TW201243500A

TW201243500A - Negative photosensitive resin composition and coating film

Info

Publication number: TW201243500A
Application number: TW101108292A
Authority: TW
Inventors: Hideyuki Takahashi; Kenji Ishizeki; Masayuki Kawashima; Yutaka Furukawa
Original assignee: Asahi Glass Co Ltd
Priority date: 2011-03-31
Filing date: 2012-03-12
Publication date: 2012-11-01
Also published as: JP2014122926A; WO2012132755A1

Abstract

Provided is a photosensitive composition that has excellent ink-repellency and can produce a barrier capable of maintaining ink-repellency when irradiated with ultraviolet light or ozone, the negative photosensitive resin composition having excellent storage stability. Also provided is a homogenous coating film obtained using the negative photosensitive resin composition. The photosensitive resin composition contains an ink repellent agent (A) comprising a fluorosiloxane compound, an alkali-soluble resin (B) having an acid group and an ethylene double bond in a single molecule, and a photopolymerization initiator (C), the negative photosensitive resin composition being characterized in that the photosensitive composition has an acid value of 6-30 mg KOH/g.

Description

201243500 六、發明說明： c發明戶斤属之技術領域3 發明領域本發明係有關負型感光性樹脂組成物及塗膜。 L· Jt 發明背景光阻組成物係當作形成諸如：彩色濾光片之像素間的隔壁、有機EL(Electro-Luminescence)顯示元件之像素間的隔壁、將有機TFT(Thin Him Transistor :薄膜電晶體）陣列的各TFT隔開的隔壁、液晶顯示元件之IT0電極的隔壁、電路配線基板的隔壁等永久膜之材料而備受矚目。於電路配線基板的製造方面，有人提出在形成電路配線時喷射塗佈金屬分散液的喷墨法。電路配線圖案的形成係由光阻組成物藉光刻法來實施，且光阻組成物之塗膜硬化物係被利用為隔壁。喷墨法方面，必須防止相鄰像素間墨水混色的發生、及防止在既定區域以外的部分有喷墨喷射之材料凝固結塊的情況，於是有人提出一種含撥墨劑的光阻組成物（專利文獻1)。先行技術文獻專利文獻1 :國際公開第2010/013816號案201243500 VI. Description of the Invention: C TECHNICAL FIELD OF THE INVENTION The present invention relates to a negative photosensitive resin composition and a coating film. L·Jt BACKGROUND OF THE INVENTION The photoresist composition is formed as a partition between pixels of a color filter, a partition between pixels of an organic EL (Electro-Luminescence) display element, and an organic TFT (Thin Him Transistor) The partition walls of the TFTs of the crystal array, the partition walls of the IT0 electrodes of the liquid crystal display element, and the partition walls of the circuit wiring board are attracting attention. In the manufacture of a circuit wiring board, an ink jet method in which a metal dispersion is sprayed at the time of forming a circuit wiring has been proposed. The formation of the circuit wiring pattern is carried out by photolithography of the photoresist composition, and the coating film of the photoresist composition is utilized as a partition wall. In the inkjet method, it is necessary to prevent the occurrence of ink color mixing between adjacent pixels and to prevent solidification and agglomeration of a material having inkjet ejection in a portion other than a predetermined region, and thus a photoresist composition containing an ink repellent has been proposed ( Patent Document 1). Advance Technical Literature Patent Document 1: International Publication No. 2010/013816

t發明内容J 發明概要發明所欲解決的課題 201243500 專利文獻1的光阻組成物’根據本發明人等的見解，會有在例如以室溫(20〜251：)保存了 2週時之儲存安定性不足的傾向’使用以室溫保存了 2週之光阻組成物形成圖案化基板時，會在塗膜上觀察到異物。本發明之目的，係提供一種能夠製造出撥墨性良好、且經紫外線/臭氧照射仍可保持撥墨性之隔壁的負型感光性樹脂組成物，儲存安定性良好的負型感光性樹脂組成物，以及使用該組成物所得之負型感光性樹脂組成物的岣勻塗膜。解決課題的手段本發明係具有以下[1]〜[10]之構成之負型感光性樹脂組成物及塗膜。 [1] 一種負型感光性樹脂紐成物，含有：撥墨劑(A) ’其係由含氟矽氧烷化合物所構成；鹼可溶性樹脂(B) ’其係於丨分子内具有酸性基與乙烯性雙鍵；以及光聚合起始劑(C); 且該負型感光性樹脂組成物之特徵在於：該負型感光性和ί知組成物之酸價為6〜3 〇mgK〇H/g。 [2] 如[1]之負型感光性樹脂組成物，其中前述負型感光性樹脂組祕之㈣部分+，驗可雜樹脂⑼的比率為 12〜40質量％。 [3] 如[1]或[2]之負型感光性樹脂組成物，其中前述含氟石夕氧烧化合物㈣包含下述水解性魏化合物㈣及水解 201243500 U物(Μ)之混合物的水解縮合生成物所構成： 3個h性魏化合物("π於外子鍵結有1個有機基及 ^解縣的水解性魏化合物，且該有絲具有碳數 3〜10且可包麵性氧原子之全氣燒基；水解性石夕院化合物(a 2):於石夕原子鍵結有p個(p伽、】浪基與(4·_水解性基的水解性魏化合物。 a U如[1][3]中任-項之負型感光性樹脂組成物，其中前述含氟錢⑨化合物之氟原子含有率為1()〜对量％。 []如[1]〜[4]中任一項之負型感光性樹脂組成物其更包含有交聯劑(D)，該交聯劑(D)係、於1分子中具有2個以上乙烯性雙鍵且不具酸性基的化合物。 [6]如[5]之負型感光性樹脂組成物，其中前述負型感光性樹脂組成物的總g)態部分巾，前碰可雜樹轉)與交聯劑(D)之合計量的比率為5〇〜95質量％，且相對於交聯劑 (D)之含量，鹼可溶性樹脂(B)之含量比率為15〜85質量％。 [7]如[1]〜[6]中任一項之負型感光性樹脂組成物，其更包含有溶劑(E)。 [8] 如[1]〜[7]中任一項之負型感光性樹脂組成物，其中前述驗可溶性樹脂(B)的酸價為1〇〜2〇〇mgKOH/g。 [9] 如[1]〜[8]中任一項之負型感光性樹脂組成物，其中前述負型感光性樹脂組成物的總固態部分中，撥墨劑(A)的比率為0.01〜10質量〇/0。 [10] —種塗膜’係於基板上由如申請專利範圍第1至9 項中任一項之負型感光性樹脂組成物所形成者。 201243500 發明之功效依據本發明，可提供一種負型感光性樹脂組成物，能夠製造撥墨性良好且即使經紫外線/臭氧照射亦能保持撥墨性之隔壁’甸存安定性良好的負型感光性樹脂組成物及使用其之負型感光性樹脂組成物之均質塗膜。圖式簡單說明第U1)〜丨(111)圖係示意地表示使用本發明負型感光性樹脂組成物的光學元件用隔壁其製造例的剖面圖。【實施冷式】較佳實施例之詳細說明本說月曰中，所謂酸價係指中和1克試料中之樹脂酸等時所需要的氫氣化鉀毫克數，為可依循JIS K 0070測定方法而測定之數值。單位為mgKOH/g。本說明書中，所謂總固態部分，係指在負型感光性樹脂組成物所含有的成分中_壁形成成分，其表示溶劑⑹ 等由於隔壁形成過程巾之加熱等而揮發的揮發性成分以外的王。P成77又，係指假設原料之水解性矽烧化合物之水解性基全部變切纽鍵結而誠水解縮合生成物的條件下’由此所計算的數值。本說明書中，所謂組成物酸價係總固態部分中的酸價。單位為mgK〇H/g。本說月曰中所明氟原子含有率，係由假設原料之水解性石浅化合物之水解性基全部變成錢⑽結而構成水解縮合生成物時的化學式所計算的數值。 6 201243500 本說明書中的「（曱基）丙烯醯基.··」，係「曱基丙稀醯基…」與「丙烯醯基…」的統稱。（甲基）丙烯酸醋、（甲基）丙烯醯胺、（甲基）丙烯醯樹脂亦與其相同。本說明書中，所謂烴基，係表示僅由碳與氫所構成的有機基。本說明書中，將塗佈負型感光性樹脂組成物而成的膜稱為「_」、使其乾燥後的狀態則稱為「膜」，再將其硬化所得之膜則稱為「硬化膜」。本說明書中的「墨水」，係指經乾燥硬化後具有例如光學性、電性機能之液體的統稱，並不缝為習知所使用的著色材料。再者’經注人前述墨水而形成之「像素」，亦同樣係用於作為表示⑽壁分隔之各概具有光學性、電性機能的區間者。本說明書中，所謂撥墨性，係指為了彈撥前述墨水而適度地兼具撥水性與撥油性兩者㈣,&，之方法予以評價。以下說明本發明之實施形態。另外，在本說明書中若無特別說明，則％係表示質量％。 [撥墨劑(Α)] 撥墨劑(Α)係由含亂石夕氧燒化合物所構成。該含氣石夕氧烧化合物’較佳係具有石夕醇基且氟原子之含有比例（以下亦稱氣原子含有率）為10〜55質量％的含氧石夕氧燒化合物。石夕醇基的數量’較佳係對每1個碎原子之平均個數為〇2〜3 5個者。 201243500 在3氟矽氧烷化合物中的氟原子含有率’係12〜40質量 3〇質里％特佳。若為前述範圍，則由負型感光組成物所獲得之隔壁，撥墨性會呈良好，且即使經 !外線/臭氧照射亦能夠保持良好的撥墨性。 3氟矽氧烷化合物的矽醇基數方面，以對每個矽原子的平均個數S十’係G.2〜3.5個較佳、G.2〜2.G個更佳、0.5〜1.5 個特佳。若為前述範圍的下限値以上，則由於對撥墨劑(A) 之’令的a解性或對負型感光性樹脂組成物中其他成分的相冷性會變彳m而提升操作性。若為前述範圍上限値以下’由負型感光性樹脂組成物所得之隔壁會有良好的撥墨性β 此外，含氟矽氧烷化合物中的矽醇基數，係 29η · ^ 測付之由具有或不具料基之各種結構而來的波峰面積比而算出。含氟石夕氧烧化合物方面，舉例而言，可為至少含有！種以上之含1水解性魏化合物的水解性賴化合物經水解縮合所得的含_魏化合物。水解性雜化合物之水解縮合生成物通常為其自身具有分子量分布的組成物。本發明之負型感光性樹脂組成物巾，作紐墨錄)之含氣石夕氧燒化合物’係由此類含1水解,㈣烧化合物之水解縮合生成物所構成’在常溫下為液體或具溶劑溶解性的固體，較佳係通稱為⑦氧樹脂的含氟硬化性料氧烧。含敗硬化性聚石夕氧貌方面，較佳為：後述之含有水解性石夕烧化合物㈣及水解性料化合物㈣作為必須成分 8 201243500 的混合物其之水解縮合生成物。水解性㈣化合物㈣’係料料上鍵結有1個有機基及3個轉性基的3官能度水触残化合物，且該有機基係，有碳數3〜H)之可含魏氧原子的全㈣基者。而且，官能度的數值’係減結於丨個㈣子上之水解性基的數量’以及視情況而定係指鍵結於“时原子之經基(石夕醇基)或可成為頻基之鍵結的數”的合計數4解性雜化合物(a-1)，係可單獨使用丨種，亦可併用2種以上。藉著使用水解性城化合物㈤），使負型感光性樹脂組成物硬化而成之硬化膜得以發_水性與撥油性（亦即撥墨性）。水解性㈣化合物(a_2)，係於碎原子鍵結有p個（p為〇、1或2)煙基與(4_p)個水解性基的(4_p)官能度水解性石夕烷化合物。水解性魏化合物㈣，較佳係p為〇的4官能度化合物’或P為1的3官能度化合物者。水解性魏化合物(a_2) 既可單獨使用1種，亦可併用2種以上。併用2種以上時，亦可將4官能度化合物及/或3官能度化合物與2官能度化合物併用。若將水解性矽烷化合物（a-Ι)及水解性矽烷化合物（a_2) 以化學式表示，則水解性矽烷化合物（a_1}為以下式（Μ)所示化合物（以下，亦稱為化合物⑷)）；水解性魏化合物(a_2) 為以下式(a2)所示化合物（以下，亦稱為化合物(a2))。 201243500 R δ,χ3 (RH)p-SiVp, (a1) (a2) 式(al)及(a2)中的符號，係如下所述者。 RF為具有碳數3〜10之可含醚性氧原子之全氟烷基的有機基； 1^為烴基； X各別表示水解性基。 p表示0、1或2的數值。另外，式（al)中的3個X係可為相同亦可相異。式（a2) 中，當p=2時，2個RH係可為相同亦可相異，且2個X係可為相同亦可相異。同樣的’當p=0時，4個X係可為相同亦可相異，當p=l時，3個X係可為相同亦可相異。本發明所使用之撥墨劑(A)中的RF基與RH基係顯現撥水性的基’而主要係藉由RF基而顯現出撥油性。撥墨劑(A)的硬化物之所以能顯現出充分撥油性，咸認是因為有Rh基存在的緣故’而其係鍵結在並未鍵結有損及撥油性之RH基的石夕原子上。此外，為能使撥墨劑(A)的硬化物顯現出充分撥油性，相對於撥墨劑(A)中的RF基與RH基之合計’較佳為RF基的相對比例較高者，當p=〇時，撥墨劑⑷ 中的RF基的相對比例變高，撥油性會增加，且具有成膜性優異的優點。當p=l或2時，由於有某種程度的尺!·!基存在，則撥墨劑(A)會變得容易溶解於烴系溶劑中，而有在基材表面上形成負型感光性樹脂組成物的塗膜時可選擇較廉價溶 201243500 劑的優點。不能=:=含氟硬氧貌’亦可使用含有物(a·2)之切性性錢化合物㈣及水解㈣貌化合物。烷化合物的混合物其之水解縮合生成 a-2) 以外it性外化合物㈣及水解性魏化合物（卜的水解性錢化合物方面砂烷化合物(a_3)、1A 了一為·下述水解性單元的下料機q氧;;度錢院狀有機聚石” 歧(a_4)、八甲基環四石夕氧烧等之環基的水解性氧燒' 通稱為石夕院偶合劑之具有含官能基有機頻化合物（前述水解性钱化合物㈣除外）、下述水魏化合物㈣等。砂r π a &佳係含有水解性魏化合物(a_3)及/或水解性疋a物㈣者。特佳係含有水解㈣㈣合物㈣者或含有水解性石夕烧化合物㈣與水解性石夕烧化合物㈣良解〖生矽烷化合物(a_3)為於矽原子上鍵結有3個有機土與1個水解絲的1官能度轉性魏化合物。較佳係以下式㈣表示的水解性魏化合物（以下亦稱化合物⑹）。 —有機二石夕氧烧㈣方面，較佳係以下式㈣表示的有機夕氧烷(以下亦稱為化合物(a4”。其等為可生成丄官能度砂氧炫單元的矽烷化合物。 [化2] 201243500 rh I W—Si—X rh rhOBJECTS OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION In the present invention, the photoresist composition of Patent Document 1 will be stored at room temperature (20 to 251:) for 2 weeks, for example, according to the findings of the present inventors. The tendency to be insufficient in stability "When a patterned substrate was formed by using a photoresist composition which was stored at room temperature for 2 weeks, foreign matter was observed on the coating film. An object of the present invention is to provide a negative photosensitive resin composition which is excellent in ink repellency and which can maintain ink repellency by ultraviolet/ozone irradiation, and which has a good storage stability and a negative photosensitive resin composition. And a uniform coating film of a negative photosensitive resin composition obtained by using the composition. Means for Solving the Problem The present invention is a negative photosensitive resin composition and a coating film having the following constitutions [1] to [10]. [1] A negative photosensitive resin composition comprising: an ink-repellent agent (A) 'which is composed of a fluorine-containing siloxane compound; the alkali-soluble resin (B) 'having an acidic group in a ruthenium molecule And an ethylenic double bond; and a photopolymerization initiator (C); and the negative photosensitive resin composition is characterized in that: the negative photosensitive property and the acid value of the composition are 6 to 3 〇mgK〇H /g. [2] The negative photosensitive resin composition of [1], wherein the ratio of the (4) part + of the negative photosensitive resin group is 12 to 40% by mass. [3] The negative photosensitive resin composition according to [1] or [2], wherein the fluorine-containing oxalate compound (IV) comprises a hydrolysis of a mixture of the hydrolyzable Wei compound (IV) and the hydrolyzed 201243500 U (Μ) The condensation product is composed of: three h-type Wei compounds (" π has one organic group in the outer bond and a hydrolyzable Wei compound in the solution, and the wire has a carbon number of 3 to 10 and can be coated The all-gas base of the oxygen atom; the hydrolyzable Shi Xiyuan compound (a 2): There are p (p gamma), wave base and (4·_hydrolyzable hydrolyzed Wei compound in the Shixi atom. The negative photosensitive resin composition of any one of [1], wherein the fluorine-containing content of the fluorine-containing money 9 compound is 1 () to a relative amount of %. [] such as [1] The negative photosensitive resin composition according to any one of [4], further comprising a crosslinking agent (D) having two or more ethylenic double bonds in one molecule and not being acidic [6] The negative photosensitive resin composition of [5], wherein the total g) state of the negative photosensitive resin composition is a part of the towel, the front touch can be mixed with a crosslinking agent (D). Ratio of total 5 to 95% by mass, and the content ratio of the alkali-soluble resin (B) to the content of the crosslinking agent (D) is 15 to 85% by mass. [7] Any of [1] to [6] The negative photosensitive resin composition of any one of [1] to [7], wherein the aforementioned soluble resin (B) The negative-type photosensitive resin composition of any one of [1] to [8], wherein the total solid state of the negative photosensitive resin composition is a solid state. In the part, the ratio of the ink-repellent (A) is 0.01 to 10 mass 〇 / 0. [10] The coating film is attached to the substrate by the negative photosensitive material according to any one of claims 1 to 9. According to the present invention, it is possible to provide a negative photosensitive resin composition capable of producing a good ink repellency and maintaining the ink repellency even under ultraviolet/ozone irradiation. A negative-type photosensitive resin composition having good stability and a homogeneous coating film of a negative-type photosensitive resin composition using the same. Brief description of the drawing U1)~丨(111 Fig. 1 is a cross-sectional view showing a manufacturing example of a partition for an optical element using the negative photosensitive resin composition of the present invention. [Implementation of the cold type] Detailed description of the preferred embodiment In the present invention, the acid value refers to the number of milligrams of potassium hydride required to neutralize the resin acid in one gram of the sample, and is determined according to JIS K 0070. The value determined by the method. The unit is mgKOH/g. In the present specification, the term "total solid portion" refers to a component which is contained in the component of the negative photosensitive resin composition, and which is a component other than the volatile component which is volatilized by the heating of the partition wall forming process or the like. king. Further, P is 77, which is a value calculated by assuming that the hydrolyzable group of the hydrolyzable terpene compound of the raw material is all chopped and bonded to the condensate. In the present specification, the acid value of the composition is the acid value in the total solid portion. The unit is mgK〇H/g. In the present invention, the fluorine atom content is a value calculated from the chemical formula when the hydrolyzable group of the hydrolyzable stone compound of the raw material is converted into a carbon (10) knot to form a hydrolyzed product. 6 201243500 "(曱基)acryloyl ruthenium.."" in this manual is a general term for "mercapto propyl amide..." and "acrylic fluorene...". (Meth)acrylic acid vinegar, (meth) acrylamide, and (meth) acryl resin are also the same. In the present specification, the hydrocarbon group means an organic group composed only of carbon and hydrogen. In the present specification, a film obtained by coating a negative photosensitive resin composition is referred to as "_", and a state in which it is dried is referred to as a "film", and a film obtained by curing the film is referred to as a "cured film." "." The term "ink" as used in the present specification refers to a liquid which has, for example, an optical property and an electrical function after drying and hardening, and is not sewn into a conventionally used coloring material. Further, the "pixel" formed by the injection of the ink is also used as a section showing optical and electrical functions of the (10) wall partition. In the present specification, the term "inking property" refers to a method in which both the water repellency and the oil repellency are appropriately combined in order to pluck the ink (4), & Embodiments of the present invention will be described below. In addition, unless otherwise indicated in this specification, % is a mass %. [Ink repellency agent (Α)] The ink repellency agent (Α) is composed of a compound containing turbid oxygen. The gas-containing gas-oxygenated compound (d) is preferably an oxo-oxygen compound having a gas atomic acid group and a fluorine atom content ratio (hereinafter also referred to as a gas atom content) of 10 to 55 mass%. The number 'the number of the base alcohol base' is preferably 〇2 to 3 5 per one broken atom. 201243500 The fluorine atom content rate in the trifluoroantimonoxane compound is '12 to 40 masses. 3% of the enamel is particularly preferable. When it is in the above range, the ink repellency obtained by the negative photosensitive composition is good, and good ink repellency can be maintained even by the external line/ozone irradiation. The number of sterol groups of the 3 fluoromethoxy siloxane compound is preferably from G. 2 to 3.5, preferably from G. 2 to 2. G, and from 0.5 to 1.5, for each 矽 atom. Very good. When the temperature is less than or equal to the lower limit 値 of the above range, the a-solution property of the ink-repellent agent (A) or the phase-cooling property of the other components in the negative-type photosensitive resin composition may become 彳m, thereby improving workability. If the upper limit of the range is 値 below, the partition obtained by the negative photosensitive resin composition will have good ink repellency β. Further, the number of sterol groups in the fluorine-containing siloxane compound is 29 η · ^ Or the peak area ratio of various structures without a material base is calculated. In terms of the fluorine-containing oxy-oxygen compound, for example, it may be at least contained! The above-mentioned wei-containing compound obtained by hydrolyzing and condensing the hydrolyzable lysine compound containing one hydrolyzable Wei compound. The hydrolysis condensation product of the hydrolyzable hetero compound is usually a composition having a molecular weight distribution by itself. The negative-type photosensitive resin composition towel of the present invention, which is a gas-containing gas-oxygenated compound of the New Zealand Record, is composed of such a hydrolysis-containing product containing 1 hydrolysis and (4) a burning compound, and is a liquid at normal temperature. The solvent-soluble solid is preferably a fluorine-containing hardenable material which is generally referred to as a 7-oxygen resin. The oxidative condensation product of the mixture containing the hydrolyzable zephyr compound (4) and the hydrolyzable compound (4) as an essential component 8 201243500 is preferable. Hydrolyzable (4) Compound (4) The material is bonded to a trifunctional water-retentive compound having one organic group and three transrading groups, and the organic group has a carbon number of 3 to H). The full (four) base of the atom. Moreover, the value of the functionality 'is the number of hydrolyzable groups that are reduced to one (four)) and, as the case may be, the bond to the base of the atom (the base of the atomic group) or may become a frequency base. The total number of the four types of the compound (a-1) may be used singly or in combination of two or more. By using the hydrolyzable compound (5)), the cured film obtained by hardening the negative photosensitive resin composition can be made to have water-based and oil-repellent properties (i.e., ink repellency). The hydrolyzable (tetra) compound (a_2) is a (4_p) functional hydrolyzable alkane compound in which p (p is 〇, 1 or 2) ketone groups and (4_p) hydrolyzable groups are bonded to a broken atom. The hydrolyzable Wei compound (IV) is preferably a 4-functional compound wherein p is oxime or a trifunctional compound having P of 1. The hydrolyzable Wei compound (a_2) may be used alone or in combination of two or more. When two or more kinds are used in combination, a tetrafunctional compound and/or a trifunctional compound may be used in combination with a bifunctional compound. When the hydrolyzable decane compound (a-oxime) and the hydrolyzable decane compound (a_2) are represented by a chemical formula, the hydrolyzable decane compound (a_1) is a compound represented by the following formula (Μ) (hereinafter, also referred to as a compound (4)). The hydrolyzable Wei compound (a_2) is a compound represented by the following formula (a2) (hereinafter, also referred to as a compound (a2)). 201243500 R δ, χ3 (RH)p-SiVp, (a1) (a2) The symbols in the formulas (al) and (a2) are as follows. RF is an organic group having a perfluoroalkyl group having an etheric oxygen atom having 3 to 10 carbon atoms; 1 is a hydrocarbon group; and X each represents a hydrolyzable group. p represents a value of 0, 1, or 2. In addition, the three X lines in the formula (al) may be the same or different. In the formula (a2), when p = 2, the two RH systems may be the same or different, and the two X systems may be the same or different. Similarly, when p=0, the four X lines may be the same or different, and when p=l, the three X lines may be the same or different. The RF group and the RH group in the ink-repellent (A) used in the present invention exhibit a water-repellent base and mainly exhibit oil-repellency by an RF group. The hardened material of the ink-repellent (A) can exhibit sufficient oil-repellency, which is believed to be due to the presence of the Rh-based group, and its bond is bonded to the RH-based RH-based, which is not bonded and oil-repellent. On the atom. Further, in order to make the cured product of the ink repellent (A) exhibit sufficient oil repellency, the relative ratio of the RF group to the RH group in the ink repellent (A) is preferably higher than the relative ratio of the RF group. When p = 〇, the relative proportion of the RF groups in the ink-repellent (4) becomes high, the oil repellency is increased, and the film forming property is excellent. When p=l or 2, the ink-repellent (A) becomes easily dissolved in the hydrocarbon-based solvent due to the presence of a certain degree of the base, and the negative-type photosensitive film is formed on the surface of the substrate. The coating film of the resin composition can be selected to have the advantage of being less expensive to dissolve the 201243500 agent. The non-===fluorine-containing oxy-morphology' can also be used as the cut-off money compound (IV) containing the substance (a·2) and the hydrolyzed (tetra) appearance compound. The mixture of the alkane compound is hydrolyzed and condensed to form a-2) an external compound (4) and a hydrolyzable Wei compound (the hydrolyzable money compound is a sand compound (a_3), 1A is a hydrolyzable unit) Cutting machine q oxygen;; money-like organic polycites" (a_4), octamethyl ring, four-stone oxygen burning, etc., the hydrolyzed oxygen-burning of the ring-based The organic organic compound (except for the hydrolyzable money compound (4)), the following water Wei compound (4), etc. Sand r π a & preferably contains a hydrolyzable Wei compound (a_3) and/or a hydrolyzable 疋a substance (four). The best system contains hydrolyzed (tetra) (tetra) compound (IV) or hydrolyzed stone compound (4) and hydrolyzed stone compound (4). The good solution of the decane compound (a_3) is bonded to the ruthenium atom with 3 organic soils and 1 The one-functionality-transfered Wei compound of the hydrolyzed silk is preferably a hydrolyzable Wei compound represented by the following formula (IV) (hereinafter also referred to as the compound (6)). - The organic two-stone oxygen-fired (four) aspect is preferably an organic compound represented by the following formula (IV). Oxantane (hereinafter also referred to as compound (a4". Silane functional compounds of sand into the oxygen Shang dazzle unit. [Formula 2] 201243500 rh I W-Si-X rh rh

