TWI711671B - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, liquid crystal alignment film and liquid crystal element manufacturing method - Google Patents

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, liquid crystal alignment film and liquid crystal element manufacturing method Download PDF

Info

Publication number
TWI711671B
TWI711671B TW105140543A TW105140543A TWI711671B TW I711671 B TWI711671 B TW I711671B TW 105140543 A TW105140543 A TW 105140543A TW 105140543 A TW105140543 A TW 105140543A TW I711671 B TWI711671 B TW I711671B
Authority
TW
Taiwan
Prior art keywords
liquid crystal
crystal alignment
polymer
group
alignment agent
Prior art date
Application number
TW105140543A
Other languages
Chinese (zh)
Other versions
TW201725242A (en
Inventor
野口峻一
Original Assignee
日商Ｊｓｒ股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日商Ｊｓｒ股份有限公司 filed Critical 日商Ｊｓｒ股份有限公司
Publication of TW201725242A publication Critical patent/TW201725242A/en
Application granted granted Critical
Publication of TWI711671B publication Critical patent/TWI711671B/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • 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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate
    • 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
    • C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F122/10—Esters
    • C08F122/12—Esters of phenols or saturated alcohols
    • C08F122/20—Esters containing oxygen in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • 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
    • 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
    • G02F1/133723—Polyimide, polyamide-imide
    • 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

Abstract

本發明提供一種可獲得初期的電壓保持率及耐光性優異的液晶元件的液晶配向劑。所述液晶配向劑包括具有光配向性基的聚有機矽氧烷（C），且在聚有機矽氧烷（C）及與聚有機矽氧烷（C）不同的聚合體的至少任一者的分子內含有顯現液晶性的部分結構。The present invention provides a liquid crystal alignment agent that can obtain a liquid crystal element excellent in initial voltage retention and light resistance. The liquid crystal alignment agent includes polyorganosiloxane (C) having a photo-alignment group, and at least any one of polyorganosiloxane (C) and a polymer different from polyorganosiloxane (C) The molecule contains a partial structure that exhibits liquid crystallinity.

Description

液晶配向劑、液晶配向膜、液晶元件、以及液晶配向膜及液晶元件的製造方法Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, liquid crystal alignment film and liquid crystal element manufacturing method

本發明關於一種液晶配向劑、液晶配向膜、液晶元件、以及液晶配向膜及液晶元件的製造方法。The invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal element, a liquid crystal alignment film and a method for manufacturing the liquid crystal element.

液晶元件具有用以使液晶分子進行配向的液晶配向膜。近年來，伴隨使用用途或使用環境的擴大，對於液晶面板的顯示性能的要求變得更嚴格。因此，正進行各種用以改善液晶面板的各種特性的液晶配向膜的研究（例如，參照專利文獻1、專利文獻2）。在專利文獻1中揭示有使用光配向劑來形成液晶配向膜，所述光配向劑含有具有光配向能力的聚合物與顯示出液晶性的聚合物，且具有光配向能力的聚合物為選自由聚醯胺酸、部分醯亞胺化聚醯胺酸及聚醯亞胺所組成的群組中的至少一種。另外，在專利文獻2中揭示有使用顯現液晶性的感光性的側鏈型高分子在基板上形成塗膜後，照射偏光的紫外線，繼而進行加熱，由此形成液晶配向膜。 [現有技術文獻] [專利文獻]The liquid crystal element has a liquid crystal alignment film for aligning liquid crystal molecules. In recent years, with the expansion of use applications or use environments, the requirements for the display performance of liquid crystal panels have become stricter. Therefore, various researches on liquid crystal alignment films for improving various characteristics of liquid crystal panels are being conducted (for example, refer to Patent Document 1 and Patent Document 2). Patent Document 1 discloses the use of a photo-aligning agent to form a liquid crystal alignment film. The photo-aligning agent contains a polymer having photo-alignment capability and a polymer exhibiting liquid crystallinity, and the polymer having photo-alignment capability is selected from At least one of the group consisting of polyamide, partially imidized polyamide, and polyimide. In addition, Patent Document 2 discloses that after forming a coating film on a substrate using a photosensitive side chain polymer that exhibits liquid crystallinity, it is irradiated with polarized ultraviolet rays and then heated to form a liquid crystal alignment film. [Prior Art Document] [Patent Document]

[專利文獻1]日本專利第5407394號公報 [專利文獻2]國際公開第2013/081066號[Patent Document 1] Japanese Patent No. 5407394 [Patent Document 2] International Publication No. 2013/081066

[發明所欲解決之課題] 在伴隨液晶元件的多用途化，而設想長時間的連續驅動或在存在光應力的地方的使用等在嚴酷的環境下的使用的過程中，液晶元件重要的是在使用時難以產生由光所引起的劣化（例如電壓保持率的下降），也可以經得起在嚴酷的環境下的使用。另外，為了提高液晶元件的顯示品質，初期的電壓保持率高也重要，若鑒於近年來的對於液晶元件的高性能化的要求，則需要一種用以獲得初期的電壓保持率高、且耐光性優異的液晶元件的新的技術。[Problem to be Solved by the Invention] In the process of use in harsh environments, such as continuous driving for a long time or use in places where light stress exists, as the versatility of liquid crystal elements is expected, the important thing about liquid crystal elements is It is difficult to produce degradation caused by light (such as a decrease in voltage retention) during use, and it can withstand use in harsh environments. In addition, in order to improve the display quality of liquid crystal elements, it is also important to have a high initial voltage retention rate. In view of the recent requirements for higher performance of liquid crystal elements, it is necessary to achieve a high initial voltage retention rate and light resistance. New technology of excellent liquid crystal element.

本發明是鑒於所述課題而完成的發明，其一個目的在於提供一種可獲得初期的電壓保持率及耐光性優異的液晶元件的液晶配向劑 [解決問題的技術手段]The present invention was made in view of the above-mentioned problems, and one of its objects is to provide a liquid crystal alignment agent that can obtain a liquid crystal element excellent in initial voltage retention and light resistance [Technical Means for Solving Problems]

本發明者為了達成如上所述的現有技術的課題而進行努力研究，發現藉由將液晶配向劑的聚合體成分設為特定的組成而可解決所述課題，從而完成了本發明。具體而言，提供以下的手段。The inventors of the present invention conducted diligent studies to achieve the above-mentioned problems of the prior art, and found that the problems can be solved by setting the polymer component of the liquid crystal alignment agent to a specific composition, and completed the present invention. Specifically, the following means are provided.

＜1＞ 一種液晶配向劑，其包括具有光配向性基的聚有機矽氧烷（C），且在所述聚有機矽氧烷（C）及與所述聚有機矽氧烷（C）不同的聚合體的至少任一者的分子內含有顯現液晶性的部分結構。 ＜2＞ 一種液晶配向膜，其使用所述＜1＞中記載的液晶配向劑來形成。 ＜3＞ 一種液晶元件，其包括所述＜2＞中記載的液晶配向膜。 ＜4＞ 一種液晶配向膜的製造方法，其包括：將所述＜1＞的液晶配向劑塗布在基板上而形成塗膜的步驟、及對塗布有所述液晶配向劑的基板面進行光照射來對所述塗膜賦予液晶配向能力的步驟。 ＜5＞ 一種液晶元件的製造方法，其包括：藉由所述＜4＞的方法而在一對基板各自的表面上形成液晶配向膜的步驟；以各自的液晶配向膜對向的方式，隔著含有聚合性單體的液晶層來配置所述一對基板而構築液晶單元的步驟；以及對所述液晶單元進行光照射的步驟。 ＜6＞ 一種液晶元件的製造方法，其包括：藉由所述＜4＞的方法，並使用含有聚合性單體的液晶配向劑在一對基板各自的表面上形成液晶配向膜的步驟；以各自的液晶配向膜對向的方式，隔著液晶層來配置所述一對基板而構築液晶單元的步驟；以及對所述液晶單元進行光照射的步驟。 [發明的效果]<1> A liquid crystal alignment agent comprising a polyorganosiloxane (C) having a photo-alignment group, and is different from the polyorganosiloxane (C) and the polyorganosiloxane (C) At least any one of the polymers contains a partial structure expressing liquid crystallinity in the molecule. <2> A liquid crystal alignment film formed using the liquid crystal alignment agent described in the above <1>. <3> A liquid crystal element including the liquid crystal alignment film described in <2>. <4> A method for manufacturing a liquid crystal alignment film, comprising: applying the liquid crystal alignment agent of <1> on a substrate to form a coating film, and irradiating light on the surface of the substrate coated with the liquid crystal alignment agent To impart the liquid crystal alignment ability to the coating film. <5> A method for manufacturing a liquid crystal element, comprising: forming a liquid crystal alignment film on the respective surfaces of a pair of substrates by the method described in <4>; A step of arranging the pair of substrates with a liquid crystal layer containing a polymerizable monomer to construct a liquid crystal cell; and a step of irradiating the liquid crystal cell with light. <6> A method of manufacturing a liquid crystal element, comprising: using the method of <4> and using a liquid crystal alignment agent containing a polymerizable monomer to form a liquid crystal alignment film on each surface of a pair of substrates; The respective liquid crystal alignment films are opposed to each other, a step of arranging the pair of substrates through a liquid crystal layer to construct a liquid crystal cell; and a step of irradiating the liquid crystal cell with light. [Effects of the invention]

根據本揭示的液晶配向劑，可獲得初期的電壓保持率高、且耐光性優異的液晶元件。另外，本揭示的液晶配向劑可應用光配向法來製造液晶配向膜，因此與先前的摩擦法相比，可抑制由灰塵或靜電的產生等所引起的顯示不良的產生或良率的下降，另外，就可對形成在基板上的有機薄膜均勻地賦予液晶配向能力的觀點而言優異。According to the liquid crystal alignment agent of the present disclosure, a liquid crystal element having a high initial voltage retention rate and excellent light resistance can be obtained. In addition, the liquid crystal alignment agent of the present disclosure can be applied to the photo-alignment method to manufacture the liquid crystal alignment film. Therefore, compared with the previous rubbing method, it can suppress the generation of display defects or the decrease in yield caused by the generation of dust or static electricity. This is excellent in terms of uniformly imparting liquid crystal alignment ability to the organic thin film formed on the substrate.

本揭示的液晶配向劑含有具有光配向性基的聚有機矽氧烷（C）。另外，含有具有顯現液晶性的部分結構的聚合體作為聚有機矽氧烷（C）及與其不同的聚合體的至少任一者。 顯現液晶性的部分結構可包含在聚有機矽氧烷（C）中，也可以包含在與聚有機矽氧烷（C）不同的聚合體中，也可以包含在所述兩種聚合體中。就液晶元件的初期的電壓保持率及耐光性的觀點而言，顯現液晶性的部分結構優選包含在與聚有機矽氧烷（C）不同的聚合體中。即，本揭示的液晶配向劑優選含有在規定的溫度範圍內顯示出液晶性的聚合體（A）、及具有光配向性基的聚有機矽氧烷（C）。以下，對聚合體（A）及聚有機矽氧烷（C）進行詳細說明，並且對視需要而任意地調配至本揭示的液晶配向劑中的其他成分進行說明。The liquid crystal alignment agent of the present disclosure contains polyorganosiloxane (C) having a photo-alignment group. In addition, a polymer having a partial structure exhibiting liquid crystallinity is contained as at least any one of polyorganosiloxane (C) and a polymer different from it. The partial structure exhibiting liquid crystallinity may be contained in the polyorganosiloxane (C), may be contained in a polymer different from the polyorganosiloxane (C), or may be contained in the two types of polymers. From the viewpoint of the initial voltage retention rate and light resistance of the liquid crystal element, the partial structure expressing liquid crystallinity is preferably contained in a polymer different from the polyorganosiloxane (C). That is, the liquid crystal alignment agent of the present disclosure preferably contains a polymer (A) that exhibits liquid crystallinity in a predetermined temperature range, and a polyorganosiloxane (C) having a photo-alignment group. Hereinafter, the polymer (A) and the polyorganosiloxane (C) will be described in detail, and other components that are optionally blended into the liquid crystal alignment agent of the present disclosure will be described as needed.

＜聚合體（A）＞ 聚合體（A）只要是在規定的溫度範圍內顯示出液晶性者，則其結構並無特別限制，可列舉具有剛性的部位（液晶原（mesogen）結構）作為顯現液晶性的部分結構的聚合體。作為聚合體（A）所具有的液晶原結構，例如可列舉由下述式（1）所表示的結構等。 [化1]

Figure 02_image001
（式（1）中，Ar1 及Ar2 分別獨立地為經取代或未經取代的伸苯基或伸環己基，X1 為單鍵、-CO-、-COO-、-C＝C-、-C≡C-、-N=N-或-CONR1 -（R1 為氫原子或一價的有機基）。n為1～3的整數。當n為2或3時，Ar2 、X1 分別獨立地具有所述定義。“﹡”表示結合鍵）<Polymer (A)> As long as the polymer (A) exhibits liquid crystallinity within a predetermined temperature range, its structure is not particularly limited, and a rigid part (mesogen structure) can be cited as the display Liquid crystal partially structured polymer. As the mesogen structure possessed by the polymer (A), for example, a structure represented by the following formula (1) and the like can be cited. [化1]
Figure 02_image001
(In formula (1), Ar 1 and Ar 2 are each independently substituted or unsubstituted phenylene or cyclohexylene, X 1 is a single bond, -CO-, -COO-, -C=C- , -C≡C-, -N=N- or -CONR 1- (R 1 is a hydrogen atom or a monovalent organic group). n is an integer of 1 to 3. When n is 2 or 3, Ar 2 , X 1 has the above-mentioned definition independently. "*" means a bond)

所述式（1）中，X1 優選單鍵或-COO-。作為R1 的一價的有機基，例如可列舉：碳數1～6的烷基、保護基等。作為保護基的具體例，例如可列舉：第三丁氧基羰基、苄氧基羰基、1,1-二甲基-2-鹵代乙氧基羰基、烯丙氧基羰基等。 Ar1 及Ar2 的環部分的取代基優選碳數1～5的烷基或鹵素原子，更優選甲基或氟原子。 作為由所述式（1）所表示的部分結構的優選的具體例，例如可列舉：4-聯苯基、4-雙環己基、對三聯苯基、4,4'-伸聯苯基、4,4'-亞雙環己基、對伸三聯苯基及分別由下述式（1-1）～式（1-4）所表示的基、以及在這些基的環部分上具有甲基或氟原子的基等。 [化2]

Figure 02_image003
（式中，“﹡”表示結合鍵）In the formula (1), X 1 is preferably a single bond or -COO-. Examples of the monovalent organic group for R 1 include an alkyl group having 1 to 6 carbon atoms, a protective group, and the like. Specific examples of the protective group include, for example, a tertiary butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethoxycarbonyl group, an allyloxycarbonyl group, and the like. The substituent of the ring portion of Ar 1 and Ar 2 is preferably an alkyl group having 1 to 5 carbon atoms or a halogen atom, and more preferably a methyl group or a fluorine atom. As preferred specific examples of the partial structure represented by the formula (1), for example, 4-biphenyl, 4-bicyclohexyl, p-terphenyl, 4,4'-biphenyl, 4 ,4'-Bicyclohexylene, p-terphenylene, and groups represented by the following formulas (1-1) to (1-4), and having a methyl group or a fluorine atom on the ring portion of these groups The base and so on. [化2]
Figure 02_image003
(In the formula, "﹡" means the combination bond)

聚合體（A）可在聚合體的主鏈及側鏈的任一者上具有液晶原結構，但就液晶元件的耐光性的改善效果高的觀點而言，優選在側鏈上具有液晶原結構的側鏈型的液晶性聚合物。此處，在本說明書中，所謂聚合體的“主鏈”，是指聚合體之中包含最長的原子的鏈的“幹”的部分。容許該“幹”的部分含有環結構。因此，所謂“在聚合體的主鏈上具有液晶原結構”，是指該結構構成主鏈的一部分。所謂聚合體的“側鏈”，是指從聚合體的“幹”中分支的部分。再者，聚合體（A）可僅在聚合體的主鏈上具有液晶原結構，也可以僅在側鏈上具有液晶原結構，也可以在主鏈及側鏈兩者上具有液晶原結構。The polymer (A) may have a mesogen structure on either the main chain or the side chain of the polymer, but from the viewpoint of the high effect of improving the light resistance of the liquid crystal element, it is preferable to have a mesogen structure on the side chain The side chain type liquid crystalline polymer. Here, in this specification, the "main chain" of the polymer refers to the "dry" part of the chain including the longest atom in the polymer. The "dry" part is allowed to contain a ring structure. Therefore, the so-called "has a mesogen structure in the main chain of the polymer" means that the structure constitutes a part of the main chain. The so-called "side chain" of the polymer refers to the part branched from the "stem" of the polymer. Furthermore, the polymer (A) may have a mesogen structure only in the main chain of the polymer, may have a mesogen structure only in the side chain, or may have a mesogen structure in both the main chain and the side chain.

