TWI591126B - Liquid crystal display element, manufacturing method and liquid crystal alignment agent - Google Patents

Description

液晶顯示元件及其製造方法、以及液晶配向劑 Liquid crystal display element, method of manufacturing the same, and liquid crystal alignment agent

本發明關於液晶顯示元件及其製造方法以及液晶配向劑，詳言之，關於具有藉由光配向法賦予液晶配向能力的液晶配向膜的液晶顯示元件及其製造方法以及用於得到該液晶顯示元件的液晶配向劑。 The present invention relates to a liquid crystal display device, a method for producing the same, and a liquid crystal alignment agent, and more particularly to a liquid crystal display device having a liquid crystal alignment film imparting liquid crystal alignment ability by a photo-alignment method, a method for producing the same, and a method for producing the liquid crystal display device. Liquid crystal alignment agent.

目前，作為液晶顯示元件，例如已知的有使液晶分子相對基板垂直配向的VA(垂直配向)型液晶顯示元件等。VA型液晶顯示元件是在不施加電壓的狀態下，使液晶分子相對基板表面垂直地配向；在施加電壓的狀態下，使液晶分子相對基板表面水準方向地配向。這種VA型液晶顯示元件目前例如藉由設置肋(rib)或電極狹縫，控制垂直配向狀態的液晶分子的傾斜方向。 At present, as the liquid crystal display element, for example, a VA (Vertical Alignment) type liquid crystal display element in which liquid crystal molecules are aligned perpendicularly to the substrate is known. In the VA liquid crystal display device, liquid crystal molecules are aligned perpendicularly to the substrate surface in a state where no voltage is applied, and liquid crystal molecules are aligned in the direction of the substrate surface in a state where a voltage is applied. Such a VA type liquid crystal display element is currently controlling the tilt direction of liquid crystal molecules in a vertically aligned state by, for example, providing ribs or electrode slits.

另外，近年來作為液晶配向技術，集中關注於對基板表面上形成的塗膜照射光，從而在該塗膜上賦予液晶配向能力的光配向法，以代替現有的摩擦法。根據該方法，具有可以使塗膜本身顯現出使液晶傾斜配向(歪斜配向)的性能，使液晶分子相對電壓變化的回應速度良好的優點。另外，還具有可以高精度地控制此時液晶分子相對基板表面的預傾角的優點。 Further, in recent years, as a liquid crystal alignment technique, attention has been focused on a light alignment method in which a coating film formed on a surface of a substrate is irradiated with light to impart a liquid crystal alignment ability to the coating film, instead of the conventional rubbing method. According to this method, there is an advantage that the coating film itself can exhibit the property of tilting and aligning the liquid crystal (skew alignment), and the response speed of the liquid crystal molecules with respect to the voltage change is good. In addition, there is an advantage that the pretilt angle of the liquid crystal molecules with respect to the substrate surface at this time can be controlled with high precision.

針對具有藉由這種光配向法形成的液晶配向膜的液晶顯示元件提出有各種方案(例如，參照專利文獻1或專利文獻2)。在專利文獻1、2中，公開了在兩塊基板各自的表面上，使用包含感放射線性聚有機矽氧烷的液晶配 向劑而形成塗膜，使用具有對這些塗膜照射光的光配向膜的基板，製作液晶顯示元件。 Various proposals have been made for a liquid crystal display element having a liquid crystal alignment film formed by such a photo-alignment method (for example, refer to Patent Document 1 or Patent Document 2). In Patent Documents 1 and 2, it is disclosed that a liquid crystal containing a radiation-sensitive polyorganosiloxane is used on the surface of each of the two substrates. A coating film is formed on the agent, and a liquid crystal display element is produced by using a substrate having a photo-alignment film that irradiates the coating film with light.

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

[專利文獻1]日本特許第4416054號公報[專利文獻2]日本特開2010-185001號公報 [Patent Document 1] Japanese Patent No. 4416054 (Patent Document 2) Japanese Patent Laid-Open Publication No. 2010-185001

近年來，具有進一步提高液晶顯示裝置實現高畫質的要求，為了實現這個目標，液晶顯示元件有必要進一步改善液晶分子對電壓變化的回應性(回應速度)。 In recent years, there has been a demand for further improvement in high image quality of liquid crystal display devices. In order to achieve this goal, it is necessary for liquid crystal display elements to further improve the responsiveness (response speed) of liquid crystal molecules to voltage changes.

本發明是鑒於上述問題而提出的，其主要目的在於提供液晶分子對電壓變化的回應性質優異的液晶顯示元件及其製造方法，用於製造該液晶顯示元件的液晶配向劑。 The present invention has been made in view of the above problems, and a main object thereof is to provide a liquid crystal display element excellent in response property of a liquid crystal molecule to a voltage change, and a method of manufacturing the same, and a liquid crystal alignment agent for producing the liquid crystal display element.

本發明為了實現上述目的，採用以下手段。 In order to achieve the above object, the present invention employs the following means.

本發明的液晶顯示元件是具有一對基板的液晶顯示元件，其特徵在於：在前述一對基板中的一個基板表面上，形成使液晶分子相對垂直該基板表面的方向傾斜配向的第1配向膜，並且在另一個基板表面上，形成使液晶分子垂直配向的第2配向膜，前述第1配向膜使用包含具有光配向性基的感放射線性化合物的液晶配向劑而形成，該光配向性基具有來自包含偶氮苯、二苯乙烯、α-亞胺基-β-酮酯、螺吡喃、螺、肉桂酸、查耳酮、芪唑 、亞苄基苄甲內醯胺(benzylidene phthalimidine)、香豆素、二苯基乙炔和蒽醌的群組中選出的至少一種化合物的結構。 The liquid crystal display device of the present invention is a liquid crystal display device having a pair of substrates, wherein a first alignment film is formed on the surface of one of the pair of substrates so that liquid crystal molecules are obliquely aligned with respect to a direction perpendicular to the surface of the substrate. And forming a second alignment film that vertically aligns the liquid crystal molecules on the surface of the other substrate, wherein the first alignment film is formed using a liquid crystal alignment agent containing a radiation-sensitive compound having a photo-alignment group, and the photo-alignment group is formed. Having azobenzene, stilbene, α-imino-β-ketoester, spiropyran, snail The structure of at least one compound selected from the group consisting of cinnamic acid, chalcone, carbazole, benzylidene phthalimidine, coumarin, diphenylacetylene and hydrazine.

另外，本發明的液晶顯示元件的製造方法是具有一對基板的液晶顯示元件的製造方法，其特徵在於：包括製造液晶顯示元件的製造步驟，該液晶顯示元件在前述一對基板中的一個基板表面上，形成使液晶分子相對垂直該基板表面的方向傾斜配向的第1配向膜，並且在另一個基板表面上，形成使液晶分子垂直配向的第2配向膜，前述第1配向膜使用包含具有光配向性基的感放射線性化合物的光配向用液晶配向劑而形成，該光配向性基具有來自包含偶氮苯、二苯乙烯、α-亞胺基-β-酮酯、螺吡喃、螺、肉桂酸、查耳酮、芪唑、亞苄基苄甲內醯胺、香豆素、二苯基乙炔和蒽醌的群組中選出的至少一種化合物的結構。 Further, a method of manufacturing a liquid crystal display element of the present invention is a method of manufacturing a liquid crystal display element having a pair of substrates, comprising: a manufacturing step of manufacturing a liquid crystal display element, wherein the liquid crystal display element is on one of the pair of substrates a first alignment film that aligns the liquid crystal molecules in a direction perpendicular to the surface of the substrate, and a second alignment film that vertically aligns the liquid crystal molecules is formed on the surface of the other substrate, and the first alignment film is used to include The photoalignment-based radiation-sensitive compound is formed by a liquid crystal alignment agent having a photo-alignment group derived from azobenzene, stilbene, α-imino-β-ketoester, spiropyran, screw The structure of at least one compound selected from the group consisting of cinnamic acid, chalcone, oxazole, benzalbenzamide, coumarin, diphenylacetylene and hydrazine.

根據本發明，在液晶顯示元件中，一對基板所具有的液晶配向膜中的一個作為使液晶分子相對垂直基板表面的方向傾斜配向的配向膜，另一個作為垂直配向膜，同時，前一個配向膜是藉由包含具有特定光配向性基的感放射線性化合物的液晶配向劑而形成，可以得到液晶分子相對電壓變化的液晶分子的回應特性優異的液晶顯示元件。 According to the invention, in the liquid crystal display device, one of the liquid crystal alignment films of the pair of substrates serves as an alignment film which obliquely aligns the liquid crystal molecules with respect to the direction of the vertical substrate surface, and the other serves as a vertical alignment film, and at the same time, the former alignment The film is formed by a liquid crystal alignment agent containing a radiation-sensitive compound having a specific photo-alignment group, and a liquid crystal display element having excellent response characteristics of liquid crystal molecules with respect to changes in voltage of liquid crystal molecules can be obtained.

在本發明中，前述光配向性基也可以具有來自肉桂酸的結構。另外，作為前述感放射線性化合物可以是包含具有前述光配向性基的聚有機矽氧烷的化合物，在這 種情況下，可以作為進一步對長時間光照射的耐久性(耐光性)優異的化合物。 In the present invention, the photo-alignment group may have a structure derived from cinnamic acid. Further, the radiation sensitive compound may be a compound containing a polyorganosiloxane having the above photoalignment group, and In this case, it can be used as a compound which is excellent in durability (light resistance) for further long-term light irradiation.

此處，作為本發明的液晶顯示元件的製造方法，具體地可以列舉出下述兩種方案。首先，作為第一種方案，可以列舉出下述方案，即前述製造步驟包括：在前述一對基板中的一個基板的表面上，使用前述光配向用液晶配向劑，形成第1塗膜的第1膜形成步驟；藉由對前述第1塗膜照射光，使該第1塗膜成為前述第1配向膜的光照射步驟；在前述一對基板中的另一個基板表面上，使用可以形成垂直配向膜的液晶配向劑，形成作為前述第2配向膜的第2塗膜的第2膜形成步驟；以及配置前述一對基板使前述第1配向膜和前述第2塗膜相對，而且在該基板間填充液晶分子，構成液晶胞的胞構成步驟。 Here, as a method of manufacturing the liquid crystal display element of the present invention, the following two aspects can be specifically exemplified. First, the first aspect of the invention includes the step of forming the first coating film by using the liquid alignment alignment agent for photoalignment on the surface of one of the pair of substrates. a film forming step of irradiating light onto the first coating film to cause the first coating film to be a light irradiation step of the first alignment film; and on the other substrate surface of the pair of substrates, vertical to be formed a liquid crystal alignment agent of an alignment film, a second film formation step of forming a second coating film as the second alignment film, and a pair of substrates disposed to face the first alignment film and the second coating film, and the substrate The liquid crystal molecules are filled to form a cell constituent step of the liquid crystal cell.

另外，作為第二種方案，可以列舉出下述方案，即前述製造步驟包括：在前述一對基板中的一個基板的表面上，使用前述光配向用液晶配向劑，形成塗膜的第1膜形成步驟；在前述一對基板中的另一個基板表面上，使用實質上不含具有光配向性基的化合物的液晶配向劑，形成前述第2配向膜的第2膜形成步驟；配置前述一對基板使前述塗膜和前述第2配向膜相對，而且在該基板間填充液晶分子，構成液晶胞的胞構成步驟；以及對前述胞構成步驟構成的前述液晶胞，在前述一對基板間施加電壓的狀態下，照射光的光照射步驟。在這兩種方案中，從液晶分子對電壓變化的回應性的觀點出發，更佳為上述第一種方案。 In addition, as a second aspect, the manufacturing process includes forming a first film of a coating film by using the liquid alignment alignment agent for photoalignment on the surface of one of the pair of substrates. a forming step; forming a second film forming step of forming the second alignment film on the surface of the other of the pair of substrates by using a liquid crystal alignment agent that does not substantially contain a compound having a photo-alignment group; and disposing the pair a substrate in which the coating film and the second alignment film are opposed to each other, and a liquid crystal molecule is filled between the substrates to form a cell structure of the liquid crystal cell; and a voltage is applied between the pair of substrates in the liquid crystal cell including the cell formation step In the state of the light, the light irradiation step of the illumination light. Among the two schemes, the first scheme described above is more preferable from the viewpoint of the responsiveness of the liquid crystal molecules to the voltage change.

[實施發明之形態] [Formation of the Invention]

[液晶顯示元件] [Liquid Crystal Display Element]

以下，適當地參照附圖對本發明的液晶顯示元件進行說明。圖1是表示本發明的液晶顯示元件的一個例子的示意圖。 Hereinafter, the liquid crystal display element of the present invention will be described with reference to the drawings as appropriate. Fig. 1 is a schematic view showing an example of a liquid crystal display element of the present invention.

如圖1所示，液晶顯示元件10具有一對基板11a、11b，它們相互分開地配置。基板11a、11b可以藉由例如由浮法玻璃、鈉玻璃等玻璃；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(脂環式烯烴)等塑膠形成的透明基板構成。 As shown in FIG. 1, the liquid crystal display element 10 has a pair of substrates 11a and 11b which are disposed apart from each other. The substrates 11a, 11b may be made of, for example, glass such as float glass or soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly(alicyclic olefin) It is composed of a transparent substrate formed of plastic.

在一對基板中，在一個基板11a上，和另一個基板11b對面側的表面上，設置第1電極12。作為第1電極12只要是一般作為液晶顯示元件的電極使用的，就沒有特別的限定，可以使用例如透明導電膜。作為透明導電膜，可以使用由氧化錫(SnO₂)形成的NESA膜(美國PPG公司的註冊商標)、由氧化銦-氧化錫(In₂O₃-SnO₂)形成的ITO膜等。 In the pair of substrates, the first electrode 12 is provided on the surface of the one substrate 11a opposite to the other substrate 11b. The first electrode 12 is not particularly limited as long as it is generally used as an electrode of a liquid crystal display element, and for example, a transparent conductive film can be used. As the transparent conductive film, a NESA film (registered trademark of PPG, USA) formed of tin oxide (SnO ₂ ), an ITO film formed of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), or the like can be used.

在第1電極12中，在和基板11b對面側的表面上，形成第1配向膜13。第1配向膜13由相對垂直基板表面的方向，可以使液晶分子傾斜配向的有機薄膜而構成。換言之，如圖1所示，第1配向膜13中，液晶分子從基板表面伸出的角度(預傾角)是θ(0<θ<90°)。第1配向膜13的膜厚較佳為0.001~1μm，更佳為0.005~0.5μm。 In the first electrode 12, the first alignment film 13 is formed on the surface on the side opposite to the substrate 11b. The first alignment film 13 is formed of an organic thin film which can align the liquid crystal molecules in a direction opposite to the surface of the vertical substrate. In other words, as shown in FIG. 1, in the first alignment film 13, the angle (pretilt angle) at which liquid crystal molecules protrude from the surface of the substrate is θ (0 < θ < 90°). The film thickness of the first alignment film 13 is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

在基板11b中，在和基板11a的對面側的表面上，設置第2電極14。作為該第2電極14可以使用和第1電極12 例示的透明導電膜同樣的電極。例如，在將本發明的液晶顯示元件應用於使用TFT的方式時，可以將第1電極12和第2電極14中的一個作為對向電極，將另一個作為像素電極。 In the substrate 11b, the second electrode 14 is provided on the surface on the opposite side to the substrate 11a. As the second electrode 14, the first electrode 12 can be used. The same electrode of the exemplified transparent conductive film. For example, when the liquid crystal display device of the present invention is applied to a method using a TFT, one of the first electrode 12 and the second electrode 14 can be used as a counter electrode, and the other can be used as a pixel electrode.

在第2電極14中，在和基板11a對面側的表面形成第2配向膜15。第2配向膜15藉由使液晶分子相對基板表面垂直配向的有機薄膜構成。第2配向膜15的膜厚較佳為0.001~1μm，更佳為0.005~0.5μm。 In the second electrode 14, the second alignment film 15 is formed on the surface on the side opposite to the substrate 11a. The second alignment film 15 is formed of an organic thin film in which liquid crystal molecules are aligned perpendicularly to the surface of the substrate. The film thickness of the second alignment film 15 is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

在第1配向膜13和第2配向膜15間，形成填充液晶分子16的液晶層17。作為液晶分子16，較佳為使用例如向列型液晶、碟型液晶等。特別是，較佳為具有負的介電各向異性的向列型液晶，具體而言，可以使用例如二氰基苯類液晶、噠類液晶、西夫鹼類液晶、氧化偶氮基類液晶、聯苯類液晶、苯基環己烷類液晶等。液晶層17的厚度較佳為1.2~8.0μm，更佳為1.3~5.5μm，進一步更佳為1.4~4.0μm。 A liquid crystal layer 17 filled with the liquid crystal molecules 16 is formed between the first alignment film 13 and the second alignment film 15. As the liquid crystal molecules 16, for example, a nematic liquid crystal, a dish liquid crystal or the like is preferably used. In particular, a nematic liquid crystal having a negative dielectric anisotropy is preferable, and specifically, for example, a dicyanobenzene liquid crystal or a ruthenium can be used. Liquid crystal, Schiff base liquid crystal, oxidized azo liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, and the like. The thickness of the liquid crystal layer 17 is preferably 1.2 to 8.0 μm, more preferably 1.3 to 5.5 μm, still more preferably 1.4 to 4.0 μm.

在一對基板11a、11b的外表面分別安裝偏光板18、19。作為偏光板18、19，可以使用將聚乙烯醇延展配向的同時，用醋酸纖維素保護膜夾住吸收碘稱作「H膜」的偏光膜形成的偏光板或由H膜本身形成的偏光板。 Polarizing plates 18 and 19 are attached to the outer surfaces of the pair of substrates 11a and 11b, respectively. As the polarizing plates 18 and 19, a polarizing plate formed by sandwiching a polarizing film called absorbing iodine called "H film" with a cellulose acetate protective film and a polarizing plate formed of the H film itself can be used. .

接著，對本發明中的第1配向膜13和第2配向膜15進行說明。本發明中的第1配向膜13和第2配向膜15分別使用包含聚醯胺酸和聚醯亞胺的至少任意一種聚合物作為聚合物成分的液晶配向劑(第1配向劑、第2配向劑)而形成。 Next, the first alignment film 13 and the second alignment film 15 in the present invention will be described. In the first alignment film 13 and the second alignment film 15 in the present invention, a liquid crystal alignment agent (first alignment agent, second alignment) containing at least one polymer of polyamic acid and polyimine as a polymer component is used. Formed by the agent).

[第1配向劑] [1st alignment agent]

用於形成第1配向膜13的第1配向劑包含具有光配向性基的感放射線性化合物構成。 The first alignment agent for forming the first alignment film 13 is composed of a radiation-sensitive compound having a photo-alignment group.

<感放射線性化合物> <Sense Radiation Compound>

本發明中的感放射線性化合物所具有的光配向性基是藉由光照射對膜賦予各向異性的官能基，在本發明中，特別是藉由產生光異性化反應和光二聚化反應的至少任意一種，對膜賦予各向異性的基。 The photo-alignment group possessed by the radiation-sensitive compound in the present invention is a functional group which imparts anisotropy to the film by light irradiation, and in the present invention, in particular, by generating photo-isoning reaction and photodimerization reaction. At least any one of them imparts an anisotropic group to the film.

作為形成第1配向膜13時適合使用的光配向性基，具體的是具有來自包含偶氮苯、二苯乙烯、α-亞胺基-β-酮酯、螺吡喃、螺、肉桂酸、查耳酮、芪唑、亞苄基苄甲內醯胺、香豆素、二苯基乙炔和蒽醌的群組中選出的至少一種化合物的結構的基。作為上光配向性基，它們之中，特佳為具有來自肉桂酸結構的基。作為來自肉桂酸的結構，具體地可以用下述式(c1)所示， The photo-alignment group which is suitably used when the first alignment film 13 is formed specifically includes azobenzene, stilbene, α-imino-β-ketoester, spiropyran, and snail. a group of structures of at least one compound selected from the group consisting of cinnamic acid, chalcone, carbazole, benzalbenzamide, coumarin, diphenylacetylene and hydrazine. As the glazing group, among them, it is particularly preferred to have a group derived from a cinnamic acid structure. As the structure derived from cinnamic acid, specifically, it can be represented by the following formula (c1).

式中，R是碳原子數為1~6的烷基或烷氧基、氟原子或氰基。a是0~4的整數，a為2~4時，多個R各自獨立地具有上述定義。「^＊」表示連接鍵。 In the formula, R is an alkyl group having 1 to 6 carbon atoms or an alkoxy group, a fluorine atom or a cyano group. a is an integer of 0 to 4, and when a is 2 to 4, a plurality of Rs each independently have the above definition. ^"*" Indicates a bond.

作為上述式(c1)的R中的碳原子數為1~6的烷基，可以列舉出例如甲基、乙基、丁基等。另外，作為碳原子數為1~6的烷氧基，可以列舉出例如甲氧基、乙氧基、丙氧基等。 The alkyl group having 1 to 6 carbon atoms in R in the above formula (c1) may, for example, be a methyl group, an ethyl group or a butyl group. Further, examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

作為a，較佳為0或1，更佳為0。 As a, it is preferably 0 or 1, more preferably 0.

作為具有上述式(c1)所示的結構的光配向性基，具體地較佳為下述式(c1-1)或式(c1-2)所示的基， The photo-alignment group having the structure represented by the above formula (c1) is specifically preferably a group represented by the following formula (c1-1) or formula (c1-2).