W—Si—〇—Si—W I I rh rh 式(a3)及(a4)中的符號X與Rh係與式(al)及(a2)中的x與 RH相同。式(a3)及(a4)中，W係獨立地表示為前述ri:、rh或將選自於由丙烯醯基及曱基丙烯醯基所構成之群組中之聚合性官能基之一個以上作為部分結構的有機基。式(a4)*w 係可彼此相同’亦可相異。另外’式(a3)中，2個rh(w為Rh 時則為3個Rh)彼此係可相同亦可相異；式(a4)中，^^rH(w 為Rh時則為5或6個Rh)係彼此可相同亦可相異。使用水解性矽烷化合物(a3)或有機二矽氧烷(a4)時，若使用如該化合物的W為RF2化合物，則撥墨劑(A)的rf基相對比例較高而能顯現優良撥油性，故係較佳。若使用如霤為RH之化合物’則撥墨劑對烴系溶劑的溶解性會提升，故係較佳。若使用如W為具有將選自丙烯醯基及甲基丙歸醯基之聚合性官能基之1個以上作為部分結構的有機基的化合物’則撥墨劑(A)的硬化性會提升’且對烴系溶劑的溶解性會提升，故係較佳。水解性矽烷化合物(a - 5)係於矽原子上鍵結有q個（q為i 或2)具有選自於由丙烯醯基及甲基丙烯醯基所構成之群組中至少一種之聚合性官能基的有機基、r個（r為〇或1、為1或2之數）烴基及(4-q-r)個水解性基的水解性矽烷化入 12 201243500 ^使用水解性魏化合物(a_5)時，所得撥墨劑⑷係於曝、’後易留雜隔壁上面’而有使隔壁上面具撥墨性、隔壁側面具親墨性的效果^ 另方面車乂佳地構成撥墨劑⑷之前述水解縮合生成物的原料共縮合成分’若不使用具有此Μ合性官能基之欠解f生夕烧化0物，則曝光後，撥墨劑⑷易往隔壁側面移動，故會有隔壁上面與隔壁側面同具撥墨性的效果。此等係可因應用途而分別使用。水解性石夕院化合物(a_5)方面，較佳係以下式㈣所示之水解性矽烷化合物（以下亦稱為化合物(a5))。 [化3] (RH)rW—Si—〇—Si—W I I rh rh The symbols X and Rh in the formulas (a3) and (a4) are the same as x and RH in the formulas (al) and (a2). In the formulas (a3) and (a4), W is independently represented by the above ri:, rh or one or more polymerizable functional groups selected from the group consisting of an acryloyl group and a fluorenyl fluorenyl group. As an organic group of a partial structure. The formulas (a4)*w may be identical to each other' or may be different. In addition, in the formula (a3), two rh (when Rh is 3 Rh) may be the same or different from each other; in the formula (a4), ^^rH (w is 5 or 6 when Rh is Rh) The Rh) systems may be the same or different from each other. When a hydrolyzable decane compound (a3) or an organic dioxane (a4) is used, if W as an RF2 compound is used as the compound, the relative proportion of the rf group of the ink-repellent (A) is high, and excellent oil repellency can be exhibited. Therefore, it is better. If a compound such as RH is used, the solubility of the ink-repellent agent in the hydrocarbon-based solvent is improved, which is preferable. When W is a compound having an organic group having a partial structure of a polymerizable functional group selected from an acryloyl group and a methyl propyl group, the hardenability of the ink-removing agent (A) is improved. Further, the solubility in the hydrocarbon solvent is improved, so that it is preferred. The hydrolyzable decane compound (a-5) is bonded to the ruthenium atom with q (q is i or 2) having a polymerization selected from at least one of the group consisting of an acryloyl group and a methacryl group. Organic group of a functional group, r (r is 〇 or 1, number 1 or 2) hydrocarbon group and (4-qr) hydrolyzable group hydrolyzed decane into 12 201243500 ^ using hydrolyzable Wei compound (a_5) When the ink-repellent agent (4) is exposed to the top of the partition wall, the ink-repellent property of the mask on the partition wall and the ink-repellency of the mask on the partition wall are also provided. If the raw material co-condensation component of the hydrolysis-condensation product is not used, the ink-repellent agent (4) is easily moved to the side of the partition wall after exposure, and there is a partition wall. The upper surface has the same effect as the side of the partition wall. These can be used separately depending on the purpose. The hydrolyzable sulfonium compound (a-5) is preferably a hydrolyzable decane compound (hereinafter also referred to as a compound (a5)) represented by the following formula (4). [Ration 3] (RH)r

I (Q)q - SiX(4_q_r) (a5) 式〇5)中的符號χ與係與式(al)及(a2)中的χ與rh相同。式(a5)中，Q係表示具有選自於由丙烯醯基及曱基丙烯醯基所構成之群組之聚合性官能基的有機基。q係表示 2、r係表示〇或1，且或2之數。而且，式⑷）中，當 q=2時’ 2個Q係可彼此相同亦可相異；當q+r=1時，3個χ係彼此可相同亦可相異；當q+r=2時，2個X係彼此可相同亦可相異。水解性矽烷化合物(a-5)，較佳係q為1且r為1的2官能度 13 201243500 單體、或q為a 且r為〇的3官能度單體。又，使用水解性矽烷化合物（a-5)時，-^ po T 可以单獨使用1種亦可併用2種以上。、十對别述化合物（al)〜化合物（a5) ’進一步具體I (Q)q - SiX(4_q_r) (a5) The symbol χ and system in equation )5) are the same as χ and rh in equations (al) and (a2). In the formula (a5), Q represents an organic group having a polymerizable functional group selected from the group consisting of an acryloyl group and a fluorenyl fluorenyl group. q indicates 2, r indicates 〇 or 1, and or 2. Moreover, in the formula (4)), when q=2, the two Q systems may be identical to each other or different; when q+r=1, the three lanthanides may be the same or different from each other; when q+r= At 2 o'clock, the two X lines may be the same or different from each other. The hydrolyzable decane compound (a-5) is preferably a bifunctional group having a q of 1 and r of 1 13 201243500 monomer, or a trifunctional monomer wherein q is a and r is ruthenium. In addition, when the hydrolyzable decane compound (a-5) is used, one type may be used alone or two or more types may be used in combination. , ten pairs of other compounds (al) ~ compound (a5) ' further specific

舉例加以說明。s L 另外，化合物（al)〜化合物（a5)，各別亦可因應而求’使用由複數個歸屬各化合物之單體水解縮合而成之化合物的寡聚物。化〇物(al)〜化合物05)所具有的χ為水解性基其係例如·源自單醇之已去除㈣巾氫原子的錢基、_素原子、酿基、異氣酸8旨基、源、自胺化合物之已去除胺基中氫原子的有機基等。X係碳數4以下的院減或i素原子較佳， CHsO-、如5〇·、α_特佳。該等基⑷係會因水解反應而變成經基(料基）’且進一步因分子間反應而形成队⑽鍵結。化合物（al)所具有、且化合物（a3)及化合物（a4)所任意具有的RF基’較佳係.以Rh_Y·表示的基。惟’ rF1係表示碳數3〜10之可含喊性氧原子的全敗院基，γ係表示不含氣原子之2價連結基。 u RFI係碳數4〜8的全氟烷基或碳數4〜9之含醚性氧原子的全氟烷基較佳；碳數6的全氟烷基特佳。當rF1為前述範圍時，由負型感光性樹脂組成物所得之隔壁，撥墨性良好，且即使經紫外線/臭氧照射仍可保持良好的撥墨性。並、且，’ 撥墨劑(A)對通用溶劑的溶解性良好，故係較佳。Give an example to illustrate. Further, the compound (al) to the compound (a5) may each be used as an oligomer of a compound obtained by hydrolyzing and condensing a plurality of monomers belonging to each compound. The hydrazine of the chemical (al) to the compound 05) is a hydrolyzable group, for example, a hydroxy group derived from a monool, and a hydroxy group of a hydrogen atom, a sulfonyl group, a sulphur group, and an isogastric acid. The source, the organic group from the amine compound from which the hydrogen atom in the amine group has been removed, and the like. The X-system has a carbon number of 4 or less, and the i-cell atom is preferred, and CHsO-, such as 5〇· and α_ are particularly preferable. These groups (4) are converted into a radical (base) by the hydrolysis reaction and further form a bond of the group (10) due to the intermolecular reaction. The RF group which is possessed by the compound (al) and which is optionally possessed by the compound (a3) and the compound (a4) is preferably a group represented by Rh_Y. However, the 'rF1 system represents a total defeated base of a carbon atom of 3 to 10, and the γ system represents a divalent linking group which does not contain a gas atom. u RFI is preferably a perfluoroalkyl group having 4 to 8 carbon atoms or a perfluoroalkyl group having an etheric oxygen atom having 4 to 9 carbon atoms; and a perfluoroalkyl group having 6 carbon atoms is particularly preferred. When rF1 is in the above range, the partition wall obtained from the negative photosensitive resin composition is excellent in ink repellency, and good ink repellency can be maintained even by ultraviolet/ozone irradiation. Further, the ink repellent (A) is preferred because it has good solubility in a general-purpose solvent.

Rfi的結構’係哪㈣直鏈結構、分枝結構、環結構、或部分具有環之結構，但以直鏈結構較佳。 201243500 R的具體例係可舉例為如下的基團。 F(CF2)4_、f(cf2)6·、F(CF2)8_。 CF3CF2〇CF2CF2〇CF2- , CF3CF2OCF2CF2OCF2CF2- ' CF3CF2〇CF2CF2〇CF2CF2〇CF2CF2〇CF2- 、 cF3CF2〇CF2CF2QCF2CF2〇CF2CF2OCF2CF2-。 CF3〇F2CF2〇CF2- 、 CF3CF2CF2OCF2CF2- 、 CF3CF2CF2〇CF(CF3)-、CF3CF2CF20CF(CF3)CF2-、 cF3CF2CF2〇CF(CF3)CF2〇CF2CF2- 、 CF3CF2CF2〇CF(CF3)CF2〇CF(CF3)- 、 CF3CF2CF2〇CF(CF3)CF2〇CF(CF3)CF2-。前述Y僅需為2價連結基即可，並無特殊限制，但較佳係以 _(CH2)g-、-CH20(CH2)g-、-S02NR2-(CH2)g-、或 _(〇0)_NR2_(cH2)g-表示之基。惟，g表示1〜5的整數；R2 表不氫原子、甲基、或乙基。γ係以g為2或3時的-(CH2)g- 特佳。並且，該基Y的方向，係意指右側鍵結於Si而左側鍵結於RF1者。 RFI為碳數4〜8之全氟烷基的情況下，前述Y較佳係以 _(CH2)g-表示的基。g係以2〜4的整數較佳，而g為2之-(CH2)2-特佳。 RF1為碳數4〜9之含醚性氧原子的全氟烷基時，前述Y較佳係以 _(CH2)h-、-CH20(CH2)h-、-S02NR2-(CH2)h-、或 KC=〇)-NR2-(CH2)h-表示的基。惟，h係表示卜5的整數；r2 係表示氩原子、甲基、或乙基。Y係h為2之-(CH2)2-特佳。另外，該Y基的鍵結方向，係意指右側鍵結於Si而左側鍵結 15 201243500 mrf 丨。化合物（a2)、化合物（a3)、化合物（a4)及化合物（a5)所具有的RH，係碳數卜4之烷基或苯基較佳，甲基或乙基更佳，曱基特佳》化合物（a5)所具有的Q較佳係以β-Ζ-表示的基。惟， Ql係表示（曱基）丙烯醯氧基。Z係表示-(CH2)3-、-(CH2)4-、 -(CH2)5-、或_((^2)6-，較佳為-(CH2)3-。又，化合物(a3)、化合物（a4)所任意具有的選自於由丙烯醯基及甲基丙烯醯基所構成之群組之聚合性官能基，亦以相同的基較佳。化合物（al)的具體例，較佳係為下例。 F(CF2)4CH2CH2Si(OCH3)3、 F(CF2)6CH2CH2Si(OCH3)3、 F(CF2)8CH2CH2Si(OCH3)3、 CF3CF2CF2〇CF(CF3)CF2OCF2CF2CH2CH2Si(OCH3)3。化合物（a2)的具體例，較佳係為下例。The structure of Rfi is a linear structure, a branched structure, a ring structure, or a structure partially having a ring, but is preferably a linear structure. Specific examples of 201243500 R can be exemplified by the following groups. F(CF2)4_, f(cf2)6·, F(CF2)8_. CF3CF2〇CF2CF2〇CF2- , CF3CF2OCF2CF2OCF2CF2- 'CF3CF2〇CF2CF2〇CF2CF2〇CF2CF2〇CF2-, cF3CF2〇CF2CF2QCF2CF2〇CF2CF2OCF2CF2-. CF3〇F2CF2〇CF2-, CF3CF2CF2OCF2CF2-, CF3CF2CF2〇CF(CF3)-, CF3CF2CF20CF(CF3)CF2-, cF3CF2CF2〇CF(CF3)CF2〇CF2CF2-, CF3CF2CF2〇CF(CF3)CF2〇CF(CF3)- , CF3CF2CF2〇CF(CF3)CF2〇CF(CF3)CF2-. The above Y is only required to be a divalent linking group, and is not particularly limited, but is preferably _(CH2)g-, -CH20(CH2)g-, -S02NR2-(CH2)g-, or _(〇 0) _NR2_(cH2)g- represents the base. However, g represents an integer of 1 to 5; and R2 represents a hydrogen atom, a methyl group, or an ethyl group. The γ system is particularly preferably -(CH2)g- when g is 2 or 3. Further, the direction of the base Y means that the right side is bonded to Si and the left side is bonded to RF1. In the case where the RFI is a perfluoroalkyl group having 4 to 8 carbon atoms, the above Y is preferably a group represented by _(CH2)g-. g is preferably an integer of 2 to 4, and g is -(CH2)2-extra. When RF1 is a perfluoroalkyl group having an etheric oxygen atom having 4 to 9 carbon atoms, the Y is preferably _(CH2)h-, -CH20(CH2)h-, -S02NR2-(CH2)h-, Or KC=〇)-NR2-(CH2)h- represents a group. However, h represents an integer of 5; and r2 represents an argon atom, a methyl group, or an ethyl group. The Y system h is 2 - (CH2) 2 - particularly good. In addition, the bonding direction of the Y-base means that the right side is bonded to Si and the left side is bonded to 15 201243500 mrf 丨. RH of the compound (a2), the compound (a3), the compound (a4) and the compound (a5) is preferably an alkyl group or a phenyl group having a carbon number of 4, preferably a methyl group or an ethyl group. The Q which the compound (a5) has is preferably a group represented by β-Ζ-. However, Ql represents a fluorenyloxy group. The Z series represents -(CH2)3-, -(CH2)4-, -(CH2)5-, or _((^2)6-, preferably -(CH2)3-. Further, the compound (a3) Further, the polymerizable functional group selected from the group consisting of an acryloyl group and a methacryl fluorenyl group which is optionally contained in the compound (a4) is preferably the same group. Specific examples of the compound (al) are The following is an example: F(CF2)4CH2CH2Si(OCH3)3, F(CF2)6CH2CH2Si(OCH3)3, F(CF2)8CH2CH2Si(OCH3)3, CF3CF2CF2〇CF(CF3)CF2OCF2CF2CH2CH2Si(OCH3)3. A specific example of a2) is preferably the following.

Si(OCH3)4、Si(OCH2CH3)4、CH3Si(OCH3)3、 CH3Si(OCH2CH3)3、CH3CH2Si(OCH3)3、 CH3CH2Si(OCH2CH3)3、（CH3)2Si(OCH3)2、 (CH3)2Si(OCH2CH3)2、Si(OCH3)4, Si(OCH2CH3)4, CH3Si(OCH3)3, CH3Si(OCH2CH3)3, CH3CH2Si(OCH3)3, CH3CH2Si(OCH2CH3)3, (CH3)2Si(OCH3)2, (CH3)2Si ( OCH2CH3)2

Si(OCH3)4經水解縮合之化合物（例如c〇LCOAT公司製的 Methyl Silicate51(商品名））、a compound obtained by hydrolysis-condensation of Si(OCH3)4 (for example, Methyl Silicate 51 (trade name) manufactured by c〇LCOAT Co., Ltd.),

Si(OCH2CH3)4經水解縮合之化合物（例如c〇LCOAT公司製的 Ethyl Silicate 40、Ethyl Silicate 48(均為商品名））。化合物（a3)的具體例，較佳係為下例。 16 201243500 F(CF2)6CH2CH2(CH3)2Si(OCH3) 、（CH3)3Si(OCH3)、 [CH2=C(CH3)COO(CH2)3](CH3)2Si(OCH3)。化合物(a4)的具體例，較佳係為下例。 (CH3)3SiOSi(CH3)3。化合物（a5)的具體例，較佳係為下例。 CH2=C(CH3)COO(CH2)3Si(OCH3)3、 CH2=C(CH3)COO(CH2)3Si(OCH2CH3)3、 CH2=CHCOO(CH2)3Si(OCH3)3、 CH2=CHCOO(CH2)3Si(OCH2CH3)3、 [CH2=C(CH3)COO(CH2)3]CH3Si(OCH3)2、 [CH2=C(CH3)COO(CH2)3]CH3Si(〇CH2CH3)2。撥墨劑（A)係使前述各化合物反應而得的反應生成物。該反應係由水解性基之水解性反應而來的矽醇基之生成，與由矽醇基彼此之脱水縮合反應而來的矽氧烷鍵結之生成。使用於本發明負型感光性樹脂組成物的撥墨劑’ 在如此所得之水解縮合生成物中，較佳態樣係經分子設計為由前述水解性反應所生成之矽醇基有所殘留者，其較佳矽醇基數為每個矽原子平均〇 2〜3 5個。製造撥墨劑(A)時，錢用水解性石夕院化合物㈣與水解性魏化合物(a_2)的情況下，水解性魏化 ^性魏化合物㈣的共縮合比例，若為可得前述款原人3有率者’則無特別限制’但相對於1莫耳水解性魏化 =(a 1)使肢丨〜9莫耳水解性魏化合物㈣用0.5〜9莫耳者特佳。征便 17 201243500 製造撥墨劑⑷時，在除了水解性石夕燒化合物㈣及水解性石夕烧化合物(a_2)外、再加上使用水解性錢化合物㈣及/或有機二料烧㈣等能生成丨官能度錢料元的石夕烧化合物的情況下，相對於轉性錢化合物㈣及水解性石夕烧化合物㈣之合計量，水解性魏化合物㈣及/或有機-錢烧(a_4)的共縮合比例，係、_莫耳％以下較佳， 2〇0莫耳％以下更佳。惟，僅使用有機二石夕氧燒㈣的情況下，係50莫耳％以下較佳’ 5莫耳％以下特佳。製造撥墨劑⑷時，在除了水解性石夕烧化合物㈣及水解性石夕院化合物(a-2)外、再加上使用水解性石夕烧化合物㈣的情況下，相對於水解性石夕貌化合物㈣及水解性石夕院化合物㈣之合計量，水解性錢化合物(a姻共縮合比例’係500莫耳％以下較佳，莫耳％以下特佳。再者，製造撥墨劑⑷時，在除了水解性石夕烧化合物㈣及水解性魏化合物㈣外、再加上細官能度水解性石夕烷化合物㈣及水解性石夕烧化合物㈣的情況下，相對於水解性石夕烧化合物㈣及水解性石夕炫化合物㈣之合計量’水解性魏化合物(a·3)的共縮合比例係_莫耳％以下較佳’水解时烧化合物(Μ)的共縮合比例係卿莫耳％以下較佳。特佳係相對於水解性㈣化合物㈣及水解性石夕院化合物(a-2)之合計量的水解性石夕燒化合物㈣)共縮合比例為2〇〇莫耳％以下、水解性石夕貌化合物㈣的共縮合比例為400莫耳。/。以下。本發明的撥墨劑(A)，亦可為以單-化合物所構成者， 18 201243500 仁通㊉係以聚合度等相異之複數個化合物所構成的混合物。亦即，撥墨劑(A)為使用水解性矽烷化合物及水解性矽烷化合物(a-2)作為必須成分、並任意地使用水解性矽烷化合物(a-3)及/或有機二矽氧烷(a_4)而製造時，係為具有以下式U)所示平均組成式之結構的化合物。惟，由於實際上為殘留有水解性基或矽醇基的生成物（部分水解縮合2 ^勿）’而該生成物不易以化學式表示，以式⑴表示的;均組成式，係於如前述製造之水解縮合生成物中水解性基或矽醇基全部變成矽氧烷鍵結的假設條件下的化學式。 [化4]A compound obtained by hydrolysis-condensation of Si(OCH2CH3)4 (e.g., Ethyl Silicate 40 and Ethyl Silicate 48 (all trade names) manufactured by C〇LCOAT Co., Ltd.). Specific examples of the compound (a3) are preferably the following examples. 16 201243500 F(CF2)6CH2CH2(CH3)2Si(OCH3), (CH3)3Si(OCH3), [CH2=C(CH3)COO(CH2)3](CH3)2Si(OCH3). Specific examples of the compound (a4) are preferably the following examples. (CH3)3SiOSi(CH3)3. Specific examples of the compound (a5) are preferably the following examples. CH2=C(CH3)COO(CH2)3Si(OCH3)3, CH2=C(CH3)COO(CH2)3Si(OCH2CH3)3, CH2=CHCOO(CH2)3Si(OCH3)3, CH2=CHCOO(CH2) 3Si(OCH2CH3)3, [CH2=C(CH3)COO(CH2)3]CH3Si(OCH3)2, [CH2=C(CH3)COO(CH2)3]CH3Si(〇CH2CH3)2. The ink-repellent (A) is a reaction product obtained by reacting each of the above compounds. This reaction is produced by a sterol group derived from a hydrolyzable reaction of a hydrolyzable group, and is bonded to a siloxane coupling derived from dehydration condensation reaction of sterol groups. The ink-repellent agent used in the negative-type photosensitive resin composition of the present invention is preferred in the hydrolysis-condensation product thus obtained, which is molecularly designed to have a residual sterol group formed by the aforementioned hydrolyzable reaction. Preferably, the number of sterol groups is 2 to 3 5 per 矽 atom. When the ink-repellent agent (A) is produced, the co-condensation ratio of the hydrolyzable Shi Xiyuan compound (4) and the hydrolyzable Wei compound (a_2) to the hydrolyzable Wei-wei compound (4) is obtained. 3 rate of 'there is no special limit' but relative to 1 mole hydrolyzed Weihua = (a 1) so that the limbs ~ 9 moles of hydrolyzed Wei compound (four) with 0.5 ~ 9 moles are particularly good. In the case of the ink-repellent agent (4), in addition to the hydrolyzable compound (4) and the hydrolyzable compound (a_2), the hydrolyzable money compound (4) and/or the organic second material (four) are added. In the case of a smelting compound capable of producing a hydrazine functional money element, the hydrolyzable Wei compound (IV) and/or the organic-money burning (a_4) relative to the total amount of the transgenic money compound (4) and the hydrolyzable zephyr compound (4) The co-condensation ratio is preferably _mol% or less, more preferably 2 〇0 mol% or less. However, in the case of using only organic radix (4), it is preferably 50 mol% or less and preferably 5 mol% or less. When the ink-repellent agent (4) is produced, in addition to the hydrolyzable compound (4) and the hydrolyzable Shixia compound (a-2), in addition to the hydrolyzable compound (4), the hydrolyzed stone is used. The total amount of the compound (4) and the hydrolyzable Shi Xiyuan compound (4), the hydrolyzable money compound (a marriage co-condensation ratio ' is preferably 500 mol% or less, and the molar content is preferably less or less. Further, the ink-repellent agent is produced. (4) In the case of the hydrolyzable stone compound (4) and the hydrolyzable Wei compound (4), in addition to the fine functional hydrolyzable stone compound (4) and the hydrolyzable stone compound (4), relative to the hydrolyzed stone The total condensation ratio of the compound (4) and the hydrolyzable Shi Xiu compound (4) 'co-condensation ratio of the hydrolyzable Wei compound (a·3) is preferably _mol% or less. The co-condensation ratio of the compound (Μ) during hydrolysis is The following is preferred. The co-condensation ratio of the hydrolyzable compound (4) relative to the hydrolyzable (tetra) compound (IV) and the hydrolyzable Shixia compound (a-2) is 2 〇〇 mo Less than or equal to the ear, hydrolyzed stone compound (four) Condensation mole ratio of 400. /. the following. The ink-repellent agent (A) of the present invention may be a mixture of a single compound, and a composition of a plurality of compounds having a different degree of polymerization, etc., 18 201243500. In other words, the ink repellent (A) is a hydrolyzable decane compound and a hydrolyzable decane compound (a-2) as an essential component, and a hydrolyzable decane compound (a-3) and/or an organic dioxane are optionally used. When it is produced (a_4), it is a compound having a structure having an average composition formula represented by the following formula U). However, since it is actually a product in which a hydrolyzable group or a sterol group remains (partially hydrolyzed and condensed), the product is not easily represented by a chemical formula, and is represented by the formula (1); The chemical formula under the assumption that the hydrolyzable group or the sterol group in the produced hydrolysis condensation product becomes a siloxane coupling. [Chemical 4]

