噻唑啉、2-(β-萘甲醯基伸甲基)-3-甲基苯并噻唑啉、2-(α-萘甲醯基伸甲基)-3-甲基苯并噻唑啉、2-(4- 聯苯基伸甲基)-3-甲基苯并噻唑啉、2-(β-萘甲醯基伸甲基)-3-甲基-β-萘并噻唑啉、2-(4-聯苯基伸甲基)-3-甲基-β-萘并噻唑啉、2-(p-氟苯甲醯基伸甲基)-3-甲基-β-萘并噻唑啉)、噁唑啉(2-苯甲醯基伸甲基-3-甲基-β-萘并噁唑啉、2-(β-萘甲醯基伸甲基)-3-甲基苯并噁唑啉、2-(α-萘甲醯基伸甲基)-3-甲基苯并噁唑啉、2-(4-聯苯基伸甲基)-3-甲基苯并噁唑啉、2-(β-萘甲醯基伸甲基)-3-甲基-β-萘并噁唑啉、2-(4-聯苯基伸甲基)-3-甲基-β-萘并噁唑啉、2-(p-氟苯甲醯基伸甲基)-3-甲基-β-萘并噁唑啉)、苯并噻唑、硝基苯胺(m-或是p-硝基苯胺、2,4,6-三硝基苯胺)或硝基苊萘(5-硝基苊萘)、(2-[(m-羥基-p-甲氧基)苯乙烯基]苯并噻唑、安息香烷基醚、N-烷基化酞、苯乙酮縮酮(2,2-二甲氧基苯基乙酮)、萘、蒽(2-萘甲醇、2-萘羧酸、9-蒽甲醇、及9-蒽羧酸)、苯并哌喃、氮雜吲哚嗪、問香豆素等。 As photosensitizers, they are aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), coumarin, Carbonylbiscoumarin, aromatic 2-hydroxy ketones, and amine-substituted, aromatic 2-hydroxy ketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino)- 2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzoxanthone, thiazoline (2-benzylidenemethyl-3-methyl-β-naphthobenzo Thiazoline, 2- (β-naphthylmethylidenemethyl) -3-methylbenzothiazoline, 2- (α-naphthylmethylidenemethyl) -3-methylbenzothiazoline, 2- ( 4- Biphenylmethylene) -3-methylbenzothiazoline, 2- (β-naphthylmethylidenemethyl) -3-methyl-β-naphthothiazoline, 2- (4-biphenylmethylene) Yl) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzylmethylidene) -3-methyl-β-naphthothiazoline), oxazoline (2-benzoyl Fluorenylmethyl-3-methyl-β-naphthoxazoline, 2- (β-naphthylmethyloxomethyl) -3-methylbenzoxazoline, 2- (α-naphthomethyloxoline) (Methyl) -3-methylbenzoxazoline, 2- (4-biphenylmethylene) -3-methylbenzoxazoline, 2- (β-naphthylmethylidene) -3 -Methyl-β-naphthoxazoline, 2- (4-biphenylmethylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzylidenemethyl) -3-methyl-β-naphthoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitropanaphthalene ( 5-nitropanaphthalene), (2-[(m-hydroxy-p-methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalate, acetophenone ketal (2 , 2-dimethoxyphenyl ethyl ketone), naphthalene, anthracene (2-naphthyl alcohol, 2-naphthalenecarboxylic acid, 9-anthracene methanol, and 9-anthracenecarboxylic acid), benzopiperan, azaindole Hydrazine, coumarin, etc.

較佳為芳香族2-羥基酮(二苯甲酮)、香豆素、香豆素酮、羰基雙香豆素、苯乙酮、蒽醌、呫噸酮、噻噸酮、及苯乙酮縮酮。 Aromatic 2-hydroxy ketone (benzophenone), coumarin, coumarin, carbonylbiscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone Acetal.

聚合物組成物中除了上述之外，若為不損及本發明效果之範圍，以使液晶配向膜之介電常數或導電性等電氣特性變化為目的，電介質或導電物質、進而以提高於液晶配向膜時之膜硬度或精緻度為目的，亦可添加交聯性化合物。 In addition to the above, if the polymer composition is in a range that does not impair the effects of the present invention, the purpose is to change the dielectric constant or conductivity of the liquid crystal alignment film, such as electrical properties, such as a dielectric or a conductive substance, and further improve the liquid crystal. For the purpose of film hardness or fineness when aligning a film, a crosslinkable compound may be added.

將上述之聚合物組成物塗佈於具有橫向電場 驅動用導電膜之基板上之方法並未特別限定。 Applying the above polymer composition to a lateral electric field The method for driving the conductive film substrate is not particularly limited.

塗佈方法於工業上，一般以網板印刷、平板印刷、快乾印刷或噴墨法等進行之方法。作為其他之塗佈方法，有浸漬法、輥塗佈法、狹縫塗佈法、旋轉法(回轉塗佈法)或噴霧法等，因應目的亦可使用此等。 The coating method is industrially generally performed by screen printing, lithography, quick-drying printing, or inkjet. As other coating methods, there are a dipping method, a roll coating method, a slit coating method, a spin method (rotary coating method), or a spray method, and these may be used depending on the purpose.

塗佈聚合物組成物於具有橫向電場驅動用之導電膜之基板上之後，可藉由熱板、熱循環型烤箱或IR(紅外線)型烤箱等之加熱手段以50~200℃，較佳為50~150℃使溶劑蒸發而得到塗膜。此時之乾燥溫度以低於側鏈型高分子之液晶相表現溫度為佳。 After coating the polymer composition on a substrate having a conductive film for lateral electric field drive, it can be heated at a temperature of 50 to 200 ° C by a heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven, preferably The coating was obtained by evaporating the solvent at 50 to 150 ° C. The drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain polymer.

塗膜之厚度，因為有過厚時於液晶顯示元件之消費電力面變為不利，過薄時液晶顯示元件之信賴性降低的情況，較佳為5nm~300nm，更佳為、10nm~150nm。 The thickness of the coating film is disadvantageous when the power consumption surface of the liquid crystal display element becomes unfavorable when it is too thick, and the reliability of the liquid crystal display element is reduced when it is too thin. The thickness is preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm.

尚，於[I]步驟之後、繼續[II]步驟之前亦有可能設置將塗膜之經形成基板冷卻至室溫之步驟。 It is also possible to provide a step of cooling the formed substrate of the coating film to room temperature after the step [I] and before continuing the step [II].

<步驟[II]> <Step [II]>

於步驟[II]，照射經偏光之紫外線於步驟[I]所得到之塗膜。照射經偏光之紫外線於塗膜之膜面時，係從對於基板之一定方向透過偏光板照射經偏光之紫外線。作為使用之紫外線經偏光之紫外線可使用波長100nm~400nm範圍之紫外線。較佳係由所使用塗膜之種類透過過濾器等選擇最適當波長。而且，例如以選擇性引發光交聯反應的方式，可選擇使用波長290nm~400nm範圍之紫外線。作為 紫外線，例如可用從高壓水銀燈所放射的光。 In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When the polarized ultraviolet rays are irradiated on the film surface of the coating film, the polarized ultraviolet rays are irradiated through the polarizing plate from a certain direction with respect to the substrate. As the ultraviolet rays to be used as polarized ultraviolet rays, ultraviolet rays having a wavelength of 100 nm to 400 nm can be used. It is preferable to select the most appropriate wavelength according to the type of the coating film used, such as a filter. In addition, for example, in order to selectively initiate a photo-crosslinking reaction, ultraviolet rays having a wavelength in a range of 290 nm to 400 nm can be selected to be used. As As ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

經偏光之紫外線之照射量，依存所使用之塗膜。照射量在該塗膜，係以成為實現與經偏光之紫外線之偏光方向平行的方向之紫外線吸光度與垂直的方向之紫外線吸光度的差△A之最大值(以下亦稱為△Amax)之偏光紫外線量的1%~70%範圍內為佳，較佳係成為1%~50%之範圍內。 The amount of polarized ultraviolet radiation depends on the coating film used. The amount of irradiation on this coating film is polarized ultraviolet rays that achieve the maximum value of the difference ΔA between ultraviolet absorption in a direction parallel to the polarization direction of polarized ultraviolet rays and ultraviolet absorption in a vertical direction (hereinafter also referred to as ΔAmax) The amount is preferably within a range of 1% to 70%, and more preferably within a range of 1% to 50%.

<步驟[III]> <Step [III]>

於步驟[III]，係加熱於步驟[II]經偏光之紫外線所照射之塗膜。由加熱可賦予塗膜配向控制功能。 In step [III], the coating film irradiated with polarized ultraviolet rays in step [II] is heated. The coating film can be given an orientation control function by heating.

加熱可使用熱板、熱循環型烤箱或IR(紅外線)型烤箱等之加熱手段。加熱溫度可考慮表現所使用塗膜之液晶性的溫度來決定。 For heating, heating means such as a hot plate, a thermal cycle oven, or an IR (infrared) oven can be used. The heating temperature may be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is expressed.

加熱溫度以於側鏈型高分子表現液晶性之溫度(以下稱為表現液晶性之溫度)的溫度範圍內為佳。如塗膜之薄膜表面時，塗膜表面之表現液晶性之溫度預料要比將可表現液晶性之感光性之側鏈型高分子於大量觀察時之表現液晶性之溫度更低。因此，加熱溫度以於塗膜表面之表現液晶性之溫度的溫度範圍內為更佳。亦即，偏光紫外線照射後加熱溫度的溫度範圍係以將所使用鏈型高分子之表現液晶性之溫度的溫度範圍下限更低10℃之溫度作為下限，該液晶溫度範圍上限更低10℃之溫度作為上限之範圍溫度為佳。加熱溫度亦低於上述溫度範圍時，有由在塗 膜之熱造成各向異性之增幅效果變成不夠充分之傾向，又加熱溫度亦高於上述溫度範圍時，有塗膜之狀態為接近於各向同性之液體狀態(等方相)之傾向，此時，會有藉由自我組織化使再配向於一方向變為困難。 The heating temperature is preferably within a temperature range of a temperature at which a side chain polymer exhibits liquid crystallinity (hereinafter referred to as a temperature at which liquid crystallinity is exhibited). For example, when the film surface of the coating film is used, the temperature at which the liquid crystallinity of the coating film surface is expected to be lower than the temperature at which the side-chain polymer that can express liquid crystallinity exhibits liquid crystallinity when observed in a large amount. Therefore, the heating temperature is more preferably within a temperature range of the temperature at which the liquid crystallinity of the coating film surface is expressed. That is, the temperature range of the heating temperature after the irradiation of polarized ultraviolet light is the lower limit of the lower limit of the temperature range of the temperature range of the temperature of the liquid crystal properties of the chain polymer to be used, which is lower than the lower limit of 10 ° C. The temperature is preferably in the range of the upper limit. When the heating temperature is lower than the above temperature range, The heat of the film tends to cause the anisotropic amplification effect to become insufficient, and when the heating temperature is higher than the above temperature range, the state of the coating film tends to be close to the isotropic liquid state (isotropic phase). Sometimes, it becomes difficult to reorient in one direction through self-organization.

尚且，表現液晶性之溫度係指側鏈型高分子或塗膜表面從固體相至液晶相發生相轉移之玻璃轉移溫度(Tg)以上，從液晶相至各向同性相(等方相)引發相轉移之各向同性相轉移溫度(Tiso)以下之溫度。 Moreover, the temperature at which the liquid crystallinity is expressed refers to a temperature above the glass transition temperature (Tg) of the side chain polymer or the surface of the coating film where the phase transition from the solid phase to the liquid crystal phase occurs. Temperature below the isotropic phase transition temperature (Tiso) of phase transition.

加熱後所形成之塗膜的厚度，因為與於步驟[I]記錄為相同理由，較佳為5nm~300nm，更佳為50nm~150nm即可。 The thickness of the coating film formed after heating is the same as that recorded in step [I], and is preferably 5 nm to 300 nm, and more preferably 50 nm to 150 nm.

藉由具有以上之步驟，於本發明之製造方法，可實現高效率、對塗膜之各向異性的導入。而且，可高效率製造附液晶配向膜之基板。 By having the above steps, in the manufacturing method of the present invention, it is possible to achieve high efficiency and introduction of anisotropy into a coating film. Moreover, a substrate with a liquid crystal alignment film can be manufactured with high efficiency.

<步驟[IV]> <Step [IV]>

[IV]步驟係將[III]所得到之於橫向電場驅動用之導電膜上具有液晶配向膜之基板(第1基板)、與同樣將上述[I’]~[III’]所得到之不具有導電膜之附液晶配向膜之基板(第2基板)，透過液晶，使雙方之液晶配向膜成為相對的方式進行對向配置，以公知之方法製造液晶晶胞，為製造橫向電場驅動型液晶顯示元件之步驟。尚且，步驟[I’]~[III’]係在步驟[I]，取代具有橫向電場驅動用之導電膜之基板，除了使用不具有該橫向電場驅動用導電膜之基板 以外，可與步驟[I]~[III]相同之方式進行。步驟[I]~[III]與步驟[I’]~[III’]的不同點，因為僅是上述導電膜的有無，故省略步驟[I’]~[III’]之說明。 [IV] The step is to obtain the substrate (first substrate) having a liquid crystal alignment film on the conductive film for lateral electric field driving obtained in [III], and the same as obtained in [I '] to [III'] above. A substrate (second substrate) with a liquid crystal alignment film having a conductive film is arranged opposite to each other through the liquid crystal so that the two liquid crystal alignment films are opposite to each other. The liquid crystal cell is manufactured by a known method, and the liquid crystal is driven by a lateral electric field. Steps to display components. Moreover, steps [I '] to [III'] are in step [I], replacing the substrate with a conductive film for lateral electric field drive, except for using a substrate without the conductive film for lateral electric field drive Other than that, it can be performed in the same manner as steps [I] to [III]. The difference between steps [I] to [III] and steps [I '] to [III'] is only the presence or absence of the above-mentioned conductive film, so the description of steps [I '] to [III'] is omitted.

若列舉液晶晶胞或液晶顯示元件之製造一例，可例示準備上述之第1及第2基板，散布間隔於單側基板之液晶配向膜上，以液晶配向膜面成為內側之方式進行，貼合另一側之基板，減壓注入液晶進行密封之方法、或於散布間隔之液晶配向膜面滴下液晶之後，貼合基板進行密封之方法等。此時，於單側之基板較佳為使用具有如橫向電場驅動用之櫛齒般構造之電極之基板。此時間隔之徑較佳為1μm~30μm，更佳為2μm~10μm。此間隔徑係挾持液晶層之一對基板間距離，亦即，變成決定液晶層之厚度。 If an example of manufacturing a liquid crystal cell or a liquid crystal display device is listed, the above-mentioned first and second substrates may be prepared, and the liquid crystal alignment film interspersed on the single-sided substrate may be exemplified so that the liquid crystal alignment film surface becomes the inner side, and bonding On the other side of the substrate, a method of injecting liquid crystal under reduced pressure to seal it, or a method of bonding the substrate to the substrate after dropping liquid crystals on the liquid crystal alignment film surface with a gap therebetween. At this time, the substrate on one side is preferably a substrate using an electrode having a structure like a tooth structure for driving a lateral electric field. The diameter of the interval at this time is preferably 1 μm to 30 μm, and more preferably 2 μm to 10 μm. This spacing diameter holds the distance between one pair of substrates of the liquid crystal layer, that is, it determines the thickness of the liquid crystal layer.

本發明之塗膜附基板的製造方法係將聚合物組成物塗佈於基板上形成塗膜之後，照射經偏光之紫外線。其次，藉由進行加熱實現對側鏈型高分子膜之高效率各向異性的導入，製造具備液晶之配向控制功能之附液晶配向膜之基板。 The method for producing a coating film with substrate of the present invention is a method in which a polymer composition is applied to a substrate to form a coating film, and then the polarized ultraviolet rays are irradiated. Secondly, the introduction of high-efficiency anisotropy to the side-chain type polymer film by heating is performed to manufacture a substrate with a liquid crystal alignment film having an alignment control function of the liquid crystal.

於本發明所使用之塗膜，基於側鏈之光反應與液晶性藉由自我組織化利用所誘導分子再配向之原理，實現對塗膜之高效率各向異性的導入。於本發明之製造方法，於側鏈型高分子具有光交聯性基作為光反應性基之構造時，使用側鏈型高分子於基板上形成塗膜之後，照射經偏光之紫外線，其次，進行加熱之後，作成液晶顯示元件。 The coating film used in the present invention realizes the introduction of high-efficiency anisotropy into the coating film based on the principle of photoreaction of the side chain and the liquid crystal property through self-organization using the principle of induced molecular realignment. In the manufacturing method of the present invention, when the side chain polymer has a structure having a photocrosslinkable group as a photoreactive group, the side chain polymer is used to form a coating film on a substrate, and then the polarized ultraviolet light is irradiated. After heating, a liquid crystal display element was produced.

以下，將使用具有光交聯性基作為光反應性基構造之側鏈型高分子的實施形態稱為第1形態，將使用具有引起光弗賴斯重排基或異構化之基作為光反應性基構造之側鏈型高分子的實施形態稱為第2形態進行說明。 Hereinafter, an embodiment using a side chain polymer having a photo-crosslinkable group as a photoreactive group structure is referred to as a first embodiment, and a group having a photo-Fries rearrangement group or isomerization is used as the light. An embodiment of a side chain polymer having a reactive base structure will be described as a second embodiment.

圖1為在本發明之第1形態中，進行模式說明在使用具有光交聯性基作為光反應性基構造之側鏈型高分子液晶配向膜的製造方法之各向異性的導入處理之一個例示圖。圖1(a)為模式表示偏光照射前側鏈型高分子膜狀態之圖，圖1(b)為模式表示偏光照射後側鏈型高分子膜狀態之圖，圖1(c)為模式表示加熱後側鏈型高分子膜狀態之圖，尤其是導入之各向異性小時，亦即，在本發明之第1形態，[II]步驟之紫外線照射量為將△A成為最大之紫外線照射量的1%~15%範圍內時之模式圖。 FIG. 1 is a schematic diagram illustrating an anisotropic introduction process of a method for manufacturing a side chain polymer liquid crystal alignment film having a photocrosslinkable group as a photoreactive group structure in a first aspect of the present invention. Illustrated diagram. Fig. 1 (a) is a diagram schematically showing a state of a side chain polymer film before polarized light irradiation, Fig. 1 (b) is a diagram schematically showing a state of a side chain polymer film after polarized light irradiation, and Fig. 1 (c) is a mode diagram showing heating A diagram of the state of the backside chain polymer film, especially when the anisotropy introduced is small, that is, in the first form of the present invention, the amount of ultraviolet irradiation in the step [II] is The pattern diagram when the range is 1% ~ 15%.

圖2係在本發明之第1形態中，進行模式說明在使用具有光交聯性基作為光反應性基構造之側鏈型高分子液晶配向膜的製造方法之各向異性的導入處理之一個例示圖。圖2(a)為模式表示偏光照射前側鏈型高分子膜狀態之圖，圖2(b)為模式表示偏光照射後側鏈型高分子膜狀態之圖，圖2(c)為模式表示加熱後側鏈型高分子膜狀態之圖，尤其是導入之各向異性大時，亦即，在本發明之第1形態，[II]步驟之紫外線照射量為將△A成為最大之紫外線照射量的15%~70%範圍內時之模式圖。 FIG. 2 is a first mode for explaining an anisotropic introduction process of a method for manufacturing a side-chain polymer liquid crystal alignment film having a photo-crosslinkable group as a photo-reactive group structure in the first aspect of the present invention. Illustrated diagram. Fig. 2 (a) is a diagram schematically showing a state of a side chain polymer film before polarized light irradiation, Fig. 2 (b) is a diagram schematically showing a state of a side chain polymer film after polarized light irradiation, and Fig. 2 (c) is a mode diagram showing heating Diagram of the state of the backside chain polymer film, especially when the anisotropy introduced is large, that is, in the first aspect of the present invention, the amount of ultraviolet radiation in the step [II] is the amount of ultraviolet radiation that maximizes △ A The pattern diagram when the range is 15% ~ 70%.

圖3係在本發明之第2形態中，進行模式說明在使用具有光異構化性基作為光反應性基、或使用上述 之式(18)所示之具有引起光弗賴斯重排基構造之側鏈型高分子之液晶配向膜的製造方法之各向異性的導入處理之一個例示圖。圖3(a)為模式表示偏光照射前側鏈型高分子膜狀態之圖，圖3(b)為模式表示偏光照射後側鏈型高分子膜狀態之圖，圖3(c)為模式表示加熱後側鏈型高分子膜狀態之圖，尤其是導入之各向異性小時，亦即，在本發明之第2形態，[II]步驟之紫外線照射量為將△A成為最大之紫外線照射量的1%~70%範圍內時之模式圖。 FIG. 3 is a mode description in the second aspect of the present invention, in which a group having photoisomerization is used as a photoreactive group, or the above is used An example of an anisotropic introduction process of a method for manufacturing a liquid crystal alignment film having a side chain polymer having a photo-Fries rearrangement structure as shown in the formula (18). Fig. 3 (a) is a diagram showing the state of the side chain polymer film before polarized light irradiation, Fig. 3 (b) is a diagram showing the state of the side chain polymer film after polarized light irradiation, and Fig. 3 (c) is mode showing heating A diagram of the state of the backside chain polymer film, especially when the anisotropy is small, that is, in the second aspect of the present invention, the amount of ultraviolet radiation in the step [II] is a value in which ΔA becomes the maximum ultraviolet radiation The pattern diagram when the range is 1% ~ 70%.

圖4係在本發明之第2形態中，進行模式說明在作為光反應性基使用上述之式(19)所示之具有引起光弗賴斯重排基構造之側鏈型高分子之液晶配向膜的製造方法之各向異性的導入處理之一個例示圖。圖4(a)為模式表示偏光照射前側鏈型高分子膜狀態之圖，圖4(b)為模式表示偏光照射後側鏈型高分子膜狀態之圖，圖4(c)為模式表示加熱後側鏈型高分子膜狀態之圖，尤其是導入之各向異性大時，亦即，在本發明之第2形態，[II]步驟之紫外線照射量為將△A成為最大之紫外線照射量的1%~70%範圍內時之模式圖。 FIG. 4 is a mode illustration of the second embodiment of the present invention. As a photoreactive group, a liquid crystal alignment using a side chain polymer having a light-Fries rearrangement structure shown in the above formula (19) is used as a photoreactive group. An example of the anisotropic introduction process of the manufacturing method of a film. Fig. 4 (a) is a diagram schematically showing a state of a side chain polymer film before polarized light irradiation, Fig. 4 (b) is a diagram schematically showing a state of a side chain polymer film after polarized light irradiation, and Fig. 4 (c) is a mode diagram showing heating The diagram of the state of the backside chain polymer film, especially when the anisotropy introduced is large, that is, in the second aspect of the present invention, the amount of ultraviolet irradiation in step [II] is the amount of ultraviolet irradiation that maximizes △ A The pattern diagram when it is within the range of 1% ~ 70%.

在本發明之第1形態中，以對塗膜之各向異性的導入處理，[II]步驟之紫外線照射量係將△A成為最大之紫外線照射量的1%~15%範圍內時，首先，於基板上形成塗膜1。如圖1(a)所示，於基板上所形成之塗膜1，側鏈2為具有隨機排列之構造。遵循塗膜1之側鏈2 的隨機排列，側鏈2之液晶基成分及感光性基亦隨機配向，其塗膜1為各向同性。 In the first aspect of the present invention, when the anisotropic introduction process is applied to the coating film, when the ultraviolet irradiation amount in the step [II] is within the range of 1% to 15% of the maximum ultraviolet irradiation amount, ΔA first, A coating film 1 is formed on the substrate. As shown in FIG. 1 (a), the coating film 1 and the side chains 2 formed on the substrate have a structure having a random arrangement. Follow the side chain 2 of the coating film 1 Random arrangement, the liquid crystal-based component and the photosensitive group of the side chain 2 are also randomly aligned, and its coating film 1 is isotropic.

在本發明之第1形態中，以對塗膜之各向異性的導入處理，[II]步驟之紫外線照射量係將△A成為最大之紫外線照射量的15%~70%範圍內時，首先，於基板上形成塗膜3。如圖2(a)所示，於基板上所形成之塗膜3，側鏈4為具有隨機排列之構造。遵循塗膜3之側鏈4的隨機排列，側鏈4之液晶基成分及感光性基亦隨機配向，其塗膜2為各向同性。 In the first aspect of the present invention, when the anisotropic introduction process is applied to the coating film, when the ultraviolet irradiation amount in the step [II] is within a range of 15% to 70% of the maximum ultraviolet irradiation amount, ΔA is first, A coating film 3 is formed on the substrate. As shown in FIG. 2 (a), the coating film 3 and the side chains 4 formed on the substrate have a structure having a random arrangement. Following the random arrangement of the side chains 4 of the coating film 3, the liquid crystal-based components and photosensitive groups of the side chains 4 are also randomly aligned, and its coating film 2 is isotropic.

在本發明之第2形態中，以對塗膜之各向異性的導入處理，在使用光異構化性基、或使用上述之具有式(18)所示之光弗賴斯重排基構造之側鏈型高分子之液晶配向膜時，[II]步驟之紫外線照射量係將△A成為最大之紫外線照射量的1%~70%範圍內時，首先，於基板上形成塗膜5。如圖3(a)所示，於基板上所形成之塗膜5，側鏈6為具有隨機排列之構造。依塗膜5之側鏈6的隨機排列，側鏈6之液晶基成分及感光性基亦隨機配向，其側鏈型高分子膜5為各向同性。 In the second aspect of the present invention, the photo-isomerizable group is used in the introduction treatment of the anisotropy to the coating film, or the above-mentioned light-Fries rearrangement structure having the formula (18) is used. When the liquid crystal alignment film of the side chain polymer is used, when the ultraviolet irradiation amount in the step [II] is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, first, a coating film 5 is formed on the substrate. As shown in FIG. 3 (a), the coating film 5 formed on the substrate and the side chains 6 have a structure having a random arrangement. According to the random arrangement of the side chains 6 of the coating film 5, the liquid crystal-based components and the photosensitive groups of the side chains 6 are also randomly aligned, and the side-chain type polymer film 5 is isotropic.

在本發明之第2形態中，以對塗膜之各向異性的導入處理，在使用上述之式(19)所示之使用具有光弗賴斯重排基構造之側鏈型高分子之液晶配向膜時，[II]步驟之紫外線照射量係將△A成為最大之紫外線照射量的1%~70%範圍內時，首先，於基板上形成塗膜7。如圖4(a)所示，於基板上所形成之塗膜7，側鏈8係具有隨 機排列之構造。遵循塗膜7之側鏈8的隨機排列，側鏈8之液晶基成分及感光性基亦隨機配向，其塗膜7為各向同性。 In the second aspect of the present invention, the liquid crystal using a side-chain polymer having a light-Fries rearrangement structure as shown in the above formula (19) is used in an anisotropic introduction process to the coating film. In the case of an alignment film, when the ultraviolet irradiation amount in the step [II] is within a range of 1% to 70% of the maximum ultraviolet irradiation amount ΔA, first, a coating film 7 is formed on a substrate. As shown in Fig. 4 (a), the side film 8 of the coating film 7 formed on the substrate has a Structure of machine arrangement. Following the random arrangement of the side chains 8 of the coating film 7, the liquid crystal-based components and the photosensitive groups of the side chains 8 are also randomly aligned, and the coating film 7 is isotropic.

