201222104 %r- 六、發明說明： 【發明所屬之技術領域] 本發明係有義晶元件巾的液晶分子的配向控制技術。 【先前技術】 配向控制技術為液晶元件製造中的 得較高預傾角的技術，例如日本輯門承Hi 狻 公開的技術是眾所周知的。但報(專利文獻υ中 雖然可以得到預期的G。〜9G。的預傾s f '文獻中公開的技術時’ 等使得製程複雜，因而加卫費用古#向性乾式#刻 買用巧，並且由於需要多種材料(顆粒、樹 月曰^，因而材料費用兩，在此等方面還存在改良的空間。另外，液晶 進”子設計以長期穩定地保持液晶分子的配向狀 =的，，錢作可祕高的液晶元件方面扮演重要角色，但專利文 ri)在因 直接接觸的部分係使用非為配向膜材料的物質(樹 r曰广，夠保持液晶元件之高可靠性的勝 【先刚技術文獻】 【專利文獻1】曰本特開平6_95115號公報 【發明内容】 具體方式的目的之—在於提供—種能夠在較寬範圍内設 疋液日日分子的預傾角的新技術。 /其發明的—個方式（態樣）的液晶用配向膜的製造方法係用於 以i ΐ晶用配向膜’其特徵在於包括以τ步驟：_1步驟， 3!材料液與上述基板之間相對地提供電位差的狀態排出上述第 Lit 使上述第1材料液形成霧狀並散佈於上述基板上；⑻ 排屮卜n Γ在第2材料液與上述基板之間相對地提供電位差的狀態 2材料液，從而使上述第2材料液形成霧狀並散佈於上述 9 第3步驟，使散佈於上述基板上的上述第1材料液和上 第材料液111化。又，該液晶肢向膜製造方法中，較佳上述第ί 201222104 材料液和上述第2材料液之中的任一個含有垂直配向材料 人 有水平配向材料。另外’該液晶用配向膜製造方法中， ^ 述第1步驟和上述第2步驟重複2次以上後實行上述第3步 况下’亦較佳上述第1步驟中的上述第！材料液的散佈量和上月 步驟中的上述第2材料液的散佈量分別隨著上述第i步驟 =^ 步驟的重複次數的增加而遞減。 迅弟2 ⑺本發明的另—個方式的液晶用配向臈的製造方法係用於 板上製造液晶用配向膜’其特徵在於包括以下步驟：⑷第丨 ς 上述基板配置於與第1噴射裝置时射方向對應的位置 7 ^用上述第1喷射裝置，以在第丨材料液與上述基板之間相對地提供 電位差的狀態排出上述第！材料液，從而使上 狀 2佈於上麟板上；⑷第3步驟，使上述基板移向與第 =應的位置;⑷第4步驟’使用上述第2喷射裝置，以在 材料液與上述基板之間相對地提供電位差的狀⑽出上述 ΓΓ挪從⑽上述第2㈣液形成霧狀並散佈於上述基板上；和⑷第 '驟，使散佈於上述基板上的上述第i材料液和上述第2材料液固 笛該液晶用配向膜製造方法卜亦較佳上述第1材料液和上述 ^ 2材^液之中的任—個含有垂直配向材料，另—者含有水平配向材 + f外’雜晶用配向膜製造方法中’還較佳將上述第4步驟中的 ΐ迷第2材料液的散佈量設定為相對少於上述第2步驟中的上述第！ °此時’還較佳將上述第2步驟中的上述第1材料液 個面的ir疋為上述第1材料液形絲狀並可遍佈上述基板的幾乎整 射if ί述⑴或(2)的任—種方案，適當地設定第1材料液和第2材 β，便能夠以高角度任意地控制液晶元件中的預傾角。特別 而上85以下的預傾角不易在一般的液晶用配向膜來獲得，然 斜由使第1材料液和第2材料液之中的任—個含有垂直配向材 ⑽。/—者含^水平配向材料’使用這樣的材料液，能夠實現40。 :隹甚至更高的高預傾角。本發明㈣造方法巾，能夠直接利用 市。的垂直配向材料和水平配向材料，因此液Μ財的配向之長期 201222104 穩定性高’且液晶配向的錯定強度(anchoring strength)高，因而具有元 件的可靠性高、響應(特別是下降)快的優點。另外，藉由交替散佈第j 材料液和第2材料液’或者在其他步驟中依次散佈第1材料液和第2 材料液，散佈條件的自由度得以提升，因而預傾角的控制性更優異， 並且能夠在更廣的範圍形成均質的配向膜。 (3)本發明的一個方式的液晶元件的製造方法的特徵在於，其包括 以下步驟：（a)在第1基板的一個面上形成配向膜的配向膜形成步驟； (b)對向配置上述第〗基板和第2基板的基板配置步驟；和(〇在上述第 1基板與上述第2基板之間形成液晶層的液晶層形成步驟；（d)配向膜 形成步驟係使用上述(1)或(2)的任一方案的配向膜製造方法來形成配 向膜。 根據上述(3)的方案，能夠在較寬範圍内設定液晶元件中的液晶分 子的預傾角，因而能夠製造具有高預傾角的液晶元件。 (4)本發明的一個方式的液晶用配向膜的製造裝置的特徵在於包 t下裝置：⑷第1喷射裝置，其使第1材料液形«狀並進行喷霧； 2喷射裝置，其與上述第！喷射裝置相鄰配置，使第2材料液形 喷霧;⑷基板保持架，其保持基板，使該基板的一個面 電麼2h射裝置和上述第2喷射裝置各個的喷射方向對向；和⑷ 在上iiiti糾其與上述第1嘴射裝置和上述第2喷射裝置分別連接， 地施料液和上述第2材料液的任—個與上述基板之間選擇性 板上製(IT 1 —個方式騎晶用配⑽的㈣裝置剌於在基 其使第i 狀^徵^包括以下裝置：⑷第1喷射裝置， 述第1噴射ΐϊΐί 喷霧’· (b)第1電壓施加裝置，其與上 (二’在上述第1材料液與上述基板之間施加電壓； 2材料液形成霧狀並：二 相分離的方式配置’使第 噴射裝置連接，在上m_、第電塵施加裝置，其與上述第2 板保持架’其用於保持上述基板液壓;和⑷基 ㈣第2喷射裝置的任 201222104 個面與上述第1噴射裝置或上述第2噴射跋置的喷射方向對向。 實現可表現出尚預傾角的配向膜的製造裝置。 ⑹本發明的-個方式的液晶元件的特徵在於，其包括：⑷對向 配置的第1基板和第2基板；（b)至少設置於上述第}基板的一個面上 的配向膜；和⑷設置於上述第！基板與上述第2基板之間的液晶層， (d)上述配向财，多種配⑽片核舰分散於上述第〗基板的一個 面上’且4多種配向膜片在上述第〗基板的板厚方向上不規則地堆積。 ⑺本發明的-個方式的液晶元件的特徵在於，其包括：⑷對向 配置的第1基板和第2基板；（b)至少設置於上述第i基板的一個面上 的配向臈；和⑷設置於上述第i基板與上述第2基板之_液晶層， ⑷上述配向膜中，多片第！配向膜片和多片第2配向膜片不規則地分 散於上述第1基板的-個面上，且上述多片配向膜片的至少—部分與 上述多片第1配向膜片的一部分在上述第丨基板的板厚方向上堆積。 根據上述(6)或(7)的任一方案，藉由適當地設定配向膜片的組合， 能夠以高角度任意地控制液晶元件的預傾角。特別是1〇。以上、85〇以 下的預傾角不易以通常的液晶用配向膜來獲得，例如藉由使一者的配 向膜片含有垂直配向材料、使另一者的配向膜片含有水平配向材料， 使用這樣的配向膜片，能夠實現40。〜5〇。左右或其以上的高預傾角。 【實施方式】 以下’參照附圖對本發明的實施方式進行說明。 (第1實施方式） 第1圖是示出第1實施方式之配向膜的製造裝置的結構的示竟 圖。第1圖所示的配向膜的製造裝置具有兩個喷射裝置10、U、基板 保持架（基板固定裝置）12和電廢施加裝置13,所述兩個喷射裝置1〇、 11具有圓筒狀等的注射器（筒）和設置於此等注射器一端的中空的微小 針’該注射器（筒）用於在内部保持配向膜的材料液(下文中稱為「配向 膜液」）’所述基板保持架(基板固定裝置}12用於保持藉由此等喷射裝 置10、11形成配向膜的對象，即基板100,所述電壓施加裝置13用於 201222104 對各喷射裝置10、11施加電壓❶如圖所示，噴射裝置10和噴射裝置 11相鄰配置》電壓施加裝置13的結構包含：高壓直流電源2〇 ;分別 與該高壓直流電源20連接的高電壓繼電器(reiay)2l、22 ;和用於^制 此等高電壓繼電器21、22的開關動作的微電腦23。 、工 如圖所示，適當地(例如數釐米左右)確保噴射裝置1〇、u的各個 針與基板100之間的距離h。並且’在喷射裝置1〇、u的各個針與基 板1〇〇之間使用電壓施加裝置13施加高電壓（例如數千伏的直流$ 壓），同時將注射器内的配向膜液供給到針的前端。此時，例如如=所 示預先將基板100和基板保持架12接地(基準電位），對各噴射裝置 10、11的針提供與基板100相比相對較高的電位（又，電位的關係也可 以相反）。由此，從各喷射裝置10、U的針排出的配向膜液形成帶正 電位的狀態的液體顆粒。帶該電位的㈣顆粒發生電排斥，同時細小 地分裂、擴散’形成霧狀的微小液滴（霧狀體該微小的液滴被帶負電 的基板100吸引，附著於基板刚上。其後，藉由對到達基板1〇〇的 微小液滴適當進行熱處理等而使其成膜(固化），從而㈣包含多個微細 的配向膜片而構成的配向膜。 此處’為了徹底地散佈液滴’則以配向膜液的黏度低為佳。因此， y =丙崎溶劑稀釋配向材料來調製配向膜液。作為稀釋用的溶 、揮發性高的材料。其原因是：在利用電喷 述溶劑會形成非常細小的液滴，而在飛向基板的期 發I·生^目11蒸發。因此認為’此處所使用的稀釋用溶劑只要揮 響。冋’論選擇何種溶綱不會對液晶分子的配向性造成很大影 繼㈣町優點： (b) 能夠在常溫常壓下成膜; (c) 能夠利用乾燥製程成臈 (d) 裝置結構比較簡約（簡單）； (e) 能夠成膜的材料多； (0成臈僅需少量材料即可。 201222104 另外，如第i圖所示’準備兩個喷射裝置1〇、u，向各喷射裝置 10、11巾分別導入性質不同的配向膜液(配向材料），從而可以使形成 有各，向膜液的微小區域(數百奈米至數十微米左右)混雜形成。由此， 可以得到迄今為止難以達朗複合液晶配向狀t。另外，使利用各喷 射裝置10 11散佈配向膜液的時間點不同而分時交替地進行散佈，便 可以使配向膜液的散佈狀態更加良好。關於配向媒液的散佈時間點與 配向膜液的散佈狀態的關係，下文中藉由實補進行詳細說明。 第2圖是電噴灑堆積法令的較佳散佈電壓的說明圖。第2圖示 出各喷射裝置10、11的針與基板则之間的電壓（電極間電壓)和總離 子量的關係。如圖所示，在將電極間電壓設為比閾值電壓高2〇〇v左右 的同電壓時’電®大多呈穩^。如第2圖(B)所示，配向膜液的散佈模 式根據該電極間電壓的大小而變化。電極間電壓相對較低時，乃為液 滴尺寸較大的微滴模式，隨著電極間電壓增大，表現為液滴尺寸均勻 且微小的錐狀喷流(cone-jet)模式，接著則形成液滴尺寸的均勻性降低 的多股喷流(multi-jet)模式。 第3圖是對藉由第丨實施方式的電喷灑堆積法形成的配向膜的結 構進行說明的圖。如第3圖（A)所示，係為在基板上得到某種配向膜液 A堆積而成的配向膜區域(配向膜片）和另一種配向膜液B堆積而成的 配向膜區域(配向膜片）隨機混合的狀態的配向膜。即，得到.多個配向膜 區域在基板上以平面的方式分散且立體地堆積而成的結構的配向膜。 利用電喷灑堆積法散佈多種配向膜液可獲得即使各配向膜區域堆積， 區域比例也不會發生變化的效果。與此相對的比較例係示於第3圖 (B)。比較例為一種配向臈，其利用配向膜液B藉由旋塗等在基板上形 成平坦的配向膜，並於其上利用配向膜液A藉由電喷灑堆積法形成配 向膜區域而得到此配向膜。 接下來’對可以適用藉由上述電喷灑堆積法形成之配向膜的液晶 元件的一例進行說明。 第4圖是示意性示出第1實施方式的液晶元件的剖面圖。第4圖 所示的液晶元件具有液晶層59夾在第1基板51與第2基板55之間的 基本構成。在第1基板51的外側配置有第1偏光板61，在第2基板 201222104 t- 55的外側配置有第2偏光板62。以下，對液晶元件的結構進行更詳細 .^ ^ %於對液晶層59的周圍進行密封的密封材料等構件，省 略圖不和說明。 第1基板51和第2基板55分別例如為玻璃基板、塑膠基板等透 明土板。如圖所示，第1基板51和第2基板55以各自的-個面相對 向的方式並保留預定的間隙(例如數微米）而貼合。又，雖省略了特別的 圖示’但所有基板上均可以形成薄膜電晶體等開關元件。 液晶層59設置於第1基板51與第2基板55的彼此之間。構成液 晶層59的液晶材料的介電各向異性&可以為正(&〉〇)，也可以為負 (△ε<〇) °液晶層59中圖示的粗線示意性地示出未對液晶層59施加電 壓的初期狀痗下的液晶分子的配向方位。例如，如圖所示液晶層％形 成經賦予較高預傾角的相同初始配向狀態。 曰 第1電極52設置於第丨基板51的一面側。另外，第2電極允設 置於第2基板55的一面側。第！電極52和第2電極56係分別藉由將 例如氧化銦錫(ITO)等透明導電膜適當地圖案化而構成。 配向膜53以覆蓋第！電極52的方式設置於第1基板51的一面 側。另外，配向膜57以覆蓋第2電極56的方式設置於第2基板55的 一面側。此等配向膜53、57之中，至少其中之一（或者兩者)可以使用 藉由上述電喷灑堆積法形成的配向膜。 實施例 (實施例1) 準備形成有ITO等透明電極的1對玻璃基板(ιτο的厚度：15〇〇 埃、玻璃板厚：0.7mm、玻璃材質：無鹼玻璃）。對此等基板進行清洗， 使用通常的光微影步驟進行IT0的圖案化。在此，作為IT〇蝕刻方法 係使用濕式蝕刻（氣化鐵）。 接下來’在將ΙΤΟ圖案化後的玻璃基板上，利用電噴灑堆積法進 行配向膜液(配向材料)的散佈。在其中一個喷射裝置10的注射器中填 充水平配向材料(ΡΙ-Α日產化學工業股份有限公司製造：4wt%)和溶劑 (二氣甲烷)的混合溶液，在另一個喷射裝置11的注射器中填充垂直配 向材料（日產化學工業股份有限公司製造SE-1211: 4wt%)和溶劑(DCM) 201222104201222104 %r- VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an alignment control technique of liquid crystal molecules of a right-crystal element. [Prior Art] The alignment control technique is a technique for obtaining a high pretilt angle in the manufacture of a liquid crystal element, and a technique disclosed in, for example, Japanese Patent Publication No. He 狻 is well known. However, the newspaper (in the patent document, although it can obtain the expected G. ~ 9G. The pre-dip sf 'the technology disclosed in the literature' etc. makes the process complicated, thus cultivating the cost of the ancient #向性干式#, Due to the need for a variety of materials (particles, tree moons, and therefore material costs two, there is still room for improvement in this area. In addition, the liquid crystal into the sub-design to maintain the alignment of liquid crystal molecules in a stable manner for a long time, It plays an important role in the high-definition liquid crystal element, but the patent ri) uses a substance other than the alignment film material in the direct contact part (the tree is wide enough to maintain the high reliability of the liquid crystal element) [Technical Document] [Patent Document 1] JP-A-6-95115 SUMMARY OF INVENTION A specific aspect of the present invention is to provide a new technique capable of providing a pretilt angle of a sputum day molecule in a wide range. The method for producing an alignment film for liquid crystal according to an aspect of the invention is for use in an alignment film for crystallizing, which is characterized by comprising a step of τ: _1, a step of: 3! material liquid and the substrate In a state in which a potential difference is provided, the first material liquid is discharged to form a mist and dispersed on the substrate; and (8) a material liquid in a state in which a potential difference is relatively provided between the second material liquid and the substrate, Therefore, the second material liquid is formed into a mist and dispersed in the third step, and the first material liquid and the upper material liquid dispersed on the substrate are 111. Further, in the method for producing a liquid crystal limb film, It is preferable that any one of the material liquid and the second material liquid described above contains a vertical alignment material for a human horizontal alignment material. In addition, in the method for producing a liquid crystal alignment film, the first step and the second step are described. After repeating the second step or more, the third step is performed, and it is preferable that the amount of the material liquid to be dispersed in the first step and the amount of the second material liquid in the previous step are respectively the same as the first Step = ^ The number of repetitions of the step is decreased. 