RF-Sj〇3/2 • m (R\—SiO<4，V2 畢 'rh ' w-si〇1/2 - m - η RH (1) 式（1)中，RF、RH、W及P的較佳範圍係與前述相同。爪、 η係各別為1以上的整數’ k為〇或1以上的整數。具有以式（1)表示之平均組成式之結構的水解縮合生成物中，刀別源自於化合物(al)及化合物(a2)、任意現人之化合物(a3)及/或化合物(34)的單體單元，推測係為無規排列者。另外，m、η的値，以撥墨劑(A)全體之平均値計，較佳係m : η作為水解性矽烷化合物(a_2)相對於各個水解性二俨化合物(a-Ι)的共縮合比例而在前述範圍内者。打百，k値方面，以撥墨劑(A)全體之平均値計，（m+n):k為前述範圍、亦即相對於(m+n)為1時]^為丨以下者較佳、〇5以下者更^佳' 19 201243500 o.i以下者特佳。撥墨劑(A)為使用水解性石夕烧化合物（a_ i)及水解性石夕烧化合物(a_2)作為必須成分且㈣使用水解性魏化合物 (a-5)而製造㈣況下，會成為具有以下式(2)表示之平均組成式的結構的化合物。$，由於實際上為殘留有水解性基或石夕醇基之生成物(部分水解縮合生成物），而該生二以化學式表*，以式(2)表示的平均組成式，係以如前述方式製造的水解縮合生成物中水解性基或料基全部變成石夕氧烷鍵結的假設條件下的化學式。 [化5] • — RF-Si〇3/2 • (R»)p - Si〇(4n))/2 • on _ 1 L _ S - t ⑼q — Si〇〜V2 ⑵ ,π χ久P、q、r的較佳範圍係盥〕相同。W上的整數；咖u以上的整數具有叫(2)表示之平均組成式的結構物令’細式⑴絲的水解縮合生成物_，== 化合:(·化合物㈣、任意混合之化合物(二: 兀，推測係為無規排列。而且， J的早邀RF-Sj〇3/2 • m (R\—SiO<4, V2 Bi 'rh ' w-si〇1/2 - m - η RH (1) In equation (1), RF, RH, W and P The preferred range of the above is the same as the above. The integer 'k of each of the claws and the η series is 1 or more, or an integer of 1 or more. The hydrolyzed condensation product having the structure of the average composition formula represented by the formula (1), The cleavage is derived from the monomer units of the compound (al) and the compound (a2), any of the existing compounds (a3) and/or the compound (34), and is estimated to be a random arrangement. The average enthalpy of the total amount of the ink-repellent agent (A) is preferably m: η as a co-condensation ratio of the hydrolyzable decane compound (a_2) to each hydrolyzable diterpene compound (a-Ι) within the above range In the case of hundreds, k値, the average of the total amount of ink (A), (m+n): k is the above range, that is, when it is 1 with respect to (m+n)] It is better, 〇5 or less is better. 19 201243500 oi is particularly good. The ink-repellent (A) is a hydrolyzable zephyr compound (a_i) and a hydrolyzable zephyr compound (a_2). Component and (4) using hydrolyzable Wei compound (a-5) In the case of (4), it is a compound having a structure having an average composition formula represented by the following formula (2): $, since a product having a hydrolyzable group or a linalool group (partially hydrolyzed and condensed product) remains in fact, And the average composition formula represented by the formula (2) in the chemical formula * is a hypothetical condition in which the hydrolyzable group or the base of the hydrolyzed condensation product produced as described above is all converted into a rock oxide bond. Chemical formula [RF5] • — RF-Si〇3/2 • (R»)p - Si〇(4n))/2 • on _ 1 L _ S - t (9)q — Si〇~V2 (2) , π χ The preferred range of long-term P, q, and r is the same. An integer above W; an integer above the coffee u has a structure of the average composition of (2), and the hydrolytic condensation product of the fine (1) filament _, == compound: (· compound (4), compound of any mixture ( Two: Hey, the speculation is randomly arranged. Moreover, J’s early invitation

體之平均値計，較佳係8 ，以撥墨劑(A ㈣，水純靜„ 4㈣於各财雜頻化合者。又的共縮合^财前述範圍The average enthalpy of the body is preferably 8 to administer the ink (A (four), water pure static „ 4 (four) in each of the financial complexes.

，f r III 墨M(A)全體之平均値計，（s+t) . UA 解亦即相對於㈣為 (：‘ 更佳，0.1以下者特佳。 T者巍，(U以下; 20 201243500 炫化合物(=解性繼合物㈣及水解及水解成分、並使用水解一合物㈣中具有—5物㈣而製造的情況下，會成為於式⑴ ” ^料(2)之化合物(a5)之單體單元進一步址縮八 =之平馳成式的結構者。各化合物的例係; 例舉為前述之範圍。 H 糸了 /發明中，撥墨劑⑷的數量平均分子量(Μη)係500以、，車又佳未達丨，000,000者較佳，未達10,000者特佳。數量平均分子量(Μη)為下限值以上時，❹負型感光性樹脂組成物所得之Μ的撥祕會呈良好。數量平均分子量(Μη) 未達上限㈣，@對溶劑的轉性會呈良好之故，具有提升操作性的優點。撥，㈣(Α)龍量平均分子量(Μη)可藉由選擇反應件件等而予以調整。 (拇墨劑(Α)的製造）含氟矽氧烷化合物所構成之撥墨劑(Α)，可藉由使前述水解性石夕烧化合物之混合物進行水解及縮合反應而製造之。該反應中，可無特殊限制地適用使水解性矽烷化合物進行水解縮合之反應時常用的反應條件。再者，該反應中，將常用的鹽酸、硫酸、硝酸、磷酸等無機酸；醋酸、草酸、馬來酸等有機酸作為觸媒使用者較佳。觸媒用量係相對於水解性矽烷化合物的總量為0.01〜10質量。/。較佳、0丨〜丨質量 °/°特佳。前述反應中亦可使用溶劑。該溶劑可舉例為：水；甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、異丁醇、2_ 21 201243500 曱基-2-丙醇、乙二醇、丙三醇、丙二醇等醇類；丙酮、曱基異丁酮、環己酮等酮類；2-曱氧基乙醇、2-乙氧基乙醇等賽珞蘇類；2-(2-曱氧基乙氧基）乙醇、2-(2-乙氧基乙氧基) 乙醇、2-(2-丁氧基乙氧基）乙醇等卡必醇類；乙酸曱酯、乙酸乙酯、丙二醇單甲基醚乙酸酯、4-乳酸丁酯、乙酸丁酯、3-甲氧基丁基乙酸酯等酯類；丙二醇單甲基醚、二乙二醇單甲基醚、二乙二醇單丁基醚、二丙二醇單甲基醚等二醇的單烷基醚類；二乙二醇二曱基醚、二乙二醇乙基曱基醚、二丙二醇二曱基醚等二醇的二烷基醚類。其他尚可舉例如：苄基醇、N，N-二曱基曱醯胺、二甲基亞砜、二甲基乙醯胺、N-甲基吡咯啶酮等。溶劑係可單獨使用1種，亦可併用2種以上。溶劑係以撥墨劑溶液的形態摻混於本發明之負型感光性樹脂組成物。本發明之負型感光性樹脂組成物中的撥墨劑（A)含有率，於負型感光性樹脂組成物之總固態部分中，係以 0.01〜10質量％較佳、0.1〜6質量％更佳、0.5〜3質量％特佳。經由使撥墨劑(A)之含有率在前述範圍中，負型感光性樹脂組成物的儲存安定性會呈良好，且由該負型感光性樹脂組成物所得之光學元件之隔壁的撥墨性會呈良好，可獲得具有光滑表面的隔壁。 [鹼可溶性樹脂(B)] 鹼可溶性樹脂(B)係於1分子内具有酸性基與乙烯性雙鍵的感光性樹脂。由於具有分子内乙稀性雙鍵，負型感光 22 201243500 之性樹脂組成物的曝光部分，係、藉由光聚合起始劑（c)所產生的自由基進行聚合而硬化。因具有酸性基，使祕性顯影液能夠選擇性地去除未被硬化㈣㈣光性樹脂組成物未曝光部’其結果即能形成隔壁。前述酸性基並無特殊限制，惟可舉例為緩基、紛性經基、《基、雜基等，其等可單獨使用丨種，亦·可併用2 種以上。前述乙烯性雙鍵並無特殊限制，惟可舉例為：（甲基) 丙稀醯基、稀丙基、乙稀基、乙締氧基等加成聚合性基所具有的雙鍵，其等可單獨使用丨種，亦可併用2種以上。再者’該加絲合性基所具有的氫原子，亦可—部份或全部被取代為烴基，並以曱基較佳。鹼可溶性樹脂⑼並無特殊限制，惟可舉例為：含有具酸性基之顯與具乙_雙鍵之側制伽(bm)、於環氧樹脂導入酸性基與乙稀性雙鍵之樹月旨(Β1_2)等。其等可單獨使用1種，亦可併用2種以上。樹脂(Β1·υ，係可射述來合成，即，將具錢基、缓基、％氧基等反應性基之單體與具有酸性基之單體進行共聚合，而彳獲得含有狀應性基之側鏈與具酸性基之側鏈的共聚合物，且使該共聚合物、與具有能夠對反應性基鍵結之g旎基與乙烯性雙鍵的化合物，溶解於溶劑中以使發生反應，藉此合成者。具經基的單體，可舉例為：2_經乙基（甲基^丙稀酸西旨、 2-羥丙基（甲基）丙烯酸酯、3·羥丙基（甲基）丙烯酸酯、屯羥 23 201243500 丁基（曱基）丙烯酸酯、5-經戊基（甲基）丙烯酸酯、6-經己基 (曱基）丙烯酸酯、4_經環己基（曱基）丙烯酸酯、新戊二醇單 (甲基）丙稀酸酯、3-氣-2-經丙基（曱基）丙烯酸酯、丙三醇單 (甲基）丙稀酸酯、2-羥乙基乙稀驗、4-經丁基乙稀基喊、環己烷二醇單乙烯基醚、2-羥乙基烯丙基醚、N_羥甲基（甲基) 丙烯醯胺、N，N-雙(羥甲基)（甲基）丙烯醯胺等。具羧基的單體’可舉例為：丙烯酸、甲基丙烯酸、醋酸乙烯酯、巴豆酸、衣康酸、馬來酸、反丁烯二酸、桂皮酸及其等之鹽等。另外，該等單體亦可使用作為具有酸性基的單體。具環氧基之單體，可舉例為：縮水甘油（甲基）丙烯酸酯、3,4-環氧基環己基甲基丙烯酸醋等。具酸性基的單體並無特殊限制，惟除前述具艘基之單體外’具填酸基之單體方面可舉例如2_(曱基)丙稀醯氧基乙烷磷酸等。前述具反應性基之單體與具酸性基之單體的共聚合，可依習知方法實施。具有經基以作為反應性基的單體，可舉例為：具乙稀性雙鍵的酸酐、具有異氰酸基與乙稀性雙鍵的化合物、具有氣化醯基與乙烯性雙鍵的化合物等。具乙烯性雙鍵的酸酐，可m j舉例為：馬來酸酐、衣康酸酐、檸康酸酐、甲基-5-降冰片秘，，技水片歸·2,3-二複酸gf、3,4,5,6_四氫酞酸酐、順式-1，2,3,6-四f灿缺吻虱酞酸酐、2_丁烯-1-基琥珀酸酐 24 201243500 具有異氰酸酯基與乙烯性雙鍵的化合物，可舉例為 2-(甲基）丙烯醯氧乙基異氰酸酯、^卜雙“曱基）丙烯醯二. 基）乙基異氰酸S旨等。甲可舉例為（曱基) 具有氣化醯基與乙烯性雙鍵的化合物丙烯醯氣等。具有羧基作為反應性基的單體，舉例可為具有羧式乙烯性雙鍵的化合物。該化合物的具體例，舉例可為.、烯酸、曱基丙烯酸、醋酸乙烯酯、巴豆酸、衣康酸、馬來酸、反丁烯二酸、桂皮酸及其等之鹽等。亦可使由此而生的羧基與以羧酸之脱水縮合部分為環狀結構一部分的釀發生反應，於樹脂(B1-1)中導入羧基。具有環氧基作為反應性基的單體，可舉例為具有環氡基與乙烯性雙鍵的化合物。該化合物可舉例為：縮水甘由 (曱基）丙烯酸酯、3,4-環氧基環己基甲基丙烯酸酯等。，樹脂(B1-2)係可藉由使環氧樹脂與具有羧基與乙烯性雙鍵的化合物反應後，與多鹽基性羧酸或其脫水物發生反應而合成。具體上，藉由使環氧樹脂與具有叛基和乙稀性雙鍵之化合物發生反應，乙烯性雙鍵會導入至環氧樹脂中。接著，使多鹽基性㈣或其脫水物對導人了乙祕雙鍵之環氧樹月曰發生反應，藉此可將竣基導入。環氧樹脂並祕絲制’惟可舉料：雙_型環氧樹脂、雙酴F型環氧樹脂、紛祕型環氧樹脂、甲紛轉型環氧樹脂、三酚曱烷型環氧樹脂、具萘骨架的環氧樹脂、以 25 201243500 下式(Bl-2a)表示的具聯苯骨架的環氧樹脂、以下式(Bl-2b) 表示的環氧樹脂、以下式(Bl-2c)表示之具聯苯骨架的環氧樹脂等。 [化6], fr III Ink M (A) The average total, (s + t). UA solution is relative to (four) is (: 'better, 0.1 or less is particularly good. T is 巍, (U below; 20 201243500 In the case where the compound (=) and the hydrolyzed and hydrolyzed component are produced by using the compound (4) in the hydrolyzate (4), it will become a compound of the formula (1) (2) (a5) The monomer unit is further condensed to the structure of the octave formula. Examples of each compound; exemplified by the foregoing range. H 糸/Invention, the number average molecular weight (Μη) of the ink-repellent (4) It is preferred that the vehicle is 500, and the car is not as good as ,000,000, and the amount is less than 10,000. When the number average molecular weight (?η) is more than the lower limit, the composition of the negative photosensitive resin composition is The secret is good. The number average molecular weight (Μη) does not reach the upper limit (4), and the conversion of the solvent to the solvent is good, which has the advantage of improving the operability. Dial, (4) (Α) The average molecular weight of the dragon (Μη) can be borrowed It is adjusted by selecting a reaction piece or the like. (Manufacture of a thumb ink (Α)) An ink-repellent (Α) composed of a fluorine-containing siloxane compound, The mixture of the hydrolyzable cerium compound can be subjected to hydrolysis and condensation reaction. In the reaction, the reaction conditions conventionally used for the hydrolysis condensation reaction of the hydrolyzable decane compound can be applied without particular limitation. In the reaction, a commonly used inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid; an organic acid such as acetic acid, oxalic acid or maleic acid is preferred as a catalyst user. The amount of the catalyst is relative to the total amount of the hydrolyzable decane compound. It is preferably 0.01 to 10 mass%, preferably 0 丨丨丨 mass ° / °. The solvent may also be used in the above reaction. The solvent may be exemplified by water, methanol, ethanol, 1-propanol, 2-propane. Alcohol, 1-butanol, 2-butanol, isobutanol, 2_ 21 201243500 mercapto-2-propanol, ethylene glycol, glycerol, propylene glycol and other alcohols; acetone, mercapto isobutyl ketone, cyclohexyl Ketones such as ketones; cyanoquinones such as 2-methoxyethanol and 2-ethoxyethanol; 2-(2-decyloxyethoxy)ethanol, 2-(2-ethoxyethoxy) Carbitol such as ethanol, 2-(2-butoxyethoxy)ethanol; decyl acetate, ethyl acetate, propylene glycol monomethyl ether Esters such as acetate, 4-butyl lactate, butyl acetate, 3-methoxybutyl acetate; propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl a monoalkyl ether of a diol such as an ether or a dipropylene glycol monomethyl ether; a dialkyl group of a diol such as diethylene glycol didecyl ether, diethylene glycol ethyl decyl ether or dipropylene glycol didecyl ether; Other examples include benzyl alcohol, N,N-didecylguanamine, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, etc. The solvent system can be used alone. One type may be used, or two or more types may be used in combination. The solvent is blended in the form of a toner solution in the negative photosensitive resin composition of the present invention. The content of the ink repellent (A) in the negative photosensitive resin composition of the present invention is preferably 0.01 to 10% by mass, preferably 0.1 to 6% by mass in the total solid portion of the negative photosensitive resin composition. More preferably, 0.5 to 3 mass% is particularly good. When the content of the ink repellent (A) is in the above range, the storage stability of the negative photosensitive resin composition is good, and the ink of the partition of the optical element obtained from the negative photosensitive resin composition is good. The sex will be good and a partition with a smooth surface can be obtained. [Alkali-soluble resin (B)] The alkali-soluble resin (B) is a photosensitive resin having an acidic group and an ethylenic double bond in one molecule. The exposed portion of the resin composition of the negative photosensitive film 22 201243500 is polymerized by the radical generated by the photopolymerization initiator (c) to be hardened by the intramolecular ethylene double bond. By having an acidic group, the secret developing solution can be selectively removed without being hardened. (IV) (IV) Light-based resin composition Unexposed portion The result is that a partition wall can be formed. The acidic group is not particularly limited, and examples thereof include a slow base, a divalent base, a "base", a hetero group, etc., and the like may be used alone or in combination of two or more. The ethylenic double bond is not particularly limited, and may, for example, be a double bond of an addition polymerizable group such as a (meth) propyl sulfhydryl group, a dipropyl group, an ethylene group or an ethyl ethoxy group; The cockroach species may be used alone or in combination of two or more. Further, the hydrogen atom of the silk-bonding group may be partially or wholly substituted with a hydrocarbon group, and a mercapto group is preferred. The alkali-soluble resin (9) is not particularly limited, and may, for example, be a tree having an acidic group and a side gamma (bm) having a B-double bond, and an epoxy group introducing an acidic group and an ethylene double bond. Purpose (Β1_2) and so on. These may be used alone or in combination of two or more. The resin (Β1·υ, which can be synthesized by synthesizing, that is, a monomer having a reactive group such as a hydroxy group, a slow group, or a % oxy group is copolymerized with a monomer having an acidic group, and a side chain of a group and a side chain having an acidic group, and dissolving the copolymer in a solvent with a compound having a g-group capable of bonding a reactive group to an ethylenic double bond The reaction can be carried out to synthesize the monomer. The monomer having a mercapto group can be exemplified by 2_ethyl (methyl propyl acrylate, 2-hydroxypropyl (meth) acrylate, 3 hydroxy Propyl (meth) acrylate, hydrazine hydroxy 23 201243500 butyl (fluorenyl) acrylate, 5-pentyl (meth) acrylate, 6-hexyl (decyl) acrylate, 4 _ cyclohexyl (fluorenyl) acrylate, neopentyl glycol mono (meth) acrylate, 3-gas-2-propyl (meth) acrylate, glycerol mono (meth) acrylate, 2-Hydroxyethyl ethene test, 4-butylethyl sulfonate, cyclohexanediol monovinyl ether, 2-hydroxyethyl allyl ether, N-hydroxymethyl (meth) propylene oxime Amine, N, N-bis (hydroxyl Methyl) (meth) acrylamide, etc. The monomer having a carboxyl group can be exemplified by acrylic acid, methacrylic acid, vinyl acetate, crotonic acid, itaconic acid, maleic acid, fumaric acid, and cinnamon. The acid and its salts, etc. Further, these monomers can also be used as the monomer having an acidic group. The monomer having an epoxy group can be exemplified by glycidyl (meth) acrylate, 3, 4-. Epoxycyclohexyl methacrylate vinegar, etc. The monomer having an acidic group is not particularly limited, but in addition to the above-mentioned monomer having a base group, the monomer having an acid-filling group may, for example, be 2_(mercapto)propyl Dilute methoxy ethane phosphoric acid, etc. The copolymerization of the monomer having a reactive group and a monomer having an acidic group can be carried out by a conventional method. The monomer having a trans group as a reactive group can be exemplified as An acid anhydride having an ethylene double bond, a compound having an isocyanate group and an ethylene double bond, a compound having a vaporized thiol group and an ethylenic double bond, etc. An acid anhydride having an ethylenic double bond, mj can be exemplified as : Maleic anhydride, itaconic anhydride, citraconic anhydride, methyl-5-norborne tablets, technical water tablets, 2 3-di-acid acid gf, 3,4,5,6-tetrahydrophthalic anhydride, cis-1,2,3,6-tetraf-cannic acid anhydride, 2-buten-1-yl succinic anhydride 24 201243500 A compound having an isocyanate group and an ethylenic double bond, and is exemplified by 2-(meth)acryloyloxyethyl isocyanate, bis-(fluorenyl) propylene oxime. A can be exemplified by a (fluorenyl) propylene compound having a vaporized thiol group and an ethylenic double bond, etc. The monomer having a carboxyl group as a reactive group may, for example, be a compound having a carboxy-type ethylenic double bond. Specific examples of the compound may be, for example, an enoic acid, a methacrylic acid, a vinyl acetate, a crotonic acid, an itaconic acid, a maleic acid, a fumaric acid, a cinnamic acid, or the like. The carboxyl group thus produced reacts with the brewing in which the dehydrated condensed portion of the carboxylic acid is a part of the cyclic structure, and the carboxyl group is introduced into the resin (B1-1). The monomer having an epoxy group as a reactive group may, for example, be a compound having a cycloalkyl group and an ethylenic double bond. The compound can be exemplified by glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methacrylate and the like. The resin (B1-2) can be synthesized by reacting an epoxy resin with a compound having a carboxyl group and an ethylenic double bond, and then reacting with a polybasic carboxylic acid or an anhydrate thereof. Specifically, an ethylenic double bond is introduced into the epoxy resin by reacting the epoxy resin with a compound having a thiol and an ethylene double bond. Next, the polybasic group (IV) or its dehydrated product is allowed to react with the epoxide group which induces the bismuth double bond, whereby the thiol group can be introduced. Epoxy resin and secret silk system's only material: double _ epoxy resin, double 酴 F-type epoxy resin, secret epoxy resin, A transformation epoxy resin, trisphenol decane epoxy resin An epoxy resin having a naphthalene skeleton, an epoxy resin having a biphenyl skeleton represented by the following formula (Bl-2a) 25 201243500, an epoxy resin represented by the following formula (Bl-2b), and the following formula (Bl-2c) An epoxy resin or the like having a biphenyl skeleton. [Chemical 6]

(B1-2a) (式(Bl-2a)中，v係1〜50，較佳係2〜10。且苯環的氫原子係各自獨立地亦可被取代為碳數1〜12的烷基、i素原子或可具有取代基之苯基。） [化7](B1-2a) (In the formula (Bl-2a), v is 1 to 50, preferably 2 to 10. The hydrogen atom of the benzene ring may be independently substituted with an alkyl group having 1 to 12 carbon atoms. , i atom or a phenyl group which may have a substituent.) [Chem. 7]

(式(Bl-2b)中、R31、R32、R33及R34係各自獨立地為氩原子、氣原子或碳數1〜5的烷基；w為0〜10。） [化8](In the formula (Bl-2b), R31, R32, R33 and R34 are each independently an argon atom, a gas atom or an alkyl group having 1 to 5 carbon atoms; w is 0 to 10%.) [Chem. 8]

