TWI593710B - Method of manufacturing liquid crystal alignment film, liquid crystal alignment film and liquid crystal display element - Google Patents

Method of manufacturing liquid crystal alignment film, liquid crystal alignment film and liquid crystal display element Download PDF

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TWI593710B
TWI593710B TW101144769A TW101144769A TWI593710B TW I593710 B TWI593710 B TW I593710B TW 101144769 A TW101144769 A TW 101144769A TW 101144769 A TW101144769 A TW 101144769A TW I593710 B TWI593710 B TW I593710B
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liquid crystal
side chain
chain type
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TW201341413A (en
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後藤耕平
川月喜弘
近藤瑞穗
安藤昌幸
北川大桂夫
椿幸樹
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日產化學工業股份有限公司
大阪有機化學工業股份有限公司
公立大學法人兵庫縣立大學
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • 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
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133715—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films by first depositing a monomer
    • 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

Description

液晶配向膜之製造方法，液晶配向膜及液晶顯示元件 Method for manufacturing liquid crystal alignment film, liquid crystal alignment film and liquid crystal display element

本發明係關於液晶配向膜之製造方法、液晶配向膜及液晶顯示元件，尤其是用於液晶顯示元件之液晶配向膜之製造方法，藉由其製造方法而得到之液晶配向膜及使用其液晶配向膜之液晶顯示元件。 The present invention relates to a method for producing a liquid crystal alignment film, a liquid crystal alignment film, and a liquid crystal display device, particularly a method for producing a liquid crystal alignment film for a liquid crystal display device, a liquid crystal alignment film obtained by the method of the same, and a liquid crystal alignment thereof Liquid crystal display element of the film.

液晶顯示元件已知作為輕量、薄型且低耗電之顯示裝置，於近年來則用於大型電視用途等、已經歷顯著發展。作為液晶顯示元件，例如由具備電極之一對透明基板挾持液晶層而構成。然後於液晶顯示元件，液晶於基板間，由成為如所期望之配向狀態之有機材料所構成之有機膜作為液晶配向膜使用。 Liquid crystal display elements are known as lightweight, thin, and low-power display devices, and have been undergoing significant development in recent years for use in large-scale television applications. The liquid crystal display element is configured by, for example, holding one of the electrodes and holding the liquid crystal layer on the transparent substrate. Then, in the liquid crystal display element, the liquid crystal is used between the substrates, and an organic film composed of an organic material which is in a desired alignment state is used as the liquid crystal alignment film.

亦即液晶配向膜係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，擔任於其基板間使液晶配向於一定方向之角色。而且於液晶配向膜，將液晶例如對於基板除了配向於一定方向、平行方向等之角色，有時被要求擔任控制液晶之預傾角的角色。在如此之液晶配向膜，控制液晶配向之能力(以下，稱為配向控制能)，藉由對於構成液晶配向膜之有機膜進行配向處理而給予。 In other words, the constituent members of the liquid crystal alignment film-type liquid crystal display device are formed on the surface in contact with the liquid crystal of the substrate on which the liquid crystal is held, and serve as a function of aligning the liquid crystal in a predetermined direction between the substrates. Further, in the liquid crystal alignment film, for example, the liquid crystal is required to function as a pretilt angle for controlling the liquid crystal, in addition to the role of the substrate in a certain direction or a parallel direction. In such a liquid crystal alignment film, the ability to control the alignment of the liquid crystal (hereinafter referred to as alignment control energy) is given by the alignment treatment of the organic film constituting the liquid crystal alignment film.

作為用以賦予配向控制能之液晶配向膜的配向處理方法，一直以來已知之摩擦(rubbing)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之有機 膜，將其表面以綿、尼龍、聚酯等布以一定方向擦拭(進行摩擦)，使液晶配向於擦拭方向(摩擦方向)之方法。此摩擦法因為可簡單地實現比較安定之液晶配向狀態，已被利用在以往之液晶顯示元件的製造製程。而且，作為用於液晶配向膜之有機膜，主要已選定耐熱性等之信賴性或電氣特性優異之聚醯亞胺系有機膜。 As an alignment treatment method of a liquid crystal alignment film for imparting alignment control energy, a rubbing method has been known. The rubbing method refers to organic matter such as polyvinyl alcohol or polyamine or polyimine on a substrate. The film is a method in which the surface is wiped (frictionally) in a certain direction with a cloth such as cotton, nylon or polyester to align the liquid crystal in the wiping direction (friction direction). This rubbing method has been utilized in the manufacturing process of a conventional liquid crystal display element because it can easily realize a relatively stable liquid crystal alignment state. In addition, as the organic film used for the liquid crystal alignment film, a polyimide-based organic film excellent in reliability or electrical properties such as heat resistance has been selected.

然而，擦拭聚醯亞胺等所構成之液晶配向膜表面之摩擦法，有產生發塵或靜電之問題。又，近年來液晶表元件之高精細化、或為了對應因基板上之電極或液晶驅動用之開關主動元件而造成之凹凸，有時會無法將液晶配向膜之表面以布均勻擦拭，無法實現均勻之液晶配向。 However, the rubbing method of wiping the surface of the liquid crystal alignment film composed of polyimide or the like has a problem of generating dust or static electricity. In addition, in recent years, the liquid crystal display element is highly refined, or the surface of the liquid crystal alignment film cannot be uniformly wiped by the cloth in order to cope with the unevenness caused by the electrode on the substrate or the switching active element for driving the liquid crystal. Uniform liquid crystal alignment.

於此，作為不進行摩擦之液晶配向膜其他的配向處理方法，目前盛行研究光配向法。 Here, as another alignment treatment method of the liquid crystal alignment film which does not rub, the optical alignment method is currently being studied.

於光配向法雖有各式各樣之方法，藉由經直線偏光或準直(Collimate)之光構成液晶配向膜而於有機膜內形成各向異性，依照其各向異性使液晶配向。 Although there are various methods in the photo-alignment method, an anisotropy is formed in the organic film by forming a liquid crystal alignment film by linearly polarized or collimated light, and the liquid crystal is aligned according to the anisotropy thereof.

作為主要主光配向法，已知有分解型之光配向法。例如於聚醯亞胺膜照射偏光紫外線，利用分子構造之紫外線吸收偏光方向依存性而產生異方性分解。而且，由未分解而殘留之聚醯亞胺使液晶配向(參照專利文獻1)。 As a main main light alignment method, a decomposition type photoalignment method is known. For example, when a polyimide film is irradiated with a polarized ultraviolet ray, the ultraviolet ray of a molecular structure absorbs the polarization direction dependence to cause an anisotropy decomposition. In addition, the liquid crystal is aligned by the polyimine which remains without being decomposed (see Patent Document 1).

又，亦已知光交聯型或光異構化型之光配向法。例如使用聚乙烯基肉桂酸酯，照射偏光紫外線，以偏光與平行之2個側鏈的雙鍵部分使其產生二聚化反應(交聯反應)。而且，將液晶配向於與偏光方向垂直之方向(參照 非專利文獻1)。又，使用於側鏈具有偶氮苯之側鏈型高分子時，照射偏光紫外線，以偏光與平行之側鏈的偶氮苯部使其產生異構化反應，將液晶配向於與偏光方向垂直之方向(參照非專利文獻2)。 Further, a photo-alignment type or a photo-isomerization type photo-alignment method is also known. For example, polyvinyl cinnamate is used, and a polarized ultraviolet ray is irradiated to cause a dimerization reaction (crosslinking reaction) by polarizing a double bond portion of two side chains in parallel. Moreover, the liquid crystal is aligned in a direction perpendicular to the polarization direction (refer to Non-patent document 1). Further, when a side chain type polymer having an azobenzene in a side chain is used, a polarized ultraviolet ray is irradiated, and an isomerization reaction is carried out by polarizing the azobenzene portion of the side chain in parallel, and the liquid crystal is aligned perpendicular to the polarization direction. Direction (see Non-Patent Document 2).

如以上之例，於由光配向法之液晶配向膜的配向處理方法，不需要摩擦，無產生發塵或靜電之懸念。而且，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，成為工業性生產製程上合適之液晶配向膜的配向處理方法。 As described above, in the alignment treatment method of the liquid crystal alignment film by the photoalignment method, no rubbing is required, and no suspense of dust generation or static electricity is generated. Further, the substrate of the liquid crystal display element having irregularities on the surface can be subjected to alignment treatment, and is an alignment treatment method of a suitable liquid crystal alignment film in an industrial production process.

〔先前技術文獻〕 [Previous Technical Literature] 〔專利文獻〕 [Patent Document]

專利文獻1：日本特許第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. lchimura et al., Chem. Rev 100, 1847 (2000) Non-Patent Document 2: K. lchimura et al., Chem. Rev 100, 1847 (2000)

如以上，光配向法作為液晶顯示元件之配向處理方法，與從以往被利用於工業上之摩擦法相比較不需要摩擦步驟，因此具備莫大優點。而且與藉由摩擦使配向控制能維持幾乎一定之摩擦法相比，於光配向法，可以使經偏光 之光的照射量變化而控制配向控制能。然而於光配向法，於為了實現與由摩擦法時相同程度之配向控制能的情況，大量經偏光之光照射量變為必要，或會有無法實現穩定之液晶配向的情況。 As described above, the photo-alignment method is an alignment treatment method for a liquid crystal display element, and it does not require a rubbing step as compared with a conventional rubbing method used in the industry, and therefore has a great advantage. Moreover, compared with the friction method in which the alignment control can maintain almost constant by friction, the photo-alignment method can make the polarized light The amount of illumination of the light changes to control the alignment control energy. However, in the case of the light alignment method, in order to achieve the same degree of alignment control energy as in the case of the rubbing method, a large amount of polarized light irradiation amount becomes necessary, or a stable liquid crystal alignment may not be achieved.

例如，於經上述之專利文獻1所記載之分解型的光配向法，係有必要從輸出500W之高壓水銀燈照射60分鐘紫外光於聚醯亞胺膜等，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之光配向法的情況，會有照射數J(焦耳)~數十J左右之多量紫外線成為必要的情況。進而，於光交聯型或光異構化型之光配向法時，因為液晶配向之熱安定性或光安定性劣化，於作為液晶顯示元件時，會有發生配向不良或顯示燒附之類的問題。 For example, in the photo-alignment method of the decomposition type described in the above-mentioned Patent Document 1, it is necessary to irradiate ultraviolet light to a polyimide film for 60 minutes from a high-pressure mercury lamp outputting 500 W, and it is necessary to irradiate a large amount of ultraviolet rays for a long period of time. . Further, even in the case of the dimerization type or the photoisomerization type photo-alignment method, it is necessary to irradiate a large amount of ultraviolet rays having a number J (joules) to several tens of J. Further, in the photo-alignment type or the photo-isomerization type photo-alignment method, since the thermal stability or the photostability of the liquid crystal alignment deteriorates, when it is used as a liquid crystal display element, alignment failure or display burn-up occurs. The problem.

從而於光配向法，係追求配向處理之高效率化或安定液晶配向之實現，正追求可高效率進行賦予對液晶配向膜之高度配向控制能之液晶配向膜之製造方法的開發。 In the optical alignment method, the development of a liquid crystal alignment film that imparts high alignment control energy to a liquid crystal alignment film with high efficiency is being pursued in pursuit of high efficiency of alignment treatment or stabilization of liquid crystal alignment.

於此，本發明之目的係以提供一種使用光並可高效率且良好控制液晶配向之液晶配向膜的製造方法。 Accordingly, an object of the present invention is to provide a method for producing a liquid crystal alignment film which uses light and can efficiently control liquid crystal alignment.

又，本發明之目的係以提供一種使用其液晶配向膜的製造方法，並實現使用光之高效率配向處理而製造之液晶配向膜。 Further, an object of the present invention is to provide a liquid crystal alignment film produced by using a method for producing a liquid crystal alignment film and using a high-efficiency alignment treatment of light.

進而，本發明之目的係以提供一種實現使用光之高效率配向處理而製造具備液晶配向膜的液晶顯示元件。 Further, an object of the present invention is to provide a liquid crystal display element comprising a liquid crystal alignment film which realizes high-efficiency alignment treatment using light.

本發明者，進行努力研究的結果，得到以下之發現終而完成本發明。 The inventors of the present invention conducted the research and obtained the following findings to complete the present invention.

本發明之液晶配向膜之製造方法，使用表現液晶性而得到感光性之側鏈型高分子膜，不進行摩擦處理，利用藉由偏光照射進行配向處理之方法。而且，偏光照射之後，設置加熱其側鏈型高分子膜之步驟製造液晶配向膜。此時，藉由最適化偏光之照射量與於偏光照射後之加熱步驟之加熱溫度，在液晶配向膜實現高效率之配向處理，可實現以高效率且良好之配向控制能的賦予。 In the method for producing a liquid crystal alignment film of the present invention, a side chain type polymer film which exhibits liquid crystallinity and which is photosensitive is used, and a method of performing alignment treatment by polarized light irradiation without performing rubbing treatment is used. Further, after the polarized light irradiation, a step of heating the side chain type polymer film is provided to produce a liquid crystal alignment film. At this time, by optimizing the irradiation amount of the polarized light and the heating temperature of the heating step after the polarized light irradiation, high-efficiency alignment treatment is realized in the liquid crystal alignment film, and high-efficiency and good alignment control energy can be imparted.

本發明，係將以下作為要旨者。 The present invention has the following gist.

(1)一種液晶配向膜之製造方法，其係具有[I]~[III]步驟之液晶配向膜之製造方法：[I]於基板上，於特定溫度範圍形成表現液晶性之感光性的側鏈型高分子膜之步驟、[II]照射經偏光之紫外線於前述側鏈型高分子膜之步驟、及[III]加熱前述經紫外線照射之側鏈型高分子膜之步驟，其特徵為[II]步驟之紫外線照射量，係於前述側鏈型高分子膜之△A為最大時之紫外線照射量的1%~70%範圍內，其中△A係與前述經偏光之紫外線的偏光方向平行方向之紫外線吸光度與垂直方向之紫外線吸光度之差。 (1) A method for producing a liquid crystal alignment film, which is a method for producing a liquid crystal alignment film having the steps [I] to [III]: [I] forming a photosensitive side exhibiting liquid crystallinity on a substrate at a specific temperature range a step of a chain type polymer film, [II] a step of irradiating the polarized ultraviolet light to the side chain type polymer film, and [III] a step of heating the ultraviolet side irradiated side chain type polymer film, which is characterized by [ The ultraviolet irradiation amount in the step II] is in the range of 1% to 70% of the ultraviolet irradiation amount when the ΔA of the side chain type polymer film is the maximum, wherein the ΔA system is parallel to the polarization direction of the polarized ultraviolet light. The difference between the ultraviolet absorbance of the direction and the ultraviolet absorbance of the vertical direction.

(2)如上述(1)之液晶配向膜之製造方法，其中 [II]步驟之紫外線照射量，係將前述△A為最大時之紫外線照射量1%~50%之範圍內。 (2) The method for producing a liquid crystal alignment film according to (1) above, wherein The amount of ultraviolet irradiation in the step [II] is in the range of 1% to 50% of the ultraviolet irradiation amount when the ΔA is the maximum.

(3)如上述(1)或(2)之液晶配向膜之製造方法，其中[III]步驟之加熱溫度，為從比前述側鏈型高分子膜表現液晶性之溫度範圍下限高10℃溫度至比該溫度範圍上限低10℃溫度之範圍的溫度。 (3) The method for producing a liquid crystal alignment film according to the above (1) or (2), wherein the heating temperature in the step [III] is a temperature higher than a lower limit of a temperature range in which the liquid crystallinity of the side chain type polymer film is higher than 10 ° C To a temperature within a range of 10 ° C lower than the upper limit of the temperature range.

(4)如上述(1)~(3)中任一項之液晶配向膜之製造方法，其中含有於表現前述液晶性之感光性的側鏈型高分子之感光性基為偶氮苯、二苯乙烯、桂皮酸、桂皮酸酯、查酮、香豆素、二苯乙炔(Tolan)、苯甲酸苯酯、或其衍生物。 (4) The method for producing a liquid crystal alignment film according to any one of the above (1), wherein the photosensitive group of the side chain type polymer which exhibits the liquid crystallinity is azobenzene or Styrene, cinnamic acid, cinnamic acid ester, ketone, coumarin, tolan, phenyl benzoate, or derivatives thereof.

