TWI245164B - Photocurable composition, color filter, and crystal display device - Google Patents

Photocurable composition, color filter, and crystal display device Download PDF

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Publication number
TWI245164B
TWI245164B TW092136794A TW92136794A TWI245164B TW I245164 B TWI245164 B TW I245164B TW 092136794 A TW092136794 A TW 092136794A TW 92136794 A TW92136794 A TW 92136794A TW I245164 B TWI245164 B TW I245164B
Authority
TW
Taiwan
Prior art keywords
acrylate
photocurable composition
meth
group
acid
Prior art date
Application number
TW092136794A
Other languages
Chinese (zh)
Other versions
TW200420690A (en
Inventor
Norikuni Suzuki
Youichi Nemoto
Original Assignee
Fujifilm Electronic Material S
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Electronic Material S filed Critical Fujifilm Electronic Material S
Publication of TW200420690A publication Critical patent/TW200420690A/en
Application granted granted Critical
Publication of TWI245164B publication Critical patent/TWI245164B/en

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)

Abstract

The present invention is to provide a photocurable composition used for color filter which there is no pinhole-cissing produced on coating surface of the overcoat layer and whose developing margin and developing latitude are excellent. And there are provided the color filter as well as the crystal display device which are made by using the composition mentioned above. In the photocurable composition containing (a) coloring agent, (b) alkali dissolvable resin, (c) photosensitive polymerizable component, (d) photo initiator of polymerization, and (e) solvent, for the (b) alkali dissolvable resin, the photocurable composition is used, which contains the acrylic copolymer A made of (i) acidic component monomer, (ii) alkyl polyoxyethylene polyoxypropylene (metha)acrylate, and (iii) at least one compound with carbon-carbon unsaturated bond chosen from specific acrylate species, styrenic species, and vinylester species, and the color filter as well as crystal display device which are made by using the composition mentioned above.

Description

1245164 玖、發明說明： (一） 發明所屬之技術領域： 本發明係關於適合於製作用於液晶顯示元件或固體攝 影元件之濾色片、特別是如黑色矩陣或高色度濾色片之著 色劑含有率高之濾色片之光硬化性組成物，及使用該組成 物之濾色片以及液晶顯示裝置。 (二） 先前技術： 近年，作爲平面顯示器之彩色液晶顯示裝置受到矚目， 而進行各式各樣之技術開發。一般液晶顯示裝置之構成方 面，係將液晶層夾於2片基板之間，配置個別朝向於該2 片基板之對向電極，然後於另一面基板之內側與液晶層相 向，配置由紅色（R)、綠色（G)、藍色（B)、及黑色等各畫素 所形成之濾色片層。然後，黑色畫素係一方面防止不同顏 色之混色，一方面有隱藏電極圖案之作用，通常區畫R、G、 B各色畫素地配置成矩陣狀，稱爲黑色矩陣。 濾色片一般係以光阻法製成。具體來說，係均勻地塗 佈、乾燥（預烘烤）已分散有機顏料、染料或碳黑等之著色 劑於光硬化性樹脂成分中或者已溶解組成物之塗佈液於玻 璃等之基板上後，針對構成濾色片之各色圖案來進行曝光 後，以鹼性顯像液等進行顯像處理而得到畫素圖案，乾燥 後，進行加熱處理（後烘烤），對於畫素圖案賦予作爲永久 膜之機械強度。對於R、G、B各色均重複該步驟而形成濾 色片層。通常，由最初形成黑色矩陣開始，於所區畫之部 分形成各色畫素之規則圖案。 因此，由於構成濾色片之各畫素係針對每一種顏色來進 1245164 行’於濾色片表面上產生凹凸，不能均勻厚度地形成濾色 片層，因而由於不能正常地配向液晶分子，而有所謂招致 顯示於液晶顯示裝置之畫質顯著降低之問題。爲了改善該 等之問題’已知要形成用來平坦化鄰接於濾色片層之液晶 層之罩面層（平坦化層）。對於該罩面層係要求於可見光範 圍爲透明 '或亦耐於ITO (透明電極）濺鍍等之耐熱性、再者 與濾色片層之密著性等，而使用丙烯酸系光硬化性樹脂組 成物、環氧系樹脂組成物、聚醯亞胺樹脂組成物等。 Λ外’黑色矩陣材料用之黑色著色劑方面，已知有碳 黑、欽黑等，特別以碳黑爲最爲一般使用。對於濾色片用 黑色矩陣組成物係由於要求高遮光性，黑色著色劑之含量 係通常要求爲35質量％以上，而希望爲40質量％。 近年，在液晶顯示裝置之用途方面，亦從習知之監視 器用途、個人電腦用途擴大至TV用途，亦有隨之而來之顯 示器畫面尺寸大面積化之傾向，變成要求比習知用品更高 色濃度、高色度。由於該等色特性上之要求，故正硏究亦 較習知提局亦作爲遮光膜（黑色矩陣）以外之各畫素之濾色 片用組成物中之著色劑含量。在該等用途中希望作爲固體 成分之含量爲30質量％以上。 但是’濾色片中之著色劑含量變高，則在塗佈形成被 覆膜於濾色片層上時，屢屢有所謂於該塗佈面上產生針孔 狀之凹形斑（針孔凹形斑）之問題。所謂該針孔凹形斑表示 直徑約100 // m〜1，000 “ m之圓形狀之塗佈遺漏之意思者， 於該中心係不存在異物，從作爲被塗佈物之下層濾色片表 面以如局部地沾不上塗佈液之形狀而產生，r、G、B各畫 1245164 素單位（Pixel)全體亦沾不上。 產生該針孔凹形斑則濾色片層變成直接與液晶層接 觸，濾色片層成分溶於液晶層，而不能對於電極間之施加 電壓來正常地配向液晶，該結果爲一方面在畫面上產生歪 斜，一方面有變得不能忠實顏色再現等、使畫面缺陷或不 能形成正常畫面等之問題。 另外，在濾色片製造上之其他問題方面，有顯像界限 或顯像寬容度之問題。 其中，所謂顯像界限係對於在圖案曝光後之光硬化性 塗佈膜以鹼性顯像液等顯像時之所顯像之線寬變化相對於 顯像時間之餘裕度。在濾色片用光硬化性組成物爲負型之 情況爲對於顯像時間之線寬之減少。換言之有線寬變化之 時間依存性之問題。 另外，所謂顯像寬容度係從開始顯像、圖案出現，直 到開始在該圖案上產生缺陷或變形、幾乎畫面消滅之時 間。顯像界限及顯像寬容度共同爲在顯像步驟中之主要特 性。 在濾色片用組成物之情況下，含有吸收光之著色劑， 通常，光不會完全通過直到塗佈層之內部，例如在其爲負 型之情況下，光照射部分大多不會完全硬化。因而，顯像 時間變長則線寬變瘦細是普通之情形。爲了處理該等問 題，鑽硏曝光條件之調節或曝光光罩之開口部分形狀而使 線寬符合設計値來處理。 由於如該等情況，除了對於顯像時間之線寬變化小， 又，維持顯像圖案線寬之時間長，即，顯像界限或顯像寬 1245164 容度大之外，對步驟設計之外或對生產良率之觀點來看均 爲有利。該顯像界限或顯像寬容度之問題係黑色著色劑之 情況表現得最爲顯著，又，有著色劑之含有率變高且變大 之傾向。 即，由於如上述隨著著色劑之含有率變高，因著色劑 導致之圖案曝光之照射光吸收變大，直到濾色片用組成物 之塗佈層內部之照射就變得不充分。 又，在黑色矩陣之情況下，由於相較於其他顏色之畫 素相對地對於線寬精度要求嚴格，如何控制顯像界限或顯 像寬容度則變得特別重要。 以往，爲了控制顯像速度，提案濾色片用光硬化性組 成物之樹脂成分之改良。 例如，於專利文獻1(特開2000- 1 94 1 32號公報）中，揭 示於含有著色劑、含有羧基之（甲基）丙烯酸共聚物、光聚 合性單體、光聚合起始劑、及溶劑之濾色片用著色感光性 樹脂組成物中，藉由進一步含有於側鏈具有氧化乙烯骨架 之共聚物，可使顯像時間變短且賦予適切之間歇時間。具 體來說，揭示於側鏈具有如聚氧化乙烯聚氧化丙烯單烯丙 基醚單院基醚或聚氧化乙嫌聚氧化丙烯單烯丙基醚單芳基 醚之氧化乙烯骨架之共聚物作爲於側鏈具有氧化乙烯骨架 之共聚物，記載有甲基丙烯酸苄酯或舉例說明之已舉例說 明之各種有（甲基）丙烯酸酯、順丁烯二酐、衣康酸酐之不 飽和二羧酸酐之一作爲可共聚合之單體。再者，揭示於側 鏈具有重複數目η爲1〜100之氧化乙烯骨架之聚氧化乙烯 烯丙基醚、苯乙烯、及/或順丁烯二酐爲單體成分之共聚物 1245164 作爲最佳共聚物。 再者，使用已取出聚氧化乙烯或聚氧化丙烯等單體成 分一部分之共聚物之濾色片用組成物方面，在專利文獻 2 (特開平7 - 1 8 04 2號公報）中，揭示藉由使用由環氧乙烷（Eq) 與環氧丙烷（PO)之嵌段共聚物之二丙烯酸酯或甲基丙烯酸 酯所構成，EO與P◦之平均加成莫耳數比爲〇.1〜1.〇 : 1(=1/10〜10/10)，藉由使用平均加成莫耳數合計爲20〜46之 化合物（單體）作爲光聚合性樹脂之稀釋劑，改良光聚合性 樹脂組成物之低黏度化、皮膚刺激性、硬化速度、密著性、 可撓性等。記載著於該光聚合性樹脂組成物中可添加顏料 或染料，或亦可使用於液晶濾色片。 於專利文獻3 (特開2 0 0 2 - 2 8 5 0 0 7號公報）中，揭示黑色 矩陣用黑色樹脂組成物，用於賦予感光性之反應性單體方 面，舉例有已聚氧乙基化、聚氧丙基化之三羥甲基丙烷丙 烯酸酯。 又，於專利文獻4(特開平1 0-7982號公報）中，揭示於 形成具有碳系黑色顏料之濾色片用遮光性薄膜（黑色矩陣） 之光硬化性塗料組成物中，含有具有聚環氧烷鏈之環氧樹 脂與乙儲性不飽和酸反應之光硬化性樹脂。聚環氧院鏈方 面，舉例有氧化乙烯、氧化丙烯，藉由該等之構成，可形 成保存安定性、分散安定性優異之薄膜。 其他方面，亦揭示控制樹脂成分之酸價來改良顯像界 限之技術（參照專利文獻5〜6)，或改良樹脂單體成分來改良 顯像寬容度之技術（參照專利文獻7〜8)。 再者，於專利文獻9(特開2002-22934號公報）中揭示在 1245164 濾色片用光硬性組成物中，添加具有聚氧化乙烯·聚氧化 丙烯鏈之非離子性界面活性劑，來改良塗佈性與顯像寬容 度之技術。然而，揭示於該專利技術文獻中之非離子系界 面活性劑，在塗佈適合性之改良方面有效果，同時罩面層 之塗佈時之針孔凹形斑則無充分之效果，特別地，著色劑 含量變多則針孔凹形斑發現效果，同時相反地顯像寬容度 降低，難以使改良針孔針孔凹形斑與顯像寬容度兩者並存。 於專利文獻1 0 (專利第2 6 6 5 9 6 9號公報）中，揭示在以 顏料分散組成物、單體、光聚合起始劑、及溶劑爲主成分鲁 之濾色片用光聚合性組成物中，在該顏料分散組成物中， 含有包含丙烯酸或甲基丙烯酸、苯乙烯類、及乙二醇醚（甲 基）丙烯酸酯單體之共聚物作爲黏結劑。 即使具有揭示於以上專利文獻資料之技術，仍不能充 分地改良前述之針孔凹形斑或顯像界限之問題，特別是變 成著色劑含量多之黑色矩陣或高色度濾色片之製造上之問 題。 【專利文獻1】 _ 特開2000-194132號公報 【專利文獻2】 特開平7 - 1 8 0 4 2號公報 【專利文獻3】 特開2002-285007號公報 【專利文獻4】 特開平1 0-7 9 8 2號公報 — 【專利文獻5】 -10- 1245164 特開平9 - 3 254 94號公報 【專利文獻6】 特開平1 1 - 2 5 604 9號公報 【專利文獻7】 特開平9 - 1 8 4 9 1 1號公報 【專利文獻8】 特開平1 0-2049 6號公報 【專利文獻9】 特開2002-22934號公報 【專利文獻1 0】 專利第2 6 6 5 6 9 6號公報 (三）發明內容： 發明所欲解決之課穎 本發明之目的係在於在黑色矩陣上、或著色劑含有率高 之濾色片用畫素上，最適於在罩面層上不易產生針孔凹形 斑之濾色片用之光硬化性組成物之提供，因而，提供不易 產生畫面缺陷或畫面形成障礙之液晶顯示裝置。 本發明之其他目的係提供最適於顯像界限或顯像寬容 度高、顯像特性良好之製程適合性優異之濾色片用之光硬 化性組成物。 本發明再其他之目的係提供賦予不易產生畫面缺陷或 畫面形成障礙之高色度畫面之液晶顯示裝置。 解決問題之手段 本發明者等，特別爲了消除形成於如於黑色矩陣或高色 度之濾色片之著色劑含有率高之濾色片層上之罩面層之針 -11- 1245164 孔凹形斑’同時減輕如黑色矩陣或高色度用濾色片用組成 物之著色劑含有率高之光硬化性組成物之顯像寬容度或顯 像界限之問題，而專心一志硏究之結果，發現使用酸成分、 (甲基）丙烯酸苄酯、及烷基聚氧化乙烯•聚氧化丙烯（甲基） 丙烯酸酯作爲鹼可溶性樹脂之共聚合成分用單體，藉由限 定該烷基聚氧化乙烯•聚氧化丙烯（甲基）丙烯酸酯之聚氧 化乙烯部分與聚氧化丙烯部分之比例於特定之範圍，而達 成上述目的，並完成本發明。 即，本發明之目的係藉由下述構成而達成。 (1)一種光硬化性組成物，其包括（a)著色劑、（b)鹼可溶性樹 脂、（c)感光性聚合成分、（d)光聚合起始劑及（e)溶劑，其中 該（b)鹼可溶性樹脂含有由 (〇酸成分單體， (ii) 以下述通式（1)或（2)表示之烷基聚氧化乙烯•聚氧 化丙烯（甲基）丙烯酸酯，1245164 (1) Description of the invention: (1) The technical field to which the invention belongs: The present invention relates to coloring suitable for the production of color filters for liquid crystal display elements or solid-state photographic elements, especially such as black matrix or high-chroma color filters A photocurable composition of a color filter having a high agent content rate, and a color filter and a liquid crystal display device using the composition. (2) Prior technology: In recent years, color liquid crystal display devices, which are flat-panel displays, have attracted attention, and various technologies have been developed. In terms of the structure of a general liquid crystal display device, a liquid crystal layer is sandwiched between two substrates, and an opposing electrode facing each of the two substrates is arranged, and then the inside of the other substrate is opposed to the liquid crystal layer, and the red (R ), Green (G), blue (B), and black. Then, the black pixels prevent the mixing of different colors on the one hand and hide the electrode patterns on the other hand. Usually, the R, G, and B pixels are arranged in a matrix, which is called a black matrix. The color filter is generally made by a photoresist method. Specifically, the substrate is uniformly coated and dried (pre-baked) with a coloring agent in which an organic pigment, dye, or carbon black has been dispersed in a photocurable resin component, or a coating solution in which the composition has been dissolved on a substrate such as glass. After the exposure, the color patterns constituting the color filter are exposed, and then subjected to a development process with an alkaline developer to obtain a pixel pattern. After drying, heat treatment (post-baking) is performed to give the pixel pattern. Mechanical strength as a permanent film. This step is repeated for each color of R, G, and B to form a color filter layer. Generally, starting from the initial formation of a black matrix, a regular pattern of pixels of each color is formed in the area of the painting in the area. Therefore, since the pixels constituting the color filter are 1245164 lines for each color, the unevenness is generated on the surface of the color filter, and the color filter layer cannot be formed uniformly. Therefore, the liquid crystal molecules cannot be aligned normally, and There is a problem that the picture quality of the liquid crystal display device is significantly lowered. In order to improve these problems, it is known to form a cover layer (planarization layer) for planarizing a liquid crystal layer adjacent to a color filter layer. For this cover layer, it is required to be transparent in the visible light range, or to be resistant to ITO (transparent electrode) sputtering, etc., and the adhesion to the color filter layer, etc., and an acrylic photocurable resin is used. Composition, epoxy resin composition, polyimide resin composition, and the like. As for the black colorant used in the Λ outer 'black matrix material, carbon black and black are known, and carbon black is most commonly used. The black matrix composition for a color filter is required to have a high light-shielding property, and the content of the black colorant is generally required to be 35% by mass or more, and preferably 40% by mass. In recent years, the use of liquid crystal display devices has also expanded from conventional monitor applications and personal computer applications to TV applications. There has also been a tendency to increase the size of display screens, which has become more demanding than conventional products. Color density, high chroma. Due to these color characteristics requirements, it is being studied more than the conventional mention of the colorant content in the composition for color filters of pixels other than the light-shielding film (black matrix). In these applications, the content of the solid component is preferably 30% by mass or more. However, when the content of the coloring agent in the color filter becomes higher, when a coating film is formed on the color filter layer, it is often said that pinhole-like concave spots (pinhole depressions) occur on the coating surface. Plaque). The so-called pinhole concave spot means that the diameter of a circle-shaped coating of about 100 // m to 1,000 "m is missing, and there is no foreign matter in the center. The surface is caused by the shape of the coating solution not being locally attached, and the 1245164 pixel units (pixels) of each of r, G, and B can not be adhered. If the pinhole concave spot is generated, the color filter layer becomes directly connected to The liquid crystal layer is in contact, and the components of the color filter layer are dissolved in the liquid crystal layer, and the liquid crystal cannot be normally aligned by applying a voltage between the electrodes. Problems such as screen defects or inability to form normal screens. In addition, in terms of other problems in the manufacture of color filters, there are problems with development limits or development latitude. Among them, the so-called development limits refer to The margin of the change in the line width of the photocurable coating film when it is developed with an alkaline developer or the like with respect to the development time. The case where the photocurable composition for a color filter is negative is Line width of development time In other words, the time dependence of the line width change. In addition, the so-called development latitude is the time from the start of development and the appearance of the pattern to the time when defects or deformation begin to appear on the pattern and the screen almost disappears. The development latitude is a main characteristic in the development step. In the case of a composition for a color filter, a color-absorbing agent is contained, and generally, light does not pass completely until the inside of the coating layer, for example, in the coating layer. In the case of a negative type, most of the light-irradiated parts will not be completely hardened. Therefore, it is common for the line time to become thinner and thinner as the imaging time becomes longer. The shape of the opening portion is adjusted so that the line width conforms to the design. In this case, in addition to the small change in line width for the development time, and the long time to maintain the line width of the development pattern, that is, the development limit or development The image width of 1245164 is beyond the large capacity, which is advantageous from the viewpoint of step design or production yield. The problem of the imaging limit or imaging latitude is that of the black colorant. The situation is most significant, and the content of the colorant tends to be higher and larger. That is, as the content of the colorant becomes higher as described above, the light absorption of the pattern exposure caused by the colorant changes. It is too large until the inside of the coating layer of the color filter composition becomes insufficiently irradiated. In the case of a black matrix, the requirements for line width accuracy are relatively strict compared to pixels of other colors. It is particularly important to control the development limit or development latitude. In the past, in order to control the development speed, improvement of the resin component of the photocurable composition for color filters has been proposed. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 2000-2000) 1 94 1 32) discloses a coloring photosensitive resin composition for a color filter containing a colorant, a (meth) acrylic copolymer containing a carboxyl group, a photopolymerizable monomer, a photopolymerization initiator, and a solvent. In addition, by further containing a copolymer having an ethylene oxide skeleton in the side chain, the development time can be shortened and a suitable intermittent time can be provided. Specifically, a copolymer disclosed in a side chain with an ethylene oxide skeleton such as polyethylene oxide, polyoxypropylene monoallyl ether, or polyethylene oxide, polyoxypropylene monoallyl ether, and monoaryl ether is used as Copolymers with an ethylene oxide skeleton in the side chain, which include benzyl methacrylate or various types of unsaturated dicarboxylic acid anhydrides (meth) acrylates, maleic anhydride, and itaconic anhydride, which are exemplified. One acts as a copolymerizable monomer. Furthermore, a copolymer 1245164 of polyoxyethylene allyl ether, styrene, and / or maleic anhydride as monomer components, which has an ethylene oxide skeleton having a repeating number η of 1 to 100 in the side chain, is disclosed as the best. Copolymer. In addition, in regard to a composition for a color filter using a copolymer in which a part of a monomer component such as polyethylene oxide or polyoxypropylene is taken out, Patent Document 2 (Japanese Patent Application Laid-Open No. 7-1 8 04 2) discloses borrowing It consists of a diacrylate or methacrylate composed of a block copolymer of ethylene oxide (Eq) and propylene oxide (PO), and the average addition mole ratio of EO and P◦ is 0.1. ~ 1.0: 1 (= 1/10 ~ 10/10), by using compounds (monomers) with a total average addition mole number of 20 ~ 46 as the diluent of the photopolymerizable resin, the photopolymerizability is improved Resin composition has reduced viscosity, skin irritation, hardening speed, adhesion, flexibility, etc. It is described that a pigment or a dye may be added to the photopolymerizable resin composition, or it may be used in a liquid crystal color filter. Patent Document 3 (Japanese Laid-Open Patent Publication No. 2002-2 8 5 0 0 7) discloses a black resin composition for a black matrix and a reactive monomer for imparting photosensitivity. Polyoxyethylene has been exemplified. Trimethylolpropane acrylate is a basic, polyoxypropylated. Furthermore, Patent Document 4 (Japanese Patent Application Laid-Open No. 10-7982) discloses that a photocurable coating composition that forms a light-shielding film (black matrix) for a color filter having a carbon-based black pigment contains a polymer having A light-curing resin in which an epoxy resin of an alkylene oxide chain reacts with an ethylenically unsaturated acid. Examples of the polyepoxy resin chain include ethylene oxide and propylene oxide. With these structures, a film having excellent storage stability and dispersion stability can be formed. In other respects, techniques for controlling the acid value of the resin component to improve the development limit (see Patent Documents 5 to 6), or techniques for improving the monomer tolerance to improve the development latitude (see Patent Documents 7 to 8) are also disclosed. Furthermore, Patent Document 9 (Japanese Patent Application Laid-Open No. 2002-22934) discloses that a non-ionic surfactant having a polyethylene oxide / polypropylene oxide chain is added to the photo-hardening composition for a color filter 1245164 to improve it. Coating technology and development latitude. However, the non-ionic surfactants disclosed in the patent technical literature are effective in improving the coating suitability, and the pinhole concave spots at the time of coating of the cover layer are not sufficient, particularly When the content of the colorant is increased, the pinhole concave spot is found to have an effect, and at the same time, the development latitude is reduced, and it is difficult to coexist both the improved pinhole concave spot and the development latitude. Patent Document 10 (Patent No. 2 6 6 5 9 6 9) discloses photopolymerization for a color filter using a pigment dispersion composition, a monomer, a photopolymerization initiator, and a solvent as main components. The pigment dispersion composition contains a copolymer containing acrylic acid or methacrylic acid, styrenes, and a glycol ether (meth) acrylate monomer as a binder. Even with the technology disclosed in the above patent documents, the aforementioned problems of pinhole concave spots or development boundaries cannot be sufficiently improved, especially in the manufacture of black matrices or high-chroma filters with high colorant content. Problem. [Patent Document 1] _ JP 2000-194132 [Patent Document 2] JP 7- 1 8 0 4 JP 2 [Patent Document 3] JP 2002-285007 [Patent Document 4] JP 10 -7 9 8 Publication No. 2-[Patent Document 5] -10- 1245164 JP 9-3 254 94 Publication [Patent Literature 6] JP 1 1-2 5 604 9 Publication [Patent Literature 7] JP 9 -1 8 4 9 1 JP [Patent Document 8] JP 1 0-2049 6 [Patent Document 9] JP 2002-22934 [Patent Document 1 0] Patent No. 2 6 6 5 6 9 6 Announcement (3) Summary of the invention: The lesson to be solved by the invention The object of the present invention is to locate the black matrix or the pixels for color filters with a high colorant content rate, which is most suitable for the surface layer which is difficult to produce. The provision of a photocurable composition for a pinhole concave spot color filter provides a liquid crystal display device that is less prone to screen defects or screen formation obstacles. Another object of the present invention is to provide a light-hardening composition suitable for a color filter which is most suitable for a process having a high development limit or a high development latitude and good development characteristics. Still another object of the present invention is to provide a liquid crystal display device which imparts a high-chroma screen which is less likely to cause screen defects or screen formation obstacles. Means for Solving the Problem The present inventors and others, in particular, eliminated the pin of the cover layer formed on a color filter layer having a high colorant content rate, such as on a black matrix or a high color filter. "Spotting" also alleviates the problems of imaging latitude or imaging margin of a photocurable composition with a high colorant content, such as a black matrix or a color filter composition for high colorimetric composition. The acid component, benzyl (meth) acrylate, and alkyl polyoxyethylene and polyoxypropylene (meth) acrylate are used as monomers for the copolymerization component of the alkali-soluble resin, and the alkyl polyoxyethylene is limited. The ratio of the polyethylene oxide part to the polyoxypropylene part of the polyoxypropylene (meth) acrylate is within a specific range, so as to achieve the above-mentioned object and complete the present invention. That is, the objective of this invention is achieved by the following structure. (1) A photocurable composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photosensitive polymerization component, (d) a photopolymerization initiator, and (e) a solvent, wherein ( b) the alkali-soluble resin contains (0) acid component monomer, (ii) an alkyl polyoxyethylene • polyoxypropylene (meth) acrylate represented by the following general formula (1) or (2),

