TW200921278A - Negative-working resist for formation of protrusions for liquid crystal alignment - Google Patents

Abstract

This invention provides a negative-working resist for the formation of protrusions for liquid crystal alignment, which can realize the formation of protrusions for regulating liquid crystal alignment in a liquid crystal display device and can realize the prevention of seizing of a liquid crystal in a produced liquid crystal display device. The negative-working resist contains an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator and is used for the formation of protrusions for liquid crystal alignment in an MVA liquid crystal display device. The polymerizable monomer is a negative-working resist containing a novolac epoxy (meth)acrylate for the formation of protrusions for liquid crystal alignment.

Description

200921278 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種液晶配向用突起形成用負型抗蝕 劑，其可形成用以對液晶顯示裝置之液晶配向進行控制的 突起，且可防止所製造之液晶顯示裝置產生液晶殘像現象。 【先前技術】 液晶顯示裝置具有下述結構：於形成有彩色濾光片、 黑色矩陣、線狀透明電極、配向膜等的兩張基板間，注入 有在與該基板垂直之方向或平行之方向上配向之液晶。在 不施加電場的狀態下，注入至基板間之液晶係在與基板垂 直之方向或平行之方向上配向等，可施加電場而使配向狀 態變化，從而可調整透過液晶之光的透過量。 液晶顯示裝置與先前使用布朗管的顯示裝置相比，由 於薄型且消耗電力少，故被實用化為用於大畫面電視的液 曰曰電視。然而，液晶顯示元件與使用布朗管之顯示裝置相 比，卻有視角狹窄之問題。伴隨大畫面液晶電視之普及， 而強烈要求對視角進行改良。 ▲作為改善液晶顯示裝置之視角的方法，提出有下述所 明之 MVA (Multid〇main Vertical Alignmen〇 方式，亦即 於透明電極上形成弓形（areh)的突起，利用該突起之斜度 (si，）將液晶局部地傾斜’從而於_像素内使液晶多方 向地分割.配向。 作為形成上述於透明電極上所形成之弓形突起的方 有如下方法.藉由使用正型抗則彳之光微影方法， 5 200921278 來形成剖面大致呈矩形的突起，其後，加熱該突起而使其 炼焊㈣叫，藉此形成弓形。用於在透明電極上形成弓形 f起^正型抗㈣，例如於專利文獻1中，揭示有含有二 1氮萘鳊（naphthoquinone diazide)化合物與具有羥基之包 含特定結構單元之共聚物的正型抗蝕劑。 然而，使用正型抗韻劑來於透明基板上形《突起時， 需要使其加熱熔焊而形成為弓形的步驟，故由於所形成之 圖案的底部寬度或加熱溫度而導致有所獲得之突起的弓形 的高度、與基板接觸之角度等不同之問題。若突起之高度 及角度不Θ，則會發生液晶的配向不均，甚至發生顯示不 均。又’專利文獻1所揭示之正型抗㈣，存在 . #，、、 使未反應的2墨氮萘藏與具有經基之包含特定結構單元 的共聚物進行偶合反應，從而使抗姓㈣紅之問題。又， 專利文獻1所揭不之正型抗钱劑，由於二疊1蔡酿之光分 解中所生成的鹼溶性羧酸’而表現出曝光部與未曝光部於 驗性顯影液中之溶解性的差。因此，若與負型錢劑相比， 則正型抗钱劑的顯影條件之範圍狹窄，難以對由空氣中的 氧所引起的顯影劣化等顯影狀態進行管理。並且，液晶顯 示裝置之製造過程中，了包含於透明電極上形成突起之 步驟以外，，亦包含各種使用抗蚀劑的㈣，但該等步驟中 之大部分係使用負型抗韻劑。故僅於形成突起之步驟中使 用正型抗蝕劑會導致製造步驟繁雜化。 對此，專利文獻2揭示有使用以驗溶性樹脂、光聚合 起始劑及光聚合性單體為主成分之負型抗餘劑來於電極上 200921278 又置犬起x⑨專利文獻3，係揭示有一種以乙稀性不飽 和化合物、光聚合起始劑、鹼溶性樹脂為主成分之感光性 树月曰組成物’來作為液晶分割配向用突起形成用之負型抗 餘劑 < 為可藉由使用該等負型抗#劑*實現液晶顯示装 置之製造的簡單化。 然而使用先前負型抗蝕劑來形成液晶配向用突起之 液曰曰顯裝置’若長時間進行顯示，則有在形成有液晶配 向用犬起之。Ρ刀產生液晶的異常配向，從而產生顯示影像 殘留之液晶殘像現象的問題。 [專利文獻1]曰本特開平7_92689號公報 [專利文獻2]日本特開2003-33001 1號公報 [專利文獻3]日本特開2006-1 1359號公報 【發明内容】 本發明之目的，在於提供一種液晶配向用突起形成用 負型抗钱劑’其可形成用以對液晶顯示裝置之液晶配向進 订控制的突起’且可防止所製造之液晶顯示裝置產生液晶 殘像現象。 本發明’係一種液晶配向突起形成用負型抗蝕劑，其 含有鹼溶性樹脂、聚合性單體及光聚合起始劑，且使用於 形成MVA方式之液晶顯示裝置的液晶配向用的突起，上述 聚合性單體含有酚醛環氧（甲基）丙烯酸酯。 以下詳細說明本發明。 本發明人等發現當使用含有酚醛環氧（甲基）丙烯酸酯 作為聚合性單體之負型抗蝕劑，來形成用以使MVA方式之 200921278 液aa顯示裝置的液晶於一像素内多方向地分割配向之突起 時，即使長時間進行顯示亦不會於突起形成部分產生液晶 的異常配向，不會產生液晶殘像現象，從而完成本發明。 本發明之液晶配向用突起形成用負型抗姓劑（以下亦 稱作本發明之負型抗姓劑），係用以於Mva方式之液晶顯 示裝置中形成用以使液晶部分地分割配向之形成於基板上 的弓形突起（液晶配向用突起）。再者，本發明之負型抗 蝕劑除了可製造上述液晶配向用突起以外，例如亦可製造 對液aa顯示裝置之兩片基板的間隙進行限制之柱狀間隔物 (column spacer) 〇 本發明之負型抗蝕劑含有鹼溶性樹脂、聚合性單體及 光聚合起始劑。 上述聚合性單體，係利用對本發明之負型抗蝕劑進行 光照射，而使後述鹼溶性樹脂產生交聯之交聯成分。藉由 使用酚路環氧（甲基）丙浠酸酯作為上述聚合性單體，使用本 發明之負型抗蝕劑來設置液晶配向用突起的MVA方式之液 晶顯示裝置，可抑制液晶殘像現象的發生。其理由如下所 述。 MVA方式之液晶顯示裝置中所產生的液晶殘像現象， 係由突起形成部分與對向基板之間所產生的殘留電場所引 起。該殘留電場之發生，係由於突起所具有之介電損耗正 切（dielectric I〇ss tangent)、與配向膜及液晶所具有之介電 抽耗正切的差較大所導致。一般認為，使用含有酚醛環氧（甲 基）丙烯酸酯作為聚合性單體之本發明之負型抗蝕劑所形成 200921278 的液晶配向用突起’由於其介電損耗正切與配向膜及液晶 之介電損耗正切接近’故可防止上述殘留電場之發生。因 此’具有使用本發明之負型抗餘劑所形成之液晶配向用突 起的MVA方式之液晶顯示裝置’即使進行長時間顯示，亦 不會出現液晶殘像現象。 上述紛經環氧（曱基）丙烯酸酯，並無特別限制，例如可 列舉：苯酚酚搭環氧（甲基）丙烯酸酯、鄰甲酚酚醛環氧（甲 基）丙烯酸酯、間甲酚酚醛環氧（甲基）丙烯酸酯、對甲紛紛 醛環氧（曱基）丙烯酸酯、萘酚改質酚醛環氧（甲基）丙烯酸 酯、鹵化苯酚酚醛環氧（甲基）丙烯酸酯等。 再者，本說明書中，（甲基）丙烯酸酯係指丙烯酸酯或甲 基丙烯酸醋。 表示上述酚酿環氧（曱基）丙烯酸酯之通式示於下述式 (1 )中。[Technical Field] The present invention relates to a negative resist for forming a protrusion for liquid crystal alignment, which can form a protrusion for controlling liquid crystal alignment of a liquid crystal display device, and can prevent The manufactured liquid crystal display device produces a phenomenon of liquid crystal afterimage. [Prior Art] The liquid crystal display device has a structure in which a direction in which the color filter, the black matrix, the linear transparent electrode, the alignment film, and the like are formed is perpendicular or parallel to the substrate The matching liquid crystal. In a state where no electric field is applied, the liquid crystal injected between the substrates is aligned in a direction perpendicular to the substrate or in a direction parallel to the substrate, and an electric field can be applied to change the alignment state, whereby the amount of light transmitted through the liquid crystal can be adjusted. The liquid crystal display device is practically used as a liquid-tanned television for a large-screen television because it is thinner and consumes less power than a display device using a Brown tube. However, the liquid crystal display element has a problem of narrow viewing angle as compared with a display device using a Brown tube. With the popularity of large-screen LCD TVs, there is a strong demand for improvements in viewing angles. ▲ As a method for improving the viewing angle of the liquid crystal display device, there is proposed an MVA (Multid〇 main Vertical Alignment) method in which an arcuate protrusion is formed on a transparent electrode, and the inclination of the protrusion (si, The liquid crystal is locally tilted to divide the liquid crystal into multiple directions in the _pixel. The alignment is performed as the arcuate protrusion formed on the transparent electrode. The method is as follows. Shadow method, 5 200921278 to form a protrusion having a substantially rectangular cross section, and thereafter heating the protrusion to be welded (four), thereby forming a bow shape for forming an arcuate shape on the transparent electrode, for example, Patent Document 1 discloses a positive resist containing a naphthoquinone diazide compound and a copolymer having a specific structural unit having a hydroxyl group. However, a positive anti-rheing agent is used on a transparent substrate. When the protrusion is formed, it needs to be heated and welded to form an arcuate shape, so that the obtained protrusion is obtained due to the bottom width or the heating temperature of the formed pattern. The height of the bow and the angle of contact with the substrate are different. If the height and angle of the protrusion are not good, the alignment of the liquid crystal may be uneven, and even display unevenness may occur. Further, the positive type resistance disclosed in Patent Document 1 (4) , the existence of #, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , The positive-type anti-money agent exhibits a difference in solubility between the exposed portion and the unexposed portion in the in-situ developer due to the alkali-soluble carboxylic acid produced in the photolysis of the photopolymer of the second stack. Therefore, if it is negative Compared with the type of money agent, the range of development conditions of the positive type anti-money agent is narrow, and it is difficult to manage the development state such as development deterioration caused by oxygen in the air. Moreover, the manufacturing process of the liquid crystal display device is included in In addition to the step of forming a protrusion on the transparent electrode, (4) various resists are also used, but most of the steps use a negative type anti-noise agent. Therefore, a positive type resist is used only in the step of forming the protrusion. meeting The manufacturing process is complicated. In this regard, Patent Document 2 discloses that a negative-type anti-surplus agent containing a solvent-soluble resin, a photopolymerization initiator, and a photopolymerizable monomer as a main component is used for the electrode on the electrode 200921278. Patent Document 3 discloses a photosensitive dendrimer composition which is mainly composed of a ethylenically unsaturated compound, a photopolymerization initiator, and an alkali-soluble resin, and is used as a negative-resistance for forming a projection for liquid crystal division and alignment. Residual agent < simplification of the manufacture of the liquid crystal display device by using the negative type anti-agent*. However, the use of the previous negative resist to form a liquid crystal alignment protrusion liquid 曰曰 display device When the time is displayed, there is a problem in that a liquid crystal alignment dog is formed. The squeegee generates an abnormal alignment of the liquid crystal, which causes a problem of displaying a liquid crystal afterimage phenomenon in which an image remains. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-33001 (Patent Document 3) [Patent Document 3] JP-A-2006-1 1359 SUMMARY OF THE INVENTION The object of the present invention is to Provided is a negative-type anti-money agent for forming a liquid crystal alignment protrusion which can form a protrusion for controlling alignment of a liquid crystal alignment of a liquid crystal display device and can prevent a liquid crystal afterimage phenomenon from occurring in the liquid crystal display device manufactured. The present invention is a negative resist for forming a liquid crystal alignment protrusion, which contains an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator, and is used for forming a protrusion for liquid crystal alignment of an MVA liquid crystal display device. The above polymerizable monomer contains a novolac epoxy (meth) acrylate. The invention is described in detail below. The present inventors have found that when a negative resist containing a phenolic epoxy (meth) acrylate as a polymerizable monomer is used, a liquid crystal for forming an MVA type 200921278 liquid aa display device is multidirectional in one pixel. When the protrusions are divided and aligned, even if the display is performed for a long period of time, the abnormal alignment of the liquid crystal does not occur in the protrusion forming portion, and the liquid crystal afterimage phenomenon does not occur, and the present invention has been completed. The negative-type anti-surname agent for forming a liquid crystal alignment protrusion of the present invention (hereinafter also referred to as a negative anti-surname agent of the present invention) is used for forming a liquid crystal partial division and alignment in an Mva liquid crystal display device. An arcuate protrusion (a projection for liquid crystal alignment) formed on the substrate. Further, in addition to the above-described liquid crystal alignment protrusion, the negative resist of the present invention can be used, for example, to manufacture a column spacer which restricts the gap between the two substrates of the liquid aa display device. The negative resist contains an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator. The polymerizable monomer is a cross-linking component which causes cross-linking of an alkali-soluble resin to be described later by light irradiation of the negative resist of the present invention. By using a phenolic epoxy (meth)propionate as the polymerizable monomer, an MVA liquid crystal display device in which a liquid crystal alignment protrusion is provided using the negative resist of the present invention can suppress liquid crystal afterimage The phenomenon occurs. The reasons are as follows. The liquid crystal afterimage phenomenon generated in the MVA liquid crystal display device is caused by the residual electric field generated between the protrusion forming portion and the counter substrate. This residual electric field is caused by a dielectric loss tangent of the protrusions and a large difference in dielectric tangential tangent with the alignment film and the liquid crystal. It is considered that the negative-type resist of the present invention containing a phenolic epoxy (meth) acrylate as a polymerizable monomer forms a liquid crystal alignment protrusion of 200921278 because of its dielectric loss tangent and alignment film and liquid crystal. The electric loss tangent is close to 'therefore, the above residual electric field can be prevented from occurring. Therefore, the MVA liquid crystal display device having the liquid crystal alignment protrusion formed by using the negative-type anti-surplus agent of the present invention does not exhibit a liquid crystal afterimage phenomenon even if it is displayed for a long period of time. The above-mentioned epoxy (fluorenyl) acrylate is not particularly limited, and examples thereof include phenol phenol epoxy (meth) acrylate, o-cresol novolac epoxy (meth) acrylate, and m-cresol phenol aldehyde. Epoxy (meth) acrylate, p-formaldehyde aldehyde epoxy (meth) acrylate, naphthol modified phenolic epoxy (meth) acrylate, halogenated phenol novolac epoxy (meth) acrylate, and the like. Further, in the present specification, (meth) acrylate means acrylate or methacrylate. The general formula indicating the above phenol-based epoxy (fluorenyl) acrylate is shown in the following formula (1).