於本實施之第1形態，在[II]步驟之紫外線照射量係將△A成為最大之紫外線照射量的1%~15%範圍內時，對於其各向同性之塗膜1，照射經偏光之紫外線。如此一來，如圖1(b)所示，與紫外線之偏光方向排列成平行方向之側鏈2當中具有感光性基之側鏈2a的感光性基係優先引起二聚化反應等之光反應。其結果，進行光反應之側鏈2a的密度僅僅於照射紫外線之偏光方向變高，作為結果可說賦予塗膜1非常小的各向異性。 In the first aspect of the present embodiment, when the ultraviolet irradiation amount in the step [II] is within the range of 1% to 15% of the maximum ultraviolet irradiation amount, △ A, the isotropic coating film 1 is irradiated with polarized light. Of ultraviolet. In this way, as shown in FIG. 1 (b), the photosensitive group of the side chain 2a having a photosensitive group among the side chains 2 aligned in parallel with the polarization direction of the ultraviolet rays preferentially causes a light reaction such as a dimerization reaction. . As a result, the density of the side chains 2a undergoing photoreaction becomes higher only in the direction of polarized light irradiated with ultraviolet rays. As a result, it can be said that the coating film 1 is imparted with very little anisotropy.

於本實施之第1形態，在[II]步驟之紫外線照射量係將△A成為最大之紫外線照射量的15%~70%範圍內時，對於其各向同性之塗膜3，照射經偏光之紫外線。如此一來，如圖2(b)所示，與紫外線之偏光方向排列成平行方向之側鏈4當中具有感光性基之側鏈4a的感光性基係優先引起二聚化反應等之光反應。其結果，進行光反應之側鏈4a的密度於照射紫外線之偏光方向變高，作為結果可說賦予塗膜3小的各向異性。 In the first aspect of this implementation, when the ultraviolet irradiation amount in step [II] is within a range of 15% to 70% of the maximum ultraviolet irradiation amount, △ A, the isotropic coating film 3 is irradiated with polarized light. Of ultraviolet. In this way, as shown in FIG. 2 (b), the photosensitive group of the side chain 4a having a photosensitive group among the side chains 4 aligned in parallel with the polarization direction of the ultraviolet rays preferentially causes a light reaction such as a dimerization reaction. . As a result, the density of the side chain 4a that undergoes the photoreaction becomes higher in the polarization direction of the ultraviolet rays, and as a result, it can be said that the coating film 3 is imparted with small anisotropy.

於本實施之第2形態，使用光異構化性基、或上述之式(18)所示之具有光弗賴斯重排基構造之側鏈型高分子之液晶配向膜，在[II]步驟之紫外線照射量係將△A成為最大之紫外線照射量的1%~70%範圍內時，對於其各向同性之塗膜5，照射經偏光之紫外線。如此一來， 如圖3(b)所示，與紫外線之偏光方向排列成平行方向之側鏈6當中具有感光性基之側鏈6a的感光性基係優先引起光弗賴斯重排等之光反應。其結果，進行光反應之側鏈6a的密度僅僅於照射紫外線之偏光方向變高，作為結果可說賦予塗膜5非常小的各向異性。 In the second embodiment of the present embodiment, a liquid crystal alignment film of a side chain polymer having a photo-Fries rearrangement structure as shown in the above formula (18) is used as the photoisomerizable group, and in [II] When the ultraviolet irradiation amount in the step is within a range of 1% to 70% of the maximum ultraviolet irradiation amount, the isotropic coating film 5 is irradiated with polarized ultraviolet rays. As a result, As shown in FIG. 3 (b), the photosensitive group of the side chain 6a having a photosensitive group among the side chains 6 aligned in parallel with the polarization direction of the ultraviolet rays preferentially causes a photoreaction such as light rearrangement. As a result, the density of the side chains 6a undergoing photoreaction becomes higher only in the direction of polarized light irradiated with ultraviolet rays. As a result, it can be said that the coating film 5 is provided with very little anisotropy.

於本實施之第2形態，使用上述之式(19)所示之使用具有光弗賴斯重排基構造之側鏈型高分子之塗膜，在[II]步驟之紫外線照射量係將△A成為最大之紫外線照射量的1%~70%範圍內時，對於此各向同性之塗膜7，照射經偏光之紫外線。如此一來，如圖4(b)所示，與紫外線之偏光方向排列成平行方向之側鏈8當中具有感光性基之側鏈8a的感光性基係優先引起光弗賴斯重排等之光反應。其結果，進行光反應之側鏈8a的密度於照射紫外線之偏光方向變高，作為結果可說賦予塗膜7小的各向異性。 In the second aspect of this implementation, a coating film using a side chain polymer having a light-Fries rearrangement structure shown in the above formula (19) is used, and the amount of ultraviolet radiation in step [II] is △ When A is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, the isotropic coating film 7 is irradiated with polarized ultraviolet rays. In this way, as shown in FIG. 4 (b), the photosensitive group of the side chain 8a having a photosensitive group among the side chains 8 arranged in parallel with the polarization direction of the ultraviolet rays preferentially causes photo-Fries rearrangement and the like. Photoreaction. As a result, the density of the side chain 8a undergoing photoreaction becomes higher in the direction of polarized light irradiated with ultraviolet rays, and as a result, it can be said that the coating film 7 is given a small anisotropy.

其次，於本實施之第1形態，在[II]步驟之紫外線照射量係將△A成為最大之紫外線照射量的1%~15%範圍內時，加熱偏光照射後之塗膜1，而成為液晶狀態。如此則如圖1(c)所示，於塗膜1，於與照射紫外線之偏光方向的平行方向與垂直方向之間，所產生之交聯反應的量不同。此時，因為於與照射紫外線之偏光方向平行的方向所產生之交聯反應的量非常小，此交聯反應部位進行作為可塑劑的功能。因此，與照射紫外線之偏光方向垂直的方向的液晶性比平行方向的液晶性更高，於與照射紫外線 之偏光方向平行的方向包含經自我組織化之液晶基成分之側鏈2進行再配向。其結果，於光交聯反應所誘導之塗膜1之非常小的各向異性，藉由熱而增幅，成為賦予比塗膜1更大的各向異性。 Next, in the first embodiment of the present embodiment, when the ultraviolet irradiation amount in step [II] is within the range of 1% to 15% of the maximum ultraviolet irradiation amount, ΔA is heated, and the coating film 1 after polarized light irradiation is heated to become LCD status. In this way, as shown in FIG. 1 (c), the amount of the cross-linking reaction generated in the coating film 1 is different between the parallel direction and the vertical direction with the polarization direction of the ultraviolet rays. At this time, since the amount of cross-linking reaction generated in a direction parallel to the direction of polarized light irradiated with ultraviolet rays is very small, this cross-linking reaction site functions as a plasticizer. Therefore, the liquid crystallinity in the direction perpendicular to the direction of polarized light irradiated with ultraviolet rays is higher than that in the parallel direction. The direction in which the polarization directions are parallel includes the self-organized side chain 2 of the liquid crystal-based component for realignment. As a result, the extremely small anisotropy of the coating film 1 induced by the photo-crosslinking reaction is amplified by heat, so that it gives greater anisotropy than the coating film 1.

同樣地，於本實施之第1形態，在[II]步驟之紫外線照射量係將△A成為最大之紫外線照射量的15%~70%範圍內時，加熱偏光照射後之塗膜3，而成為液晶狀態。如此則如圖2(c)所示，於側鏈型高分子膜3，於與照射紫外線之偏光方向的平行方向與垂直方向之間，所產生之交聯反應的量不同。因此，於與照射紫外線之偏光方向平行的方向包含經自我組織化之液晶基成分之側鏈4進行再配向。其結果，於光交聯反應所誘導之塗膜3之小的各向異性，藉由熱而增幅，成為賦予比塗膜3更大的各向異性。 Similarly, in the first aspect of the present embodiment, when the ultraviolet irradiation amount in the step [II] is within a range of 15% to 70% of the maximum ultraviolet irradiation amount, ΔA is heated, and the coating film 3 after the polarized light irradiation is heated, and It becomes a liquid crystal state. In this way, as shown in FIG. 2 (c), in the side chain polymer film 3, the amount of the cross-linking reaction generated is different between the parallel direction and the vertical direction with the polarization direction of the ultraviolet rays. Therefore, the side chains 4 including the self-organized liquid crystal-based component are aligned in a direction parallel to the polarization direction of the ultraviolet rays. As a result, the small anisotropy of the coating film 3 induced by the photo-crosslinking reaction is increased by heat, and it is given a greater anisotropy than the coating film 3.

同樣地，於本實施之第2形態，使用光異構化性基、或上述之具有式(18)所示之光弗賴斯重排基構造之側鏈型高分子之塗膜，在[II]步驟之紫外線照射量係將△A成為最大之紫外線照射量的1%~70%範圍內時，加熱偏光照射後之塗膜5，而成為液晶狀態。如此則如圖3(c)所示，於塗膜5，於與照射紫外線之偏光方向的平行方向與垂直方向之間，所產生之光弗賴斯重排反應的量不同。此時，因為於與照射紫外線之偏光方向垂直的方向所產生之光弗賴斯重排體的液晶配向力係比反應前之側鏈的液晶配向力更強，於與照射紫外線之偏光方向垂直的方 向包含經自我組織化之液晶基成分之側鏈6進行再配向。其結果，以光弗賴斯重排反應所誘導之塗膜5之非常小的各向異性，藉由熱而增幅，成為賦予比塗膜5更大的各向異性。 Similarly, in the second aspect of the present embodiment, a photo-isomerizable group or a coating film of a side chain polymer having a light Friss rearrangement group structure represented by the formula (18) described above is used. II] The ultraviolet irradiation amount in the step is that when ΔA is within the range of 1% to 70% of the maximum ultraviolet irradiation amount, the coating film 5 after the polarized light irradiation is heated to become a liquid crystal state. In this way, as shown in FIG. 3 (c), in the coating film 5, the amount of light Fries rearrangement reaction generated is different between the parallel direction and the vertical direction with the polarization direction of the ultraviolet rays. At this time, the liquid crystal alignment force of the Friesian rearrangement is lighter than the liquid crystal alignment force of the side chain before the reaction, and is perpendicular to the polarization direction of the ultraviolet light. Fang Realignment is performed to the side chain 6 containing the self-organized liquid crystal-based component. As a result, the very small anisotropy of the coating film 5 induced by the light-Fries rearrangement reaction is increased by heat, and it is given a greater anisotropy than the coating film 5.

同樣地，於本實施之第2形態，使用上述之式(19)所示之使用具有光弗賴斯重排基構造之側鏈型高分子之塗膜，在[II]步驟之紫外線照射量係將△A成為最大之紫外線照射量的1%~70%範圍內時，加熱偏光照射後之塗膜7，而成為液晶狀態。如此則如圖4(c)所示，於側鏈型高分子膜7，於與照射紫外線之偏光方向的平行方向與垂直方向之間，所產生之光弗賴斯重排反應的量不同。因為光弗賴斯重排體8(a)之錨定力比轉位前之側鏈8更強，產生一定量以上之光弗賴斯重排體時，於與照射紫外線之偏光方向平行的方向包含經自我組織化之液晶基成分之側鏈8進行再配向。其結果，以光弗賴斯重排反應所誘導之塗膜7之小的各向異性，藉由熱而增幅，成為賦予比塗膜7更大的各向異性。 Similarly, in the second aspect of the present embodiment, a coating film using a side chain polymer having a light-Fries rearrangement structure shown in the above formula (19) is used, and the amount of ultraviolet radiation in step [II] When ΔA is within the range of 1% to 70% of the maximum ultraviolet irradiation amount, the coating film 7 after polarized light irradiation is heated to become a liquid crystal state. In this way, as shown in FIG. 4 (c), in the side chain polymer film 7, the amount of the light Fries rearrangement reaction generated is different between the parallel direction and the vertical direction with the polarization direction of the ultraviolet rays. Because the light Frisian rearrangement body 8 (a) has stronger anchoring force than the side chain 8 before transposition, when a certain amount of light Frisian rearrangement body is generated, it is parallel to the direction of polarized light irradiated by ultraviolet rays. The side chains 8 containing self-organized liquid crystal-based components are realigned. As a result, the small anisotropy of the coating film 7 induced by the photo-Fries rearrangement reaction is increased by heat, and it is given a greater anisotropy than the coating film 7.

據此，本發明之方法所用之塗膜係藉由依序進行對塗膜之經偏光之紫外線照射與加熱處理，高效率地導入各向異性，可成為配向控制功能優異之液晶配向膜。 According to this, the coating film used in the method of the present invention can be a liquid crystal alignment film with excellent alignment control function by sequentially introducing anisotropy into the coating film by sequentially performing polarized ultraviolet irradiation and heating treatment on the coating film.

而且，於本發明之方法所用之塗膜，對塗膜之經偏光之紫外線的照射量、與在加熱處理之加熱溫度進行最佳化。並藉由此可實現高效率地對塗膜之各向異性的導入。 In addition, the coating film used in the method of the present invention optimizes the irradiation amount of the polarized ultraviolet rays of the coating film and the heating temperature in the heat treatment. In this way, the anisotropy of the coating film can be introduced efficiently.

於對本發明所使用之塗膜之高效率各向異性的導入，最適當之偏光紫外線的照射量，係在其塗膜中進行最適當之感光性基將光交聯反應或光異構化反應、或是光弗賴斯重排反應之量對應於偏光紫外線的照射量。對於本發明所使用之塗膜照射經偏光之紫外線之結果，進行光交聯反應或光異構化反應、或是光弗賴斯重排反應之側鏈的感光性基為少時，無法成為充分之光反應量。在此情況下，之後即使再進行加熱亦無法進行充分之自我組織化。另外，於本發明所使用之塗膜，對於具有光交聯性基之構造照射經偏光之紫外線之結果，進行交聯反應之側鏈的感光性基成為過剩時，於側鏈間之交聯反應變成過度進行。在此情況下，所得到之膜變為剛直，由於其後之加熱有時變成妨礙自我組織化的進行。又，於本發明所使用之塗膜，對於具有光弗賴斯重排基之構造照射經偏光之紫外線之結果，進行光弗賴斯重排反應之側鏈的感光性基成為過剩時，塗膜之液晶性變成過低。在此情況下，所得到膜之液晶性亦低迷，由於其後之加熱有時變成妨礙自我組織化的進行。進而，對於具有光弗賴斯重排基之構造照射經偏光之紫外線的情況，紫外線的照射量過多時，側鏈型高分子進行光分解，由於其後之加熱有時變成妨礙自我組織化的進行。 For the introduction of the highly efficient anisotropy of the coating film used in the present invention, the most appropriate irradiation amount of polarized ultraviolet light is to perform the most appropriate photosensitive group in the coating film to photocrosslink or react isomerization. Or the amount of light-Fries rearrangement reaction corresponds to the amount of polarized ultraviolet radiation. When the coating film used in the present invention is irradiated with polarized ultraviolet rays, when the photo-crosslinking reaction, photoisomerization reaction, or photo-Fries rearrangement reaction has a small number of photosensitive groups on the side chain, it cannot become Sufficient light response. In this case, even if heating is subsequently performed, sufficient self-organization cannot be performed. In addition, in the coating film used in the present invention, when a structure having a photo-crosslinkable group is irradiated with polarized ultraviolet light, when the photosensitive group of the side chain undergoing the cross-linking reaction becomes excessive, cross-linking between the side chains The reaction became excessive. In this case, the obtained film becomes rigid, and the subsequent heating sometimes hinders the progress of self-organization. In addition, in the coating film used in the present invention, when the structure having a photo-Fries rearrangement group is irradiated with polarized ultraviolet light, when the photosensitive group of the side chain undergoing the photo-Fries rearrangement reaction becomes excessive, the coating is applied. The liquid crystallinity of the film becomes too low. In this case, the liquid crystallinity of the obtained film is also low, and subsequent heating may sometimes hinder the progress of self-organization. Furthermore, in the case where a structure having a light-Fries rearrangement is irradiated with polarized ultraviolet light, when the amount of ultraviolet radiation is excessive, the side chain polymer undergoes photodecomposition, and subsequent heating may sometimes prevent self-organization. get on.

據此，在本發明所使用之塗膜，藉由偏光紫外線之照射，側鏈之感光性基進行光交聯反應或光異構化反應、或是光弗賴斯重排反應最適當之量，以其側鏈型高 分子膜成為具有感光性基之0.1莫耳%~40莫耳%為佳，以成為0.1莫耳%~20莫耳%更佳。藉由將進行光反應之側鏈之感光性基的量成定為於如此之範圍，於其後有效率地進行加熱之自我組織化，使於膜中高效率之各向異性的形成變為可能。 Accordingly, in the coating film used in the present invention, the most appropriate amount of the photo-crosslinking reaction or the photo-isomerization reaction or the photo-Fries rearrangement reaction of the photosensitive group of the side chain by irradiation of polarized ultraviolet rays. High The molecular film is preferably 0.1 mol% to 40 mol% with a photosensitive group, and more preferably 0.1 mol% to 20 mol%. By setting the amount of the photosensitive group of the side chain that undergoes the photoreaction to be in such a range, and then efficiently self-organizing by heating, it becomes possible to form a highly efficient anisotropy in the film. .

於本發明之方法所用之塗膜，藉由經偏光之紫外線的照射量之最佳化，在側鏈型高分子膜之側鏈，進行最佳化感光性基之光交聯反應或光異構化反應、或光弗賴斯重排反應的量。而且，合法其後之加熱處理，實現高效率地對本發明所使用之塗膜之各向異性的導入。在此情況下，對於適當之偏光紫外線的量，基於本發明所使用之塗膜的紫外吸收之評價有可能進行。 The coating film used in the method of the present invention optimizes the photocrosslinking reaction or photoisolation of the photosensitive group on the side chain of the side chain polymer film by optimizing the irradiation amount of polarized ultraviolet light. The amount of a chemical reaction, or a photo-Fries rearrangement reaction. In addition, the subsequent heat treatment allows efficient introduction of the anisotropy of the coating film used in the present invention. In this case, it is possible to perform an evaluation based on the ultraviolet absorption of the coating film used for the appropriate amount of polarized ultraviolet rays.

亦即，對於本發明所使用之塗膜，分別測定偏光紫外線照射後之與經偏光之紫外線之偏光方向平行的方向之紫外線吸收、與垂直的方向之紫外線吸收。從紫外吸收的測定結果，在其塗膜，評價△A，其係與經偏光之紫外線之偏光方向平行的方向之紫外線吸光度與垂直的方向之紫外線吸光度的差。而且，在本發明所使用之塗膜求得經實現之△A的最大值(△Amax)與實現其之偏光紫外線的照射量。於本發明之製造方法，將實現此△Amax之偏光紫外線照射量作為基準，在液晶配向膜之製造進行照射，可決定較佳量之經偏光之紫外線量。 That is, for the coating film used in the present invention, the ultraviolet absorption in a direction parallel to the polarization direction of the polarized ultraviolet radiation and the ultraviolet absorption in a vertical direction after the polarized ultraviolet radiation were measured. From the measurement result of ultraviolet absorption, ΔA was evaluated on the coating film, which is the difference between the ultraviolet absorbance in a direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in a vertical direction. In addition, in the coating film used in the present invention, the realized maximum value of ΔA (ΔAmax) and the amount of polarized ultraviolet radiation to achieve it were obtained. In the manufacturing method of the present invention, the amount of polarized ultraviolet rays that achieves this ΔAmax is used as a reference, and the irradiation of the liquid crystal alignment film is performed to determine a preferable amount of polarized ultraviolet rays.

本發明之製造方法，將對本發明所使用之塗膜之經偏光之紫外線的照射量，以成為實現△Amax之偏 光紫外線的量1%~70%範圍內為佳，以成為1%~50%之範圍內更佳。在本發明所使用之塗膜，實現△Amax之偏光紫外線的量之1%~50%範圍內之偏光紫外線的照射量，係相當於使該側鏈型高分子膜之具有感光性基整體之0.1莫耳%~20莫耳%進行光交聯反應之偏光紫外線的量。 The manufacturing method of the present invention will irradiate the polarized ultraviolet rays of the coating film used in the present invention so as to achieve the ΔAmax bias. The amount of light ultraviolet is preferably within a range of 1% to 70%, and more preferably within a range of 1% to 50%. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet rays in the range of 1% to 50% of the amount of polarized ultraviolet rays of △ Amax is equivalent to that of the side chain polymer film having a photosensitive group as a whole. 0.1 mol% to 20 mol% The amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.

由以上，於本發明之製造方法，為了實現對塗膜之高效率各向異性的導入，將該側鏈型高分子之液晶溫度範圍作為基準，定為如上述之適當加熱溫度即可。據此，例如本發明所使用之側鏈型高分子之液晶溫度範圍為100℃~200℃時，期望偏光紫外線照射後之加熱溫度成為90℃~190℃。藉由如此進行，在本發明所使用之塗膜，變成被賦予更大的各向異性。 From the above, in the manufacturing method of the present invention, in order to achieve the introduction of high-efficiency anisotropy in the coating film, the liquid crystal temperature range of the side chain polymer may be used as a reference, and the appropriate heating temperature may be set as described above. According to this, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 100 ° C. to 200 ° C., it is desirable that the heating temperature after polarized ultraviolet light irradiation is 90 ° C. to 190 ° C. By doing so, the coating film used in the present invention is given greater anisotropy.

藉由如此進行，藉由本發明所提供之液晶顯示元件對於光或熱等之外部壓力變成展示高度信賴性。 By doing so, the liquid crystal display element provided by the present invention exhibits high reliability against external pressure such as light or heat.

如以上之進行，藉由本發明之方法所製造之橫向電場驅動型液晶顯示元件用基板或具有該基板之橫向電場驅動型液晶顯示元件，成為信賴性優異者，可適合利用在以大螢幕之高精細液晶電視等。 As described above, the substrate for a lateral electric field drive type liquid crystal display element manufactured by the method of the present invention or a lateral electric field drive type liquid crystal display element having the substrate becomes a person with excellent reliability and can be suitably used in a high screen. Fine LCD TV and more.

[實施例] [Example]

於實施例所使用之簡稱如以下所述。 The abbreviations used in the examples are as follows.

(甲基丙烯醯基單體) (Methacryl fluorenyl monomer)

MA1係以專利文獻(WO2011-084546)所記載之合成法合成。 MA1 is synthesized by a synthesis method described in a patent document (WO2011-084546).

MA2係以專利文獻(日本特開平9-118717)所記載之合成法合成。 MA2 is synthesized by a synthesis method described in a patent document (Japanese Patent Application Laid-Open No. 9-118717).

MA3係以非專利文獻(Macromolecules 2002,35,706-713)所記載之合成法合成。 MA3 was synthesized by a synthesis method described in a non-patent literature (Macromolecules 2002, 35, 706-713).

MA4係文獻等未公開之新穎化合物，於以下之合成例1詳述其合成法。 MA4 is a novel compound not disclosed in the literature. The synthesis method will be described in detail in Synthesis Example 1 below.

MA5係以專利文獻(日本特開2010-18807)所記載之合成法合成。 MA5 is synthesized by a synthesis method described in a patent document (Japanese Patent Laid-Open No. 2010-18807).

MA6~MA9係文獻等未公開之新穎化合物，於以下之合成例2~5詳述其合成法。 MA6 ~ MA9 are novel compounds not disclosed in the literature, etc. The synthesis methods are detailed in Synthesis Examples 2 to 5 below.

MA10係使用可購入市售之M6BC(綠化學股份有限公司製)。 MA10 uses commercially available M6BC (manufactured by Green Chemical Co., Ltd.).

MA11~13係文獻等未公開之新穎化合物，於以下之合成例6~8詳述其合成法。 MA11 ~ 13 are unpublished novel compounds such as literature. The synthesis methods are detailed in Synthesis Examples 6 to 8 below.

MA14~18係可購入市售，分別使用M4CA、M4BA、M2CA、M3CA、及M5CA(此等皆為綠化學股份有限公司製)。 MA14 ~ 18 series are commercially available, using M4CA, M4BA, M2CA, M3CA, and M5CA (all of which are manufactured by Green Chemical Co., Ltd.).

MA19~23係文獻等未公開之新穎化合物，於以下之合成例9~13詳述其合成法。 MA19 ~ 23 are unpublished novel compounds such as literature. The synthesis methods are detailed in the following Synthesis Examples 9-13.

MA24係以非專利文獻(Polymer Journal,Vol.29,No.4,pp303-308(1997))所記載之合成方法進行合成。 MA24 was synthesized by a synthesis method described in a non-patent literature (Polymer Journal, Vol. 29, No. 4, pp303-308 (1997)).

MA25係文獻等未公開之新穎化合物，於以下之合成例14詳述其合成法。 MA25 is a novel compound not disclosed in the literature. The synthesis method is described in detail in Synthesis Example 14 below.

MA26及MA27各別於非專利文獻(Macromolecules(2012),45(21),8547-8554)、非專利文獻(Liquid Crystals(1995),19(4),433-40)所記載之合成方法進 行合成。 MA26 and MA27 are different from the synthesis methods described in non-patent literature (Macromolecules (2012), 45 (21), 8547-8554) and non-patent literature (Liquid Crystals (1995), 19 (4), 433-40). Line synthesis.

MA28~33係文獻等未公開之新穎化合物，於以下之合成例15~20詳述其合成法。 MA28 ~ 33 are unpublished novel compounds such as literature. The synthesis methods are detailed in Synthesis Examples 15-20 below.

MA34~39係文獻等未公開之新穎化合物，於以下之合成例21~26詳述其合成法。 MA34 ~ 39 are unpublished novel compounds such as literature. The synthesis methods are detailed in the following Synthesis Examples 21-26.

MA40及41係以專利文獻(日本特表2009-511431號)所記載之合成方法進行合成。 MA40 and 41 were synthesized by a synthesis method described in a patent document (Japanese Patent Application No. 2009-511431).

MA42係文獻等未公開之新穎化合物，於以下之合成例27詳述其合成法。 MA42 is a novel compound not disclosed in the literature. The synthesis method is described in detail in Synthesis Example 27 below.

MA43係以專利文獻(WO2012-115129)所記載之合成方法進行合成。 MA43 was synthesized by a synthesis method described in a patent document (WO2012-115129).

MA44係以專利文獻(WO2013-133078)所記載之合成方法進行合成。 MA44 was synthesized by a synthesis method described in a patent document (WO2013-133078).

MA45係以專利文獻(WO2008-072652)所記載之合成方法進行合成。 MA45 was synthesized by a synthesis method described in a patent document (WO2008-072652).

MA46係文獻等未公開之新穎化合物，於以下之合成例28詳述其合成法。 MA46 is a novel compound not disclosed in the literature. The synthesis method is described in Synthesis Example 28 below.

<合成例1> <Synthesis example 1> 化合物[MA4]之合成 Synthesis of compound [MA4]

於3L四口燒瓶，加入4-溴-4’-羥基聯苯基[MA4-1](150g、0.60mol)、丙烯酸tert-丁基[MA4-2](162g、1.3mol)、乙酸鈀(2.7g、12mmol)、三(o-甲苯基)膦(7.3g、24mmol)、三丁基胺(334g、1.8mol)、N,N-二甲基乙醯胺(750g)，於100℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止之後，將反應溶液冷卻至室溫附近後，注入1.8L 1M鹽酸水溶液。於此加入乙酸乙酯(1L)，在分液操作去除水層。將有機層以1L 10%鹽酸水溶液進行2次、以1L飽和食鹽水進行3次洗淨之後，將有機層以硫酸鎂乾燥。然後藉由過濾、在蒸發器進行溶劑餾除，得到作為油狀化合物之174g化合物[MA4-3](收率98%)。 In a 3L four-necked flask, 4-bromo-4'-hydroxybiphenyl [MA4-1] (150g, 0.60mol), tert-butyl [MA4-2] acrylic acid (162g, 1.3mol), and palladium acetate ( 2.7 g, 12 mmol), tris (o-tolyl) phosphine (7.3 g, 24 mmol), tributylamine (334 g, 1.8 mol), N, N-dimethylacetamide (750 g), performed at 100 ° C Heat and stir. The reaction was followed by HPLC to confirm the termination of the reaction. After cooling the reaction solution to around room temperature, 1.8 L of a 1 M aqueous hydrochloric acid solution was injected. Ethyl acetate (1 L) was added thereto, and the aqueous layer was removed in a liquid separation operation. After the organic layer was washed twice with 1 L of a 10% aqueous hydrochloric acid solution and three times with 1 L of a saturated saline solution, the organic layer was dried over magnesium sulfate. Then, 174 g of a compound [MA4-3] was obtained as an oily compound by filtration and solvent distillation in an evaporator (yield: 98%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：9.68(1H,S),7.72(2H,d),7.63(2H,d),7.59-7.55(9H,m),6.87-6.85(2H,m),1.44(9H,s)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 9.68 (1H, S), 7.72 (2H, d), 7.63 (2H, d), 7.59-7.55 (9H, m), 6.87-6.85 (2H , m), 1.44 (9H, s).