式中，R¹和R³各自獨立地是氫原子、具有脂環式基的碳原子數為3~40的1價有機基、或者具有氟原子的碳原子數為1~40的烷基。R²和R⁴各自獨立地是亞甲基、-Si(CH₃)₂-、-CH=CH-、-C≡C-或具有環式結構的2價基。X¹、X²和X³各自獨立地是單鍵、氧原子、-CO-、-COO-、-NR^a-、-CO-NR^a、-NR^a-CO-O-、-NR^a-CO-NR^a-、-O-CO-O-(其中，R^a各自獨立地是氫原子或碳原子數為1~4的烷基)。X⁴是單鍵或氧原子。b和c各自獨立地是0~3的整數，b、c為2或3時，多個R²、R⁴、X²、X⁴各自獨立地具有上述定義。R、a和「^＊」分別和上述式(c1)的定義相同。 In the formula, R ¹ and R ³ each independently represent a hydrogen atom, a monovalent organic group having 3 to 40 carbon atoms having an alicyclic group, or an alkyl group having 1 to 40 carbon atoms having a fluorine atom. R ² and R ⁴ are each independently methylene, -Si(CH ₃ ) ₂ -, -CH=CH-, -C≡C- or a divalent group having a cyclic structure. X ¹ , X ² and X ³ are each independently a single bond, an oxygen atom, -CO-, -COO-, -NR ^a -, -CO-NR ^a , -NR ^a -CO-O-, -NR ^a - ^{CO-NR a -, - O} -CO-O- ( wherein, R ^a is independently a hydrogen atom or an alkyl group having a carbon number of 1 to 4). X ⁴ is a single bond or an oxygen atom. b and c are each independently an integer of 0 to 3, and when b and c are 2 or 3, a plurality of R ² , R ⁴ , X ² and X ⁴ each independently have the above definition. R, a, and " ^* " are the same as defined in the above formula (c1).

作為上述式(c1-1)的R¹和上述式(c1-2)的R³中的具有脂環式基的碳原子數為3~40的1價有機基，可以列舉出例如環己基甲基、環己基丙基、環己基戊基、環己基庚基、環辛基、金剛烷基、膽甾烷基、膽甾烯基、羊毛甾烷基等。 The R ^{1 of the} above formula (c1-1) and the monovalent organic group having 3 to 40 carbon atoms having an alicyclic group in R ³ of the above formula (c1-2) include, for example, cyclohexyl group. Base, cyclohexylpropyl, cyclohexylpentyl, cyclohexylheptyl, cyclooctyl, adamantyl, cholestyl, cholesteryl, lanthyl, and the like.

作為R¹和R³中的碳原子數為1~40的烷基，可以是直鏈狀的，也可以是支鏈狀的。作為該烷基，較佳為碳原子數為1~20，具體地可以列舉出例如甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基、正十七烷基、正十八烷基、正十九烷基、正二十烷基等。該烷基如果從可以顯現出良好的液晶配向性的觀點出發，它們之中，較佳為碳原子數為1~12的直鏈狀的烷基，特佳為碳原子數為4~12的直鏈狀的烷基。 The alkyl group having 1 to 40 carbon atoms in R ¹ and R ³ may be linear or branched. The alkyl group preferably has 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, and an n-octyl group. , n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl , n-octadecyl, n-nonadecyl, n-icosyl and the like. From the viewpoint of exhibiting good liquid crystal alignment, the alkyl group is preferably a linear alkyl group having 1 to 12 carbon atoms, particularly preferably 4 to 12 carbon atoms. Linear alkyl group.

R¹和R³中的烷基的碳原子所具有的至少1個氫原子可以被氟原子取代。作為這種氟烷基的具體例子，可以列舉出例如3,3,3-三氟丙基、4,4,4-三氟丁基、4,4,5,5,5-五氟戊基、4,4,5,5,6,6,6-七氟己基、3,3,4,4,5,5,5-七氟戊基、2,2,2-三氟乙基、2,2,3,3,3-五氟丙基、2-(全氟丁基)乙基、2-(全氟辛基)乙基、2-(全氟癸基)乙基等。作為R¹和R³中的氟烷基，特別是從使液晶配向性良好的觀點出發，較佳為碳原子數為3~6的直鏈狀的。 At least one hydrogen atom of the carbon atom of the alkyl group in R ¹ and R ³ may be substituted by a fluorine atom. Specific examples of such a fluoroalkyl group include, for example, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,5,5,5-pentafluoropentyl. , 4,4,5,5,6,6,6-heptafluorohexyl, 3,3,4,4,5,5,5-heptafluoropentyl, 2,2,2-trifluoroethyl, 2 2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 2-(perfluorooctyl)ethyl, 2-(perfluorodecyl)ethyl, and the like. R ¹ and R ³ fluoroalkyl group, in particular from a good liquid crystal alignment property point of view, preferred is a linear carbon atoms of 3 to 6.

上述式(c1-1)的R²和上述式(c1-2)的R⁴中的具有環式結構的2價基，可以列舉出2價芳香族基、脂環式基、雜環式基、稠環式基，而且也可以是結合多個這些基形成的2價基。 The divalent group having a cyclic structure in R ^{2 of the} above formula (c1-1) and R ⁴ in the above formula (c1-2) may, for example, be a divalent aromatic group, an alicyclic group or a heterocyclic group. A fused ring group, and may also be a divalent group formed by combining a plurality of these groups.

它們之中，分別是作為2價芳香族基，可以列舉出例如1,4-伸苯基、2-氟-1,4-伸苯基、3-氟-1,4-伸苯基、2,3,5,6-四氟-1,4-伸苯基等； 作為2價脂環式基，可以列舉出例如1,4-伸環己基、2-氟-1,4-伸環己基、3-氟-1,4-伸環己基、2,3,5,6-四氟-1,4-伸環己基等；作為2價雜環式基，可以列舉出例如1,4-伸吡啶基、2,5-伸吡啶基、1,4-伸呋喃基等；作為2價稠環式基，可以列舉出例如伸萘基等。 Among them, each is a divalent aromatic group, and examples thereof include 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, and 2 , 3,5,6-tetrafluoro-1,4-phenylene, etc.; Examples of the divalent alicyclic group include, for example, 1,4-cyclohexylene, 2-fluoro-1,4-cyclohexylene, 3-fluoro-1,4-cyclohexylene, 2,3,5. 6-tetrafluoro-1,4-cyclohexylene and the like; examples of the divalent heterocyclic group include, for example, 1,4-pyridylpyridyl, 2,5-extended pyridyl, 1,4-furfuryl, and the like. The divalent fused ring group may, for example, be a naphthyl group or the like.

作為X¹、X²和X³，分別較佳為單鍵、氧原子或-COO-。 As X ¹ , X ² and X ³ , each is preferably a single bond, an oxygen atom or -COO-.

b較佳為0~2的整數，更佳為1或2。 b is preferably an integer of 0 to 2, more preferably 1 or 2.

作為上述式(c1-1)所示的基，具體地可以例示下述式(c1-1-1)~(c1-1-28)所示的基， Specific examples of the group represented by the above formula (c1-1) include the groups represented by the following formulas (c1-1-1) to (c1-1-28).

式中，R¹和「^＊」分別和式(c1-1)的定義相同，d是1~10的整數。 In the formula, R ¹ and " ^* " are respectively the same as the definition of the formula (c1-1), and d is an integer of 1 to 10.

作為上述式(c1-2)所示的基，可以例示下述式(c1-2-1)~(c1-2-4)所示的基， The group represented by the following formula (c1-2) can be exemplified by the groups represented by the following formulas (c1-2-1) to (c1-2-4).

式中，R³和「^＊」分別和式(c1-2)的定義相同。 In the formula, R ³ and " ^* " are the same as defined in the formula (c1-2), respectively.

作為具有光配向性基的感放射線性化合物，較佳為直接或藉由連接基連接上述光配向性基的聚合物。作為該聚合物，可以列舉出例如在聚醯胺酸和聚醯亞胺的至少任一種聚合物上連接上述光配向性基形成的聚合物，在和聚醯胺酸和聚醯亞胺不同的聚合物上連接上述光配向性基形成的聚合物。在後一種情況下，作為具有光配向性基的聚合物的基本骨架，可以列舉出例如聚(甲基)丙烯酸酯、聚(甲基)丙烯醯胺、聚乙烯醚、聚烯烴、聚有機矽氧烷等。另外，在本說明書中，所述的「(甲基)丙烯基」是指丙烯基和甲基丙烯基。 As the radiation-sensitive compound having a photo-alignment group, a polymer in which the above photo-alignment group is bonded directly or via a linking group is preferred. The polymer may be, for example, a polymer formed by attaching the above photo-alignment group to at least one of polyacrylic acid and polyamidiamine, and is different from polyglycine and polyimine. A polymer formed by attaching the above photo-alignment group to the polymer. In the latter case, examples of the basic skeleton of the polymer having a photo-alignment group include poly(meth)acrylate, poly(meth)acrylamide, polyvinyl ether, polyolefin, and polyorganoquinone. Oxytomane, etc. In the present specification, the term "(meth)acrylyl" means a propylene group and a methacryl group.

在可以有效地提高液晶顯示元件中液晶分子對電壓變化的回應速度方面，作為感放射線性化合物較佳為以聚醯胺酸、聚醯亞胺或聚有機矽氧烷作為基本骨架。另外，它們之中，特佳為聚有機矽氧烷。藉由在第1配向劑中含有具有上述光配向性基的聚矽氧烷，從而使液晶顯示元件中，液晶分子對電壓變化的回應速度更好，並且對長時間的光照射的耐久性(耐光性)也更好。 In terms of the speed at which the liquid crystal molecules in the liquid crystal display element can effectively increase the response to voltage changes, the radiation sensitive compound is preferably a polyamine, a polyamidene or a polyorganosiloxane. Further, among them, polyorganosiloxane is particularly preferred. By including the polyoxyalkylene having the above photo-alignment group in the first alignment agent, the liquid crystal molecules have a higher response speed to voltage change in the liquid crystal display element, and durability against long-term light irradiation ( Lightfastness) is also better.

<特定聚有機矽氧烷> <Specific polyorganosiloxanes>

具有上述光配向性基的聚有機矽氧烷(以下，也稱作特定聚有機矽氧烷)，例如可以藉由使具有環氧基的聚有 機矽氧烷(聚矽氧烷前驅物)和具有與環氧基反應的基和上述光配向性基的化合物(以下，也稱作反應性化合物X1)反應得到。 A polyorganosiloxane having the above photo-alignment group (hereinafter, also referred to as a specific polyorganosiloxane) can be, for example, obtained by having an epoxy group The oxime (polyoxane precursor) is obtained by reacting a compound having a group reactive with an epoxy group and the above photo-alignment group (hereinafter also referred to as a reactive compound X1).

(聚矽氧烷前驅物) (polyoxane precursor)

聚矽氧烷前驅物例如可以藉由使具有環氧基和水解性基的矽烷化合物(1)較佳在有機溶劑、水和催化劑的存在下，水解、縮合得到。 The polyoxyalkylene precursor can be obtained, for example, by hydrolyzing and condensing a decane compound (1) having an epoxy group and a hydrolyzable group in the presence of an organic solvent, water and a catalyst.

作為矽烷化合物(1)，可以列舉出例如3-縮水甘油氧基丙基三甲氧基矽烷、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甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基二甲基甲氧基矽烷、3-縮水甘油氧基丙基二甲基乙氧基矽烷、2-縮水甘油氧基乙基三甲氧基矽烷、2-縮水甘油氧基乙基三乙氧基矽烷、2-縮水甘油氧基乙基甲基二甲氧基矽烷、2-縮水甘油氧基乙基甲基二乙氧基矽烷、2-縮水甘油氧基乙基二甲基甲氧基矽烷、2-縮水甘油氧基乙基二甲基乙氧基矽烷、4-縮水甘油氧基丁基三甲氧基矽烷、4-縮水甘油氧基丁基三乙氧基矽烷、4-縮水甘油氧基丁基甲基二甲氧基矽烷、4-縮水甘油氧基丁基甲基二乙氧基矽烷、4-縮水甘油氧基丁基二甲基甲氧基矽烷、4-縮水甘油氧基丁基二甲基乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷、3-(3,4-環氧環己基)丙基三甲氧基矽烷、3-(3,4-環氧環己基)丙基三乙氧基矽烷等；可以使用選自於它們之中的一種以上。 The decane compound (1) may, for example, be 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane or 3-glycidoxypropylmethyldimethacrylate. Oxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyldimethylmethoxydecane, 3-glycidoxypropyldimethylethoxy Decane, 2-glycidoxyethyltrimethoxydecane, 2-glycidoxyethyltriethoxydecane, 2-glycidoxyethylmethyldimethoxydecane, 2-glycidyloxy Ethylethyldiethoxy decane, 2-glycidoxyethyl dimethyl methoxy decane, 2-glycidoxyethyl dimethyl ethoxy decane, 4-glycidoxy butyl Trimethoxy decane, 4-glycidoxy butyl triethoxy decane, 4-glycidoxy butyl methyl dimethoxy decane, 4-glycidoxy butyl methyl diethoxy decane, 4- Glycidoxybutyl dimethyl methoxy decane, 4-glycidoxy butyl dimethyl ethoxy decane, 2-(3,4-epoxycyclohexyl)ethyl three Oxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3-(3,4- Epoxycyclohexyl)propyltriethoxydecane or the like; one or more selected from them may be used.

用於合成聚矽氧烷前驅物的矽烷化合物，可以只是矽烷化合物(1)，除了矽烷化合物(1)以外，還可以包含沒有環氧基的矽烷化合物(以下，稱作「矽烷化合物(2)」)。 The decane compound for synthesizing the polyoxane precursor may be a decane compound (1), and may contain a decane compound having no epoxy group in addition to the decane compound (1) (hereinafter, referred to as "decane compound (2)) ").

作為可以在這裡使用的矽烷化合物(2)，可以列舉出具有1個矽原子的矽烷化合物，以及用商品名表示的例如KC-89以及X-21-3153(都是信越化學工業(股)製造)等部分縮合物等。作為矽烷化合物(2)較佳的具體例子，可以列舉出四甲氧基矽烷、四乙氧基矽烷、甲基三甲氧基矽烷、甲基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、烯丙基三甲氧基矽烷、烯丙基三乙氧基矽烷、苯基三甲氧基矽烷、苯基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、巰基甲基三甲氧基矽烷、巰基甲基三乙氧基矽烷、二甲基二甲氧基矽烷或二甲基二乙氧基矽烷。 Examples of the decane compound (2) which can be used herein include a decane compound having one ruthenium atom, and, for example, KC-89 and X-21-3153 which are represented by trade names (both manufactured by Shin-Etsu Chemical Co., Ltd.). ) a partial condensate or the like. Preferable specific examples of the decane compound (2) include tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, and 3-(methyl) propylene oxime. Oxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, allyltrimethoxydecane, Allyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, 3-mercaptopropyl trimethoxy decane, 3-mercaptopropyl triethoxy decane, decyl methyl trimethoxy Alkane, mercaptomethyltriethoxydecane, dimethyldimethoxydecane or dimethyldiethoxydecane.

聚矽氧烷前驅物的環氧當量較佳為100~10,000g/mol，更佳為150~1,000g/mol，特佳為150~300g/mol。因此，在合成聚矽氧烷前驅物時，矽烷化合物(1)和矽烷化合物(2)的使用比例較佳為製備得到的聚有機矽氧烷的環氧當量在上述範圍內。合成上述聚矽氧烷前驅物時，較佳為只使用矽烷化合物(1)。 The epoxy equivalent of the polyoxyalkylene precursor is preferably from 100 to 10,000 g/mol, more preferably from 150 to 1,000 g/mol, particularly preferably from 150 to 300 g/mol. Therefore, in the synthesis of the polyoxane precursor, the use ratio of the decane compound (1) and the decane compound (2) is preferably such that the epoxy equivalent of the prepared polyorganosiloxane is within the above range. When synthesizing the above polyoxyalkylene precursor, it is preferred to use only the decane compound (1).

作為可以用於合成聚矽氧烷前驅物的有機溶劑，可以列舉出例如烴、酮、酯、醚、醇等，它們之中較佳為 非水溶性的。另外，作為上述有機溶劑，可以單獨或將兩種以上混合使用。另外，相對於100重量份全部的矽烷化合物，有機溶劑的用量較佳為10~10,000重量份，更佳為50~1,000重量份。 Examples of the organic solvent which can be used for the synthesis of the polyoxane precursor include a hydrocarbon, a ketone, an ester, an ether, an alcohol, etc., among which are preferably Water insoluble. Further, the organic solvent may be used singly or in combination of two or more. Further, the organic solvent is preferably used in an amount of 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, per 100 parts by weight of the total of the decane compound.

合成聚矽氧烷前驅物時的水的用量，相對於全部矽烷化合物較佳為0.5~100倍莫耳，更佳為1~30倍莫耳。 The amount of water used in the synthesis of the polyoxyalkylene precursor is preferably from 0.5 to 100 moles, more preferably from 1 to 30 moles, per mole of the decane compound.

作為用於合成聚矽氧烷前驅物的催化劑，可以列舉出例如酸、鹼金屬化合物、有機鹼，鈦化合物、鋯化合物等。它們之中，作為鹼金屬化合物，可以列舉出例如氫氧化鈉、氫氧化鉀等；作為有機鹼，可以列舉出例如三乙胺、二乙基胺、哌等有機一級胺、有機二級胺，三乙胺、吡啶、4-二甲基胺基吡啶等有機三級胺；氫氧化四甲基銨等有機四級胺等。作為上述催化劑，它們之中，較佳為鹼金屬化合物或有機鹼，更佳為有機溶劑。另外，作為有機鹼，特佳為有機三級胺或有機四級胺。 Examples of the catalyst for synthesizing the polyoxyalkylene precursor include an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound, and the like. Among them, examples of the alkali metal compound include sodium hydroxide and potassium hydroxide; and examples of the organic base include triethylamine, diethylamine and piperidine. The organic primary amine, the organic secondary amine, the organic tertiary amine such as triethylamine, pyridine or 4-dimethylaminopyridine; the organic quaternary amine such as tetramethylammonium hydroxide. Among the above catalysts, among them, an alkali metal compound or an organic base is preferred, and an organic solvent is more preferred. Further, as the organic base, an organic tertiary amine or an organic quaternary amine is particularly preferred.

在使用有機鹼作為催化劑時，其用量可以根據有機鹼的種類、溫度等反應條件適當設定，例如，相對全部矽烷化合物，較佳為0.01~3倍莫耳，更佳為0.05~1倍莫耳。 When an organic base is used as the catalyst, the amount thereof can be appropriately set depending on the reaction conditions such as the kind and temperature of the organic base. For example, it is preferably 0.01 to 3 moles, more preferably 0.05 to 1 mole, relative to the total of the decane compound. .

聚矽氧烷前驅物的合成反應(水解、縮合反應)例如，將矽烷化合物(1)和根據需要使用的矽烷化合物(2)溶解到有機溶劑中，將該溶液與作為催化劑的有機鹼和水混合，藉由例如油浴等加熱進行。該水解縮合反應時，期待加熱溫度較佳為130℃以下，更佳為40~100℃，較佳為加熱0.5~12小時，更佳為加熱1~8小時。加熱時，可以攪 拌混合液，在回流下進行。另外，反應結束後，較佳為用水洗滌從反應液分取的有機溶劑層。洗滌進行到洗滌後的水層為中性之後，根據需要將有機溶劑層用無水硫酸鈣、分子篩等乾燥劑乾燥後，除去溶劑。由此，可以得到所需要的聚矽氧烷前驅物。 Synthesis reaction (hydrolysis, condensation reaction) of a polyoxyalkylene precursor, for example, dissolving a decane compound (1) and a decane compound (2) used as needed in an organic solvent, the solution and an organic base and water as a catalyst The mixing is carried out by heating, for example, an oil bath. In the hydrolysis condensation reaction, the heating temperature is preferably 130 ° C or lower, more preferably 40 to 100 ° C, preferably 0.5 to 12 hours, more preferably 1 to 8 hours. When heated, it can be stirred The mixture was mixed and refluxed. Further, after completion of the reaction, it is preferred to wash the organic solvent layer separated from the reaction liquid with water. After the washing is carried out until the aqueous layer after washing is neutral, the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve as necessary, and then the solvent is removed. Thereby, the desired polyoxyalkylene precursor can be obtained.

聚矽氧烷前驅物藉由凝膠滲透層析法測定的聚苯乙烯換算的重量平均分子量Mw較佳為1,000~1,000,000，更佳為1,500~300,000。 The polystyrene-equivalent precursor has a polystyrene-equivalent weight average molecular weight Mw measured by gel permeation chromatography of preferably 1,000 to 1,000,000, more preferably 1,500 to 300,000.

另外，作為聚矽氧烷前驅物在使用市售的商品時，可以使用例如DMS-E01、DMS-E12、DMS-E21、EMS-32(以上，Chisso(股)製造)等。 Further, when a commercially available product is used as the polyoxane precursor, for example, DMS-E01, DMS-E12, DMS-E21, EMS-32 (above, Chisso) can be used.