(5)一種液晶配向膜之製造方法，其係具有[I]~[IV]步驟之液晶配向膜之製造方法：[I]於基板上，於特定溫度範圍形成表現液晶性之光交聯性的側鏈型高分子膜之步驟、[II]照射經偏光之紫外線於前述光交聯性側鏈型高分子膜之步驟、及[III]加熱前述經紫外線照射之側鏈型高分子膜之步驟、[IV]照射無偏光之紫外線於經照射前述紫外線之後再經加熱之側鏈型高分子膜之步驟，其特徵為[II]步驟之紫外線照射量，係於前述側鏈型高分子膜之△A為最大時之紫外線照射量的1%~70%範圍內，其中△A係與前述經偏光之紫外線的偏光方向平行方向之紫外 線吸光度與垂直方向之紫外線吸光度之差。 (5) A method for producing a liquid crystal alignment film, which is a method for producing a liquid crystal alignment film having the steps [I] to [IV]: [I] forming a photocrosslinkability exhibiting liquid crystallinity on a substrate at a specific temperature range a step of a side chain type polymer film, [II] a step of irradiating the polarized ultraviolet light to the photocrosslinkable side chain type polymer film, and [III] heating the ultraviolet side-irradiated side chain type polymer film Step, [IV] a step of irradiating the unpolarized ultraviolet ray to the side chain type polymer film which is heated after the irradiation of the ultraviolet ray, wherein the ultraviolet ray irradiation amount of the step [II] is the side chain type polymer film ΔA is in the range of 1% to 70% of the ultraviolet irradiation amount at the maximum, wherein ΔA is in the ultraviolet direction parallel to the polarization direction of the polarized ultraviolet light. The difference between the line absorbance and the UV absorbance in the vertical direction.

(6)如上述(5)之液晶配向膜之製造方法，其中[II]步驟之紫外線照射量，係將前述△A為最大時之紫外線照射量1%~50%之範圍內。 (6) The method for producing a liquid crystal alignment film according to the above (5), wherein the ultraviolet irradiation amount in the step [II] is in a range of 1% to 50% of the ultraviolet irradiation amount when the ΔA is maximum.

(7)如上述(5)或(6)之液晶配向膜之製造方法，其中[III]步驟之加熱溫度，為從比前述側鏈型高分子膜表現液晶性之溫度範圍下限高10℃溫度至比該溫度範圍上限低10℃溫度之範圍的溫度。 (7) The method for producing a liquid crystal alignment film according to the above (5) or (6), wherein the heating temperature in the step [III] is 10 ° C higher than a lower limit of a temperature range in which the liquid crystallinity of the side chain type polymer film is expressed. To a temperature within a range of 10 ° C lower than the upper limit of the temperature range.

(8)如上述(5)~(7)中任一項之液晶配向膜之製造方法，其中由[IV]步驟之紫外線照射，使具有前述側鏈型高分子膜之光交聯性基之20莫耳%以上進行反應。 (8) The method for producing a liquid crystal alignment film according to any one of the above (5), wherein the photocrosslinkable group having the side chain type polymer film is irradiated with ultraviolet rays of the step [IV]. 20 mol% or more of the reaction.

(9)如上述(5)~(8)中任一項之液晶配向膜之製造方法，其中含有於表現前述液晶性之光交聯性的側鏈型高分子之感光性基為桂皮酸、桂皮酸酯、查酮、香豆素、二苯乙炔(Tolan)、或其衍生物。 (9) The method for producing a liquid crystal alignment film according to any one of the above (5), wherein the photosensitive group of the side chain type polymer which exhibits light crosslinkability of the liquid crystal property is cinnamic acid. Cinnamate, Chalcone, Coumarin, Tolan, or a derivative thereof.

(10)如上述(1)~(9)中任一項之液晶配向膜之製造方法，其中前述側鏈型高分子膜，係具有從選自由烴、丙烯酸酯、及甲基丙烯酸酯所構成之群中至少1種所構成之主鏈、與下述式(1)~(7)至少1種所表示之側鏈的構造； The method for producing a liquid crystal alignment film according to any one of the above aspects, wherein the side chain type polymer film has a structure selected from the group consisting of hydrocarbons, acrylates, and methacrylates. a structure of at least one of the main chain and a side chain represented by at least one of the following formulas (1) to (7);

(式(1)中，A1、B1各自獨立表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-或NH-CO-，Y1為選自由苯環、萘環、聯苯環、呋喃環、吡咯環、及碳數5~8之環狀烴所構成之群中至少一種之基，鍵結於該等之氫原子可各自獨立為經-NO2、-CN、-C=C(CN)2、-C=CH-CN、鹵基、烷基、或烷氧基所取代；X1表示單鍵、-COO-、-OCO-、-N=N-、-C=C-、-C≡C-、或C6H4-，I1(亦稱為I1)表示1~12之整數，m1表示1~3之整數，n1表示1~12之整數；式(2)中，A2、B2、D1各自獨立表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-或NH-CO-，Y2為選自由苯環、萘環、聯苯環、呋喃環、吡咯環、及碳數 5~8之環狀烴所構成之群中至少一種之基，鍵結於該等之氫原子可各自獨立為經-NO2、-CN、-C=C(CN)2、-C=CH-CN、鹵基、烷基、或烷氧基所取代；X2表示單鍵、-COO-、-OCO-、-N=N-、-C=C-、-C≡C-、或C6H4-，R1表示氫原子、或碳數1~6之烷基，I2(亦稱為I2)表示1~12之整數，m2表示1~3之整數，n2表示1~]2之整數；式(3)中，A3表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、或NH-CO-，X3表示單鍵、-COO-、-OCO-、-N=N-、-C=C-、-C≡C-、或C6H4-，R2表示氫原子、或碳數1~6之烷基，I3(亦稱為I3)表示1~12之整數，m3表示1~3之整數；式(4)中，I4(亦稱為I4)表示1~12之整數；式(5)中，A4表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、或NH-CO-，X4表示-COO-，Y3表示苯環、萘環、及聯苯環所構成之群中至少一種之基，鍵結於該等之氫原子可各自獨立為經-NO2、-CN、-C=C(CN)2、-C=CH-CN、鹵基、烷基、或烷氧基所取代；I5(亦稱為I5)表示1~12之整數，m4表示1~3之整數；式(6)中，A5表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、或NH-CO-，R3表示選自由氫原子、-NO2、-CN、-C=C(CN)2、-C=CH-CN、鹵基、碳數1~6之烷基、及碳數1~6之烷氧基所構成之群中至少一種之基，I6(亦稱為I6)表示1~12之整數；鍵結於式(6)中之苯環之氫原子可各自獨立為經-NO2、-CN、-C=C(CN)2、-C=CH-CN、鹵基、烷基、或烷氧基所取代； 式(7)中，A6表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、或NH-CO-，B3表示單鍵、-COO-、-OCO-、-N=N-、-C=C-、-C≡C-、或C6H4-；W1表示選自由苯環、萘環、聯苯環、呋喃環、吡咯環、及碳數5~8之環狀烴所構成之群中至少一種之基，鍵結於該等之氫原子可各自獨立為經-NO2、-CN、-C=C(CN)2、-C=CH-CN、鹵基、烷基、或烷氧基所取代，I7表示1~12之整數，m5、m6各自表示1~3之整數)。 (In the formula (1), A 1 and B 1 each independently represent a single bond, -O-, -CH 2 -, -COO-, -OCO-, -CONH- or NH-CO-, and Y 1 is selected from benzene. a group of at least one of a group consisting of a ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a cyclic hydrocarbon having 5 to 8 carbon atoms, and the hydrogen atoms bonded to the hydrogen atoms may each independently be a -NO 2 , -CN, -C=C(CN) 2 , -C=CH-CN, halo, alkyl, or alkoxy; X 1 represents a single bond, -COO-, -OCO-, -N =N-, -C=C-, -C≡C-, or C 6 H 4 -, I1 (also known as I 1 ) represents an integer from 1 to 12, m1 represents an integer from 1 to 3, and n1 represents 1~ An integer of 12; in the formula (2), A 2 , B 2 , and D 1 each independently represent a single bond, -O-, -CH 2 -, -COO-, -OCO-, -CONH-, or NH-CO-, Y 2 is a group selected from the group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a cyclic hydrocarbon having 5 to 8 carbon atoms, and is bonded to the hydrogen atom. Each is independently substituted by -NO 2 , -CN, -C=C(CN) 2 , -C=CH-CN, halo, alkyl, or alkoxy; X 2 represents a single bond, -COO-, -OCO -, - N = N - , - C = C -, - C≡C-, or C 6 H 4 -, R 1 represents a hydrogen atom, or 1 to 6 carbon atoms Alkyl, I2 (also referred to as the I 2) represents an integer of 1 to 12, m2 represents an integer of 1 to 3, n2 represents an integer of 1 ~] 2 of; of formula (3), A 3 represents a single bond, -O- , -CH 2 -, -COO-, -OCO-, -CONH-, or NH-CO-, X 3 represents a single bond, -COO-, -OCO-, -N=N-, -C=C-, -C≡C-, or C 6 H 4 -, R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, I3 (also referred to as I 3 ) represents an integer of 1 to 12, and m3 represents 1 to 3 In the formula (4), I4 (also referred to as I 4 ) represents an integer from 1 to 12; in the formula (5), A 4 represents a single bond, -O-, -CH 2 -, -COO-, -OCO -, -CONH-, or NH-CO-, X 4 represents -COO-, and Y 3 represents at least one of a group consisting of a benzene ring, a naphthalene ring, and a biphenyl ring, bonded to the hydrogen atom Each may be independently substituted by -NO 2 , -CN, -C=C(CN) 2 , -C=CH-CN, halo, alkyl, or alkoxy; I5 (also referred to as I 5 ) An integer from 1 to 12, m4 represents an integer from 1 to 3; in the formula (6), A 5 represents a single bond, -O-, -CH 2 -, -COO-, -OCO-, -CONH-, or NH- CO-, R 3 represents an alkyl group selected from a hydrogen atom, -NO 2 , -CN, -C=C(CN) 2 , -C=CH-CN, a halogen group, a carbon number of 1 to 6, and a carbon number of 1. ~6 alkoxy At least one group of group, I6 (also referred to as the I 6) represents an integer of from 1 to 12; a hydrogen atom bonded to the formula (6) may each independently benzene ring by -NO 2, -CN, -C =C(CN) 2 , -C=CH-CN, a halogen group, an alkyl group, or an alkoxy group; in the formula (7), A 6 represents a single bond, -O-, -CH 2 -, -COO -, -OCO-, -CONH-, or NH-CO-, B 3 represents a single bond, -COO-, -OCO-, -N=N-, -C=C-, -C≡C-, or C 6 H 4 -; W 1 represents a group selected from at least one of the group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a cyclic hydrocarbon having 5 to 8 carbon atoms, bonded thereto. The hydrogen atoms may be independently substituted by -NO 2 , -CN, -C=C(CN) 2 , -C=CH-CN, halo, alkyl or alkoxy, and I7 represents 1~12. The integers, m5 and m6 each represent an integer from 1 to 3).

(11)一種液晶配向膜，其係由如上述(1)~(10)中任一項之液晶配向膜之製造方法所製造。 (11) A liquid crystal alignment film produced by the method for producing a liquid crystal alignment film according to any one of the above (1) to (10).

(12)一種液晶顯示元件，其係具有如上述(11)之液晶配向膜。 (12) A liquid crystal display element comprising the liquid crystal alignment film of (11) above.

依據本發明，係提供一種可高效率配向處理之液晶配向膜的製造方法。 According to the present invention, there is provided a method of producing a liquid crystal alignment film which can be processed with high efficiency.

又，可提供使用其液晶配向膜之製造方法，可高效率配向處理液晶配向膜。進而，提供一種使用其液晶配向膜可實現高效率配向處理而製造具備液晶配向膜之液晶顯示元件。 Further, a method of producing a liquid crystal alignment film using the same can be provided, and the liquid crystal alignment film can be processed with high efficiency. Further, there is provided a liquid crystal display element comprising a liquid crystal alignment film which can realize high-efficiency alignment treatment using the liquid crystal alignment film.

在本發明之液晶配向膜之製造方法使用表現液晶性而得到感光性之側鏈型高分子膜，為於特定溫度範圍下表現 液晶性之感光性的側鏈型高分子膜。而且，結合於主鏈之側鏈具有感光性，感應於光可引起交聯反應、異構化反應、或光富萊士重排(Fries rearrangement)。結合於主鏈之具有感光性之基雖並未特別限定，但期望為感應於光而引起交聯反應或光富萊士重排的構造。此情況下，即使曝露於熱等之外部壓力，亦可長時間穩定保持經實現之配向控制能。表現液晶性而得到感光性之側鏈型高分子膜的構造，若為滿足如此特性者即可雖並未特別限定，以於側鏈構造具有剛直液晶基成分為佳。 In the method for producing a liquid crystal alignment film of the present invention, a side chain type polymer film which exhibits liquid crystallinity and which is photosensitive is used, and is expressed in a specific temperature range. A liquid crystalline photosensitive side chain type polymer film. Moreover, the side chain bonded to the main chain is photosensitive, and the light induced may cause a crosslinking reaction, an isomerization reaction, or a Fries rearrangement. The photosensitive group to be bonded to the main chain is not particularly limited, but a structure in which a cross-linking reaction or a light-French rearrangement is caused by induction of light is desired. In this case, even if it is exposed to external pressure such as heat, the achieved alignment control energy can be stably maintained for a long period of time. The structure of the side chain type polymer film which exhibits liquid crystallinity and is photosensitive is not particularly limited as long as it satisfies such characteristics, and it is preferable to have a rigid liquid crystal based component in the side chain structure.

此情況下，於將該側鏈型高分子作為液晶配向膜之際，可得到穩定之液晶配向。該高分子之構造，例如具有主鏈與結合於其之側鏈，其側鏈可與聯苯基、三聯苯基、苯基環己基、苯甲酸苯酯基、偶氮苯基等之液晶基成分結合於先端部，具有感應於光而與進行交聯反應或異構化反應之感光性基的構造、或具有主鏈與結合於其之側鏈，其側鏈可為液晶基成分，且具有進行光富萊士重排反應之苯甲酸苯酯基的構造。 In this case, when the side chain type polymer is used as a liquid crystal alignment film, stable liquid crystal alignment can be obtained. The structure of the polymer has, for example, a main chain and a side chain bonded thereto, and a side chain thereof may be a liquid crystal group such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenyl benzoate group or an azobenzene group. a component having a structure in which a component is bonded to a tip end, has a photosensitive group which is inductive to light and undergoes a crosslinking reaction or an isomerization reaction, or has a main chain and a side chain bonded thereto, and a side chain thereof may be a liquid crystal group component, and A structure having a phenyl benzoate group for performing a light Flencide rearrangement reaction.

作為由表現液晶性而得到感光性之側鏈型高分子膜的構造之具體例子，以具有從選自由烴、丙烯酸酯、甲基丙烯酸酯、馬來亞醯胺及矽氧烷所構成之群中至少一種所構成之主鏈、與下述式(1)~(7)之至少一種所構成之側鏈的構造為佳。 Specific examples of the structure of the side chain type polymer film obtained by exhibiting liquid crystallinity have a group selected from the group consisting of hydrocarbons, acrylates, methacrylates, maleimides, and decanes. The structure of at least one of the main chain and the side chain formed by at least one of the following formulas (1) to (7) is preferable.

(式(1)中之A1、B1、X1、Y1、I1、m1、n1係與上述所定義相同，式(2)中之A2、B2、D1、X2、Y2、R1、I2、m2、n2係與上述所定義相同，式(3)中之A3、X3、R2、I3、m3係與上述所定義相同，式(4)中之I4係與上述所定義相同，式(5)中之A4、X4、Y3、I5、m4係與上述所定義相同，式(6)中之A5、R3、I6係與上述所定義相同。式(7)中之A6、B3、W1、I7、m5、m6係與上述所定義相同)。 (A 1 , B 1 , X 1 , Y 1 , I1, m1, and n1 in the formula (1) are the same as defined above, and A 2 , B 2 , D 1 , X 2 , Y in the formula (2) 2 , R 1 , I2, m2, and n2 are the same as defined above, and A 3 , X 3 , R 2 , I3, and m3 in the formula (3) are the same as defined above, and the I4 system in the formula (4) In the same manner as defined above, A 4 , X 4 , Y 3 , I5, and m4 in the formula (5) are the same as defined above, and A 5 , R 3 and I6 in the formula (6) are the same as defined above. A 6 , B 3 , W 1 , I7, m5, and m6 in the formula (7) are the same as defined above.

上述式(1)~(7)所表示之側鏈，係具備具有將聯苯、聯三苯、苯基環己基、苯甲酸苯酯、偶氮苯等之基作為液晶基成分之構造。而且，於其先端部，係具有具引起 感應於光之二聚化反應，並進行交聯反應之感光性基、或具有與主鏈結合於該之側鏈、其側鏈可為液晶基成分，且具有進行光富萊士重排反應之苯甲酸苯酯基之至少任一種。 The side chain represented by the above formulas (1) to (7) has a structure in which a group such as biphenyl, terphenyl, phenylcyclohexyl, phenyl benzoate or azobenzene is used as a liquid crystal group component. Moreover, at its apex, it has a photosensitive group which is induced to undergo a dimerization reaction of light and which undergoes a crosslinking reaction, or which has a side chain bonded to the main chain, a side chain thereof which may be a liquid crystal group component, and which has a light fulcene rearrangement reaction At least any one of phenyl benzoate groups.