於配備機械攪拌器、攪拌羽之2L四口燒瓶加入於上述所得之化合物[MA4-3](174g、0.59mol)、6-氯-1-己醇(96.7g、0.71mol)、碳酸鉀(163g、1.2mol)、碘化鉀(9.8g、59mmol)、N,N-二甲基甲醯胺(1600g) ，於80℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液冷卻至室溫附近後，於2L蒸餾水注入反應溶液。濾別所析出之固體後，注入於甲醇/蒸餾水(1：1)溶液，再度進行濾別。藉由減壓乾燥所得到之固體，得到221g化合物[MA4-4](收率95%)。 In a 2 L four-neck flask equipped with a mechanical stirrer and a stirring feather, the compound [MA4-3] (174 g, 0.59 mol), 6-chloro-1-hexanol (96.7 g, 0.71 mol), and potassium carbonate ( 163g, 1.2mol), potassium iodide (9.8g, 59mmol), N, N-dimethylformamide (1600g) , And heat and stir at 80 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was cooled to around room temperature, and then the reaction solution was poured into 2 L of distilled water. After filtering off the precipitated solid, it was poured into a methanol / distilled water (1: 1) solution, and filtered again. The obtained solid was dried under reduced pressure to obtain 221 g of a compound [MA4-4] (yield: 95%).

1H-NMR(400MHz,CDCl3,δ ppm)：7.61(1H,d),7.56-7.52(6H,m),6.98-6.95(2H,m),6.38(1H,d),4.02(2H,t),3.67(2H,t),1.84-1.44(17H,m)。 1 H-NMR (400MHz, CDCl 3 , δ ppm): 7.61 (1H, d), 7.56-7.52 (6H, m), 6.98-6.95 (2H, m), 6.38 (1H, d), 4.02 (2H, t), 3.67 (2H, t), 1.84-1.44 (17H, m).

於3L四口燒瓶加入於上述所得之化合物[MA4-4](221g、0.56mol)、三乙基胺(67.7g、0.67mol)、四氫呋喃(1800g)，並冷卻反應溶液。還有，將甲基丙烯醯氯(70.0g、0.67mmol)之四氫呋喃(200g)溶液一邊注意內溫不超過10℃一邊滴下。滴下終止後，將反應溶液進一步於23℃進行反應。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於6L蒸餾水，加入2L乙酸乙酯，於分液操作去除水層。然後，以5%氫氧化鉀水溶液、1M鹽酸水溶液、飽和食鹽水順序洗淨有機層，將有機層以硫酸鎂乾燥。然後過濾，以蒸發器溶劑餾除而得到粗產物。將所得到之粗產物以100g 2-丙醇洗淨，藉由進行過濾、乾燥，得到127g化合物[MA4-5](收率49%)。 The compound [MA4-4] (221 g, 0.56 mol), triethylamine (67.7 g, 0.67 mol), and tetrahydrofuran (1800 g) were added to a 3 L four-necked flask, and the reaction solution was cooled. In addition, a solution of methacrylic acid chloride (70.0 g, 0.67 mmol) in tetrahydrofuran (200 g) was dropped while taking care that the internal temperature did not exceed 10 ° C. After the dropping was completed, the reaction solution was further reacted at 23 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was poured into 6 L of distilled water, 2 L of ethyl acetate was added, and the aqueous layer was removed in a liquid separation operation. Then, the organic layer was washed sequentially with a 5% potassium hydroxide aqueous solution, a 1M hydrochloric acid aqueous solution, and a saturated saline solution, and the organic layer was dried over magnesium sulfate. It was then filtered and distilled off in an evaporator to obtain the crude product. The obtained crude product was washed with 100 g of 2-propanol, and then filtered and dried to obtain 127 g of a compound [MA4-5] (yield: 49%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：7.73(2H,d),7.70-7.63(4H,m),7.58(1H,d),7.02-7.00(2H,m),6.53(1H,d),6.03-6.02(1H,m),5.67-5.66(1H, m),4.11(2H,t),4.00(2H,t),1.88-1.87(3H,m),1.79-1.25(17H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 7.73 (2H, d), 7.70-7.63 (4H, m), 7.58 (1H, d), 7.02-7.00 (2H, m), 6.53 (1H , d), 6.03-6.02 (1H, m), 5.67-5.66 (1H, m), 4.11 (2H, t), 4.00 (2H, t), 1.88-1.87 (3H, m), 1.79-1.25 (17H , m).

於1L四口燒瓶加入於上述所得之化合物[MA4-5](81g、0.17mol)、蟻酸(400g)，於40℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入3L蒸餾水進行過濾。將所得到之固體以甲醇200g進行洗淨，藉由使固體乾燥而得到56g化合物[MA4](收率79%)。 The compound [MA4-5] (81 g, 0.17 mol) and formic acid (400 g) obtained above were added to a 1 L four-necked flask, and the mixture was heated and stirred at 40 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was poured into 3 L of distilled water and filtered. The obtained solid was washed with 200 g of methanol, and the solid was dried to obtain 56 g of a compound [MA4] (yield: 79%).

1H-NMR(400MHz,CDCl3,δ ppm)：7.81(1H,d),7.60(4H,s),7.55(2H,d),6.97(2H,d),6.47(2H,d),6.11-6.10(1H,m),5.56-5.52(1H,m),4.17(2H,t),4.00(2H,t),1.95-1.94(2H,m),1.85-1.82(3H,m),1.75-1.71(2H,m),1.55-1.48(4H,m)。 1 H-NMR (400MHz, CDCl 3 , δ ppm): 7.81 (1H, d), 7.60 (4H, s), 7.55 (2H, d), 6.97 (2H, d), 6.47 (2H, d), 6.11 -6.10 (1H, m), 5.56-5.52 (1H, m), 4.17 (2H, t), 4.00 (2H, t), 1.95-1.94 (2H, m), 1.85-1.82 (3H, m), 1.75 -1.71 (2H, m), 1.55-1.48 (4H, m).

<合成例2> <Synthesis example 2> 化合物[MA6]之合成 Synthesis of compound [MA6]

於1L四口燒瓶，加入甲基丙烯酸2-羥乙酯[MA6-1](63.42g、487mmol)、異菸鹼酸鹽酸鹽[MA6-2](50.00g、406mmol)、1-(3-二甲基胺基丙基)-3-乙基 碳二醯亞胺鹽酸鹽(以下省略為EDC)(93.43g、487mmol)、4-二甲基胺基吡啶(以下省略為DMAP)(4.96g、40.6mmol)、THF(500g)並於23℃進行反應。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於蒸餾水(3L)，並加入乙酸乙酯(1L)，於分液操作去除水層。將有機層以蒸餾水(1L)洗淨2次之後，將有機層以硫酸鎂乾燥。然後藉由過濾，於蒸發器進行溶劑餾除，得到作為油狀化合物之86.3g化合物[MA6](收率93%)。 In a 1L four-neck flask, add 2-hydroxyethyl methacrylate [MA6-1] (63.42 g, 487 mmol), isonicotinyl hydrochloride [MA6-2] (50.00 g, 406 mmol), 1- (3 -Dimethylaminopropyl) -3-ethyl Carbodiimide hydrochloride (hereinafter abbreviated as EDC) (93.43 g, 487 mmol), 4-dimethylaminopyridine (hereinafter abbreviated as DMAP) (4.96 g, 40.6 mmol), THF (500 g) The reaction was carried out at ° C. The reaction was tracked by HPLC. After confirming the termination of the reaction, the reaction solution was poured into distilled water (3L), ethyl acetate (1L) was added, and the aqueous layer was removed in a liquid separation operation. After the organic layer was washed twice with distilled water (1 L), the organic layer was dried over magnesium sulfate. Then, the solvent was distilled off in an evaporator by filtration to obtain 86.3 g of a compound [MA6] as an oily compound (yield: 93%).

1H-NMR(400MHz,CDCl3,δ ppm)：8.80(2H,dd),7.85(2H,dd),6.14-6.12(1H,m),5.62-5.60(1H,m),4.63-4.61(2H,m),4.52-4.50(2H,m),1.96-1.95(3H,m)。 1 H-NMR (400MHz, CDCl3, δ ppm): 8.80 (2H, dd), 7.85 (2H, dd), 6.14-6.12 (1H, m), 5.62-5.60 (1H, m), 4.63-4.61 (2H m), 4.52-4.50 (2H, m), 1.96-1.95 (3H, m).

<合成例3> <Synthesis example 3> 化合物[MA7]之合成 Synthesis of compound [MA7]

於200mL四口燒瓶，加入化合物[MA7-1](20.00g、86.9mmol)、4-羥基吡啶(8.26g、86.9mmol)、EDC(20.00g、104mmol)、DMAP (1.06g、8.7mmol)、THF(80g)並於23℃進行反應。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於蒸餾水(800mL)，並加入乙酸乙酯(500mL)，於分液操作去除水層。將有機層以蒸餾水(300mL)洗淨3次之後，將有機層以硫酸鎂乾燥。然後藉由過濾，在蒸發器進行溶劑餾除，而得到作為油狀化合物之23.1g化合物[MA6](收率87%)。 In a 200 mL four-necked flask, compound [MA7-1] (20.00 g, 86.9 mmol), 4-hydroxypyridine (8.26 g, 86.9 mmol), EDC (20.00 g, 104 mmol), and DMAP were added. (1.06 g, 8.7 mmol), THF (80 g), and reacted at 23 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was poured into distilled water (800 mL), ethyl acetate (500 mL) was added, and the aqueous layer was removed in a liquid separation operation. After the organic layer was washed three times with distilled water (300 mL), the organic layer was dried over magnesium sulfate. Then, the solvent was distilled off in an evaporator by filtration to obtain 23.1 g of a compound [MA6] as an oily compound (yield: 87%).

1H-NMR(400MHz,CDCl3,δ ppm)：8.50-8.48(1H,m),8.44-8.43(1H,m),7.51-7.48(1H,m),7.35-7.32(1H,m),6.18-6.12(1H,m),5.91-5.58(1H,m),4.41-4.35(4H,m),2.95-2.92(2H,m),2.81-2.78(2H,m),2.05-1.93(3H,m) 1 H-NMR (400MHz, CDCl3, δ ppm): 8.50-8.48 (1H, m), 8.44-8.43 (1H, m), 7.51-7.48 (1H, m), 7.35-7.32 (1H, m), 6.18 -6.12 (1H, m), 5.91-5.58 (1H, m), 4.41-4.35 (4H, m), 2.95-2.92 (2H, m), 2.81-2.78 (2H, m), 2.05-1.93 (3H, m)

<合成例4> <Synthesis example 4> 化合物[MA8]之合成 Synthesis of compound [MA8]

除了將於合成例2所使用之異菸鹼酸鹽酸鹽[MA6-2]變更為菸鹼酸鹽酸鹽[MA8-1]之外其他與合成例2進行同樣的操作，得到作為油狀化合物之80.13g化合物 [MA8](收率86%)。 The same operation as in Synthesis Example 2 was performed, except that the isonicotinate hydrochloride [MA6-2] used in Synthesis Example 2 was changed to nicotinate hydrochloride [MA8-1], and it was obtained as an oil. 80.13g of compound [MA8] (yield 86%).

1H-NMR(400MHz,CDCl3,δ ppm)：9.24-9.23(1H,m),8.80(1H,dd),8.32-8.29(1H,m),7.43-7.40(1H,m),6.16-6.14(1H,m),5.62-5.60(1H,m),4.64-4.61(2H,m),4.52-4.51(2H,m),1.97-1.95(3H,m)。 1 H-NMR (400MHz, CDCl3, δ ppm): 9.24-9.23 (1H, m), 8.80 (1H, dd), 8.32-8.29 (1H, m), 7.43-7.40 (1H, m), 6.16-6.14 (1H, m), 5.62-5.60 (1H, m), 4.64-4.61 (2H, m), 4.52-4.51 (2H, m), 1.97-1.95 (3H, m).

<合成例5> <Synthesis example 5> 化合物[MA9]之合成 Synthesis of compound [MA9]

於500mL四口燒瓶，加入化合物[MA2](20.00g、65.3mmol)、化合物[MA9-1](14.09g、71.8mmol)、EDC(15.02g、78.4mmol)、DMAP(0.80g、6.53mmol)、THF(200g)並於23℃進行反應。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於蒸餾水(1.2L)，並加入乙酸乙酯(2L)，於分液操作去除水層。將有機層以蒸餾水(500mL)洗淨3次之後，將有機層以硫酸鎂乾燥。然後藉由過濾，於蒸發器進行溶劑餾除，得到作為油狀化合物之化合物[MA9-2]。 In a 500 mL four-necked flask, compound [MA2] (20.00 g, 65.3 mmol), compound [MA9-1] (14.09 g, 71.8 mmol), EDC (15.02 g, 78.4 mmol), DMAP (0.80 g, 6.53 mmol) were added. , THF (200 g), and reacted at 23 ° C. The reaction was tracked by HPLC. After confirming the termination of the reaction, the reaction solution was poured into distilled water (1.2 L), ethyl acetate (2 L) was added, and the aqueous layer was removed in a liquid separation operation. After the organic layer was washed three times with distilled water (500 mL), the organic layer was dried over magnesium sulfate. Then, the solvent was distilled off in an evaporator by filtration to obtain a compound [MA9-2] as an oily compound.

接著，於所得到之化合物[MA9-2]加入吡啶陽 離子(Pyridinium)p-甲苯磺酸(表記為PPTS)(1.59g、6.3mmol)、乙醇(100g)，於60℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液於冰浴冷卻，過濾所析出之固體，以乙醇洗淨。藉由減壓乾燥所得到之固體，得到19.2g化合物[MA9](收率69%)。 Next, pyridine is added to the obtained compound [MA9-2]. Pyridinium p-toluenesulfonic acid (designated as PPTS) (1.59 g, 6.3 mmol) and ethanol (100 g) were heated and stirred at 60 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was cooled in an ice bath, and the precipitated solid was filtered and washed with ethanol. The obtained solid was dried under reduced pressure to obtain 19.2 g of a compound [MA9] (yield: 69%).

1H-NMR(400MHz,CDCl3,δ ppm)：8.22-8.18(2H,m),8.17-8.14(2H,m),7.36-7.32(2H,m),7.00-6.96(2H,m),6.12-6.11(1H,m),5.57-5.55(1H,m),4.20-4.16(2H,m),4.06(2H,t),1.96-1.95(3H,m),1.90-1.46(8H,m)。 1 H-NMR (400MHz, CDCl3, δ ppm): 8.22-8.18 (2H, m), 8.17-8.14 (2H, m), 7.36-7.32 (2H, m), 7.00-6.96 (2H, m), 6.12 -6.11 (1H, m), 5.57-5.55 (1H, m), 4.20-4.16 (2H, m), 4.06 (2H, t), 1.96-1.95 (3H, m), 1.90-1.46 (8H, m) .

<合成例6> <Synthesis example 6> 化合物[MA11]之合成 Synthesis of compound [MA11]

於2L四口燒瓶，加入化合物[MA11-1](50.00g、256mmol)、6-氯-1-己醇(36.74g、268mmol)、碳酸鉀(106.2g、768mmol)、碘化鉀(21.3g、128mmol)、DMF(500g)並於85℃進行加熱反應。於HPLC進行反應追蹤，確認反應終止後，將反應 溶液注入於蒸餾水(3L)，並過濾，以蒸餾水得到洗淨之粗產物。然後，將所得到之粗產物以甲醇洗淨並過濾，得到61.9g減壓乾燥之化合物[MA11-2](收率82%)。 In a 2L four-necked flask, compound [MA11-1] (50.00g, 256mmol), 6-chloro-1-hexanol (36.74g, 268mmol), potassium carbonate (106.2g, 768mmol), and potassium iodide (21.3g, 128mmol) were added. ), DMF (500 g) and heating reaction at 85 ° C. The reaction was tracked by HPLC. After confirming the termination of the reaction, the reaction was The solution was poured into distilled water (3 L) and filtered to obtain a washed crude product with distilled water. Then, the obtained crude product was washed with methanol and filtered to obtain 61.9 g of the compound [MA11-2] dried under reduced pressure (yield: 82%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：7.89-7.84(4H,m),7.72-7.68(2H,m),7.07-7.03(2H,m),4.37(1H,brs),4.07-4.00(2H,m),3.42-3.38(2H,m),1.77-1.29(8H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 7.89-7.84 (4H, m), 7.72-7.68 (2H, m), 7.07-7.03 (2H, m), 4.37 (1H, brs), 4.07 -4.00 (2H, m), 3.42-3.38 (2H, m), 1.77-1.29 (8H, m).

於2L四口燒瓶加入於上述所得之化合物[MA11-2](61.9g、210mol)、三乙基胺(25.45g、252mol)、THF(520g)，冷卻反應溶液。還有，將甲基丙烯醯氯(26.3g、252mmol)之THF(120g)溶液一邊注意內溫不超過10℃一邊滴下。滴下終止後，將反應溶液進一步於23℃進行反應。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於4L蒸餾水，濾別析出之固體。將所得到之粗產物以甲醇洗淨後，進行減壓乾燥得到47.5g化合物[MA11](收率77%)。 The compound [MA11-2] (61.9 g, 210 mol), triethylamine (25.45 g, 252 mol), and THF (520 g) were added to a 2 L four-necked flask, and the reaction solution was cooled. In addition, a solution of methacrylic acid chloride (26.3 g, 252 mmol) in THF (120 g) was dropped while taking care that the internal temperature did not exceed 10 ° C. After the dropping was completed, the reaction solution was further reacted at 23 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was poured into 4 L of distilled water, and the precipitated solid was filtered. The obtained crude product was washed with methanol and then dried under reduced pressure to obtain 47.5 g of a compound [MA11] (yield 77%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：7.89-7.86(2H,m),7.84-7.82(2H,m),7.72-7.68(2H,m),7.07-7.03(2H,m),6.02-6.01(1H,m),5.67-5.66(1H,m),4.11(2H,t),4.03(2H,t),1.88-1.87(3H,m),1.76-1.41(8H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 7.89-7.86 (2H, m), 7.84-7.82 (2H, m), 7.72-7.68 (2H, m), 7.07-7.03 (2H, m) , 6.02-6.01 (1H, m), 5.67-5.66 (1H, m), 4.11 (2H, t), 4.03 (2H, t), 1.88-1.87 (3H, m), 1.76-1.41 (8H, m) .

<合成例7> <Synthesis example 7> 化合物[MA12]之合成 Synthesis of compound [MA12]

於2L四口燒瓶，加入化合物[MA4-1](4-溴-4’-羥基聯苯基)(50.00g、201mmol)、6-氯-1-己醇(32.90g、241mmol)、碳酸鉀(83.2、602mmol)、碘化鉀(16.7g、100mmol)、DMF(500g)並於85℃進行加熱反應。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於蒸餾水(3L)並過濾，得到以蒸餾水洗淨之粗產物。然後，將所得到之粗產物以甲醇洗淨並過濾，得到減壓乾燥之化合物[MA12-1]之粗產物。 In a 2L four-necked flask, compound [MA4-1] (4-bromo-4'-hydroxybiphenyl) (50.00g, 201mmol), 6-chloro-1-hexanol (32.90g, 241mmol), and potassium carbonate were added. (83.2, 602 mmol), potassium iodide (16.7 g, 100 mmol), DMF (500 g), and a heating reaction was performed at 85 ° C. The reaction was tracked by HPLC. After confirming the termination of the reaction, the reaction solution was poured into distilled water (3 L) and filtered to obtain a crude product washed with distilled water. Then, the obtained crude product was washed with methanol and filtered to obtain a crude product of the compound [MA12-1] dried under reduced pressure.

1H-NMR(400MHz,DMSO-d6,δ ppm)：7.62-7.56(6H,m),7.02-6.98(2H,m),4.00(2H,t),3.44(2H,t),1.76-1.26(8H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 7.62-7.56 (6H, m), 7.02-6.98 (2H, m), 4.00 (2H, t), 3.44 (2H, t), 1.76-1.26 (8H, m).

於2L四口燒瓶加入於上述所得之化合物[MA12-1](70.10g、201mol)、三乙基胺(28.43g、281mol)、THF(950g)，冷卻反應溶液。還有，將甲基丙烯醯氯(29.37g、281mmol)之THF(100g)溶液一邊注意內溫不超過10℃一邊滴下。滴下終止後，將反應溶液進一步於23℃進行反應。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於5L蒸餾水。於此加入乙酸乙酯(2L)，於分液操作去除水層後，將有機層以飽和食 鹽水(500g)洗淨3次。將有機層以硫酸鎂乾燥後，並藉由過濾，於蒸發器進行溶劑餾除，而得到粗產物。藉由將所得到之粗產物以甲醇洗淨，並進行減壓乾燥，得到68.4g化合物[MA12](收率82%)。 The compound [MA12-1] (70.10 g, 201 mol), triethylamine (28.43 g, 281 mol), and THF (950 g) were added to a 2 L four-necked flask, and the reaction solution was cooled. In addition, a solution of methacrylic acid chloride (29.37 g, 281 mmol) in THF (100 g) was dropped while taking care that the internal temperature did not exceed 10 ° C. After the dropping was completed, the reaction solution was further reacted at 23 ° C. The reaction was followed by HPLC, and after confirming the termination of the reaction, the reaction solution was poured into 5 L of distilled water. Ethyl acetate (2L) was added here, and the aqueous layer was removed in a liquid separation operation. Wash with brine (500g) 3 times. The organic layer was dried over magnesium sulfate, and then filtered, and the solvent was distilled off in an evaporator to obtain a crude product. The obtained crude product was washed with methanol and dried under reduced pressure to obtain 68.4 g of a compound [MA12] (yield: 82%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：7.61-7.56(6H,m),7.02-6.99(2H,m),6.02-6.01(1H,m),5.67-5.62(1H,m),4.09(2H,t),4.00(2H,t),1.99-1.85(3H,m),1.77-1.32(8H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 7.61-7.56 (6H, m), 7.02-6.99 (2H, m), 6.02-6.01 (1H, m), 5.67-5.62 (1H, m) , 4.09 (2H, t), 4.00 (2H, t), 1.99-1.85 (3H, m), 1.77-1.32 (8H, m).

<合成例8> <Synthesis example 8> 化合物[MA13]之合成 Synthesis of compound [MA13]

於500mL四口燒瓶將[MA2](38.6g、126mmol)、4-氟-4’-羥基聯苯基[MA13-1](25g、136mmol)、EDC(31g、151mmol)、DMAP(630mg、6.3mmol)溶解於THF(200g)中，並於室溫進行攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於3L蒸餾水。濾別析出之固體，將所得到之固體以IPA(300g)與甲醇(300g)洗淨，藉由乾燥固體而得到50g化合物[MA13](收率83%)。 In a 500 mL four-necked flask, [MA2] (38.6 g, 126 mmol), 4-fluoro-4'-hydroxybiphenyl [MA13-1] (25 g, 136 mmol), EDC (31 g, 151 mmol), DMAP (630 mg, 6.3 mmol) was dissolved in THF (200 g) and stirred at room temperature. The reaction was followed by HPLC, and after confirming the termination of the reaction, the reaction solution was poured into 3 L of distilled water. The precipitated solid was filtered, and the obtained solid was washed with IPA (300 g) and methanol (300 g), and 50 g of the compound [MA13] was obtained by drying the solid (yield: 83%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：8.08(2H,d),7.74(4H,m),7.37-7.29(4H,m),7.12(2H,d),6.03-6.02(1H,m),5.68-5.66(1H,m),4.11(2H,t),4.09(2H,t),1.88(3H,s),1.79-1.73(2H,m),1.69-1.62(2H,m),1.49-1.40(4H,m) 1 H-NMR (400MHz, DMSO-d6, δ ppm): 8.08 (2H, d), 7.74 (4H, m), 7.37-7.29 (4H, m), 7.12 (2H, d), 6.03-6.02 (1H , m), 5.68-5.66 (1H, m), 4.11 (2H, t), 4.09 (2H, t), 1.88 (3H, s), 1.79-1.73 (2H, m), 1.69-1.62 (2H, m ), 1.49-1.40 (4H, m)

<合成例9> <Synthesis example 9> 化合物[MA19]之合成 Synthesis of compound [MA19]

於500mL四口燒瓶加入[MA1](30.00g、98mmol)、化合物[MA19-1](23.91g、98mmol)、EDC(20.65g、108mmol)、DMAP(1.2g、9.8mmol)、THF(300g)，並於23℃進行反應。於HPLC進行反應追蹤，確認反應終止後，於蒸餾水1.5L注入反應溶液，過濾析出之固體。其次，使所得到之固體懸濁於IPA(400g)，於40℃進行加熱攪拌之後，將反應溶液冷卻至室溫並藉由進行過濾、減壓乾燥，得到41g化合物[MA19](收率75%)。 In a 500 mL four-necked flask, [MA1] (30.00g, 98mmol), compound [MA19-1] (23.91g, 98mmol), EDC (20.65g, 108mmol), DMAP (1.2g, 9.8mmol), and THF (300g) were added. And react at 23 ° C. The reaction was tracked by HPLC. After confirming the termination of the reaction, the reaction solution was poured into 1.5 L of distilled water, and the precipitated solid was filtered. Next, the obtained solid was suspended in IPA (400 g), and after heating and stirring at 40 ° C, the reaction solution was cooled to room temperature and filtered and dried under reduced pressure to obtain 41 g of a compound [MA19] (yield 75) %).

1H-NMR(400MHz,DMSO-d6,δ ppm)：8.21-8.18(2H,m),7.87(1H,d),7.77(1H,d),7.46-7.43(2H, m),7.23-7.20(2H,m),7.03-7.00(4H,m),6.74(1H,m),6.02-6.01(1H,m),5.68-5.66(1H,m),4.11(2H,t),4.06(2H,t),4.03(3H,s),1.88-1.87(3H,m),1.76-1.40(8H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 8.21-8.18 (2H, m), 7.87 (1H, d), 7.77 (1H, d), 7.46-7.43 (2H, m), 7.23-7.20 (2H, m), 7.03-7.00 (4H, m), 6.74 (1H, m), 6.02-6.01 (1H, m), 5.68-5.66 (1H, m), 4.11 (2H, t), 4.06 (2H , t), 4.03 (3H, s), 1.88-1.87 (3H, m), 1.76-1.40 (8H, m).

<合成例10> <Synthesis example 10> 化合物[MA20]之合成 Synthesis of compound [MA20]

除了將於合成化合物[MA4]之中間體之化合物[MA4-4]之際所使用之6-氯-1-己醇變更為8-氯-1-辛醇之外，其他與合成例1進行同樣的操作，得到40.82g化合物[MA20]。 The procedure was performed in the same manner as in Synthesis Example 1 except that the 6-chloro-1-hexanol used in the synthesis of the intermediate compound [MA4-4] of the compound [MA4] was changed to 8-chloro-1-octanol. By the same operation, 40.82 g of the compound [MA20] was obtained.