式（1)中’ R^R2表示氫或甲基，m表示〇或正整數。 上述酚醛環氧（甲基）丙烯酸酯，例如可藉由酚醛環氧樹 200921278 脂與不飽和一元酸之酯化反應而獲得。 上述紛㈣氧樹脂’例如可列舉：苯㈣料氧樹脂、 鄰甲酴粉路環氧樹脂、間w紛駿環氧樹腊、對甲齡㈣ 壞乳樹腊、萘齡改質紛酸環氧樹脂、幽化苯㈣搭環氧樹 脂。 上述不飽和一元酸，就反應性方面而言，較佳為具有（甲 基）丙稀酸基與幾基之化合物，例如（甲基）丙稀酸、伊康酸、 丁稀酸、肉桂酸，其中較佳為（甲基）丙婦酸。 上述醋化反應，例如可列舉如下方法等：於環氧酉旨化 觸媒、。聚合抑㈣、抗氧化劑等穩定劑之存在下，且於3〇 〜150°C的溫度下使上述盼搭環氧樹脂與上述不飽和一元 酸反應。 三級胺類、咪唑化合物 :對苯二酚、甲基對苯 上述醋化觸媒，例如可列舉： 類、磷化合物類、有機金屬類等。 上述聚合抑制劑’例如可列舉 二酚、4-甲氧基苯酚等。 上述抗氧化劑’例如可列舉：亞磷酸系、亞磷酸醋類、 亞磷酸二酯類等。 上述（甲基）丙烯酸醋之改質率，並無特別限制，可將酚 醛環氧樹脂之一部分或全部進行（曱基）丙烯酸酯改質。 上述紛搭環氧（曱基）丙稀酸醋，較佳為具有驗溶性官能 基。藉由具有鹼溶性官能基，以使所獲得的本發明之負型 抗蚀劑的顯雜提高。驗溶性官能基，可藉由使盼搭環氧（甲 基）丙烯酸酯所含有之羥基與多鹼酸酐反應來導入。反應方 200921278 法，例如可拉+ 根田在與上述酯化反應相同之條件下使其繼續 反應而獲得。 ' 表不具有上述鹼溶性官能基之酚醛環氧（甲基）丙烯酸 酯之通式示於下述式（2)中。In the formula (1), R 2 represents a hydrogen or a methyl group, and m represents a fluorene or a positive integer. The above phenolic epoxy (meth) acrylate can be obtained, for example, by an esterification reaction of a phenolic epoxy resin 200921278 with an unsaturated monobasic acid. For example, the above-mentioned sulfonated resin may be exemplified by benzene (tetra) oxy-resin, o-methyl sulfonate epoxy resin, m-brown epoxy wax, opposite age (four) bad milk wax, and naphthalene-age modified acid ring Oxygen resin, phenolized benzene (tetra) epoxy resin. The above unsaturated monobasic acid is preferably a compound having a (meth)acrylic acid group and a few groups in terms of reactivity, such as (meth)acrylic acid, itaconic acid, butyric acid, cinnamic acid. Among them, (meth)propanoid acid is preferred. The acetalization reaction may, for example, be carried out by a method such as a catalyst for epoxy oxime. The above-mentioned desired epoxy resin is reacted with the above unsaturated monobasic acid in the presence of a stabilizer such as polymerization (IV), an antioxidant, and the like at a temperature of from 3 Torr to 150 °C. Tertiary amines, imidazole compounds: hydroquinone, methyl p-benzene The above-mentioned vinegar catalysts include, for example, phosphorus compounds, organometallics, and the like. Examples of the above polymerization inhibitors include diphenol and 4-methoxyphenol. Examples of the above antioxidants include a phosphorous acid system, a phosphorous acid vinegar, and a phosphite diester. The reforming ratio of the above (meth)acrylic acid vinegar is not particularly limited, and some or all of the phenolic epoxy resin may be modified with (mercapto) acrylate. The above-mentioned conjugated epoxy (fluorenyl) acrylate vinegar preferably has a test functional group. By having an alkali-soluble functional group, the obtained negative resist of the present invention is improved. The test functional group can be introduced by reacting a hydroxyl group contained in the epoxy (meth) acrylate with a polybasic acid anhydride. The reaction method 200921278, for example, Kola + Root Field is obtained by continuing the reaction under the same conditions as the above esterification reaction. The general formula of the phenolic epoxy (meth) acrylate having no such alkali-soluble functional group is shown in the following formula (2).

式（2)中’ri、r2表示氫或曱基，r3表示來源於多鹼 k肝且具有竣基之原子團。又，m、n表示〇或正整數。 上述多鹼酸酐，例如可列舉：丁二酸酐、鄰苯二甲酸 酐、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、順丁烯二酸 酐、伊康酸酐、均苯四甲酸酐、偏苯三曱酸酐等。其中， 就反應性方面而言’較佳為丁二酸酐或鄰苯二甲酸酐。 上述酚醛環氧（甲基）丙烯酸酯具有鹼溶性官能基時，其 氧化之較佳上限為250mgKOH/g。若具有上述鹼溶性官能基 之酚醛環氧（曱基）丙烯酸酯的氧化超過250mgKOH/g，則密 合性會降低。具有上述鹼溶性官能基之酚醛環氧（甲基）兩稀 酸酯之氧化的更佳上限為200mgKOH/g。 上述酚醛環氧（甲基）丙烯酸酯之重量平均分子量的較 200921278 佳下限為600，較佳上限為2000。若上述酚醛環氧（曱基） 丙烯酸酯之重量平均分子量未滿600，則樹脂中之未反應的 低分子化合物量會增多，所殘存之低分子化合物會溶出至 液晶中而引起面板顯示不良，若超過2000，則顯影時會產 生殘渣、或所獲得之突起並非為弓形。上述酚醛環氧（曱基） 丙烯酸酯之重量平均分子量的更佳下限為800，更佳上限為 1800 ° 再者，本發明中，酚醛環氧（甲基）丙烯酸酯之重量平均 分子量，係指例如使用昭和電工公司製造之Shodex LF-804 等的管柱，利用將四氫呋喃作為展開溶劑之凝膠滲透層析 (GPC，Gel Permeation Chromatography)法進行測量，並 藉由聚苯乙烯換算所求得之值。 上述酚醛環氧（曱基）丙烯酸酯之市售品，例如可列舉： EA-1020、EA-1025、EA-1026、EA-1028、EA-6320、EA-6340 (以上均為新中村化學工業公司製造），Ebecryl 150、 Ebecryl 1150(以上均為 DAICEL UCB 公司製造），M-208、 M-210 (以上均為東亞合成公司製造），PNA-161H、 CNA-142H、PCR-1169H、CCR-1159H (以上均為日本化藥 公司製造），EPICLON N-695、EPICLON N-775 (以上均為 大曰本油墨化學公司製造），PR-300、PR-310、PR-320、 HRM-1004、HRM-1005、HRM-101 卜 HRM-1013、HRM-2019、 HRM-202 1、HRM-2027、HRM-203 1 (以上均為昭和高分子 公司製造）等。 上述酚醛環氧（曱基）丙烯酸酯之摻合量，並無特別限 12 200921278 ”相：於上述驗溶性樹脂100重量份，較佳下限為2〇重 虿伤’較佳上限為200重量份 伤右上述酚醛環氧（甲基）丙浠 ㈣之摻合量未滿2G重量份，則會損及防止殘像之效果， 右超過200重量份，則易於導致顯影溶解速度降低等。上 述㈣環氧（甲基）丙稀酸酯之摻合量的更佳下限為3〇重量 份，更佳上限為180重量份。其中，於使其溶解於溶劑等 中而得之㈣時，上述重量份係指固體成分換算後之值。 以提高密合性、顯影性、耐熱性、耐酸性、耐驗性、 耐化學性、與驗溶性樹脂之相溶性為目的，本發明之負型 抗敍劑’亦可含有上述賴環氧（甲基）丙婦酸醋以外之聚合 性單體。上述聚合性單體，係指於分子内具有i個以上2 乙稀性不飽和鍵的化合物。 於刀子内具有1個之乙烯性不飽和鍵的化合物並無 特別限制，例如可列舉：（甲基）丙烯酸、丁晞酸、異丁烯酸二 順丁烯二酸、伊康酸、甲基順丁烯二酸等不飽和羧酸及其 烧基S曰、（甲基）丙稀腈、（曱基）丙蝉醯胺、苯乙烯等。、 於分子内具有2個乙烯性不飽和鍵之化合物，並無特 別限制，例如可列舉：新戊二醇二（甲基）丙烯酸酯、夂甲基 -1，5-戊二醇二（甲基）丙烯酸酯、2_丁基_2_乙基-丨，^丙二醇_ (甲基）丙烯酸酯、i，4_ 丁二醇二丙烯酸酯、丨，6-己二醇二 烯酸酯、羥基特戊酸新戊二醇酯二丙烯酸酯、二乙二醇（甲 基）丙烯酸酯、三乙二醇（曱基）丙烯酸酯、四乙二醇（甲基） 丙烯酸酯、六乙二醇（曱基）丙烯酸酯、九乙二醇（甲基）丙烯 酸酯等聚乙二醇（曱基）丙烯酸酯，或二乙二醇二（甲基）丙烯 13 200921278 酸酯、二乙二醇二（甲基）丙稀酸酯、四乙二醇二（甲基）丙稀 酸酯、六乙二醇二（甲基）丙稀酸酯、九乙二醇二（甲基）丙烯 酸酯等聚乙二醇二（曱基）丙烯酸酯等。 於分子内具有3個以上的乙烯性不飽和鍵之化合物， 並無特別限制，例如可列舉：三羥曱基乙烷三（曱基）丙烯酸 酯、三羥曱基丙烷三（甲基）丙烯酸酯、二（三羥甲基丙烷）四 (曱基）丙烯酸酯、季戊四醇三（甲基）丙稀酸酯、季戊四醇四 《 （曱基）丙烯酸酯、二季戊四醇四（甲基）丙烯酸酯、二季戊四 醇五（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯等多官 能（甲基）丙烯酸酯化合物等。該等於分子内具有3個以上的 乙烯性不飽和鍵之化合物，由於聚合反應進行較快，易於 提同曝光靈敏度，故尤佳。其中，季戊四醇三（甲基）丙烯酸 酯由於可提高顯影性、與鹼溶樹脂之相溶性，故較佳。 該等聚合性單體可單獨使用，亦可併用兩種以上。 併用上述酚醛環氧（甲基）丙烯酸酯以外之聚合性單體 U 時，於上述聚合性單體整體中所占之上述酚醛環氧（曱基） 。丙烯酸醋以外之聚合性單體的比率之較佳上限為80重量 ^若上述酚醛環氧（甲基）丙烯酸酯以外的具有鹼溶性基之 聚口性單體之比率超過80重量％，則會損及防止殘像之效 果。上述酚醛環氧（甲基）丙烯酸酯以外之具有鹼溶性基之聚 合性單體的比率的更佳上限為75重量％。 本發明之負型抗蝕劑含有鹼溶性樹脂。 上述鹼溶性樹脂，並無特別限制，可適當使用於分子 内/、有聚口性雙鍵者。具體而言，例如可列舉：將含有羧 200921278 基之單官能不飽和化合物與具有不飽和雙鍵之單官能化合 物加以共聚合而形成之共聚物等含有鹼溶性羧基之高分子 化合物。 上述含有羧基之單官能不飽和化合物，並無特別限 制’例如可列舉：丙烯酸、甲基丙烯酸等。 上述具有不飽和雙鍵之單官能化合物，並無特別限 制’例如可列舉：（曱基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（曱 基）丙稀酸丙酯、（甲基）丙稀酸丁酯、（甲基）丙烯酸2_乙基己 醋、（甲基）丙烯酸羥乙酯、（甲基）丙烯酸環己酯、（甲基）丙 稀酸2-甲基環己酯、（甲基）丙稀酸二環戊氧基乙酯、（甲基） 丙稀酸異冰片酯、（甲基）丙烯酸二環戊酯、（甲基）丙烯酸节 醋等（甲基）丙烯酸酯系單體。 上述含有鹼溶性羧基之高分子化合物，亦可含有來源 於下述化合物之成分：苯乙烯、α·甲基苯乙烯、對甲基苯 乙烯、對氯苯乙烯等芳香族乙烯系單體，丙烯腈、曱基丙 烯腈等氰化乙烯化合物，順丁烯二酸酐等不飽和二緩酸 肝’苯基馬來醯亞胺、苄基馬來醯亞胺、萘基馬來醯亞胺、 鄰氣苯基馬來醯亞胺等經芳香族取代之馬來醯亞胺，曱基 馬來醯亞胺、乙基馬來醯亞胺、丙基馬來醯亞胺、異丙基 馬來醯亞胺等經烷基取代之馬來醯亞胺等。 上述含有鹼溶性羧基之高分子化合物’亦可以控制顯 影時之溶解性等為目的，而含有來源於具有羥基之單官能 不飽和化合物的成分。 上述具有羥基之單官能不飽和化合物，並無特別限 15 200921278 制，例如作為於分子内具有丨個羥基之單體，例如可列舉： 丙烯酸2-羥乙酯、曱基丙烯酸2_羥乙酯、丙烯酸2_羥丙酯、 曱基丙烯酸2-羥丙酯、丙烯酸4_羥丁酯、甲基丙烯酸4_羥 丁酯等。 上述含有鹼溶性羧基之高分子化合物中，來源於含有 羧基之單官能不飽和化合物的成分之比率之較佳下限為5 重篁％，較佳上限為50重量％。若來源於上述含有羧基之 單官能不飽和化合物的成分之比率未滿5重量％，則難以 賦予鹼溶性，若超過5〇%，則顯影時之膨潤將會顯著而難 =形成圖案。來源於含有羧基之單官能不飽和化合物的成 刀之比率的更佳下限為1〇重量％，更佳上限為重量％。 述3有敌基之單官能不飽和化合物與具有不飽和 雙鍵之單g能化合物加以共聚合之方法，並無特別限制， J如可歹j舉如下方法：使用自由基聚合起始劑及視需要的 :子量調節劑’利用塊狀聚合、溶液聚合、懸浮聚合、分 散小合、乳化聚合等先前公知的方法進行聚合。其中較佳 為溶液聚合。 利用溶液聚合法來製造上述含有驗溶性缓基之高分子 化合物時的溶劑，如可使用：曱醇、乙醇、異丙醇、乙 —醇專脂肪族醇翻，金Α μ ^ 坪類賽珞穌、丁基赛珞蘇等赛珞蘇類，卡 必醇、丁基卡必醇笼上 畔等卡必醇類’乙酸赛珞蘇、乙酸卡必醇、 丙二醇單甲醚乙醅 ^ 酸知等酯類’二乙二醇二曱醚等醚類，四 氫吱喃等環狀驗，提 展己酮、曱基乙基酮、甲基異丁基酮等 嗣類 9 二甲武jr rg! 土 風、二甲基甲醯胺等具有極性之有機溶劑 16 200921278In the formula (2), 'ri, r2 represents hydrogen or a sulfhydryl group, and r3 represents an atomic group derived from a polybasic k-hepatic group and having a mercapto group. Also, m and n represent 〇 or a positive integer. Examples of the polybasic acid anhydride include succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, itaconic anhydride, and pyromellitic anhydride. , trimellitic anhydride, and the like. Among them, succinic anhydride or phthalic anhydride is preferred in terms of reactivity. When the above phenolic epoxy (meth) acrylate has an alkali-soluble functional group, the upper limit of oxidation is preferably 250 mgKOH/g. When the oxidation of the phenolic epoxy (fluorenyl) acrylate having the above alkali-soluble functional group exceeds 250 mgKOH/g, the adhesion is lowered. A more preferable upper limit of the oxidation of the phenolic epoxy (methyl) diacid ester having the above alkali-soluble functional group is 200 mgKOH/g. The lower limit of the weight average molecular weight of the above phenolic epoxy (meth) acrylate is 600 in comparison with the lower limit of 200921278, and the upper limit is preferably 2,000. When the weight average molecular weight of the above phenolic epoxy (fluorenyl) acrylate is less than 600, the amount of unreacted low molecular compound in the resin increases, and the remaining low molecular compound is eluted into the liquid crystal to cause poor display of the panel. If it exceeds 2,000, residue may be generated during development, or the obtained protrusions may not be arcuate. The lower limit of the weight average molecular weight of the above phenolic epoxy (fluorenyl) acrylate is 800, and the upper limit is more preferably 1800 °. Further, in the present invention, the weight average molecular weight of the phenolic epoxy (meth) acrylate is For example, a column of Shodex LF-804 manufactured by Showa Denko Co., Ltd. is used, and is measured by a gel permeation chromatography (GPC) method using tetrahydrofuran as a developing solvent, and is obtained by polystyrene conversion. value. Commercial products of the above-mentioned novolac epoxy (fluorenyl) acrylate include, for example, EA-1020, EA-1025, EA-1026, EA-1028, EA-6320, EA-6340 (all of which are Xinzhongcun Chemical Industry) Made by the company), Ebecryl 150, Ebecryl 1150 (all manufactured by DAICEL UCB), M-208, M-210 (all manufactured by East Asia Synthesis), PNA-161H, CNA-142H, PCR-1169H, CCR- 1159H (all of which are manufactured by Nippon Kayaku Co., Ltd.), EPICLON N-695, EPICLON N-775 (all of which are manufactured by Otsuka Ink Chemical Co., Ltd.), PR-300, PR-310, PR-320, HRM-1004, HRM-1005, HRM-101, HRM-1013, HRM-2019, HRM-202 1, HRM-2027, HRM-203 1 (all of which are manufactured by Showa Polymer Co., Ltd.). The blending amount of the above phenolic epoxy (mercapto) acrylate is not particularly limited to 12 200921278 "phase: 100 parts by weight of the above-mentioned test-soluble resin, preferably lower limit of 2 虿 heavy smashing' is preferably an upper limit of 200 parts by weight. When the amount of the above-mentioned phenolic epoxy (methyl)propene (4) is less than 2 G by weight, the effect of preventing afterimage is impaired, and if it exceeds 200 parts by weight on the right, the developing dissolution rate is liable to decrease. A more preferred lower limit of the blending amount of the epoxy (meth) acrylate is 3 parts by weight, and a still more preferred upper limit is 180 parts by weight, wherein the above weight is obtained by dissolving it in a solvent or the like (4). The part refers to a value obtained by converting a solid component. The negative anti-synthesis of the present invention is aimed at improving adhesion, developability, heat resistance, acid resistance, testability, chemical resistance, and compatibility with a test resin. The agent ' may also contain a polymerizable monomer other than the above epoxy (meth) acetoacetate. The above polymerizable monomer means a compound having one or more ethylidene unsaturated bonds in the molecule. a compound having one ethylenically unsaturated bond in the knives and There is no particular limitation, and examples thereof include unsaturated carboxylic acids such as (meth)acrylic acid, butyric acid, methacrylic acid dimaleic acid, itaconic acid, and methyl maleic acid, and the alkyl group thereof. (meth)acrylonitrile, (fluorenyl) acrylamide, styrene, etc., and a compound having two ethylenically unsaturated bonds in the molecule, and is not particularly limited, and examples thereof include: neopentyl glycol (meth) acrylate, fluorenylmethyl-1,5-pentanediol di(meth) acrylate, 2-butyl-2-ethyl-hydrazine, propylene glycol _ (meth) acrylate, i, 4_ Butanediol diacrylate, hydrazine, 6-hexanediol dicarboxylate, hydroxypivalic acid neopentyl glycol ester diacrylate, diethylene glycol (meth) acrylate, triethylene glycol (曱a polyethylene glycol (meth) acrylate such as acrylate, tetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, pentylene glycol (meth) acrylate, or Diethylene glycol di(meth) propylene 13 200921278 acid ester, diethylene glycol di(methyl) acrylate, tetraethylene glycol di (meth) acrylate Polyethylene glycol bis(indenyl) acrylate such as hexaethylene glycol di(meth) acrylate or pentylene glycol di(meth) acrylate, etc. It has three or more ethylenic groups in the molecule. The compound of the saturated bond is not particularly limited, and examples thereof include tris(hydroxy) ethane tri(indenyl) acrylate, trishydroxypropyl propane tri(meth) acrylate, and di(trimethylolpropane) four. (fluorenyl) acrylate, pentaerythritol tri(methyl) acrylate, pentaerythritol tetra (indenyl) acrylate, dipentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol A polyfunctional (meth) acrylate compound such as hexa(meth) acrylate or the like, which is equivalent to a compound having three or more ethylenically unsaturated bonds in the molecule, and the polymerization reaction proceeds quickly, and the exposure sensitivity is easily improved. Especially good. Among them, pentaerythritol tri(meth)acrylate is preferred because it can improve developability and compatibility with an alkali-soluble resin. These polymerizable monomers may be used singly or in combination of two or more. When the polymerizable monomer U other than the above-mentioned novolac epoxy (meth) acrylate is used in combination, the above-mentioned phenolic epoxy (fluorenyl) is contained in the entire polymerizable monomer. A preferred upper limit of the ratio of the polymerizable monomer other than the acryl vinegar is 80% by weight, and if the ratio of the polyfunctional monomer having an alkali-soluble group other than the above phenolic epoxy (meth) acrylate is more than 80% by weight, Damage and the effect of preventing afterimages. A more preferable upper limit of the ratio of the polymerizable monomer having an alkali-soluble group other than the above phenolic epoxy (meth) acrylate is 75% by weight. The negative resist of the present invention contains an alkali-soluble resin. The alkali-soluble resin is not particularly limited, and can be suitably used in the molecule/there is a polycyclic double bond. Specifically, for example, a polymer compound containing an alkali-soluble carboxyl group such as a copolymer obtained by copolymerizing a monofunctional unsaturated compound having a carboxyl group 200921278 group and a monofunctional compound having an unsaturated double bond can be mentioned. The monofunctional unsaturated compound containing a carboxyl group is not particularly limited. For example, acrylic acid, methacrylic acid or the like can be mentioned. The monofunctional compound having an unsaturated double bond is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (methyl). Butyl acrylate, 2-ethylhexyl acrylate (meth)acrylate, hydroxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate , (meth)acrylic acid dicyclopentyloxyethyl ester, (meth)acrylic acid isobornyl ester, (meth)acrylic acid dicyclopentyl ester, (meth)acrylic acid vinegar, etc. (meth)acrylic acid Ester monomer. The polymer compound containing an alkali-soluble carboxyl group may further contain a component derived from an aromatic vinyl monomer such as styrene, α-methylstyrene, p-methylstyrene or p-chlorostyrene, or propylene. A vinyl cyanide compound such as a nitrile or a mercapto acrylonitrile, an unsaturated diacidified liver such as maleic anhydride, 'phenyl maleimide, benzyl maleimide, naphthyl maleimide, ortho Aromatically substituted maleic imine, such as phenyl phenyl maleimide, fluorenyl maleimide, ethyl maleimide, propyl maleimide, isopropyl mala An alkylamine-substituted maleimide or the like such as an imine. The polymer compound containing an alkali-soluble carboxyl group can also contain a component derived from a monofunctional unsaturated compound having a hydroxyl group for the purpose of controlling solubility in development and the like. The above-mentioned monofunctional unsaturated compound having a hydroxyl group is not particularly limited to 15 200921278, and is, for example, a monomer having a hydroxyl group in the molecule, and examples thereof include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. 2, hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and the like. In the polymer compound containing an alkali-soluble carboxyl group, a preferred lower limit of the ratio of the component derived from the monofunctional unsaturated compound containing a carboxyl group is 5% by weight, and a preferred upper limit is 50% by weight. When the ratio of the component derived from the carboxyl group-containing monofunctional unsaturated compound is less than 5% by weight, it is difficult to impart alkali solubility, and if it exceeds 5% by weight, swelling during development is remarkable and it is difficult to form a pattern. A more preferred lower limit of the ratio of the dicing derived from the monofunctional unsaturated compound having a carboxyl group is 1% by weight, and more preferably the upper limit is % by weight. The method for copolymerizing a monofunctional unsaturated compound having an ester group with a mono-g-energy compound having an unsaturated double bond is not particularly limited, and J may be as follows: a radical polymerization initiator and If necessary, the sub-quantity adjuster 'polymerizes by a conventionally known method such as bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, emulsion polymerization, or the like. Among them, solution polymerization is preferred. The solvent used in the above-mentioned polymer compound containing a test-solvent retarding group by a solution polymerization method can be used, for example, decyl alcohol, ethanol, isopropanol, ethyl alcohol-specific aliphatic alcohol, and gold Α μ ^ ping-type celluloid 、, butyl 赛 珞 等 等 珞 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Ethers such as esters such as diethylene glycol dioxime ether, tetrahydrofuran, etc., and oxime, such as hexanone, mercaptoethyl ketone, and methyl isobutyl ketone, 9 dimethyl sulphide jr rg Earthy, dimethylformamide and other polar organic solvents 16 200921278