迅弟 2 (7) Another method for producing a liquid crystal alignment yoke according to another aspect of the present invention is for use in an on-board manufacturing alignment film for liquid crystals, which is characterized by Step: (4) 丨ς The substrate is disposed at a position 7 corresponding to the direction of the first injection device, and the first injection device is configured to discharge the potential difference between the second material liquid and the substrate. The material liquid is such that the upper shape 2 is placed on the upper plate; (4) the third step is to move the substrate toward the position of the first position; (4) the fourth step 'using the second spraying device to The substrate is relatively provided with a potential difference (10), and the second (four) liquid is formed into a mist and dispersed on the substrate; and (4) the second step, the ith material liquid and the second material liquid dispersed on the substrate are Preferably, the second material liquid turf is used in the method for producing an alignment film for liquid crystal, and any one of the first material liquid and the liquid material contains a vertical alignment material, and the other contains a horizontal alignment material + f Further, in the method of producing an alignment film for a heterocrystal, it is preferable to set the amount of dispersion of the second material liquid in the fourth step to be relatively smaller than the above-described first step in the second step! In this case, it is preferable that the ir 疋 of the first material liquid surface in the second step is a liquid shape of the first material, and may be spread over the substrate. (1) or (2) In any of the above, the first material liquid and the second material β are appropriately set, and the pretilt angle in the liquid crystal element can be arbitrarily controlled at a high angle. In particular, the pretilt angle of 85 or less is not easily obtained in the general alignment film for liquid crystal, and the vertical alignment material (10) is contained in any of the first material liquid and the second material liquid. / - Containing a horizontal alignment material ' With such a material liquid, 40 can be achieved. : 隹 even higher high pretilt angle. According to the fourth aspect of the invention, the method towel can be directly utilized. The vertical alignment material and the horizontal alignment material, so the liquidity of the long-term alignment of 201222104 is high, and the liquid crystal alignment has high anchoring strength, so the reliability of the component is high, and the response (especially falling) is fast. The advantages. Further, by alternately dispersing the j-th material liquid and the second material liquid or sequentially spreading the first material liquid and the second material liquid in other steps, the degree of freedom of the dispersion condition is improved, and the pretilt angle is more excellent in controllability. And it is possible to form a homogeneous alignment film over a wider range. (3) A method of manufacturing a liquid crystal element according to an aspect of the present invention, comprising the steps of: (a) forming an alignment film forming an alignment film on one surface of a first substrate; (b) arranging the above alignment a substrate arrangement step of the first substrate and the second substrate; and (a liquid crystal layer forming step of forming a liquid crystal layer between the first substrate and the second substrate; (d) an alignment film forming step using the above (1) or The alignment film production method according to any one of (2), wherein the alignment film is formed. According to the aspect (3), the pretilt angle of the liquid crystal molecules in the liquid crystal element can be set in a wide range, and thus it is possible to manufacture a high pretilt angle. (4) The apparatus for producing a liquid crystal alignment film according to one aspect of the present invention is characterized in that the apparatus is provided in a package t: (4) a first ejection device that sprays a first material in a liquid state; And disposed adjacent to the first injection device to cause the second material to be liquid-sprayed; and (4) a substrate holder that holds the substrate and electrically ejects one surface of the substrate and the second injection device Direction opposite; (4) In the upper iiiti, it is connected to the first nozzle device and the second injection device, respectively, and any one of the ground application liquid and the second material liquid is selectively formed on the substrate (IT 1 - one) The apparatus for riding a crystal (10) is provided with the following means: (4) a first injection device, a first injection ΐϊΐ ί spray, and a (b) first voltage application device. The first injection device is connected to the upper (m', the voltage is applied between the first material liquid and the substrate; the material liquid is misted and the two phases are separated), and the upper m_ and the second dust application device are connected. And the second plate holder 'for holding the substrate hydraulic pressure; and (4) the base (four) second injection device, the 201222104 faces are opposed to the injection direction of the first injection device or the second injection device. (6) A liquid crystal element according to another aspect of the present invention includes: (4) a first substrate and a second substrate disposed opposite to each other; and (b) at least provided in the above Alignment film on one side of the substrate; and (4) a liquid crystal layer interposed between the first substrate and the second substrate, (d) the above-mentioned alignment, a plurality of (10) core ships dispersed on one surface of the first substrate, and four kinds of alignment films are in the above-mentioned (7) The liquid crystal element according to the invention is characterized in that: (4) the first substrate and the second substrate which are disposed opposite to each other, and (b) at least And (4) the liquid crystal layer disposed on the i-th substrate and the second substrate, and (4) the alignment film, the plurality of the first alignment film and the plurality of second alignment films are not Regularly dispersed on one surface of the first substrate, and at least a portion of the plurality of alignment films and a part of the plurality of first alignment films are stacked in a thickness direction of the second substrate. According to any one of the above (6) or (7), the pretilt angle of the liquid crystal element can be arbitrarily controlled at a high angle by appropriately setting the combination of the alignment films. Especially 1〇. The above pre-tilt angle of 85 Å or less is not easily obtained by a normal alignment film for liquid crystal. For example, by using one of the alignment films to contain the vertical alignment material and the other of the alignment films to contain the horizontal alignment material, the use is such that The alignment diaphragm can achieve 40. ~5〇. High