在本發明，側鏈型高分子膜，於不失液晶性或光反應性之範圍內亦可併用不具光反應性之側鏈構造。舉例時可列舉如下述式(8)之構造。 In the present invention, the side chain type polymer film may be used in combination with a side chain structure having no photoreactivity in the range of no liquid crystallinity or photoreactivity. As an example, the structure of the following formula (8) is mentioned.

上述式(8)中，E1表示單鍵、-O-、-CH2-、-COO、-OCO-、-CONH-、-NH-CO-，Z表示單鍵、-COO、-OCO-、-N=N-、-C=C-、-C≡C-、或C6H4-，k1表示1~12之整數，p1、q1各自獨立表示0~3之整數，R4表示氫原子、-NO2、-CN、-C=C(CN)2、-C=CH-CN、鹵基、碳數1~6之烷氧基、羧基、或其組合所構成之基。 In the above formula (8), E 1 represents a single bond, -O-, -CH 2 -, -COO, -OCO-, -CONH-, -NH-CO-, and Z represents a single bond, -COO, -OCO- , -N=N-, -C=C-, -C≡C-, or C 6 H 4 -, k1 represents an integer from 1 to 12, p1 and q1 each independently represent an integer from 0 to 3, and R 4 represents hydrogen. A group consisting of an atom, -NO 2 , -CN, -C=C(CN) 2 , -C=CH-CN, a halogen group, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, or a combination thereof.

於以下，對於在本發明之液晶配向膜之製造方法所使用之表現液晶性而得到感光性之側鏈型高分子膜，簡單稱為本發明之側鏈型高分子膜。 In the following, the side chain type polymer film which exhibits liquid crystallinity which is used for the method for producing a liquid crystal alignment film of the present invention to obtain photosensitivity is simply referred to as a side chain type polymer film of the present invention.

本發明之液晶配向膜之製造方法，於使用本發明之側鏈型高分子之基板上形成塗膜之後，照射經偏光之紫外線。接著，藉由進行加熱實現對側鏈型高分子膜之高效率各向異性之導入，製造具備液晶配向控制能之液晶配向 膜。於本發明之液晶配向膜之製造方法，基於與本發明之側鏈型高分子膜之光反應的液晶性藉由自動組合化利用經誘發之分子再配向的原理，實現對側鏈型高分子膜之高效率各向異性之導入。進而，於本發明之液晶配向膜之製造方法，具有將光交聯性基作為光反應性基之構造時，於使用本發明之側鏈型高分子之基板上形成塗膜之後，照射經偏光之紫外線，接著進行加熱後，藉由照射無偏光之紫外線，可將導入高分子膜中之各向異性固定化。 In the method for producing a liquid crystal alignment film of the present invention, after the coating film is formed on the substrate using the side chain type polymer of the present invention, the polarized ultraviolet light is irradiated. Then, by introducing the high-efficiency anisotropy of the side chain type polymer film by heating, a liquid crystal alignment having liquid crystal alignment control energy is produced. membrane. In the method for producing a liquid crystal alignment film of the present invention, the liquid crystal property based on the light reaction with the side chain type polymer film of the present invention realizes the side chain type polymer by the automatic combination using the principle of induced molecular reorientation. Introduction of high-efficiency anisotropy of the membrane. Further, in the method for producing a liquid crystal alignment film of the present invention, when a photocrosslinkable group is used as a photoreactive group, a coating film is formed on a substrate using the side chain type polymer of the present invention, and then the polarized light is irradiated. After the ultraviolet rays are heated, the anisotropy introduced into the polymer film can be fixed by irradiating the ultraviolet rays without polarization.

圖1係以模式說明在本發明之液晶配向膜之製造方法，在使用具有將光交聯性基作為光反應性基之構造的側鏈型高分子之液晶配向膜之製造方法中各向異性之導入處理之一個例圖。圖1(a)為以模式表示之偏光照射前之側鏈型高分子膜之狀態的圖，圖1(b)為以模式表示偏光照射後之側鏈型高分子膜之狀態的圖，圖1(c)為以模式表示加熱後之側鏈型高分子膜之狀態的圖，圖1(d)為以模式表示無偏光照射後之側鏈型高分子膜之狀態的圖，尤其是經導入之各向異性小時，亦即在具有本發明之上述[I]~[IV]步驟之液晶配向膜之製造方法，[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於1%~15%之範圍內時之模式圖。 1 is a mode for explaining an anisotropic method for producing a liquid crystal alignment film of the present invention in a method for producing a liquid crystal alignment film having a side chain type polymer having a photocrosslinkable group as a photoreactive group. An example of the import process. Fig. 1 (a) is a view showing a state of a side chain type polymer film before polarized light irradiation in a mode, and Fig. 1 (b) is a view showing a state of a side chain type polymer film after polarized light irradiation. 1(c) is a view showing a state of the side chain type polymer film after heating in a mode, and FIG. 1(d) is a view showing a state of the side chain type polymer film after the non-polarized light irradiation, in particular, When the anisotropy of introduction is small, that is, the method for producing a liquid crystal alignment film having the above steps [I] to [IV] of the present invention, the ultraviolet irradiation amount of the step [II] is ultraviolet irradiation when ΔA is the maximum. A pattern diagram when the amount is in the range of 1% to 15%.

圖2係以模式說明在本發明之液晶配向膜之製造方法，在使用具有將光交聯性基作為光反應性基之構造的側鏈型高分子之液晶配向膜之製造方法中各向異性之導入處理之一個例圖。圖2(a)為以模式表示之偏光照射前之側 鏈型高分子膜之狀態的圖，圖2(b)為以模式表示偏光照射後之側鏈型高分子膜之狀態的圖，圖2(c)為以模式表示加熱後之側鏈型高分子膜之狀態的圖，圖2(d)為以模式表示無偏光照射後之側鏈型高分子膜之狀態的圖，尤其是經導入之各向異性大時，亦即在具有本發明之上述[I]~[IV]步驟之液晶配向膜之製造方法，[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於15%~70%之範圍內時之模式圖。 2 is a mode for explaining an anisotropic method for producing a liquid crystal alignment film of the present invention in a method for producing a liquid crystal alignment film having a side chain type polymer having a photocrosslinkable group as a photoreactive group. An example of the import process. Figure 2 (a) shows the side before the polarized light in mode FIG. 2(b) is a view showing a state of a side chain type polymer film after polarized light irradiation, and FIG. 2(c) is a mode showing a side chain type after heating. FIG. 2(d) is a view showing a state of the side chain type polymer film after the non-polarized light irradiation, in particular, when the anisotropy introduced is large, that is, having the present invention The method for producing a liquid crystal alignment film in the above steps [I] to [IV], and the ultraviolet irradiation amount in the step [II] is a pattern diagram in which the ultraviolet irradiation amount in the range of 15% to 70% when ΔA is maximum .

圖3為在係以模式說明將在本發明之液晶配向膜之製造方法，在使用具有上述之式(6)所表示之光富萊士重排基之構造的側鏈型高分子作為光反應性基之液晶配向膜之製造方法中各向異性之導入處理之一個例圖。圖3(a)為以模式表示之偏光照射前之側鏈型高分子膜之狀態的圖，圖3(b)為以模式表示偏光照射後之側鏈型高分子膜之狀態的圖，圖3(c)為以模式表示加熱後之側鏈型高分子膜之狀態的圖，尤其是經導入之各向異性小時，亦即在具有本發明之上述[I]~[III]步驟之製造方法，[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於1%~70%之範圍內時之模式圖。 3 is a side view of a method for producing a liquid crystal alignment film according to the present invention, in which a side chain type polymer having a structure of a photoplecide rearrangement group represented by the above formula (6) is used as a photoreaction. An example of an anisotropic introduction process in a method for producing a liquid crystal alignment film. Fig. 3 (a) is a view showing a state of a side chain type polymer film before polarized light irradiation in a mode, and Fig. 3 (b) is a view showing a state of a side chain type polymer film after polarized light irradiation. 3(c) is a view showing the state of the side chain type polymer film after heating in a mode, in particular, the anisotropy of the introduction is small, that is, the manufacturing of the above [I] to [III] steps of the present invention. The method, the ultraviolet irradiation amount of the step [II] is a mode diagram when the ultraviolet irradiation amount when ΔA is the maximum is in the range of 1% to 70%.

圖4為在係以模式說明將在本發明之液晶配向膜之製造方法，在使用具有上述之式(7)所表示之光富萊士重排基之構造的側鏈型高分子作為光反應性基之液晶配向膜之製造方法中各向異性之導入處理之一個例圖。圖4(a)為以模式表示之偏光照射前之側鏈型高分子膜之狀態的 圖，圖4(b)為以模式表示偏光照射後之側鏈型高分子膜之狀態的圖，圖4(c)為以模式表示加熱後之側鏈型高分子膜之狀態的圖，尤其是經導入之各向異性大時，亦即在具有本發明之上述[I]~[III]步驟之製造方法，[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於1%~70%之範圍內時之模式圖。 4 is a side view of a method for producing a liquid crystal alignment film according to the present invention, in which a side chain type polymer having a structure of a photoplecide rearrangement group represented by the above formula (7) is used as a photoreaction. An example of an anisotropic introduction process in a method for producing a liquid crystal alignment film. Fig. 4 (a) shows the state of the side chain type polymer film before the polarized light irradiation in the mode 4(b) is a view showing a state of a side chain type polymer film after polarized light irradiation, and FIG. 4(c) is a view showing a state of a side chain type polymer film after heating, in particular, When the anisotropy is large, that is, in the manufacturing method having the above steps [I] to [III] of the present invention, the ultraviolet irradiation amount in the step [II] is the ultraviolet irradiation amount when ΔA is the maximum. Pattern diagram in the range of 1% to 70%.

以下，將使用具有將光交聯性基作為光反應性基之構造的側鏈型高分子之實施形態稱為第1形態，將使用具有光富萊士重排基之構造的側鏈型高分子作為光反應性基之實施形態稱為第2形態並進行說明。 In the following, an embodiment in which a side chain type polymer having a photocrosslinkable group is used as a photoreactive group is referred to as a first embodiment, and a side chain type having a structure having a photorelate rearrangement group is used. The embodiment in which the molecule is a photoreactive group is referred to as a second embodiment and will be described.

在本發明之第1形態之液晶配向膜的製造方法，於對側鏈型高分子膜之各向異性之導入處理，[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於1%~15%之範圍內時，首先於基板上形成本發明之側鏈型高分子膜1。如圖1(a)所示，於基板上所形成之本發明之側鏈型高分子膜1，側鏈2具有無規排列之構造。依照側鏈型高分子膜1之側鏈2之無規排列，側鏈2之液晶基成分及感光性基亦無規配向，其側鏈型高分子膜1為各向同性。 In the method for producing a liquid crystal alignment film according to the first aspect of the present invention, the anisotropic introduction treatment of the opposite side chain type polymer film, and the ultraviolet irradiation amount in the step [II] are ultraviolet irradiation when ΔA is maximized. When the amount is in the range of 1% to 15%, the side chain type polymer film 1 of the present invention is first formed on a substrate. As shown in Fig. 1(a), the side chain type polymer film 1 of the present invention formed on a substrate has a structure in which the side chains 2 have a random arrangement. According to the random arrangement of the side chains 2 of the side chain type polymer film 1, the liquid crystal group component and the photosensitive group of the side chain 2 are also randomly aligned, and the side chain type polymer film 1 is isotropic.

在本發明之第1形態之液晶配向膜的製造方法，於對側鏈型高分子膜之各向異性之導入處理，[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於15%~70%之範圍內時，首先於基板上形成本實施形態之側鏈型高分子膜3。如圖2(a)所示，於基板上所形成之本發明之側鏈型高分子膜3，側鏈4具有無規排列之構造。依照 側鏈型高分子膜3之側鏈4之無規排列，側鏈4之液晶基成分及感光性基亦無規配向，其側鏈型高分子膜2為各向同性。 In the method for producing a liquid crystal alignment film according to the first aspect of the present invention, the anisotropic introduction treatment of the opposite side chain type polymer film, and the ultraviolet irradiation amount in the step [II] are ultraviolet irradiation when ΔA is maximized. When the amount is in the range of 15% to 70%, the side chain type polymer film 3 of the present embodiment is first formed on the substrate. As shown in Fig. 2(a), the side chain type polymer film 3 of the present invention formed on a substrate has a structure in which the side chains 4 have a random arrangement. according to The side chain 4 of the side chain type polymer film 3 is randomly arranged, and the liquid crystal group component and the photosensitive group of the side chain 4 are also randomly aligned, and the side chain type polymer film 2 is isotropic.

在本發明之第2形態之液晶配向膜的製造方法，於對側鏈型高分子膜之各向異性之導入處理，在使用具有上述式(6)所表示之具有光富萊士重排基之構造的使用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為最大時之紫外線照射量於1%~70%之範圍內時，首先於基板上形成本發明之側鏈型高分子膜5。如圖3(a)所示，於基板上所形成之本發明之側鏈型高分子膜5，側鏈6具有無規排列之構造。依照側鏈型高分子膜5之側鏈6之無規排列，側鏈6之液晶基成分及感光性基亦無規配向，其側鏈型高分子膜5為各向同性。 In the method for producing a liquid crystal alignment film according to the second aspect of the present invention, the anisotropic introduction process of the opposite side chain type polymer film is carried out using the photoplecide rearrangement group represented by the above formula (6). When the liquid crystal alignment film of the side chain type polymer is used as the structure, the ultraviolet irradiation amount in the step [II] is such that when the ultraviolet irradiation amount when ΔA is the maximum is in the range of 1% to 70%, first on the substrate The side chain type polymer film 5 of the present invention is formed. As shown in Fig. 3 (a), the side chain type polymer film 5 of the present invention formed on the substrate has a structure in which the side chains 6 have a random arrangement. According to the random arrangement of the side chains 6 of the side chain type polymer film 5, the liquid crystal group component and the photosensitive group of the side chain 6 are also randomly aligned, and the side chain type polymer film 5 is isotropic.

在本發明之第2形態之液晶配向膜的製造方法，於對側鏈型高分子膜之各向異性之導入處理，在使用具有上述之式(7)所表示之光富萊士重排基之構造的使用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為最大時之紫外線照射量於1%~70%之範圍內時，首先於基板上形成本發明之側鏈型高分子膜7。如圖4(a)所示，於基板上所形成之本發明之側鏈型高分子膜7，側鏈8具有無規排列之構造。依照側鏈型高分子膜7之側鏈8之無規排列，側鏈8之液晶基成分及感光性基亦無規配向，其側鏈型高分子膜7為各向同性。 In the method for producing a liquid crystal alignment film according to the second aspect of the present invention, the anisotropic introduction process of the opposite side chain type polymer film is carried out using the photoplecide rearrangement group represented by the above formula (7). When the liquid crystal alignment film of the side chain type polymer is used as the structure, the ultraviolet irradiation amount in the step [II] is such that when the ultraviolet irradiation amount when ΔA is the maximum is in the range of 1% to 70%, first on the substrate The side chain type polymer film 7 of the present invention is formed. As shown in Fig. 4 (a), the side chain type polymer film 7 of the present invention formed on a substrate has a structure in which the side chains 8 have a random arrangement. According to the random arrangement of the side chains 8 of the side chain type polymer film 7, the liquid crystal group component and the photosensitive group of the side chain 8 are also randomly aligned, and the side chain type polymer film 7 is isotropic.

於本發明之第1形態，在[II]步驟之紫外線照射量， 係將△A為最大時之紫外線照射量於1%~15%之範圍內時，對於此各向同性之本發明的側鏈型高分子膜1，照射經偏光之紫外線。如此時，如圖1(b)所示，於與紫外線之偏光方向平行之方向排列側鏈2當中之具有感光性基之側鏈2a的感光性基優先引起二聚化反應等之光反應。其結果，經光反應之側鏈2a的密度於照射紫外線之偏光方向僅僅提高些微，作為結果賦予於本發明之側鏈型高分子膜1非常小之各向異性。 In the first aspect of the present invention, the amount of ultraviolet irradiation in the step [II] is When the ultraviolet irradiation amount when ΔA is the maximum is in the range of 1% to 15%, the isotropic ultraviolet light is irradiated to the isotropic side chain type polymer film 1 of the present invention. In this case, as shown in FIG. 1(b), the photosensitive group of the side chain 2a having the photosensitive group among the side chains 2 is arranged in a direction parallel to the polarization direction of the ultraviolet light to preferentially cause a photoreaction such as a dimerization reaction. As a result, the density of the photoreactive side chain 2a is only slightly increased in the direction of polarization of the ultraviolet ray, and as a result, the side chain type polymer film 1 of the present invention is imparted with an extremely small anisotropy.