1H-NMR(400MHz,DMSO-d6,δ ppm)：7.70-7.56(7H,m),6.97(2H,d),6.51(1H,d),5.98(1H,s),5.62(1H,s),4.04(2H,t),3.94(2H,t),1.83(3H,s),1.70-1.10(12H)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 7.70-7.56 (7H, m), 6.97 (2H, d), 6.51 (1H, d), 5.98 (1H, s), 5.62 (1H, s ), 4.04 (2H, t), 3.94 (2H, t), 1.83 (3H, s), 1.70-1.10 (12H).

<合成例11> <Synthesis example 11> 化合物[MA21]之合成 Synthesis of compound [MA21]

於2L四口燒瓶，加入4-溴苯基-4’-trans-羥基環己酮[MA21-1](500g、2.21mol)、丙烯酸tert-丁基[MA4-2](598g、4.66mol)、乙酸鈀(9.92g、44mmol)、三(o-甲苯基)膦(26.91g、88mmol)、三丙基胺(950g、6.63mol)、DMAc(2500g)，並於100℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液冷卻至室溫附近後，注入於6L 1M鹽酸水溶液。於此，加入乙酸乙酯(3L)，於分液操作去除水層。將有機層以1L 10%鹽酸水溶液洗淨2次、以1L飽和食鹽水洗淨3次之後，將有機層以硫酸鎂乾燥。然後藉由過濾、於蒸發器進行溶劑餾除，得到561.9g化合物[MA21-2](收率84%)。 In a 2L four-necked flask, 4-bromophenyl-4'-trans-hydroxycyclohexanone [MA21-1] (500 g, 2.21 mol) and tert-butyl [MA4-2] acrylic acid (598 g, 4.66 mol) were added. , Palladium acetate (9.92 g, 44 mmol), tris (o-tolyl) phosphine (26.91 g, 88 mmol), tripropylamine (950 g, 6.63 mol), DMAc (2500 g), and heat and stir at 100 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was cooled to around room temperature, and then poured into 6 L of a 1 M aqueous hydrochloric acid solution. Here, ethyl acetate (3 L) was added, and the aqueous layer was removed in a liquid separation operation. The organic layer was washed twice with 1 L of a 10% hydrochloric acid aqueous solution and three times with 1 L of a saturated saline solution, and then the organic layer was dried with magnesium sulfate. Then, the solvent was distilled off in an evaporator by filtration to obtain 561.9 g of a compound [MA21-2] (yield 84%).

1H-NMR(400MHz,CDCl3,δ ppm)：7.56(1H,d), 7.45-7.43(2H,m),7.22-7.19(2H,m),6.32(1H,d),3.78-3.65(1H,m),2.58-2.44(1H,m),2.13-2.09(2H,m),1.96-1.91(2H,m),1.60-1.41(13H,m)。 1 H-NMR (400MHz, CDCl3, δ ppm): 7.56 (1H, d), 7.45-7.43 (2H, m), 7.22-7.19 (2H, m), 6.32 (1H, d), 3.78-3.65 (1H , m), 2.58-2.44 (1H, m), 2.13-2.09 (2H, m), 1.96-1.91 (2H, m), 1.60-1.41 (13H, m).

於2L四口燒瓶加入於上述所得之化合物[MA21-2](100g、331mmol)、tert-4-甲氧基-桂皮酸(58.92g、331mol)、EDC(76.07g、397mol)、DMAP(4.04g、33mmol)、THF(885g)，並於23℃進行攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於8L蒸餾水，過濾析出之固體，並以蒸餾水洗淨，得到粗產物。其次將粗產物懸濁於甲醇(3L)，攪拌一時之後，再度藉由進行過濾、減壓乾燥而得到82.17g化合物[MA21-3](收率54%)。 In a 2L four-necked flask, the compound [MA21-2] (100 g, 331 mmol), tert-4-methoxy-cinnamic acid (58.92 g, 331 mol), EDC (76.07 g, 397 mol), and DMAP (4.04) were added. g, 33 mmol), THF (885 g), and stirred at 23 ° C. The reaction was tracked by HPLC. After confirming the termination of the reaction, the reaction solution was poured into 8 L of distilled water, and the precipitated solid was filtered and washed with distilled water to obtain a crude product. Next, the crude product was suspended in methanol (3 L), and after stirring for a while, 82.17 g of a compound [MA21-3] was obtained by filtering and drying under reduced pressure again (yield 54%).

1H-NMR(400MHz,CDCl3,δ ppm)：7.64(1H,d),7.56(1H,d),7.51-7.48(2H,m),7.46-7.44(2H,m),7.23-7.21(2H,m),6.92-6.90(2H,m),6.34(1H,d),6.30(1H,d),4.95-4.89(1H,m),3.84(3H,s),2.59-2.54(1H,m),2.20-2.18(2H,m),2.00-1.97(2H,m),1.69-1.37(13H,m)。 1 H-NMR (400MHz, CDCl3, δ ppm): 7.64 (1H, d), 7.56 (1H, d), 7.51-7.48 (2H, m), 7.46-7.44 (2H, m), 7.23-7.21 (2H , m), 6.92-6.90 (2H, m), 6.34 (1H, d), 6.30 (1H, d), 4.95-4.89 (1H, m), 3.84 (3H, s), 2.59-2.54 (1H, m ), 2.20-2.18 (2H, m), 2.0-1.97 (2H, m), 1.69-1.37 (13H, m).

(9H,m),6.87-6.85(2H,m),1.44(9H,s)。 (9H, m), 6.87-6.85 (2H, m), 1.44 (9H, s).

於2L四口燒瓶加入於上述所得之化合物[MA21-3](82.17g、178mmol)、蟻酸(410g)，並於40℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液冷卻至室溫附近後，於3L蒸餾水注入反應溶液。濾別所析出之固體後，並藉由以乙酸乙酯洗 淨，進行減壓乾燥而得到54.4g化合物[MA21-4](收率75%)。 The compound [MA21-3] (82.17 g, 178 mmol) and formic acid (410 g) obtained above were added to a 2 L four-necked flask, and the mixture was heated and stirred at 40 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was cooled to around room temperature, and then the reaction solution was poured into 3 L of distilled water. The precipitated solid was filtered, and washed with ethyl acetate. Then, it was dried under reduced pressure to obtain 54.4 g of a compound [MA21-4] (yield 75%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：7.70-7.68(2H,m),7.62(1H,d),7.60(2H,s),7.56(2H,d),7.31(2H,d),7.00-6.97(2H,m),6.50(1H,d),6.46(1H,d),4.91-4.82(1H,m),3.80(3H,s),2.62-2.48(1H,m),2.10-2.07(2H,m),1.87-1.84(2H,m),1.65-1.48(4H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 7.70-7.68 (2H, m), 7.62 (1H, d), 7.60 (2H, s), 7.56 (2H, d), 7.31 (2H, d ), 7.00-6.97 (2H, m), 6.50 (1H, d), 6.46 (1H, d), 4.1-4.82 (1H, m), 3.80 (3H, s), 2.62-2.48 (1H, m), 2.10-2.07 (2H, m), 1.87-1.84 (2H, m), 1.65-1.48 (4H, m).

於1L四口燒瓶加入於上述所得之化合物[MA21-5](30.00g、73.8mmol)、甲基丙烯酸2-羥乙酯[MA6-1](10.57g、81.2mmol)、EDC(17.0g、88.6mmol)、DMAP(0.90g、7.38mmol)、THF(450g)，並於23℃進行攪拌。於HPLC進行反應追蹤，確認反應終止後，於2L蒸餾水注入反應溶液，以乙酸乙酯(600g)進行萃取。將有機層以蒸餾水(500g)洗淨2次，將有機層以硫酸鎂脫水、過濾，而得到溶劑餾除之32.8g化合物[MA21](收率86%)。 In a 1 L four-necked flask, the compound [MA21-5] (30.00 g, 73.8 mmol), 2-hydroxyethyl methacrylate [MA6-1] (10.57 g, 81.2 mmol), and EDC (17.0 g, 88.6 mmol), DMAP (0.90 g, 7.38 mmol), THF (450 g), and stirred at 23 ° C. The reaction was followed by HPLC. After confirming the completion of the reaction, the reaction solution was poured into 2 L of distilled water and extracted with ethyl acetate (600 g). The organic layer was washed twice with distilled water (500 g), and the organic layer was dehydrated with magnesium sulfate and filtered to obtain 32.8 g of a compound [MA21] distilled away by a solvent (yield: 86%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：7.70-7.68(2H,m),7.7.67(2H,s),7.65-7.63(1H,m),7.60(1H,d),7.32(2H,d),7.00-6.97(2H,m),6.62(1H,d),6.50(1H,d),6.05-6.04(1H,m),5.71-5.70(1H,m),4.87-4.81(1H,m),4.43-4.36(4H,m),3.80(3H,s),2.62-2.58(1H,m),2.10-2.06(2H,m),1.89-1.88(5H,m),1.66-1.48(4H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 7.70-7.68 (2H, m), 7.7.67 (2H, s), 7.65-7.63 (1H, m), 7.60 (1H, d), 7.32 (2H, d), 7.00-6.97 (2H, m), 6.62 (1H, d), 6.50 (1H, d), 6.05-6.04 (1H, m), 5.71-5.70 (1H, m), 4.87-4.81 (1H, m), 4.43-4.36 (4H, m), 3.80 (3H, s), 2.62-2.58 (1H, m), 2.10-2.06 (2H, m), 1.89-1.88 (5H, m), 1.66 -1.48 (4H, m).

<合成例12> <Synthesis example 12> 化合物[MA22]之合成 Synthesis of compound [MA22]

於1L四口燒瓶，加入化合物[MA2](50.00g、163mmol)、化合物[MA22-1](39.90g、180mmol)、EDC(37.54g、196mmol)、DMAP(1.99g、16.3mmol)、THF(500g)，並於23℃進行反應。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於蒸餾水(3L)，並加入乙酸乙酯(1L)，於分液操作去除水層。將有機層以蒸餾水(1L)洗淨3次之後，將有機層以硫酸鎂乾燥。然後藉由過濾，於蒸發器進行溶劑餾除，得到作為油狀化合物之74.95g化合物[MA22-2](收率90%)。 In a 1 L four-necked flask, compound [MA2] (50.00 g, 163 mmol), compound [MA22-1] (39.90 g, 180 mmol), EDC (37.54 g, 196 mmol), DMAP (1.99 g, 16.3 mmol), and THF ( 500 g), and reacted at 23 ° C. The reaction was tracked by HPLC. After confirming the termination of the reaction, the reaction solution was poured into distilled water (3L), ethyl acetate (1L) was added, and the aqueous layer was removed in a liquid separation operation. After the organic layer was washed three times with distilled water (1 L), the organic layer was dried over magnesium sulfate. Then, the solvent was distilled off in an evaporator by filtration to obtain 74.95 g of a compound [MA22-2] as an oily compound (yield: 90%).

1H-NMR(400MHz,CDCl3,δ ppm)：8.13(2H,d),7.74(1H,d),7.60(2H,d),7.25(2H,d),7.00-6.96(2H,m),6.43(2H,d),6.11-6.10(1H,m),5.96-5.54(1H,m),5.44(2H,s),4.17(2H,t),4.06(2H,t),3.79-3.73(2H,m),1.95-1.94(3H,m),1.85-1.43(8H, m),1.25(3H,t)。 1 H-NMR (400MHz, CDCl3, δ ppm): 8.13 (2H, d), 7.74 (1H, d), 7.60 (2H, d), 7.25 (2H, d), 7.00-6.96 (2H, m), 6.43 (2H, d), 6.11-6.10 (1H, m), 5.96-5.54 (1H, m), 5.44 (2H, s), 4.17 (2H, t), 4.06 (2H, t), 3.79-3.73 ( 2H, m), 1.95-1.94 (3H, m), 1.85-1.43 (8H, m), 1.25 (3H, t).

於上述所得到之化合物[MA22-2](74.95g、147mmol)加入PPTS(3.69g、14.7mmol)、乙醇(480g)，並於60℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液以冰浴冷卻，過濾析出之固體，並以乙醇洗淨。藉由減壓乾燥所得到之固體，得到44.9g化合物[MA22](收率68%)。 To the obtained compound [MA22-2] (74.95 g, 147 mmol) were added PPTS (3.69 g, 14.7 mmol) and ethanol (480 g), and the mixture was heated and stirred at 60 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was cooled in an ice bath, the precipitated solid was filtered, and washed with ethanol. The obtained solid was dried under reduced pressure to obtain 44.9 g of a compound [MA22] (yield 68%).

1H-NMR(400MHz,CDCl3,δ ppm)：8.14(2H,d),7.79(1H,d),7.61(2H,d),7.26(2H,d),6.97(2H,d),6.43(1H,d),6.11-6.09(1H,m),5.56-5.55(1H,m),4.16(2H,t),4.06(2H,t),1.95(3H,s),1.88-1.43(8H,m)。 1 H-NMR (400MHz, CDCl3, δ ppm): 8.14 (2H, d), 7.79 (1H, d), 7.61 (2H, d), 7.26 (2H, d), 6.97 (2H, d), 6.43 ( 1H, d), 6.11-6.09 (1H, m), 5.56-5.55 (1H, m), 4.16 (2H, t), 4.06 (2H, t), 1.95 (3H, s), 1.88-1.43 (8H, m).

<合成例13> <Synthesis Example 13> 化合物[MA23]之合成 Synthesis of compound [MA23]

於1L四口燒瓶，加入化合物[MA1](50.00g、150mmol)、化合物[MA9-1](32.46g、166mmol)、EDC(34.6g、181mmol)、DMAP(1.84g、 15.0mmol)、THF(500g)，並於23℃進行反應。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於蒸餾水(3L)，並加入乙酸乙酯(1L)，於分液操作去除水層。將有機層以蒸餾水(1L)洗淨3次之後，將有機層以硫酸鎂乾燥。然後藉由過濾，於蒸發器進行溶劑餾除，得到作為油狀化合物之76.5g化合物[MA23-1](收率99%)。 In a 1 L four-necked flask, compound [MA1] (50.00 g, 150 mmol), compound [MA9-1] (32.46 g, 166 mmol), EDC (34.6 g, 181 mmol), DMAP (1.84 g, 15.0 mmol), THF (500 g), and reacted at 23 ° C. The reaction was tracked by HPLC. After confirming the termination of the reaction, the reaction solution was poured into distilled water (3L), ethyl acetate (1L) was added, and the aqueous layer was removed in a liquid separation operation. After the organic layer was washed three times with distilled water (1 L), the organic layer was dried over magnesium sulfate. Then, the solvent was distilled off in an evaporator by filtration to obtain 76.5 g of a compound [MA23-1] as an oily compound (yield: 99%).

1H-NMR(400MHz,CDCl3,δ ppm)：8.14(2H,d),7.84(1H,d),7.55-7.53(2H,m),7.28-7.26(2H,m),6.95-6.92(2H,m),6.48(1H,d),6.11-6.10(1H,m),5.56-5.55(3H,m),4.18-4.10(2H,m),4.01(2H,t),3.82-3.74(2H,m),1.95(3H,s),1.86-1.43(8H,m),1.26(3H,t)。 1 H-NMR (400MHz, CDCl3, δ ppm): 8.14 (2H, d), 7.84 (1H, d), 7.55-7.53 (2H, m), 7.28-7.26 (2H, m), 6.95-6.92 (2H , m), 6.48 (1H, d), 6.11-6.10 (1H, m), 5.56-5.55 (3H, m), 4.18-4.10 (2H, m), 4.01 (2H, t), 3.82-3.74 (2H , m), 1.95 (3H, s), 1.86-1.43 (8H, m), 1.26 (3H, t).

於上述所得到之化合物[MA23-1](76.5g、150mmol)加入PPTS(3.77g、15.0mmol)、乙醇(540g)，並於60℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液以冰浴冷卻，過濾析出之固體，並以乙醇洗淨。藉由減壓乾燥所得到之固體，得到16.9g化合物[MA23](收率48%)。 PPTS (3.77 g, 15.0 mmol) and ethanol (540 g) were added to the obtained compound [MA23-1] (76.5 g, 150 mmol), and the mixture was heated and stirred at 60 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was cooled in an ice bath, the precipitated solid was filtered, and washed with ethanol. The obtained solid was dried under reduced pressure to obtain 16.9 g of a compound [MA23] (yield: 48%).

1H-NMR(400MHz,CDCl3,δ ppm)：8.18(2H,d),7.84(1H,d),7.54(2H,d),7.29(2H,d),6.93(2H,d),6.49(1H,d),6.11-6.10(1H,m),5.56-5.55(1H,m),4.17(2H,t),4.01(2H,t),1.95-1.94(3H,m),1.88-1.43(8H,m)。 1 H-NMR (400MHz, CDCl3, δ ppm): 8.18 (2H, d), 7.84 (1H, d), 7.54 (2H, d), 7.29 (2H, d), 6.93 (2H, d), 6.49 ( 1H, d), 6.11-6.10 (1H, m), 5.56-5.55 (1H, m), 4.17 (2H, t), 4.01 (2H, t), 1.95-1.94 (3H, m), 1.88-1.43 ( 8H, m).

<合成例14> <Synthesis Example 14> 化合物[MA25]之合成 Synthesis of compound [MA25]

於2L四口燒瓶，加入4-溴安息香酸tert-丁基[MA25-1](126.0g、488mmol)、丙烯酸(73.86g、1.03mol)、乙酸鈀(2.19g、9.77mmol)、三(o-甲苯基)膦(5.94g、19.53mmol)、三丁基胺(271.5g、1.46mol)、DMAc(630g)，並於100℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液冷卻至室溫附近後，注入於4L 1M鹽酸水溶液。過濾析出之固體，以蒸餾水、甲醇順序洗淨，藉由從乙酸乙酯/己烷進行再結晶，得到116.1g化合物[MA25-2](收率96%)。 In a 2L four-necked flask, 4-bromobenzoic acid tert-butyl [MA25-1] (126.0 g, 488 mmol), acrylic acid (73.86 g, 1.03 mol), palladium acetate (2.19 g, 9.77 mmol), and tri (o -Tolyl) phosphine (5.94 g, 19.53 mmol), tributylamine (271.5 g, 1.46 mol), DMAc (630 g), and heated and stirred at 100 ° C. The reaction was followed by HPLC. After confirming the completion of the reaction, the reaction solution was cooled to around room temperature, and then poured into 4 L of a 1 M aqueous hydrochloric acid solution. The precipitated solid was filtered, washed with distilled water and methanol in this order, and recrystallized from ethyl acetate / hexane to obtain 116.1 g of a compound [MA25-2] (yield 96%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：10.01(1H,s),12.49(1H,brs),7.92-7.90(2H,m),7.82-7.80 (2H,m),7.63(1H,d),6.65(1H,d),1.55(9H,s)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 10.01 (1H, s), 12.49 (1H, brs), 7.92-7.90 (2H, m), 7.82-7.80 (2H, m), 7.63 (1H , d), 6.65 (1H, d), 1.55 (9H, s).

於配備機械攪拌器、攪拌羽之2L四口燒瓶加入於上述所得之化合物[MA25-2](50.00g、201mmol)、6-氯-1-己醇(30.27g、222mol)、碳酸鉀(30.63g、222mmol)、碘化鉀(3.34g、20.14mmol)、DMF(250g)，並於80℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於1.5L蒸餾水，以乙酸乙酯(500mL)進行2次洗淨。配合有機層之後，以5%氫氧化鉀水溶液(300g)、飽和食鹽水(300g)進行2次洗淨，以硫酸鎂使有機層乾燥，並過濾後，得到餾除溶劑之62.5g化合物[MA25-3](收率89%)。 In a 2L four-neck flask equipped with a mechanical stirrer and a stirring feather, the compound [MA25-2] (50.00g, 201mmol), 6-chloro-1-hexanol (30.27g, 222mol), and potassium carbonate (30.63) obtained above were added. g, 222 mmol), potassium iodide (3.34 g, 20.14 mmol), DMF (250 g), and heated and stirred at 80 ° C. The reaction was followed by HPLC. After confirming the completion of the reaction, the reaction solution was poured into 1.5 L of distilled water and washed twice with ethyl acetate (500 mL). After the organic layer was mixed, it was washed twice with a 5% potassium hydroxide aqueous solution (300 g) and a saturated saline solution (300 g). The organic layer was dried with magnesium sulfate and filtered to obtain 62.5 g of a distillative solvent [MA25 -3] (yield 89%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：7.92-7.90(2H,m),7.86-7.84(2H,d),7.68(1H,d),6.76(1H,d),4.16(2H,t),3.39(2H,t),1.65-1.28(15H,d)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 7.92-7.90 (2H, m), 7.86-7.84 (2H, d), 7.68 (1H, d), 6.76 (1H, d), 4.16 (2H , t), 3.39 (2H, t), 1.65-1.28 (15H, d).

於2L四口燒瓶加入於上述所得之化合物[MA25-3](62.5g、179mmol)、三乙基胺(21.78g、215mmol)、THF(400g)，並冷卻反應溶液。還有，將甲基丙烯醯氯(20.63g、197mmol)之THF(100g)溶液一邊注意內溫不超過10℃一邊滴下。滴下終止後，將反應溶液進一步於23℃進行反應。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於4L蒸餾水，並加入1L乙酸乙酯，於分液操作去除水層。然後，以5%氫氧化鉀水溶液、1M鹽酸水溶液、飽和食鹽水順序洗淨有機 層，將有機層以硫酸鎂乾燥。然後過濾，得到以蒸發器溶劑餾除之65.19g化合物[MA25-4](收率87%)。 The compound [MA25-3] (62.5 g, 179 mmol), triethylamine (21.78 g, 215 mmol), and THF (400 g) were added to a 2 L four-necked flask, and the reaction solution was cooled. In addition, a solution of methacrylic acid chloride (20.63 g, 197 mmol) in THF (100 g) was dropped while taking care that the internal temperature did not exceed 10 ° C. After the dropping was completed, the reaction solution was further reacted at 23 ° C. The reaction was tracked by HPLC. After confirming the termination of the reaction, the reaction solution was poured into 4 L of distilled water, and 1 L of ethyl acetate was added, and the aqueous layer was removed in a liquid separation operation. Then, the organics were washed sequentially with a 5% potassium hydroxide aqueous solution, a 1M hydrochloric acid aqueous solution, and a saturated saline solution. Layer, and the organic layer was dried over magnesium sulfate. Then, it was filtered to obtain 65.19 g of a compound [MA25-4] distilled away by an evaporator solvent (yield 87%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：7.92-7.90(2H,m),7.87-7.84(2H,m),7.68(2H,d),6.75(1H,d),6.02-6.01(1H,m),5.67-5.65(1H,m),4.16(2H,t),4.06-4.00(2H,m),1.88-1.87(3H,m),1.66-1.36(15H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 7.92-7.90 (2H, m), 7.87-7.84 (2H, m), 7.68 (2H, d), 6.75 (1H, d), 6.02-6.01 (1H, m), 5.67-5.65 (1H, m), 4.16 (2H, t), 4.06-4.00 (2H, m), 1.88-1.87 (3H, m), 1.66-1.36 (15H, m).

於2L四口燒瓶加入於上述所得之化合物[MA25-4](65.19g、157mmol)、蟻酸(325g)，並於40℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於2L蒸餾水並過濾。藉由將所得到之固體以甲醇洗淨，使固體乾燥而得到26.8g化合物[MA25](收率48%)。 The compound [MA25-4] (65.19 g, 157 mmol) and formic acid (325 g) obtained above were added to a 2 L four-necked flask, and the mixture was heated and stirred at 40 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was poured into 2 L of distilled water and filtered. The obtained solid was washed with methanol, and the solid was dried to obtain 26.8 g of a compound [MA25] (yield: 48%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：13.1(1H,brs),7.97-7.95(2H,m),7.86-7.84(2H,m),7.69(1H,d),6.75(1H,d),6.02-6.01(1H,m),5.68-5.65(1H,m),4.16-4.03(4H,m),1.88-1.87(3H,m),1.68-1.32(8H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 13.1 (1H, brs), 7.97-7.95 (2H, m), 7.86-7.84 (2H, m), 7.69 (1H, d), 6.75 (1H , d), 6.02-6.01 (1H, m), 5.68-5.65 (1H, m), 4.16-4.03 (4H, m), 1.88-1.87 (3H, m), 1.68-1.32 (8H, m).

<合成例15> <Synthesis Example 15> 化合物[MA28]之合成 Synthesis of compound [MA28]

加入於上述合成例11所合成之化合物[MA21-2](50.00g、165mmol)、4-甲氧基安息香酸(25.16g、165mol)、EDC(38.0g、198mol)、DMAP(2.02g、16.5mmol)、THF(380g)，並於23℃進行攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於2.5L蒸餾水，加入乙酸乙酯將有機層以分液操作進行分取。將所得到之有機層以蒸餾水(1L)洗淨3次之後，將有機層以硫酸鎂乾燥。然後藉由過濾，於蒸發器進行溶劑餾除，得到作為油狀化合物之65.5g化合物[MA28-1](收率91%)。 Added the compound [MA21-2] (50.00g, 165mmol), 4-methoxybenzoic acid (25.16g, 165mol), EDC (38.0g, 198mol), DMAP (2.02g, 16.5) synthesized in Synthesis Example 11 above. mmol), THF (380 g), and stirred at 23 ° C. The reaction was tracked by HPLC. After confirming the termination of the reaction, the reaction solution was poured into 2.5 L of distilled water, and ethyl acetate was added to separate the organic layer by a liquid separation operation. The obtained organic layer was washed three times with distilled water (1 L), and then the organic layer was dried over magnesium sulfate. Then, the solvent was distilled off in an evaporator by filtration to obtain 65.5 g of a compound [MA28-1] as an oily compound (yield 91%).

1H-NMR(400MHz,CDCl3,δ ppm)：8.10(2H,d),7.56(1H,d),7.45-7.43(2H,d),7.22-7.19(2H,m),7.00-6.97(2H,m),6.33(1H,d),3.90(3H,s),3.73-3.66(1H,m),2.58-2.42(1H,m),2.12-1.43(17H,m)。 1 H-NMR (400MHz, CDCl3, δ ppm): 8.10 (2H, d), 7.56 (1H, d), 7.45-7.43 (2H, d), 7.22-7.19 (2H, m), 7.00-6.97 (2H , m), 6.33 (1H, d), 3.90 (3H, s), 3.73-3.66 (1H, m), 2.58-2.42 (1H, m), 2.12-1.43 (17H, m).

於2L四口燒瓶加入於上述所得之化合物[MA28-1](65.5g、150mmol)、蟻酸(650g)，並於 40℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液冷卻至室溫附近後，於4L蒸餾水注入反應溶液。濾別所析出之固體後，藉由以乙酸乙酯洗淨，並進行減壓乾燥，而得到29.9g化合物[MA28-2](收率52%)。 In a 2L four-necked flask, the compound [MA28-1] (65.5 g, 150 mmol) and formic acid (650 g) obtained above were added. Heat and stir at 40 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was cooled to around room temperature, and then the reaction solution was poured into 4 L of distilled water. After filtering off the precipitated solid, it was washed with ethyl acetate and dried under reduced pressure to obtain 29.9 g of a compound [MA28-2] (yield 52%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：7.94-7.88(2H,m),7.62-7.54(3H,m),7.33-7.79(2H,m),7.07-7.01(2H,m),6.48(1H,d),4.95-4.92(1H,m),4.84-4.77(1H,m),3.83(3H,s),2.65-1.48(8H)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 7.94-7.88 (2H, m), 7.62-7.54 (3H, m), 7.33-7.79 (2H, m), 7.07-7.01 (2H, m) , 6.48 (1H, d), 4.95-4.92 (1H, m), 4.84-4.77 (1H, m), 3.83 (3H, s), 2.65-1.48 (8H).