VV

OH IOH I

(式(Bl-2c)中，苯環的氫原子亦可各自獨立地被取代為碳數1〜12的烷基、鹵素原子、或可具取代基之苯基。u為 26 201243500 0〜10 〇 ) 另外，令以式(Bl-2a)〜(Bl-2c)表示的環氧樹脂與具有羧基及乙烯性雙鍵的化合物進行反應後、與多鹽基性敌酸酐進行反應的情況下，多鹽基性羧酸酐係使用二羧酸酐及四羧酸二酐的混合物者較佳。藉由改變二羧酸酐及四羧酸二肝的比率可控制分子量。樹脂(B1-2)係可使用市售商品。市售商品可舉例如（均為商品名）：KAYARAD PCR-1069、K-48C、CCR-1105、 CCR-1115 ' CCR-1159H、CCR-1235、TCR-1025、 TCR-1064H、TCR-1286H、ZAR-1535H、ZAR-2002H、 ZFR-1491H、ZFR-1492H、ZCR-1571H ' ZCR-1569H ' ZCR-1580H、ZCR-1581H、ZCR-1588H、ZCR-1642H、 ZCR-1664H(以上均為曰本化藥公司製）、EXi〇i〇(Nagase chemtex公司製）等。單體(B1-3)係可舉例如：2,2,2-三丙烯醯氧基甲基乙基酞酸酯(NK酯CBX-1新中村化學工業社製）等。驗可溶性樹脂(B)方面，由能夠抑制顯影時的塗膜剝離而得到高解析度圖案的觀點、配線的直線性呈良好的觀點及維持後培步驟後的外觀而易於獲得平滑塗膜表面的觀點’係以使用樹脂(B1-2)者較佳。樹脂(B1-2)方面，特佳的是對雙酚a型環氧樹脂導入了酸性基與乙烯性雙鍵的樹脂、對雙酚F型環氧樹脂導入了酸性基與乙烯性雙鍵的樹脂、對酚酚醛型環氧樹脂導入了酸性基與乙烯性雙鍵的樹脂、對甲酚酚醛型環氧樹脂導入了 27 201243500 sd生基與乙稀性雙鍵的樹脂、或對三紛甲㈣環氧樹脂導入了酸性基與乙烯性雙鍵的樹脂，以及對以式 (Bl-2a)〜(Bl-2c)表不之環氧樹月旨導入了酸性基與乙稀性雙鍵的樹脂。用於本發明之前述鹼可溶性樹脂（B)的質量平均分子里（Mw)，係以 ι_5χΐ〇3〜3〇χΐ〇3者較佳、2χ1〇3〜15χ1〇3特佳。又，數量平均分子量（Μη)係以5〇〇〜2〇xl〇3者較佳、 1.0X10〜10X103特佳。質量平均分子量(M幻及質量平均分子莖(Μη)為前述範圍的下限値以上時，曝光時之硬化係為充为的，為前述範圍的上限値以下時，顯影性會呈良好。鹼可溶性樹脂（Β)於1分子内具有的乙烯性雙鍵數量，係以平均3個以上者較佳、6個以上特佳。乙烯性雙鍵的數量為前述範圍的下限値以上時，曝光部分與未曝光部分的鹼性/容解度較易於出現差異，俾能以更低的曝光量形成細微圖案驗可溶性樹脂（Β)的酸價，係以1 〇〜2〇〇mgKOH/g者較佳、30〜150mgKOH/g更佳、50〜i〇〇mgKOH/g特佳。酸價為前述範圍時，負型感光性樹脂組成物的儲存安定性及顯影性會呈良好。負型感光性樹脂組成物所含有的鹼可溶性樹脂(B)，可為1種亦可為2種以上的混合物。本發明的負型感光性樹脂組成物申，總固態部分中的鹼可溶性樹脂(B)含有率，係12〜40質量％較佳、14〜38質量 %更佳、16〜36質量％特佳。含有率為前述範圍時，負型感 28 201243500 光性樹脂組成物的儲存安定性會呈良好。 [光聚合起始劑(c)] 光聚合起始劑（c)，物，則並無特別的限制佳。若具有光聚合起始劑機能之化合惟以由光產生自由基的化合物較光聚合起始劑(C)係可舉例如：节基 '二乙酿基、甲基本j路SUa 9，1G_核等a_n苯偶姻等醯偶姻類；苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚等醯偶姻鍵類；剌酮、、2_甲基㈣_ m 基嗔侧、異丙基·_、2,4·二乙基制請、2,4_二氣嗟噸酮、2,4-二異丙基嗟嘴酮"塞侧_4_石黃酸等養_類；二苯綱、4,4'_雙(二甲胺基)二苯酮、4,4，-雙(二乙胺基)二苯酮等二苯酮類；笨乙酮、2_(4_甲苯績醯氧基峰苯基笨乙酮、對二甲胺基苯乙酮、2,2，_二甲氧基_2_苯基苯乙嗣、對甲氧基苯乙_、2-曱基-[4·(甲硫基）苯基]_2_嗎琳基小丙酮、2-苄基-2-二甲胺基·^(心嗎啉基苯基丁烷酮等苯乙酮類；蒽醌、2-乙基蒽醌、莰醌、丨，4_萘醌等醌類；2_二甲胺基笨曱酸乙酯、4-二甲胺基苯曱酸乙酯、4·二曱胺基笨甲酸(正丁氧基）乙酯、4_二曱胺基苯曱酸異戊酯、4_二曱胺基苯甲酸-2-乙基己酯等胺基苯曱酸類；氣笨乙酮、三函化甲基笨硬等_化合物；醯基氧化膦類；過氧化二第三丁基等過氧化物；1，2-辛二酮、Η4_(笨硫基)_，2_(〇·笨曱醯肪）、乙鋼1-[9-乙基-6-(2-甲基苯曱醯基)_9Η-甲醯基-3-基]-卜(〇-乙醯肟）等肟酯類；三乙醇胺、曱基二乙醇胺、三異丙醇胺、 29 201243500 正丁胺、N-甲基二乙醇胺、甲基丙烯酸二乙胺基乙酯等脂肪族胺類；2-硫醇基苯并咪唑、2-硫醇基苯并噚唑、2_硫醇基苯并噻唑、丨，4-丁醇雙(3-硫醇基丁酸酯）、三(2-硫醇基丙醯氧基乙基）異三聚氰酸酯、新戊四醇四（3_硫醇基丁酸酯）等硫醇化合物等。其中，二苯酮類、胺基苯甲酸類、脂肪族胺類及硫醇化合物，若與其他自由基起始劑一起使用會顯現出增感效果而為較佳。光聚合起始劑(C)較佳係2-甲基-[4-(甲硫基）苯基]-孓嗎啉基-1-丙酮、2-苄基二甲胺基_i-(4-嗎啉基苯基)_丁烷嗣、辛二酮、苯硫基)-，2-(〇-苯甲醯肟）、乙乙基-6-(2-甲基苯曱醯基)·9Η_甲醯基_3_基]1(〇乙醯聘）、 4,4’-雙（一乙胺基)二笨酮、或2,4二乙基噻噸酮。再者特佳係該等與前述二苯_的組合。光聚合起始劑(C)係可使用市售商品。市售品係可舉例如：IRGACURE907(商品名，BASF公司製，2_甲基小[心（甲硫基）苯基]-2-嗎啉基丙烷·卜酮）；IRGACURE369(商品名， BASF公司製，2·$基二甲胺基小(4_嗎淋基笨基)丁燒 -1-酮）等。儿負型感光性樹脂組成物所含光聚合起始劑(c)係種亦可為2種以上的混合物。負型感光性樹脂組成物的總固態部分中的光聚合起如劑(C)含有率’係〇_ 1〜50質量％較佳、〇 5〜3〇質量％更佳、5 質量％特佳°為前述範圍時，負型感光性樹脂組成物的: 30 201243500 影性係呈良好。 [交聯劑(D)] 本發明的負型感光性樹脂組成物，亦可含有作為促進自由基硬化之任意成分的交聯劑(D)。交聯劑（D)，較佳係於1分子中具有2個以上乙烯性雙鍵且不具酸性基的化合物。藉由使負型感光性樹脂組成物含有交聯劑(D)，可以提升曝光時前述鹼可溶性樹脂的硬化性、且可降低在形成隔壁時的曝光量。於1分子中具有2個以上乙烯性雙鍵且不具酸性基的交聯劑(D)，若為具有此一條件之化合物則並無特別限制，惟可舉例如：二乙二酵二（曱基）丙烯酸酯、四乙二醇二（曱基) 丙烯酸酯、三丙二醇二（曱基）丙烯酸酯、新戊二醇二（曱基) 丙烯酸酯、1，9-壬二醇二（甲基）丙烯酸酯、三羥甲基丙烷三 (甲基）丙烯酸酯、新戊四醇三（甲基）丙烯酸酯、新戊四醇四 (甲基）丙烯酸酯、二三羥甲基丙烷四（甲基）丙烯酸酯、二新戊四醇五（曱基）丙烯酸酯、二新戊四醇六（甲基）丙烯酸酯等、乙氧化三聚異氰酸三丙烯酸酯、ε-己内酯改性三-(2-丙烯酿氧乙基)三聚異氰酸酯、雙{4-(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺）苯基}甲烷、Ν,Ν’-間-伸茬基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺）、胺甲酸乙酯丙烯酸酯等。該等係可單獨使用1種，亦可併用2種以上。交聯劑（D)可使用市售商品。市售品可舉例如： KAYARAD DPHA(商品名、日本化藥公司製、二新戊四醇五丙烯酸酯與二新戊四醇六丙烯酸酯的混合物）；NK_ 31 201243500 A-9530(商品名、新中村化學工業社製、二新戊四醇五丙烯酸酯與二新戊四醇六丙烯酸酯的混合物））；NK酯 A-9300(商品名、新中村化學工業社製、乙氧化三聚異氰酸三丙烯酸酯）；NK酯A-9300-lCL(商品名、新中村化學工業社製、ε-己内酯改性三_(2_丙烯醯氧乙基)三聚異氰酸酯）； ΒΑΝΙ-Μ(商品名、丸善石油化學社製、雙{4-(烯丙基雙環 [2.2.1]庚-5-烯-2,3-二羧基醢亞胺）苯基}甲烷）；及 ΒΑΝΙ-Χ(商品名、丸善石油化學社製、Ν，Ν，_間-伸茬基-雙(烯丙基雙環[2.2.1]庚-5-烯-2,3-二羧基醯亞胺))等。胺甲酸乙酯丙烯酸酯舉例可為日本化藥公司製的KAYARAD UX系列’具體的商品名可舉例為：UX-3204、UX-61(H、UX-0937、 DPHA-40H、UX-5000、UX-5002D-P20、V#802(商品名、大阪有機化學工業社製、二新戊四醇丙烯酸酯、三新戊四醇丙烯酸酯及四新戊四醇丙烯酸酯的混合物）等。其中，KAYARAD DPHA及NK酯A-9530，由於可提升從負型感光性樹脂組成物所得硬化膜的敏感度，故屬較佳者。NK酯A-9300、BANI-M及BANI-X，從賦予硬化膜硬度而抑制熱塌的觀點出發係屬較佳者β NK醋 A-9300-1CL，由賦予硬化膜柔軟性的觀點出發係屬較佳者。胺甲酸乙㈣稀酸S旨’因著能夠實現適當的顯影時間且顯影性呈良好故屬較佳者。負型感光性樹脂組成物所含交聯劑(D)的含有率，係如以下的範圍難邊可溶簡財聯細)的合計量為總固態部分中的务95質量％’且相對於交聯劑(d)含量，驗 32 201243500 可溶性樹脂(B)含量的質量％也就是鹼可溶性樹脂(B)的質量/交聯劑(D)的質量χίοο，係調整成15〜85質量％較佳。更佳的是鹼可溶性樹脂(B)與交聯劑的合計量為總固態部分中的60〜92質量％，且鹼可溶性樹脂(B)的質量/交聯劑(D) 的質量xlOO為20〜70質量％者；特佳的是鹼可溶性樹脂(B) 與交聯劑(D)的合計量為總固態部分中的65〜9〇質量％，且鹼可溶性樹脂(B)的質量/交聯劑（D)的質量乂丨⑼為⑽〜”質量 %者。若為前述範圍，則負型感光性樹脂組成物的儲存安定性會呈良好，在形成一使用負型感光性樹脂組成物所得之圖案化基板時，像素内噴墨墨水的潤濕性會呈良好。 [溶劑(E)] 本發明之負型感光性樹脂組成物係視需要而含有溶劑 (E)。若含有溶劑(E) ’則由於負型感光性樹脂組成物的黏度降低，負型感光性樹脂組成物對基板上的塗佈會較容易進行。均勻的負型感光性樹脂組成物塗膜係可形成。另外，負型感光性樹脂組成物為不含溶劑的情況下，負型感光性樹脂組成物的塗膜，即與負型感光性樹脂組成物之膜為同一物。本發明的負型感光性樹脂組成物所含有的溶劑(E)，若月b將負型感光性樹脂組成物所含之前述撥墨劑(A)、驗可溶性樹脂(B)、光聚合起始劑（〇、視需要之交聯劑(D)、還有後述的任意成分均勻溶解或分散，且具有使負型感光性樹脂組成物對形成隔壁之基材的塗佈均一且簡便的機能，並對該等成分不具反應性，則溶劑並無特別限制，惟可使用 33 201243500 例如與在合成撥墨劑(A)時所用溶劑相同的溶劑。負型感光性樹脂組成物所含溶劑(E)的含有率，雖因負型感光性樹脂組成物的組成或用途等而異，但較佳的是在負型感光性樹脂組成物中以50〜99質量％混合者，60〜95質量％更佳，65〜90質量％特佳。 [負型感光性樹脂組成物及塗膜] 本發明之負型感光性樹脂組成物的酸價（以下亦稱為組成物酸價）係6〜30mgKOH/g，8〜25mgKOH/g較佳， 10〜22mgKOH/g特佳。負型感光性樹脂組成物之酸價為前述範圍時，負型感光性樹脂組成物的儲存安定性會呈良好，在基板上形成有該負型感光性樹脂組成物之塗膜時，能夠得到外觀優良之本發明的塗膜。塗膜的形成，可實施與例如後述之光學元件用隔壁之塗膜形成步驟相同者。負型感光性樹脂組成物的酸價為前述範圍時儲存安定性就會呈良好的理由並不十分確定。惟撥墨劑(A)係存在有矽醇基’容易因酸觸媒而自我縮合》咸認組成物酸價為前述範圍之下限値以上時，負型感光性樹脂組成物之塗膜的顯影性會呈良好；為前述範圍之上限値以下時，負型感光性樹脂組成物的儲存安定性係屬優良。組成物酸價，係以鹼可溶性樹脂(B)之酸價與含量所決定。各別的較佳範圍係如上所述。本發明的負型感光性樹脂組成物，係含有撥墨劑(A)、鹼可溶性樹脂(B)及光聚合起始劑(c)(>並且，因應需求而含有交聯劑(D)及溶劑(E)。再者，亦可含有下述之熱交聯劑 34 201243500 (F)、黑色著色劑(G)、高分子分散劑、分散助劑⑴、矽烷偶合劑（J)、微粒子(K)、磷酸化合物（L)及其他添加劑。 (熱交聯劑(F)) 熱交聯劑(F)係具有2個以上能與羧基及/或羥基反應之基團的化合物。熱交聯劑(F)，在鹼可溶性樹脂(B)為具有羧基及/或經基的情況下，係具有與鹼可溶性樹脂反應、使硬化膜交聯密度增高而使耐熱性提升的作用。熱交聯劑(F)較佳係可舉例為選自於由胺基樹脂、環氧化合物、。f唑啉化合物、聚異氰酸酯化合物、及聚羰二醯亞胺化合物所構成之群組中至少一種者。該等化合物係可早獨使用’亦可併用2種以上。here 本發明之負型感光性樹脂組成物之總固態部分中的熱交聯劑(F)含有率，較佳為1〜5〇質量％、更佳5〜30質量％。若在該範圍内，則所得之負型感光性樹脂組成物的顯影性便呈良好。 (黑色著色劑(G)) 當將本發明之負型感光性樹脂組成物使用於黑矩陣 (其係將液晶顯示元件的彩色濾光片之R' G、B三色像素包圍的格子狀黑色部分)形成時，較佳係含有黑色著色劑(G)。黑色著色劑(G)係可舉例如：碳黑、苯胺黑、蒽醌系黑色顏料、茈系黑色顏料，具體係有如C.I.色料黑1、6、7、12、 20、31等。黑色著色劑(G)亦可使用例如：將紅色顏料、藍色顏料、綠色顏料、azomethine系顏料等有機顏料或無機顏料的混合物。黑色著色劑（G)係就從價格、遮光性大小的 35 201243500 觀點，較佳為碳黑，且碳黑亦可利用諸如樹脂等施行表面處理。此外，為調整色調亦可併用藍色顏料或紫色顏料。碳黑係就從黑矩陣形狀的觀點，較佳為依BET法所測得之比表面積50~200m2/g者。當比表面積為5〇m2/g以上時’黑矩陣形狀不易劣化。而為200m2/g以下時，碳黑不會過度吸附分散助劑，因此不需要為能顯現出諸物性而混合大量的分散助劑。再者’碳黑就感度的觀點出發，較佳為酜酸二丁醋的吸油量在120cm3/100g以下者，越少越佳。再者’碳黑之利用穿透式電子顯微鏡觀察所測得之平均一次粒徑較佳係20〜5 Onm。平均一次粒徑為2〇nm以上時，能夠高濃度地分散，容易得到經時安定性良好的負型感光性樹脂組成物。為50nm以下時，黑矩陣形狀不易劣化》此外，利用穿透式電子顯微鏡觀察之平均二次粒徑較佳係 80〜200nm。在使本發明之負型感光性樹脂組成物中含有黑色著色劑(G)而使用於黑矩陣形成等的情況下，該負型感光性樹脂組成物的總固態部分中’黑色著色劑（G)的含有率較佳為 15~65質量％、更佳20〜50質量°/。。若為前述範圍，則所得之負变感光性樹脂組成物的感度便呈良好’且所形成之隔壁的遮光性優異。 (高分子分散劑(H)) 負型感光性樹脂組成物在含有前述黑色著色劑(G)等分散性材料的情況時，為提升分散性’較佳係含有高分子 36 201243500 分散劑(Η)者。高分子分散劑(Η)並無特別限制，係可舉例為：胺曱酸乙酯系、聚醯亞胺系、醇酸樹脂系、環氧系、聚酯系、三聚氰胺系、酚系、丙烯醯系、聚醚系、氯化乙稀系、氣化乙晞醋酸乙烯系共聚合體系、聚醯胺系、聚碳酸酯系等，惟較佳係胺甲酸乙酯系與聚酯系。此外，高分子分散劑(Η)亦可具有源自於環氧乙烯及/或環氧丙稀之構成單元。在使用高分子分散劑(Η)以分散黑色著色劑(G)的情況時’考量到對黑色著色劑（G)的親和性’而以使用具鹽基性基之高分子分散劑(H)者較佳。鹽基性基並無特別限制，惟可舉例為1級、2級或3級胺基。高分子分散劑(H)亦可使用市售商品《市售商品方面可舉例有：DISPARLONDA-7301(商品名，楠本化成公司製）、 BYK161、BYK162、BYK163、BYK182(以上皆為商品名、 BYK-CHEMIE 公司製）、SOLSPERSE5000 、 SOLSPERSE17〇00(以上皆為商品名、Zeneca公司製）等。高分子分散劑(H)的使用量，相對於黑色著色劑(G)，係5〜30質量％者較佳，10〜25質量％特佳。使用量為前述範圍之下限値以上時，黑色著色劑(G)之分散性則有.所提升；為前述範圍之上限値以下時，負型感光性樹脂組成物之顯影性係呈良好。 (分散助劑⑴）本發明之負型感光性樹脂組成物，在分散助劑⑴方面’亦可含有酞花青系顏料衍生物或金屬酞花青磺胺化合 37 201243500 物。分散助劑（I) ’咸認具有吸附於黑色著色劑（G)等之分散性材料與高分子分散劑(H)而提升分散安定性的功能。 (石夕烷偶合劑（J)) 若使用矽烷偶合劑(J)，則從所得之負型感光性樹脂組成物所形成之硬化膜的基材密接性會有所提升。石夕烧偶合劑(J)的具體例，係可舉例如：四乙氧基石夕烧、 3-環氧丙氧基丙基三曱氧基矽烷、曱基三甲氧基石夕烧、乙稀基二甲氧基石夕院、3-曱基丙烯醯氧基丙基三甲氧基石夕烷、3-氣丙基三甲氧基矽烷、3-硫醇基呙基三曱氧基石夕烧、 3-胺基丙基三乙氧基矽烷、十七氟辛基乙基三曱氧基矽烷、含聚氧化伸烷鏈的三乙氧基矽烷等。該等係可單獨使用，亦可併用2種以上本發明之負型感光性組成物中，其總固態部分中的矽烷偶合劑(J)的含有率，較佳為0.^20質量％、更佳卜1〇質量 %。若為前述範圍之下限値以上，則從負型感光性樹脂組成物所形成之硬化膜的基材密著性會增加；若為前述範圍之上限値以下，則撥墨性會呈良好。 (微粒子(K)) 負型感光性樹脂組成物，視需要亦可含有微粒子(κ)。藉著混入餘子(Κ)，係可防止從貞型感紐樹驗成物所得之隔壁發生熱塌。微粒子(Κ)係無特別限制，可舉例為：氧化石夕、氧化錯、氟化鎂、銦摻雜氧化錫(ΙΤ0)、銻摻雜氧化錫(ΑΤΟ)等無機系微粒子’聚乙晞 '聚曱基丙稀酸甲酿(ΡΜΜΑ)等有機系微 38 201243500 粒子，惟考量耐熱性時，係無機系微粒子較佳；若考量取得容易性或分散安定性，則以氧化矽及氧化鍅特佳。此外，負型感光性树月曰組成物為含有黑色著色劑（G)及高分子八散劑(H)的情況時，若考量該高分子分散劑(H)的吸附能，則微粒子(K)係帶負電者較佳。再者，若考量負型感光性樹脂組成物之曝光感度，微粒子，係以在曝光時不吸收所照射的光者較佳，而以不吸收超高壓水銀燈之主發光波長的工射線(365nm)、Η射線(4〇5mn)、（^射線⑷如叫者特佳。微粒子（K)的粒徑，由隔壁之表面平滑性呈良好者而言，係平均粒徑為Ιμηι以下者較佳、2〇〇nm以下特佳。 (磷酸化合物(L)) 本發明之負型感光性樹脂組成物，視需要亦可含有碟酸化合物(L)。負型感光性樹脂組成物若為包含磷酸化合物 (L)者，則能夠提尚與基板的密著性。填酸化合物(l)係可舉例如：單（甲基）丙烯醯氧基乙基磷酸酯、二（甲基）丙烯醯氧基乙基碌酸酯、三（曱基）丙稀醯氧基乙基填酸酯等。 (其他添加劑）本發明之負型感光性樹脂組成物中，還可視需要包含有硬化促進劑、增贴劑' 可塑劑、消泡劑、流平劑、抗縮孔劑、紫外線吸收劑等。 (負型感光性樹脂組成物的較佳組合）本發明之負型感光性樹脂組成物，係合併用途或要求特性而選擇組成與配比較佳。本發明之負型感光性樹脂組成物中，各種混合成分的 39 201243500 較佳組成係如下所示。 <組合1> “ —解性石夕燒化合物（a-l)、（a-2)和（a-3) 的水解性共縮合物、欠紐地 ^ _ 水解性钱化合物⑹）、㈣和(a_5) 奶以及水解性石夕烧化合物（a l)、（a_2)、㈣和(a-5)的水解性共縮合物之至少—者的撥墨劑，於負型感光性樹脂組成物的總固態部分中佔質量％ . 驗可溶性樹脂⑼：選自於由於雙型環氧獅導入酸性基與乙舰雙鍵賴脂、於雙自_環氧㈣旨導入酸性基與乙稀性雙敎樹脂、㈣㈣魏氧樹料人酸性基與乙烯性雙鍵的樹脂、於曱苯酚酚醛型環氧樹脂導入酸性基與乙烯性雙鍵的樹脂、及於三酚基曱烷型環氧樹脂導入酸性基與乙烯性雙鍵的樹脂所構成之群組之至少一者的樹脂，於負型感光性樹脂組成物的總固態部分中佔12〜4〇質量 %; 光聚合起始劑(C):選自2-曱基-[4-(甲硫基）苯基]嗎啉基-1-丙酮、2-苄基-2-二甲基胺-1-(4-嗎啉基苯基丁 _、及1，2-辛二酮及4,4·-雙（二乙基胺）二苯甲酮中至少—者的光聚合起始劑，於負型感光性樹脂組成物的總固態部分中佔0.1~50質量％ ; 溶劑(E):選自於由水、2-丙醇、丙二醇單甲基鱗、内二醇單甲基_乙酸酯、3-曱氧基丁基乙酸酯、二乙二醇乙基曱基醚、丁基乙酸酯、及4-丁内酯、環己酮所構成之群組之至少一者的溶劑，於負型感光性樹脂組成物中佔 40 201243500 質量％。 <組合2> 撥墨劑(A):選自於由水解性錢化合物㈣、㈣和 (a-3)的水解性共縮合物、水解性残化合物㈣、㈣和㈣的水解性共縮合物、及水解性魏化合物⑹）、㈣、 (a-3)和（a-5)的水解性共縮合物所構成之群組之至少一者的撥墨劑，&負型感光性樹脂組成物的總固態部分中佔〇.〇1〜ίο質量％ ; 驗可溶性樹脂(B) L由於雙心型環氧樹脂導入酸性基與乙烯性雙鍵的樹脂、於雙酚!^型環氧樹脂導入酸性基與乙烯性雙鍵之樹脂、於酚酚醛型環氧樹脂導入酸性基與乙烯性雙鍵的樹脂、於曱苯酚酚醛型環氧樹脂導入酸性基與乙稀性雙鍵的樹脂、及於三紛基曱烧型環氧樹脂導入酸性基與乙烯性雙鍵的樹脂所構成之群組之至少—者的樹脂，於負型感光性樹脂組成物的總固態部分中佔12〜4〇質量 % ；光聚合起始劑（C):選自2-曱基-[4-(曱硫基）笨基]_2_嗎啉基-1-丙酮、2-苄基-2-二曱基胺-1-(4-嗎啉基笨基)_丁酮、及1，2-辛二酮及4,[雙（二乙基胺）二苯甲酮中至少一者的光聚合起始劑，於負型感光性樹脂組成物的總固態部分中佔0.1〜50質量％ ; 交聯劑（D):選自於由新戊四醇四（曱基）丙烯酸酯、二三羥曱基丙烷四（曱基）丙烯酸酯、二新戍四醇六（甲基）丙烯酸酯、二新戊四醇五（曱基）丙烯酸酯、乙氧化三聚異氰酸三 201243500 丙烯酸酯、及胺甲酸乙酯丙烯酸酯所構成之群組之至少一者的交聯劑，於負型感光性樹脂組成物的總固態部分中佔 50〜75質量°/〇 ; 溶劑(E):選自於由水、2-丙醇、丙二醇單曱基醚、丙二醇單甲基醚乙酸酯、3-曱氧基丁基乙酸酯、二乙二醇乙基曱基醚、丁基乙酸酯、及4-丁内酯、環己酮所構成之群組之至少一者的溶劑，於負型感光性樹脂組成物中佔50〜99 質量％。 <組合3> 撥墨劑（A):選自於由水解性矽烷化合物（a-1)、（a-2)和 (a-3)的水解性共縮合物、水解性ί夕烧化合物（a-1)、（a-2)和 (a-5)的水解性共縮合物、及水解性>5夕烧化合物（a-1 )、（a-2)、 (a-3)和（a-5)的水解性共縮合物所構成之群組之至少一者的撥墨劑，於負型感光性樹脂組成物的總固態部分中佔 0.01 〜10質量°/〇 ; 鹼可溶性樹脂(B):選自於由以一般式(B1-2A)表示之具有聯苯骨架的環氧樹脂、以一般式（B1-2B)表示的環氧樹脂、及以一般式(B1-2C)表示之具有聯苯骨架的環氧樹脂所構成之群組之至少一者的樹脂，於負型感光性樹脂組成物的總固態部分中為12〜40質量％ ; 光聚合起始劑（C):選自於由1,2-辛二酮，1-[4-(苯硫基）-，2-(0-苯甲醯肟）、及乙酮-l-[9-乙基-6-(2-曱基苯曱醯基)-9H-咔唑-3-基]-1 -(0-乙醯肟）所構成之群組之至少一者的光聚合起始劑，於負型感光性樹脂組成物的總固態部分 42 201243500 中佔0.1〜50質量％ ; 交聯劑(D):選自於由新戊四醇四（曱基）丙烯酸酯、二三羥曱基丙烷四（曱基）丙烯酸酯、二新戊四醇六（甲基）丙烯酸酯、二新戊四醇五（甲基）丙烯酸酯、乙氧化三聚異氰酸三丙烯酸酯、及胺甲酸乙酯丙烯酸酯所構成之群組之至少— 者的交聯劑，於負型感光性樹脂組成物的總固態部分中為 20〜50質量％ ; 溶劑(E):選自於由水、2_丙醇、丙二醇單甲基趟、丙二醇單甲基醚乙酸酯、3_甲氧基丁基乙酸酯、二乙二醇乙基甲基醚、丁基乙酸酯、及4-丁内酯、環己鲷所構成之群組之至少一者的溶劑，於負型感光性樹脂組成物中佔5〇〜99 質量％黑色著色劑(G):選自於由碳黑、紅色顏料、藍色顏料、綠色顏料4之有機顏料的混合物、及次甲基偶氮染料所構成之群組之至沙一者的黑色著色劑’於負型感光性樹脂組成物的總固態部分中為15〜65質量％。 [負型感光性樹脂組成物的製造方法] 製造負型感光性樹脂組成物之方法，係撥墨劑（A)、鹼可溶性樹脂(B)、光聚合起始劑(C)、視需要之交聯劑〇D)、溶劑(E)、交聯劑(F)、黑色著色劑(G)、高分子分散劑(Η)、分散助劑(I)、矽烷偶合劑(J)、微粒子(Κ)、磷酸化合物(L) 及其他添加劑相混合之方法較佳。本發明之負型感光性樹脂組成物’係如同一般的負型感光性組成物，可使用為光刻法等的材料’而所得之感光 43 201243500 硬化物係可使用作為：使用—般得之硬化赌顧料學树之構/紐樹餘成物所 η刑件之構件。特別係若將本發明之負^紐彳指㈣缺料林 ::複:::素及位於鄰接像素間之隔壁== ，係細寻到即使經紫外線/臭氧洗淨處理等親墨化處理後’仍具有充分撥墨性的隔壁，因而較佳。 [光學元件用隔壁的製造方法] 適用於在基板上具有複數個像素與位於鄰接像素間之隔壁的光學元件用隔壁之製造。將本發明之負型感光性樹脂組成物塗佈於前述基板上而形成塗膜（塗_齡驟；隨後，對前述㈣施行加細培步驟隨後，僅將前述塗膜屬成為隔壁的部分施行曝光而使其感光硬化(曝光步驟）；隨後，將前述經感光硬化部分以外的塗膜去除’而㊉成由前述塗膜之感光硬化部分所構成之隔壁(顯影步驟）；隨後，對前述已形成之隔壁施行加熱 (後焙步驟）’藉此即可製作光學元件用之隔壁。基板的材質並無特別的限制，惟可使用例如：各種玻璃板；聚酯（聚對苯二甲酸乙二酯等）、聚烯烴（聚乙烯、聚丙烯等）、聚碳酸酯、聚甲基丙烯酸曱酯、聚硬、聚醯亞胺、聚（甲基）丙烯酸樹脂等熱可塑性塑膠片；環氧樹脂、不飽和聚酯等熱硬化性樹脂的硬化片等等。尤其，若從耐熱性的觀點出發，較佳係使用玻璃板、聚醯亞胺等耐熱性塑膠。第1圖係示意地顯示使用了本發明之負型感光性樹脂組成物之光學元件用隔壁之製造例的截面圖。第1(1)圖係顯 44 201243500 示在基板1上形成了本發明之負型感光性樹脂組成物所構成之塗膜2的狀態的截面圆。第1(11)圖係示意地顯示曝光步驟的圖。第1(111)圖係顯示顯影步驟後的基板1與在基板上所形成之隔壁6的截面圖。以下，使用第1圖具體說明使用了本發明之負型感光性樹脂組成物之光學元件用隔壁的製造方法。 (塗膜形成步驟）如第1(1)圖的截面所示，在基板1上塗佈前述本發明之負型感光性樹脂組成物，而形成由負型感光性樹脂組成物所構成的塗膜2。另外，在基板1上形成負型感光性樹脂組成物的塗膜2前，最好先將基板1的負型感光性樹脂組成物的塗佈面，利用醇洗淨或紫外線/臭氧洗淨等方法施行洗淨。負型感光性樹脂組成物的塗佈方法，若為形成膜厚均勻之塗膜的方法則並無特殊限制，可舉例如：旋塗法、噴塗法、狹縫式塗佈法、滾筒塗佈法 '旋轉塗佈法、棒塗佈法等一般塗膜形成所用方法。塗膜2之膜厚係考量最終所得之隔壁的高度而決定。塗膜2 的膜厚，較佳係最終所得之隔壁的高度的刚〜2〇〇%， 13()/°特佳。塗膜2的膜厚為0.3〜325μιη較佳、1.3~65μπι 特佳。 (預焙步驟）將依則述塗膜形成步驟在基板1上所形成的塗膜2施行加熱，得到膜2。μ & # 错由s亥加熱，構成塗膜2的負型感光性樹 45 201243500(In the formula (Bl-2c), the hydrogen atom of the benzene ring may be independently substituted with an alkyl group having 1 to 12 carbon atoms, a halogen atom, or a phenyl group which may have a substituent. u is 26 201243500 0 to 10 In the case where the epoxy resin represented by the formula (Bl-2a) to (Bl-2c) is reacted with a compound having a carboxyl group and an ethylenic double bond, and then reacted with a polybasic acid anhydride, The polybasic carboxylic anhydride is preferably a mixture of a dicarboxylic anhydride and a tetracarboxylic dianhydride. The molecular weight can be controlled by varying the ratio of dicarboxylic anhydride to tetracarboxylic acid. A commercially available product can be used for the resin (B1-2). Commercially available products include, for example, all trade names: KAYARAD PCR-1069, K-48C, CCR-1105, CCR-1115 'CCR-1159H, CCR-1235, TCR-1025, TCR-1064H, TCR-1286H, ZAR-1535H, ZAR-2002H, ZFR-1491H, ZFR-1492H, ZCR-1571H 'ZCR-1569H 'ZCR-1580H, ZCR-1581H, ZCR-1588H, ZCR-1642H, ZCR-1664H (all of which are 曰本化Manufactured by a pharmaceutical company, EXi〇i〇 (manufactured by Nagase Chemex Co., Ltd.). The monomer (B1-3) may, for example, be 2,2,2-tripropenyloxymethylethyl phthalate (manufactured by NK Ester CBX-1, manufactured by Shin-Nakamura Chemical Co., Ltd.). In the aspect of the test of the soluble resin (B), the high-resolution pattern can be obtained by suppressing the peeling of the coating film during development, the linearity of the wiring is good, and the appearance after the post-peeling step is maintained, and the surface of the smooth coating film can be easily obtained. The viewpoint 'is preferred to use a resin (B1-2). In the case of the resin (B1-2), a resin in which an acidic group and an ethylenic double bond are introduced to a bisphenol a type epoxy resin, and an acidic group and an ethylenic double bond are introduced to the bisphenol F type epoxy resin. a resin, a resin in which a phenolic novolac type epoxy resin is introduced with an acidic group and an ethylenic double bond, and a p-cresol novolac type epoxy resin is introduced with a resin of 27 201243500 sd and ethylene double bonds, or (4) A resin in which an epoxy group is introduced with an acidic group and an ethylenic double bond, and an acidic group and an ethylidene double bond are introduced to the epoxy resin represented by the formula (Bl-2a) to (Bl-2c). Resin. The mass average molecular weight (Mw) of the above-mentioned alkali-soluble resin (B) used in the present invention is preferably ι_5 χΐ〇 3 to 3 〇χΐ〇 3, and particularly preferably 2 χ 1 〇 3 〜 15 χ 1 〇 3 . Further, the number average molecular weight (??) is preferably 5 Å to 2 〇 x 〇 3, and particularly preferably 1.0 X 10 10 10 10 10 . When the mass average molecular weight (M-magic and mass-average molecular stem (Μη) is equal to or greater than the lower limit 前述 of the above range, the hardening at the time of exposure is sufficient, and when the upper limit is less than or equal to the upper limit of the above range, the developability is good. The number of the ethylenic double bonds which the resin (Β) has in one molecule is preferably 3 or more, and more preferably 6 or more. When the number of the ethylenic double bonds is at least the lower limit of the above range, the exposed portion is The alkali/capacitance of the unexposed portion is more likely to be different, and the acidity of the soluble resin (Β) can be formed by forming a fine pattern with a lower exposure amount, preferably 1 〇 2 〇〇 mg KOH / g. 30 to 150 mgKOH/g is more preferable, and 50 to i〇〇mgKOH/g is particularly preferable. When the acid value is in the above range, the storage stability and developability of the negative photosensitive resin composition are good. Negative photosensitive resin The alkali-soluble resin (B) contained in the composition may be one type or a mixture of two or more types. The negative photosensitive resin composition of the present invention has an alkali-soluble resin (B) content in the total solid portion. , 12 to 40% by mass, preferably 14 to 38% by mass It is preferably 16 to 36% by mass. When the content is in the above range, the storage stability of the negative resin 28 201243500 optical resin composition is good. [Photopolymerization initiator (c)] Photopolymerization initiator (c), the substance is not particularly limited. If the compound having a photopolymerization initiator function is a compound which generates a radical by light, the photopolymerization initiator (C) may be, for example, a node group. Diethyl ketone, methyl sulphate SUa 9, 1G_ nucleus, etc. a_n benzoin and other samarium benzoin; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, etc. Affinity bond; anthrone, 2_methyl (tetra) _ m 嗔 side, isopropyl · _, 2, 4 · diethyl make, 2, 4 2 dioxanone, 2,4-di Propyl peptone " plug side _4_hemeic acid, etc.; diphenyl, 4,4'-bis(dimethylamino)benzophenone, 4,4,-bis (diethylamine) Benzophenones such as benzophenone; acetophenone, 2_(4_toluene oxime phenyl acetophenone, p-dimethylaminoacetophenone, 2,2,_dimethoxy _ 2-phenylphenyl hydrazine, p-methoxyphenylethyl _, 2-mercapto-[4.(methylthio)phenyl]_2-morphine-based small acetone, 2-benzyl-2 - dimethylamino group ^ (Acetophenone phenylbutanone and other acetophenones; anthracene, 2-ethyl hydrazine, hydrazine, hydrazine, 4_naphthoquinone, etc.; 2 - dimethyl Ethyl alumic acid ethyl ester, 4-dimethylamino benzoic acid ethyl ester, 4 · diammonium benzoic acid (n-butoxy) ethyl ester, 4-diamyl benzoic acid isoamyl ester, 4_Aminoguanidinobenzoic acid-2-ethylhexyl ester and other aminobenzoic acid; gas acetophenone, trifunctional methyl benzoic acid, etc. _ compound; fluorenyl phosphine oxide; Base and other peroxides; 1,2-octanedione, Η4_(stupyl)_, 2_(〇·曱醯曱醯肥), ethylene-steel 1-[9-ethyl-6-(2-methylbenzene Anthracene esters such as sulfhydryl, hydrazine, hydrazin-3-yl]-b (〇-acetamidine); triethanolamine, decyldiethanolamine, triisopropanolamine, 29 201243500 n-butylamine, N- An aliphatic amine such as methyldiethanolamine or diethylaminoethyl methacrylate; 2-thiol benzimidazole, 2-thiol benzoxazole, 2-thiolbenzothiazole, anthracene, 4-butanol bis(3-thiol butyrate), tris(2-thiolpropoxyethyl)isocyanate, neopentyl alcohol tetrakis(3-thiolbutyric acid) Ester) And thiol compounds. Among them, benzophenones, aminobenzoic acids, aliphatic amines, and thiol compounds are preferred because they are used together with other radical initiators to exhibit a sensitizing effect. The photopolymerization initiator (C) is preferably 2-methyl-[4-(methylthio)phenyl]-nonylmorpholinyl-1-propanone, 2-benzyldimethylamino group _i-(4) -morpholinylphenyl)-butane oxime, octanedione, phenylthio)-, 2-(anthracene-benzoic acid), ethylethyl-6-(2-methylphenylhydrazino) 9Η_甲醯基_3_基]1 (〇乙醯), 4,4'-bis(monoethylamino)diketone, or 2,4 diethylthioxanthone. Further preferred are combinations of these with the aforementioned diphenyl groups. A commercially available product can be used as the photopolymerization initiator (C). Commercially available products include, for example, IRGACURE 907 (trade name, manufactured by BASF Corporation, 2-methylso [methane (methylthio)phenyl]-2-morpholinylpropane); IRGACURE 369 (trade name, BASF) Company system, 2 · dimethyl dimethylamine (4 _ 淋笨笨 )) Butane-1-one) and so on. The photopolymerization initiator (c) contained in the negative photosensitive resin composition may be a mixture of two or more kinds. The photopolymerization in the total solid portion of the negative photosensitive resin composition is such that the content of the agent (C) is preferably 〇 1 to 50% by mass, more preferably 〇 5 to 3 % by mass, and particularly preferably 5 % by mass. When the range is within the above range, the negative photosensitive resin composition: 30 201243500 The film system is good. [Crosslinking agent (D)] The negative photosensitive resin composition of the present invention may contain a crosslinking agent (D) as an optional component for promoting radical curing. The crosslinking agent (D) is preferably a compound having two or more ethylenic double bonds in one molecule and having no acidic group. By including the crosslinking agent (D) in the negative photosensitive resin composition, the curability of the alkali-soluble resin at the time of exposure can be improved, and the amount of exposure at the time of forming the partition walls can be reduced. The crosslinking agent (D) having two or more ethylenic double bonds in one molecule and having no acidic group is not particularly limited as long as it is a compound having such a condition, and for example, diethyldiacetate (曱) Acrylate, tetraethylene glycol bis(indenyl) acrylate, tripropylene glycol bis(indenyl) acrylate, neopentyl glycol bis(indenyl) acrylate, 1,9-nonanediol di(methyl) ) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl alcohol tri (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, ditrimethylolpropane tetra (a) Acrylate, dipentaerythritol penta(indenyl) acrylate, dipentaerythritol hexa(meth) acrylate, etc., ethoxylated trimeric isocyanate triacrylate, ε-caprolactone modification Tris-(2-propene oxyethyl)trimeric isocyanate, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenimido)phenyl}methane, Ν, Ν '-m--extended thiol-bis (allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), urethane acrylate, and the like. These may be used alone or in combination of two or more. A commercially available product can be used as the crosslinking agent (D). Commercially available products include, for example, KAYARAD DPHA (trade name, manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate); NK_ 31 201243500 A-9530 (trade name, KK ester A-9300 (trade name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., ethoxylated trimeric), manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) Cyanate triacrylate); NK ester A-9300-lCL (trade name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., ε-caprolactone modified tris-(2-propenyloxyethyl) trimeric isocyanate); Μ(trade name, manufactured by Maruzen Petrochemical Co., Ltd., bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)phenyl}methane); Χ(trade name, Maruzen Petrochemical Co., Ltd., Ν, Ν, _ - - 茬茬 - bis (allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinazoline)) Wait. The urethane acrylate can be exemplified by the KAYARAD UX series manufactured by Nippon Kayaku Co., Ltd. 