pretilt angles above or above. [Embodiment] Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings. (First Embodiment) Fig. 1 is a view showing the configuration of an apparatus for manufacturing an alignment film according to a first embodiment. The manufacturing apparatus of the alignment film shown in Fig. 1 has two ejection devices 10, U, a substrate holder (substrate fixing device) 12, and an electric waste application device 13, and the two ejection devices 1 and 11 have a cylindrical shape. a syringe (cylinder) and a hollow microneedle provided at one end of the syringe. The syringe (cylinder) is used to hold a material liquid of an alignment film (hereinafter referred to as "alignment membrane liquid"). A rack (substrate fixing device) 12 is for holding an object which forms an alignment film by the ejection devices 10, 11, and the substrate 100, and the voltage applying device 13 is used for applying a voltage to each of the ejection devices 10, 11 as shown in FIG. As shown, the configuration of the injection device 10 and the injection device 11 adjacent to the voltage application device 13 includes: a high voltage DC power source 2; high voltage relays (reiay) 21, 22 respectively connected to the high voltage DC power source 20; The microcomputer 23 for controlling the switching operation of the high-voltage relays 21 and 22, as shown in the figure, appropriately (for example, several centimeters or so) ensures the distance h between the respective needles of the ejection devices 1〇, u and the substrate 100. And 'in A high voltage (for example, a DC voltage of several thousand volts) is applied between the respective pins of the radiation devices 1 and u and the substrate 1A, and the alignment film liquid in the syringe is supplied to the tip end of the needle. When the substrate 100 and the substrate holder 12 are grounded (reference potential) in advance, for example, as shown by =, the needles of the respective ejection devices 10 and 11 are supplied with a relatively higher potential than the substrate 100 (again, the potential relationship may be On the contrary, the alignment film liquid discharged from the needles of the respective ejection devices 10 and U forms liquid particles in a state of positive potential. The (four) particles having the potential are electrically repelled while finely splitting and diffusing to form a mist. The fine droplets (the mist is attracted by the negatively charged substrate 100 and adhered to the substrate). Thereafter, the fine droplets reaching the substrate 1 are appropriately heat-treated or the like. The film (cured), and (4) an alignment film comprising a plurality of fine alignment films. Here, in order to completely spread the droplets, the viscosity of the alignment film liquid is preferably low. Therefore, y = azide solvent dilution Orienting material It is used as a film-forming liquid. It is used as a material for high solubility and high volatility for dilution. The reason is that very fine droplets are formed by electrospraying the solvent, and the evaporation of the substrate to the substrate is accelerated. Therefore, it is considered that the solvent used for dilution here is only required to be swayed. The choice of which solute does not cause a great influence on the alignment of liquid crystal molecules (4) Advantages of the town: (b) It can be formed under normal temperature and pressure. (c) It is possible to use the drying process to form a crucible (d). The structure of the device is relatively simple (simple); (e) There are many materials that can be formed into a film; (0 is only required to be a small amount of material. 201222104 In addition, as in the figure i "Prepare two injection devices 1〇, u, and introduce the alignment film liquid (alignment material) of different properties to each of the injection devices 10 and 11 respectively, so that a minute area (each of several) can be formed. Nano to tens of microns or so) mixed formation. Thereby, it is possible to obtain a composite liquid crystal alignment t which has hitherto been difficult. Further, by dispersing the timing of the distribution of the alignment film liquid by the respective ejection devices 10 11 and alternately distributing them in a time-division manner, the dispersion state of the alignment film liquid can be further improved. The relationship between the dispersion time point of the alignment medium and the dispersion state of the alignment film liquid will be described in detail below by actual compensation. Fig. 2 is an explanatory diagram of a preferred dispersion voltage of the electric spray deposition method. Second, the relationship between the voltage between the needles and the substrate of each of the injection devices 10 and 11 (the voltage between the electrodes) and the total ion amount is shown. As shown in the figure, when the voltage between the electrodes is set to the same voltage higher than the threshold voltage by about 2 〇〇 v, the electric meter is mostly stabilized. As shown in Fig. 2(B), the dispersion pattern of the alignment film liquid changes depending on the magnitude of the voltage between the electrodes. When the voltage between the electrodes is relatively low, it is a droplet mode with a large droplet size. As the voltage between the electrodes increases, the droplet size is uniform and a small cone-jet mode, followed by a cone-jet mode. A multi-jet mode with reduced uniformity of droplet size is formed. Fig. 3 is a view for explaining the structure of an alignment film formed by the electrospray deposition method of the second embodiment. As shown in Fig. 3(A), an alignment film region (alignment film) in which a certain alignment film liquid A is deposited on a substrate and an alignment film region in which another alignment film liquid B is deposited are formed (alignment). Diaphragm) An alignment film in a state of random mixing. In other words, an alignment film having a structure in which a plurality of alignment film regions are dispersed in a planar manner on the substrate and three-dimensionally stacked is obtained. By dispersing a plurality of alignment film liquids by the electrospray deposition method, it is possible to obtain an effect that the area ratio does not change even if the respective alignment film regions are deposited. A comparative example opposite to this is shown in Fig. 3(B). The comparative example is an alignment enthalpy which forms a flat alignment film on a substrate by spin coating or the like using an alignment film liquid B, and forms an alignment film region by an electrospray deposition method using the alignment film liquid A thereon. Orientation film. Next, an example of a liquid crystal element to which an alignment film formed by the above-described electrospray deposition method can be applied will be described. Fig. 4 is a cross-sectional view schematically showing the liquid crystal element of the first embodiment. The liquid crystal element shown in Fig. 4 has a basic configuration in which a liquid crystal layer 59 is interposed between the first substrate 51 and the second substrate 55. The first polarizing plate 61 is disposed outside the first substrate 51, and the second polarizing plate 62 is disposed outside the second substrate 201222104 t-55. Hereinafter, the structure of the liquid crystal element will be described in more detail, such as a sealing material that seals the periphery of the liquid crystal layer 59, and the description thereof will be omitted. Each of the first substrate 51 and the second substrate 55 is, for example, a transparent earth plate such as a glass substrate or a plastic substrate. As shown in the figure, the first substrate 51 and the second substrate 55 are bonded to each other with a predetermined gap (for example, several micrometers) so as to face each other. Further, although a special illustration is omitted, a switching element such as a thin film transistor can be formed on all of the substrates. The liquid crystal layer 59 is provided between the first substrate 51 and the second substrate 55. The dielectric anisotropy of the liquid crystal material constituting the liquid crystal layer 59 may be positive (& 〇), or may be negative (Δε < 〇) ° the thick line shown in the liquid crystal layer 59 is schematically shown The alignment direction of the liquid crystal molecules in the initial state in which the voltage is not applied to the liquid crystal layer 59. For example, as shown, the liquid crystal layer % forms the same initial alignment state imparted with a higher pretilt angle.