聚合體（A）的主骨架的種類並無特別限定，但就與液晶的親和性或機械強度等的觀點而言，優選選自由具有聚合性不飽和鍵的單體的聚合體（以下，也稱為“聚合體（PAc）”）、聚醯胺酸、聚醯亞胺及聚醯胺酸酯所組成的群組中的至少一種，就可使液晶元件的電壓保持率及耐光性變得更良好的觀點而言，更優選聚合體（PAc）。The type of the main skeleton of the polymer (A) is not particularly limited, but from the viewpoint of affinity with liquid crystals, mechanical strength, etc., it is preferably a polymer selected from a monomer having a polymerizable unsaturated bond (hereinafter, also At least one of the group consisting of “polymer (PAc)”), polyamide, polyimide, and polyamide can make the voltage retention and light resistance of the liquid crystal element become From a more favorable viewpoint, a polymer (PAc) is more preferable.

・聚合體（PAc） 用於聚合體（PAc）的聚合的單體只要具有聚合性不飽和鍵，則並無特別限定，例如可列舉：(甲基)丙烯酸系化合物、共軛二烯化合物、芳香族乙烯基化合物、順丁烯二醯亞胺化合物等。就液晶元件的耐光性的改善效果高的觀點而言，聚合體（PAc）優選將含有(甲基)丙烯酸系化合物的單體用作原料所獲得的聚合體。當合成聚合體（PAc）時，相對於用於合成的單體的合計量，(甲基)丙烯酸系化合物的使用比例優選設為50莫耳%以上，更優選設為60莫耳%以上，進而更優選設為70莫耳以上。再者，在本說明書中，“(甲基)丙烯酸”是包含丙烯酸及甲基丙烯酸的含義。・Polymer (PAc) The monomer used for the polymerization of the polymer (PAc) is not particularly limited as long as it has a polymerizable unsaturated bond. Examples include (meth)acrylic compounds, conjugated diene compounds, Aromatic vinyl compounds, maleimide compounds, etc. From the viewpoint that the light resistance improvement effect of the liquid crystal element is high, the polymer (PAc) is preferably a polymer obtained by using a monomer containing a (meth)acrylic compound as a raw material. When synthesizing the polymer (PAc), the use ratio of the (meth)acrylic compound is preferably 50 mol% or more, and more preferably 60 mol% or more with respect to the total amount of monomers used for synthesis. Furthermore, it is more preferable to set it as 70 mol or more. In addition, in this specification, "(meth)acrylic acid" means including acrylic acid and methacrylic acid.

聚合體（PAc）可具有顯現液晶性的部分結構，並且具有感應光而產生交聯反應、異構化反應、光二聚化反應或弗裡斯重排（Fries rearrangement）反應的官能基（以下稱為“光反應性基”）。作為該光反應性基，例如可列舉：將(甲基)丙烯酸或其衍生物作為基本骨架的含有(甲基)丙烯酸的基、具有乙烯基的基（烯基、苯乙烯基等）、乙炔基、環氧基（環氧乙烷基、氧雜環丁基）、包含苯甲酸苯酯或其衍生物作為基本骨架的含有苯甲酸苯酯的基、包含偶氮苯或其衍生物作為基本骨架的含有偶氮苯的基、包含桂皮酸或其衍生物作為基本骨架的含有桂皮酸結構的基、包含查耳酮或其衍生物作為基本骨架的含有查耳酮的基、包含二苯甲酮或其衍生物作為基本骨架的含有二苯甲酮的基、包含香豆素或其衍生物作為基本骨架的含有香豆素的基等。The polymer (PAc) may have a partial structure that exhibits liquid crystallinity, and has a functional group (hereinafter referred to as Fries rearrangement) that induces light to cause crosslinking reaction, isomerization reaction, photodimerization reaction, or Fries rearrangement reaction "Photoreactive group"). As the photoreactive group, for example, a (meth)acrylic acid-containing group having (meth)acrylic acid or its derivative as a basic skeleton, a vinyl group (alkenyl, styryl, etc.), acetylene Group, epoxy group (oxiranyl group, oxetanyl group), group containing phenyl benzoate or its derivative as the basic skeleton, containing azobenzene or its derivative as the basic skeleton The azobenzene-containing group of the skeleton, the cinnamic acid structure-containing group containing cinnamic acid or its derivative as the basic skeleton, the chalcone-containing group containing chalcone or its derivative as the basic skeleton, the benzyl group containing A benzophenone-containing group having a ketone or a derivative thereof as a basic skeleton, a coumarin-containing group having a coumarin or a derivative thereof as a basic skeleton, and the like.

聚合體（PAc）例如可藉由在聚合起始劑的存在下使具有聚合性不飽和鍵的單體進行聚合而獲得。所使用的單體優選包含具有聚合性不飽和鍵與顯現液晶性的部分結構的化合物。作為具有聚合性不飽和鍵與顯現液晶性的部分結構的單體的具體例，例如可列舉分別由下述式（2-1）～式（2-5）所表示的化合物等。再者，這些單體可單獨使用一種，也可以將兩種以上組合使用。 [化3]

Figure 02_image005
（式（2-1）～式（2-5）中，R2 為氫原子或甲基，R3 為碳數1～12的烷二基、或利用-O-取代該烷二基的至少1個亞甲基而成的二價的基，R4 為碳數1～20的烷基、烷氧基或氟烷基、或氟原子）The polymer (PAc) can be obtained, for example, by polymerizing a monomer having a polymerizable unsaturated bond in the presence of a polymerization initiator. The monomer used preferably contains a compound having a polymerizable unsaturated bond and a partial structure exhibiting liquid crystallinity. As specific examples of the monomer having a polymerizable unsaturated bond and a partial structure expressing liquid crystallinity, for example, compounds represented by the following formulas (2-1) to (2-5) and the like can be cited. In addition, these monomers may be used individually by 1 type, and may be used in combination of 2 or more types. [化3]
Figure 02_image005
(In formulas (2-1) to (2-5), R 2 is a hydrogen atom or a methyl group, R 3 is an alkanediyl group having 1 to 12 carbons, or at least one of the alkanediyl groups substituted with -O- A divalent group consisting of a methylene group, R 4 is a C 1-20 alkyl group, alkoxy group or fluoroalkyl group, or a fluorine atom)

再者，當合成聚合體（PAc）時，也可以並用不具有顯現液晶性的部分結構的化合物作為具有聚合性不飽和鍵的單體。相對於用於聚合體（PAc）的合成的單體的合計量，不具有顯現液晶性的部分結構的化合物的使用比例優選設為50莫耳%以下，更優選設為40莫耳%以下。In addition, when synthesizing a polymer (PAc), a compound that does not have a partial structure that exhibits liquid crystallinity may be used together as a monomer having a polymerizable unsaturated bond. The usage ratio of the compound which does not have a partial structure expressing liquid crystallinity is preferably 50 mol% or less, and more preferably 40 mol% or less with respect to the total amount of monomers used for the synthesis of the polymer (PAc).

作為用於所述聚合的聚合起始劑，例如可列舉：2,2'-偶氮雙(異丁腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(4-甲氧基-2,4-二甲基戊腈)等偶氮化合物。相對於用於反應的所有單體100質量份，聚合起始劑的使用比例優選設為0.01質量份～30質量份。所述聚合優選在有機溶媒中進行。作為用於反應的有機溶媒，例如可列舉：醇、醚、酮、醯胺、酯、烴化合物等，作為具體例，例如可列舉：二乙二醇乙基甲基醚、丙二醇單甲基醚乙酸酯、四氫呋喃等。反應溫度優選設為30℃～120℃，反應時間優選設為1小時～36小時。有機溶媒的使用量（a）優選設為如用於反應的單體的合計量（b）相對於反應溶液的總量（a＋b）變成0.1質量%～60質量%般的量。As the polymerization initiator used for the polymerization, for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), Azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). The use ratio of the polymerization initiator is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of all monomers used for the reaction. The polymerization is preferably carried out in an organic solvent. Examples of organic solvents used in the reaction include alcohols, ethers, ketones, amides, esters, and hydrocarbon compounds. Specific examples include diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether. Acetate, tetrahydrofuran, etc. The reaction temperature is preferably 30°C to 120°C, and the reaction time is preferably 1 hour to 36 hours. The use amount (a) of the organic solvent is preferably set to such an amount that the total amount (b) of the monomers used for the reaction becomes 0.1% by mass to 60% by mass relative to the total amount (a+b) of the reaction solution.

聚合體（PAc）的藉由凝膠滲透色譜法（Gel Permeation Chromatography，GPC）所測定的聚苯乙烯換算的重量平均分子量（Mw）優選250～500,000，更優選500～100,000，進而更優選1,000～50,000。再者，聚合體（PAc）可單獨使用一種、或將兩種以上組合使用。The weight average molecular weight (Mw) of the polymer (PAc) in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) is preferably 250 to 500,000, more preferably 500 to 100,000, and even more preferably 1,000 to 50,000. Furthermore, the polymer (PAc) can be used alone or in combination of two or more.

・聚醯胺酸 作為聚合體（A）的聚醯胺酸（以下也稱為“聚醯胺酸（A）”）只要是顯示出液晶性者，則並無特別限定，但可優選地使用在聚合體的主鏈中具有液晶原結構者。當要獲得此種聚醯胺酸時，例如可藉由將在主鏈中具有液晶原結構的四羧酸二酐、及在主鏈中具有液晶原結構的二胺化合物的至少任一者用於原料的聚合來獲得。作為顯示出液晶性的聚醯胺酸的一例，可列舉使在主鏈中具有三聯苯骨架的四羧酸二酐與二胺化合物進行反應所獲得的聚合體，具體而言，可列舉具有由下述式（3）所表示的部分結構的聚合體。 [化4]

Figure 02_image007
（式（3）中，R5 為二價的有機基）・Polyamic acid as the polymer (A) polyamic acid (hereinafter also referred to as "polyamic acid (A)") is not particularly limited as long as it exhibits liquid crystallinity, but it can be preferably used Those with a mesogen structure in the main chain of the polymer. When such a polyamide acid is to be obtained, for example, at least any one of a tetracarboxylic dianhydride having a mesogen structure in the main chain and a diamine compound having a mesogen structure in the main chain can be used It is obtained by polymerization of raw materials. As an example of a polyamide acid exhibiting liquid crystallinity, a polymer obtained by reacting a tetracarboxylic dianhydride having a terphenyl skeleton in the main chain with a diamine compound can be cited. Specifically, there can be cited A polymer having a partial structure represented by the following formula (3). [化4]
Figure 02_image007
(In formula (3), R 5 is a divalent organic group)

所述式（3）中，R5 的二價的有機基為從二胺化合物中去除2個一級氨基所殘存的基。就使聚醯胺酸顯現液晶性的觀點而言，R5 優選碳數4～20的直鏈狀的烷二基、或在該烷二基的碳-碳鍵間含有-O-的二價的基。In the formula (3), the divalent organic group of R 5 is a group remaining after removing two primary amino groups from the diamine compound. From the viewpoint of making polyamic acid exhibit liquid crystallinity, R 5 is preferably a linear alkanediyl group having 4 to 20 carbon atoms, or a divalent group containing -O- between the carbon-carbon bonds of the alkanediyl group.的基。 The base.

用於聚醯胺酸（A）的合成的四羧酸二酐可僅設為具有液晶原結構的四羧酸二酐，但也可以並用不具有液晶原結構的四羧酸二酐。所述四羧酸二酐並無特別限定，可使用公知的四羧酸二酐。當合成顯示出液晶性的聚醯胺酸時，相對於用於合成的四羧酸二酐的合計量，具有液晶原結構的四羧酸二酐的使用比例優選設為50莫耳%以上，更優選設為70莫耳%以上。The tetracarboxylic dianhydride used for the synthesis of the polyamide acid (A) may be only tetracarboxylic dianhydride having a mesogen structure, but tetracarboxylic dianhydride not having a mesogen structure may be used in combination. The said tetracarboxylic dianhydride is not specifically limited, A well-known tetracarboxylic dianhydride can be used. When synthesizing polyamide acid exhibiting liquid crystallinity, the use ratio of tetracarboxylic dianhydride having a mesogen structure is preferably 50 mol% or more with respect to the total amount of tetracarboxylic dianhydride used for synthesis. More preferably, it is set to 70 mol% or more.

作為用於聚醯胺酸（A）的合成的二胺化合物，例如可列舉：脂肪族二胺、脂環式二胺、芳香族二胺、二氨基有機矽氧烷等。這些之中，可優選地使用脂肪族二胺，更優選1,4-二氨基丁烷、六亞甲基二胺、八亞甲基二胺等伸烷基二胺。當合成聚醯胺酸（A）時，相對於用於合成的二胺化合物的合計量，伸烷基二胺的使用比例優選設為50莫耳%以上，更優選設為60莫耳%以上。As a diamine compound used for the synthesis of polyamide acid (A), aliphatic diamine, alicyclic diamine, aromatic diamine, diamino organosiloxane etc. are mentioned, for example. Among these, aliphatic diamines can be preferably used, and alkylene diamines such as 1,4-diaminobutane, hexamethylene diamine, and octamethylene diamine are more preferable. When synthesizing polyamide acid (A), relative to the total amount of the diamine compound used in the synthesis, the use ratio of alkylene diamine is preferably 50 mol% or more, more preferably 60 mol% or more .

聚醯胺酸（A）可藉由使如上所述的四羧酸二酐及二胺化合物視需要與分子量調整劑一同進行反應而獲得。供於聚醯胺酸的合成反應的四羧酸二酐與二胺化合物的使用比例優選相對於二胺化合物的氨基1當量，四羧酸二酐的酸酐基變成0.2當量～2當量的比例。作為分子量調整劑，例如可列舉：順丁烯二酸酐、鄰苯二甲酸酐等酸單酐，苯胺、環己基胺、正丁基胺等單胺化合物，異氰酸苯酯、異氰酸萘酯等單異氰酸酯化合物等。相對於四羧酸二酐及二胺化合物的合計100質量份，分子量調整劑的使用比例優選設為20質量份以下。The polyamide acid (A) can be obtained by reacting the above-mentioned tetracarboxylic dianhydride and diamine compound with a molecular weight modifier as necessary. The use ratio of the tetracarboxylic dianhydride to the diamine compound used in the synthesis reaction of the polyamide acid is preferably a ratio of 0.2 to 2 equivalents of the acid anhydride group of the tetracarboxylic dianhydride with respect to 1 equivalent of the amino group of the diamine compound. Examples of molecular weight modifiers include acid monoanhydrides such as maleic anhydride and phthalic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, phenyl isocyanate, and naphthalene isocyanate. Monoisocyanate compounds such as esters. The use ratio of the molecular weight modifier is preferably set to 20 parts by mass or less with respect to the total of 100 parts by mass of the tetracarboxylic dianhydride and the diamine compound.

聚醯胺酸（A）的合成反應優選在有機溶媒中進行。此時的反應溫度優選-20℃～150℃，反應時間優選0.1小時～24小時。 作為用於反應的有機溶媒，例如可列舉：非質子性極性溶媒、酚系溶媒、醇、酮、酯、醚、鹵化烴、烴等。特優選的有機溶媒優選將選自由N-甲基-2-吡咯烷酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、二甲基亞碸、γ-丁內酯、四甲基脲、六甲基磷醯三胺、間甲酚、二甲酚及鹵化酚所組成的群組中的一種以上用作溶媒，或使用這些有機溶媒的一種以上與其他有機溶媒（例如丁基溶纖劑、二乙二醇二乙基醚等）的混合物。有機溶媒的使用量（a）優選設為四羧酸二酐及二胺的合計量（b）相對於反應溶液的總量（a＋b）變成0.1質量%～50質量%的量。 以所述方式，可獲得使聚醯胺酸（A）溶解而成的反應溶液。可將該反應溶液直接供於液晶配向劑的製備，也可以在使反應溶液中所含有的聚醯胺酸離析後供於液晶配向劑的製備。The synthesis reaction of polyamide acid (A) is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, and the reaction time is preferably 0.1 hour to 24 hours. Examples of the organic solvent used for the reaction include aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Particularly preferred organic solvents are preferably selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfene, γ-butyrolactone One or more of the group consisting of ester, tetramethylurea, hexamethylphosphotriamine, m-cresol, xylenol, and halogenated phenol are used as a solvent, or one or more of these organic solvents can be used with other organic solvents (For example, butyl cellosolve, diethylene glycol diethyl ether, etc.) mixture. The use amount (a) of the organic solvent is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine becomes 0.1% by mass to 50% by mass relative to the total amount (a+b) of the reaction solution. In this manner, a reaction solution obtained by dissolving polyamide acid (A) can be obtained. The reaction solution may be directly used for the preparation of the liquid crystal alignment agent, or may be used for the preparation of the liquid crystal alignment agent after isolating the polyamide acid contained in the reaction solution.