Ri[(OC2H4)m(OC3H6)n]OCOCR2=CHR3 (1)Ri [(OC2H4) m (OC3H6) n] OCOCR2 = CHR3 (1)

Ri[(〇C2H4)m(〇C3H6)n]〇C〇C(CH3) = CHR3 (2) 及 (iii) 至少1種具有碳-碳不飽和鍵的選自下述I族群之 丙烯酸酯類、苯乙烯類及乙烯酯類之化合物所構成之丙烯 酸系共聚物A。 其中，Ri [(〇C2H4) m (〇C3H6) n] 〇C〇C (CH3) = CHR3 (2) and (iii) at least one acrylate having a carbon-carbon unsaturated bond selected from the group I below Acrylic copolymer A composed of styrene, vinyl ester compounds. among them,

Rl表示1〜20碳數之直鏈或分枝烷基。 R2表示氫原子或甲基。 R3表示氫原子、甲基或乙基。 -12- 1245164 m及η係各爲2〜20之整數，m/n爲3 0/7 0〜80/20。 但是，於上述通式（1)及通式（2)中，對於氧化乙烯基 (OC2H4) 及氧化丙烯基（OC3H6)之鍵結順序並無限制，非限定於上述 表述者。 I族群： (甲基）丙烯酸苄酯、（甲基）丙烯酸苯酯、（甲基）丙烯酸辛 酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸甲基環己酯、（甲 基）丙烯酸己酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸正丁酯、 (甲基）丙烯酸異丁酯、苯乙烯、甲基苯乙烯、二甲基苯乙 烯、甲氧基苯乙烯、環己基苯乙烯、乙酸乙烯酯、丙酸乙 烯酯 (2) 記載於前述（1)之光硬化性組成物，其中前述⑴酸成分單 體爲至少1種選自順式丁烯二酐、丙烯酸、甲基丙烯酸及 富馬酸之酸成分單體。 (3) 記載於申請專利範圍第1項或前述（2)之光硬化性組成 物’其更含有非前述丙烯酸系共聚物A之丙烯酸系共聚物 B作爲前述（b)鹼可溶性樹脂。 (4) S己載於前述（1)〜（3)中任一項之光硬化性組成物，其中已 除去前述（e)溶劑之光硬化性組成物中之前述（a)著色劑之 含有率爲30質量％〜70質量％。 (5) 記載於前述（1)〜（4)中任一項之光硬化性組成物，其中前 述（b)鹼可溶性樹脂中之（1)酸成分單體、（il)烷基聚氧化乙 儲•聚氧化丙烯（甲基）丙烯酸酯及（ili)I族群之化合物組成 質量比爲10〜25/5〜25/5 0〜85，且聚苯乙烯換算質量平均分 1245164 子量（^1\¥)爲3,0〇〇〜5〇,〇〇〇。 (6) 記載於前述（1)〜（5)中之任一項之光硬化性組成物，其中 前述（a)著色劑爲碳黑。 (7) —種漉色片，其係於基板上塗佈、乾燥（預乾燥）記載於 前述（1)〜（6)中任一項之光硬化性組成物後，進行圖案曝 光、驗性顯像而得。 (8) —種液晶顯示裝置，其中在記載於前述（7)之濾色片層上 具有由已直接形成之光硬化性（甲基）丙烯酸系樹脂組成物 所構成之罩面層。 本發明之上述效果係推論非藉由導入由聚氧化乙烯（E〇） 與聚氧化丙烯（P0)爲特定比例所構成之側鏈於形成塗膜之 主要骨架成分所構成之鹼可溶性樹脂分子上，而賦予塗膜 適度之親油性，成爲罩面層與濾色片層之親和性爲適切 者，不易產生針孔凹形斑，又，對於顯像步驟則藉由對於 顯像液保持適度溶解性來改良顯像寬容度與顯像界限。 (四）實施方式： 以下，針對本發明來詳細地說明。 首先，針對本發明之光硬化性組成物之各成分來說明。 [I]成分（a)〜（e) (a)著色劑 可用於本發明之著色劑方面，可混合使用一種或二種以 上習知公認之各種顏料、（絕緣性）碳黑、染料。 可用於本發明之顏料方面，可使用習知公認之各種無機 顏料或有機顏料。又，顏料無論爲無機顏料、無機顏料， 係考慮以高透過率爲佳，亦考慮盡可能細微同時使用佳、 -14 - 1245164 處理性，則使用以0.01 // m〜Ο ·1 // m爲佳、以0.01 μ m〜0.05 // m爲較佳之平均粒徑之顏料。無機顏料方面，以金屬氧 化物、金屬複合鹽等所表示之金屬化合物，具體來說，可 舉出鐵、鈷、鎘、鉛、銅、鈦、鎂、鉻、鋅、銻等之金屬 氧化物、及前述金屬之複合氧化物。 有機顏料方面，可舉出 C.I.顏料黃 11、24、31、53、83、93、99、108、109、 110、138、139、147、150、15 卜 154、155、167、180、185、 199 ； C.I.顏料橙 36、38、43、 71 ； C.I·顏料紅 81、105、122、149、150、155、171、175、 176 、 177 、 209 、 220 > 224 、 242 、 254 、 255 、 264 、 270 ； C . I.顏料紫 1 9、2 3、3 2、3 9 ; C.I.顏料藍 1、2、15、15: 1、15: 3、15: 6、16、22、 60 、 66 ； C.I.顏料黑1、7等。 本發明中，可較佳地使用特別於顔料之構造式中具有 鹼性基之氮原子者。具有該等鹼性基之氮原子之顏料係於 本發明之組成物中顯示良好之分散性。雖然對於其原因並 不十分瞭解，推斷爲感光性聚合成分與顏料之親和性好壞 所影響。 於前述各種顏料中，亦可舉出以下作爲可進一步於本 申請發明中較佳地使用之顏料，但是不受該等所限制。 C.I.顏料黃 11、24、108、109、110、138、139、150、 151 、 154 、 167 、 180 、 185 、 -15- 1245164 c . I.顏料橙 3 6、7 1、 C.I·顏料紅 122、150、171、175、177、209、224、242、 254 、 255 、 264 > C · I.顏料紫 1 9、2 3、3 2、 C.I.顏料藍 15: 1、15: 3、15: 6、16、22、60、66、 C . I.顏料黑i 該等有機顏料係可單獨或以用來提高色純度之各種組 合來使用。以下顯示具體範例。紅色顏料方面，係使用蒽 醌系顏料、茈系顏料、二酮毗咯并吡咯系顏料單獨或該等 至少一種與重氮系黃色顏料、異卩引哄滿系黃色顏料、U奎酉太 酮系黃色顏料或茈系紅色顏料之混合等。例如蒽醌系顏料 方面舉出有C.I·顏料紅177 ;茈系顏料方面舉出有C.I.顏料 紅155、C.I.顏料紅224 ;二酮吡咯并吡咯系顏料方面舉出 有C · I.顏料紅2 5 4，由色再現性之觀點來看，以與c . I.顏料 黃8 3或C · I ·顏料黃1 3 9之混合爲佳。紅色顏料與黃色顏料 之質量比係以1 〇〇 : 5〜1 00 ·· 5 0爲佳。1 00 : 4以下則不能抑 制400nm〜500nm之光透過率而不能提高色純度。又，ι〇〇: 5 1以上則主波長由短波場所構成而導致從NTSC目標色相 而來之不均勻變大。特別以1〇〇: 10〜1〇〇: 3〇之範圍爲最 適當。在紅色顏料類之組合之情況下，合倂成色度來調整。 綠色顏料方面，單獨使用鹵化酞青素系顏料或與重氮系 黃色顏料、喹酞酮系黃色顏料、偶氮次甲基系黃色顏料或 異吲哚滿系黃色顏料之混合，例如以C.I.顏料綠7、36、37 與C.I·顏料黃83、C.I·顏料黃138、C.I·顏料黃139、•顏 料黃1 5 0、C · I.顏料黃1 8 0或C · I ·顏料黃1 8 5之混合爲佳。 -16 - 1245164 綠顏料與黃色顏料之質量比係以1 Ο Ο : 5〜1 Ο Ο : 1 5 0爲佳。 未滿100 : 5則不能抑制400nm〜4 5 0nm之光透過率而不能 提高色純度。又，超過1〇〇 : 150則主波長由長波場所構成 而導致從NTSC目標色相而來之不均勻變大。較佳之質量 比爲100: 30〜100: 120之範圍。 藍色顏料方面，單獨使用酞青素系顏料或與二曙阱系 紫色顏料之混合，例如以C · I ·顏料藍1 5 : 6與C . I.顏料紫 2 3之混合爲佳。藍色顏料與紫色顏料之質量比係以1 〇 〇 : 0〜1 00 : 30爲佳，而以100 : 10以下爲較佳。 再者可藉由使用已微分散上述顏料於丙烯酸系樹脂.、順 式丁烯二酸系樹脂、氯乙烯-乙酸乙烯共聚物及乙基纖維素 樹脂等之粉末狀加工顏料而得到分散性及分散安定性良好 之含有顏料感光樹脂。 又，黑色矩陣用著色劑方面，單獨或混合使用碳、碳化 鈦、氧化鐵、氧化鈦，而以碳和碳化鈦之情況爲佳。質量 比係以1 0 0 ·· 0〜1 0 0 ·· 6 0之範圍爲佳。於1 〇 〇 ·· 6 1以上則有 分散安定性降低之傾向。 可使用作爲關於本發明之著色劑之碳黑方面，可舉例有 三菱化學公司製之碳黑#2400、 #2350、 #2300、 #2200、 # 1 000、# 9 80、# 97 0、# 9 60、# 95 0、# 900、# 8 5 0、 MCF88、 # 65 0、 MA600、 MA7、 MA8、 MA11、 MA100、 MA220 、 IL30B、 IL31B、 IL7B、 IL11B、 IL52B、 #4000、 #4010、 #55、#52、#50、#47、#45、#44、#40、#33、#32、 #30、#20、#10、#5、CF9、#3050、#3150、#3250、 # 3750、# 3950、迪亞黑A、迪亞黑N220M、迪亞黑N234、 1245164 迪亞黑I、迪亞黑LI、迪亞黑II、迪亞黑N339、迪亞黑SH、 迪亞黑SHA、迪亞黑LH、迪亞黑Η、迪亞黑HA、迪亞黑 SF、迪亞黑N55 0M、迪亞黑E、迪亞黑G、迪亞黑R、迪亞 黑N7 60M、迪亞黑LP。康卡普公司製之碳黑舍馬克思 N990、 N991、 N907、 N908、 N990、 N991、 N908。旭碳公司 製之碳黑旭#80、旭#70、旭#70L、旭F-200、旭#66、 旭 #60HN、旭 #60H' 旭 #60U、旭 #60、旭 #55、旭 #50H、 旭#51、旭#50U、旭#50、旭#35、旭#15、旭熱、迪格 薩公司製之碳黑（^〇1〇1*81&〇]<:?\^200、（1!〇1〇1-613〇]<;?〜2、（1!〇1〇1-Black Fw2V、Color Black Fwl、Color Black Fwl8、Color Black S170、Color Black S160、Special Black6、Special B 1 a c k 5、S p e c i a 1 B 1 a c k 4、S p e c i a 1 B 1 a c k 4 A、P r i n t e x U、 PrintexV、Printexl40U、Printexl40V 等。 所謂本發明中之絕緣性碳黑，係顯示例如於碳黑粒子表 面上吸附、被覆或化學鍵結（分枝化）有機物等、於碳黑粒 子表面具有有機化合物，然後，以如下述之方法測定作爲 粉末之體積電阻情況之絕緣性之碳黑。 以絕緣性碳黑和甲基丙烯酸苄酯與甲基丙烯酸以莫耳 比爲70: 30之共聚物（30,000質量平均分子量）形成20: 80 質量比，分散於丙二醇單甲基醚中來調製塗佈液，塗佈於 1.1mm厚、lOcmxiOcm之鉻基板上來製作3//m乾燥膜厚之 塗膜’在進一步於烤箱中以200°C熱處理該塗膜1小時之 後’以依照JIS SK6911之三菱化學股份有限公司製高電阻 率計、氨雷斯塔-UP(MCP-HT450)施加電壓，於23°C相對溼 度65 %之環境下測定體積電阻値。然後，該體積電阻値方 -18- 1245164 面，以顯示1〇6 Ω · cm以上、以ΙΟ8 Ω · cm以上爲較佳、 特別以1 Ο9 Ω · cm以上爲較佳之絕緣性碳黑爲佳。 絕緣性碳黑方面，可使用於例如特開平1 1 - 609 8 8號公 報、特開平1卜6 0 9 8 9號公報、特開平1 〇 - 3 3 0 6 4 3號公報、 特開平1卜805 8 3號公報、特開平1 1 - 8 05 84號公報、特開平 9- 1 24 9 69號公報、特開平9 -95 625號公報所揭示之樹脂被 覆碳黑。 其他，以適宜樹脂被覆碳黑者亦可。 以樹脂（被覆樹脂）被覆碳黑之中，添加被覆樹脂及溶劑 於碳黑來製造硏磨基台，藉由沖刷處理或捏合機、球磨機、 砂磨機、珠粒硏磨機、2支或3支輥煉機、脹管機、塗料 振動機、超音波、均化器等方法來進行分散處理。必要時 可使用用於均勻地分散碳黑之分散劑。 被覆樹脂方面，可舉例有以下者。 1) 聚烯烴系聚合物 聚乙烯、聚丙烯、聚異丁烯等 2) 二烯系聚合物 聚丁二烯、聚異戊間二烯等 3) 具有共軛多烯構造之聚合物 聚乙炔系聚合物、聚伸苯系聚合等 4) 乙烯聚合物 聚氯乙烯、聚苯乙烯、乙酸乙烯酯、聚乙烯醇、聚（甲 基）丙烯酸、聚（甲基）丙烯酸酯、聚丙烯醯胺、聚丙烯腈、 聚乙烯酚等 5) 聚醚 -19- 1245164 聚伸苯基醚、聚氧化乙烯、聚氧雜環丁烷、聚四氫呋喃、 聚醚酮、聚醚醚酮、聚縮醛等 6) 苯酚樹脂 酚醛清漆樹脂、可溶酚醛樹脂等 7) 聚酯 聚對苯二甲酸乙二醇酯、聚對苯二甲酸酚酞酯、聚碳酸 酯、醇酸樹脂、不飽和聚酯樹脂等 8) 聚醯胺 耐綸6、耐綸6 6、水溶性耐綸、聚伸苯基醯胺等 9) 聚肽 明膠、酪蛋白等 10) 環氧樹脂及其改質物 酚醛清漆環氧樹脂、雙酚環氧樹脂、酚醛清漆環氧化丙 烯酸酯樹脂及以酸酐之改質樹脂等 1 1)其他 聚胺甲酸酯、聚醯亞胺、三聚氰胺樹脂、尿素樹脂、聚 咪唑、聚噚唑、聚吡咯、聚苯胺、聚亞礪、聚颯、纖維素 類等 較具體來說，含有羧基之丙烯酸樹脂係可舉例有共聚合 (甲基）丙烯酸、順式丁烯二酸（酐）、丁烯酸、衣康酸、富馬 酸等具有羧基之單體與苯乙烯、α-甲基苯乙烯、（甲基）丙 烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基） 丙烯酸異丙酯、（甲基）丙烯酸丁酯、乙酸乙烯酯、丙烯腈、 (甲基）丙烯醯胺、（甲基）丙烯酸環氧丙酯、丙烯基環氧丙 酯、乙基丙烯酸環氧丙酯、丁烯二酸環氧丙酯、（甲基）丙 -20- 1245164 烯酸丁酸酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸羥基乙酯、 N -羥甲基丙烯醯胺、N，N -二甲基丙烯醯胺、N -甲基丙烯醯 基嗎啉、（甲基）丙烯酸-N，N -二甲基胺乙酯、N，N -二甲基胺 乙基丙烯醯胺等之共聚合成分之聚合物。其中以至少含有 作爲構成單體之（甲基）丙烯酸或（甲基）丙烯酸烷基酯之丙 烯酸樹脂爲特佳，而以含有（甲基）丙烯酸及苯乙烯之丙烯 酸樹脂爲更佳。 又，該等樹脂亦可於樹脂側鏈加成乙烯性雙鍵。由於藉 由賦予雙鍵於樹脂側鏈而提高光硬化性，可進一步提高解 像性、密著性而佳。 導入乙烯性雙鍵之合成手段方面，舉例有記載於特公昭 50-34443號公報、特公昭50-34444號公報等之方法。具體 來說，舉出有使於羧基或羥基合倂具有縮水甘油基、環氧 環己基及（甲基）丙烯醯基之化合物或丙烯酸丁酸酯等反應 之方法。例如，（甲基）丙烯酸環氧丙酯、丙烯酸縮水甘油 醚、α -乙基丙烯酸環氧丙酯、丙烯醯基縮水甘油醚、（異） 丁烯酸縮水甘油醚、（甲基）丙烯酸（3,4-環氧環己基）甲酯、 (甲基）丙烯酸丁酸酯、（甲基）烯丙基丁酸等之化合物，可藉 由於具有羧基或羥基之樹脂上反應而得到於側鏈具有聚合 基之樹脂。特別地’以反應（甲基）丙烯酸（3，4-環氧環己基） 甲酯之樹脂爲佳。 又，亦可使用藉由至少以通式[1]表示之單體與至少具 有酸性基之單體（可舉出有上述之共聚合成分）之共聚合反 應而得之聚合物。 -21- 3 1± 45 12 ο = R-c丨c~ϊόII c 2 1 \ / 2 Rici R 一 QC 丨 C3 4 5 RICIR far-·- ua^i \—/ —ϋ /ί\ (式中，R表示氫原子或甲基原子，Ri〜R5係個別獨立地選 自氫原子、鹵素原子、氰基、烷基及芳基之官能基。） 其中，鹵素原子之具體實例方面’舉出有氯、溴、碘等。 院基方面，爲直鏈、分枝、或環狀均可，舉出有甲基、正 丙基、異丙基、第三丁基等，以1〜7碳數者爲佳。芳基方 面，舉出有苯基、雙呋喃甲醯基、萘基等。 又，亦可使用如下述之樹脂作爲被覆樹脂。 以直線狀有機高分子量聚合物、可溶於有機溶劑、可藉 由弱鹼性水溶液顯像者爲佳。該等直線狀有機高分子量聚 合物方面，由於在樹脂側鏈或主鏈上具有羧基或酚性羥基 等酸性基者可鹼性顯像，因公害防止之觀點而佳。特別是 以具有羧基之樹脂、例如丙烯酸（共）聚合物、苯乙烯/順式 丁烯二酸酐樹脂、酚醛清漆環氧化丙烯酸酯之酸酐改質樹 脂等爲高鹼性顯像性而佳。於側鏈具有羧酸之聚合物方 面，有如記載於例如特開昭5 9 - 4 4 6 1 5號公報、特公昭 5 4 - 3 4 3 27號公報、特公昭5 8 - 1 25 7 7號公報、特公昭54-25 95 7 號公報、特開昭5 9 - 5 3 8 3 6號公報、特開昭5 9 - 7 1 0 4 8號公報 -22- 1245164 之甲基丙烯酸共聚物、丙烯酸共聚物、衣康酸共聚物、丁 烯酸共聚物、順式丁烯二酸共聚物、部分酯化順式丁烯二 酸共聚物等，又有同樣地於側鏈具有羧酸之酸性纖維素衍 生物。於其他具有羥基之聚合物中加成酸酐者等亦有用。 於該等中，亦以（甲基）丙烯酸τ酯/(甲基）丙烯酸共聚物或 (甲基）丙烯酸苄酯/(甲基）丙烯酸/及其他單體之多元共聚物 爲佳。 於其他水溶性聚合物方面，以甲基丙烯酸-2 -羥乙酯、 聚乙烯吡咯酮或聚氧化乙烯、聚乙烯醇等亦有用。又以用 於提高硬化皮膜強度之醇可溶性耐綸或2,2-雙（4-羥苯基） 丙烷與環氧氯丙烷之聚酯等亦有用。該等聚合物係可混合 任意量。 再者，亦可使用如下述之環氧樹脂。 1 .縮水甘油基胺型環氧樹脂 2.三苯基縮水甘油基甲烷型環氧樹脂 3 .四苯基縮水甘油基甲烷型環氧樹脂 4. 胺基酚型環氧樹脂 5. 二胺二苯基甲烷型環氧樹脂 6. 酚-酚醛清漆型環氧樹脂 7 .鄰甲酚型環氧樹脂 8 .雙酚A酚醛清漆型環氧樹脂 於上述之中，被覆樹脂方面，選擇各種單體，由可控 制溶解度與酸價來看，以（甲基）丙烯酸與（甲基）丙烯酸酯之 共聚物爲佳。 該等被覆樹脂之以膠體滲透層析譜法（GPC)所測定之質 -23- 1245164 量平均分子量（重量平均分子量）之較佳範圍爲 1,000〜3 00,〇〇〇，而以 3,000〜150,000 爲較佳。於 300,000 以 下可得到良好之顯像性。 於上述顏料或碳黑之分散中，通常使用分散劑。分散劑 中除了使用原來之上述被覆樹脂之外，可倂用如後述之分 散劑。該等分散劑可單獨地使用、或亦可使用複數種組合。 藉由分散處理來吸附樹脂於碳黑表面則同時使破壞碳黑粒 子之凝結之粒徑而使細微化。 本發明中，以上述樹脂所被覆之碳黑形態方面，舉出有 粉末 '糊狀、粒狀、糊狀、片狀等。 以樹脂所被覆之碳黑較佳平均粒徑爲0.003〜0.5// m之 範圍，以0.005〜0.3//m之範圍爲較佳，因而本發明之各種 效果、特別是顯像性與畫面再現性變得更優異。 分散劑方面，可使用BYK公司製之Anti-Terra-U、 Disperbyk-160、161、162、163; ZENECA 公司製之 Solspers20000、24000GR、26000、2 8 000;楠本化成公司製 之 DA-703-50、NDC-8194 L、NDC- 8 20 3 L、NDC-8257L、 KS-860;花王公司製之均化劑 L-18、 L1820、 L-95、 L-100; 曰本塗料公司製之VP5000 ;固得力奇公司製之E5 7 03P ;聯 合製碳公司製之VAGH ;東洋紡織公司製之UR8200 ;日本 製王公司製之MR 1 1 3等公認之分散樹脂。 又，亦可舉出酞青素衍生物（市售品EFKA-745 (森下產業 製））；有機矽氧烷聚合物KP341(信越化學工業製）、（甲基） 丙烯酸系（共）聚物聚夫龍No. 75、No. 90、No .95(共榮社油脂 化學工業製）、W001 (裕商製）等陽離子系界面活性劑；聚氧 >24- 1245164 化乙烯十二烷基醚、聚氧化乙烯十八烷基醚、聚氧化乙烯 十八碳烯基醚、聚氧化乙烯辛苯基醚、聚氧化乙烯壬苯基 醚、聚二-十二酸乙二酯、聚二-十八酸乙二酯、山梨糖醇 脂肪酸酯等之非離子系界面活性劑；耶氟脫譜EF30 1、 EF3 0 3、EF3 5 2 (新秋田化成製）；鎂佳伐克F17卜F172、F173(大 曰本油墨製）；氟羅特FC430、FC431(住友3M製）、朝日佳 特 AG710、薩福隆 S382、 SC-101、 SC-102、 SC-103、 SC-104、 SC-105、SC- 1 068 (旭硝子製）等氟系界面活性劑；W004、 W005、W017(裕商製）等之陰離子系界面活性劑；efkA-46、 EFKA-47、EFKA-47EA、EFKA 聚合物 100、EFKA 聚合物 400、 EFKA聚合物401、EFKA聚合物450(以上森下產業製）、分 散添加劑6、分散添加劑8、分散添加劑15、分散添加劑 9 100(桑諾譜科製）等聚合物分散劑；梭耳斯帕斯3000、 5000、 9000、 12000、 13240、 13940、 17000、 24000、 26000、 2 8 000等之各種溶膠分散分散劑（傑內卡股份有限公司 製）；阿迪卡譜耳羅尼克L31、F38、L42、L44、L61、L64、 F68、L72、P95、F77、P84、F87、P94、L101、P013、F108、 L121、P-123(旭電化製）及伊索尼特S-20(三洋化成製）。 本發明中，在著色劑爲染料之情況下，均勻地溶解於 組成物中得到光硬化性組成物。 可使用作爲構成本發明組成物之著色劑之染料並無特 別之限制’可使用作爲習知濾色片用之公認染料。可使用 揭示於例如特開昭64-90403號公報、特開昭64-9 1 1 02號公 報、特開平1 -9430 1號公報、特開平6-11614號公報、特登 2592207 5虎、美國專利第4,808,501號說明書、美國專利弟 -25- 1245164 5，6 6 7，9 2 0號說明書、美國專利第5 , 〇 5 9，5 Ο 0號說明書、特 開平5 -3 3 3 207號公報、特開平6-35 1 8 3號公報、特開平 6 - 5 1 Π 5號公報、特開平6 - 1 9 4 8 2 8號公報、特開平8 - 2 1 1 5 9 9 號公報、特開平4- 24 95 49號公報、特開平1 0- 1 2 3 3 1 6號公 報、特開平1 1 - 3 0 2 2 8 3號公報、特開平7 - 2 8 6 1 0 7號公報、 特開2 Ο (Η - 4 8 2 3號公報、特開平8 - 1 5 5 2 2號公報、特開平 8 - 2977 1號公報、特開平8- 1 462 1 5號公報、特開平1 1 -34343 7 號公報、特開平8 -624 1 6號公報、特開2002- 1 4220號公報、 特開2002- 1 422 1號公報、特開2002- 1 4222號公報、特開 2002- 1 422 3號公報、特開平8-302224號公報、特開平8 - 7 3 7 5 8 號公報、特開平8-179120號公報、特開平8-151531號公報 等之色素。 化學構造方面，可使用吡唑偶氮系、苯胺偶氮系、三苯 甲烷系、蒽醌系、蒽吡咯酮系、苯亞甲基系、氧醇系、吡 唑啉三唑偶氮系、吡啶酮偶氮系、花青素系、啡噻畊系、 吡咯并吡咯偶氮次甲基系、二苯駢哌喃系、酞青系、苯并 吡喃系、靛藍系等染料。 本發明光硬化性組成物中之著色劑含有率係除去溶劑 成分，爲30〜70質量％，以40〜70質量％爲佳，以45〜70質 量％爲更佳。由於含有率爲3 0質量％以上，可得到良好之 遮光率與高色度之顏色特性，又，由於含有率爲70質量％ 以下，可得到良好之顯像處理性。 (b)鹼可溶性樹脂 用於本發明之組成物之（b)鹼可溶性樹脂係包含由（i)酸 成分單體、（η)以下述通式（1)或（2)所表示之烷基聚氧化乙 -26- 1245164 烯•聚氧化丙烯（甲基）丙烯酸酯，R1 represents a linear or branched alkyl group having 1 to 20 carbon numbers. R2 represents a hydrogen atom or a methyl group. R3 represents a hydrogen atom, a methyl group or an ethyl group. -12- 1245164 m and η are each an integer from 2 to 20, and m / n is 3 0/7 0 to 80/20. However, in the general formulae (1) and (2), the bonding order of the oxyethylene group (OC2H4) and the oxypropylene group (OC3H6) is not limited, and it is not limited to those described above. Group I: Benzyl (meth) acrylate, phenyl (meth) acrylate, octyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, (meth) ) Hexyl acrylate, amyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, styrene, methylstyrene, dimethylstyrene, methoxystyrene , Cyclohexylstyrene, vinyl acetate, vinyl propionate (2) The photocurable composition described in the above (1), wherein the osmic acid component monomer is at least one selected from the group consisting of cis-butene dianhydride, Acrylic acid, methacrylic acid and fumaric acid monomers. (3) The photocurable composition 'described in item 1 of the patent application scope or (2) above further contains an acrylic copolymer B other than the aforementioned acrylic copolymer A as the aforementioned (b) alkali-soluble resin. (4) The photocurable composition contained in any one of the above (1) to (3), wherein the content of the aforementioned (a) colorant is removed from the photocurable composition of the (e) solvent The rate is from 30% by mass to 70% by mass. (5) The photocurable composition described in any one of (1) to (4), wherein (1) an acid component monomer and (il) an alkyl polyethylene oxide in the (b) alkali-soluble resin Storage • Polyoxypropylene (meth) acrylate and (ili) I group compound composition mass ratio is 10 ~ 25/5 ~ 25/5 0 ~ 85, and the average mass of polystyrene conversion is 1245164 (\ ¥) is 3,000 to 50,000. (6) The photocurable composition described in any one of the above (1) to (5), wherein the (a) colorant is carbon black. (7) A kind of ochre sheet, which is coated on a substrate and dried (pre-dried) the photocurable composition described in any one of (1) to (6) above, and then subjected to pattern exposure and inspection. Developed. (8) A liquid crystal display device having a cover layer composed of a photocurable (meth) acrylic resin composition formed directly on the color filter layer described in (7) above. The above-mentioned effect of the present invention is inferred that by not introducing a side chain composed of polyethylene oxide (E0) and polypropylene oxide (P0) in a specific ratio to an alkali-soluble resin molecule composed of a main skeleton component forming a coating film And give the coating film a moderate degree of lipophilicity, become the affinity between the cover layer and the color filter layer is appropriate, it is not easy to produce pinhole concave spots, and for the development step, by maintaining a moderate dissolution for the imaging solution Sex to improve imaging latitude and imaging boundaries. (4) Embodiments: The present invention will be described in detail below. First, each component of the photocurable composition of the present invention will be described. [I] Ingredients (a) to (e) (a) Coloring agent The coloring agent can be used in the coloring agent of the present invention, and one or two or more conventionally recognized various pigments, (insulating) carbon black, and dye can be mixed and used. As the pigment which can be used in the present invention, various conventionally recognized inorganic pigments or organic pigments can be used. Regardless of whether the pigment is an inorganic pigment or an inorganic pigment, it is considered to have a high transmittance, and also to use it as finely as possible, and -14 to 1245164. For handling properties, use 0.01 // m ~ 〇 · 1 // m Pigments with a preferred average particle size of 0.01 μm to 0.05 // m are preferred. In terms of inorganic pigments, metal compounds represented by metal oxides and metal composite salts, and specifically, metal oxides such as iron, cobalt, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And composite oxides of the aforementioned metals. For organic pigments, CI Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 15 and 154, 155, 167, 180, 185, 199; CI Pigment Orange 36, 38, 43, 71; CI · Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220 > 224, 242, 254, 255, 264, 270; C. I. Pigment Violet 1, 9, 2, 3, 3 2, 3 9; CI Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66 ; CI Pigment Black 1, 7, etc. In the present invention, a nitrogen atom having a basic group in the structural formula of a pigment is particularly preferably used. The pigment having such a basic nitrogen atom shows good dispersibility in the composition of the present invention. Although the reason for this is not well understood, it is presumed to be affected by the affinity of the photosensitive polymerization component and the pigment. Among the aforementioned various pigments, the following can also be cited as pigments which can be further preferably used in the invention of the present application, but they are not limited thereto. CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185, -15-1245164 c. I. Pigment Orange 3 6, 7 1, CI · Pigment Red 122 , 150, 171, 175, 177, 209, 224, 242, 254, 255, 264 > C. I. Pigment Violet 1 9, 2 3, 3 2, CI Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66, C. I. Pigment black i These organic pigments can be used alone or in various combinations to improve color purity. Specific examples are shown below. In terms of red pigments, anthraquinone-based pigments, fluorene-based pigments, and diketopyrrolopyrrole-based pigments are used alone or in combination with at least one of the diazo-based yellow pigments, isocyanate-based yellow pigments, and U-quinolone. Mixing of yellow pigments and rhenium red pigments. For example, anthraquinone-based pigments include CI · Pigment Red 177; fluorene-based pigments include CI Pigment Red 155 and CI Pigment Red 224; and diketopyrrolopyrrole-based pigments include C · I. Pigment Red 2 From the viewpoint of color reproducibility, it is preferable to mix with c. I. Pigment Yellow 8 3 or C · I · Pigment Yellow 1 3 9. The mass ratio of the red pigment to the yellow pigment is preferably from 100: 5 to 100 ... 