TWI783946B - Manufacturing method of substrate with liquid crystal alignment film and liquid crystal display element - Google Patents

Manufacturing method of substrate with liquid crystal alignment film and liquid crystal display element Download PDF

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TWI783946B
TWI783946B TW106131658A TW106131658A TWI783946B TW I783946 B TWI783946 B TW I783946B TW 106131658 A TW106131658 A TW 106131658A TW 106131658 A TW106131658 A TW 106131658A TW I783946 B TWI783946 B TW I783946B
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liquid crystal
substrate
formula
crystal alignment
display element
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TW201823309A (en
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鉄谷尚士
石井秀則
名木達哉
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日商日產化學工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Abstract

本發明係提供具有以高效率賦予配向控制能、且燒灼特性為優異的橫向電場驅動型液晶顯示元件用液晶配向膜之基板及具有該基板之橫向電場驅動型液晶顯示元件。 　　本發明係提供一種具有下述液晶配向膜之基板之製造方法，其係藉由具有下述步驟從而得到被賦予配向控制能之橫向電場驅動型液晶顯示元件用液晶配向膜，包括： 　　[I] 將含有(A)由二胺成分與酸二酐成分所得之聚合物、及(B)有機溶劑之聚合物組成物塗佈至具有橫向電場驅動用導電膜之基板上後，進行乾燥從而形成塗膜之步驟，前述二胺成分包含下述式(1)(式(1)中，L係碳數2以上的二價有機基且同時包含伸烷基、與選自醚鍵及酯鍵之鍵結中之任1種，R1 及R2 係分別獨立為一價有機基，p1及p2係分別獨立為0~4的整數，p係0或1，q1及q2係分別獨立為1或2)所表示之二胺，前述酸二酐成分包含下述式(2)(式(2)中，R6 ~R9 係分別獨立為氫原子、烷基、鹵素原子或苯基)所表示之四羧酸二酐； 　　[II] 對[I]所得之塗膜照射偏光的紫外線之步驟；及 　　[III] 將[II]所得之塗膜進行加熱之步驟；

Figure 106131658-A0101-11-0002-1
。The present invention provides a substrate having a liquid crystal alignment film for a lateral electric field driven liquid crystal display element that imparts alignment control ability with high efficiency and has excellent burning characteristics, and a lateral electric field driven liquid crystal display element having the substrate. The present invention provides a method for manufacturing a substrate having the following liquid crystal alignment film, which is obtained by having the following steps to obtain a liquid crystal alignment film for a lateral electric field driven liquid crystal display element endowed with alignment control energy, including: [I] A polymer composition containing (A) a polymer obtained from a diamine component and an acid dianhydride component, and (B) an organic solvent is coated on a substrate having a conductive film for driving a transverse electric field, and then dried to form a coating. In the step of film, the aforementioned diamine component includes the following formula (1) (in formula (1), L is a divalent organic group with carbon number of 2 or more and includes alkylene group, and a bond selected from ether bond and ester bond In any one of the knots, R1 and R2 are independently monovalent organic groups, p1 and p2 are independently integers from 0 to 4, p is 0 or 1, q1 and q2 are independently 1 or 2 ) represented by the diamine, the aforementioned acid dianhydride components include the following formula (2) (in formula (2), R 6 ~ R 9 are independently represented by hydrogen atom, alkyl group, halogen atom or phenyl group) Tetracarboxylic dianhydride; [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [III] a step of heating the coating film obtained in [II];
Figure 106131658-A0101-11-0002-1
.

Description

具有液晶配向膜之基板之製造方法及液晶顯示元件Manufacturing method of substrate with liquid crystal alignment film and liquid crystal display element

[0001] 本發明係有關用於製造燒灼特性(burn-in)為優異的液晶顯示元件之液晶配向膜、液晶顯示元件及其製造方法。[0001] The present invention relates to a liquid crystal alignment film, a liquid crystal display element and a manufacturing method thereof for manufacturing a liquid crystal display element having excellent burn-in characteristics.

[0002] 液晶顯示元件係已知為輕量、薄型且低消耗電力的顯示裝置，近年被使用於大型的電視用途等而達到顯著的發展。液晶顯示元件係藉由例如具備電極之透明的一對基板挾持液晶層所構成。又，液晶顯示元件中，以使液晶在基板間達到所期望的配向狀態之方式，使用由有機材料所成之有機膜來作為液晶配向膜。 　　[0003] 即，液晶配向膜係液晶顯示元件的構成構件，且形成於挾持液晶的基板與液晶接觸的面，發揮在該基板間使液晶朝一定的方向配向之作用。又，對於液晶配向膜，除了發揮要求使液晶朝例如與基板平行的方向等之一定的方向配向之作用外，有時還要求控制液晶的預傾角之作用。如此的液晶配向膜中，控制液晶的配向之能力(以下稱為配向控制能)，可藉由對構成液晶配向膜的有機膜來進行配向處理而賦予。 　　[0004] 作為用於賦予配向控制能的液晶配向膜之配向處理方法，一直以來已知有摩擦法。所謂摩擦法係指對於基板上的聚乙烯醇或聚醯胺或聚醯亞胺等的有機膜，利用綿、尼龍、聚酯等的布，對其表面沿一定方向擦拭(摩擦)，使液晶沿擦拭的方向(摩擦方向)配向之方法。該摩擦法由於能夠簡便地實現較穩定的液晶的配向狀態，故被利用於以往的液晶顯示元件之製造製程中。又，作為液晶配向膜所使用的有機膜，主要選擇耐熱性等的可靠性或電特性為優異的聚醯亞胺系的有機膜。 　　[0005] 然而，對於由聚醯亞胺等所成之液晶配向膜的表面進行摩擦的摩擦法，存在有揚塵或產生靜電的問題。又，由於近年的液晶顯示元件的高精細化、或因對應的基板上的電極或液晶驅動用的主動開關元件所產生的凹凸，有時無法用布對液晶配向膜的表面進行均勻地摩擦，故無法實現均勻的液晶配向。 　　[0006] 因此，作為無法進行摩擦的液晶配向膜之其他的配向處理方法，正積極地研究光配向法。 　　[0007] 光配向法有各種的方法，利用直線偏光或視準後的光，在構成液晶配向膜之有機膜內形成異向性，並依據其異向性來使液晶配向。 　　[0008] 作為主要的光配向法，已知有分解型的光配向法。例如對聚醯亞胺膜照射偏光紫外線，利用分子構造的紫外線吸收的偏光方向依賴性使其產生異向性的分解。又，藉由未分解而殘留的聚醯亞胺來使液晶配向(例如參考專利文獻1)。 　　[0009] 又，還已知光交聯型或光異構化型之光配向法。例如使用聚乙烯肉桂酸酯，照射偏光紫外線，使與偏光平行的2個側鏈的雙鍵部分產生二聚合反應(交聯反應)。又，使液晶在與偏光方向垂直的方向上配向(例如參考非專利文獻1)。又，使用側鏈具有偶氮苯的側鏈型高分子之情形時，照射偏光紫外線，使與偏光平行的側鏈的偶氮苯部分產生異構化反應，使液晶在與偏光方向垂直的方向上配向(例如參考非專利文獻2)。 　　[0010] 如以上之例子般，藉由光配向法之液晶配向膜之配向處理方法中，不需要摩擦，沒有揚塵或產生靜電之虞。又，即使對於表面有凹凸的液晶顯示元件的基板亦能施予配向處理，成為適合於工業上的生產製程之液晶配向膜之配向處理方法。 [先前技術文獻] [專利文獻] 　　[0011] 　　[專利文獻1] 日本專利第3893659號公報 [非專利文獻] 　　[0012] 　　[非專利文獻1] M.Shadt et al., Jpn.J.Appl.Phys.31, 2155(1992). 　　[非專利文獻2]K.Ichimura et al., Chem.Rev.100, 1847(2000).[0002] Liquid crystal display devices are known as light-weight, thin and low-power display devices. In recent years, they have been used in large-scale television applications and have achieved remarkable development. A liquid crystal display element is comprised, for example by sandwiching a liquid crystal layer between a pair of transparent substrates equipped with electrodes. In addition, in a liquid crystal display element, an organic film made of an organic material is used as a liquid crystal alignment film so that liquid crystals may be aligned in a desired state between substrates. [0003] That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, and is formed on the surface where the substrate holding the liquid crystal is in contact with the liquid crystal, and plays the role of aligning the liquid crystal in a certain direction between the substrates. In addition, the liquid crystal alignment film may also be required to control the pretilt angle of the liquid crystal in addition to the function of aligning the liquid crystal in a certain direction such as a direction parallel to the substrate. In such a liquid crystal alignment film, the ability to control the alignment of liquid crystals (hereinafter referred to as alignment control ability) can be imparted by performing an alignment treatment on the organic film constituting the liquid crystal alignment film. [0004] As an alignment treatment method for a liquid crystal alignment film for imparting alignment control capability, a rubbing method has been known. The so-called rubbing method refers to wiping (rubbing) the surface of an organic film such as polyvinyl alcohol or polyamide or polyimide on a substrate in a certain direction with cotton, nylon, polyester, etc., to make the liquid crystal A method of aligning in the direction of wiping (rubbing direction). Since this rubbing method can easily realize a relatively stable alignment state of liquid crystals, it is used in the conventional manufacturing process of liquid crystal display elements. In addition, as the organic film used in the liquid crystal alignment film, a polyimide-based organic film excellent in reliability such as heat resistance or in electrical characteristics is mainly selected. [0005] However, for the rubbing method of rubbing the surface of the liquid crystal alignment film made of polyimide or the like, there are problems of raising dust or generating static electricity. In addition, due to the high-definition of liquid crystal display elements in recent years, or the unevenness generated by the electrodes on the corresponding substrate or the active switching elements for liquid crystal driving, it is sometimes impossible to rub the surface of the liquid crystal alignment film evenly with a cloth, Therefore, uniform liquid crystal alignment cannot be realized. [0006] Therefore, as other alignment treatment methods for liquid crystal alignment films that cannot be rubbed, photo-alignment methods are actively being studied. [0007] There are various methods for photo-alignment. Linearly polarized light or collimated light is used to form anisotropy in the organic film constituting the liquid crystal alignment film, and the liquid crystal is aligned according to the anisotropy. [0008] As a main photo-alignment method, a decomposition-type photo-alignment method is known. For example, a polyimide film is irradiated with polarized ultraviolet rays, and the polarization direction dependence of ultraviolet absorption of the molecular structure is used to cause anisotropic decomposition. Moreover, the liquid crystal is aligned by the polyimide which remains undecomposed (for example, refer patent document 1). [0009] Also, photo-crosslinking or photo-isomerization photo-alignment methods are known. For example, polyvinyl cinnamate is used to irradiate polarized ultraviolet rays to cause a dimerization reaction (crosslinking reaction) at the double bond portion of the two side chains parallel to the polarized light. Also, liquid crystals are aligned in a direction perpendicular to the polarization direction (for example, refer to Non-Patent Document 1). In addition, when using a side chain type polymer having azobenzene in the side chain, irradiate polarized ultraviolet rays to cause an isomerization reaction of the azobenzene part of the side chain parallel to the polarized light, and make the liquid crystal in the direction perpendicular to the polarized light direction. Up alignment (for example, refer to Non-Patent Document 2). [0010] As in the above examples, in the alignment treatment method of the liquid crystal alignment film by the photo-alignment method, no rubbing is required, and there is no risk of dust or static electricity. In addition, alignment treatment can be applied even to substrates of liquid crystal display elements with concavo-convex surfaces, and it becomes an alignment treatment method for liquid crystal alignment films suitable for industrial production processes. [Prior Art Document] [Patent Document] [0011] [Patent Document 1] Japanese Patent No. 3893659 [Non-Patent Document] [0012] [Non-Patent Document 1] M.Shadt et al., Jpn.J.Appl. Phys.31, 2155(1992). [Non-Patent Document 2]K.Ichimura et al., Chem.Rev.100, 1847(2000).