曰 The first electrode 52 is provided on one surface side of the second substrate 51. Further, the second electrode is placed on one surface side of the second substrate 55. The first! Each of the electrode 52 and the second electrode 56 is formed by appropriately patterning a transparent conductive film such as indium tin oxide (ITO). Alignment film 53 to cover the first! The electrode 52 is provided on one side of the first substrate 51. Further, the alignment film 57 is provided on one surface side of the second substrate 55 so as to cover the second electrode 56. At least one of the alignment films 53, 57 (or both) may use an alignment film formed by the above-described electrospray deposition method. EXAMPLES (Example 1) A pair of glass substrates on which a transparent electrode such as ITO was formed (thickness: 15 Å, glass plate thickness: 0.7 mm, glass material: alkali-free glass) was prepared. These substrates are cleaned, and the pattern of IT0 is patterned using a normal photolithography step. Here, wet etching (vaporized iron) is used as the IT 〇 etching method. Next, the dispersion of the alignment film liquid (alignment material) was carried out by electrospray deposition on the glass substrate on which the ruthenium was patterned. A syringe of one of the injection devices 10 is filled with a mixed solution of a horizontal alignment material (manufactured by ΡΙ-Α Nissan Chemical Co., Ltd.: 4 wt%) and a solvent (diqi methane), and the syringe of the other ejection device 11 is filled with a vertical Orientation materials (SE-1211: 4wt% manufactured by Nissan Chemical Industries Co., Ltd.) and solvent (DCM) 201222104
V 的混合溶液，由各喷射裝置10、11同時散佈各混合溶液。具體地說， 係藉由微電腦23將各高電壓繼電器21、22在相同時刻控制為導通狀 態’利用高壓直流電源20對各喷射裝置1〇、11的針施加電壓。又， 以下示出作為水平配向材料使用的PI-A的化學結構。 【化一】In the mixed solution of V, each mixed solution was simultaneously dispensed from each of the spraying devices 10, 11. Specifically, the high voltage relays 21 and 22 are controlled to be in an on state at the same time by the microcomputer 23. A voltage is applied to the needles of the respective injection devices 1A and 11 by the high voltage DC power source 20. Further, the chemical structure of PI-A used as a horizontal alignment material is shown below. 【化一】
PI-API-A
此時，將各喷射裝置10、11的針與基板100之間的距離h設為 6cm ’對各針施加7kV的直流電壓（電場強度：ukV/cm)，利用外徑為 75μιη的針在鉛直方向以175nL/s的速度分別散佈1〇μί各溶液。另外， 為了控制水平配向膜與垂直配向膜的各區域的尺寸之比，將水平配向 材料與溶劑的混合比固定為20:80，將垂直配向材料與溶劑的混合比變 化為20:80、1:99。各配向材料的預煅燒係在1〇〇»c下進行1〇分鐘，正 式煅燒（燒結成完成品）則在250°C下進行60分鐘。對該基板實施摩 擦配向處理(rubbing treatment)。另外’作為對向基板係準備利用習知 方法預先形成垂直配向膜的基板，使該基板與具有藉由電噴灑堆積法 形成的配向膜的基板對向而貼合。為了將基板間的距離(液晶胞厚)保持 :定，在一側的基板面上利用乾式散佈法散佈間隙控制材料。間隙材 料係使用粒徑為6微米的塑膠球，也可以使用Shinshikyu(商品名，日 本觸媒化成公司製）。在另一基板上形成主密封圖案（和導通材料圖 ，）。此處的印刷係使用網版印刷法，也可以使用點膠機(dispenser)等。 ，封劑係使職E]性密封劑，也可以使用光@性密封劑、光/熱併用型 密封劑等。該密封劑中含有數個％之粒徑為6微米的玻璃纖維。另外 ，預定的位置印刷包含金珠等的導通材料。在此，在㈣劑中加入上 述玻璃纖維’以含有數個％之各雜彳f比該玻璃纖維的純約大i微 米的金珠的物質為導通材料，進行網版印刷。導通材料圖案也可以印 201222104At this time, the distance h between the needles of the respective ejection devices 10 and 11 and the substrate 100 was set to 6 cm. A DC voltage of 7 kV (electric field strength: ukV/cm) was applied to each needle, and a needle having an outer diameter of 75 μm was used in the vertical direction. The direction was spread at a rate of 175 nL/s for each solution. In addition, in order to control the ratio of the size of each of the horizontal alignment film and the vertical alignment film, the mixing ratio of the horizontal alignment material and the solvent is fixed to 20:80, and the mixing ratio of the vertical alignment material to the solvent is changed to 20:80,1 :99. The pre-calcination of each of the alignment materials was carried out for 1 minute at 1 〇〇»c, and the normal calcination (sintered into a finished product) was carried out at 250 ° C for 60 minutes. The substrate was subjected to a rubbing treatment. Further, a substrate on which a vertical alignment film is formed in advance by a conventional method is prepared as a counter substrate, and the substrate is bonded to a substrate having an alignment film formed by an electrospray deposition method. In order to maintain the distance between the substrates (liquid crystal cell thickness), the gap control material is spread by a dry dispersion method on the substrate surface on one side. For the gap material, a plastic ball having a particle size of 6 μm is used, and Shinshikyu (trade name, manufactured by Nippon Shokubai Chemical Co., Ltd.) can also be used. A main seal pattern (and a conductive material pattern,) is formed on the other substrate. The printing system here uses a screen printing method, and a dispenser or the like can also be used. The sealant is an E-type sealant, and a light-seal sealant or a light/heat sealant can also be used. The sealant contains several % of glass fibers having a particle size of 6 microns. Further, a conductive material containing gold beads or the like is printed at a predetermined position. Here, the above-mentioned glass fiber ‘ is added to the (four) agent to perform screen printing by using a material containing a plurality of % of the xanthene f which is about i μm larger than the pure glass fiber of the glass fiber as a conductive material. The conductive material pattern can also be printed 201222104
V 刷到主密封材料之相反側的基板上。將上下基板在預定的位置疊合而 製成液晶胞’以壓擠狀態藉由熱處理將密封劑固化。在此利用熱壓法 進行熱固化(150°c煅燒）。 接著，利用切割裝置在玻璃上劃出痕，藉由分切(breaking)步驟分 割成長條狀(待注入之單位)。利用真空注入法向該液晶胞中注入液晶材 料。作為液晶材料係使用介電各向異性為正值的代表性液晶材料 5CB(Merck公司製）。其後’利用末端密封材料將注入口密封。為了使 配向一致’將液晶胞加熱到液晶的相變溫度以上。在此利用烘箱以6〇。〇 熱處理30分鐘。使被切割裝置劃出痕的部分斷開而小型分割成個別的 液晶胞。利用清潔劑、有機溶劑等對液晶胞進行清洗，洗掉液晶和倒 角時的粉末。其後，以預定的角度黏貼切割成預定大小的偏光板。由 此製作混成型的液晶元件’並利用偏光顯微鏡對配向狀態進行觀察。 另外，作為預傾角測定用的試樣液晶胞，係製作將基板彼此貼合而成 的構成物，該基板係於使用電喷灑堆積法形成配向膜後實施摩擦配向 處理，並藉由磁場零位法(null method)測定預傾、角。 利用偏光顯微鏡在正交尼科爾狀態下觀察所製作的液晶元件，其 形貌見第5圖。第5圖(A)是使垂直配向材料與溶劑的混合比為2〇 8〇 時的觀察影像，第5圖(B)是使垂直配向材料與溶劑的混合比為υ99 時的觀察影像。若為利用習知方法散佈的液晶元件時，觀°察到被直徑 為數微米〜數十微米的垂直配向膜區域覆蓋的形貌，但在本實施例: 液晶元件中則為可觀察到1μπι以下的高預傾角的區域之程度。由此爷 為，即使產生堆積，也可以保持水平配向材料和垂直配向=料的均g 分佈。另外’預⑽的贼結果見第6 I其結果，與散佈的溶液中 所含有的垂直配向材料多的液晶元件相比，垂直配向材料少的液晶元 件其預傾角較低。其原因是由於積層致使基板表面的形狀產生了 $ 2 的不〉響。 (實施例2) 作為實施例2係在不同時間交替地散佈不同材料的方法進行 究。除了配向臈的形成步驟以外，使用與實施例丨同樣的步驟。I: 中一個喷射裝置10的注射器中填充水平配向材料(與上述實施例【、 11 201222104 ·4wt%)和*劑（H院和了㈣）的混合溶液，在另- SE-1211 . 4 ΙΓΛ射/中填充垂直配向材料(與上述實施例1相同的 裝署10、'厂\〇广谷劑(二氣甲烧和γ_丁内醋)的混合溶液’由各喷射 雷厳騎Λ Β地散佈各混合溶液。具體地說，藉由微電腦23將各 亩^器、21、22按照預定的時間比選擇性地控制為導通狀態，藉 夂1 :電源20對各噴射裝置1G、11的針施加電壓。將實行如下 人的週期(散佈週期)設定為1G秒：湘喷射裝置1G散佈含有 7、 ’配向材料的混合溶液以及利用喷射裝置⑽佈含有垂直配向材料 t混合溶液。將該散佈週期内的含有水平配向材料的混合溶液的散佈 8、 間與3，垂直配向材料的混合紐的散佈時間之比設定為8:2、&4、 4:6、2:8這4種模式。散佈時間料為15分鐘(9()個週期）。 另外，將各喷射裝置10、11的針與基板100之間的距離h設為 6cm ’對各針施加6.5kv的直流霞，利用外徑為75岬的針在錯直方 向以70nL㈣速度散佈各混合溶液。為了控制水平配向膜與垂直配向 膜的各區域的尺寸之比，將水平配向材料與溶劑的混合比固定為 20:80，將垂直配向材料與溶劑的混合比變化為2〇:8〇、1:99。各配向材 料的預烺燒係在1G(TC下進行1G分鐘，正式锻燒則在25(rc下進行6〇 分鐘。對該基板實施摩擦配向處理。另外，使垂直配向材料與溶劑的 混合比為1:9，使水平配向材料與溶劑的混合比為1:4，對於散布量， 係以垂直配向材料的混合溶液和水平配向材料的混合溶液均為 20μί、垂直配向材料的混合溶液為2〇μΙν且水平配向材料的混合溶液 為30μί、垂直配向材料的混合溶液為3〇μ[且水平配向材料的混合溶 液為20μί此3種模式來製作配向膜。