TW593602B

TW593602B - A liquid crystal orientated solvent varnish and a liquid crystal display element

Info

Publication number: TW593602B
Application number: TW091101536A
Authority: TW
Inventors: Yoshiharu Hirai; Satoshi Tanioka; Shizuo Murata
Original assignee: Chisso Corp; Chisso Petrochemical Corp
Priority date: 2001-03-29
Filing date: 2002-01-30
Publication date: 2004-06-21
Also published as: KR100443443B1; KR20020077249A

Abstract

In an orientated process by rubbing, a scar of an orientated film surface is common orientated defects. Because the orientated film be cut, this cutting scum is a cause of display defects. Further, for using plastic plate recently, because the forming temperature is lower, a polyamide film has question that hardness hasn't enough. In the present invention, a liquid crystal orientated solvent varnish is including a polyorganosilsesquioxane and a condensation polymer. The polyorganosilsesquioxane is polyorganosilsesquioxane that having a functional group, and the functional group is including epoxy group, carboxyl group, hydroxyl group, amino group, acryloyl oxy group, or methacryloyl oxy group. The condensation polymer is including polyamide acid, solubility polyimide, polyamide, or over two kind of the compound. In the present invention, a liquid crystal display element has a orientated film that forming from the varnish. The ratio of polyorganosilsesquioxane is 0.01 weight % to 50 weight % of total contents of non-volatile constituents of the varnish. At the same time, the ratio of the condensation polymer is 50 weight % to 99.9 weight % of total contents of non-volatile constituents of the varnish. When using the varnish of the present invention, the liquid crystal orientated film has stronger resistance to friction for rubbing and better hardness of surface.

Description

8804pif1 玖、發明說明：發明領域本發明是關於一種液晶配向劑淸漆（varnish)，且特別是關於顯示品位較高且可靠度較佳的液晶顯示元件。發明背景液晶顯示元件係以用於向列的（nematic)液晶的顯示元件爲主流，關於此方面之提案包括旋轉（twist)90 °之 TN型液晶顯示元件、通常旋轉180 °以上之STN型液晶顯示元件、以及使用薄膜電晶體（transistor)的所謂TFT 型液晶顯示元件。近來，更有改良視覺特性之橫向電場方式的內平面轉移（In-Plane Switching)(以下簡稱「IPS」）型液晶顯示元件、利用垂直配向狀態之垂直配列(Vertical Alignment)(以下簡稱「VA」）型液晶顯示元件、或應答速度極快且視野角也較廣之光學補償雙折射（Optically Compensated Birefringence)(以下簡稱「0CB」）型液晶顯示元件。在此種液晶顯示元件中，液晶分子之長軸方向是否均一的配向係爲重要的。使液晶分子均一的配向之工業上之具有代表性之方法習知係爲下述之摩擦（rubbing) 法°亦即’在基板表面上設置由有機披覆膜所形成之配向膜，其表面係藉由棉、尼龍(nyl〇n)、聚酯(polyester)等的布於一定之方向上進行摩擦，以於其摩擦方向上進行液晶分子之配向的方法。此摩擦法，可以比較容易的得到均一配向’且同時具有較佳之生產性，因而成爲工業 8804pifl 上之主流。配向膜之材料例如是聚乙烯醇（polyvinyl alcohol)、聚氧乙烯（polyoxy ethylene)、聚醯胺 (polyamide)、聚亞醯胺（polyimide)、聚醯胺-亞醯胺 (polyamide-imide)等聚合物（polymer)。其中以聚亞醯胺使用最多。其理由爲具有較佳之化學及熱安定性，可以耐得住工業上的量產。以摩擦形成配向膜之配向處理方法係可於簡便之情形下得到較佳之生產性，而爲工業上有用的方法。然而，液晶顯示元件於各領域使用之際，儘管可以提高液晶顯示元件之性能，但也可指出種種的問題。例如，在摩擦時，將配向膜剝下之際，其撥除後之渣滓（scum)會成爲顯示缺陷的原因。在STN型元件中，爲得到較高之對比，係不希望見到因摩擦而產生之配向膜表面之傷痕所造成之配向缺陷。再者，在TFT型元件中，摩擦所使用之機械力會有破壞轉移元件的結果。更甚之，近年來，爲降低製造成本（cost)或輕量化，而使用塑膠(plastic)基板替代玻璃（glass)基板之際，液晶配向劑淸漆嘗試在未滿攝氏 200度之低溫下進行燒成。然而，在具有聚亞醯胺之前驅物之下將聚醯胺塗佈於基板上，於低溫下燒成之情形時，無法完全進行聚醯胺之脫水閉環（亞醯胺化）反應’ 導致因聚亞醯胺之硬度不足而造成配向膜之傷痕的深刻問題。關於摩擦法之上述問題，起因係爲配向膜使用聚合物所形成。例如，當原因爲表面硬度不足之情形時，對 8804pif1 應摩擦時之磨擦而造成配向膜之毀壞。再者，當原因爲玻璃基板等的密著性不足之情形時，會發生配向膜被削割。因此，爲改善上述之問題點較佳係爲配向膜之開發。對表面硬度不足而言，變更配向膜之分子結構可以獲得某種程度之改良。然而，難以在値得的定價上同時進行變動配向膜之電性特性或液晶之前傾（pre-tilt)角的改良。再者，對與玻璃基板之密著性而言，使用偶合 (coupling)劑可以獲得某種程度之改良。然而，由於偶合劑會受到加水分解之影響，因而會有配向劑淸漆之保存安定性的問題。更甚之，爲防止剝離而使用過多之偶合劑之際，反而會有降低液晶顯示元件之性能的問題。發明槪述本發明者係提出含有聚有機矽倍半氧烷 (polyorganosilsesquioxane)(在下述之說明中聚有機矽倍半氧烷係以PSQ表示）的液晶配向劑淸漆，已解決前述問題點。由於PSQ係爲高度架橋交聯體，因此不易發生加水分解反應。爲此，比起使用偶合劑之情形，沒有配向劑淸漆之保存安定性的問題。再者，當用量過剩時，也不會對液晶顯示元件之顯示性能等產生不良的影響。當用量較少時，也可以形成高可靠度的液晶配向膜。而且，雖然有以有機矽倍半氧烷低聚合物(oligomer) 做爲成分之樹脂組成物之揭露之實例存在，然而其係爲與本發明之目的相異之技術。例如在日本專利特開平 8^59895號公報所揭露之技術中，主要之目的係在液晶 8804pif1 顯示元件中作爲透明基板或彩色濾光片（color filter)等的保護膜。再者，在日本專利特開平6-186570號公報所揭露之技術中，則是以改善雙安定強介電性液晶顯示裝置 (device)之曲折（zigzag)缺陷等爲目的。至目前爲止仍未有針對起因於配向處理之問題點進行改善的文獻。本發明係具有下述Π]〜[7]之結構。 [1] 一種液晶配向劑淸漆，包括由聚有機矽倍半氧烷與聚縮合高分子所形成的聚合物成分及溶媒，其中聚合物成分中之聚有機矽倍半氧烷之比率係爲〇·01重量％〜 50重量％左右’且聚合物成分之比率係佔液晶配向劑淸漆全量的0·1重量％〜40重量％左右，且同時溶劑之比率係佔液晶配向劑淸漆全量的60重量％〜99.9重量％左右。 [2] 如[1]所述之液晶配向劑淸漆，其中聚縮合高分子係選自於聚醯胺酸、可溶性聚亞醯胺、聚醯胺或前述任二種以上之混合物等所組成之族群其中之一。 [3] 如[1]所述之液晶配向劑淸漆’其中當聚縮合高分子係選自於聚醯胺酸、可溶性聚亞醯胺、聚醯胺或前述任二種以上之混合物等所組成之族群其中之一之際，聚有機矽倍半氧烷係爲式（1)所不之含有重複單位之官能基的聚有機矽倍半氧院。 8804pif18804pif1 发明, Description of the invention: Field of the invention The present invention relates to a liquid crystal alignment agent varnish, and more particularly to a liquid crystal display element with higher display quality and better reliability. BACKGROUND OF THE INVENTION Liquid crystal display elements are mainly used for nematic liquid crystal display elements. Proposals in this regard include TN-type liquid crystal display elements that are rotated by 90 °, and STN-type liquid crystals that are usually rotated by more than 180 °. A display element and a so-called TFT-type liquid crystal display element using a thin film transistor. Recently, in-plane switching (hereinafter referred to as "IPS") type liquid crystal display elements with improved horizontal visual field characteristics and vertical alignment (Vertical Alignment) (hereinafter referred to as "VA") ) Type liquid crystal display elements, or optically compensated birefringence (Optically Compensated Birefringence) (hereinafter referred to as "0CB") type liquid crystal display elements with extremely fast response speed and wide viewing angle. In such a liquid crystal display element, it is important whether the alignment system of the long axis direction of the liquid crystal molecules is uniform. An industrially representative method for uniformly aligning liquid crystal molecules is a rubbing method described below, that is, an alignment film formed of an organic coating film is provided on a substrate surface, and the surface is A method of rubbing a cloth such as cotton, nylon, polyester, or the like in a certain direction to align liquid crystal molecules in the rubbing direction. This friction method can relatively easily obtain a uniform orientation 'and at the same time has better productivity, thus becoming the mainstream on the industrial 8804pifl. The material of the alignment film is, for example, polyvinyl alcohol, polyoxy ethylene, polyamide, polyimide, polyamide-imide, etc. Polymer. Among them, polyimide is most used. The reason is that it has better chemical and thermal stability and can withstand industrial mass production. The alignment treatment method for forming an alignment film by rubbing can obtain better productivity in a simple manner, and is an industrially useful method. However, when the liquid crystal display element is used in various fields, although the performance of the liquid crystal display element can be improved, various problems can be pointed out. For example, during rubbing, when the alignment film is peeled off, the scum after removal thereof becomes a cause of display defects. In STN type elements, in order to obtain a high contrast, it is not desirable to see alignment defects caused by scratches on the surface of the alignment film due to friction. Furthermore, in a TFT type element, the mechanical force used for friction has the effect of damaging the transfer element. What's more, in recent years, in order to reduce the manufacturing cost or light weight, when plastic substrates are used instead of glass substrates, liquid crystal alignment agent varnishes have been tried at temperatures as low as 200 degrees Celsius. Sintered. However, when polyamine is coated on the substrate under the precursor of polyimide, and it is fired at a low temperature, the dehydration ring closure (imidization) reaction of polyamine cannot be performed completely. The deep problem of the scar of the alignment film caused by insufficient hardness of the polyimide. The above-mentioned problems of the friction method are caused by the use of polymers in the alignment film. For example, when the cause is insufficient surface hardness, the 8804pif1 should be rubbed to cause damage to the alignment film. Furthermore, when the cause is insufficient adhesion of a glass substrate or the like, the alignment film may be cut. Therefore, it is preferable to develop an alignment film in order to improve the above problems. For insufficient surface hardness, the molecular structure of the alignment film can be improved to some extent. However, it is difficult to simultaneously improve the electrical characteristics of the alignment film or the pre-tilt angle of the liquid crystal in the obtained pricing. Moreover, the adhesion to the glass substrate can be improved to some extent by using a coupling agent. However, because the coupling agent is affected by hydrolysis, there is a problem in the preservation stability of the alignment agent lacquer. Furthermore, when too much coupling agent is used to prevent peeling, there is a problem that the performance of the liquid crystal display element is lowered. SUMMARY OF THE INVENTION The present inventors have proposed a liquid crystal alignment agent varnish containing polyorganosilsesquioxane (polyorganosilsesquioxane is represented by PSQ in the following description), which has solved the aforementioned problems. Because PSQ is a highly bridged crosslinked body, it does not easily undergo hydrolytic reaction. For this reason, compared with the case of using a coupling agent, there is no problem of storage stability of the alignment agent paint. Furthermore, when the amount is excessive, it will not adversely affect the display performance of the liquid crystal display element. When the amount is small, a highly reliable liquid crystal alignment film can also be formed. Moreover, although there are examples of the disclosure of a resin composition using an organic oligomeric silsesquioxane oligomer as an ingredient, it is a technique different from the object of the present invention. For example, in the technology disclosed in Japanese Patent Laid-Open No. 8 ^ 59895, the main purpose is to use a liquid crystal 8804pif1 display element as a protective film such as a transparent substrate or a color filter. Furthermore, the technology disclosed in Japanese Patent Laid-Open No. 6-186570 aims to improve the zigzag defects of the dual-stable ferroelectric liquid crystal display device. To date, there has been no literature on improving the problems caused by the alignment process. The present invention has the following structures Π] to [7]. [1] A liquid crystal alignment agent lacquer, comprising a polymer component and a solvent formed by a polyorganosilsesquioxane and a polycondensed polymer, wherein the ratio of the polyorganosilsesquioxane in the polymer component is 〇01% to 50% by weight and the ratio of the polymer component is about 0.1% to 40% by weight of the total amount of the liquid crystal alignment agent lacquer, and the ratio of the solvent accounts for the entire amount of the liquid crystal aligning agent lacquer 60% to 99.9% by weight. [2] The liquid crystal alignment agent paint according to [1], wherein the polycondensation polymer is selected from the group consisting of polyamic acid, soluble polyimide, polyamidine, or a mixture of any two or more of the foregoing. One of the ethnic groups. [3] The liquid crystal alignment agent lacquer according to [1], wherein the polycondensation polymer is selected from the group consisting of polyamic acid, soluble polyimide, polyamidine, or a mixture of any two or more of the foregoing. In the case of one of the constituent groups, the polyorganosilsesquioxane is a polyorganosilsesquioxane containing a functional unit having a repeating unit which is not included in the formula (1). 8804pif1