(反應性化合物X1) (Reactive Compound X1)

反應性化合物X1是具有和聚矽氧烷前驅物所具有的環氧基反應的基以及上述光配向性基的化合物。作為和環氧基反應的基較佳為羧基。作為該反應性化合物X的具體例子，可以列舉出上述式(c1-1-1)~(c1-1-28)所示的基中的連接鍵和羥基連接的化合物，上述式(c1-2-1)~(c1-2-4)所示的基中的連接鍵和羧基連接的化合物。 The reactive compound X1 is a compound having a group reactive with an epoxy group possessed by a polyoxane precursor and the above photo-alignment group. The group which reacts with the epoxy group is preferably a carboxyl group. Specific examples of the reactive compound X include a compound in which a bond in the group represented by the above formulas (c1-1-1) to (c1-1-28) is bonded to a hydroxyl group, and the above formula (c1-2) a compound in which a linking bond and a carboxyl group are bonded to a group represented by -1) to (c1-2-4).

相對聚矽氧烷前驅物所具有的矽原子，合成聚有機矽氧烷時使用的反應性化合物X1的比例較佳為5~80莫耳%，更佳為10~65莫耳%，進一步更佳為15~50莫耳%。 The ratio of the reactive compound X1 used in the synthesis of the polyorganosiloxane is preferably from 5 to 80 mol%, more preferably from 10 to 65 mol%, further to the rhodium atom of the polyoxane precursor. Good for 15~50%.

聚矽氧烷前驅物和反應性化合物X1反應時，可以將沒有光配向性基而具有和環氧基反應的基的化合物(以下，稱作其他反應性化合物X2)和反應性化合物X1一起含有。作為其他反應性化合物X2，可以列舉出例如[1] 有助於顯現出得到的液晶配向膜的預傾角的化合物(X2-1)、[2]具有選自於藉由光照射產生自由基的結構和有光增敏功能的結構中的至少一種的化合物(X2-2)、[3]上述以外的其他化合物(X2-3)。 When the polyoxyalkylene precursor is reacted with the reactive compound X1, a compound having a group having no photo-alignment group and having a group reactive with an epoxy group (hereinafter referred to as another reactive compound X2) and the reactive compound X1 may be contained together. . As another reactive compound X2, for example, [1] The compound (X2-1), [2] which contributes to the pretilt angle of the obtained liquid crystal alignment film has at least one selected from the group consisting of a structure which generates a radical by light irradiation and a structure which has a photo-sensitization function. Compound (X2-2), [3] other compound (X2-3) other than the above.

[1]其他反應性化合物(X2-1) [1] Other reactive compounds (X2-1)

作為其他反應性化合物(X2-1)，可以使用例如下述式(x2-1)所示的化合物，A¹-L⁰-L¹-Z (x2-1) As the other reactive compound (X2-1), for example, a compound represented by the following formula (x2-1), A ¹ -L ⁰ -L ¹ -Z (x2-1) can be used.

式中，A¹是碳原子數為1~30的烷基、可以被碳原子數為1~20的烷基或烷氧基取代的碳原子數為3~10的環烷基、或者具有甾類骨架的碳原子數為17~51的烴基。其中，A¹中的烷基和烷氧基中的氫原子的至少一部分可以被取代。L⁰是單鍵、^＊-O-、^＊-COO-或^＊-OCO-，帶「^＊」的連接基和A¹連接。L¹是單鍵、碳原子數為1~20的伸烷基、伸苯基、伸聯苯基、伸環己基、伸二環己基或下述式(L¹-1)或(L¹-2)所示的基， In the formula, A ¹ is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms which may be substituted by an alkyl group or an alkoxy group having 1 to 20 carbon atoms, or a fluorene group; The skeleton of the skeleton has a hydrocarbon group of 17 to 51. Here, at least a part of the hydrogen atom in the alkyl group and the alkoxy group in A ¹ may be substituted. L ⁰ is a single ^{bond, * -O-, *} -COO- or ^* -OCO-, with ^"*" of the linker and A ¹ is connected. L ¹ is a single bond, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a phenyl group, a cyclohexylene group, a dicyclohexylene group or a formula (L ¹ -1) or (L ¹ -2) ) the base shown,

式中，「^＊」表示連接到Z上的連接鍵。 In the formula, " ^* " indicates the connection key connected to Z.

Z是能夠和環氧基反應形成連接基的1價有機基。其中，L¹是單鍵時，L⁰是單鍵。 Z is a monovalent organic group capable of reacting with an epoxy group to form a linking group. Wherein, when L ¹ is a single bond, L ⁰ is a single bond.

作為上述式(4)的A¹中的碳原子數為1~30的烷基，可以是直鏈狀的，也可以是支鏈狀的，可以列舉出例如甲基、乙基、正丙基、異丙基、正丁基、二級丁基、三級丁基、正戊基、3-甲基丁基、2-甲基丁基、1-甲基丁基、 2,2-二甲基丙基、正己基、4-甲基戊基、3-甲基戊基、2-甲基戊基、1-甲基戊基、3,3-二甲基丁基、2,3-二甲基丁基、1,3-二甲基丁基、2,2-二甲基丁基、1,2-二甲基丁基、1,2-二甲基丁基、1,1-二甲基丁基、正庚基、5-甲基己基、4-甲基己基、3-甲基己基、2-甲基己基、1-甲基己基、4,4-二甲基戊基、3,4-二甲基戊基、2,4-二甲基戊基、1,4-二甲基戊基、3,3-二甲基戊基、2,3-二甲基戊基、1,3-二甲基戊基、2,2-二甲基戊基、1,2-二甲基戊基、1,1-二甲基戊基、2,3,3-三甲基丁基、1,3,3-三甲基丁基、1,2,3-三甲基丁基、正辛基、6-甲基庚基、5-甲基庚基、4-甲基庚基、3-甲基庚基、2-甲基庚基、1-甲基庚基、2-乙基己基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十七烷基、正十六烷基、正十七烷基、正十八烷基、正十九烷基等。 The alkyl group having 1 to 30 carbon atoms in A ¹ in the above formula (4) may be linear or branched, and examples thereof include a methyl group, an ethyl group, and a n-propyl group. , isopropyl, n-butyl, secondary butyl, tert-butyl, n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-methylbutyl, 2,2-dimethyl Propyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,3-di Methyl butyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-di Methyl butyl, n-heptyl, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl, 4,4-dimethylpentyl, 3 , 4-dimethylpentyl, 2,4-dimethylpentyl, 1,4-dimethylpentyl, 3,3-dimethylpentyl, 2,3-dimethylpentyl, 1 ,3-dimethylpentyl, 2,2-dimethylpentyl, 1,2-dimethylpentyl, 1,1-dimethylpentyl, 2,3,3-trimethylbutyl 1,3,3-trimethylbutyl, 1,2,3-trimethylbutyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylglycol Base, 2-methylheptyl, 1-methylheptyl, 2-ethylhexyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-ten Tetraalkyl, n-heptadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl and the like.

A¹中，作為碳原子數為3~10的環烷基，可以列舉出例如環戊基、環己基、環庚基、環辛基、環壬基、環癸基等。這些環烷基可以被碳原子數為1~20的烷基或烷氧基取代。作為碳原子數為1~20的烷基的具體例子，適合使用上述碳原子數為1~30的烷基的說明中列舉的具體例子，作為碳原子數為1~20的烷氧基，可以列舉出上述碳原子數為1~30的烷基的說明中列舉的具體例子的烷基上連接氧原子形成的基。 In the A ¹ , examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclodecyl group. These cycloalkyl groups may be substituted by an alkyl group or an alkoxy group having 1 to 20 carbon atoms. Specific examples of the alkyl group having 1 to 20 carbon atoms are preferably those exemplified in the description of the alkyl group having 1 to 30 carbon atoms, and the alkoxy group having 1 to 20 carbon atoms may be used. A group formed by linking an oxygen atom to an alkyl group of a specific example described in the above description of the alkyl group having 1 to 30 carbon atoms is exemplified.

A¹中的烷基和烷氧基的至少一部分氫原子可以被取代，作為這種情況的取代基可以列舉出氰基、氟原子、三氟甲基等。 At least a part of the hydrogen atoms of the alkyl group and the alkoxy group in A ¹ may be substituted, and examples of the substituent in this case include a cyano group, a fluorine atom, a trifluoromethyl group and the like.

作為具有甾類骨架的碳原子數為17~51的烴基，可以列舉出例如下述式(s-1)~(s-3)所示的基， The hydrocarbon group having a quinone skeleton having a carbon number of from 17 to 51, for example, a group represented by the following formulas (s-1) to (s-3).

式中，「^＊」表示連接到L⁰上的連接鍵。 In the formula, " ^* " indicates the connection key connected to L ⁰ .

作為A¹，較佳為從碳原子數為1~20的烷基、碳原子數為1~20的氟烷基、上述式(s-1)所示的基和(s-3)所示的基中選出的基。 A ^{1 is} preferably an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, a group represented by the above formula (s-1), and (s-3). The base selected from the base.

Z較佳為羧基。 Z is preferably a carboxyl group.

作為L¹中的碳原子數為1~20的伸烷基，可以列舉出從上述碳原子數為1~30的烷基的說明中列舉的各個基中除去1個氫原子形成的基。 The alkylene group having 1 to 20 carbon atoms in the L ¹ may be a group formed by removing one hydrogen atom from each of the groups exemplified in the above description of the alkyl group having 1 to 30 carbon atoms.

作為上述式(x2-1)所示的化合物，較佳為下述式(x2-1-1)~(x2-1-8)任一項所示的化合物， C_uF_2u+1-C_vH_2v-COOH (x2-1-1) C_wH_2w+1-COOH (x2-1-2) The compound represented by the above formula (x2-1) is preferably a compound represented by any one of the following formulas (x2-1-1) to (x2-1-8), C _u F _2u+1 -C _v H _2v -COOH (x2-1-1) C _w H _2w+1 -COOH (x2-1-2)

式中，u是1~5的整數，v是1~18的整數，w是1~20的整數。k是1~5的整數，p是0或1，q是1~18的整數。r是0~18的整數，j是1~18的整數。s和t各自獨立地是0~2的整數。其中，s和t不同時為0。 In the formula, u is an integer of 1 to 5, v is an integer of 1 to 18, and w is an integer of 1 to 20. k is an integer from 1 to 5, p is 0 or 1, and q is an integer from 1 to 18. r is an integer from 0 to 18, and j is an integer from 1 to 18. s and t are each independently an integer of 0-2. Where s and t are not 0 at the same time.

作為上述式(x2-1-1)的v較佳為1~18的整數，更佳為1~12的整數。 v as the above formula (x2-1-1) is preferably an integer of 1 to 18, and more preferably an integer of 1 to 12.

對於w，作為上述式(x2-1-2)的w較佳為5~20的整數，更佳為10~18的整數。另外，作為上述式(x2-1-3)的w較佳為1~17的整數，更佳為3~12的整數。作為上述式(x2-1-4)的w較佳為1~15的整數，更佳為1~8的整數。作為上述式(x2-1-8)的w較佳為1~15的整數，更佳為1~8的整數。 w is preferably an integer of 5 to 20, and more preferably an integer of 10 to 18, as the above formula (x2-1-2). Further, w as the above formula (x2-1-3) is preferably an integer of from 1 to 17, more preferably an integer of from 3 to 12. w as the above formula (x2-1-4) is preferably an integer of from 1 to 15, more preferably an integer of from 1 to 8. w as the above formula (x2-1-8) is preferably an integer of 1 to 15, more preferably an integer of 1 to 8.

作為上述式(x2-1-5)和式(x2-1-6)的r較佳為0~15的整數，更佳為0~8的整數。 r as the above formula (x2-1-5) and formula (x2-1-6) is preferably an integer of 0 to 15, more preferably an integer of 0-8.

作為上述式(x2-1-6)的q較佳為1~12的整數，更佳為1~5的整數。 q as the above formula (x2-1-6) is preferably an integer of 1 to 12, more preferably an integer of 1 to 5.

作為上述式(x2-1-8)的j較佳為1~15的整數，更佳為1~8的整數。 j as the above formula (x2-1-8) is preferably an integer of 1 to 15, more preferably an integer of 1 to 8.

這些化合物中，較佳為上述式(x2-1-2)~(x2-1-5)、(x2-1-7)和(x2-1-8)的至少任一項所示的化合物，具體地較佳為下述式(x2-2-1)~(x2-2-8)所示的化合物，C₁₇H₃₅-COOH (x2-2-1) Among these compounds, a compound represented by at least one of the above formulae (x2-1-2) to (x2-1-5), (x2-1-7), and (x2-1-8) is preferred. Specifically, a compound represented by the following formula (x2-2-1) to (x2-2-8), C ₁₇ H ₃₅ -COOH (x2-2-1) is preferred.

上述式(x2-1)所示的化合物是使具有環氧基的聚有機矽氧烷和反應性化合物X1一起反應，在得到的液晶配 向膜中形成賦予預傾角顯現性部位的化合物。在本說明書中，以下有時將上述式(x2-1)所示的化合物稱作「其他預傾角顯現性化合物」。 The compound represented by the above formula (x2-1) is obtained by reacting a polyorganosiloxane having an epoxy group with a reactive compound X1. A compound that imparts a pretilt appearance site to the film is formed. In the present specification, the compound represented by the above formula (x2-1) is sometimes referred to as "another pretilt angle developing compound".

相對於聚有機矽氧烷所具有的矽原子，其他預傾角顯現性化合物的使用比例較佳為0~50莫耳%，更佳為0~35莫耳%，進一步更佳為0~20莫耳%。另外，相對於和反應性化合物X1的總量，其他預傾角顯現性化合物較佳為以75莫耳%以下，更佳為以50莫耳%以下的範圍使用。藉由使其他預傾角顯現性化合物的使用比例為75莫耳%以下，可以使液晶的高速反應性更好。 The ratio of use of other pretilt angle developing compounds is preferably from 0 to 50 mol%, more preferably from 0 to 35 mol%, and even more preferably from 0 to 20 mol, with respect to the germanium atom possessed by the polyorganosiloxane. ear%. Further, the other pretilt angle developing compound is preferably used in an amount of 75 mol% or less, more preferably 50 mol% or less, based on the total amount of the reactive compound X1. By using the ratio of the other pretilt-developing compound to 75 mol% or less, the high-speed reactivity of the liquid crystal can be made better.

[2]其他反應性化合物(X2-2) [2] Other reactive compounds (X2-2)

在其他反應性化合物(X2-2)中，作為藉由光照射產生自由基的結構和具有光增敏功能的結構，可以列舉出例如二苯甲酮結構、1,3-二硝基苯結構、9,10-二側氧二氫蒽醌結構、1,4-二側氧環己基-2,5-二烯結構等。此處，所述的光增敏功能是指藉由光照射形成單態的激發狀態後，快速產生項間交叉，遷移到三重激發狀態，在該三重激發狀態中，和其他分子撞擊，將元件改變為激發狀態，自然恢復到基底狀態的功能。該光增敏功能可以和藉由光照射產生自由基的功能並存。 In the other reactive compound (X2-2), as a structure which generates a radical by light irradiation and a structure which has a photo-sensitization function, for example, a benzophenone structure and a 1,3-dinitrobenzene structure can be cited. , 9,10-two-sided oxadihydroanthracene structure, 1,4-dihydrocyclohexyl-2,5-diene structure, and the like. Here, the light sensitization function refers to a state in which a single state is excited by light irradiation, and an inter-term intersection is quickly generated, and a triple-excitation state is migrated, and in the triple-excited state, an element is struck, and the element is struck. The function of changing to the excited state and naturally returning to the base state. The light sensitizing function can coexist with a function of generating radicals by light irradiation.

作為具有這種結構的化合物，具體而言可以列舉出例如3-苯甲醯基苯甲酸、4-苯甲醯基苯甲酸、3-(4-二乙基胺基-2-羥基苯甲醯基)苯甲酸、4-(2-羥基苯甲醯基)苯甲酸、3-(2-羥基苯甲醯基)苯甲酸、2-(2-羥基苯甲醯基)苯甲酸、4-(4-甲基苯甲醯基)苯甲酸、4-(3,4-二甲基苯甲 醯基)苯甲酸、3-(4-苯甲醯基-苯氧基)丙酸、9,10-二側氧二氫蒽-2-羧酸(蒽醌-2-羧酸)、3-(9,10-二側氧-9,10-二氫蒽-2-基)丙酸、[3-(4,5-二甲氧基-3,6-二側氧環己-1,4-二烯基)丙氧基]乙酸、3,5-二硝基苯甲酸、4-甲基-3,5-二硝基苯甲酸、3-(3,5-二硝基苯氧基)丙酸、2-甲基-3,5-二硝基苯甲酸等。 Specific examples of the compound having such a structure include 3-benzylidenebenzoic acid, 4-benzylidenebenzoic acid, and 3-(4-diethylamino-2-hydroxybenzhydrazide. Benzoic acid, 4-(2-hydroxybenzhydryl)benzoic acid, 3-(2-hydroxybenzhydryl)benzoic acid, 2-(2-hydroxybenzhydryl)benzoic acid, 4-( 4-methylbenzhydryl)benzoic acid, 4-(3,4-dimethylbenzyl Benzoic acid, 3-(4-benzylidene-phenoxy)propionic acid, 9,10-dihydroindole-2-carboxylic acid (indole-2-carboxylic acid), 3- (9,10-di-oxo-9,10-dihydroindol-2-yl)propionic acid, [3-(4,5-dimethoxy-3,6-di-oxocyclohexyl-1,4) -dienyl)propoxy]acetic acid, 3,5-dinitrobenzoic acid, 4-methyl-3,5-dinitrobenzoic acid, 3-(3,5-dinitrophenoxy) Propionic acid, 2-methyl-3,5-dinitrobenzoic acid, and the like.

相對於聚有機矽氧烷所具有的矽原子，其他反應性化合物(X2-2)的總使用比例較佳為0~10莫耳%，更佳為0~5莫耳%。 The total use ratio of the other reactive compound (X2-2) is preferably from 0 to 10 mol%, more preferably from 0 to 5 mol%, based on the ruthenium atom possessed by the polyorganosiloxane.

[3]其他反應性化合物(X2-3) [3] Other reactive compounds (X2-3)

作為其他反應性化合物(X2-3)，可以列舉出例如甲酸、乙酸、丙酸、苯甲酸等羧酸。相對於聚有機矽氧烷所具有的矽原子，其他反應性化合物(X2-3)的使用比例較佳為0~25莫耳%，更佳為0~10莫耳%。 Examples of the other reactive compound (X2-3) include carboxylic acids such as formic acid, acetic acid, propionic acid, and benzoic acid. The ratio of use of the other reactive compound (X2-3) to the ruthenium atom of the polyorganosiloxane is preferably from 0 to 25 mol%, more preferably from 0 to 10 mol%.

含有其他反應性化合物X2時的反應性化合物X1的用量，相對於反應性化合物X1和其他反應性化合物X2的總量，較佳為10莫耳%以上。另外，反應性化合物X1和其他反應性化合物X2的總量Q1，相對於聚有機矽氧烷前驅物所具有的矽原子，較佳為5~90莫耳%，更佳為10~70莫耳%。另外，使用其他反應性化合物(X2-2)時，為了確保更好的殘影性質，相對於上述總量Q1，較佳為30莫耳%以下，更佳為15莫耳%以下。 The amount of the reactive compound X1 when the other reactive compound X2 is contained is preferably 10 mol% or more based on the total amount of the reactive compound X1 and the other reactive compound X2. Further, the total amount Q1 of the reactive compound X1 and the other reactive compound X2 is preferably from 5 to 90 mol%, more preferably from 10 to 70 mol%, based on the hafnium atom of the polyorganosiloxane precursor. %. Further, when the other reactive compound (X2-2) is used, it is preferably 30 mol% or less, and more preferably 15 mol% or less, based on the total amount Q1 in order to ensure better residual image properties.

聚矽氧烷前驅物和反應性化合物X1的反應可以在適當的催化劑的存在下，較佳在適當的有機溶劑中進行。 The reaction of the polyoxyalkylene precursor and the reactive compound X1 can be carried out in the presence of a suitable catalyst, preferably in a suitable organic solvent.

作為這裡使用的催化劑，例如可以使用作為聚矽氧 烷前驅物的合成使用的催化劑例示的有機鹼，以及作為促進聚矽氧烷前驅物所具有的環氧基與能夠和反應性化合物X1所具有的環氧基反應的基的反應這樣所謂的硬化促進劑而公知的化合物。 As the catalyst used here, for example, it can be used as a polyoxyl The organic base exemplified by the catalyst used for the synthesis of the alkane precursor, and the so-called hardening as a reaction for promoting the reaction of the epoxy group of the precursor of the polyoxyalkylene with the epoxy group which the reactive compound X1 has. A compound known as a promoter.

相對於100重量份聚矽氧烷前驅物，催化劑的用量較佳為100重量份以下，更佳為0.01~100重量份，進一步更佳為0.1~20重量份。 The amount of the catalyst is preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, still more preferably 0.1 to 20 parts by weight, per 100 parts by weight of the polyoxyalkylene precursor.

作為聚矽氧烷前驅物和反應性化合物X1的反應時使用的有機溶劑，可以列舉出例如烴化合物、醚化合物、酯化合物、酮化合物、醯胺化合物、醇化合物等。它們之中，醚化合物、酯化合物、酮化合物從原料、產物的溶解性、產物的精製容易性的觀點出發是較佳的。溶劑以固體成分濃度(反應溶液中的溶劑以外的成分的總重量佔據溶液全部重量的比例)較佳為以0.1重量%以上，更佳為以5~50重量%的量使用。 The organic solvent to be used in the reaction of the polyoxane precursor and the reactive compound X1 may, for example, be a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, a guanamine compound or an alcohol compound. Among them, the ether compound, the ester compound, and the ketone compound are preferred from the viewpoints of the solubility of the raw material and the product, and the ease of purification of the product. The solvent is preferably used in an amount of 0.1% by weight or more, and more preferably 5 to 50% by weight, based on the solid content concentration (the ratio of the total weight of the components other than the solvent in the reaction solution).