[發明所欲解決之課題] 　　[0013] 如以上般，光配向法係與一直以來作為液晶顯示元件的配向處理方法在工業上所利用的摩擦法相比，不需要摩擦步驟本身，因此具有很大的優點。又，與藉由摩擦而進行配向控制能大致一定的摩擦法相比，光配向法能改變偏光的光照射量從而控制配向控制能。然而，光配向法中，在想要實現與藉由摩擦法而進行之情形為相同程度的配向控制能時，有時需要大量的偏光的光照射量，或無法實現穩定的液晶配向。 　　[0014] 例如上述之專利文獻1中所記載的分解型的光配向法中，需要對聚醯亞胺膜照射60分鐘的來自輸出功率500W的高壓水銀燈的紫外光等，需要長時間且大量的紫外線照射。又，即使是二聚合型或光異構化型的光配向法之情形時，有時也需要數J(焦耳)~數十J左右的大量的紫外線照射。進而，光交聯型或光異構化型的光配向法之情形時，由於液晶的配向之熱穩定性或光穩定性差，故製成液晶顯示元件時將存在產生配向不良或顯示燒灼之類的問題。特別是橫向電場驅動型液晶顯示元件中，因為在面內進行液晶分子之開關，所以容易產生液晶驅動後的液晶的配向錯位，起因於AC驅動而引起顯示燒灼將成為較大的課題。 　　[0015] 因此，光配向法中，要求實現配向處理之高效率化或穩定的液晶配向，要求能高效率進行對液晶配向膜賦予高配向控制能之液晶配向膜及其製造方法。 　　[0016] 本發明之目的在於提供具有以高效率賦予配向控制能、且燒灼特性為優異的橫向電場驅動型液晶顯示元件用液晶配向膜之基板及具有該基板之橫向電場驅動型液晶顯示元件及其製造方法。 [解決課題之手段] 　　[0017] 本發明人為了達成上述課題經深入研究之結果發現以下之發明。 　　1. 一種具有下述液晶配向膜之基板之製造方法，其特徵係藉由具有下述步驟從而得到被賦予配向控制能之橫向電場驅動型液晶顯示元件用液晶配向膜，包括： 　　[I] 將含有(A)由二胺成分與酸二酐成分所得之聚合物、及(B)有機溶劑之聚合物組成物塗佈至具有橫向電場驅動用導電膜之基板上後，以由前述二胺成分與前述酸二酐成分所得之聚醯胺酸或聚醯胺酸酯為實質上未進行熱醯亞胺化之溫度下來予以乾燥從而形成塗膜之步驟，前述二胺成分包含下述式(1)(式(1)中，L係碳數2以上的二價有機基且同時包含伸烷基、與選自醚鍵及酯鍵之鍵結中之任1種，R1 及R2 係分別獨立為一價有機基，p1及p2係分別獨立為0~4的整數，p係0或1，q1及q2係分別獨立為1或2)所表示之二胺，前述酸二酐成分包含下述式(2)(式(2)中，R6 ~R9 係分別獨立為氫原子、烷基、鹵素原子或苯基)所表示之四羧酸二酐； 　　[II] 對[I]所得之塗膜照射偏光的紫外線之步驟；及 　　[III] 將[II]所得之塗膜進行加熱之步驟。 　　[0018]

Figure 02_image003
[0019] 2. 如上述1之基板之製造方法，其中，上述聚合物係選自由聚醯亞胺前驅物及該醯亞胺化物的聚醯亞胺所成之群之至少1種。 3. 如上述1或2中任一項之基板之製造方法，其中，上述式(2)中之R6 ~R9 係皆為氫原子。 　　4. 如上述1~3中任一任之基板之製造方法，其中，前述聚醯亞胺前驅物係下述式(3)(式(3)中，X1 係源自上述式(2)所表示之四羧酸衍生物之四價有機基，Y1 係源自包含式(1)的構造之二胺之二價有機基，R11 係氫原子或碳數1~5的烷基)所表示。 　　[0020]
Figure 02_image005
[0021] 5. 如上述4之基板之製造方法，其中，對於液晶配向劑中所含有的全聚合物，含有10莫耳%以上的具有前述式(3)所表示之構造單位的聚合物。 　　6. 一種基板，其特徵係具有藉由上述1~5中任一項之方法所製造之橫向電場驅動型液晶顯示元件用液晶配向膜。 　　7. 一種橫向電場驅動型液晶顯示元件，其特徵係具有上述6之基板。 　　8. 一種液晶顯示元件之製造方法，其特徵係藉由具有： 　　準備上述6之基板(第1基板)之步驟、 　　得到第2基板之步驟、及 　　得到液晶顯示元件之步驟，從而得到橫向電場驅動型液晶顯示元件； 　　前述第2基板所具有的液晶配向膜，係藉由具有下述步驟從而得到被賦予配向控制能之液晶配向膜，包括： 　　[I’] 將上述1~5中任一項之組成物塗佈於第2基板上來形成塗膜之步驟、 　　[II’] 對[I’]所得之塗膜照射偏光的紫外線之步驟、 　　[III’] 將[II’]所得之塗膜進行加熱之步驟； 　　前述得到液晶顯示元件之步驟，係[IV]使前述第1及第2基板的液晶配向膜介隔著液晶並相對之方式來對向配置前述第1及第2基板。 　　9.一種橫向電場驅動型液晶顯示元件，其係藉由上述8之方法所製造。 [發明的效果] 　　[0022] 依據本發明可提供具有以高效率賦予配向控制能、且燒灼特性為優異的橫向電場驅動型液晶顯示元件用液晶配向膜的基板及具有該基板的橫向電場驅動型液晶顯示元件。 　　依據本發明之方法所製造的橫向電場驅動型液晶顯示元件由於可高效率地賦予配向控制能，故即使是長時間連續驅動亦不會損及顯示特性。 　　[0023] 本發明之製造方法中所使用的聚合物組成物，具有能夠展現出自我組織能的感光性主鏈型高分子(以下亦簡稱為主鏈型高分子)，使用前述聚合物組成物而得之塗膜係具有能夠展現出自我組織能的感光性主鏈型高分子的膜。對於該塗膜無需進行摩擦處理，藉由偏光照射來進行配向處理。又，偏光照射後，經過對該主鏈型高分子膜進行加熱之步驟，形成被賦予配向控制能的塗膜(以下亦稱為液晶配向膜)。此時，藉由偏光照射而呈現的微小的異向性將成為驅動力(driving force)，主鏈型高分子本身藉由自我組織化而更有效率地再配向。其結果是作為液晶配向膜可得到實現高效率的配向處理、賦予高配向控制能的液晶配向膜。[Problems to be Solved by the Invention] [0013] As above, compared with the rubbing method conventionally used industrially as an alignment treatment method for liquid crystal display elements, the photo-alignment method does not require the rubbing step itself, so it has great advantages. The advantages. In addition, compared with the rubbing method in which the alignment control can be substantially constant by rubbing, the photo-alignment method can change the light irradiation amount of polarized light to control the alignment control ability. However, in the photo-alignment method, in order to achieve the same level of alignment control as that achieved by the rubbing method, a large amount of polarized light irradiation may be required, or stable liquid crystal alignment may not be achieved. For example, in the decomposed photoalignment method described in the above-mentioned patent document 1, it is necessary to irradiate the polyimide film with ultraviolet light from a high-pressure mercury lamp with an output power of 500W for 60 minutes, which requires a long time and a large amount of UV exposure. Also, even in the case of dimerization-type or photo-isomerization-type photoalignment methods, a large amount of ultraviolet irradiation of about several J (joules) to several tens of J may be required. Furthermore, in the case of photo-crosslinking or photo-isomerization photo-alignment methods, due to the poor thermal stability or light stability of liquid crystal alignment, there will be problems such as poor alignment or display burning when making liquid crystal display elements. The problem. Especially in the lateral electric field driven liquid crystal display element, since liquid crystal molecules are switched on and off in the plane, misalignment of the liquid crystal after liquid crystal driving is easy to occur, and display burn-in due to AC driving will become a big problem. Therefore, in the photo-alignment method, it is required to realize high-efficiency alignment treatment or stable liquid crystal alignment, and a liquid crystal alignment film capable of imparting high alignment control ability to the liquid crystal alignment film and its manufacturing method are required to be performed efficiently. The object of the present invention is to provide the substrate having the liquid crystal alignment film for the lateral electric field driven type liquid crystal display element with high efficiency endowing alignment control ability, and the burning characteristic is excellent and the lateral electric field driven type liquid crystal display element having the substrate and its method of manufacture. [Means for Solving the Problems] [0017] The present inventors have found the following inventions as a result of intensive research to achieve the above-mentioned problems. 1. A method of manufacturing a substrate having the following liquid crystal alignment film, characterized in that the liquid crystal alignment film for a transverse electric field driven liquid crystal display element endowed with alignment control energy is obtained by having the following steps, comprising: [I] A polymer composition containing (A) a polymer obtained from a diamine component and an acid dianhydride component, and (B) an organic solvent is coated on a substrate having a conductive film for driving a transverse electric field, and the diamine component The polyamic acid or polyamic acid ester obtained with the aforementioned acid dianhydride component is a step of drying at a temperature at which thermal imidization is not substantially performed to form a coating film. The aforementioned diamine component contains the following formula (1 ) (In formula (1), L is a divalent organic group with more than 2 carbon atoms and simultaneously includes an alkylene group, and any one of bonds selected from ether bonds and ester bonds, and R 1 and R 2 are respectively are independently monovalent organic groups, p1 and p2 are independently integers from 0 to 4, p is 0 or 1, q1 and q2 are independently 1 or 2) and represent diamines, and the aforementioned acid dianhydride components include the following Described formula (2) (in formula (2), R 6 ～R 9 are tetracarboxylic dianhydrides represented by hydrogen atom, alkyl, halogen atom or phenyl respectively independently; [II] to [I] obtained The step of irradiating the coating film with polarized ultraviolet rays; and [III] the step of heating the coating film obtained in [II]. [0018]
Figure 02_image003
2. The manufacturing method of the substrate as in the above 1, wherein the polymer is at least one selected from the group consisting of polyimide precursors and polyimides of the imides. 3. The manufacturing method of the substrate according to any one of the above 1 or 2, wherein R 6 to R 9 in the above formula (2) are all hydrogen atoms. 4. The manufacturing method of any one of the substrates in the above 1 to 3, wherein the aforementioned polyimide precursor is the following formula (3) (in the formula ( 3 ), X is derived from the above formula (2) The tetravalent organic group of the tetracarboxylic acid derivative represented, Y1 is derived from the divalent organic group of diamine comprising the structure of formula ( 1 ), R11 is a hydrogen atom or an alkyl group with 1 to 5 carbons) express. [0020]
Figure 02_image005
5. The manufacturing method of the substrate as above 4, wherein, for the total polymer contained in the liquid crystal alignment agent, more than 10 mole % of the polymer having the structural unit represented by the aforementioned formula (3) is contained. 6. A substrate characterized by having a liquid crystal alignment film for a lateral electric field driven liquid crystal display element manufactured by any one of the methods in 1 to 5 above. 7. A liquid crystal display element driven by a transverse electric field, characterized by having the substrate of the above-mentioned 6. 8. A method of manufacturing a liquid crystal display element, characterized by comprising: the step of preparing the substrate (first substrate) of the above-mentioned 6, the step of obtaining the second substrate, and the step of obtaining the liquid crystal display element, thereby obtaining lateral electric field drive type liquid crystal display element; the liquid crystal alignment film that the aforementioned second substrate has is to obtain the liquid crystal alignment film endowed with alignment control ability by having the following steps, including: [I'] any one of the above-mentioned 1~5 The step of applying the composition on the second substrate to form a coating film, [II'] the step of irradiating polarized ultraviolet rays to the coating film obtained in [I'], [III'] applying the coating film obtained in [II'] to Step of heating; The aforementioned step of obtaining a liquid crystal display element is [IV] arranging the aforementioned first and second substrates facing each other in such a way that the liquid crystal alignment films of the aforementioned first and second substrates face each other through liquid crystals. 9. A lateral electric field driven liquid crystal display element manufactured by the method of the above 8. [Effect of the invention] [0022] According to the present invention, it is possible to provide a substrate having a liquid crystal alignment film for a lateral electric field driven type liquid crystal display element with high efficiency imparting alignment control ability and excellent burning characteristics, and a lateral electric field driven type liquid crystal alignment film having the substrate. Liquid crystal display element. The lateral electric field driven liquid crystal display element manufactured by the method of the present invention can be efficiently endowed with alignment control ability, so even if it is driven continuously for a long time, the display characteristics will not be damaged. The polymer composition used in the production method of the present invention has a photosensitive main chain polymer (hereinafter also referred to as the main chain polymer) capable of exhibiting self-organization, and the aforementioned polymer composition The obtained coating film is a film having a photosensitive main chain type polymer capable of exhibiting self-organization. There is no need to perform rubbing treatment on this coating film, and alignment treatment is performed by polarized light irradiation. Moreover, after polarized light irradiation, the process of heating this main chain type polymer film forms the coating film (it is also called a liquid crystal alignment film hereafter) which provided the alignment control ability. At this time, the slight anisotropy presented by the polarized light irradiation will act as a driving force, and the main chain polymer itself can re-align more efficiently through self-organization. As a result, as a liquid crystal alignment film, a liquid crystal alignment film that realizes efficient alignment treatment and imparts high alignment control ability can be obtained.