50. Below 1 00: 4, the light transmittance of 400nm to 500nm cannot be suppressed and the color purity cannot be improved. In addition, if ιOM: 51 or higher, the dominant wavelength is composed of a short-wave field, and the unevenness from the NTSC target hue becomes large. In particular, a range of 100: 10 to 100: 30 is most suitable. In the case of a combination of red pigments, it can be adjusted by combining the chroma. For green pigments, halogenated phthalocyanin pigments alone or mixed with diazo yellow pigments, quinophthalone yellow pigments, azomethine yellow pigments, or isoindolin yellow pigments, such as CI pigments Green 7, 36, 37 and CI · Pigment Yellow 83, CI · Pigment Yellow 138, CI · Pigment Yellow 139, · Pigment Yellow 1 50, C · I. Pigment Yellow 1 8 0 or C · I · Pigment Yellow 1 8 Mixing of 5 is preferred. -16-1245164 The mass ratio of green pigment to yellow pigment is preferably 1 Ο Ο: 5 ~ 1 Ο Ο: 150. Below 100: 5, the light transmittance of 400nm ~ 450nm cannot be suppressed and the color purity cannot be improved. In addition, if it exceeds 100: 150, the dominant wavelength is composed of a long-wave field, and the unevenness from the NTSC target hue becomes large. The preferred mass ratio is in the range of 100: 30 to 100: 120. As for the blue pigment, a phthalocyanin-based pigment alone or a mixture with an Ershujing purple pigment, for example, a mixture of C · I · Pigment Blue 15: 6 and C.I.Pigment Purple 2 3 is preferred. The mass ratio of the blue pigment to the purple pigment is preferably 100: 0 to 100: 30, and more preferably 100 or less. Furthermore, the dispersibility and dispersibility can be obtained by using powders which have been finely dispersed in the above-mentioned pigments in acrylic resins, cis-butadiene-based resins, vinyl chloride-vinyl acetate copolymers, and ethyl cellulose resins. Pigment-containing photosensitive resin with good dispersion stability. As for the colorant for the black matrix, carbon, titanium carbide, iron oxide, and titanium oxide are used singly or in combination. Carbon and titanium carbide are preferred. The mass ratio is preferably in the range of 1 0 0 ·· 0 to 1 0 0 ·· 6 0. Above 100 1 · 6, the dispersion stability tends to decrease. The carbon black which can be used as the coloring agent of the present invention can be exemplified by carbon black # 2400, # 2350, # 2300, # 2200, # 1 000, # 9 80, # 97 0, # 9 manufactured by Mitsubishi Chemical Corporation. 60, # 95 0, # 900, # 8 5 0, MCF88, # 65 0, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55 , # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750 , # 3950, Dia Black A, Dia Black N220M, Dia Black N234, 1245164 Dia Black I, Dia Black LI, Dia Black II, Dia Black N339, Dia Black SH, Dia Black SHA, Diahei LH, Diahei, Diahei HA, Diahei SF, Diahei N55 0M, Diahei E, Diahei G, Diahei R, Diahei N7 60M, Diahei LP. Carbon black Shex Marx N990, N991, N907, N908, N990, N991, N908 manufactured by Concap. Carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 60HN, Asahi # 60H 'Asahi # 60U, Asahi # 60, Asahi # 55, Asahi ## 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi, Carbon black manufactured by Digesa (^ 〇1〇1 * 81 & 〇) <:? \ ^ 200, (1! 〇1〇1-613〇) <? ~ 2, (1! 〇1〇1-Black Fw2V, Color Black Fwl, Color Black Fwl8, Color Black S170, Color Black S160, Special Black6, Special B 1 ack 5, Specia 1 B 1 ack 4, Specia 1 B 1 ack 4 A, Princess U, PrintexV, Printexl40U, Printexl40V, etc. The so-called insulating carbon black in the present invention is shown, for example, in carbon black Carbon black particles have organic compounds adsorbed on, coated with, or chemically bonded (branched) organic substances on the surface of the particles, and then the carbon black, which is the insulation of the volume resistance of the powder, is measured by the following method. Carbon black, benzyl methacrylate and methacrylic acid form a copolymer with a molar ratio of 70: 30 (30,000 mass average molecular weight) to form a mass ratio of 20: 80 and are dispersed in acrylic Glycol monomethyl ether was used to prepare a coating solution, which was coated on a 1.1 mm thick, 10 cmxiOcm chromium substrate to make a 3 // m dry film thickness coating film. The coating film was further heat-treated at 200 ° C in an oven. One hour later, the volume resistivity was measured in an environment where the relative resistance was 65% at 23 ° C using a high resistivity meter manufactured by Mitsubishi Chemical Co., Ltd. in accordance with JIS SK6911, amresta-UP (MCP-HT450). Then, the volume resistance is square -18 to 1245164 planes, so as to display more than 10 6 Ω · cm, more preferably 10 8 Ω · cm or more, and particularly preferably more than 10 9 Ω · cm is better insulating carbon black. As for the insulating carbon black, it can be used in, for example, Japanese Patent Application Laid-Open No. 1 1-609 88, Japanese Patent Application Laid-Open No. 6 0 9 89, Japanese Patent Application Laid-Open No. 10- 3 3 0 6 4 3, Japanese Patent Application Laid-Open No. 1 The resin-coated carbon black disclosed in Japanese Patent Publication No. 805 8 3, Japanese Patent Application Laid-Open No. 1 1-8 05 84, Japanese Patent Application Laid-Open No. 9- 1 24 9 69, Japanese Patent Application Laid-Open No. 9-95 625. Other, as appropriate Resin-coated carbon black can also be used. Carbon black is coated with resin (coated resin), and coated resin and solvent are added to carbon. To manufacture honing abutment, by scouring or kneading machine, ball mill, sand mill, bead honing machine, 2 or 3 roll mill, tube expander, paint shaker, ultrasonic, homogenizer And other methods to perform dispersion processing. If necessary, a dispersant for uniformly dispersing carbon black may be used. For the coating resin, the following can be exemplified. 1) Polyolefin polymers such as polyethylene, polypropylene, polyisobutylene, etc. 2) Diene polymers such as polybutadiene, polyisoprene, etc. 3) Polymers with conjugated polyene structure, polyacetylene based polymerization Polymers, polystyrene polymerization, etc. 4) Ethylene polymers Polyvinyl chloride, polystyrene, vinyl acetate, polyvinyl alcohol, poly (meth) acrylic acid, poly (meth) acrylate, polyacrylamide, poly Acrylonitrile, polyvinyl phenol, etc. 5) polyether-19-1245164 polyphenylene ether, polyethylene oxide, polyoxetane, polytetrahydrofuran, polyetherketone, polyetheretherketone, polyacetal, etc. 6) Phenol resin novolac resin, soluble phenol resin, etc. 7) polyester polyethylene terephthalate, polyphenol terephthalate, polycarbonate, alkyd resin, unsaturated polyester resin, etc. 8) poly Phenamide Nylon 6, Nylon 6 6, Water-soluble Nylon, Polyphenylene Pyramide, etc. 9) Polypeptide gelatin, casein, etc. 10) Epoxy resin and its modification Novolac epoxy resin, bisphenol ring Oxygen resin, novolac epoxidized acrylate resin, modified resin with acid anhydride, etc. 1 1) Other polymer More specifically, formate, polyimide, melamine resin, urea resin, polyimidazole, polyoxazole, polypyrrole, polyaniline, polyurethane, polyfluorene, cellulose, etc. are more specifically acrylic resins containing a carboxyl group. Examples include monomers having a carboxyl group such as copolymerized (meth) acrylic acid, cis-butenedioic acid (anhydride), butenoic acid, itaconic acid, fumaric acid, and styrene, α-methylstyrene, ( Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) ) Acrylamide, Glycidyl (meth) acrylate, Glycidyl acrylate, Glycidyl acrylate, Glycidyl butyrate, (12) 1245164 Glycolic acid Butyrate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-hydroxymethacrylamide, N, N-dimethylacrylamide, N-methacrylfluorenylmorpholine , (Meth) acrylic acid-N, N-dimethylamine ethyl ester, N, N-dimethylamine ethylpropenamide, etc. Polymer of polymer. Among these, an acrylic resin containing at least (meth) acrylic acid or an alkyl (meth) acrylate as a constituent monomer is particularly preferred, and an acrylic resin containing (meth) acrylic acid and styrene is more preferred. In addition, these resins may have an ethylene-based double bond added to the resin side chain. The addition of a double bond to the side chain of the resin improves the photo-hardening property, which further improves the resolution and adhesion. Examples of synthetic means for introducing an ethylenic double bond include methods described in Japanese Patent Publication No. 50-34443 and Japanese Patent Publication No. 50-34444. Specific examples include a method of reacting a compound having a glycidyl group, an epoxy cyclohexyl group, a (meth) acrylfluorenyl group, or an acrylic acid butyrate at a carboxyl group or a hydroxyl group. For example, glycidyl (meth) acrylate, glycidyl acrylic acid, glycidyl α-ethyl acrylate, glycidyl glycidyl acrylate, (glycidyl ether), (meth) acrylic acid ( Compounds such as 3,4-epoxycyclohexyl) methyl ester, (meth) acrylic acid butyrate, (meth) allyl butyric acid, etc. can be obtained on the side chain by reaction on a resin having a carboxyl group or a hydroxyl group. Polymer-based resin. In particular, a resin which reacts with (3,4-epoxycyclohexyl) methyl (meth) acrylate is preferred. Alternatively, a polymer obtained by copolymerizing a monomer represented by at least the general formula [1] and a monomer having at least an acidic group (including the above-mentioned copolymerization component) may be used. -21- 3 1 ± 45 12 ο = Rc 丨 c ~ ϊόII c 2 1 \ / 2 Rici R-QC 丨 C3 4 5 RICIR far- ·-ua ^ i \ — / —ϋ / ί \ (where, R Represents a hydrogen atom or a methyl atom, and Ri to R5 are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a cyano group, an alkyl group, and an aryl group.) Among them, specific examples of the halogen atom include chlorine, Bromine, iodine, etc. As for the base, it may be linear, branched, or cyclic, and examples thereof include methyl, n-propyl, isopropyl, and third butyl, and those having 1 to 7 carbon atoms are preferred. Examples of the aryl group include phenyl, bisfurylmethyl, and naphthyl. Moreover, you may use the following resin as a coating resin. A linear organic high molecular weight polymer that is soluble in organic solvents and can be developed with a weakly alkaline aqueous solution is preferred. For these linear organic high molecular weight polymers, those having acidic groups such as carboxyl groups or phenolic hydroxyl groups on the resin side chain or main chain can be developed basicly, which is preferable from the viewpoint of prevention of pollution. In particular, resins having a carboxyl group, such as acrylic (co) polymers, styrene / cis-butadiene anhydride resins, and novolak epoxidized acrylic acid anhydride-modified resins, etc., are superior in high alkali developability. The polymer having a carboxylic acid in a side chain is as described in, for example, Japanese Patent Application Laid-Open No. 5 9-4 4 6 1 5, Japanese Patent Application No. 5 4-3 4 3 27, Japanese Patent Application No. 5 8-1 25 7 7 Japanese Patent Publication No. 54-25 95 7, Japanese Patent Publication No. 5 9-5 3 8 36, Japanese Patent Publication No. 5 9-7 1 0 4 8 and methacrylic acid copolymer , Acrylic copolymers, itaconic acid copolymers, butenes copolymers, cis-butadiene copolymers, partially esterified cis-butadiene copolymers, etc. Acid cellulose derivatives. Addition of an anhydride to other polymers having a hydroxyl group is also useful. Among these, multi-component copolymers of t (meth) acrylate / (meth) acrylic acid copolymer or benzyl (meth) acrylate / (meth) acrylic acid / and other monomers are also preferred. For other water-soluble polymers, 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful. Alcohol-soluble nylons for improving the strength of hardened films or polyesters of 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin are also useful. These polymers can be mixed in any amount. Furthermore, epoxy resins such as those described below can also be used. 1. Glycidylamine type epoxy resin 2. Triphenylglycidyl methane type epoxy resin 3. Tetraphenylglycidyl methane type epoxy resin 4. Aminophenol type epoxy resin 5. Diaminedi Phenyl methane type epoxy resin 6. Phenol-Novolac type epoxy resin 7. O-cresol type epoxy resin 8. Bisphenol A novolac type epoxy resin among the above, in terms of coating resin, various monomers are selected From the viewpoint of controllable solubility and acid value, a copolymer of (meth) acrylic acid and (meth) acrylate is preferable. The mass range of these coating resins determined by colloidal permeation chromatography (GPC) is 23-1245164. The preferred range of the weight-average molecular weight (weight-average molecular weight) is 1,000 to 3,000,000, and 3,000 to 150,000. Is better. Below 300,000, good developability is obtained. In the dispersion of the pigment or carbon black, a dispersant is usually used. As the dispersant, a dispersant as described below can be used in addition to the original coating resin. These dispersants may be used alone or in combination of plural kinds. Adsorption of the resin on the surface of the carbon black by the dispersion treatment makes the particle size of the carbon black particles destroyed and finer at the same time. In the present invention, in terms of the form of the carbon black covered by the resin, powders such as a paste, a granule, a paste, and a sheet are exemplified. The average particle diameter of the carbon black covered with the resin is preferably in the range of 0.003 to 0.5 // m, and more preferably in the range of 0.005 to 0.3 // m. Therefore, the various effects of the present invention, especially the developability and screen reproduction Sex becomes more excellent. As for the dispersant, Anti-Terra-U, Disperbyk-160, 161, 162, 163 manufactured by BYK company; Solspers 20000, 24000GR, 26000, 2 8 000 manufactured by ZENECA company; DA-703-50 manufactured by Nanben Chemical Co., Ltd. , NDC-8194 L, NDC-8 20 3 L, NDC-8257L, KS-860; leveling agents L-18, L1820, L-95, L-100 made by Kao Corporation; VP5000 made by Benben Coatings; E5 7 03P manufactured by Goodrich Co., Ltd .; VAGH manufactured by United Carbon Corporation; UR8200 manufactured by Toyo Textile Co., Ltd .; MR 1 1 3 manufactured by King of Japan Co., Ltd. and other recognized dispersion resins. In addition, phthalocyanin derivatives (commercial product EFKA-745 (manufactured by Morishita Industrial Co., Ltd.)); organosilicon polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); (meth) acrylic (co) polymer Polyuron No. 75, No. 90, No. 95 (manufactured by Kyoeisha Oil Chemical Industry Co., Ltd.), W001 (manufactured by Yusho), etc .; cationic surfactants; polyoxygen> 24-1245164 ethylene dodecyl Ether, polyoxyethylene octadecyl ether, polyoxyethylene octadecenyl ether, polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polydi-dodecanoate, polydi- Non-ionic surfactants such as ethylene stearate, sorbitol fatty acid esters, etc .; Yefu despectrum EF30 1, EF3 0 3, EF3 5 2 (made by Shin Akita Kasei); Magnesium Falcon F17, F172 , F173 (made by Daiyoshi Ink); Flurot FC430, FC431 (made by Sumitomo 3M), Asahi Kaite AG710, Saffron S382, SC-101, SC-102, SC-103, SC-104, SC- 105, SC-1 068 (made by Asahi Glass) and other fluorine-based surfactants; W004, W005, W017 (made by Yusho) and other anionic surfactants; efkA-46, EFKA-47, EFKA-47EA EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Industries), dispersing additive 6, dispersing additive 8, dispersing additive 15, dispersing additive 9 100 (made by Sonoma Spectrum) And other polymer dispersants; Sole Spas 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 2 8 000, etc. various sol dispersants (manufactured by Geneca Corporation); Adi Kapronik L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P013, F108, L121, P-123 (made by Asahi Denka) and Isoni Special S-20 (Sanyo Kasei). In the present invention, when the colorant is a dye, it is uniformly dissolved in the composition to obtain a photocurable composition. The dye which can be used as the coloring agent constituting the composition of the present invention is not particularly limited 'and it can be used as a recognized dye for a conventional color filter. For example, it can be used as disclosed in JP-A-Sho 64-90403, JP-A-Sho 64-9 1 1 02, JP-A-H 1-9430 1, JP-A-H 6-11614, TD-A 2592207 5 Tiger, U.S.A. Patent No. 4,808,501, U.S. Patent No. 25-1245164 5, 6 6 7, 9 2 0, U.S. Patent No. 5, 05, 5, 00, Japanese Unexamined Patent Publication No. 5 -3 3 3 3 207 Japanese Unexamined Patent Publication No. 6-35 1 8 3, Japanese Unexamined Patent Publication No. 6-5 1 Π 5, Japanese Unexamined Patent Publication No. 6-1 9 4 8 2 8, Japanese Unexamined Patent Publication No. 8-2 1 1 5 9 9 Kaihei 4-24 95 49, Japanese Patent Laid-Open No. 1 0- 1 2 3 3 1 6 Japanese-Launched Japanese Patent Laid-open No. 1 1-3 0 2 2 8 Japanese Patent Laid-Open No. 7-2 8 6 1 0 7 JP 2 0 (Η-4 8 2 3, JP 8-1 5 5 2 2, JP 8-2977 1, JP 8-1 462 1, JP 5/1, JP 1 -34343 7, Japanese Patent Application Laid-Open No. 8-624 1, Japanese Patent Application Laid-Open Publication No. 2002- 1 4220, Japanese Patent Application Laid-Open Publication No. 2002- 1 422, Japanese Patent Application Laid-Open Publication No. 2002- 1 4222, Japanese Patent Application Laid-Open Publication No. 2002- 1 422 JP 3, JP 8-302224, JP 8- Pigments of JP 7 3 7 5 8, JP 8-179120, JP 8-151531, etc. In terms of chemical structure, pyrazole azo-based, aniline azo-based, triphenylmethane-based, anthracene can be used. Quinone-based, anthracene-based, benzylidene-based, oxyalcohol-based, pyrazoline-triazole azo-based, pyridone azo-based, anthocyanin-based, phenanthrene-based, pyrrolopyrrole azomethine Dyes such as base, diphenylphosphonium, phthalocyanine, benzopyran, and indigo. The coloring agent content rate in the photocurable composition of the present invention is 30 to 70% by mass after removing solvent components. The content is preferably 40 to 70% by mass, and more preferably 45 to 70% by mass. Since the content rate is 30% by mass or more, good light shading ratio and high chromaticity color characteristics can be obtained, and since the content rate is 70 (B) Alkali-soluble resin (b) Alkali-soluble resin used in the composition of the present invention includes (i) an acid component monomer and (η) in the following manner. Alkyl polyoxyethylene-26-1245164 represented by formula (1) or (2) Polyoxypropylene (meth) acrylic acid ester,