・聚醯胺酸酯 作為聚合體（A）的聚醯胺酸酯例如可藉由如下方法等而獲得：使藉由所述合成反應所獲得的聚醯胺酸（A）與酯化劑（例如醇類等）進行反應的方法；使四羧酸二酯與二胺化合物進行反應的方法；使四羧酸二酯二鹵化物與二胺化合物進行反應的方法。所獲得的聚醯胺酸酯可僅具有醯胺酸酯結構，也可以是醯胺酸結構與醯胺酸酯結構並存的部分酯化物。再者，使聚醯胺酸酯溶解而成的反應溶液可直接供於液晶配向劑的製備，也可以在使反應溶液中所含有的聚醯胺酸酯離析後供於液晶配向劑的製備。・Polyurate as the polymer (A), for example, can be obtained by the following method: the polyamide (A) obtained by the synthesis reaction and the esterification agent ( For example, alcohols, etc.) method of reaction; method of reacting tetracarboxylic acid diester and diamine compound; method of reacting tetracarboxylic acid diester dihalide and diamine compound. The obtained polyamide ester may have only an amide acid ester structure, or may be a partial ester product in which an amide acid structure and an amide acid ester structure coexist. Furthermore, the reaction solution obtained by dissolving the polyamide ester may be directly used for the preparation of the liquid crystal alignment agent, or may be used for the preparation of the liquid crystal alignment agent after isolating the polyamide ester contained in the reaction solution.

・聚醯亞胺 作為聚合體（A）的聚醯亞胺例如可藉由對以所述方式合成的聚醯胺酸（A）進行脫水閉環來加以醯亞胺化而獲得。聚醯亞胺可為對作為其前驅物的聚醯胺酸所具有的醯胺酸結構的全部進行脫水閉環而成的完全醯亞胺化物，也可以是僅對醯胺酸結構的一部分進行脫水閉環、且醯胺酸結構與醯亞胺環結構並存的部分醯亞胺化物。用於反應的聚醯亞胺的醯亞胺化率優選20%～99%，更優選30%～90%。該醯亞胺化率是以百分率表示醯亞胺環結構的數量相對於聚醯亞胺的醯胺酸結構的數量與醯亞胺環結構的數量的合計所占的比例者。・Polyimine Polyimine as the polymer (A) can be obtained, for example, by dehydrating and ring-closing the polyimide (A) synthesized in the manner described above and then imidizing it. Polyimide may be a complete amide compound formed by dehydrating and ring-closing all the amide acid structure of the polyamide acid as its precursor, or it may be dehydrated only a part of the amide acid structure A partial amide compound in which the ring is closed and the amide structure and amide ring structure coexist. The imidization rate of the polyimide used for the reaction is preferably 20% to 99%, more preferably 30% to 90%. The imidization rate is expressed as a percentage of the ratio of the number of amide ring structures to the sum of the number of amide acid structures of polyimide and the number of amide ring structures.

聚醯胺酸的脫水閉環例如藉由如下的方法來進行：使聚醯胺酸溶解在有機溶媒中，向該溶液中添加脫水劑及脫水閉環催化劑且視需要進行加熱。作為脫水劑，例如可使用：乙酸酐、丙酸酐、三氟乙酸酐等酸酐。相對於聚醯胺酸的醯胺酸結構的1莫耳，脫水劑的使用量優選設為0.01莫耳～20莫耳。作為脫水閉環催化劑，例如可使用：吡啶、三甲基吡啶、二甲基吡啶、三乙基胺等三級胺。相對於所使用的脫水劑1莫耳，脫水閉環催化劑的使用量優選設為0.01莫耳～10莫耳。作為脫水閉環反應中所使用的有機溶媒，可列舉作為聚醯胺酸的合成中所使用的有機溶媒所例示的有機溶媒。脫水閉環反應的反應溫度優選0℃～180℃。反應時間優選1.0小時～120小時。以所述方式可獲得含有聚醯亞胺的反應溶液。該反應溶液可直接供於液晶配向劑的製備，也可以在使聚醯亞胺離析後供於液晶配向劑的製備。The dehydration ring-closure of polyamide acid is performed by, for example, the following method: dissolving polyamide acid in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, and heating if necessary. As the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The amount of the dehydrating agent used is preferably 0.01 mol to 20 mol relative to 1 mol of the amide acid structure of the polyamide acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The amount of the dehydration ring-closing catalyst used is preferably 0.01 mol to 10 mol relative to 1 mol of the dehydrating agent used. As the organic solvent used in the dehydration ring-closure reaction, the organic solvent exemplified as the organic solvent used in the synthesis of polyamide acid can be cited. The reaction temperature of the dehydration ring-closing reaction is preferably 0°C to 180°C. The reaction time is preferably 1.0 hour to 120 hours. In this way, a reaction solution containing polyimine can be obtained. The reaction solution can be directly used for the preparation of the liquid crystal alignment agent, or can be used for the preparation of the liquid crystal alignment agent after the polyimide is isolated.

當製成濃度為10質量%的溶液時，作為聚合體（A）的聚醯胺酸、聚醯胺酸酯及聚醯亞胺的溶液黏度優選具有10 mPa・s～800 mPa・s的溶液黏度，更優選具有15 mPa・s～500 mPa・s的溶液黏度。再者，該溶液黏度（mPa・s）是針對使用這些聚合體的良溶媒（例如γ-丁內酯、N-甲基-2-吡咯烷酮等）所製備的濃度為10質量%的聚合體溶液，利用E型旋轉黏度計在25℃下所測定的值。 聚醯胺酸、聚醯胺酸酯及聚醯亞胺的藉由GPC所測定的聚苯乙烯換算的重量平均分子量（Mw）優選1,000～500,000，更優選2,000～300,000。另外，由Mw與藉由GPC所測定的聚苯乙烯換算的數量平均分子量（Mn）的比所表示的分子量分佈（Mw/Mn）優選15以下，更優選10以下。When a solution with a concentration of 10% by mass is made, the solution viscosity of polyamide acid, polyamide ester, and polyimide as the polymer (A) is preferably a solution with a viscosity of 10 mPa·s to 800 mPa·s The viscosity is more preferably a solution viscosity of 15 mPa·s to 500 mPa·s. Furthermore, the solution viscosity (mPa·s) is for a polymer solution with a concentration of 10% by mass prepared using a good solvent for these polymers (such as γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) , The value measured at 25°C using an E-type rotary viscometer. The weight average molecular weight (Mw) in terms of polystyrene measured by GPC of the polyamide acid, polyamide ester, and polyimide is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw and the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, and more preferably 10 or less.

聚合體（A）顯示出液晶性的溫度範圍（以下也稱為“液晶溫度範圍”）並無特別限制，但就充分地提高所獲得的液晶配向膜的配向控制力及配向穩定性的觀點而言，液晶溫度範圍優選處於90℃～380℃的範圍內，更優選處於100℃～350℃的範圍內。The temperature range in which the polymer (A) exhibits liquid crystallinity (hereinafter also referred to as "liquid crystal temperature range") is not particularly limited, but from the viewpoint of sufficiently improving the alignment control power and alignment stability of the obtained liquid crystal alignment film In other words, the liquid crystal temperature range is preferably in the range of 90°C to 380°C, more preferably in the range of 100°C to 350°C.

＜聚有機矽氧烷（C）＞ 聚有機矽氧烷（C）所具有的光配向性基是利用由光照射所引起的光異構化反應、光二聚化反應或光分解反應等對膜賦予各向異性的官能基。聚有機矽氧烷（C）可在主鏈及側鏈的任一者上具有光配向性基，但可優選地使用在側鏈上具有光配向性基者。作為聚有機矽氧烷（C）所具有的光配向性基的具體例，例如可列舉：所述含有偶氮苯的基、含有桂皮酸結構的基、含有查耳酮的基、含有二苯甲酮的基、含有香豆素的基等。這些之中，就光感度高的觀點及容易導入至側鏈的觀點而言，優選含有桂皮酸結構的基。其中，聚有機矽氧烷（C）所具有的含有桂皮酸結構的基特優選選自由以下述式（cn-1）所表示的基及以下述式（cn-2）所表示的基所組成的群組中的至少一種。 [化5]

Figure 02_image009
（式（cn-1）中，R11 為氫原子、鹵素原子、碳數1～3的烷基、碳數1～3的烷氧基或氰基。R12 為伸苯基、伸聯苯基、伸三聯苯基或伸環己基，或這些基所具有的氫原子的至少一部分經鹵素原子、碳數1～10的烷基、碳數1～10的烷氧基或氰基取代的基。A11 為單鍵、氧原子、硫原子、碳數1～3的烷二基、-CH=CH-、-NH-、﹡1 -COO-、﹡1 -OCO-、﹡1 -NH-CO-、﹡1 -CO-NH-、﹡1 -CH2 -O-或﹡1 -O-CH2 -（“﹡1 ”表示與R12 的結合鍵）。R13 為鹵素原子、碳數1～3的烷基、碳數1～3的烷氧基或氰基。a為0或1，b為0～4的整數。其中，當b為2以上時，多個R13 可相同，也可以不同。“﹡”表示結合鍵） [化6]
Figure 02_image011
（式（cn-2）中，R14 為碳數1～20的一價的有機基。R15 為鹵素原子、碳數1～3的烷基、碳數1～3的烷氧基或氰基。A12 為氧原子、﹡1 -COO-、﹡1 -OCO-、﹡1 -NH-CO-或﹡1 -CO-NH-（“﹡1 ”表示與R16 的結合鍵）。R16 為碳數1～6的烷二基。c為0或1，d為0～4的整數。其中，當d為2以上時，多個R15 可相同，也可以不同。“﹡”表示結合鍵）<Polyorganosiloxane (C)> The photo-alignment group of polyorganosiloxane (C) uses photoisomerization reaction, photodimerization reaction or photolysis reaction caused by light irradiation to film Give anisotropic functional groups. The polyorganosiloxane (C) may have a photoalignment group on either the main chain or the side chain, but one having a photoalignment group on the side chain can be preferably used. Specific examples of the photoalignment group possessed by polyorganosiloxane (C) include: the azobenzene-containing group, the cinnamic acid structure-containing group, the chalcone-containing group, and the diphenyl group The base of ketone, the base containing coumarin, etc. Among these, it is preferable to contain the group of a cinnamic acid structure from a viewpoint of high photosensitivity and a viewpoint of easy introduction into a side chain. Among them, the cinnamic acid structure-containing group of the polyorganosiloxane (C) is preferably selected from groups represented by the following formula (cn-1) and groups represented by the following formula (cn-2) At least one of the group of. [化5]
Figure 02_image009
(In formula (cn-1), R 11 is a hydrogen atom, a halogen atom, an alkyl group with 1 to 3 carbons, an alkoxy group with 1 to 3 carbons, or a cyano group. R 12 is a phenylene group, a biphenylene group Group, terphenylene or cyclohexylene, or a group in which at least part of the hydrogen atoms of these groups is substituted with a halogen atom, an alkyl group having 1 to 10 carbons, an alkoxy group having 1 to 10 carbons, or a cyano group 。A 11 is a single bond, oxygen atom, sulfur atom, alkanediyl group with 1 to 3 carbon atoms, -CH=CH-, -NH-, * 1 -COO-, * 1 -OCO-, * 1 -NH- CO-, ﹡ 1 -CO-NH-, ﹡ 1 -CH 2 -O- or ﹡ 1 -O-CH 2 -("﹡ 1 " represents the bond with R 12 ). R 13 is a halogen atom, carbon number An alkyl group having 1 to 3, an alkoxy group having 1 to 3 carbons or a cyano group. a is 0 or 1, and b is an integer of 0 to 4. However, when b is 2 or more, multiple R 13 may be the same, It can also be different. "﹡" means a bond) [化6]
Figure 02_image011
(In formula (cn-2), R 14 is a monovalent organic group having 1 to 20 carbons. R 15 is a halogen atom, an alkyl group having 1 to 3 carbons, an alkoxy group having 1 to 3 carbons, or a cyano group. A 12 is an oxygen atom, * 1 -COO-, * 1 -OCO-, * 1 -NH-CO- or * 1 -CO-NH- ("* 1 " represents the bond with R 16 ). R 16 is an alkanediyl group having 1 to 6 carbon atoms. c is 0 or 1, and d is an integer of 0 to 4. However, when d is 2 or more, multiple R 15 may be the same or different. "*" means Combination key)

作為R14 的一價的有機基，例如可列舉：碳數1～3的烷基、-R21 -X2 -R22 、-R22 （R21 為經取代或未經取代的伸苯基或伸環己基，R22 為經取代或未經取代的苯基或環己基，X2 為單鍵、氧原子、硫原子、碳數1～3的烷二基、-CH=CH-、-NH-、-COO-、-NH-CO-或-CH2 -O-）等。作為R21 、R22 的取代基，例如可列舉：鹵素原子、碳數1～3的烷基、碳數1～3的烷氧基、氰基等。Examples of the monovalent organic group for R 14 include alkyl groups having 1 to 3 carbon atoms, -R 21 -X 2 -R 22 , and -R 22 (R 21 is a substituted or unsubstituted phenylene group). Or cyclohexylene, R 22 is substituted or unsubstituted phenyl or cyclohexyl, X 2 is a single bond, oxygen atom, sulfur atom, alkanediyl group with 1 to 3 carbons, -CH=CH-,- NH-, -COO-, -NH-CO- or -CH 2 -O-) etc. Examples of the substituent of R 21 and R 22 include a halogen atom, an alkyl group having 1 to 3 carbons, an alkoxy group having 1 to 3 carbons, and a cyano group.

合成聚有機矽氧烷（C）的方法並無特別限制。作为一例，可列舉如下的方法：視需要對含有環氧基的水解性的矽烷化合物與其他矽烷化合物進行水解・縮合，繼而使具有光配向性基的羧酸進行反應。 作為含有環氧基的矽烷化合物，例如可列舉：3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等。作為其他矽烷化合物，只要是水解性的化合物，則並無特別限制，例如可列舉：四甲氧基矽烷、甲基三乙氧基矽烷、苯基三甲氧基矽烷、對苯乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、3-巰基丙基三乙氧基矽烷、3-氨基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、三甲氧基矽烷基丙基丁二酸酐等。再者，矽烷化合物可單獨使用一種，也可以將兩種以上組合使用。The method of synthesizing polyorganosiloxane (C) is not particularly limited. As an example, a method of hydrolyzing and condensing an epoxy-containing hydrolyzable silane compound and other silane compounds as necessary, and then reacting a carboxylic acid having a photoalignment group. As an epoxy group-containing silane compound, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. Other silane compounds are not particularly limited as long as they are hydrolyzable compounds. Examples include tetramethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and p-styryltrimethoxysilane. Silane, vinyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, trimethoxysilane Base silyl propyl succinic anhydride, etc. In addition, the silane compound may be used alone or in combination of two or more.

水解・縮合反應藉由優選在適當的催化劑及有機溶媒的存在下，使一種或兩種以上的矽烷化合物與水進行反應來進行。反應時，相對於矽烷化合物（合計量）1莫耳，水的使用比例優選1莫耳～30莫耳。作為所使用的催化劑，例如可列舉：酸、鹼金屬化合物、有機鹼、鈦化合物、鋯化合物等。催化劑的使用量根據催化劑的種類、溫度等反應條件等而不同，例如相對於矽烷化合物的合計量為0.01倍莫耳～3倍莫耳。作為所使用的有機溶媒，例如可列舉烴、酮、酯、醚、醇等，優選使用非水溶性或難水溶性的有機溶媒。相對於用於反應的矽烷化合物的合計100質量份，有機溶媒的使用比例優選10質量份～10,000質量份。另外，所述反應優選利用油浴等進行加熱來實施。此時，加熱溫度優選設為130℃以下，加熱時間優選設為0.5小時～12小時。反應結束後，視需要利用乾燥劑對從反應液中分離取出的有機溶媒層進行乾燥後，去除溶媒，由此可獲得含有環氧基的聚有機矽氧烷。The hydrolysis/condensation reaction is carried out by reacting one or two or more silane compounds with water, preferably in the presence of a suitable catalyst and organic solvent. During the reaction, the use ratio of water is preferably 1 mol to 30 mol relative to 1 mol of the silane compound (total amount). Examples of the catalyst used include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, and the like. The amount of the catalyst used varies depending on the type of the catalyst, reaction conditions such as temperature, and the like. For example, it is 0.01 times mol to 3 times mol relative to the total amount of the silane compound. As the organic solvent to be used, for example, hydrocarbons, ketones, esters, ethers, alcohols, etc. are mentioned, and it is preferable to use a water-insoluble or poorly water-soluble organic solvent. The use ratio of the organic solvent is preferably 10 parts by mass to 10,000 parts by mass relative to the total 100 parts by mass of the silane compound used for the reaction. In addition, the reaction is preferably carried out by heating with an oil bath or the like. At this time, the heating temperature is preferably 130°C or lower, and the heating time is preferably 0.5 hour to 12 hours. After the reaction is completed, the organic solvent layer separated from the reaction solution is dried with a desiccant as needed, and then the solvent is removed, thereby obtaining an epoxy group-containing polyorganosiloxane.