反應溫度較佳為0~200℃，更佳為50~150℃。反應時間較佳為0.1~50小時，更佳為0.5~20小時。 The reaction temperature is preferably from 0 to 200 ° C, more preferably from 50 to 150 ° C. The reaction time is preferably from 0.1 to 50 hours, more preferably from 0.5 to 20 hours.

特定聚有機矽氧烷藉由凝膠滲透層析法(GPC)測定的聚苯乙烯換算的重量平均分子量較佳為1,000~500,000。藉由為1,000以上，可以對膜賦予適當的各向異性，藉由為500,000以下，容易形成均勻的塗膜。更佳為2,000~200,000。另外，Mw相對於GPC的聚苯乙烯換算的數量平均分子量(以下，稱作「Mn」)的比(Mw/Mn)較佳為1.0~5.0，更佳為1.0~3.5，進一步更佳為1.0~2.5。 The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) of a specific polyorganosiloxane is preferably from 1,000 to 500,000. When it is 1,000 or more, an appropriate anisotropy can be imparted to the film, and if it is 500,000 or less, a uniform coating film can be easily formed. More preferably 2,000 to 200,000. Further, the ratio (Mw/Mn) of the polystyrene-equivalent number average molecular weight (hereinafter referred to as "Mn") of Mw to GPC is preferably 1.0 to 5.0, more preferably 1.0 to 3.5, still more preferably 1.0. ~2.5.

在第1配向劑中含有的聚醯胺酸和聚醯亞胺的總量 為100重量份時，第1配向劑中含有的聚合物成分中，特定聚有機矽氧烷的含有比例較佳為0.1~100重量份，更佳為1~50重量份，進一步更佳為5~15重量份。藉由在上述範圍內，可以維持所得到的液晶配向劑的塗布性和印刷性，而且可以顯示出適當的預傾角。 Total amount of polyamic acid and polyimine contained in the first alignment agent When the amount is 100 parts by weight, the content of the specific polyorganosiloxane in the polymer component contained in the first alignment agent is preferably 0.1 to 100 parts by weight, more preferably 1 to 50 parts by weight, still more preferably 5 parts by weight. ~15 parts by weight. By the above range, the coatability and printability of the obtained liquid crystal alignment agent can be maintained, and an appropriate pretilt angle can be exhibited.

<特定聚醯胺酸> <Specific polyglycolic acid>

另一方面，本發明中的第1配向劑在包含具有上述光配向性基的聚醯胺酸(以下，稱作特定聚醯胺酸)作為感放射線性化合物時，該特定聚醯胺酸例如可以藉由使四羧酸二酐和具有上述光配向性基的二胺反應得到。 On the other hand, when the first alignment agent in the present invention contains a poly-proline (hereinafter referred to as a specific polyamine) having the photo-alignment group as a radiation-sensitive compound, the specific polyamine is, for example, It can be obtained by reacting a tetracarboxylic dianhydride with a diamine having the above photo-alignment group.

(四羧酸二酐) (tetracarboxylic dianhydride)

作為合成特定聚醯胺酸時使用的四羧酸二酐，可以列舉出例如脂肪族四羧酸二酐、脂環式四羧酸二酐、芳香族四羧酸二酐等。作為它們的具體地例子，分別是作為脂肪族四羧酸二酐，可以列舉出例如丁四羧酸二酐等；作為脂環式四羧酸二酐，可以列舉出例如1,2,3,4-環丁四甲酸二酐、2,3,5-三羧基環戊基乙酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二側氧-3-呋喃基)-萘并[1,2-c]呋喃-1,3-二酮、1,3,3a,4,5,9b-六氫-8-甲基-5-(四氫-2,5-二側氧-3-呋喃基)-萘并[1,2-c]呋喃-1,3-二酮、3-氧雜二環[3.2.1]辛-2,4-二酮-6-螺-3’-(四氫呋喃-2',5'-二酮)、5-(2,5-二側氧四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二甲酸酐、3,5,6-三羧基-2-羧甲基降烷-2：3,5：6-二酐、2,4,6,8-四羧基二環[3.3.0]辛烷-2：4,6：8-二酐、4,9-二氧雜三環[5.3.1.0^2.6]十一烷-3,5,8,10-四酮等； 作為芳香族四羧酸二酐，可以列舉出例如均苯四羧酸二酐等；以及使用日本特開2010-97188號公報中記載的四羧酸二酐。 Examples of the tetracarboxylic dianhydride used in the synthesis of the specific polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples of the aliphatic tetracarboxylic dianhydride include, for example, tetrabutyl carboxylic acid dianhydride; and examples of the alicyclic tetracarboxylic dianhydride include 1, 2, and 3, 4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di Side oxy-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-( Tetrahydro-2,5-di-oxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2, 4-diketo-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-di-oxotetrahydro-3-furanyl)-3-methyl-3 -cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethyl group Alkane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 4,9-dioxo a heterotricyclo[5.3.1.0 ^2.6 ]undecane-3,5,8,10-tetraketone or the like; examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride; and The tetracarboxylic dianhydride described in JP-A-2010-97188.

作為四羧酸二酐，它們之中，較佳為包含脂環式四羧酸二酐的，特佳為從2,3,5-三羧基環戊基乙酸二酐，3,5,6-三羧基-2-羧甲基降烷-2：3,5：6-二酐和2,4,6,8-四羧基二環[3.3.0]辛烷-2：4,6：8-二酐所構成的群組中選出的至少一種。 As the tetracarboxylic dianhydride, among them, it is preferred to contain an alicyclic tetracarboxylic dianhydride, particularly preferably from 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5,6- Tricarboxy-2-carboxymethyl group Selected from the group consisting of alkane-2:3,5:6-dianhydride and 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride At least one of them.

(二胺) (diamine)

作為合成特定聚醯胺酸使用的二酐，包含具有上述光配向性基的二胺(以下，稱作特定二胺)。作為這種情況下的光配向性基，較佳為具有來自肉桂酸的結構的基。 The dianhydride used for synthesizing a specific polyamic acid includes a diamine having the above photoalignment group (hereinafter referred to as a specific diamine). The photo-alignment group in this case is preferably a group having a structure derived from cinnamic acid.

特定二胺可以在一分子中具有一個以上的上述光配向性基，較佳為具有一個或兩個。作為這種特定二胺，可以列舉出例如上述光配向性基藉由例如^＊-COO-(CH₂)_r-O-、^＊-(CH₂)_r-(其中，r表示1~10的整數，「^＊」表示連接到二胺結構的連接鍵)等連接基，連接到二胺結構上的化合物。 The specific diamine may have one or more of the above photoalignment groups in one molecule, and preferably one or two. As such a specific diamine, for example, the above photoalignment group can be exemplified by, for example, ^* -COO-(CH ₂ ) _r -O-, ^* -(CH ₂ ) _r - (wherein r represents an integer of 1 to 10) " ^* " indicates a linking group such as a linking bond to a diamine structure, and a compound attached to a diamine structure.

作為特定二胺的具體例子，可以列舉出下述式(d1-1)~(d1-15)所示的化合物， Specific examples of the specific diamine include compounds represented by the following formulas (d1-1) to (d1-15).

作為用於合成特定聚醯胺酸的二胺，可以和特定二胺以外的二胺(以下，稱作其他二胺)一起使用。作為該 其他二胺，具體而言，分別是作為脂肪族二胺，可以列舉出例如間二甲苯二胺、1,3-丙二胺、1,4-丁二胺、1,5-戊二胺、1,6-己二胺等；作為脂環式二胺，可以列舉出例如1,4-二胺基環己烷、4,4’-亞甲基雙(環己基胺)、1,3-雙(胺基甲基)環己烷等；作為芳香族二胺，可以列舉出例如鄰苯二胺、間苯二胺、對苯二胺、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基硫醚、1,5-二胺基萘、2,2’-二甲基-4,4’-二胺基聯苯、4,4’-二胺基-2,2’-雙(三氟甲基)聯苯、2,7-二胺基茀、4,4’-二胺基二苯基醚、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、9,9-雙(4-胺基苯基)茀、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、2,2-雙(4-胺基苯基)六氟丙烷、4,4’-(對伸苯基二亞異丙基)雙(苯胺)、4,4’-(間伸苯基二亞異丙基)雙(苯胺)、1,4-雙(4-胺基苯氧基)苯、4,4’-雙(4-胺基苯氧基)聯苯、2,6-二胺基吡啶、3,4-二胺基吡啶、2,4-二胺基嘧啶、3,6-二胺基吖啶、3,6-二胺基咔唑、N-甲基-3,6-二胺基咔唑、N-乙基-3,6-二胺基咔唑、N-苯基-3,6-二胺基咔唑、N,N’-雙(4-胺基苯基)-聯苯胺、N,N’-雙(4-胺基苯基)-N,N’-二甲基聯苯胺、1,4-雙(4-胺基苯基)哌、3,5-二胺基苯甲酸、十二烷氧基-2,4-二胺基苯、十四烷氧基-2,4-二胺基苯、十五烷氧基-2,4-二胺基苯、十六烷氧基-2,4-二胺基苯、十八烷氧基-2,4-二胺基苯、十二烷氧基-2,5-二胺基苯、十四烷氧基-2,5-二胺基苯、十五烷氧基-2,5-二胺基苯、十六烷氧基-2,5-二胺基苯、十八烷氧基-2,5-二胺基苯、膽甾烷氧基-3,5-二胺基苯、膽甾烯氧基 -3,5-二胺基苯、膽甾烷氧基-2,4-二胺基苯、膽甾烯氧基-2,4-二胺基苯、3,5-二胺基苯甲酸膽甾烷基酯、3,5-二胺基苯甲酸膽甾烯基酯、3,5-二胺基苯甲酸羊毛甾烷基酯、3,6-雙(4-胺基苯甲醯氧基)膽甾烷、3,6-雙(4-胺基苯氧基)膽甾烷、4-(4’-三氟甲氧基苯甲醯氧基)環己基-3,5-二胺基苯甲酸酯、4-(4’-三氟甲基苯甲醯氧基)環己基-3,5-二胺基苯甲酸酯、1,1-雙(4-((胺基苯基)甲基)苯基)-4-丁基環己烷、1,1-雙(4-((胺基苯基)甲基)苯基)-4-庚基環己烷、1,1-雙(4-((胺基苯氧基)甲基)苯基)-4-庚基環己烷、1,1-雙(4-((胺基苯基)甲基)苯基)-4-(4-庚基環己基)環己烷、2,4-二胺基-N,N-二烯丙基苯胺、4-胺基苄基胺、3-胺基苄基胺、1-(2,4-二胺基苯基)哌-4-酸、4-(啉-4-基)苯-1,3-二胺、1,3-雙(N-(4-胺基苯基)哌啶基)丙烷、α-胺基-ω-胺基苯基伸烷基等；作為二胺基有機矽氧烷，可以列舉出例如1,3-雙(3-胺基丙基)-四甲基二矽氧烷等；以及日本特開2010-97188號公報中記載的二胺。 As the diamine for synthesizing a specific polyamine, it can be used together with a diamine other than a specific diamine (hereinafter referred to as another diamine). Specific examples of the other diamines include aliphatic diamines, and examples thereof include meta-xylene diamine, 1,3-propanediamine, 1,4-butanediamine, and 1,5-pentane. An amine, 1,6-hexanediamine or the like; examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and 1, 3-bis(aminomethyl)cyclohexane; etc.; as the aromatic diamine, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'- Diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,7-diaminostilbene, 4,4'-diaminodiphenyl ether, 2,2-bis[4-( 4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylenediphenylene)bis(aniline), 4,4'-(inter)phenyl Diisopropylidene) bis(aniline), 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-di Aminopyridine, 3,4-diaminopyridine, 2,4 -diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6- Diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-bis(4-amino group Phenyl)-N,N'-dimethylbenzidine, 1,4-bis(4-aminophenyl)perazine , 3,5-diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4 -diaminobenzene,hexadecanyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene , tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene, cetyloxy-2,5-diaminobenzene, octadecyloxy Base-2,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-2,4 -diaminobenzene, cholesteneoxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate , 3,5-diaminobenzoic acid lanthanum alkyl ester, 3,6-bis(4-aminobenzylideneoxy)cholestane, 3,6-bis(4-aminophenoxy) Cholestane, 4-(4'-trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzonitrileoxy) Cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1 - bis(4-((aminophenyl)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4- ((Aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-(4- Heptylcyclohexyl)cyclohexane, 2,4-diamino-N,N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1-(2,4- Diaminophenyl)per -4-acid, 4-( Phenyl-4-yl)benzene-1,3-diamine, 1,3-bis(N-(4-aminophenyl)piperidinyl)propane, α-amino-ω-aminophenylalkylene Examples of the diamine-based organooxane include, for example, 1,3-bis(3-aminopropyl)-tetramethyldioxane; and those described in JP-A-2010-97188 Diamine.

另外，基於使預傾角性質良好的目的，作為特定聚醯胺酸的合成時使用的二胺，可以同時含有特定二胺和下述式(A-1)所示的化合物和下述式(A-2)所示的化合物的至少任意一種， In addition, for the purpose of making the pretilt property to be good, the diamine used in the synthesis of the specific polyaminic acid may contain a specific diamine and a compound represented by the following formula (A-1) and the following formula (A). -2) at least any one of the compounds shown,

式中，X^I、X^II和X^III各自獨立地是單鍵、^＊-O-、^＊-COO-或^＊-OCO-(其中，帶「^＊」的連接鍵連接到苯環上)，R^I 是碳原子數為1~3的伸烷基，a是0或1，b是0~2的整數，c是1~20的整數，n是0或1， Wherein X ^I , X ^II and X ^III are each independently a single bond, ^* -O-, ^* -COO- or ^* -OCO- (wherein a linkage with " ^* " is attached to the phenyl ring), R ^I is an alkylene group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and n is 0 or 1,

式中，R^III各自獨立地是氫原子或碳原子數為1~12的烷基，R^IV和R^V各自獨立地是氫原子或甲基 Wherein R ^III are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ^IV and R ^V are each independently a hydrogen atom or a methyl group.

作為上述式(A-1)中的-X^I-(R^I-X^II)_n-所示的2價基較佳為碳原子數為1~3的伸烷基、^＊-O-、^＊-COO-或^＊-OCH₂CH₂-O-(其中，帶「^＊」的連接鍵和二胺基苯基連接)。作為基C_cH_2c+1-的具體例子，可以列舉出例如甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基、正十七烷基、正十八烷基、正十九烷基、正二十烷基等。二胺基苯基中的2個一級胺基，相對於其他基較佳為2,4-位或3,5-位。 The divalent group represented by -X ^I -(R ^I -X ^II ) _n - in the above formula (A-1) is preferably an alkylene group having 1 to 3 carbon atoms, ^* -O-, ^* -COO- or ^* -OCH ₂ CH ₂ -O- (wherein the " ^* " linkage is linked to the diaminophenyl group). Specific examples of the group C _c H _2c+1 - may, for example, be methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, N-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecane Base, n-icosyl group, etc. The two primary amine groups in the diaminophenyl group are preferably the 2,4-position or the 3,5-position relative to the other groups.

作為上述式(A-1)所示的化合物的具體例子，可以列舉出例如下述式(d2-1)~(d2-7)分別表示的化合物等， Specific examples of the compound represented by the above formula (A-1) include compounds represented by the following formulas (d2-1) to (d2-7), respectively.

作為上述式(A-2)所示的化合物，較佳為N,N-二烯丙基-2,4-二胺基苯胺。 The compound represented by the above formula (A-2) is preferably N,N-diallyl-2,4-diaminoaniline.

用於合成特定聚醯胺酸的二胺是相對於全部二胺，特定二胺的含有比例較佳為50~100莫耳%，更佳為80~100莫耳%。 The diamine used for the synthesis of the specific polyamine is preferably contained in an amount of from 50 to 100 mol%, more preferably from 80 to 100 mol%, based on the total of the diamine.

(特定聚醯胺酸的合成) (Synthesis of specific polylysine)

作為聚醯胺酸的合成反應中使用的四羧酸二酐和二胺的使用比例，相對於1當量二胺的胺基，四羧酸二酐的酸酐基較佳為0.2~2當量的比例，更佳為0.3~1.2當量的比例。 The ratio of use of the tetracarboxylic dianhydride and the diamine used in the synthesis reaction of polyproline is preferably 0.2 to 2 equivalents based on 1 equivalent of the amine group of the diamine. More preferably, it is a ratio of 0.3 to 1.2 equivalents.

聚醯胺酸的合成反應較佳在有機溶劑中進行，較佳在-20℃~150℃，更佳為在0℃~100℃下，較佳為進行0.1~120小時，更佳為進行0.5~48小時。 The synthesis reaction of polylysine is preferably carried out in an organic solvent, preferably at -20 ° C to 150 ° C, more preferably at 0 ° C to 100 ° C, preferably 0.1 to 120 hours, more preferably 0.5. ~48 hours.

此處作為有機溶劑，可以列舉出例如N-甲基-2-吡咯 啶酮、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、六甲基磷醯三胺等非質子性極性溶劑；間甲酚、二甲酚、苯酚、鹵苯酚等酚性溶劑。有機溶劑的用量(a)較佳為四羧酸二酐和二胺的總量(b)相對於反應溶液的全部量(a+b)是0.1~50重量%的量。 Here, as the organic solvent, for example, N-methyl-2-pyrrole may be mentioned. Pyridone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylhydrazine, γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine, etc. An aprotic polar solvent; a phenolic solvent such as m-cresol, xylenol, phenol or halophenol. The amount (a) of the organic solvent is preferably such that the total amount (b) of the tetracarboxylic dianhydride and the diamine is from 0.1 to 50% by weight based on the total amount (a+b) of the reaction solution.

對特定聚醯胺酸而言，藉由凝膠滲透層析法(GPC)測定的聚苯乙烯換算的重量平均分子量較佳為1,000~500,000，更佳為5,000~300,000。藉由在上述範圍內，可以對膜賦予適當的各向異性，而且可以形成更均勻的塗膜。 The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) is preferably from 1,000 to 500,000, more preferably from 5,000 to 300,000, for the specific polyamine. By being within the above range, appropriate anisotropy can be imparted to the film, and a more uniform coating film can be formed.

<特定聚醯亞胺> <Specific Polyimine>

本發明中的第1配向劑在包含具有上述光配向性基的聚醯亞胺(以下，稱作特定聚醯亞胺)作為感放射線性化合物時，該特定聚醯亞胺可以藉由將上述特定聚醯胺酸脫水閉環醯亞胺化得到。 When the first alignment agent in the present invention contains a polyimine (hereinafter referred to as a specific polyimine) having the above photo-alignment group as a radiation-sensitive compound, the specific polyimine can be obtained by The specific polyglycine dehydration is obtained by ring imidization.

特定聚醯亞胺可以是作為其前驅物的聚醯胺酸所具有的醯胺酸結構全部脫水閉環的完全醯亞胺化物；也可以只是醯胺酸結構的一部分脫水閉環，醯胺酸結構和醯亞胺環結構並存的部分醯亞胺化物。特定聚醯亞胺的醯亞胺化率較佳為30%以上，更佳為40~90%。另外，該醯亞胺化率是以百分率表示醯亞胺環結構的數量佔據聚醯亞胺的醯胺酸結構的數量和醯亞胺環結構的數量的總量的比例。 The specific polyimine may be a complete hydrazine imide of a glycine structure having a glycine structure as a precursor of the prolyl acid; or a part of the structure of the proline may be dehydrated and closed, the structure of the proline is Part of the quinone imine compound coexisting with the quinone imine ring structure. The oxime imidization ratio of the specific polyimine is preferably 30% or more, more preferably 40 to 90%. Further, the ruthenium imidization ratio is a ratio indicating the number of the quinone ring structure in the percentage of the amount of the guanine structure of the polyimine and the total amount of the quinone ring structure.

聚醯胺酸的脫水閉環較佳為以藉由加熱聚醯胺酸的方法，或者將聚醯胺酸溶解在有機溶劑中，在該溶液中 添加脫水劑和脫水閉環催化劑，根據需要加熱的方法進行。其中，較佳為後一種方法。 The dehydration ring closure of polylysine is preferably carried out by heating poly-proline, or dissolving poly-proline in an organic solvent. The dehydrating agent and the dehydration ring-closing catalyst are added, and the heating is carried out as needed. Among them, the latter method is preferred.

在上述聚醯胺酸溶液中添加脫水劑和脫水閉環催化劑的方法中，作為脫水劑，可以使用例如乙酸酐、丙酸酐、三氟乙酸酐等酸酐。脫水劑的用量，相對於1mol聚醯胺酸的醯胺酸結構，較佳為0.01~20mol。作為脫水閉環催化劑，可以列舉出例如吡啶、三甲基吡啶、二甲基吡啶、三乙胺等三級胺。作為脫水閉環催化劑的用量，相對於1mol使用的脫水劑，較佳為0.01~10mol。作為脫水閉環反應中使用的有機溶劑，可以列舉出作為合成聚醯胺酸使用的溶劑例示的有機溶劑。脫水閉環反應的反應溫度較佳為0~180℃，更佳為10~150℃。反應時間較佳為1.0~120小時，更佳為2.0~30小時。 In the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent is preferably 0.01 to 20 mol based on the structure of the proline of 1 mol of polyamic acid. The dehydration ring-closing catalyst may, for example, be a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine. The amount of the dehydration ring-closure catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. The organic solvent used for the dehydration ring-closure reaction may, for example, be an organic solvent exemplified as a solvent used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably from 0 to 180 ° C, more preferably from 10 to 150 ° C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours.