'The specific trade names can be exemplified by: UX-3204, UX-61 (H, UX-0937, DPHA-40H, UX-5000, UX). -5002D-P20, V#802 (trade name, Osaka Organic Chemical Industry Co., Ltd., dipentaerythritol acrylate, a mixture of tripentaerythritol acrylate and tetrapentaerythritol acrylate), etc. Among them, KAYARAD DPHA and NK ester A-9530 are preferred because they enhance the sensitivity of the cured film obtained from the negative photosensitive resin composition. NK esters A-9300, BANI-M and BANI-X are imparted to the cured film. From the viewpoint of hardness and suppression of thermal collapse, it is preferred as β NK vinegar A-9300-1CL, which is preferred from the viewpoint of imparting flexibility to the cured film. Ethyl formate B (di) acid S is intended to be realized It is preferable that the development time is good and the developability is good. The content of the crosslinking agent (D) contained in the negative photosensitive resin composition is as large as the following range: The amount is 95% by mass in the total solid portion and relative to the content of crosslinker (d), check 32 201243500 Solubility Fat mass (B) content is mass% alkali-soluble resin (B) is / crosslinking agent (D) quality χίοο, based adjusted to 15~85 mass% is preferred. More preferably, the total amount of the alkali-soluble resin (B) and the crosslinking agent is 60 to 92% by mass in the total solid portion, and the mass of the alkali-soluble resin (B) / the mass of the crosslinking agent (D) is 1000. ~70% by mass; particularly preferably, the total amount of the alkali-soluble resin (B) and the crosslinking agent (D) is 65 to 9 % by mass in the total solid portion, and the mass/cross of the alkali-soluble resin (B) The mass 乂丨(9) of the crosslinking agent (D) is (10) to "% by mass." If it is in the above range, the storage stability of the negative photosensitive resin composition is good, and a negative photosensitive resin composition is formed. When the obtained patterned substrate is used, the wettability of the inkjet ink in the pixel is good. [Solvent (E)] The negative photosensitive resin composition of the present invention contains a solvent (E) as needed. E) 'The viscosity of the negative photosensitive resin composition is lowered, and the negative photosensitive resin composition can be easily applied to the substrate. A uniform negative photosensitive resin composition coating film can be formed. , the negative photosensitive resin composition is a solvent-free, negative photosensitive resin group The film of the negative photosensitive resin composition is the same as the film of the negative photosensitive resin composition. The solvent (E) contained in the negative photosensitive resin composition of the present invention is a negative photosensitive resin composition. The above-mentioned ink-repellent (A), the soluble resin (B), the photopolymerization initiator (〇, the optional crosslinking agent (D), and any components described later are uniformly dissolved or dispersed, and have a negative The solvent of the photosensitive resin composition is uniform and simple to the coating of the substrate forming the partition wall, and the solvent is not particularly limited, and the solvent is not particularly limited, but it is possible to use 33 201243500, for example, and in the synthetic ink-repellent agent ( A) The solvent of the solvent (E) contained in the negative photosensitive resin composition varies depending on the composition or use of the negative photosensitive resin composition, but is preferably negative. The photosensitive resin composition is mixed with 50 to 99% by mass, more preferably 60 to 95% by mass, and particularly preferably 65 to 90% by mass. [Negative photosensitive resin composition and coating film] The negative photosensitive material of the present invention The acid value of the resin composition (hereinafter also referred to as the acid value of the composition) is 6 30 mg KOH/g, preferably 8 to 25 mg KOH/g, more preferably 10 to 22 mg KOH/g. When the acid value of the negative photosensitive resin composition is within the above range, the storage stability of the negative photosensitive resin composition is good. When the coating film of the negative photosensitive resin composition is formed on the substrate, the coating film of the present invention having an excellent appearance can be obtained. The coating film can be formed in the same manner as the coating film forming step of the optical element partition wall to be described later. The reason why the acidity of the negative photosensitive resin composition is in the above range is good when the storage stability is good. However, the toner (A) is present in the presence of a sterol group, which is easily caused by an acid catalyst. When the acid value of the self-condensation composition is at least the lower limit of the above range, the developability of the coating film of the negative photosensitive resin composition is good, and when it is below the upper limit of the above range, the negative photosensitive resin is composed. The storage stability of the substance is excellent. The acid value of the composition is determined by the acid value and content of the alkali-soluble resin (B). The respective preferred ranges are as described above. The negative photosensitive resin composition of the present invention contains an ink-repellent agent (A), an alkali-soluble resin (B), and a photopolymerization initiator (c) (> and, if necessary, a crosslinking agent (D) And solvent (E). Further, it may contain the following thermal crosslinking agent 34 201243500 (F), black coloring agent (G), polymer dispersing agent, dispersing aid (1), decane coupling agent (J), fine particles (K), a phosphoric acid compound (L), and other additives. (Thermal crosslinking agent (F)) The thermal crosslinking agent (F) is a compound having two or more groups capable of reacting with a carboxyl group and/or a hydroxyl group. When the alkali-soluble resin (B) has a carboxyl group and/or a warp group, the crosslinking agent (F) has a function of reacting with an alkali-soluble resin to increase the crosslinking density of the cured film and improving heat resistance. The crosslinking agent (F) is preferably exemplified by at least one selected from the group consisting of an amine resin, an epoxy compound, an .f oxazoline compound, a polyisocyanate compound, and a polycarbodiimide compound. These compounds may be used alone or in combination of two or more kinds. Here, the total solid of the negative photosensitive resin composition of the present invention The content of the thermal crosslinking agent (F) in the portion is preferably from 1 to 5 % by mass, more preferably from 5 to 30% by mass. If it is within this range, the developability of the resulting negative photosensitive resin composition (Black colorant (G)) When the negative photosensitive resin composition of the present invention is used for a black matrix (which is surrounded by R' G, B color pixels of a color filter of a liquid crystal display element) When the lattice-shaped black portion is formed, it is preferable to contain a black coloring agent (G). Examples of the black coloring agent (G) include carbon black, aniline black, an anthraquinone black pigment, and an anthraquinone black pigment. Like CI color black 1, 6, 7, 12, 20, 31, etc. Black colorant (G) can also be used, for example, red pigment, blue pigment, green pigment, azomethine pigment, etc. The black colorant (G) is preferably carbon black from the viewpoint of the price and the light-shielding size of 35 201243500, and the carbon black may be subjected to surface treatment such as a resin. In addition, the color tone may be used in combination with blue. Pigment or purple pigment. Carbon black is viewed from the shape of the black matrix Preferably, the specific surface area measured by the BET method is 50 to 200 m 2 /g. When the specific surface area is 5 〇 m 2 /g or more, the shape of the black matrix is not easily deteriorated, and when it is 200 m 2 /g or less, the carbon black does not. Since the dispersing aid is excessively adsorbed, it is not necessary to mix a large amount of dispersing aid in order to exhibit various physical properties. Further, from the viewpoint of sensitivity of carbon black, it is preferred that the oil absorption amount of dibutyl vinegar is 120 cm 3 /100 g or less. The smaller the better, the better the average primary particle size measured by the transmission electron microscope is 20~5 Onm. The average primary particle size is 2〇nm or more, and the concentration is high. Dispersion is easy to obtain a negative photosensitive resin composition having good stability over time. When the thickness is 50 nm or less, the shape of the black matrix is not easily deteriorated. Further, the average secondary particle diameter observed by a transmission electron microscope is preferably 80 to 200 nm. When the negative photosensitive resin composition of the present invention contains a black coloring agent (G) and is used for black matrix formation or the like, a black coloring agent (G) is used in the total solid portion of the negative photosensitive resin composition. The content of the material is preferably 15 to 65% by mass, more preferably 20 to 50% by mass. . When it is in the above range, the sensitivity of the obtained negative-change photosensitive resin composition is good, and the barrier rib formed is excellent in light-shielding property. (Polymer dispersing agent (H)) When the negative photosensitive resin composition contains a dispersing material such as the black coloring agent (G), it is preferable to contain a polymer 36 201243500 dispersing agent. )By. The polymer dispersant (Η) is not particularly limited, and examples thereof include an amine phthalate type, a poly phthalimide type, an alkyd resin type, an epoxy type, a polyester type, a melamine type, a phenol type, and a propylene group. An anthraquinone type, a polyether type, a chlorinated ethylene type, a vaporized acetonitrile vinyl acetate type copolymerization system, a polyamidamide type, a polycarbonate type, etc., but it is preferable that it is an urethane type and a polyester type. Further, the high molecular dispersant (Η) may have a constituent unit derived from ethylene oxide and/or epoxy propylene. When a polymer dispersant (Η) is used to disperse the black colorant (G), 'the affinity for the black colorant (G) is taken into consideration', and the polymer-dispersing agent (H) having a salt-based group is used. Better. The salt-based group is not particularly limited, and may be exemplified by a grade 1, a grade 2 or a grade 3 amine group. For the polymer dispersant (H), commercially available products can be used, for example, DISPARLONDA-7301 (trade name, manufactured by Nanben Chemical Co., Ltd.), BYK161, BYK162, BYK163, and BYK182 (all of which are trade names, BYK). -CHEMIE company, SOLSPERSE5000, SOLSPERSE17〇00 (all of which are trade names, manufactured by Zeneca). The amount of the polymer dispersant (H) to be used is preferably from 5 to 30% by mass, particularly preferably from 10 to 25% by mass, based on the black colorant (G). When the amount of use is at least the lower limit of the above range, the dispersibility of the black colorant (G) is improved. When the amount is less than or equal to the upper limit of the above range, the development of the negative photosensitive resin composition is good. (Dispersing aid (1)) The negative photosensitive resin composition of the present invention may further contain a phthalocyanine pigment derivative or a metal phthalocyanine compound 37 201243500 in the side of the dispersing aid (1). The dispersing aid (I) ’ has a function of adsorbing a dispersing material such as a black coloring agent (G) and a polymer dispersing agent (H) to enhance dispersion stability. (Alkane coupling agent (J)) When the decane coupling agent (J) is used, the substrate adhesion of the cured film formed from the obtained negative photosensitive resin composition is improved. Specific examples of the Shiki siu coupling agent (J) include, for example, tetraethoxy cerium oxide, 3-glycidoxypropyltrimethoxy decane, decyltrimethoxy sulphur, and ethylene. Dimethoxy zeshi, 3-mercapto propylene methoxy propyl trimethoxy oxalate, 3- propyl propyl trimethoxy decane, 3-thiol fluorenyl ruthenium trioxane, 3-amine Propyltriethoxydecane, heptadecafluorooctyltrimethoxydecane, triethoxydecane containing a polyoxyalkylene chain, and the like. The content of the decane coupling agent (J) in the total solid portion of the negative photosensitive composition of the present invention is preferably 0.^20% by mass, More preferably, 1% by mass. When the thickness is less than or equal to the lower limit of the above range, the substrate adhesion of the cured film formed from the negative photosensitive resin composition increases, and if it is less than or equal to the upper limit of the above range, the ink repellency is good. (Microparticle (K)) The negative photosensitive resin composition may contain fine particles (κ) as needed. By mixing the remainder (Κ), it is possible to prevent thermal collapse from the next door obtained from the test of the scorpion-type sensation tree. The microparticles (Κ) are not particularly limited, and may be, for example, an inorganic microparticle such as oxidized oxide, oxidized, magnesium fluoride, indium-doped tin oxide (ΙΤ0), or antimony-doped tin oxide (ΑΤΟ). Polyorganic acrylic acid (ΡΜΜΑ) and other organic micro-38 201243500 particles, only when considering heat resistance, inorganic micro-particles are preferred; if easy to measure or dispersion stability, then yttrium oxide and yttrium oxide good. Further, when the negative photosensitive tree sap composition is a black coloring agent (G) or a polymer octagonal agent (H), the fine particles (K) are considered in consideration of the adsorption energy of the polymer dispersing agent (H). It is preferred that the tie is negative. Further, in consideration of the exposure sensitivity of the negative photosensitive resin composition, the fine particles are preferably those which do not absorb the irradiated light during exposure, and which do not absorb the main emission wavelength of the ultrahigh pressure mercury lamp (365 nm). Η ray (4〇5mn), (^ ray (4) is particularly good. The particle size of the microparticle (K) is better if the surface smoothness of the partition is good, and the average particle size is Ιμηι or less. (2. Phosphate compound (L)) The negative photosensitive resin composition of the present invention may contain a disc acid compound (L) as needed. The negative photosensitive resin composition contains a phosphoric acid compound. (L), the adhesion to the substrate can be improved. The acid-filling compound (1) may, for example, be mono(methyl)acryloxyethyl phosphate or di(meth)acryloxy group. Ethyl phthalate, tris(fluorenyl) propylene oxiranyl ethyl ester, etc. (Other additives) The negative photosensitive resin composition of the present invention may further contain a hardening accelerator and an additional affixing as needed. Agent' plasticizer, defoamer, leveling agent, anti-cratering agent, UV absorber, etc. (Preferred Combination of Negative Photosensitive Resin Composition) The negative photosensitive resin composition of the present invention is preferably used in combination with a desired composition or a desired property. The negative photosensitive resin composition of the present invention 39 201243500 The preferred composition of various mixed components is as follows: <Combination 1> "- Hydrolyzable co-condensate of decomposing sulphur compound (al), (a-2) and (a-3)地 _ Hydrolyzable money compounds (6)), (4) and (a_5) milk and at least one of the hydrolyzable co-condensates of (a), (a), (d) and (a-5) The ink accounts for % by mass in the total solid portion of the negative photosensitive resin composition. The soluble resin (9) is selected from the group consisting of a double-type epoxy lion introduced into an acidic group and a double-bonded lyophile, and a double-self-ring Oxygen (4) is a resin which introduces an acidic group and an ethylene double bond, and (4) (4) a resin of a human acid group and an ethylenic double bond of a Wei oxygen tree, a resin which introduces an acidic group and an ethylenic double bond in a phenolic phenolic type epoxy resin, and Introducing an acidic group with an ethylenic double bond in a trisphenol decane type epoxy resin The resin of at least one of the groups consisting of the resin accounts for 12 to 4% by mass in the total solid portion of the negative photosensitive resin composition; the photopolymerization initiator (C): is selected from the group consisting of 2-mercapto- [4-(Methylthio)phenyl]morpholinyl-1-propanone, 2-benzyl-2-dimethylamine-1-(4-morpholinylphenylbutane), and 1,2-octyl The photopolymerization initiator of at least one of diketone and 4,4·-bis(diethylamine)benzophenone accounts for 0.1 to 50% by mass in the total solid portion of the negative photosensitive resin composition; Solvent (E): selected from the group consisting of water, 2-propanol, propylene glycol monomethyl scale, lactone monomethyl-acetate, 3-decyloxybutyl acetate, diethylene glycol ethyl The solvent of at least one of the group consisting of mercaptoether, butyl acetate, and 4-butyrolactone and cyclohexanone accounts for 40 201243500% by mass in the negative photosensitive resin composition. <Combination 2> Ink-repellent (A): Hydrolyzable co-condensation selected from hydrolyzable co-condensates of hydrolyzable money compounds (4), (4) and (a-3), hydrolyzable residual compounds (4), (4) and (4) And an ink-repellent agent of at least one of the group consisting of hydrolyzable Wei compounds (6)), (4), (a-3) and (a-5) hydrolyzable co-condensates, & negative photosensitive resin The total solid portion of the composition accounts for 〇.〇1~ίο% by mass; the soluble resin (B) L is a resin of a double-core epoxy resin introduced into an acidic group and an ethylenic double bond, and is a bisphenol-type epoxy. a resin in which an acid group and an ethylenic double bond are introduced into a resin, a resin in which an acidic group and an ethylenic double bond are introduced into a phenol novolac type epoxy resin, and a resin in which an acidic group and an ethylene double bond are introduced in a nonylphenol novolac type epoxy resin; And at least the resin of the group consisting of a resin in which an acidic group and an ethylenic double bond are introduced into the tri-sulfonated epoxy resin, which accounts for 12 to 4 in the total solid portion of the negative photosensitive resin composition. 〇质量%; photopolymerization initiator (C): selected from 2-mercapto-[4-(indolyl)phenyl]_2-morpholinyl-1-propanone, 2- At least one of keto-2-didecylamine-1-(4-morpholinylphenyl)-butanone, and 1,2-octanedione, and 4,[bis(diethylamine)benzophenone The photopolymerization initiator accounts for 0.1 to 50% by mass in the total solid portion of the negative photosensitive resin composition; the crosslinking agent (D): is selected from tetrakis(yl) acrylate from pentaerythritol. , ditrihydroxyhydrin propane tetra(indenyl) acrylate, diterpene tetraol hexa(meth) acrylate, dipentaerythritol penta(indenyl) acrylate, ethoxylated trimeric isocyanate three 201243500 a crosslinking agent of at least one of the group consisting of acrylate and urethane acrylate, which accounts for 50 to 75 mass%/〇 in the total solid portion of the negative photosensitive resin composition; solvent (E) : selected from water, 2-propanol, propylene glycol monodecyl ether, propylene glycol monomethyl ether acetate, 3-decyloxybutyl acetate, diethylene glycol ethyl decyl ether, butyl The solvent of at least one of the group consisting of acetate and 4-butyrolactone and cyclohexanone accounts for 50 to 99% by mass in the negative photosensitive resin composition. <Combination 3> Ink-repellent (A): a hydrolyzable co-condensate selected from the hydrolyzable decane compounds (a-1), (a-2) and (a-3), and a hydrolyzable lysate compound Hydrolyzable co-condensate of (a-1), (a-2) and (a-5), and hydrolyzability>5 kiln compound (a-1), (a-2), (a-3) The ink-repellent agent of at least one of the group consisting of the hydrolyzable co-condensate of (a-5) accounts for 0.01 to 10 mass%/〇 in the total solid portion of the negative photosensitive resin composition; alkali solubility Resin (B): selected from the group consisting of an epoxy resin having a biphenyl skeleton represented by the general formula (B1-2A), an epoxy resin represented by the general formula (B1-2B), and a general formula (B1-2C) The resin of at least one of the group consisting of the epoxy resins having a biphenyl skeleton is 12 to 40% by mass in the total solid portion of the negative photosensitive resin composition; Photopolymerization initiator (C) ): selected from 1,2-octanedione, 1-[4-(phenylthio)-, 2-(0-benzamide), and ethyl ketone-l-[9-ethyl-6 a photopolymerization initiator of at least one of the group consisting of -(2-mercaptophenylhydrazino)-9H-carbazol-3-yl]-1 -(0-acetamidine), The total solid portion 42 of the photosensitive resin composition accounts for 0.1 to 50% by mass in 201243500; the crosslinking agent (D): is selected from the group consisting of neopentaerythritol tetrakis(meth)acrylate, ditrihydroxydecylpropane (fluorenyl) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated trimeric isocyanate triacrylate, and urethane acrylate At least a crosslinking agent of the group consisting of esters is 20 to 50% by mass in the total solid portion of the negative photosensitive resin composition; solvent (E): selected from water, 2-propanol , propylene glycol monomethyl hydrazine, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol ethyl methyl ether, butyl acetate, and 4-butyrolactone, The solvent of at least one of the groups consisting of cyclohexanone accounts for 5 to 99% by mass of the negative photosensitive resin composition. Black colorant (G): selected from carbon black, red pigment, blue a mixture of pigments, green pigments, 4 organic pigments, and a group of black azo dyes to the sand of the black colorant' The total solid portion of the photosensitive resin composition is 15 to 65% by mass. [Method for Producing Negative Photosensitive Resin Composition] A method for producing a negative photosensitive resin composition is an ink repellent (A), an alkali soluble resin (B), a photopolymerization initiator (C), and optionally Crosslinking agent 〇D), solvent (E), crosslinking agent (F), black coloring agent (G), polymer dispersing agent (Η), dispersing aid (I), decane coupling agent (J), fine particles ( Preferably, the method of mixing the phosphoric acid compound (L) and other additives is preferred. The negative photosensitive resin composition of the present invention is a general negative photosensitive composition, and a photosensitive material which can be obtained by using a material such as photolithography can be used as: The structure of the hardened gambling materials tree structure / New Tree Yucheng things η criminal pieces. In particular, if the negative electrode of the present invention is referred to as (4) lacking material:: complex::: and the partition wall between adjacent pixels ==, it is finely found to be ink-repellent even after ultraviolet/ozone cleaning treatment. It is preferable to have a partition wall which is still sufficiently ink-repellent. [Manufacturing Method of Partition for Optical Element] It is applied to the production of a partition wall for an optical element having a plurality of pixels on a substrate and a partition wall between adjacent pixels. The negative photosensitive resin composition of the present invention is applied onto the substrate to form a coating film (coating age); subsequently, the above-mentioned (4) is subjected to a fine-grinding step, and then only the part of the coating film which is a partition wall is subjected to Exposure to photohardening (exposure step); subsequently, removing the coating film other than the photosensitive hardened portion described above and forming a partition wall composed of the photosensitive hardened portion of the coating film (developing step); The forming partition wall is subjected to heating (post-baking step) to thereby form a partition wall for the optical element. The material of the substrate is not particularly limited, but for example, various glass sheets can be used; polyester (polyethylene terephthalate) Thermoplastic plastic sheet such as ester, etc., polyolefin (polyethylene, polypropylene, etc.), polycarbonate, polymethyl methacrylate, polyhard, polyimine, poly(meth)acrylic resin; epoxy resin A cured sheet of a thermosetting resin such as an unsaturated polyester, etc. In particular, from the viewpoint of heat resistance, a heat-resistant plastic such as a glass plate or a polyimide is preferably used. A cross-sectional view of a production example of a partition for an optical element using a negative photosensitive resin composition of the present invention. Fig. 1(1) shows a liquid crystal 44 201243500. The negative photosensitive resin composition of the present invention is formed on a substrate 1. The cross section of the state of the coating film 2 formed of the object is shown in Fig. 1 (11) schematically showing the exposure step. The first (111) diagram shows the substrate 1 after the development step and the partition wall formed on the substrate. In the following, a method for producing an optical element partition using the negative photosensitive resin composition of the present invention will be specifically described with reference to Fig. 1 (coating film forming step) as shown in the first (1) cross section. The negative photosensitive resin composition of the present invention is applied onto the substrate 1 to form a coating film 2 composed of a negative photosensitive resin composition. Further, a negative photosensitive resin composition is formed on the substrate 1. Before coating the coating film 2, it is preferable to wash the coated surface of the negative photosensitive resin composition of the substrate 1 by alcohol washing or ultraviolet/ozone cleaning, etc. Negative photosensitive resin composition Coating method, if the film thickness is uniform The method of the film is not particularly limited, and examples thereof include a method of forming a general coating film such as a spin coating method, a spray coating method, a slit coating method, a roll coating method, a spin coating method, and a bar coating method. The film thickness of the film 2 is determined in consideration of the height of the partition wall finally obtained. The film thickness of the coating film 2 is preferably about 2% by mass, preferably 13 () / °, which is the height of the finally obtained partition wall. The film thickness of 2 is preferably from 0.3 to 325 μm, preferably from 1.3 to 65 μm. (Prebaking step) The coating film 2 formed on the substrate 1 is heated by the coating film forming step to obtain a film 2. μ &#错的加热heating, the negative photosensitive tree that constitutes the coating film 2 201243500