又，作為利用懸浮聚合、分散聚合、乳化聚合等非水 系刀政聚口來製造上述含有鹼溶性羧基之高分子化合物時 的貝例如可使用：苯、甲苯、己烧、環己烧等液狀的 烴，或其他非極性有機溶劑等。 上述自由基聚合起始劑，並無特別限制，例如可使用 過氧化物、偶氮起始劑等先前公知之自由基聚合起始劑。 又，上述分子量調節劑，例如可使用甲基苯乙烯二聚物、 硫醇系鏈轉移劑等。 本發明之負型抗蝕劑中，上述鹼溶性樹脂，其中較佳 為於側鏈上具有（甲基）丙烯酸基與羧基之鹼溶性（甲基）丙烯 酸共聚物°選#於側鏈上具有（甲基）丙稀酸基與羧基之驗溶 性（甲基）丙烯酸共聚物作為上述鹼溶性樹脂時，本發明之負 型抗钱劑具有冑靈敏纟，且使其硬化而形成之液晶配向用 突起具有優異之解析度及與基板的密合性。一般認為其理 由在於，因鹼溶性樹脂之側鏈上的丙烯酸基於曝光時進行 反應，故鹼溶性樹脂自身亦進入交聯結構中，結果抑制圖 案剝離。 又’由於上述鹼溶性（甲基）丙烯酸共聚物之片段 (segment)的極性低，故與本發明之負型抗蝕劑的其他成 分之相溶性優異。藉此，製造液晶配向用突起時之顯影處 理中，亦不會出現顯影不均等不良情況。 上述驗溶性（甲基）丙烯酸共聚物，較佳為由下述式 (3a)、（3b)、（3c)、（3d)及（36)所表示之結構單 17 200921278 元所構成的共聚物。In addition, as a raw material for producing the above-mentioned polymer compound containing an alkali-soluble carboxyl group by a non-aqueous knife-forming polyport such as a suspension polymerization, a dispersion polymerization or an emulsion polymerization, for example, a liquid such as benzene, toluene, hexane or cyclohexane may be used. Hydrocarbons, or other non-polar organic solvents, etc. The radical polymerization initiator is not particularly limited, and for example, a conventionally known radical polymerization initiator such as a peroxide or an azo initiator can be used. Further, as the molecular weight modifier, for example, a methylstyrene dimer, a thiol-based chain transfer agent or the like can be used. In the negative resist of the present invention, the alkali-soluble resin preferably has an alkali-soluble (meth)acrylic copolymer having a (meth)acrylic group and a carboxyl group in a side chain, and has a side chain. When the (meth)acrylic acid group of the (meth)acrylic acid group and the carboxyl group is used as the alkali-soluble resin, the negative-type anti-money agent of the present invention has an antimony-sensitive antimony agent and is hardened to form a liquid crystal alignment. The protrusions have excellent resolution and adhesion to the substrate. It is considered that the reason is that since the acrylic acid on the side chain of the alkali-soluble resin is reacted based on the exposure, the alkali-soluble resin itself also enters the crosslinked structure, and as a result, the pattern peeling is suppressed. Further, since the segment of the alkali-soluble (meth)acrylic copolymer has a low polarity, it is excellent in compatibility with other components of the negative resist of the present invention. As a result, in the development process for producing the projections for liquid crystal alignment, defects such as development unevenness do not occur. The above-mentioned test-soluble (meth)acrylic copolymer is preferably a copolymer composed of the structural formula 17 200921278 represented by the following formulas (3a), (3b), (3c), (3d) and (36). .

COOHCOOH

(3b)(3b)

CH,——CR4- (3 d) COOA1CH,——CR4- (3 d) COOA1

(3 e)(3 e)

式（3a) 、 （3b) 、 （3c)、（Equations (3a), (3b), (3c), (

及A2表示氫及下述式（4a) 、（4b) 及（3e)中，A 當A1或A2中之任一者為氫時，另一去（4C)或（4d)， 韦'為下述式（4a)、（ 4b)、 (4c)或（4d)中之任-者。R4表示氫及/或f基，r5表示 烷基、苯基、包含烷基或烷氧基之苯基、羥基烷基或脂環 200921278 式烴，R6表示腈基或苯基，R7表示烷基、羥基烷基或含有 自由基聚合性基之脂肪族煙。又，a、b、c、d、e表示各成 分之莫耳比率（％) ，a+b+c+d+e=100時，a、b及d 為0〜90，c為5〜50，e為5〜60。 △'A2: -R7 (4a) f -C—N——R7 (4 b)And A2 represents hydrogen and in the following formulas (4a), (4b) and (3e), A when either of A1 or A2 is hydrogen, the other is (4C) or (4d), and Wei' is Any one of the formulae (4a), (4b), (4c) or (4d). R4 represents hydrogen and/or a f group, r5 represents an alkyl group, a phenyl group, a phenyl group containing an alkyl group or an alkoxy group, a hydroxyalkyl group or an alicyclic hydrocarbon of the formula 200921278, R6 represents a nitrile group or a phenyl group, and R7 represents an alkyl group. A hydroxyalkyl group or an aliphatic cigarette containing a radical polymerizable group. Further, a, b, c, d, and e represent the molar ratio (%) of each component, and when a+b+c+d+e=100, a, b, and d are 0 to 90, and c is 5 to 50. , e is 5~60. △'A2: -R7 (4a) f -C-N——R7 (4 b)

^ II I^ II I

Ο H CH2—CH-R7 (4c)Ο H CH2—CH-R7 (4c)

II

OH CH2 —R? (4 d)OH CH2 —R? (4 d)