CH2CH2 —R10—YCH2CH2 —R10—Y

Rl_Si ^)_si _R^(〇_R4)m〇(3 nm)/2 (1) R3 (式中，R1、R2及R3分別爲各自獨立之碳數爲1〜 18的直鏈狀、分枝狀或環狀的飽和碳氫基、或碳數爲2 〜6的直鏈狀、分枝狀或環狀的不飽和碳氫基、或碳數爲 10以下的芳基（aryl) ; R4係爲碳數爲1〜4的直鏈狀或分枝狀的飽和碳氫基、CH3CO—、CH2=CHCO—、或Ch2 = C(CH3)CO— ; m係爲0或0·05〜2.0之數値；η之數値當m爲0時，η係爲0.1〜2.0，而當m不爲0而爲〇.〇5 〜2.0時，貝f] n+m之總和係爲0.1〜3.0 ; R1Q係爲碳數爲 1〜8的烯烴基(alkylene)，且此烯烴基中之1個或未相鄰接之2個的一CH2—也可以置換成一〇—或一NH—； Y係爲環氧基(epoxy)、竣基(carboxyl)、氫氧基、氨基(amino)、丙氧烯醯基(acryloyl oxy)、或異丁氧烯醯基(methacryloyl 〇xy)，另外，也可以爲混合前述2種以上而成之官能基。） [4] 如[3]所述之液晶配向劑淸漆，其中聚有機矽倍半氧烷係爲式（1)所示之含有m爲〇且η爲0.1〜2.0的重複單位之官能基的聚有機矽倍半氧《完° [5] 如[3]所述之液晶配向劑淸漆’其中聚有機砂倍半氧烷係爲式（1)所示之含有m爲〇·05〜2力且11爲〇_〇5 〜2.0的重複單位之官能基的聚有機砂倍半氧院。 [6] 如[3]所述之液晶配向劑淸漆’其中聚有機砍倍半氧烷係藉由下述之步驟（a)〜步驟（d)所示之反應路徑得 593602 8804pifl 到含有官能基之聚有機矽倍半氧烷。 (a) 將式（2)所示之有機三氯矽烷與η倍莫爾量之式 (3)所示之有機一氯矽烷進行混合。 (b) 將（a)所得之混合物與m倍有機三氯矽烷之莫爾量之式（4)所示之至少一種化合物進行反應。 (c) 將（b)所得之反應生成物與[(3+n-m)/2]倍有機三氯矽烷之莫爾量之水進行反應，即可得到具有式（5)所示之重複單位且數平均分子量爲500〜5000的聚有機矽倍半氧院化合物。 (d) 將（c)所得之聚有機矽倍半氧烷化合物與一種以上之式（6)所示之化合物進行反應。 π 593602 8804pif1Rl_Si ^) _ si _R ^ (〇_R4) m〇 (3 nm) / 2 (1) R3 (where R1, R2, and R3 are each a linear, branched, independent carbon number of 1 to 18 Shaped or cyclic saturated hydrocarbon group, or linear, branched or cyclic unsaturated hydrocarbon group having 2 to 6 carbon atoms, or aryl group having 10 or less carbon atoms; R4 series It is a linear or branched saturated hydrocarbon group having 1 to 4 carbon atoms, CH3CO—, CH2 = CHCO—, or Ch2 = C (CH3) CO—; m is 0 or 0.05 to 2.0 Number 値; η number 値 When m is 0, η is 0.1 ~ 2.0, and when m is not 0 and is 0.05 ~ 2.0, the sum of f] n + m is 0.1 ~ 3.0; R1Q is an alkylene group having 1 to 8 carbon atoms, and one of the alkene groups or two CH2 which are not adjacent to each other can also be replaced with one 10 or one NH—; Y series It is epoxy, carboxyl, hydroxyl, amino, amino, acrylyloxy (methacryloyloxy), or methacrylyloxy (methacryloyloxy). It is a functional group formed by mixing two or more of the foregoing.) [4] The liquid crystal alignment agent varnish according to [3], wherein the polyorganosilsesquioxane system is (1) Polyorganosilicon silsesquioxane containing functional groups with repeating units of m 0 and η from 0.1 to 2.0 shown in (1) [5] The liquid crystal alignment agent lacquer as described in [3], wherein The organic sand silsesquioxane is a polyorganic sand silsesquioxane represented by the formula (1) and having a functional unit having a repeating unit of m of 0.05 to 2 and 11 of 0.05 to 2.0. [6] The liquid crystal alignment agent lacquer as described in [3], wherein the polyorganic chossesquioxane is 593602 8804pifl to the functional group by the reaction path shown in the following steps (a) to (d). Polysilsesquioxane. (a) An organotrichlorosilane represented by the formula (2) and an organomonochlorosilane represented by the formula (3) in an amount of η times the mole are mixed. (b) The mixture obtained in (a) is reacted with at least one compound represented by the formula (4) in m times the molar amount of the organotrichlorosilane. (c) By reacting the reaction product obtained in (b) with water at a molar amount of [(3 + nm) / 2] times the organic trichlorosilane, a repeating unit represented by formula (5) can be obtained and Polyorganosilsesquioxane compounds having a number average molecular weight of 500 to 5000. (d) The polyorganosilsesquioxane compound obtained in (c) is reacted with a compound represented by the above formula (6). π 593602 8804pif1

Cl R1Cl R1

I (2) (3) (4)I (2) (3) (4)