Ri[(OC2H4)m(OC3H5)n]OCOR2= CHR3 ⑴Ri [(OC2H4) m (OC3H5) n] OCOR2 = CHR3 ⑴

Ri[(OC2H4)m(OC3H6)n]〇C〇C(CH3)二 CHR3 (2) 及（in)具有碳-碳不飽和鍵的選自下述I族群之丙烯酸酯 類、苯乙烯類及乙烯酯類之至少1種化合物所構成之丙烯 酸系共聚物A作爲必要成分。 I族群： (甲基）丙烯酸苄酯、（甲基）丙烯酸苯酯、（甲基）丙烯酸辛 酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸甲基環己酯、（甲 基）丙烯酸己酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸正丁酯、 (甲基）丙烯酸異丁酯、苯乙烯、甲基苯乙烯、二甲基苯乙 烯、甲氧基苯乙烯、環己基苯乙烯、乙酸乙烯酯、丙酸乙 烯酯 上述通式（1)及（2)中，R!表示1〜20碳數之直鏈或分枝烷 基，而以2〜10碳數爲佳，以2〜8碳數爲較佳，以2〜6碳數 爲更佳。R2表不氣原子或甲基，R3表不氫原子、甲基或乙 基。 m及η係個別爲2〜20之整數，而以2〜15之整數爲佳， 以2〜1 0之整數爲更佳。m及η小則因作爲本發明光硬化性 組成物之塗佈液之液體物性或流動性之觀點而有塗佈適合 性降低之情況，過大則變得容易溶解於顯像液中，仍有顯 像適合性降低之情況。 Ε〇與ΡΟ之比例m/n爲30/70〜80/20,而以40/60〜70/30 爲佳，以45/55〜65/35爲較佳，以50/50〜60/40爲更佳。該 比例過小則有塗佈適合性降低之傾向，又，過大則有顯像 -27- 1245164 適合性降低之傾向。 〇C3H6之丙烯鏈爲可爲直鏈（正丙烯），亦可爲分枝（異 丙烯）。又，上述通式（1)及通式（2)中，對於氧化乙烯基（〇C2H4) 及氧化丙烯基（〇C3H6)之鍵結順序並無限制，雖未限制上述 表記，但考慮到顯示特性，則以從氧化丙烯鏈之外側配置 氧化乙烯鏈爲佳。 還有，在針孔凹形斑之面上，即使配置任何環氧烷基 於外側，該效果亦不變。 用於本發明組成物之鹼可溶性樹脂之丙烯酸系共聚物 A中之（i)酸成分單體方面，係以順式丁烯二酸酐（MAA)、丙 烯酸（AA)、甲基丙烯酸（MA)及富馬酸（FA)等爲佳，而以丙 烯酸（AA)及甲基丙烯酸（MA)爲特佳。又，（iii)具有碳-碳不 飽和鍵之丙烯酸酯類、苯乙烯類及乙烯酯類方面，係以（甲 基）丙烯酸苄酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸異丁 酯等之（甲基）丙烯酸酯類、苯乙烯、甲基苯乙烯等之苯乙 烯類爲佳。 前述丙烯酸系共聚物A中，（i)酸成分單體、（ii)烷基聚 氧化乙烯•聚氧化丙烯（甲基）丙烯酸酯、及（Hi)特定之丙烯 酸酯類、苯乙烯類及/或乙烯酯類之組成質量比係以 10〜25/5〜25/50〜85爲佳，以15〜2 0/5〜20/60〜80爲較佳。又， 丙烯酸系共聚物之以GPC所得之聚苯乙烯換算質量平均分 子量（Mw)方面係以3,000〜50,000爲佳，以5,000〜3 0,000爲 較佳。 用於本發明組成物之鹼可溶性樹脂中，（i)酸成分單體 之組成比未滿足上述範圍，則有鹼可溶性降低之傾向，又 -28- 1245164 超過上述範圍則有對於溶劑之溶解性降低之傾向。又，（1 υ 烷基聚氧化乙烯•聚氧化丙烯（甲基）丙烯酸酯之組成質量 比未滿上述範圍，則變成容易在形成於濾色片層上之罩面 層（平坦化層）上產生針孔凹形斑，又，有顯像寬容度或顯 像界限降低之傾向。又，亦有塗佈適合性或著色劑之分散 性降低之傾向。再者，（ιη)選自前述I族群之特定丙烯酸酯 類、苯乙烯類及/或乙烯酯類之組成質量比未滿足上述範 圍，則有著色劑之分散安定性或對於組成物中之溶解性降 低之傾向，又超出上述範圍，則有塗佈膜之鹼性顯像適合 性降低之傾向。 在本發明組成物中，除了作爲鹼可溶性樹脂之上述丙烯 酸系共聚物Α之外，亦可進一步含有其他鹼可溶性樹脂（丙 烯酸系共聚物B)。可含有之鹼可溶性樹脂方面，係以爲直 線狀有機高分子量聚合物、可溶於有機溶劑、可藉由弱鹼 性水溶液顯像者爲佳。 該等直線狀有機高分子量聚合物方面，有於側鏈具有羧 酸之聚合物，如記載於例如特開昭5 9-446 1 5號、特公昭 5 4 -3 4 3 27號、特公昭5 8 - 1 25 7 7號、特公昭54_ 2 5 9 5 7號、特 開昭5 9 - 5 3 8 3 6號、特開昭5 9 -7 1 04 8號各公報之甲基丙烯酸 共聚物、丙烯酸共聚物、衣康酸共聚物、丁烯酸共聚物、 順式丁烯二酸共聚物、部分酯化順式丁烯二酸共聚物等， 又有同樣地於側鏈具有羧酸之酸性纖維素衍生體。其他方 面，加成酸酐於具有羥基之聚合物等亦爲有用。 該等之中特別以（甲基）丙烯酸苄酯/(甲基）丙烯酸共聚 物、或（甲基）丙烯酸苄酯/(甲基）丙烯酸共聚物/其他聚合物 -29- 1245164 之多元共聚物爲佳。其他方面，水溶性聚合物方面以甲基 丙稀酸-2-羥基乙酯、聚乙烯毗咯酮或聚氧化乙烯、聚乙烯 醇等亦爲有用。又爲了提昇硬化皮膜之強度，亦可含有醇 可溶性耐綸或2,2-雙（4-羥基苯基）丙烷與環氧氯丙烷等之 聚醚等。 以上之丙烯酸系共聚物A以外之丙烯酸系共聚物B方 面’較佳者有例如（甲基）丙烯酸苄酯/(甲基）丙烯酸共聚 物 '或（甲基）丙烯酸苄酯/(甲基）丙烯酸共聚物/其他聚合物 之多元共聚物、記載於特開平7 - 1 4 0 6 5 4號公報之（甲基）丙 嫌酸-2 -羥基丙酯/聚苯乙烯巨大分子/甲基丙烯酸苄酯/甲 基丙燒酸共聚物、丙烯酸-2-羥基-3-苯氧基丙酯/聚甲基丙 稀酸甲酯巨大分子/甲基丙烯酸苄酯/甲基丙烯酸共聚物、甲 基丙嫌酸-2-羥基乙酯/聚苯乙烯巨大分子/甲基丙烯酸甲酯 /甲基丙烯酸共聚物、甲基丙烯酸-2-羥基乙酯/聚苯乙烯巨 大分子/甲基丙烯酸苄酯/甲基丙烯酸共聚物等。藉由倂用該 丙_酸系共聚物B與丙烯酸系共聚物 A ’可進一步改良本發明之光硬化性組成物之顯像特性。 在倂用丙烯酸系共聚物A與丙烯酸系共聚物b作爲鹼 可溶性樹脂之情況下，該使用比例方面，以質量比爲8 〇 : 2〇〜40 ·· 60 ’ 而以 75 : 25 〜45 : 5 5 爲佳，以 7〇 : 3〇〜5〇 : 5〇 爲更佳。丙烯酸系共聚物B之使用比例過大則在針孔凹形 斑面上有產生問題之傾向。 本發明之光硬化性組成物中，亦可倂用前述丙烯酸系共 #物A及前述丙烯酸系共聚物b以外之樹脂，該情況下該 樹脂之含有率爲鹼可溶性樹脂全體之2 〇質量％以下，而以 -30- 1245164 1 〇質量％以下爲佳。 (c)感光性聚合成分 其次，針對本發明光硬化性組成物中所使用之感光性聚 合成分來說明。 上述感光性聚合成分方面，以具有至少1個可加成聚合 之乙烯基、具有於常壓下具有1 00 °c以上沸點之乙烯性不飽 和基之化合物爲佳，特別以4官能基以上之丙烯酸酯化合 物爲佳。 具有上述至少1個可加成聚合之乙烯性不飽和基、於常 φ 壓下沸點爲1 00°c以上之化合物方面，可舉出於聚乙二醇單 (甲基）丙烯酸酯、聚丙二醇單（甲基）丙烯酸酯、（甲基）丙烯 酸苯氧基乙酯等單官能基之丙烯酸酯或甲基丙烯酸酯；聚 乙二醇二（甲基）丙烯酸酯、三甲氧基乙烷三（甲基）丙烯酸 酯、季戊二醇二（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸 酯、季戊四醇四（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯 酸酯、己二醇（甲基）丙烯酸酯、三甲氧基丙烷三（丙烯腈氧 丙基）酯、三甲氧基丙烷三（丙烯腈氧乙基）異氰酸酯、甘油 I 酸或二甲氧基乙垸等多官能基醇上加成氧化乙儲或氧化丙 烯後（甲基）丙烯酸酯化者、季戊四醇或二季戊四醇之聚（甲 基）丙烯酸酯化者、如記載於特公昭4 8 - 4 1 7 0 8號公報、特公 昭5 0-6034號公報、特開昭5 1 - 3 7 1 93號公報之丙烯酸胺甲 酸乙酯類、記載於特開昭4 8 - 6 4 1 8 3號公報、特公昭4 9 - 4 3 1 9 1 _ 號公報、特公昭5 2- 3 0490號公報之聚酯丙烯酸酯類、爲環 氧樹脂與（甲基）丙烯酸之反應生成物之環氧化丙烯酸酯類 -等多官能基之丙烯酸酯或甲基丙烯酸酯。再者，亦可使用 -31 - 1245164 於日本接著協會誌VOl·20、NQ.7、第 300〜 3 0 8 頁介紹作爲 光硬化性單體及寡聚物者。 又，於上述多官能醇加成氧化乙烯或氧化丙烯後之（甲 基）丙烯酸酯化之化合物，與該具體實例同時記載於特開平 10-62986號公報作爲通式（1)及（2)，亦可使用該等作爲感光 性聚合成分。 特別地，以二季戊四醇五（甲基）丙烯酸酯 '二季戊四醇 六（甲基）丙烯酸酯及該等之丙烯醯基介在乙二醇、丙二醇 之殘餘官能基之構造爲佳。亦可使用該等之寡聚物型式。 該等之感光性聚合成分係可單獨1種或組合2種以上來使 用。 該等感光性聚合成分之使用量係相對於1 00份本發明之 光硬化性組成物之全部固體成分，以20〜200質量％爲佳， 以50〜120質量％爲較佳。感光性聚合成分之使用量較上述 範圍過少、或過多則由於硬化變得不充分而不佳。 (d)光聚合起始劑 光聚合起始劑方面，可舉出有鹵化甲基噚二唑或鹵化甲 基-s-三阱等之活性鹵素化合物、3-芳基取代香豆滿化合 物、至少1種之洛芬鹼二聚物等。 鹵化甲基氧二唑或鹵化甲基-s -三阱等之活性鹵素化合 物之中，鹵化甲基氧二唑方面，可舉出記載於特公昭 56-6096號公報之以下述通式IV所示之2-鹵化甲基-5-乙烯 基-1，3，4 -氧二唑化合物。Ri [(OC2H4) m (OC3H6) n] 〇C〇C (CH3) DiCHR3 (2) and (in) Acrylic esters, styrenes, and An acrylic copolymer A composed of at least one compound of vinyl esters is an essential component. Group I: Benzyl (meth) acrylate, phenyl (meth) acrylate, octyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, (meth) ) Hexyl acrylate, amyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, styrene, methylstyrene, dimethylstyrene, methoxystyrene , Cyclohexylstyrene, vinyl acetate, vinyl propionate In the above general formulae (1) and (2), R! Represents a linear or branched alkyl group having 1 to 20 carbon numbers, and 2 to 10 carbon numbers Preferably, 2 to 8 carbons are more preferred, and 2 to 6 carbons are more preferred. R2 represents a gas atom or a methyl group, and R3 represents a hydrogen atom, a methyl group, or an ethyl group. m and η are each an integer of 2 to 20, preferably an integer of 2 to 15 and more preferably an integer of 2 to 10. If m and η are small, the coating suitability may be reduced from the viewpoint of the liquid physical properties or fluidity of the coating liquid of the photocurable composition of the present invention. If the m and η are too large, the coating suitability may be easily dissolved in the developing solution. Cases where imaging suitability is reduced. The ratio m / n of 〇 and ΡΟ is 30/70 ~ 80/20, preferably 40/60 ~ 70/30, more preferably 45/55 ~ 65/35, and 50/50 ~ 60/40 For the better. If the ratio is too small, the coating suitability tends to decrease, and if it is too large, the developability tends to decrease -27-1245164. The propylene chain of 〇3H6 can be straight chain (n-propylene) or branched (isopropylene). In addition, in the general formulae (1) and (2), there is no limitation on the bonding order of the oxyethylene group (〇C2H4) and the propylene oxide group (〇C3H6). For characteristics, it is preferable to arrange an ethylene oxide chain from the outside of the propylene oxide chain. In addition, on the surface of the pinhole concave spot, even if any epoxy alkyl group is arranged on the outside, the effect remains unchanged. In the (i) acid component monomer in the acrylic copolymer A of the alkali-soluble resin used in the composition of the present invention, cis-butadiene anhydride (MAA), acrylic acid (AA), and methacrylic acid (MA) are used. And fumaric acid (FA), etc., and acrylic acid (AA) and methacrylic acid (MA) are particularly preferred. In addition, (iii) acrylates, styrenes, and vinyl esters having carbon-carbon unsaturated bonds include benzyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. (Meth) acrylates such as isobutyl ester, and styrenes such as styrene and methylstyrene are preferred. In the above-mentioned acrylic copolymer A, (i) an acid component monomer, (ii) an alkyl polyoxyethylene / polyoxypropylene (meth) acrylate, and (Hi) specific acrylates, styrenes, and / Or the composition and mass ratio of vinyl esters is preferably 10 ~ 25/5 ~ 25/50 ~ 85, and more preferably 15 ~ 2 0/5 ~ 20/60 ~ 80. The polystyrene-equivalent mass average molecular weight (Mw) of the acrylic copolymer based on GPC is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. In the alkali-soluble resin used in the composition of the present invention, (i) the composition ratio of the monomers of the acid component does not satisfy the above range, the alkali solubility tends to decrease, and -28-1245164 exceeds the above range, it has solubility in solvents Declining tendency. In addition, if the composition-to-mass ratio of (1 υ alkyl polyethylene oxide • polyoxypropylene (meth) acrylate) is less than the above range, it becomes easy to form on the cover layer (planarization layer) formed on the color filter layer. Pinhole concave spots occur, and there is a tendency that the development latitude or the development limit is reduced. Also, there is a tendency that the coating suitability or the dispersibility of the colorant is reduced. Furthermore, (ιη) is selected from the aforementioned I The composition-to-mass ratio of specific acrylates, styrenics, and / or vinyl esters of the group does not satisfy the above range, the dispersion stability of the colorant or the tendency to reduce the solubility in the composition tends to exceed the above range, In the composition of the present invention, in addition to the above-mentioned acrylic copolymer A, which is an alkali-soluble resin, other alkali-soluble resins (acrylic copolymers) may be further contained in the composition of the present invention. B). The alkali-soluble resin that can be contained is preferably a linear organic high-molecular-weight polymer, which is soluble in organic solvents and can be developed by a weakly alkaline aqueous solution. As for organic high molecular weight polymers, there are polymers having a carboxylic acid in a side chain, as described in, for example, Japanese Patent Application Laid-Open No. 5 9-446 1 No. 5, Japanese Patent No. 5 4 -3 4 3 27, Japanese Patent No. 5 8-1 25 7 7, JP 54_ 2 5 9 5 7, JP 5 9-5 3 8 3 6, JP 5 9 -7 1 04 8, methacrylic acid copolymers and acrylic acid copolymers Polymers, itaconic acid copolymers, butadiene acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like, and acidic cellulose having a carboxylic acid in the side chain similarly Derivatives. In other respects, addition of anhydrides to polymers with hydroxyl groups is also useful. Among them, benzyl (meth) acrylate / (meth) acrylic copolymer or benzyl (meth) acrylate is particularly useful. / (Meth) acrylic copolymer / other polymers-29-1245164 is a multi-component copolymer. In other aspects, water-soluble polymers are methyl 2-hydroxyethyl 2-hydroxyethyl, polyvinylpyrrolidone or Polyethylene oxide, polyvinyl alcohol, etc. are also useful. In order to improve the strength of the hardened film, it may also contain alcohol-soluble nylon or 2,2 -Polyethers such as bis (4-hydroxyphenyl) propane and epichlorohydrin, etc. As for the acrylic copolymer B other than the acrylic copolymer A described above, preferred examples include benzyl (meth) acrylate / (Meth) acrylic acid copolymer 'or benzyl (meth) acrylic acid / (meth) acrylic acid copolymer / multipolymers of other polymers are described in Japanese Unexamined Patent Publication No. 7-1 4 0 6 5 4 (A Based) Propanoic acid-2-hydroxypropyl ester / polystyrene macromolecule / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethylpropane Macromolecules of dilute acid / benzyl methacrylate / methacrylic acid copolymer, methylpropionic acid 2-hydroxyethyl ester / polystyrene macromolecules / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl acrylate / polystyrene macromolecule / benzyl methacrylate / methacrylic acid copolymer and the like. By using the acrylic acid copolymer B and the acrylic copolymer A ', the development characteristics of the photocurable composition of the present invention can be further improved. In the case where the acrylic copolymer A and the acrylic copolymer b are used as the alkali-soluble resin, in terms of the use ratio, the mass ratio is 80:20 to 40 ... 60 'and 75:25 to 45: 5 5 is more preferable, and 70:30 to 50:50 is more preferable. If the acrylic copolymer B is used in an excessively large proportion, there is a tendency that problems occur on the concave surface of the pinhole. In the photocurable composition of the present invention, a resin other than the acrylic copolymer A and the acrylic copolymer b may be used. In this case, the content of the resin is 20% by mass of the entire alkali-soluble resin. The content is preferably -30-1245164 1 mass% or less. (c) Photosensitive polymer component Next, the photopolymerizable component used in the photocurable composition of the present invention will be described. As for the above-mentioned photosensitive polymerization component, compounds having at least one addition-polymerizable vinyl group and an ethylenically unsaturated group having a boiling point of 100 ° C or higher under normal pressure are preferred, and a compound having 4 or more functional groups is particularly preferred. Acrylate compounds are preferred. Examples of compounds having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C or more at a constant φ pressure include polyethylene glycol mono (meth) acrylate and polypropylene glycol Monofunctional (meth) acrylate, phenoxyethyl (meth) acrylate, and other monofunctional acrylates or methacrylates; polyethylene glycol di (meth) acrylate, trimethoxyethane tri ( (Meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol ( Polyfunctional alcohols such as meth) acrylates, trimethoxypropane tris (acrylonitrileoxypropyl) esters, trimethoxypropane tris (acrylonitrileoxyethyl) isocyanates, glycerol I acid or dimethoxyacetamidine (Meth) acrylic esters after addition of ethylene oxide or propylene oxide, poly (meth) acrylates of pentaerythritol or dipentaerythritol, as described in Japanese Patent Publication No. 4 8-4 1 7 0 8 Ko Sho 5 0-6034, JP-A The urethane acrylates of Sho 5 1-3 7 1 93 are described in JP 4 8-6 4 1 8 3, Sho 4 9-4 3 1 9 1 _ and Sho 4 Polyester acrylates of No. 5 2- 3 0490, epoxidized acrylates which are reaction products of epoxy resin and (meth) acrylic acid-polyfunctional acrylates or methacrylates. In addition, you can use -31-1245164 as the photo-curable monomer and oligomer in Japan Adhesive Association Vol. 20, NQ.7, pages 300 ~ 308. The (meth) acrylic acid-esterified compound after addition of the above-mentioned polyfunctional alcohol to ethylene oxide or propylene oxide is described in Japanese Patent Application Laid-Open No. 10-62986 together with the specific examples as the general formulae (1) and (2) These can also be used as a photosensitive polymerization component. In particular, the structure of dipentaerythritol penta (meth) acrylate 'dipentaerythritol hexa (meth) acrylate and the acryl fluorenyl groups interposed between the residual functional groups of ethylene glycol and propylene glycol is preferred. These oligomer types can also be used. These photosensitive polymerization components can be used alone or in combination of two or more. The use amount of these photosensitive polymerization components is preferably 20 to 200% by mass, and more preferably 50 to 120% by mass based on 100 parts of the total solid content of the photocurable composition of the present invention. When the amount of the photosensitive polymerization component used is too small or too large, the curing becomes insufficient due to insufficient curing. (d) Photopolymerization initiators In terms of photopolymerization initiators, active halogen compounds such as halogenated methylimidazole or halogenated methyl-s-triple, 3-aryl-substituted coumarin compounds, At least one kind of diphenylated base dimer and the like. Among the active halogen compounds such as a halogenated methyloxadiazole or a halogenated methyl-s-triple, examples of the halogenated methyloxadiazole are listed in Japanese Patent Publication No. 56-6096 and represented by the following general formula IV: Shown is a 2-halogenated methyl-5-vinyl-1,3,4-oxadiazole compound.