於1L四口燒瓶加入於上述所得之化合物[MA28-2](29.9g、78.6mmol)、甲基丙烯酸2-羥乙酯(12.27g、94.3mmol)、EDC(21.1g、110mmol)、DMAP(0.96g、7.86mmol)、THF(450g)，並於23℃進行攪拌。於HPLC進行反應追蹤，確認反應終止後，於2.7L蒸餾水注入反應溶液，以乙酸乙酯(600g)進行萃取。將有機層以蒸餾水(500g)洗淨2次，將有機層以硫酸鎂脫水、過濾，得到溶劑餾除之23.6g化合物[MA28](收率56%)。 In a 1 L four-necked flask, the compound [MA28-2] (29.9 g, 78.6 mmol), 2-hydroxyethyl methacrylate (12.27 g, 94.3 mmol), EDC (21.1 g, 110 mmol), DMAP ( 0.96 g, 7.86 mmol), THF (450 g), and stirred at 23 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was poured into 2.7 L of distilled water and extracted with ethyl acetate (600 g). The organic layer was washed twice with distilled water (500 g), and the organic layer was dehydrated with magnesium sulfate and filtered to obtain 23.6 g of a compound [MA28] distilled off by a solvent (yield 56%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：8.08-8.02(2H,m),7.68(1H,d),7.48-7.46(2H,m),7.24-7.22(2H,m),6.92(2H,d),6.42(1H,d),6.16(1H,s),5.61-5.60(1H,m),5.12-4.93(2H,m),4.47-4.22(4H,m),3.86(3H,s),2.60-1.43(11H)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 8.08-8.02 (2H, m), 7.68 (1H, d), 7.48-7.46 (2H, m), 7.24-7.22 (2H, m), 6.92 (2H, d), 6.42 (1H, d), 6.16 (1H, s), 5.61-5.60 (1H, m), 5.12-4.93 (2H, m), 4.47-4.22 (4H, m), 3.86 (3H , s), 2.60-1.43 (11H).

<合成例16> <Synthesis example 16> 化合物[MA29]之合成 Synthesis of compound [MA29]

於2L四口燒瓶，加入6-溴-2-萘酚[MA29-1](150g、672mol)、丙烯酸tert-丁基[MA4-2](103.4g、807mmol)、乙酸鈀(3.02g、13.5mmol)、三(o-甲苯基)膦(8.19g、26.9mmol)、三丙基胺(289.0g、2.02mol)、DMAc(700g)，並於100℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液冷卻至室溫附近後，注入於3L 1M鹽酸水溶液。於此加入乙酸乙酯(2L)，於分液操作去除水層。將有機層以1L 10%鹽酸水溶液洗淨2次、以1L飽和食鹽水洗淨3次之後，將有機層以硫酸鎂乾燥。然後藉由過濾，於蒸發器進行溶劑餾除，得到181g化合物[MA29-2](收率99%)。 In a 2L four-necked flask, 6-bromo-2-naphthol [MA29-1] (150g, 672mol), tert-butyl [MA4-2] acrylic acid (103.4g, 807mmol), and palladium acetate (3.02g, 13.5) were added. mmol), tris (o-tolyl) phosphine (8.19 g, 26.9 mmol), tripropylamine (289.0 g, 2.02 mol), DMAc (700 g), and heated and stirred at 100 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was cooled to around room temperature, and then poured into 3 L of a 1 M aqueous hydrochloric acid solution. Ethyl acetate (2 L) was added thereto, and the aqueous layer was removed in a liquid separation operation. The organic layer was washed twice with 1 L of a 10% hydrochloric acid aqueous solution and three times with 1 L of a saturated saline solution, and then the organic layer was dried with magnesium sulfate. Then, the solvent was distilled off in an evaporator by filtration to obtain 181 g of a compound [MA29-2] (yield: 99%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：10.01(1H,s),8.04(1H,s),7.81-7.74(2H,m),7.70-7.63(2H,m),7.14-7.10(2H,m),6.54(1H,d),1.51-1.48(9H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 10.01 (1H, s), 8.04 (1H, s), 7.81-7.74 (2H, m), 7.70-7.63 (2H, m), 7.14-7.10 (2H, m), 6.54 (1H, d), 1.51-1.48 (9H, m).

於配備機械攪拌器、攪拌羽之2L四口燒瓶加 入於上述所得之化合物[MA29-2](181g、672mmol)、6-氯-1-己醇(110.2g、806mol)、碳酸鉀(111.5g、806mmol)、碘化鉀(1.12g、6.7mmol)、DMF(900g)，並於80℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於2L蒸餾水，並加入乙酸乙酯(2L)，由分液操作去除水層。然後，將有機層以飽和食鹽水(1L)洗淨2次，以硫酸鎂使有機層乾燥並過濾後，得到餾除溶劑之粗產物。將所得到之粗產物以乙酸乙酯/己烷混合溶劑進行再結晶，得到185g化合物[MA29-3](收率74%)。 Add to a 2L four-neck flask equipped with a mechanical stirrer and stirring feather. The compound [MA29-2] (181 g, 672 mmol), 6-chloro-1-hexanol (110.2 g, 806 mol), potassium carbonate (111.5 g, 806 mmol), potassium iodide (1.12 g, 6.7 mmol), DMF (900g), and heated and stirred at 80 ° C. The reaction was tracked by HPLC. After confirming the termination of the reaction, the reaction solution was poured into 2 L of distilled water, and ethyl acetate (2 L) was added, and the aqueous layer was removed by a liquid separation operation. Then, the organic layer was washed twice with saturated saline (1 L), and the organic layer was dried with magnesium sulfate and filtered to obtain a crude product from which the solvent was distilled off. The obtained crude product was recrystallized with a mixed solvent of ethyl acetate / hexane to obtain 185 g of a compound [MA29-3] (yield 74%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：8.06(1H,s),7.80(1H,d),7.77-7.76(2H,m),7.62(1H,d),7.34(1H,d),7.15(1H,dd),6.53(1H,d),4.34(1H,t),4.05(2H,t),3.39-3.33(2H,m),1.73(2H,t),1.46-1.31(15H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 8.06 (1H, s), 7.80 (1H, d), 7.77-7.76 (2H, m), 7.62 (1H, d), 7.34 (1H, d ), 7.15 (1H, dd), 6.53 (1H, d), 4.34 (1H, t), 4.05 (2H, t), 3.39-3.33 (2H, m), 1.73 (2H, t), 1.46-1.31 ( 15H, m).

於3L四口燒瓶加入於上述所得之化合物[MA29-3](130.5g、352mmol)、三乙基胺(42.76g、423mmol)、THF(950g)，並冷卻反應溶液。還有，將甲基丙烯醯氯(44.2g、423mmol)之THF(100g)溶液一邊注意內溫不超過10℃一邊滴下。滴下終止後，將反應溶液進一步於23℃進行反應。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於6L蒸餾水，並加入2L乙酸乙酯，於分液操作去除水層。然後，以5%氫氧化鉀水溶液、1M鹽酸水溶液、飽和食鹽水順序洗淨有機層， 將有機層以硫酸鎂乾燥。然後過濾，得到以蒸發器溶劑餾除之140.9g化合物[MA29-4](收率92%)。 The compound [MA29-3] (130.5 g, 352 mmol), triethylamine (42.76 g, 423 mmol), and THF (950 g) were added to a 3 L four-necked flask, and the reaction solution was cooled. In addition, a solution of methacrylic acid chloride (44.2 g, 423 mmol) in THF (100 g) was dropped while taking care that the internal temperature did not exceed 10 ° C. After the dropping was completed, the reaction solution was further reacted at 23 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was poured into 6 L of distilled water, 2 L of ethyl acetate was added, and the aqueous layer was removed in a liquid separation operation. Then, the organic layer was washed sequentially with a 5% potassium hydroxide aqueous solution, a 1M hydrochloric acid aqueous solution, and a saturated saline solution. The organic layer was dried over magnesium sulfate. Then, it was filtered to obtain 140.9 g of a compound [MA29-4] which was distilled off by an evaporator solvent (yield: 92%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：8.09(1H,s),7.83(1H,d),7.80-7.79(2H,m),7.66(1H,d),7.33(1H,d),7.18(1H,dd),6.57(1H,d),6.02-6.01(1H,m),5.66-5.65(1H,m),4.12-4.06(4H,m),1.88-1.87(3H,m),1.84-1.42(15H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 8.09 (1H, s), 7.83 (1H, d), 7.80-7.79 (2H, m), 7.66 (1H, d), 7.33 (1H, d ), 7.18 (1H, dd), 6.57 (1H, d), 6.02-6.01 (1H, m), 5.66-5.65 (1H, m), 4.12-4.06 (4H, m), 1.88-1.87 (3H, m ), 1.84-1.42 (15H, m).

於3L四口燒瓶加入於上述所得之化合物[MA29-4](140.9g、321mmol)、蟻酸(700g)，並於40℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於4.5L蒸餾水並過濾。藉由將所得到之固體以IPA/己烷混合溶劑洗淨，並使固體乾燥而得到95.9g化合物[MA29](收率78%)。 The compound [MA29-4] (140.9 g, 321 mmol) and formic acid (700 g) obtained above were added to a 3 L four-necked flask, and the mixture was heated and stirred at 40 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was poured into 4.5 L of distilled water and filtered. The obtained solid was washed with an IPA / hexane mixed solvent, and the solid was dried to obtain 95.9 g of a compound [MA29] (yield: 78%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：12.4(1H,brs),8.10(1H,s),7.84(1H,d),7.81-7.80(2H,m),7.70(1H,d),7.35(1H,d),7.19(1H,dd),6.59(1H,d),6.03-6.02(1H,m),5.67-5.65(1H,m),4.13-4.07(4H,m),1.88-1.87(3H,m),1.83-1.41(8H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 12.4 (1H, brs), 8.10 (1H, s), 7.84 (1H, d), 7.81-7.80 (2H, m), 7.70 (1H, d ), 7.35 (1H, d), 7.19 (1H, dd), 6.59 (1H, d), 6.03-6.02 (1H, m), 5.67-5.65 (1H, m), 4.13-4.07 (4H, m), 1.88-1.87 (3H, m), 1.83-1.41 (8H, m).

<合成例17> <Synthesis example 17> 化合物[MA30]之合成 Synthesis of compound [MA30]

在合成例16，除了將於合成化合物[MA29-3]之際所使用之6-氯-1-己醇變更為8-氯-1-辛醇之外，其他與合成例16進行同樣的操作，得到171g化合物[MA30]。 In Synthesis Example 16, the same operation as in Synthesis Example 16 was performed except that the 6-chloro-1-hexanol used in the synthesis of the compound [MA29-3] was changed to 8-chloro-1-octanol. Thus, 171 g of a compound [MA30] was obtained.

1H-NMR(400MHz,CDCl3,δ ppm)：12.4(1H,brs),7.94-7.88(2H,m),7.77-7.71(2H,m),7.70-7.63(1H,m),7.17(1H,dd),7.12-7.11(1H,m),6.51(1H,d),6.11-6.10(1H,m),5.55-5.54(1H,m),4.17-4.06(4H,m),1.95-1.94(3H,m),1.87-1.40(12H,m)。 1 H-NMR (400MHz, CDCl3, δ ppm): 12.4 (1H, brs), 7.94-7.88 (2H, m), 7.77-7.71 (2H, m), 7.70-7.63 (1H, m), 7.17 (1H , dd), 7.12-7.11 (1H, m), 6.51 (1H, d), 6.11-6.10 (1H, m), 5.55-5.54 (1H, m), 4.17-4.06 (4H, m), 1.95-1.94 (3H, m), 1.87-1.40 (12H, m).

<合成例18> <Synthesis example 18> 化合物[MA31]之合成 Synthesis of compound [MA31]

於2L四口燒瓶加入6-羥基-2-萘羧酸[MA31-1](300g、1.59mol)、氫氧化鉀(205g、3.66mol)、蒸 餾水(1200g)，並於100℃進行加熱攪拌。於此，滴下6-氯-1-己醇(261g、1.91mol)。滴下終止後，於HPLC進行反應追蹤，確認反應終止後，將反應溶液冷卻至室溫附近後，於冰水(3L)注入反應溶液，並加入35%鹽酸進行中和。然後，過濾析出之固體，以蒸餾水洗淨後，藉由減壓乾燥固體，得到275g化合物[MA31-2](收率60%)。 In a 2L four-necked flask, 6-hydroxy-2-naphthalenecarboxylic acid [MA31-1] (300 g, 1.59 mol), potassium hydroxide (205 g, 3.66 mol), and steam were added. Distilled water (1200 g) was heated and stirred at 100 ° C. Here, 6-chloro-1-hexanol (261 g, 1.91 mol) was dropped. After completion of the dropping, the reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was cooled to room temperature, and then the reaction solution was poured into ice water (3L), and 35% hydrochloric acid was added to neutralize the reaction solution. Then, the precipitated solid was filtered and washed with distilled water, and then the solid was dried under reduced pressure to obtain 275 g of a compound [MA31-2] (yield 60%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：8.53-8.52(1H,m),8.06-7.87(3H,m),7.40(1H,d),7.27-7.23(1H,m),4.32(1H,t),4.12(2H,m),3.44-3.33(2H,m),1.82-1.76(2H,m),1.51-1.3(6H)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 8.53-8.52 (1H, m), 8.06-7.87 (3H, m), 7.40 (1H, d), 7.27-7.23 (1H, m), 4.32 (1H, t), 4.12 (2H, m), 3.44-3.33 (2H, m), 1.82-1.76 (2H, m), 1.51-1.3 (6H).

於2L四口燒瓶加入於上述所得之化合物[MA31-2](50.00g、173mmol)、二甲基胺基苯酚(46.23g、382mmol)、硝基苯(2.13g、17.3mmol)、THF(500g)並取代氮之後，於加熱回流下進行攪拌。還有，將甲基丙烯醯氯(38.1g、361mmol)之THF(100g)溶液緩緩滴下。滴下終止後，於HPLC進行反應追蹤，確認反應終止後，將反應溶液冷卻至室溫。然後，於3L 1M鹽酸水溶液注入反應溶液，過濾析出之固體而得到粗產物。其次，將所得到之粗產物以乙醇/己烷混合溶劑、再以丙酮洗淨之後，藉由進行減壓乾燥，得到38.4g化合物[MA31](收率62%)。 In a 2L four-necked flask, the compound [MA31-2] (50.00g, 173mmol), dimethylaminophenol (46.23g, 382mmol), nitrobenzene (2.13g, 17.3mmol), and THF (500g) obtained above were added. ) And replaced with nitrogen, and then stirred under heating and reflux. A THF (100 g) solution of methacrylic acid chloride (38.1 g, 361 mmol) was gradually dropped. After completion of the dropping, the reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was cooled to room temperature. Then, the reaction solution was poured into 3 L of a 1 M aqueous hydrochloric acid solution, and the precipitated solid was filtered to obtain a crude product. Next, the obtained crude product was washed with an ethanol / hexane mixed solvent, and then washed with acetone, and then dried under reduced pressure to obtain 38.4 g of a compound [MA31] (yield: 62%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：8.63(1H,s),8.08(1H,dd),7.87(1H,d),7.76(1H,d),7.22- 7.19(1H,m),7.16-7.15(1H,m),6.11-6.10(1H,m),5.56-5.54(1H,m),4.20-4.10(4H,m),1.97-1.95(3H,m),1.92-1.85(2H,m),1.78-1.71(2H,m),1.60-1.47(4HH,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 8.63 (1H, s), 8.08 (1H, dd), 7.87 (1H, d), 7.76 (1H, d), 7.22- 7.19 (1H, m ), 7.16-7.15 (1H, m), 6.11-6.10 (1H, m), 5.56-5.54 (1H, m), 4.20-4.10 (4H, m), 1.97-1.95 (3H, m), 1.92-1.85 (2H, m), 1.78-1.71 (2H, m), 1.60-1.47 (4HH, m).

<合成例19> <Synthesis example 19> 化合物[MA32]之合成 Synthesis of compound [MA32]

於1L四口燒瓶，加入化合物[MA1](50.00g、150mmol)、化合物[MA22-1](37.10g、165mmol)、EDC(34.6g、181mmol)、DMAP(1.89g、15.0mmol)、THF(500g)，並於23℃進行反應。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於蒸餾水(3L)，過濾析出之固體，以蒸餾水、甲醇順序洗淨，藉由減壓乾燥所得到之固體，得到79.8g化合物[MA32-1](收率99%)。 In a 1 L four-necked flask, compound [MA1] (50.00 g, 150 mmol), compound [MA22-1] (37.10 g, 165 mmol), EDC (34.6 g, 181 mmol), DMAP (1.89 g, 15.0 mmol), and THF ( 500 g), and reacted at 23 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was poured into distilled water (3L), and the precipitated solid was filtered, washed with distilled water and methanol in that order, and the obtained solid was dried under reduced pressure to obtain 79.8 g of the compound [MA32 -1] (yield: 99%).

1H-NMR(400MHz,CDCl3,δ ppm)：7.83(1H,d),7.73(1H,d),7.60-7.57(2H,m),7.56-7.53(2H,m),7.23-7.21(2H,m),6.94-6.92(2H,m),6.48(1H,d),6.42(1H,d),6.11-6.10(1H,m),5.57-5.55(1H,m), 5.43(2H,s),4.17(2H,t),4.01(2H,t),3.76(2H,q),1.95(3H,s),1.85-1.43(6H,m),1.26(3H,t)。 1 H-NMR (400MHz, CDCl3, δ ppm): 7.83 (1H, d), 7.73 (1H, d), 7.60-7.57 (2H, m), 7.56-7.53 (2H, m), 7.23-7.21 (2H , m), 6.94-6.92 (2H, m), 6.48 (1H, d), 6.42 (1H, d), 6.11-6.10 (1H, m), 5.57-5.55 (1H, m), 5.43 (2H, s ), 4.17 (2H, t), 4.01 (2H, t), 3.76 (2H, q), 1.95 (3H, s), 1.85-1.43 (6H, m), 1.26 (3H, t).

於上述所得到之化合物[MA32-1](79.8g、150mmol)加入PPTS(3.78g、15.0mmol)、乙醇(565g)，並於60℃進行加熱攪拌。於HPLC進行反應追蹤，確認反應終止後，將反應溶液以冰浴冷卻，過濾析出之固體，並以乙醇洗淨。藉由減壓乾燥所得到之固體，得到63.0g化合物[MA32](收率88%)。 PPTS (3.78 g, 15.0 mmol) and ethanol (565 g) were added to the obtained compound [MA32-1] (79.8 g, 150 mmol), and the mixture was heated and stirred at 60 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was cooled in an ice bath, the precipitated solid was filtered, and washed with ethanol. The obtained solid was dried under reduced pressure to obtain 63.0 g of a compound [MA32] (yield: 88%).

1H-NMR(400MHz,CDCl3,δ ppm)：7.83(1H,d),7.78(1H,d),7.62-7.59(2H,m),7.55-7.53(2H,m),7.24-7.22(2H,m),6.94-6.91(2H,m),6.48(1H,d),6.43(1H,d),6.11-6.10(1H,m),5.56-5.55(1H,m),4.18(2H,t),4.01(2H,t),1.95-1.94(3H,m),1.85-1.45(6H,m)。 1 H-NMR (400MHz, CDCl3, δ ppm): 7.83 (1H, d), 7.78 (1H, d), 7.62-7.59 (2H, m), 7.55-7.53 (2H, m), 7.24-7.22 (2H , m), 6.94-6.91 (2H, m), 6.48 (1H, d), 6.43 (1H, d), 6.11-6.10 (1H, m), 5.56-5.55 (1H, m), 4.18 (2H, t ), 4.01 (2H, t), 1.95-1.94 (3H, m), 1.85-1.45 (6H, m).

<合成例20> <Synthesis example 20> 化合物[MA33]之合成 Synthesis of compound [MA33]

於500mL四口燒瓶，加入化合物[MA2](20.00g、65.3mmol)、4-羥基吡啶(6.83g、71.8mmol)、EDC(15.02g、78.4mmol)、DMAP (0.80g、6.53mmol)、THF(200g)，並於23℃進行反應。於HPLC進行反應追蹤，確認反應終止後，將反應溶液注入於蒸餾水(1.2L)，並加入乙酸乙酯(1L)，於分液操作去除水層。將有機層以蒸餾水(500mL)洗淨3次之後，將有機層以硫酸鎂乾燥。然後藉由過濾，於蒸發器進行溶劑餾除，得到24.31g化合物[MA33](收率97%)。 In a 500 mL four-necked flask, compound [MA2] (20.00 g, 65.3 mmol), 4-hydroxypyridine (6.83 g, 71.8 mmol), EDC (15.02 g, 78.4 mmol), and DMAP were added. (0.80 g, 6.53 mmol), THF (200 g), and reacted at 23 ° C. The reaction was followed by HPLC. After confirming the termination of the reaction, the reaction solution was poured into distilled water (1.2 L), ethyl acetate (1 L) was added, and the aqueous layer was removed in a liquid separation operation. After the organic layer was washed three times with distilled water (500 mL), the organic layer was dried over magnesium sulfate. Then, the solvent was distilled off in an evaporator by filtration to obtain 24.31 g of a compound [MA33] (yield 97%).

1H-NMR(400MHz,CDCl3,δ ppm)：8.66(2H,d),8.15-8.11(2H,m),7.24-7.23(2H,m),7.00-6.96(2H,m),6.10-6.11(1H,m),5.57-5.56(1H,m),4.19-4.16(2H,m),4.06(2H,t),1.96-1.95(3H,m),1.90-1.46(8H,m)。 1 H-NMR (400MHz, CDCl3, δ ppm): 8.66 (2H, d), 8.15-8.11 (2H, m), 7.24-7.23 (2H, m), 7.00-6.96 (2H, m), 6.10-6.11 (1H, m), 5.57-5.56 (1H, m), 4.19-4.16 (2H, m), 4.06 (2H, t), 1.96-1.95 (3H, m), 1.90-1.46 (8H, m).

<合成例21> <Synthesis example 21> 化合物[MA34]之合成 Synthesis of compound [MA34]

於2L四口燒瓶，加入化合物[MA34-1] (264g、1.0mol)、三乙基胺(111g、1.1mol)、THF(1300g)，並將反應溶液冷卻至0℃。還有，將氯甲基乙基醚(103g、1.1mol)適下，然後於25℃攪拌。反應終止後，將反應溶液注入於乙酸乙酯(2L)，以蒸餾水(1L)洗淨3次之後，將有機層以硫酸鈉乾燥。然後過濾，於蒸發器進行溶劑餾除，將所得到之粗產物於己烷(1L)進行再製漿洗淨，並藉由進行過濾、乾燥，得到212g化合物[MA34-2](收率65%)。 In a 2L four-necked flask, add the compound [MA34-1] (264 g, 1.0 mol), triethylamine (111 g, 1.1 mol), THF (1300 g), and the reaction solution was cooled to 0 ° C. In addition, chloromethylethyl ether (103 g, 1.1 mol) was moderately stirred at 25 ° C. After the completion of the reaction, the reaction solution was poured into ethyl acetate (2L), and washed three times with distilled water (1L), and then the organic layer was dried over sodium sulfate. Then, it was filtered, and the solvent was distilled off in an evaporator. The obtained crude product was repulped and washed in hexane (1L), and then filtered and dried to obtain 212 g of a compound [MA34-2] (yield 65). %).

1H-NMR(400MHz,DMSO-d6,δ ppm)：7.64-7.70(3H,m),6.95-6.99(2H,d),6.48-6.52(1H,d),5.34(2H,s),4.34-4.37(1H,t),3.99-4.03(2H,t),3.64-3.69(2H,t),3.37-3.41(2H,m),1.68-1.73(2H,m),1.31-1.45(6H,m),1.11-1.17(3H,t)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 7.64-7.70 (3H, m), 6.95-6.99 (2H, d), 6.48-6.52 (1H, d), 5.34 (2H, s), 4.34 -4.37 (1H, t), 3.99-4.03 (2H, t), 3.64-3.69 (2H, t), 3.37-3.41 (2H, m), 1.68-1.73 (2H, m), 1.31-1.45 (6H, m), 1.11-1.17 (3H, t).

於1L四口燒瓶，加入化合物[MA34-2](54.5g、0.17mol)、4-乙烯基安息香酸(25.0g、0.17mol)、EDC(48.7g、0.25mol)、DMAP(2.1g、17mmol)、THF(250g)，並於25℃進行攪拌。反應終止後，將反應溶液注入於乙酸乙酯(250mL)，以飽和食鹽水(200mL)洗淨3次之後，將有機層以硫酸鈉乾燥。然後過濾，於蒸發器進行溶劑餾除，於所得到之殘渣加入吡啶陽離子(Pyridinium)p-甲苯磺酸(表記為PPTS)(4.3g、34mmol)、乙醇(375g)，並於65℃進行加熱攪拌。確認反應終止後，將反應溶液以冰浴冷卻，過濾析出之固體，並以乙腈洗淨。將所得到之粗產物以乙酸乙酯 /己烷=1/1溶液(250g)進行再製漿洗淨，並藉由進行過濾、乾燥，得到46.6g化合物[MA34](收率70%)。 In a 1L four-necked flask, add the compound [MA34-2] (54.5g, 0.17mol), 4-vinylbenzoic acid (25.0g, 0.17mol), EDC (48.7g, 0.25mol), DMAP (2.1g, 17mmol) ), THF (250 g), and stirred at 25 ° C. After completion of the reaction, the reaction solution was poured into ethyl acetate (250 mL), and washed three times with saturated brine (200 mL), and then the organic layer was dried over sodium sulfate. It was then filtered, and the solvent was distilled off in an evaporator. Pyridinium p-toluenesulfonic acid (designated as PPTS) (4.3 g, 34 mmol) and ethanol (375 g) were added to the obtained residue, and the mixture was heated at 65 ° C. Stir. After confirming the termination of the reaction, the reaction solution was cooled in an ice bath, and the precipitated solid was filtered and washed with acetonitrile. The obtained crude product was ethyl acetate / Hexane = 1/1 solution (250 g) was repulped and washed, and then filtered and dried to obtain 46.6 g of a compound [MA34] (yield 70%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：12.23(1H,s),7.92-7.94(2H,d),7.52-7.61(5H,m),6.94-6.96(2H,m),6.78-6.85(1H,m),6.35-6.39(1H,d),5.97-6.01(1H,d),5.42-5.44(1H,d),4.26-4.30(2H,m),3.98-4.02(2H,m),1.72-1.75(4H,m),1.46-1.48(4H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 12.23 (1H, s), 7.92-7.94 (2H, d), 7.52-7.61 (5H, m), 6.94-6.96 (2H, m), 6.78 -6.85 (1H, m), 6.35-6.39 (1H, d), 5.97-6.01 (1H, d), 5.42-5.44 (1H, d), 4.26-4.30 (2H, m), 3.98-4.02 (2H, m), 1.72-1.75 (4H, m), 1.46-1.48 (4H, m).

<合成例22> <Synthesis example 22> 化合物[MA35]之合成 Synthesis of compound [MA35]

於3L四口燒瓶，加入化合物[MA35-1](402g、1.7mol)、三乙基胺(188g、1.9mol)、THF(2000g)，並將反應溶液冷卻至0℃。還有，將氯甲基乙基醚(176g、1.9mol)適下，然後於25℃攪拌。反應終止後，將反應溶液注入於乙酸乙酯(1L)，以飽和食鹽水 (500mL)洗淨3次之後，將有機層以硫酸鈉乾燥。然後過濾，於蒸發器進行溶劑餾除，將所得到之粗產物於異丙基醇/己烷=1/2(300g)進行再製漿洗淨，藉由進行過濾、乾燥，得到505g化合物[MA35-2](收率99%)。 In a 3 L four-necked flask, the compound [MA35-1] (402 g, 1.7 mol), triethylamine (188 g, 1.9 mol), and THF (2000 g) were added, and the reaction solution was cooled to 0 ° C. In addition, chloromethylethyl ether (176 g, 1.9 mol) was moderately mixed, and then stirred at 25 ° C. After the reaction was completed, the reaction solution was poured into ethyl acetate (1 L), and the solution was saturated with brine. (500 mL) After washing three times, the organic layer was dried over sodium sulfate. Then, it was filtered, and the solvent was distilled off in an evaporator. The obtained crude product was repulped and washed with isopropyl alcohol / hexane = 1/2 (300 g), and then filtered and dried to obtain 505 g of a compound [ MA35-2] (yield 99%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：7.92-7.94(2H,d),7.03-7.06(2H,d),5.45(2H,s),4.37(1H,s),4.01-4.07(2H,t),3.69-3.74(2H,t),3.41-3.52(2H,m),1.70-1.75(2H,m),1.32-1.46(6H,m),1.14-1.20(3H,t)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 7.92-7.94 (2H, d), 7.03-7.06 (2H, d), 5.45 (2H, s), 4.37 (1H, s), 4.01-4.07 (2H, t), 3.69-3.74 (2H, t), 3.41-3.52 (2H, m), 1.70-1.75 (2H, m), 1.32-1.46 (6H, m), 1.14-1.20 (3H, t) .