[實施發明之最佳形態] 　　[0024] 以下，對於本發明之實施形態進行詳細說明。 　　本發明之液晶配向劑，其係含有由二胺成分與酸二酐成分所得之聚合物(以下，亦稱為特定聚合物，或亦稱為主鏈型高分子)之液晶配向劑，該二胺成分包含上述式(1)所表示之二胺，該酸二酐成分包含上述式(2)所表示之四羧酸二酐。以下對於各條件來進行詳述。 　　[0025] ＜具有特定構造之二胺＞ 　　本發明之液晶配向劑，其係含有聚合物與有機溶劑之液晶配向劑，該聚合物係由二胺成分與酸二酐成分所得，該二胺成分包含式(1)所表示之二胺(本發明中亦稱為特定二胺)，該酸二酐成分包含式(2)所表示之四羧酸二酐(本發明中亦稱為特定四羧酸二酐)。 　　[0026]

Figure 02_image007
[0027] 式(1)中，L係碳數2以上的二價有機基且同時包含伸烷基、與選自醚鍵及酯鍵之鍵結中之任1種，R1 及R2 係分別獨立為一價有機基，p1及p2係分別獨立為0~4的整數，p係0或1，q1及q2係分別獨立為1或2。 　　[0028] 作為於此之一價有機基，可舉出具有碳數1~10(較佳為1~3)的烷基、烯基、烷氧基、氟烷基、氟烯基、或氟烷氧基。其中，作為一價有機基係以甲基為較佳。 　　[0029] 作為二價有機基，可舉出：以伸烷基與醚鍵所構成的基、或以伸烷基與酯鍵所構成的基、氫原子的一部分或全部被鹵素所取代的以伸烷基與醚鍵所構成的基、或氫原子的一部分或全部被鹵素所取代的以伸烷基與酯鍵所構成的基。其中，作為二價有機基係以伸烷基與醚鍵所構成的基為較佳。碳數係以2以上20以下者為較佳，以2以上10以下者為又較佳。 　　[0030] 又，L的原子數之中，與主鏈的長度有關的碳原子和氧原子的原子數的合計若為偶數之情形時，所得之聚合物之直線性會變高，其結果，於偏光照射後之加熱步驟中，藉由更高秩序地進行再配向，而可得到賦予高配向控制能的液晶配向膜，故為較佳。尚，與主鏈的長度有關的碳原子和氧原子的原子數的合計，係指將主鏈的每一個亞甲基的數設為1，將每一個醚鍵的數設為1，將每一個酯鍵的數設為2時的合計。 　　[0031] 作為p1及p2，就立體阻礙少而苯基彼此容易重疊、並以更高秩序地進行再配向之點而言，以0為較佳。 　　作為p，就具有作為自由旋轉部位功能的伸烷基能以更高秩序地進行再配向之點而言，以1為較佳。 　　上述式(1)之二胺中，作為p為1之二胺之具體例係可示例如下，但並非限定於該等。 　　[0032]
Figure 02_image009
[0033]
Figure 02_image011
[0034]
Figure 02_image013
[0035] 於此，若r、t及u的合計為2、4、6、8及10等的偶數之情形時，所得之聚合物之直線性會變高，其結果，於偏光照射後之加熱步驟中，藉由更高秩序地進行再配向，而可得到賦予高配向控制能的液晶配向膜。 　　s為1、3、5等的奇數，但依上述之理由為較佳。 　　上述式(1)所表示之二胺之中，作為p為0之二胺之具體例，可舉出p-苯二胺。 　　[0036] ＜聚合物＞ 　　本發明之聚合物，其係由二胺成分與酸二酐成分所得之聚合物，該二胺成分包含上述式(1)所表示之二胺，該酸二酐成分包含上述式(2)所表示之四羧酸二酐。 作為具體例，可舉出聚醯胺酸、聚醯胺酸酯、聚醯亞胺、聚脲、聚醯胺等，但就作為液晶配向劑使用之觀點而言，以選自包含下述式(3)所表示之構造單位之聚醯亞胺前驅物、及該醯亞胺化物的聚醯亞胺之至少1種為較佳。於偏光照射後的加熱步驟中，就在聚合物中自由旋轉部位越多可更高秩序地進行再配向之點而言，以聚醯亞胺前驅物為又較佳。 　　[0037]
Figure 02_image015
[0038] 上述式(3)中，X1 係源自上述式(2)所表示之四羧酸衍生物之四價有機基，Y1 係源自包含式(1)的構造之二胺之二價有機基，R11 係氫原子或碳數1~5的烷基。就容易藉由加熱而醯亞胺化之點而言，R11 係以氫原子、甲基或乙基為較佳，以氫原子為又較佳。 　　[0039] ＜四羧酸二酐＞ 　　X1 係源自上述式(2)所表示之四羧酸衍生物之四價有機基。 　　式(2)中，R6 ~R9 係分別獨立為氫原子、烷基、鹵素原子或苯基 　　下述構造之中，就液晶配向性之觀點而言，以R6 ~R9 為氫原子者為較佳。 　　[0040]
Figure 02_image017
[0041] ＜二胺＞ 　　式(3)中，作為Y1 之具體例可舉出由前述式(1)之二胺中除去2個胺基而成之構造。其中，以由上述較佳的二胺中除去2個胺基而成之構造為較佳。 　　[0042] ＜聚合物(其他的構造單位)＞ 　　包含式(3)所表示之構造單位之聚醯亞胺前驅物，在不損及本發明之效果之範圍內，亦可包含選自下述式(4)所表示之構造單位、及該醯亞胺化物的聚醯亞胺之至少1種。 　　[0043]
Figure 02_image019
[0044] 式(4)中，X2 為源自四羧酸衍生物之四價有機基，Y2 係源自二胺之二價有機基，R12 係與前述式(3)之R11 的定義為相同，R22 係表示氫原子或碳數1~4的烷基。又，2個R22 之至少一者係以氫原子為較佳。 　　X2 係源自四羧酸衍生物之四價有機基，其構造並無特別限定。又，聚醯亞胺前驅物中之X2 係因應聚合物對溶劑之溶解性或液晶配向劑之塗佈性、製成液晶配向膜時之液晶的配向性、電壓保持率、儲存電荷等所需要的特性之程度來做適當選擇，在相同聚合物中可存在1種類、或亦可混合存在2種類以上。 　　[0045] 若要表示X2 之具體例時，可舉出國際公開公報2015/119168的第13~14頁所刊載之式(X-1)~(X-46)之構造等。 　　以下雖表示較佳的X2 之構造，但本發明並非被限定於該等。 　　[0046]
Figure 02_image021
[0047]
Figure 02_image023
[0048] 又，聚醯亞胺前驅物中之Y2 係源自二胺之二價有機基，其構造並無特別限定。又，Y2 係因應聚合物對溶劑之溶解性或液晶配向劑之塗佈性、製成液晶配向膜時之液晶的配向性、電壓保持率、儲存電荷等所需要的特性之程度來做適當選擇，在相同聚合物中可存在1種類、或亦可混合存在2種類以上。 　　[0049] 若要表示Y2 之具體例時，可舉出國際公開公報2015/119168的第4頁所刊載之式(2)之構造、及第8~12頁所刊載之式(Y-1)~(Y-97)、(Y-101)~(Y-118)之構造；國際公開公報2013/008906第6頁所刊載之由式(2)中除去2個胺基而成之二價有機基；國際公開公報2015/122413的第8頁所刊載之由式(1)中除去2個胺基而成之二價有機基；國際公開公報2015/060360的第8頁所刊載之式(3)之構造；日本國公開專利公報2012-173514的第8頁所刊載之由式(1)中除去2個胺基而成之二價有機基；國際公開公報2010-050523第9頁所刊載之由式(A)~(F)中除去2個胺基而成之二價有機基等。 　　[0050] 作為較佳的Y2 之構造，可舉出下述式(5)之構造。尚，Y2 之構造可為源自特定二胺(1)之構造也無妨。 　　[0051]
Figure 02_image025
[0052] 式(5)中，R32 係單鍵或二價有機基，以單鍵為較佳。 　　R33 係-(CH2 )n -所表示之構造。n係2~10的整數，以3~7為較佳。又，任意的-CH2 -係以分別不鄰接之條件下，亦可被醚、酯、醯胺、脲、胺甲酸酯鍵所取代。 　　R34 係單鍵或二價有機基。 　　苯環上之任意的氫原子係亦可以一價有機基所取代，以氟原子或甲基為較佳。 　　作為式(5)所表示之構造，具體而言可舉出如以下般的構造，但並非被限定於該等。 　　[0053]
Figure 02_image027
[0054]
Figure 02_image029
[0055]
Figure 02_image031
[0056]
Figure 02_image033
[0057]
Figure 02_image035
[0058] 其中，就不阻礙選自包含式(3)所表示之構造單位之聚醯亞胺前驅物、及該醯亞胺化物的聚醯亞胺之至少1種的再配向之點而言，以包含與特定二胺(1)共通的部分構造者為較佳。 　　[0059] 包含式(3)所表示之構造單位之聚醯亞胺前驅物，若同時包含式(4)所表示之構造單位之情形時，式(3)所表示之構造單位相對於式(3)與式(4)的合計以30莫耳%~100莫耳%為較佳，又較佳為50莫耳%~100莫耳%，特佳為70莫耳%~100莫耳%。 　　[0060] 本發明中使用之聚醯亞胺前驅物的分子量係以重量平均分子量為2,000~500,000為較佳，又較佳為5,000~300,000，更佳為10,000~100,000。 　　作為本發明中使用之聚醯亞胺，可舉出使前述之聚醯亞胺前驅物閉環而得到的聚醯亞胺。該聚醯亞胺中，醯胺酸基的閉環率(亦稱為醯亞胺化率)不一定需要100%，可依據用途或目的來任意地調整。關於本發明之聚合物，就液晶配向性之觀點而言，醯亞胺化率係以0~70%為較佳，又較佳為0~50%。 　　作為使聚醯亞胺前驅物醯亞胺化之方法，可舉出將聚醯亞胺前驅物的溶液直接加熱之熱醯亞胺化、或添加觸媒至聚醯亞胺前驅物的溶液中之觸媒醯亞胺化。 　　[0061] ＜液晶配向劑＞ 　　本發明之液晶配向劑係含有由二胺成分與酸二酐成分所得之聚合物(特定聚合物)，該二胺成分包含上述式(1)所表示之二胺，該酸二酐成分包含上述式(2)所表示之四羧酸二酐，但在可發揮本發明所記載的效果之限度內，亦可含有2種以上不同構造的特定聚合物。又，除了特定聚合物之外，亦可含有其他的聚合物，即，不具有源自式(1)所表示之二胺之二價的基之聚合物。作為其他的聚合物的種類，可舉出聚醯胺酸、聚醯亞胺、聚醯胺酸酯、聚酯、聚醯胺、聚脲、聚有機矽氧烷、纖維素衍生物、聚縮醛、聚苯乙烯或其衍生物、聚(苯乙烯-苯基馬來醯亞胺)衍生物、聚(甲基)丙烯酸酯等。本發明之液晶配向劑若含有其他的聚合物之情形時，相對於全聚合物成分之特定聚合物的比例係以10質量%以上為較佳，作為其一例子可舉出為10~100質量%。 　　[0062] 液晶配向劑係用於製作液晶配向膜而被使用，就可形成均勻的薄膜之觀點而言，一般為採用塗佈液之形態。即使是本發明之液晶配向劑，亦以含有前述之聚合物成分、與使該聚合物成分溶解之有機溶劑之塗佈液為較佳。此時，液晶配向劑中之聚合物的濃度係可依據想要形成的塗膜的厚度設定來做適當變更。就形成均勻且無缺點的塗膜之點而言，以1質量%以上為較佳，就溶液的保存穩定性之點而言，以設為10質量%以下為較佳。特佳的聚合物的濃度為2~8質量%。 　　[0063] 液晶配向劑中所含有的有機溶劑只要是能均勻溶解聚合物成分者即可並無特別限定。若舉出其具體例時，可舉出N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、二甲基亞碸、γ-丁內酯、1,3-二甲基-咪唑啉酮、甲基乙基酮、環己酮、環戊酮等。其中，以使用N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、或γ-丁內酯為較佳。 　　[0064] 又，液晶配向劑中所含有的有機溶劑除了如上述般的溶劑之外，通常可以併用使塗佈液晶配向劑時的塗佈性或塗膜的表面平滑性提升之溶劑的混合溶劑來使用，即使是本發明之液晶配向劑，亦可適合使用如此般的混合溶劑。將併用的有機溶劑之具體例可舉出於下述，但並非被限定於該等之例子。 　　[0065] 可舉出例如乙醇、異丙醇、1-丁醇、2-丁醇、異丁醇、tert-丁醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、異戊醇、tert-戊醇、3-甲基-2-丁醇、新戊醇、1-己醇、2-甲基-1-戊醇、2-甲基-2-戊醇、2-乙基-1-丁醇、1-庚醇、2-庚醇、3-庚醇、1-辛醇、2-辛醇、2-乙基-1-己醇、環己醇、1-甲基環己醇、2-甲基環己醇、3-甲基環己醇、1,2-乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、1,4-丁二醇、2,3-丁二醇、1,5-戊二醇、2-甲基-2,4-戊二醇、2-乙基-1,3-己二醇、二丙基醚、二丁基醚、二己基醚、二噁烷、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二丁基醚、1,2-丁氧基乙烷、二乙二醇二甲基醚、二乙二醇二乙基醚、4-羥基-4-甲基-2-戊酮、二乙二醇甲基乙基醚、二乙二醇二丁基醚、2-戊酮、3-戊酮、2-己酮、2-庚酮、4-庚酮、3-乙氧基丁基乙酸酯、1-甲基戊基乙酸酯、2-乙基丁基乙酸酯、2-乙基己基乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、碳酸伸丙酯、碳酸伸乙酯、2-(甲氧基甲氧基)乙醇、乙二醇單丁基醚、乙二醇單異戊基醚、乙二醇單己基醚、2-(己氧基)乙醇、糠醇、二乙二醇、丙二醇、丙二醇單丁基醚、1-(丁氧基乙氧基)丙醇、丙二醇單甲基醚乙酸酯、二丙二醇、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇二甲基醚、三丙二醇單甲基醚、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丁基醚乙酸酯、乙二醇單乙酸酯、乙二醇二乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丁基醚乙酸酯、2-(2-乙氧基乙氧基)乙基乙酸酯、二乙二醇乙酸酯、三乙二醇、三乙二醇單甲基醚、三乙二醇單乙基醚、乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸n-丁酯、乙酸丙二醇單乙基醚、丙酮酸甲酯、丙酮酸乙酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸甲基乙酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸、3-甲氧基丙酸、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸n-丙酯、乳酸n-丁酯、乳酸異戊酯、下述式[D-1]~[D-3]所表示之溶劑等。 　　[0066]
Figure 02_image037
[0067] 式[D-1]中，D1 係表示碳數1~3的烷基，式[D-2]中，D2 係表示碳數1~3的烷基，式[D-3]中，D3 係表示碳數1~4的烷基。 　　[0068] 如此般的溶劑的種類及含有量係可因應液晶配向劑的塗佈裝置、塗佈條件、塗佈環境等來做適當選擇。 　　[0069] 本發明之液晶配向劑，在不損及本發明之效果的範圍內，亦可追加含有除了聚合物成分及有機溶劑以外的成分。作為如此般的追加成分，可舉出用於使液晶配向膜與基板的密著性或使液晶配向膜與密封材的密著性提高的密著輔助劑、用於提高液晶配向膜的強度的交聯劑、用於調整液晶配向膜的介電率或電阻的介電質或導電物質等。作為該等追加成分之具體例係如液晶配向劑相關之周知的文獻中所揭示般，若要表示其一例子可舉出公開公報2015/060357號說明書第53頁[0105]~55頁[0116]所揭示的成分等。 　　[0070] ＜具有液晶配向膜之基板之製造方法＞及＜液晶顯示元件之製造方法＞ 　　本發明之具有液晶配向膜之基板之製造方法係具有下述步驟： 　　[I] 將含有(A)由二胺成分與酸二酐成分所得之聚合物、及(B)有機溶劑之聚合物組成物塗佈至具有橫向電場驅動用導電膜之基板上後，進行乾燥從而形成塗膜之步驟，該二胺成分由包上述式(1)所表示之二胺，該酸二酐成分包含上述式(2)所表示之四羧酸二酐； 　　[II] 對[I]所得之塗膜照射偏光的紫外線之步驟；及 　　[III] 將[II]所得之塗膜進行加熱之步驟。 　　藉由上述步驟，從而可得到被賦予配向控制能之橫向電場驅動型液晶顯示元件用液晶配向膜，並可得到具有該液晶配向膜之基板。 　　[0071] 又，除了上述所得之基板(第1基板)之外，藉由準備第2基板，從而可得到橫向電場驅動型液晶顯示元件。 　　第2基板係除了使用不具有橫向電場驅動用導電膜之基板，來替代具有橫向電場驅動用導電膜之基板以外，藉由採用上述步驟[I]~[III](因為使用不具有橫向電場驅動用導電膜之基板，故方便起見，本案中有時也簡稱為步驟[I’]~[III’])，從而可得到具有被賦予配向控制能之液晶配向膜之第2基板。 　　[0072] 橫向電場驅動型液晶顯示元件之製造方法係具有下述步驟： 　　[IV] 使第1及第2基板的液晶配向膜介隔著液晶並相對之方式來對向配置上述所得之第1及第2基板，從而得到液晶顯示元件之步驟。據此，可得到橫向電場驅動型液晶顯示元件。 　　[0073] 以下，對於本發明之製造方法所具有之[I]~[III]、及[IV]的各步驟來進行說明。 ＜步驟[I]＞ 　　步驟[I]中，在具有橫向電場驅動用導電膜之基板上塗佈含有感光性主鏈型高分子及有機溶劑之聚合物組成物後，進行乾燥來形成塗膜。 　　[0074] ＜基板＞ 　　關於基板並無特別限定，若所製造的液晶顯示元件為透射型之情形時，以使用透明性高的基板為較佳。此情形時，無特別限定可使用玻璃基板、或丙烯酸基板或聚碳酸酯基板等的塑膠基板等。 　　又，考慮適用於反射型液晶顯示元件，亦可使用矽晶圓等的不透明的基板。 　　[0075] ＜橫向電場驅動用導電膜＞ 　　基板係具有橫向電場驅動用導電膜。 　　作為該導電膜，若液晶顯示元件為透射型之情形時，可舉出ITO(Indium Tin Oxide：氧化銦錫)、IZO(Indium Zinc Oxide：氧化銦鋅)等，但並非被限定於該等。 　　又，若為反射型液晶顯示元件之情形時，作為導電膜可舉出鋁等的反射光之材料等，但並非被限定於該等。 　　在基板上形成導電膜之方法係可使用以往周知的手法。 　　[0076] 將上述之聚合物組成物塗佈至具有橫向電場驅動用導電膜之基板上之方法並無特別限定。 　　塗佈方法係以工業上而言採用網板印刷、平板印刷、柔版印刷或噴墨法等來進行之方法為一般的。作為其他的塗佈方法係有浸漬法、輥塗佈機法、縫塗佈機法、旋轉器法(旋轉塗佈法)或噴霧法等，可因應目的來使用該等。 　　[0077] 在具有橫向電場驅動用導電膜之基板上塗佈聚合物組成物後，可藉由加熱板、熱循環型烘箱或IR(紅外線)型烘箱等的加熱手段，以30~150℃，較佳為70~110℃下使溶劑蒸發從而得到塗膜。若乾燥溫度過低時，溶劑的乾燥將會有變得不足之傾向；又若加熱溫度過高時，則會進行熱醯亞胺化，其結果，因偏光曝光而光分解反應將會過量地進行，此情形時，難以藉由自我組織化而朝單一方向進行再配向，故將會損及配向穩定性。因此，就液晶配向穩定性之觀點而言，此時的乾燥溫度係以特定聚合物實質上未進行熱醯亞胺化的溫度為較佳。 　　塗膜的厚度過厚時，則在液晶顯示元件的消耗電力方面不利，若過薄時，則有時液晶顯示元件的可靠性將會降低，故較佳為5nm~300nm，又較佳為10nm~150nm。 　　尚，亦可於[I]步驟之後，接下來的[II]步驟之前，設置將形成有塗膜之基板冷卻至室溫之步驟。 　　[0078] ＜步驟[II]＞ 　　於步驟[II]中，對步驟[I]所得之塗膜照射偏光的紫外線。對塗膜的膜面照射偏光的紫外線之情形時，從相對於基板為一定的方向介隔著偏光板來照射經偏光的紫外線。作為使用的紫外線係可使用在波長100nm~400nm的範圍內的紫外線。較佳為依據使用的塗膜的種類，介隔著過濾器等來選擇最佳的波長。又，例如為能夠選擇性的誘發光分解反應，可選擇波長240nm~400nm的範圍內的紫外線來使用。作為紫外線可使用例如從高壓水銀燈或金屬鹵素燈所放射的光。 　　[0079] 偏光的紫外線的照射量係取決於使用的塗膜。照射量係以設為可實現∆A的最大值(以下亦稱為∆Amax)之偏光紫外線的量的1%~70%的範圍內為較佳，以設為1%~50%的範圍內為又較佳，所述∆A係該塗膜中與偏光紫外線之偏光方向為平行方向之紫外線吸光度、和垂直方向之紫外線吸光度之差。 　　[0080] ＜步驟[III]＞ 　　於步驟[III]中，對步驟[II]中照射了偏光的紫外線之塗膜進行加熱。藉由加熱，可賦予塗膜配向控制能。 　　加熱係可使用加熱板、熱循環型烘箱或IR(紅外線)型烘箱等的加熱手段。加熱溫度係可考慮使用的塗膜所展現出良好的液晶配向穩定性及電特性的溫度來做決定。 　　[0081] 加熱溫度係以在主鏈型高分子展現出良好的液晶配向穩定性的溫度範圍內為較佳。若加熱溫度過低時，則因為熱所致之異向性的增大效果或熱醯亞胺化將會變得不足之傾向，又若加熱溫度高於溫度範圍時，藉由偏光曝光而被賦予的異向性將會有消失之傾向，此情形時，藉由自我組織化而在一方向上進行再配向會變得困難。 　　[0082] 加熱後所形成的塗膜的厚度，由於與步驟[I]中所記載之相同理由，故較佳為5nm~300nm，又較佳以50nm~150nm為宜。 　　[0083] 藉由具有以上之步驟，依據本發明之製造方法能夠實現高效率的對塗膜的異向性的導入。又，可高效率地製造附有液晶配向膜之基板。 　　[0084] ＜步驟[IV]＞ 　　[IV]步驟係如以下：將[III]所得之在橫向電場驅動用導電膜上具有液晶配向膜之基板(第1基板)、與相同地在上述[I’]~[III’]中所得之不具有導電膜之附有液晶配向膜之基板(第2基板)，介隔著液晶並以雙方的液晶配向膜相對之方式來進行對向配置，並藉由周知的方法製作液晶晶胞，從而製作橫向電場驅動型液晶顯示元件之步驟。尚，步驟[I’]~[III’]，除了在步驟[I]中使用不具有該橫向電場驅動用導電膜之基板，來替代具有橫向電場驅動用導電膜之基板以外，可與步驟[I]~[III]相同地來進行。步驟[I]~[III]與步驟[I’]~[III’]之不同點僅在於有無上述之導電膜，因此省略步驟[I’]~[III’]的說明。 　　[0085] 若要舉出液晶晶胞或液晶顯示元件之製作之一例子時，可示例下述方法：準備上述之第1及第2基板，在一片的基板的液晶配向膜上散布間隔件，以液晶配向膜面成為內側之方式來貼合另一片基板，減壓注入液晶並密封之方法，或是在散布間隔件的液晶配向膜面上滴加液晶後，將基板貼合並進行密封之方法等。此時，一側的基板係以使用具有如橫向電場驅動用的梳齒般的構造的電極之基板為較佳。此時的間隔件的直徑，係較佳為1μm~30μm，又較佳為2μm~10μm。該間隔件直徑決定挾持液晶層的一對基板間距離，即液晶層的厚度。 　　[0086] 本發明之附有塗膜之基板之製造方法係將聚合物組成物塗佈至基板上形成塗膜後，照射偏光的紫外線。接下來藉由進行加熱，實現對主鏈型高分子膜的高效率的異向性的導入，製造具備液晶的配向控制能之附有液晶配向膜之基板。 　　本發明中使用的塗膜中，利用藉由基於主鏈的光反應之自我組織化而誘發之分子再配向之原理，來實現對塗膜的高效率的異向性的導入。本發明之製造方法中，若在主鏈型高分子中具有光分解性基來作為光反應性基的構造之情形時，使用主鏈型高分子在基板上形成塗膜後，照射偏光的紫外線，接下來進行加熱後，製成液晶顯示元件。 　　[0087] 因此，本發明之方法中使用的塗膜，係藉由依序進行對塗膜照射偏光的紫外線與加熱處理，從而高效率地導入異向性，故可製成配向控制能為優異的液晶配向膜。 　　[0088] 又，本發明之方法中使用的塗膜中，將對塗膜照射之偏光的紫外線的照射量、與加熱處理中之加熱溫度進行最佳化。藉此，可實現高效率的對塗膜的異向性的導入。 　　[0089] 對本發明中所使用的塗膜以高效率導入異向性，作為最佳的偏光紫外線的照射量，係對應於該塗膜中感光性基產生光分解反應的量達到最佳時的偏光紫外線的照射量。若對本發明中所使用的塗膜照射偏光的紫外線之結果是進行光分解反應的感光性基少時，則達不到充分的光反應量。此情形時，之後即使加熱亦不會進行充分的自我組織化。 　　[0090] 因此，本發明中所使用的塗膜中，藉由偏光紫外線的照射而使感光性基進行光分解反應的最佳量，係以該高分子膜設為0.1莫耳%~90莫耳%為較佳，以0.1莫耳% ~80莫耳%為又較佳。藉由使進行光反應的感光性基的量設為如此般的範圍內，藉由之後的加熱處理，自我組織化將可效率佳地進行，將能高效率的在膜中形成異向性。 　　[0091] 本發明之方法中使用的塗膜中，藉由偏光的紫外線的照射量之最佳化，可將高分子膜的主鏈中之感光性基的光分解反應的量予以最佳化。又，合併之後的加熱處理，可實現高效率的、對本發明中所使用的塗膜的異向性的導入。此情形時，關於適合的偏光紫外線的量，可以基於本發明中所使用的塗膜的紫外吸收的評估來進行。 　　[0092] 即，對於本發明中所使用的塗膜，分別測定偏光紫外線照射後的與偏光的紫外線之偏光方向為平行方向之紫外線吸收，和垂直方向之紫外線吸收。從紫外吸收之測定結果，評估該塗膜中與偏光的紫外線之偏光方向為平行方向之紫外線吸光度、和垂直方向之紫外線吸光度之差(∆A)。又，求出本發明中所使用的塗膜中所實現的∆A的最大值(∆Amax)，與實現該最大值的偏光紫外線的照射量。本發明之製造方法中，將實現該∆Amax的偏光紫外線照射量作為基準，可決定液晶配向膜的製造中所照射的偏光的紫外線量的較佳量。 　　[0093] 根據以上，本發明之製造方法中，為了實現對塗膜的高效率的異向性的導入，將該主鏈型高分子可賦予液晶配向穩定性的溫度範圍作為基準，來決定如上述般的適合的加熱溫度。因此，例如，本發明中所使用的主鏈型高分子為賦予液晶配向穩定性的溫度範圍，係可考慮使用的塗膜所展現出良好的液晶配向穩定性及電特性的溫度來做決定，可依據由以往的聚醯亞胺等所成之液晶配向膜的溫度範圍來做設定。即，偏光紫外線照射後的加熱溫度係以設為150℃~300℃為較佳，更希望設為180℃~250℃。藉此，本發明中所使用的塗膜中，將可賦予更大的異向性。 　　[0094] 藉此，由本發明所提供的液晶顯示元件對於光或熱等的外部應力將展現出高的可靠性。 　　[0095] 如以上般之方式，使用本發明之聚合物所製造的橫向電場驅動型液晶顯示元件用基板或具有該基板的橫向電場驅動型液晶顯示元件，由於可靠性為優異，故可適合利用於大畫面且高精細的液晶電視等。又，藉由本發明之方法所製造的液晶配向膜，由於具有優異的液晶配向穩定性與可靠性，故亦可利用於使用液晶的可變相移器，該可變相移器係可適合利用於例如能改變共振周波數的天線等。 [實施例] 　　[0096] 實施例中使用的簡稱係如以下般。 　　NMP：N-甲基-2-吡咯啶酮 　　BCS：丁基溶纖劑 　　DA-1：下述構造式(DA-1) 　　DA-2：下述構造式(DA-2) 　　DA-3：下述構造式(DA-3) 　　DA-4：下述構造式(DA-4) 　　DA-5：下述構造式(DA-5) 　　DA-6：下述構造式(DA-6) 　　DA-7：下述構造式(DA-7) 　　DA-8：下述構造式(DA-8) 　　DA-9：下述構造式(DA-9) 　　DA-10：下述構造式(DA-10) 　　CA-1：下述構造式(CA-1) 　　[0097]
Figure 02_image039
[0098]
Figure 02_image041