通式IV -32- 1245164Formula IV -32- 1245164

N— NN— N

W—CH=(p—c c—C_Y I 〇i X H3.n 通式IV中： w表示已取代或未取代之芳基、X表示氫原子、烷基或 芳基。 Y表示氟原子、氯原子或溴原子。 η表示1〜3之整數。 通式IV之具體化合物方面，舉出有2-三氯甲基-5-苯乙 烯基-1，3,4-曙二唑、2-三氯甲基- 5-(對氰基苯乙烯基）-1，3，4-曙二唑、2-三氯甲基-5-(對甲氧基苯乙烯基）-1,3,4-噚二唑 等。 鹵化甲基-s -三畊系化合物方面，舉出有記載於特公昭 59-1281號公報之以下述通式V所示之乙烯基-鹵化甲基- s-三阱化合物、記載於特公昭5 3 - 1 3 3 4 2 8號公報之通式VI所 示之2-(萘-1-醯基）-4,6-雙鹵化甲基-s-三阱化合物及以下述 通式VII所示之4-(對胺苯基）-2,6-二鹵化甲基三阱化合 物。W—CH = (p—cc—C_Y I 〇i X H3.n In the general formula IV: w represents a substituted or unsubstituted aryl group, X represents a hydrogen atom, an alkyl group or an aryl group. Y represents a fluorine atom, chlorine Atom or bromine atom. Η represents an integer of 1 to 3. Specific examples of the compound of the general formula IV include 2-trichloromethyl-5-styryl-1,3,4-aradiazole and 2-triazol. Chloromethyl- 5- (p-cyanostyryl) -1,3,4-eostilazol, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4- Obadiazol, etc. As regards the halogenated methyl-s-tricotyl compounds, vinyl-halogenated methyl-s-triple compounds described in Japanese Patent Publication No. 59-1281 and represented by the following general formula V are listed. 2. The 2- (naphthalene-1-fluorenyl) -4,6-dihalogenated methyl-s-triple compound shown in the general formula VI of JP 5 3-1 3 3 4 2 8 and the following The 4- (p-aminophenyl) -2,6-dihalogenated methyl triple well compound represented by the general formula VII is described.

通式V -33- 1245164 3 QcFormula V -33- 1245164 3 Qc

\ / CNN ci p\ / CNN ci p

CIN w 1 η c II H(c 通式V中： Q表示溴或氯。 P表示- CQ3(Q係與上述同義）、-NH2、-NHR、-N(R)2、或 _NR(其中，R表示苯基或烷基）。 η表示0〜3之整數。 W表示已取代亦可之芳香族基、已取代亦可之雜環基、 或以下述通式VA表示之一價基。CIN w 1 η c II H (c in the general formula V: Q represents bromine or chlorine. P represents-CQ3 (Q is synonymous with the above), -NH2, -NHR, -N (R) 2, or _NR (where (R represents a phenyl group or an alkyl group). Η represents an integer of 0 to 3. W represents a substituted aromatic group, a substituted or heterocyclic group, or a monovalent group represented by the following general formula VA.

通式VA /Formula VA /

CH=CCH = C

R CHnX3_nR CHnX3_n

通式VA中，Z係-〇-或-S-，R係與上述同義 通式VIIn the general formula VA, Z is -0- or -S-, and R is synonymous with the above.

N一 C 奢f \\N-C luxury f \\

R· 一 C N \ /R · C N \ /

N=C m CH^ -34- 1245164 通式VI中： X表示溴或氯。 m、η係0〜3之整數。 R’表示以通式VIA所示之官能基。N = C m CH ^ -34-1245164 In the general formula VI: X represents bromine or chlorine. m and η are integers of 0 to 3. R 'represents a functional group represented by the general formula VIA.

通式VIAFormula VIA

RiRi

r2 (上述通式VIA中，Ri表示氫原子或〇Rc(Rc係烷基、環烷 基、傭基、方基）’ R2表不氯、漠、院基、傭基、方基、或 烷氧基。）r2 (in the above general formula VIA, Ri represents a hydrogen atom or 〇Rc (Rc-based alkyl, cycloalkyl, carbyl, or square group) ' Oxy.)

通式VIIFormula VII

Rs 通式VII中： R i、R2係相同或不同、表示氫原子、烷基、取代烷基、 芳基、取代芳基、以下述通式VIIA或VIIB所示之官能基。 R3、R4係相同或不同、表示氫原子、鹵素原子、烷基、 -35- 1245164 烷氧基。 x、Y係相同或亇 主一 a寸、自 Λ不同、表不《I或溴。Rs in the general formula VII: R i and R 2 are the same or different and represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, and a functional group represented by the following general formula VIIA or VIIB. R3 and R4 are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, and -35-1245164 alkoxy group. x and Y are the same or 亇 main one a inch, different from Λ, it means "I or bromine.

m η # Μ胃或不同、表示0、1或2。 通式VII A 〇m η # Μ stomach or different, meaning 0, 1 or 2. Formula VII A

II R5—c-II R5--c-

通式VIIBFormula VIIB

Re、 ΟRe, Ο

\ II Ν—C — 通式VIIA及VIIB中，r5、r6、R7表示烷基、f _ 収代烷基、 芳基、取代芳基。取代烷基及取代芳基中之取代基範例方 面，舉出有苯基等之芳基、鹵素原子、烷氧基、焼氧基鑛\ II Ν—C — In the general formulas VIIA and VIIB, r5, r6, and R7 represent alkyl groups, f_ substituted alkyl groups, aryl groups, and substituted aryl groups. Examples of the substituted group in the substituted alkyl group and the substituted aryl group include an aryl group such as a phenyl group, a halogen atom, an alkoxy group, and a fluorenite.

基、芳氧基羰基、醯基 '硝基、二烷基胺基、礎基衍生物 等。 通式VII中，R!與R2亦可形成同時由與該等鍵結之氮 原子與非金屬原子所構成之雜環，於該情況下，雜環方面 舉出有示於下述者。Group, aryloxycarbonyl group, fluorenyl'nitro group, dialkylamino group, basic group derivative and the like. In the general formula VII, R! And R2 may form a heterocyclic ring composed of a nitrogen atom and a non-metal atom bonded to these atoms. In this case, the heterocyclic ring is listed below.