Si—ClSi-Cl

II

Cl R3Cl R3

II

Si—HSi-H

II

ClCl

R4—OHR4—OH

(3-n-m)/2 (5) ⑹ ch2 =CH—R10 —γ (在上列各式中之R1〜R4、R1G、Y、m及n之含意係與[3]所述相同。） [7] —種液晶顯示元件，係具有使用如[1]〜[6]中任一項所述之液晶配向劑淸漆形成之配向膜。爲讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉較佳實施例，作詳細說明如下：較佳實施例之詳細說明在本發明中所使用之PSQ例如是由具含有機基之官能基的三官能矽（silicon)所構成的PSQ。此含有機基之官 12 593602 8804pifl 能基之實例例如是烷基（alkyl)及苯基（phenyl)。此PSQ之實例例如是聚甲基-矽倍半氧烷 (polymethylsilsesquioxane)、聚丙基-砂倍半氧院 (polypropylsilsesquioxane)、及聚苯基-砂倍半氧院 (polyphenylsilsesquioxane)。前述化合物例如是參照 Chemical Reviews 1995, vol.95? No.5? 1409-1430 中戶斤言己載之方法進行合成。此PSQ並不以僅含有1種類之有機基爲限，也可以含有2種類以上之有機基。例如是聚苯基-甲基-砂倍半氧院（polypheny 1-methylsilsesquioxane)、聚苯基-丙基-矽倍半氧烷 (polyphenyl-propylsilsesquioxane)、聚甲基-丙基-砂倍半氧院（polymethyl-propylsilsesquioxane)。如此，當具有轉類各自相異之有機基之情形時，可利用2種類之三氯矽院（trichlorosilane)共加水分解而合成得到。再者，在本發明中雖然列舉數種含有機基之官能基的PSQ的實例進行說明，然並不以此爲限。在本發明中所使用之PSQ之次一個實例係爲含有官能基之PSQ。此官能基例如是聚合性不飽和結合的疊氮基（azido)、順丁烯二醯胺（maleamide)基、環氧基、2-笨基丙烯酸（cinnamic acid)基、氫氧基（hydroxyl)、硫遷基 (thiol)、甲醯基（formyl)、乙縮醒基（acetal)、異氰酸酉旨 (isocyanate)、氰基(cyano)、氨基、醯胺基、酯基、羧基、硫醯基（sulfonyl)、酸基（aldehydo)、后（oxime)、氣硫基 (meixapto)。其中，在上述所使用之官能基中，較佳係爲 13 $93602 88〇4Pif1 環氧基、羧基、氫氧基、氨基及聚合性雙重結合。再者’ 在本發明中所使用之PSQ可以可以含有單一之官能基’ 也可以含有2種以上之官能基。另外’也可以使用2種以上之具有相異種類之官能基的PSQ。總之，在本發明中，psQ較佳係使用下述之式（1)所示之含有具重複單位之官能基的PSQ ° ch2ch2 —r10—y(3-nm) / 2 (5) ⑹ ch2 = CH—R10 —γ (R1 to R4, R1G, Y, m, and n in the above formulae have the same meanings as described in [3].) [ 7] A liquid crystal display device having an alignment film formed using the liquid crystal alignment agent varnish according to any one of [1] to [6]. In order to make the above and other objects, features, and advantages of the present invention more comprehensible, the preferred embodiments are described below in detail as follows: Detailed description of the preferred embodiments The PSQ used in the present invention is, for example, PSQ consists of trifunctional silicon with organic functional groups. Examples of this organo-containing official 12 593602 8804pifl energy group are, for example, alkyl and phenyl. Examples of this PSQ are, for example, polymethylsilsesquioxane, polypropylsilsesquioxane, and polyphenylsilsesquioxane. The aforementioned compound is synthesized, for example, by referring to the method described in Chemical Reviews 1995, vol. 95? No. 5? 1409-1430. The PSQ is not limited to containing only one type of organic group, and may include two or more types of organic group. For example, polyphenyly-methyl-silsesquioxane, polyphenyl-propyl-silsesquioxane, polymethyl-propyl-silsesquioxane, polymethyl-propyl-silsesquioxane Hospital (polymethyl-propylsilsesquioxane). In this way, when there is a case where the organic groups are different from each other, they can be synthesized by co-hydrolysis of two types of trichlorosilanes. In the present invention, although examples of several types of PSQ containing organic functional groups will be described, it is not limited thereto. A next example of a PSQ used in the present invention is a PSQ containing a functional base. This functional group is, for example, a polymerizable unsaturated azido group, a maleamide group, an epoxy group, a 2-cinnamic acid group, or a hydroxyl group. , Thiol, formyl, acetal, isocyanate, cyano, amino, amido, ester, carboxyl, sulfur Sulfonyl, aldehydo, oxime, meixapto. Among them, among the functional groups used above, it is preferably 13 $ 93602 88〇4Pif1 dual combination of epoxy group, carboxyl group, hydroxyl group, amino group and polymerizability. Furthermore, the PSQ used in the present invention may contain a single functional group or two or more functional groups. Alternatively, two or more kinds of PSQs having different kinds of functional groups may be used. In short, in the present invention, psQ is preferably a PSQ containing a functional group with a repeating unit shown in the following formula (1) ° ch2ch2 —r10—y

I R1—Si p —Si —R2)n(〇—R4)m〇(3.n-m)/2 ⑴ R3 在此式中，R1、1^2及r3分別爲各自獨立之碳數爲1 〜18的直鏈狀、分枝狀或環狀的飽和碳氫基、或碳數爲 2〜6的直鏈狀、分枝狀或環狀的不飽和碳氫基、或碳數爲10以下的芳基。R1〜R3之較佳實例係爲碳數爲1〜4 的直鏈狀或分枝狀的烷基、乙烯基（vinyl)、丙烯基 (allyl)、環己基（cyclohexyl)、及苯基。R4係爲碳數爲1 〜4的直鏈狀或分枝狀的飽和碳氫基、CH3CO—、CH2 = CHCO—、或 CH2= C(CH3)CO—-。m 係爲 0 或 0.05 〜2.0 之數値，η之數値當m爲〇時，係爲0.1〜2.0，而當m 不爲0而爲0 · 0 5〜2.0時，則n+m之總和係爲0.1〜3 · 0。 R1()係爲碳數爲1〜8的烯烴基，且此烯烴基中之1個或未相鄰接之2個的一CH2—也可以置換成一〇—或一 NH—。Y較佳係爲環氧基、羧基、氫氧基、氨基、丙氧烯醯基、或異丁氧烯醯基，另外，也可以爲混合前述2 種以上而成之官能基。 14 593602 8804pif1 —CH2CH2—R1G—Y亦即爲後述之式（6)的化合物’係爲利用氫矽烷化(hydrosilylation)反應結合於Si上的基。此基之較佳實例係爲3-氨丙基（3-aminopropyl)、4-氨丁基 (4_aminobutyl)、N-( 2-氨乙基（2-aminoethyl)) -3-氨丙基、 3-環氧丙氧丙基（3-glycidoxy propyl)、丙氧烯醯乙基 (acryloyloxy ethyl)、丙氧烯醯丙基(acryloyloxy propyl)、異丁氧烯醯乙基（methacryloyloxy ethyl)、異丁氧烯醯丙基（methacryloyloxy propyl)、碳數爲3〜10之氫氧院基 (hydroxy alkyl)、及碳數爲4〜11的竣院基（carboxyl alkyl)。式（6)之化合物較佳係爲於前述基之官能基的相反側之末端上具有不飽和結合的化合物。此PSQ不僅可以使用上述之方法製造，也可以使用日本專利特願2000-64498號公報之說明書內所記載之製造方法製造而得。亦即，藉由下述之（a)〜(d)所示之反應路徑即可得到含有官能基之PSQ ° (a) 將式（2)所示之有機三氯矽烷與η倍莫爾(mole)量之式（3)所示之有機一氯矽烷進行混合。 (b) 將（a)所得之混合物與m倍有機三氯矽烷之莫爾量之式（4)所示之至少一種化合物進行反應。 (c) 將（b)所得之反應生成物與[(3+n-m)/2]倍有機三氯矽烷之莫爾量之水進行反應，即可得到具有式 (5)所示之重複單位且數平均分子量爲500〜5000 的 PSQ 〇 15 593602 8804pifl (d)將（c)所得之PSQ與一種以上之式（6)所示之化合物進行反應。 C1I R1—Si p —Si —R2) n (〇—R4) m〇 (3.nm) / 2 ⑴ R3 In this formula, R1, 1 ^ 2, and r3 are each independent carbon numbers of 1 to 18 Straight chain, branched or cyclic saturated hydrocarbon group, or straight chain, branched or cyclic unsaturated hydrocarbon group with 2 to 6 carbon atoms, or aromatic group with 10 or less carbon atoms base. Preferable examples of R1 to R3 are a linear or branched alkyl group having 1 to 4 carbon atoms, a vinyl group, a vinyl group, an allyl group, a cyclohexyl group, and a phenyl group. R4 is a linear or branched saturated hydrocarbon group having 1 to 4 carbon atoms, CH3CO—, CH2 = CHCO—, or CH2 = C (CH3) CO—-. m is a number of 0 or 0.05 to 2.0, and η is a number of 0.1 to 2.0 when m is 0, and a sum of n + m when m is not 0 and 0 to 0 5 to 2.0 The range is 0.1 to 3.0. R1 () is an olefin group having 1 to 8 carbon atoms, and one of the olefin groups or two CH2 which are not adjacent to each other may also be replaced with one 0—or one NH—. Y is preferably an epoxy group, a carboxyl group, a hydroxyl group, an amino group, a propoxyfluorenyl group, or an isobutoxyfluorenyl group, and may be a functional group obtained by mixing two or more of the foregoing. 14 593602 8804pif1 —CH2CH2 —R1G—Y, which is a compound of formula (6) described later, is a group bonded to Si by a hydrosilylation reaction. Preferred examples of this group are 3-aminopropyl, 4-aminobutyl, N- (2-aminoethyl) -3-aminopropyl, 3 -3-glycidoxy propyl, acryloyloxy ethyl, acryloyloxy propyl, metharyloyloxy ethyl, isobutyl Methacryloyloxy propyl, a hydroxy alkyl group having 3 to 10 carbon atoms, and a carboxyl alkyl group having 4 to 11 carbon atoms. The compound of formula (6) is preferably a compound having an unsaturated bond at the terminal on the opposite side of the functional group of the aforementioned group. This PSQ can be manufactured not only by the method described above, but also by the manufacturing method described in the specification of Japanese Patent Application No. 2000-64498. That is, PSQ containing a functional group can be obtained by the reaction paths shown in the following (a) to (d). (A) The organic trichlorosilane represented by formula (2) and η-beamole ( The organic monochlorosilane shown in formula (3) was mixed in an amount of mole). (b) The mixture obtained in (a) is reacted with at least one compound represented by the formula (4) in m times the molar amount of the organotrichlorosilane. (c) By reacting the reaction product obtained in (b) with water with a molar amount of [(3 + nm) / 2] times the organic trichlorosilane, a repeating unit represented by formula (5) can be obtained and PSQ having a number average molecular weight of 500 to 5000 015 593602 8804pifl (d) The PSQ obtained in (c) is reacted with one or more compounds represented by the formula (6). C1

I R1— Si—C1 (2)I R1— Si—C1 (2)

II

Cl R3Cl R3

I R*- Si—H (3)I R *-Si—H (3)

II

Cl R4—OH (4)Cl R4—OH (4)