在作為聚合物成分含有的聚醯胺酸和聚醯亞胺的總量為100重量份時，特定聚醯胺酸和特定聚醯亞胺的含有比例較佳為5~100重量份，更佳為10~100重量份。 When the total amount of the polyamic acid and the polyimine contained as the polymer component is 100 parts by weight, the content ratio of the specific polyamine and the specific polyimine is preferably 5 to 100 parts by weight, more preferably It is 10 to 100 parts by weight.

<聚醯胺酸和聚醯亞胺> <Polyuric acid and polyimine>

在上述感放射線性化合物為特定聚有機矽氧烷時，第1配向劑含有沒有光配向性基的聚醯胺酸或聚醯亞胺的至少任意一種作為必要成分；或者在上述感放射線性化合物為特定聚醯胺酸或特定聚醯亞胺時，第1配向劑含有沒有光配向性基的聚醯胺酸或聚醯亞胺的至少任意一種作為任意成分。該聚醯胺酸可以使用例如作為特定聚醯胺酸的合成中使用的羧酸二酐而例示的化合物與作為其他二胺例示的化合物的反應產物。另外，該聚醯亞胺 可以使用將上述反應的產物聚醯胺酸脫水閉環醯亞胺化得到的物質。 When the radiation sensitive compound is a specific polyorganosiloxane, the first alignment agent contains at least one of polyamine or polyimine having no photo-alignment group as an essential component; or the above-mentioned radiation-sensitive compound In the case of a specific polyamine or a specific polyimine, the first alignment agent contains at least one of polyamine or polyamidiamine having no photo-alignment group as an optional component. As the polyamine acid, for example, a reaction product of a compound exemplified as a carboxylic acid dianhydride used in the synthesis of a specific polyamic acid and a compound exemplified as another diamine can be used. In addition, the polyimine A substance obtained by subjecting the product of the above reaction to polyhydrazide dehydration ring-opening oxime can be used.

(第1配向劑的其他成分) (Other components of the first alignment agent)

第1配向劑較佳為將該配向劑中含有的聚合物成分溶解到適當的有機溶劑中，製備為溶液組成物。作為這種有機溶劑，可以是溶解上述聚合物成分，而且不和它們反應的溶劑，可以列舉出例如作為合成上述特定聚有機矽氧烷使用的溶劑而例示的有機溶劑。 The first alignment agent is preferably prepared by dissolving the polymer component contained in the alignment agent in a suitable organic solvent to prepare a solution composition. The organic solvent may be a solvent which dissolves the above-mentioned polymer component and does not react with them, and examples thereof include an organic solvent exemplified as a solvent used for synthesizing the specific polyorganosiloxane.

另外，第1配向劑任意含有聚合物成分以外的其他成分。作為該其他成分，可以列舉出例如聚有機矽氧烷、聚醯胺酸以及醯亞胺化聚合物以外的聚合物、硬化劑、硬化催化劑、硬化促進劑、環氧化合物、官能性矽烷化合物、界面活性劑、光增敏劑等。 Further, the first alignment agent optionally contains other components than the polymer component. Examples of the other component include a polymer other than polyorganosiloxane, polyglycolic acid, and a ruthenium-based polymer, a curing agent, a curing catalyst, a curing accelerator, an epoxy compound, and a functional decane compound. Surfactant, photo sensitizer, etc.

<第2配向劑> <2nd alignment agent>

用於形成第2配向膜15的第2配向劑，可以形成使液晶分子垂直配向的垂直配向膜。作為第2配向劑可以是(1)基本上不含具有光配向性基的化合物的配向劑，(2)含有上述感放射線性化合物的配向劑的任一種。在(1)的情況下，例如，作為聚合物成分使用包含作為上述特定聚醯胺酸的合成時使用的羧酸二酐而例示的化合物與作為上述其他二胺例示的化合物的反應得到的聚醯胺酸或其醯亞胺化聚合物的成分。另一方面，在(2)的情況下，可以使用和上述第1配向劑例示的成分相同的成分。另外，形成第2配向膜時，根據製造上述液晶顯示元件的步驟，適當選擇使用(1)、(2)中任意的液晶配向劑。 The second alignment agent for forming the second alignment film 15 can form a vertical alignment film in which liquid crystal molecules are vertically aligned. The second alignment agent may be (1) an alignment agent which does not substantially contain a compound having a photo-alignment group, and (2) an alignment agent containing the above-mentioned radiation-sensitive compound. In the case of (1), for example, a polymer obtained by reacting a compound exemplified as the carboxylic acid dianhydride used in the synthesis of the specific polyaminic acid with a compound exemplified as the above other diamine is used as the polymer component. A component of a proline or a ruthenium imidized polymer thereof. On the other hand, in the case of (2), the same component as the component exemplified as the above first alignment agent can be used. Further, when the second alignment film is formed, any one of the liquid crystal alignment agents (1) and (2) is appropriately selected and used according to the step of producing the liquid crystal display element.

[液晶顯示元件的製造方法] [Method of Manufacturing Liquid Crystal Display Element]

本發明的液晶顯示元件的製造方法包括下述步驟：在一對基板中的一個基板的表面，使液晶分子相對垂直該基板表面的方向傾斜配向，形成第1配向膜13，在另一個基板表面形成使液晶分子垂直配向的第2配向膜15，製造液晶顯示元件10。作為這種製造方法，具體地較佳為下述兩種方案。 A method of manufacturing a liquid crystal display device of the present invention includes the steps of: aligning liquid crystal molecules in a direction perpendicular to a surface of the substrate on a surface of one of the pair of substrates to form a first alignment film 13 on the surface of the other substrate The second alignment film 15 that vertically aligns the liquid crystal molecules is formed, and the liquid crystal display element 10 is manufactured. As such a production method, specifically, the following two schemes are preferable.

[第1製造方法] [First Manufacturing Method]

用於製造本發明的液晶顯示元件10的第1製造方法是使用形成第1配向膜13的基板構成液晶胞，從而製造本發明的液晶顯示元件10，具體而言包括以下步驟。 The first manufacturing method for producing the liquid crystal display element 10 of the present invention is to form a liquid crystal cell using a substrate on which the first alignment film 13 is formed, thereby producing the liquid crystal display element 10 of the present invention, and specifically includes the following steps.

[第1膜形成步驟] [First film forming step]

本步驟是使用作為光配向用液晶配向劑的上述第1配向劑，在一對基板中的一個基板的表面形成第1塗膜的步驟。更詳細而言首先，藉由例如輥塗法、旋塗法、印刷法、噴墨法等適當的塗布方法，在具有第1電極12的基板11a的電極面側，塗布第1配向劑。這裡使用的基板11a可以是藉由形成狹縫狀圖案的狹縫電極或肋(突起)控制液晶分子的傾斜方向的基板，也可以是沒有設置狹縫電極或肋的基板。另外，在使用形成狹縫狀圖案的導電膜作為第1電極12時，為了得到該電極，例如可以在形成沒有圖案的導電膜後，藉由光蝕刻形成圖案的方法，或者在形成導電膜時，使用具有所希望的圖案的光罩的方法等進行。 This step is a step of forming a first coating film on the surface of one of a pair of substrates by using the above first alignment agent as a liquid alignment alignment agent for photoalignment. More specifically, first, the first alignment agent is applied to the electrode surface side of the substrate 11a having the first electrode 12 by an appropriate coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method. The substrate 11a used herein may be a substrate that controls the oblique direction of the liquid crystal molecules by slit electrodes or ribs (protrusions) forming a slit-like pattern, or may be a substrate in which no slit electrodes or ribs are provided. Further, when a conductive film forming a slit-like pattern is used as the first electrode 12, in order to obtain the electrode, for example, a method of forming a pattern by photo-etching after forming a conductive film having no pattern, or a method of forming a conductive film may be employed. It is carried out by a method of using a photomask having a desired pattern or the like.

接著，藉由將該塗布面預加熱(預烘烤)，然後燒製( 後烘烤)形成塗膜。預烘烤條件例如是在40~120℃下進行0.1~5分鐘，後烘烤條件較佳在120~300℃，更佳為150~250℃下，較佳為進行5~200分鐘，更佳為進行10~100分鐘。後烘烤後的塗膜的膜厚較佳為0.001~1μm，更佳為0.005~0.5μm。 Next, by preheating (pre-baking) the coated surface, and then firing ( Post-baking) forms a coating film. The prebaking conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C, and the post-baking conditions are preferably 120 to 300 ° C, more preferably 150 to 250 ° C, more preferably 5 to 200 minutes, more preferably For 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

在基板上塗布液晶配向劑時使用的液晶配向劑的固體成分濃度(液晶配向劑的溶劑以外的成分的總重量佔據液晶配向劑的全部重量的比例)，考慮黏性、揮發性等適當選擇，較佳為1~10重量%的範圍。固體成分濃度不足1重量%時，塗膜的膜厚過小，難以得到良好的液晶配向膜。另一方面，在固體成分濃度超過10重量%時，塗膜的膜厚過大，難以得到良好的液晶配向膜，或者液晶配向劑的黏性增大，塗布性質可能不足。 The solid content concentration of the liquid crystal alignment agent used when the liquid crystal alignment agent is applied to the substrate (the total weight of the components other than the solvent of the liquid crystal alignment agent occupies the total weight of the liquid crystal alignment agent), and is appropriately selected in consideration of viscosity, volatility, and the like. It is preferably in the range of 1 to 10% by weight. When the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small, and it is difficult to obtain a favorable liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film is too large, and it is difficult to obtain a favorable liquid crystal alignment film, or the viscosity of the liquid crystal alignment agent is increased, and the coating property may be insufficient.

特佳的固體成分濃度的範圍根據在基板上塗布液晶配向劑時採用的方法而異。例如，在使用旋塗法進行時，固體成分濃度特佳為1.5~4.5重量%的範圍。在使用膠印法進行時，特佳為固體成分濃度為3~9重量%的範圍，由此，溶液黏度為12~50mPa．s的範圍。在使用噴墨印刷法進行時，固體成分濃度為1~5重量%的範圍，由此，溶液黏度特佳為3~15mPa．s的範圍。 The range of the particularly preferable solid content concentration varies depending on the method employed when the liquid crystal alignment agent is coated on the substrate. For example, when it is carried out by a spin coating method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. When using the offset printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, whereby the solution viscosity is 12 to 50 mPa. The scope of s. When using the inkjet printing method, the solid content concentration is in the range of 1 to 5% by weight, whereby the solution viscosity is particularly preferably 3 to 15 mPa. The scope of s.

另外，在塗布液晶配向劑前，為了使基板表面(第1電極12)和塗膜的黏結性更好，可以在基板表面中，應當形成塗膜的面上，預先塗布官能性矽烷化合物、官能性鈦化合物等進行前處理。 Further, before the liquid crystal alignment agent is applied, in order to make the surface of the substrate (the first electrode 12) and the coating film more adhesive, a functional decane compound or a functional group may be previously coated on the surface of the substrate on which the coating film should be formed. A titanium compound or the like is pretreated.

[光照射步驟] [Light irradiation step]

本步驟是藉由對基板11a上形成的第1塗膜照射光，將該第1塗膜形成作為光配向膜的第1配向膜13的步驟。對第1塗膜照射光可以使用偏光的放射線和非偏光的放射線的任意一種，在使用偏光的放射線時，可以使用直線偏光、部分偏光等，較佳為直線偏光。另外，作為放射線，可以使用包含150nm~800nm的波長的光的紫外線和可見光線。其中，較佳為包含300nm~400nm的波長的光的紫外線。 In this step, the first coating film is formed as a first alignment film 13 as a photo-alignment film by irradiating light onto the first coating film formed on the substrate 11a. For the first coating film, it is possible to use either a polarized radiation or a non-polarized radiation. When polarized radiation is used, linear polarization, partial polarization, or the like can be used, and linear polarization is preferable. Further, as the radiation, ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm can be used. Among them, ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable.

為了賦予預傾角，對第1塗膜照射光的方向是相對基板表面傾斜的方向。此時的照射角度可以根據第1塗膜中顯現出的預傾角適當設定。藉由這種光照射，較佳為使第1配向膜13中的預傾角為85~89.5°，更佳為87~89°。 In order to impart a pretilt angle, the direction in which the first coating film is irradiated with light is a direction inclined with respect to the substrate surface. The irradiation angle at this time can be appropriately set according to the pretilt angle appearing in the first coating film. By such light irradiation, the pretilt angle in the first alignment film 13 is preferably 85 to 89.5°, more preferably 87 to 89°.

作為照射放射線的光源，可以使用例如低壓水銀燈、高壓水銀燈、水銀氙燈、重氫燈、鹵素燈、金屬鹵化物燈、氬共振燈、氙燈、准分子鐳射等。上述較佳的波長區域的紫外線可以藉由將前述光源和例如濾光器、繞射光柵等一起使用的機構等得到。 As the light source for irradiating the radiation, for example, a low pressure mercury lamp, a high pressure mercury lamp, a mercury xenon lamp, a deuterium lamp, a halogen lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. The ultraviolet light in the above preferred wavelength region can be obtained by a mechanism for using the light source together with, for example, a filter, a diffraction grating, or the like.

放射線的照射量較佳為1J/m²以上、不足10,000J/m²，更佳為10~3,000J/m²。 Radiation irradiation amount is preferably 1J / m ² or more and less 10,000J / m ^2, more preferably 10 ~ 3,000J / m ^2.

[第2膜形成步驟] [Second film forming step]

本步驟是在一對基板11a、11b中，沒有形成第1塗膜的另一個基板11b的表面，使用第2配向劑作為可以形成垂直配向膜的液晶配向劑，形成第2塗膜的步驟。第2塗膜基本上藉由和上述第1膜形成步驟中形成塗膜的相同的方法進行。另外，這裡使用的基板11b，也可以藉由狹 縫電極或肋控制液晶分子的傾斜方向，也可以不設置這些電極。 This step is a step of forming a second coating film on the surface of the other substrate 11b in which the first coating film is not formed in the pair of substrates 11a and 11b, and using the second alignment agent as a liquid crystal alignment agent capable of forming a vertical alignment film. The second coating film is basically carried out by the same method as the formation of the coating film in the first film forming step. In addition, the substrate 11b used here can also be narrowed by The slit electrodes or ribs control the tilt direction of the liquid crystal molecules, and these electrodes may not be provided.

作為本製造方法中的第2配向劑可以使用(1)實質上不含具有光配向性基的化合物的配向劑，(2)含有上述感放射線性化合物的配向劑中的任意一種。在使用(2)的配向劑作為第2配向劑時，可以使用作為上述第1配向劑例示的配向劑相同的物質，此時，可以和第1塗膜的形成時使用的物質相同的種類，也可以是不同的種類。其中，在使用(2)的配向劑作為第2配向劑時，不對該基板11b上形成的第2塗膜照射光。 As the second alignment agent in the production method, (1) an alignment agent which does not substantially contain a compound having a photo-alignment group, and (2) an alignment agent containing the above-mentioned radiation-sensitive compound can be used. When the alignment agent of the above (2) is used as the second alignment agent, the same type of the alignment agent as the first alignment agent can be used. In this case, the same type as the one used in the formation of the first coating film can be used. It can also be a different kind. However, when the alignment agent of (2) is used as the second alignment agent, the second coating film formed on the substrate 11b is not irradiated with light.

另外，如上形成的第2塗膜可以直接作為垂直配向膜(第2配向膜15)使用，藉由例如藉由捲繞了由尼龍、人造絲、棉花等纖維形成的布的輥，將形成的塗膜在一定方向上摩擦處理(摩擦處理)。 Further, the second coating film formed as described above can be used as a vertical alignment film (second alignment film 15), and is formed by, for example, a roll of a cloth formed of fibers such as nylon, rayon, or cotton. The coating film is rubbed in a certain direction (friction treatment).

[胞構成步驟] [Cell composition step]

接著，將分別形成液晶配向膜的兩塊基板11a、11b配置成使第1配向膜13和作為第2塗膜的垂直配向膜(第2配向膜15)相對，構成液晶胞。在構成液晶胞時，可以列舉出例如下述兩種方法。 Then, the two substrates 11a and 11b each forming the liquid crystal alignment film are disposed such that the first alignment film 13 and the vertical alignment film (the second alignment film 15) as the second coating film face each other to constitute a liquid crystal cell. When forming a liquid crystal cell, the following two methods are mentioned, for example.

第1種方法是首先藉由間隙(胞間隙)，將各個液晶配向膜對向，將兩塊基板11a、11b對向配置，使用密封劑將兩塊基板11a、11b的周圍部貼合。接著，在藉由基板表面和密封劑劃分的胞間隙內注入填充液晶後，密封注入孔。由此，構成液晶胞。 In the first method, first, the respective liquid crystal alignment films are opposed by a gap (cell gap), and the two substrates 11a and 11b are opposed to each other, and the peripheral portions of the two substrates 11a and 11b are bonded together using a sealant. Next, after the filling liquid crystal is injected into the interstitial space defined by the surface of the substrate and the sealant, the injection hole is sealed. Thereby, a liquid crystal cell is formed.

第二種方法是稱作ODF(液晶滴下)方式的方法。也就 是，在形成液晶配向膜的兩塊基板11a、11b中的一個基板上的規定位置，塗布例如紫外光硬化性的密封劑，然後在液晶配向膜面上滴加液晶後，貼合另一個基板並使液晶配向膜對向。然後，在基板的整面照射紫外光，使密封劑硬化。由此，構成液晶胞。 The second method is a method called the ODF (Liquid Crystal Drop) method. Also In a predetermined position on one of the two substrates 11a and 11b forming the liquid crystal alignment film, for example, an ultraviolet curable sealant is applied, and then liquid crystal is dropped on the liquid crystal alignment film surface, and the other substrate is bonded. The liquid crystal alignment film is opposed to the film. Then, ultraviolet light is irradiated on the entire surface of the substrate to harden the sealant. Thereby, a liquid crystal cell is formed.

另外，在任意一種方法中，基於除去液晶填充時的流動配向的目的，較佳為將上述製造的液晶胞加熱到使用的液晶為各向同性的溫度後，緩慢冷卻到室溫。 Further, in any of the methods, for the purpose of removing the flow alignment during liquid crystal filling, it is preferred to heat the liquid crystal cell produced above to a temperature at which the liquid crystal used is isotropic, and then slowly cool to room temperature.

對上述構成的液晶胞，在兩塊基板11a、11b的各個外側表面，貼合偏光板18、19，得到本發明的液晶顯示元件10。此時，偏光板18、19的偏光方向相互正交，而且在形成第1配向膜13的基板上，紫外線的光軸往基板面的投影方向形成45°的角度，貼合偏光板。 In the liquid crystal cell having the above configuration, the polarizing plates 18 and 19 are bonded to the respective outer surfaces of the two substrates 11a and 11b to obtain the liquid crystal display element 10 of the present invention. At this time, the polarizing directions of the polarizing plates 18 and 19 are orthogonal to each other, and on the substrate on which the first alignment film 13 is formed, the optical axis of the ultraviolet light is formed at an angle of 45° toward the projection direction of the substrate surface, and the polarizing plate is bonded thereto.

作為前述密封劑，可以使用例如含有作為隔片的氧化鋁球和硬化劑的環氧樹脂等。 As the sealant, for example, an epoxy resin containing an alumina ball as a separator and a curing agent can be used.

[第2製造方法] [Second Manufacturing Method]

用於製造本發明的液晶顯示元件10的第2製造方法是使用液晶配向劑，在各個基板表面形成塗膜，使用形成該塗膜的基板構成液晶胞後，對液晶胞照射光，從而製造本發明的液晶顯示元件10。具體而言包含以下步驟。 In the second manufacturing method for producing the liquid crystal display element 10 of the present invention, a liquid crystal alignment agent is used, a coating film is formed on the surface of each substrate, and a liquid crystal cell is formed using the substrate on which the coating film is formed, and the liquid crystal cell is irradiated with light to thereby produce the present invention. The liquid crystal display element 10 of the invention. Specifically, the following steps are included.

[第1膜形成步驟] [First film forming step]

本步驟是使用作為光配向用液晶配向劑的第1配向劑，在一對基板11a、11b中的一個基板11a的表面形成塗膜的步驟。其中，在本發明的製造方法中，作為形成塗膜的基板11a、11b，使用包含具有狹縫狀圖案的電極(第 1電極12、第2電極14)的基板。另外，對於塗膜的形成方法，可以使用上述第1製造方法中的第1膜形成步驟記載的方法。 This step is a step of forming a coating film on the surface of one of the pair of substrates 11a and 11b by using the first alignment agent as the liquid alignment alignment agent for photoalignment. In the manufacturing method of the present invention, as the substrates 11a and 11b on which the coating film is formed, an electrode including a slit-like pattern is used. A substrate of the first electrode 12 and the second electrode 14). Further, as a method of forming the coating film, the method described in the first film forming step in the first production method described above can be used.

[第2膜形成步驟] [Second film forming step]

本步驟是使用第2配向劑在一對基板11a、11b中的另一個基板11b的表面形成第2配向膜15的步驟。此時，作為第2配向劑，使用實質上不含具有光配向性基的化合物的液晶配向劑，也就是上述第1製造方法中的第2膜形成步驟中例示的第2配向劑(1)、(2)中的(1)。 This step is a step of forming the second alignment film 15 on the surface of the other of the pair of substrates 11a and 11b using the second alignment agent. In this case, a liquid crystal alignment agent which does not substantially contain a compound having a photo-alignment group is used as the second alignment agent, that is, the second alignment agent (1) exemplified in the second film formation step in the first production method. (1) in (2).