St::::包含溶劑之揮發成分會揮發、去除，而獲近。加埶、的犋。此外，撥墨劑(A)將遷移至塗膜表面附加熱：:、=可舉例如將基板1與塗膜2 一起利用諸如、寺加熱裝置，施予50〜120°C且10〜2,〇〇〇秒鐘左右之加熱處理的方法。另外，雖然利用如前述在預焙步驟的加熱亦可將溶劑。刀去除，但亦可在預焙步驟前另外設置除加熱(乾燥）以外的真技料乾齡驟以錯溶辦揮發成分。此卜為不致發生塗膜外觀的不均，並為有效率地施行乾燥，糸將由刚述預培步驟所施行之兼具乾燥功能的加熱，與真空乾燥合併㈣。真空賴祕件雖亦依照各成分的種類、調配比例等而異，較佳係可在5〇〇〜ι〇ρ以錶壓）且 10〜300秒鐘左右的寬廣範圍内實施。 (曝光步驟）僅前述遮罩4缺口的既定圖案部分才有光5穿透，並到達基板1上的膜，而僅該部分會感光硬化。所以，在施行隔壁之幵> 成時，刚述既定圖案的形狀係設計成適當的型式。例如，後焙步驟後，隔壁寬度平均為1〇〇μπι以下較佳、 20μηι以下更佳。且鄰近隔壁間的距離平均為5〇〇μιη以下較佳、300μηι以下更佳，ΙΟΟμηι以下特佳。使用會令圖案形成如該範圍的遮罩較佳。第1(11)圖中’經光照射的膜之曝光部分3，係由負型感光性樹脂組成物的硬化膜構成；另一方面，未曝光部分則呈未硬化之負型感光性樹脂組成物之膜2本身殘存的狀態。 46 201243500 所照射的光5’可舉例如：可見光；紫外線；遠紫外線； KrF準分子雷射、ArF準分子雷射、F2準分子雷射、準分子雷射、KrAr準分子雷射、Ah準分子雷射等準分子雷射； X射線，電子束等。此外，照射光5較佳係波長1〇〇〜6〇〇nm 的電磁波，更佳係具有分佈於3〇〇〜5〇〇nm範圍内的光線，特佳為i射線(365nm)、h射線(405nm)、g射線(436mn)。照射裝置（未圖示）係可使用公知超高壓水銀燈或深紫外光燈等。曝光量較佳係SLOOOmj/cm2範圍、更佳 50〜400mJ/cm2。若曝光量為前述範圍的下限值以上，則成為隔壁之負型感光性樹脂組成物的硬化會足夠，不易在後續顯影巾料轉或絲板1±_。㈣在前述範圍的上限值以下，貝可獲得高解析度。曝光時間係依照曝光量、感光組成物的組成、塗膜的厚度等而異，惟較佳係丨〜6〇秒、更佳5〜20秒。 (顯影步驟）使用顯影液施行顯影，將第UII)圖所表示之基板丨上的未曝光部分2去除。藉此，便獲得如第1(ΙΠ)圖之剖面圖所表示之基板1無壁6(錢在前絲板上由㈣感光性樹脂組成物的硬化膜所形成者）的構造。此外，由隔壁6與基板i 所包圍的部分，係_墨水注人料成像素之通稱點陣7的部分。所得之基板1〇，經後述後財驟，會成為可使用於以噴墨式製作光學元件用的基板。顯影液係可使用含有例如無機驗類、胺類、醇胺類、四級敍鹽等_的驗水溶液^此外，在顯影液中，為求溶 47 201243500 解性的提升與去除殘渣，可添加諸如界面活性劑或醇等有機溶劑。顯影時間（接觸顯影液的時間）較佳5〜180秒鐘。此外，顯影方法係可舉例為諸如滿液法、浸塗法、淋灑法等。顯影後’藉由施行高壓水洗或流水洗淨，並利用壓縮空氣或壓縮氮氣使其風乾，便可將基板1與隔壁6上的水分去除。 (後焙步驟）加熱基板1上的隔壁6。加熱的方法係有例如將基板1 一起與隔壁6利用諸如加熱板、烘箱等加熱裝置，施行150〜250 °C、5~90分鐘之加熱處理的方法。藉由該加熱處理，便使基板1上由負型感光性樹脂組成物之硬化膜所構成之隔壁6 更進一步硬化，且由隔壁6與基板丨所圍成的點陣7形狀亦會更固定化。另外’前述加熱溫度更佳係180。(：以上。若加熱溫度過低，則因為隔壁6的硬化嫌不足，會無法獲得充分的财化性，在其後的喷墨塗佈步驟中將墨水注入點陣7中時，恐有因該墨水中所含的溶劑導致隔壁6發生膨潤、或墨水滲出的可能性《反之，若加熱溫度過高，則恐會有導致隔壁6 發生熱分解的可能性。本發明之負型感光性樹脂組成物，隔壁寬度的平均係 ΙΟΟμηι以下較佳、5〇μηι以下更佳、20μηι以下特佳。再者，鄰接隔壁間的距離（點陣寬度）的平均係500μίη以下較佳、 300μη1以下更佳、ΙΟΟμιη以下特佳。此外，隔壁高度的平均係0.05~50μηι較佳、〇·2〜1〇μιη特佳。 [光學元件的製造方法] 48 201243500 利用前述製造方法在基板上形成隔壁之後，再對於由前述基板與前述隔壁所包圍之區域内露出的基板表面施行親墨化處理(親墨化處理步驟）；捿*，對前述區域利用嗔墨法注入墨水，而形成前述像素（墨水注入步驟）。 (親墨化處理步驟）親墨化處理的方法係可舉例如：利用驗水溶液施行的洗淨處理、料麟料理、紫請/臭氧洗淨處理、準分子洗淨處理、電暈放電處理、氧電漿處理等方法。利用驗水溶液施行的洗淨處理，係使用驗水溶液(氨氧化鉀、四甲基氫氧倾水溶料）洗淨基板表面的濕式處理。紫外線洗淨處理，係使用紫外線洗淨基板表面的乾式處理。务、外線/臭氧洗淨處理，係使用發出185細與254邮光的低壓水銀燈洗淨基板表_乾式處理。 <準分子洗淨處理’係使用發出1?施光的氣準分子燈洗淨基板表面的乾式處理。 θ電暈放電處理，係利用高頻高電壓’使大氣中產生電軍放電’而將基板表面洗淨的乾式處理。觸；^電核理主要係使用在真空巾將高頻電源等作為 1錢氧激發，形成反應性高的「電《態」，並用其將基板表面洗淨的乾式處理。外線親墨化處理的方法，以簡便性之觀點而言，較佳係紫、、、氧洗淨處理等乾式處理法。紫外線/臭氧係可使用市 49 201243500 售裝置產生。《料/純裝㈣部放置已職隔壁的基板，再於空氣中’以室溫下、卜1()分鐘左右、且不損及隔壁之撥油性的範圍内施行處理，藉此便可進行親墨化處理。另外’關於處理時間，只要配合各個紫外線/臭氧聚置，調整為不會損及隔壁之撥油性範圍的時間便可。經由該親墨化處理’藉著充分地實施在前述隔壁形成後殘留於點陣中的不純物去除工作等，便可充分求得點陣的親墨化，而讓防止使用所得之光學元件的彩色顯示裝置等發生白點現象之事變成可能。此外，若使用由本發明之負型感光性樹脂組成物所得之隔壁，藉前述紫外線洗淨處理等，便可在不致降低隔壁之撥墨性的情況下施行親墨化。在此，由負型感光性樹脂組成物所形成之硬化膜的撥墨性(撥水撥油性），亦可藉水及PGMEA(丙二醇單曱基喊乙酸酯：經常被使用為墨水之溶劑的有機溶劑）的接觸角予以評估。使用具有前述使用本發明之負型感光性樹脂組成物所形成之隔壁的基板而製造光學元件時，隔壁係被要求即使經前述親墨化處理後仍具有充分撥墨性。所以，隔壁的水接觸角較佳係90度以上、更佳95度以上。此外，同樣的，隔壁的PGMEA接觸角較佳係40度以上、更佳50度以上。另一方面，使用具有前述使用本發明之負型感光性樹脂組成物所形成之隔壁的基板而製造光學元件時，關於點陣，係被要求為屬親墨性者，其水接觸角較佳係20度以下、更佳 10度以下。 (墨水注入步驟） 50 201243500 係在親墨化處理步驟後的點陣中，利用喷墨法注入墨水而形成像素的步驟。該步驟係可使用喷墨法中一般所使用的喷墨裝置，並依常見方法依樣實施。此種像素形成時所使用的喷墨裝置並無特別的限制，可使用例如：連續喷射出帶電墨水並利用磁場進行控制的方法、使用壓電元件間歇性喷射出墨水的方法、對墨水施行加熱並利用其發泡而間歇性喷射出的方法等各種方法的喷墨裝置。使用本發明之負型感光性樹脂組成物製造的光學元件，係可舉例如彩色濾光片、有機EL顯示元件、有機TFT 陣列等。 [彩色濾光片的製造] 隔壁的形成、點陣的親墨化處理、利用喷墨法施行的墨水注入係如上所述。在彩色濾光片中，所形成的像素形狀係可為例如：條紋型、馬賽克型、三角型、4像素配置型等公知的任一排列型式。像素形成時所使用的墨水主要係含有著色成分、黏結樹脂成分及溶劑。著色成分較佳係使用财熱性、对光性等均優異的顏料與染料。黏結樹脂成分較佳係透明且財熱性優異的樹脂，可舉例如：丙烯酸樹脂、三聚氰胺樹脂、胺曱酸酯樹脂等。水性墨水含有：作為溶劑的水及視需要的水溶性有機溶劑，且含有作為黏結樹脂成分的水溶性樹脂或水分散性樹脂，並視需要含有各種助劑。此外，油性墨水係含有作為溶劑的有機溶劑，且含有作為黏結樹脂成分的可溶於有機溶劑中的樹脂，並視需要含有各種助劑。 51 201243500 再者，經利用喷墨法注入墨水之後，最好視需要施行乾燥、加熱硬化及紫外線硬化。在像素形成後，視需要，形成保護膜層。保護犋層，係在提升表面平坦性之目的下，以及阻止來自隔壁或像素部之墨水溶出物到達液晶層之目的下形成者較佳。若有形成保護膜層的情況，最好事先將隔壁的撥墨性去除。若未將撥墨性去除’則會排斥保護用塗佈液，導致無法獲得均勻的膜厚’因而最好避免。將隔壁的撥墨性去除的方法，係有如：電漿灰化加工(Plasma Ashing)處理、光灰化加工處理等。再者’視需要，為求使用彩色濾光片所製得之液晶面板的尚品質化，最好將光阻式間隙子(photo spacer)形成於由隔壁構成的黑矩陣上。 [有機EL顯示元件的製造] 在形成隔壁之前，於玻璃等透明基材上，利用濺鍍法等進行諸如銦錫氧化物(IT0)等透明電極的製膜，並視需要將透明電極蝕刻為所欲圖案。接著，在使用本發明之負型感光性樹脂組成物形成隔壁、並施行點陣的親墨化處理後’便使用喷墨法對點陣將電洞輸送材料、發光材料之溶液依序進行塗佈、乾燥，形成電洞輸送層、發光層。其後，利用蒸鍍法等形成諸如鋁等電極，便可獲得有機EL顯示元件的像素。 [有機TFT陣列的製造] 經由以上（1)〜(3)之步驟即可製造有機TFT陣列。 52 201243500 在玻^透明基材上使用本發明之貞㈣紐樹脂組成㈣成隔壁。在點陣的親墨化處理後，使时墨法，對點陣施行閘極電極材料溶液的塗佈而形成閘極電極。 ()在使閘極電㈣錢，便在其均成閘絕賴。在問絕、使用本㉝明之負型感光性樹脂組成物形成隔壁並施行點陣的親墨化處理後，使时墨法對點陣施行源極•沒極電極材料溶液的塗佈，而形成源極·汲極電極。 (3)在使源極•汲極電極形成之後，便依包圍涵蓋一對源極 •沒極電極在内之區域的方式，使用本發明之負型感光性樹脂組成物形成隔壁，在施行點陣的親墨化處理後，使用喷墨法對點陣施行有機半導體溶液的塗佈，使有機半導體層形成於源極•汲極電極之間。另外’前述（1)〜(3)步驟中，亦可分別僅於一個步驟中有利用使用了本發明之負型感光性樹脂組成物的隔壁，亦可在 —個以上步驟中有利用使用了本發明之負型感光性樹脂組成物的隔壁》實施例以下使用實施例進一步詳細說明本發明，惟本發明不又忒等實施例之限制。此外，例卜7為實施例，例8、9為比較例。各測定係依以下方法實施。 [數量平均分子量(Mn)] 作為分子量測定用的標準樣本，將市售聚合度各異的數種單分散聚苯乙料合體之GPC以市售之GPC測定裝置 53 201243500 (TOSOH公司製、裝置名：HLC-8320GPC)測定，以聚苯乙烯分子量與滯留時間（retention time)的關係為基準作成校正曲線。將樣本以四氫呋喃稀釋為1_〇質量％，使其通過〇.5μηι 的過濾器後，使用前述GPC測試裝置測定該試料的GPC。使用前述校正曲線’將樣本之GPC圖譜作計算機分析，求得該樣本的數量平均分子量(Μη)。 [對水的接觸角] 依照靜態液滴法’根據JISR3257「基板玻璃表面之濕潤性試驗方法」，在基材上的測定表面的3個地方載置水滴，並針對各水滴進行測定。液滴係2pL/滴，測定係依2〇 °C實施。接觸角係以3個測定值的平均值(η=3)表示。 [對PGMEA的接觸角] 依照靜態液滴法，根據JIS R3257「基板玻璃表面之濕潤性試驗方法」’在基材上的測定表面的3個地方載置 PGMEA液滴，並針對各PGMEA液滴進行測定。液滴係2μ17 滴，測定係依20°C實施。接觸角係以3個測定值的平均值 (n=3)表示。 [儲存安定性的評價方法] 將負型感光性樹脂組成物於玻璃製螺旋瓶中以23 (室溫)保存2週。保存2週後，在經與後述的硬化膜之製造1 相同的方法施行洗淨之iOcmxiOcm玻璃基板上，使用旋轉塗佈機，塗佈負型感光性樹脂組成物，形成塗膜。接著，以i〇〇°C2分鐘於加熱板上使其乾燥’形成臈厚1μιη的膜。 54 201243500 對膜的外觀以目視觀察，依以下方式評價。 ◎(優良）：膜上異物在5個以下者。〇（良好）：膜上異物為6〜20個者。 x(不良）：膜上異物為21個以上，觀察到由玻璃基板中心部放射狀的條紋者。 [光刻評價方法] 將玻璃基板藉雷射顯微鏡(KEYENCE公司製）進行觀察’測定20μηι之線部分的膜厚與線寬(底部）。在合成例及實施例所用之化合物的簡稱如下所示。 (鹼可溶性樹脂(Β)) ZAR2002H :商品名；KAYARAD ZAR-2002H、日本化藥公司製、於雙酚Α型環氧樹脂導入羧基與乙烯性雙鍵之樹脂、固形分60%、酸價60ingKOH/g。 CCR1235 :商品名；KAYARAD CCR-1235、日本化藥公司製、於甲酚酚醛型環氧樹脂導入羧基與乙烯性雙鍵之樹脂、固形分60%、酸價60mgKOH/g。 CCR1115 :商品名；KAYARAD CCR-1115、日本化藥公司製、於曱酚酚醛型環氧樹脂導入羧基與乙烯性雙鍵之樹脂、酸價100mgKOH/g。 (光聚合起始劑(C)) IR9〇7 :商品名；IRGACURE907、BASF社製、2-甲基 -1-[4-(曱硫基)苯基]-2-嗎啉基丙-1-酮。 IR369 :商品名：IRGACURE369、BASF社製、2-节基 -2-〆甲基胺-1-(4-嗎啉基苯基)-丁-1-酮。 55 201243500 EAB:4,4·-雙（二乙胺基)二苯甲酮（東京化成工業社製）。 (交聯劑(D)) A9530:商品名；NK酯A-9530、新中村化學工業社製、一新戊四醇六丙稀酸醋與二新戊四醇五丙稀酸g旨的混合物。 (溶劑(E)) PGMEA :丙二醇單曱基驗乙酸酯。 PGME :丙二醇單甲基醚。 [合成例1 :撥墨劑(A1)的合成及(A1-1)液的調整] 在具備攪拌機的50cm3三口燒瓶中’裝入：為前述化合物(al)之CF3(CF2)5CH2CH2Si(OCH3)3 (旭硝，子公司製)〇.5g、為前述化合物(a2)之Si(OC2H5)4(COLCOAT公司製）l_llg、為前述化合物（a5)之CH2=CHCOO(CH2)3Si(OCH3)3(東京化成工業社製)0.63g、及為前述化合物⑷)之(CH3)3SiOCH3(東京化成工業社製)〇.28g。接著，裝入PGME10.26g，得到混合物。將該混合物在室溫下一邊搜:拌一邊滴下1.0%硝酸水溶液1.27g。滴下結束後’再攪拌5小時。將該液、即以1〇質量％含有撥墨劑（A1)之PGME溶液，作為（A1-1)液《所得 (A1-1)液之經去除溶劑後的組成物之含氟含有率（氟原子的質量％)係18.8質量％。此外，（A1-1)液之經去除溶劑後的組成物的數量平均分子量(Μη)為740。 [合成例2 :撥墨劑(Α2)的合成及(Α2-1)液的調整] 除了使用乙基矽酸酯48(COLCOAT公司製）0.76g作為 56 201243500 前述化合物（a2)、及PGME10.26g以外，其餘依照與合成例1 相同方式製作混合物。將該混合物在室溫下一邊攪拌，一邊滴下1〇%硝酸水溶液0.93g。滴下結束後’再攪拌5小時。將該液、即以1〇質量％含有撥墨劑(A2)之PGME溶液，作為(A2-1)液。所得 (A2-1)液之經去除溶劑後的組成物之含氟含有率（氟原子的貝里/ό)係18.8貝里％。此外，（A2-1)液之經去除溶劑後的組成物的數量平均分子量(Μη)為866。 [合成例3 :撥墨劑(A3)的合成及(Α3-1)液的調整] 在具備攪拌機的50cm3三口燒瓶中，裝入：為前述化合物(al)之CF3(CF2)5CH2CH2Si(OCH3)3 (旭硝子公司製)〇.5g、為前述化合物(a2)之Si(OC2H5)4(COLCOAT公司製)〇.83g、及為前述化合物㈤）之CH2=CHCOO(CH2)3Si(OCH3)3(東京化成工業社製)0.94g。接著，裝入PGME9.89g，得到混合物。將該混合物在室溫下一邊攪拌一邊滴下1 .〇%硝酸水溶液l_12g。滴下結束後’再攪拌5小時。將該液、即以1〇質量％含有撥墨劑(A3)之PGME溶液，作為（A3-1)液。所得 (A3-1)液之經去除溶劑後的組成物之含氟含有率（氟原子的質量％)係18.8質量°/〇。此外，（A3-1)液之經去除溶劑後的組成物的數量平均分子量(Μη)為768。 [合成例4 :撥墨劑(a4)的合成及(a4-l)液的調整] 在具備攪拌機的50cm3三口燒瓶中，裝入：為前述化合物(al)之CF3(CF2)5CH2CH2Si(OCH3)3 (旭硝子公司製)〇.5g、為前述化合物(a2)之SKOQHsMCOLCOAT公司製)〇.22g、及 57 201243500 為前述化合物⑷）之CH2=CHCOO(CH2)3Si(OCH3)3(東京化成工業社製）1.00g。接著’裝入PGME9.5lg，得到混合物。將該混合物在室溫下一邊搜拌一邊滴下1 〇%硕酸水溶液0.73g。滴下結束後’再攪拌5小時。將該液、即以1〇質量％含有撥墨劑（A4)之PGME溶液，作為（A4-1)液。所得 (A4-1)液之經去除溶劑後的組成物之含氟含有率（氟原子的質量％)係22_1質量％。此外，（A4-1)液之經去除溶劑後的組成物的數量平均分子量(Μη)為678。 [例1] (負型感光性樹脂組成物的調製）將10g的（Α1-1)液（固形分i.〇g)、45g的ZAR2002 (固形分27g' 其餘 18g為溶劑PGMEA)、5.4g的IR907、3.6g的EAB、 63g的A9530及240g的PGME裝入l，〇〇〇cm3的攪拌用容器、攪拌30分鐘、製成負型感光性樹脂組成物1。負型感光性樹脂組成物1的組成及該組成物1中固形分的組成（質量％)顯示於第1表。在第1表中，記載有負型感光性樹脂組成物的固形分中的組成與組成物中的組成兩者。 (硬化膜的製造1) 將5cm正方形玻璃基板利用乙醇施行3〇秒鐘超音波洗淨，接著，施行5分鐘的紫外線/臭氧洗淨。紫外線/臭氧洗淨中，紫外線/臭氧發生裝置係使用pL7_2〇〇(CENT ENGINEERING公司製）。另外’關於以下的全部紫外線/臭氧處理亦係使用本裝置作為紫外線/臭氧發生裝置。 58 201243500 在經上述洗淨後的玻璃基板上，使用旋轉塗佈機，塗佈負型感光性樹脂組成物1後’依10 0 C在加熱板上施行2分鐘加熱乾燥，便形成膜厚Ιμιη的膜。對所獲得之膜的表面上，從膜側，隔著設有開孔圖案（2.5cmx5cm)的光罩及距離 50μηι的間隙、將高壓水銀燈的紫外線以25Mw/cm2照射1〇秒’得到硬化膜。接著，將經曝光處理過的玻璃基板在〇·4°Λ四曱基氫氧化錢水溶液中浸潰40秒鐘而顯影，再將未曝光部分的塗膜利用水進行沖洗，並使其乾燥。接著，將其在加熱板上依 230°C施行20分鐘加熱，藉此便獲得在前述開孔圖案部以外區域形成有負型感光性樹脂組成物1之硬化膜的玻璃基板 ⑴。 (硬化膜的製造2) 除了使用線寬/線距為20μιη的光罩以外，以與硬化膜的製造1相同方式，得到形成有負型感光性樹脂組成物之硬化膜的玻璃基板(2)。 (評價）測定所得之玻璃基板⑴的硬化膜表面（曝光部分）的對 PGMEA接觸角、以及經由顯影而去除了塗膜之部分(玻璃基板表面）的對水接觸角。其後，對玻璃基板(1)中的形成有硬化膜之—側的表面整體，施行紫外線/臭氧照射處理2分鐘。測試經2分鐘照射後，便測定硬化膜表面的對PGMEA 接觸角以及玻璃基板表面的對水接觸角。測定方法如果所述。結果如第1表所示。 59 201243500 [例2〜7、例8、9] 除了將組成依照第1表所示者變更以外，依照與例1相同方式調製負型感光性樹脂組成物，得到負型感光性樹脂組成物之膜、硬化膜、玻璃基板。此外，例3係使用240g的 PGMEA替代 240g的 PGME。所得的負型感光性樹脂組成物之膜、硬化膜、玻璃基板，依照與例1相同方式予以評價。結果顯示於第1表。第1表例1 例2 例3 例4 例5 例6 例7 例8 例9 6 型感光性組成物固形分組座 η a % 撥墨劑(A) 種類 A1-1 Α2-1 Α2-1 Α2-Ι Α3-Ι Α4-1 Α2-1 Α2-1 Α2·Ι 混合5 1 1 1 1 1 1 2 1 1 鹼可溶性樹脂(B) CCRI235 — 36 27 18 27 27 27 - 9 ZAR2002 27 - - 一 - - — _ 術 CCR1115 36 — 光聚合起始劑(c> IR907 5.4 5.4 5.4 5.4 5.4 5.4 12 5.4 IR369 — - - - - 5.4 - - 一 EAB 3.6 3.6 3.6 3.6 3.6 3.6 3.6 16 3.6 交聯劑(〇) A9530 63 54 63 72 63 63 62 36 81 組成 t 的組座 η a % 撥墨赍㈧ 0.28 0.28 0.28 0.28 0.28 0.28 0.54 0.27 0.28 鹼可溶性樹脂(B) CCR1235 - 9.91 7.50 5.05 7.50 7.50 7.32 - 2.55 ZAR2002 7.50 CCR1115 9.88 — 光聚合起始劑(C) IR907 1.50 1.49 1.50 1.52 1.50 一 1.46 3.29 1.53 IR369 - - - - — 1.50 - — — EAB 1.00 0.99 1.00 1.01 1.00 1.00 0.98 4.39 1.02 交聯剞(D) A9530 17,51 I486 17.51 20.21 17.51 17.51 16.81 9.88 22.97 溶劑(E) PGME 69.21 68.52 2.50 69.90 69.21 69.21 69.96 68.33 70.62 PGMEA 3.00 3.96 69.71 2.02 3.00 3.00 2.93 3.95 1.02 組成物酸價(mgKOH/g) 16.2 21.6 16.2 10.8 16.2 16.2 16.2 36.0 5.4 全因形分中鹼可溶性樹脂(B)的比例(質S%) 27 36 27 18 27 27 27 36 9 全固形分中(B)與(D)的合計(質S%) 90 90 90 90 90 90 89 72 90 全固形分中的(B)/(D)(ifa%) 43 67 43 25 43 43 43 100 11 評價撥墨性•親墨性的評價無紫外線/ 奐氧照射硬化膜表面 PGMEA接觸角(°) 45 46 44 44 45 47 50 45 42 玻璃基板表面水接觸角(。） 61 60 59 57 58 59 62 58 58 紫外線/臭氧照射2 分硬化骐表面 PGMEA接觸角(。) 39 40 40 39 40 41 44 40 37 玻璃基板表面水接觸角(°) <10 <10 <10 <10 <10 <10 15 <10 <10 储存安定性初期 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 2周後(室溫）〇〇〇 ◎ 〇〇〇 X ◎ 光刻評價膜厚(μπι) 1.0 1.1 1.0 1.0 1.0 1.0 1.1 1.1 1.0 線 ΪΚμηι) 20.1 20.3 20.2 20.1 20.3 20.2 20.3 19.5 無法顯影由第1表可知，組成物酸價為6〜30mgKOH/g的例1~7之負型感光性樹脂組成物，即便在23°C下儲存2週後而形成塗 60 201243500 膜的情况下，膜外觀仍呈良好。此外，由負型感光性樹脂組成物所得之硬化膜，顯示良好的撥墨性，且即便在紫外線/臭氣照射後仍維持高撥墨性，及玻璃基板表面具有良好的親水性。另一方面，由於例8係組成物酸價為36mgKOH/g 者’使用以23°C儲存2週後的負型感光性樹脂組成物來形成膜的情況下，會觀察到許多異物，並觀察到由玻璃中心部至放射狀的條紋。另外’由於例9係組成物酸價為 5.4mgK：〇H/g ’因此無法顯影。産業上可利用性本發明之負型感光性樹脂組成物，係一種能夠製造撥墨性良好、且經紫外線/臭氧照射仍可保持撥墨性之隔壁的負型感光性樹脂組成物，儲存安定性良好，若使用該負型感光性樹脂組成物能夠形成均勻的塗膜。本發明的負型感光性樹脂組成物，係頗適用於：利用喷墨記錄技術法的彩色濾光片製造用、有機EL顯示元件製造用、有機TFT陣列製造用之隔壁之形成。另外，在此爰引2011年3月31曰提出申請之曰本專利申請案第2011-079394號之說明書、申請專利範圍、圖式及摘要等全部内容，合併作為本發明說明書之揭示。 ί：圖式簡單說明3 第1圖（I)〜(III)係示意地表示使用本發明之負型感光性樹脂組成物的光學元件用隔壁的製造例的剖面圖。【主要元件符號說明】 1…基板 2···負型感光性樹脂組成物的 201243500 塗膜 7…點陣 3···塗膜曝光部分 4…遮罩 10…應用於喷墨方式的光學元 5…光 6···隔壁件用基板 62St:::: Volatile components containing solvents will be volatilized, removed, and brought closer. Coronation, 犋. In addition, the ink-repellent (A) will migrate to the surface of the coating film to add heat::, = for example, the substrate 1 and the coating film 2 are applied together with, for example, a temple heating device, 50 to 120 ° C and 10 to 2, The method of heat treatment for about sec. Further, the solvent may be used although it is heated by the pre-baking step as described above. The knives are removed, but it is also possible to additionally provide a virgin material other than heating (drying) before the pre-bake step to dissolve the volatile components. Therefore, in order to prevent uneven appearance of the coating film and to perform drying efficiently, the heat-drying function which is carried out by the pre-forming step is combined with vacuum drying (4). The vacuum cleaning member may be carried out in a wide range of about 10 to 300 seconds, depending on the type of each component, the mixing ratio, and the like. (Exposure step) Only the portion of the predetermined pattern of the gap of the aforementioned mask 4 penetrates the light 5 and reaches the film on the substrate 1, and only that portion is photohardened. Therefore, when the partition wall is applied, the shape of the predetermined pattern is designed to be an appropriate pattern. For example, after the post-baking step, the width of the partition wall is preferably 1 μm or less, more preferably 20 μm or less. The distance between adjacent partitions is preferably 5 〇〇 μηη or less, more preferably 300 μηι or less, and ΙΟΟμηι is particularly preferable. It is preferable to use a mask which forms a pattern such as this range. In the first (11) diagram, the exposed portion 3 of the light-irradiated film is composed of a cured film of a negative photosensitive resin composition; on the other hand, the unexposed portion is composed of an uncured negative photosensitive resin. The state in which the film 2 itself remains. 46 201243500 Illuminated light 5' can be, for example, visible light; ultraviolet light; far ultraviolet light; KrF excimer laser, ArF excimer laser, F2 excimer laser, excimer laser, KrAr excimer laser, Ah quasi Excimer lasers such as molecular lasers; X-rays, electron beams, etc. Further, the illumination light 5 is preferably an electromagnetic wave having a wavelength of 1 〇〇 to 6 〇〇 nm, more preferably having a light distribution in the range of 3 〇〇 to 5 〇〇 nm, particularly preferably an i-ray (365 nm), h-ray. (405 nm), g-ray (436mn). As the irradiation device (not shown), a known ultrahigh pressure mercury lamp or a deep ultraviolet lamp or the like can be used. The exposure amount is preferably in the range of SLOOOmj/cm2, more preferably 50 to 400 mJ/cm2. When the amount of exposure is at least the lower limit of the above range, the hardening of the negative photosensitive resin composition which becomes the partition wall is sufficient, and it is difficult to develop the roll or the wire 1±. (4) Below the upper limit of the above range, high resolution can be obtained. The exposure time varies depending on the amount of exposure, the composition of the photosensitive composition, the thickness of the coating film, and the like, but is preferably 丨6 sec, more preferably 5 to 20 seconds. (Developing step) Development is carried out using a developing solution to remove the unexposed portion 2 on the substrate 表示 indicated by the UII). Thereby, the structure of the substrate 1 having no wall 6 (the one formed by the cured film of the (4) photosensitive resin composition on the front yarn sheet) as shown in the sectional view of Fig. 1 is obtained. Further, the portion surrounded by the partition wall 6 and the substrate i is a portion in which the ink is incident on the dot matrix 7 of the pixel. The obtained substrate 1 is a substrate which can be used for ink-jet type optical elements, which will be described later. For the developer, an aqueous solution containing, for example, an inorganic test, an amine, an alcohol amine, a quaternary salt, or the like can be used. Further, in the developer, it is possible to add and remove the residue in order to improve the solubility of the solution 47 201243500. An organic solvent such as a surfactant or an alcohol. The development time (time to contact the developer) is preferably 5 to 180 seconds. Further, the developing method can be exemplified by, for example, a flooding method, a dip coating method, a shower method, and the like. After the development, the water on the substrate 1 and the partition wall 6 can be removed by performing high-pressure water washing or running water washing and air drying with compressed air or compressed nitrogen. (Post-baking step) The partition wall 6 on the substrate 1 is heated. The heating method is, for example, a method in which the substrate 1 and the partition wall 6 are heated by a heating means such as a heating plate or an oven at 150 to 250 ° C for 5 to 90 minutes. By this heat treatment, the partition wall 6 composed of the cured film of the negative photosensitive resin composition on the substrate 1 is further cured, and the shape of the dot matrix 7 surrounded by the partition walls 6 and the substrate stack is also fixed. Chemical. Further, the aforementioned heating temperature is more preferably 180. (: Above. If the heating temperature is too low, since the hardening of the partition wall 6 is insufficient, sufficient chemical property cannot be obtained, and when the ink is injected into the dot matrix 7 in the subsequent inkjet coating step, there is a fear. The solvent contained in the ink causes the partition wall 6 to swell or the ink to bleed out. Conversely, if the heating temperature is too high, the partition wall 6 may be thermally decomposed. The negative photosensitive resin of the present invention may be used. The composition has an average ΙΟΟμηι or less of the width of the partition wall, preferably 5 〇μηι or less, and more preferably 20 μηη or less. Further, the average distance between the partition walls (dot array width) is preferably 500 μίη or less, and more preferably 300 μηη or less. In addition, the average height of the partition walls is preferably 0.05 to 50 μm, and preferably 2 to 1 μm is particularly good. [Method of Manufacturing Optical Element] 48 201243500 After forming a partition wall on a substrate by the above-described manufacturing method, Performing an ink receptive treatment on the surface of the substrate exposed in the region surrounded by the substrate and the partition wall (ink treatment step); 捿*, using ink for the aforementioned region The ink is injected to form the pixel (ink injection step). (Ink-repellent treatment step) The method of the ink-removing treatment may be, for example, a washing treatment using an aqueous solution, a material preparation, and a purple/ozone cleaning method. Treatment, excimer washing treatment, corona discharge treatment, oxygen plasma treatment, etc. The washing treatment performed by the aqueous solution is used to wash the substrate using an aqueous solution (potassium ammoxide, tetramethylhydrogen peroxide) Wet treatment of the surface. Ultraviolet cleaning treatment is a dry treatment of the surface of the substrate by ultraviolet cleaning. The external line/ozone cleaning treatment is performed by using a low-pressure mercury lamp that emits 185 fine and 254 mail light. <Excimer cleaning treatment' is a dry treatment for cleaning the surface of a substrate by using a gas-emitting molecular light emitting a light source. θ Corona discharge treatment uses a high-frequency high-voltage to generate an electric discharge in the atmosphere. The dry treatment of the surface of the substrate is washed. The electrolysis is mainly performed by using a vacuum towel to excite a high-frequency power source or the like as a "reactive" state, and a highly reactive "electric state" is formed. Dry treatment for washing the surface of the substrate. The method of the external ink re-inking treatment is preferably a dry treatment such as purple, or oxygen washing treatment from the viewpoint of simplicity. The ultraviolet/ozone system can be used. 49 201243500 The equipment is sold. The material in the material/pure (4) part is placed in the partition wall of the partition, and then treated in the air at room temperature, for about 1 minute, without damaging the oil repellency of the partition wall. In this way, it is possible to carry out the ink repellent treatment. In addition, the treatment time can be adjusted so as not to damage the oil repellency range of the partition wall in accordance with the respective ultraviolet/ozone accumulation. By sufficiently performing the impurity removal operation or the like remaining in the lattice after the formation of the partition walls, it is possible to sufficiently obtain the inking of the dot matrix, and to prevent the occurrence of white spots in the color display device or the like using the obtained optical element. It becomes possible. Further, by using the partition wall obtained from the negative photosensitive resin composition of the present invention, by the ultraviolet cleaning treatment or the like, it is possible to perform ink receptive without lowering the ink repellency of the partition walls. Here, the ink repellency (water repellency) of the cured film formed of the negative photosensitive resin composition can also be borrowed from water and PGMEA (propylene glycol monodecyl ketone acetate: a solvent which is often used as an ink) The contact angle of the organic solvent) was evaluated. When an optical element is produced by using the substrate having the partition wall formed using the negative photosensitive resin composition of the present invention, the partition wall is required to have sufficient ink repellent property even after the ink repellent treatment. Therefore, the water contact angle of the partition wall is preferably 90 degrees or more, more preferably 95 degrees or more. Further, similarly, the PGMEA contact angle of the partition wall is preferably 40 degrees or more, more preferably 50 degrees or more. On the other hand, when an optical element is produced using the substrate having the partition wall formed using the negative photosensitive resin composition of the present invention, the dot matrix is required to be an ink-receptive member, and the water contact angle is preferably It is 20 degrees or less, more preferably 10 degrees or less. (Ink Injection Step) 50 201243500 A step of forming a pixel by injecting ink by an inkjet method in a lattice after the ink retouching step. This step can be carried out by using an ink jet apparatus generally used in the ink jet method, and is carried out in accordance with a usual method. The ink jet device used in the formation of such a pixel is not particularly limited, and for example, a method of continuously ejecting charged ink and controlling by a magnetic field, a method of intermittently ejecting ink using a piezoelectric element, and heating the ink can be used. An ink jet apparatus of various methods such as a method of foaming and intermittent ejection is used. The optical element produced by using the negative photosensitive resin composition of the present invention may, for example, be a color filter, an organic EL display element, an organic TFT array or the like. [Production of Color Filter] The formation of the partition walls, the ink repellent treatment of the dot matrix, and the ink injection by the ink jet method are as described above. In the color filter, the pixel shape to be formed may be any known pattern such as a stripe type, a mosaic type, a triangle type, or a 4-pixel arrangement type. The ink used in the formation of the pixel mainly contains a coloring component, a binder resin component, and a solvent. The coloring component is preferably a pigment or a dye which is excellent in both heat and light properties. The binder resin component is preferably a resin which is transparent and excellent in heat recovery, and examples thereof include an acrylic resin, a melamine resin, and an amine phthalate resin. The aqueous ink contains water as a solvent and, if necessary, a water-soluble organic solvent, and contains a water-soluble resin or a water-dispersible resin as a binder resin component, and optionally contains various auxiliary agents. Further, the oil-based ink contains an organic solvent as a solvent, and contains a resin which is soluble in an organic solvent as a binder resin component, and optionally contains various auxiliary agents. 