(5) CH2 =CH—R10—Y (6) (在上列各式中之R1〜R4、R1G、Y、m及n之含意係與上述相同。）本發明之液晶配向劑淸漆係爲具將由PSQ與聚縮合高分子所形成之聚合物成分溶解於溶劑狀態的淸漆組成物。其中，在此組成物中之PSQ之含有量中，聚合物成分之重量百分比係爲0.01〜50.0重量％，較佳之重量百分比係爲0.1〜10.0重量％，更佳之重量百分比係爲0.3 〜3.0重量％。當此含有量過多時，則會有PSQ在配向膜表面析出的可能性，進而成爲發生液晶配向不佳的原 16 593602 8804pif1 因。再者，當此含有量過低時，則會有使提升配向膜硬度之效果降低的傾向。本發明之液晶配向劑淸漆中之聚縮合高分子含有量係爲聚合物成分之50〜99.9重量％。此聚縮合高分子也可以爲隨機（random)共聚合物或嵌段（block)共聚合物等的共聚合高分子（copolymer)。再者，也可以同時使用多種聚縮合高分子。聚縮合高分子較佳係爲由四羧酸 (tetracarboxylic acid)二無水物與二元胺（diamine)反應而得之聚醯胺酸、由此聚醯胺酸之脫水反應而得之可溶性聚亞醯胺、及由二羧酸（dicarboxylic acid)或二羧酸二鹵 (dihalide)與二元胺反應而得之聚醯胺等。而且，此聚醯胺之醯胺結合（CONH)之氫原子也可以置換成其他基。在上述之四羧酸二無水物之選擇條件係爲可與二元胺反應生成聚醯胺酸即可，而二羧酸或二羧酸二鹵之選擇條件係爲可與二元胺反應生成聚醯胺即可，兩者並無其他任何限制。對二元胺而言，也與前述相同其選擇條件係爲可與四羧酸二無水物反應生成聚醯胺酸且可與二羧酸或二羧酸二鹵反應生成聚醯胺即可，並無其他任何限制。再者，上述之四羧酸二無水物、二羧酸或二羧酸二鹵、及二元胺也可以分別倂用二種以上，對此全部皆無限制。聚醯胺酸或聚醯胺之原料所使用之酸類或二元胺之中，四羧酸二無水物與二元胺的具體實例，例如是任意(5) CH2 = CH—R10—Y (6) (The meanings of R1 to R4, R1G, Y, m, and n in the formulas above are the same as above.) The liquid crystal alignment agent lacquer of the present invention is A paint composition having a polymer component formed of PSQ and a polycondensation polymer dissolved in a solvent state. Among them, in the content of PSQ in this composition, the weight percentage of the polymer component is 0.01 to 50.0% by weight, the preferred weight percentage is 0.1 to 10.0% by weight, and the more preferred weight percentage is 0.3 to 3.0% by weight. %. When this content is too large, PSQ may precipitate on the surface of the alignment film, and it may become a cause of poor liquid crystal alignment 16 593602 8804pif1. Furthermore, when the content is too low, the effect of increasing the hardness of the alignment film tends to decrease. The content of the polycondensed polymer in the liquid crystal alignment agent paint of the present invention is 50 to 99.9% by weight of the polymer component. The polycondensation polymer may be a copolymer such as a random copolymer or a block copolymer. Furthermore, a plurality of polycondensation polymers may be used simultaneously. The polycondensation polymer is preferably a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride with a diamine, and a soluble polyimide obtained from the dehydration reaction of the polyamino acid. Ammonium amine, polyamine and the like obtained by reacting dicarboxylic acid or dihalide with diamine. In addition, the hydrogen atom of the fluorene bond (CONH) of this polyamine may be replaced with another group. The above-mentioned selection conditions of the tetracarboxylic acid dianhydrous are that they can react with diamines to form polyphosphonic acid, and the selection conditions of dicarboxylic acids or dicarboxylic acid dihalides are that they can react with diamines to form Polyamine is sufficient, and there are no other restrictions on the two. For diamines, the selection conditions are the same as those described above, as long as they can react with tetracarboxylic acid dianhydrous to form polyamines and can react with dicarboxylic acids or dicarboxylic dihalides to form polyamines. There are no other restrictions. In addition, two or more of the above-mentioned tetracarboxylic acid dianhydrous, dicarboxylic acid or dicarboxylic acid dihalide, and diamine may be used, respectively, and all of them are not limited. Among the acids or diamines used for the polyamic acid or polyamine raw materials, specific examples of the tetracarboxylic acid dianhydride and the diamine are, for example, arbitrary