OH U 上述驗溶性（甲基）丙烯酸共聚物之重量平均分子量，並 無特別限制，較佳下限為3000，較佳上限為1〇萬。若上述 =溶性（甲基）丙烯酸共聚物之重量平均分子量未滿3〇〇〇， 斤獲得之液晶配向用突起的密合性會降低，若超過1〇 萬’則解析度會降低。更佳下限為5_，更佳上限為5萬。 再者，本說明書中，上述重量平均分子量係利用凝膠 ’’層析法進行測量，且制聚苯乙稀換算所求得之值。 上述驗溶性（甲基）丙_共聚物之製造方法， 限制，例如可列舉下述方法：使含有脂環式環氧基之不」 19 200921278 和化合物與在側鏈上具有羧基之（甲基）丙烯酸共聚物進行 開環加成聚合，而將羧基之一部分改質，並且使異氰酸酯 化合物、環氧化合物、内酯化合物、醇化合物等與由改質 所生成之羥基及/或殘存之羧基的一部分進行反應。 上述於侧鏈上具有羧基之（甲基）丙烯酸共聚物的製造 方法，並無特別限制，例如可列舉下述方法：使用自由基 聚合起始劑及視需要的分子量調節劑，利用塊狀聚合': 液聚合、懸浮聚合、分散聚合、乳化聚合等先前公知之方 法，將含有缓基之單官能不飽和化合物與（甲基）丙稀酸醋系 單體進行共聚合。 上述含有脂環式環氧基之不飽和化合物，並無特別限 制，例如可適當使用（甲基）丙稀酸3,4_環氧環己醋等。 上述異氰酸西旨化合物，並無特別限制，例如可適 用碳數為2〜18之異氰酸院基醋、含有聚合性基之異氰酸 醋。若使用上述含有聚合性基之異氰酸酿，則 化時之靈敏度，且可進一步提高耐熱性、 门 著㈣-f㈣性等各種物性。 _化子性、不黏 =含有聚合性基之異㈣醋，並無特職制，例如 較佳為使用.（甲基）丙稀醯基經由碳數為Μ之伸烧 與異氰酸醋基鍵結而形成者。具體凡土 婦酿氧基乙基異氛酸醋、2_甲基丙稀酿基^如;；舉丙 丙稀醯基乙基異氰酸醋等，且2_甲基心、 醋及W祕以基異㈣醋㈣ 6基異氰酸 “nzA〇I (均為昭和電工公司製造）為細及 20 200921278 使上述異氰酸醋化合物與由上述改質所生成之於側鍵 上具有羥基及/或羧基的（，基）丙烯酸共聚物進行反應之方 法，並無特別限制，可列舉下述方法··於少量觸媒之存在 下’將上述異氰酸醋化合物滴加或混合入由上述改質所生 =侧鍵上具有經基及/或幾基之(甲基)丙締酸 溶液中。 此時所使用之觸媒，並盔特別 酸、二丁基錫等。 …、特綱，例如可列舉月桂 又，視需要亦可使用對甲氧基苯齡、對苯二齡、 胺、第二丁基兒茶酚、2 3_二= 劑。 弟一丁基-對尹酚等聚合抑制 並且’財卩制增料為目的，亦可利用 丙酵、丁醇、戊醇、己醇、庚 乙酵 理。 料辛醇、匈等醇進行處 按照上述製造方法，使 所“夕私" 使異氰酸西曰化合物與由上述改質 成之於側鏈上具有羥基及羧基之 進行反應時，將可形成< )烯酸共聚物 L、…. 式（2b)所示之結構單元。 述私氧化合物，並無特別限制，例如可 18之貌基環氧化合物、碳數為2〜18之"其碳數 化合物或含有聚合性基之環氧化合物。 &氧基環氧 化二使:：:::::之環氧化合物作為上_ 熱性=學性，著性等之各靈:物度性且可進一步提高耐 上述3有聚合性基之提备νι_ Λ 乳化°物，並無特別限制，例 21 200921278 如較佳為（甲基）丙烯醯基經由碳數為2〜ό之伸烷基而與環 氧基鍵結所形成者。具體而言，例如可列舉（甲基）丙烯酸縮 水甘油醋等。 使上述環氧化合物與由上述改質所生成之於側鏈上具 有羥基及/或羧基之（甲基）丙烯酸共聚物進行反應之方法， 並無特別限制，可列舉下述方法：於少量觸媒之存在下， 將上述環氧化合物滴加或混合入由上述改質所生成之於侧 鏈上具有羥基及/或羧基之（曱基）丙烯酸共聚物的溶液中。 此時所使用之觸媒，並無特別限制，例如可列舉：三乙胺、 二丙胺、四甲基伸乙基二胺、二甲基月桂基胺、三乙基苄 基氯化銨、三甲基十六烷基溴化銨、四丁基溴化銨、三甲 基丁基溴化鱗、四丁基溴化鱗等。 又，視需要亦可使用對甲氧基苯酚、對苯二酚、萘基 胺、第三Τ基兒茶龄、2,3·二第三丁基·對甲料聚合抑制 劑。 按照上述製造方法，使環氧化合物與由上述改質所生 成之於側鏈上具有羥基及/或羧基之（甲基）丙烯酸共聚物進 行反應時，將可形成式（2c)及（2d)所示之結構單元。 使上述異氰酸酯化合物或環氧化合物、内酯化合物、 醇化合物等與由上述改質所生成之於側鏈上具有羥基及/或 羧基之（甲基）丙烯酸共聚物進行反應時，可使上述（曱基）丙 烯酸共聚物中所包含之羥基中相當於〇〜1〇〇莫耳％之量反 應。 又，使上述異氰酸酯化合物或環氧化合物、内酯化合 22 200921278 物、醇化合物等與由改質所生成之於側鏈上具有經基及/或 幾基之（甲基）丙烯酸共聚物進行反應時，τ使上述（甲基）丙 烯酸共聚物中所包含之羧基中相當於0〜90莫耳％之量反 應。若超過90莫耳％，則殘存之叛基量會過少，故會損及 鹼溶性，導致顯影性降低。 上述式 a、b、c、d )、（3b)、（ 3e)、（ 3d)及（3e)中之 係表示各成分的莫耳比率（％) ，a+b+c + d+e=i〇0時，a、b & d之下限為〇%，上限為9〇%。又， c的下限為5% ’上限為5〇%。又，6的下限為5%，上限 為60%。c的下限為5%，上限為㈣若未滿州，即若 含有缓基之結構單元的莫耳比率未滿5%，則難以賦予驗溶 若超過50/^，則顯影時之膨潤顯著而難以形成圖案。 又’ e之較佳下限為5%，較佳上限為6〇%，若未滿， 則驗溶性樹脂進人交聯結射並不充分而導致交聯密度降 低，=結果為顯影步驟中之破壞過於增大，而出現液晶配 向用突，之高度不均’若超過6〇%’則交聯結構之交聯密 度會過高，而導致難以穩定地形成弓形。 ^並且，本發明之負型抗蝕劑中，較佳為上述鹼溶性樹 t ;刀子内具有芳香王裒。藉自含有具有芳香環之驗溶性樹 °進步降低液晶配向用突起之介電損耗正切，具有 使用本發明之負型抗蝕劑所形成之液晶配向用突起的液晶 厂、裝置進行長時間顯示時，可更適於防止出現液晶殘像 現象。 八有芳香環之驗溶性樹脂，並無特別限制，由於（甲基） 23 200921278 丙烯酸苄酯共聚物之密合性、顯影性良好，故較佳。 本發明之負型抗蝕劑中，上述驗溶性樹脂的酸值之較 佳下限為50mgKOH/g。若上述驗溶性樹脂之酸值未滿 50mgKOH/g，則將會導致本發明之負型抗蝕劑的解析性降 低，而無法穩定地形成弓形之液晶配向用突起。上述鹼溶 性樹脂的酸值之上限，並無特別限制，較佳上限為 15〇mgKOH/g。若上述鹼溶性樹脂之酸值超過 15〇mgKOH/g，則將會導致使用本發明之負型抗蝕劑而形成 之液晶配向用突起與基板之密合性降低。上述鹼溶性樹脂 的酸值之更佳下限為6〇mgK〇H/g，更佳上限為 14〇mgKOH/g。 再者本說月書中，上述驗溶性樹脂之酸值係以下述 數值表示：將鹼溶性樹脂lg溶解於有機溶劑中，將酚酞作 為指示劑而利用氫氧化卸進行滴定時，直 要的氫氧化鉀的吨數。 需 本發明之負型抗蝕劑中的上述鹼溶性樹脂之含量，相 對於總固體成分，通常為25重量％以上，較佳為3〇重量 %以上，且通常為90重量％以下，較佳為8〇重量％以下。 若驗溶性樹脂之量過少，„於導㈣降低，顯影溶 解速度降低等，若過乡，貞lU於導致$敏度降低， 面形狀的再現性不良。 $於本發明之負型抗餘劑而言，為了使液晶配向用突 起的尚度、及與基板接觸的形狀穩定，較佳為鹼溶性樹脂 之含量與上述聚合性單體之含量純定比率。具體而言， 24 200921278 單體之含量）的重量比之 ’更佳下限為0.35，更佳 (鹼溶性樹脂之含量）/ (聚合性 較佳下限為0.25’較佳上限為3 $ 上限為3。 本發明之負型抗餘劑含有光聚合起始劑。 述光聚σ起始劑’並無特別限制，可列舉先前公知 之光聚合起始劑，例如可列I . 夕J舉·可利用紫外線而產生使乙 稀性不飽和基聚合之自由其沾儿人 由基的化合物以及利用紫外線而產 生酸之化合物等。 上述光聚&起始劑之具體例，例如可列舉：甲氧 基苯基）-4,6-雙（三氣甲基）_均三„秦' 2_(4_甲氧基蔡基）_4,6_ 雙（三氯甲基）-均三嗪、2·(4·乙氧基萘基）_4,6_雙（三氣甲基）· 均二嗪、2-(4-乙氧基羰基萘基）_4,6_雙（三氯曱基>均三嗪等 鹵甲基化二嗪衍生物，齒甲基化噁二唑衍生物，2_(鄰氣苯 基）-4,5-二苯基咪唑二聚物、2-(鄰氣苯基）_4,5-雙（3'-甲氧基 苯基）咪唾二聚物、2-(鄰氟苯基）_4,5_二苯基咪唑二聚物、 2-(鄰甲氧基苯基）-4,5_二苯基咪唑二聚物、2_(鄰甲氧基苯 基）-4,5-二苯基°米嗤二聚物等咪咬衍生物，安息香甲醚、安 息香苯醚、安息香異丁醚、安息香異丙醚等安息香、安息 香烧基醚類’ 2-曱基蒽g昆、2-乙基蒽酿^、2-第三丁基蒽目昆、 1 -氯蒽醌等蒽醌衍生物，苯并蒽酮衍生物，二苯甲酮、米其 勒酮、2-甲基二苯甲酮、3-曱基二苯甲酮、4-曱基二苯甲鲖、 2-氣二苯甲酮、4-溴二苯甲酮、2-羧基二苯甲酮等二苯曱酮 衍生物，2,2-二甲氧基_2-苯基苯乙酮、2,2-二乙氧基苯乙 酮、1-羥基環己基苯基酮、α-羥基-2-曱基苯基丙酮、1-羥 25 200921278 基-i-甲基乙基-(對異丙基苯基）酮、r經基_1(對十二院基苯 基）酮、2-甲基-(4，-(f硫基）苯基）_2_嗎琳基小丙_二丄卜 三氯甲基-(對丁基苯基）酮等苯乙酮衍生物，噻噸_、2-乙基 噻噸酮、2-異丙基噻噸酮、2_氯噻噸酮、2,4_二甲基噻噸酮、 2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等噻噸酮衍生物， 對二甲基胺基苯曱酸乙酯、對二乙基胺基苯曱酸乙酯等苯 甲酸酯衍生物，9-苯基吖啶、9_(對甲氧基笨基）吖啶等吖啶 衍生物，9,10-二甲基苯并吩嗪等吩嗪衍生物，二環戊二烯 -二氣化鈦、二-環戊二烯基-鈦·雙-苯基、二_環戊二烯基_鈦 -雙-2,3,4,5,6-五氟苯基-1-基、二-環戊二稀基_鈦_雙_2,3,5,6_ 四氟苯基-1-基、二-環戊二烯基·鈦·雙_2,4,6_三氟苯基4· 基、二-環戊二烯基-鈥_2，6-二氟苯基-1-基、二-環戊二稀基_ 鈦-2,4-二氟苯基-1-基、二_甲基環戊二烯基_鈥_雙_2,3,4,5,6_ 五氟苯基-1-基、二-曱基環戊二烯基-鈦-雙-2,6-二氟苯基-1-基、二-環戊二烯基-鈦-2,6-二氟-3-(芘-1-基）-苯基-1-基等二 茂鈦衍生物，2-甲基-1[4-(甲硫基）苯基]-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基）-丁酮-1、2-苄 基-2-二甲基胺基-1-(4-嗎啉基苯基）丁烷-1·酮、4-二甲基胺 基乙基苯甲酸酯、4-二甲基胺基異戊基苯甲酸酯、4-二乙基 胺基苯乙酮、4-二曱基胺基笨丙酮、乙基己基-I，4·二甲基 胺基苯甲酸酯、2,5-雙（4-二乙基胺基亞苄基）環己酮、7-二 乙基胺基-3-(4-二乙基胺基苯甲醯基）香豆素、4-(二乙基胺 基）查耳酮等α-胺基烷基笨酮系化合物，丨，2·辛二酮、 1-[4-(苯硫基）苯基]-2-(〇-苯甲醢基肟）、乙酮-l-[9-乙基 26 200921278 冬(2-甲基苯甲酿基）_9H+坐_3_基] + (〇乙酿基⑹等辟衍 生物類，雙（2,4,6·三甲基苯曱醢基）_苯基氧化膦等氧化麟系 化合物等。該等光聚合起始劑可單獨使用，亦可併用兩種 以上。其中，氧化膦系起始劑由於易於將所獲得之液晶配 向用突起的形狀成形為弓形，故較佳。 阳 上述氧化膦系起始劑中，有在市售者，例如可列舉. Irgacure 8 ί 9 (汽巴精化公司製造）、__ 8! 9 (汽巴精 化公司製造）、Darocure TP〇 (汽巴精化公司製造）、sp_246 (ADEKA公司製造）等。 本發明之負型抗蝕劑中，上述光聚合起始劑的含量， 並無特別限制，相對於鹼溶性樹脂及聚合性單體之合計1 〇〇 重量份，較佳下限為0」重量份，較佳上限為4〇重°量份。 若上述光聚合起始劑的含量未滿〇1重量份，則光硬化將會 不充分，而導致液晶配向用突起與基板之密合性降低若 超過40重量份，則光硬化反應會過度進行而產生顯影殘 渣、或所獲得之液晶配向用突起的形狀並非為弓形，從而 導致出現液晶配向異常。上述光聚合起始劑的含量之更佳 下限為0.2重量份，更佳上限為3〇重量份，再更佳之下限 為0.5重量份，再更佳之上限為2〇重量份。 為了減輕由氧所引起的反應阻礙，本發明之負型抗蝕 劑亦可含有反應助劑。藉由將上述反應助劑與去氫型光反 應起始劑併用’可提高照射光時的硬化速度。 上述反應助劑’可列舉：正丁基胺、二正丁基胺、三 乙胺、三伸乙基四胺、對二甲基胺基苯甲酸乙酯、對二曱 27 200921278 基胺基笨曱酸異戊酯等胺系反應助劑，三正丁基膦等膦系 反應助劑，s-节基異硫脲-對甲苯磺酸酯等磺酸系反應助劑 等。該等反應助劑可單獨使用，亦可併用兩種以上。 本發明之負型抗蝕劑亦可含有矽烷偶合劑。 上述矽烷偶合劑具有提高本發明之負型抗蝕劑與基板 之密合性的作用。 上述矽烷偶合劑，並無特別限制，可使用先前公知之 石夕烧偶合劑。其中’較佳為具有丙稀醯氧基或甲基丙稀酿 氧基作為官能基者。藉由含有具有丙稀酿氧基或甲基丙稀 酿氧基作為官能基之梦燒偶合劑，可使本發明之負型抗蝕 劑的與基材之密合性大幅提高。 具有上述丙烯醯氧基之矽烷偶合劑，例如可列舉：3_ 丙婦醯氧基丙基三甲氧基石m㈣酿氧基丙基三乙氧基 矽烷等。 又，具有上述f基丙烯醯氧基之矽烷偶合劑，例如可 列舉：3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、％甲基丙 烯醯氧基丙基三甲氧基碎烧、3_甲基丙稀酿氧基丙基甲基二 乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷等。 該等矽烷偶合劑可單獨使用，亦可併用兩種以上。 本發明之負型抗蝕劑中，上述矽烷偶合劑的含量，並 無特別限制，當使驗溶性樹赌與聚合性單體的合計為⑽ $量份時，較佳下限為〇.丨重量份，較佳上限為4〇重量份。 若上述石夕烧偶合劑的含量未滿〇1重量份，則與基板之密合 性會降低’若超過4〇重量份，則光微影中會產生鹼性顯影 28 200921278 殘存現象。上述矽烷偶合劑的含 更佳上限為30重量份。 下限為1重董份， 劑之抗'劑，其構成上述本發明之負型抗- 成為Γ重::機溶劑’調整成固體成分濃度的下限 ^重里％、上限成為5G重量％，較佳為下限成為10 量％、上限成為40重量％之範圍，來加以使用。 操作可使上述各成分溶解或分散、且 優異之有機溶劑，則並無特別限制。具體而 一可列舉.甲基赛珞蘇、乙基赛珞蘇、丁基赛路蘇、二乙 二醇單甲冑、二乙二醇二乙鱗、二乙二醇甲基乙峻、丙二 醇單甲趟乙酸醋（以下簡稱作「PGMAe」）、甲基乙基網、 甲基異丁基酮、環己_、甲苯、氣仿、二氣甲院、乙酸乙 醋、乳酸甲醋、乳酸乙醋、甲醇、乙醇、丙醇、丁醇、四 氫呋喃等。 上述有機溶劑，較佳為使用沸點為100〜200。(：之範圍 的有機溶劑，更佳為使用沸點為120〜18(TC之範圍内的有 機溶劑。 製造本發明之負型抗蝕劑的方法，並無特別限制，例 如可列舉如下方法等：將上述驗溶性樹脂、含有酚醛環氧（甲 基）丙烯酸酯之聚合性單體、光聚合起始劑、有機溶劑及任 意的添加劑投入攪拌槽中，使用攪拌翼等進行混合。 就使用本發明之負型抗蝕劑來製造液晶配向用突起之 方法加以說明。 使用本發明之負型抗蚀劑來製造液晶配向用突起時， 29 200921278 首先’係將本發明之負型抗餘劑塗佈於基板上以使其具有 特定厚度’從而形成被膜。 上述塗佈方法，並無特別限制，例如可使用：旋塗法、 狹縫旋轉法、狹縫塗佈法、喷塗法、浸塗法、棒塗法等先 前公知之塗佈法。 接著，經由形成有特定圖案之光罩，將紫外線等活性 光線照射於所形成之被膜上。藉此，使本發明之負型抗蝕 劑中所包含之鹼溶性樹脂、聚合性單體及光聚合起始劑於 光照射部進行反應而光硬化。 上述活性光線，並無特別限制，例如可使用可見光線、 紫外線、遠紫外線、電子束、X射線f，較佳為紫外線。 上述液晶配向用突起，例如可藉由調整對上述塗膜之 液晶配向用突起形成部分所照射之光量而形成。調整照射 量之方法，使用先前所使用之方法即可， 方法等：經由上述光罩而照射活性光線時 例如可列舉下述 ’為了於後述之 鹼性顯影處理中形成弓形之液晶配向用突起，而使用灰階 或半階光罩（halftone mask)等。 所照射之紫外線等活性光線的波長並無特別限制，較 佳為使用波長為200〜600nm左右之紫外線。 上述活性光線之照射量的較佳下限為1〇mj/em2，較佳 上限為SOOmJ/cm2 ^若上述活性光線之照射量未滿 1〇mW，則光硬化將會不充分，於顯影步驟中圖荦將會 流動而產生密合性不良。若上述活性光線之照射量超過 500mJ/cm2，則易於生成顯影殘渣。 30 200921278 接著，對光硬化後之光硬化物進行鹼性顯影，於基板 上形成由本發明之負型抗蝕劑之光硬化物所構成的特=圖 案之液晶配向用突起。 ' 上述鹼性顯影處理所使用之溶劑，若為具有使未硬化 部之塗佈膜溶解之能力的溶劑’則並無特別限制，例如可 列舉含有碳酸納、碳酸氫納、碳_、碳酸氫卸、♦酸納、 矽酸鉀、氫氧化納、氫氧化卸等無機驗性化合物，或二乙 醇奴、二乙胺、三乙醇胺、歲氧 軋化四烷基銨、氳氧化四甲 基叙專有機鹼性化合物之水溶液。 於上述驗性顯影液，亦可視需要而含有界面活性 水溶性，有機溶劑、濁濕劑、具有經基或幾酸基之低分子 化合物等。尤其界面活性 ' 叫布/·玍劑中對顯影性、解 具有改良效果者較多，故較w 乏先等 較佳為添加界面活性劑。 上述驗性顯影液所使用夕臾二X 且古裳^ 所使用之界面活性劑，例如可列舉： 古本續酸納基之陰離子性界面活性劑，且 有聚伸烷氧基之非離早M w I . 陽離子蛙炅<&、 活性劑，具有四烷基銨基之 陽離子性界面活性劑等。 驗性顯影處理之方法，廿么成士 抑、較佳為15〜45t之=，、特職制，通㈣於10〜 霧顯影、毛刷顯影、二溫度下，利用浸潰顯影、喷 ^超口波顯影等方法進行。 最終於乾燥烘箱中使复 。(：以下，乾焊，、充刀乾燥。乾燥溫度較佳為250 乾燥時間較佳為6〇分 ^ 且乾燥時間延長超過6〇分 下。、右溫度超過250X：， 成於彩色濃光片上:，則將上述液晶配向用突起形 上時’有對開口部之著色顏料或染料造成 31 200921278 損害而使顯示品質自身降低之虞。 使用本發明之負型抗蝕劑而形成之液晶配向用突起， 亦為本發明之一。 具有本發明之液晶配向用突起之彩色濾光片，亦為 發明之一。 當本發明之彩色濾光片具有上述由本發明之負型抗蝕 劑所構成之液晶配向用突起時，使用該彩色濾光片而形成 之液晶顯示裝置的視角寬廣。使用本發明之負型抗蝕劑、 或本發明之彩色濾光片而形成的液晶顯示裝置，亦為本 明之一。 再者，使用本發明之負型抗蝕劑，亦可形成用以限制 液晶顯示裝置之單元間隙之呈柱狀的柱狀間隔物。 使用本發明之負型抗蝕劑來形成柱狀間隔物之方法， 例如可列舉下述方法：對利用上述方法而於基板上形成之 被膜的成為柱狀間隔物之部分，例如照射比製作液晶配向 用突起所需要之曝光能量更多的光後’進行上述鹼性顯 影。若利用上述方法，則可藉由對上述被膜所照射之光， 使本發明之負型抗㈣充分地聚合硬化，從而可形成高於 上述液晶配向用突起之呈柱狀的柱狀間隔物。 依據本發明，可提供一種液晶配向用突起形成用負型 抗蝕齊]其可开）成用以對液晶顯示裝置之液晶配向進行控 制的犬起’且可防止所製造之液晶顯示裝置產生液晶殘像 現象。 【實施方式】 32 200921278 以下列舉實施例來進一步詳細說明本發明之態樣，但 本發明並非僅限於該等實施例。 (實施例1 ) (1)彩色濾光片之製造 利用光蝕刻法，將Cr薄膜圖案形成於透明基板上。於 其上利用光微影法，將紅色、藍色、綠色感光性樹脂組成 物圖案化，形成紅色、藍色、綠色像素。並且，藉由滅錢 於整個面上形成ITO膜，作為透明導電膜層，從而製造彩 色渡光片。 (2 )鹼溶性樹脂之合成 於具備授拌裝置、滴加漏斗、冷凝器、溫度計、氣體 導入管之燒瓶中投入150重量份之PGMAe，一邊進行氮氣 置換’一邊攪拌，升溫至1丨〇。〇。 接著’自滴加漏斗以2小時將由3 2 · 6重量份（〇 · 3 8莫 耳）之甲基丙烯酸、31.1重量份（0.31莫耳）之甲基丙烯 酸甲酯所構成之單體混合物，及3.6重量份之氫過氧化第三 丁基（日本油脂公司製造，PERBUTYL 〇)滴加至燒瓶中， 並且於110。(：下繼續攪拌3小時而進行老化。 "接著，添加36.4重量份（0.20莫耳）之甲基丙烯酸3,4_ 環氧環己酯、0.36重量份之三苯基膦及〇15重量份之曱基 對苯使該等於im：下反應1M、時。反應係於空氣/ 氮氣環境氣氛下進行。藉此可獲得酸值為IGGmgKOH/g、雙 鍵當量（每1莫耳不飽和基之樹脂的g重量）為5〇 平均分子量為15_之驗溶性樹脂溶液^(固體成分為 33 200921278 %)。 (3) 液晶配向用突起形成用負型抗钮劑之製備 將200重量份之所獲得的驗溶性樹脂溶液p_卜8〇重量 份之作為聚合性單體的苯酚酚醛環氧丙烯酸酯（固體成 分：80%，PGMAc : 20%，EA-6320，新中村化學工業公司 製造）、10重量份之作為光反應起始劑的Irgacure 819 (汽 巴精化公司製造，醯基氧化膦）、1〇重量份之作為具有丙 烯醯氧基之矽烷偶合劑的3-丙烯醯氧基丙基三甲氧基石夕烧 (ΚΒΜ-5 ΙΟ3’^^越化學公司製造）、ι〇〇重量份之作為溶 劑之PGMAc加以混合，製備液晶配向用突起形成用負型抗 蚀劑。 (4) 形成有液晶配向用突起之彩色濾光片基板的製造 將所獲得之液晶配向用突起形成用負型抗蝕劑旋塗於 (1 )中所製造之彩色濾光片上後，於8〇°c下乾燥2分鐘， 獲得塗膜。經由8 // m圓形圖案光罩對所獲得之塗膜照射 lOOmJ/cm2的紫外線後，藉由〇_1%碳酸鈉水溶液顯影 秒，然後用純水清洗30秒。其後，於200°c下進行3〇分鐘 的烘乾處理，獲得具有配向控制用突起之彩色濾光片基板。 (實施例2 ) 於具備攪拌裝置、滴加漏斗、冷凝器、溫度計、氣體 導入管之燒瓶中投入150重量份之PGMAc，—邊進行氮氣 置換，一邊攪拌，升溫至11 〇 °c。 接著’自滴加漏斗以2小時將由32.6重量份（〇 38莫 耳）之曱基丙婦酸、31.1重量份（0.18莫耳）之曱基丙浠 34 200921278 酸苄酯所構成之單體混合物，及3.6重量份之氫過氧化第三 丁基（日本油脂公司製造，PERBUTYL Ο )滴加至燒瓶中， 並且於11 〇 下繼續擾拌3小時而進行老化。 接著，添加36.4重量份（0.20莫耳）之甲基丙烯酸3,4-環氧環己酯、0.36重量份之三苯基膦及0.15重量份之甲基 對苯二酚’使該等於100。(：下反應1〇小時。反應係於空氣/ 氮氣環境氣氛下進行。藉此可獲得酸值為l〇〇mgKOH/g、重 量平均分子量為15000之鹼溶性樹脂溶液P-2(固體成分40 % )。 除了使用所獲得之鹼溶性樹脂溶液P-2以外，以與實施 例1相同之方式’獲得具有液晶配向用突起之彩色攄光片 基板。 (實施例3) 除了使用Irgacure 65 1作為光起始劑以外，以與實施例 1相同之方式，獲得具有液晶配向用突起之彩色遽光片基 板0 (實施例4〜1 8 ) 摻合抗姑劑以使其達到表中記載之摻合比率，以與實 施例1相同之方式，獲得具有液晶配向用突起之彩色濾光 片基板。 (比較例1 ) 除了使用季戊四醇三丙烯酸酯（pe_3a，共榮公司製造） 來代替苯酚酚醛環氧丙烯酸酯（ΕΑ·6320)以外，以與實施 例1相同之方式，製備液晶配向用突起形成用負型抗蝕劑， 35 200921278 使用該液晶配向用突起形成用負型抗蝕劑，而獲得具有液 晶配向用突起之彩色濾光片基板。 (比較例2 ) 除了使用季戊四醇四丙烯酸酯（SR295，SARTOMER 公司製造）來代替苯酚酚醛環氧丙烯酸酯（EA-6320 )以外， 以與實施例1相同之方式，製備液晶配向用突起形成用負 型抗蚀劑’使用該液晶配向用突起形成用負型抗姓劑，而 獲得具有液晶配向用突起之彩色濾光片基板。 (比較例3 ) 除了使用二季戊四醇六丙烯酸酯（DPHA，日本化藥公 司製造）來代替苯酚酚醛環氧丙烯酸酯（EA-6320)以外， 以與實施例1相同之方式，製備液晶配向用突起形成用負 型抗蝕劑，使用該液晶配向用突起形成用負型抗蝕劑，而 獲得具有液晶配向用突起之彩色濾光片基板。 (比較例4 ) 除了使用1，4· 丁二醇二縮水甘油醚二丙烯酸酯 (ARONIX M450，東亞合成公司製造）來代替苯酚酚醛環 氧丙烯酸酯（EA-6320 )以外，以與實施例1相同之方式， 製備液晶配向用突起形成用負型抗蝕劑，使用該液晶配向 用突起形成用負型抗蝕劑，而獲得具有液晶配向用突起之 彩色濾光片基板。 (比較例5) 除了使用三（丙烯醯氧基乙基）異氰尿酸酯（TEICA，第 工業製藥公司製造）來代替苯紛龄搭環氧丙烯酸酯 36OH U The weight average molecular weight of the above-mentioned test-soluble (meth)acrylic copolymer is not particularly limited, and a preferred lower limit is 3,000, and a preferred upper limit is 1,000,000. When the weight average molecular weight of the above-mentioned soluble (meth)acrylic copolymer is less than 3 Å, the adhesion of the liquid crystal alignment protrusion obtained by the jin is lowered, and if it exceeds 10,000 Å, the resolution is lowered. A lower limit is 5_, and a lower limit is 50,000. In the present specification, the weight average molecular weight is measured by a gel' chromatography method, and the value obtained by the conversion of polystyrene is determined. The method for producing the above-mentioned test-soluble (meth)propane-copolymer is, for example, a method in which an alicyclic epoxy group is contained, and a compound having a carboxyl group in a side chain (methyl group) The acrylic copolymer is subjected to ring-opening addition polymerization, and one part of the carboxyl group is modified, and an isocyanate compound, an epoxy compound, a lactone compound, an alcohol compound, etc., and a hydroxyl group formed by the modification and/or a residual carboxyl group are A part of the reaction. The method for producing the (meth)acrylic copolymer having a carboxyl group in the side chain is not particularly limited, and examples thereof include a method of using a radical polymerization initiator and an optional molecular weight modifier to form a bulk polymerization. ': A conventionally known method such as liquid polymerization, suspension polymerization, dispersion polymerization, emulsion polymerization, or the like, wherein a monofunctional unsaturated compound containing a slow group is copolymerized with a (meth)acrylic acid vinegar monomer. The alicyclic epoxy group-containing unsaturated compound is not particularly limited, and, for example, (meth)acrylic acid 3,4-epoxycyclohexanoic acid or the like can be suitably used. The above-mentioned isocyanate compound is not particularly limited, and for example, an isocyanate-based vinegar having a carbon number of 2 to 18 and an isocyanic acid vinegar containing a polymerizable group can be used. When the above-mentioned isocyanic acid-containing polymerizable group is used, the sensitivity at the time of chemical conversion can be further improved, and various physical properties such as heat resistance and (4)-f (tetra) properties can be further improved. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Bonded to form. Specific virgin oxyethyl oleic acid vinegar, 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The basic (4) vinegar (4) 6-base isocyanic acid "nzA〇I (made by Showa Denko)) and 20 200921278 The above isocyanate compound and the above-mentioned modification of the side bond has a hydroxyl group The method of reacting the carboxyl group-containing (meth)acrylic copolymer is not particularly limited, and examples thereof include the following methods: adding or mixing the above-mentioned isocyanate compound into the presence of a small amount of a catalyst The above-mentioned modification is carried out in a (meth)propionic acid solution having a radical and/or a few groups on the side bond. The catalyst used at this time is a special acid, a dibutyltin or the like. For example, laurel may be used, and if necessary, p-methoxybenzoate, p-benzoate, amine, t-butylcatechol, and 2 3_di=agent may be used. For the purpose of suppressing and increasing the amount of money, it is also possible to use propanol, butanol, pentanol, hexanol, and heptyl alcohol. According to the above production method, when the oxime compound is reacted with the hydroxyl group and the carboxyl group in the side chain by the above modification, the olefinic acid copolymer L can be formed. ,.. The structural unit shown by the formula (2b). The oxygen compound is not particularly limited, and examples thereof include an epoxy compound having a carbon number of 2 to 18, a carbon number compound or an epoxy compound containing a polymerizable group. &oxyepoxidation two makes the epoxy compound of ::::::: as the upper_heat=study, the nature of the sex, etc.: physical properties and can further improve the resistance to the above 3 polymerizable groups The emulsification product is not particularly limited, and Example 21 200921278 is preferably a group in which a (meth)acryl fluorenyl group is bonded to an epoxy group via an alkyl group having a carbon number of 2 to fluorene. Specifically, for example, glycidol vinegar (meth)acrylate or the like can be mentioned. The method for reacting the above epoxy compound with a (meth)acrylic copolymer having a hydroxyl group and/or a carboxyl group formed on the side chain by the above modification is not particularly limited, and the following method may be mentioned: In the presence of a solvent, the above epoxy compound is added dropwise or mixed into a solution of the (fluorenyl)acrylic acid copolymer having a hydroxyl group and/or a carboxyl group in the side chain formed by the above modification. The catalyst to be used at this time is not particularly limited, and examples thereof include triethylamine, dipropylamine, tetramethylethylenediamine, dimethyllaurylamine, triethylbenzylammonium chloride, and the like. Methyl cetyl ammonium bromide, tetrabutylammonium bromide, trimethylbutyl bromide scale, tetrabutyl bromide scale, and the like. Further, if necessary, p-methoxyphenol, hydroquinone, naphthylamine, third decyl tea age, and 2,3·di-t-butyl-p-methyl polymerization inhibitor may be used. According to the above production method, when the epoxy compound is reacted with the (meth)acrylic copolymer having a hydroxyl group and/or a carboxyl group formed on the side chain by the above modification, the formula (2c) and (2d) can be formed. The structural unit shown. When the above isocyanate compound, epoxy compound, lactone compound, alcohol compound or the like is reacted with a (meth)acrylic copolymer having a hydroxyl group and/or a carboxyl group formed on the side chain by the above modification, the above ( The amount of the hydroxyl group contained in the fluorenyl-acrylic acid copolymer is equivalent to the amount of 〇~1〇〇mol%. Further, the isocyanate compound, the epoxy compound, the lactone compound 22, the organic compound, and the like are reacted with a (meth)acrylic copolymer having a radical and/or a group formed on the side chain by modification. In the case, τ is caused to react in an amount corresponding to 0 to 90 mol% of the carboxyl group contained in the (meth)acrylic copolymer. If it exceeds 90% by mole, the amount of remnant base remaining will be too small, which may impair alkali solubility and cause deterioration in developability. The above formulas a, b, c, d), (3b), (3e), (3d) and (3e) represent the molar ratio (%) of each component, a+b+c + d+e= When i 〇 0, the lower limit of a, b & d is 〇%, and the upper limit is 9〇%. Further, the lower limit of c is 5% 'the upper limit is 5 %. Further, the lower limit of 6 is 5%, and the upper limit is 60%. The lower limit of c is 5%, and the upper limit is (4) if the state is not full, that is, if the molar ratio of the structural unit containing the slow-base is less than 5%, it is difficult to give the test more than 50/^, and the swelling during development is remarkable. It is difficult to form a pattern. Further, the preferred lower limit of 'e is 5%, and the upper limit is preferably 6〇%. If it is not full, the cross-linking of the test-soluble resin is insufficient, resulting in a decrease in cross-linking density, and the result is destruction in the development step. If it is too large, and the liquid crystal alignment is used, the height unevenness 'if it exceeds 6〇%', the crosslink density of the crosslinked structure may be too high, resulting in difficulty in stably forming an arc shape. Further, in the negative resist of the present invention, the above-mentioned alkali-soluble tree t is preferable; and the knife has an aromatic king. When a liquid crystal factory or apparatus having a projection for liquid crystal alignment formed by using the negative resist of the present invention is used for a long time display, the dielectric loss tangent of the liquid crystal alignment protrusion is reduced by the improvement of the solubility of the aromatic ring. It is more suitable for preventing the phenomenon of liquid crystal afterimage. The test resin having an aromatic ring is not particularly limited, and it is preferred because (meth) 23 200921278 benzyl acrylate copolymer has good adhesion and developability. In the negative resist of the present invention, the lower limit of the acid value of the above-mentioned test-soluble resin is 50 mgKOH/g. When the acid value of the above-mentioned test-soluble resin is less than 50 mgKOH/g, the resolution of the negative resist of the present invention is lowered, and the arcuate liquid crystal alignment protrusion cannot be stably formed. The upper limit of the acid value of the above alkali-soluble resin is not particularly limited, and a preferred upper limit is 15 〇 mgKOH/g. When the acid value of the alkali-soluble resin exceeds 15 〇 mgKOH/g, the adhesion between the liquid crystal alignment protrusion formed by using the negative resist of the present invention and the substrate is lowered. The lower limit of the acid value of the above alkali-soluble resin is 6 〇 mg K 〇 H / g, and the upper limit is more preferably 14 〇 mg KOH / g. In addition, in the present report, the acid value of the above-mentioned test-soluble resin is represented by the following numerical values: the alkali-soluble resin lg is dissolved in an organic solvent, and phenolphthalein is used as an indicator to perform titration by hydrogenation, and the desired hydrogen Tons of potassium oxide. The content of the alkali-soluble resin in the negative resist of the present invention is usually 25% by weight or more, preferably 3% by weight or more, and usually 90% by weight or less, based on the total solid content. It is 8 〇 wt% or less. If the amount of the test-soluble resin is too small, the amount of the test-reducing resin is lowered, the development dissolution rate is lowered, and the like, if it is used, the 敏lU causes a decrease in the sensitivity of the surface, and the reproducibility of the surface shape is poor. In order to stabilize the degree of the liquid crystal alignment protrusion and the shape in contact with the substrate, the content of the alkali-soluble resin is preferably a pure ratio with the content of the polymerizable monomer. Specifically, 24 200921278 The weight ratio of the content is preferably a lower limit of 0.35, more preferably (the content of the alkali-soluble resin) / (the lower limit of the polymerizable property is 0.25', the upper limit is preferably 3 $, and the upper limit is 3. The negative anti-surplus agent of the present invention. The photopolymerization initiator is not particularly limited, and a conventionally known photopolymerization initiator can be used, for example, it can be listed as I. It can be produced by using ultraviolet rays to make ethylene inferior. The radical polymerization is free of a compound derived from a base, a compound which generates an acid by ultraviolet rays, etc. Specific examples of the above-mentioned photopolymerization & initiator include, for example, methoxyphenyl)-4,6- Double (three gas methyl) _ uniform three "Qin" 2_ (4_A克基基)_4,6_ bis(trichloromethyl)-s-triazine, 2·(4·ethoxynaphthyl)_4,6_bis(trismethyl)·s-diazine, 2-(4 -ethoxycarbonylnaphthyl)_4,6_bis(trichloroindenyl)-halothiazine and other halomethylated diazine derivatives, tooth methylated oxadiazole derivatives, 2_(o-phenyl) -4,5-diphenylimidazole dimer, 2-(o-phenyl)-4,5-bis(3'-methoxyphenyl)meridene dimer, 2-(o-fluorophenyl) _4,5_diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2_(o-methoxyphenyl)-4,5-di A timidine derivative such as phenyl glutamic acid dimer, benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether and other benzoin, benzoin alkyl ether '2-曱基蒽g Kun, 2- Ethyl hydrazine, 2-tert-butyl fluorene, 1 - chlorohydrazine and other hydrazine derivatives, benzofluorenone derivatives, benzophenone, mazinone, 2-methyldiphenyl Dibenzophenone derivatives such as ketone, 3-mercaptobenzophenone, 4-mercaptobenzophenone, 2-benzophenone, 4-bromobenzophenone, 2-carboxybenzophenone 2,2-dimethoxy-2- -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-mercaptophenylacetone, 1-hydroxy-25 200921278 base-i-A Ethyl ethyl-(p-isopropylphenyl) ketone, r via benzyl 1 (p-docentylphenyl) ketone, 2-methyl-(4,-(f thio)phenyl)_2_? Acetophenone derivatives such as linke xiao _ 丄 三 trichloromethyl-(p-butylphenyl) ketone, thioxanthene, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2 Thiophenone derivatives such as chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, p-dimethyl a benzoate derivative such as ethyl benzoate, ethyl p-ethylaminobenzoate, acridine derivative such as 9-phenyl acridine or 9-(p-methoxyphenyl) acridine , phenazine derivatives such as 9,10-dimethylbenzophenazine, dicyclopentadiene-di-titanium dihydride, di-cyclopentadienyl-titanium-bis-phenyl, di-cyclopentadiene Base_titanium-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-cyclopentadienyl_titanium_bis-2,3,5,6-tetrafluorophenyl-1 -yl, di-cyclopentadienyl, titanium, bis-2,4,6-trifluorophenyl 4,yl,di-cyclopentadienyl-indole_2,6 -difluorophenyl-1-yl, di-cyclopentadienyl _ titanium-2,4-difluorophenyl-1-yl, di-methylcyclopentadienyl 鈥 双 double _2,3 ,4,5,6-pentafluorophenyl-1-yl, bis-indolylcyclopentadienyl-titanium-bis-2,6-difluorophenyl-1-yl, di-cyclopentadienyl- Titanocene derivative such as titanium-2,6-difluoro-3-(indol-1-yl)-phenyl-1-yl, 2-methyl-1[4-(methylthio)phenyl]- 2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-benzyl-2-dimethyl Amino-1-(4-morpholinylphenyl)butane-1.one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate , 4-diethylaminoacetophenone, 4-didecylaminopyrrolidone, ethylhexyl-I,4-dimethylaminobenzoate, 2,5-bis(4-diethyl) Aminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone And other α-aminoalkyl ketone-based compounds, hydrazine, 2·octanedione, 1-[4-(phenylthio)phenyl]-2-(indolyl-benzhydrylhydrazine), ethyl ketone-l -[9-ethyl 26 200921278 winter (2-methyl benzoyl) _9H+ sitting _3_ base] + (Ethylene-based (6) and other biological products, bis (2,4,6-trimethylphenyl fluorenyl) _ phenyl phosphine oxide and other oxidized lining compounds. These photopolymerization initiators may be used singly or in combination of two or more. Among them, the phosphine oxide-based initiator is preferred because it can easily form the shape of the obtained projection for liquid crystal alignment into a bow shape. Among the above-mentioned phosphine oxide-based initiators, there are commercially available ones, for example, Irgacure 8 ί 9 (manufactured by Ciba Specialty Chemicals Co., Ltd.), __ 8! 9 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and Darocure TP〇 ( Made by Ciba Specialty Chemicals Co., Ltd., sp_246 (made by ADEKA). In the negative resist of the present invention, the content of the photopolymerization initiator is not particularly limited, and a preferred lower limit is 0" by weight based on 1 part by weight of the total of the alkali-soluble resin and the polymerizable monomer. The upper limit is preferably 4 〇 by weight. When the content of the photopolymerization initiator is less than 1 part by weight, the photocuring will be insufficient, and if the adhesion between the liquid crystal alignment protrusion and the substrate is lowered, if it exceeds 40 parts by weight, the photohardening reaction may excessively proceed. The shape of the developing residue or the obtained liquid crystal alignment protrusion is not bow-shaped, resulting in abnormal liquid crystal alignment. A more preferred lower limit of the content of the photopolymerization initiator is 0.2 parts by weight, more preferably 3 parts by weight, still more preferably 0.5 parts by weight, and still more preferably 2 parts by weight. In order to alleviate the reaction hindrance caused by oxygen, the negative resist of the present invention may further contain a reaction assistant. By using the above-mentioned reaction assistant together with the dehydrogenation type photoinitiator, the rate of hardening upon irradiation with light can be increased. The above reaction assistants may be exemplified by n-butylamine, di-n-butylamine, triethylamine, tri-ethylidene tetraamine, p-dimethylaminobenzoic acid ethyl ester, p-terracer 27 200921278-amino group stupid An amine-based reaction aid such as isoamyl phthalate, a phosphine-based reaction aid such as tri-n-butylphosphine, or a sulfonic acid-based reaction aid such as s-nodal isothiourea-p-toluenesulfonate. These reaction assistants may be used singly or in combination of two or more. The negative resist of the present invention may also contain a decane coupling agent. The above decane coupling agent has an effect of improving the adhesion between the negative resist of the present invention and the substrate. The above decane coupling agent is not particularly limited, and a previously known stone sinter coupling agent can be used. Wherein ' is preferably one having an acryloxy group or a methyl propylene oxide group as a functional group. By containing a dreaming coupling agent having an acryloxy group or a methyl propylene oxide as a functional group, the adhesion of the negative resist of the present invention to a substrate can be greatly improved. Examples of the decane coupling agent having the above propylene hydroxy group include 3-propyl methoxypropyltrimethoxysilane m (tetra)oxypropyltriethoxy decane. Further, examples of the decane coupling agent having the above-mentioned f-group acryloxy group include 3-methyl propylene methoxy propyl methyl dimethoxy decane and % methacryl methoxy propyl trimethoxy hydride. Burned, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, and the like. These decane coupling agents may be used singly or in combination of two or more. In the negative resist of the present invention, the content of the above-mentioned decane coupling agent is not particularly limited. When the total of the solubility-reducing gambling and the polymerizable monomer is (10) $ parts, the preferred lower limit is 〇.丨 weight. The upper limit is preferably 4 parts by weight. When the content of the above-mentioned sulphur coupling agent is less than 1 part by weight, the adhesion to the substrate is lowered. If it exceeds 4 parts by weight, an alkaline development occurs in the photolithography 28 200921278. A more preferable upper limit of the content of the above decane coupling agent is 30 parts by weight. The lower limit is 1 weight of Dong, the agent's anti-agent, which constitutes the negative resistance of the present invention - becomes the weight: the solvent is adjusted to the lower limit of the solid concentration, the upper limit is 5 G weight%, preferably The lower limit is 10% by weight and the upper limit is 40% by weight. The organic solvent which is soluble or dispersible in the above respective components and which is excellent in the operation is not particularly limited. Specifically, one can be exemplified by methyl acesulfame, ethyl acesulfame, butyl celecoxib, diethylene glycol monomethyl hydrazine, diethylene glycol di butyl sulphate, diethylene glycol methyl sulphur, propylene glycol Hyperthyroid acetic acid vinegar (hereinafter referred to as "PGMAe"), methyl ethyl net, methyl isobutyl ketone, cyclohexyl, toluene, gas imitation, digastric hospital, ethyl acetate, methyl lactate, lactate B Vinegar, methanol, ethanol, propanol, butanol, tetrahydrofuran, etc. The above organic solvent preferably has a boiling point of from 100 to 200. More preferably, the organic solvent having a boiling point of 120 to 18 (the range of TC) is used. The method for producing the negative resist of the present invention is not particularly limited, and examples thereof include the following methods: The above-mentioned test-soluble resin, a polymerizable monomer containing a phenolic epoxy (meth) acrylate, a photopolymerization initiator, an organic solvent, and an optional additive are placed in a stirring tank, and are mixed using a stirring blade or the like. A method of manufacturing a projection for liquid crystal alignment by using a negative resist. When a negative resist of the present invention is used to produce a projection for liquid crystal alignment, 29 200921278 First, the negative resist of the present invention is coated. The coating film is formed to have a specific thickness to form a film. The coating method is not particularly limited, and examples thereof include spin coating, slit rotation, slit coating, spray coating, and dip coating. A conventionally known coating method such as a bar coating method, etc. Next, an active light such as ultraviolet rays is irradiated onto the formed film through a mask having a specific pattern, thereby making the negative of the present invention The alkali-soluble resin, the polymerizable monomer, and the photopolymerization initiator contained in the resist are photocured by the reaction in the light-irradiating portion. The active light is not particularly limited, and for example, visible light, ultraviolet light, or far ultraviolet light can be used. The electron beam and the X-ray f are preferably ultraviolet rays. The liquid crystal alignment protrusion can be formed, for example, by adjusting the amount of light irradiated to the liquid crystal alignment protrusion forming portion of the coating film. The method to be used, the method and the like: when the active light is irradiated through the mask, for example, a gray scale or a half-order light is used in order to form a bow-shaped liquid crystal alignment protrusion in an alkali development treatment to be described later. The wavelength of the active light such as ultraviolet rays to be irradiated is not particularly limited, and ultraviolet rays having a wavelength of about 200 to 600 nm are preferably used. The preferred lower limit of the irradiation amount of the active light is 1 〇mj/em 2 . The upper limit is preferably SOOmJ/cm2 ^ If the irradiation dose of the above active light is less than 1 〇mW, the photohardening will be insufficient, and the image is developed during the development step. If the irradiation amount of the active light rays exceeds 500 mJ/cm 2 , the development residue is likely to be formed. 30 200921278 Next, the photocured material after photocuring is subjected to alkaline development to form a substrate on the substrate. A liquid crystal alignment protrusion formed by a photo-cured material of a negative resist. The solvent used in the alkaline development treatment is a solvent having the ability to dissolve the coating film of the uncured portion. There is no particular limitation, and examples thereof include inorganic compounds such as sodium carbonate, sodium hydrogencarbonate, carbon _, hydrogencarbon hydride, sodium phthalate, potassium citrate, sodium hydroxide, and hydrazine, or diethanol slaves. An aqueous solution of diethylamine, triethanolamine, oxidized tetraalkylammonium oxide, and cerium oxide tetramethyl-specific organic basic compound. The above-mentioned organic developer may also contain an interfacially active water-soluble, an organic solvent, a wet agent, a low molecular compound having a transbasic group or a few acid groups, as needed. In particular, the interface activity is called "cloth", and there are many improvement effects on developability and solution. Therefore, it is preferable to add a surfactant in comparison with w. The surfactant used in the above-mentioned animated developer is, for example, an anionic surfactant of the ancient sodium sulfonate, and a non-dissociating M of the polyalkylene group. w I. cationic frog frog <&, active agent, cationic surfactant having a tetraalkylammonium group, and the like. The method of qualitative development treatment, 廿 成 成 抑, preferably 15~45t =, special system, pass (four) in 10~ fog development, brush development, two temperatures, using immersion development, spray ^ super Method such as oral wave development. It is finally reconstituted in a drying oven. (: The following, dry welding, dry knife filling. The drying temperature is preferably 250. The drying time is preferably 6〇 minutes^ and the drying time is extended by more than 6〇. The right temperature is over 250X:, on the color concentrating sheet. When the liquid crystal alignment protrusion is formed, the coloring pigment or dye to the opening portion is damaged by 31 200921278, and the display quality itself is lowered. The liquid crystal alignment formed by using the negative resist of the present invention is used. The protrusion is also one of the inventions. The color filter having the protrusion for liquid crystal alignment of the present invention is also one of the inventions. The color filter of the present invention has the above-described negative resist of the present invention. In the liquid crystal display device, the liquid crystal display device formed by using the color filter has a wide viewing angle. The liquid crystal display device formed by using the negative resist of the present invention or the color filter of the present invention is also Further, by using the negative resist of the present invention, columnar spacers for limiting the cell gap of the liquid crystal display device can be formed. The negative resist of the present invention is used. In the method of forming the columnar spacer, for example, a portion which becomes a columnar spacer on the substrate formed on the substrate by the above method, for example, is irradiated more than the exposure energy required for producing the protrusion for liquid crystal alignment. After a large amount of light, the above alkaline development is carried out. According to the above method, the negative electrode (4) of the present invention can be sufficiently polymerized and cured by the light irradiated to the film, thereby forming higher than the liquid crystal alignment. According to the present invention, a columnar spacer for forming a liquid crystal alignment protrusion can be provided, which can be opened to control the liquid crystal alignment of the liquid crystal display device. Moreover, the liquid crystal afterimage phenomenon can be prevented from occurring in the manufactured liquid crystal display device. [Embodiment] 32 200921278 The following examples are given to further illustrate the aspects of the invention, but the invention is not limited to the embodiments. (Example 1) (1) Production of color filter A Cr thin film pattern was formed on a transparent substrate by photolithography. On the above, a red, blue, and green photosensitive resin composition is patterned by photolithography to form red, blue, and green pixels. Further, an ITO film was formed on the entire surface by extinction of money to form a transparent conductive film layer, thereby producing a color light-emitting sheet. (2) Synthesis of alkali-soluble resin 150 parts by weight of PGMAe was placed in a flask equipped with a mixing device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the mixture was stirred while stirring, and the temperature was raised to 1 Torr. Hey. Then, a monomer mixture composed of 3 2 · 6 parts by weight of methacrylic acid and 31.1 parts by weight (0.31 mol) of methyl methacrylate was added from a dropping funnel over 2 hours. And 3.6 parts by weight of a third butyl hydroperoxide (manufactured by NOF, PERBUTYL®) was added dropwise to the flask at 110. (: aging was continued for 3 hours while stirring. " Next, 36.4 parts by weight (0.20 mol) of 3,4_epoxycyclohexyl methacrylate, 0.36 part by weight of triphenylphosphine, and 15 parts by weight of hydrazine were added. The hydrazine-based benzene is equal to im: the next reaction is 1 M. The reaction is carried out under an air/nitrogen atmosphere, whereby an acid value of IGGmgKOH/g and a double bond equivalent (per 1 mole of unsaturated group) can be obtained. The g-weight of the resin is 5 Å of a test resin solution having an average molecular weight of 15 Å (solid content: 33 200921278 %). (3) Preparation of a negative-type resist agent for forming a liquid crystal alignment protrusion 200 parts by weight The phenolic phenolic epoxy acrylate as a polymerizable monomer (solid content: 80%, PGMAc: 20%, EA-6320, manufactured by Shin-Nakamura Chemical Co., Ltd.), 10 parts by weight of Irgacure 819 as a photoreaction initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., fluorenylphosphine oxide), and 1 part by weight of 3-propenyloxypropane as a decane coupling agent having an acryloxy group. Base trimethoxy stone shochu (ΚΒΜ-5 ΙΟ3'^^ Vietnam Chemical Co., Ltd. And a PGMAc as a solvent, and a negative resist for forming a liquid crystal alignment protrusion is prepared. (4) Production of a color filter substrate on which a liquid crystal alignment protrusion is formed, the obtained liquid crystal The alignment protrusion formation negative-working resist was spin-coated on the color filter manufactured in (1), and then dried at 8 ° C for 2 minutes to obtain a coating film. The circular pattern light was passed through 8 // m After the obtained coating film was irradiated with ultraviolet rays of 100 mJ/cm 2 , it was developed with 〇 1 % sodium carbonate aqueous solution for a second, and then washed with pure water for 30 seconds. Thereafter, it was dried at 200 ° C for 3 minutes. The color filter substrate having the protrusion for the alignment control was obtained. (Example 2) 150 parts by weight of PGMAc was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube. Nitrogen replacement, while stirring, the temperature was raised to 11 〇 ° C. Next, 'from the dropping funnel, 22.6 parts by weight (〇38 mol) of thioglycolic acid, 31.1 parts by weight (0.18 mol) of sulfhydryl group was added for 2 hours.丙浠34 200921278 Monomer mixture of benzyl acetate The compound and 3.6 parts by weight of a third butyl hydroperoxide (manufactured by Nippon Oil & Fats Co., Ltd., PERBUTYL®) were added dropwise to the flask, and aging was continued for 3 hours under 11 Torr. Next, 36.4 parts by weight were added. (0.20 mol) of 3,4-epoxycyclohexyl methacrylate, 0.36 part by weight of triphenylphosphine, and 0.15 part by weight of methyl hydroquinone'. This is equal to 100. (: 1 reaction) Hour. The reaction was carried out under an air/nitrogen atmosphere. Thus, an alkali-soluble resin solution P-2 (solid content: 40%) having an acid value of 10 mg/kg and a weight average molecular weight of 15,000 was obtained. A color light-emitting sheet substrate having protrusions for liquid crystal alignment was obtained in the same manner as in Example 1 except that the obtained alkali-soluble resin solution P-2 was used. (Example 3) A color calender substrate 0 having a projection for liquid crystal alignment (Examples 4 to 18) was obtained in the same manner as in Example 1 except that Irgacure 65 1 was used as the photoinitiator. The color filter substrate having the protrusions for liquid crystal alignment was obtained in the same manner as in Example 1 so that the blending ratio was as shown in the table. (Comparative Example 1) A liquid crystal alignment protrusion was formed in the same manner as in Example 1 except that pentaerythritol triacrylate (pe_3a, manufactured by Kyoei Co., Ltd.) was used instead of phenol novolac epoxy acrylate (ΕΑ·6320). Negative Resist, 35 200921278 A negative-type resist for forming a projection for liquid crystal alignment is used to obtain a color filter substrate having projections for liquid crystal alignment. (Comparative Example 2) In the same manner as in Example 1, except that pentaerythritol tetraacrylate (SR295, manufactured by SARTOMER Co., Ltd.) was used instead of phenol novolac epoxy acrylate (EA-6320), a negative electrode for liquid crystal alignment was prepared. In the type of the resist, a negative-type anti-surname agent for forming a projection for liquid crystal alignment is used to obtain a color filter substrate having protrusions for liquid crystal alignment. (Comparative Example 3) A liquid crystal alignment protrusion was prepared in the same manner as in Example 1 except that dipentaerythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) was used instead of phenol novolac epoxy acrylate (EA-6320). A negative-type resist is formed, and a negative-type resist for forming a projection for liquid crystal alignment is used to obtain a color filter substrate having projections for liquid crystal alignment. (Comparative Example 4) In the same manner as Example 1, except that 1,4-butanediol diglycidyl ether diacrylate (ARONIX M450, manufactured by Toagosei Co., Ltd.) was used instead of phenol novolac epoxy acrylate (EA-6320). In the same manner, a negative resist for forming a projection for liquid crystal alignment is prepared, and a negative resist for forming a projection for liquid crystal alignment is used to obtain a color filter substrate having projections for liquid crystal alignment. (Comparative Example 5) In place of benzoic acid epoxy acrylate, tris(propylene oxyethyl) isocyanurate (TEICA, manufactured by Industrial Pharmaceutical Co., Ltd.) was used instead.