[0099] ＜黏度之測定＞ 　　合成例中，聚合物溶液的黏度係使用E型黏度計TVE-22H (東機產業公司製)，以樣品量1.1mL、錐形轉子TE-1(1°34’、R24)、溫度25℃下來進行測定。 　　[0100] (合成例1) 　　於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取2.93g(12.0mmol)DA-1，加入32.3gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加2.22g(11.3mmol)CA-1，進而加入13.8gNMP，在氮環境下以23℃攪拌8小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係130mPa·s。 　　將該聚醯胺酸的溶液分離14.5g至已放入攪拌子的100mL三角燒瓶中，加入5.8gNMP、及8.7gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(A-1)。 　　[0101] (合成例2) 　　於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取4.30g(15.0mmol)DA-2、加入40.6gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加2.79g(14.3mmol)CA-1，進而加入10.1gNMP，在氮環境下以23℃攪拌5小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係322mPa·s。 　　將該聚醯胺酸的溶液分離14.9g至已放入攪拌子的100mL三角燒瓶中，加入10.2gNMP、及10.7gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(A-2)。 　　[0102] (合成例3) 　　於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取3.60g(12.0mmol)DA-3，加入33.4gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加2.22g(11.3mmol)CA-1，進而加入8.35gNMP，在氮環境下以23℃攪拌3小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係370mPa·s。 　　將該聚醯胺酸的溶液分離14.5g至已放入攪拌子的100mL三角燒瓶中，加入9.90gNMP、及10.4gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(A-3)。 　　[0103] (合成例4) 　　於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取4.11g(12.0mmol)DA-4，加入36.4gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加2.19g(11.2mmol)CA-1，進而加入9.10gNMP，在氮環境下以23℃攪拌5小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係349mPa·s。 　　將該聚醯胺酸的溶液分離14.6g至已放入攪拌子的100mL三角燒瓶中，加入9.90gNMP、及10.5gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(A-4)。 　　[0104] (合成例5) 　　於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取4.17g(13.0mmol)DA-5，加入38.2gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加2.36g(12.0mmol)CA-1，進而加入9.55gNMP，在氮環境下以23℃攪拌6小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係247mPa·s。 　　將該聚醯胺酸的溶液分離14.7g至已放入攪拌子的100mL三角燒瓶中，加入9.98gNMP、及10.6gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(A-5)。 　　[0105] (合成例6) 　　於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取2.49g(23.0mmol)DA-6，加入37.9gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加4.33g(22.1mmol)CA-1，進而加入9.47gNMP，在環境下以23℃攪拌4小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係321mPa·s。 　　將該聚醯胺酸的溶液分離14.6g至已放入攪拌子的100mL三角燒瓶中，加入9.94gNMP、及10.5gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(A-6)。 　　[0106] (比較合成例1) 　　於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取3.45g(15.0mmol)DA-7，加入35.6gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加2.82g(14.4mmol)CA-1，進而加入8.91gNMP，在氮環境下以23℃攪拌20小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係277mPa·s。 　　將該聚醯胺酸的溶液分離14.9g至已放入攪拌子的100mL三角燒瓶中，加入10.2gNMP、及10.7gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(B-1)。 　　[0107] (比較合成例2) 　　於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取3.57g(18.0mmol)DA-8，加入39.4g NMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加3.46g(17.6mmol)CA-1，進而加入9.84gNMP，在環境下以23℃攪拌4小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係218mPa·s。 　　將該聚醯胺酸的溶液分離14.6g至已放入攪拌子的100mL三角燒瓶中，加入9.94gNMP、及10.5gBCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(B-2)。 　　[0108] (比較合成例3) 　　於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取2.59g(19.0mmol)DA-9，加入35.3gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加3.54g(18.1mmol)CA-1，進而加入8.82gNMP，在氮環境下以23℃攪拌20小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係336mPa·s。 　　將該聚醯胺酸的溶液分離14.8g至已放入攪拌子的100mL三角燒瓶中，加入10.0g NMP、及10.7g BCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(B-3)。 　　[0109] (比較合成例4) 　　於附有攪拌裝置及氮導入管的100mL的四頸燒瓶中，量取2.70g(25.0mmol)DA-10，加入34.0gNMP，一邊送入氮一邊攪拌來使其溶解。在水冷下一邊攪拌該二胺溶液，一邊添加4.80g(24.5mmol)CA-1，進而加入8.51gNMP，在氮環境下以23℃攪拌8小時從而得到聚醯胺酸的溶液。該聚醯胺酸的溶液於溫度25℃中之黏度係301mPa·s。 　　將該聚醯胺酸的溶液分離12.0g至已放入攪拌子的100mL三角燒瓶中，加入13.2gNMP、及10.8g BCS，利用磁攪拌器攪拌2小時，從而得到液晶配向劑(B-4)。 　　[0110] ＜液晶配向性評估用液晶晶胞之製作＞ 　　以下表示用於評估液晶配向性之液晶晶胞之製作方法。 　　製作具備FFS方式之液晶顯示元件之構成的液晶晶胞。首先，準備附有電極的基板。基板為30mm×35mm的大小、厚度為0.7mm的玻璃基板。於基板上作為第1層全面地形成構成對向電極的IZO電極。於第1層的對向電極之上，作為第2層形成了藉由CVD法而成膜的SiN(氮化矽)膜。第2層的SiN膜的膜厚為500nm，作為層間絕緣膜發揮作用。於第2層的SiN膜之上，作為第3層配置了將IZO膜圖型化而形成的梳齒狀的像素電極，以形成了第1像素及第2像素這2個像素。各像素的尺寸為長10mm、寬約5mm。此時，第1層的對向電極與第3層的像素電極係藉由第2層的SiN膜的作用而為電絕緣。 　　第3層的像素電極與特開2014-77845(日本國公開專利公報)所記載的圖相同，具有排列多個中央部分彎曲的“く”字形狀的電極要素所構成的梳齒狀的形狀。各電極要素的寬度方向的寬為3μm，電極要素間的間隔為6μm。形成各像素的像素電極由排列多個中央部分彎曲的“く”字形狀的電極要素所構成，因此各像素的形狀不是長方形，而是具備與電極要素相同地在中央部分彎曲的、與粗體的“く”字相似的形狀。而且，各像素係以其中央的彎曲部分為界被上下分割，具有彎曲部分的上側的第1區域與下側的第2區域。 　　若比較各像素的第1區域與第2區域時，則構成此等的像素電極的電極要素的形成方向為不同。即，將對基板投影後述之偏光紫外線的偏光面之線段的方向作為基準時，像素的第1區域中，像素電極的電極要素以成為+10°的角度(順時針轉)之方式形成，像素的第2區域中，像素電極的電極要素以成為-10°的角度(順時針轉)之方式形成。即，各像素的第1區域與第2區域中，以藉由像素電極與對向電極之間的電壓外加而所誘發的液晶的、在基板面內的旋轉動作(面內轉向)的方向互為相反方向之方式來構成。 　　[0111] 接下來，利用1.0μm的過濾器來過濾合成例及比較合成例所得之液晶配向劑後，藉由旋轉塗佈來塗佈至所準備的上述附有電極的基板上。接下來，於設定成70℃的加熱板上使其乾燥90秒鐘。接下來，利用Ushio電機(股)製曝光裝置：APL-L050121S1S-APW01，介隔著波長選擇過濾器及偏光板，從鉛垂方向對基板來照射紫外線的直線偏光。此時，對基板投影的偏光紫外線的偏光面之線段的方向，係以相對於第3層IZO梳齒電極成為傾斜10°的方向之方式來設定偏光面方向。接下來，利用設定成230℃的IR(紅外線)型烘箱進行30分鐘燒成，從而得到施予配向處理的膜厚100nm之附有聚醯亞胺液晶配向膜的基板。又，作為對向基板，對於在裏面形成有ITO電極的具有高度4μm的柱狀間隔件的玻璃基板，亦與上述相同之方式，從而得到施予配向處理的附有聚醯亞胺液晶配向膜的基板。將該等2片附有液晶配向膜的基板作為1組，於一片的基板上以保留液晶注入口之形式下印刷密封劑，將另1片基板以液晶配向膜面彼此相對、且對基板投影偏光紫外線的偏光面之線段的方向成平行之方式來貼合並壓黏。之後，使密封劑硬化從而製作晶胞間距為4μm的空晶胞。藉由減壓注入法對該空晶胞注入液晶MLC-7026-100(Merck公司製負型液晶)，並密封注入口從而得到FFS方式之液晶晶胞。之後，將所得之液晶晶胞以120℃下加熱30分鐘，以23℃下放置一晩後使用於液晶配向性之評估。 　　[0112] ＜液晶配向性之評估＞ 　　使用該液晶晶胞，以70℃的恆溫環境下，外加168小時周波數30Hz下16VPP的交流電壓。之後，使液晶晶胞的像素電極與對向電極之間成為短路狀態，保持其狀態以23℃下放置一晩。 　　放置後，將液晶晶胞設置在以偏光軸為垂直之方式所配置的2片的偏光板之間，在無外加電壓之狀態下點亮背光源，以透射光的輝度達到最小之方式來調整液晶晶胞的配置角度。而且，計算使液晶晶胞從第1像素的第2區域達到最暗的角度旋轉至第1區域達到最暗的角度為止的旋轉角度作為角度∆。針對第2像素亦為相同地，將第2區域與第1區域進行比較並算出相同的角度∆。而且，計算第1像素與第2像素的角度∆值的平均值作為液晶晶胞的角度∆。若該液晶晶胞的角度∆的值未滿1.0°時定義為「良好」，若角度∆的值為1.0°以上時則定義為「不良」來評估。 　　[0113] (實施例1) 　　使用合成例1所得之液晶配向劑(A-1)，來製作如上述記載般的液晶晶胞。偏光紫外線的照射係利用高壓水銀燈，介隔著波長選擇過濾器：240LCF、及254nm型的偏光板來進行。偏光紫外線的照射量係藉由利用Ushio電機(股)製照度計UVD-S254SB來測定光量，並在波長254nm下分別變更以600~1500mJ/cm2 的範圍內來實施，從而製作3個以上的偏光紫外線照射量不同的液晶晶胞。 　　對於該等之液晶晶胞進行評估液晶配向性之結果，角度∆為最佳的偏光紫外線照射量為1200mJ/cm2 ，角度∆係以0.13°為良好。 　　[0114] (實施例2~6) 　　除了使用合成例2~6所得之液晶配向劑以外，採用與實施例1相同之方法來評估液晶配向性。 　　[0115] (比較例1~4) 　　除了使用比較合成例1~4所得之液晶配向劑以外，採用與實施例1相同之方法來評估液晶配向性。 　　[0116] 表1中表示使用合成例及比較合成例所得之液晶配向劑時，角度∆為最佳的偏光紫外線照射量、及液晶配向性之評估的結果。 　　[0117]
Figure 02_image043
[0118] 如表1所表示般，實施例1~6中，交流驅動前後的配向方位角的差(角度∆)未滿1.0°為良好，因此液晶顯示元件之顯示品質提升為優異。另一方面，比較例1~4中，角度∆為1.0°以上而為不良。 　　如此般地藉由本發明之方法所製造之液晶顯示元件係可確認展現出非常優異的殘影特性。 [產業利用性] 　　[0119] 使用本發明之組成物所製造的橫向電場驅動型液晶顯示元件用基板或具有該基板的橫向電場驅動型液晶顯示元件，由於液晶配向的長期穩定性為優異，故可適合利用於大畫面且高精細的液晶電視等。又，藉由本發明之方法所製造的液晶配向膜係亦可利用於使用液晶的可變相移器，該可變相移器係可適合利用於例如能改變共振周波數的天線等。[Best Mode for Carrying Out the Invention] [0024] Hereinafter, embodiments of the present invention will be described in detail. The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent containing a polymer obtained from a diamine component and an acid dianhydride component (hereinafter, also referred to as a specific polymer, or also referred to as a main chain polymer). The amine component contains the diamine represented by said formula (1), and this acid dianhydride component contains the tetracarboxylic dianhydride represented by said formula (2). Each condition will be described in detail below. <Diamine with a specific structure> The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent containing a polymer and an organic solvent. The polymer is obtained from a diamine component and an acid dianhydride component. The diamine component Containing diamine represented by formula (1) (also referred to as specific diamine in the present invention), the acid dianhydride component contains tetracarboxylic dianhydride represented by formula (2) (also referred to as specific tetracarboxylic acid dianhydride in the present invention) acid dianhydride). [0026]
Figure 02_image007
In formula (1), L is a divalent organic group with more than 2 carbon numbers and includes alkylene, and any one selected from the bonding of ether bond and ester bond, R and R are are independently monovalent organic groups, p1 and p2 are independently integers from 0 to 4, p is 0 or 1, and q1 and q2 are independently 1 or 2. As the valent organic group here, an alkyl group, alkenyl group, alkoxyl group, fluoroalkyl group, fluoroalkenyl group, or fluorine group having a carbon number of 1 to 10 (preferably 1 to 3) can be enumerated. alkoxy. Among them, methyl is preferred as the monovalent organic group. As the divalent organic group, can enumerate: the base that constitutes with alkylene and ether bond, or the base that constitutes with alkylene and ester bond, a part or all of hydrogen atom is substituted by halogen A group consisting of an alkylene group and an ether bond, or a group consisting of an alkylene group and an ester bond in which a part or all of the hydrogen atoms are substituted by halogen. Among them, a group composed of an alkylene group and an ether bond is preferable as the divalent organic group. The carbon number is preferably from 2 to 20, and more preferably from 2 to 10. Also, among the number of atoms of L, if the total number of atoms of carbon atoms and oxygen atoms related to the length of the main chain is an even number, the linearity of the obtained polymer will become higher, and as a result, In the heating step after polarized light irradiation, it is preferable to obtain a liquid crystal alignment film with high alignment control ability by carrying out higher order realignment. Still, the total number of carbon atoms and oxygen atoms related to the length of the main chain means that the number of each methylene group in the main chain is set to 1, the number of each ether bond is set to 1, and the number of each ether bond is set to 1. The total when the number of one ester bond is 2. [0031] As p1 and p2, 0 is preferable in terms of less steric hindrance, easy overlapping of phenyl groups, and higher order rearrangement. As p, 1 is preferable in that the alkylene group functioning as a freely rotating site can be rearranged in a higher order. Among the diamines of the above-mentioned formula (1), specific examples of diamines in which p is 1 can be illustrated as follows, but are not limited thereto. [0032]
Figure 02_image009
[0033]
Figure 02_image011
[0034]
Figure 02_image013
Here, if the total of r, t and u is an even number such as 2, 4, 6, 8 and 10, the linearity of the obtained polymer will become higher, and as a result, after polarized light irradiation In the heating step, by re-aligning with a higher order, a liquid crystal alignment film endowed with high alignment control ability can be obtained. s is an odd number such as 1, 3, 5, etc., but it is preferable for the reason mentioned above. Among the diamines represented by the above formula (1), p-phenylenediamine is mentioned as a specific example of the diamine in which p is 0. <Polymer> The polymer of the present invention is a polymer obtained from a diamine component and an acid dianhydride component. The diamine component includes the diamine represented by the above formula (1), and the acid dianhydride component Tetracarboxylic dianhydride represented by said formula (2) is contained. As specific examples, polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide, etc. can be mentioned, but from the viewpoint of use as a liquid crystal alignment agent, it can be selected from the following formula: (3) At least one kind of polyimide precursor of the structural unit represented by the polyimide, and the polyimide of this imidate is preferable. In the heating step after polarized light irradiation, the polyimide precursor is more preferable in terms of the more freely rotating sites in the polymer and the more orderly rearrangement. [0037]
Figure 02_image015
In above-mentioned formula (3), X Be derived from the tetravalent organic group of the tetracarboxylic acid derivative represented by above-mentioned formula (2), Y Be derived from the diamine of the structure comprising formula ( 1 ) A divalent organic group, R11 is a hydrogen atom or an alkyl group with 1 to 5 carbons. R 11 is preferably a hydrogen atom, a methyl group or an ethyl group, and more preferably a hydrogen atom, from the point of being easily imidized by heating. <Tetracarboxylic dianhydride> X is a tetravalent organic group derived from a tetracarboxylic acid derivative represented by the above formula (2). In formula (2), R 6 ~ R 9 are independently hydrogen atoms, alkyl groups, halogen atoms or phenyl groups. Among the following structures, from the viewpoint of liquid crystal alignment, R 6 ~ R 9 are hydrogen atoms Whichever is better. [0040]
Figure 02_image017
<Diamine> In the formula (3), specific examples of Y1 include a structure obtained by removing two amino groups from the diamine of the aforementioned formula (1). Among them, the structure obtained by removing two amine groups from the above-mentioned preferable diamine is preferable. <Polymer (other structural unit)> The polyimide precursor comprising the structural unit represented by formula (3) may also contain a polyimide precursor selected from the following within the scope of not impairing the effect of the present invention At least one kind of structural unit represented by formula (4) and polyimide of the imide compound. [0043]
Figure 02_image019
In formula (4), X 2 is derived from tetravalent organic radicals of tetracarboxylic acid derivatives, Y 2 is derived from divalent organic radicals of diamines, R 12 is the same as R of aforementioned formula (3) 11 The definition of is the same, and R22 represents a hydrogen atom or an alkyl group with 1 to 4 carbons. Also, at least one of the two R 22 is preferably a hydrogen atom. X 2 is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited. In addition, X2 in the polyimide precursor is determined according to the solubility of the polymer to the solvent or the coatability of the liquid crystal alignment agent, the alignment of the liquid crystal when the liquid crystal alignment film is made, the voltage retention rate, and the stored charge. Depending on the degree of desired properties, one type may exist in the same polymer, or two or more types may exist in admixture. When expressing the concrete example of X2, can enumerate the structure etc. of formula (X- 1 )～(X-46) published in the 13～14 pages of International Publication 2015/119168. Although the preferred structure of X2 is shown below, the present invention is not limited thereto. [0046]