於本發明之第1形態，在[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於15%~70%之範圍內時，對於此各向同性之本發明的側鏈型高分子膜3，照射經偏光之紫外線。如此時，如圖2(b)所示，於與紫外線之偏光方向平行之方向排列側鏈4當中之具有感光性基之側鏈4a的感光性基優先引起二聚化反應等之光反應。其結果，經光反應之側鏈4a的密度於照射紫外線之偏光方向提高，作為結果賦予於本發明之側鏈型高分子膜3小之各向異性。 In the first aspect of the present invention, when the ultraviolet irradiation amount in the step [II] is such that the ultraviolet irradiation amount when ΔA is the maximum is in the range of 15% to 70%, the side of the isotropic invention is used. The chain type polymer film 3 irradiates the polarized ultraviolet rays. In this case, as shown in FIG. 2(b), the photosensitive group of the side chain 4a having the photosensitive group among the side chains 4 is arranged in a direction parallel to the direction in which the ultraviolet light is polarized, and a photoreaction such as a dimerization reaction is preferentially caused. As a result, the density of the side chain 4a which is photoreacted is increased in the direction in which the ultraviolet ray is irradiated, and as a result, the side chain type polymer film 3 of the present invention has a small anisotropy.

在本發明之第2形態，使用具有式(6)所表示之光富萊士重排基之構造的使用側鏈型高分子之液晶配向膜時，在[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於1%~70%之範圍內的情況下，對於此各向同性之本發明的側鏈型高分子膜5，照射經偏光之紫外線。如此時，如圖3(b)所示，於與紫外線之偏光方向平行之方向排列側鏈6當中之具有感光性基之側鏈6a的感光性基 優先引起光富萊士重排等等之光反應。其結果，經光反應之側鏈6a的密度於照射紫外線之偏光方向僅僅提高些許，作為結果賦予於本發明之側鏈型高分子膜5非常小之各向異性。 In the second aspect of the present invention, when the liquid crystal alignment film using the side chain type polymer having the structure of the optical Frye rearrangement group represented by the formula (6) is used, the amount of ultraviolet irradiation in the step [II] is When the ultraviolet irradiation amount when ΔA is the maximum is in the range of 1% to 70%, the isotropic ultraviolet light is irradiated to the isotropic side chain type polymer film 5 of the present invention. In this case, as shown in FIG. 3(b), the photosensitive groups of the side chain 6a having the photosensitive group among the side chains 6 are arranged in a direction parallel to the polarizing direction of the ultraviolet rays. Priority is given to the light reaction of the light fulfilment rearrangement and so on. As a result, the density of the side chain 6a which is photoreacted is only slightly increased in the direction of polarization of the ultraviolet ray, and as a result, the side chain type polymer film 5 of the present invention is given an extremely small anisotropy.

在本發明之第2形態，使用具有式(7)所表示之光富萊士重排基之構造的使用側鏈型高分子之液晶配向膜時，在[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於1%~70%之範圍內的情況下，對於此各向同性之本發明的側鏈型高分子膜7，照射經偏光之紫外線。如此時，如圖4(b)所示，於與紫外線之偏光方向平行之方向排列側鏈8當中之具有感光性基之側鏈8a的感光性基優先引起光富萊士重排等等之光反應。其結果，經光反應之側鏈8a的密度於照射紫外線之偏光方向提高，作為結果賦予於本發明之側鏈型高分子膜7小之各向異性。 In the second aspect of the present invention, when the liquid crystal alignment film using the side chain type polymer having the structure of the optical Frye rearrangement group represented by the formula (7) is used, the ultraviolet irradiation amount in the step [II] is When the ultraviolet irradiation amount when ΔA is the maximum is in the range of 1% to 70%, the isotropic ultraviolet light is irradiated to the isotropic side chain type polymer film 7 of the present invention. In this case, as shown in FIG. 4(b), the photosensitive groups of the side chain 8a having the photosensitive group among the side chains 8 are arranged in a direction parallel to the polarizing direction of the ultraviolet light to preferentially cause light fulfilment rearrangement or the like. Photoreaction. As a result, the density of the photoreactive side chain 8a is increased in the direction in which the ultraviolet light is irradiated, and as a result, the side chain type polymer film 7 of the present invention is given a small anisotropy.

接著，於本發明之第1形態，在[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於1%~15%之範圍內時，加熱偏光照射後之本發明之側鏈型高分子膜1，而成液晶狀態。如此時如圖1(c)所示，於側鏈型高分子膜1，在垂直於與照射紫外線之偏光方向平行之方向之間，所產生之交聯反應的量變為不同。此時，因為產生於與照射紫外線之偏光方向平行之方向的交聯反應量非常小，此交聯反應部位作為可塑劑利用，因此，與照射紫外線之偏光方向垂直之方向的液晶性高於平行方向之液晶性，於與照射紫外線之偏光方向平行之方向，再配向含有 經自動組合化之液晶基成分的側鏈2。其結果，因光交聯反應所誘發之本發明之側鏈型高分子膜1之非常小的各向異性，藉由熱而增幅，變成可賦予比在本發明之側鏈型高分子膜1更大之各向異性。 Next, in the first aspect of the present invention, when the ultraviolet irradiation amount in the step [II] is such that the ultraviolet irradiation amount when ΔA is the maximum is in the range of 1% to 15%, the present invention after heating the polarized light is used. The side chain type polymer film 1 is in a liquid crystal state. In this case, as shown in FIG. 1(c), the amount of the crosslinking reaction generated in the side chain type polymer film 1 which is perpendicular to the direction parallel to the direction in which the ultraviolet light is irradiated is different. At this time, since the amount of crosslinking reaction occurring in a direction parallel to the direction in which the ultraviolet light is irradiated is extremely small, the crosslinking reaction site is used as a plasticizer, and therefore, the liquid crystallinity in a direction perpendicular to the direction in which the ultraviolet light is irradiated is higher than parallel. The liquid crystality of the direction is in the direction parallel to the direction of the polarized light that is irradiated with ultraviolet rays. The side chain 2 of the liquid crystal based component that is automatically combined. As a result, the very small anisotropy of the side chain type polymer film 1 of the present invention, which is induced by the photocrosslinking reaction, is increased by heat, and becomes a side chain type polymer film 1 which can be imparted to the present invention. Greater anisotropy.

同樣地，於本發明之第1形態，在[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於15%~70%之範圍內時，加熱偏光照射後之本發明之側鏈型高分子膜3，而成液晶狀態。如此時如圖2(c)所示，於側鏈型高分子膜3，在垂直於與照射紫外線之偏光方向平行之方向之間，所產生之交聯反應的量變為不同。因此，於與照射紫外線之偏光方向平行之方向，再配向含有經自動組合化之液晶基成分的側鏈4。其結果，因光交聯反應所誘發之本發明之側鏈型高分子膜3之小的各向異性，藉由熱而增幅，變成可賦予比在本發明之側鏈型高分子膜3更大之各向異性。 Similarly, in the first aspect of the present invention, when the ultraviolet irradiation amount in the step [II] is such that the ultraviolet irradiation amount when ΔA is the maximum is in the range of 15% to 70%, the present invention after heating the polarized light irradiation The side chain type polymer film 3 is in a liquid crystal state. In this case, as shown in FIG. 2(c), the amount of the crosslinking reaction generated in the side chain type polymer film 3 which is perpendicular to the direction parallel to the direction in which the ultraviolet light is irradiated is different. Therefore, the side chain 4 containing the liquid crystal group component which is automatically combined is realigned in a direction parallel to the direction in which the ultraviolet light is irradiated. As a result, the small anisotropy of the side chain type polymer film 3 of the present invention induced by the photocrosslinking reaction is increased by heat, and the ratio can be increased to be more than that of the side chain type polymer film 3 of the present invention. Great anisotropy.

同樣地，在本發明之第2形態，使用具有式(6)所表示之光富萊士重排基之構造的使用側鏈型高分子之液晶配向膜時，在[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於1%~70%之範圍內的情況下，加熱偏光照射後之本發明之側鏈型高分子膜5，而成液晶狀態。如此時如圖3(c)所示，於側鏈型高分子膜5，在垂直於與照射紫外線之偏光方向平行之方向之間，所產生之光富萊士重排反應的量變為不同。此情況，因為產生於與照射紫外線之偏光方向垂直之方向的光富萊士重排體之液晶配向 力，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之方向，再配向含有經自動組合化之液晶基成分的側鏈6。其結果，因光富萊士重排反應所誘發之本發明之側鏈型高分子膜5之非常小的各向異性，藉由熱而增幅，變成可賦予比在本發明之側鏈型高分子膜5更大之各向異性。 Similarly, in the second aspect of the present invention, when a liquid crystal alignment film using a side chain type polymer having a structure of a photoplecene rearrangement group represented by the formula (6) is used, ultraviolet irradiation in the step [II] is employed. In the case where the ultraviolet irradiation amount when ΔA is the maximum is in the range of 1% to 70%, the side chain type polymer film 5 of the present invention after the polarized light irradiation is heated to have a liquid crystal state. In this case, as shown in FIG. 3(c), the amount of the light-recene rearrangement reaction generated between the side chain type polymer film 5 in a direction perpendicular to the direction parallel to the direction in which the ultraviolet rays are irradiated is different. In this case, because of the liquid crystal alignment of the light-Flourish rearrangement body in a direction perpendicular to the direction in which the ultraviolet light is irradiated. The force is stronger than the liquid crystal alignment force of the side chain before the reaction, and is aligned with the side chain 6 containing the liquid crystal group component which is automatically combined in a direction perpendicular to the direction in which the ultraviolet light is irradiated. As a result, the very small anisotropy of the side chain type polymer film 5 of the present invention, which is induced by the light fluffy rearrangement reaction, is increased by heat, and becomes higher than that of the side chain type of the present invention. The molecular film 5 is more anisotropic.

同樣地，在本發明之第2形態，使用具有式(7)所表示之光富萊士重排基之構造的使用側鏈型高分子之液晶配向膜時，在[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於1%~70%之範圍內的情況下，加熱偏光照射後之本發明之側鏈型高分子膜7，而成液晶狀態。如此時如圖4(c)所示，於側鏈型高分子膜7，在垂直於與照射紫外線之偏光方向平行之方向之間，所產生之光富萊士重排反應的量變為不同。因為光富萊士重排體8(a)之錨定力(Anchoring power)比移位前之側鏈8更強，當產生某一定量以上之光富萊士重排體時，於與照射紫外線之偏光方向平行之方向，再配向含有經自動組合化之液晶基成分的側鏈8。其結果，因光富萊士重排反應所誘發之本發明之側鏈型高分子膜7之小的各向異性，藉由熱而增幅，變成可賦予比在本發明之側鏈型高分子膜7更大之各向異性。 Similarly, in the second aspect of the present invention, when a liquid crystal alignment film using a side chain type polymer having a structure of a photoplecene rearrangement group represented by the formula (7) is used, ultraviolet irradiation in the step [II] is employed. When the amount of ultraviolet irradiation when ΔA is the maximum is in the range of 1% to 70%, the side chain type polymer film 7 of the present invention after the polarized light irradiation is heated to have a liquid crystal state. In this case, as shown in FIG. 4(c), the amount of the light-Fuller rearrangement reaction generated in the side chain type polymer film 7 in a direction perpendicular to the direction parallel to the direction in which the ultraviolet rays are irradiated is different. Because the anchoring power of the light frisbee rearrangement 8(a) is stronger than the side chain 8 before the displacement, when a certain amount of light fulfilment rearrangement is produced, The direction in which the polarization directions of the ultraviolet rays are parallel is aligned to the side chain 8 containing the liquid crystal based component which is automatically combined. As a result, the small anisotropy of the side chain type polymer film 7 of the present invention, which is induced by the light fulfilment rearrangement reaction, is increased by heat, and becomes a side chain type polymer which can be imparted to the present invention. The film 7 is more anisotropic.

進而，在本發明之第1形態，如圖1(d)或圖2(d)所示，當本發明之側鏈型高分子之光反應性基為光交聯性基時，如圖1(c)或圖2(c)所示，由液晶基之 自動組合化而誘發於側鏈高分子膜之各向異性後，藉由無偏光照射，固定化經誘發之大各向異性。 Further, in the first aspect of the present invention, as shown in Fig. 1 (d) or Fig. 2 (d), when the photoreactive group of the side chain type polymer of the present invention is a photocrosslinkable group, as shown in Fig. 1, (c) or as shown in Figure 2(c), by liquid crystal After being automatically combined and induced by the anisotropy of the side chain polymer film, the induced anisotropy is fixed by the non-polarized light irradiation.

從而，在本發明之液晶配向膜的製造方法，對本發明之側鏈型高分子膜之經偏光之紫外線照射與加熱處理，進而，本發明之第1形態的情況為藉由依序進行與加熱處理後之無偏光照射，可得到高效率導入各向異性之液晶配向膜。 Therefore, in the method for producing a liquid crystal alignment film of the present invention, the polarized ultraviolet light irradiation and heat treatment of the side chain type polymer film of the present invention, and further, the first aspect of the present invention is performed by sequential heat treatment. After the non-polarized light irradiation, an anisotropic liquid crystal alignment film can be obtained with high efficiency.

而且，在本發明之液晶配向膜的製造方法，在對本發明之側鏈型高分子膜之經偏光之紫外線的照射量與加熱處理，最適化加熱溫度。據此可實現高效率導入對側鏈型高分子膜之各向異性。 Further, in the method for producing a liquid crystal alignment film of the present invention, the irradiation temperature of the polarized ultraviolet light of the side chain type polymer film of the present invention and the heat treatment are performed to optimize the heating temperature. According to this, the anisotropy of the side chain type polymer film can be introduced with high efficiency.

本發明者，進行努力研究後之結果，得到以下之發現。亦即，於高效率導入對本發明之側鏈型高分子膜的各向異性最適當偏光紫外線之照射量，在其側鏈型高分子膜，感光性基係對應偏光紫外線之照射量最適化進行光交聯反應或光異構化反應、或是光富萊士重排反應的量。對於本發明之側鏈型高分子膜之照射經偏光之紫外線的結果，當進行光交聯反應或光異構化反應、或是光富萊士重排反應之側鏈的感光性基稀少時，無法有充分之光反應量。此情況，然後即使加熱亦無法進行充分之自動組合化。 The inventors of the present invention conducted the following research and obtained the following findings. In other words, the irradiation amount of the anisotropic most appropriate polarized ultraviolet ray of the side chain type polymer film of the present invention is introduced at a high efficiency, and the amount of the photosensitive base system corresponding to the polarized ultraviolet ray is optimized in the side chain type polymer film. The amount of photocrosslinking reaction or photoisomerization reaction, or light fulfilment rearrangement reaction. When the side chain type polymer film of the present invention is irradiated with the polarized ultraviolet light, when the photocrosslinking reaction or the photoisomerization reaction or the photoreceptor group of the photo-Fuller rearrangement reaction is scarce There is no way to have sufficient light response. In this case, then sufficient automatic combination cannot be performed even if heated.

另一方面，於本發明之側鏈型高分子膜，對於具有光交聯性基構造之照射經偏光之紫外線的結果，當進行交聯反應之側鏈的感光性基變為過剩時，會造成過分進行於側 鏈之交聯反應。此時所得到之膜變為剛直，由之後的加熱有時造成自動組合化進行的妨礙。又，於本發明之側鏈型高分子膜，對於具有光富萊士重排基之構造照射經偏光之紫外線的結果，當進行光富萊士重排反應之側鏈的感光性基變為過剩時，會造成側鏈型高分子膜之液晶性過於低迷。此時所得到膜之液晶體亦低迷，由之後的加熱有時造成自動組合化進行的妨礙。進而，對於具有光富萊士重排基之構造照射經偏光之紫外線時，當紫外線之照射量過多時，會造成光分解本發明之側鏈型高分子，由之後的加熱有時造成自動組合化進行的妨礙。 On the other hand, in the side chain type polymer film of the present invention, when the photosensitive group having the photocrosslinking structure is irradiated with polarized light, when the photosensitive group of the side chain in which the crosslinking reaction is carried out becomes excessive, Cause excessively on the side Chain crosslinking reaction. The film obtained at this time becomes straight, and the subsequent heating may cause an obstacle to the automatic combination. Further, in the side chain type polymer film of the present invention, when the polarized ultraviolet light is irradiated to the structure having the light fulcene rearrangement group, the photosensitive group of the side chain in which the light fulfil rearrangement reaction is performed becomes When it is excessive, the liquid crystal property of the side chain type polymer film is too low. At this time, the liquid crystal body of the obtained film is also low, and the subsequent heating may cause an obstacle to the automatic combination. Further, when the polarized ultraviolet light is irradiated to the structure having the light fulfilment rearrangement, when the amount of ultraviolet light irradiation is too large, the side chain type polymer of the present invention is photodecomposed, and the subsequent heating sometimes causes automatic combination. Obstruction of the process.

從而，在本發明之側鏈型高分子膜，藉由偏光紫外線之照射，使側鏈之感光性基進行光交聯反應或光異構化反應、或是光富萊士重排反應之最適量，以具有其側鏈型高分子膜之感光性基為0.1莫耳%~40莫耳%為佳，為0.1莫耳%~20莫耳%為更佳。在本發明，藉由將進行光反應之側鏈之感光性基的量限於如此之範圍，於之後的加熱處理之自動組合化效率變佳，於膜中高效率之各向異性的形成變為可能。 Therefore, in the side chain type polymer film of the present invention, the photosensitive group of the side chain is subjected to photocrosslinking reaction or photoisomerization reaction by irradiation of polarized ultraviolet rays, or the light fulcene rearrangement reaction is optimal. The amount of the photosensitive group having the side chain type polymer film is preferably from 0.1 mol% to 40 mol%, more preferably from 0.1 mol% to 20 mol%. In the present invention, by limiting the amount of the photosensitive group of the side chain for photoreaction to such a range, the automatic combination efficiency of the subsequent heat treatment is improved, and the formation of high-efficiency anisotropy in the film becomes possible. .