V'..， 使用實施例1〜1 8及比較例 T所後得之具有液晶 200921278 (ΕΑ_6320 )以外’以與實施例1相同之方式，製備液晶配 向用突起形成用負型抗蝕劑，使用該液晶配向用突起形成 用負型抗姓劑’而獲得具有液晶配向用突起之彩色滤光片 基板。 (評價） 對實施例1〜1 8及比較例1〜5進行以下評價。 結果示於表1〜3中。 (殘像評價） ， ，八 VI 日日 配向用突起之彩色濾光片基板來製作MVA_LCD。其後，於 常溫下24小時連續對MVA_LCD施加電壓，進行影像顯示。 以目視觀察連續顯示24小時後之影像。將顯示圖案立即、、肖 失，情況評價為「◎」，録i分鐘以内消失之情況評價 為「〇」，將在1分鐘以内並未消失之情況評價為「X : (顯影殘渣評價） X」° 藉由光學顯微鏡及SEM,對液晶配向用 渣進行評價。將於一 起之顯影殘 仃干價冑於圖案周邊部完全未看到顯 評價為「◎,，將於_安H泛加立， 戈/查的情況 ^」將於圖案周邊部看到極少之顯影& + 況評價為「〇」，將於圖宏岡，軎却说i "殘凌的情 情況評價為「八,^ "貝衫殘渣的 △」將看到較多顯影殘渣之情況評 (突起形狀及去光評價） ’、、、X」。 藉由光學顯微鏡及SEM，觀察液晶配向用， 巧之形狀。 37 200921278 38 (霉蛛14)务笛 突起形狀 顯影殘渣評價 殘像評價 其他 溶劑 光聚合起始劑 i 聚合性單體 鹼溶性樹脂 矽烷偶合劑 PGMAc s c 3 1 Os C rS 垂 «> SO 5 w Q a in* L· ^ p> >>芦 '^<· 1，4-丁二醇二縮水甘油醚二丙烯酸酯 | (ARONIXM450:東亞合成公司製造） /—N α s ι» > * .•洚 ^ a 扦碟 ί分 3漭 婢爵 V^- 00 δ Ό 以伸 Η ^ 〇 @ 实$ ϊΐ>离 *511 溫 ψ ^ ^ S >tt * ^ t s^/ 2 t ^ IW o u 14® ·.二 |；E * ^ s ·. Η ^ ^ ^ 5 W ^ Q ^ W O ru _ .，S nl nj —峰s ..Η ^ § >>抻 Ο f ·ν>| W *211 G障 » o f _每§; ..H ^ ^ >yn S ϋ w /-~S U) 14 S舛 1φ ·霉 卡驾霉 今耸銦 4i c^ ^ _ Η幕 S，簿 8冷屝 y 1 1 〇 〇 〇 I—· 〇 〇 1 5 1 1 1 1 1 1 1 1 g 1 200 實施例1 ου 〇 ◎ 〇 >—· 〇 1 1 1 1 1 1 1 1 1 g 200 1 實施例2 ； 梯形 〇 〇 〇 1 1 1 1 1 1 1 1 1 g 1 200 實施例3 1 μ 1 ◎ 〇 5 〇 垂 〇 ί 1 1 1 1 1 1 g 1 1 200 實施例4 ㈣1 ◎ 〇 〇 〇 1 o 1 1 1 « 1 1 1 1 I o 實施例5 1弓形 ◎ 〇 〇 1 1 > 1 垂 1 1 t 1-^ g 1 1 200 實施例6 I弓形| ◎ 〇 〇 ο t 1 1 1 1 g 1 1 g 1 1 200 實施例7 «Λ ◎ ◎ ο t 1 1 1 1 1 1 δ 1 M 〇 1 實施例8 , 弓形 ◎ 〇 〇 ο 1 s t 1 1 1 1 1 g 1 t to o 實施例9 ◎ 〇 5 ο 1 5 1 1 ( m* 1 1 i g 1 200 |實施例ίο | 200921278 39In the same manner as in Example 1, except that the liquid crystal 200921278 (ΕΑ_6320) was used, the negative resist for forming a liquid crystal alignment protrusion was prepared, using the examples 1 to 18 and the comparative example T. A color filter substrate having a projection for liquid crystal alignment is obtained by forming a negative anti-surname agent for the liquid crystal alignment protrusions. (Evaluation) The following evaluations were performed on Examples 1 to 18 and Comparative Examples 1 to 5. The results are shown in Tables 1 to 3. (Residual image evaluation) , , 8 VI Days The MVA_LCD was fabricated by using a raised color filter substrate. Thereafter, a voltage was continuously applied to the MVA_LCD at room temperature for 24 hours to perform image display. The images after 24 hours of continuous display were visually observed. The display pattern was evaluated immediately as "Zy", and the case was evaluated as "?", and the case where it disappeared within 1 minute was evaluated as "〇", and the case where it did not disappear within 1 minute was evaluated as "X: (Development residue evaluation) X ° The liquid crystal alignment slag was evaluated by optical microscopy and SEM. The developer's dry residue will be smothered at the periphery of the pattern and will not be seen as "◎, will be in the _ An H pan, the situation of Go / check ^" will see very few in the periphery of the pattern The development & + condition is evaluated as "〇", and it will be evaluated in the picture of Honggang, but the situation of i " residual is evaluated as "eight, ^ " △ of the shell residue" will see more development residue (protrusion shape and light removal evaluation) ', ,, X". By optical microscopy and SEM, the shape of the liquid crystal alignment is observed. 37 200921278 38 (Moldworm 14) Flute protrusion shape Development residue evaluation afterimage evaluation Other solvent Photopolymerization initiator i Polymerizable monomer alkali-soluble resin decane coupling agent PGMAc sc 3 1 Os C rS 垂«> SO 5 w Q a in* L· ^ p>>>Lu'^<· 1,4-butanediol diglycidyl ether diacrylate | (ARONIXM450: manufactured by Toagosei Co., Ltd.) /—N α s ι» &gt ; * .•洚^ a 扦 ί ί 漭婢 漭婢 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ V 〇 〇 511 511 511 511 511 511 511 511 511 511 511 511 511 511 ^ ^ ^ ^ ^ ^ ^ ^ ^ IW ou 14® ·.二|;E * ^ s ·. Η ^ ^ ^ 5 W ^ Q ^ WO ru _ .,S nl nj —peak s ..Η ^ § >>抻Ο f ·ν> | W *211 G Barrier » of _Every §; ..H ^ ^ >yn S ϋ w /-~SU) 14 S舛1φ ·Mold Card Dicky Insect Today 4i c^ ^ _ Curtain S, Book 8冷屝 y 1 1 〇〇〇I—· 〇〇1 5 1 1 1 1 1 1 1 1 g 1 200 Example 1 ου 〇◎ 〇>—· 〇1 1 1 1 1 1 1 1 1 g 200 1 Example 2; trapezoidal 〇〇〇 1 1 1 1 1 1 1 1 1 g 1 200 Example 3 1 μ 1 ◎ 〇 5 〇 〇 〇 1 1 1 1 1 1 1 1 1 1 1 Example 4 (4) 1 ◎ 〇〇〇 1 o 1 1 1 « 1 1 1 1 I o Example 5 1 bow ◎ 〇〇 1 1 > 1 垂 1 1 t 1-^ g 1 1 200 Example 6 I bow | ◎ 〇〇ο t 1 1 1 1 g 1 1 g 1 1 200 Example 7 «Λ ◎ ◎ ο t 1 1 1 1 1 1 δ 1 M 〇 1 Example 8 , bow ◎ 〇〇 ο 1 st 1 1 1 1 1 g 1 t to o Example 9 ◎ 〇 5 ο 1 5 1 1 ( m* 1 1 ig 1 200 | Example ίο | 200921278 39