51 201243500 In addition, after injecting ink by an inkjet method, it is preferable to perform drying, heat curing, and ultraviolet curing as needed. After the formation of the pixel, a protective film layer is formed as needed. The protective layer is preferably formed for the purpose of improving the flatness of the surface and for preventing the ink elution from the partition or the pixel portion from reaching the liquid crystal layer. In the case where a protective film layer is formed, it is preferable to remove the ink repellency of the partition wall in advance. If the ink removing property is not removed, the protective coating liquid is repelled, resulting in a failure to obtain a uniform film thickness, and it is preferably avoided. The method of removing the ink repellency of the partition wall is, for example, a plasma ashing process or a light ashing process. Further, as needed, in order to optimize the quality of the liquid crystal panel obtained by using the color filter, it is preferable to form a photo spacer on the black matrix composed of the partition walls. [Production of Organic EL Display Element] Before forming the partition walls, a transparent electrode such as indium tin oxide (ITO) is formed on a transparent substrate such as glass by a sputtering method or the like, and the transparent electrode is etched as needed. The desired pattern. Next, after forming a partition wall using the negative photosensitive resin composition of the present invention and performing a dot-inking process, the inkjet method is used to sequentially apply a solution of the hole transporting material and the luminescent material to the dot matrix. Cloth, drying, forming a hole transport layer, a light-emitting layer. Thereafter, an electrode such as aluminum is formed by an evaporation method or the like to obtain a pixel of the organic EL display element. [Production of Organic TFT Array] An organic TFT array can be manufactured through the above steps (1) to (3). 52 201243500 The composition of the bismuth (four) resin of the present invention is used on a glass transparent substrate. (IV) The partition wall is formed. After the ink retouching treatment of the dot matrix, the ink is applied to the dot matrix to apply a gate electrode material solution to form a gate electrode. () In making the gates electric (four) money, it will be in the gates. After the negative-type photosensitive resin composition of the present invention is used to form a partition wall and a dot-matrix ink-repellent treatment is performed, the time-and-ink method is applied to the dot matrix to apply a source/dot electrode material solution. Source and drain electrodes. (3) After the source/drain electrodes are formed, the negative photosensitive resin composition of the present invention is used to form the partition walls in such a manner as to surround the region including the pair of source and the electrodeless electrodes, at the execution point. After the ink receptive treatment of the array, the organic semiconductor solution is applied to the lattice by an inkjet method to form an organic semiconductor layer between the source and the drain electrodes. Further, in the steps (1) to (3), the partition wall using the negative photosensitive resin composition of the present invention may be used in only one step, and may be used in one or more steps. The partition of the negative photosensitive resin composition of the present invention. The present invention will be described in further detail below by way of examples, but the present invention is not limited by the examples. Further, Example 7 is an example, and Examples 8 and 9 are comparative examples. Each measurement was carried out in the following manner. [Quantum average molecular weight (Mn)] As a standard sample for molecular weight measurement, commercially available GPC measuring devices 53 201243500 (manufactured by TOSOH Co., Ltd.) are commercially available as GPCs of several kinds of monodisperse polystyrene materials having different polymerization degrees. Name: HLC-8320GPC) Measurement, a calibration curve was prepared based on the relationship between the molecular weight of polystyrene and the retention time. The sample was diluted with tetrahydrofuran to 1 〇 mass%, and passed through a filter of 〇.5 μηι, and the GPC of the sample was measured using the aforementioned GPC test apparatus. The GPC spectrum of the sample was subjected to computer analysis using the aforementioned calibration curve ', and the number average molecular weight (?n) of the sample was determined. [Contact angle to water] According to JIS R3257 "Test method for wettability of substrate glass surface", water droplets were placed on three places on the measurement surface of the substrate, and the water droplets were measured for each water drop. The droplet system was 2 pL/drop, and the measurement was carried out at 2 °C. The contact angle is represented by the average of three measured values (η = 3). [Contact angle to PGMEA] According to the static droplet method, PGMEA droplets are placed in three places on the measurement surface of the substrate according to JIS R3257 "Test method for wettability of substrate glass surface", and for each PGMEA droplet The measurement was carried out. The droplets were 2 μ17 drops, and the measurement was carried out at 20 °C. The contact angle is expressed as the average of three measured values (n = 3). [Evaluation Method of Storage Stability] The negative photosensitive resin composition was stored in a glass spiral bottle at 23 (room temperature) for 2 weeks. After the storage for 2 weeks, the negative photosensitive resin composition was applied onto the iOcmxiOcm glass substrate which was subjected to the same method as the production of the cured film described later, and a coating film was formed by using a spin coater. Subsequently, it was dried on a hot plate at 2 ° C for 2 minutes to form a film having a thickness of 1 μm. 54 201243500 The appearance of the film was visually observed and evaluated in the following manner. ◎ (Excellent): There are 5 or less foreign bodies on the film. 〇 (good): 6 to 20 foreign bodies on the film. x (defect): 21 or more foreign substances on the film were observed, and a stripe which was radially formed at the center of the glass substrate was observed. [Photolithography evaluation method] The glass substrate was observed by a laser microscope (manufactured by KEYENCE Co., Ltd.) to measure the film thickness and line width (bottom) of the line portion of 20 μm. The abbreviations of the compounds used in the synthesis examples and examples are as follows. (alkali-soluble resin (Β)) ZAR2002H: trade name; KAYARAD ZAR-2002H, a resin made of Nippon Chemical Co., Ltd., which introduces a carboxyl group and an ethylenic double bond in a bisphenolphthalein type epoxy resin, a solid content of 60%, and an acid value of 60 KOH /g. CCR1235: trade name; KAYARAD CCR-1235, manufactured by Nippon Kayaku Co., Ltd., a resin obtained by introducing a carboxyl group and an ethylenic double bond to a cresol novolac type epoxy resin, a solid content of 60%, and an acid value of 60 mgKOH/g. CCR1115: trade name; KAYARAD CCR-1115, manufactured by Nippon Kayaku Co., Ltd., a resin obtained by introducing a carboxyl group and an ethylenic double bond in an anthraquinone phenolic epoxy resin, and an acid value of 100 mgKOH/g. (Photopolymerization initiator (C)) IR9〇7: trade name; IRGACURE 907, manufactured by BASF, 2-methyl-1-[4-(indolylthio)phenyl]-2-morpholinylpropane-1 -ketone. IR369: trade name: IRGACURE 369, manufactured by BASF, 2-mercapto-2-indolyl-1-(4-morpholinylphenyl)-butan-1-one. 55 201243500 EAB: 4,4·-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.). (crosslinking agent (D)) A9530: trade name; NK ester A-9530, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., a mixture of neopentyl alcohol hexaacetic acid vinegar and dipentaerythritol pentapropan acid . (Solvent (E)) PGMEA: propylene glycol monothiol acetate. PGME: propylene glycol monomethyl ether. [Synthesis Example 1: Synthesis of Ink Repellent (A1) and Adjustment of (A1-1) Liquid] In a 50 cm3 three-necked flask equipped with a stirrer, "Loading: CF3(CF2)5CH2CH2Si (OCH3) of the above compound (al) 3 (Asahi Nippon, manufactured by the company) 〇.5g, Si(OC2H5)4 (manufactured by COLCOAT Co., Ltd.) l_llg of the compound (a2), and CH2=CHCOO(CH2)3Si(OCH3)3 of the above compound (a5) (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.63 g, and (CH3)3SiOCH3 (manufactured by Tokyo Chemical Industry Co., Ltd.) of the above compound (4)). Next, 10.26 g of PGME was charged to obtain a mixture. The mixture was searched at room temperature while pouring 1.27 g of a 1.0% aqueous solution of nitric acid. After the end of the dropping, the mixture was stirred for another 5 hours. This liquid, that is, the PGME solution containing the ink-repellent (A1) in an amount of 1% by mass, is used as the fluorine-containing content of the composition obtained by removing the solvent of the (A1-1) liquid (A1-1) liquid ( The mass % of the fluorine atom is 18.8% by mass. Further, the number average molecular weight (?n) of the composition of the (A1-1) liquid after removing the solvent was 740. [Synthesis Example 2: Synthesis of ink repellent (Α2) and adjustment of (Α2-1) liquid] In addition to the use of ethyl phthalate 48 (manufactured by COLCOAT), 0.76 g was used as 56 201243500, the aforementioned compound (a2), and PGME10. A mixture was prepared in the same manner as in Synthesis Example 1, except for 26 g. The mixture was stirred at room temperature while dropping 0.93 g of a 1% by weight aqueous solution of nitric acid. After the end of the dropping, the mixture was stirred for another 5 hours. This liquid, that is, a PGME solution containing an ink-repellent (A2) in an amount of 1% by mass, was used as the (A2-1) solution. The fluorine-containing content (Beri/ό of the fluorine atom) of the composition obtained by removing the solvent of the obtained (A2-1) liquid was 18.8 mil %. Further, the number average molecular weight (?η) of the composition of the (A2-1) liquid after removing the solvent was 866. [Synthesis Example 3: Synthesis of Ink Repellent (A3) and Adjustment of (Α3-1) Liquid] In a 50 cm3 three-necked flask equipped with a stirrer, CF3(CF2)5CH2CH2Si (OCH3) of the above compound (al) was charged. 3 (manufactured by Asahi Glass Co., Ltd.) 〇.5g, which is Si(OC2H5)4 (manufactured by COLCOAT Co., Ltd.) 〇.83g of the compound (a2), and CH2=CHCOO(CH2)3Si(OCH3)3 of the above compound (5)) Tokyo Chemical Industry Co., Ltd.) 0.94g. Next, PGME 9.89 g was charged to obtain a mixture. The mixture was stirred at room temperature while stirring 1. 〇% aqueous solution of nitric acid l_12 g. After the end of the dropping, the mixture was stirred for another 5 hours. This liquid, i.e., a PGME solution containing an ink-repellent (A3) at a mass% of 1 ,, was used as the (A3-1) solution. The fluorine content (% by mass of fluorine atom) of the composition obtained by removing the solvent of the obtained (A3-1) liquid was 18.8 mass%/〇. Further, the number average molecular weight (?n) of the composition of the (A3-1) liquid after removing the solvent was 768. [Synthesis Example 4: Synthesis of Ink Repellent (a4) and Adjustment of (a4-1) Liquid] In a 50 cm3 three-necked flask equipped with a stirrer, CF3(CF2)5CH2CH2Si (OCH3) of the above compound (al) was charged. 3 (manufactured by Asahi Glass Co., Ltd.) 5.5g, which is a product of the above-mentioned compound (a2), 〇.22g, and 57 201243500 is CH2=CHCOO(CH2)3Si(OCH3)3 of the above compound (4)) (Tokyo Chemical Industry Co., Ltd.) System) 1.00g. Next, PGME 9.5 lg was charged to obtain a mixture. The mixture was dropped while stirring at room temperature with 0.73 g of a 1% aqueous solution of souric acid. After the end of the dropping, the mixture was stirred for another 5 hours. This liquid, that is, a PGME solution containing an ink-repellent (A4) at a mass ratio of 1 , was used as the (A4-1) solution. The fluorine-containing content (% by mass of fluorine atom) of the composition obtained by removing the solvent of the obtained (A4-1) liquid was 22 to 1% by mass. Further, the number average molecular weight (?n) of the composition of the (A4-1) liquid after solvent removal was 678. [Example 1] (Preparation of negative photosensitive resin composition) 10 g of (Α1-1) liquid (solid content i.〇g), 45 g of ZAR2002 (solid content: 27 g', and the remaining 18 g of solvent PGMEA), 5.4 g IR907, 3.6 g of EAB, 63 g of A9530, and 240 g of PGME were charged into a stirring container of 〇〇〇cm3, and stirred for 30 minutes to prepare a negative photosensitive resin composition 1. The composition of the negative photosensitive resin composition 1 and the composition (% by mass) of the solid content in the composition 1 are shown in Table 1. In the first table, both the composition in the solid content of the negative photosensitive resin composition and the composition in the composition are described. (Manufacturing of Cured Film 1) A 5 cm square glass substrate was ultrasonically washed with ethanol for 3 seconds, and then subjected to ultraviolet/ozone cleaning for 5 minutes. In the ultraviolet/ozone cleaning, pL7_2(R) (manufactured by CENT ENGINEERING) was used for the ultraviolet/ozone generating device. In addition, this apparatus is also used as an ultraviolet/ozone generating apparatus for all of the following ultraviolet/ozone treatments. 58 201243500 After coating the negative photosensitive resin composition 1 on the glass substrate after the above-mentioned washing, the coating was carried out by heating on a hot plate for 2 minutes on a hot plate to form a film thickness Ιμιη. Membrane. On the surface of the obtained film, a cured film was obtained from the film side through a mask provided with an opening pattern (2.5 cm x 5 cm) and a gap of 50 μm from the ultraviolet light of the high pressure mercury lamp at 25 Mw/cm 2 for 1 ' second. . Next, the exposed glass substrate was immersed in a 〇·4° Λtetradecyl oxyhydroxide aqueous solution for 40 seconds to develop, and the unexposed portion of the coating film was rinsed with water and dried. Then, this was heated on a hot plate at 230 ° C for 20 minutes to obtain a glass substrate (1) in which a cured film of the negative photosensitive resin composition 1 was formed in a region other than the opening pattern portion. (Manufacturing 2 of Cured Film) A glass substrate (2) in which a cured film of a negative photosensitive resin composition was formed was obtained in the same manner as in the production of the cured film except that a mask having a line width/line pitch of 20 μm was used. . (Evaluation) The PGMEA contact angle of the surface (exposure portion) of the cured film of the obtained glass substrate (1) and the water contact angle of the portion (glass substrate surface) from which the coating film was removed by development were measured. Thereafter, the entire surface of the glass substrate (1) on which the hard film was formed was subjected to ultraviolet/ozone irradiation treatment for 2 minutes. After the test was irradiated for 2 minutes, the PGMEA contact angle on the surface of the cured film and the water contact angle of the surface of the glass substrate were measured. The method of measurement is as described. The results are shown in Table 1. 59 201243500 [Examples 2 to 7, Examples 8 and 9] A negative photosensitive resin composition was prepared in the same manner as in Example 1 except that the composition was changed according to the first table. Film, cured film, glass substrate. In addition, Example 3 used 240 g of PGMEA instead of 240 g of PGME. The film, cured film, and glass substrate of the obtained negative photosensitive resin composition were evaluated in the same manner as in Example 1. The results are shown in Table 1. 1st Example 1 Example 2 Example 3 Example 4 Example 5 Case 6 Case 7 Case 8 Case 9 Type 6 Photosensitive Composition Solid Grouping Block η a % Toner (A) Type A1-1 Α2-1 Α2-1 Α2 -Ι Α3-Ι Α4-1 Α2-1 Α2-1 Α2·Ι Mixed 5 1 1 1 1 1 1 2 1 1 Alkali-soluble resin (B) CCRI235 — 36 27 18 27 27 27 - 9 ZAR2002 27 - - One - - _ _ CCR1115 36 - photopolymerization initiator (c > IR907 5.4 5.4 5.4 5.4 5.4 5.4 12 5.4 IR369 — - - - - 5.4 - - EAB 3.6 3.6 3.6 3.6 3.6 3.6 3.6 16 3.6 Crosslinker (〇) A9530 63 54 63 72 63 63 62 36 81 Group t consisting of t η a % ink 赍 (8) 0.28 0.28 0.28 0.28 0.28 0.28 0.54 0.27 0.28 Alkali-soluble resin (B) CCR1235 - 9.91 7.50 5.05 7.50 7.50 7.32 - 2.55 ZAR2002 7.50 CCR1115 9.88 — Photopolymerization initiator (C) IR907 1.50 1.49 1.50 1.52 1.50 1.46 3.29 1.53 IR369 - - - - - 1.50 - — — EAB 1.00 0.99 1.00 1.01 1.00 1.00 0.98 4.39 1.02 Crosslinked crucible (D) A9530 17,51 I486 17.51 20.21 17.51 17.51 16.81 9.88 22.97 Solvent (E) PGME 69.21 68.52 2.50 69.90 69.21 69.21 6 9.96 68.33 70.62 PGMEA 3.00 3.96 69.71 2.02 3.00 3.00 2.93 3.95 1.02 Composition acid value (mgKOH/g) 16.2 21.6 16.2 10.8 16.2 16.2 16.2 36.0 5.4 Proportion of alkali-soluble resin (B) in all-effects (mass S%) 27 36 27 18 27 27 27 36 9 Total of total solids (B) and (D) (mass S%) 90 90 90 90 90 90 89 72 90 (B)/(D) (ifa%) of the total solids 43 67 43 25 43 43 43 100 11 Evaluation of ink repellency • Evaluation of ink retention No UV/Oxygen irradiation Curing film surface PGMEA contact angle (°) 45 46 44 44 45 47 50 45 42 Glass substrate surface water contact angle (. 61 60 59 57 58 59 62 58 58 UV/ozone irradiation 2 points Hardened 骐 Surface PGMEA contact angle (.) 39 40 40 39 40 41 44 40 37 Glass substrate surface water contact angle (°) <10 <10 <10 10 <10 <10 <10 15 <10 <10 Storage stability initial ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 2 weeks later (room temperature) 〇〇〇 ◎ 〇〇〇 X ◎ lithography evaluation Film thickness (μπι) 1.0 1.1 1.0 1.0 1.0 1.0 1.1 1.1 1.0 ΪΚμηι) 20.1 20.3 20.2 20.1 20.3 20.2 20.3 19.5 Unable to develop The first table shows that the acid value of the composition is 6~30mgKOH/g. The photosensitive resin composition was excellent in the appearance of the film even when it was stored at 23 ° C for 2 weeks to form a coating of 60 201243500 film. Further, the cured film obtained from the negative photosensitive resin composition exhibits good ink repellency, maintains high ink repellency even after ultraviolet/odor irradiation, and has good hydrophilicity on the surface of the glass substrate. On the other hand, in the case where the acid value of the composition of Example 8 is 36 mgKOH/g, when a film is formed using a negative photosensitive resin composition stored at 23 ° C for 2 weeks, many foreign matters are observed and observed. From the center of the glass to the radial stripes. Further, since the acid value of the composition of the ninth embodiment was 5.4 mgK: 〇H/g', development was impossible. INDUSTRIAL APPLICABILITY The negative-type photosensitive resin composition of the present invention is a negative-type photosensitive resin composition capable of producing a partition wall having good ink-repellent property and maintaining ink repellent property by ultraviolet/ozone irradiation, and is stored and stabilized. The properties are good, and a uniform coating film can be formed by using the negative photosensitive resin composition. The negative photosensitive resin composition of the present invention is suitably used for the production of a color filter by the ink jet recording technique, the production of an organic EL display device, and the formation of a partition wall for the production of an organic TFT array. In addition, the entire contents of the specification, the patent application, the drawings and the abstracts of the patent application No. 2011-079394, filed on March 31, 2011, are incorporated herein by reference. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view showing a manufacturing example of a partition for an optical element using the negative photosensitive resin composition of the present invention. [Description of main component symbols] 1...Substrate 2···201243500 of negative photosensitive resin composition Coating film 7...Dot 3··· Coating film exposure part 4...Mask 10...Applicable to inkjet optical element 5...light 6···substrate for substrate 62