(三氯甲基）-6 -對甲氧基苯乙基-s-三畊、2,4 -雙（三氯甲 基）-6-(1-對二甲胺基苯基-1，3 -丁二烯基）-s_三阱、2 -三氯甲 -36- 1245164 基-4-胺基-6-對甲氧基苯乙基-s-三阱等。 通式VI之具體範例方面，舉出有2-(萘-1-醯基）-4,6-雙-三氯甲基-s-三畊、2-(4-甲氧基萘醯基）-4,6-雙-三氯甲基 -s-三阱、2-(4 -乙氧基萘-1-醯基）-4,6 -雙-三氯甲基-s-三畊、 2-(4-丁氧基萘-1-醯基）-4,6-雙-三氯甲基-s-三阱、2-[4-(2· 甲氧基乙基）萘-l-醯基l·4,6-雙-三氯甲基-s-三阱、2-[4-(2-乙氧基乙基）萘-1-醯基]-4,6-雙-三氯甲基-8-三阱、2-[4-(2-丁氧基乙基）萘-1-醯基：Μ ,6-雙-三氯甲基-s-三阱、2-(2-甲氧 基萘-1-醯基）-4,6 -雙-三氯甲基-s-三阱、2-(6 -甲氧基-5-甲基 萘-2-醯基）-4,6-雙-三氯甲基-s-三畊、2-(6-甲氧基萘-2-醯 基）-4,6-雙-三氯甲基-s-三畊、2-(5-甲氧基萘-1-醯基）-4,6-雙-三氯甲基-s-三哄、2-(4,7-二甲氧基萘-1-醯基）-4,6-雙-三氯甲基-s-三畊、2-(6-乙氧基萘-2-醯基）-4,6-雙-三氯甲基 -s-三畊、2-(4,5-二甲氧基萘-1-醯基）-4,6-雙-三氯甲基-s-三 畊等。 通式VII之具體例方面，舉出有4-[對-N，N-二（乙氧羧甲 基）胺基苯基卜2,6-二（三氯甲基）-s-三畊、4-[鄰甲基-對- N，N-二（乙氧羧甲基）胺基苯基]-2,6-二（三氯甲基）-s-三畊、4-[對 -Ν,Ν-二（氯乙基）胺基苯基]-2,6-二（三氯甲基）-s-三畊、4-[鄰 甲基-對- N，N-二（氯乙基）胺基苯基]-2,6-二（三氯甲基）-s·三 畊、4-(對氯乙基胺基苯基）-2,6-二（三氯甲基）-s-三畊、 4-(對-N-乙氧羧甲基胺基苯基）-2,6-二（三氯甲基）-s-三畊、 4-[對- Ν,Ν-二（苯基）胺基苯基]•2,6-二（三氯甲基）4-三阱、 4-(對-Ν-氯乙基羧基胺基苯基）-2,6-二（三氯甲基）-s-三畊、 4-[對-N-(對甲氧苯基）羧基胺基苯基]-2,6-二（三氯甲基）-s- -37- 1245164 三阱、4-[間-N，N-二（乙氧羧甲基）胺基苯基]-2,6-二（三氯甲 基）-s ·三畊、4 -[間溴-對-N , N -二（乙氧羧甲基）胺基苯基]-2，6 -二（三氯甲基）-s-三阱、4-[間氯-對- N，N-二（乙氧羧甲基）胺基 苯基卜2,6-二（三氯甲基）-s-三畊、4-[間氟-對- N，N-二（乙氧羧 甲基）胺基苯基；1-2,6-二（三氯甲基）_s-三畊、4-[鄰溴-對- N，N-二（乙氧羧甲基）胺基苯基]-2,6-二（三氯甲基）-s-三哄、4-[鄰 氯-對- N，N-二（乙氧羧甲基）胺基苯基]-2,6-二（三氯甲基）-s-三哄、4-[鄰氟-對- N，N-二（乙氧羧甲基）胺基苯基]-2,6-二（三 氯甲基）-s-三畊、4-[鄰溴-對- N，N-二（氯乙基）胺基苯基]-2,6-二（三氯甲基）-s-三哄、4-[鄰氯-對-N，N-二（氯乙基）胺基苯 基]·2,6-二（三氯甲基）-s-三阱、4-[鄰氟-對-N，N-二（氯乙基） 胺基苯基]-2,6-二（三氯甲基）-s-三畊、4-[間溴-對- N，N-二（氯 乙基）胺基苯基]-2,6-二（三氯甲基）-s-三畊、4-[間氯-對- Ν,Ν-二（氯乙基）胺基苯基]-2,6-二（三氯甲基）-s-三畊、4-[間氟-對- Ν,Ν-二（氯乙基）胺基苯基]-2,6-二（三氯甲基）-s-三阱、 4-(間溴-對乙氧基羧甲基胺基苯基）-2,6-二（三氯甲 基）-s-三畊、4_(間氯-對-N-乙氧基羧甲基胺基苯基）-2,6-二 (三氯甲基）-s-三阱、4-(間鄰氟-對-N-乙氧基羧甲基胺基苯 基）-2,6-二（三氯甲基）-s-三阱、4-(鄰溴-對-N-乙氧基羧甲基 胺基苯基）-2,6-二（三氯甲基）-s-三畊、4-(鄰氯-對-N-乙氧基 羧甲基胺基苯基）-2,6-二（三氯甲基）-s-三阱、4-(鄰氟-對-N-乙氧基羧甲基胺基苯基）-2,6-二（三氯甲基）-s-三阱、4-(間溴 -對-N-氯乙基胺基苯基）-2,6-二（三氯甲基）-s-三阱、4-(間氯 -對-N-氯乙基胺基苯基）-2,6-二（三氯甲基）-s-三阱、4-(間氟 -對-N-氯乙基胺基苯基）-2,6-二（三氯甲基）-s-三阱、4-(鄰溴 -38- 1245164 -對-N-氯乙基胺基苯基）-2,6 -二（三氯甲基）-s -三阱、4-(鄰氯 -對氯乙基胺基苯基）-2,6-二（三氯甲基）-s-三畊、4-(鄰氟 -對-N-氯乙基胺基苯基）-2,6-二（三氯甲基）-s-三畊、2,4-雙 (三氯甲基）-6-[3-溴-[Ν,Ν-雙（乙氧基羧甲基）胺基]苯 基]-1，3,5 -三阱等 該等起始劑中係可倂用以下之增感劑。該具體例方面，舉 出有安息香、安息香甲基醚、安息香、9-苐酮、2-氯-9-莽 酮、2-甲基-9-莽酮、9-蒽酮、2-溴-9-蒽酮、2-乙基-9-蒽酮、 9，10-蒽醌、2 -乙基-9,10-蒽醌、2-第三丁基-9,10蒽醌、2,6-二氯-9，1 0 -蒽醌、卩山酮、2 -甲基Ρ山酮、2 -甲氧基卩山酮、硫代 口山酮、二苯乙二酮、二苄叉丙酮、對（二甲胺基）苯基苯乙 烯基酮、對（二甲胺基）苯基對甲基苯乙烯基酮、二苯甲酮、 對（二甲胺基）二苯甲酮（或米其勒酮）、對（二乙胺基）二苯甲 酮、苯并蒽酮、7-{L-4-氯-6-(二乙胺基）-s-三阱（2)，1-胺 基卜3-苯基薰草素等或特公昭51-48516號公報記載之苯并 噻唑系化合物。 又，上述3-芳基取代薰草素化合物係以利如下述通式 VIII所示之化合物。(Trichloromethyl) -6-p-methoxyphenethyl-s-trigen, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3 -Butadienyl) -s_triple, 2-trichloromethyl-36-1245164-based-4-amino-6-p-methoxyphenethyl-s-triple, and the like. Specific examples of the general formula VI include 2- (naphthalene-1-fluorenyl) -4,6-bis-trichloromethyl-s-trigon, 2- (4-methoxynaphthalenyl) -4,6-bis-trichloromethyl-s-triple, 2- (4-ethoxynaphthalene-1-fluorenyl) -4,6-bis-trichloromethyl-s-trigon, 2 -(4-butoxynaphthalene-1-fluorenyl) -4,6-bis-trichloromethyl-s-triple, 2- [4- (2 · methoxyethyl) naphthalene-l-fluorene 1,2,6-bis-trichloromethyl-s-triple, 2- [4- (2-ethoxyethyl) naphthalene-1-fluorenyl] -4,6-bis-trichloromethyl Base-8-triple, 2- [4- (2-butoxyethyl) naphthalene-1-fluorenyl: M, 6-bis-trichloromethyl-s-triple, 2- (2-formyl Oxynaphthalene-1-fluorenyl) -4,6 -bis-trichloromethyl-s-triple, 2- (6-methoxy-5-methylnaphthalene-2-fluorenyl) -4,6 -Bis-trichloromethyl-s-trigon, 2- (6-methoxynaphthalene-2-fluorenyl) -4,6-bis-trichloromethyl-s-trigon, 2- (5- Methoxynaphthalene-1-fluorenyl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxynaphthalene-1-fluorenyl) -4,6- Bis-trichloromethyl-s-trigon, 2- (6-ethoxynaphthalene-2-fluorenyl) -4,6-bis-trichloromethyl-s-trigon, 2- (4,5 -Dimethoxynaphthalene-1-fluorenyl) -4,6-bis-trichloromethyl-s-trigonol. Specific examples of the general formula VII include 4- [p-N, N-bis (ethoxycarboxymethyl) aminophenylphenyl 2,6-bis (trichloromethyl) -s-three farming, 4- [o-methyl-p-N, N-bis (ethoxycarboxymethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-three plough, 4- [p-N , N-bis (chloroethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-tri-cult, 4- [o-methyl-p-N, N-di (chloroethyl) ) Aminophenyl] -2,6-bis (trichloromethyl) -s · Sangen, 4- (p-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s -Sangen, 4- (p-N-ethoxycarboxymethylaminophenyl) -2,6-bis (trichloromethyl) -s-trigen, 4- [p-N, N-di ( Phenyl) aminophenyl] • 2,6-bis (trichloromethyl) 4-triple, 4- (p-N-chloroethylcarboxyaminoaminophenyl) -2,6-bis (trichloro Methyl) -s-Sangen, 4- [p-N- (p-methoxyphenyl) carboxyaminophenyl] -2,6-bis (trichloromethyl) -s- -37-1245164 triple well , 4- [m-N, N-bis (ethoxycarboxymethyl) aminophenyl] -2,6-bis (trichloromethyl) -s · Sangen, 4-[m-bromo-p-N , N -bis (ethoxycarboxymethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-tri , 4- [m-Chloro-p-N, N-bis (ethoxycarboxymethyl) aminophenylb, 2,6-bis (trichloromethyl) -s-three farming, 4- [m-fluoro-p -N, N-bis (ethoxycarboxymethyl) aminophenyl; 1-2,6-bis (trichloromethyl) _s-Sanken, 4- [o-bromo-p-N, N-di ( Ethoxycarboxymethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-triazine, 4- [o-chloro-p-N, N-di (ethoxycarboxymethyl) amine Phenyl] -2,6-bis (trichloromethyl) -s-trioxo, 4- [o-fluoro-p-N, N-bis (ethoxycarboxymethyl) aminophenyl] -2, 6-bis (trichloromethyl) -s-trigon, 4- [o-bromo-p-N, N-di (chloroethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-trio, 4- [o-chloro-p-N, N-di (chloroethyl) aminophenyl] · 2,6-bis (trichloromethyl) -s-triple, 4- [ O-Fluoro-p-N, N-bis (chloroethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-Sanken, 4- [m-Bromo-p-N, N- Bis (chloroethyl) aminophenyl] -2,6-bis (trichloromethyl) -s-trigeno, 4- [m-chloro-p-N, N-bis (chloroethyl) aminobenzene Group] -2,6-bis (trichloromethyl) -s-trigeno, 4- [m-fluoro-p-N, N-di (chloroethyl) aminophenyl] -2, 6-bis (trichloromethyl) -s-triple, 4- (m-bromo-p-ethoxycarboxymethylaminophenyl) -2,6-bis (trichloromethyl) -s-trigon , 4_ (m-chloro-p-N-ethoxycarboxymethylaminophenyl) -2,6-bis (trichloromethyl) -s-triple, 4- (m-o-fluoro-p-N- Ethoxycarboxymethylaminophenyl) -2,6-bis (trichloromethyl) -s-triple, 4- (o-bromo-p-N-ethoxycarboxymethylaminophenyl) -2,6-bis (trichloromethyl) -s-Sanken, 4- (o-chloro-p-N-ethoxycarboxymethylaminophenyl) -2,6-bis (trichloromethyl) ) -S-triple, 4- (o-fluoro-p-N-ethoxycarboxymethylaminophenyl) -2,6-bis (trichloromethyl) -s-triple, 4- (m Bromine-p-N-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s-triple, 4- (m-chloro-p-N-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s-triple, 4- (m-fluoro-p-N-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s -Tritrap, 4- (o-bromo-38-1245164-p-N-chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s -Tritrap, 4- (o-chloro- P-Chloroethylaminophenyl) -2,6-bis (trichloromethyl) -s-tri-cult, 4- (o-fluoro-p-N-chloroethylamino) Phenyl) -2,6-bis (trichloromethyl) -s-trigon, 2,4-bis (trichloromethyl) -6- [3-bromo- [Ν, Ν-bis (ethoxy) Among these initiators such as carboxymethyl) amino] phenyl] -1,3,5-tritrap, the following sensitizers can be used. In this specific example, benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-imidone, 2-methyl-9-imidone, 9-anthrone, 2-bromo- 9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-tert-butyl-9,10 anthraquinone, 2,6 -Dichloro-9,1 0-anthraquinone, ketone ketone, 2-methyl phenyl ketone ketone, 2-methoxy ketone ketone, thioxanthone, diphenylethylene diketone, dibenzylidene acetone, P- (dimethylamino) phenylstyryl ketone, p- (dimethylamino) phenyl-p-methylstyryl ketone, benzophenone, p- (dimethylamino) benzophenone (or rice Its ketone), p- (diethylamino) benzophenone, benzoxanthone, 7- {L-4-chloro-6- (diethylamino) -s-triple (2), 1- Aminobenzo3-phenylhumulin and the like or a benzothiazole-based compound described in Japanese Patent Publication No. 51-48516. The 3-aryl substituted humor compound is a compound represented by the following general formula VIII.

通式VIIIFormula VIII

-39- 1245164 R8表示1〜8碳數之烷基、6〜10碳數之芳基（以氫原子、甲基、 乙基、丙基、丁基爲佳）、R9表示氫原子、1〜8碳數之烷基、 6〜10碳數之芳基、以下述通式VIIIA所示之官能基（以甲 基、乙基、丙基、丁基、以通式VIIIA所示之官能基爲佳， 以通式VIIIA所示之官能基爲特佳）。 R!。、Rn係個別表示氫原子、1〜8碳數之烷基（例如甲基、 乙基、丙基、丁基、辛基）、1〜8碳數之鹵化烷基（例如氯甲 基、氯乙基、三氯甲基等）、1〜8碳數之烷氧基（例如甲氧基、 乙氧基、丁氧基）、已取代亦可之6〜10碳數之芳基（例如苯 基）、胺基、-n(r“）（r17)、鹵素原子（例如氯、溴、氟）。以 氫原子、甲基、乙基、甲氧基、苯基、-N(Rl6)(Rl7)、氯爲 佳。 R12表示已取代亦可之6〜16碳數之芳基（例如苯基、萘 基、甲苯基、茴香素基）。取代基方面舉出有胺基、 -mRMKR!7)、1〜8碳數之烷基（例如甲基、乙基、丙基、丁 基、辛基）、1〜8碳數之鹵化院基（例如氯甲基、氯乙基、三 氯甲基等）、1〜8碳數之烷氧基（例如甲氧基、乙氧基、丁氧 基）、羥基、氰基、鹵素原子（例如氯、溴、氟）。-39- 1245164 R8 represents an alkyl group having 1 to 8 carbon atoms, aryl group having 6 to 10 carbon atoms (preferably a hydrogen atom, methyl, ethyl, propyl, or butyl), R9 represents a hydrogen atom, and 1 to An alkyl group of 8 carbons, an aryl group of 6 to 10 carbons, a functional group represented by the following general formula VIIIA (methyl, ethyl, propyl, butyl, and a functional group represented by the general formula VIIIA are The functional group represented by the general formula VIIIA is particularly preferred). R !. , Rn is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, butyl, octyl), a halogenated alkyl group having 1 to 8 carbon atoms (for example, chloromethyl, chlorine) Ethyl, trichloromethyl, etc.), alkoxy groups (such as methoxy, ethoxy, butoxy) with 1 to 8 carbon atoms, substituted aryl groups (such as benzene with 6 to 10 carbon atoms) Group), amine group, -n (r ") (r17), halogen atom (such as chlorine, bromine, fluorine). With hydrogen atom, methyl, ethyl, methoxy, phenyl, -N (Rl6) ( R17) and chlorine are preferred. R12 represents a substituted aryl group having 6 to 16 carbon atoms (for example, phenyl, naphthyl, tolyl, anisinyl). Examples of the substituent include an amine group, -mRMKR! 7), alkyl groups of 1 to 8 carbons (eg methyl, ethyl, propyl, butyl, octyl), halogenated alkyl groups of 1 to 8 carbons (eg chloromethyl, chloroethyl, trichloro Methyl, etc.), alkoxy (e.g. methoxy, ethoxy, butoxy) with 1 to 8 carbons, hydroxyl, cyano, halogen (e.g. chlorine, bromine, fluorine).

Rl3、Rl4、Rl6、Rl7係相同或不同、個別表示爲氫原子、 1〜8碳數之烷基（例如甲基、乙基、丙基、丁基、辛基^Rl3、 R ! 4、R i 6與R i 7係亦可與互相鍵結之氮原子同時形成雜環（例 如六氫毗D定環、六氫吡畊環、嗎林環、吡唑環、二π坐環、 三唑環、苯并三唑環等）。Rl3, Rl4, Rl6, Rl7 are the same or different, and are individually represented as hydrogen atoms, alkyl groups of 1 to 8 carbons (such as methyl, ethyl, propyl, butyl, octyl ^ Rl3, R! 4, R The i 6 and R i 7 series can also form a heterocyclic ring with the nitrogen atoms bonded to each other (such as a hexahydropyridine ring, a hexahydropyridine ring, a morphine ring, a pyrazole ring, a diπ sitting ring, and a triazole Ring, benzotriazole ring, etc.).

Ri5表示氫原子、1〜8碳數之烷基（例如甲基、乙基、丙 基、丁基、辛基）、1〜8碳數之院氧基（例如甲氧基、乙氧基、 •40- 1245164 丁氧基）、已取代亦可之6〜10碳數之芳基（例如苯基）、胺 基、-N(R16)(R17)、鹵素原子（例如氯、溴、氟）。Zb表示=〇、 =S或以=〇、=S、=C(CN)2爲佳，以二〇爲特佳。Ri5 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, butyl, octyl), and an oxygen group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, • 40-1245164 butoxy), substituted aryl groups (such as phenyl), amines, -N (R16) (R17), halogen atoms (such as chlorine, bromine, fluorine) . Zb represents = 0, = S or preferably = 0, = S, = C (CN) 2, and particularly preferably 20.

Ru、R"係相同或不同、表示氰基、-C〇〇R2。、-CORn。R20、 R21係個別表示1〜8碳數之烷基（例如甲基、乙基、丙基、 丁基、辛基）、1〜8碳數之鹵化烷基（例如氯甲基、氟甲基、 三氯甲基等）、已取代亦可之6〜10碳數之芳基（例如苯基）。 特佳之3-芳基取代薰草素化合物係以通式IX所示之 {(s-三阱-2-醯基）胺基卜3-芳基薰草素化合物類。 馨Ru and R " are the same or different and represent cyano and -CO〇R2. , -CORn. R20 and R21 are alkyl groups of 1 to 8 carbons (eg methyl, ethyl, propyl, butyl, octyl), and halogenated alkyls of 1 to 8 carbon (eg chloromethyl, fluoromethyl) , Trichloromethyl, etc.), substituted aryl groups with 6 to 10 carbon atoms (such as phenyl). Particularly preferred 3-aryl-substituted lavender compounds are {(s-triple-2-fluorenyl) amino-b-aryl lavender compounds represented by the general formula IX. Xin

通式VIIIAFormula VIIIA

RR

R 13R 13

16 C一N〇 、\N C — \ /^C = N16 C-N〇, \ N C — \ / ^ C = N

NN

R 14R 14

通式IXFormula IX

-41 - 1245164 洛芬鹼二聚物表示由2個洛芬鹼殘基所構成之2,4,5-三 苯基咪唑二聚物之意思，該基本構造示於下述。-41-1245164 Luffin base dimer means 2,4,5-triphenylimidazole dimer composed of two loffin base residues. The basic structure is shown below.