於1L四口燒瓶，加入化合物[MA35-2](45.6g、0.15mol)、4-乙烯基安息香酸(29.6g、0.20mol)、EDC(50.3g、0.26mol)、DMAP(2.9g、24mmol)、THF(250g)，並於25℃進行攪拌。反應終止後，將反應溶液注入於乙酸乙酯(250mL)，以飽和食鹽水(200mL)洗淨3次之後，將有機層以硫酸鈉乾燥。然後過濾，於蒸發器進行溶劑餾除，於所得到之殘渣加入吡啶陽離子(Pyridinium)p-甲苯磺酸(表記為PPTS)(3.9g、16mmol)、乙醇(350g)，並於65℃進行加熱攪拌。確認反應終止後，將反應溶液以冰浴冷卻，過濾析出之固體，並以乙腈洗淨。將所得到之粗產物以乙酸乙酯(300g)進行再製漿洗淨，藉由進行過濾、乾燥，得到24.5g化合物[MA35](收率43%)。 In a 1L four-necked flask, compound [MA35-2] (45.6g, 0.15mol), 4-vinylbenzoic acid (29.6g, 0.20mol), EDC (50.3g, 0.26mol), DMAP (2.9g, 24mmol) were added. ), THF (250 g), and stirred at 25 ° C. After completion of the reaction, the reaction solution was poured into ethyl acetate (250 mL), and washed three times with saturated brine (200 mL), and then the organic layer was dried over sodium sulfate. Then, it was filtered, and the solvent was distilled off in an evaporator. Pyridinium p-toluenesulfonic acid (designated as PPTS) (3.9 g, 16 mmol) and ethanol (350 g) were added to the obtained residue, and heated at 65 ° C Stir. After confirming the termination of the reaction, the reaction solution was cooled in an ice bath, and the precipitated solid was filtered and washed with acetonitrile. The obtained crude product was repulped and washed with ethyl acetate (300 g), and filtered and dried to obtain 24.5 g of a compound [MA35] (yield: 43%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：12.66(1H,s),7.86-7.94(4H,m),7.59-7.61(2H,d),6.98-7.00 (2H,d),6.78-6.85(1H,m),5.97-6.01(1H,d),5.42-5.45(1H,d),4.26-4.29(2H,m),4.03-4.06(2H,m),1.74-1.76(4H,m),1.48-1.50(4H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 12.66 (1H, s), 7.86-7.94 (4H, m), 7.59-7.61 (2H, d), 6.98-7.00 (2H, d), 6.78 -6.85 (1H, m), 5.97-6.01 (1H, d), 5.42-5.45 (1H, d), 4.26-4.29 (2H, m), 4.03-4.06 (2H, m), 1.74-1.76 (4H, m), 1.48-1.50 (4H, m).

<合成例23> <Synthesis example 23> 化合物[MA36]之合成 Synthesis of compound [MA36]

於1L四口燒瓶，加入化合物[MA36-1](52.0g、0.24mol)、6-馬來醯亞胺己烷酸(50.0g、0.24mol)、EDC(67.9g、0.35mol)、DMAP(2.9g、24mmol)、THF(250g)，並於25℃進行攪拌。反應終止後，將反應溶液注入於乙酸乙酯(2L)，以飽和食鹽水(200mL)洗淨3次之後，將有機層以硫酸鈉乾燥。然後過濾，於蒸發器進行溶劑餾除，於所得到之殘渣加入蟻酸(280g)，並於50℃進行加熱攪拌。確認反應終止後，將反應溶液以冰浴冷卻，然後，將反應溶液注入於蒸餾水(1.5L)並過濾析出之固體，以乙腈洗淨。將所得到之粗產物以乙酸乙酯(90g)進行再製漿洗淨，藉由進行過濾、乾燥，得到24.5g化合物[MA36](收率43%)。 In a 1L four-necked flask, compound [MA36-1] (52.0 g, 0.24 mol), 6-maleimine hexane acid (50.0 g, 0.24 mol), EDC (67.9 g, 0.35 mol), DMAP ( 2.9 g, 24 mmol) and THF (250 g) were stirred at 25 ° C. After completion of the reaction, the reaction solution was poured into ethyl acetate (2 L), and washed three times with saturated brine (200 mL), and then the organic layer was dried over sodium sulfate. It was then filtered, and the solvent was distilled off in an evaporator. Formic acid (280 g) was added to the obtained residue, and the mixture was heated and stirred at 50 ° C. After confirming the completion of the reaction, the reaction solution was cooled in an ice bath, and then the reaction solution was poured into distilled water (1.5 L), and the precipitated solid was filtered and washed with acetonitrile. The obtained crude product was repulped and washed with ethyl acetate (90 g), and then filtered and dried to obtain 24.5 g of a compound [MA36] (yield: 43%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：12.43(1H,s),7.73-7.76(2H,d),7.57-7.61(1H,d),7.14-7.17(2H,d),7.02(2H,s),6.50-6.54(1H,d),3.40-3.43(2H,t),2.56-2.59(2H,t),1.60-1.68(2H,m),1.50-1.58(2H,m),1.27-1.34(2H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 12.43 (1H, s), 7.73-7.76 (2H, d), 7.57-7.61 (1H, d), 7.14-7.17 (2H, d), 7.02 (2H, s), 6.50-6.54 (1H, d), 3.40-3.43 (2H, t), 2.56-2.59 (2H, t), 1.60-1.68 (2H, m), 1.50-1.58 (2H, m) , 1.27-1.34 (2H, m).

<合成例24> <Synthesis example 24> 化合物[MA37]之合成 Synthesis of compound [MA37]

於1L四口燒瓶，加入化合物[MA37-1](39.5g、0.20mol)、6-馬來醯亞胺己烷酸(50.0g、0.24mol)、EDC(56.9g、0.30mol)、DMAP(2.4g、20mmol)、THF(500g)，並於25℃進行攪拌。反應終止後，將反應溶液注入於乙酸乙酯(2L)，以飽和食鹽水(200mL)洗淨3次之後，將有機層以硫酸鈉乾燥。然後過濾，於蒸發器進行溶劑餾除，於所得到之殘渣加入蟻酸(200g)，並於50℃進行加熱攪拌。確認反應終止後，將反應溶液以冰浴冷卻，然後，將反應溶液注入於蒸餾水(1L)，過濾析出之固體。將所得到之粗產物以乙酸乙酯/己烷=2/1溶 液(90g)進行再製漿洗淨，藉由進行過濾、乾燥，得到29.8g化合物[MA37](收率45%)。 In a 1-L four-necked flask, compound [MA37-1] (39.5 g, 0.20 mol), 6-maleimine hexane acid (50.0 g, 0.24 mol), EDC (56.9 g, 0.30 mol), DMAP ( 2.4 g, 20 mmol), THF (500 g), and stirred at 25 ° C. After completion of the reaction, the reaction solution was poured into ethyl acetate (2 L), and washed three times with saturated brine (200 mL), and then the organic layer was dried over sodium sulfate. It was then filtered, and the solvent was distilled off in an evaporator. Formic acid (200 g) was added to the obtained residue, and the mixture was heated and stirred at 50 ° C. After confirming the termination of the reaction, the reaction solution was cooled in an ice bath, and then the reaction solution was poured into distilled water (1 L), and the precipitated solid was filtered. The obtained crude product was dissolved in ethyl acetate / hexane = 2/1 The liquid (90 g) was repulped and washed, and then filtered and dried to obtain 29.8 g of a compound [MA37] (yield 45%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：13.04(1H,s),7.97-8.00(2H,d),7.22-7.26(2H,d),7.02(2H,s),3.40-3.44(2H,t),2.58-2.61(2H,t),1.61-1.68(2H,m),1.50-1.58(2H,m),1.27-1.35(2H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 13.04 (1H, s), 7.97-8.00 (2H, d), 7.22-7.26 (2H, d), 7.02 (2H, s), 3.40-3.44 (2H, t), 2.58-2.61 (2H, t), 1.61-1.68 (2H, m), 1.50-1.58 (2H, m), 1.27-1.35 (2H, m).

<合成例25> <Synthesis example 25> 化合物[MA38]之合成 Synthesis of compound [MA38]

於1L四口燒瓶，加入化合物[MA38-1](20.0g、0.06mol)、衣康酸單甲酯(13.4g、0.09mol)、EDC(23.8g、0.12mol)、DMAP(0.8g、6.0mmol)、CH2Cl2(200g)，並於25℃進行攪拌。反應終止後，將反應溶液注入於乙酸乙酯(500mL)，以飽和食鹽水(200mL)洗淨3次之後，將有機層以硫酸鈉乾燥。然後過濾，於蒸發器進行溶劑餾除，於所得到之殘渣加入蟻酸(150g)，並於50℃進行加熱攪拌。確認反應終止後，將反應溶液以冰浴冷卻，然後將反應溶液注入於蒸餾水( 700ml)，過濾析出之固體，並以乙腈洗淨。將所得到之粗產物以乙酸乙酯(100g)進行再製漿洗淨，藉由進行過濾、乾燥，得到10.7g化合物[MA38](收率44%)。 In a 1L four-necked flask, add compound [MA38-1] (20.0g, 0.06mol), monomethyl itaconic acid (13.4g, 0.09mol), EDC (23.8g, 0.12mol), DMAP (0.8g, 6.0 mmol), CH 2 Cl 2 (200 g), and stirred at 25 ° C. After completion of the reaction, the reaction solution was poured into ethyl acetate (500 mL), and washed three times with saturated brine (200 mL), and then the organic layer was dried over sodium sulfate. It was then filtered, and the solvent was distilled off in an evaporator. Formic acid (150 g) was added to the obtained residue, and the mixture was heated and stirred at 50 ° C. After confirming the termination of the reaction, the reaction solution was cooled in an ice bath, and then the reaction solution was poured into distilled water (700 ml), and the precipitated solid was filtered and washed with acetonitrile. The obtained crude product was repulped and washed with ethyl acetate (100 g), and then filtered and dried to obtain 10.7 g of a compound [MA38] (yield: 44%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：12.21(1H,s),7.61-7.63(2H,d),7.51-7.55(1H,d),6.94-6.97(2H,d),6.35-6.39(1H,d),6.20(1H,s),5.82(1H,s),4.08-4.11(2H,t),3.99-4.02(2H,t),3.59(3H,s),3.37(2H,s),1.70-1.74(2H,m),1.59-1.63(2H,m),1.37-1.44(4H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 12.21 (1H, s), 7.61-7.63 (2H, d), 7.51-7.55 (1H, d), 6.94-6.97 (2H, d), 6.35 -6.39 (1H, d), 6.20 (1H, s), 5.82 (1H, s), 4.08-4.11 (2H, t), 3.99-4.02 (2H, t), 3.59 (3H, s), 3.37 (2H , s), 1.70-1.7 (2H, m), 1.59-1.63 (2H, m), 1.37-1.44 (4H, m).

<合成例26> <Synthesis example 26> 化合物[MA39]之合成 Synthesis of compound [MA39]

於2L四口燒瓶，加入化合物[MA2](75.6g、0.25mol)、繖形酮(40.0g、0.09mol)、EDC(70.93g、0.25mol)、DMAP(3.0g、25mmol)、THF(750g)，並於25℃進行攪拌。反應終止後，將反應溶液注入於蒸餾水(3L)，過濾析出之固體，藉由以異丙基醇洗淨、及進行乾燥，得到91.9g化合物[MA39](收率83%)。 In a 2L four-necked flask, compound [MA2] (75.6g, 0.25mol), umbelliferone (40.0g, 0.09mol), EDC (70.93g, 0.25mol), DMAP (3.0g, 25mmol), and THF (750g) were added. ) And stirred at 25 ° C. After completion of the reaction, the reaction solution was poured into distilled water (3 L), and the precipitated solid was filtered, washed with isopropyl alcohol, and dried to obtain 91.9 g of a compound [MA39] (yield: 83%).

1H-NMR(400MHz,DMSO-d6,δ ppm)：8.08-8.12 (3H,m),7.81-7.83(1H,d),7.45(1H,s),7.30-7.32(1H,d),7.12-7.14(2H,d),6.49-6.52(1H,d),6.02(1H,s),5.67(1H,s),4.09-4.13(4H,m),1.88(3H,s),1.75-1.79(3H,m),1.64-1.67(2H,m),1.41-1.47(4H,m)。 1 H-NMR (400MHz, DMSO-d6, δ ppm): 8.08-8.12 (3H, m), 7.81-7.83 (1H, d), 7.45 (1H, s), 7.30-7.32 (1H, d), 7.12 -7.14 (2H, d), 6.49-6.52 (1H, d), 6.02 (1H, s), 5.67 (1H, s), 4.09-4.13 (4H, m), 1.88 (3H, s), 1.75-1.79 (3H, m), 1.64-1.67 (2H, m), 1.41-1.47 (4H, m).

<合成例27> <Synthesis example 27> 化合物[MA42]之合成 Synthesis of compound [MA42]

於附冷卻管之100ml茄型燒瓶，加入甲基4-羥基桂皮酸酯(Cinnamate)3.6g(20.0mmol)、2-(4-溴-1-丁基)-1,3-二氧戊環(Dioxolane)4.2g(20.0mmol)、碳酸鉀5.5g(40mmol)、及丙酮50ml而成為混合物，並一邊於溫度64℃攪拌24小時一邊使其反應。反應終止後，將反應液注入於500ml純水，得到6.0g之白色固體。將此固體以NMR測定之結果展示於以下。從次結果，確認此白色固體為中間體化合物[MA42-1](收率98%)。 In a 100 ml eggplant-shaped flask with a cooling tube, 3.6 g (20.0 mmol) of methyl 4-hydroxycinnamate (20.0 mmol) and 2- (4-bromo-1-butyl) -1,3-dioxolane were added. (Dioxolane) 4.2 g (20.0 mmol), 5.5 g (40 mmol) of potassium carbonate, and 50 ml of acetone were used as a mixture, and reacted while stirring at a temperature of 64 ° C for 24 hours. After the reaction was terminated, the reaction solution was poured into 500 ml of pure water to obtain 6.0 g of a white solid. The results of NMR measurement of this solid are shown below. From this result, it was confirmed that this white solid was an intermediate compound [MA42-1] (yield: 98%).

1H NMR(CDCl3)δ：1.62(m,2H),1.76(m,2H),1.87(m,2H),3.79(s,3H),3.85(m,2H),4.00(m,4H),4.90(m,1H),6.29(d,1H),6.90(d,2H), 7.45(d,2H),7.64(d,1H)。 1 H NMR (CDCl3) δ: 1.62 (m, 2H), 1.76 (m, 2H), 1.87 (m, 2H), 3.79 (s, 3H), 3.85 (m, 2H), 4.00 (m, 4H), 4.90 (m, 1H), 6.29 (d, 1H), 6.90 (d, 2H), 7.45 (d, 2H), 7.64 (d, 1H).

其次，於附冷卻管之200ml茄型燒瓶，加入上述所得到之中間體化合物[MA42-1]6.0g(20mmol)、2-(溴甲基)丙烯酸3.3g(20mmol)、THF55.0ml、氯化錫(II)4.3g(23mmol)、及10質量%HCl水溶液17.0ml並成為混合物，於溫度70℃攪拌20小時使其反應。反應終止後，減壓過濾反應液並與40ml純水混合，於此加入50ml氯仿進行萃取。萃取進行3次。 Next, in a 200 ml eggplant-type flask with a cooling tube, 6.0 g (20 mmol) of the intermediate compound [MA42-1] obtained above, 3.3 g (20 mmol) of 2- (bromomethyl) acrylic acid, 55.0 ml of THF, and chlorine were added. 4.3 g (23 mmol) of tin (II) and 17.0 ml of a 10% by mass aqueous solution of HCl were mixed and the mixture was stirred at a temperature of 70 ° C. for 20 hours to react. After the reaction was terminated, the reaction solution was filtered under reduced pressure and mixed with 40 ml of pure water, and 50 ml of chloroform was added thereto for extraction. The extraction was performed 3 times.

於萃取後之有機層，加入無水硫酸鎂進行乾燥，從經減壓過濾後之溶液餾除溶劑，得到4.3g黏稠性液體。此黏稠性液體以NMR測定之結果展示於以下。從此結果，確認此黏稠性液體為中間體化合物[MA42-2](收率65%)。 An anhydrous magnesium sulfate was added to the organic layer after extraction, and the solvent was distilled off from the solution filtered under reduced pressure to obtain 4.3 g of a viscous liquid. The results of NMR measurement of this viscous liquid are shown below. From this result, it was confirmed that this viscous liquid was an intermediate compound [MA42-2] (yield 65%).

1H NMR(CDCl3)δ：1.5-1.9(m,6H),2.63(m,1H),3.07(s,1H),3.80(s,3H),4.03(t,2H),4.58(m,1H),5.64(m,1H),6.23(m,1H),6.30(d,1H),6.90(d,2H),7.45(d,2H),7.64(d,1H)。 1 H NMR (CDCl3) δ: 1.5-1.9 (m, 6H), 2.63 (m, 1H), 3.07 (s, 1H), 3.80 (s, 3H), 4.03 (t, 2H), 4.58 (m, 1H ), 5.64 (m, 1H), 6.23 (m, 1H), 6.30 (d, 1H), 6.90 (d, 2H), 7.45 (d, 2H), 7.64 (d, 1H).

於附冷卻管之200ml茄型燒瓶，加入乙醇60ml、上述所得到之化合物[MA42-2]4.3g(13mmol)、及10%水酸化鈉水溶液15ml並成為混合物，於溫度85℃一邊攪拌5小時一邊使其反應。反應終止後，於500ml之燒杯加入300ml水與反應液，於室溫攪拌30分鐘之後，滴下15ml 10質量%HCl水溶液之後，過濾而得到白色固體。 In a 200 ml eggplant-type flask with a cooling tube, 60 ml of ethanol, 4.3 g (13 mmol) of the compound [MA42-2] obtained above, and 15 ml of a 10% aqueous sodium acidified aqueous solution were added to a mixture, and the mixture was stirred at a temperature of 85 ° C. for 5 hours. Make it react. After the reaction was terminated, 300 ml of water and the reaction solution were added to a 500 ml beaker, and after stirring at room temperature for 30 minutes, 15 ml of a 10% by mass aqueous HCl solution was dropped, and then filtered to obtain a white solid.

其次，於附冷卻管之50ml茄型燒瓶，加入所得到之白色固體、10質量%HCl水溶液15ml、及四氫呋喃60.0ml並成為混合物，於溫度70℃攪拌5小時使其反應。反應終止後，將反應液注入於500ml純水，得到白色固體。將此白色固體以再結晶(己烷/四氫呋喃=2/1)純化之後，得到3.0g白色固體。將此固體以NMR測定之結果展示於以下。從此結果，確認此白色固體為目的之聚合性液晶化合物[MA42](收率73%)。 Next, in a 50 ml eggplant-type flask with a cooling tube, the obtained white solid, 15 ml of a 10% by mass HCl aqueous solution, and 60.0 ml of tetrahydrofuran were added to form a mixture, and the mixture was stirred at a temperature of 70 ° C. for 5 hours for reaction. After the reaction was terminated, the reaction solution was poured into 500 ml of pure water to obtain a white solid. This white solid was purified by recrystallization (hexane / tetrahydrofuran = 2/1) to obtain 3.0 g of a white solid. The results of NMR measurement of this solid are shown below. From the results, it was confirmed that the polymerizable liquid crystal compound [MA42] (yield: 73%) was intended for the white solid.

1H NMR(DMSO-d6)δ：1.45(m,2H),1.53(m,2H),1.74(m,2H),2.62(m,1H),3.12(m,1H),4.04(m,2H),4.60(m,1H),5.70(s,1H),6.03(s,1H),6.97(d,2H),7.52(d,1H),7.63(d,2H),12.22(s,1H)。 1H NMR (DMSO-d6) δ: 1.45 (m, 2H), 1.53 (m, 2H), 1.74 (m, 2H), 2.62 (m, 1H), 3.12 (m, 1H), 4.04 (m, 2H) , 4.60 (m, 1H), 5.70 (s, 1H), 6.03 (s, 1H), 6.97 (d, 2H), 7.52 (d, 1H), 7.63 (d, 2H), 12.22 (s, 1H).

<合成例28> <Synthesis example 28> 化合物[MA46]之合成 Synthesis of compound [MA46]

於6-氯己醇(544g、4000mmol)與PPTS(1.01g、4mmol)之二氯甲烷(1632g)溶液，耗費3小時滴下二氫吡喃(403g、480mmol)，並於室溫攪拌18小時。於此溶液加入純水(1500g)，洗淨3次有機相之後，以硫酸鎂使其乾燥。由過濾去除硫酸鎂之後，進行濃縮，得到作為無色油之[MA46-1](收量：870g、收率：98.5%)。 In a solution of 6-chlorohexanol (544 g, 4000 mmol) and PPTS (1.01 g, 4 mmol) in dichloromethane (1632 g), dihydropyran (403 g, 480 mmol) was dropped over 3 hours, and stirred at room temperature for 18 hours. Pure water (1500 g) was added to this solution, and the organic phase was washed three times, and then dried with magnesium sulfate. After removing magnesium sulfate by filtration, it was concentrated to obtain [MA46-1] as a colorless oil (yield: 870 g, yield: 98.5%).

1H-NMR(400MHz,CDCl3,δ ppm)：4.59-4.56(1H,m),3.89-3.84(1H,m),3.78-3.71(1H,m),3.56-3.47(3H,m),3.42-3.36(1H,m),1.88-1.35(14H,m)。 1 H-NMR (400MHz, CDCl3, δ ppm): 4.59-4.56 (1H, m), 3.89-3.84 (1H, m), 3.78-3.71 (1H, m), 3.56-3.47 (3H, m), 3.42 -3.36 (1H, m), 1.88-1.35 (14H, m).

將加入4-反式-4-羥基環己基苯酚(96.1g、500mol)、MAX-1(121g、550mmol)、碳酸鉀(89.8g、650mmol)與碘化鉀(8.33g、50mmol)之DMF(二甲基 甲醯胺)溶液(288g)，於80℃攪拌18小時。然後，由過濾去除碳酸鉀，以乙酸乙酯(1400g)稀釋之後，使用純水(840g)洗淨3次有機相，以硫酸鎂使其乾燥。由過濾去除硫酸鎂之後，藉由進行濃縮得到粗產物[MA46-2](粗收量：232g、粗收率：123%)。所得到之粗產物[MA46-2]並未純化，而使用於以下之反應。 Add DMF (dimethylformamide, 4-trans-4-hydroxycyclohexylphenol (96.1g, 500mol), MAX-1 (121g, 550mmol), potassium carbonate (89.8g, 650mmol) and potassium iodide (8.33g, 50mmol) base Formamidine) solution (288 g), and stirred at 80 ° C. for 18 hours. Then, potassium carbonate was removed by filtration and diluted with ethyl acetate (1400 g), and then the organic phase was washed three times with pure water (840 g) and dried with magnesium sulfate. After removing magnesium sulfate by filtration, the crude product [MA46-2] was obtained by concentration (crude yield: 232 g, crude yield: 123%). The obtained crude product [MA46-2] was used in the following reaction without purification.

1H-NMR(400MHz,CDCl3,δ ppm)：7.10(2H,d),6.82(2H,m),4.59-4.56(1H,m),3.93-3.84(3H,m),3.78-3.62(2H,m),3.56-3.49(1H,m),3.41-3.38(1H,m),2.48-2.41(1H,m),2.10-2.04(1H,m),1.92-1.29(20H,m)。 1 H-NMR (400MHz, CDCl3, δ ppm): 7.10 (2H, d), 6.82 (2H, m), 4.59-4.56 (1H, m), 3.93-3.84 (3H, m), 3.78-3.62 (2H , m), 3.56-3.49 (1H, m), 3.41-3.38 (1H, m), 2.48-2.41 (1H, m), 2.10-2.04 (1H, m), 1.92-1.29 (20H, m).

加入[MA46-2](116g、250mmol)、4-甲氧基桂皮酸(49.0g、275mmol)、1-(3-二甲基胺基丙基)-3-乙基碳二醯亞胺(57.5g、300mmol)、4-二甲基胺基吡啶(36.7g、30mmol)、THF(575g)，並於室溫使其反應24小時。將於反應液所析出之黏性物質藉由過濾去除，並以乙酸乙酯(2000g)稀釋之後，以水(1000g)洗淨3次，以硫酸鎂乾燥。由過濾去除硫酸鎂之後，於經濃縮而得到之殘渣，加入PPTS(12.6g、50mmol)、乙醇(862g)，並於70℃攪拌18小時。將所得到之反應液注入於水(4000g)，攪拌2小時。將析出來之固體由過濾進行回收之後，使用2-丙醇，藉由進行再結晶而得到[MA46-3](收量：93.3g、收率：82.4%)。 [MA46-2] (116 g, 250 mmol), 4-methoxycinnamic acid (49.0 g, 275 mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide ( 57.5 g, 300 mmol), 4-dimethylaminopyridine (36.7 g, 30 mmol), and THF (575 g) were allowed to react at room temperature for 24 hours. The viscous substance precipitated from the reaction solution was removed by filtration, diluted with ethyl acetate (2000 g), washed with water (1000 g) 3 times, and dried over magnesium sulfate. After removing magnesium sulfate by filtration, the residue obtained after concentration was added with PPTS (12.6 g, 50 mmol) and ethanol (862 g), and stirred at 70 ° C. for 18 hours. The obtained reaction solution was poured into water (4000 g) and stirred for 2 hours. The precipitated solid was recovered by filtration, and then recrystallized using 2-propanol to obtain [MA46-3] (yield: 93.3 g, yield: 82.4%).

1H-NMR(400MHz,DMSO,δ ppm)：7.59(2H,d), 7.61(1H,d),7.15(2H,d),6.97(2H,d),6.83(2H,d),6.49(1H,d),4.84-4.78(1H,m),4.34(1H,t),3.91(2H,t),3.80(3H,s),3.41-3.36(2H,m),2.07-2.04(2H,m),1.84-1.81(2H,m),1.81-1.30(13H,m)。 1 H-NMR (400MHz, DMSO, δ ppm): 7.59 (2H, d), 7.61 (1H, d), 7.15 (2H, d), 6.97 (2H, d), 6.83 (2H, d), 6.49 ( 1H, d), 4.84-4.78 (1H, m), 4.34 (1H, t), 3.91 (2H, t), 3.80 (3H, s), 3.41-3.36 (2H, m), 2.07-2.04 (2H, m), 1.84-1.81 (2H, m), 1.81-1.30 (13H, m).