另外，如上形成的第2配向膜15可以直接使用，也可以對形成的塗膜進行摩擦處理。 Further, the second alignment film 15 formed as described above may be used as it is, or the formed coating film may be subjected to a rubbing treatment.

[胞構成步驟] [Cell composition step]

在本步驟中，將形成膜的兩塊基板11a、11b配置成使各個膜相對，構成液晶胞。作為構成液晶胞的方法，可以列舉出上述第1製造方法中的胞構成步驟中說明的兩種方法。 In this step, the two substrates 11a and 11b forming the film are disposed such that the respective films face each other to constitute a liquid crystal cell. Examples of the method of constituting the liquid crystal cell include the two methods described in the cell constitution step in the first production method.

[光照射步驟] [Light irradiation step]

在本步驟中，對上述構成的液晶胞，藉由在一對基板間施加電壓的狀態下照射光，對第1配向劑形成的塗膜賦予光配向性。由此，該塗膜成為液晶分子可以相對基板表面垂直的方向傾斜配向的膜(第1配向膜13)。 In this step, the liquid crystal cell having the above-described configuration is irradiated with light by applying a voltage between the pair of substrates, thereby imparting light-alignment properties to the coating film formed by the first alignment agent. Thereby, this coating film becomes a film (first alignment film 13) in which liquid crystal molecules can be obliquely aligned in a direction perpendicular to the surface of the substrate.

作為施加的電壓可以是例如5~50V的直流或交流電壓。此時，作為基板表面的導電膜，在形成劃分為多個區域的圖案狀導電膜時，施加該電壓時，藉由在各個區域施加不同的電壓，可以改變上述塗膜中，各個區域中 液晶分子的傾斜方向。由此，可以使視角性質進一步擴大。 The applied voltage may be, for example, a direct current or an alternating current voltage of 5 to 50 volts. In this case, when the pattern-shaped conductive film divided into a plurality of regions is formed as the conductive film on the surface of the substrate, when the voltage is applied, the coating film can be changed in each region by applying a different voltage to each region. The tilt direction of the liquid crystal molecules. Thereby, the viewing angle property can be further expanded.

對液晶胞照射的光可以使用偏光的放射線和非偏光的放射線中的任意一種，較佳為非偏光的。另外，照射非偏光的放射線時，較佳為從相對基板表面垂直的方向進行。 The light irradiated to the liquid crystal cell may be any one of polarized radiation and non-polarized radiation, preferably non-polarized. Further, when the non-polarized radiation is irradiated, it is preferably carried out in a direction perpendicular to the surface of the substrate.

作為放射線，可以使用例如包含150nm~800nm的波長的光的紫外線和可見光線，較佳為包含300nm~400nm的波長的光的紫外線。作為照射放射線的光源，可以例示和上述第1製造方法中例示的光源相同的光源。 As the radiation, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm can be used, and ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable. As the light source that irradiates the radiation, the same light source as the light source exemplified in the above first manufacturing method can be exemplified.

作為放射線的照射量較佳為1,000J/m²以上、不足100,000J/m²，更佳為1,000~50,000J/m²。 The irradiation amount of the radiation is preferably 1,000 J/m ² or more, less than 100,000 J/m ² , and more preferably 1,000 to 50,000 J/m ² .

藉由這種光照射，較佳為使第1配向膜13中的預傾角為85~89.5°，更佳為87~89°。 By such light irradiation, the pretilt angle in the first alignment film 13 is preferably 85 to 89.5°, more preferably 87 to 89°.

對光照射後的液晶胞，藉由和上述第1製造方法相同的方法，在兩塊基板11a、11b的各個外側表面，貼合偏光板18、19，得到本發明的液晶顯示元件10。 The liquid crystal cell after the light irradiation is bonded to the outer surfaces of the two substrates 11a and 11b by the polarizing plates 18 and 19 in the same manner as in the above-described first manufacturing method to obtain the liquid crystal display element 10 of the present invention.

本發明的液晶顯示元件，作為VA型液晶顯示元件，可以有效地適用於各種裝置，例如可以在鐘錶、攜帶型遊戲機、文字處理器、筆記型電腦、車用導航系統、攝影機-錄影機、PDA、數位相機、行動電話、各種監視器、液晶電視等顯示裝置中使用。 The liquid crystal display element of the present invention can be effectively applied to various devices as a VA type liquid crystal display element, and can be, for example, a clock, a portable game machine, a word processor, a notebook computer, a car navigation system, a camera-video recorder, It is used in display devices such as PDAs, digital cameras, mobile phones, various monitors, and LCD TVs.

[實施例] [Examples]

以下，藉由實施例，對本發明進行更具體地說明，但是本發明並不受到這些實施例的限定。 Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited by these examples.

另外，在下文中，重量平均分子量Mw、數量平均分子量Mn、環氧當量、聚合物溶液的溶液黏度以及聚醯亞胺的醯亞胺化率如下測定。 Further, hereinafter, the weight average molecular weight Mw, the number average molecular weight Mn, the epoxy equivalent, the solution viscosity of the polymer solution, and the oxime imidization ratio of the polyimine are determined as follows.

重量平均分子量Mw和數量平均分子量Mn藉由下述條件進行的以單分散聚苯乙烯為標準的凝膠滲透層析法(GPC)測定。 The weight average molecular weight Mw and the number average molecular weight Mn were measured by gel permeation chromatography (GPC) based on monodisperse polystyrene by the following conditions.

柱：Tosoh(股)製造，TSK gel GRCXLII溶劑：四氫呋喃溫度：40℃壓力：68kgf/cm² Column: manufactured by Tosoh (stock), TSK gel GRCXLII solvent: tetrahydrofuran temperature: 40 ° C pressure: 68 kgf / cm ²

環氧當量根據JIS C2105的「鹽酸-甲乙酮法」測定。 The epoxy equivalent is measured in accordance with the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105.

聚合物溶液的溶液黏度(mPa．s)是使用E型旋轉黏度計，在25℃下測定在NMP溶劑中各個聚醯胺酸的濃度20重量%的黏度。 The solution viscosity (mPa.s) of the polymer solution was measured by using an E-type rotational viscometer to measure the viscosity of each polyamine in a NMP solvent at 20 ° C at a concentration of 20% by weight.

聚醯亞胺的醯亞胺化率是將聚醯亞胺的NMP溶液投入純水中，將所得的沉澱在室溫下充分減壓乾燥後，溶解到重氫化二甲基亞碸中，以四甲基矽烷作為基準物質，在室溫下測定¹H-NMR。從所得的¹H-NMR光譜，藉由下述數學式(1)所示的式子求得醯亞胺化率。 The ruthenium iodide ratio of the polyimine is obtained by adding a poly(imine) NMP solution to pure water, and the obtained precipitate is sufficiently dried under reduced pressure at room temperature, and then dissolved in dimethyl hydrazine. Tetramethyl decane was used as a reference material, and ¹ H-NMR was measured at room temperature. From the obtained ¹ H-NMR spectrum, the oxime imidization ratio was determined by the formula represented by the following formula (1).

醯亞胺化率(%)=(1-A¹/A²×α)×100 (1)(數學式(1)中，A¹是來自化學位移10ppm附近顯現出的NH基的質子的波峰面積，A²是來自其他質子的波峰面積，α是其他質子的個數相對於1個聚合物的前驅物(聚醯胺酸)中的NH基的質子的比例)。 Amidation rate (%) = (1 - A ¹ / A ² × α) × 100 (1) (In the mathematical formula (1), A ¹ is a peak of a proton derived from an NH group which appears near a chemical shift of 10 ppm. The area, A ² is the peak area from other protons, and α is the ratio of the number of other protons to the proton of the NH group in the precursor of one polymer (polyproline).

¹H-NMR分析使用核磁共振裝置(商品名：JNM- ECX400，日本電子公司製造)。 ¹ H-NMR analysis was performed using a nuclear magnetic resonance apparatus (trade name: JNM-ECX400, manufactured by JEOL Ltd.).

原料化合物和聚合物的合成根據下述合成規模，根據需要重複進行，以確保以下的合成使用的必要量。 The synthesis of the starting compound and the polymer is repeated as needed according to the following synthesis scale to ensure the necessary amount of the following synthetic use.

[具有環氧基的聚有機矽氧烷的合成] [Synthesis of polyorganosiloxane having an epoxy group]

(合成例E-1) (Synthesis Example E-1)

在帶有攪拌器、溫度計、滴液漏斗和回流冷凝管的反應容器中，加入100.0g的2-(3,4-環氧環己基)乙基三甲氧基矽烷、500g甲基異丁基酮以及10.0g三乙胺，在室溫下混合。接著，從滴液漏斗，用30分鐘滴加100g去離子水後，在回流下邊混合，邊在80℃下反應6小時。反應結束後，取出有機層，藉由0.2重量%的硝酸銨水溶液洗滌到洗滌後的水為中性後，在減壓下餾出溶劑和水，得到具有環氧基的聚有機矽氧烷(EPS-1)，為黏稠的透明液體。 In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 100.0 g of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 500 g of methyl isobutyl ketone were added. And 10.0 g of triethylamine was mixed at room temperature. Next, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was mixed under reflux, and reacted at 80 ° C for 6 hours. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous solution of ammonium nitrate until the washed water was neutral, and then the solvent and water were distilled off under reduced pressure to give a polyorganooxane having an epoxy group ( EPS-1) is a viscous transparent liquid.

對該聚有機矽氧烷(EPS-1)進行¹H-NMR分析，在化學位移(δ)=3.2ppm附近得到理論強度的基於環氧基的波峰。由此，確認在反應中環氧基沒有產生副反應。 The polyorganosiloxane (EPS-1) was subjected to ¹ H-NMR analysis to obtain a theoretically based epoxy group-based peak at a chemical shift (δ) of 3.2 ppm. From this, it was confirmed that no side reaction occurred in the epoxy group in the reaction.

得到的聚有機矽氧烷(EPS-1)的重量平均分子量Mw是2,200，環氧當量是186g/mol。 The obtained polyorganosiloxane (EPS-1) had a weight average molecular weight Mw of 2,200 and an epoxy equivalent of 186 g/mol.

[肉桂酸衍生物(A)的合成] [Synthesis of cinnamic acid derivative (A)]

(合成例A-1) (Synthesis Example A-1)

根據下述合成示意圖1，合成肉桂酸衍生物(A-1)。 The cinnamic acid derivative (A-1) was synthesized according to the following Synthesis Scheme 1.

在1L的茄型燒瓶中，加入91.3g的4-羥基苯甲酸甲酯、182.4g碳酸鉀和320mL的N-甲基-2-吡咯啶酮，在室溫下攪拌1小時後，加入157.1g的1-碘化-4,4,4-三氟丁烷，在100℃下攪拌5小時。反應結束後，用水再次沉澱。接著，在該沉澱中加入48g氫氧化鈉和400mL水，回流3小時，進行水解反應。反應結束後，藉由鹽酸中和，產生的沉澱藉由乙醇再結晶，得到110g化合物(A-1-1)的白色結晶。 In a 1 L eggplant type flask, 91.3 g of methyl 4-hydroxybenzoate, 182.4 g of potassium carbonate and 320 mL of N-methyl-2-pyrrolidone were added, and after stirring at room temperature for 1 hour, 157.1 g was added. 1-Iodide-4,4,4-trifluorobutane was stirred at 100 ° C for 5 hours. After the reaction was completed, it was precipitated again with water. Next, 48 g of sodium hydroxide and 400 mL of water were added to the precipitate, and the mixture was refluxed for 3 hours to carry out a hydrolysis reaction. After completion of the reaction, the precipitate formed by neutralization with hydrochloric acid was recrystallized from ethanol to obtain white crystals of 110 g of Compound (A-1-1).

將該化合物(A-1-1)中的12.41g裝入反應容器，在其中加入100mL亞硫醯氯和77μL的N,N-二甲基甲醯胺，在80℃下攪拌1小時。接著，在減壓下餾出亞硫醯氯，加入二氯甲烷，用碳酸氫鈉水溶液洗滌，用硫酸鎂乾燥，濃縮後，加入四氫呋喃，形成溶液。 12.41 g of the compound (A-1-1) was placed in a reaction vessel, and 100 mL of sulfinium chloride and 77 μL of N,N-dimethylformamide were added thereto, and the mixture was stirred at 80 ° C for 1 hour. Next, sulfinium chloride was distilled off under reduced pressure, dichloromethane was added, and the mixture was washed with a sodium hydrogencarbonate aqueous solution, dried over magnesium sulfate

接著，在和上述不同的500mL的三口燒瓶中，加入7.39g的4-羥基肉桂酸、13.82g碳酸鉀、0.48g四丁基銨、50mL四氫呋喃和100mL水。冰冷卻該水溶液，緩慢滴加上述四氫呋喃溶液，然後攪拌2小時進行反應。反應結束後，加入鹽酸中和，用乙酸乙酯萃取後，用硫酸鎂乾燥，濃縮後，藉由乙醇再結晶，得到10.0g肉桂酸衍生物(A-1) 的白色結晶。 Next, in a 500 mL three-necked flask different from the above, 7.39 g of 4-hydroxycinnamic acid, 13.82 g of potassium carbonate, 0.48 g of tetrabutylammonium, 50 mL of tetrahydrofuran, and 100 mL of water were added. The aqueous solution was ice-cooled, and the above tetrahydrofuran solution was slowly added dropwise, followed by stirring for 2 hours to carry out a reaction. After completion of the reaction, the mixture was neutralized with hydrochloric acid, extracted with ethyl acetate, dried over magnesium sulfate, and concentrated, and then recrystallized from ethanol to obtain 10.0 g of cinnamic acid (A-1) White crystals.

(合成例A-2) (Synthesis Example A-2)

根據下述合成示意圖2，合成肉桂酸衍生物(A-2)。 The cinnamic acid derivative (A-2) was synthesized according to the following Synthesis Scheme 2.

在帶有回流冷凝管、溫度計和氮氣導入管的500mL的三口燒瓶中，加入31g的化合物(A-2-1)、0.23g醋酸鈀、1.2g三(鄰-甲苯基)膦、56mL三乙胺、8.2mL丙烯酸和200mL的N,N-二甲基乙醯胺，在120℃下攪拌3小時進行反應。反應結束後，過濾反應混合物，在得到的濾液中加入1L乙酸乙酯，得到的有機層依次用稀鹽酸洗滌2次，用水洗滌3次，用硫酸鎂乾燥。之後，在減壓下除去溶劑，得到的固體從乙酸乙酯和四氫呋喃的混合溶劑再結晶，得到15g肉桂酸衍生物(A-2)的結晶。 In a 500 mL three-necked flask equipped with a reflux condenser, a thermometer, and a nitrogen introduction tube, 31 g of the compound (A-2-1), 0.23 g of palladium acetate, 1.2 g of tris(o-tolyl)phosphine, and 56 mL of triethyl were added. The amine, 8.2 mL of acrylic acid and 200 mL of N,N-dimethylacetamide were stirred at 120 ° C for 3 hours to carry out a reaction. After the reaction was completed, the reaction mixture was filtered, and ethyl acetate (1 mL) was evaporated. Then, the solvent was removed under reduced pressure, and the obtained solid was recrystallized from a mixed solvent of ethyl acetate and tetrahydrofuran to obtain crystals of 15 g of the cinnamic acid derivative (A-2).

(合成例A-3) (Synthesis Example A-3)

根據下述合成示意圖3，合成肉桂酸衍生物(A-3)。 The cinnamic acid derivative (A-3) was synthesized according to the following Synthesis Scheme 3.

在帶有回流冷凝管和氮氣導入管的300mL的茄型燒瓶中，加入21g化合物(A-3-1)、80mL亞硫醯氯和0.1mL的N,N-二甲基甲醯胺，在80℃下攪拌1小時進行反應。反應結束後，從反應混合物餾出亞硫醯氯，然後加入150mL二氯甲烷，得到的有機層用水洗滌3次。該有機層用硫酸鎂乾燥後，減壓除去溶劑，在得到的固體中加入400mL四氫呋喃。 In a 300 mL eggplant flask with a reflux condenser and a nitrogen inlet tube, 21 g of compound (A-3-1), 80 mL of sulfinium chloride and 0.1 mL of N,N-dimethylformamide were added. The reaction was carried out by stirring at 80 ° C for 1 hour. After the completion of the reaction, sulfinium chloride was distilled off from the reaction mixture, and then 150 mL of dichloromethane was added, and the obtained organic layer was washed three times with water. After the organic layer was dried over magnesium sulfate, solvent was evaporated under reduced pressure, and 400 mL of tetrahydrofurane was added to the obtained solid.

另一方面，在帶有滴液漏斗和溫度計的1L的三口燒瓶中，加入16g對羥基肉桂酸、24g碳酸鉀、0.87g溴化四丁基銨、200mL水和100mL四氫呋喃，冰冷到5℃以下。在其中用3小時滴加上述四氫呋喃溶液，然後攪拌1小時進行反應。反應結束後，在反應混合物中加入稀鹽酸，使pH為4以下後，加入3L甲苯和1L四氫呋喃，得到的有機層用水洗滌3次。該有機層用硫酸鎂乾燥後，減壓除去溶劑，所得的固體藉由由乙醇和四氫呋喃的混合溶劑再結晶，從而得到21g作為肉桂酸衍生物的化合物(A-3)。 On the other hand, in a 1 L three-necked flask equipped with a dropping funnel and a thermometer, 16 g of p-hydroxycinnamic acid, 24 g of potassium carbonate, 0.87 g of tetrabutylammonium bromide, 200 mL of water and 100 mL of tetrahydrofuran were added, and the mixture was ice-cooled to below 5 ° C. . The above tetrahydrofuran solution was added dropwise thereto over 3 hours, followed by stirring for 1 hour to carry out the reaction. After completion of the reaction, dilute hydrochloric acid was added to the reaction mixture to adjust the pH to 4 or less, and then 3 L of toluene and 1 L of tetrahydrofuran were added, and the obtained organic layer was washed three times with water. After the organic layer was dried over magnesium sulfate, the solvent was evaporated under reduced pressure, and the obtained solid was recrystallized from a solvent mixture of ethanol and tetrahydrofuran to obtain 21 g of the compound (A-3) as a cinnamic acid derivative.

[感放射線性聚有機矽氧烷的合成] [Synthesis of Radiation-Specific Polyorganosiloxanes]

(合成例S-1) (Synthesis Example S-1)

在300mL的三口燒瓶中，加入30.1g作為具有環氧基的聚有機矽氧烷的上述合成例E-1得到的化合物(EPS-1)、140g甲基異丁基酮、31.9g上述合成例A-1得到的肉桂酸衍生物(A-1)(相對於化合物(EPS-1)所具有的矽原子，相當於50莫耳%)、4.60g硬脂酸(相對於化合物(EPS-1)所具有的矽原子，相當於10莫耳%)、0.0686g的3,5二硝基苯甲酸(相對於化合物(EPS-1)所具有的矽原子，相當於 0.2莫耳%)和3.00g溴化四丁基銨，在80℃下攪拌5小時，進行反應。反應結束後，用甲醇再次沉澱，沉澱物溶於乙酸乙酯中，得到溶液，該溶液水洗5次後，餾出溶劑，作為感放射線性聚有機矽氧烷，得到55.6g重量平均分子量(Mw)是12,600(Mw/Mn=1.42)的化合物(S-1)的白色粉末。 Into a 300 mL three-necked flask, 30.1 g of the compound (EPS-1) obtained in the above Synthesis Example E-1 as a polyorganosiloxane having an epoxy group, 140 g of methyl isobutyl ketone, and 31.9 g of the above synthesis example were added. The cinnamic acid derivative (A-1) obtained in A-1 (corresponding to a halogen atom possessed by the compound (EPS-1), equivalent to 50 mol%), and 4.60 g of stearic acid (relative to the compound (EPS-1) ) a helium atom (corresponding to 10 mol%) and 0.0686 g of 3,5 dinitrobenzoic acid (relative to the ruthenium atom of the compound (EPS-1)) 0.2 mol%) and 3.00 g of tetrabutylammonium bromide were stirred at 80 ° C for 5 hours to carry out a reaction. After completion of the reaction, the precipitate was reprecipitated with methanol, and the precipitate was dissolved in ethyl acetate to give a solution. After the mixture was washed with water for 5 times, the solvent was distilled off to obtain a radiation-concentrating polyorganooxane to obtain a weight average molecular weight of 55.6 g (Mw). ) is a white powder of the compound (S-1) at 12,600 (Mw/Mn = 1.42).