(麥_14)麥r荦 突起形狀 ； 顯影殘渣評價 殘像評價 其他 落劑 光聚合起始 劑 聚合性單體 驗溶性樹脂 矽烷偶合劑 PGMAc 〇 C 1 GS 1—* β Ρ 1 00 s 5 W 5 ^ ^:審 Η 5? >> ^ 辟靡 Vw/ 1,4-丁二醇二縮水甘油醚二丙烯酸酯 (ARONIXM450:東亞合成公司製造） 〇 S 1' > ^ ••洚 计猓 CT ^ 3踝 \w/ ，~\ ζΛ S Ό ^ * ί a 〇 a 工> 1U W ^ ：»審 >> ^ *5!i 溫 鸿 S k ^ ^ @ » ^ ^ S 体Μ Ν««* m盔 >蘚 » ° | Ι4ί · it ^>5 J + ξ s H® # 5; ..H ^ έ _迕 Ο »婢 健審 ^ S atr G脔 > ^ ϊέ| ^>55 _呢§ ..Η ^ S ， § ^ ^ 錄幕 辟s： 、_✓ ΠΓΓ ς;蔺 s*u- > ^ » έ | W r, !z ni ^11 H® S ..H ^ rt ^ ^ is v—^ ΠΚΓ W > os /s UJ 1# o辦 w® ·.霉 卡驾:霉 今5雜 4ι π- pt 一來③ ·. Η萬 5 _琛 〇 t*> » 〇 · οσ w 3 辟· "TJ NJ y 弓形 ◎ ◎ 〇 1—* 〇 1 1 1 1 1 1 1 1 g > 〇 1 實施例11 i 梯形 ◎ 〇 〇 〇 〇 1 1 1 垂 t 1 1 1 g 1 1 200 1實施例12 「弓形| ◎ 〇 〇 〇 1 1 1 1 1 1 1 g 1 1 1 200 實施例13 丨弓形| ◎ ◎ 〇 1 t 1 1 垂 1 1 g 1 1 200 1 實施例14 梯形 ◎ 〇 〇 〇 1 1 1 1 < 1 1 g 1 1 1 200 實施例15 丨弓形| 〇 〇 〇 〇 1 1 1 1 1 1 g 1 t 1 1 ο 實施例16 i I弓形 | > ◎ 5 〇 垂 1 1 垂 1 1 g 垂 t 1 200 1 |實施例17 梯形 > 〇 〇 〇 1 垂 1 1 1 1 g 1 < 1 1 200 |實施例18 I 【沐2】 200921278 :κί PGMAc(Mg_14) Mai r荦 protrusion shape; Development residue evaluation afterimage evaluation Other agent photopolymerization initiator Polymerizable single experience solvent resin decane coupling agent PGMAc 〇C 1 GS 1—* β Ρ 1 00 s 5 W 5 ^ ^: REVIEW 5? >> ^ 靡Vw/ 1,4-butanediol diglycidyl ether diacrylate (ARONIXM450: manufactured by Toagosei Co., Ltd.) 〇S 1' > ^ ••洚CT ^ 3踝\w/ ,~\ ζΛ S Ό ^ * ί a 〇a工> 1U W ^ :»审>> ^ *5!i Wen Hong S k ^ ^ @ » ^ ^ S Ν««* m helmet>藓» ° | Ι4ί · it ^>5 J + ξ s H® # 5; ..H ^ έ _迕Ο »婢健审^ S atr G脔> ^ ϊέ| ^>55 _ ́ § ..Η ^ S , § ^ ^ Screening s: , _✓ ΠΓΓ ς; 蔺 s*u- > ^ » έ | W r, !z ni ^11 H® S . .H ^ rt ^ ^ is v-^ ΠΚΓ W > os /s UJ 1# o do w® ·.Muscle card drive: moldy today 5 miscellaneous 4ι π- pt one to 3 ·. Η万5 _琛〇t *> » 〇· οσ w 3 辟·"TJ NJ y bow ◎ ◎ 〇1—* 〇1 1 1 1 1 1 1 1 g > 〇1 Example 11 i trapezoid ◎ 〇〇〇〇1 1 1垂t 1 1 1 g 1 1 2 00 1 Embodiment 12 "Bow shape| ◎ 〇〇〇 1 1 1 1 1 1 1 g 1 1 1 200 Example 13 丨 bow shape| ◎ ◎ 〇 1 t 1 1 垂 1 1 g 1 1 200 1 Example 14 trapezoid ◎ 〇〇〇1 1 1 1 < 1 1 g 1 1 1 200 Example 15 丨 bow shape | 〇〇〇〇 1 1 1 1 1 1 g 1 t 1 1 ο Example 16 i I bow | > ◎ 5 〇垂1 1 垂1 1 g 垂t t 1 200 1 |Example 17 Trapezoidal > 〇〇〇1 垂1 1 1 1 g 1 < 1 1 200 |Example 18 I [Mu 2] 200921278 :κί PGMAc