另外，作為對向基板係預先準備 利用習知方法形成垂直配向膜的基板，使該基板與具有藉由電喷灑堆 積法形成的配向臈的基板相對向地貼合。 利用偏光顯微鏡對所製作的液晶元件進行觀察，結果在對形成有 基底配向膜而製作的基板進行電喷灑堆積法的方法中，約2〇〇μιη左右 的區域中出現了雙軸性，則在實施例2的方法中則約5〇μηι左右的區 域中出現了雙軸性。即’藉由分時散佈各混合溶液，能夠在更細小的 區域控制配向。具體而言係形成5μιη左右的微小區域。又，在各嗔射 12 201222104 10的散佈和利用另-個喷射裝w 地進订利用其中一個喷射裝置 裝置㈣合溶㈣散佈量„有效。= 佈時^慢地減少（遞減)各個 =緩地減少絕對量時’較能以更高的 向t^(%)與由配V is brushed onto the substrate on the opposite side of the main sealing material. The upper and lower substrates are laminated at predetermined positions to form liquid crystal cells, and the sealant is cured by heat treatment in a pressed state. Here, thermal curing (150 °c calcination) was carried out by a hot press method. Next, a mark is drawn on the glass by a cutting device, and a strip shape (unit to be injected) is divided by a breaking step. A liquid crystal material is injected into the liquid crystal cell by a vacuum injection method. As a liquid crystal material, a representative liquid crystal material 5CB (manufactured by Merck Co., Ltd.) having a positive dielectric anisotropy was used. Thereafter, the injection port is sealed with an end seal material. In order to make the alignment uniform, the liquid crystal cell is heated to a temperature higher than the phase transition temperature of the liquid crystal. Here, the oven is used for 6 inches.热处理 Heat treatment for 30 minutes. The portion where the cut portion of the device to be cut is cut off is divided into individual liquid crystal cells. The liquid crystal cell is washed with a cleaning agent, an organic solvent, or the like to wash off the liquid crystal and the powder at the time of chamfering. Thereafter, the polarizing plate cut into a predetermined size is pasted at a predetermined angle. Thus, a mixed liquid crystal element was produced and the alignment state was observed by a polarizing microscope. In addition, as a sample liquid crystal cell for pretilt angle measurement, a structure in which substrates are bonded to each other is formed by forming an alignment film by an electric spray deposition method, and then performing a rubbing alignment process by zero magnetic field The pretilt and angle were measured by the null method. The liquid crystal cell produced was observed under a crossed Nicols state using a polarizing microscope, and its morphology is shown in Fig. 5. Fig. 5(A) is an observation image when the mixing ratio of the vertical alignment material and the solvent is 2 〇 8 ,, and Fig. 5 (B) is an observation image when the mixing ratio of the vertical alignment material and the solvent is υ99. In the case of a liquid crystal element dispersed by a conventional method, the topography of the vertical alignment film area having a diameter of several micrometers to several tens of micrometers is observed, but in the present embodiment: the liquid crystal element is observed to be 1 μm or less. The extent of the area of high pretilt angle. Therefore, even if the accumulation occurs, the uniform distribution of the horizontal alignment material and the vertical alignment material can be maintained. Further, as a result of the thief of the pre-(10), as a result of the sixth aspect, the liquid crystal element having a small amount of the vertical alignment material has a lower pretilt angle than the liquid crystal element having a larger amount of the vertical alignment material contained in the dispersed solution. The reason for this is that the shape of the substrate surface causes a value of $2. (Example 2) As Example 2, a method of alternately spreading different materials at different times was carried out. The same procedure as in Example 使用 was used except for the step of forming the alignment enthalpy. I: The syringe of one of the injection devices 10 is filled with a horizontal alignment material (mixed solution with the above-mentioned examples [, 11 201222104 · 4wt%) and * agent (H hospital and (4)), in another - SE-1211 . 4 ΙΓΛ Shot/medium filled vertical alignment material (mixed solution of the same installation 10, 'factory\〇广谷剂(二气甲烧和γ_丁内醋) with the above example 1' by each jet thunder rider Β Specifically, each mixed solution is dispersed. Specifically, the microcomputers 23, 21, 22 are selectively controlled to be in a conductive state for a predetermined time ratio, by means of a power source 20 for each of the spraying devices 1G, 11. The needle is applied with a voltage. The following human cycle (dispersion period) is set to 1 G seconds: the Xiang spray device 1G spreads a mixed solution containing 7, 'alignment material, and the vertical alignment material t mixed solution is sprayed by the spray device (10). The ratio of the dispersion time of the mixed solution containing the horizontal alignment material in the cycle, the interval between the 3 and the 3, and the vertical alignment material is set to 8:2, & 4, 4:6, 2:8. The spreading time is 15 minutes (9 () cycles). In addition, each spray The distance h between the needles of the devices 10 and 11 and the substrate 100 was set to 6 cm. 6.5 kV of direct current was applied to each needle, and each mixed solution was spread at a speed of 70 nL (four) in the wrong direction by a needle having an outer diameter of 75 。. The ratio of the size of each of the horizontal alignment film and the vertical alignment film is fixed to 20:80 by the mixing ratio of the horizontal alignment material and the solvent, and the mixing ratio of the vertical alignment material to the solvent is changed to 2〇:8〇, 1:99 The pre-sintering of each alignment material is carried out at 1 G for 1 G minutes under TC, and for 6 minutes at rc under formal calcination. The substrate is subjected to rubbing alignment treatment. In addition, the mixture of the vertical alignment material and the solvent is mixed. The ratio is 1:9, the mixing ratio of the horizontal alignment material to the solvent is 1:4, and for the dispersion amount, the mixed solution of the vertical alignment material and the horizontal alignment material is 20 μί, and the mixed solution of the vertical alignment material is 2 〇μΙν and the mixed solution of the horizontal alignment material is 30 μί, the mixed solution of the vertical alignment material is 3 μμ [and the mixed solution of the horizontal alignment material is 20 μί 3 patterns to prepare the alignment film. In addition, as the opposite substrate system The substrate on which the vertical alignment film is formed by a conventional method is prepared in advance, and the substrate is bonded to the substrate having the alignment yoke formed by the electrospray deposition method. The liquid crystal element thus produced is observed by a polarizing microscope. In the method of performing the electrospray deposition method on the substrate formed by forming the underlying alignment film, biaxiality occurs in a region of about 2 〇〇μηη, and about 5 〇μηι in the method of the second embodiment. Biaxiality occurs in the region. That is, by arranging the respective mixed solutions in a time-sharing manner, the alignment can be controlled in a finer region. Specifically, a minute region of about 5 μm is formed. In addition, in the distribution of each shot 12 201222104 10 and the use of another spray device w, one of the spray device devices (4) is used to dissolve (4) the amount of dispersion „effective. = cloth time ^ slowly decrease (decrease) each = slow When the ground is reduced by an absolute amount, it can be used with a higher degree of t^(%)