在本發明之液晶配向膜的製造方法，由最適化經偏光之紫外線的照射量，在側鏈型高分子膜之側鏈，最適化感光性基之光交聯反應或光異構化反應、或光富萊士重排反應的量。而且，合併之後的加熱處理，實現高效率導入對側鏈型高分子膜之各向異性。此時，關於適當偏光紫外線的量，可基於本發明之側鏈型高分子膜之紫外吸收的評估 進行。 In the method for producing a liquid crystal alignment film of the present invention, the photocrosslinking reaction or photoisomerization reaction of the photosensitive group is optimized in the side chain of the side chain type polymer film by optimizing the amount of the polarized ultraviolet light. Or the amount of light refreshment rearrangement reaction. Further, the heat treatment after the combination realizes high-efficiency introduction of the anisotropy of the side chain type polymer film. At this time, regarding the amount of appropriate polarized ultraviolet rays, evaluation of ultraviolet absorption based on the side chain type polymer film of the present invention can be performed. get on.

亦即，關於本發明之側鏈型高分子膜，各自測定偏光紫外線照射後之與經偏光之紫外線的偏光方向平行之方向的紫外線吸收與垂直之方向的紫外線吸收。從紫外吸收之測定結果，在其側鏈型高分子膜，將與經偏光之紫外線的偏光方向平行之方向的紫外線吸光度和垂直方向之紫外線吸光度的差評估為△A。而且，求得在本發明之側鏈型高分子膜被實現之△A的最大值(△Amax)與將其實現之偏光紫外線的照射量。在本發明之液晶配向膜的製造方法，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的紫外線量。 In other words, in the side chain type polymer film of the present invention, ultraviolet ray absorption in the direction parallel to the polarization direction of the polarized ultraviolet light and ultraviolet ray absorption in the vertical direction after the polarized ultraviolet ray irradiation are measured. As a result of measurement by ultraviolet absorption, in the side chain type polymer film, the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance in the vertical direction was evaluated as ΔA. Further, the maximum value (ΔAmax) of ΔA achieved in the side chain type polymer film of the present invention and the amount of polarized ultraviolet light to be realized by the side chain type polymer film were determined. In the method for producing a liquid crystal alignment film of the present invention, the amount of polarized ultraviolet light of a preferred amount can be determined by irradiating the liquid crystal alignment film with the amount of the polarized ultraviolet radiation of ΔAmax as a standard.

在本發明之液晶配向膜的製造方法，將對本發明之側鏈型高分子膜之經偏光的紫外線照射量，以實現△Amax之偏光紫外線量的1%~70%範圍內為佳，以1%~50%範圍內為更佳。在本發明之側鏈型高分子膜，實現△Amax之偏光紫外線量的1%~50%範圍內之偏光紫外線的照射量，具有其側鏈型高分子膜之感光性基全體0.1莫耳%~20莫耳%相當於使光交聯反應之偏光紫外線的量。 In the method for producing a liquid crystal alignment film of the present invention, it is preferred that the amount of the polarized ultraviolet light of the side chain type polymer film of the present invention is in the range of 1% to 70% of the amount of polarized ultraviolet light of ΔAmax, and is 1 It is better in the range of %~50%. In the side chain type polymer film of the present invention, the amount of polarized ultraviolet light in the range of 1% to 50% of the amount of polarized ultraviolet light of ΔAmax is achieved, and the photosensitive base of the side chain type polymer film has a total of 0.1 mol%. ~20 mol% corresponds to the amount of polarized ultraviolet light that causes the photocrosslinking reaction.

其次，在本發明之液晶配向膜的製造方法，於本發明之側鏈型高分子膜照射經偏光之紫外線後，進行其側鏈型高分子膜之加熱。本發明之側鏈型高分子膜，係於特定溫度範圍表現液晶性而得到高分子膜。偏光紫外線照射後之加熱處理，可決定將表現此側鏈型高分子膜之液晶性的溫 度當作基準。亦即，偏光紫外線照射後之加熱溫度，本發明之側鏈型高分子膜表現液晶性之溫度範圍(以下，稱為液晶溫度範圍)為以從高於下限10℃溫度至比該溫度範圍上限低10℃溫度之範圍的溫度為佳。 Next, in the method for producing a liquid crystal alignment film of the present invention, after the side chain type polymer film of the present invention is irradiated with polarized ultraviolet rays, the side chain type polymer film is heated. The side chain type polymer film of the present invention exhibits liquid crystallinity in a specific temperature range to obtain a polymer film. The heat treatment after polarized ultraviolet irradiation can determine the temperature at which the liquid crystal property of the side chain type polymer film is expressed. Degree is used as a benchmark. That is, the heating temperature after the polarized ultraviolet ray irradiation, the temperature range in which the side chain type polymer film of the present invention exhibits liquid crystallinity (hereinafter, referred to as a liquid crystal temperature range) is from a temperature higher than the lower limit of 10 ° C to an upper limit than the temperature range A temperature in the range of 10 ° C lower is preferred.

本發明之側鏈型高分子膜，於經偏光之紫外線的照射後，經加熱而成液晶狀態，於與偏光方向平行之方向再配向自動組合化。其結果，因光交聯反應或光異構化反應、及光富萊士重排反應所誘發之本發明之側鏈型高分子膜之小的各向異性，藉由熱而增幅。惟，本發明之側鏈型高分子膜即使於由加熱呈現液晶狀態的情況，當加熱溫度低時，液晶狀態之側鏈型高分子膜黏度提高，使因自動組合化而產生再配向變為困難。例如，當加熱溫度為高於本發明之側鏈型高分子膜的液晶溫度範圍之下限10℃的溫度為止的範圍時，在本發明之側鏈型高分子膜上因熱而無法使各向異性之增幅效果成為充分者。 The side chain type polymer film of the present invention is heated to form a liquid crystal state after being irradiated by polarized ultraviolet rays, and is automatically combined in a direction parallel to the polarization direction. As a result, the small anisotropy of the side chain type polymer film of the present invention, which is induced by the photocrosslinking reaction, the photoisomerization reaction, and the photorecovery reaction, is increased by heat. However, in the case where the side chain type polymer film of the present invention exhibits a liquid crystal state by heating, when the heating temperature is low, the viscosity of the side chain type polymer film in the liquid crystal state is improved, and the realignment is caused by the automatic combination. difficult. For example, when the heating temperature is in a range higher than the lower limit of 10 ° C of the liquid crystal temperature range of the side chain type polymer film of the present invention, the side chain type polymer film of the present invention cannot be made to be hot due to heat. The effect of the increase in the opposite sex becomes sufficient.

又，本發明之側鏈型高分子膜即使由加熱而呈現液晶狀態，當加熱溫度高時，側鏈型高分子膜之狀態變成接近各向同性之液體狀態，藉由自動組合化使再配向於同一方向變為困難。例如，當加熱溫度為比本發明之側鏈型高分子膜之液晶溫度範圍上限低10℃的溫度更高的溫度時，在本發明之側鏈型高分子膜上因熱而無法使各向異性之增幅效果成為充分者。 Further, the side chain type polymer film of the present invention exhibits a liquid crystal state even when heated, and when the heating temperature is high, the state of the side chain type polymer film becomes a near-isotropic liquid state, and realignment is performed by automatic combination. It becomes difficult in the same direction. For example, when the heating temperature is higher than the temperature lower than the upper limit of the liquid crystal temperature range of the side chain type polymer film of the present invention, the side chain type polymer film of the present invention cannot be made to be hot due to heat. The effect of the increase in the opposite sex becomes sufficient.

由以上，於本發明之液晶配向膜的製造方法，為了實現高效率導入對側鏈型高分子膜之各向異性，將其側鏈型 高分子膜之液晶溫度範圍作為基準而決定適當之加熱溫度。而且如上述，偏光紫外線照射後之加熱溫度係以高於其側鏈型高分子膜之液晶溫度範圍下限10℃之溫度作為下限，以低於液晶溫度範圍上限10℃的溫度作為上限之範圍內的溫度。從而，例如本發明之側鏈型高分子膜之液晶溫度範圍為100℃~200℃時，期望偏光紫外線照射後之加熱溫度為110℃~190℃。藉由如此進行，在本發明之側鏈型高分子膜，變成可賦予更大之各向異性。 As described above, in the method for producing a liquid crystal alignment film of the present invention, in order to achieve high efficiency, the anisotropy of the opposite side chain type polymer film is introduced, and the side chain type is formed. The liquid crystal temperature range of the polymer film is used as a reference to determine an appropriate heating temperature. Further, as described above, the heating temperature after the polarized ultraviolet ray irradiation is a lower limit of 10 ° C higher than the lower limit of the liquid crystal temperature range of the side chain type polymer film, and a temperature lower than the upper limit of 10 ° C of the liquid crystal temperature range as the upper limit. temperature. Therefore, for example, when the liquid crystal temperature range of the side chain type polymer film of the present invention is from 100 ° C to 200 ° C, the heating temperature after the polarized ultraviolet ray irradiation is desirably 110 ° C to 190 ° C. By doing so, the side chain type polymer film of the present invention can impart greater anisotropy.

於以上，在本發明之液晶配向膜的製造方法雖已說明配向處理，接著對於本發明之液晶配向膜的製造方法進行說明。 As described above, the alignment treatment has been described in the method for producing a liquid crystal alignment film of the present invention, and then the method for producing the liquid crystal alignment film of the present invention will be described.

本發明之液晶配向膜的製造方法，係由以下的順序具有以下[I]~[III]之步驟、或以下[I]~[IV]之步驟。而且，製造以高效率導入各向異性之液晶配向。 The method for producing a liquid crystal alignment film of the present invention has the following steps [I] to [III] or the following steps [I] to [IV] in the following order. Further, a liquid crystal alignment in which anisotropy is introduced with high efficiency is manufactured.

[I]於基板上，形成能表現液晶性之感光性的側鏈型高分子膜之步驟、[II]於步驟[I]所得到之側鏈型高分子膜照射經偏光之紫外線之步驟、[III]加熱於步驟[II]經偏光之紫外線照射之側鏈型高分子膜之步驟、[IV]照射無偏光之紫外線於經照射紫外線之後再經加熱之前述側鏈型高分子膜之步驟、以下，關於本發明之液晶配向膜的製造方法具有之[I]~[III]步驟或以下之[I]~[IV]步驟的各步驟進行說明。 [I] a step of forming a side chain type polymer film capable of exhibiting liquid crystallinity on a substrate, and [II] a step of irradiating the polarized ultraviolet light to the side chain type polymer film obtained in the step [I], [III] a step of heating the side chain type polymer film irradiated by the polarized ultraviolet light in the step [II], and [IV] the step of irradiating the unpolarized ultraviolet light to the side chain type polymer film heated after the irradiation of the ultraviolet ray Hereinafter, each step of the steps [I] to [III] or the following steps [I] to [IV] of the method for producing a liquid crystal alignment film of the present invention will be described.

於步驟[I]，形成基板上之本發明的側鏈型高分子膜。對於基板，並未特別限定。例如，玻璃基板之外，可使用丙烯酸系基板或聚碳酸酯基板等之塑料基板等透明基板。考慮所得到液晶配向膜之適用，從簡素化液晶顯示元件之製造製程的觀點來看，亦可使用用以形成液晶驅動之ITO(Indium Tin Oxide：氧化銦錫)電極等之基板。又，考慮對反射型之液晶顯示元件的適用，亦可使用矽晶圓等之不透明基板，作為此情況之電極亦可使用已使用氧化鋁等之反射光的材料者。 In the step [I], the side chain type polymer film of the present invention on the substrate is formed. The substrate is not particularly limited. For example, a transparent substrate such as an acrylic substrate or a polycarbonate substrate such as a polycarbonate substrate can be used in addition to the glass substrate. In consideration of the application of the obtained liquid crystal alignment film, a substrate for forming a liquid crystal driven ITO (Indium Tin Oxide) electrode or the like can be used from the viewpoint of the manufacturing process of the liquid crystal display element. Further, in consideration of the application to the reflective liquid crystal display device, an opaque substrate such as a germanium wafer or the like may be used, and as the electrode in this case, a material using reflected light such as alumina may be used.

本發明之側鏈型高分子膜溶解於所期望之溶劑而為溶液狀時，基板上之膜形成，係藉由塗佈其溶液狀之側鏈型高分子膜進行。塗佈方法雖並未特別限制，然而工業上一般以網版印刷、平板印刷、柔印印刷或噴墨法等方法進行。作為其他塗佈方法，為浸漬法、輥塗佈機法、狹縫塗佈法、旋轉器法(旋轉塗佈法)或噴霧法等，亦可因應目的使用此等。 When the side chain type polymer film of the present invention is dissolved in a desired solvent and is in the form of a solution, the film on the substrate is formed by applying a solution-like side chain type polymer film. The coating method is not particularly limited, but industrially, it is generally carried out by a method such as screen printing, lithography, flexo printing or ink jet method. As another coating method, a dipping method, a roll coater method, a slit coating method, a spinner method (spin coating method), a spray method, or the like may be used, and these may be used depending on the purpose.

將溶液狀之本發明的側鏈型高分子膜塗佈於基板上之後，由熱板、熱循環型烘烤箱或IR(紅外線)型烘烤箱等之加熱手段於20℃~180℃，較佳為40℃~150℃下可得到使溶媒蒸發之本發明的側鏈型高分子膜。側鏈型高分子膜之厚度，太厚時於適用液晶配向膜之液晶顯示元件的消費電力面上變為不利，太薄時因為會有液晶顯示元件之信賴性降低的情況，較佳為5nm~300nm，更佳為10nm~100nm。 After applying the side chain type polymer film of the present invention in a solution form on a substrate, it is heated at 20 ° C to 180 ° C by a heating means such as a hot plate, a heat cycle type baking oven or an IR (infrared) type baking box. The side chain type polymer film of the present invention which evaporates the solvent is preferably obtained at 40 ° C to 150 ° C. When the thickness of the side chain type polymer film is too thick, it becomes unfavorable on the power consumption surface of the liquid crystal display element to which the liquid crystal alignment film is applied. When it is too thin, the reliability of the liquid crystal display element is lowered, preferably 5 nm. ~300nm, more preferably 10nm~100nm.

尚，[I]步驟之後，在繼續[II]步驟之前，將側鏈型高分子膜形成之基板亦可設置冷卻至室溫的步驟。 Further, after the step [I], the substrate on which the side chain type polymer film is formed may be further cooled to room temperature before the step [II] is continued.

於步驟[II]，照射經偏光之紫外線於步驟[I]所得到之側鏈型高分子膜。照射經偏光之紫外線於側鏈型高分子膜之膜面時，對於基板從一定方向透過偏光板照射經偏光之紫外線。作為所使用之紫外線，可使用波長100nm~400nm範圍之紫外線。較佳為由使用側鏈型高分子膜之種類透過過濾器等選擇最適當之波長。而且，例如如同可選擇性地誘發光交聯反應，可選擇波長250nm~400nm範圍之紫外線使用。作為紫外線，例如可使用從高壓水銀燈放射之光。 In the step [II], the polarized ultraviolet light is irradiated to the side chain type polymer film obtained in the step [I]. When the polarized ultraviolet light is irradiated on the film surface of the side chain type polymer film, the polarized ultraviolet light is irradiated to the substrate through the polarizing plate from a certain direction. As the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. It is preferable to select an optimum wavelength by a filter or the like by using a type of a side chain type polymer film. Further, for example, as the photocrosslinking reaction can be selectively induced, ultraviolet rays having a wavelength in the range of 250 nm to 400 nm can be selected. As the ultraviolet rays, for example, light emitted from a high pressure mercury lamp can be used.

對於經偏光之紫外線的照射量，如上述，以使用本發明之側鏈型高分子膜之實現△Amax之偏光紫外線量的1%~70%範圍內為佳，以1%~50%範圍內為更佳。 The irradiation amount of the polarized ultraviolet light is preferably in the range of 1% to 70% of the amount of polarized ultraviolet light which realizes ΔAmax using the side chain type polymer film of the present invention, and is in the range of 1% to 50%. For better.