Irgacur? 651Irgacur? 651

Irgacure - 819 1,4-1-卜磷.^爺矢砵穿黑l·31荼踝溫 (ARONIXM450 :^商命许冷^濉緙) 卜^^@驟^亦審踝-(DPHA: 3^-^^3雔辟) (SR295 : SARTOMER.^·^^^) (PE-3A:氺澉、雔硌) 窩錄簿驾涔tef琴翠磷錮坪⑧審琛爵 (EA-7440 :驾士茸-啷卜鰣冷^鸿蝌) (衅4-^苏今屮*: 4000) 蔺漭辫眾烊鸡卜f^翠磷if^a^stsl (EA-7140 :鸯卡^-噼卜棘冷^嫜辟) (時t卡甚今屮t二800) 障漭萍埤涔f Λ舛零琴磷鍊鉀^莓琛溫 (ΕΑ-6340 :驾+茸-啷卜鱗冷^濉辟) _^1+苏今屮*:1200) 舛零翠磷痲衅31粢踝si (EA-6320 :驾卡戽-噼卜鵃冷3嬅娲) (tt卡苏今屮t : 1000) ρ·2 P-1 〇 5 50 5 °°0 200Irgacure - 819 1,4-1-Bu Pho.^Yayao wears black l·31荼踝温(ARONIXM450:^商命许冷^濉缂) Bu ^^@骤^也审踝-(DPHA: 3 ^-^^3雔)) (SR295: SARTOMER.^·^^^) (PE-3A: 氺澉, 雔硌) 录 簿 涔 涔 涔 涔 涔 涔 涔 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( (驾士士-啷卜鲥冷^鸿蝌) (衅4-^苏今屮*: 4000) 蔺漭辫众烊鸡卜f^翠磷if^a^stsl (EA-7140: 鸯卡^-噼卜刺冷^嫜辟) (Time t card even today 屮t two 800) 漭 漭 埤涔 埤涔 Λ舛 Λ舛 磷 磷 Phosphorus chain potassium ^ 琛 琛 ΕΑ ΕΑ 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340 340辟) _^1+苏今屮*:1200) 舛零翠磷麻衅31粢踝si (EA-6320: Driving card 噼-噼卜鵃冷3嬅娲) (tt Kasu today 屮t: 1000) ρ·2 P-1 〇5 50 5 °°0 200

S Δ 10 100 5 80 200 > s 100 s § 200 -游重3 > 10 100 5 § 200S Δ 10 100 5 80 200 > s 100 s § 200 - swim weight 3 > 10 100 5 § 200

S Δ 5 50 10 § 200 -齊^5 200921278 [產業上之可利用性] 依據本發明，可提供一種液晶配向用突起形成用負型 抗蝕劑，其可形成用以對液晶顯示裝置之液晶配向進行控 制的突起，且可防止所製造之液晶顯示裝置產生液晶殘像 現象。 【圖式簡單說明】 無 【主要元件符號說明】 無 41S Δ 5 50 10 § 200 - 齐^5 200921278 [Industrial Applicability] According to the present invention, a negative resist for forming a liquid crystal alignment protrusion can be provided, which can form a liquid crystal for a liquid crystal display device The protrusions are controlled to be controlled, and the phenomenon of liquid crystal afterimage of the liquid crystal display device produced can be prevented. [Simple description of the diagram] None [Key component symbol description] None 41

Claims (1)

200921278 十、申請專利範困： 1 · 一種液晶配向用突起形成用負型抗蝕劑，係含有鹼溶 性樹脂、聚合性單體及光聚合起始劑，用以形成MVA方式 之液晶顯示裝置的液晶配向用突起，其特徵在於： 該聚合性單體含有酚醛環氧（曱基）丙烯酸酯。 2.如申請專利範圍第1項之液晶配向用突起形成用負 型抗蚀劑’其中，酚醛環氧（曱基）丙烯酸酯之重量平均分子 量為600〜2000。 3 ·如申請專利範圍第1或2項之液晶配向用突起形成用 負型抗钱劑’其中’紛經環氧（甲基）丙稀酸酯具有驗溶性官 能基。 4. 如申請專利範圍第1、2或3項之液晶配向用突起形 成用負型抗蝕劑’其中，鹼溶性樹脂係具有（曱基）丙烯酸 基、缓基及节基者。 5. 如申凊專利範圍第1、2、3或4項之液晶配向用突起 形成用負型抗蝕劑，其中，光聚合性起始劑係含有氧化膦 糸起始劑。 十一、圖式： 益 42200921278 X. Patent application: 1 · A negative resist for forming a liquid crystal alignment protrusion, comprising an alkali-soluble resin, a polymerizable monomer, and a photopolymerization initiator for forming an MVA liquid crystal display device The liquid crystal alignment protrusion is characterized in that the polymerizable monomer contains a novolac epoxy (fluorenyl) acrylate. 2. The negative resist for forming a projection for liquid crystal alignment according to the first aspect of the invention, wherein the phenolic epoxy (fluorenyl) acrylate has a weight average molecular weight of 600 to 2,000. 3. The negative-type anti-money agent for forming a liquid crystal alignment protrusion according to claim 1 or 2, wherein the epoxy (meth) acrylate has a solubility functional group. 4. The negative resist for forming a projection for liquid crystal alignment according to the first, second or third aspect of the patent application, wherein the alkali-soluble resin has a (fluorenyl)acrylic group, a slow-base group and a sulfhydryl group. 5. The negative resist for forming a liquid crystal alignment protrusion according to the first, second, third or fourth aspect of the invention, wherein the photopolymerizable initiator contains a phosphine oxide ruthenium initiator. XI. Schema: Benefit 42