含有環氧基的聚有機矽氧烷與羧酸的反應優選在催化劑及有機溶媒的存在下進行。相對於含有環氧基的聚有機矽氧烷所具有的環氧基，羧酸的使用比例優選5莫耳%以上，更優選10莫耳%～80莫耳%。作為所述催化劑，例如可使用有機鹼、作為促進環氧化合物的反應的所謂的硬化促進劑所公知的化合物等。相對於含有環氧基的聚矽氧烷100重量份，催化劑的使用比例優選100重量份以下。作為所使用的有機溶媒的優選的具體例，可列舉：2-丁酮、2-己酮、甲基異丁基酮、環戊酮、環己酮及乙酸丁酯等。有機溶媒優選以固體成分濃度變成5 重量%～50 重量%的比例使用。所述反應中的反應溫度優選0℃～200℃，反應時間優選0.1小時～50小時。反應結束後，視需要利用乾燥劑對從反應液中分離取出的有機溶媒層進行乾燥後，去除溶媒，由此可獲得具有光配向性基的聚有機矽氧烷（C）。 再者，聚有機矽氧烷（C）的合成方法並不限於所述水解・縮合反應，例如也可以藉由在草酸及醇的存在下使水解性矽烷化合物進行反應的方法等來進行。另外，當要獲得在側鏈上具有光配向性基的聚有機矽氧烷時，也可以採用利用將具有光配向性基的水解性矽烷化合物用於原料的聚合的方法。The reaction of the epoxy-containing polyorganosiloxane and carboxylic acid is preferably carried out in the presence of a catalyst and an organic solvent. The use ratio of the carboxylic acid is preferably 5 mol% or more, and more preferably 10 mol% to 80 mol% relative to the epoxy group of the epoxy group-containing polyorganosiloxane. As the catalyst, for example, an organic base, a compound known as a so-called hardening accelerator that promotes the reaction of an epoxy compound, and the like can be used. The use ratio of the catalyst is preferably 100 parts by weight or less with respect to 100 parts by weight of epoxy group-containing polysiloxane. Preferable specific examples of the organic solvent used include 2-butanone, 2-hexanone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and butyl acetate. The organic solvent is preferably used at a ratio such that the solid content concentration becomes 5 wt% to 50 wt%. The reaction temperature in the reaction is preferably 0°C to 200°C, and the reaction time is preferably 0.1 hour to 50 hours. After the reaction is completed, the organic solvent layer separated from the reaction solution is dried with a desiccant as needed, and the solvent is removed, thereby obtaining a polyorganosiloxane (C) having a photo-alignment group. In addition, the synthesis method of polyorganosiloxane (C) is not limited to the above-mentioned hydrolysis/condensation reaction. For example, it may be carried out by a method of reacting a hydrolyzable silane compound in the presence of oxalic acid and alcohol. In addition, when a polyorganosiloxane having a photoalignment group on the side chain is to be obtained, a method of using a hydrolyzable silane compound having a photoalignment group for the polymerization of the raw material can also be adopted.

針對聚有機矽氧烷（C），藉由GPC所測定的聚苯乙烯換算的重量平均分子量優選500～1,000,000，更優選1,000～100,000，進而更優選1,000～50,000。再者，聚有機矽氧烷（C）可單獨使用一種，也可以將兩種以上組合使用。For the polyorganosiloxane (C), the weight average molecular weight in terms of polystyrene measured by GPC is preferably 500 to 1,000,000, more preferably 1,000 to 100,000, and still more preferably 1,000 to 50,000. Furthermore, the polyorganosiloxane (C) may be used singly or in combination of two or more.

本揭示的液晶配向劑優選在聚合體成分中含有選自由聚醯胺酸、聚醯胺酸酯及聚醯亞胺所組成的群組中的至少一種聚合體。該聚合體可為在規定的溫度範圍內顯示出液晶性的聚合體（A），也可以是不顯示液晶性的聚合體。本揭示的液晶配向劑的優選的形態是進而含有作為選自由聚醯胺酸、聚醯胺酸酯及聚醯亞胺所組成的群組中的至少一種、且為非液晶性的聚合體（以下也稱為“聚合體（B）”）作為聚合體成分者。藉由設為含有此種聚合體（B）者，就可提高液晶元件的初期電壓保持率及耐光性的改善效果的觀點而言適宜。The liquid crystal alignment agent of the present disclosure preferably contains at least one polymer selected from the group consisting of polyamide acid, polyamide acid ester, and polyimide in the polymer component. The polymer may be a polymer (A) exhibiting liquid crystallinity in a predetermined temperature range, or a polymer not exhibiting liquid crystallinity. The preferred form of the liquid crystal alignment agent of the present disclosure further contains at least one selected from the group consisting of polyamide acid, polyamide acid ester and polyimide, and is a non-liquid crystal polymer ( Hereinafter, it is also referred to as "polymer (B)") as a polymer component. By containing such a polymer (B), it is suitable from the viewpoint that the initial voltage retention rate of the liquid crystal element and the improvement effect of light resistance can be improved.

作為聚合體（B）的聚醯胺酸（以下也稱為“聚醯胺酸（B）”）例如可藉由使四羧酸二酐與二胺化合物進行反應而獲得。作為用於聚醯胺酸的合成的四羧酸二酐的具體例，作為脂肪族四羧酸二酐，例如可列舉1,2,3,4-丁烷四羧酸二酐、乙二胺四乙酸二酐等；作為脂環式四羧酸二酐，例如可列舉1,2,3,4-環丁烷四羧酸二酐、1,3-二甲基-1,2,3,4-環丁烷四羧酸二酐、2,3,5-三羧基環戊基乙酸二酐、5-(2,5-二氧代四氫呋喃-3-基)-3a,4,5,9b-四氫萘並[1,2-c]呋喃-1,3-二酮、5-(2,5-二氧代四氫呋喃-3-基)-8-甲基-3a,4,5,9b-四氫萘並[1,2-c]呋喃-1,3-二酮、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、2,4,6,8-四羧基雙環[3.3.0]辛烷-2：4,6：8-二酐、環己烷四羧酸二酐等；作為芳香族四羧酸二酐，例如可列舉均苯四甲酸二酐、4,4'-(六氟亞異丙基)二鄰苯二甲酸酐、對伸苯基雙(偏苯三甲酸單酯酐)、乙二醇雙(脫水偏苯三酸酯)、1,3-丙二醇雙(脫水偏苯三酸酯)等；除此以外，可使用日本專利特開2010-97188號公報中所記載的四羧酸二酐。再者，四羧酸二酐可單獨使用一種，或將兩種以上組合使用。 The polyamide (hereinafter also referred to as "polyamide (B)") as the polymer (B) can be obtained, for example, by reacting tetracarboxylic dianhydride and a diamine compound. As specific examples of the tetracarboxylic dianhydride used in the synthesis of polyamide acid, examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride and ethylenediamine Tetraacetic dianhydride, etc.; as alicyclic tetracarboxylic dianhydride, for example, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5-(2,5-dioxotetrahydrofuran-3-yl)-3a,4,5,9b -Tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b -Tetrahydronaphtho[1,2-c]furan-1,3-dione, 5-(2,5-dioxotetrahydro-3-furyl)-3-methyl-3-cyclohexene -1,2-Dicarboxylic anhydride, 2,4,6,8-tetracarboxylic bicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclohexanetetracarboxylic dianhydride, etc.; as Aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic anhydride, p-phenylene bis(trimellitic acid monoester) Anhydride), ethylene glycol bis(dehydrated trimellitate), 1,3-propanediol bis(dehydrated trimellitate), etc.; otherwise, the description in Japanese Patent Laid-Open No. 2010-97188 can be used的tetracarboxylic dianhydride. Furthermore, tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

作為用於聚醯胺酸(B)的合成的二胺化合物的具體例，作為脂肪族二胺，例如可列舉間苯二甲胺、1,3-丙二胺、六亞甲基二胺等；作為脂環式二胺，例如可列舉1,4-二氨基環己烷、4,4'-亞甲基雙(環己基胺)等；作為芳香族二胺，例如可列舉十二烷氧基二氨基苯、十八烷氧基二氨基苯、膽甾烷氧基二氨基苯、膽甾烯氧基二氨基苯、二氨基苯甲酸膽甾烷基酯、二氨基苯甲酸膽甾烯基酯、二氨基苯甲酸羊毛甾烷基酯、3,6-雙(4-氨基苯甲醯氧基)膽甾烷、1,1-雙(4-((氨基苯基)甲基)苯基)-4-丁基環己烷、2,5-二氨基-N,N-二烯丙基苯胺、由下述式(E-1)所表示的化合物等側鏈型二胺：

Figure 105140543-A0305-02-0017-1
As specific examples of the diamine compound used in the synthesis of polyamide acid (B), examples of the aliphatic diamine include metaxylylenediamine, 1,3-propanediamine, hexamethylenediamine, etc. ; As alicyclic diamines, for example, 1,4-diaminocyclohexane, 4,4'-methylene bis(cyclohexylamine), etc.; as aromatic diamines, for example, dodecyloxy Diaminobenzene, octadecyloxydiaminobenzene, cholesteryloxydiaminobenzene, cholesteryloxydiaminobenzene, cholesteryl diaminobenzoate, cholesteryl diaminobenzoate Esters, lanosteryl diaminobenzoate, 3,6-bis(4-aminobenzyloxy)cholestane, 1,1-bis(4-((aminophenyl)methyl)phenyl ) Side-chain type diamines such as 4-butylcyclohexane, 2,5-diamino-N,N-diallylaniline, and the compound represented by the following formula (E-1):
Figure 105140543-A0305-02-0017-1

(式(E-1)中，XI及XII分別獨立地為單鍵、-O-、-COO-或-OCO-，RI為碳數1~3的烷二基，RII為單鍵或碳數1~3的烷二基，a為0或1，b為0~2的整數(其中，a及b不同時變成0)，c為1~20的整數，d為0或1。)(In formula (E-1), X I and X II are each independently a single bond, -O-, -COO- or -OCO-, R I is an alkanediyl group with 1 to 3 carbon atoms, and R II is a single bond Bond or alkanediyl group with 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2 (wherein a and b are not changed to 0 at the same time), c is an integer of 1 to 20, and d is 0 or 1 .)

對苯二胺、4,4'-二氨基二苯基甲烷、4-氨基苯基-4'-氨基苯甲酸酯、4,4'-二氨基偶氮苯、1,5-雙(4-氨基苯氧基)戊烷、雙[2-(4-氨基苯基)乙基]己烷二酸、N,N-雙(4-氨基苯基)甲基胺、2,6-二氨基吡啶、1,4-雙-(4-氨基苯基)-呱嗪、N,N'-雙(4-氨基苯基)-聯苯胺、2,2'-二甲基-4,4'-二氨基聯苯、2,2'-雙(三氟甲基)-4,4'-二氨基聯苯、二氨基苯甲酸、4,4'-二氨基二苯基醚、2,2-雙[4-(4-氨基苯氧基)苯基]丙烷、2,2-雙(4-氨基苯基)六氟丙烷、4,4'-(伸苯基二亞異丙基)雙苯胺、4-(4-氨基苯氧基羰基)-1-(4-氨基苯基)呱啶、4,4'-[4,4'-丙烷-1,3-二基雙(呱啶-1,4-二基)]二苯胺、含有桂皮酸結構的二胺等主鏈型二胺；作為二氨基有機矽氧烷，例如可列舉1,3-雙(3-氨基丙基)-四甲基二矽氧烷等；除此以外，可使用日本專利特開2010-97188號公報中所記載的二胺。再者，二胺化合物可單獨使用一種、或將兩種以上組合使用。P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4-aminophenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 1,5-bis(4 -Aminophenoxy)pentane, bis[2-(4-aminophenyl)ethyl]hexanedioic acid, N,N-bis(4-aminophenyl)methylamine, 2,6-diamino Pyridine, 1,4-bis-(4-aminophenyl)-piperazine, N,N'-bis(4-aminophenyl)-benzidine, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, diaminobenzoic acid, 4,4'-diaminodiphenyl ether, 2,2-bis [4-(4-Aminophenoxy)phenyl]propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(phenylene diisopropylidene) bisaniline, 4-(4-Aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1, 4-Diyl)] diphenylamine, diamine containing cinnamic acid structure and other main chain diamines; as diaminoorganosiloxanes, for example, 1,3-bis(3-aminopropyl)-tetramethyl Disiloxane, etc.; in addition, the diamine described in JP 2010-97188 A can be used. Furthermore, the diamine compound can be used individually by 1 type or in combination of 2 or more types.

聚醯胺酸（B）可藉由使如上所述的四羧酸二酐及二胺化合物視需要與分子量調整劑一同進行反應而獲得。關於該反應中所使用的分子量調整劑、聚合溶媒、反應條件等，可應用聚醯胺酸（A）的說明。 作為聚合體（B）的聚醯胺酸酯及聚醯亞胺例如除使用聚醯胺酸（B）來代替聚醯胺酸（A）以外，能夠以與聚合體（A）的情況相同的方式獲得。關於聚合體（B）的溶液黏度、重量平均分子量及數量平均分子量，應用聚合體（A）的說明。The polyamide acid (B) can be obtained by reacting the above-mentioned tetracarboxylic dianhydride and diamine compound with a molecular weight modifier as necessary. Regarding the molecular weight modifier, polymerization solvent, reaction conditions, etc. used in this reaction, the description of polyamide acid (A) can be applied. As the polymer (B), the polyamide and polyimide can be the same as the case of the polymer (A), except that polyamide (B) is used instead of polyamide (A). Way to get. Regarding the solution viscosity, weight average molecular weight and number average molecular weight of the polymer (B), the description of the polymer (A) applies.

本揭示的液晶配向劑中的聚合體成分優選下述的[1]～[4]的任一種形態。 [1]含有聚合體（A）與聚有機矽氧烷（C）作為聚合體成分，且聚合體（A）為聚合體（PAc）的形態。 [2]含有聚合體（A）與聚有機矽氧烷（C）作為聚合體成分，且聚合體（A）為選自由聚醯胺酸、聚醯胺酸酯及聚醯亞胺所組成的群組中的至少一種的形態。 [3]含有聚合體（A）與聚合體（B）及聚有機矽氧烷（C）作為聚合體成分，且聚合體（A）為聚合體（PAc）的形態。 [4]含有聚合體（A）與聚合體（B）及聚有機矽氧烷（C）作為聚合體成分，且聚合體（A）為選自由聚醯胺酸、聚醯胺酸酯及聚醯亞胺所組成的群組中的至少一種的形態。 這些形態之中，就液晶元件的初期電壓保持率及耐光性的觀點而言，更優選[1]、[3]，特優選[3]。再者，聚合體（A）及聚合體（B）可為對於用以藉由光誘導來使聚有機矽氧烷（C）顯現各向異性的曝光顯示出感光性者，也可以是對於該曝光為非感光性者。就液晶元件的初期電壓保持率及耐光性的觀點而言，優選非感光性。The polymer component in the liquid crystal alignment agent of this disclosure is preferably any one of the following [1] to [4]. [1] Containing polymer (A) and polyorganosiloxane (C) as polymer components, and polymer (A) is in the form of polymer (PAc). [2] Contains polymer (A) and polyorganosiloxane (C) as polymer components, and polymer (A) is selected from polyamide acid, polyamide ester and polyimide At least one form of the group. [3] Containing polymer (A), polymer (B), and polyorganosiloxane (C) as polymer components, and polymer (A) is in the form of polymer (PAc). [4] Containing polymer (A), polymer (B) and polyorganosiloxane (C) as polymer components, and polymer (A) is selected from the group consisting of polyamide acid, polyamide ester and poly The form of at least one of the group consisting of imines. Among these aspects, [1] and [3] are more preferable from the viewpoint of the initial voltage retention rate and light resistance of the liquid crystal element, and [3] is particularly preferable. In addition, the polymer (A) and the polymer (B) may be those exhibiting photosensitivity to the exposure used to make the polyorganosiloxane (C) anisotropically induced by light, or they may be The exposure is non-photosensitive. From the viewpoint of the initial voltage retention rate and light resistance of the liquid crystal element, non-photosensitive is preferable.

在本揭示的液晶配向劑中，聚合體（A）及聚有機矽氧烷（C）的含有比例就充分地獲得液晶元件的初期電壓保持率與耐光性的改善效果的觀點而言，相對於液晶配向劑中所含有的聚合體成分的合計100質量份，聚合體（A）優選設為1質量份～80質量份，更優選設為3質量份～70質量份，進而更優選設為5質量份～60質量份。相對於液晶配向劑中所含有的聚合體成分的合計100質量份，聚有機矽氧烷（C）優選設為1質量份～99質量份，更優選設為5質量份～95質量份，進而更優選設為10質量份～90質量份。另外，聚合體（A）與聚有機矽氧烷（C）的比率以質量比計，優選設為聚合體（A）：聚有機矽氧烷（C）＝5：95～70：30，更優選設為10：90～60：40。 當在本揭示的液晶配向劑中調配聚合體（B）時，相對於液晶配向劑中所含有的聚合體成分的合計100質量份，聚合體（B）的含有比例優選設為1質量份～95質量份，更優選設為20質量份～90質量份，進而更優選設為40質量份～80質量份。In the liquid crystal alignment agent of the present disclosure, the content ratio of the polymer (A) and the polyorganosiloxane (C) is relative to the viewpoint that the initial voltage retention rate and the light resistance improvement effect of the liquid crystal element can be sufficiently obtained The total amount of the polymer components contained in the liquid crystal alignment agent is 100 parts by mass. The polymer (A) is preferably 1 part by mass to 80 parts by mass, more preferably 3 parts by mass to 70 parts by mass, and still more preferably 5 parts by mass. Parts by mass ~ 60 parts by mass. The polyorganosiloxane (C) is preferably 1 part by mass to 99 parts by mass, more preferably 5 parts by mass to 95 parts by mass, with respect to 100 parts by mass of the total polymer components contained in the liquid crystal alignment agent. More preferably, it is 10 mass parts-90 mass parts. In addition, the ratio of polymer (A) to polyorganosiloxane (C) is calculated by mass ratio, and is preferably set to polymer (A): polyorganosiloxane (C) = 5:95 to 70:30, more It is preferably set to 10:90 to 60:40. When the polymer (B) is blended in the liquid crystal alignment agent of the present disclosure, the content ratio of the polymer (B) is preferably set to 1 part by mass relative to 100 parts by mass of the total of the polymer components contained in the liquid crystal alignment agent. 95 parts by mass, more preferably 20 parts by mass to 90 parts by mass, and still more preferably 40 parts by mass to 80 parts by mass.