選擇使用在 WO 98/31725A1、WO 99/33902A1、WO 17 593602 8804pif1 99/33923A1、WO 99/34252A1 及 WO 01/00732A1 等公報中所記載之關於此部分的化合物。再者，二羧酸之具體實例，例如是任意選擇使用在WO 01/14457A1公報中所記載之關於此部分的化合物及此化合物之酸二鹵。而且，在前述之部分聚醯胺酸或聚醯胺之原料中也可以使用用以停止此高分子之末端的一元胺（monoamine) 化合物、一殘酸（monocarboxylic acid)無水物、或同時使用前述兩者。再者，爲增加與基板之間的密著性，也可以使用氨砂（amino silicon)化合物。其中氨砍化合物之具體實例，例如是對氨苯三甲氧基砂院（para-aminophenyl trimethoxy silane)、對氨苯三乙氧基砂院 (para-aminophenyl triethoxy silane)、間氨苯三甲氧基石夕院（meta-aminophenyl trimethoxy silane)、間氨苯三乙氧基石夕院（meta-aminophenyl triethoxy silane)、氨丙基三甲氧基石夕院（aminopropyl trimethoxy silane)、氨丙基三乙氧基石夕院（aminopropyl triethoxy silane)等。本發明之液晶配向劑淸漆中之聚合物成分之濃度較佳係爲〇·1〜40重量％。當聚合物成分之濃度超過40重量％之際，會提高液晶配向劑淸漆的黏度。且習知爲調整膜厚而稀釋淸漆之際，通常係傾向於將溶劑混入淸漆中。當使用旋塗（spinner)法或印刷法之際，通常爲保持良好的膜厚，大多係爲10重量％以下。而其他之塗佈方法，例如是染梢（tipping)法，則是需要低濃度。另一方面，當聚合物成分之濃度不足0.1重量％之際，容易發生所得到 18 593602 8804pif1 之配向膜之膜厚過薄的問題。因此聚合物成分之濃度在使用通常之旋塗法或印刷法之際，係爲0.1重量％以上，較佳係爲0.5〜10重量。％然而，在液晶配向劑淸漆之塗佈方法中，也可以使用更稀薄之濃度。本發明之液晶配向劑淸漆之溶媒所使用之溶劑之選擇條件只要是具有可溶解聚合物成分之能力即可，而無其他方面的限制。因此，在製造或利用聚醯胺酸、可溶性聚亞醯胺或聚醯胺等之際，所使用之溶劑係爲一般的溶劑，僅需就使用之目的進行適當地選擇即可。對淸漆之全量而言，溶媒之比率係爲60〜99.9重量％。對醯胺酸、可溶性聚亞醯胺及聚醯胺而言，其親近之溶劑係爲非質子(proton)性之極性有機溶劑。此溶劑例如是 N-甲基-2-口比略院酮(N-methyl-2_pyrrolidone)、二甲咪唑烷酮（dimethyl-imidazolidinone)、N-甲基己內醯胺 (N-methyl caprolactam)、N-甲基丙醯胺（N-methyl propionamide)、N，N-二甲基乙醯胺（N，N-dimethyl acetamide)、二甲基磺氧化物（dimethyl sulfo oxide)、N，N-二甲基甲醯胺（N，N-dimethyl formamide)、N，N-二乙基甲醯胺（N，N-diethyl formamide)、二乙基乙醯胺（diethyl acetamide)、及 γ -丁內酯（γ -butyrolactone)。而且，當目的爲改善塗佈性之際，也可以改用其他的溶劑，此時之溶劑例如是烷基乳酸、3-甲基-3-甲氧基丁醇 (3_methyl-3-methoxy butanol)、萘滿（tetraline)、異佛爾酮 (isophorone)、乙二醇一院基醚（ethylene glycol monoalkyl 19 593602 8804pifl ether)、二乙二醇一院基醚（diethylene glycol monoalkyl ether)、丙二醇一院基醚（propylene glycol monoalkyl ether)、二院基丙二酸（malonic acid dialkyl)、二丙二醇一院基醚（dipropylene glycol monoalkyl ether)、及三甘醇一院基醚（triethylene glycol monoalkyl ether)。再者’也可以使用上述之有機酸酯。例如是乙酸鹽（acetate)類等的酯化合物系溶劑等。乙二醇一烷基醚例如是乙二醇一丁基醚（ethylene glycol monobutyl ether)。二乙二醇一院基醚例如是二乙二醇一***（diethylene glycol monoethyl ether)。丙二醇一烷基醚例如是丙二醇一丁基醚（pr〇pylene glycol monobutyl ether)。二院基丙二酸例如是二乙基丙二酸(malonic acid diethyl)。二丙二醇一烷基醚例如是二丙二醇一甲基醚（dipropylene glycol monomethyl ether)。本發明之液晶配向劑淸漆也可以於必要之際含有各種添加劑。例如是當期望提升塗佈性之際，可以混入界面活性劑，而當必需提高待電防止的情形時，則可以混入防止帶電劑。將使用本發明之液晶配向劑淸漆而形成有液晶配向膜的基板與形成有同一或相異的液晶配向膜的基板相互重疊，當此二者之間挾持有液晶之際及成爲液晶挾持基板。在此液晶挾持基板上可藉由習知之方法得到液晶顯示元件。液晶顯示元件之動作模式（m〇de)係包括TN型、STN型、IPS型、VA型、0CB型、強介電性型、以及反強介電性型。使用本發明之配向劑淸漆的液晶顯示元件係爲藉由液晶配向膜進行液晶分子之排列 20 593602 8804pifl 而使所使用之液晶分子之排列狀態發生變化的液晶顯示元件。除此之外，沒有其他關於液晶顯示元件的限制。配向膜之形成，係進行將液晶配向劑塗佈至基板上的製程，再繼續進行燒結成形之製程而得到。基板例如是使用玻璃基板及塑膠基板。另外，塑膠基板較佳係爲薄膜（film)狀。塗佈之方法例如是旋塗法、印刷法、染梢法或滴下法等一般習知之方法，皆可以適用於本發明中。再者，燒成液晶配向劑淸漆之方法例如是在烤爐(oven) 或紅外爐中進行加熱處理的方法或在加熱板(hot plate)上進行加熱處理的方法等一般已知之方法，同樣也可以適用於本發明中。而且，通常加熱處理製程較佳係在攝氏 120度〜攝氏300度左右之溫度範圍內進行。當使用塑膠基板之際，則必需考慮基板之耐熱溫度，因而較佳係於攝氏120度〜攝氏160度左右之低溫度下進行。對可與本發明共同使用之液晶組成物而言，例如是日本專利特開平8-157828號公報、日本專利特開平 8431960號公報、日本專利特開平9-241644號公報（EP 885272A1)、日本專利特開平9-302346號公報（EP 806466A1 )、日本專利特開平8-199168號公報（EP 722998A1)、日本專利特開平9-235552號公報、日本專利特開平9-241643號公報（EP 885271A1 )、日本專利特開平10_2〇4016號公報（EP 844229A1)、日本專利特開平10-204436號公報、日本專利特開平10-231482號公報、及日本專利特開2000-087040號公報所揭露之液晶組 21 593602 8804pif1 成物。 [實施本發明之最佳方法] 以下雖以實例對本發明進行說明，然本發明並不以此實例爲限。 (製造例1) <液晶配向劑淸漆A之製造> 於具有溫度計、攪拌機、原料投入等安裝口及氮氣倒入口的200ml的四口燒瓶(flask)中，加入0.3215g之 4,4’· 一氨基二苯基甲院（4,4’-diaminodiphenylmethane)、 3-91〇lg之1，1-二（4- (4-氨基苯氧基）苯基）-4_ (反式 -4- 戊基環己基）環己烷 (1，1 -bis (4-(4-aminophenoxy)pheny 1)-4-(trans-4-pentyl cyclohexyl)cyclohexane)、以及 54.00g 之脫水 N-甲基-2-%咯烷酮（以下簡稱「NMP」），並於乾燥之氮氣氣氛氣之下攪拌溶解。將反應系統之溫度保持於攝氏5度，並添加1.7684g之均苯四甲酸(pyromellitic acid)二無水物 (以下簡稱「PMDA」），之後將溫度控制（control)於特定之溫度反應.30小時。最後，加入40.00g之丁基纖維素 (butyl cellui〇se)(以下簡稱「BC」），即可製造得到聚合物成分濃度爲6重量％的聚醯胺酸淸漆。此淸漆即作爲液晶配向劑淸漆A。而且，在本發明之實例中，係藉由檢查（check)反應中之黏度進行反應，亦即當添加丁基纖維素之後之液晶配向劑淸漆A之黏度爲55〜65mpa*s(使用E型黏度計， 22 593602 8804pifl 且測定溫度爲攝氏25度）之時間點時，係爲反應完成，並以保存於低溫下。 (製造例2) <液晶配向劑淸漆B之製造〉除了將二元胺化合物改使用0.8118g之4,4’-二氨基 —苯基乙院（4,4’-(1丨&111丨11〇(1丨011611丫16111&1^)、以及2.52〇〇8 之1，1-二（4- (4-氨基苯氧基）苯基）-4- (2-(反式-4-戊基環己基）乙基）環己院（1，1 -bis(4-(4_aminophenoxy) phenyl) _4-(2-(trans-4_pentyl cyclohexyl)ethyl)cyclohexane)之外，其他之步驟皆與製造例1相同的方式製造得到液晶配向劑淸漆B。 (製造例3) <液晶配向劑淸漆C之製造> 除了將二元胺化合物改使用3.9891g之5-(4-(反式 -4-(反式-4-戊基環己基）環己基）苯基）甲基-l，3-二氨基苯（5_(4-(trans-4-(trans-4-pentyl cyclohexyl)cyclohexyl) phenyl)methyl-l，3-diaminobenzene)之外，其他之步驟皆與製造例1相同的方式製造得到液晶配向劑淸漆C。 (製造例4) <液晶配向劑淸漆D之製造> 除了將二元胺化合物改使用1.4514g之4,45-二氨基二苯基甲院，且使用1.4357g之環丁院四殘酸（cyclobutane tetracarboxylic acid)二無水物替代PMDA之外，其他之步驟皆與製造例1相同的方式製造得到液晶配向劑淸漆D。 23 593602 8804pifl (混合淸漆之調製）混合液晶配向劑淸漆A與液晶配向劑淸漆D得到混合淸漆A-D，混合液晶配向劑淸漆B與液晶配向劑淸漆 D得到混合淸漆B-D，以及混合液晶配向劑淸漆C與液晶配向劑淸漆D得到混合淸漆C-D。在前述之混合淸漆中，液晶配向劑淸漆D之比率皆爲90重量％。 (實例1 ) 以日本專利特願2001-64498號公報之較佳實施例所記載之方法爲準合成得到具有羧基癸基（carboxyl decyl) 的PSQ (數平均分子量2300，且羧基之含有量爲178毫莫爾（millimole)/g)。將此PSQ與製造1所得之液晶配向劑淸漆A相混合，其中聚合物成分總量對於PSQ之比率爲3重量％。亦即，將此混合物利用NMP-BC之混合溶劑（重量比1/1)稀釋，以調整成全聚合物成分之濃度爲 3重量％爲止。此稀釋淸漆以旋塗法塗佈於具有透明電極之基板上’再於攝氏80度下預備燒結5分鐘左右。接著，於攝氏140度下燒結12〇分鐘左右，以形成膜厚60nm之配向膜。再於其表面之全面上藉由摩擦進行配向處理。做一片與前述相同的基板，於一片基板的配向膜面上散佈2〇//m之間隙（gap)材料，再以另一片基板之朝向配向膜面重合之面上之環氧樹脂硬化劑進行封印（seal)，以做成間隙2〇//m之自動平行單元（anti-paraUel cell)。再於此單兀中注入下述之液晶組成物，完成後以光硬化劑封閉注入口。之後’於攝氏110度之下進行30分鐘左右之 24 593602 8804pifl 加熱處理，以製作得到均一（homogeneous)配向之單元。此單元在正交尼科耳偏光鏡（cross Nicol)之旋轉觀察下，無法確認因摩擦而得之螺旋（screw)狀之痕跡。由於可以均一地確認明顯的明暗，因而可以確認其在朝摩擦方向上具有良好的配向。 25 593602 8804pif1 C2H5OCH2The compounds described in this publication such as WO 98 / 31725A1, WO 99 / 33902A1, WO 17 593602 8804pif1 99 / 33923A1, WO 99 / 34252A1, and WO 01 / 00732A1 are selected for use. In addition, specific examples of the dicarboxylic acid include, for example, the compounds described in WO 01 / 14457A1 and the dihalides of the compounds. In addition, in the aforementioned partial polyamidic acid or raw material of polyamidoamine, a monoamine compound, a monocarboxylic acid anhydrous substance to stop the end of the polymer can also be used, or the foregoing can be used simultaneously. Both. Furthermore, in order to increase the adhesion with the substrate, an amino silicon compound may be used. Specific examples of the ammonium compounds include para-aminophenyl trimethoxy silane, para-aminophenyl triethoxy silane, and meta-aminotrimethoxysilane. (Meta-aminophenyl trimethoxy silane), meta-aminophenyl triethoxy silane, aminopropyl trimethoxy silane, aminopropyl trimethoxy silane, aminopropyl triethoxy silane) and the like. The concentration of the polymer component in the liquid crystal alignment agent paint of the present invention is preferably from 0.1 to 40% by weight. When the concentration of the polymer component exceeds 40% by weight, the viscosity of the liquid crystal alignment agent lacquer will increase. When dilute varnishes are used to adjust the film thickness, it is common to tend to mix solvents into varnishes. When a spinner method or a printing method is used, it is usually 10% by weight or less in order to maintain a good film thickness. Other coating methods, such as the tipping method, require a low concentration. On the other hand, when the concentration of the polymer component is less than 0.1% by weight, the problem of excessively thin film thickness of the obtained alignment film of 18 593602 8804 pif1 easily occurs. Therefore, the concentration of the polymer component is 0.1% by weight or more when a conventional spin coating method or printing method is used, and preferably 0.5 to 10% by weight. % However, in the coating method of the liquid crystal alignment agent varnish, a thinner concentration may be used. The selection conditions of the solvent used in the liquid crystal alignment agent lacquer solvent of the present invention are not limited as long as it has the ability to dissolve the polymer component. Therefore, when manufacturing or using polyamic acid, soluble polyimide, polyamidine, etc., the solvent used is a general solvent, and it is only necessary to appropriately select the purpose of use. For the total amount of lacquer, the solvent ratio is 60 to 99.9% by weight. For ammonium acid, soluble polyimide, and polyamine, the closest solvents are polar organic solvents that are proton-free. The solvent is, for example, N-methyl-2_pyrrolidone, dimethyl-imidazolidinone, N-methyl caprolactam, N-methyl propionamide, N, N-dimethyl acetamide, dimethyl sulfo oxide, N, N-dimethyl N, N-dimethyl formamide, N, N-diethyl formamide, diethyl acetamide, and γ-butyrolactone (Γ-butyrolactone). In addition, when the purpose is to improve the coating property, other solvents may be used instead. In this case, the solvents are, for example, alkyl lactic acid and 3-methyl-3-methoxy butanol. , Tetraline, isophorone, ethylene glycol monoalkyl 19 593602 8804pifl ether, diethylene glycol monoalkyl ether, propylene glycol first hospital Propylene glycol monoalkyl ether, malonic acid dialkyl, dipropylene glycol monoalkyl ether, and triethylene glycol monoalkyl ether. It is also possible to use the above-mentioned organic acid ester. For example, it is an ester compound solvent such as acetate. The ethylene glycol monoalkyl ether is, for example, ethylene glycol monobutyl ether. Diethylene glycol monoethyl ether is, for example, diethylene glycol monoethyl ether. The propylene glycol monoalkyl ether is, for example, propylene glycol monobutyl ether. The dihomonyl malonic acid is, for example, malonic acid diethyl. The dipropylene glycol monoalkyl ether is, for example, dipropylene glycol monomethyl ether. The liquid crystal alignment agent varnish of the present invention may contain various additives if necessary. For example, when it is desired to improve the coating property, a surfactant may be mixed, and when it is necessary to improve the prevention of electricity, a charge preventing agent may be mixed. The substrate on which the liquid crystal alignment film is formed using the liquid crystal alignment agent of the present invention and the substrate on which the same or different liquid crystal alignment film is formed are overlapped with each other. When the two liquid crystals are held, the substrate becomes a liquid crystal holding substrate . A liquid crystal display element can be obtained on this liquid crystal holding substrate by a known method. The operation mode (mode) of the liquid crystal display device includes TN type, STN type, IPS type, VA type, 0CB type, ferroelectric type, and anti-ferroelectric type. The liquid crystal display element using the alignment agent varnish of the present invention is a liquid crystal display element in which liquid crystal molecules are aligned by a liquid crystal alignment film. 20 593602 8804pifl changes the arrangement state of liquid crystal molecules used. Other than that, there are no other restrictions on the liquid crystal display element. The alignment film is formed by a process of applying a liquid crystal alignment agent to a substrate, and then continuing a process of sintering and forming. The substrate is, for example, a glass substrate or a plastic substrate. In addition, the plastic substrate is preferably in the shape of a film. The coating method is a conventionally known method such as a spin coating method, a printing method, a dye tip method, or a dropping method, and can be applied to the present invention. In addition, the method of firing the liquid crystal alignment agent lacquer is generally known methods such as a method of performing a heat treatment in an oven or an infrared oven or a method of performing a heat treatment on a hot plate. It can also be applied to the present invention. In addition, usually, the heat treatment process is preferably performed in a temperature range of about 120 ° C to about 300 ° C. When using a plastic substrate, it is necessary to consider the heat-resistant temperature of the substrate. Therefore, it is preferable to perform it at a low temperature of about 120 ° C to 160 ° C. Examples of the liquid crystal composition that can be used with the present invention include Japanese Patent Laid-Open No. 8-157828, Japanese Patent Laid-Open No. 8431960, Japanese Patent Laid-Open No. 9-241644 (EP 885272A1), and Japanese Patent Japanese Patent Laid-Open No. 9-302346 (EP 806466A1), Japanese Patent Laid-Open No. 8-199168 (EP 722998A1), Japanese Patent Laid-Open No. 9-235552, Japanese Patent Laid-Open No. 9-241643 (EP 885271A1), The liquid crystal group 21 disclosed in Japanese Patent Laid-Open No. 10_20401 (EP 844229A1), Japanese Patent Laid-Open No. 10-204436, Japanese Patent Laid-Open No. 10-231482, and Japanese Patent Laid-Open No. 2000-087040. 593602 8804pif1. [Best Method for Carrying Out the Invention] Although the present invention is described below by way of example, the present invention is not limited to this example. (Manufacturing example 1) < Production of liquid crystal alignment agent lacquer A > In a 200 ml four-necked flask having a mounting port for a thermometer, a stirrer, raw material input, and the like, and a nitrogen pouring port, 0.3215 g of 4,4 was added. '· Aminodiphenylmethane (4,4'-diaminodiphenylmethane), 3-91〇lg of 1,1-bis (4- (4-aminophenoxy) phenyl) -4_ (trans-4 -Pentylcyclohexyl) cyclohexane (1,1-bis (4- (4-aminophenoxy) pheny 1) -4- (trans-4-pentyl cyclohexyl) cyclohexane), and 54.00g of dehydrated N-methyl- 2-% pyrrolidone (hereinafter referred to as "NMP"), and dissolve by stirring under a dry nitrogen atmosphere. The temperature of the reaction system was maintained at 5 degrees Celsius, and 1.7684 g of pyromellitic acid dihydrate (hereinafter referred to as "PMDA") was added, and then the temperature was controlled to react at a specific temperature for 30 hours. . Finally, 40.00 g of butyl celluiose (hereinafter referred to as "BC") was added to produce a polyamic acid lacquer having a polymer content concentration of 6% by weight. This varnish is referred to as varnish A for liquid crystal alignment agent. Moreover, in the example of the present invention, the reaction is performed by checking the viscosity in the reaction, that is, the viscosity of the liquid crystal alignment agent lacquer A after adding butyl cellulose is 55 ~ 65mpa * s (using E Type viscometer, 22 593602 8804pifl, and the measurement temperature is 25 degrees Celsius) at the time point, the reaction is completed and stored at low temperature. (Manufacturing example 2) < Production of liquid crystal alignment agent lacquer B> In addition to using a diamine compound instead of 0.8118 g of 4,4'-diamino-phenyl ethyl compound (4,4 '-(1 丨 & 111 丨 11〇 (101101161116111 & 1 ^), and 2.51-2008 of 1,1-bis (4- (4-aminophenoxy) phenyl) -4- (2- (trans- In addition to 4-pentylcyclohexyl) ethyl) cyclohexane (1,1-bis (4- (4_aminophenoxy) phenyl) _4- (2- (trans-4_pentyl cyclohexyl) ethyl) cyclohexane), other steps are the same as In the same manner as in Production Example 1, a liquid crystal alignment agent lacquer B was produced. (Production example 3) < Production of a liquid crystal alignment agent lacquer C > Formula-4- (trans-4-pentylcyclohexyl) cyclohexyl) phenyl) methyl-l, 3-diaminobenzene (5_ (4- (trans-4- (trans-4-pentyl cyclohexyl) cyclohexyl ) Except for phenyl) methyl-1,3-diaminobenzene), the other steps were the same as those in Production Example 1 to obtain a liquid crystal alignment agent lacquer C. (Production example 4) < Production of liquid crystal alignment agent lacquer D & gt In addition to changing the diamine compound to 1.4514g of 4,45-diaminodiphenyl formaldehyde In addition to using 1.4357 g of cyclobutane tetracarboxylic acid dianhydride instead of PMDA, the other steps were the same as those in Manufacturing Example 1 to obtain a liquid crystal alignment agent lacquer D. 23 593602 8804pifl (mixed Preparation of lacquer) Mixing liquid crystal alignment agent lacquer A and liquid crystal alignment agent lacquer D to obtain mixed lacquer AD, mixing liquid crystal alignment agent lacquer B and liquid crystal alignment agent lacquer D to obtain mixed lacquer BD, and mixing liquid crystal alignment The lacquer C and the liquid crystal alignment agent lacquer D obtain a mixed lacquer CD. In the aforementioned mixed lacquer, the ratio of the liquid crystal alignment agent lacquer D is 90% by weight. (Example 1) Japanese Patent Application No. 2001-64498 The method described in the preferred embodiment of the publication No. is to quasi-synthesize PSQ (carboxyl decyl) with a number average molecular weight of 2300 and a carboxyl content of 178 millimole / g. PSQ is mixed with the liquid crystal alignment agent lacquer A obtained in Manufacturing 1, wherein the ratio of the total amount of polymer components to PSQ is 3% by weight. That is, this mixture uses a mixed solvent of NMP-BC (weight ratio 1/1) Dilute to adjust The concentration of the whole polymer component was 3% by weight. This dilute lacquer is applied on a substrate with transparent electrodes by spin coating method 'and then sintered for about 5 minutes at 80 ° C. Next, it is sintered at 140 ° C for about 12 minutes to form an alignment film with a film thickness of 60 nm. Then, the entire surface is aligned by friction. Make a piece of the same substrate as above, spread a gap material of 20 // m on the alignment film surface of one substrate, and then use the epoxy hardener on the surface of the other substrate facing the alignment film surface to overlap Seal to make an anti-paraUel cell with a gap of 20 // m. Then, the following liquid crystal composition is injected into this unit, and after completion, the injection port is closed with a photohardener. After that, a heating process of 24 593602 8804pifl for about 30 minutes at 110 degrees Celsius is performed to produce a homogeneous alignment unit. Under the rotation observation of a cross Nicol, this unit cannot confirm the spiral-like traces obtained by friction. Since the obvious light and dark can be uniformly confirmed, it can be confirmed that it has a good alignment in the rubbing direction. 25 593602 8804pif1 C2H5OCH2