Figure 02_image021
[0047]
Figure 02_image023
[ 0048 ] Also, Y in the polyimide precursor is a divalent organic group derived from diamine, and its structure is not particularly limited. In addition, Y2 is appropriate according to the degree of the solubility of the polymer to the solvent or the coating property of the liquid crystal alignment agent, the alignment of the liquid crystal when the liquid crystal alignment film is made, the voltage retention rate, and the storage charge. Optionally, 1 type may exist in the same polymer, or 2 or more types may mix and exist. When expressing the specific example of Y 2 , the structure of the formula (2) published on the 4th page of International Publication 2015/119168 and the formula (Y-1) published on the 8th to 12 pages can be cited )~(Y-97), (Y-101)~(Y-118); the bivalent compound obtained by removing two amino groups from formula (2) published on page 6 of International Publication 2013/008906 Organic group; the divalent organic group formed by removing 2 amine groups in the formula (1) published on the 8th page of the international publication 2015/122413; the formula published on the 8th page of the international publication 2015/060360 ( 3) structure; the divalent organic group formed by removing 2 amine groups in formula (1) as published on page 8 of Japanese Laid-Open Patent Publication 2012-173514; published on page 9 of International Publication Publication 2010-050523 It is a divalent organic group obtained by removing two amine groups from formulas (A)~(F), etc. As the structure of preferred Y2 , the structure of following formula (5) can be enumerated. Furthermore, the structure of Y2 may be derived from the specific diamine (1). [0051]
Figure 02_image025
In formula (5), R 32 is a single bond or a divalent organic group, preferably a single bond. R 33 is a structure represented by -(CH 2 ) n -. n is an integer of 2-10, preferably 3-7. In addition, any -CH 2 - may be substituted by an ether, ester, amide, urea, or urethane bond as long as they are not adjacent to each other. R 34 is a single bond or a divalent organic group. Any hydrogen atom on the benzene ring can also be replaced by a monovalent organic group, preferably fluorine atom or methyl group. As a structure represented by formula (5), the following structures are mentioned concretely, However, It is not limited to these. [0053]
Figure 02_image027
[0054]
Figure 02_image029
[0055]
Figure 02_image031
[0056]
Figure 02_image033
[0057]
Figure 02_image035
Wherein, do not hinder at least one rearrangement point selected from the polyimide precursor comprising the structural unit represented by formula (3) and the polyimide of the imidate , which preferably contains a partial structure common to the specific diamine (1). Comprise the polyimide precursor of the structural unit represented by formula (3), if comprise the situation of the structural unit represented by formula (4) simultaneously, the structural unit represented by formula (3) is relative to formula ( 3) The sum of formula (4) is preferably 30 mol% to 100 mol%, more preferably 50 mol% to 100 mol%, and most preferably 70 mol% to 100 mol%. [0060] The molecular weight of the polyimide precursor used in the present invention is preferably 2,000-500,000 with a weight-average molecular weight, preferably 5,000-300,000, more preferably 10,000-100,000. Examples of the polyimide used in the present invention include polyimide obtained by ring-closing the aforementioned polyimide precursor. In this polyimide, the ring-closing rate (also referred to as the imidization rate) of the amide acid group does not necessarily need to be 100%, and can be adjusted arbitrarily according to the application or purpose. Regarding the polymer of the present invention, from the viewpoint of liquid crystal alignment, the imidization rate is preferably 0-70%, and more preferably 0-50%. As a method for imidizing a polyimide precursor, thermal imidization by directly heating a solution of a polyimide precursor, or adding a catalyst to a solution of a polyimide precursor Catalytic imidization. <Liquid Crystal Alignment Agent> The liquid crystal alignment agent of the present invention contains a polymer (specific polymer) obtained from a diamine component and an acid dianhydride component. The diamine component includes the diamine represented by the above formula (1) , The acid dianhydride component contains tetracarboxylic dianhydride represented by the above formula (2), but may contain two or more specific polymers with different structures within the limit that the effects described in the present invention can be exhibited. Moreover, other polymers other than the specific polymer may be included, that is, polymers that do not have a divalent group derived from the diamine represented by formula (1). Examples of other types of polymers include polyamic acid, polyimide, polyamide ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polycondensate Aldehydes, polystyrene or its derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, and the like. When the liquid crystal alignment agent of the present invention contains other polymers, the ratio of the specific polymer to the total polymer component is preferably 10% by mass or more, and an example thereof is 10 to 100% by mass. %. [0062] The liquid crystal alignment agent is used to make a liquid crystal alignment film. From the viewpoint of forming a uniform film, it is generally in the form of a coating solution. Even the liquid crystal alignment agent of the present invention is preferably a coating solution containing the aforementioned polymer component and an organic solvent for dissolving the polymer component. At this time, the concentration of the polymer in the liquid crystal alignment agent can be appropriately changed according to the thickness setting of the coating film to be formed. From the point of forming a uniform and flawless coating film, it is preferably 1% by mass or more, and from the point of storage stability of the solution, it is preferably 10% by mass or less. A particularly preferable concentration of the polymer is 2 to 8% by mass. [0063] The organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as it can dissolve the polymer components uniformly. When specific examples are given, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2 -Pyrrolidone, dimethylsulfene, γ-butyrolactone, 1,3-dimethyl-imidazolinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, etc. Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or γ-butyrolactone. Also, the organic solvent contained in the liquid crystal alignment agent, in addition to the above-mentioned solvents, can usually be used in combination with a mixed solvent of a solvent that improves the applicability of the liquid crystal alignment agent or the surface smoothness of the coating film. Even for the liquid crystal alignment agent of the present invention, such a mixed solvent can be suitably used. Although the specific example of the organic solvent used together is mentioned below, it is not limited to these examples. Can enumerate such as ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methanol 1-butanol, isoamyl alcohol, tert-pentanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl- 2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, Cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1, 2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol , 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol Alcohol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethyl Glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, 3-ethoxybutyl ethyl ether ester, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, biscarbonate Propyl ester, ethyl carbonate, 2-(methoxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy ) ethanol, furfuryl alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy) propanol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, Dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether Acetate, Ethylene Glycol Monoacetate, Ethylene Glycol Diacetate, Diethylene Glycol Monoethyl Ether Acetate, Diethylene Glycol Monobutyl Ether Acetate, 2-(2-Ethanol Oxyethoxy) ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate , methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate, 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, Methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isopentyl lactate, solvents represented by the following formulas [D-1] to [D-3], etc. [0066]
Figure 02_image037
In formula [D-1], D 1 represents the alkyl group of carbon number 1～3, and in formula [D-2], D 2 represents the alkyl group of carbon number 1～3, formula [D-3 ], D 3 represents an alkyl group with 1 to 4 carbon atoms. [0068] The type and content of such a solvent can be appropriately selected in response to the coating device, coating conditions, and coating environment of the liquid crystal alignment agent. [0069] The liquid crystal alignment agent of the present invention may additionally contain components other than polymer components and organic solvents within the scope of not impairing the effects of the present invention. Examples of such additional components include adhesion aids for improving the adhesion between the liquid crystal alignment film and the substrate, or for improving the adhesion between the liquid crystal alignment film and the sealing material, and those for increasing the strength of the liquid crystal alignment film. Crosslinking agent, dielectric or conductive substance used to adjust the dielectric rate or resistance of the liquid crystal alignment film, etc. Specific examples of these additional components are as disclosed in well-known documents related to liquid crystal alignment agents. If one example is to be shown, it can be cited on pages 53 [0105] to 55 [0116] of the publication No. 2015/060357 specification ] The disclosed ingredients etc. <Manufacturing method of substrate with liquid crystal alignment film> and <Manufacturing method of liquid crystal display element> The manufacturing method of the substrate with liquid crystal alignment film of the present invention has the following steps: [I] will contain (A) by A step of coating the polymer composition obtained by the diamine component and the acid dianhydride component, and (B) the polymer composition of the organic solvent on a substrate having a conductive film for driving a transverse electric field, and then drying to form a coating film. The amine component consists of diamine represented by the above formula (1), and the acid dianhydride component contains tetracarboxylic dianhydride represented by the above formula (2); and [III] the step of heating the coating film obtained in [II]. Through the above steps, a liquid crystal alignment film for a lateral electric field driven liquid crystal display element endowed with alignment control ability can be obtained, and a substrate having the liquid crystal alignment film can be obtained. [0071] Also, in addition to the substrate (first substrate) obtained above, by preparing a second substrate, a lateral electric field drive type liquid crystal display element can be obtained. In addition to using a substrate without a transverse electric field drive conductive film instead of a substrate with a transverse electric field drive conductive film, the second substrate is obtained by using the above steps [I]~[III] (because the substrate without a transverse electric field drive For the sake of convenience, this case is sometimes referred to as steps [I']~[III']), so as to obtain a second substrate with a liquid crystal alignment film endowed with alignment control ability. The manufacture method of lateral electric field drive type liquid crystal display element is to have following steps: [IV] make the liquid crystal alignment film of the 1st and the 2nd substrate interpose the liquid crystal and the mode opposite to dispose the 1st of above-mentioned gain and the second substrate to obtain a liquid crystal display element. Accordingly, a lateral electric field drive type liquid crystal display element can be obtained. [0073] Hereinafter, each step of [I] to [III] and [IV] in the production method of the present invention will be described. <Step [I]> In step [I], a polymer composition containing a photosensitive main chain type polymer and an organic solvent is coated on a substrate having a conductive film for driving a transverse electric field, and then dried to form a coating film. [0074] <Substrate> There is no particular limitation on the substrate. If the manufactured liquid crystal display element is a transmissive type, it is better to use a highly transparent substrate. In this