本揭示的液晶配向劑可一併含有聚合體（A）與聚有機矽氧烷（C）、以及聚合體（A）與聚有機矽氧烷（C）以外的其他成分。作為其他成分，除聚合體（B）以外，例如可列舉：聚合體（A）、聚合體（B）及聚有機矽氧烷（C）以外的其他聚合體，分子內具有至少一個環氧基的化合物，官能性矽烷化合物，抗氧化劑，金屬螯合化合物，硬化促進劑，界面活性劑，填充劑，分散劑，光增感劑等。其他成分的調配比例可在無損本揭示的效果的範圍內，對應於各化合物而適宜選擇。The liquid crystal alignment agent of the present disclosure may contain other components other than the polymer (A) and polyorganosiloxane (C), and the polymer (A) and polyorganosiloxane (C). As other components, in addition to the polymer (B), for example, other polymers other than the polymer (A), the polymer (B), and polyorganosiloxane (C), which have at least one epoxy group in the molecule Compounds, functional silane compounds, antioxidants, metal chelating compounds, hardening accelerators, surfactants, fillers, dispersants, photosensitizers, etc. The blending ratio of other components can be appropriately selected corresponding to each compound within a range that does not impair the effects of the present disclosure.

（溶劑） 本揭示的液晶配向劑作為使聚合體成分及視需要而使用的其他成分優選在適當的溶媒中分散或溶解而成的液狀的組合物來製備。作為所使用的有機溶媒，例如可列舉：N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、1,2-二甲基-2-咪唑啉酮、γ-丁內酯、γ-丁內醯胺、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、4-羥基-4-甲基-2-戊酮、乙二醇單甲基醚、乳酸丁酯、乙酸丁酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯、乙二醇甲基醚、乙二醇乙基醚、乙二醇-正丙基醚、乙二醇-異丙基醚、乙二醇-正丁基醚（丁基溶纖劑）、乙二醇二甲基醚、乙二醇乙基醚乙酸酯、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二異丁基酮、丙酸異戊酯、異丁酸異戊酯、二異戊基醚、碳酸亞乙酯、碳酸亞丙酯等。這些有機溶媒可單獨使用一種、或將兩種以上混合使用。(Solvent) The liquid crystal alignment agent of the present disclosure is preferably prepared as a liquid composition in which a polymer component and other components used as needed are dispersed or dissolved in an appropriate solvent. As the organic solvent used, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolinone, γ-butyrolactone, γ -Butyrolactamide, N,N-dimethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, Butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol -Isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene two Alcohol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diiso Butyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, etc. These organic solvents can be used alone or in combination of two or more.

液晶配向劑中的固體成分濃度（液晶配向劑的溶媒以外的成分的合計質量在液晶配向劑的總質量中所占的比例）是考慮黏性、揮發性等而適宜地選擇，但優選1質量%～10質量%的範圍。即，將液晶配向劑如後述般塗布在基板表面上，優選進行加熱，由此形成作為液晶配向膜的塗膜或成為液晶配向膜的塗膜。此時，當固體成分濃度小於1質量%時，塗膜的膜厚變得過小而難以獲得良好的液晶配向膜。另一方面，當固體成分濃度超過10質量%時，塗膜的膜厚變得過大而難以獲得良好的液晶配向膜，另外，存在液晶配向劑的黏性增大且塗布性下降的傾向。The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., but 1 mass is preferred %～10% by mass. That is, the liquid crystal alignment agent is coated on the surface of the substrate as described later, and it is preferably heated to form a coating film that is a liquid crystal alignment film or a coating film that is a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by mass, the film thickness of the coating film becomes too small and it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film becomes too large and it is difficult to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal alignment agent tends to increase and coatability decreases.

＜液晶元件＞ 本揭示的液晶元件具備使用以上所說明的液晶配向劑所形成的液晶配向膜。液晶元件中的液晶的動作模式並無特別限定，例如可應用於扭曲向列（Twisted Nematic，TN）型、超扭曲向列（Super Twisted Nematic，STN）型、垂直配向型（包含垂直配向（Vertical Alignment，VA）-多域垂直配向（Multi-Domain Vertical Alignment，MVA）型、VA-圖案垂直配向（Patterned Vertical Alignment，PVA）型等）、面內切換（In-Plane Switching，IPS）型、邊緣場切換（Fringe Field Switching，FFS）型、光學補償彎曲（Optically Compensated Bend，OCB）型等各種模式。液晶元件例如可藉由包含以下的步驟1～步驟3的方法來製造。步驟1中，使用基板根據所期望的動作模式而不同。步驟2及步驟3為各動作模式共用。<Liquid crystal element> The liquid crystal element of this disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited. For example, it can be applied to twisted nematic (TN) type, super twisted nematic (STN) type, and vertical alignment type (including vertical alignment (Vertical)). Alignment, VA)-Multi-Domain Vertical Alignment (MVA) type, VA-Patterned Vertical Alignment (PVA) type, etc.), In-Plane Switching (IPS) type, edge Various modes such as Fringe Field Switching (FFS) type and Optically Compensated Bend (OCB) type. The liquid crystal element can be manufactured by a method including the following steps 1 to 3, for example. In step 1, the substrate used varies according to the desired operation mode. Steps 2 and 3 are shared by all operation modes.

[步驟1：塗膜的形成] 首先，將液晶配向劑塗布在基板上，其次，視需要對塗布面進行加熱，由此在基板上形成塗膜。作為基板，例如可使用：浮法玻璃、鈉玻璃等玻璃；包含聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚醚碸、聚碳酸酯、聚(脂環族烯烴)等塑料的透明基板。作為設置在基板的一面上的透明導電膜，可使用包含氧化錫（SnO2 ）的NESA膜（美國PPG公司的注冊商標）、包含氧化銦-氧化錫（In2 O3 -SnO2 ）的氧化銦錫（Indium Tin Oxide，ITO）膜等。當製造TN型、STN型或垂直配向型的液晶元件時，使用兩片設置有經圖案化的透明導電膜的基板。當製造IPS型或FFS型等橫電場式的液晶元件時，使用設置有包含圖案化成梳齒狀的透明導電膜或金屬膜的電極的基板、及未設置電極的對向基板。作為金屬膜，例如可使用包含鉻等金屬的膜。朝基板上的塗布是在電極形成面上，優選利用平板印刷法、旋塗法、輥塗機法或噴墨印刷法來進行。[Step 1: Formation of Coating Film] First, the liquid crystal alignment agent is coated on the substrate, and then, if necessary, the coated surface is heated, thereby forming a coating film on the substrate. As the substrate, for example, glass such as float glass, soda glass, etc. can be used; including polyethylene terephthalate, polybutylene terephthalate, polyether alkene, polycarbonate, and poly(alicyclic olefin) Such as plastic transparent substrate. As the transparent conductive film provided on one side of the substrate, NESA film (registered trademark of PPG Corporation, USA) containing tin oxide (SnO 2 ), oxide containing indium oxide-tin oxide (In 2 O 3 -SnO 2 ) can be used Indium Tin Oxide (ITO) film, etc. When manufacturing TN type, STN type or vertical alignment type liquid crystal elements, two substrates provided with patterned transparent conductive films are used. When manufacturing a liquid crystal element of a transverse electric field type such as an IPS type or an FFS type, a substrate provided with electrodes including a transparent conductive film or a metal film patterned in a comb-like shape and a counter substrate without electrodes are used. As the metal film, for example, a film containing metal such as chromium can be used. The coating on the substrate is on the electrode formation surface, and is preferably performed by a lithography method, a spin coating method, a roll coater method, or an inkjet printing method.

在塗布液晶配向劑後，為了防止所塗布的液晶配向劑的流掛等，優選實施預加熱（預烘烤）。預烘烤溫度優選30℃～200℃，預烘烤時間優選0.25分鐘～10分鐘。其後，將溶劑完全去除，視需要以對聚合體中所存在的醯胺酸結構進行熱醯亞胺化為目的而實施煆燒（後烘烤）步驟。此時的煆燒溫度（後烘烤溫度）優選80℃～300℃，後烘烤時間優選5分鐘～200分鐘。以所述方式形成的膜的膜厚優選0.001 μm～1 μm。After the liquid crystal alignment agent is applied, in order to prevent sagging of the applied liquid crystal alignment agent, etc., it is preferable to perform preheating (prebaking). The pre-baking temperature is preferably 30°C to 200°C, and the pre-baking time is preferably 0.25 minutes to 10 minutes. After that, the solvent is completely removed, and if necessary, a sintering (post-baking) step is performed for the purpose of thermally imidizing the amide structure existing in the polymer. The firing temperature (post-baking temperature) at this time is preferably 80°C to 300°C, and the post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the film formed in this manner is preferably 0.001 μm to 1 μm.

[步驟2：配向處理] 當製造TN型、STN型、IPS型或FFS型的液晶元件時，實施對所述步驟1中所形成的塗膜賦予液晶配向能力的處理（配向處理）。由此，液晶分子的配向能力被賦予至塗膜中而成為液晶配向膜。作為配向處理，可列舉：利用例如捲繞有包含尼龍、人造絲、棉等纖維的布的輥，在固定方向上對塗膜進行摩擦，由此對塗膜賦予液晶配向能力的摩擦處理；對塗布有液晶配向劑的基板面進行光照射來對塗膜賦予液晶配向能力的光配向處理等。就藉由對於塗膜的光照射來賦予充分的液晶配向控制力的觀點、或可抑制由灰塵或靜電的產生等所引起的顯示不良的產生或良率的下降的觀點、可對形成在基板上的有機薄膜均勻地賦予液晶配向能力的觀點而言，本揭示的液晶配向劑可優選地應用光配向處理。當製造垂直配向型的液晶元件時，可將所述步驟1中所形成的塗膜直接用作液晶配向膜，但也可以對該塗膜實施配向處理。[Step 2: Alignment Treatment] When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal element, a treatment (alignment treatment) for imparting liquid crystal alignment ability to the coating film formed in the step 1 is performed. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to become a liquid crystal alignment film. As the alignment treatment, for example, a rubbing treatment in which a cloth containing nylon, rayon, cotton and other fibers is wound, rubs the coating film in a fixed direction, thereby imparting liquid crystal alignment ability to the coating film; The surface of the substrate coated with the liquid crystal alignment agent is irradiated with light to impart the liquid crystal alignment ability to the coating film by photo alignment treatment or the like. From the viewpoint of imparting sufficient liquid crystal alignment control power by light irradiation to the coating film, or suppressing the generation of display defects or the decrease in yield caused by the generation of dust or static electricity, it can be used to form a substrate From the viewpoint that the above organic film uniformly imparts the alignment ability to the liquid crystal, the liquid crystal alignment agent of the present disclosure can preferably be applied with a photo-alignment treatment. When manufacturing a vertical alignment type liquid crystal element, the coating film formed in step 1 can be directly used as a liquid crystal alignment film, but the coating film can also be subjected to alignment treatment.

在光配向處理中，對塗膜進行照射的光例如可使用包含150 nm～800 nm的波長的光的紫外線及可見光線。優選包含200 nm～400 nm的波長的光的紫外線。當照射光為直線偏光或部分偏光時，可從垂直的方向對基板面進行照射，也可以從傾斜方向對基板面進行照射，或者也可以將兩者加以組合來進行。當照射非偏光的放射線時，將照射的方向設為傾斜方向。 作為所使用的光源，例如可使用：低壓水銀燈、高壓水銀燈、氘燈、金屬鹵化物燈、氬共振燈、氙燈、准分子激光器等。優選的波長區域的紫外線可藉由將光源與例如濾光器、衍射光柵等並用的方法等而獲得。放射線的照射量優選200 J/m2 ～50,000 J/m2 ，更優選400 J/m2 ～20,000 J/m2 。可對後烘烤步驟後的塗膜進行用以賦予配向能力的光照射，也可以對預烘烤步驟後且後烘烤步驟前的塗膜進行用以賦予配向能力的光照射，或者也可以在預烘烤步驟及後烘烤步驟的至少任一者中，在加熱過程中對塗膜進行用以賦予配向能力的光照射。In the photo-alignment process, the light for irradiating the coating film can use, for example, ultraviolet rays and visible rays including light with a wavelength of 150 nm to 800 nm. It is preferable to include ultraviolet light having a wavelength of 200 nm to 400 nm. When the irradiated light is linearly polarized light or partially polarized light, the substrate surface may be irradiated from a vertical direction, the substrate surface may be irradiated from an oblique direction, or both may be combined. When irradiating non-polarized radiation, the direction of irradiation is set as an oblique direction. As the light source used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used. Ultraviolet rays in the preferred wavelength range can be obtained by a method of using a light source in combination with, for example, an optical filter and a diffraction grating. The radiation dose is preferably 200 J/m 2 to 50,000 J/m 2 , and more preferably 400 J/m 2 to 20,000 J/m 2 . The coating film after the post-baking step can be irradiated with light for imparting alignment ability, or the coating film after the pre-baking step and before the post-baking step can be irradiated with light for imparting alignment ability, or In at least any one of the pre-baking step and the post-baking step, the coating film is irradiated with light for imparting alignment ability during the heating process.

[步驟3：液晶單元的構築] 準備2片以所述方式形成有液晶配向膜的基板，並在對向配置的2片基板間配置液晶，由此製造液晶單元。具體而言，可列舉：利用密封劑將該一對基板的周邊部貼合，朝由基板表面及密封劑所劃分的單元間隙內注入填充液晶後，對注入孔進行密封的方法；將密封劑塗布在一個基板的液晶配向膜側的周邊部，進而將液晶滴加至液晶配向膜面上的規定的幾個部位後，以液晶配向膜對向的方式貼合另一個基板，並且將液晶擠壓擴散至基板的整個面上，其後對密封劑進行硬化的方法（滴注（One Drop Fill，ODF）方式）等。 作為密封劑，例如可列舉：含有硬化劑及作為間隔物的氧化鋁球的環氧樹脂等。作為液晶，可列舉向列型液晶及層列型液晶，其中，優選向列型液晶，例如可列舉：希夫鹼（schiff base）系液晶、氧化偶氮（azoxy）系液晶、聯苯系液晶、苯基環己烷系液晶、酯系液晶、三聯苯系液晶、聯苯環己烷系液晶、嘧啶系液晶、二噁烷系液晶、雙環辛烷系液晶、立方烷系液晶等。另外，可在這些液晶中添加膽甾醇型液晶、手性試劑、強介電性液晶等來使用。[Step 3: Construction of a liquid crystal cell] Two substrates on which a liquid crystal alignment film is formed in the manner described above are prepared, and liquid crystals are arranged between the two substrates arranged opposite to each other, thereby manufacturing a liquid crystal cell. Specifically, a method of bonding the peripheral parts of the pair of substrates with a sealant, injecting and filling liquid crystal into the cell gap defined by the substrate surface and the sealant, and sealing the injection hole; Coated on the peripheral part of the liquid crystal alignment film side of one substrate, and then drop the liquid crystal on the predetermined spots on the liquid crystal alignment film surface, then bond the other substrate so that the liquid crystal alignment film faces the other substrate, and squeeze the liquid crystal A method (One Drop Fill (ODF) method) in which the pressure spreads over the entire surface of the substrate and then hardens the sealant. As the sealing agent, for example, an epoxy resin containing a curing agent and alumina balls as a spacer, etc. may be mentioned. Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferred. Examples include schiff base liquid crystals, azoxy liquid crystals, and biphenyl liquid crystals. , Phenylcyclohexane-based liquid crystal, ester-based liquid crystal, terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, cubaane-based liquid crystal, etc. In addition, cholesteric liquid crystals, chiral reagents, ferroelectric liquid crystals, etc. can be added to these liquid crystals for use.

在步驟3中可進行如下的處理：構築在液晶層中含有聚合性單體的液晶單元，並對所構築的液晶單元進行光照射，由此使聚合性單體進行聚合，而賦予液晶的初期配向。藉由進行該處理，當應用於IPS型或FFS型等橫電場式時，就可獲得初期電壓保持率高、且耐光性優異的液晶元件的觀點而言適宜。In step 3, the following treatments can be performed: construct a liquid crystal cell containing a polymerizable monomer in the liquid crystal layer, and irradiate the constructed liquid crystal cell with light to polymerize the polymerizable monomer to give the initial stage of the liquid crystal Alignment. By performing this treatment, when applied to a transverse electric field type such as an IPS type or an FFS type, it is suitable in terms of obtaining a liquid crystal element having a high initial voltage retention rate and excellent light resistance.