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4wt.-% 4wt.-% 4wt.-% 26 593602 8804pif1 (實例2〜實例10) 將PSQ之官能基及有機基依據表1之記載進行變更，並以前述之日本專利特願2001-64498號公報所記載之方法爲基準進行合成，除了各別的添加量有所變更之外，調整成與實例1相同之稀釋淸漆。再者，製作與實例1相同之單元，此單元在正交尼科耳偏光鏡之旋轉觀察下，無法確認因摩擦而得之螺旋狀之痕跡。由於可以均一地確認明顯的明暗，因而可以確認其在朝摩擦方向上具有良好的配向。實例2〜實例 10之結果如表1所τκ。 (實例11〜實例14) 除了使用聚甲基-矽倍半氧烷或聚苯基-矽倍半氧烷之外，製作與實例1相同之單元，且確認有經摩擦後之傷痕或刻痕。與實例1之差異點係爲在摩擦方向上確認有若干螺旋狀痕跡，而且觀察得到有若干部分之配向性具有雜亂之部分，此表示液晶顯示元件之充分使用之耐性不足。實例11〜實例14之結果如表1所示。 (比較例1 ) 除了不添加PSQ至液晶配向劑淸漆A內之外，製作與實例1相同之單元。此單元在正交尼科耳偏光鏡之旋轉觀察下，確認在摩擦方向上具有顯著地螺旋狀傷痕。並且觀察得到其配向性雜亂。比較例1之結果如表1所 27 7[\ ° 593602 ΓΗΜ-Ι-Hd 寸〇88 1« ^srlf (gEffi/p)4wt .-% 4wt .-% 4wt .-% 26 593602 8804pif1 (Example 2 to Example 10) The functional group and organic group of PSQ were changed according to the description in Table 1, and the aforementioned Japanese Patent No. 2001-64498 The method described in the publication was synthesized on the basis of the method, except that the addition amount was changed, and adjusted to the same dilute lacquer as in Example 1. Furthermore, the same unit as in Example 1 was produced. This unit could not be confirmed to have spiral traces due to rubbing under the rotation observation of a crossed Nicols polarizer. Since the obvious brightness and darkness can be uniformly confirmed, it can be confirmed that it has a good orientation in the rubbing direction. The results of Examples 2 to 10 are shown in Table 1 as τκ. (Example 11 to Example 14) Except using polymethyl-silsesquioxane or polyphenyl-silsesquioxane, the same unit as in Example 1 was produced, and it was confirmed that there were scratches or nicks after rubbing . The point of difference from Example 1 is that several spiral traces were confirmed in the rubbing direction, and some alignments were observed to have disordered portions, which indicates that the liquid crystal display element has insufficient resistance to full use. The results of Examples 11 to 14 are shown in Table 1. (Comparative Example 1) The same unit as in Example 1 was produced except that PSQ was not added to the liquid crystal alignment agent varnish A. Under the observation of the rotation of a crossed Nicols polarizer, this unit was confirmed to have a significant spiral wound in the rubbing direction. And observing its disordered alignment. The results of Comparative Example 1 are shown in Table 1. 27 7 [\ ° 593602 ΓΗΜ-Ι-Hd inch 〇88 1 «^ srlf (gEffi / p)