(合成例S-2) (Synthesis Example S-2)

在200mL的三口燒瓶中，加入10.0g作為具有環氧基的聚有機矽氧烷的上述合成例E-1得到的化合物(EPS-1)、60g甲基異丁基酮、1.62g上述合成例A-2得到的肉桂酸衍生物(A-2)(相對於化合物(EPS-1)所具有的矽原子，相當於10莫耳%)、3.45g上述合成例A-3得到的肉桂酸衍生物(A-3)(相對於化合物(EPS-1)所具有的矽原子，相當於15莫耳%)以及1.00g溴化四丁基銨，在80℃下攪拌2小時，進行反應。反應結束後，用甲醇再次沉澱，沉澱物溶於乙酸乙酯中，得到溶液，該溶液水洗5次後，餾出溶劑，作為感放射線性聚有機矽氧烷，得到12.8g重量平均分子量(Mw)是11,200(Mw/Mn=1.13)的化合物(S-2)的白色粉末。 Into a 200 mL three-necked flask, 10.0 g of the compound (EPS-1) obtained in the above Synthesis Example E-1 as a polyorganosiloxane having an epoxy group, 60 g of methyl isobutyl ketone, and 1.62 g of the above synthesis example were added. The cinnamic acid derivative (A-2) obtained in A-2 (corresponding to a ruthenium atom of the compound (EPS-1), corresponding to 10 mol%), 3.45 g of the cinnamic acid derivative obtained in the above Synthesis Example A-3 The compound (A-3) (corresponding to 15 atom% of a ruthenium atom of the compound (EPS-1)) and 1.00 g of tetrabutylammonium bromide were stirred at 80 ° C for 2 hours to carry out a reaction. After completion of the reaction, the precipitate was reprecipitated with methanol, and the precipitate was dissolved in ethyl acetate to give a solution. After the mixture was washed with water for 5 times, the solvent was distilled off to obtain a radiation-sensitive polyorganooxane to obtain a weight average molecular weight of 12.8 g (Mw). ) is a white powder of the compound (S-2) at 11,200 (Mw/Mn = 1.13).

(實施例S-3) (Example S-3)

在50mL的三口燒瓶中，加入2.01g作為具有環氧基的聚有機矽氧烷的上述合成例E-1得到的化合物(EPS-1)、16g甲基異丁基酮、1.61g上述合成例A-2得到的肉桂酸衍生物(A-2)(相對於化合物(EPS-1)所具有的矽原子，相當於50莫耳%)、0.356g的4-三級丁基氧基羰基苯甲酸(相對 於化合物(EPS-1)所具有的矽原子，相當於15莫耳%)以及0.20g溴化四丁基銨，在80℃下攪拌2小時，進行反應。反應結束後，用甲醇再次沉澱，沉澱物溶於乙酸乙酯中，得到溶液，該溶液水洗5次後，餾出溶劑，作為感放射線性聚有機矽氧烷，得到3.46g重量平均分子量(Mw)是14,700(Mw/Mn=1.51)的化合物(S-3)的白色粉末。 Into a 50 mL three-necked flask, 2.01 g of the compound (EPS-1) obtained in the above Synthesis Example E-1 as a polyorganosiloxane having an epoxy group, 16 g of methyl isobutyl ketone, and 1.61 g of the above synthesis example were added. The cinnamic acid derivative (A-2) obtained in A-2 (corresponding to a halogen atom possessed by the compound (EPS-1), equivalent to 50 mol%), 0.356 g of 4-tributyloxycarbonylbenzene Formic acid The reaction was carried out by stirring at 80 ° C for 2 hours at a compound (EPS-1) having a halogen atom corresponding to 15 mol%) and 0.20 g of tetrabutylammonium bromide. After completion of the reaction, the precipitate was reprecipitated with methanol, and the precipitate was dissolved in ethyl acetate to give a solution. After the mixture was washed with water for 5 times, the solvent was distilled off to obtain a radiation-concentrating polyorganooxane to obtain a weight average molecular weight of 3.46 g (Mw). ) is a white powder of the compound (S-3) of 14,700 (Mw/Mn = 1.51).

[聚醯胺酸和聚醯亞胺的合成] [Synthesis of polyaminic acid and polyimine]

(合成例P-1) (Synthesis Example P-1)

將19.61g(0.1mol)的1,2,3,4-環丁四甲酸二酐和21.23g(0.1mol)4,4’-二胺基-2,2’-二甲基聯苯溶解到367.6g的N-甲基-2-吡咯啶酮中，在室溫下反應6小時。接著，將反應混合物注入大量過量的甲醇中，使反應產物沉澱。沉澱物用甲醇洗滌，減壓、40℃下乾燥15小時，得到35g聚醯胺酸(PA-1)。 Dissolve 19.61 g (0.1 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 21.23 g (0.1 mol) of 4,4'-diamino-2,2'-dimethylbiphenyl to In 367.6 g of N-methyl-2-pyrrolidone, the reaction was carried out for 6 hours at room temperature. Next, the reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain 35 g of polyamine (PA-1).

(合成例P-2) (Synthesis Example P-2)

將21.81g(0.0973mol)2,3,5-三羧基環戊基乙酸二酐和19.29g(0.0390mol)下述式(p1)所示的5ξ-膽甾烷-3-基2,4-二胺基苯基醚、8.90g(0.0585mol)的3,5-二胺基苯甲酸溶解到200g的N-甲基-2-吡咯啶酮中，在60℃下反應5小時。測定該聚合溶液的黏度是1450mPa．s。接著，在該溶液中加入250g的N-甲基-2-吡咯啶酮，攪拌一會後，加入11.55g吡啶和14.90g乙酸酐，在110℃下脫水閉環4小時。之後，將反應混合物注入大量過量的甲醇中，使反應產物沉澱。沉澱物用甲醇洗滌，在減壓下40℃乾燥15小時，得到37.5g醯亞胺化率69%的聚醯亞胺(PI-1)。 21.81 g (0.0973 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 19.29 g (0.0390 mol) of 5ξ-cholest-3-yl 2,4- represented by the following formula (p1) Diaminophenyl ether, 8.90 g (0.0585 mol) of 3,5-diaminobenzoic acid was dissolved in 200 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 5 hours. The viscosity of the polymerization solution was determined to be 1450 mPa. s. Next, 250 g of N-methyl-2-pyrrolidone was added to the solution, and after stirring for a while, 11.55 g of pyridine and 14.90 g of acetic anhydride were added, and the mixture was dehydrated and closed at 110 ° C for 4 hours. Thereafter, the reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain 37.5 g of polyimine (PI-1) having a oxime imidization ratio of 69%.

(合成例P-3) (Synthesis Example P-3)

將23.38g(0.104mol)2,3,5-三羧基環戊基乙酸二酐和15.50g(0.0313mol)下述式(p1)所示的5ξ-膽甾烷-3-基2,4-二胺基苯基醚、11.12g(0.0731mol)的3,5-二胺基苯甲酸溶解到200g的N-甲基-2-吡咯啶酮中，在60℃下反應5小時。接著，在該溶液中加入250g的N-甲基-2-吡咯啶酮，攪拌一會後，加入12.37g吡啶和15.97g乙酸酐，在110℃下脫水閉環4小時。之後，將反應混合物注入大量過量的甲醇中，使反應產物沉澱。沉澱物用甲醇洗滌，減壓、40℃下乾燥15小時，得到36.4g醯亞胺化率71%的聚醯亞胺(PI-2)。 23.38 g (0.104 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 15.50 g (0.0313 mol) of 5ξ-cholest-3-yl 2,4- represented by the following formula (p1) Diaminophenyl ether, 11.12 g (0.0731 mol) of 3,5-diaminobenzoic acid was dissolved in 200 g of N-methyl-2-pyrrolidone, and reacted at 60 ° C for 5 hours. Next, 250 g of N-methyl-2-pyrrolidone was added to the solution, and after stirring for a while, 12.37 g of pyridine and 15.97 g of acetic anhydride were added, and the mixture was dehydrated and closed at 110 ° C for 4 hours. Thereafter, the reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain 36.4 g of polyimine (PI-2) having a ruthenium iodide ratio of 71%.

(合成例P-4) (Synthesis Example P-4)

將26.73g(0.119mol)2,3,5-三羧基環戊基乙酸二酐和73.27g(0.119mol)下述式(p2)所示的6-{[((2E)-3-{4-[(4-(3,3,3-三氟丙氧基)苯甲醯基)氧基]苯基}丙-2-醯基)氧基]}苄基-3,5二胺基苯甲酸酯溶解到185.7g的N-甲基-2-吡咯啶酮中，在60℃下反應24小時。測定該聚合溶液的黏度是4800mPa．s。接著，將反應混合物注入大過量的甲醇中，使反應產物沉澱。沉澱物用甲醇洗滌，在減壓下40℃乾燥15小時，得到70g聚醯胺酸(PA-2)。 26.73 g (0.119 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 73.27 g (0.119 mol) of 6-{[((2E)-3-{4) represented by the following formula (p2) -[(4-(3,3,3-trifluoropropoxy)benzylidenyl)oxy]phenyl}propan-2-yl)oxy]}benzyl-3,5-diaminobenzene The formate was dissolved in 185.7 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 24 hours. The viscosity of the polymerization solution was determined to be 4800 mPa. s. Next, the reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain 70 g of polyamine (PA-2).

(合成例P-5) (Synthesis Example P-5)

將27.07g(0.121mol)2,3,5-三羧基環戊基乙酸二酐和66.79g(0.109mol)上述式(p2)所示的6-{[((2E)-3-{4-[(4-(3,3,3-三氟丙氧基)苯甲醯基)氧基]苯基}丙-2-醯基)氧基]}苄基-3,5二胺基苯甲酸酯、2.99g(0.00604mol)上述式(p1)所示的5ξ-膽甾烷-3-基2,4-二胺基苯基醚、以及3.16g(0.00604mol)下述式(p3)所示的3,5-二胺基苯甲酸=5ξ-膽甾烷-3-基酯溶解到185.7g的N-甲基3-吡咯啶酮中，在60℃下反應24小時。測定該聚合溶液的黏度是2100mPa．s。接著，將反應混合物注入大過量的甲醇中，使反應產物沉澱。沉澱物用甲醇洗滌，在減壓下40℃乾燥15小時，得到68g聚醯胺酸(PA-3)。 27.07 g (0.121 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 66.79 g (0.109 mol) of 6-{[((2E)-3-{4-) represented by the above formula (p2) [(4-(3,3,3-Trifluoropropoxy)benzylidenyl)oxy]phenyl}propan-2-yl)oxy]}benzyl-3,5-diaminobenzoic acid Acid ester, 2.99 g (0.00604 mol) of 5ξ-cholest-3-yl 2,4-diaminophenyl ether represented by the above formula (p1), and 3.16 g (0.00604 mol) of the following formula (p3) The 3,5-diaminobenzoic acid = 5 ξ-cholest-3-yl ester shown was dissolved in 185.7 g of N-methyl 3-pyrrolidone and reacted at 60 ° C for 24 hours. The viscosity of the polymerization solution was determined to be 2100 mPa. s. Next, the reaction mixture was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to give 68 g of polyamine (PA-3).

(合成例P-6) (Synthesis Example P-6)

將18.75g(0.0836mol)作為四羧酸二酐的2,3,5-三羧基環戊基乙酸二酐、7.359g(0.0681mol)作為二胺化合物的對伸苯基二胺、以及8.895g(0.0170mol)上述式(p3)所 示的3,5-二胺基苯甲酸=5ξ-膽甾烷-3-基酯溶解到140g的N-甲基-2-吡咯啶酮中，在60℃下反應5小時。測定該聚合溶液的黏度是2000mPa．s。接著，在該溶液中加入325g的N-甲基-2-吡咯啶酮，攪拌一會後，加入6.61g吡啶和8.54g乙酸酐，在110℃下脫水閉環4小時。之後，將反應溶液注入大過量的甲醇中，使反應產物沉澱。沉澱物用甲醇洗滌，在減壓下40℃乾燥15小時，得到26.6g醯亞胺化率51%的聚醯亞胺(PI-3)。 18.75 g (0.0836 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, 7.359 g (0.0681 mol) of p-phenylenediamine as a diamine compound, and 8.895 g (0.0170 mol) of the above formula (p3) The 3,5-diaminobenzoic acid = 5 ξ-cholest-3-yl ester shown was dissolved in 140 g of N-methyl-2-pyrrolidone and reacted at 60 ° C for 5 hours. The viscosity of the polymerization solution was determined to be 2000 mPa. s. Next, 325 g of N-methyl-2-pyrrolidone was added to the solution, and after stirring for a while, 6.61 g of pyridine and 8.54 g of acetic anhydride were added, and the mixture was dehydrated and closed at 110 ° C for 4 hours. Thereafter, the reaction solution was poured into a large excess of methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried under reduced pressure at 40 ° C for 15 hours to obtain 26.6 g of polyethylenimine (PI-3) having a ruthenium iodide ratio of 51%.

[液晶配向劑的製備] [Preparation of Liquid Crystal Aligning Agent]

(製備例1) (Preparation Example 1)

相對30重量份上述合成例P-1得到的聚醯胺酸(PA-1)、70重量份合成例P-2得到的聚醯亞胺(PI-1)，加入10重量份合成例S-1得到的感放射線性聚有機矽氧烷(S-1)、N-甲基-2-吡咯啶酮(NMP)和丁基賽璐蘇(BC)並使溶劑組成為NMP：BC=45：55(重量比)，形成固體成分濃度3.5重量%的溶液。該溶液使用孔徑0.2μm的篩檢程式過濾，製備液晶配向劑(AF-1)。 30 parts by weight of the polyimine (PA-1) obtained in the above Synthesis Example P-1, 70 parts by weight of the polyimine (PI-1) obtained in Synthesis Example P-2, and 10 parts by weight of Synthesis Example S- 1 obtained radiation-sensitive polyorganosiloxane (S-1), N-methyl-2-pyrrolidone (NMP) and butyl cyanidin (BC) and the solvent composition was NMP: BC=45: 55 (weight ratio), a solution having a solid concentration of 3.5% by weight was formed. This solution was filtered using a screening procedure having a pore size of 0.2 μm to prepare a liquid crystal alignment agent (AF-1).

(製備例2~7) (Preparation examples 2 to 7)

除了感放射線性聚有機矽氧烷的種類和添加量、聚醯胺酸和聚醯亞胺的種類和添加量、溶劑組成分別如下述表1所記載以外，和製備例1同樣地分別製備液晶配向劑(AF-2)~(AF-7)。 Liquid crystals were prepared in the same manner as in Preparation Example 1 except that the type and amount of the radiation-sensitive polyorganosiloxane were changed, the type and amount of the poly-proline and the polyimide, and the solvent composition were as described in Table 1 below. Orientation agent (AF-2) ~ (AF-7).

(製備例8) (Preparation Example 8)

相對100重量份上述合成例P-6得到的聚醯胺酸(PI-3)，加入20重量份N,N,N’,N’-四縮水甘油基-4,4’-二胺基二苯基甲烷、N-甲基-2-吡咯啶酮(NMP)和丁基賽璐蘇(BC)並使溶劑組成為NMP：BC=50：50(重量比)，形成固體成分濃度3.5重量%的溶液。該溶液使用孔徑0.2μm的篩檢程式過濾，製備液晶配向劑(AF-8)。 20 parts by weight of N,N,N',N'-tetraglycidyl-4,4'-diamino group 2 was added to 100 parts by weight of the polylysine (PI-3) obtained in the above Synthesis Example P-6. Phenylmethane, N-methyl-2-pyrrolidone (NMP) and butyl quercetin (BC) and the solvent composition was NMP: BC = 50:50 (weight ratio) to form a solid concentration of 3.5% by weight. The solution. This solution was filtered using a screening procedure having a pore size of 0.2 μm to prepare a liquid crystal alignment agent (AF-8).

[液晶顯示元件的製造] [Manufacture of liquid crystal display elements]

(實施例1) (Example 1)

在帶有由ITO膜形成的透明電極的玻璃基板的透明電極面上，使用旋塗器，塗布上述製備例1製備的液晶配向劑(AF-1)，在80℃的熱板上，預烘烤1分鐘後，在內部氮氣置換的烘箱中，在200℃下，加熱1小時，形成膜厚80nm的塗膜。接著，在該塗膜的表面，使用Hg-Xe燈和格蘭-泰勒棱鏡，從相對垂直基板表面的方向傾斜40°的方向，照射含有313nm的輝線的偏光紫外線200J/m²，製造基板A。 On the transparent electrode surface of the glass substrate with the transparent electrode formed of the ITO film, the liquid crystal alignment agent (AF-1) prepared in the above Preparation Example 1 was applied using a spin coater, and prebaked on a hot plate at 80 ° C. After baking for 1 minute, it was heated at 200 ° C for 1 hour in an internal nitrogen-substituted oven to form a coating film having a film thickness of 80 nm. Next, on the surface of the coating film, using a Hg-Xe lamp and a Glan-Taylor prism, a polarized ultraviolet ray of 200 J/m ² containing a bright wire of 313 nm was irradiated from a direction inclined by 40° with respect to the direction of the surface of the vertical substrate to fabricate the substrate A. .

另外，同樣地在帶有由ITO膜形成的透明電極的玻璃基板的透明電極面上，使用旋塗器，塗布上述製備例1製備的液晶配向劑(AF-1)，在80℃的熱板上，預烘烤1分鐘後，在內部氮氣置換的烘箱中，在200℃下，加熱1小時，形成膜厚80nm的塗膜，製造基板B。另外，基板B側不照射偏光UV。 Further, in the same manner, on the transparent electrode surface of the glass substrate with the transparent electrode formed of the ITO film, the liquid crystal alignment agent (AF-1) prepared in the above Preparation Example 1 was applied using a spin coater, and the hot plate at 80 ° C was applied. After prebaking for 1 minute, the film was heated at 200 ° C for 1 hour in an internal nitrogen-substituted oven to form a coating film having a film thickness of 80 nm, thereby producing a substrate B. Further, the substrate B side is not irradiated with the polarized light UV.

在上述基板B的具有塗膜的面的外周，藉由絲網印刷塗布加入了直徑5.5μm的氧化鋁球的環氧樹脂黏合劑後，將基板A的塗膜面對向壓接，在150℃下花1小時將黏合劑熱硬化。接著，從液晶注入口，在基板間的間隙中，填充負型液晶(Merck公司製造，MLC-6608)後，通過丙烯酸類光硬化黏合劑密封液晶注入口。然後，為了除去液晶注入時的流動配向，將其在150℃加熱10分鐘後，緩慢冷卻到室溫。接著，在基板A、B的外側兩面，貼合偏光板以使其偏光方向相互正交，而且在基板A中，和紫外線光軸往基板面的投影方向形成45°的角度，製造液晶顯示元件。 On the outer periphery of the surface of the substrate B having the coating film, an epoxy resin adhesive having a diameter of 5.5 μm is applied by screen printing, and then the coating film of the substrate A is pressed against the surface. The adhesive was thermally hardened by flowering at 150 ° C for 1 hour. Next, a negative liquid crystal (MLC-6608, manufactured by Merck Co., Ltd.) was filled in the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive. Then, in order to remove the flow alignment at the time of liquid crystal injection, it was heated at 150 ° C for 10 minutes, and then slowly cooled to room temperature. Next, the polarizing plates are bonded to the outer surfaces of the substrates A and B so that the polarization directions thereof are orthogonal to each other, and the substrate A is formed at an angle of 45° with the projection direction of the ultraviolet light axis toward the substrate surface to manufacture a liquid crystal display element. .

(實施例2~7) (Examples 2 to 7)

使用下述表2所記載的物質作為液晶配向劑以外，藉由和實施例1同樣的方法製造液晶胞。 A liquid crystal cell was produced by the same method as in Example 1 except that the material described in the following Table 2 was used as the liquid crystal alignment agent.

(實施例8) (Example 8)

1.評價用胞[1]的製造 1. Evaluation of the manufacture of cells [1]

首先，在具有形成狹縫狀圖案的透明導電膜(ITO膜)的剝離基板的透明電極面上，藉由旋塗器塗布上述製備例1製備的液晶配向劑(AF-1)。作為透明電極的圖案使用 圖2所示的這種基線和間隔分別是5μm的狹縫狀的圖案。接著，在80℃的熱板上，預烘烤1分鐘後，在內部氮氣置換的烘箱中，在200℃下，加熱1小時，形成膜厚80nm的塗膜，製造基板A。同樣地，在圖2所示的具有形成狹縫狀圖案的ITO膜的玻璃基板的透明電極面上，使用旋塗器，塗布上述製備例8製備的液晶配向劑(AF-8)，在80℃的熱板上，預烘烤1分鐘後，在內部氮氣置換的烘箱中，在200℃下，加熱1小時，形成膜厚80nm的液晶配向膜，製造基板B。 First, the liquid crystal alignment agent (AF-1) prepared in the above Preparation Example 1 was applied onto the transparent electrode surface of the release substrate having the transparent conductive film (ITO film) forming the slit-like pattern by a spin coater. Use as a pattern of transparent electrodes The base line and the interval shown in Fig. 2 are each a slit-like pattern of 5 μm. Subsequently, the film was prebaked on a hot plate at 80 ° C for 1 minute, and then heated in an internal nitrogen-substituted oven at 200 ° C for 1 hour to form a coating film having a film thickness of 80 nm, thereby producing a substrate A. Similarly, on the transparent electrode surface of the glass substrate having the ITO film forming the slit-like pattern shown in FIG. 2, the liquid crystal alignment agent (AF-8) prepared in the above Preparation Example 8 was applied using a spin coater at 80 After prebaking for 1 minute on a hot plate of ° C, the film was heated at 200 ° C for 1 hour in an internal nitrogen-substituted oven to form a liquid crystal alignment film having a film thickness of 80 nm, thereby producing a substrate B.