作為聚合性單體，就由光所產生的聚合性高的觀點而言，可優選地使用具有2個以上的(甲基)丙烯醯基的化合物。作為其具體例，例如可列舉：具有聯苯結構的二(甲基)丙烯酸酯、具有苯基-環己基結構的二(甲基)丙烯酸酯、具有2,2-二苯基丙烷結構的二(甲基)丙烯酸酯、具有二苯基甲烷結構的二(甲基)丙烯酸酯、具有二苯硫醚結構的二-硫代(甲基)丙烯酸酯、具有萘結構的二(甲基)丙烯酸酯、具有蒽結構的二(甲基)丙烯酸酯、具有菲結構的二(甲基)丙烯酸酯、具有藉由光照射而生成自由基的結構的二(甲基)丙烯酸酯等。相對於用於液晶層的形成的液晶組合物的總量，聚合性單體的調配比例優選設為0.1質量%～1.0質量%。再者，聚合性單體可單獨使用一種，也可以將兩種以上組合使用。As the polymerizable monomer, from the viewpoint of high polymerizability by light, a compound having two or more (meth)acryloyl groups can be preferably used. Specific examples thereof include, for example, di(meth)acrylate having a biphenyl structure, di(meth)acrylate having a phenyl-cyclohexyl structure, and di(meth)acrylate having a 2,2-diphenylpropane structure. (Meth) acrylate, di(meth)acrylate with diphenylmethane structure, di-thio(meth)acrylate with diphenyl sulfide structure, di(meth)acrylic acid with naphthalene structure Ester, di(meth)acrylate having an anthracene structure, di(meth)acrylate having a phenanthrene structure, di(meth)acrylate having a structure that generates radicals by light irradiation, and the like. The blending ratio of the polymerizable monomer is preferably 0.1% by mass to 1.0% by mass relative to the total amount of the liquid crystal composition used for the formation of the liquid crystal layer. In addition, a polymerizable monomer may be used individually by 1 type, and may be used in combination of 2 or more types.

對於液晶單元的光照射可在對一對電極間不施加電壓的狀態下進行，也可以在施加液晶層中的液晶分子不驅動的規定電壓（例如0 V）的狀態下進行，或者也可以在施加液晶分子驅動的規定電壓的狀態下進行。當將本揭示的液晶配向劑應用於具備橫電場式的液晶單元的液晶元件時，優選在對一對電極間不施加電壓的狀態下對液晶單元進行光照射。作為所照射的光，例如可使用包含150 nm～800 nm的波長的光的紫外線及可見光線，優選包含300 nm～400 nm的波長的光的紫外線。光的照射方向在所使用的放射線為直線偏光或部分偏光的情況下，可從垂直的方向對基板面進行照射，也可以從傾斜方向對基板面進行照射，或者也可以將兩者加以組合來進行。當照射非偏光的放射線時，將照射方向設為傾斜方向。The light irradiation to the liquid crystal cell can be performed in a state where no voltage is applied between a pair of electrodes, or in a state where a predetermined voltage (for example, 0 V) at which the liquid crystal molecules in the liquid crystal layer are not driven is applied, or it can be performed It is performed in a state where a predetermined voltage driven by the liquid crystal molecules is applied. When the liquid crystal alignment agent of the present disclosure is applied to a liquid crystal element including a liquid crystal cell of a lateral electric field type, it is preferable to irradiate the liquid crystal cell with light in a state where no voltage is applied between a pair of electrodes. As the light to be irradiated, for example, ultraviolet rays and visible rays including light with a wavelength of 150 nm to 800 nm can be used, and ultraviolet rays including light with a wavelength of 300 nm to 400 nm are preferable. When the radiation used is linearly polarized or partially polarized, the light irradiation direction can be irradiated from the vertical direction to the substrate surface, or from the oblique direction to the substrate surface, or a combination of the two get on. When irradiating non-polarized radiation, the irradiation direction is set to an oblique direction.

作為照射光的光源，例如可使用：低壓水銀燈、高壓水銀燈、氘燈、金屬鹵化物燈、氬共振燈、氙燈、准分子激光器等。再者。所述優選的波長區域的紫外線可藉由將光源與例如濾光器、衍射光柵等並用的方法等而獲得。作為光的照射量，優選1,000 J/m2 ～200,000 J/m2 ，更優選1,000 J/m2 ～100,000 J/m2 。As a light source for irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used. Furthermore. The ultraviolet rays in the preferred wavelength range can be obtained by a method of using a light source together with, for example, an optical filter, a diffraction grating, or the like. The amount of light irradiation is preferably 1,000 J/m 2 to 200,000 J/m 2 , and more preferably 1,000 J/m 2 to 100,000 J/m 2 .

也可以先將聚合性單體混入至液晶配向膜中來代替將聚合性單體混入至液晶層中，並對液晶單元進行光照射，由此對液晶賦予初期配向。在此情況下，在步驟1中，使用含有聚合性單體的液晶配向劑在基板上形成塗膜。作為液晶配向劑中所含有的聚合性單體，應用液晶層中所含有的聚合性單體的說明。相對於液晶配向劑中所含有的聚合體成分的合計100質量份，聚合性單體的含有比例優選設為1質量份～100質量份，更優選設為5質量份～50質量份。It is also possible to first mix the polymerizable monomer into the liquid crystal alignment film instead of mixing the polymerizable monomer into the liquid crystal layer, and irradiate the liquid crystal cell with light, thereby imparting initial alignment to the liquid crystal. In this case, in step 1, a liquid crystal alignment agent containing a polymerizable monomer is used to form a coating film on the substrate. As the polymerizable monomer contained in the liquid crystal alignment agent, the description of the polymerizable monomer contained in the liquid crystal layer is applied. The content ratio of the polymerizable monomer is preferably 1 part by mass to 100 parts by mass, and more preferably 5 parts by mass to 50 parts by mass relative to 100 parts by mass of the total polymer components contained in the liquid crystal alignment agent.

繼而，視需要在液晶單元的外側表面貼合偏光板，由此可獲得液晶元件。作為偏光板，可列舉利用乙酸纖維素保護膜夾持被稱為“H膜”的偏光膜而成的偏光板、或包含H膜本身的偏光板，所述“H膜”是一面使聚乙烯醇延伸配向一面吸收碘而成者。Then, if necessary, a polarizing plate is bonded to the outer surface of the liquid crystal cell to obtain a liquid crystal element. Examples of the polarizing plate include a polarizing plate formed by sandwiching a polarizing film called "H film" with a protective film of cellulose acetate, or a polarizing plate including the H film itself. The "H film" is made of polyethylene on one side. Alcohol is formed by absorbing iodine on one side of extending alignment.

本揭示的液晶元件可有效地應用於各種用途，例如可用於時鐘、便攜式遊戲機、文字處理機、筆記型個人電腦、汽車導航系統、攝錄機（camcorder）、個人數字助理（Personal Digital Assistant，PDA）、數碼照相機、手機、智能手機、各種監視器、液晶電視機、信息顯示器等各種顯示裝置，或調光膜等。另外，使用本揭示的液晶配向劑所形成的液晶元件也可以應用於相位差膜。 [實施例]The liquid crystal element of the present disclosure can be effectively applied to various purposes, such as clocks, portable game consoles, word processors, notebook personal computers, car navigation systems, camcorders, and personal digital assistants (Personal Digital Assistant, PDA), digital cameras, mobile phones, smart phones, various monitors, LCD TVs, information displays and other display devices, or dimming films. In addition, the liquid crystal element formed using the liquid crystal alignment agent of the present disclosure can also be applied to a retardation film. [Example]

以下，藉由實施例來更具體地說明，但本發明並不限定於這些實施例。Hereinafter, examples will be used to explain more specifically, but the present invention is not limited to these examples.

在以下的例中，聚合體的重量平均分子量Mw及環氧當量藉由以下的方法來測定。 [聚合體的重量平均分子量Mw]：根據利用以下的裝置，藉由以下的條件下的凝膠滲透色譜法所測定的結果，將單分散聚苯乙烯用作標準物質而作為聚苯乙烯換算值來求出。 測定裝置：東曹（Tosoh）（股份）製造，型號“8120-GPC” 管柱：東曹（股份）製造，“TSKgelGRCXLII” 溶媒：四氫呋喃 試樣濃度：5 重量% 試樣注入量：100 μL 管柱溫度：40℃ 管柱壓力：68 kgf/cm2 [環氧當量]：依據JIS C2105的“鹽酸-甲基乙基酮法”進行測定。In the following examples, the weight average molecular weight Mw and epoxy equivalent of the polymer are measured by the following method. [The weight average molecular weight Mw of the polymer]: Based on the results measured by gel permeation chromatography under the following conditions using the following equipment, monodisperse polystyrene is used as a standard substance as a polystyrene conversion value Come find out. Measuring device: manufactured by Tosoh (Stock), model "8120-GPC" Column: manufactured by Tosoh (Stock), "TSKgelGRCXLII" Solvent: Tetrahydrofuran Sample concentration: 5 wt% Sample injection volume: 100 μL tube Column temperature: 40°C Column pressure: 68 kgf/cm 2 [Epoxy equivalent]: Measured in accordance with the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105.

＜聚合體（A）的合成＞ [合成例1] 使由下述式（m-1）所表示的化合物溶解在四氫呋喃中，並添加作為聚合起始劑的偶氮雙異丁腈進行聚合，由此獲得含有聚合體（A-1）的溶液。針對所獲得的聚合體溶液，利用N-甲基-2-吡咯烷酮（N-Methyl-2-pyrrolidone，NMP）對系統內的溶媒進行溶媒置換，而獲得聚合體（A-1）。該聚合體（A-1）在116℃～315℃的溫度範圍內顯示出液晶性。 [化8]

Figure 02_image015
[合成例2] 除使用由下述式（m-2）所表示的化合物來代替由所述式（m-1）所表示的化合物以外，藉由與所述合成例1相同的操作來獲得聚合體（A-2）。該聚合體（A-2）在108℃～313℃的溫度範圍內顯示出液晶性。 [化9]
Figure 02_image017
[合成例3] 使1,8-二氨基辛烷0.7009 g（4.858 mmol）溶解在N-甲基-2-吡咯烷酮（NMP）22.5 g中，並在室溫下添加由下述式（m-3）所表示的化合物1.7991 g（4.858 mmol）。在60℃下攪拌2小時後，冷卻至室溫，而獲得含有聚合體（A-3）的溶液。將所獲得的聚合體溶液注入至十分過剩的甲醇中，而使反應產物沉澱。利用甲醇對該沉澱物進行清洗，並在減壓下以40℃乾燥15小時，由此獲得聚合體（A-3）。該聚合體（A-3）在100℃～235℃的溫度範圍內顯示出液晶性。 [化10]
Figure 02_image019
<Synthesis of Polymer (A)> [Synthesis Example 1] The compound represented by the following formula (m-1) was dissolved in tetrahydrofuran, and azobisisobutyronitrile was added as a polymerization initiator to perform polymerization. Thus, a solution containing polymer (A-1) was obtained. With respect to the obtained polymer solution, the solvent in the system was replaced with N-Methyl-2-pyrrolidone (NMP) to obtain a polymer (A-1). This polymer (A-1) showed liquid crystallinity in a temperature range of 116°C to 315°C. [化8]
Figure 02_image015
[Synthesis Example 2] It was obtained by the same operation as in Synthesis Example 1 except that the compound represented by the following formula (m-2) was used instead of the compound represented by the formula (m-1) Polymer (A-2). This polymer (A-2) showed liquid crystallinity in a temperature range of 108°C to 313°C. [化9]
Figure 02_image017
[Synthesis Example 3] 0.7009 g (4.858 mmol) of 1,8-diaminooctane was dissolved in 22.5 g of N-methyl-2-pyrrolidone (NMP), and added at room temperature by the following formula (m- 3) 1.7991 g (4.858 mmol) of the compound represented. After stirring for 2 hours at 60°C, it was cooled to room temperature to obtain a solution containing a polymer (A-3). The obtained polymer solution was poured into a sufficiently excessive amount of methanol to precipitate the reaction product. This deposit was washed with methanol and dried at 40° C. for 15 hours under reduced pressure, thereby obtaining a polymer (A-3). This polymer (A-3) shows liquid crystallinity in a temperature range of 100°C to 235°C. [化10]
Figure 02_image019

＜聚有機矽氧烷（C）的合成＞ [合成例4] 向具備攪拌機、溫度計、滴加漏斗及回流冷卻管的反應容器中加入2-(3,4-環氧環己基)乙基三甲氧基矽烷100.0 g、甲基異丁基酮500 g及三乙基胺10.0 g，並在室溫下進行混合。繼而，從滴加漏斗歷時30分鐘滴加去離子水100 g後，在回流下進行混合，並在80℃下反應6小時。反應結束後，取出有機層，利用0.2質量%硝酸銨水溶液對其進行清洗直至清洗後的水變成中性為止後，在減壓下將溶媒及水餾去，由此以黏稠的透明液體的形態獲得作為含有環氧基的聚有機矽氧烷的聚合體（EPS-1）。對該聚合體（EPS-1）進行1 H-NMR分析，結果在化學位移（δ）=3.2 ppm附近如理論強度般獲得基於環氧乙烷基的峰值，確認在反應中未產生環氧基的副反應。該聚合體（EPS-1）的重量平均分子量為2,200，環氧當量為186 g/mol。 繼而，向100 mL的三口燒瓶中加入以上所獲得的聚合體（EPS-1）9.3 g、甲基異丁基酮26 g、由下述式（m-4）所表示的化合物3.0 g、及商品名“UCAT 18X”（三亞普羅（San-Apro）公司製造的四級胺鹽）0.10 g，並在攪拌下以80℃進行12小時反應。反應結束後，將反應混合物投入至甲醇中並回收所生成的沉澱物，使其溶解在乙酸乙酯中而製成溶液，對該溶液進行3次水洗後，將溶劑餾去，由此以白色粉末的形態獲得作為聚有機矽氧烷（C）的聚合體（C-1）6.3 g。該聚合體（C-1）的重量平均分子量Mw為3,500。 [化11]

Figure 02_image021
<Synthesis of polyorganosiloxane (C)> [Synthesis example 4] Add 2-(3,4-epoxycyclohexyl)ethyltrimethyl to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube 100.0 g of oxysilane, 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine were mixed at room temperature. Then, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, mixed under reflux, and reacted at 80°C for 6 hours. After the reaction, the organic layer was taken out and washed with a 0.2% by mass ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to form a viscous transparent liquid Obtained as a polymer (EPS-1) of epoxy-containing polyorganosiloxane. The polymer (EPS-1) was analyzed by 1 H-NMR, and as a result, a peak based on an oxirane group was obtained at a chemical shift (δ)=3.2 ppm as the theoretical strength. It was confirmed that no epoxy group was generated during the reaction. The side reaction. The weight average molecular weight of the polymer (EPS-1) is 2,200, and the epoxy equivalent is 186 g/mol. Then, 9.3 g of the polymer (EPS-1) obtained above, 26 g of methyl isobutyl ketone, 3.0 g of the compound represented by the following formula (m-4), and 0.10 g of the trade name "UCAT 18X" (quaternary amine salt manufactured by San-Apro) was reacted at 80°C for 12 hours under stirring. After the reaction, the reaction mixture was poured into methanol and the resulting precipitate was recovered and dissolved in ethyl acetate to prepare a solution. After washing the solution three times with water, the solvent was distilled off to give a white In the form of powder, 6.3 g of polymer (C-1) as polyorganosiloxane (C) was obtained. The weight average molecular weight Mw of this polymer (C-1) was 3,500. [化11]
Figure 02_image021

＜其他成分＞ [合成例5] 使作為四羧酸二酐的1,2,3,4-環丁烷四羧酸二酐100莫耳份、及作為二胺的4,4'-二氨基二苯基醚100莫耳份溶解在NMP中，並在40℃下反應3小時，由此獲得含有作為聚醯胺酸的聚合體（B-1）10質量%的溶液。 [合成例6] 使作為四羧酸二酐的1,2,3,4-環丁烷四羧酸二酐100莫耳份、及作為二胺的4-氨基苯基-4'-氨基偶氮苯100莫耳份溶解在NMP中，並在40℃下反應3小時，由此獲得含有作為聚醯胺酸的聚合體（B-2）10質量%的溶液。 [合成例7] 除使用甲基丙烯酸辛酯來代替由所述式（m-1）所表示的化合物以外，藉由與所述合成例1相同的操作來獲得聚合體（D-1）。<Other components> [Synthesis example 5] 100 mole parts of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 4,4'-diamino as diamine 100 mole parts of diphenyl ether was dissolved in NMP and reacted at 40° C. for 3 hours, thereby obtaining a solution containing 10% by mass of the polymer (B-1) as polyamide acid. [Synthesis Example 6] 100 mole parts of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride, and 4-aminophenyl-4'-amino as diamine 100 mole parts of nitrobenzene was dissolved in NMP, and reacted at 40° C. for 3 hours, thereby obtaining a solution containing 10% by mass of the polymer (B-2) as a polyamide acid. [Synthesis Example 7] The polymer (D-1) was obtained by the same operation as in Synthesis Example 1 except that octyl methacrylate was used instead of the compound represented by the formula (m-1).