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匡鎰Ή 寸一ei(NI IIοι 6 00 L 593602 8804pif1 在表l中之省略代號、記號等之含意如下所示。省略代號： PSQ :聚有機矽倍半氧烷 Me :甲基 Ph :苯基 Π-Ργ · ΙΊ·•内 PSQ添加量：相對於全部聚合物之重量％ PSQ之分子量：所使用之PSQ之數平均分子量 PSQ之官能基含有量的單位：毫莫爾/g 表示有無損傷之記號的含意： ◎:沒有損傷之情形〇：有些許損傷之情形 χ :有損傷之情形顯示不均(unevenness)，係爲觀察並評估緊接著作成的顯示不均。其記號的含意如下所示： ◎:沒有顯示不均之情形〇：有些許顯示不均之情形 x :有顯示不均之情形 (實例15〜實例18) 調製與實例1相同之塗佈用液晶配向劑淸漆，除了在表2所示之4種燒結溫度下進行3〇分鐘左右的加熱處理之外，分別製作與實例丨相同的單元。此單元在正交 ^科耳偏光鏡之旋轉觀察下，無法確認因摩擦而得之螺麵狀之痕跡。由於可以均〜地確認明顯的明暗，因而可 29 593602 8804pifl 以確認其在朝摩擦方向上具有良好的配向。此結果如表2 所示。 (比較例2〜比較例5) 除了使用不添加PSQ的液晶配向劑淸漆之外，分別製作與實例15〜實例18相同之單元。此單元在正交尼科耳偏光鏡之旋轉觀察下，此時，確認在摩擦方向上具有顯著地螺旋狀傷痕。並且觀察得到其配向性雜亂。比較例2〜比較例5之結果如表2所示。 (實例19〜實例25及比較例6〜12) 使用表2所示之7種淸漆，此時添加實例1所記載之含有羧基之基的PSQ，並分別調製成塗佈用液晶配向劑淸漆。之後，使用此塗佈用淸漆，並作成與實例1相同的單元。觀察此配向膜之摩擦所導致之損害，藉由晶體旋轉（crystal rotation)法測定前傾角所得之結果與比較例一同顯示於表2中。镒 Ή 省略 Inch ei (NI IIοι 6 00 L 593602 8804pif1 In Table 1, the meanings of the omitted codes, symbols, etc. are as follows. Omitted codes: PSQ: polyorganosilicon silsesquioxane Me: methyl Ph: phenyl Π-Ργ · Ι Ί · • Internal PSQ added amount:% by weight relative to the total polymer Molecular weight of PSQ: Number of PSQ used Average molecular weight PSQ Functional group content unit: millimoles / g Indicates whether there is damage Meaning of symbols: ◎: No damage. 0: Some damage. Χ: Damage. Display unevenness. It is used to observe and evaluate the display unevenness immediately after writing. The meaning of the symbol is shown below. : ◎: No display unevenness 0: Some display unevenness x: Some display unevenness (Example 15 to Example 18) The same liquid crystal alignment agent paint for coating as in Example 1 was prepared, except that The same unit as in Example 丨 was prepared separately for the 30 kinds of sintering temperatures shown in Table 2 except for about 30 minutes of heat treatment. This unit could not be confirmed due to friction under the rotation observation of an orthogonal ^ Kohler polarizer. Spiral shape Traces. Since the obvious brightness and darkness can be confirmed evenly and uniformly, 29 593602 8804pifl can be confirmed to have a good orientation in the rubbing direction. The results are shown in Table 2. (Comparative Example 2 to Comparative Example 5) Except for use The same units as in Examples 15 to 18 were made separately without adding the PSQ liquid crystal alignment agent varnish. This unit was observed under the rotation of a crossed Nicols polarizer, at this time, it was confirmed that it had a significant difference in the rubbing direction. Spiral flaws. Observed alignment disorder. The results of Comparative Examples 2 to 5 are shown in Table 2. (Examples 19 to 25 and Comparative Examples 6 to 12) Seven types of varnishes shown in Table 2 were used. At this time, the PSQ containing the carboxyl group described in Example 1 is added, and each is prepared into a coating liquid crystal alignment agent paint. Thereafter, this coating paint is used to make the same unit as in Example 1. Observe this The damage caused by the friction of the alignment film is shown in Table 2 together with the comparative example, and the results obtained by measuring the rake angle by the crystal rotation method are shown in Table 2.

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V V V V V V V V 二一吃鎰丑 001 卜一 91 ◎ ◎◎◎◎◎◎ 「o/olCN 『0/0I(N 100/013 2/ol(N loo/ol<N 5/013 『0/0I<N 50/013 ro/OICN 2/oi(n ”0/0I<N 2/ol(N 2/01(n Γ0/0ΙΖ oo卜 I ΟΟΓΠΖ £ά jj-u HOOu.^Hu;KH^ffiuI 00卜 I 00s £ά £ά ΗΟΟυ.^Ηονβκ^κυ3S οοζ,ι—ηοοΓΟίΝ£έ JPH-U ΗΟΟυ-^Ηυνκυκυi ΟΟΔΙ 00S £ά ΗΟΟυ-^Ηο^ΗοΜΗυI οοζ.1—ηooroCN£ά JJ.U ΗΟΟυ-^Ηο)」κ^κυI 00卜 I ooroCN£ά ffiooo—^HuHKyHuI 00卜一 oorn(N£ά HOOu-^Huvffi^Hum ie ρύ αώ α-ν α υ e ν ρύ αώ α_ν α υ PQ ν ^ siοι 匡ΚΉ 6冕鎰丑 00冢鎰另寸(N 一一 13 0Z61 593602 8804pif1 在表2中之省略代號、記號等之含意係與表1所示相同。由表2可知在前傾角爲1.1 °〜89.3 °的液晶配向劑淸漆中，確認了 PSQ對摩擦傷痕、刻痕的效果。因此，對TN 型液晶顯示元件、STN液晶顯示元件、TFT型液晶顯示元件、IPS型液晶顯示元件、VA型液晶顯示元件、OCB型液晶顯示元件、強介電性液晶顯示元件、反強介電性液晶顯示元件等種種類型之液晶顯示元件而言，本發明之效果可以獲得充分地認可。 [產業上之利用可能性] 使用含有PSQ之液晶配向劑淸漆，可以提高配向膜之硬度，並得到防止進行摩擦操作之際在配向膜上之螺旋狀的傷痕的效果。亦即，使用本發明，對TN型液晶顯示元件、 STN液晶顯示元件、TFT型液晶顯示元件、IPS型液晶顯示元件、VA型液晶顯示元件、OCB型液晶顯示元件、強介電性液晶顯示元件、反強介電性液晶顯示元件等而言，可以實現較高之性能。 32VVVVVVVV Two one eat ugly 001 bu one 91 ◎ ◎ ◎ ◎ ◎ ◎ `` o / olCN 『0 / 0I (N 100/013 2 / ol (N loo / ol < N 5/013『 0 / 0I < N 50 / 013 ro / OICN 2 / oi (n ”0 / 0I < N 2 / ol (N 2/01 (n Γ0 / 0 ΙΙΟ oo 卜 I ΟΟΓΠIZ £ jj-u HOOu. ^ Hu; KH ^ ffiuI 00 卜 I 00s £ ά £ ά ΗΟΟυ. ^ Ηονβκ ^ κυ3S οοζ, ι—ηοοΓΟίΝ £ έ JPH-U ΗΟΟυ- ^ Ηυνκυκυi ΟΟΔΙ 00S £ ά ΗΟΟυ- ^ Ηο ^ ΗοMΗυI οοζ.1—ηooroCN £ οο κ ^ κυI 00 卜 I ooroCN £ ά ffiooo— ^ HuHKyHuI 00 卜一 oorn (N £ ά HOOu- ^ Huvffi ^ Hum ie ρύ αώ α-ν α υ e ν ρύ αώ α_ν α υ PQ ν ^ siοι uang KΉ 6 crown The meaning of the omission code, symbol, etc. in Table 2 is the same as that shown in Table 1. From Table 2, it can be seen that the LCD with a forward tilt of 1.1 ° to 89.3 ° The effect of PSQ on friction scars and nicks has been confirmed in the alignment agent lacquer. Therefore, the TN type liquid crystal display element, the STN liquid crystal display element, the TFT liquid crystal display element, the IPS liquid crystal display element, and the VA liquid crystal display element For various types of liquid crystal display elements such as glass, OCB-type liquid crystal display elements, ferroelectric liquid crystal display elements, and anti-ferroelectric liquid crystal display elements, the effects of the present invention can be fully recognized. [Industrial use is possible [Properties] The use of PSQ-containing liquid crystal alignment agent varnish can increase the hardness of the alignment film and prevent the effect of spiral wounds on the alignment film during the rubbing operation. That is, using the present invention, the TN liquid crystal Display elements, STN liquid crystal display elements, TFT type liquid crystal display elements, IPS type liquid crystal display elements, VA type liquid crystal display elements, OCB type liquid crystal display elements, ferroelectric liquid crystal display elements, anti-ferroelectric liquid crystal display elements, etc. In other words, higher performance can be achieved.