於步驟[III]，加熱於步驟[II]經偏光之紫外線照射的側鏈型高分子膜。加熱係使用熱板、熱循環型烘烤箱或IR(紅外線)型烘烤箱等之加熱手段。對於加熱溫度，如上述，可考慮表現所使用之本發明之側鏈型高分子膜的液晶性之溫度來決定。亦即，偏光紫外線照射後之加熱溫度，係以高於使用本發明之側鏈型高分子膜表現液晶性之液晶溫度範圍下限10℃之溫度作為下限，以低於液晶溫度範圍上限10℃的溫度作為上限之範圍內的溫度為佳。 In the step [III], the side chain type polymer film irradiated with the polarized ultraviolet light in the step [II] is heated. The heating system uses a heating means such as a hot plate, a heat cycle type baking oven, or an IR (infrared) type baking box. The heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the side chain type polymer film of the present invention to be used is expressed as described above. That is, the heating temperature after the polarized ultraviolet ray irradiation is lower than the lower limit of the liquid crystal temperature range of 10 ° C which is higher than the liquid crystal temperature range in which the side chain type polymer film of the present invention is used, and is lower than the upper limit of the liquid crystal temperature range by 10 ° C. The temperature is preferably within the range of the upper limit.

藉由具有以上之步驟，於本發明之液晶配向膜的製造方法，實現高效率導入對側鏈型高分子膜之各向異性。而 且，可高效率製造本發明之液晶配向膜。 By the above method, in the method for producing a liquid crystal alignment film of the present invention, the anisotropy of the side chain type polymer film is introduced with high efficiency. and Moreover, the liquid crystal alignment film of the present invention can be produced with high efficiency.

於步驟[IV]，照射無偏光之紫外線於經照射前述紫外線之後再經加熱之側鏈型高分子膜。由此步驟，於[II]步驟未反應而殘留，於[III]步驟經再配向之本發明的側鏈型高分子膜引起交聯反應，使配向安定化。 In the step [IV], the unpolarized ultraviolet light is irradiated to the side chain type polymer film which is heated after the irradiation of the ultraviolet rays. In this step, the side chain type polymer film of the present invention which has been re-aligned in the step [III] is subjected to a crosslinking reaction in the step [II], and the alignment is stabilized.

由[IV]步驟之紫外線照射，以使前述側鏈型高分子膜所具有之光交聯性基之20莫耳%以上反應為佳。換言之，於[II]步驟光交聯性基未殘留20莫耳%以上時，在此步驟不容易充分使配向安定化。係因為經再配向之光反應性基難以於其配向狀態下固定化。上述式(6)(7)之情況，當進行此步驟時反而發揮本發明效果並不容易。 In the ultraviolet irradiation of the step [IV], it is preferred to react 20 mol% or more of the photocrosslinkable group of the side chain type polymer film. In other words, when the photocrosslinkable group does not remain at 20 mol% or more in the step [II], it is not easy to sufficiently stabilize the alignment in this step. It is because the re-aligned photoreactive group is difficult to immobilize in its alignment state. In the case of the above formulas (6) and (7), it is not easy to exert the effects of the present invention when performing this step.

實施例 Example

關於本發明之實施形態，由列舉實施例詳細說明。尚且，本發明並非被限定於此等所解釋者。 Embodiments of the present invention will be described in detail by way of examples. Further, the present invention is not limited to the ones explained herein.

<合成例1> <Synthesis Example 1>

藉由將4,4'-聯苯二醇與1,6-二溴己烷於鹼條件下加熱，而合成4'-(6-溴己氧基)聯苯-4-醇。於此生成物中使甲基丙烯酸鋰反應，得到2-(4'-羥基聯苯-4-基氧代)己氧基甲基丙烯酸酯。接著在鹼性條件化下，加入4-甲氧基桂皮醯氯合成下述式(9)所示之化合物。 4'-(6-bromohexyloxy)biphenyl-4-ol was synthesized by heating 4,4'-biphenyldiol and 1,6-dibromohexane under basic conditions. Lithium methacrylate was reacted in the product to obtain 2-(4'-hydroxybiphenyl-4-yloxy)hexyloxymethacrylate. Next, under basic conditions, 4-methoxy cinnabarin chloride is added to synthesize a compound represented by the following formula (9).

<合成例2> <Synthesis Example 2>

藉由將1-羥基桂皮酸與1-羥基-6-己醇於鹼條件下加熱而合成4-(6-羥基己氧基)桂皮酸。於鹼性條件下使氯化甲基丙烯酸反應於此生成物中，得到下述式(10)所示之化合物。 4-(6-Hydroxyhexyloxy)cinnamic acid was synthesized by heating 1-hydroxycinnamic acid and 1-hydroxy-6-hexanol under basic conditions. The chlorinated methacrylic acid is allowed to react in the product under basic conditions to obtain a compound represented by the following formula (10).

<合成例3> <Synthesis Example 3>

藉由將1-羥基安息香酸與1-羥基-6-己醇於鹼條件下加熱而合成4-(6-羥基己氧基)安息香酸。於鹼性條件下使氯化甲基丙烯酸反應於此生成物中，得到下述式(11)所示之化合物。 4-(6-Hydroxyhexyloxy)benzoic acid was synthesized by heating 1-hydroxybenzoic acid with 1-hydroxy-6-hexanol under basic conditions. The chlorinated methacrylic acid is allowed to react in the product under basic conditions to obtain a compound represented by the following formula (11).

<合成例4> <Synthesis Example 4>

藉由將4-碘酚與6-氯-1-己醇於鹼條件化加熱而合成4-(6-羥基己氧基)碘酚。使2-甲基-3-丁炔-2-醇反應於此生成物之後，於鹼條件化下藉由過熱得到4-(6-羥基己氧基)乙炔基苯(化合物A)。又，在其他路徑，使4-甲氧基桂皮酸氯化物與4-碘酚反應，而合成4-碘苯基-3-(4-甲氧苯基)丙烯酸酯(化合物B)。接著，於鹼性條件下藉由使化合物A與化合物B反應，得到下述式(12)所示之化合物。 4-(6-Hydroxyhexyloxy)iodophenol was synthesized by subjecting 4-iodophenol to 6-chloro-1-hexanol under basic conditions. After reacting 2-methyl-3-butyn-2-ol with this product, 4-(6-hydroxyhexyloxy)ethynylbenzene (Compound A) was obtained by superheating under basic conditions. Further, in another route, 4-methoxycinnamic acid chloride was reacted with 4-iodophenol to synthesize 4-iodophenyl-3-(4-methoxyphenyl)acrylate (Compound B). Next, the compound represented by the following formula (12) is obtained by reacting the compound A with the compound B under basic conditions.

<合成例5> <Synthesis Example 5>

藉由將1-羥基安息香酸與1-羥基-6-己醇於鹼條件下加熱而合成4-(6-羥基己氧基)安息香酸之後，藉由加入 亞硫醯氯，得到4-(6-羥基己氧基)安息香酸氯化物。於鹼性條件下使p-甲氧基酚反應於此生成物中，得到下述式(13)所示之化合物。 By synthesizing 1-hydroxybenzoic acid and 1-hydroxy-6-hexanol under basic conditions to synthesize 4-(6-hydroxyhexyloxy)benzoic acid, by adding Thionium chloride gives 4-(6-hydroxyhexyloxy)benzoic acid chloride. The p-methoxyphenol is reacted in the product under basic conditions to obtain a compound represented by the following formula (13).

<合成例6> <Synthesis Example 6>

將上述式(9)所示之甲基丙烯酸酯溶解於四氫呋喃中，藉由添加偶氮雙異丁腈(AIBN)作為反應起始劑聚合而得到聚合物1。此聚合物1表示於116℃~315℃溫度範圍之液晶性。 The methacrylate represented by the above formula (9) was dissolved in tetrahydrofuran, and polymer 1 was obtained by polymerization by adding azobisisobutyronitrile (AIBN) as a reaction initiator. This polymer 1 represents liquid crystallinity in the temperature range of 116 ° C to 315 ° C.

<合成例7> <Synthesis Example 7>

將上述式(10)所示之甲基丙烯酸酯溶解於四氫呋喃中，藉由添加偶氮雙異丁腈(AIBN)作為反應起始劑聚合而得到聚合物2。此聚合物2表示於135℃~187℃溫度範圍之液晶性。 The methacrylate represented by the above formula (10) was dissolved in tetrahydrofuran, and polymer 2 was obtained by polymerization by adding azobisisobutyronitrile (AIBN) as a reaction initiator. This polymer 2 represents liquid crystallinity in a temperature range of 135 ° C to 187 ° C.

<合成例8> <Synthesis Example 8>

將上述式(10)所示之甲基丙烯酸酯與上述式(11)所示之甲基丙烯酸酯成為25對75比例溶解於四氫呋喃中，藉由添加偶氮雙異丁腈(AIBN)作為反應起始劑聚合而得到聚合物3。此聚合物3表示於146℃~183℃溫度範圍之液晶性。 The methacrylate represented by the above formula (10) and the methacrylate represented by the above formula (11) are dissolved in tetrahydrofuran in a ratio of 25 to 75, and azobisisobutyronitrile (AIBN) is added as a reaction. The initiator is polymerized to give polymer 3. This polymer 3 represents liquid crystallinity in a temperature range of 146 ° C to 183 ° C.

<合成例9> <Synthesis Example 9>

將上述式(12)所示之甲基丙烯酸酯溶解於四氫呋喃中，藉由添加偶氮雙異丁腈(AIBN)作為反應起始劑聚合而得到聚合物4。此聚合物4表示於66℃~320℃溫度範圍之液晶性。 The methacrylate represented by the above formula (12) was dissolved in tetrahydrofuran, and polymer 4 was obtained by polymerization by adding azobisisobutyronitrile (AIBN) as a reaction initiator. This polymer 4 represents liquid crystallinity in a temperature range of from 66 ° C to 320 ° C.

<合成例10> <Synthesis Example 10>

將上述式(13)所示之甲基丙烯酸酯溶解於四氫呋喃中，藉由添加偶氮雙異丁腈(AIBN)作為反應起始劑聚合而得聚合物5。此聚合物5表示於143℃~283℃溫度範圍之液晶性。 The methacrylate represented by the above formula (13) is dissolved in tetrahydrofuran, and polymer 5 is obtained by polymerization by adding azobisisobutyronitrile (AIBN) as a reaction initiator. This polymer 5 represents liquid crystallinity in a temperature range of 143 ° C to 283 ° C.

<經導入各向異性之液晶配向膜的作成> <Preparation of anisotropic liquid crystal alignment film> <實施例1> <Example 1>

使用合成例6所得到之聚合物1，溶解於二氯甲烷，於光學性各向同性之基板，藉由以約190nm厚度旋轉塗佈而形成側鏈型高分子膜於基板上。測定使用此基板之紫外吸收光譜時，最大吸光度於314nm為0.89。於所得到基板上之側鏈型高分子膜，使用格蘭．泰勒棱鏡(Glan Taylor Prism)照射變換成直線偏光之紫外線。 The polymer 1 obtained in Synthesis Example 6 was dissolved in methylene chloride, and optically isotropic substrate was spin-coated at a thickness of about 190 nm to form a side chain type polymer film on the substrate. When the ultraviolet absorption spectrum of this substrate was measured, the maximum absorbance was 0.89 at 314 nm. For the side chain type polymer film on the obtained substrate, use Gran. Glan Taylor Prism illuminates the ultraviolet light into a linearly polarized light.

使用經如此而得到之基板上的側鏈型高分子膜測定紫外吸收光譜，對側鏈型高分子膜，評估與經照射之偏光紫外線的偏光方向平行之方向的紫外線吸光度與垂直方向之紫外線吸光度之差△A。△A照射以波長365nm換算為4500mJ之偏光紫外線之際，於314nm最大雖為0.2，照射650mJ偏光紫外線使△A成為0.065(相對於最大值為32之差)，接著，將此基板加熱至155℃，並將側鏈型高分子膜作為液晶相，直接保持5分鐘。然後，冷卻至室溫，於膜中得到具有經導入各向異性之側鏈型高分子膜之基板。此時之△A增幅為1.8，配向度成為0.73。其次，於具有經導入各向異性之側鏈型高分子膜之基板藉由照射以波長365nm換算為1500mJ之無偏光紫外線，得到具有液晶配向膜之基板。 The ultraviolet absorption spectrum was measured using the side chain type polymer film on the substrate thus obtained, and the ultraviolet absorbance in the direction parallel to the polarized direction of the irradiated polarized ultraviolet light and the ultraviolet absorbance in the vertical direction were evaluated for the side chain type polymer film. The difference is ΔA. ΔA irradiation was performed at a wavelength of 365 nm in the range of 4,500 mJ of polarized ultraviolet light, and the maximum was 0.2 at 314 nm, and 650 mJ of polarized ultraviolet light was irradiated so that ΔA became 0.065 (the difference from the maximum value of 32), and then the substrate was heated to 155. °C, and the side chain type polymer film was used as a liquid crystal phase, and it was kept for 5 minutes. Then, it was cooled to room temperature, and a substrate having a side chain type polymer film into which anisotropy was introduced was obtained in the film. At this time, the ΔA increase was 1.8, and the degree of alignment became 0.73. Next, a substrate having a liquid crystal alignment film was obtained by irradiating a substrate having a side chain type polymer film into which anisotropy was introduced to 1500 mJ at a wavelength of 365 nm.

<實施例2> <Example 2>

使用於合成例6所得到之聚合物1，除了將偏光紫外線之照射量作為500mJ(將△A最大值之25%作為△A之照射量)之外其他與實施例1同樣進行偏光紫外線照射與 其後之熱處理。其結果，熱處理前後之△A從0.05增幅為1.85，此時之配向度於314nm成為0.74。然後，與實施例1同樣照射無偏光紫外線，得到具有液晶配向膜之基板。 The polymer 1 obtained in the synthesis example 6 was subjected to polarized ultraviolet irradiation in the same manner as in Example 1 except that the amount of irradiation of the polarized ultraviolet rays was 500 mJ (the amount of ΔA maximum was 25% as the irradiation amount of ΔA). Subsequent heat treatment. As a result, the ΔA before and after the heat treatment increased from 0.05 to 1.85, and the degree of alignment at this time became 0.74 at 314 nm. Then, the polarized ultraviolet light was irradiated in the same manner as in Example 1 to obtain a substrate having a liquid crystal alignment film.

<實施例3> <Example 3>

將合成例7所得到之聚合物2溶解於四氫呋喃，於光學性各向同性之基板，藉由以約150nm厚度旋轉塗佈，除了將偏光紫外線之照射量作為5mJ(將△A最大值之10%作為△A之照射量)以及將其後之熱處理定為於165℃下5分鐘之外其他與實施例1同樣進行偏光紫外線照射與其後之熱處理。其結果，熱處理前後之△A從0.03增幅為1.6，此時之配向度於314nm成為0.72。然後，與實施例1同樣照射1000mJ無偏光紫外線，得到具有液晶配向膜之基板。 The polymer 2 obtained in Synthesis Example 7 was dissolved in tetrahydrofuran on an optically isotropic substrate by spin coating at a thickness of about 150 nm, except that the amount of polarized ultraviolet light was 5 mJ (10 of the maximum value of ΔA). The heat treatment was carried out in the same manner as in Example 1 except that % was used as the irradiation amount of ΔA) and the subsequent heat treatment was performed at 165 ° C for 5 minutes. As a result, the ΔA before and after the heat treatment increased from 0.03 to 1.6, and the degree of alignment at this time became 0.72 at 314 nm. Then, 1000 mJ of non-polarized ultraviolet light was irradiated in the same manner as in Example 1 to obtain a substrate having a liquid crystal alignment film.

<實施例4> <Example 4>

使用於合成例8所得到之聚合物3，除了將偏光紫外線之照射量作為20mJ(將△A最大值之40%作為△A之照射量)之外其他與實施例3同樣進行偏光紫外線照射與其後之熱處理。其結果，熱處理前後之△A從0.12增幅為1.6，此時之配向度於314nm成為0.62。然後，與實施例1同樣照射1000mJ無偏光紫外線，得到具有液晶配向膜之基板。 The polymer 3 obtained in the synthesis example 8 was subjected to polarized ultraviolet ray irradiation in the same manner as in the example 3 except that the amount of the polarized ultraviolet ray was 20 mJ (the ΔA maximum value was 40% as the ΔA irradiation amount). After the heat treatment. As a result, the ΔA before and after the heat treatment increased from 0.12 to 1.6, and the degree of alignment at this time became 0.62 at 314 nm. Then, 1000 mJ of non-polarized ultraviolet light was irradiated in the same manner as in Example 1 to obtain a substrate having a liquid crystal alignment film.

<實施例5> <Example 5>

將合成例9所得到之聚合物4溶解於二氯甲烷，於光學性各向同性之基板，藉由以約220nm厚度旋轉塗佈於基板上形成側鏈型高分子膜，除了將偏光紫外線之照射量作為300mJ(將△A最大值之29%作為△A之照射量)以及將其後之熱處理定為於200℃下5分鐘之外其他與實施例1同樣進行偏光紫外線照射與其後之熱處理。其結果，熱處理前後之△A從0.04增幅為1.4，此時之配向度於294nm成為0.62。然後，與實施例1同樣照射5000mJ無偏光紫外線，得到具有液晶配向膜之基板。 The polymer 4 obtained in Synthesis Example 9 was dissolved in dichloromethane, and optically isotropic substrate was spin-coated on the substrate at a thickness of about 220 nm to form a side chain type polymer film, except for polarized ultraviolet rays. The irradiation amount was 300 mJ (the irradiation amount of ΔA was 29% as the ΔA irradiation amount) and the subsequent heat treatment was set to 200 ° C for 5 minutes, and other polarized ultraviolet rays were irradiated in the same manner as in Example 1 and the subsequent heat treatment. . As a result, the ΔA before and after the heat treatment increased from 0.04 to 1.4, and the degree of alignment at this time became 0.62 at 294 nm. Then, 5000 mJ of non-polarized ultraviolet light was irradiated in the same manner as in Example 1 to obtain a substrate having a liquid crystal alignment film.