[實施例1] （1）液晶配向劑的製備 將作為聚合體（A）的所述合成例1中所獲得的聚合體（A-1）20質量份、作為聚合體（B）的所述合成例5中所獲得的含有聚合體（B-1）的溶液換算成聚合體（B-1）為相當於60質量份的量、及作為聚有機矽氧烷（C）的所述合成例4中所獲得的聚合體（C-1）20質量份混合，並向其中添加N-甲基-2-吡咯烷酮（NMP）及丁基溶纖劑（Butyl Cellosolve，BC），而製成溶媒組成為NMP：BC=50：50（質量比）、固體成分濃度為4.0質量%的溶液。利用孔徑為1 μm的過濾器對該溶液進行過濾，由此製備液晶配向劑。 （2）液晶顯示元件的製造 準備2片帶有包含ITO膜的透明電極的玻璃基板，並使用旋塗機將所述（1）中所製備的液晶配向劑塗布在各自的透明電極面上。繼而，在80℃的加熱板上進行1分鐘預烘烤後，在對庫內進行了氮氣置換的烘箱中，以230℃進行30分鐘加熱（後烘烤）而形成膜厚為0.1 μm的塗膜。繼而，使用Hg-Xe燈及格蘭-泰勒棱鏡（Glan-Taylor prism），從基板法線方向對各自的塗膜表面照射包含313 nm的明線的偏光紫外線500 mJ/cm2 ，而製作一對（2片）具有液晶配向膜的基板。再者，該照射量是使用以波長313 nm為基準進行測量的光量計所測量的值。繼而，針對一對基板中的一個基板，將放入有直徑為5.5 μm的氧化鋁球的環氧樹脂黏結劑塗布在具有液晶配向膜的面的外緣後，以液晶配向膜面相對的方式使一對基板重疊並進行壓接，而使黏結劑硬化。繼而，從液晶注入口朝一對基板間填充向列型液晶（默克（Merck）公司製造，MLC-6221）後，利用丙烯酸系光硬化黏結劑將液晶注入口密封，而製造液晶單元。進而，在該液晶單元的基板的外側兩面，以2片偏光板的偏光方向相互正交的方式貼合偏光板，而製作液晶顯示元件。[Example 1] (1) Preparation of liquid crystal alignment agent 20 parts by mass of the polymer (A-1) obtained in the synthesis example 1 as the polymer (A) and the polymer (B) The solution containing the polymer (B-1) obtained in Synthesis Example 5 is converted into an amount equivalent to 60 parts by mass of the polymer (B-1), and the above-mentioned synthesis example as polyorganosiloxane (C) 20 parts by mass of the polymer (C-1) obtained in 4 were mixed, and N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (Butyl Cellosolve, BC) were added to it, and the solvent composition was NMP : BC=50:50 (mass ratio), a solution with a solid content concentration of 4.0% by mass. The solution was filtered with a filter with a pore diameter of 1 μm, thereby preparing a liquid crystal alignment agent. (2) Manufacture of liquid crystal display element Two glass substrates with transparent electrodes containing ITO films were prepared, and the liquid crystal alignment agent prepared in (1) was coated on the respective transparent electrode surfaces using a spin coater. Then, after pre-baking on a hot plate at 80°C for 1 minute, in an oven that replaced the interior with nitrogen, heating (post-baking) at 230°C for 30 minutes to form a coating with a thickness of 0.1 μm membrane. Then, using Hg-Xe lamp and Glan-Taylor prism, the respective coating film surface was irradiated with 313 nm bright line polarized ultraviolet light 500 mJ/cm 2 from the normal direction of the substrate to produce a pair (2 pieces) A substrate with a liquid crystal alignment film. In addition, the irradiation amount is a value measured using a light meter that measures with a wavelength of 313 nm as a reference. Then, for one of the pair of substrates, an epoxy resin adhesive containing aluminum oxide balls with a diameter of 5.5 μm was applied to the outer edge of the surface with the liquid crystal alignment film, and the liquid crystal alignment film faces facing each other. A pair of substrates are overlapped and pressure-bonded to harden the adhesive. Next, nematic liquid crystal (MLC-6221, manufactured by Merck) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic light-curing adhesive to manufacture a liquid crystal cell. Furthermore, on both outer sides of the substrate of the liquid crystal cell, the polarizing plates were bonded so that the polarization directions of the two polarizing plates were orthogonal to each other to produce a liquid crystal display element.

（3）初期電壓保持率的評價 在60℃的溫度下，以60微秒的施加時間、167毫秒的跨度對在所述（2）中剛製造之後的液晶顯示元件施加5 V的電壓後，測定自解除施加起167毫秒後的電壓保持率（初期電壓保持率VH1 ）。測定裝置使用東陽特克尼卡（TOYO Corporation）（股份）製造的品名“VHR-1”。其結果，在實施例1中，VH1 ＝99.6%。 （4）耐光性的評價 使用將碳弧設為光源的耐候試驗機（Weather Meter），對測定初期電壓保持率VH1 後的液晶顯示元件進行500小時的光照射。針對光照射後的液晶顯示元件，以與所述（3）相同的方式測定電壓保持率。將該值設為VH2 ，將VH1 減去VH2 所求出的電壓保持率的減少量設為ΔVHR，並藉由ΔVHR來評價耐光性。其結果，在實施例1中，ΔVHR＝0.6%，耐光性良好。 （5）液晶配向性的評價 在未設置電極的一對玻璃基板各自的表面上，以與所述（2）相同的方式對所述（1）中所製備的液晶配向劑進行塗布及光配向處理而形成液晶配向膜，並且使用具有該液晶配向膜的一對基板，以與所述（2）相同的方式製造液晶單元。在正交尼科耳（crossed nicols）下觀察所獲得的液晶單元，結果觀察到無配向不良的均勻的液晶配向。 另外，藉由目視來觀察對所述（2）中所獲得的液晶顯示元件接通・斷開（施加・解除）5 V的電壓時的明暗的變化中的配向缺陷（異常區域）的有無，結果該液晶顯示元件遍及整個面無配向缺陷，觀察到由電壓施加所引起的均勻的液晶的配向變化。(3) Evaluation of the initial voltage retention rate After applying a voltage of 5 V to the liquid crystal display element immediately after manufacturing in (2) at a temperature of 60°C with an application time of 60 microseconds and a span of 167 milliseconds, The voltage holding rate (initial voltage holding rate VH 1 ) after 167 milliseconds from the release of application was measured. The product name "VHR-1" manufactured by TOYO Corporation (Stock) was used for the measuring device. As a result, in Example 1, VH 1 =99.6%. (4) Evaluation of light resistance Using a weather meter using a carbon arc as a light source, the liquid crystal display element after measuring the initial voltage holding ratio VH 1 was subjected to light irradiation for 500 hours. With respect to the liquid crystal display element after light irradiation, the voltage holding ratio was measured in the same manner as in (3) above. This value was set to VH 2 , the decrease in the voltage holding ratio obtained by subtracting VH 2 from VH 1 was set to ΔVHR, and the light resistance was evaluated by ΔVHR. As a result, in Example 1, ΔVHR=0.6%, and light resistance was good. (5) Evaluation of liquid crystal alignment On the respective surfaces of a pair of glass substrates without electrodes, the liquid crystal alignment agent prepared in (1) was coated and photo-aligned in the same manner as in (2) The liquid crystal alignment film is formed by processing, and a pair of substrates having the liquid crystal alignment film is used to manufacture a liquid crystal cell in the same manner as in (2). The obtained liquid crystal cell was observed under crossed nicols, and as a result, uniform liquid crystal alignment without poor alignment was observed. In addition, by visually observing the presence or absence of alignment defects (abnormal regions) in the changes in brightness when the liquid crystal display element obtained in (2) is turned on/off (applied/released) at a voltage of 5 V, As a result, the liquid crystal display element had no alignment defects over the entire surface, and uniform alignment changes of the liquid crystals caused by voltage application were observed.

[實施例2～實施例8、比較例1～比較例11] 除如下述表1中所示般變更用於液晶配向劑的製備的聚合體成分的種類及量（質量份）以外，以與所述實施例1相同的溶劑比及固體成分濃度分別製備液晶配向劑。另外，除如下述表1般變更所使用的液晶配向劑這一點，及針對比較例3、比較例4、比較例6、比較例9～比較例11將光配向處理時的曝光波長從313 nm變更成365 nm，將照射量從500 mJ/cm2 變更成4,000 mJ/cm2 這一點以外，以與實施例1相同的方式製造液晶顯示元件，並且與實施例1同樣地進行電特性、耐光性及液晶配向性的評價。將它們的結果示於下述表1中。再者，在以500 mJ/cm2 對聚合體（B-1）照射包含313 nm的明線的偏光紫外線的條件下，在聚合體（B-1）中不產生光裂解反應。因此，相對於聚有機矽氧烷（C），聚合體（B-1）相當於非感光性的聚合體。[Example 2 to Example 8, Comparative Example 1 to Comparative Example 11] Except for changing the type and amount (parts by mass) of the polymer component used in the preparation of the liquid crystal alignment agent as shown in Table 1 below, The liquid crystal alignment agent was prepared with the same solvent ratio and solid content concentration in Example 1. In addition, in addition to changing the liquid crystal alignment agent used as shown in Table 1 below, and for Comparative Example 3, Comparative Example 4, Comparative Example 6, Comparative Example 9 to Comparative Example 11, the exposure wavelength during the photo-alignment treatment was changed from 313 nm Except for changing to 365 nm and changing the irradiation dose from 500 mJ/cm 2 to 4,000 mJ/cm 2 , a liquid crystal display element was manufactured in the same manner as in Example 1, and the electrical characteristics and light resistance were measured in the same manner as in Example 1. Evaluation of properties and liquid crystal orientation. The results are shown in Table 1 below. In addition, under the condition that the polymer (B-1) was irradiated with polarized ultraviolet rays including bright rays of 313 nm at 500 mJ/cm 2 , no photolysis reaction occurred in the polymer (B-1). Therefore, the polymer (B-1) corresponds to a non-photosensitive polymer with respect to the polyorganosiloxane (C).

[實施例9] （1）液晶組合物的製備 在向列型液晶（默克公司製造，MLC-6221）中，相對於向列型液晶的總量，添加作為聚合性單體的由下述式（L-1）所表示的化合物及由下述式（L-2）所表示的化合物的混合物（質量混合比（L-1）：（L-2）＝50：50）0.5質量%並進行混合，由此獲得液晶組合物LC1。 [化12]

Figure 02_image023
[Example 9] (1) Preparation of liquid crystal composition In nematic liquid crystal (Merck, MLC-6221), with respect to the total amount of nematic liquid crystal, the polymerizable monomer was added as follows: A mixture of the compound represented by the formula (L-1) and the compound represented by the following formula (L-2) (mass mixing ratio (L-1): (L-2)=50:50) 0.5% by mass and The mixing was carried out, thereby obtaining a liquid crystal composition LC1. [化12]
Figure 02_image023

（2）橫電場式液晶顯示元件的製造 將在一面上具有圖案化成梳齒狀的包含鉻的金屬電極的玻璃基板與未設置電極的對向玻璃基板設為一對，使用旋轉器將液晶配向劑E（實施例4中所使用的液晶配向劑）塗布在玻璃基板的具有電極的面與對向玻璃基板的一面上，在80℃的加熱板上進行1分鐘預烘烤後，在對庫內進行了氮氣置換的烘箱中，以200℃進行1小時加熱（後烘烤）而形成膜厚為0.1 μm的塗膜。 繼而，使用Hg-Xe燈及格蘭-泰勒棱鏡，從基板法線方向對各塗膜表面照射包含313 nm的明線的偏光紫外線300 mJ/cm2 （光配向處理），而獲得具有液晶配向膜的一對基板。在所述基板中的一片基板的具有液晶配向膜的面的外周，藉由網版印刷來塗布放入有直徑為5.5 μm的氧化鋁球的環氧樹脂黏結劑後，使一對基板的液晶配向膜面對向，以照射偏光紫外線時的各基板的朝向變成相反的方式重疊並進行壓接，並在150℃下歷時1小時對黏結劑進行熱硬化。 繼而，從液晶注入口朝基板間的間隙中填充所述（1）中所製備的液晶組合物LC1後，利用環氧系黏結劑將液晶注入口密封。其後，為了去除液晶注入時的流動配向，在150℃下對其進行加熱後緩慢冷卻至室溫為止，進而，在對一對電極間不施加電壓的狀態下，從液晶單元的外側實施紫外線（Ultraviolet，UV）光照射（照射量：2,000 mJ/cm2 （λ＝365 nm））。繼而，將偏光板以其偏光方向相互正交、且與液晶配向膜的偏光紫外線的光軸的對於基板面的射影方向正交的方式貼合在基板的外側兩面，由此製造液晶顯示元件。(2) Manufacture of horizontal electric field type liquid crystal display element. A glass substrate with chromium-containing metal electrodes patterned into comb teeth on one surface and a counter glass substrate without electrodes are set as a pair, and the liquid crystal is aligned using a spinner Agent E (liquid crystal alignment agent used in Example 4) was coated on the side of the glass substrate with electrodes and the side of the opposite glass substrate. After pre-baking on a hot plate at 80°C for 1 minute, In an oven in which the inside was replaced with nitrogen, heating (post-baking) was performed at 200°C for 1 hour to form a coating film with a film thickness of 0.1 μm. Then, using Hg-Xe lamps and Glan-Taylor prisms, the surface of each coating film was irradiated with 300 mJ/cm 2 of polarized ultraviolet light containing 313 nm bright lines from the normal direction of the substrate (photoalignment treatment) to obtain a liquid crystal alignment film A pair of substrates. On the outer periphery of the surface with the liquid crystal alignment film of one of the substrates, screen printing is used to apply an epoxy resin adhesive containing an alumina ball with a diameter of 5.5 μm to make the liquid crystal of a pair of substrates The alignment films face each other, overlapped so that the directions of the substrates when irradiated with polarized ultraviolet rays are reversed, and pressure-bonded, and the adhesive is thermally cured at 150°C for 1 hour. Then, after filling the liquid crystal composition LC1 prepared in (1) from the liquid crystal injection port toward the gap between the substrates, the liquid crystal injection port is sealed with an epoxy-based adhesive. Thereafter, in order to remove the flow alignment during liquid crystal injection, it was heated at 150°C and then slowly cooled to room temperature. Furthermore, with no voltage applied between a pair of electrodes, ultraviolet rays were applied from the outside of the liquid crystal cell (Ultraviolet, UV) light irradiation (irradiation amount: 2,000 mJ/cm 2 (λ=365 nm)). Then, the polarizing plates were bonded to the outer sides of the substrate so that their polarization directions were orthogonal to each other and the optical axis of the polarized ultraviolet rays of the liquid crystal alignment film were orthogonal to the projection direction of the substrate surface, thereby manufacturing a liquid crystal display element.

（2）評價 針對所述（1）中所製造的液晶顯示元件，與實施例1同樣地進行電特性、耐光性及液晶配向性的評價。其結果，在該實施例中，VH1 ＝99.2%，ΔVHR＝0.3%。另外，液晶配向性也與實施例1同樣地良好。(2) Evaluation With respect to the liquid crystal display element manufactured in (1) above, the electrical characteristics, light resistance, and liquid crystal orientation were evaluated in the same manner as in Example 1. As a result, in this example, VH 1 = 99.2%, and ΔVHR = 0.3%. In addition, the liquid crystal orientation was also good as in Example 1.

[實施例10及比較例12、比較例13] 除如下述表1中所示般變更所使用的液晶配向劑這一點，及針對比較例13將光配向處理時的曝光波長從313 nm變更成365 nm，將照射量從500 mJ/cm2 變更成4,000 mJ/cm2 這一點以外，以與實施例9相同的方式製造液晶顯示元件，並且與實施例1同樣地進行電特性、耐光性及液晶配向性的評價。將它們的結果示於下述表1中。[Example 10, Comparative Example 12, and Comparative Example 13] Except for changing the liquid crystal alignment agent used as shown in Table 1 below, and for Comparative Example 13, the exposure wavelength during the photo-alignment process was changed from 313 nm to 365 nm, except that the irradiation dose was changed from 500 mJ/cm 2 to 4,000 mJ/cm 2 , a liquid crystal display element was manufactured in the same manner as in Example 9, and the electrical characteristics, light resistance, and light resistance were measured in the same manner as in Example 1. Evaluation of liquid crystal orientation. The results are shown in Table 1 below.