Claims

593602 8804pif1 拾、申請專利範圍： L-種液晶配向劑淸漆，包括由一聚有機矽倍半氧烷與一聚縮合高分子所形成的一聚合物成分及一溶媒，其中該聚合物成分中之該聚有機矽倍半氧烷之比率係爲0.01重量％〜50重量％左右，且該聚合物成分之比率係佔該液晶配向劑淸漆全量的0.1重量％〜40重量％左右，且同時該溶劑之比率係佔該液晶配向劑淸漆全量的60重量％〜99.9 重量％左右。 2·如申請專利範圍第1項所述之液晶配向劑淸漆，其中該聚縮合高分子係選自於聚醯胺酸、可溶性聚亞醯胺、聚醯胺或前述任二種以上之混合物等所組成之族群其中之 —〇 3·如申請專利範圍第1項所述之液晶配向劑淸漆，其中當該聚縮合高分子係選自於聚醯胺酸、可溶性聚亞醯胺、聚醯胺或前述任二種以上之混合物等所組成之族群其中之一之際，該聚有機矽倍半氧烷係爲式（1)所示之含有重複單位之官能基的聚有機矽倍半氧烷。 CH2CH2 —Ri〇—Y R^Si ()-Si _R2)n(〇-R4)m〇(3n_m)/2 (1) R3 (式中，R1、R2及R3分別爲各自獨立之碳數爲1〜18 的直鏈狀、分枝狀或環狀的飽和碳氫基、或碳數爲2〜6的直鏈狀、分枝狀或環狀的不飽和碳氫基、或碳數爲10以下的芳基；R4係爲碳數爲1〜4的直鏈狀或分枝狀的飽和碳氫 33 593602 8804pif1 基、CH3CO—、CH2=CHCO—、或 CH2=C(CH3)CO— ; m 係爲〇或〇·〇5〜2.0之數値；n之數値當m爲0時，n係爲 0.1〜2.0，而當m不爲〇而爲〜2.0時，則n+m之總和係爲0.1〜3.0 ; 係爲碳數爲1〜8的烯烴基，且此烯烴基中之1個或未相鄰接之2個的一 CH2—也可以置換成一〇—或一NH—； Y係爲環氧基、殘基、氫氧基、氨基、丙氧燦醯基、或異丁氧嫌酸基’另外’也可以爲混合則述2 種以上而成之官能基） 4. 如申請專利範圍第3項所述之液晶配向劑淸漆’其中該聚有機矽倍半氧烷係爲式（1)所示之含有ηι爲0且η爲 0.1〜2.0的重複單位之官能基的聚有機矽倍半氧烷。 5. 如申請專利範圍第3項所述之液晶配向劑淸漆’其中該聚有機砂倍半氧院係爲式（1)所不之含有πι爲0.05〜 .2.0且η爲0.05〜2.0的重複單位之官能基的聚有機矽倍半氧烷。 6. 如申請專利範圍第3項所述之液晶配向劑淸漆，其中該聚有機矽倍半氧烷係藉由下述之步驟（a)〜步驟（d)所示之反應路徑得到含有官能基之聚有機矽倍半氧烷， (a) 將式（2)所示之有機三氯矽烷與η倍莫爾量之式（3) 所示之有機一*氯砍院進彳了混合； (b) 將（a)所得之混合物與m倍有機三氯矽烷之莫爾量之式(4)所示之至少一種化合物進行反應； (c) 將（b)所得之反應生成物與[(3+n_m)/2]倍有機三氯矽烷之莫爾量之水進行反應，即可得到具有式（5)所示之重 34 593602 8804pif1 複單位且數平均分子量爲500〜5000的聚有機矽倍半氧烷化合物； (d)將（c)所得之聚有機矽倍半氧烷化合物與一種以上之式（6)所示之化合物進行反應。 C1 I R1— Si—Cl (2) I Cl593602 8804pif1 Scope of patent application: L-type liquid crystal alignment agent lacquer, including a polymer component and a solvent formed by a polyorganosilsesquioxane and a polycondensation polymer, wherein the polymer component is The ratio of the polyorganosilsesquioxane is about 0.01% to 50% by weight, and the ratio of the polymer component is about 0.1% to 40% by weight of the total amount of the liquid crystal alignment agent lacquer, and at the same time The ratio of the solvent accounts for about 60% to 99.9% by weight of the total amount of the liquid crystal alignment agent lacquer. 2. The liquid crystal alignment agent paint according to item 1 of the scope of the patent application, wherein the polycondensation polymer is selected from the group consisting of polyamic acid, soluble polyimide, polyamidine, or a mixture of any two or more of the foregoing. Among them, the group consisting of -03. The liquid crystal alignment agent paint as described in item 1 of the scope of application for patent, wherein when the polycondensation polymer is selected from polyamic acid, soluble polyimide, polyimide In the case of one of the groups consisting of amidine or a mixture of any two or more of the foregoing, the polyorganosilsesquioxane is a polyorganosilsesquioxane having a functional unit containing a repeating unit represented by formula (1) Oxane. CH2CH2 —Ri〇—YR ^ Si () -Si _R2) n (〇-R4) m〇 (3n_m) / 2 (1) R3 (where R1, R2, and R3 are each independent carbon numbers from 1 to 18 linear, branched or cyclic saturated hydrocarbon groups, or linear, branched or cyclic unsaturated hydrocarbon groups having 2 to 6 carbon atoms, or carbon atoms of 10 or less Aryl; R4 is a linear or branched saturated hydrocarbon with 1 to 4 carbon atoms 33 593602 8804pif1, CH3CO—, CH2 = CHCO—, or CH2 = C (CH3) CO—; m is 〇 or 〇 · 〇5 ~ 2.0 number 値; when the number of n is 0, n is 0.1 ~ 2.0, and when m is not 〇 and is ~ 2.0, then the sum of n + m is 0.1 ~ 3.0; It is an alkene group having 1 to 8 carbon atoms, and one of the olefin groups or two of the non-adjacent two-CH2- can also be replaced with one 10- or one NH-; Y is Epoxy group, residue, hydroxyl group, amino group, propoxycannyl group, or isobutoxyacid group 'in addition' may be a functional group composed of two or more types) 4. If the scope of patent application The liquid crystal alignment agent paint according to item 3, wherein the polyorganosilsesquioxane is represented by formula (1) Is 0 and η ηι containing functional group is a repeating unit of poly silicones 0.1~2.0 silsesquioxane. 5. The liquid crystal alignment agent lacquer as described in item 3 of the scope of the patent application, wherein the polyorganic sand silsesquioxane system is not included in formula (1) and contains π of 0.05 to .2.0 and η of 0.05 to 2.0. Polyorganosilsesquioxane with repeating functional groups. 6. The liquid crystal alignment agent paint according to item 3 of the scope of patent application, wherein the polyorganosilsesquioxane is obtained through the reaction path shown in the following steps (a) to (d). Based polyorganosilsesquioxane, (a) organic trichlorosilane shown in formula (2) and organic- * chlorocholine shown in formula (3) in the amount of n-fold mole are mixed; (b) reacting the mixture obtained in (a) with at least one compound represented by formula (4) in m times the molar amount of organotrichlorosilane; (c) reacting the reaction product obtained in (b) with [( 3 + n_m) / 2] times the molar amount of organic trichlorosilane and react with it to obtain a polyorganic silicon having a weight 34 593602 8804pif1 complex unit with a number average molecular weight of 500 to 5000 as shown in formula (5). Silsesquioxane compound; (d) reacting the polyorganosilsesquioxane compound obtained in (c) with one or more compounds represented by formula (6). C1 I R1— Si—Cl (2) I Cl

R3 I R2— Si—H (3) I ClR3 I R2— Si—H (3) I Cl

R4—OH (4)R4—OH (4)

(5) CH2=CH—R10—Y (6) (在上列各式中之R1〜R4、R1G、Y、m及n之含意係申請專利範圍第3項所述相同） 7.—種液晶顯示元件，係具有使用如申請專利範圍第1 項至第6項中任一項所述之液晶配向劑淸漆形成之一配向膜。 35(5) CH2 = CH—R10—Y (6) (The meanings of R1 to R4, R1G, Y, m, and n in the formulas above are the same as those described in item 3 of the scope of patent application) 7. A type of liquid crystal The display element has an alignment film formed using the liquid crystal alignment agent varnish as described in any one of claims 1 to 6 of the patent application scope. 35

修正日期93年4月29日 593602 發明專利說明書 (本說明書格式、順序及粗體字，請勿任意更動，※記號部分請勿填寫） ※申請案號：V， ※申請曰期：Λ 3。壹、發明名稱：（中文/英文）液晶配向劑清漆及液晶顯示元件 A LIQUID CRYSTAL ORIENTATED SOLVENT VARNISH AND A LIQUID CRYSTAL DISPLAY ELEMENT 貳、申請人：（共2人）姓名或名稱中文/英文）智索股份有限公司/CHISSO CORPORATION 2.智索石油化學股份有限公司 CHISSO PETROCHEMICAL CORPORATION 代表人··（中文/英文）1.後藤舜吉/GOTO, SHUNKICHI 2.抬野修平 / KASENO, SHUHEI 住居所或營業所地址：（中文/英文） h曰本大阪府大阪市北區中之島三丁目6番32號 6- 32, Nakanoshima 3-chome，Kita-ku，Osaka-shi，Osaka, Japan 2·曰本東京都千代田區丸之内二丁目7番3號 7- 3, Marunouchi 2-choume，Chiyoda，ku, Tokyo, Japan 國籍··（中文/英文）1〜2，日本JP 參、發明人：（共3人）姓名：（中文/英文） 1·平井吉治 / HIRAI，YOSHIHARU 2·谷岡聰 /TANIOKA，SATOSHI 3·村田鎮男 /MURATA，SHIZUO 住居所地址：（中文/英文）Date of amendment: April 29, 1993 593602 Description of invention patent (The format, order and boldface of this specification, please do not change it arbitrarily, ※ Please do not fill in the marked part) ※ Application number: V, ※ Application date: Λ 3. I. Name of the invention: (Chinese / English) Liquid crystal alignment agent varnish and liquid crystal display element A LIQUID CRYSTAL ORIENTATED SOLVENT VARNISH AND A LIQUID CRYSTAL DISPLAY ELEMENT, Applicant: (2 persons in total) Name or Name Chinese / English Co., Ltd./CHISSO CORPORATION 2. Representative of CHISSO PETROCHEMICAL CORPORATION · (Chinese / English) 1. Goto Shunji / GOTO, SHUNKICHI 2. Takeno Shupin / KASENO, SHUHEI Address of residence or business office : (Chinese / English) h Yueben 6-6 32, Nakanoshima 3-chome, Kita-ku, Osaka-shi, Osaka, Japan 2 · 32, Chiyoda-ku, Tokyo Marunouchi 2-chome 7 Ban 3-7- 3, Marunouchi 2-choume, Chiyoda, ku, Tokyo, Japan Nationality ·· (Chinese / English) 1 ~ 2, Japanese JP Participants and inventors: (Total 3 persons) Name: (Total 3 persons) Chinese / English) 1. Hirai Jiji / HIRAI, YOSHIHARU 2. Tanioka Satoshi / TANIOKA, SATOSHI 3. Murata Town Man / MURATA, SHIZUO Address: (Chinese / English)