case, a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used without particular limitation. In addition, in consideration of application to reflective liquid crystal display elements, opaque substrates such as silicon wafers may also be used. [0075] <Conductive film for lateral electric field driving> The substrate has a conductive film for lateral electric field driving. As the conductive film, when the liquid crystal display device is a transmissive type, ITO (Indium Tin Oxide: Indium Tin Oxide), IZO (Indium Zinc Oxide: Indium Zinc Oxide) and the like can be mentioned, but not limited thereto. Moreover, in the case of a reflection type liquid crystal display element, although the material etc. which reflect light, such as aluminum, are mentioned as a conductive film, it is not limited to these. As a method of forming a conductive film on a substrate, conventionally known methods can be used. [0076] The method of coating the above-mentioned polymer composition onto a substrate having a conductive film for driving a transverse electric field is not particularly limited. Coating methods are generally industrially performed by screen printing, offset printing, flexographic printing, or inkjet methods. As other coating methods, there are dipping method, roll coater method, slot coater method, spinner method (spin coater method), spray method, etc., and these can be used depending on the purpose. After the polymer composition is coated on the substrate with the conductive film for driving by the transverse electric field, it can be heated at 30 to 150° C. by heating means such as a heating plate, a thermal cycle oven or an IR (infrared) oven, etc. Preferably, the solvent is evaporated at 70 to 110° C. to obtain a coating film. If the drying temperature is too low, the drying of the solvent tends to become insufficient; and if the heating temperature is too high, thermal imidization will proceed, and as a result, the photodecomposition reaction due to polarized light exposure will be excessive. In this case, it is difficult to re-align in a single direction through self-organization, so the alignment stability will be impaired. Therefore, from the viewpoint of liquid crystal alignment stability, the drying temperature at this time is preferably a temperature at which the thermal imidization of the specific polymer is not substantially performed. When the thickness of the coating film is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may decrease, so it is preferably 5nm to 300nm, and more preferably 10nm ~150nm. Furthermore, a step of cooling the substrate on which the coating film is formed to room temperature may be provided after the step [I] and before the next step [II]. [0078] <Step [II]> In step [II], polarized ultraviolet rays are irradiated to the coating film obtained in step [I]. When irradiating the polarized ultraviolet ray to the film surface of a coating film, the polarized ultraviolet ray is irradiated from the direction fixed with respect to a board|substrate through a polarizing plate. As the ultraviolet system used, ultraviolet rays within a wavelength range of 100 nm to 400 nm can be used. It is preferable to select an optimal wavelength through a filter or the like depending on the type of coating film to be used. In addition, for example, in order to selectively induce a photodecomposition reaction, ultraviolet rays within a wavelength range of 240 nm to 400 nm can be selected and used. As ultraviolet rays, for example, light emitted from a high-pressure mercury lamp or a metal halide lamp can be used. [0079] The irradiation amount of polarized ultraviolet rays depends on the coating film used. It is better to set the irradiation dose within the range of 1% to 70% of the amount of polarized ultraviolet rays that can realize the maximum value of ∆A (hereinafter also referred to as ∆Amax), and to set it within the range of 1% to 50%. More preferably, said ∆A is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of polarized ultraviolet rays in the coating film and the ultraviolet absorbance in the vertical direction. [0080] <Step [III]> In step [III], the coating film irradiated with polarized ultraviolet rays in step [II] is heated. By heating, an orientation control function can be imparted to the coating film. For the heating system, heating means such as a hot plate, a heat circulation type oven, or an IR (infrared ray) type oven can be used. The heating temperature can be determined by considering the temperature at which the coating film used exhibits good liquid crystal alignment stability and electrical characteristics. [0081] The heating temperature is preferably in the temperature range where the main chain type polymer exhibits good liquid crystal alignment stability. If the heating temperature is too low, the effect of increasing the anisotropy due to heat or thermal imidization tends to be insufficient, and if the heating temperature is higher than the temperature range, it will be exposed by polarized light The endowed anisotropy will tend to disappear, in which case reorientation in one direction by self-organization becomes difficult. The thickness of the formed coating film after heating, owing to the same reason as being recorded in the step [1], so preferably 5nm～300nm, is preferably again advisable with 50nm～150nm. [0083] By having the above steps, the manufacturing method according to the present invention can realize efficient introduction of anisotropy to the coating film. In addition, substrates with liquid crystal alignment films can be manufactured efficiently. <step [IV]> [IV] step is as follows: the substrate (the 1st substrate) that has liquid crystal alignment film on the conductive film of lateral electric field driving with [III] gained, same as above-mentioned [I The substrate (second substrate) with a liquid crystal alignment film without a conductive film obtained in ']~[III'] is arranged in opposite directions with the liquid crystal alignment films on both sides facing each other through the liquid crystal, and by The process of fabricating a liquid crystal cell by a well-known method, thereby fabricating a lateral electric field-driven liquid crystal display element. Still, steps [I']~[III'], except that in step [I], a substrate that does not have the conductive film for driving the transverse electric field is used to replace the substrate with the conductive film for driving the transverse electric field, and the step [ I]~[III] are carried out in the same way. The difference between steps [I]~[III] and steps [I']~[III'] lies in the presence or absence of the above-mentioned conductive film, so the description of steps [I']~[III'] is omitted. When enumerating one example of the making of liquid crystal cell or liquid crystal display element, following method can be exemplified: prepare above-mentioned 1st and the 2nd substrate, spread spacer on the liquid crystal alignment film of a substrate, Lay another substrate with the surface of the liquid crystal alignment film on the inside, inject liquid crystal under reduced pressure and seal it, or drop liquid crystal on the surface of the liquid crystal alignment film where spacers are scattered, and then bond the substrate and seal it Wait. In this case, it is preferable to use a substrate having an electrode having a comb-like structure for driving in a transverse electric field as one of the substrates. At this time, the diameter of the spacer is preferably 1 μm to 30 μm, and more preferably 2 μm to 10 μm. The diameter of the spacer determines the distance between a pair of substrates sandwiching the liquid crystal layer, that is, the thickness of the liquid crystal layer. [0086] The method of manufacturing a substrate with a coating film of the present invention is to apply a polymer composition to a substrate to form a coating film, and then irradiate polarized ultraviolet rays. Next, by heating, high-efficiency introduction of anisotropy to the main chain type polymer film is realized, and a substrate with a liquid crystal alignment film with alignment control ability of liquid crystal is manufactured. In the coating film used in the present invention, efficient introduction of anisotropy into the coating film is realized by utilizing the principle of molecular reorientation induced by self-organization based on the photoreaction of the main chain. In the production method of the present invention, in the case where the main chain type polymer has a photodecomposable group as the structure of the photoreactive group, after forming a coating film on the substrate using the main chain type polymer, irradiate polarized ultraviolet rays , and then heated to make a liquid crystal display element. Therefore, the coating film used in the method of the present invention can efficiently introduce anisotropy by sequentially irradiating polarized ultraviolet rays and heat treatment on the coating film, so that it can be made to have excellent alignment control performance. Liquid crystal alignment film. [0088] Also, in the coating film used in the method of the present invention, the irradiation amount of polarized ultraviolet rays irradiated to the coating film and the heating temperature in the heat treatment are optimized. Thereby, efficient introduction of anisotropy to the coating film can be realized. The coating film used in the present invention introduces anisotropy with high efficiency, and as the best irradiation amount of polarized ultraviolet rays, it is corresponding to the amount when the photodecomposition reaction of the photosensitive group in the coating film is optimal. Exposure to polarized UV rays. As a result of irradiating polarized ultraviolet rays to the coating film used in the present invention, if there are few photosensitive groups that undergo a photodecomposition reaction, a sufficient amount of photoreaction will not be achieved. In this case, sufficient self-organization will not proceed even after heating. Therefore, in the coating film used among the present invention, by the irradiation of polarizing ultraviolet ray, the optimal amount that makes photosensitive group carry out photolysis reaction, is set as 0.1 mol %～90 mol with this macromolecule film Mole% is better, and 0.1 mol% ~ 80 mol% is more preferably. By setting the amount of the photosensitive group that undergoes photoreaction within such a range, self-organization can be efficiently performed by subsequent heat treatment, and anisotropy can be efficiently formed in the film. In the coating film used in the method of the present invention, by optimizing the irradiation amount of polarized ultraviolet rays, the amount of photodecomposition reaction of the photosensitive group in the main chain of the polymer film can be optimized . In addition, the heat treatment after combining enables efficient introduction of anisotropy to the coating film used in the present invention. In this case, the amount of suitable polarized ultraviolet rays can be based on the evaluation of the ultraviolet absorption of the coating film used in the present invention. That is, for the coating film used in the present invention, the ultraviolet absorption in the parallel direction and the ultraviolet absorption in the vertical direction after the polarized ultraviolet irradiation are measured respectively. From the measurement results of ultraviolet absorption, the difference (∆A) between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays in the coating film and the ultraviolet absorbance in the perpendicular direction is evaluated. Also, the maximum value of ΔA (ΔAmax) realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet rays to realize the maximum value were obtained. In the manufacturing method of the present invention, the optimal amount of polarized ultraviolet rays irradiated in the manufacture of the liquid crystal alignment film can be determined by taking the amount of polarized ultraviolet rays that realizes the ΔAmax as a reference. Based on the above, in the manufacturing method of the present invention, in order to realize the introduction of the high-efficiency anisotropy of the coating film, the temperature range that the main chain type macromolecule can give liquid crystal alignment stability is used as a benchmark to determine such as Suitable heating temperature as above. Therefore, for example, the main chain type polymer used in the present invention is the temperature range for imparting liquid crystal alignment stability, which can be determined by considering the temperature at which the coating film used exhibits good liquid crystal alignment stability and electrical properties. It can be set according to the temperature range of the liquid crystal alignment film made of conventional polyimide, etc. That is, the heating temperature after polarized ultraviolet irradiation is preferably 150°C to 300°C, more preferably 180°C to 250°C. Thereby, larger anisotropy can be imparted to the coating film used by this invention. [0094] Accordingly, the liquid crystal display element provided by the present invention exhibits high reliability against external stress such as light or heat. As above, the substrate for the transverse electric field driven liquid crystal display element manufactured by the polymer of the present invention or the transverse electric field driven liquid crystal display element with the substrate is excellent in reliability, so it can be suitably used For large-screen and high-definition LCD TVs, etc. In addition, the liquid crystal alignment film manufactured by the method of the present invention has excellent liquid crystal alignment stability and reliability, so it can also be used in a variable phase shifter using liquid crystals. The variable phase shifter can be used in, for example, Antennas that can change the frequency of resonance, etc. [Example] [0096] The abbreviations used in the examples are as follows. NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve DA-1: The following structural formula (DA-1) DA-2: The following structural formula (DA-2) DA-3: The following structural formula Formula (DA-3) DA-4: the following structural formula (DA-4) DA-5: the following structural formula (DA-5) DA-6: the following structural formula (DA-6) DA-7: the following The above structural formula (DA-7) DA-8: the following structural formula (DA-8) DA-9: the following structural formula (DA-9) DA-10: the following structural formula (DA-10) CA-1 : following structural formula (CA-1) [0097]