[實施例11] （1）液晶配向劑的製備 將作為聚合體（A）的所述合成例2中所獲得的聚合體（A-2）20質量份、作為聚合體（B）的所述合成例5中所獲得的含有聚合體（B-1）的溶液換算成聚合體（B-1）為相當於60質量份的量、及作為聚有機矽氧烷（C）的所述合成例4中所獲得的聚合體（C-1）20質量份混合，並向其中添加N-甲基-2-吡咯烷酮（NMP）及丁基溶纖劑（BC），進而添加作為聚合性單體的由下述式（E-1）所表示的化合物20質量份，而製成溶媒組成為NMP：BC=50：50（質量比）、固體成分濃度為4.0質量%的溶液。利用孔徑為1 μm的過濾器對該溶液進行過濾，由此製備液晶配向劑T。 [化13]

Figure 02_image025
[Example 11] (1) Preparation of liquid crystal alignment agent 20 parts by mass of the polymer (A-2) obtained in the synthesis example 2 as the polymer (A) and the polymer (B) The solution containing the polymer (B-1) obtained in Synthesis Example 5 is converted into an amount equivalent to 60 parts by mass of the polymer (B-1), and the above-mentioned synthesis example as polyorganosiloxane (C) 20 parts by mass of the polymer (C-1) obtained in 4 were mixed, and N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) were added to it, and the polymerizable monomer was added as the following 20 parts by mass of the compound represented by the formula (E-1) was prepared as a solution having a solvent composition of NMP:BC=50:50 (mass ratio) and a solid content concentration of 4.0% by mass. The solution was filtered with a filter having a pore diameter of 1 μm, thereby preparing a liquid crystal alignment agent T. [化13]
Figure 02_image025

（2）液晶顯示元件的製造及評價 除將所使用的液晶配向劑設為所述（1）中所製備的液晶配向劑T這一點，及將MLC-6221（默克公司製造）代替液晶組合物LC1填充至基板間的間隙中這一點以外，以與實施例9相同的方式製造液晶顯示元件，並且與實施例1同樣地進行電特性、耐光性及液晶配向性的評價。將其結果示於下述表1中。(2) Manufacture and evaluation of liquid crystal display elements, except that the liquid crystal alignment agent used is the liquid crystal alignment agent T prepared in (1) above, and MLC-6221 (manufactured by Merck) is used instead of the liquid crystal assembly Except that the substance LC1 was filled in the gap between the substrates, a liquid crystal display element was manufactured in the same manner as in Example 9, and the electrical characteristics, light resistance, and liquid crystal alignment were evaluated in the same manner as in Example 1. The results are shown in Table 1 below.

[表1]

Figure 105140543-A0304-0001
[Table 1]
Figure 105140543-A0304-0001

如根據表1而明確般，實施例1～實施例11的液晶顯示元件的初期電壓保持率均高達98.0%以上。另外，ΔVHR均為0.9%以下，耐光性也良好。另外，在實施例1～實施例11中，液晶的配向性也良好。相對於此，比較例1～比較例13的液晶配向劑在與實施例1～實施例11的液晶配向劑的對比中，初期電壓保持率及耐光性的至少任一者欠佳。關於液晶配向性，在比較例2中未觀察到液晶的配向，在使用不顯示液晶性的(甲基)丙烯酸系聚合體來代替聚合體（A）的例子（比較例5～比較例9）中，當施加・解除電壓時觀察到許多配向缺陷。另外，在使用作為感光性聚醯胺酸的聚合體（B-2）來代替感光性聚有機矽氧烷（聚有機矽氧烷（C））的比較例10中，也觀察到許多配向缺陷。As is clear from Table 1, the initial voltage retention rates of the liquid crystal display elements of Examples 1 to 11 were as high as 98.0% or more. In addition, ΔVHR was all 0.9% or less, and light resistance was also good. In addition, in Example 1 to Example 11, the alignment of the liquid crystal was also good. In contrast, in comparison with the liquid crystal alignment agents of Comparative Examples 1 to 13 and the liquid crystal alignment agents of Examples 1 to 11, at least any one of the initial voltage retention and light resistance was poor. Regarding the alignment of the liquid crystal, the alignment of the liquid crystal was not observed in Comparative Example 2, and a (meth)acrylic polymer that does not exhibit liquid crystallinity was used instead of the polymer (A) (Comparative Example 5 to Comparative Example 9) In, many alignment defects were observed when voltage was applied and released. In addition, in Comparative Example 10 where the photosensitive polyamide acid polymer (B-2) was used instead of the photosensitive polyorganosiloxane (polyorganosiloxane (C)), many alignment defects were also observed .

無no

無no

Claims (7)

一種液晶配向劑，其包括顯示出液晶性的聚合體(A)以及具有光配向性基的聚有機矽氧烷(C)，其中所述聚合體(A)為具有聚合性不飽和鍵的單體的聚合體，且所述聚合性不飽和鍵的單體包括下述式(2-1)~式(2-5)所表示的化合物中的任一個的一個以上，且在所述聚有機矽氧烷(C)及與所述聚有機矽氧烷(C)不同的聚合體的至少任一者的分子內含有顯現液晶性的部分結構，
Figure 105140543-A0305-02-0037-5
 式(2-1)~式(2-5)中，R2為氫原子或甲基，R3為碳數1~12的烷二基、或利用-O-取代該烷二基的至少1個亞甲基而成的二價的基，R4為碳數1~20的烷基、烷氧基或氟烷基、或氟原子。 A liquid crystal alignment agent, comprising a polymer (A) exhibiting liquid crystallinity and a polyorganosiloxane (C) having a photo-alignment group, wherein the polymer (A) is a monomer having a polymerizable unsaturated bond The monomer of the polymerizable unsaturated bond includes one or more of the compounds represented by the following formula (2-1) to formula (2-5), and the polymer is At least one of the silicone (C) and the polymer different from the polyorganosiloxane (C) has a partial structure exhibiting liquid crystallinity in the molecule,
Figure 105140543-A0305-02-0037-5
 In formulas (2-1) to (2-5), R 2 is a hydrogen atom or a methyl group, and R 3 is an alkanediyl group with 1 to 12 carbons, or at least 1 of the alkanediyl group is substituted with -O- A divalent group consisting of a methylene group, and R 4 is a C 1-20 alkyl group, alkoxy group or fluoroalkyl group, or a fluorine atom. 如申請專利範圍第1項所述的液晶配向劑，其中包括選自由聚醯胺酸、聚醯胺酸酯及聚醯亞胺所組成的群組中的至少一種聚合體。 The liquid crystal alignment agent described in item 1 of the scope of the patent application includes at least one polymer selected from the group consisting of polyamide acid, polyamide ester and polyimide. 一種液晶配向膜，其使用如申請專利範圍第1項或第2項所述的液晶配向劑來形成。 A liquid crystal alignment film, which is formed using the liquid crystal alignment agent described in item 1 or item 2 of the scope of patent application. 一種液晶元件，其包括如申請專利範圍第3項所述的液晶配向膜。 A liquid crystal element comprising the liquid crystal alignment film as described in item 3 of the scope of patent application. 一種液晶配向膜的製造方法，其包括將如申請專利範圍第1項或第2項所述的液晶配向劑塗布在基板上而形成塗膜的步驟、及對塗布有所 述液晶配向劑的基板面進行光照射來對所述塗膜賦予液晶配向能力的步驟。 A method for manufacturing a liquid crystal alignment film, which includes the steps of coating the liquid crystal alignment agent as described in item 1 or item 2 of the scope of the patent application on a substrate to form a coating film, and coating The step of irradiating the substrate surface of the liquid crystal alignment agent with light to impart liquid crystal alignment ability to the coating film. 一種液晶元件的製造方法，包括：藉由如申請專利範圍第5項所述的液晶配向膜的製造方法而在一對基板各自的表面上形成液晶配向膜的步驟；以各自的液晶配向膜對向的方式，隔著含有聚合性單體的液晶層來配置所述一對基板而構築液晶單元的步驟；以及對所述液晶單元進行光照射的步驟。 A method for manufacturing a liquid crystal element, comprising: forming a liquid crystal alignment film on the respective surfaces of a pair of substrates by the method for manufacturing a liquid crystal alignment film as described in item 5 of the scope of patent application; In the method of orientation, a step of arranging the pair of substrates to construct a liquid crystal cell via a liquid crystal layer containing a polymerizable monomer; and a step of irradiating the liquid crystal cell with light. 一種液晶元件的製造方法，包括：藉由如申請專利範圍第5項所述的液晶配向膜的製造方法，並使用含有聚合性單體的液晶配向劑在一對基板各自的表面上形成液晶配向膜的步驟；以各自的液晶配向膜對向的方式，隔著液晶層來配置所述一對基板而構築液晶單元的步驟；以及對所述液晶單元進行光照射的步驟。 A method for manufacturing a liquid crystal element, comprising: forming a liquid crystal alignment on the respective surfaces of a pair of substrates by using the method for manufacturing a liquid crystal alignment film as described in item 5 of the scope of patent application, and using a liquid crystal alignment agent containing a polymerizable monomer The step of filming; the step of arranging the pair of substrates to construct a liquid crystal cell with the respective liquid crystal alignment films facing each other through the liquid crystal layer; and the step of irradiating the liquid crystal cell with light.
TW105140543A 2016-01-07 2016-12-08 Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, liquid crystal alignment film and liquid crystal element manufacturing method TWI711671B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016002060 2016-01-07
JP2016-002060 2016-01-07

Publications (2)

Publication Number Publication Date
TW201725242A TW201725242A (en) 2017-07-16
TWI711671B true TWI711671B (en) 2020-12-01

Family

ID=59365220

Family Applications (1)

Application Number Title Priority Date Filing Date
TW105140543A TWI711671B (en) 2016-01-07 2016-12-08 Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, liquid crystal alignment film and liquid crystal element manufacturing method

Country Status (4)

Country Link
JP (1) JP6828360B2 (en)
KR (1) KR20170082969A (en)
CN (1) CN106947498B (en)
TW (1) TWI711671B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101997109B1 (en) 2017-11-21 2019-07-05 인천대학교 산학협력단 Apparatus and method for storing movement history data using route information
JP7136187B2 (en) 2018-03-16 2022-09-13 Jsr株式会社 Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5407394B2 (en) * 2008-03-21 2014-02-05 Ｊｎｃ株式会社 Photo-alignment agent, alignment film, and liquid crystal display device using the same
TW201408729A (en) * 2012-08-30 2014-03-01 Jsr Corp Liquid crystal alignment agent, liquid crystal alignment film, method for manufacturing liquid crystal alignment film and liquid crystal display device

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5138010A (en) * 1990-06-25 1992-08-11 University Of Colorado Foundation, Inc. Fast switching polysiloxane ferroelectric liquid crystals
SG64893A1 (en) * 1993-02-17 1999-08-17 Rolic Ag Orientating layers for liquid crystals
JPH08328005A (en) * 1995-05-26 1996-12-13 Hitachi Chem Co Ltd Liquid crystal oriented film, treatment of liquid crystal oriented film, liquid crystal holding substrate, liquid crystal display element, production of liquid crystal display element and material for liquid crystal oriented film
KR0179115B1 (en) * 1995-11-20 1999-05-01 구자홍 The photoresist material for lcd orientation layer and its application lcd
CN1061365C (en) * 1997-07-18 2001-01-31 中国科学院化学研究所 Directional liquid crystal film with ladder polysiloxane matrix and its preparation process and application
KR20000025990A (en) * 1998-10-16 2000-05-06 권문구 Light orientating polymer composition, liquid crystal alignment layer and liquid crystal display device using the same
CN1255527A (en) * 1998-12-01 2000-06-07 中国科学院化学研究所 Liquid crystal orientating membrane with base material of photosensitive trapezoidal polysiloxane and its preparing process
US6927823B1 (en) * 2000-09-07 2005-08-09 Kent State University Method for alignment of liquid crystals using irradiated liquid crystal films
JP4647694B2 (en) * 2005-11-07 2011-03-09 エルジー・ケム・リミテッド Liquid crystal alignment copolymer, liquid crystal alignment film including the same, and liquid crystal display including the same
KR100964434B1 (en) * 2007-08-21 2010-06-16 제이에스알 가부시끼가이샤 Liquid crystal aligning agent, formation method of liquid crystal aligning film, and liquid crystal display element
CN102216839B (en) * 2008-09-17 2014-09-17 三星显示有限公司 Alignment material, alignment layer, liquid crystal display device and manufacturing method thereof
JP5454772B2 (en) * 2008-11-17 2014-03-26 Ｊｓｒ株式会社 Liquid crystal aligning agent, liquid crystal aligning film, method for forming the same, and liquid crystal display element
JP5630013B2 (en) * 2009-01-30 2014-11-26 ソニー株式会社 Manufacturing method of liquid crystal display device
JP5716883B2 (en) * 2009-06-09 2015-05-13 Jsr株式会社 Manufacturing method of liquid crystal display element
JP5640471B2 (en) * 2010-06-02 2014-12-17 Jsr株式会社 Liquid crystal alignment agent, liquid crystal alignment film, method for forming liquid crystal alignment film, and liquid crystal display element
JP2012058280A (en) * 2010-09-03 2012-03-22 Jsr Corp Cholesteric liquid crystal display, method for manufacturing the same, and liquid crystal aligning agent
JP5966329B2 (en) * 2011-03-30 2016-08-10 Jsr株式会社 Manufacturing method of liquid crystal display element
US20140218667A1 (en) * 2011-08-12 2014-08-07 Sharp Kabushiki Kaisha Liquid crystal display device
JP5967094B2 (en) * 2011-08-31 2016-08-10 Jsr株式会社 Manufacturing method of liquid crystal display element
TWI593710B (en) * 2011-11-29 2017-08-01 日產化學工業股份有限公司 Method of manufacturing liquid crystal alignment film, liquid crystal alignment film and liquid crystal display element
JP6164117B2 (en) * 2013-06-18 2017-07-19 Jsr株式会社 Liquid crystal aligning agent, retardation film, and method for producing retardation film
US20160178969A1 (en) * 2013-07-30 2016-06-23 Sharp Kabushiki Kaisha Method for manufacturing liquid crystal display device
JP2015090427A (en) * 2013-11-06 2015-05-11 Dic株式会社 Manufacturing method of liquid crystal alignment film and liquid crystal display element using the same
JP6458484B2 (en) * 2014-03-24 2019-01-30 Jsr株式会社 Liquid crystal aligning agent, liquid crystal aligning film and method for producing the same, liquid crystal display element, retardation film and method for producing the same
TW201704292A (en) * 2015-07-20 2017-02-01 奇美實業股份有限公司 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element
TWI609218B (en) * 2015-12-01 2017-12-21 奇美實業股份有限公司 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5407394B2 (en) * 2008-03-21 2014-02-05 Ｊｎｃ株式会社 Photo-alignment agent, alignment film, and liquid crystal display device using the same
TW201408729A (en) * 2012-08-30 2014-03-01 Jsr Corp Liquid crystal alignment agent, liquid crystal alignment film, method for manufacturing liquid crystal alignment film and liquid crystal display device

Also Published As

Publication number Publication date
JP6828360B2 (en) 2021-02-10
TW201725242A (en) 2017-07-16
CN106947498B (en) 2022-02-11
JP2017126060A (en) 2017-07-20
KR20170082969A (en) 2017-07-17
CN106947498A (en) 2017-07-14

Similar Documents

Publication Publication Date Title
TWI709611B (en) Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display device, phase difference film and method for manufacturing the same, polymer and compound
JP6911885B2 (en) Manufacturing method of liquid crystal alignment film and manufacturing method of liquid crystal element
CN107338058B (en) Liquid crystal aligning agent, liquid crystal alignment film and method for producing same, liquid crystal element, polymer and compound
TWI675096B (en) Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, retardation film, and its production method, polymer and diamine
JP2016029465A (en) Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display device, phase difference film, and manufacturing method of phase difference film
JP6458484B2 (en) Liquid crystal aligning agent, liquid crystal aligning film and method for producing the same, liquid crystal display element, retardation film and method for producing the same
TW201815843A (en) Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal element
JP6672801B2 (en) Liquid crystal alignment agent
JP6561475B2 (en) Liquid crystal aligning agent, liquid crystal aligning film and method for producing the same, liquid crystal display element, retardation film and method for producing the same
TWI711671B (en) Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, liquid crystal alignment film and liquid crystal element manufacturing method
TWI739929B (en) Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element and polymer
TWI746668B (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal element
CN106398721B (en) Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, method for producing liquid crystal alignment film, polymer, and diamine
TWI814748B (en) Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element and manufacturing method of liquid crystal alignment film
TWI785018B (en) Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element and polyorganosiloxane
TWI683845B (en) Liquid crystal alignment agent, liquid crystal alignment film and manufacturing method thereof, liquid crystal display element, and phase difference film and manufacturing method thereof
TWI791817B (en) Liquid crystal alignment agent and manufacturing method thereof, liquid crystal alignment film and manufacturing method thereof, and liquid crystal element
TWI791838B (en) Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, and method for manufacturing liquid crystal element
TWI835861B (en) Liquid crystal alignment agents, liquid crystal alignment films, liquid crystal elements and their manufacturing methods, optical films and polymers
TWI788550B (en) Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, and method for manufacturing liquid crystal element
JP5892330B2 (en) Liquid crystal alignment agent
WO2021005888A1 (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal element
JP2022173076A (en) Liquid crystal alignment agent, liquid crystal alignment film and manufacturing method for the same, liquid crystal device, liquid crystal display, and polymer
JP2023170991A (en) Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal element
JP2020052263A (en) Liquid crystal aligning agent, liquid crystal alignment film, optical film, liquid crystal element, and polymer