料的散佈時_越大則預傾角越切趨勢。另;;可知表 〜60。左右的較大預。水平配向材料與垂直 J 間比下的液晶Μ的偏光顯微鏡照片見第8圖。第8圖2=== =為8:2時的偏光顯微鏡照m _)是散佈時間比為6:4時的偏 先顯微鏡照片’第8圖(C)是散佈時間比為4:6時的偏光顯微鏡照片， 第8圖(D)是散料間比為2:8時的偏細微鏡照片。通常認為垂直配 向材料的比例愈尚則配向控制愈困難，但由顯微鏡照片可知，在實施 例的液晶元件中無論以任何比例均為均勻的配向狀態。另外，在外觀 ===:=:反映出垂直配向材料的比例愈高 (第2實施方式） 第9圖是示出第2實施方式之配向膜的製造裝置的結構的示意 圖。第9圖所示的配向膜的製造裝置具有兩個喷射裝置11〇、m、基 板保持架(基板固定裝置)112和電壓施加裝置120、121，所述兩個喷射 裝置110、111具有用於在内部保持配向膜液的圓筒狀等的注射器（筒） 和設置於此等注射器的一端的中空的微小針，所述基板保持架（基板固 定裝置)112用於保持基板ιοί，基板ιοί為藉由此等喷射裝置uo、m 形成配向膜的物件，所述電壓施加裝置120、121用.於對各噴射裝置 110、111施加電壓。如圖所示，喷射裝置（第1噴射裝置)110和喷射裝 置（第2喷射裝置)111作為不同的裝置相互分離而配置。即，喷射裝置 110、111作為用於不同步驟的裝置而設置於不同的處所。電壓施加裝 置（第1電壓施加裝置)120與喷射裝置110連接，在第1材料液與基板 13 201222104 101之間施加電壓。電壓施加裝置（第2電壓施加裝置)121 m連接，在第2材料液與基板101之間施加電壓。基板保持架H 用於保持基板1G1，使基板1G1選擇性地向與喷射裝置ug和噴射 111的任-個對應的位置移動，並且使得該基板1G1的— 裝置110或喷射裝置U1的噴射方向。 朝Θ噴射 如圖所示，適當地確保喷射裝置110的針與基板101的距離(例如 數楚米左，），在喷射裝置11G的針與基板1G1之間使用電壓施加裝 120施加同電壓⑽如數kv的直流電壓），同時將注射器内的配向膜液 (第1材舰)供給到針的前端。同樣地，適當地確保噴射裝置⑴的 與基板101的距離(例如數餐米左右），在喷射裝置m的針與基板101 之間使=電壓施加裝置121施加高電壓(例如數〜的直流電壓）， 將注射器内的配向膜液(第2材料液)供給到針的前端。此時，例如如圖 所不預先將基板1G1和基板保持架112接地(基準電位），對各喷射裝置 110、111的針提供與基板101相比相對較高的 ，反)。由此，從各喷射裝置110、⑴的針排出的配向== π正電位的狀態的液體顆粒。帶該電位的液體顆粒發生電排斥的同時 ，·田·Ι地刀裂、擴散，开》成霧狀的微小液滴（霧狀體）^該微 負電的基板101吸引，附著於基板101上。魏，藉由對到達基== 的微小液滴適當進行熱處理等而成膜（固化），從而得到包含多個微細的 配向膜片而構成的配向膜。 、逆樣在第2實施方式中，作為配向膜形成的原理也利用電喷灑堆 積法。此處’為了徹底地散佈㈣，則趙向酿的減低為佳，因 此較佳利用丙酮等溶劑稀釋配向材料來調製配向膜液(與第1實施方式 相同）。另外，關於電噴灑堆積法中的較佳的散佈電壓，也與上述第工 實施方式相同（參照第2圖）。 如第9圖所示，準備兩個喷射裝置11〇、m，向各喷射裝置u〇、 111中分別導入性質不同的配向膜液(配向材料），從而可以使形成了各 =向，液的微小區域(數百奈米至數十微米左右)混雜形成。由此，可以 付到I5為止難以達成的複合液晶配向狀態。關於利用各喷射裝置 110、111散佈配向膜液的時間點，首先利用喷射裝置u〇進行配向膜 201222104 液的散佈，其後將基板101向與喷射裝置111對應的位置移動，隨後 利用喷射裝置111進行配向膜液的散佈。 第10圖為對藉由第2實施方式的電噴灑堆積法形成的配向膜的結 構進行說明的圖。如第10圖所示，可認為在基板上得到了某種配向膜 液A堆積而成的配向膜區域(配向膜片）和另一種配向膜液b堆積而成 的配向膜區域(配向膜片）隨機混合的狀態的配向膜。即，得到多個配向 膜區域在基板上以平面方式分散且三維立體地堆積而成的結構的配向 膜。更詳細地說，配向膜的結構為··其後堆積的配向膜液B的配向膜 區域(圖中符號B) —部分在之前堆積的配向膜液a的配向膜區域(圖中 符號A)上堆積。利用電噴灑堆積法散佈多種配向膜液可獲得即使各配 向膜區域堆積，區域比例也不發生變化的效果。關於能夠適用藉由此 種第2實施方式的電喷灑堆積法形成的配向膜的液晶元件，係與上述 第1實施方式相同（參照第4圖）。 (實施例3) 準備形成有ITO等透明電極的1對玻璃基板(IT〇的厚度：15〇〇 埃、玻璃板厚：0.7mm、玻璃材質：無域玻璃）。對此等基板進行清洗， 使用通常的光微影步驟進行IT〇的圖案化。在此，作為IT〇蝕刻方法， 使用濕式蝕刻（三氯化鐵）。 接下來，在將ΙΤΟ圖案化後的玻璃基板上，利用電喷灑堆積法進 行配向膜液(配向材料)的散佈。預先在其中一個喷射裝置11〇的注射器 中填充水平配向材料（日產化學工業股份有限公司製造ρι·Α : 4wt%)和 溶劑(二氣甲烷)的混合溶液，在另一個喷射裝置111的注射器中填充垂 直配向材料（曰產化學工業股份有限公司製造SE-1211 : 4wt%)和溶劑 (-氣甲烧)的混合溶液，首先利用喷射裝置11〇散佈混合溶液，其後移 動玻璃基板’接下來利用喷射裝置111散佈混合溶液。又，作為水平 配向材料使用的PLA的化學結構與上述第i實施方式相同。 此時，將各噴射裝置11〇、111的針與基板101之間的距離h設為 6cm ’對各針施加7kv的直流電壓（電場強度：i，利用外徑為 75μηι的針在紹直方向以㈣速度分別散佈佩各溶液。 在此，為了控制水平配向膜與垂直配向膜的各區域的尺寸之比， 15 201222104 將喷射裝置110和喷射裝置ill各個中的混合溶液的喷射量作為參數 使用。本實施例中，利用喷射裝置110散佈的混合溶液的量設定為等 於或多於玻璃基板的整個面被所散佈的混合溶液覆蓋的量。另外，其 後利用喷射裝置111散佈的混合溶液的量係設定為由散佈玻璃基板的 總面積的1/2左右的混合溶液所覆蓋的量。即，本實施例中將利用第j 臺喷射裝置110散佈的混合溶液的量與利用第2臺噴射裝置1U散佈 的混合溶液的量的比例設為1:1。 又，上述比例為一個例子，利用第丨臺喷射裝置11〇散佈的混合 溶液的量的比例低時則不在此限。例如，將比例設為1:9時，玻璃基 板上的1/2左右以上利用第1臺喷射裝置11〇進行混合溶液的散佈即 可；將比例設為2:8時，玻璃基板的2/3左右以上利用第1臺喷射裝置 110進行混合溶液的散佈即可。即，以下述方式設定混合溶液的散佈量 即可·在利用第2臺喷射裝置ill散佈混合溶液結束時，基板上的整 個面沒有未散佈混合溶液的部分。與此相對，在利用第2臺喷射裝置 111散佈混合溶液時，較佳以高精度控制其散佈量。具體地說，該散佈 量根據欲形成配向膜區域的面積與基板(或者基板保持架112)的面積 之比、混合溶液中含有的配向材料的固體成分濃度等而決定。通常， 液晶分子的配向狀態受到與液晶分子直接接觸的配向獏的性質的強列 影響，因此’對於液晶分子的配向狀態，藉由第2臺噴射裝置U1 = 佈的混合溶液所形成的配向膜區域，比藉由第i臺噴射裝置110散佈 的混合溶液所形成的配向膜區域較處於主導地位。 接下來’各配向材料的預煅燒係在l〇〇°C下進行10分鐘，正式把 燒則在25(TC下進行60分鐘。對該基板實施摩擦配向處理。另外二= 為對向基板係準備利用習知方法預先形成有垂直配向臈的基板，使該 基板與具有藉由電喷灑堆積法形成的配向膜的基板對向而二合。為 將基板間的距離(液晶胞厚)保持一定’在一側的基板面上利用乾式& 法散佈間隙控制材料《間隙材料係使用粒徑為6微米的塑膠也可 以使用ShinshikyU(商品名）。在另一基板上形成主密封圖案(和導通 料圖案）。此處的印刷係使用網版印刷法，也可以使用點膠機等六 劑係使用熱固性密封劑，也可以使用光固性密封劑、光/熱併用型 201222104 該密封劑中含有數個％之粒徑為6微米的玻璃纖維。另外在預 置印：包含金珠等的導通材料。在此，在密封劑中加入上述玻 地、”’以3有數個％之各球粒㈣該玻璃纖維的粒徑約大丨微米的 :物質為導通材料’進行網版印刷。導通材料圖案也可以印刷到 料之相反_基板上。將上下基板在預定的位置疊合而製成 轉㈣顧化。在關雜壓法進行 ’ 1㈣㈣置在玻璃上㈣痕’藉由分切步驟分割成長條 ^偏人之單位）。利用真空注人法向該液晶胞中注人液晶材料。作為 :斗係使用介電各向異性為正值的代表性液晶材料冗華erck公 其後’利用末端密封材料將注人口密封。為了使配向一致，將 八^加熱到液晶的相變溫度以上。在此利用烘箱以60。(：熱處理30 利Γ^被切割裝置劃出痕的部分斷開而小型分割成個別的液晶胞。 ::潔劑：有，劑等對液晶胞進行清洗，洗掉液晶和倒角時的粉 成型^後a以預疋的角度黏貼切割成預定大小的偏光板。由此製作混 為箱/^30元件’並彻偏光顯微鏡對配向狀態進行觀察。另外，作 該其/’則疋用白勺試樣液晶月包’係製作基板彼此貼合而成的構成物， 於使用電喷^堆積法形成配向膜後實施摩擦配向處理，並藉由 嵫％零位法測定預傾角。 無不^於^作的液晶元件的配向狀態進行了觀察，結果目視確認出 配命从!!均勻配向狀態。另外，在偏光顯微鏡中觀察到由附著有垂直 另二材Ξ:直徑為，微米〜數十微米的垂直配向膜區域覆蓋的情況。 5()°左右°g卩’可得到以往難以具有5G°高預傾角的均 9配向狀態的液晶元件。 晶元件，以上各實施方式以及各實施例，能夠以高角度任意地控制液 上、85。以的預傾角°特別是在通常的液晶用配向膜中不易獲得1〇。以 用市隹X下的預傾角，惟根據各實施方式以及各實施例，能夠直接利 響廄r姓履阳配向的錨定強度高，因而具有元件的可靠性高、 •另疋下降）快的優點。特別是，適合於利用需要高預傾角的 17 201222104 OCB(光學簡雙折射)模式、反肖τ_ 列)模式等的液晶元件。 向列)模式、STN(超扭轉向 另外，根據各實施方式以及各實施例 本的結構獲得可表現出高預傾角的配向膜了、=用較為簡單且低成 另外，在分時交替地散佈水平配向材 置 在不同步驟中散料，散佈條件的自由垂直配向㈣時，或者 性更優異的優點。另外，同時散佈水平酉:向二：得到預傾角的控制 由於各混合溶液的帶電電位相同’因而 ^和垂直配向材料時， 寬範圍内形成均質的配向膜，但藉由 j叫合’可能難以在較 在較寬範圍_成均f的配向膜。 ％不同步驟中散佈，可以 又，本發明不限於上述内容，可以在 種變形來實施。例如，在上述實施方 發月的主旨範圍内進行各 散佈的配向材料為兩種的情況進行了 ^於彻電堆積法 配向材料。另外，水平配向材料和了垂=^；可以散们種以上的 實施例的散佈順序，也可以是相反的=向㈣的散佈順序不限定於 【圖式簡單說明】 第1圖是示出第1實施方式之配向膜 第2圖是對電喷_積法中散佈電壓進行 m的結構的示意圖； 第3圖是對藉由第！實施方式的電 ° 、 ’ 構進行說_圖； 抑堆積法形成的配向膜的結 第4圖是示意性示出第i實施方式的液晶 圖；第頂是示出藉由偏光顯微鏡觀察實施例丨的液;=的情況的 實施T的液晶元件的預傾角的測定結果的圖； 第7圖疋散佈週射垂直配向材料的 現出的預傾角的_、圖； 間比與H由配向膜顯 液曰水平配向㈣與^直配树料的各㈣時間比下的 液曰日7L件的偏先顯微鏡照片的圖； 第9圖是示出第2實施方式之配向膜的製造裝置的結構的示意 18 201222104 圖；以及 第10圖是對藉由第2實施方式的電噴灑堆積法形成的配向膜的結 構進行說明的圖。 【主要元件符號說明】 10、11、110、111 噴射裝置 12、 112基板保持架(基板固定裝置) 13、 120、121 電壓施加裝置 20 高.壓直流電源 21、22高電壓繼電器 23 微電腦 51 第1基板 52 第1電極 53、57配向膜 55 第2基板 56 第2電極 59 液晶層 61 第1偏光板 62 第2偏光板 100、101 基板 t、h 距離 A、B配向膜液 19When the spread of the material is larger, the pretilt angle becomes more and more tendency. Another; can know the table ~ 60. Larger pre-orders. A polarizing microscope photograph of the liquid crystal germanium at a ratio between the horizontal alignment material and the vertical J is shown in Fig. 8. Figure 8 === = Polarized microscope at 8:2 m _) is a partial microscope photo when the dispersion time ratio is 6:4. Figure 8 (C) is when the dispersion time ratio is 4:6. The polarizing microscope photograph, Fig. 8 (D) is a photograph of a fine micromirror when the ratio between the bulk materials is 2:8. It is generally considered that the more the ratio of the vertical alignment material is, the more difficult the alignment control is. However, it is understood from the micrograph that the liquid crystal element of the embodiment has a uniform alignment state in any ratio. In addition, the higher the ratio of the vertical alignment material is reflected in the appearance (= second embodiment). FIG. 9 is a schematic view showing the configuration of the apparatus for manufacturing the alignment film according to the second embodiment. The manufacturing apparatus of the alignment film shown in Fig. 9 has two ejection devices 11A, m, a substrate holder (substrate fixing device) 112, and voltage application devices 120, 121 having the same for the ejection devices 110, 111. A syringe (cylinder) such as a cylindrical shape in which an alignment membrane liquid is held inside, and a hollow microneedle provided at one end of the syringe, the substrate holder (substrate fixing device) 112 is for holding the substrate ιοί, and the substrate ιοί is The objects of the alignment film are formed by the ejection devices uo, m, which apply voltages to the respective ejection devices 110, 111. As shown in the figure, the injection device (first injection device) 110 and the injection device (second injection device) 111 are disposed apart from each other as different devices. That is, the ejection devices 110, 111 are provided in different locations as devices for different steps. The voltage application device (first voltage application device) 120 is connected to the ejection device 110, and a voltage is applied between the first material liquid and the substrate 13 201222104 101. A voltage application device (second voltage application device) 121 m is connected, and a voltage is applied between the second material liquid and the substrate 101. The substrate holder H is for holding the substrate 1G1 such that the substrate 1G1 is selectively moved to a position corresponding to any one of the ejection device ug and the ejection 111, and the ejection direction of the device 1G1 - the device 110 or the ejection device U1. As shown in the figure, the distance between the needle of the ejection device 110 and the substrate 101 is appropriately ensured (for example, the number is left), and the voltage is applied between the needle