於[MA46-3](81.5g、180mmol)、三乙基胺(23.7g、234mol)之THF(407g)溶液，耗費1小時滴下甲基丙烯醯氯(20.5g、196mmol)，然後於室溫攪拌18小時。將所得到之反應液以乙酸乙酯(2500g)稀釋，以水(1500g)洗淨3次，以硫酸鎂乾燥。由過濾去除硫酸鎂之後，將經濃縮而得到之粗產物以THF(1000g)使其再溶解，加入活性碳(8.15g)並於室溫攪拌2小時。然後由過濾去除活性碳，經濃縮之後，以2-丙醇(400g)洗淨，得到目的化合物[MA46](收量：52.0g、收率：55.5%)。 To a solution of [MA46-3] (81.5g, 180mmol) and triethylamine (23.7g, 234mol) in THF (407g), methacrylic acid chloride (20.5g, 196mmol) was dropped over 1 hour, and then at room temperature Stir for 18 hours. The obtained reaction solution was diluted with ethyl acetate (2500 g), washed three times with water (1500 g), and dried over magnesium sulfate. After removing magnesium sulfate by filtration, the crude product obtained by concentration was re-dissolved in THF (1000 g), activated carbon (8.15 g) was added, and the mixture was stirred at room temperature for 2 hours. Then, the activated carbon was removed by filtration, and after concentrating, it was washed with 2-propanol (400 g) to obtain the target compound [MA46] (yield: 52.0 g, yield: 55.5%).

1H-NMR(400MHz,CDCl3,δ ppm)：7.65(1H,d),7.49(2H,d),7.12(2H,d),6.91(2H,d),6.83(2H,d),6.32(1H,d),6.01(1H,s),5.55(1H,s),4.93-4.88(m,1H),4.15(2H,t),3.94(2H,t),3.85(3H,s),2.51-2.47(1H,m),2.18-2.15(2H,m),1.97-1.91(5H,m),1.83-1.42(12H,m)。 1 H-NMR (400MHz, CDCl3, δ ppm): 7.65 (1H, d), 7.49 (2H, d), 7.12 (2H, d), 6.91 (2H, d), 6.83 (2H, d), 6.32 ( 1H, d), 6.01 (1H, s), 5.55 (1H, s), 4.93-4.88 (m, 1H), 4.15 (2H, t), 3.94 (2H, t), 3.85 (3H, s), 2.51 -2.47 (1H, m), 2.18-2.15 (2H, m), 1.97-1.91 (5H, m), 1.83-1.42 (12H, m).

(有機溶劑) (Organic solvents)

THF：四氫呋喃 THF: tetrahydrofuran

NMP：N-甲基-2-吡咯啶酮 NMP: N-methyl-2-pyrrolidone

BC：丁基賽珞蘇 BC: Butyl Saipan Su

CH2Cl2：二氯甲烷 CH 2 Cl 2 : dichloromethane

(聚合起始劑) (Polymerization initiator)

AIBN：2,2’-偶氮雙異丁腈 AIBN: 2,2’-azobisisobutyronitrile

[相轉移溫度之測定] [Measurement of phase transition temperature]

由實施例所得到之聚合物的表現液晶性溫度使用差示掃描熱量測定(DSC)DSC3100SR(Mac Science公司製)測定。 The liquid crystallinity temperature of the polymers obtained in the examples was measured using differential scanning calorimetry (DSC) DSC3100SR (manufactured by Mac Science).

<實施例1> <Example 1>

將MA1(9.97g、30.0mmol)溶解於THF(92.0g)中，以隔膜泵進行脫氣之後，加入AIBN(0.246g、1.5mmol)再次進行脫氣。此後於50℃使其反應30小時得到甲基丙烯酸酯之聚合物溶液。將此聚合物溶液滴下於二乙基醚(1000ml)，過濾所得到之沉澱物。將此沉澱物以二乙基醚洗淨，於40℃之烤箱中進行減壓乾燥得到甲基丙烯酸酯聚合物粉末(A)。此聚合物的數平均分子量為16000，重量平均分子量為32000。 MA1 (9.97 g, 30.0 mmol) was dissolved in THF (92.0 g), and after degassing with a diaphragm pump, AIBN (0.246 g, 1.5 mmol) was added and degassed again. Thereafter, it was reacted at 50 ° C for 30 hours to obtain a polymer solution of methacrylate. This polymer solution was dropped into diethyl ether (1000 ml), and the obtained precipitate was filtered. This precipitate was washed with diethyl ether, and dried under reduced pressure in an oven at 40 ° C to obtain a methacrylate polymer powder (A). This polymer had a number average molecular weight of 16,000 and a weight average molecular weight of 32,000.

所得到之甲基丙烯酸酯聚合物的表現液晶性溫度為145℃~190℃。 The obtained methacrylate polymer exhibited a liquid crystal temperature of 145 ° C to 190 ° C.

於所得到之甲基丙烯酸酯聚合物粉末(A)(6.0g)加入NMP(29.3g)，並於室溫攪拌5小時使其溶解。於 此溶液加入NMP(24.7g)、BC(40.0g)並藉由攪拌得到液晶配向劑(A1)。 NMP (29.3g) was added to the obtained methacrylate polymer powder (A) (6.0g), and it stirred at room temperature for 5 hours to dissolve. to This solution was added with NMP (24.7 g) and BC (40.0 g) and the liquid crystal alignment agent (A1) was obtained by stirring.

[液晶晶胞之製造] [Manufacture of liquid crystal cell]

使用上述所得到之液晶配向劑(A1)並以如下述所示之順序進行液晶晶胞的製造。 The liquid crystal cell (A1) obtained as described above was used to produce a liquid crystal cell in the order shown below.

基板係以30mm×40mm的大小，厚度為0.7mm之玻璃基板，圖案成形ITO膜而形成之櫛齒狀的像素電極係使用經配置者。 The substrate is a glass substrate having a size of 30 mm × 40 mm and a thickness of 0.7 mm, and a dentate pixel electrode formed by patterning an ITO film is used.

像素電極係具有中央部分為複數排列欲彎曲之字形狀的電極要素而構成之櫛齒狀的形狀。各電極要素之橫向方向的寬為10μm，電極要素間之間隔為20μm。形成各像素之像素電極因為係中央部分為複數排列欲彎曲之字形狀的電極要素而構成，各像素之形狀並非長方形狀，與電極要素相同係於中央部分彎曲，具備類似如粗體字顯示的字之形狀。 The pixel electrode has a dentate shape formed by arranging a plurality of zigzag-shaped electrode elements in a central portion. The width in the lateral direction of each electrode element is 10 μm, and the interval between the electrode elements is 20 μm. The pixel electrode forming each pixel is composed of a plurality of electrode elements arranged in a zigzag shape to be bent at the central portion. The shape of each pixel is not rectangular. The same as the electrode element is bent at the central portion. The shape of the word.

而且，各像素將其中央之彎曲部分作為邊境分割成上下，具有彎曲部分上側之第1區域與下側之第2區域。比較各像素之第1區域與第2區域時，構成該等之像素電極之電極要素的形成方向成為不同者。亦即，將後述之液晶配向膜之配向處理方向作為基準時，於像素之第1區域，像素電極之電極要素以成為如+15°之角度(順時針旋轉)之方式而形成，於像素之第2區域，像素電極之電極要素以成為如-15°之角度(順時針旋轉)之方式而形成。亦 即，於各像素之第1區域與第2區域，藉由像素電極與對向電極之間的施加電壓而被誘導之液晶，於基板面內之回轉動作(在平面．切換)之方向以成為如彼此反方向之方式構成。 In addition, each pixel divides the central curved portion into upper and lower portions as a border, and has a first region on the upper side of the curved portion and a second region on the lower side. When the first region and the second region of each pixel are compared, the formation direction of electrode elements constituting such pixel electrodes becomes different. That is, when the orientation processing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed in a manner such as an angle of + 15 ° (clockwise rotation) in the first region of the pixel. In the second region, the electrode elements of the pixel electrodes are formed so as to have an angle (clockwise rotation) of, for example, -15 °. also That is, in the first region and the second region of each pixel, the liquid crystal induced by the application of a voltage between the pixel electrode and the counter electrode is turned in the direction of the turning action (on the plane. Constructed in a way that opposes each other.

將上述所得到之液晶配向劑(A1)旋塗於附準備上述電極之基板。其次，於70℃之熱板90秒，形成膜厚100nm之液晶配向膜。其次，於塗膜面透過偏光板照射5mJ/cm2 313nm之紫外線之後，並於150℃之熱板加熱10分鐘，得到附液晶配向膜之基板。 The obtained liquid crystal alignment agent (A1) was spin-coated on a substrate provided with the electrode. Next, a liquid crystal alignment film with a thickness of 100 nm was formed on a hot plate at 70 ° C. for 90 seconds. Next, the coated film surface was irradiated with 5 mJ / cm 2 of 313 nm ultraviolet rays through a polarizing plate, and then heated on a hot plate at 150 ° C. for 10 minutes to obtain a substrate with a liquid crystal alignment film.

又，作為對向基板，即使於具有未形成電極之高度4μm之柱狀間隔之玻璃基板，同樣使其形成塗膜，並實施配向處理。於基板一側之液晶配向膜上印刷密封劑(協立化學製XN-1500T)。其次，將基板之另一側使液晶配向膜面面對配向方向以成為0°之方式貼合之後，熱硬化密封劑製造空晶胞。於此空晶胞藉由減壓注入法，注入液晶MLC-2041(默克股份有限公司製)，密封注入口，得到具備IPS(In-Planes Switching)模式液晶顯示元件之構成之液晶晶胞。 In addition, as a counter substrate, a glass film having a columnar space with a height of 4 μm without an electrode formed was similarly formed into a coating film and subjected to alignment treatment. A sealant (XN-1500T manufactured by Kyoritsu Chemical Co., Ltd.) was printed on the liquid crystal alignment film on the substrate side. Next, after the other side of the substrate is bonded to the liquid crystal alignment film so as to face the alignment direction so as to be 0 °, the thermosetting sealant produces an empty cell. Here, the liquid crystal cell MLC-2041 (manufactured by Merck) is injected into the empty cell by a reduced pressure injection method, and the injection port is sealed to obtain a liquid crystal cell having a structure of an IPS (In-Planes Switching) mode liquid crystal display element.

(殘像評價) (Afterimage evaluation)

將於實施例1所準備之IPS模式用液晶晶胞，偏光軸配置成正交之方式設置於2枚偏光板之間，以電壓無施加之狀態使背光點燈，透過光之輝度以成為最小的方式調整液晶晶胞之配置角度。而且，像素之第2區域從成為最暗 之角度至第1區域成為最暗之角度使液晶晶胞回轉時之回轉角度作為初期配向方位角算出。其次，於60℃之烤箱中，以頻率30Hz施加16VPP之交流電壓168小時。然後，使液晶晶胞之像素電極與對向電極之間成為短路之狀態，直接於室溫放置1小時。放置之後，以同樣方式進行測定配向方位角，將交流驅動前後之配向方位角的差作為角度△(deg.)算出。 The liquid crystal cell for the IPS mode prepared in Example 1 is arranged between the two polarizing plates so that the polarization axis is orthogonal. The backlight is turned on with no voltage applied, and the brightness of transmitted light is minimized. To adjust the configuration angle of the liquid crystal cell. In addition, the rotation angle when the liquid crystal cell is rotated from the second region to the darkest angle to the first region to the darkest angle is calculated as the initial alignment azimuth. Next, in an oven at 60 ° C, an AC voltage of 16V PP was applied at a frequency of 30Hz for 168 hours. Then, the pixel electrode and the counter electrode of the liquid crystal cell are brought into a short-circuited state, and left at room temperature for 1 hour. After standing, the orientation azimuth was measured in the same manner, and the difference between the orientation azimuths before and after the AC drive was calculated as the angle Δ (deg.).

<實施例2> <Example 2>

將MA1(4.99g、15.0mmol)、MA2(4.60g、15.0mmol)溶解於THF(88.5g)中，以隔膜泵進行脫氣之後，加入AIBN(0.246g、1.5mmol)在次進行脫氣。之後於50℃使其反應30小時得到甲基丙烯酸酯之聚合物溶液。將此聚合物溶液滴下於二乙基醚(1000ml)，過濾所得到之沉澱物。將此沉澱物以二乙基醚洗淨，於40℃之烤箱中進行減壓乾燥得到甲基丙烯酸酯聚合物粉末(B)。此聚合物之數平均分子量為14000，重量平均分子量為29000。 MA1 (4.99 g, 15.0 mmol) and MA2 (4.60 g, 15.0 mmol) were dissolved in THF (88.5 g), and after degassing with a diaphragm pump, AIBN (0.246 g, 1.5 mmol) was added to degas the next time. Then, it was made to react at 50 degreeC for 30 hours, and the methacrylate polymer solution was obtained. This polymer solution was dropped into diethyl ether (1000 ml), and the obtained precipitate was filtered. This precipitate was washed with diethyl ether, and dried under reduced pressure in an oven at 40 ° C to obtain a methacrylate polymer powder (B). This polymer had a number average molecular weight of 14,000 and a weight average molecular weight of 29,000.

所得到之甲基丙烯酸酯聚合物之表現液晶性之溫度為135℃~180℃。 The temperature at which the obtained methacrylate polymer exhibits liquid crystallinity is 135 ° C to 180 ° C.

於所得到之甲基丙烯酸酯聚合物粉末(B)(6.0g)加入NMP(29.29g)，並於室溫攪拌5小時使其溶解。於此溶液加入NMP(24.7g)、BC(450.0g)並藉由進行攪拌而得到液晶配向劑(B1)。 NMP (29.29 g) was added to the obtained methacrylate polymer powder (B) (6.0 g), and it was stirred at room temperature for 5 hours to dissolve it. NMP (24.7g) and BC (450.0g) were added to this solution, and the liquid crystal aligning agent (B1) was obtained by stirring.

對於液晶配向劑(B1)，除了將紫外線之照射量定為20mJ，於熱板之加熱溫度定為140℃之外，其他與實施例1以同樣的順序製造液晶晶胞之後，進行殘像評價。 Regarding the liquid crystal alignment agent (B1), except that the irradiation amount of ultraviolet rays was set to 20 mJ, and the heating temperature on the hot plate was set to 140 ° C, the liquid crystal cell was manufactured in the same procedure as in Example 1, and the residual image evaluation was performed. .

<實施例3> <Example 3>

將MA3(10.29g、20.0mmol)溶解於NMP(94.1g)中，以隔膜泵進行脫氣之後，加入AIBN(0.164g、1.0mmol)再次進行脫氣。之後於50℃使其反應30小時而得到甲基丙烯酸酯之聚合物溶液。將此聚合物溶液滴下於甲醇(1000ml)，過濾所得到之沉澱物。將此沉澱物以甲醇洗淨，於40℃之烤箱中進行減壓乾燥而得到甲基丙烯酸酯聚合物粉末(C)。此聚合物之數平均分子量為19000，重量平均分子量為39000。 MA3 (10.29 g, 20.0 mmol) was dissolved in NMP (94.1 g), and after degassing with a diaphragm pump, AIBN (0.164 g, 1.0 mmol) was added and degassed again. Then, it was made to react at 50 degreeC for 30 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dropped into methanol (1000 ml), and the obtained precipitate was filtered. This deposit was wash | cleaned with methanol, and it dried under reduced pressure in the oven at 40 degreeC, and obtained the methacrylate polymer powder (C). The number average molecular weight of this polymer was 19,000, and the weight average molecular weight was 39,000.

所得到之甲基丙烯酸酯聚合物之表現液晶性之溫度為150℃~300℃。 The temperature of the obtained methacrylate polymer exhibiting liquid crystallinity was 150 ° C to 300 ° C.

於所得到之甲基丙烯酸酯聚合物粉末(C)(1.0g)加入CH2Cl2(99.0g)，並於室溫攪拌5小時使其溶解而得到液晶配向劑(C1)。 CH 2 Cl 2 (99.0 g) was added to the obtained methacrylate polymer powder (C) (1.0 g), and the mixture was stirred at room temperature for 5 hours to be dissolved to obtain a liquid crystal alignment agent (C1).

對於液晶配向劑(C1)，除了將紫外線之照射量定為300mJ，於熱板之加熱溫度定為180℃之外，其他與實施例1以同樣的順序製造液晶晶胞之後，進行殘像評價。 Regarding the liquid crystal alignment agent (C1), except that the irradiation amount of ultraviolet rays was set to 300 mJ and the heating temperature on the hot plate was set to 180 ° C, the liquid crystal cell was manufactured in the same procedure as in Example 1, and the residual image evaluation was performed. .

<實施例4> <Example 4>

將MA4(8.16g、20.0mmol)溶解於NMP(75.0g) 中，以隔膜泵進行脫氣之後，加入AIBN(0.164g、1.0mmol)再次進行脫氣。之後於70℃使其反應30小時而得到甲基丙烯酸酯之聚合物溶液。將此聚合物溶液滴下於甲醇(1000ml)，過濾所得到之沉澱物。將此沉澱物以甲醇洗淨，並於40℃之烤箱中進行減壓乾燥而得到甲基丙烯酸酯聚合物粉末(D)。此聚合物之數平均分子量為18000，重量平均分子量為29000。 MA4 (8.16g, 20.0mmol) was dissolved in NMP (75.0g) After degassing with a diaphragm pump, AIBN (0.164 g, 1.0 mmol) was added and degassed again. Then, it was made to react at 70 degreeC for 30 hours, and the methacrylate polymer solution was obtained. This polymer solution was dropped into methanol (1000 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure in an oven at 40 ° C to obtain a methacrylate polymer powder (D). This polymer had a number average molecular weight of 18,000 and a weight average molecular weight of 29,000.

所得到之甲基丙烯酸酯聚合物之表現液晶性之溫度為225℃~290℃。 The temperature at which the obtained methacrylate polymer exhibits liquid crystallinity is 225 ° C to 290 ° C.

於所得到之甲基丙烯酸酯聚合物粉末(D)(6.0g)加入NMP(29.29g)，並於室溫攪拌5小時使其溶解。於此溶液加入NMP(24.7g)、BC(40.0g)並藉由進行攪拌而得到液晶配向劑(D1)。 NMP (29.29 g) was added to the obtained methacrylate polymer powder (D) (6.0 g), and it was stirred at room temperature for 5 hours to dissolve it. NMP (24.7g) and BC (40.0g) were added to this solution, and the liquid crystal aligning agent (D1) was obtained by stirring.

對於液晶配向劑(D1)，除了將紫外線之照射量定為30mJ，於熱板之加熱溫度定為240℃之外，其他與實施例1以同樣的順序製造液晶晶胞之後，進行殘像評價。 Regarding the liquid crystal alignment agent (D1), except that the irradiation amount of ultraviolet rays was set to 30 mJ and the heating temperature on the hot plate was set to 240 ° C, the liquid crystal cell was manufactured in the same procedure as in Example 1, and the residual image evaluation was performed. .

<比較例1> <Comparative example 1>

將MA5(8.66g、25.0mmol)溶解於NMP(79.8g)中，以隔膜泵進行脫氣之後，加入AIBN(0.205g、1.3mmol)再次進行脫氣。之後於70℃使其反應30小時而得到甲基丙烯酸酯之聚合物溶液。將此聚合物溶液滴下於甲醇(1000ml)，過濾所得到之沉澱物。將此沉澱物以甲醇洗淨，於40℃之烤箱中進行減壓乾燥而得到甲基丙烯 酸酯聚合物粉末(E)。此聚合物之數平均分子量為16000，重量平均分子量為31000。 MA5 (8.66 g, 25.0 mmol) was dissolved in NMP (79.8 g), and after degassing with a diaphragm pump, AIBN (0.205 g, 1.3 mmol) was added and degassed again. Then, it was made to react at 70 degreeC for 30 hours, and the methacrylate polymer solution was obtained. This polymer solution was dropped into methanol (1000 ml), and the obtained precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure in an oven at 40 ° C to obtain methacrylic acid. Ester polymer powder (E). This polymer had a number average molecular weight of 16,000 and a weight average molecular weight of 31,000.

所得到之甲基丙烯酸酯聚合物於30℃~300℃為止之溫度範圍未顯示液晶性。 The obtained methacrylate polymer did not exhibit liquid crystallinity in a temperature range from 30 ° C to 300 ° C.

於所得到之甲基丙烯酸酯聚合物粉末(E)(6.0g)加入NMP(29.29g)，並於室溫攪拌5小時使其溶解。於此溶液加入NMP(24.7g)、BC(40.0g)並藉由進行攪拌而得到液晶配向劑(E1)。 NMP (29.29 g) was added to the obtained methacrylate polymer powder (E) (6.0 g), and the mixture was stirred at room temperature for 5 hours to be dissolved. NMP (24.7g) and BC (40.0g) were added to this solution, and the liquid crystal aligning agent (E1) was obtained by stirring.

對於液晶配向劑(E1)，除了將紫外線之照射量定為500mJ，將照射後之於熱板之加熱溫度定為150℃之外，其他與實施例1以同樣的順序製造液晶晶胞之後，進行殘像評價。 Regarding the liquid crystal alignment agent (E1), except that the irradiation amount of ultraviolet rays was set to 500 mJ, and the heating temperature on the hot plate after irradiation was set to 150 ° C, the liquid crystal cells were manufactured in the same procedure as in Example 1. Perform afterimage evaluation.

<比較例2~4> <Comparative Examples 2 to 4>

使用液晶配向劑(A1)，除了將紫外線照射量定為5mJ/cm2、50mJ/cm2或500mJ/cm2、與於照射之後未進行於熱板之加熱之外，其他與實施例1同樣地作成液晶晶胞。 The liquid crystal alignment agent (A1) was used in the same manner as in Example 1 except that the ultraviolet irradiation amount was 5 mJ / cm 2 , 50 mJ / cm 2, or 500 mJ / cm 2 , and the heating was not performed on a hot plate after the irradiation. Ground is made into a liquid crystal cell.

如表1所示，在實施例1~4中，任一者皆顯示良好之配向性，係交流驅動前後之配向方位角的差之角度△(deg.)亦為極為良好的0.1以下。另外在比較例1中，未表現液晶性，未進行再配向之結果，使角度△(deg.)為1.4度之高值。又，在未進行光照射後之再加熱之比較例2~4中，液晶未配向，無法測定角度△(deg.)。 As shown in Table 1, in Examples 1 to 4, each showed good alignment, and the angle Δ (deg.) Of the difference in the alignment azimuth before and after the AC drive was also extremely good 0.1 or less. Moreover, in Comparative Example 1, the liquid crystallinity was not exhibited, and as a result of not performing realignment, the angle Δ (deg.) Was set to a high value of 1.4 degrees. In Comparative Examples 2 to 4 in which reheating was not performed after light irradiation, the liquid crystal was not aligned, and the angle Δ (deg.) Could not be measured.

<實施例5> <Example 5>

將MA1(1.99g、6.0mmol)、MA2(7.35g、24.0mmol)溶解於THF(85.5g)中，以隔膜泵進行脫氣之後，加入AIBN(1.48g、3.0mmol)再次進行脫氣。之後於50℃使其反應30小時而得到甲基丙烯酸酯之聚合物溶液。將此聚合物溶液滴下於二乙基醚(1000ml)，過濾所得到之沉澱物。將此沉澱物以二乙基醚洗淨，於40℃之烤箱中進行減壓乾燥而得到甲基丙烯酸酯聚合物粉末。 MA1 (1.99 g, 6.0 mmol) and MA2 (7.35 g, 24.0 mmol) were dissolved in THF (85.5 g), and after degassing with a diaphragm pump, AIBN (1.48 g, 3.0 mmol) was added and degassed again. Then, it was made to react at 50 degreeC for 30 hours, and the polymer solution of methacrylate was obtained. This polymer solution was dropped into diethyl ether (1000 ml), and the obtained precipitate was filtered. This precipitate was washed with diethyl ether, and dried under reduced pressure in an oven at 40 ° C to obtain a methacrylate polymer powder.

所得到之甲基丙烯酸酯聚合物之表現液晶性 之溫度為140℃~182℃。 Liquid crystallinity of the obtained methacrylate polymer The temperature is 140 ° C ~ 182 ° C.

於所得到之甲基丙烯酸酯聚合物粉末(6.0g)加入NMP(29.3g)，並於室溫攪拌5小時使其溶解。於此溶液加入NMP(24.7g)、BC(40.0g)並藉由進行攪拌而得到液晶配向劑(T1)。 NMP (29.3g) was added to the obtained methacrylate polymer powder (6.0g), and it stirred at room temperature for 5 hours to dissolve. NMP (24.7g) and BC (40.0g) were added to this solution, and the liquid crystal aligning agent (T1) was obtained by stirring.

[液晶晶胞之製造] [Manufacture of liquid crystal cell]

取代實施例1之液晶配向劑(A1)，除了使用實施例5所得到之液晶配向劑(T1)之外，其他藉由與在實施例1之[液晶晶胞之製造]同樣的方法，而得到液晶晶胞。 Instead of the liquid crystal alignment agent (A1) of Example 1, except that the liquid crystal alignment agent (T1) obtained in Example 5 was used, the same method as in [Manufacture of liquid crystal cell] in Example 1 was used, and A liquid crystal cell is obtained.

(殘像評價) (Afterimage evaluation)

除了使用於實施例5所準備之IPS模式用液晶晶胞之外，其他藉由與實施例1之(殘像評價)同樣的方法，算出角度△(deg.)。 The angle Δ (deg.) Was calculated in the same manner as in Example 1 (after-image evaluation) except that the liquid crystal cell for the IPS mode prepared in Example 5 was used.

<實施例6~51> <Examples 6 to 51>

於表2所示之組成，使用與上述實施例5同樣之方法合成實施例6~51之液晶配向劑(T2~T48)。對於所得到之液晶配向劑(T2~T30及T42~48)，除了紫外線之照射量、與於熱板之加熱溫度之外其他與實施例5以同樣之順序製造液晶晶胞。將各液晶晶胞的製造條件與殘像評價結果表示於表3。 In the composition shown in Table 2, the liquid crystal alignment agents (T2 to T48) of Examples 6 to 51 were synthesized by the same method as that of Example 5 above. With respect to the obtained liquid crystal alignment agents (T2 to T30 and T42 to 48), a liquid crystal cell was produced in the same procedure as in Example 5 except that the irradiation amount of ultraviolet rays and the heating temperature on the hot plate were the same. Table 3 shows the manufacturing conditions and afterimage evaluation results of each liquid crystal cell.

如表1及表3所示，於表現液晶性之側鏈型高分子膜照射紫外線之後，藉由於表現液晶性之溫度範圍 進行加熱，藉由自我組織化因為以高分子整體被賦予高效率液晶配向能，長期之AC驅動後幾乎亦未觀測到配向方位的移位。 As shown in Tables 1 and 3, after the side chain polymer film exhibiting liquid crystallinity is irradiated with ultraviolet rays, When heating, self-organization because the polymer is given high-efficiency liquid crystal alignment energy as a whole, almost no shift in alignment orientation is observed after long-term AC driving.

另外，如同於比較例，瞭解到於使用未表現液晶性之側鏈型高分子時，藉由長期之AC驅動造成配向方位移位。認為此係因為僅引起膜中之光反應部分液晶進行配向，高分子與液晶之相互作用微弱。 In addition, as in the comparative example, when using a side chain polymer that does not exhibit liquid crystallinity, it is understood that the alignment orientation is shifted by long-term AC driving. It is thought that this is because only the light-reactive part of the liquid crystal in the film is aligned, and the interaction between the polymer and the liquid crystal is weak.

藉由如此之本發明之方法而製造之液晶顯示元件確認顯示非常優異之殘像特性。 The liquid crystal display element manufactured by the method of the present invention is confirmed to have very excellent afterimage characteristics.