Claims

201243500 VII. Patent application scope: 1. A negative photosensitive resin composition 'containing: an ink-repellent agent (A) composed of a fluorine-containing siloxane compound; an alkali-soluble resin (B), which is 1 An acidic group and an ethylenic double bond in the molecule; and a photopolymerization initiator (C); and the negative photosensitive resin composition is characterized in that the acid value of the negative photosensitive resin composition is 6 to 30 mgKOH /g. 2. The negative photosensitive resin composition of the invention of the invention, wherein the ratio of the alkali-soluble resin (B) in the total solid portion of the negative photosensitive resin composition is π 4 to 4 % by mass. 3. If you apply for a patent scope! Or a negative photosensitive resin composition of two or more, wherein the above-mentioned hydrocarbon-containing compound is composed of a hydrolyzed condensation product comprising a mixture of the hydrolyzable Shixia compound (4) and the hydrolyzable Wei compound (IV): Water training my compound (5)): The predatory Wei compound with an organic water hetero group in the (4) sub-medullary marrow, which means that the organic group has a slave number of 3~1〇 and can contain the (tetra) oxygen atom. The compound (4) atom II (p- or 2) te group and (4_p) hydrolyzable groups, the fluorine atom content of the gas-containing conjugate is 63 201243500 5. The negative type according to any one of claims 1 to 4 The photosensitive resin composition further contains a crosslinking agent (D) which is a compound having two or more ethylenic double bonds in one molecule and having no acidic group. 6. The negative photosensitive resin composition of claim 5, wherein the total solid portion of the negative photosensitive resin composition, the total amount of the alkali-soluble resin (B) and the crosslinking agent (D) The ratio of the content of the face-soluble resin (B) is from 15 to 85% by mass based on the content of the crosslinking agent (D). 7. The negative photosensitive resin composition according to any one of claims 1 to 6, which further comprises a solvent (E). The negative photosensitive resin composition according to any one of claims 1 to 7, wherein the alkali-soluble resin (B) has an acid value of 10 to 200 mgKOH/g. 9. The negative photosensitive resin composition according to any one of claims 1 to 8, wherein, in the total solid portion of the negative photosensitive resin composition, the ratio of the ink-repellent (A) is 0.01 to 10% by mass. A coating film formed of a negative photosensitive resin composition according to any one of claims 1 to 9 on the substrate. 64