其具體例方面，舉出2-(鄰氯苯基）-4,5-二苯基咪_二聚 體、2-(鄰氟苯基）-4,5-二苯基咪唑二聚體、2-(鄰甲氧基苯 基）-4,5-二苯基咪唑二聚體、2-(對甲氧基苯基）-4,5-二苯基 咪唑二聚體、2-(對二甲氧基苯基）-4,5-二苯基咪唑二聚體、 2-(2，4-二甲氧基苯基）-4,5-二苯基咪唑二聚體、2-(對甲基氫 硫基苯基）-4,5-二苯基咪唑二聚體等。 本發明中，亦可使用以上起始劑之外之其他公知者。 例如，舉出有揭示於美國專利第2,3 67,660號說明書之 連位聚酮醇糖醒化合物、揭示於美國專利第2，3 6 7，6 6 1號及 美國專利第2,3 67,670號說明書之α -羧基化合物、揭示於 美國專利第2，4 4 8，8 2 8號說明書之酮醇醚、揭示於美國專利 -42- 1245164 第2，72 2，5 12號說明書之以α -碳氫化合物取代之芳香族醒 醇化合物、揭示於美國專利第3,046，127號及第2,95 1,7 5 8 號說明書之多核醌化合物、美國專利第3,5 49,3 67號說明書 之三烯丙基咪唑二聚物/對胺苯基酮之組合、揭示於特公昭 51-48516號公報之本并噻系化合物/二鹵化甲基三口井 系化合物等。 又，亦可使用旭電化股份有限公司製阿迪卡歐普特馬 -SP-150、151、170、171、Ν-1717、Ν-1414 等作爲聚合起始 劑。 本發明中光聚合起始劑之使用量係光硬化性組成物之 全部固體部分之0.1〜1〇·〇質量％，而以〇·5〜5.0質量％爲佳。 起始劑之使用量較〇· 1質量％少則難以進行聚合，又，超過 10.0質量％則膜強度變弱。 (e)溶劑 於調製本發明之光硬化性組成物時所使用之溶劑方 面，舉出有酯類、例如乙酸乙酯、乙酸正丁酯、乙酸異丁 酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁 酸異丙酯、丁酸乙酯、丁酸丁酯、烷基酯類、乳酸甲酯、 乳酸乙酯、羥乙酸甲酯、羥乙酸乙酯、羥乙酸丁酯、甲氧 基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基 乙酸甲酯、乙氧基乙酸乙酯、3 -羥丙酸甲酯、3 -羥丙酸乙 酯等之3 -羥丙酸甲酯烷基酯類；3 -甲氧基丙酸甲酯、3 -甲 氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-羥丙酸甲酯、2 -羥丙酸乙酯、2 -羥丙酸丙酯、2 -甲氧基丙酸 甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙 -43- 1245164 酸甲醋、2 -乙氧基丙酸乙酯、2 -氧基-2 -甲基丙酸甲酯、2-氧基-2-甲基丙酸乙酯、2 -甲氧基-2-甲基丙酸甲酯、2 -乙氧 基-2 -甲基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙 酉曰、乙醯乙酸甲酯、乙醯乙酸乙酯、2 _氧基丁酸甲酯、2 一 氧基丁酸乙酯等；醚類、例如二乙二醇二甲基醚、四氫呋 喃、乙~醇單甲基醚、乙二醇單乙基醚、甲基溶纖素乙酸 酉曰、乙基溶纖素乙酸酯、二乙二醇單甲基醚、二乙二醇單 乙基_、二乙二醇單丁基醚、丙二醇單甲基醚乙酸酯、丙 一醇乙基醚乙酸酯、丙二醇丙基醚乙酸酯等；酮類、例如 甲基乙基酮、環己酮、2-戊酮、3-戊酮等；芳香族碳氫化 合物類、例如甲苯、二甲苯等。 該等之中，以使用3 -乙氧基丙酸甲酯、3 -乙氧基丙酸乙 酯、乙基溶纖素乙酸酯、乳酸乙酯、二乙二醇二甲基醚、 乙酸丁酯、甲氧基丙酸甲酯、2_戊酮、環己酮、乙基卡 比醇乙酸酯、丁基卡比醇乙酸酯、丙二醇單甲基醚乙酸酯 等爲佳。 該等溶劑係可單獨地使用或亦可組合2種以上來使用。 [Π]其他成分 本發明之光硬化性組成物中，必要時可配合各種添加 物，例如塡充物、上述鹼可溶性樹脂以外之高分子量化合 物、上述以外之界面活性劑、密著促進劑、氧化防止劑、 紫外線吸收劑、凝結防止劑等。 該等添加物之具體例方面，可舉出玻璃、氧化鋁等之塡 充劑；衣康酸共聚物、丁烯酸共聚物、順式丁烯二酸共聚 物、部分酯化順式丁烯二酸共聚物、酸性纖維素衍生物、 • 44- 1245164 加成酸酐於具有羥基之聚合物者、醇可溶性耐綸、由雙酚 A與表氯醇所形成之本氧树脂等之鹼性可溶之樹脂；非離 子系、陽離子系、陰離子系等之界面活性劑、具體來說有 酞青衍生物（市售品EFKA-7 45 (森下產業製））；有機矽氧烷 聚合物KP341(信越化學工業製）、（甲基）丙烯酸系（共）聚合 物聚氟羅No· 75、No. 90、No· 95 (共榮社油脂化學工業製）、 W001(裕商製）等之陽離子系界面活性劑；聚氧化乙烯基十 二烷基醚、聚氧化乙烯基十八烷基醚、聚氧化乙烯基十八 碳烯基醚、聚氧化乙烯基辛苯基醚、聚氧化乙烯基壬苯基 醚、聚氧化乙烯基二十二烷基酯、聚氧化乙烯基二十八烷 基酯、山梨糖脂肪酸酯（BASF公司製）普魯羅尼克L10、 L31、L61、10R5、17R2、25R2、迪特羅尼克 304、70卜 704、 901、904、150R1等之非離子系界面活性劑；W004、W005、 W017(裕商製）等陰離子系界面活性劑；EFKA-46、 EFKA-47、EFKA47EA、EFKA 聚合物- l〇〇、EFKA 聚合物- 400、 EFKA聚合物401、EFKA聚合物450(以上森下產業製）、分 散添加劑6、分散添加劑8、分散添加劑1 5、分散添加劑 9100(三諾普扣製）等聚合物分散劑；膠體分散3000、5000、 9000、 12000、 13240、 13940、 17000、 24000、 26000、 28000 等之各種膠體分散分散劑（界內卡股份有限公司製）；阿迪 卡普耳羅尼克 L31、F38、L42、L44、L61、L64、F68、L72、 P95、F77、P48、F87、P94、L1(H、P103、F108、L121、P-123(旭 電化製）及伊索內特S-20(三洋化成製）；乙烯基三甲氧基矽 烷' 乙烯基三乙氧基矽烷、乙烯基三（2 -甲氧基乙氧基）矽 烷、N-(2-胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、N-(2- -45- 1245164 胺基乙基）-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基 矽烷、3 -縮水甘油氧基丙基三甲氧基矽烷、3 -縮水甘油氧 基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基）乙基三甲氧 基矽烷、3 -氯丙基甲基三甲氧基矽烷、3 -氯丙基三甲氧基 矽烷、3 -甲基丙烯醯氧基丙基三甲氧基矽烷、3 -硫醇基丙 基三甲氧基矽烷等密著促進劑； 2，2·硫代雙（4-甲基-6-第三丁基酚）、2,6-二-第三丁基酚等氧 化防止劑； 2-(3-第三丁基-5-甲基-2-羥苯基）-5-氯苯并三唑、烷氧基苯 并酚酮等之紫外線吸收劑； 及聚丙烯酸鈉等之凝結防止劑。 又，在促進放射線未照射部分之鹼性溶解性’並謀求本 發明組成物之顯像性更進一步之提昇之情況下，可進行於 本發明組成物中有機羧酸、以1 0 0 0分子量以下之低分子量 有機羧酸爲佳之添加。具體來說，舉出有甲酸、乙酸、丙 酸、丁酸、戊酸、三甲基乙酸、己酸、二乙基乙酸、庚酸、 辛酸等脂肪族單羧酸；乙二酸、丙二酸、丁二酸、戊二酸、 己二酸、庚二酸、辛二酸、壬二酸、癸二酸、^--烷機二 酸、甲基丙二酸、乙基丙二酸、二甲基丙二酸、甲基丁二 酸、四甲基丁二酸、檸康酸等之脂肪族二羧酸；丙三羧酸、 丙烯三羧酸、樟腦三酸等之脂肪族三羧酸；安息香酸、甲 苯甲酸、對異丙苯酸、2,3 -二甲基苯基酸、均三甲苯酸等之 芳香族單羧酸；鄰苯二酸、異苯二酸、對苯二酸、苯偏三 酸、苯均三酸、偏苯四甲酸、苯均四酸等之芳香族多羧酸； 苯乙酸、2 -苯丙酸、氫桂皮酸、苯乙醇酸、苯基丁二酸、 -46- 1245164 顛茄酸、桂皮酸、桂皮酸甲酯、桂皮酸苄酯、桂皮叉乙酸、 薰草酸、2,4-二羥桂皮酸等其他羧酸。 於本發明光硬化性組成物中係除了以上之外，以進一步 添加熱聚合防止劑爲佳，例如以氫醌、對甲氧基酚、二-第 三丁基-對甲酚、連苯三酚、第三丁基鄰苯二酚、苯醌、4,4、 硫代雙（3-甲基-6-第三丁基酚）、2,2’-亞甲基雙（4-甲基-6-第 三丁基酚）、2-氫硫基苯并三唑等爲有用。 [III]本發明組成物之製造方法及使用方法 本發明之光硬化性組成物係可藉由使用與溶劑混合著 色劑、鹼可溶性樹脂、感光性聚合成分、光聚合起始劑、 再者於必要時所使用之其他添加劑之各種混合機、分散機 來混合分散來調製。 還有，混合分散步驟雖然由捏合分散與隨之繼續進行之 微分散處理所構成者爲佳，但亦可省略捏合分散。 於捏合分散步驟中，促進原料之著色劑粒子表面與以載 色劑之樹脂成分爲主體之構成成分之浸潤，從著色劑粒子 與空氣之固體/氣體界面，變換成著色劑粒子與載色劑溶液 之固體/液（原文第44頁）體界面。於微分散步驟中，藉由與 玻璃或陶瓷微粒之分散用媒介一起混合攪拌，分散著色劑 粒子至接近於一次粒子之微小狀態。因而，捏合分散步驟 中，由於必須將著色劑粒子表面所形成之界面從空氣變換 成溶液，必須強大剪切力壓縮力，故希望適合於該步驟之 捏合機、被捏合物爲高黏度者，另外，微分散步驟中必須 均勻安定地分布粒子成爲微小之狀態，故希望如對於凝結 著的著色劑粒子不需要衝擊力與剪切力之分散機、與比較 -47- 1245164 低之被分散物爲比較低黏度者。 用於使用本發明光硬化性組成物來製成例如濾色片之 捏合分散步驟，係首先以有機顏料或碳黑等著色劑與分散 劑或表面處理劑、鹼可溶性樹脂及溶劑來捏合。捏合所使 用之機械係雙輥、三輥、球磨機、球硏磨機、分散機、捏 合機、共捏合機、均化器、攪拌機、單軸及雙軸押出機， 賦予強大之剪切力同時分散。其次，加入溶劑及鹼可溶性 樹脂（於捏合步驟中所使用之剩餘部分），以使用縱型或橫 型砂磨機、針磨機、縫型硏磨機、超音波分散機等爲主， 可由0.1〜lmm粒徑之玻璃、氧化鉻等之粒子來分散。還有， 亦可省略該捏合步驟。於該情況下，以顏料與分散劑或表 面處理劑、鹼可溶性樹脂及溶劑來進行顆粒分散。於該情 況下捏合步驟中之剩餘鹼可溶性樹脂係以於分散之途中添 加爲佳。 還有，對於捏合、分散之詳細亦記載於T.C. Patton 著” Paint Flow and 顏料 Dispersion ”（1964 年了ohn Wiley and Sons公司發行）等。 將本發明之光硬化性組成物直接或經由其他層藉由旋 轉塗佈、縫型塗佈、流延塗佈、輥塗佈等之塗佈方法塗佈 於基板上，而形成硬化性組成物層，藉由經由既定之遮罩 圖案來曝光，僅硬化經光照射之塗佈膜部分，並以顯像液 顯像，可形成包含各色（3色或4色）畫素之圖案狀皮膜來製 造濾色片。此時所使用之放射線方面，以使用g線束、i 線束等之紫外線爲佳。 其次藉由進行鹼性顯像處理，溶出以上述曝光之光未照 -48- 1245164 射部分於鹼性水溶液中，僅剩下光硬化後之部分。顯像液 方面，可使用溶解光未照射部分之感光性層，另外亦可使 用任何位溶解光照射部分者。 其次，洗淨除去剩餘之顯像液，並於實施乾燥後，以 5 0 °C〜2 4 0 °C之溫度進行加熱處理（後烘烤處理）。針對該等各 種顏色依次重複前述步驟而可製造硬化皮膜。如此一來得 到濾色片。 基板方面，舉例有用於液晶顯示元件等之無鹼玻璃、燒 鹼玻璃、硬質玻璃、石英玻璃及附著透明導電膜於該等上 者、或用於固體攝影元件等之光電變換元件基板、例如有 機矽基板等。再者，亦可用塑膠基板。於該等基板上，形 成隔離各畫素之黑柵欄。 塑膠基板之原料方面’由光學特性、耐熱性、機械強度 等觀點來看，舉出有（1)非晶型聚烯、（2)聚醚颯、（3)聚戊二 醯胺、（4)聚碳酸酯、（5 )聚對苯二甲酸乙二醇酯、（6)聚乙燃 萘酯' (7)降冰片烯聚合物、（8)以雙苯胺莽爲雙胺成分之聚 醯亞胺、（9)由雙酚苐與2元酸所構成之聚酯等。其中特別 以（2)聚醚楓、（4)聚碳酸醋、（5)聚對苯二甲酸乙二酯、及（7) 降冰片烯聚合物爲佳。上述原料係特別在LCD用途上爲佳。 對塑膠基板所要求之特性方面，有低熱膨脹（隨著濾色 片製成時硬化處理之精確度之劣化防止）、阻氣性（液晶之 安定性確保）、光透過性或光學等方向性等之光學特性、表 面平滑性等。關於熱膨脹方面係以熱膨脹係數爲丨以下 爲佳。 又’在塑膠基板方面係以於該表面具有阻氣層或/及耐 -49- 1245164 溶劑性層爲佳。 塗佈於基板上之本發明光硬化性組成物層之乾燥（預先 烘烤處理）係可於加熱板、烤箱等以5(TC〜140°C之溫度進行 1〇〜3〇0秒。 本發明光硬化性組成物之塗佈層厚度（乾燥後），一般爲 〇·3〜5.0//m，希望爲 0.5 〜3.5/zm，，最希望爲 1.0 〜2.5//m。 顯像液方面係可使用溶解本發明之光硬化性組成物，另 外必須爲不溶解放射線照射部分之組成物者。具體而言係 可使用各種有機溶劑之組合或鹼性水溶液。 有機溶劑方面，舉出有於調製本發明組成物時所使用之 前述溶劑。顯像溫度方面通常爲2 0 °C〜3 0 °C，顯像時間方面 爲2 0〜9 0秒。 鹼方面，係使用已溶解例如氫氧化鈉、氫氧化鉀、碳酸 鈉、碳酸氫鈉、矽酸鈉、甲基矽酸鈉、氨水、乙胺、二乙 基胺、二甲基乙醇胺、氫氧化四甲基銨、氫氧化四乙基銨、 膽鹼、吡咯、六氫吡啶、1，8-二雜氮聯環-[5,4,0]-7-十一烯 等鹼性化合物成爲濃度0 · 0 0 1〜1 0質量％、而以〇 · 〇 1〜1質量 %爲佳之鹼性水溶液。還有，在使用由該等鹼性水溶液構成 之顯像液之情況下，一般於顯像後以水洗淨（洗濯）。 後烘烤處理係爲了成爲完全硬化者之顯像後加熱，通常 進行約20(TC〜220°C之加熱（硬化烘烤）。 該後烘烤處理處理係如上述條件地使用加熱板或熱氣 循環式乾燥機、高周波加熱機等之加熱手段，可連續式或 批式地進行。 濾色片用各種構成元件方面，除了上述濾色片本身（著 -50- 1245164 色層）或黑色矩陣之外亦可適用墊片、保護層、導電洞形成 層等。再者，本發明之光硬化性組成物係除了上述濾色片 用各種構成元件以外，亦可使用作爲C〇B (晶舟）之運送用 密封劑或LCD用密封劑。 於使用本發明光硬化性組成物而得之濾色片層上，通常 設置罩面層（平坦化層）。形成罩面層之樹脂（0C劑）方面舉 出有丙烯酸系樹脂組成物、環氧樹脂組成物、聚醯亞胺樹 脂組成物等。特別地，因於可見光區域之透明性優異，又， 濾色片用光硬化性組成物之樹脂成分通常以丙烯酸系樹脂 爲主成分，由於密著性優異而希望丙烯酸系樹脂組成物。 特別地，作爲於濾色片中所使用之光阻用光硬化性之（甲基） 丙烯酸系樹脂則與濾色片之製造步驟之密合變良好而佳。 【實例】 以下，雖然使用實例來具體地說明本發明，但本發明 之內容係不受限於該等者。 【實例1】 首先調製下述組成之溶液，藉由8小時攪拌而得到光硬 化性組成物。 U)著色劑：碳黑分散劑（*丨） 400質量份 (b)鹼可溶性樹脂： ①丙烯酸系共聚物A:烷基聚氧化乙嫌•聚氧化丙條 (甲基）丙烯酸酯共聚物：（i)甲基丙烯酸/(ii)烷基聚氧化乙烯 •聚氧化丙烯（甲基）丙烯酸酯/(ηi)甲基丙烯酸苄酯 = 12/12/76(組成質量比）共聚物（m = 8、n = 6，質量平均分子量 (Mw)= 1 1，〇〇〇) 1245164 3〇質量份 ②丙；it S麦系共聚物B :甲基丙烯酸苄酯/甲基丙烯酸共 聚物（莫耳比70/30、=約3 0000) 20質量 份 (c) 感光性聚合成分：二戊四醇六丙烯酸酯 30質量份 (d) 光聚合起始劑：2,4-雙（三氯甲基）雙（乙 氧基竣甲基）肢基]苯基]-1，3，5 -三畊 10質量份 (e) 溶劑··丙二醇單甲基醚乙酸酯 500質量份 7-{L-4-氯-6-(二乙基胺基三哄(2),1-胺基)各苯基薰草素 3質量份 非離子性界面活性劑（* 2) 1質量份 氟系非離子性界面活性劑（* 3) 1質量份 * 1):喀伯特公司製力咯耳 粒徑·· 31nm、pH: 9、DBP 吸油量：42ml/100g、黑色度 My 値：2 3 5之碳黑爲25質量％、1〇質量％(甲基丙烯酸苄酯/ 曱基丙烯酸甲酯/甲基丙烯酸羥乙酯）之共聚物之65質量％ 丙二醇單甲基乙基乙酸酯之分散液 * 2):竹本油脂股份有限公司製紫色D-61 12W(HLB : 1 1 .9): 揭示於特開2002- 2292 3 4號公報之以通式（G)p = 3、q爲 (P〇）= 2、（E〇）= 6、r二10之化合物 * 3) : 60 %丙烯酸N-丁基全氟化辛烷颯胺乙酯與40 %聚（氧 鏈烯）丙烯酸酯之共聚物 使用旋轉塗佈機並以600rpm條件之點分散法，塗佈所 得之光性化性組成物於切割0.7 mm厚之康寧公司製無鹼玻 璃1 7 3 7成1 〇 〇 m m X 1 0 0 m m並1質量％氫氧化鈉水溶液洗淨後 之基板上，成爲1.1 // m之膜厚。使用加熱板來進行1201： -52- 1245164 預先烘烤處理處理1 2 〇秒鐘之後，以具有丨5 # m之線寬遮 卓進行闻壓水銀燈、3 〇 0 m J / c m2之曝光（照度：2 0 m W / c m2)， 以2 5 C富士軟片阿其股份有限公司製鹼性顯像液c D κ -1之 1 . 6 %顯像液來顯像，於上述基板上以丨5 ν见寬格子形成格 子間之畫素部分爲1 〇 〇 # m X 3 〇 〇 // m矩形之黑色矩陣。以針 對顯像時間（秒）之線寬變化m)表示黑色矩陣之顯像界 限，以秒數表示顯像寬容度。 顯像寬容度係由於完全地溶解於相當於畫素部分之黑 色矩陣之非畫面部分，黑色矩陣之畫面部分之線寬表示直 到安定並殘存之時間（秒）。 以同樣方法形成R、G、B各畫素圖案，製成濾色片。 所使用之R、G、B係個別爲富士軟片阿其股份有限公司製 CR-8510L、CG-8510L、CB-8510L。 於所製成之濾色片上，使用旋轉塗佈機以點分散法塗佈 實例1之包含①丙烯酸系共聚物A(30質量份）、②丙烯酸系 共聚物B(20質量份）、③感光性聚合成分（30質量份）、④光 聚合起始劑（5質量份）、⑤溶劑（5 0 0質量份）、及⑥非離子性 界面活性劑（1質量份）之組成物，成爲1 · 0mm之膜厚，並以 1 10°C加熱120秒。 以光學顯微鏡（微分干涉型、200倍）全面觀察以該方法 所製成之濾色片基板並觀察OC劑之凹形斑（30〜1 000 # ιηφ ) 之產生數目。 如下述評估針孔凹形斑之之產生數。 〇· · ·0 個、△· · ·1 〜5 個、X· · ·5 〜10 個、XX· · ·1〇 個 以上 -53- 1245164 【實例2】 於實例1中，改變前述（a)鹼可溶性樹脂中之丙烯酸系共 聚物A成爲m = 9、η = 6者之外，與實例1相同之條件調製 光硬化性組成物，與實例1相同地評估。 【實例3】 於實例1中，改變前述（a)鹼可溶性樹脂中之丙烯酸系共 聚物A成爲m = 5、η = 5者之外，與實例1相同之條件調製 光硬化性組成物，與實例1相同地評估。 【實例4】 於實例1中，改變前述（a)鹼可溶性樹脂中之丙烯酸系共 聚物A成爲m = 1 1、η = 9者之外，與實例1相同之條件調製 光硬化性組成物，與實例1相同地評估。 【比較例1】 於實例1中，改變前述U)鹼可溶性樹脂中之丙烯酸系共 聚物Α成爲m= 1 4、η = 0者之外’與實例1相同之條件調製 光硬化性組成物，與實例1相同地評估。 【比較例2】 於實例1中，不使用①之丙烯酸系共聚物Α而僅使用5 0 質量份②之丙烯酸系共聚物B作爲前述（a)鹼可溶性樹脂， 再者，使用1質量份以記載於特開2002-22934號公報之通 式A所表示之界面活性劑（竹本油脂製紫色D-65 12)之外， 與實例1相同之條件調製光硬化性組成物，與實例1相同 地評估。 【比較例3】 於實例1中，不使用①之丙烯酸系共聚物A而僅使用5 0 1245164 質量份②之丙烯酸系共聚物B作爲前述（a)鹼可溶性樹脂， 再者，使用1質量份以記載於特開20 02 - 2 2 9 3 4號公報之通 式F所表示之界面活性劑（旭電化公司製普魯羅尼克 TR-9 13 R)之外，與實例1相同之條件調製光硬化性組成物， 與實例1相同地評估。 【比較例4】 於實例1中，不使用①之丙烯酸系共聚物A而僅使用 50質量份②之丙烯酸系共聚物B作爲前述（a)鹼可溶性樹 脂，再者，使用1質量份爲聚氧化乙烯丙烯酸醚碳氫化合 物醚、順式丁烯二酐及苯乙烯之三元共聚物之日本油脂股 份有限公司製馬力亞力母AKM05 3 1之外，與實例1相同之 條件調製光硬化性組成物，與實例1相同地評估。（揭示於 特開2000- 1 94 1 32號公報） 【比較例5】 於實例1中，使用苯乙烯/甲基丙烯酸 /CH3(〇C2H4)2〇C〇C(CH3) = CHC2H 5 = 62/3 2/6(組成質量比）共 聚物（1 0,000質量平均分子量）取代①之丙烯酸系共聚物A 作爲前述U)鹼可溶性樹脂之外，與實例1相同之條件調製 光硬化性組成物，與實例1相同地評估。 【比較例6】 於實例1中，使用作爲①之丙烯酸系共聚物A之（i)甲基 丙烯酸/(ii)烷基聚氧化乙烯•聚氧化丙烯•聚氧丁烯（BO) 對甲基丙烯酸酯/甲基丙烯酸苄酯二12/1 2/76(組成質量比） 共聚物（111=8、11=6、？=；3，15,000質量平均分子量）作爲 前述（a)鹼可溶性樹脂之外，與實例1相同之條件調製光硬 -55- 1245164 化性組成物，與實例i相同地評估。 【比較例7】 於實例1中，②之丙烯酸系共聚物B之使用量爲50質 量份，再者，使用1質量份聚氧化乙烯丙烯基醚碳氫化合 物醚、聚氧化丙烯芳基醚碳氫化合物醚、順式丁烯二酸酉干 與苯乙烯之四元共聚物（日本油脂股粉有限公司製馬力亞 力母AFB 1521)之外，與實例相同之條件調製光硬化性組成 物，與實例1相同地評估。（揭示於特開2000- 1 94 1 32號公 報） 上述評估結果示於表1。 表1 針孔凹形斑產生數 顯像界限 顯像寬容度 目㈤ (βτα/ψ]?) (秒） 實例1 〇 1.0 70〜100 實例2 〇 1.0 70〜100 實例3 〇 1.3 80〜110 實例4 〇 1.3 60 〜90 比較例1 Δ 2.5 40 〜50 比較例2 X 1.3 60 〜90 比較例3 X 1.3 60 〜90 比較例4 XX 1.5 50 〜70 比較例5 X 2.0 60 〜80 比較例6 Δ 1.0 80〜110 比較例7 XX 1.3 60 〜80 (^)〇=0個、〜5個、x=5〜10個、xx=10個以上 1245164 由以上之實例及比較例得知，本發明之光硬化性組成 物係於罩面層塗佈面上亦無針孔凹形斑之產生，而且可得 到良好之顯像界限及顯像寬容度。 【發明之效果】 根據本發明，在黑色矩陣上、或、著色劑含有率高之 濾色片用畫素上，可提供最適於在罩面層上不易產生針孔 凹形斑之濾色片用之光硬化性組成物。又，因而提供不易 產生畫面缺陷或畫面形成障礙之液晶顯示裝置。再者可提 供最適於顯像界限或顯像寬容度高、顯像特性良好之工程 適合性優異之濾色片用之光硬化性組成物，而提供賦予不 易產生畫面缺陷或畫面形成障礙之高色度畫面之液晶顯 示裝置。 【圖式簡單說明】： Μ 〇 «η、、 -57-Specific examples thereof include 2- (o-chlorophenyl) -4,5-diphenylimide dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) Dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- ( P-methylhydrothiophenyl) -4,5-diphenylimidazole dimer and the like. In the present invention, other known ones than the above initiators can also be used. For example, there are vicinal polyketolose compounds disclosed in the specification of U.S. Patent No. 2,3,67,660, disclosed in U.S. Patent No. 2,3 6 7,6,61 and U.S. Patent No. 2,3,67,670. The α-carboxyl compound described in the specification, the ketol ether disclosed in the specification of U.S. Patent No. 2,4 4 8,8 2 8 and the alpha-carboxy compound disclosed in the specification of U.S. Patent No. -42-1245164 No. 2,72 2,5,12 Hydrocarbon-substituted aromatic alcohol compounds, polynuclear quinone compounds disclosed in U.S. Patent Nos. 3,046,127 and 2,95 1,7 5 8 and U.S. Patent No. 3,5 49,3 67 A combination of triallyl imidazole dimer / p-aminophenyl ketone, Benzothio compound / Dihalide methyl three well system compound disclosed in Japanese Patent Publication No. 51-48516. In addition, Adika Optoma-SP-150, 151, 170, 171, N-1717, N-1414, etc. manufactured by Asahi Kasei Corporation can also be used as a polymerization initiator. The amount of the photopolymerization initiator used in the present invention is from 0.1 to 10.0% by mass of the entire solid portion of the photocurable composition, and preferably from 0.5 to 5.0% by mass. When the amount of the initiator used is less than 0.1% by mass, it is difficult to perform polymerization, and when it exceeds 10.0% by mass, the film strength is weakened. (e) Solvents Solvents used for preparing the photocurable composition of the present invention include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , Isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl glycolate, ethyl glycolate, Butyl glycolate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-hydroxypropionate, 3- Methyl 3-hydroxypropionate alkyl esters such as ethyl hydroxypropionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropionate, 2-ethoxypropane-43-1245164 methyl acetate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate , Ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethyl 2-Ethyl methyl propionate, methyl pyruvate, ethyl pyruvate, propionate pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, 2-methyl Ethyl oxybutyrate, etc .; ethers, such as diethylene glycol dimethyl ether, tetrahydrofuran, ethyl alcohol monomethyl ether, ethylene glycol monoethyl ether, methyl lysin acetate, ethyl Fibrinolysin acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, glycerol ethyl ether ethyl Acid esters, propylene glycol propyl ether acetate, etc .; ketones, such as methyl ethyl ketone, cyclohexanone, 2-pentanone, 3-pentanone, etc .; aromatic hydrocarbons, such as toluene, xylene, etc. . Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl lysinoacetate, ethyl lactate, diethylene glycol dimethyl ether, and acetic acid are used. Butyl ester, methyl methoxypropionate, 2-pentanone, cyclohexanone, ethylcarbitol acetate, butylcarbitol acetate, propylene glycol monomethyl ether acetate, and the like are preferred. These solvents may be used alone or in combination of two or more. [Π] Other components The photocurable composition of the present invention may be supplemented with various additives as necessary, such as a filler, a high molecular weight compound other than the above-mentioned alkali-soluble resin, a surfactant other than the above, an adhesion promoter, Antioxidants, UV absorbers, anticoagulants, etc. Specific examples of these additives include glass, alumina, and other fillers; itaconic acid copolymers, butenoic acid copolymers, cis-butenedioic acid copolymers, and partially esterified cis-butene Diacid copolymers, acidic cellulose derivatives, • 44-1245164 Addition of anhydrides to polymers with hydroxyl groups, alcohol-soluble nylon, basic oxygen resins formed from bisphenol A and epichlorohydrin, etc. Soluble resins; non-ionic, cationic, and anionic surfactants, specifically phthalocyanine derivatives (commercially available EFKA-7 45 (manufactured by Morishita Industries)); organic silicone polymer KP341 ( (Shin-Etsu Chemical Industry Co., Ltd.), (meth) acrylic (co) polymer polyfluro No. 75, No. 90, No. 95 (Kyoeisha Oil Chemical Industry Co., Ltd.), W001 (made by Yusho) Series surfactants; polyoxyethylene dodecyl ether, polyoxyethylene octadecyl ether, polyoxyethylene octadecenyl ether, polyoxyethylene octyl ether, polyoxyethylene nonyl Phenyl ether, polyoxyethylene behenyl ester, polyoxyethylene behenyl Non-ionic octyl esters, sorbitan fatty acid esters (manufactured by BASF), Prionic L10, L31, L61, 10R5, 17R2, 25R2, Ditronic 304, 70, 704, 901, 904, 150R1, etc. Surfactants; anionic surfactants such as W004, W005, W017 (made by Yusho); EFKA-46, EFKA-47, EFKA47EA, EFKA polymer-100, EFKA polymer-400, EFKA polymer 401 Polymer dispersants such as EFKA polymer 450 (manufactured by Morishita Industries), dispersing additives 6, dispersing additives 8, dispersing additives 1 5, dispersing additives 9100 (three Knoop buckles); colloidal dispersion 3000, 5000, 9000, 12000 , 13240, 13940, 17000, 24000, 26000, 28000 and other colloidal dispersing and dispersing agents (manufactured by JInka Co., Ltd.); Adicapronic L31, F38, L42, L44, L61, L64, F68, L72 , P95, F77, P48, F87, P94, L1 (H, P103, F108, L121, P-123 (manufactured by Asahi Kasei) and Isonet S-20 (manufactured by Sanyo Kasei); vinyltrimethoxysilane Vinyl triethoxysilane, vinyl tri (2-methoxyethoxy) silane , N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2- -45-1245164 aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Adhesion promoters such as thiolpropyltrimethoxysilane; 2,2 · thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol, etc. Antioxidant; 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and other ultraviolet absorbers; and polyacrylic acid Anticoagulant for sodium. In addition, in the case where the alkali solubility of the non-irradiated portion is promoted and the developability of the composition of the present invention is further improved, the organic carboxylic acid in the composition of the present invention can be used with a molecular weight of 100 The following low molecular weight organic carboxylic acids are preferred additions. Specific examples include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, hexanoic acid, diethylacetic acid, heptanoic acid, and octanoic acid; oxalic acid, malonic acid, and the like Acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, alkane diacid, methylmalonic acid, ethylmalonic acid, Aliphatic dicarboxylic acids such as dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid, etc .; aliphatic tricarboxylic acids such as glyceric acid, propylene tricarboxylic acid, and camphor tricarboxylic acid Acids; aromatic monocarboxylic acids such as benzoic acid, toluic acid, p-cumene acid, 2,3-dimethylphenyl acid, mesitylene acid, etc .; phthalic acid, isophthalic acid, terephthalic acid Aromatic polycarboxylic acids such as acids, trimellitic acid, trimesic acid, trimellitic acid, pyromellitic acid, etc .; phenylacetic acid, 2-phenylpropionic acid, hydrocinnamic acid, phenylglycolic acid, phenylsuccinic acid Acids, -46-1245164 belladonnaic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylacetic acid, lavender acid, 2,4-dihydroxycinnamic acid and other carboxylic acids. In the photocurable composition of the present invention, in addition to the above, it is preferable to further add a thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-third-butyl-p-cresol, and pyrophenylene Phenol, tert-butylcatechol, benzoquinone, 4,4, thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl -6-third butylphenol), 2-hydrothiobenzotriazole, and the like are useful. [III] Production method and use method of the composition of the present invention The photocurable composition of the present invention can be mixed with a solvent by using a colorant, an alkali-soluble resin, a photosensitive polymerization component, a photopolymerization initiator, and Various mixers and dispersers used for other additives are used for mixing and dispersing to prepare. In addition, although the mixing and dispersing step is preferably constituted by kneading and dispersing and the micro-dispersing treatment continued thereafter, the kneading