of the ejection device 11G and the substrate 1G1 using the voltage application device 120 (10). For example, the DC voltage of kv is supplied to the tip of the needle at the same time as the alignment membrane liquid (the first material ship) in the syringe. Similarly, the distance from the substrate 101 (for example, several meals) is appropriately ensured, and the voltage application device 121 is applied with a high voltage (for example, a DC voltage of several to ～ between the needle of the ejection device m and the substrate 101). ), the alignment film liquid (the second material liquid) in the syringe is supplied to the tip end of the needle. At this time, for example, the substrate 1G1 and the substrate holder 112 are grounded (reference potential) in advance, and the needles of the respective ejection devices 110 and 111 are provided relatively higher than the substrate 101, and vice versa. Thereby, the liquid particles discharged from the respective ejection devices 110 and (1) are in the state of the alignment == π positive potential. When the liquid particles having the electric potential are electrically repelled, the surface of the liquid crystal is broken and diffused, and the droplets are formed into a mist (a mist). The micro-negative substrate 101 is attracted and adhered to the substrate 101. . Wei, by forming a film (curing) by appropriately heat-treating a fine droplet of the reaching base ==, thereby obtaining an alignment film comprising a plurality of fine alignment films. In the second embodiment, the electrospraying method is also used as the principle of formation of the alignment film. Here, in order to completely disperse (4), it is preferable to reduce the amount of Zhao Xiang brewing. Therefore, it is preferred to dilute the alignment material with a solvent such as acetone to prepare an alignment film liquid (the same as in the first embodiment). Further, the preferred spreading voltage in the electric spray deposition method is also the same as in the above-described first embodiment (see Fig. 2). As shown in Fig. 9, two injection devices 11A and m are prepared, and an alignment film liquid (alignment material) having different properties is introduced into each of the injection devices u and 111, so that each of the liquid crystals can be formed. Small areas (hundreds of nanometers to tens of microns) are mixed. As a result, it is possible to pay a composite liquid crystal alignment state that is difficult to achieve until I5. When the alignment film liquid is dispersed by each of the ejection devices 110 and 111, first, the liquid of the alignment film 201222104 is dispersed by the ejection device u, and then the substrate 101 is moved to a position corresponding to the ejection device 111, and then the ejection device 111 is used. The dispersion of the alignment film liquid is performed. Fig. 10 is a view for explaining the structure of an alignment film formed by the electrospray deposition method of the second embodiment. As shown in Fig. 10, it is considered that an alignment film region (alignment film) in which a certain alignment film liquid A is deposited on the substrate and an alignment film region in which another alignment film liquid b is deposited (alignment film) An alignment film in a state of random mixing. That is, an alignment film having a structure in which a plurality of alignment film regions are dispersed in a plane on the substrate and three-dimensionally stacked is obtained. More specifically, the structure of the alignment film is the alignment film region (symbol B in the figure) of the alignment film liquid B which is deposited later, and the alignment film region of the alignment film liquid a which is deposited before (symbol A in the figure) Stacked up. By dispersing a plurality of alignment film liquids by the electrospray deposition method, it is possible to obtain an effect that the area ratio does not change even if the respective alignment film regions are deposited. The liquid crystal element to which the alignment film formed by the electrospray deposition method of the second embodiment can be applied is the same as that of the first embodiment (see Fig. 4). (Example 3) A pair of glass substrates on which a transparent electrode such as ITO was formed (thickness of IT〇: 15 Å, thickness of glass plate: 0.7 mm, glass material: non-domain glass) was prepared. These substrates are cleaned, and the IT 〇 is patterned using a usual photolithography step. Here, as the IT 〇 etching method, wet etching (ferric chloride) is used. Next, the dispersion of the alignment film liquid (alignment material) was carried out by electrospray deposition on the glass substrate on which the ruthenium was patterned. A syringe in which one of the injection devices 11 is preliminarily filled with a mixed solution of a horizontal alignment material (manufactured by Nissan Chemical Industries Co., Ltd.: 4 wt%) and a solvent (diqi methane) in a syringe of another ejection device 111 Filling a mixed solution of a vertical alignment material (SE-1211: 4wt% manufactured by Seiko Chemical Industry Co., Ltd.) and a solvent (-gas-fired), firstly dispersing the mixed solution by means of a spraying device 11 and then moving the glass substrate. The mixed solution is dispersed by the spraying device 111. Further, the chemical structure of PLA used as a horizontal alignment material is the same as that of the above-described first embodiment. At this time, the distance h between the needles of the respective ejecting apparatuses 11A and 111 and the substrate 101 was set to 6 cm. A DC voltage of 7 kV was applied to each of the needles (electric field strength: i, and the needle having an outer diameter of 75 μm was used in the straight direction. The respective solutions are dispersed at a speed of (iv). Here, in order to control the ratio of the sizes of the horizontal alignment film and the respective regions of the vertical alignment film, 15 201222104 uses the injection amount of the mixed solution in each of the ejection device 110 and the ejection device ill as a parameter. In the present embodiment, the amount of the mixed solution dispersed by the spraying device 110 is set to be equal to or more than the amount of the entire surface of the glass substrate covered by the mixed solution dispersed. Further, the mixed solution which is thereafter dispersed by the spraying device 111 is used. The amount is set to an amount covered by a mixed solution of about 1/2 of the total area of the glass substrate. That is, in the present embodiment, the amount of the mixed solution dispersed by the jth injection device 110 is used and the second injection is performed. The ratio of the amount of the mixed solution dispersed in the apparatus 1U is set to 1:1. Further, the above ratio is an example, and the ratio of the amount of the mixed solution dispersed by the second jetting device 11 is low. For example, when the ratio is 1:9, the dispersion of the mixed solution may be performed by the first injection device 11 1/2 or more on the glass substrate; when the ratio is 2:8, The dispersion of the mixed solution may be performed by the first injection device 110 at about 2/3 or more of the glass substrate. That is, the amount of the mixed solution to be dispersed may be set as follows. When the second solution ejecting device ill is used to spread the mixed solution, In the case where the mixed solution is dispersed by the second injection device 111, the amount of dispersion is preferably controlled with high precision. Specifically, the amount of dispersion is determined according to the desire. The ratio of the area of the alignment film region to the area of the substrate (or the substrate