Claims (30)

一種基板的製造方法，其特徵為藉由具有[I]~[III]之步驟，而得到賦予配向控制功能之橫向電場驅動型液晶顯示元件用液晶配向膜，而具有前述液晶配向膜，[I]：將含有(A)於特定之溫度範圍表現液晶性之感光性側鏈型高分子、及(B)有機溶劑之聚合物組成物，塗佈於具有橫向電場驅動用之導電膜之基板上而形成塗膜之步驟；[II]：於[I]所得到之塗膜照射經偏光之紫外線之步驟；及[III]：加熱[II]所得到之塗膜之步驟，前述(A)成分係具有由下述式(1)~(6)所成之群中選出之任1種感光性側鏈，(式中，A、B、D分別獨立表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、或-O-CO-CH=CH-；S為碳數1~12之伸烷基，鍵結於該等之氫原子可被取代為鹵素基；T為單鍵或碳數1~12之伸烷基，鍵結於該等之氫原子可被取代為鹵素基；Y1表示選自1價之苯環、萘環、聯苯環、呋喃環、吡咯環及碳數5~8之脂環式烴之環、或選自該等之取代基相同或相異之2~6之環為透過鍵結基B鍵結而成之基，鍵結於該等之氫原子分別獨立可被-COOR0(式中，R0表示氫原子或碳數1~5之烷基)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；Y2為選自2價之苯環、萘環、聯苯環、呋喃環、吡咯環、碳數5~8之脂環式烴、及選自由該等之組合所成之群中之基、鍵結於該等之氫原子分別獨立可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；R表示羥基、碳數1~6之烷氧基、或表示與Y1相同定義；X表示單鍵、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、或-O-CO-CH=CH-，X之數成為2時，X彼此可為相同或相異；Cou表示香豆素-6-基或香豆素-7-基，鍵結於該等之氫原子分別獨立可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；q1與q2一方為1另一方為0；q3為0或1；P及Q分別獨立為2價之苯環、萘環、聯苯環、呋喃環、吡咯環、碳數5~8之脂環式烴、及選自由該等之組合所成之群中之基；惟，X為-CH=CH-CO-O-、-O-CO-CH=CH-時，於-CH=CH-鍵結側之P或Q為芳香環，P之數成為2以上時，P彼此可為相同或相異、Q之數成為2以上時，Q彼此可為相同或相異；l1為0或1；l2為0~2之整數；l1與l2皆為0時，且T為單鍵時A亦表示單鍵；l1為1時，且T為單鍵時B亦表示單鍵；H及I分別獨立為2價之苯環、萘環、聯苯環、呋喃環、吡咯環、及選自該等組合之基)；
Figure TWI636973B_C0001
A method for manufacturing a substrate, characterized by obtaining steps of [I] to [III] to obtain a liquid crystal alignment film for a lateral electric field driven liquid crystal display element with an alignment control function, and having the aforementioned liquid crystal alignment film, [I ]: A polymer composition containing (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a specific temperature range and (B) an organic solvent is coated on a substrate having a conductive film for driving a horizontal electric field And the step of forming a coating film; [II]: the step of irradiating the polarized ultraviolet light on the coating film obtained in [I]; and [III]: the step of heating the coating film obtained in [II], the aforementioned component (A) It has any one type of photosensitive side chain selected from the group consisting of the following formulas (1) to (6), (where A, B, and D independently represent a single bond, -O-, and -CH 2 -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O-CO-CH = CH-; S is the extension of carbon number 1 ~ 12 Alkyl groups, hydrogen atoms bonded to these can be substituted with halogen groups; T is a single bond or an alkylene group having 1 to 12 carbon atoms, hydrogen atoms bonded to these can be substituted with halogen groups; Y 1 It represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or from 2 to 2 having the same or different substituents. The ring of 6 is a group bonded through a bonding group B, and the hydrogen atoms bonded to these can be independently -COOR 0 (where R 0 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) , -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen group, C 1-5 alkyl group, or C 1-5 alkyloxy group; Y 2 is selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of a combination of these, The hydrogen atoms bonded to these can be independently -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen group, alkyl group with carbon number 1 to 5, or carbon number Substituted by alkyloxy groups of 1 to 5; R represents hydroxyl group, alkoxy group with 1 to 6 carbon atoms, or represents the same definition as Y 1 ; X represents single bond, -COO-, -OCO-, -N = N -, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X becomes 2, X may be the same or different from each other ; Cou means coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to these can be independently -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen, C1-C5 alkyl, or C1-C5 alkyloxy substituted; q1 and q2 are 1 and the other is 0; q3 is 0 or 1; P and Q Are independently a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and a group selected from the group consisting of these combinations; X is- When CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the -CH = CH- bonding side is an aromatic ring, and when the number of P becomes 2 or more, P may be the same as each other Or different, when the number of Q becomes 2 or more, Q can be the same or different; l1 is 0 or 1; l2 is an integer from 0 to 2; when both l1 and l2 are 0, and T is a single bond A Also represents a single bond; when l1 is 1, and T is a single bond, B also represents a single bond; H and I are each independently a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and selected from The basis of these combinations);
Figure TWI636973B_C0001
 如請求項1之方法，其中，(A)成分係具有引起光交聯、光異構化、或光弗賴斯重排(Photo Fries Rearrangement)之感光性側鏈。The method according to claim 1, wherein the component (A) has a photosensitive side chain that causes photocrosslinking, photoisomerization, or photofries rearrangement. 如請求項1或2之方法，其中，(A)成分係具有由下述式(7)~(10)所成之群中選出之任1種感光性側鏈，(式中，A、B、D分別獨立表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、或-O-CO-CH=CH-；Y1表示選自1價之苯環、萘環、聯苯環、呋喃環、吡咯環及碳數5~8之脂環式烴之環、或選自該等之取代基相同或相異之2~6之環為透過鍵結基B鍵結而成之基，鍵結於該等之氫原子分別獨立可被-COOR0(式中，R0表示氫原子或碳數1~5之烷基)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；X表示單鍵、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、或-O-CO-CH=CH-，X之數成為2時，X彼此可為相同或相異；l表示1~12之整數；m表示0~2之整數，m1、m2表示1~3之整數；n表示0~12之整數(惟，n=0時B為單鍵)；Y2為2價之苯環、萘環、聯苯環、呋喃環、吡咯環、碳數5~8之脂環式烴、及選自由該等之組合所成之群中之基，鍵結於該等之氫原子分別獨立可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；R表示羥基、碳數1~6之烷氧基、或表示與Y1相同定義)；
Figure TWI636973B_C0002
The method according to claim 1 or 2, wherein the component (A) has any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10), (where, A, B , D independently represent single bond, -O-, -CH 2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O-CO -CH = CH-; Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms, or a substitution selected from these The 2 ~ 6 rings with the same or different groups are the groups bonded through the bonding group B. The hydrogen atoms bonded to these groups can be independently -COOR 0 (where R 0 represents a hydrogen atom or carbon Alkyl with 1 to 5), -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen group, alkyl with 1 to 5 carbons, or carbon with 1 to 5 carbons Substituted by an alkyloxy group; X represents a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X becomes 2, X can be the same or different; l represents an integer of 1 ~ 12; m represents an integer of 0 ~ 2, m1, m2 represent 1 ~ 3 Integer; n represents an integer from 0 to 12 (however, when n = 0, B is a single bond); Y 2 is a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, carbon number 5-8 Alicyclic hydrocarbons, and a group selected from the group consisting of a combination of these, hydrogen atoms bonded to these can be independently -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen, C1-C5 alkyl, or C1-C5 alkyloxy; R represents hydroxyl, C1-C6 alkoxy, or Y 1 Same definition);
Figure TWI636973B_C0002
 如請求項1或2之方法，其中，(A)成分係具有由下述式(11)~(13)所成之群中選出之任1種感光性側鏈，(式中，A分別獨立表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、或-O-CO-CH=CH-；X表示單鍵、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、或-O-CO-CH=CH-，X之數成為2時，X彼此可為相同或相異；l表示1~12之整數，m表示0~2之整數，m1表示1~3之整數；R表示選自1價之苯環、萘環、聯苯環、呋喃環、吡咯環及碳數5~8之脂環式烴之環、或選自該等之取代基相同或相異之2~6之環為透過鍵結基B鍵結而成之基，鍵結於該等之氫原子分別獨立可被-COOR0(式中，R0表示氫原子或碳數1~5之烷基)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代，或表示羥基或是碳數1~6之烷氧基)；
Figure TWI636973B_C0003
The method according to claim 1 or 2, wherein the component (A) has any one of the photosensitive side chains selected from the group consisting of the following formulas (11) to (13), (where A is independently Represents a single bond, -O-, -CH 2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O-CO-CH = CH -; X represents a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X becomes 2, X may be the same or different from each other; l represents an integer of 1-12, m represents an integer of 0-2, m1 represents an integer of 1-3; R represents selected from monovalent The benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon ring with 5 to 8 carbon atoms, or 2 to 6 rings with the same or different substituents selected from these are through The base formed by the bonding group B, the hydrogen atoms bonded to these can be independently -COOR 0 (where R 0 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen group, C1-C5 alkyl group, or C1-C5 alkyloxy group, or represents hydroxyl group or Alkoxy group with carbon number 1 ~ 6);
Figure TWI636973B_C0003
 如請求項1或2之方法，其中，(A)成分係具有下述式(14)或(15)所示之感光性側鏈，(式中，A分別獨立表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、或-O-CO-CH=CH-；Y1表示選自1價之苯環、萘環、聯苯環、呋喃環、吡咯環及碳數5~8之脂環式烴之環、或選自該等之取代基相同或相異之2~6之環為透過鍵結基B鍵結而成之基，鍵結於該等之氫原子分別獨立可被-COOR0(式中，R0表示氫原子或碳數1~5之烷基)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；l表示1~12之整數，m1、m2表示1~3之整數)；
Figure TWI636973B_C0004
The method according to claim 1 or 2, wherein the component (A) has a photosensitive side chain represented by the following formula (14) or (15), (wherein, A independently represents a single bond, -O-, -CH 2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O-CO-CH = CH-; Y 1 means selected from 1 Valence benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring and alicyclic hydrocarbon ring having 5 to 8 carbon atoms, or 2 to 6 rings selected from these same or different substituents are The bases bonded through the bonding group B, the hydrogen atoms bonded to these can be independently -COOR 0 (where R 0 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen, C1-C5 alkyl, or C1-C5 alkyloxy; l means 1 ~ Integer of 12, m1 and m2 represent integers of 1 ~ 3);
Figure TWI636973B_C0004
 如請求項1或2之方法，其中，(A)成分係具有下述式(16)或(17)所示之感光性側鏈，(式中，A表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、或-O-CO-CH=CH-；X表示單鍵、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、或-O-CO-CH=CH-，X之數成為2時，X彼此可為相同或相異；l表示1~12之整數，m表示0~2之整數)；
Figure TWI636973B_C0005
The method according to claim 1 or 2, wherein (A) component has a photosensitive side chain represented by the following formula (16) or (17), (wherein, A represents a single bond, -O-, -CH 2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O-CO-CH = CH-; X represents a single bond, -COO- , -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X becomes 2, , X can be the same or different from each other; l represents an integer from 1 to 12, m represents an integer from 0 to 2);
Figure TWI636973B_C0005
 如請求項1或2之方法，其中，(A)成分係具有由下述式(18)或(19)所成之群中選出之任1種感光性側鏈，(式中，A、B分別獨立表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、或-O-CO-CH=CH-；Y1表示選自1價之苯環、萘環、聯苯環、呋喃環、吡咯環及碳數5~8之脂環式烴之環、或選自該等之取代基相同或相異之2~6之環為透過鍵結基B鍵結而成之基，鍵結於該等之氫原子分別獨立可被-COOR0(式中，R0表示氫原子或碳數1~5之烷基)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；q1與q2一方為1另一方為0；l表示1~12之整數，m1、m2表示1~3之整數；R1表示氫原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基)；
Figure TWI636973B_C0006
The method according to claim 1 or 2, wherein the component (A) has any one type of photosensitive side chain selected from the group consisting of the following formula (18) or (19), (where, A, B Respectively represent a single bond, -O-, -CH 2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O-CO-CH = CH-; Y 1 represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the substituents selected from these are the same Or the different 2 ~ 6 rings are the groups bonded through the bonding group B, and the hydrogen atoms bonded to these can be independently -COOR 0 (where R 0 represents a hydrogen atom or carbon number 1 ~ 5 alkyl group), -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen group, C 1-5 alkyl group, or C 1-5 alkyl group Substituted by an oxy group; one of q1 and q2 is 1 and the other is 0; l represents an integer of 1-12, m1, m2 represent an integer of 1-3; R 1 represents a hydrogen atom, -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen group, C 1-5 alkyl group, or C 1-5 alkyloxy group);
Figure TWI636973B_C0006
 如請求項1或2之方法，其中，(A)成分係具有下述式(20)所示之感光性側鏈，(式中，A表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、或-O-CO-CH=CH-；Y1表示選自1價之苯環、萘環、聯苯環、呋喃環、吡咯環及碳數5~8之脂環式烴之環、或選自該等之取代基相同或相異之2~6之環為透過鍵結基B鍵結而成之基，鍵結於該等之氫原子分別獨立可被-COOR0(式中，R0表示氫原子或碳數1~5之烷基)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；X表示單鍵、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、或-O-CO-CH=CH-，X之數成為2時，X彼此可為相同或相異；l表示1~12之整數，m表示0~2之整數)；
Figure TWI636973B_C0007
The method according to claim 1 or 2, wherein the component (A) has a photosensitive side chain represented by the following formula (20), (wherein, A represents a single bond, -O-, -CH 2 -,- COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O-CO-CH = CH-; Y 1 represents a monovalent benzene ring, naphthalene Rings, biphenyl rings, furan rings, pyrrole rings, and alicyclic hydrocarbon rings having 5 to 8 carbon atoms, or 2 to 6 rings selected from the same or different substituents of these are bonded through a bonding group B bond The formed base, the hydrogen atoms bonded to these can be independently -COOR 0 (wherein R 0 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen, C 1-5 alkyl, or C 1-5 alkyloxy; X represents a single bond, -COO-,- OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, when the number of X becomes 2, X Can be the same or different from each other; l represents an integer from 1 to 12, m represents an integer from 0 to 2);
Figure TWI636973B_C0007
 如請求項1或2之方法，其中，(A)成分係具有由下述式(21)~(31)所成之群中選出之任1種液晶性側鏈，(式中，A及B具有與上述相同之定義；Y3為1價之苯環、萘環、聯苯環、呋喃環、含有氮之雜環、及碳數5~8之脂環式烴、及選自由該等之組合所成之群中之基、鍵結於該等之氫原子分別獨立可被-NO2、-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；R3表示氫原子、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、1價之苯環、萘環、聯苯環、呋喃環、含有氮之雜環、碳數5~8之脂環式烴、碳數1~12之烷基、或碳數1~12之烷氧基；q1與q2一方為1另一方為0；l表示1~12之整數，m表示0~2之整數，惟，在式(23)~(24)，全部m之合計為2以上，在式(25)~(26)，全部m之合計為1以上，m1、m2及m3分別獨立表示1~3之整數；R2表示氫原子、-NO2、-CN、鹵素基、1價之苯環、萘環、聯苯環、呋喃環、含有氮之雜環、及碳數5~8之脂環式烴、及、烷基、或烷基氧基；Z1、Z2表示單鍵、-CO-、-CH2O-、-CH=N-、-CF2-)；
Figure TWI636973B_C0008
Figure TWI636973B_C0009
The method according to claim 1 or 2, wherein (A) component has any one kind of liquid crystal side chain selected from the group consisting of the following formulas (21) to (31), (where, A and B It has the same definition as above; Y 3 is a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, heterocyclic ring containing nitrogen, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and selected from these The groups in the group and the hydrogen atoms bonded to these groups can be independently -NO 2 , -CN, halogen groups, C 1-5 alkyl groups, or C 1-5 alkyl oxygen Substituted by a group; R 3 represents a hydrogen atom, -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan Rings, heterocycles containing nitrogen, alicyclic hydrocarbons with carbon numbers 5-8, alkyl groups with carbon numbers 1-12, or alkoxy groups with carbon numbers 1-12; one of q1 and q2 is 1 and the other is 0; l represents an integer from 1 to 12, and m represents an integer from 0 to 2. However, in equations (23) to (24), the total of all m is 2 or more, and in equations (25) to (26), the total of all m Is 1 or more, m1, m2 and m3 independently represent integers of 1 to 3; R 2 represents a hydrogen atom, -NO 2 , -CN, halogen group, monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, Heterocycles containing nitrogen, and alicyclic hydrocarbons having 5 to 8 carbon atoms, and alkyl or alkyloxy groups; Z 1 and Z 2 represent single bonds, -CO-, -CH 2 O-, and -CH = N-, -CF 2- );
Figure TWI636973B_C0008
Figure TWI636973B_C0009
 一種基板，其係具有藉由請求項1~9中任一項記載之方法所製造之橫向電場驅動型液晶顯示元件用液晶配向膜。A substrate having a liquid crystal alignment film for a lateral electric field driving type liquid crystal display element manufactured by the method described in any one of claims 1 to 9. 一種橫向電場驅動型液晶顯示元件，其係具有請求項10所記載之基板。A lateral electric field driven liquid crystal display element having the substrate described in claim 10. 一種液晶顯示元件之製造方法，該液晶顯示元件係藉由具有：準備請求項10所記載之基板(第1基板)之步驟、得到具有前述液晶配向膜之第2基板之步驟、及得到液晶顯示元件之步驟，而得到橫向電場驅動型液晶顯示元件；該得到具有前述液晶配向膜之第2基板之步驟為藉由具有下述[I’]~[III’]步驟，而得到賦予配向控制功能之液晶配向膜，[I’]：於第2基板上塗佈含有(A)於特定之溫度範圍表現出液晶性之感光性側鏈型高分子、及(B)有機溶劑之聚合物組成物而形成塗膜之步驟，[II’]：於[I’]所得到之塗膜照射經偏光之紫外線之步驟，及[III’]：加熱[II’]所得到之塗膜之步驟；得到液晶顯示元件之步驟為下述[IV]步驟，[IV]：透過液晶並使前述第1及第2基板之液晶配向膜以相對之方式，使前述第1及第2基板為對向配置。A method of manufacturing a liquid crystal display element comprising: a step of preparing the substrate (first substrate) described in claim 10, a step of obtaining a second substrate having the liquid crystal alignment film, and obtaining a liquid crystal display Device step to obtain a lateral electric field driven liquid crystal display device; the step of obtaining the second substrate with the aforementioned liquid crystal alignment film is to provide the alignment control function by having the following steps [I '] to [III'] Liquid crystal alignment film, [I ']: A polymer composition containing (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a specific temperature range and (B) an organic solvent is coated on the second substrate And the step of forming the coating film, [II ']: the step of irradiating the polarized ultraviolet rays on the coating film obtained in [I'], and [III ']: the step of heating the coating film obtained in [II']; The step of the liquid crystal display element is the following [IV] step, [IV]: the liquid crystal alignment films of the first and second substrates are transmitted through the liquid crystal, and the first and second substrates are arranged to face each other. 一種橫向電場驅動型液晶顯示元件，其係藉由請求項12記載之方法來製造。A lateral electric field driven liquid crystal display element manufactured by the method described in claim 12. 一種使用組成物之橫向電場驅動型液晶顯示元件用液晶配向膜的製造方法，其特徵為，前述組成物係含有(A)於特定之溫度範圍表現液晶性之感光性側鏈型高分子及(B)有機溶劑，前述(A)成分係具有由下述式(1)~(6)所成之群中選出之任1種感光性側鏈，(式中，A、B、D分別獨立表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH=CH-CO-O-、或-O-CO-CH=CH-；S為碳數1~12之伸烷基，鍵結於該等之氫原子可被取代為鹵素基；T為單鍵或碳數1~12之伸烷基，鍵結於該等之氫原子可被取代為鹵素基；Y1表示選自1價之苯環、萘環、聯苯環、呋喃環、吡咯環及碳數5~8之脂環式烴之環、或選自該等之取代基相同或相異之2~6之環為透過鍵結基B鍵結而成之基，鍵結於該等之氫原子分別獨立可被-COOR0(式中，R0表示氫原子或碳數1~5之烷基)、-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；Y2為選自2價之苯環、萘環、聯苯環、呋喃環、吡咯環、碳數5~8之脂環式烴、及選自由該等之組合所成之群中之基、鍵結於該等之氫原子分別獨立可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；R表示羥基、碳數1~6之烷氧基、或表示與Y1相同定義；X表示單鍵、-COO-、-OCO-、-N=N-、-CH=CH-、-C≡C-、-CH=CH-CO-O-、或-O-CO-CH=CH-，X之數成為2時，X彼此可為相同或相異；Cou表示香豆素-6-基或香豆素-7-基，鍵結於該等之氫原子分別獨立可被-NO2、-CN、-CH=C(CN)2、-CH=CH-CN、鹵素基、碳數1~5之烷基、或碳數1~5之烷基氧基所取代；q1與q2一方為1另一方為0；q3為0或1；P及Q分別獨立為2價之苯環、萘環、聯苯環、呋喃環、吡咯環、碳數5~8之脂環式烴、及選自由該等之組合所成之群中之基；惟，X為-CH=CH-CO-O-、-O-CO-CH=CH-時，於-CH=CH-鍵結側之P或Q為芳香環，P之數成為2以上時，P彼此可為相同或相異、Q之數成為2以上時，Q彼此可為相同或相異；l1為0或1；l2為0~2之整數；l1與l2皆為0時，且T為單鍵時A亦表示單鍵；l1為1時，且T為單鍵時B亦表示單鍵；H及I分別獨立為2價之苯環、萘環、聯苯環、呋喃環、吡咯環、及選自該等組合之基)；
Figure TWI636973B_C0010
Figure TWI636973B_C0011
A method for manufacturing a liquid crystal alignment film for a lateral electric field driven liquid crystal display element using a composition, characterized in that the composition comprises (A) a photosensitive side chain type polymer exhibiting liquid crystallinity in a specific temperature range and ( B) Organic solvent, the aforementioned (A) component has any one type of photosensitive side chain selected from the group consisting of the following formulas (1) to (6), (wherein, A, B, and D are independently represented Single bond, -O-, -CH 2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, or -O-CO-CH = CH- ; S is an alkylene group with a carbon number of 1 to 12, and hydrogen atoms bonded to these can be substituted with halogen groups; T is a single bond or an alkylene group with a carbon number of 1 to 12, bonded to these hydrogens The atom may be substituted with a halogen group; Y 1 represents a ring selected from a monovalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and alicyclic hydrocarbon having 5 to 8 carbon atoms, or selected from these The 2-6 rings with the same or different substituents are the groups bonded through the bonding group B, and the hydrogen atoms bonded to these can be independently -COOR 0 (where R 0 represents a hydrogen atom Or alkyl group with carbon number 1 ~ 5), -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen group, alkyl group with carbon number 1-5, or carbon number 1 Substituted by an alkyloxy group of ~ 5; Y 2 is selected from a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and selected from The groups in the group formed by the combination, the hydrogen atoms bonded to these can be independently -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen group, carbon number alkyl of 1 to 5, or an alkyl group having a carbon number of 1 to 5 substituted; R & lt represents a hydroxyl group, an alkoxy group having a carbon number of 1 to 6, or the same meanings as Y 1; X represents a single bond, -COO -, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = CH-, the number of X becomes 2 , X can be the same or different from each other; Cou means coumarin-6-yl or coumarin-7-yl, and the hydrogen atoms bonded to these can be independently -NO 2 , -CN, -CH = C (CN) 2 , -CH = CH-CN, halogen group, C 1-5 alkyl group, or C 1-5 alkyloxy group; q1 and q2 are 1 and the other is 0 ; Q3 is 0 or 1; P and Q are independently a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination selected from these The base in the formed group; however, when X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the -CH = CH- bonding side is an aromatic ring, When the number of P becomes 2 or more, P may be the same or different, and when the number of Q becomes 2 or more, Q may be the same or different; l1 is 0 or 1; l2 is an integer of 0 ~ 2; l1 and When l2 is 0, and T is a single bond, A is also Represents a single bond; when l1 is 1, and T is a single bond, B also represents a single bond; H and I are independently a divalent benzene ring, naphthalene ring, biphenyl ring, furan ring, pyrrole ring, and selected from the Basis of other combinations);
Figure TWI636973B_C0010
Figure TWI636973B_C0011
 一種化合物，其係如下述式(1)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)；
Figure TWI636973B_C0012
A compound which is a compound represented by the following formula (1), (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);
Figure TWI636973B_C0012
 一種化合物，其係如下述式(3)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)；
Figure TWI636973B_C0013
A compound which is represented by the following formula (3), (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);
Figure TWI636973B_C0013
 一種化合物，其係下述式(4)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基；u表示0或1)；
Figure TWI636973B_C0014
A compound which is a compound represented by the following formula (4), (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; u represents 0 or 1);
Figure TWI636973B_C0014
 一種化合物，其係下述式(5)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基；u表示0或1)；
Figure TWI636973B_C0015
A compound which is a compound represented by the following formula (5), (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; u represents 0 or 1);
Figure TWI636973B_C0015
 一種化合物，其係下述式(6)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)；
Figure TWI636973B_C0016
A compound which is a compound represented by the following formula (6), (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);
Figure TWI636973B_C0016
 一種化合物，其係下述式(7)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)；
Figure TWI636973B_C0017
A compound which is a compound represented by the following formula (7), (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);
Figure TWI636973B_C0017
 一種化合物，其係下述式(8)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)；
Figure TWI636973B_C0018
A compound which is a compound represented by the following formula (8), (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);
Figure TWI636973B_C0018
 一種化合物，其係下述式(9)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)；
Figure TWI636973B_C0019
A compound which is a compound represented by the following formula (9), (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);
Figure TWI636973B_C0019
 一種化合物，其係下述式(10)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)；
Figure TWI636973B_C0020
A compound which is a compound represented by the following formula (10), (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);
Figure TWI636973B_C0020
 一種化合物，其係下述式(11)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基；Py表示2-吡啶基、3-吡啶基或4-吡啶基；u表示0或1)；
Figure TWI636973B_C0021
A compound which is a compound represented by the following formula (11), (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms; Py represents 2-pyridyl, 3-pyridine Group or 4-pyridyl; u represents 0 or 1);
Figure TWI636973B_C0021
 一種使用化合物之橫向電場驅動型液晶顯示元件用液晶配向膜的製造方法，其特徵為，前述化合物係下述式(12)所示之化合物，(式中，S表示碳數2~9之伸烷基；v表示1或2)；
Figure TWI636973B_C0022
A method for manufacturing a liquid crystal alignment film for a lateral electric field driven liquid crystal display element using a compound, characterized in that the aforementioned compound is a compound represented by the following formula (12), (wherein, S represents an extension of carbon numbers 2 to 9 Alkyl; v represents 1 or 2);
Figure TWI636973B_C0022
 一種化合物，其係下述式(13)所示之化合物，(式中，S表示碳數2~10之伸烷基；u表示0或1)；
Figure TWI636973B_C0023
A compound which is a compound represented by the following formula (13), (wherein S represents an alkylene group having 2 to 10 carbon atoms; u represents 0 or 1);
Figure TWI636973B_C0023
 一種化合物，其係下述式(14)所示之化合物，(式中，S表示碳數1~10之伸烷基；u表示0或1)；
Figure TWI636973B_C0024
A compound which is a compound represented by the following formula (14), (wherein S represents an alkylene group having 1 to 10 carbon atoms; u represents 0 or 1);
Figure TWI636973B_C0024
 一種化合物，其係下述式(15)所示之化合物，(式中，S表示碳數2~10之伸烷基)；
Figure TWI636973B_C0025
A compound which is a compound represented by the following formula (15), (wherein S represents an alkylene group having 2 to 10 carbon atoms);
Figure TWI636973B_C0025
 一種化合物，其係下述式(16)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)；
Figure TWI636973B_C0026
A compound which is a compound represented by the following formula (16), (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);
Figure TWI636973B_C0026
 一種化合物，其係下述式(17)所示之化合物，(式中，R表示氫原子或甲基；S表示碳數2~10之伸烷基)；
Figure TWI636973B_C0027
A compound which is a compound represented by the following formula (17), (wherein R represents a hydrogen atom or a methyl group; S represents an alkylene group having 2 to 10 carbon atoms);
Figure TWI636973B_C0027
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