<實施例6> <Example 6>

將合成例10所得到之聚合物5溶解於二氯甲烷，於光學性各向同性之基板，藉由以約220nm厚度旋轉塗佈於基板上形成側鏈型高分子膜，除了將偏光紫外線之照射量作為1000mJ(將△A最大值之49%作為△A之照射量)以及將其後之熱處理定為於180℃下5分鐘之外其他與實施例1同樣進行偏光紫外線照射與其後之熱處理。其結果，熱處理前後之△A從0.07增幅為1.7，此時之配向度於262nm為0.72之具有液晶配向膜之基板。 The polymer 5 obtained in Synthesis Example 10 was dissolved in dichloromethane, and optically isotropic substrate was spin-coated on the substrate at a thickness of about 220 nm to form a side chain type polymer film, except for polarized ultraviolet rays. The irradiation amount was 1000 mJ (the irradiation amount of ΔA was 49% as the ΔA irradiation amount) and the subsequent heat treatment was set to 180 ° C for 5 minutes, and other polarized ultraviolet rays were irradiated in the same manner as in Example 1 and the subsequent heat treatment. . As a result, the ΔA before and after the heat treatment was increased from 0.07 to 1.7, and the alignment degree was 0.72 at 262 nm, which was a substrate having a liquid crystal alignment film.

<比較例1> <Comparative Example 1>

使用合成例6所得到之聚合物1，溶解於二氯甲烷，於光學性各向同性之基板，藉由以約190nm厚度旋轉塗佈 而形成側鏈型高分子膜於基板上。測定使用此基板之紫外吸收光譜時，最大吸光度於314nm為0.89。於所得到基板上之側鏈型高分子膜，使用格蘭．泰勒棱鏡照射變換成直線偏光之紫外線。 The polymer 1 obtained in Synthesis Example 6 was dissolved in methylene chloride on an optically isotropic substrate by spin coating at a thickness of about 190 nm. A side chain type polymer film is formed on the substrate. When the ultraviolet absorption spectrum of this substrate was measured, the maximum absorbance was 0.89 at 314 nm. For the side chain type polymer film on the obtained substrate, use Gran. The Taylor prism illumination is converted into a linearly polarized ultraviolet light.

使用經如此而得到之基板上的側鏈型高分子膜測定紫外吸收光譜，對側鏈型高分子膜，評估與經照射之偏光紫外線的偏光方向平行之方向的紫外線吸光度與垂直方向之紫外線吸光度之差△A。△A照射以波長365nm換算為4500mJ之偏光紫外線之際，於314nm最大雖為0.2，照射650mJ偏光紫外線使△A成為0.065(相對於最大值為32之差)，接著，將此基板加熱至155℃，並將側鏈型高分子膜作為液晶相，直接保持5分鐘。然後，冷卻至室溫，於膜中得到具有經導入各向異性之液晶配向膜之基板。此時之△A增幅為1.8，配向度成為0.73。 The ultraviolet absorption spectrum was measured using the side chain type polymer film on the substrate thus obtained, and the ultraviolet absorbance in the direction parallel to the polarized direction of the irradiated polarized ultraviolet light and the ultraviolet absorbance in the vertical direction were evaluated for the side chain type polymer film. The difference is ΔA. ΔA irradiation was performed at a wavelength of 365 nm in the range of 4,500 mJ of polarized ultraviolet light, and the maximum was 0.2 at 314 nm, and 650 mJ of polarized ultraviolet light was irradiated so that ΔA became 0.065 (the difference from the maximum value of 32), and then the substrate was heated to 155. °C, and the side chain type polymer film was used as a liquid crystal phase, and it was kept for 5 minutes. Then, it was cooled to room temperature, and a substrate having a liquid crystal alignment film into which anisotropy was introduced was obtained in the film. At this time, the ΔA increase was 1.8, and the degree of alignment became 0.73.

<比較例2> <Comparative Example 2>

將合成例6所得到之聚合物1溶解於二氯甲烷，於光學性各向同性之基板，藉由以約190nm厚度旋轉塗佈於基板上形成側鏈型高分子膜，除了將偏光紫外線之照射量作為4500mJ(將△A最大值作為△A之照射量)之外其他與比較例1同樣進行偏光紫外線照射與其後之熱處理，得到導入各向異性於膜中之液晶配向膜。此時，熱處理前後之△A從0.07至0.07並未變化，配向度於314nm為0.12，並未確認△A與配向度之增幅。 The polymer 1 obtained in Synthesis Example 6 was dissolved in dichloromethane, and optically isotropic substrate was spin-coated on the substrate at a thickness of about 190 nm to form a side chain type polymer film, except for polarized ultraviolet rays. The irradiation amount was changed to 4500 mJ (the maximum value of ΔA was used as the irradiation amount of ΔA), and the polarized ultraviolet ray irradiation was performed in the same manner as in Comparative Example 1, followed by heat treatment to obtain a liquid crystal alignment film into which anisotropy was introduced into the film. At this time, ΔA before and after the heat treatment did not change from 0.07 to 0.07, and the degree of alignment was 0.12 at 314 nm, and the increase in ΔA and the degree of alignment was not confirmed.

<比較例3> <Comparative Example 3>

將合成例7所得到之聚合物2溶解於四氫呋喃，於光學性各向同性之基板，藉由以約150nm厚度旋轉塗佈於基板上形成側鏈型高分子膜，除了將偏光紫外線之照射量作為900mJ(將△A最大值作為△A之照射量)以及將其後之熱處理定為於165℃之外其他與比較例1同樣進行偏光紫外線照射與其後之熱處理，得到導入各向異性於膜中之液晶配向膜。此時，熱處理前後之△A從0.07至0.07並未變化，配向度於314nm為0.12，並未確認△A與配向度之增幅。 The polymer 2 obtained in Synthesis Example 7 was dissolved in tetrahydrofuran, and optically isotropic substrate was spin-coated on the substrate at a thickness of about 150 nm to form a side chain type polymer film, except for the amount of polarized ultraviolet rays. The heat treatment was carried out in the same manner as in Comparative Example 1, except that 900 mJ (the maximum value of ΔA was used as the irradiation amount of ΔA) and the subsequent heat treatment was changed to 165° C., and the anisotropy was introduced into the film. In the liquid crystal alignment film. At this time, ΔA before and after the heat treatment did not change from 0.07 to 0.07, and the degree of alignment was 0.12 at 314 nm, and the increase in ΔA and the degree of alignment was not confirmed.

<比較例4> <Comparative Example 4>

將合成例7所得到之聚合物2溶解於四氫呋喃，於光學性各向同性之基板，藉由以約150nm厚度旋轉塗佈於基板上形成側鏈型高分子膜，除了將偏光紫外線之照射量作為5mJ(將△A最大值之10%作為△A之照射量)以及其後之熱處理將聚合物2之液晶溫度範圍以上定為200℃之外其他與比較例1同樣進行偏光紫外線照射與其後之熱處理，得到液晶配向膜。此時，熱處理前後之△A從0.07減少至0，配向於314nm亦變為0，高分子薄膜中之各向異性消失。 The polymer 2 obtained in Synthesis Example 7 was dissolved in tetrahydrofuran, and optically isotropic substrate was spin-coated on the substrate at a thickness of about 150 nm to form a side chain type polymer film, except for the amount of polarized ultraviolet rays. The polarized ultraviolet ray was irradiated in the same manner as in Comparative Example 1 except that 5 mJ (10% of the maximum value of ΔA was used as the ΔA irradiation amount) and the subsequent heat treatment of the polymer 2 was set to 200 ° C or higher. The heat treatment is performed to obtain a liquid crystal alignment film. At this time, ΔA before and after the heat treatment was reduced from 0.07 to 0, and the orientation became 0 at 314 nm, and the anisotropy in the polymer film disappeared.

<液晶晶胞之作成與評估> <Preparation and evaluation of liquid crystal cell> <實施例7> <Example 7>

使用具有於實施例1所作成之液晶配向膜的基板2片，挾持Merck Japan(股)製之液晶ZL1-4792而得到反平行(Anti-parallel)液晶晶胞。將所得到之液晶晶胞以正交尼科耳(crossed Nichol)下觀察時，觀察到無配向不良之均勻液晶配向。又，製作2片導入如此各向異性之附液晶配向膜的ITO基板，挾持液晶ZL1-4792於此等之間，將所得到之液晶晶胞進而藉由以一對直線偏光板挾持，作成液晶厚度為6μm之TN(Twisted Nematic)型液晶顯示元件。於此TN型液晶顯示元件由對ITO電極之外加電壓可確認液晶之驅動。液晶顯示元件經確認全面無配向缺陷，經確認由外加電壓均勻之液晶配向變化。使用本實施形態之液晶配向膜，可製造本實施之液晶顯示元件。將評估結果匯集於表1。 Two sheets of the substrate having the liquid crystal alignment film formed in Example 1 were used, and liquid crystal ZL1-4792 manufactured by Merck Japan Co., Ltd. was used to obtain an anti-parallel liquid crystal cell. When the obtained liquid crystal cell was observed under crossed Nichol, uniform liquid crystal alignment without alignment failure was observed. Further, two ITO substrates having such an anisotropic liquid crystal alignment film were introduced, and the liquid crystal cells were held between the liquid crystals ZL1-4792, and the obtained liquid crystal cells were further held by a pair of linear polarizing plates to form liquid crystals. A TN (Twisted Nematic) type liquid crystal display element having a thickness of 6 μm. In this TN type liquid crystal display element, the driving of the liquid crystal can be confirmed by applying a voltage to the ITO electrode. The liquid crystal display element was confirmed to have no overall alignment defect, and it was confirmed that the alignment of the liquid crystal with uniform applied voltage was changed. The liquid crystal display element of the present embodiment can be produced by using the liquid crystal alignment film of the present embodiment. The results of the evaluation are summarized in Table 1.

<實施例8> <Example 8>

使用具有於實施例2所作成之液晶配向膜的基板2片，與實施例7同樣方法作成液晶晶胞。將結果表示於表1。 A liquid crystal cell was produced in the same manner as in Example 7 using the substrate 2 having the liquid crystal alignment film formed in Example 2. The results are shown in Table 1.

<實施例9> <Example 9>

使用具有於實施例3所作成之液晶配向膜的基板2片，與實施例7同樣方法作成液晶晶胞。將結果表示於表1。 A liquid crystal cell was produced in the same manner as in Example 7 using two sheets of the substrate having the liquid crystal alignment film formed in Example 3. The results are shown in Table 1.

<實施例10> <Example 10>

使用具有於實施例4所作成之液晶配向膜的基板2片，與實施例7同樣方法作成液晶晶胞。將結果表示於表1。 A liquid crystal cell was produced in the same manner as in Example 7 using the substrate 2 having the liquid crystal alignment film formed in Example 4. The results are shown in Table 1.

<實施例11> <Example 11>

使用具有於實施例5所作成之液晶配向膜的基板2片，與實施例7同樣方法作成液晶晶胞。將結果表示於表1。 A liquid crystal cell was produced in the same manner as in Example 7 using two sheets of the substrate having the liquid crystal alignment film formed in Example 5. The results are shown in Table 1.

<實施例12> <Example 12>

使用具有於實施例6所作成之液晶配向膜的基板2片，與實施例7同樣方法作成液晶晶胞。將結果表示於表1。 A liquid crystal cell was produced in the same manner as in Example 7 using two sheets of the substrate having the liquid crystal alignment film formed in Example 6. The results are shown in Table 1.

<比較例5> <Comparative Example 5>

使用具有於比較例1所作成之液晶配向膜的基板2片，與實施例7同樣方法作成液晶晶胞。將結果表示於表1。 A liquid crystal cell was produced in the same manner as in Example 7 using the substrate 2 having the liquid crystal alignment film prepared in Comparative Example 1. The results are shown in Table 1.

<比較例6> <Comparative Example 6>

使用具有於比較例2所作成之液晶配向膜的基板2片，與實施例7同樣方法作成液晶晶胞。將結果表示於表 1。 A liquid crystal cell was produced in the same manner as in Example 7 except that two substrates of the liquid crystal alignment film produced in Comparative Example 2 were used. Express the results on the table 1.

<比較例7> <Comparative Example 7>

使用具有於比較例3所作成之液晶配向膜的基板2片，與實施例7同樣方法作成液晶晶胞。將結果表示於表1。 A liquid crystal cell was produced in the same manner as in Example 7 using two sheets of the substrate having the liquid crystal alignment film formed in Comparative Example 3. The results are shown in Table 1.

<比較例8> <Comparative Example 8>

使用具有於比較例4所作成之液晶配向膜的基板2片，與實施例7同樣方法作成液晶晶胞。將結果表示於表1。 A liquid crystal cell was produced in the same manner as in Example 7 except that two sheets of the substrate having the liquid crystal alignment film formed in Comparative Example 4 were used. The results are shown in Table 1.

由以上之評估結果，理解到使用本發明之液晶配向膜的製造方法，藉由少量紫外線照射量而製成本發明之液晶配向膜，可提供液晶顯示元件。 From the above evaluation results, it is understood that the liquid crystal alignment element of the present invention can be produced by using a small amount of ultraviolet irradiation amount to produce a liquid crystal display element by using the liquid crystal alignment film of the present invention.

〔產業上之可利用性〕 [Industrial Applicability]

本發明之製造方法，係有用於可高效率配向處理之液晶配向膜的製造。 The production method of the present invention is the production of a liquid crystal alignment film for high-efficiency alignment treatment.

尚且，將2011年11月29日申請之日本特許出願2011-260180號之說明書、申請專利範圍、圖面及摘要全部內容引用於此，作為本發明說明書之揭示，而擷取者。 In addition, the specification, the scope of the patent, the drawings and the abstract of the Japanese Patent Application No. 2011-260180, filed on Nov. 29, 2011, are hereby incorporated by reference.

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]係以模式說明將在本發明第1形態之液晶配向膜之製造方法之各向異性導入處理之一種例圖。(a)為以模式表示之偏光照射前之側鏈型高分子膜之狀態的圖，尤其是經導入之各向異性小時，亦即在具有本發明之上述[I]~[IV]步驟的液晶配向膜之製造方法，[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於1%~15%之範圍內時之模式圖。(b)為以模式表示偏光照射後之側鏈型高分子膜狀態之圖，(c)為以模式表示加熱後之側鏈型高分子膜狀態之圖，圖(d)為以模式表示於加熱後經無偏光照射之側鏈型高分子膜狀態之圖。對於前述第1形態，後述說明。 FIG. 1 is a view showing an example of an anisotropic introduction process of a method for producing a liquid crystal alignment film according to a first aspect of the present invention. (a) is a view showing the state of the side chain type polymer film before the polarized light irradiation in the mode, in particular, when the anisotropy of introduction is small, that is, having the above steps [I] to [IV] of the present invention In the method for producing a liquid crystal alignment film, the ultraviolet irradiation amount in the step [II] is a pattern in which the ultraviolet irradiation amount when ΔA is maximum is in the range of 1% to 15%. (b) is a view showing a state of a side chain type polymer film after polarized light irradiation, (c) is a view showing a state of a side chain type polymer film after heating in a mode, and (d) is a mode A state of a side chain type polymer film which is irradiated without polarized light after heating. The first aspect will be described later.

[圖2]為在係以模式說明將在本發明第1形態之液晶配向膜之製造方法之各向異性導入處理之一種例圖，尤其是經導入之各向異性大時，亦即在具有本發明之上述[I]~[IV]步驟之液晶配向膜之製造方法，[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於15%~70%之範圍內時之模式圖。(a)為以模式表示之偏光照射前之 側鏈型高分子膜狀態之圖，(b)為以模式表示偏光照射後之側鏈型高分子膜狀態之圖，(c)為以模式表示加熱後之側鏈型高分子膜狀態之圖，圖(d)為以模式表示於加熱後經無偏光照射之側鏈型高分子膜狀態之圖。 FIG. 2 is a view showing an example of an anisotropic introduction process of a method for producing a liquid crystal alignment film according to a first aspect of the present invention, in particular, when the anisotropy introduced is large, that is, In the method for producing a liquid crystal alignment film according to the above [I] to [IV] of the present invention, the ultraviolet irradiation amount in the step [II] is such that the ultraviolet irradiation amount when the ΔA is maximum is in the range of 15% to 70%. Schematic diagram. (a) before the polarized light indicated by the mode (b) is a diagram showing a state of a side chain type polymer film after polarized light irradiation, and (c) is a diagram showing a state of a side chain type polymer film after heating in a mode. (d) is a view showing a state of a side chain type polymer film which is irradiated with no polarized light after heating in a mode.