在上述基板B的具有液晶配向膜的面的外周，藉由絲網印刷塗布加入了直徑5.5μm的氧化鋁球的環氧樹脂黏合劑後，將基板A的液晶配向膜面對向壓接，在150℃下花1小時將黏合劑熱硬化。接著，從液晶注入口，在基板間的間隙中，填充負型液晶(Merck公司製造，MLC-6608)後，用丙烯酸類光硬化黏合劑，密封液晶注入口，製造液晶胞。然後，為了除去液晶注入時的流動配向，將其在150℃加熱10分鐘後，緩慢冷卻到室溫。然後，在施加10V的AC電壓的狀態的液晶胞，使用鹵素燈，進行50,000J/m²的光照射後，在胞基板的外側兩面，貼合偏光板並使其偏光方向相互正交，而且在基板A中，和紫外線光軸往基板面的投影方向形成45°的角度，製造液晶顯示元件，將其作為評價用胞[1]。 On the outer periphery of the surface of the substrate B having the liquid crystal alignment film, an epoxy resin adhesive having a diameter of 5.5 μm is applied by screen printing, and the liquid crystal alignment film of the substrate A is faced to the surface. The adhesive was thermally hardened by taking 1 hour at 150 °C. Next, a negative liquid crystal (MLC-6608, manufactured by Merck Co., Ltd.) was filled in the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to produce a liquid crystal cell. Then, in order to remove the flow alignment at the time of liquid crystal injection, it was heated at 150 ° C for 10 minutes, and then slowly cooled to room temperature. Then, the liquid crystal cell in a state where an AC voltage of 10 V is applied is irradiated with light of 50,000 J/m ² using a halogen lamp, and then the polarizing plates are bonded to the outer surfaces of the cell substrate so that the polarization directions thereof are orthogonal to each other. In the substrate A, an angle of 45° was formed with the ultraviolet light axis toward the projection direction of the substrate surface, and a liquid crystal display element was produced, which was used as an evaluation cell [1].

2.評價用胞[2]的製造 2. Evaluation of the manufacture of cells [2]

除了使用不形成圖案的基板作為帶透明電極的玻璃基板以外，藉由和上述評價用胞1同樣的方法，在基板上 形成塗膜，製造基板A、B。接著，使用這些基板A、B，藉由和上述評價用胞1同樣的方法構成液晶胞，為了除去液晶注入時的流動配向，將其在150℃下加熱10分鐘後，緩慢冷卻到室溫後，對未施加電壓狀態的液晶胞，使用鹵素燈，光照射50,000J/m²。之後，在胞基板的外側兩面，貼合偏光板以使其偏光方向相互正交，而且在基板A中，和紫外線光軸往基板面的投影方向形成45°的角度，製造液晶顯示元件，將其作為評價用胞[2]。 A substrate A and B were produced by forming a coating film on the substrate in the same manner as the above-described evaluation cell 1 except that the substrate on which the pattern was not formed was used as the glass substrate with the transparent electrode. Next, using these substrates A and B, a liquid crystal cell was formed by the same method as the evaluation cell 1 described above, and after removing the flow alignment at the time of liquid crystal injection, it was heated at 150 ° C for 10 minutes, and then slowly cooled to room temperature. For a liquid crystal cell to which no voltage is applied, a halogen lamp is used, and light is irradiated at 50,000 J/m ² . Thereafter, the polarizing plates are bonded to the outer surfaces of the cell substrate so that the polarization directions thereof are orthogonal to each other, and the substrate A is formed at an angle of 45° with respect to the projection direction of the ultraviolet light axis toward the substrate surface, thereby manufacturing a liquid crystal display element. It is used as an evaluation cell [2].

(實施例9~14) (Examples 9 to 14)

除了使用下述表2記載的物質作為液晶配向劑以外，和實施例8同樣地製造兩種液晶顯示元件(評價用胞[1]、[2])。 Two liquid crystal display elements (evaluation cells [1], [2]) were produced in the same manner as in Example 8 except that the materials described in Table 2 below were used as the liquid crystal alignment agent.

(比較例1~3) (Comparative examples 1 to 3)

除了使用下述表2記載的物質作為液晶配向劑，而且基板A和基板B兩者都沒有照射偏光UV以外，和實施例1同樣地製造液晶顯示元件。 A liquid crystal display element was produced in the same manner as in Example 1 except that the material described in Table 2 below was used as the liquid crystal alignment agent, and neither the substrate A nor the substrate B was irradiated with the polarized light UV.

(比較例4、5) (Comparative examples 4 and 5)

除了使用下述表2記載的物質作為液晶配向劑以外，藉由和實施例1同樣的方法，在兩塊基板的各個表面上形成塗膜。接著，在各個塗膜的表面，使用Hg-Xe燈和格蘭-泰勒棱鏡，從相對垂直基板表面的方向傾斜40°的方向，照射含有313nm的輝線的偏光紫外線200J/m²，形成液晶配向膜，製造基板A、B。 A coating film was formed on each surface of the two substrates in the same manner as in Example 1 except that the materials described in Table 2 below were used as the liquid crystal alignment agent. Next, using a Hg-Xe lamp and a Glan-Taylor prism on the surface of each coating film, a polarized ultraviolet ray of 200 J/m ² containing a bright line of 313 nm was irradiated from a direction inclined by 40° with respect to the surface of the vertical substrate to form a liquid crystal alignment. Films, substrates A and B were produced.

接著，在上述基板A的具有液晶配向膜的面的外周，藉由絲網印刷塗布加入了直徑5.5μm的氧化鋁球的環氧 樹脂黏合劑後，將基板B的液晶配向膜面對向配置，壓接以使各基板的紫外線光軸往基板面的投影方向逆平行，在150℃下用1小時將黏合劑熱硬化。接著，從液晶注入口，在基板間的間隙中，填充負型液晶(Merck公司製造，MLC-6608)後，邊將胞部分遮光，邊通過丙烯酸類光硬化黏合劑密封液晶注入口。然後，為了除去液晶注入時的流動配向，將其在150℃下加熱後，緩慢冷卻到室溫。接著，在基板的外側兩面，貼合偏光板以使其偏光方向相互正交，而且和液晶配向膜的紫外線光軸往基板面的投影方向形成45°的角度，製造液晶顯示元件。 Next, on the outer periphery of the surface of the substrate A having the liquid crystal alignment film, an epoxy resin adhesive having a diameter of 5.5 μm was applied by screen printing, and the liquid crystal alignment film of the substrate B was faced. The pressure contact was placed so that the ultraviolet light axis of each substrate was parallel to the projection direction of the substrate surface, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, a negative liquid crystal (MLC-6608, manufactured by Merck Co., Ltd.) was filled in the gap between the substrates from the liquid crystal injection port, and then the cell portion was shielded from light, and the liquid crystal injection port was sealed by an acrylic photocurable adhesive. Then, in order to remove the flow alignment at the time of liquid crystal injection, it was heated at 150 ° C, and then slowly cooled to room temperature. Next, the polarizing plates were bonded to the outer surfaces of the substrate so that the polarization directions thereof were orthogonal to each other, and the ultraviolet light axis of the liquid crystal alignment film was formed at an angle of 45° toward the projection direction of the substrate surface to fabricate a liquid crystal display element.

[液晶顯示元件的評價] [Evaluation of liquid crystal display elements]

對製造的液晶顯示元件藉由下述方法對各專案進行性質評價。 The properties of each of the projects were evaluated by the following methods for the manufactured liquid crystal display elements.

(1)電壓保持率的評價 (1) Evaluation of voltage retention rate

對上述製造的液晶顯示元件，以60微秒的施加時間、167毫秒的間隔施加5V的電壓後，測定從解除施加到167毫秒後的電壓保持率(VHR)。測定裝置使用TOYOTechnica(股)製造的VHR-1。另外，實施例8~14使用評價用胞[2]進行。 With respect to the liquid crystal display element manufactured above, a voltage of 5 V was applied at an application time of 60 microseconds and an interval of 167 milliseconds, and then the voltage holding ratio (VHR) after the application was released for 167 milliseconds was measured. The measuring device used VHR-1 manufactured by TOYO Technica Co., Ltd. Further, Examples 8 to 14 were carried out using the evaluation cells [2].

(2)回應速度(開始時的電光學回應性)的評價 (2) Evaluation of response speed (electro-optical response at the beginning)

在包括了偏光顯微鏡和光檢測器和脈衝發生器的裝置中，測定液晶回應的開始時間。這裡所述的液晶回應速度定義為在製作的液晶顯示元件中從未施加電壓的狀態到最大施加1秒鐘5V電壓時，從透光率10%變化為透光率90%所需要的時間(單位：毫秒)，進行評價。另外，實 施例8~14使用評價用胞[1]進行。 In a device including a polarizing microscope and a photodetector and a pulse generator, the start time of the liquid crystal response is measured. The liquid crystal response speed described herein is defined as the time required to change from a light transmittance of 10% to a light transmittance of 90% in a state where no voltage is applied from the produced liquid crystal display element to a maximum application voltage of 5 V for 1 second ( Unit: milliseconds), for evaluation. In addition, the real Examples 8 to 14 were carried out using the evaluation cells [1].

(3)耐光性評價 (3) Light resistance evaluation

藉由以碳弧為光源的耐候儀，和上述(1)同樣地測定照射3000小時後的VHR。評價是和照射前的測定值相比，VHR變化量為1%以內的作為○，1~3%的作為△，3%以上的作為×。另外，實施例8~14使用評價用胞[2]進行。 The VHR after irradiation for 3,000 hours was measured in the same manner as in the above (1) by a weathering instrument using a carbon arc as a light source. In the evaluation, the VHR change amount is within 1% of ○, the range of 1 to 3% is Δ, and the 3% or more is × as compared with the measured value before the irradiation. Further, Examples 8 to 14 were carried out using the evaluation cells [2].

(4)對比度評價 (4) Contrast evaluation

在下述方法中，對製造的液晶胞中配向不佳的評價光透過程度，評價黑色等級，作為對比度評價的替代評價。首先，藉由正交尼克爾條件的偏光顯微鏡觀察，使視野最暗地配置液晶胞，照相拍攝該圖像。得到的資料區分為0.2mm方形×25像素，各像素的亮度使用圖像處理軟體，數值化為255階調。各像素(25像素)的階調差為30以內時，評價為對比度良好(○)，階調差大於30時，評價為對比度不好(×)。另外，實施例8~14使用評價用胞[1]進行。 In the following method, the degree of light transmission was evaluated for poor alignment in the produced liquid crystal cells, and the black level was evaluated as an alternative evaluation for contrast evaluation. First, the liquid crystal cell was placed darkest in the field of view by a polarizing microscope observation under a Orthogonal Nikkor condition, and the image was photographed. The obtained data is divided into 0.2 mm square × 25 pixels, and the brightness of each pixel is image processing software, and the numerical value is 255 tone. When the step difference of each pixel (25 pixels) was 30 or less, the contrast was evaluated as good (○), and when the step difference was more than 30, the contrast was evaluated as poor (×). Further, Examples 8 to 14 were carried out using the evaluation cells [1].

上述(1)~(4)的評價結果在下述表2中表示。 The evaluation results of the above (1) to (4) are shown in Table 2 below.

如表2所示，實施例1~14的液晶顯示元件顯示出高的電壓保持率，同時液晶分子對電壓變化的回應性質良好。另外，這些液晶顯示元件的對比度也良好。特別是，使用包含感放射線性聚有機矽氧烷的液晶配向劑形成的液晶顯示元件(實施例1~3,8~10)，其耐久性也優異。 As shown in Table 2, the liquid crystal display elements of Examples 1 to 14 exhibited high voltage holding ratio, and the liquid crystal molecules responded well to voltage changes. In addition, the contrast of these liquid crystal display elements is also good. In particular, a liquid crystal display element (Examples 1 to 3, 8 to 10) formed using a liquid crystal alignment agent containing a radiation-sensitive polyorganosiloxane is also excellent in durability.

另外，對於實施例1~14而言，如果將塗膜光照射後構成液晶胞的實施例1~7與構成液晶胞後光照射的實施例8~14相比，前者的液晶分子的反應性質更好。 Further, in Examples 1 to 14, the reaction properties of the liquid crystal molecules of the former were compared with Examples 1 to 7 which constitute liquid crystal cells after light irradiation of the coating film, and Examples 8 to 14 which constitute light irradiation of liquid crystal cells. better.

另一方面，比較例1~5的回應速度都快，但是液晶分子對電壓變化的回應速度不好。 On the other hand, the response speeds of Comparative Examples 1 to 5 were all fast, but the response speed of the liquid crystal molecules to the voltage change was not good.

10‧‧‧液晶顯示元件 10‧‧‧Liquid display components

11a‧‧‧基板 11a‧‧‧Substrate

11b‧‧‧基板 11b‧‧‧Substrate

12‧‧‧第1電極 12‧‧‧1st electrode

13‧‧‧第1配向膜 13‧‧‧1st alignment film

14‧‧‧第2電極 14‧‧‧2nd electrode

15‧‧‧第2配向膜 15‧‧‧2nd alignment film

16‧‧‧液晶分子 16‧‧‧liquid crystal molecules

17‧‧‧液晶層 17‧‧‧Liquid layer

18‧‧‧偏光板 18‧‧‧Polar plate

19‧‧‧偏光板 19‧‧‧Polar plate

圖1是液晶顯示元件的縱剖面圖。 1 is a longitudinal sectional view of a liquid crystal display element.

圖2是表示透明導電膜的圖案形狀的圖。 2 is a view showing a pattern shape of a transparent conductive film.

10‧‧‧液晶顯示元件 10‧‧‧Liquid display components

11a‧‧‧基板 11a‧‧‧Substrate

11b‧‧‧基板 11b‧‧‧Substrate

12‧‧‧第1電極 12‧‧‧1st electrode

13‧‧‧第1配向膜 13‧‧‧1st alignment film

14‧‧‧第2電極 14‧‧‧2nd electrode

15‧‧‧第2配向膜 15‧‧‧2nd alignment film

16‧‧‧液晶分子 16‧‧‧liquid crystal molecules

17‧‧‧液晶層 17‧‧‧Liquid layer

18‧‧‧偏光板 18‧‧‧Polar plate

19‧‧‧偏光板 19‧‧‧Polar plate

Claims (8)

一種液晶顯示元件，其係具有一對基板之液晶顯示元件，其特徵在於：在該一對基板中的一個基板表面上，形成使液晶分子相對垂直該基板表面的方向傾斜配向的第1配向膜，並且在另一個基板表面上，形成使液晶分子垂直配向的第2配向膜，該第1配向膜係使用包含具有光配向性基的聚合物及不具有光配向性基的聚合物的液晶配向劑而形成，該光配向性基具有來自包含偶氮苯、二苯乙烯、α-亞胺基-β-酮酯、螺吡喃、螺、肉桂酸、查耳酮、芪唑、亞苄基苄甲內醯胺(benzylidene phthalimidine)、香豆素、二苯基乙炔和蒽醌的群組中選出的至少一種化合物的結構，該具有光配向性基的聚合物為聚有機矽氧烷，該不具有光配向性基的聚合物為聚醯胺酸及聚醯亞胺之至少一者。 A liquid crystal display element comprising a pair of substrates, wherein a first alignment film is formed on a surface of one of the pair of substrates so that liquid crystal molecules are obliquely aligned with respect to a direction perpendicular to the surface of the substrate. And forming, on the surface of the other substrate, a second alignment film that vertically aligns the liquid crystal molecules, wherein the first alignment film uses a liquid crystal alignment comprising a polymer having a photo-alignment group and a polymer having no photo-alignment group. Formed as a reagent, the photo-alignment group having azobenzene, stilbene, α-imino-β-ketoester, spiropyran, snail a structure of at least one compound selected from the group consisting of cinnamic acid, chalcone, carbazole, benzylidene phthalimidine, coumarin, diphenylacetylene, and anthracene The polymer of the alignment group is a polyorganosiloxane, and the polymer having no photo-alignment group is at least one of polyamine and polyimine. 如申請專利範圍第1項的液晶顯示元件，其中用於形成該第1配向膜的液晶配向劑中，相對於合計100重量份之該不具有光配向性基的聚合物而言，該具有光配向性基的聚合物之含有比例為0.1~100重量份。 The liquid crystal display element of claim 1, wherein the liquid crystal alignment agent for forming the first alignment film has light relative to a total of 100 parts by weight of the polymer having no photo-alignment group The content of the polymer of the alignment group is from 0.1 to 100 parts by weight. 如申請專利範圍第1或2項的液晶顯示元件，其中該光配向性基具有來自肉桂酸的結構。 A liquid crystal display element according to claim 1 or 2, wherein the photo-alignment group has a structure derived from cinnamic acid. 一種液晶顯示元件的製造方法，其係具有一對基板的 液晶顯示元件的製造方法，其特徵在於：包括製造液晶顯示元件的製造步驟，該液晶顯示元件在該一對基板中的一個基板表面上，形成使液晶分子相對垂直該基板表面的方向傾斜配向的第1配向膜，並且在另一個基板表面上，形成使液晶分子垂直配向的第2配向膜，該第1配向膜係使用包含具有光配向性基的聚合物及不具有光配向性基的聚合物的光配向用液晶配向劑而形成，該光配向性基具有來自包含偶氮苯、二苯乙烯、α-亞胺基-β-酮酯、螺吡喃、螺、肉桂酸、查耳酮、芪唑、亞苄基苄甲內醯胺、香豆素、二苯基乙炔和蒽醌的群組中選出的至少一種化合物的結構，該具有光配向性基的聚合物為聚有機矽氧烷，該不具有光配向性基的聚合物為聚醯胺酸及聚醯亞胺之至少一者。 A method of manufacturing a liquid crystal display element, which is a method of manufacturing a liquid crystal display element having a pair of substrates, comprising: a manufacturing step of manufacturing a liquid crystal display element on a substrate surface of the pair of substrates Forming a first alignment film that obliquely aligns the liquid crystal molecules with respect to a direction perpendicular to the surface of the substrate, and forming a second alignment film that vertically aligns the liquid crystal molecules on the surface of the other substrate, the first alignment film used to include light The photo-alignment of the polymer of the alignment group and the polymer having no photo-alignment group is formed by a liquid crystal alignment agent having azobenzene, stilbene, α-imido-β- Ketoester, spiropyran, snail a structure of at least one compound selected from the group consisting of cinnamic acid, chalcone, carbazole, benzylidenebenzylamine, coumarin, diphenylacetylene and hydrazine, which has a photo-alignment group The polymer is a polyorganosiloxane, and the polymer having no photo-alignment group is at least one of polyamine and polyimine. 如申請專利範圍第4項的液晶顯示元件的製造方法，其中該製造步驟包括：在該一對基板中的一個基板的表面上，使用該光配向用液晶配向劑，形成第1塗膜的第1膜形成步驟；藉由對該第1塗膜照射光，使該第1塗膜成為該第1配向膜的光照射步驟；在該一對基板中的另一個基板表面上，使用可以形成垂直配向膜的液晶配向劑，形成作為該第2配向膜的第2塗膜的第2膜形成步驟；以及 配置該一對基板使該第1配向膜和該第2塗膜相對，而且在該基板間填充液晶分子，構成液晶胞的胞構成步驟。 The method of manufacturing a liquid crystal display device of claim 4, wherein the manufacturing step comprises: forming a first coating film on the surface of one of the pair of substrates by using the liquid alignment alignment agent for photoalignment a film forming step; the first coating film is irradiated with light to cause the first coating film to be a light irradiation step of the first alignment film; and the other substrate surface of the pair of substrates is formed to be vertical a liquid crystal alignment agent of the alignment film, and a second film formation step of forming a second coating film as the second alignment film; The pair of substrates are arranged such that the first alignment film and the second coating film face each other, and liquid crystal molecules are filled between the substrates to form a cell structure step of the liquid crystal cells. 如申請專利範圍第4項的液晶顯示元件的製造方法，其中該製造步驟包括：在該一對基板中的一個基板的表面上，使用該光配向用液晶配向劑，形成塗膜的第1膜形成步驟；在該一對基板中的另一個基板表面上，使用實質上不含具有光配向性基的化合物的液晶配向劑，形成該第2配向膜的第2膜形成步驟；配置該一對基板使該塗膜和該第2配向膜相對，而且在該基板間填充液晶分子，構成液晶胞的胞構成步驟；以及對該胞構成步驟構成的該液晶胞，在該一對基板間施加電壓的狀態下，照射光的光照射步驟。 The method for producing a liquid crystal display device of claim 4, wherein the manufacturing step comprises: forming a first film of the coating film on the surface of one of the pair of substrates by using the liquid alignment agent for photoalignment a forming step; forming a second film forming step of forming the second alignment film on the surface of the other of the pair of substrates by using a liquid crystal alignment agent that does not substantially contain a compound having a photo-alignment group; a substrate is formed by facing the coating film and the second alignment film, and filling a liquid crystal molecule between the substrates to form a cell structure of the liquid crystal cell; and applying a voltage between the pair of substrates to the liquid crystal cell configured by the cell forming step In the state of the light, the light irradiation step of the illumination light. 如申請專利範圍第4至6項中任一項的液晶顯示元件的製造方法，其中在光配向用液晶配向劑中，相對於合計100重量份之該不具有光配向性基的聚合物，該具有光配向性基的聚合物之含有比例為0.1~100重量份。 The method for producing a liquid crystal display element according to any one of claims 4 to 6, wherein in the liquid alignment liquid crystal alignment agent, the polymer having no photo-alignment group is added in a total amount of 100 parts by weight. The content of the polymer having a photo-alignment group is from 0.1 to 100 parts by weight. 如申請專利範圍第4至6項中任一項的液晶顯示元件的製造方法，其中該光配向性基具有來自肉桂酸的結構。 The method of producing a liquid crystal display element according to any one of claims 4 to 6, wherein the photo-alignment group has a structure derived from cinnamic acid.