Figure 02_image039
[0098]
Figure 02_image041
<Measurement of Viscosity> In the synthesis example, the viscosity of the polymer solution is an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample size of 1.1 mL and a conical rotor TE-1 (1 ° 34 ', R24), measured at a temperature of 25°C. (Synthesis Example 1) Measure 2.93g (12.0mmol) of DA-1 in a 100mL four-neck flask with a stirring device and a nitrogen introduction tube, add 32.3g of NMP, and stir while feeding nitrogen to make it dissolve. Stirring this diamine solution under water cooling, 2.22 g (11.3 mmol) of CA-1 was added, and 13.8 g of NMP was further added, and it stirred at 23 degreeC under nitrogen atmosphere for 8 hours, and obtained the solution of the polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25° C. is 130 mPa·s. Separate 14.5 g of this polyamic acid solution into a 100 mL Erlenmeyer flask with a stirring bar, add 5.8 g of NMP and 8.7 g of BCS, and stir for 2 hours with a magnetic stirrer to obtain a liquid crystal alignment agent (A-1). (Synthesis Example 2) In a 100mL four-neck flask equipped with a stirring device and a nitrogen introduction tube, measure 4.30g (15.0mmol) of DA-2, add 40.6g of NMP, and stir while feeding nitrogen to make it dissolve. Stirring this diamine solution under water cooling, 2.79 g (14.3 mmol) of CA-1 was added, and 10.1 g of NMP was further added, and it stirred at 23 degreeC for 5 hours under nitrogen atmosphere, and obtained the solution of the polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25° C. is 322 mPa·s. 14.9 g of this polyamic acid solution was separated into a 100 mL Erlenmeyer flask with a stirring bar, 10.2 g of NMP and 10.7 g of BCS were added, and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (A-2). (Synthesis Example 3) Measure 3.60 g (12.0 mmol) of DA-3 in a 100 mL four-necked flask with a stirring device and a nitrogen introduction tube, add 33.4 g of NMP, and stir while feeding nitrogen to make it dissolve. Stirring this diamine solution under water cooling, 2.22 g (11.3 mmol) of CA-1 was added, and 8.35 g of NMP was further added, and it stirred at 23 degreeC for 3 hours under nitrogen atmosphere, and obtained the solution of the polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25° C. is 370 mPa·s. 14.5 g of this polyamic acid solution was separated into a 100 mL Erlenmeyer flask with a stirring bar, 9.90 g of NMP and 10.4 g of BCS were added, and stirred for 2 hours with a magnetic stirrer to obtain a liquid crystal alignment agent (A-3). (Synthesis Example 4) Measure 4.11 g (12.0 mmol) of DA-4 in a 100 mL four-neck flask with a stirring device and a nitrogen introduction tube, add 36.4 g of NMP, and stir while feeding nitrogen to make it dissolve. Stirring this diamine solution under water cooling, CA-1 2.19g (11.2mmol) was added, and NMP9.10g was further added, and it stirred at 23 degreeC for 5 hours under nitrogen atmosphere, and obtained the solution of the polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25° C. is 349 mPa·s. 14.6 g of this polyamic acid solution was separated into a 100 mL Erlenmeyer flask with a stirring bar, 9.90 g of NMP and 10.5 g of BCS were added, and stirred for 2 hours with a magnetic stirrer to obtain a liquid crystal alignment agent (A-4). (Synthesis Example 5) Measure 4.17g (13.0mmol) of DA-5 in a 100mL four-necked flask with a stirring device and a nitrogen introduction tube, add 38.2g of NMP, and stir while feeding nitrogen to make it dissolve. Stirring this diamine solution under water cooling, 2.36 g (12.0 mmol) of CA-1 was added, and 9.55 g of NMP was further added, and it stirred at 23 degreeC for 6 hours under nitrogen atmosphere, and obtained the solution of the polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25° C. is 247 mPa·s. 14.7 g of this polyamic acid solution was separated into a 100 mL Erlenmeyer flask with a stirring bar, 9.98 g of NMP and 10.6 g of BCS were added, and stirred for 2 hours with a magnetic stirrer to obtain a liquid crystal alignment agent (A-5). (Synthesis Example 6) In a 100mL four-necked flask with a stirring device and a nitrogen introduction tube, measure 2.49g (23.0mmol) of DA-6, add 37.9g of NMP, and stir while feeding nitrogen to make it dissolve. Stirring this diamine solution under water cooling, 4.33 g (22.1 mmol) of CA-1 was added, and 9.47 g of NMP was further added, and it stirred at 23 degreeC for 4 hours under ambient conditions, and obtained the solution of the polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25° C. is 321 mPa·s. 14.6 g of this polyamic acid solution was separated into a 100 mL Erlenmeyer flask with a stirring bar, 9.94 g of NMP and 10.5 g of BCS were added, and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal alignment agent (A-6). (Comparative Synthesis Example 1) In a 100mL four-neck flask with a stirring device and a nitrogen introduction tube, measure 3.45g (15.0mmol) of DA-7, add 35.6g of NMP, and stir while feeding nitrogen to make It dissolves. Stirring this diamine solution under water cooling, CA-1 2.82g (14.4mmol) was added, and NMP8.91g was further added, and it stirred at 23 degreeC for 20 hours under nitrogen atmosphere, and obtained the solution of the polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25° C. is 277 mPa·s. Separate 14.9 g of this polyamic acid solution into a 100 mL Erlenmeyer flask with a stirring bar, add 10.2 g of NMP and 10.7 g of BCS, and stir for 2 hours with a magnetic stirrer to obtain a liquid crystal alignment agent (B-1). (Comparative Synthesis Example 2) Measure 3.57g (18.0mmol) of DA-8 in a 100mL four-neck flask with a stirring device and a nitrogen introduction tube, add 39.4g of NMP, and stir while feeding nitrogen Let it dissolve. Stirring this diamine solution under water cooling, 3.46 g (17.6 mmol) of CA-1 was added, and 9.84 g of NMP was further added, and it stirred at 23 degreeC for 4 hours under ambient conditions, and obtained the solution of the polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25° C. is 218 mPa·s. Separate 14.6 g of this polyamic acid solution into a 100 mL Erlenmeyer flask with a stirring bar, add 9.94 g of NMP and 10.5 g of BCS, and stir for 2 hours with a magnetic stirrer to obtain a liquid crystal alignment agent (B-2). (Comparative Synthesis Example 3) Measure 2.59g (19.0mmol) of DA-9 in a 100mL four-necked flask with a stirring device and a nitrogen introduction tube, add 35.3g of NMP, and stir while feeding nitrogen to make It dissolves. Stirring this diamine solution under water cooling, 3.54 g (18.1 mmol) of CA-1 was added, and 8.82 g of NMP was further added, and it stirred at 23 degreeC for 20 hours under nitrogen atmosphere, and obtained the solution of the polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25° C. is 336 mPa·s. Separate 14.8g of this polyamic acid solution into a 100mL Erlenmeyer flask with a stirring bar, add 10.0g NMP and 10.7g BCS, and stir for 2 hours with a magnetic stirrer to obtain a liquid crystal alignment agent (B-3 ). (Comparative Synthesis Example 4) Measure 2.70 g (25.0 mmol) of DA-10 in a 100 mL four-neck flask with a stirring device and a nitrogen introduction tube, add 34.0 g of NMP, and stir while feeding nitrogen to make It dissolves. Stirring this diamine solution under water cooling, 4.80 g (24.5 mmol) of CA-1 was added, and 8.51 g of NMP was further added, and it stirred at 23 degreeC for 8 hours under nitrogen atmosphere, and obtained the solution of the polyamic acid. The viscosity of the polyamic acid solution at a temperature of 25° C. is 301 mPa·s. Separate 12.0 g of this polyamic acid solution into a 100 mL Erlenmeyer flask with a stirring bar, add 13.2 g of NMP, and 10.8 g of BCS, and stir for 2 hours with a magnetic stirrer to obtain a liquid crystal alignment agent (B-4) . <Preparation of Liquid Crystal Cell for Evaluation of Liquid Crystal Alignment> The method for preparing a liquid crystal cell for evaluation of liquid crystal alignment is shown below. A liquid crystal cell having a configuration of a liquid crystal display element of the FFS method was produced. First, a substrate with electrodes is prepared. The substrate was a glass substrate having a size of 30 mm×35 mm and a thickness of 0.7 mm. An IZO electrode constituting a counter electrode is formed entirely on the substrate as a first layer. On the counter electrode of the first layer, a SiN (silicon nitride) film formed by a CVD method was formed as a second layer. The SiN film of the second layer has a film thickness of 500 nm and functions as an interlayer insulating film. On the SiN film of the second layer, a comb-shaped pixel electrode formed by patterning an IZO film was arranged as a third layer to form two pixels of a first pixel and a second pixel. The size of each pixel is about 10 mm in length and about 5 mm in width. At this time, the counter electrode of the first layer and the pixel electrode of the third layer are electrically insulated by the action of the SiN film of the second layer. The pixel electrode of the third layer has a comb-tooth-like shape consisting of arranging a plurality of "く"-shaped electrode elements bent at the center, as shown in JP-A-2014-77845 (Japanese Laid-Open Patent Publication). The width of each electrode element in the width direction was 3 μm, and the interval between electrode elements was 6 μm. The pixel electrode forming each pixel is composed of a plurality of "く"-shaped electrode elements that are bent at the center. Therefore, the shape of each pixel is not a rectangle, but has the same electrode elements as the electrode elements. The shape of the "く" character is similar. Furthermore, each pixel is divided up and down with a curved portion at the center thereof, and has a first region above the curved portion and a second region below the curved portion. When comparing the first region and the second region of each pixel, the formation directions of the electrode elements constituting these pixel electrodes are different. That is, when the direction of the line segment of the polarizing plane that projects polarized ultraviolet light described later on the substrate is taken as a reference, in the first region of the pixel, the electrode elements of the pixel electrode are formed at an angle of +10° (turned clockwise), and the pixel In the second region of , the electrode elements of the pixel electrode are formed at an angle of -10° (clockwise). That is, in the first region and the second region of each pixel, the direction of the rotation motion (in-plane turning) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode in the substrate plane is mutually opposite. Constructed in the opposite direction. [0111] Next, after filtering the liquid crystal alignment agents obtained in the synthesis examples and comparative synthesis examples with a filter of 1.0 μm, they were coated onto the prepared above-mentioned substrate with electrodes by spin coating. Next, it was dried for 90 seconds on a hot plate set at 70°C. Next, using an exposure device made by Ushio Electric Co., Ltd.: APL-L050121S1S-APW01, through a wavelength selection filter and a polarizing plate, the substrate is irradiated with linearly polarized light of ultraviolet rays from the vertical direction. At this time, the direction of the line segment of the polarization plane of the polarized ultraviolet rays projected on the substrate is set so that the direction of the polarization plane is inclined by 10° with respect to the third-layer IZO comb electrode. Next, firing was performed for 30 minutes in an IR (infrared ray) oven set at 230° C. to obtain a 100-nm-thick polyimide liquid crystal alignment film-attached substrate subjected to alignment treatment. Also, as the opposite substrate, a glass substrate with a columnar spacer with a height of 4 μm formed on the inside of the ITO electrode was also used in the same manner as above to obtain a polyimide liquid crystal alignment film with an alignment treatment. the substrate. These 2 substrates with liquid crystal alignment film are used as a group, and the sealant is printed on one of the substrates in the form of leaving the liquid crystal injection port, and the other substrate is facing each other with the liquid crystal alignment film surface, and the substrate is projected The directions of the line segments of the polarized surface of the polarized ultraviolet light are aligned and pressed in parallel. After that, the sealant was cured to produce empty cells with a cell pitch of 4 μm. Liquid crystal MLC-7026-100 (negative type liquid crystal manufactured by Merck) was injected into the empty cell by the reduced-pressure injection method, and the injection port was sealed to obtain a liquid crystal cell of the FFS method. After that, the obtained liquid crystal cell was heated at 120° C. for 30 minutes, and left overnight at 23° C. for evaluation of liquid crystal alignment. <Evaluation of Liquid Crystal Alignment> Using the liquid crystal unit cell, an AC voltage of 16VPP was applied at a frequency of 30Hz for 168 hours under a constant temperature environment of 70°C. After that, between the pixel electrode and the counter electrode of the liquid crystal cell was made into a short-circuit state, and it was left to stand at 23 degreeC overnight while maintaining this state. After placement, the liquid crystal cell is placed between two polarizers arranged so that the polarization axis is vertical, and the backlight is turned on in the state of no external voltage, and the brightness of the transmitted light is adjusted to the minimum. The configuration angle of the liquid crystal cell. Then, the angle Δ was calculated as the angle Δ for rotating the liquid crystal cell from the angle at which the second region of the first pixel becomes darkest to the angle at which the first region becomes darkest. Similarly for the second pixel, the same angle Δ is calculated by comparing the second area with the first area. Furthermore, the average value of the angle Δ values of the first pixel and the second pixel was calculated as the angle Δ of the liquid crystal cell. When the value of the angle ∆ of the liquid crystal cell was less than 1.0°, it was defined as "good", and when the value of the angle ∆ was 1.0° or more, it was defined as "defective" and evaluated. (Example 1) Using the liquid crystal alignment agent (A-1) obtained in Synthesis Example 1, a liquid crystal unit cell as described above was prepared. Irradiation of polarized ultraviolet rays was performed using a high-pressure mercury lamp through a wavelength selection filter: 240LCF, and a 254nm type polarizing plate. The irradiation amount of polarized ultraviolet rays is measured by using an illuminance meter UVD-S254SB manufactured by Ushio Electric Co., Ltd., and it is implemented by changing the range of 600~1500mJ/ cm2 at a wavelength of 254nm, so as to make more than three Liquid crystal cells with varying amounts of polarized ultraviolet light. As a result of evaluating the liquid crystal alignment of these liquid crystal cells, the angle ∆ is the optimal polarized ultraviolet irradiation dose of 1200mJ/cm 2 , and the angle ∆ is 0.13°. (Examples 2-6) Except for using the liquid crystal alignment agent obtained in Synthesis Examples 2-6, the same method as in Example 1 was used to evaluate the liquid crystal alignment. (Comparative Examples 1-4) Except for using the liquid crystal alignment agent obtained in Comparative Synthesis Examples 1-4, the same method as in Example 1 was used to evaluate the liquid crystal alignment. [0116] Table 1 shows that when using the liquid crystal alignment agent obtained in the synthetic example and the comparative synthetic example, the angle ∆ is the best polarized ultraviolet irradiation amount and the result of the evaluation of the liquid crystal alignment. [0117]
Figure 02_image043
As shown in Table 1, in Examples 1 to 6, the difference (angle ∆) of the alignment azimuth angles before and after the AC drive is less than 1.0° is good, so the display quality of the liquid crystal display element is improved to be excellent. On the other hand, in Comparative Examples 1 to 4, the angle ∆ was 1.0° or more, which was considered unfavorable. It was confirmed that the liquid crystal display element manufactured by the method of the present invention exhibits very excellent afterimage characteristics. [Industrial Applicability] The substrate for a lateral electric field driven liquid crystal display element manufactured using the composition of the present invention or a lateral electric field driven liquid crystal display element having the substrate has excellent long-term stability of liquid crystal alignment, so It can be suitably used in large-screen and high-definition LCD TVs, etc. In addition, the liquid crystal alignment film produced by the method of the present invention can also be used in a variable phase shifter using liquid crystals, and the variable phase shifter can be suitably used in, for example, antennas capable of changing the frequency of resonance.

Claims (11)

一種具有下述液晶配向膜之基板之製造方法，其特徵係藉由具有下述步驟從而得到被賦予配向控制能之橫向電場驅動型液晶顯示元件用液晶配向膜，包括：[I]將含有(A)由二胺成分與酸二酐成分所得之聚合物、及(B)有機溶劑之聚合物組成物塗佈至具有橫向電場驅動用導電膜之基板上後，以由前述二胺成分與前述酸二酐成分所得之聚醯胺酸或聚醯胺酸酯為實質上未進行熱醯亞胺化之溫度下來予以乾燥從而形成塗膜之步驟，前述二胺成分包含下述式(1)(式(1)中，L係碳數2以上的二價有機基且僅由伸烷基、與選自醚鍵及酯鍵之鍵結中之任1種組成，並且L的原子數之中，與主鏈的長度有關的碳原子和氧原子的原子數的合計為偶數，R1及R2係分別獨立為一價有機基，p1及p2係分別獨立為0~4的整數，p係0或1，q1及q2係分別獨立為1或2)所表示之二胺，前述酸二酐成分包含下述式(2)(式(2)中，R6~R9係分別獨立為氫原子、烷基、鹵素原子或苯基)所表示之四羧酸二酐；[II]對[I]所得之塗膜照射偏光的紫外線之步驟；及[III]將[II]所得之塗膜進行加熱之步驟；
Figure 106131658-A0305-02-0052-1
Figure 106131658-A0305-02-0052-2
 A method of manufacturing a substrate having the following liquid crystal alignment film, characterized in that the liquid crystal alignment film for a transverse electric field driven liquid crystal display element endowed with alignment control energy is obtained by having the following steps, comprising: [I] containing ( A) A polymer obtained from a diamine component and an acid dianhydride component, and (B) a polymer composition of an organic solvent is coated on a substrate having a conductive film for driving a transverse electric field, and the aforementioned diamine component and the aforementioned The polyamic acid or polyamic acid ester obtained from the acid dianhydride component is a step of drying at a temperature at which thermal imidization is not substantially performed to form a coating film. The aforementioned diamine component contains the following formula (1) ( In formula (1), L is a divalent organic group with more than 2 carbon atoms and is composed only of an alkylene group and a bond selected from an ether bond and an ester bond, and among the number of atoms of L, and The total number of carbon atoms and oxygen atoms related to the length of the main chain is an even number, R 1 and R 2 are independently monovalent organic groups, p1 and p2 are independently integers of 0 to 4, and p is 0 or 1, q1 and q2 are diamines represented by 1 or 2) respectively independently, and the aforementioned acid dianhydride components include the following formula (2) (in formula (2), R 6 ~ R 9 are independently hydrogen atoms, an alkyl group, a halogen atom or a phenyl group); [II] a step of irradiating polarized ultraviolet rays to the coating film obtained in [I]; and [III] heating the coating film obtained in [II] the steps of
Figure 106131658-A0305-02-0052-1
Figure 106131658-A0305-02-0052-2
 如請求項1之基板之製造方法，其中，上述聚合物係選自由聚醯亞胺前驅物及該醯亞胺化物的聚醯亞胺所成之群之至少1種。 The method for manufacturing a substrate according to claim 1, wherein the polymer is at least one selected from the group consisting of polyimide precursors and polyimides of the imidized products. 如請求項1或2中任一之基板之製造方法，其中，上述式(2)中之R6~R9係皆為氫原子。 The method for manufacturing a substrate according to any one of claim 1 or 2, wherein R 6 to R 9 in the above formula (2) are all hydrogen atoms. 如請求項1或2中任一之基板之製造方法，其中，前述聚醯亞胺前驅物係下述式(3)(式(3)中，X1係源自上述式(2)所表示之四羧酸衍生物之四價有機基，Y1係源自包含式(1)的構造之二胺之二價有機基，R11係氫原子或碳數1~5的烷基)所表示，
Figure 106131658-A0305-02-0053-3
 The method for manufacturing the substrate as in any one of claim 1 or 2, wherein the aforementioned polyimide precursor is the following formula (3) (in the formula ( 3 ), X is derived from the expression of the above formula (2) The tetravalent organic group of the tetracarboxylic acid derivative, Y1 is a divalent organic group derived from a diamine comprising the structure of formula ( 1 ), R11 is represented by a hydrogen atom or an alkyl group with 1 to 5 carbons) ,
Figure 106131658-A0305-02-0053-3
 如請求項3之基板之製造方法，其中，前述聚醯亞胺前驅物係下述式(3)(式(3)中，X1係源自上述式(2)所表示之四羧酸衍生物之四價有機基，Y1係源自包含式(1)的構造之二胺之二價有機基，R11係氫原子或碳數1~5的烷基)所表示，
Figure 106131658-A0305-02-0053-4
 The manufacturing method of the substrate as claim item 3, wherein, the aforementioned polyimide precursor is the following formula (3) (in the formula ( 3 ), X is derived from the tetracarboxylic acid represented by the above formula (2) A tetravalent organic group of a substance, Y1 is a divalent organic group derived from a diamine comprising the structure of formula ( 1 ), R11 is represented by a hydrogen atom or an alkyl group with 1 to 5 carbons),
Figure 106131658-A0305-02-0053-4
 如請求項4之基板之製造方法，其中，相對於液晶配向劑中所含有的全聚合物，含有10莫耳%以上的具有前述式(3)所表示之構造單位的聚合物。 The manufacturing method of the substrate according to Claim 4, wherein, relative to the total polymer contained in the liquid crystal alignment agent, the polymer having the structural unit represented by the aforementioned formula (3) is contained in an amount of 10 mol % or more. 如請求項5之基板之製造方法，其中，相對於液晶配向劑中所含有的全聚合物，含有10莫耳%以上的具有前述式(3)所表示之構造單位的聚合物。 The manufacturing method of the substrate according to claim 5, wherein, relative to the total polymer contained in the liquid crystal alignment agent, the polymer having the structural unit represented by the aforementioned formula (3) is contained in an amount of 10 mol % or more. 一種基板，其特徵係具有藉由請求項1~7中任一項之方法所製造之橫向電場驅動型液晶顯示元件用液晶配向膜。 A substrate characterized by having a liquid crystal alignment film for a lateral electric field driven liquid crystal display element manufactured by the method in any one of claims 1 to 7. 一種橫向電場驅動型液晶顯示元件，其特徵係具有請求項8之基板。 A lateral electric field driven liquid crystal display element, characterized by having the substrate of Claim 8. 一種液晶顯示元件之製造方法，其特徵係藉由具有：準備請求項8之基板(第1基板)之步驟、得到第2基板之步驟、及得到液晶顯示元件之步驟，從而得到橫向電場驅動型液晶顯示元件；前述第2基板所具有的液晶配向膜，係藉由具有下述步驟從而得到被賦予配向控制能之液晶配向膜，包括：[I’]將請求項1~7中任一項之組成物塗佈於第2基板上來形成塗膜之步驟、[II’]對[I’]所得之塗膜照射偏光的紫外線之步驟、[III’]將[II’]所得之塗膜進行加熱之步驟；前述得到液晶顯示元件之步驟，係[IV]使前述第1及第2基板的液晶配向膜介隔著液晶並相對之方式來對向配置前述第1及第2基板。 A method of manufacturing a liquid crystal display element, characterized in that it has the steps of preparing the substrate (first substrate) of claim 8, the step of obtaining the second substrate, and the step of obtaining a liquid crystal display element, thereby obtaining a lateral electric field drive type Liquid crystal display element; the liquid crystal alignment film possessed by the aforementioned second substrate is obtained by having the following steps to obtain a liquid crystal alignment film endowed with alignment control ability, including: [I'] any one of claim items 1 to 7 The step of applying the composition on the second substrate to form a coating film, [II'] the step of irradiating polarized ultraviolet rays to the coating film obtained in [I'], [III'] applying the coating film obtained in [II'] to The step of heating; the aforementioned step of obtaining the liquid crystal display element is [IV] arranging the aforementioned first and second substrates facing each other in such a way that the liquid crystal alignment films of the aforementioned first and second substrates face each other through liquid crystals. 一種橫向電場驅動型液晶顯示元件，其係藉由請求項10之方法所製造。 A lateral electric field driven liquid crystal display element manufactured by the method of claim 10.
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