[圖3]為在係以模式說明將在本發明第2形態之液晶配向膜之製造方法之各向異性導入處理之一種例圖，尤其是側鏈型高分子以上述之式(6)表示構造時，亦即在具有本發明之上述[I]~[III]步驟之製造方法，在使用式(6)所表示構造之側鏈型高分子膜時，[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於1%~70%之範圍內時之模式圖。(a)為以模式表示之偏光照射前之側鏈型高分子膜狀態之圖，(b)為以模式表示偏光照射後之側鏈型高分子膜狀態之圖，(c)為以模式表示加熱後之側鏈型高分子膜狀態之圖。對於前述第2形態，後述說明。 FIG. 3 is a view showing an example of an anisotropic introduction process of a method for producing a liquid crystal alignment film according to a second aspect of the present invention, in which a side chain type polymer is represented by the above formula (6). In the case of the structure, that is, in the production method of the above steps [I] to [III] of the present invention, when the side chain type polymer film having the structure represented by the formula (6) is used, the amount of ultraviolet irradiation in the step [II], A mode diagram in which the amount of ultraviolet radiation when ΔA is the maximum is in the range of 1% to 70%. (a) is a diagram showing the state of the side chain type polymer film before the polarized light irradiation in the mode, (b) is a diagram showing the state of the side chain type polymer film after the polarized light irradiation, and (c) is a pattern A diagram of the state of the side chain type polymer film after heating. The second aspect will be described later.

[圖4]為在係以模式說明將在本發明第2形態之液晶配向膜之製造方法之各向異性導入處理之一種例圖，尤其是側鏈型高分子以上述之式(7)表示構造時，亦即在具有本發明之上述[I]~[III]步驟之製造方法，在使用式(7)所表示構造之側鏈型高分子膜時，[II]步驟之紫外線照射量，係將△A為最大時之紫外線照射量於1%~70%之範圍內時之模式圖。(a)為以模式表示之偏光照射前之側鏈型高分子膜狀態之圖，(b)為以模式表示偏光照射後之側鏈型高分子膜狀態之圖，(c)為以模式表示加熱 後之側鏈型高分子膜狀態之圖。 FIG. 4 is a view showing an example of an anisotropic introduction process of a method for producing a liquid crystal alignment film according to a second aspect of the present invention, in which a side chain type polymer is represented by the above formula (7). In the case of the structure, that is, in the production method having the above-described steps [I] to [III] of the present invention, when the side chain type polymer film having the structure represented by the formula (7) is used, the amount of ultraviolet irradiation in the step [II], A mode diagram in which the amount of ultraviolet radiation when ΔA is the maximum is in the range of 1% to 70%. (a) is a diagram showing the state of the side chain type polymer film before the polarized light irradiation in the mode, (b) is a diagram showing the state of the side chain type polymer film after the polarized light irradiation, and (c) is a pattern heating A diagram of the state of the rear side chain type polymer film.

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

2、2a‧‧‧側鏈 2, 2a‧‧‧ side chain

Claims (12)

一種液晶配向膜之製造方法，其係具有[I]~[III]步驟之液晶配向膜之製造方法：[I]於基板上，於特定溫度範圍形成表現液晶性之感光性的側鏈型高分子膜之步驟、[II]照射經偏光之紫外線於前述側鏈型高分子膜之步驟、及[III]加熱前述經紫外線照射之側鏈型高分子膜之步驟，其特徵為[II]步驟之紫外線照射量，係於前述側鏈型高分子膜之△A為最大時之紫外線照射量的1%~70%範圍內，其中△A係與前述經偏光之紫外線的偏光方向平行之方向之紫外線吸光度與垂直之方向之紫外線吸光度之差。 A method for producing a liquid crystal alignment film, which is a method for producing a liquid crystal alignment film having the steps [I] to [III]: [I] forming a side chain type high in liquid crystallinity at a specific temperature range on a substrate a step of molecular film, [II] a step of irradiating the polarized ultraviolet light to the side chain type polymer film, and [III] a step of heating the ultraviolet light-irradiated side chain type polymer film, which is characterized by [II] step The ultraviolet irradiation amount is in the range of 1% to 70% of the ultraviolet irradiation amount when ΔA of the side chain type polymer film is maximum, wherein ΔA is in a direction parallel to the polarization direction of the polarized ultraviolet light. The difference between the UV absorbance and the UV absorbance in the vertical direction. 如申請專利範圍第1項之液晶配向膜之製造方法，其中[II]步驟之紫外線照射量，係將前述△A為最大時之紫外線照射量1%~50%之範圍內。 The method for producing a liquid crystal alignment film according to the first aspect of the invention, wherein the ultraviolet irradiation amount in the step [II] is in a range of from 1% to 50% of the ultraviolet irradiation amount when the ΔA is maximum. 如申請專利範圍第1或2項之液晶配向膜之製造方法，其中[III]步驟之加熱溫度，為從比前述側鏈型高分子膜表現液晶性之溫度範圍下限高10℃溫度至比該溫度範圍上限低10℃溫度之範圍的溫度。 The method for producing a liquid crystal alignment film according to claim 1 or 2, wherein the heating temperature in the step [III] is 10 ° C higher than a lower limit of a temperature range in which the side chain type polymer film exhibits liquid crystallinity. The temperature range is lower than the upper limit of the temperature range of 10 °C. 如申請專利範圍第1或2項之液晶配向膜之製造方法，其中含有於表現前述液晶性之感光性的側鏈型高分子之感光性基為偶氮苯、二苯乙烯、桂皮酸、桂皮酸酯、查酮、香豆素、二苯乙炔(Tolan)、苯甲酸苯酯、或其 衍生物。 The method for producing a liquid crystal alignment film according to the first or second aspect of the invention, wherein the photosensitive group of the side chain type polymer which exhibits the photosensitivity of the liquid crystal property is azobenzene, stilbene, cinnamic acid, cinnamon Acid ester, ketone, coumarin, tolan, phenyl benzoate, or derivative. 一種液晶配向膜之製造方法，其係具有[I]~[IV]步驟之液晶配向膜之製造方法：[I]於基板上，於特定溫度範圍形成表現液晶性之光交聯性的側鏈型高分子膜之步驟、[II]照射經偏光之紫外線於前述光交聯性側鏈型高分子膜之步驟、及[III]加熱前述經紫外線照射之側鏈型高分子膜之步驟、[IV]照射無偏光之紫外線於經照射前述紫外線之後再經加熱之側鏈型高分子膜之步驟、，其特徵為[II]步驟之紫外線照射量，係於前述側鏈型高分子膜之△A為最大時之紫外線照射量的1%~70%範圍內，其中△A係與前述經偏光之紫外線的偏光方向平行之方向之紫外線吸光度與垂直之方向之紫外線吸光度之差。 A method for producing a liquid crystal alignment film, which is a method for producing a liquid crystal alignment film having the steps [I] to [IV]: [I] forming a light-crosslinking side chain exhibiting liquid crystallinity on a substrate at a specific temperature range a step of forming a polymer film, [II] a step of irradiating the polarized ultraviolet light to the photocrosslinkable side chain type polymer film, and [III] a step of heating the ultraviolet side-irradiated side chain type polymer film, [ IV] a step of irradiating a non-polarized ultraviolet ray to a side chain type polymer film which is heated after being irradiated with the ultraviolet ray, and is characterized in that the ultraviolet ray irradiation amount of the step [II] is Δ of the side chain type polymer film A is in the range of 1% to 70% of the maximum ultraviolet irradiation amount, wherein ΔA is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance in the vertical direction. 如申請專利範圍第5項之液晶配向膜之製造方法，其中[II]步驟之紫外線照射量，係將前述△A為最大時之紫外線照射量1%~50%之範圍內。 The method for producing a liquid crystal alignment film according to the fifth aspect of the invention, wherein the ultraviolet irradiation amount in the step [II] is in a range of from 1% to 50% of the ultraviolet irradiation amount when the ΔA is maximum. 如申請專利範圍第5或6項之液晶配向膜之製造方法，其中[III]步驟之加熱溫度，為從比前述側鏈型高分子膜表現液晶性之溫度範圍下限高10℃溫度至比該溫度範圍上限低10℃溫度之範圍的溫度。 The method for producing a liquid crystal alignment film according to the fifth or sixth aspect of the invention, wherein the heating temperature in the step [III] is higher than a lower limit of a temperature range of the liquid crystal property of the side chain type polymer film by 10 ° C. The temperature range is lower than the upper limit of the temperature range of 10 °C. 如申請專利範圍第5或6項之液晶配向膜之製造 方法，其中由[IV]步驟之紫外線照射，使具有前述側鏈型高分子膜之光交聯性基之20莫耳%以上進行反應。 Manufacture of liquid crystal alignment film as claimed in claim 5 or 6 In the method, in the ultraviolet irradiation of the step [IV], 20 mol% or more of the photocrosslinkable group having the side chain type polymer film is reacted. 如申請專利範圍第5或6項之液晶配向膜之製造方法，其中含有於表現前述液晶性之光交聯性的側鏈型高分子之感光性基為桂皮酸、桂皮酸酯、查酮、香豆素、二苯乙炔(Tolan)、或其衍生物。 The method for producing a liquid crystal alignment film according to the fifth or sixth aspect of the invention, wherein the photosensitive group of the side chain type polymer which exhibits light crosslinkability of the liquid crystal property is cinnamic acid, cinnamic acid ester, and ketone. Coumarin, tolan, or a derivative thereof. 如申請專利範圍第1或2項之液晶配向膜之製造方法，其中前述側鏈型高分子膜，係具有從選自由烴、丙烯酸酯、及甲基丙烯酸酯所構成之群中至少1種所構成之主鏈、與下述式(1)~(7)至少1種所表示之側鏈的構造； (式(1)中，A1、B1各自獨立表示單鍵、-O-、 -CH2-、-COO-、-OCO-、-CONH-或-NH-CO-，Y1為選自由苯環、萘環、聯苯環、呋喃環、吡咯環、及碳數5~8之環狀烴所構成之群中至少一種之基，鍵結於該等之氫原子可各自獨立為經-NO2、-CN、-C=C(CN)2、-C=CH-CN、鹵基、烷基、或烷氧基所取代，X1表示單鍵、-COO-、-OCO-、-N=N-、-C=C-、-C≡C-或-C6H4-，I1表示1~12之整數，m1表示1~3之整數，n1表示1~12之整數，式(2)中，A2、B2、D1各自獨立表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-或-NH-CO-，Y2為選自由苯環、萘環、聯苯環、呋喃環、吡咯環、及碳數5~8之環狀烴所構成之群中至少一種之基，鍵結於該等之氫原子可各自獨立為經-NO2、-CN、-C=C(CN)2、-C=CH-CN、鹵基、烷基、或烷氧基所取代，X2表示單鍵、-COO-、-OCO-、-N=N-、-C=C-、-C≡C-、或-C6H4-，R1表示氫原子、或碳數1~6之烷基，I2表示1~12之整數，m2表示1~3之整數，n2表示1~12之整數；式(3)中，A3表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、或-NH-CO-，X3表示單鍵、-COO-、-OCO-、-N=N-、-C=C-、-C≡C-、或-C6H4-，R2表示氫原子、或碳數1~6之烷基，I3表示1~12之整數，m3表示1~3之整數；式(4)中，I4表示1~12之整數；式(5)中，A4表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、或-NH-CO-，X4表示-COO-，Y3表示苯環、萘環、及聯苯環所構成之群中至少一種之基，鍵結於該等之氫原子可各自獨立為經-NO2、-CN、 -C=C(CN)2、-C=CH-CN、鹵基、烷基、或烷氧基所取代，I5表示1~12之整數，m4表示1~3之整數；式(6)中，A5表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、或-NH-CO-，R3表示選自由氫原子、-NO2、-CN、-C=C(CN)2、-C=CH-CN、鹵基、碳數1~6之烷基、及碳數1~6之烷氧基所構成之群中至少一種之基，I6表示1~12之整數；鍵結於式(6)中之苯環之氫原子可各自獨立為經-NO2、-CN、-C=C(CN)2、-C=CH-CN、鹵基、烷基、或烷氧基所取代；式(7)中，A6表示單鍵、-O-、-CH2-、-COO-、-OCO-、-CONH-、或-NH-CO-，B3表示單鍵、-COO-、-OCO-、-N=N-、-C=C-、-C≡C-、或-C6H4-；W1表示選自由苯環、萘環、聯苯環、呋喃環、吡咯環、及碳數5~8之環狀烴所構成之群中至少一種之基，鍵結於該等之氫原子可各自獨立為經-NO2、-CN、-C=C(CN)2、-C=CH-CN、鹵基、烷基、或烷氧基所取代，I7表示1~12之整數，m5、m6各自表示1~3之整數)。 The method for producing a liquid crystal alignment film according to the first or second aspect of the invention, wherein the side chain type polymer film has at least one selected from the group consisting of hydrocarbons, acrylates, and methacrylates. a structure of a main chain and a side chain represented by at least one of the following formulas (1) to (7); (In the formula (1), A 1 and B 1 each independently represent a single bond, -O-, -CH 2 -, -COO-, -OCO-, -CONH- or -NH-CO-, and Y 1 is selected from a group of at least one of a group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a cyclic hydrocarbon having 5 to 8 carbon atoms, and the hydrogen atoms bonded to the hydrogen atoms may be independently NO 2 , -CN, -C=C(CN) 2 , -C=CH-CN, halo, alkyl, or alkoxy are substituted, X 1 represents a single bond, -COO-, -OCO-, - N=N-, -C=C-, -C≡C- or -C 6 H 4 -, I1 represents an integer from 1 to 12, m1 represents an integer from 1 to 3, and n1 represents an integer from 1 to 12, In 2), A 2 , B 2 and D 1 each independently represent a single bond, -O-, -CH 2 -, -COO-, -OCO-, -CONH- or -NH-CO-, and Y 2 is selected from a group of at least one of a group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a cyclic hydrocarbon having 5 to 8 carbon atoms, and the hydrogen atoms bonded to the hydrogen atoms may be independently NO 2 , -CN, -C=C(CN) 2 , -C=CH-CN, halo, alkyl, or alkoxy, X 2 represents a single bond, -COO-, -OCO-, - N=N-, -C=C-, -C≡C-, or -C 6 H 4 -, R 1 represents a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms, I2 Indicates an integer from 1 to 12, m2 represents an integer from 1 to 3, n2 represents an integer from 1 to 12; in the formula (3), A 3 represents a single bond, -O-, -CH 2 -, -COO-, -OCO -, -CONH-, or -NH-CO-, X 3 represents a single bond, -COO-, -OCO-, -N=N-, -C=C-, -C≡C-, or -C 6 H 4 -, R 2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, I3 represents an integer of 1 to 12, m3 represents an integer of 1 to 3, and in the formula (4), I4 represents an integer of 1 to 12; In (5), A 4 represents a single bond, -O-, -CH 2 -, -COO-, -OCO-, -CONH-, or -NH-CO-, X 4 represents -COO-, and Y 3 represents benzene. a group of at least one of a group consisting of a ring, a naphthalene ring, and a biphenyl ring, each of which may be independently a -NO 2 , -CN, -C=C(CN) 2 , -C =CH-CN, a halogen group, an alkyl group, or an alkoxy group, wherein I5 represents an integer from 1 to 12, and m4 represents an integer from 1 to 3; in the formula (6), A 5 represents a single bond, -O-, -CH 2 -, -COO-, -OCO-, -CONH-, or -NH-CO-, R 3 represents a group selected from a hydrogen atom, -NO 2 , -CN, -C=C(CN) 2 , -C a group of at least one of CH-CN, a halogen group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms, and I6 represents an integer of 1 to 12; 6) The hydrogen atom of the benzene ring may be independently substituted by -NO 2 , -CN, -C=C(CN) 2 , -C=CH-CN, a halogen group, an alkyl group, or an alkoxy group; In 7), A 6 represents a single bond, -O-, -CH 2 -, -COO-, -OCO-, -CONH-, or -NH-CO-, and B 3 represents a single bond, -COO-, -OCO -, -N=N-, -C=C-, -C≡C-, or -C 6 H 4 -; W 1 represents a group selected from the group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a group of at least one of the group consisting of cyclic hydrocarbons having 5 to 8 carbon atoms, and each of the hydrogen atoms bonded to the hydrogen atoms may be independently -NO 2 , -CN, -C=C(CN) 2 , -C =CH-CN, a halogen group, an alkyl group, or an alkoxy group, and I7 represents an integer of 1 to 12, and m5 and m6 each represent an integer of 1 to 3). 一種液晶配向膜，其係由申請專利範圍第1~10項中任一項之液晶配向膜之製造方法所製造。 A liquid crystal alignment film produced by the method for producing a liquid crystal alignment film according to any one of claims 1 to 10. 一種液晶顯示元件，其係具有申請專利範圍第11項之液晶配向膜。 A liquid crystal display element having a liquid crystal alignment film of claim 11 of the patent application.
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