holder 112), the solid content concentration of the alignment material contained in the mixed solution, and the like are determined. Usually, the alignment state of the liquid crystal molecules is directly in contact with the liquid crystal molecules. The strong influence of the nature of the ruthenium, therefore, the alignment film region formed by the mixed solution of the second spray device U1 = cloth is used for the alignment state of the liquid crystal molecules. The alignment film area formed by the mixed solution dispersed by the injecting device 110 is in a dominant position. Next, the pre-calcination of each of the alignment materials is performed at 10 ° C for 10 minutes, and the burning is performed at 25 (TC). The substrate was subjected to a rubbing alignment treatment, and the second substrate was prepared by preparing a substrate having a vertical alignment enthalpy in advance by a conventional method, and the substrate was provided with an alignment film formed by an electric spray deposition method. The substrate is aligned in the opposite direction. In order to keep the distance between the substrates (the liquid crystal cell thickness) constant, the gap control material is spread by the dry & method on the substrate surface of one side. The gap material is a plastic having a particle diameter of 6 μm. It is also possible to use ShinshikyU (trade name). A main seal pattern (and a conductive material pattern) is formed on another substrate. The printing method here uses a screen printing method, and it is also possible to use a thermosetting sealant in six doses such as a dispenser, or a photocurable sealant or a photo/heat combination type 201222104. The sealant contains several %. Glass fiber with a particle size of 6 microns. In addition, it is pre-printed: a conductive material containing gold beads or the like. Here, the above-mentioned glassy surface is added to the sealant, and "the particle diameter of the glass fiber is about tens of micrometers: the material is a conductive material" for screen printing. It can be printed on the opposite side of the substrate. The upper and lower substrates are superposed at a predetermined position to make a turn (four). In the close-mixing method, '1 (four) (four) is placed on the glass (four) mark 'by dividing the growth bar by the slitting step ^Personal unit). The liquid crystal material is injected into the liquid crystal cell by a vacuum injection method. As a representative liquid crystal material with a positive dielectric anisotropy, the block liquid is used for the erck. The material will be sealed to the population. In order to make the alignment uniform, the heating temperature is above the phase transition temperature of the liquid crystal. Here, the oven is used for 60. (: Heat treatment 30) The portion of the cut by the cutting device is broken and the small segmentation is performed. Into the individual liquid crystal cells. :: Cleaner: There are, agents, etc. to clean the liquid crystal cell, wash off the liquid crystal and the powder molding when chamfering ^ after a pre-twisted angle is cut into a polarizing plate of a predetermined size. Make a mix of boxes / ^ 30 components ' and The alignment state was observed by a polarizing microscope, and the composition in which the substrate was bonded to each other by using the sample liquid crystal package was used to form an alignment film by an electrospray deposition method. The rubbing alignment treatment was carried out, and the pretilt angle was measured by the 嵫% zero method. The alignment state of the liquid crystal element was observed, and the result was visually confirmed to be in the uniform alignment state. In addition, in the polarizing microscope It is observed that the vertical alignment film region is attached with a vertical other material: a diameter of micrometers to several tens of micrometers. 5()°°°g卩' can be obtained in the past, which is difficult to have a high pretilt angle of 5G°. Liquid crystal element in the alignment state. In the above embodiments and each of the above embodiments, the liquid crystal can be arbitrarily controlled at a high angle of 85. The pretilt angle is particularly difficult to obtain in a normal liquid crystal alignment film. In order to use the pretilt angle under the market X, according to the respective embodiments and the respective embodiments, the anchoring strength of the 履r surname of the 阳r can be directly improved, and thus the reliability of the component is high, and the other is lowered. In particular, it is suitable for liquid crystal elements such as 17 201222104 OCB (optical simple birefringence) mode, anti-short τ_column mode, etc., which require a high pretilt angle. Nematic mode, STN (super-twisting to another, According to the embodiments and the structures of the respective embodiments, an alignment film capable of exhibiting a high pretilt angle is obtained, = is simpler and lower, and the horizontal alignment material is alternately dispersed in a time division, and the bulk material is placed in different steps. The condition of the free vertical alignment (four), or the superiority of the superiority. In addition, the horizontal spread 酉: to two: the pre-tilt control is obtained because the charged potential of each mixed solution is the same 'and thus the vertical alignment material, a wide range Forming a homogeneous alignment film, but it may be difficult to spread in an aligning film which is more widely distributed in a wider range of %. In different steps, it may be further, the present invention is not limited to the above, and may be deformed in kind. Implementation. For example, in the case of the above-mentioned embodiment, the distribution of the aligning materials in two types is carried out in the case of the electroplating method. In addition, the horizontal alignment material and the vertical = ^; may be scattered or more than the embodiment of the order of dispersion, may also be the opposite = the direction of (four) is not limited to [schematic description] Figure 1 shows 1 Alignment film of the embodiment Fig. 2 is a schematic view showing a structure in which the dispersion voltage is m in the EFI_product method; The fourth embodiment of the junction of the alignment film formed by the deposition method is a liquid crystal diagram schematically showing the i-th embodiment, and the top is a view of the embodiment observed by a polarizing microscope. Fig. 7 is a diagram showing the results of measurement of the pretilt angle of the liquid crystal element of the case where T is performed; Fig. 7 is a diagram showing the appearance of the pretilt angle of the circumferentially perpendicularly aligning material, and the ratio of H to the film by the alignment film Fig. 9 is a view showing a partial microscope photograph of a liquid helium day 7L of each of the four (4) time ratios of the liquid sputum horizontal alignment (4) and the straight tree material; and Fig. 9 is a view showing the structure of the aligning film manufacturing apparatus of the second embodiment; The diagrams of 201222104 and Fig. 10 are diagrams for explaining the structure of the alignment film formed by the electrospray deposition method of the second embodiment. [Description of main component symbols] 10, 11, 110, 111 Spraying device 12, 112 substrate holder (substrate fixing device) 13, 120, 121 Voltage applying device 20 High voltage DC power supply 21, 22 High voltage relay 23 Microcomputer 51 1 substrate 52 first electrode 53, 57 alignment film 55 second substrate 56 second electrode 59 liquid crystal layer 61 first polarizing plate 62 second polarizing plate 100, 101 substrate t, h distance A, B alignment film liquid 19