and dispersing may be omitted. In the kneading and dispersing step, the infiltration of the surface of the toner particles of the raw material and the constituent components mainly composed of the resin component of the vehicle is promoted, and the solid / gas interface between the colorant particles and air is transformed into the colorant particles and the vehicle. Solution solid / liquid (original page 44) body interface. In the micro-dispersion step, the colorant particles are dispersed to a minute state close to the primary particles by mixing and stirring together with a dispersion medium of glass or ceramic particles. Therefore, in the kneading and dispersing step, since the interface formed on the surface of the colorant particles must be changed from air to a solution, and the shearing force and compressive force must be strong, it is desirable that the kneader and the kneaded compound suitable for this step have high viscosity. In addition, in the microdispersing step, particles must be uniformly and stably distributed to be in a fine state. Therefore, if a dispersing machine for impacting and shearing forces is not required for the condensed toner particles, compared with -47-1245164, the dispersion is low. For those with lower viscosity. The kneading and dispersing step for forming a color filter using the photocurable composition of the present invention is to knead a colorant such as an organic pigment or carbon black with a dispersant or a surface treatment agent, an alkali-soluble resin, and a solvent. The machinery used for kneading is double-roller, three-roller, ball mill, ball honing machine, disperser, kneader, co-kneader, homogenizer, mixer, single-shaft and double-shaft extruder, giving strong shearing force at the same time dispersion. Secondly, add the solvent and alkali-soluble resin (the remaining part used in the kneading step), mainly using a vertical or horizontal sand mill, pin mill, slot honing machine, ultrasonic disperser, etc. Particles such as glass and chromium oxide with a particle size of 0.1 to 1 mm are dispersed. The kneading step may be omitted. In this case, the particles are dispersed with a pigment, a dispersant or a surface treatment agent, an alkali-soluble resin, and a solvent. In this case, the remaining alkali-soluble resin in the kneading step is preferably added during dispersion. The details of kneading and dispersing are also described in T.C. Patton's "Paint Flow and Pigment Dispersion" (published by Ohn Wiley and Sons in 1964). The photocurable composition of the present invention is directly or through another layer applied to a substrate by a coating method such as spin coating, slit coating, cast coating, or roll coating to form a curable composition. Layer, by exposing through a predetermined mask pattern, hardening only the portion of the coating film irradiated with light, and developing it with a developing solution, a patterned film containing pixels of each color (3 or 4 colors) can be formed Manufacture of color filters. As for the radiation to be used at this time, ultraviolet rays such as a g-beam and an i-beam are preferably used. Secondly, by performing alkaline development treatment, the unexposed light of the above-exposed light -48-1245164 is dissolved in the alkaline aqueous solution, and only the light-hardened portion remains. For the developer, a photosensitive layer that dissolves the unirradiated portion of light can be used, and any portion that dissolves the light-irradiated portion can be used. Next, the remaining developing solution is washed and removed, and after drying, the heat treatment is performed at a temperature of 50 ° C to 240 ° C (post-baking treatment). The foregoing steps are repeated for each of these colors in order to produce a hardened film. In this way, a color filter is obtained. For the substrate, examples include alkali-free glass, caustic soda glass, hard glass, quartz glass, and a transparent conductive film attached to the above for a liquid crystal display element, or a photoelectric conversion element substrate for a solid-state imaging element, such as an organic silicon. Substrate, etc. Furthermore, plastic substrates can also be used. On these substrates, a black fence is formed to isolate each pixel. In terms of raw materials of plastic substrates, from the viewpoints of optical characteristics, heat resistance, mechanical strength, etc., (1) amorphous polyene, (2) polyether fluorene, (3) polypentamidine, and (4) ) Polycarbonate, (5) polyethylene terephthalate, (6) polyethylene naphthyl ester '(7) norbornene polymer, (8) polyfluorene containing dianiline as a diamine component Imine, (9) Polyester composed of bisphenol hydrazone and dibasic acid. Among these, (2) polyether maple, (4) polycarbonate, (5) polyethylene terephthalate, and (7) norbornene polymer are preferred. The above raw materials are particularly suitable for LCD applications. For the characteristics required for plastic substrates, there are low thermal expansion (prevention of deterioration in the accuracy of the hardening process when the color filter is made), gas barrier properties (ensure the stability of the liquid crystal), light transmission, or optical directivity. Optical properties, surface smoothness, etc. Regarding thermal expansion, it is preferable that the thermal expansion coefficient is ≦ or less. In terms of plastic substrates, it is preferable that the surface has a gas barrier layer or / and a -49-1245164 solvent-resistant layer. The drying (pre-baking treatment) of the photocurable composition layer of the present invention applied on a substrate can be performed on a hot plate, an oven, etc. at a temperature of 5 (TC to 140 ° C) for 10 to 3,000 seconds. The thickness (after drying) of the coating layer of the photocurable composition of the invention is generally 0.3 to 5.0 // m, preferably 0.5 to 3.5 / zm, and most preferably 1.0 to 2.5 // m. For the developing solution It is possible to use a composition that dissolves the photocurable composition of the present invention, and it must be a composition that does not dissolve the radiation irradiated portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution may be used. In terms of organic solvents, examples include The aforementioned solvents used in preparing the composition of the present invention. The development temperature is usually 20 ° C to 30 ° C, and the development time is 20 to 90 seconds. For the alkali, it is used to dissolve, for example, hydroxide Sodium, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium methyl silicate, ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl hydroxide Ammonium, choline, pyrrole, hexahydropyridine, 1,8-diazabicyclo- [5,4,0] -7-ten Alkaline compounds such as alkenes are alkaline aqueous solutions having a concentration of 0. 0 0 1 to 10% by mass, and preferably 0.001 to 1% by mass. In addition, a developing solution composed of these basic aqueous solutions is used. In the case, it is usually washed with water after development (washing). Post-baking treatment is heating after development to become a fully hardened person, usually about 20 (TC ~ 220 ° C) (hardening baking) The post-baking treatment can be performed continuously or in batches using heating means such as a hot plate, a hot-air circulation dryer, a high-frequency heater, etc. as described above. In addition to the above-mentioned aspects of various constituent elements for color filters In addition to the color filter itself (with a color layer of -50-1245164) or a black matrix, a gasket, a protective layer, a conductive hole forming layer, etc. can also be applied. Furthermore, the photocurable composition of the present invention is in addition to the color filter described above. In addition to various constituent elements, it is also possible to use a sealant for transportation of COB (crystal boat) or a sealant for LCD. The color filter layer obtained by using the photocurable composition of the present invention is usually provided with a cover. Layer (planarization layer). The resin (0C agent) of the surface layer includes an acrylic resin composition, an epoxy resin composition, a polyimide resin composition, etc. In particular, since it has excellent transparency in the visible light region, it is also a color filter. The resin component of the photocurable composition is usually an acrylic resin as the main component, and an acrylic resin composition is desirable because of its excellent adhesion. In particular, it is used as a photocurable material for photoresist used in color filters. The (meth) acrylic resin is in good contact with the manufacturing steps of the color filter. [Example] Hereinafter, although the present invention is specifically described using examples, the content of the present invention is not limited to these. [Example 1] First, a solution having the following composition was prepared, and a photocurable composition was obtained by stirring for 8 hours. U) Colorant: Carbon black dispersant (* 丨) 400 parts by mass (b) Alkali-soluble resin: ① Acrylic copolymer A: Alkyl polyoxyethylene • Polypropylene oxide (meth) acrylate copolymer: (I) methacrylic acid / (ii) alkyl polyoxyethylene • polyoxypropylene (meth) acrylate / (ηi) benzyl methacrylate = 12/12/76 (composition-to-mass ratio) copolymer (m = 8. n = 6, mass average molecular weight (Mw) = 11, 000) 1245164 3 mass parts ② C; it S wheat-based copolymer B: benzyl methacrylate / methacrylic acid copolymer (Mole Ratio 70/30, = approximately 30,000) 20 parts by mass (c) photosensitive polymerization component: dipentaerythritol hexaacrylate 30 parts by mass (d) photopolymerization initiator: 2,4-bis (trichloromethyl) ) Bis (ethoxylmethyl) limyl] phenyl] -1,3,5-triso 10 parts by mass (e) Solvent · 500 parts by mass of propylene glycol monomethyl ether acetate 7- {L- 4-Chloro-6- (diethylaminotris (2), 1-amino) each phenylhumulin 3 parts by mass non-ionic surfactant (* 2) 1 part by mass fluorine-based nonionic Surfactant (* 3) 1 part by mass * 1): Cabot Corporation Particle size · 31nm, pH: 9, DBP oil absorption: 42ml / 100g, blackness My 値: 25% by mass of carbon black of 25%, 10% by mass (benzyl methacrylate / methyl methacrylate) / Hydroxyethyl methacrylate) copolymer 65% by mass of propylene glycol monomethyl ethyl acetate dispersion * 2): Purple D-61 12W (HLB: 1 1 .9) manufactured by Takemoto Oil Co., Ltd. : Compound disclosed in Japanese Patent Application Laid-Open No. 2002- 2292 3 with general formula (G) p = 3, q is (P〇) = 2, (E〇) = 6, and r = 10 * 3): 60% Copolymer of N-butyl perfluorinated octylamine ethyl acrylate and 40% poly (oxyalkene) acrylate using a spin coater and a dot dispersion method at 600 rpm. The composition was cut to a thickness of 1.1 // m on a substrate having a thickness of 0.7 mm and an alkali-free glass manufactured by Corning Corporation, which was 173 mm to 100 mm X 100 mm and washed with a 1% by mass sodium hydroxide aqueous solution. thick. Use a hot plate to perform 1201: -52- 1245164 pre-baking treatment for 120 seconds, and then exposure to a pressure mercury lamp with a line width of 5 # m and exposure of 3,000 m J / c m2 ( Illumination: 20 m W / c m2), developed with 2.5 C Fuji Film Aka Corporation Co., Ltd. alkaline imaging solution c D κ -1 1.6% developing solution, and was developed on the above substrate with丨 5 ν See the wide grid forming a black matrix with a pixel portion between the grids of 〇〇 # m X 3 〇 // m. The line width change m) with respect to the development time (second) represents the development limit of the black matrix, and the development latitude is expressed in seconds. The development latitude is completely dissolved in the non-screen portion of the black matrix corresponding to the pixel portion, and the line width of the screen portion of the black matrix indicates the time (seconds) until it is stable. In the same manner, each pixel pattern of R, G, and B is formed to produce a color filter. The R, G, and B used are CR-8510L, CG-8510L, and CB-8510L manufactured by Fujifilm Aki Co., Ltd., respectively. On the prepared color filter, a spin coater was used to apply a dot dispersion method to coat the sample containing ① acrylic copolymer A (30 parts by mass), ② acrylic copolymer B (20 parts by mass), and ③ photosensitive. The composition of the polymerization component (30 parts by mass), ④ photopolymerization initiator (5 parts by mass), ⑤ solvent (500 parts by mass), and ⑥ nonionic surfactant (1 part by mass) becomes 1 · Film thickness of 0mm and heating at 110 ° C for 120 seconds. An optical microscope (differential interference type, 200 times) was used to comprehensively observe the color filter substrate produced by this method and observe the number of concave spots (30 ~ 1 000 # ιηφ) of the OC agent. The number of pinhole concave spots was evaluated as described below. 〇 ·· 0, △ ··· 1 ~ 5, X ··· 5 ~ 10, XX ··· 10 or more -53-1245164 [Example 2] In Example 1, the foregoing (a ) The acrylic copolymer A in the alkali-soluble resin is a photocurable composition prepared under the same conditions as in Example 1 except that m = 9 and η = 6, and evaluated in the same manner as in Example 1. [Example 3] In Example 1, except that the acrylic copolymer A in the aforementioned (a) alkali-soluble resin was changed to m = 5, η = 5, the photocurable composition was prepared under the same conditions as in Example 1, and Example 1 was evaluated identically. [Example 4] In Example 1, the photo-curable composition was prepared under the same conditions as in Example 1 except that the acrylic copolymer A in the (a) alkali-soluble resin was changed to m = 1 1 and η = 9. Evaluation was the same as in Example 1. [Comparative Example 1] In Example 1, the photo-curable composition was adjusted under the same conditions as in Example 1 except that the acrylic copolymer A in the aforementioned U) alkali-soluble resin was changed to m = 1, 4 and η = 0. Evaluation was the same as in Example 1. [Comparative Example 2] In Example 1, the acrylic copolymer A of ① was not used but only 50 parts by mass of the acrylic copolymer B of ② was used as the (a) alkali-soluble resin, and more than 1 part by mass was used. Except for the surfactant (Purple D-65 12 made by Takemoto Oils and Fats) described in General Formula A of Japanese Patent Application Laid-Open No. 2002-22934, a photocurable composition was prepared under the same conditions as in Example 1, and was the same as in Example 1. Evaluation. [Comparative Example 3] In Example 1, acrylic copolymer A of ① was not used, but only 5 0 1245164 parts by mass of acrylic copolymer B of ② was used as the (a) alkali-soluble resin, and 1 part by mass was used. It is prepared under the same conditions as in Example 1 except that the surfactant (Pulonic TR-9 13 R manufactured by Asahi Kasei Corporation) is represented by the general formula F described in JP-A 20 02-2 2 9 3 4 The photocurable composition was evaluated in the same manner as in Example 1. [Comparative Example 4] In Example 1, instead of using acrylic copolymer A of ①, only 50 parts by mass of acrylic copolymer B of ② was used as the aforementioned (a) alkali-soluble resin, and 1 part by mass of polyacrylic copolymer was used. The terpolymer of ethylene oxide acrylic ether hydrocarbon ether, cis-butene dianhydride, and styrene was produced by Japan Oil Co., Ltd., and made of Mariam AKM05 3 1 under the same conditions as in Example 1 to modulate photohardenability. The composition was evaluated in the same manner as in Example 1. (Revealed in Japanese Patent Application Laid-Open No. 2000- 1 94 1 32) [Comparative Example 5] In Example 1, styrene / methacrylic acid / CH3 (〇C2H4) 2〇 COC (CH3) = CHC2H 5 = 62 / 3 2/6 (composition-to-mass ratio) copolymer (1,000 mass average molecular weight) replaces acrylic copolymer A of ① as the above U) alkali-soluble resin, and prepares a photocurable composition under the same conditions as in Example 1, Evaluation was the same as in Example 1. [Comparative Example 6] In Example 1, (i) methacrylic acid / (ii) alkyl polyoxyethylene • polyoxypropylene • polyoxybutylene (BO) paramethyl group of acrylic copolymer A as (1) was used. Acrylate / benzyl methacrylate di 12/1 2/76 (composition and mass ratio) copolymer (111 = 8, 11 = 6,? =; 3,15,000 mass average molecular weight) is used as the (a) alkali-soluble resin In addition, the light-hardened-55-1245164 chemical composition was modulated under the same conditions as in Example 1, and evaluated in the same manner as in Example i. [Comparative Example 7] In Example 1, the amount of acrylic copolymer B used in (2) was 50 parts by mass, and 1 part by mass of polyoxyethylene propylene ether hydrocarbon ether and polyoxypropylene aryl ether carbon were used. A photo-hardenable composition was prepared under the same conditions as in the example except that the compound is a quaternary copolymer of hydrogen compound ether, cis-butanedioic acid, and styrene (Nippon Oil & Fat Co., Ltd., made of AMF 1521). Evaluation was the same as in Example 1. (Revealed in JP 2000- 1 94 1 32) The evaluation results are shown in Table 1. Table 1 Pinhole concave plaques produced by digital imaging limit imaging tolerance (βτα / ψ)? (Seconds) Example 1 〇1.0 70 ～ 100 Example 2 〇1.0 70 ～ 100 Example 3 〇1.3 80 ～ 110 Example 4 〇1.3 60 to 90 Comparative Example 1 Δ 2.5 40 to 50 Comparative Example 2 X 1.3 60 to 90 Comparative Example 3 X 1.3 60 to 90 Comparative Example 4 XX 1.5 50 to 70 Comparative Example 5 X 2.0 60 to 80 Comparative Example 6 Δ 1.0 80 to 110 Comparative Example 7 XX 1.3 60 to 80 (^) 0 = 0, ~ 5, x = 5 to 10, xx = 10 or more 1245164 From the above examples and comparative examples, it is known that the light of the present invention The hardening composition is free of pinhole concave spots on the coating surface of the cover layer, and it can obtain a good development limit and development latitude. [Effects of the Invention] According to the present invention, on a black matrix or on a pixel for a color filter having a high content of a colorant, a color filter that is most suitable for preventing pinhole concave spots from forming on the cover layer can be provided. Photo-curable composition. In addition, a liquid crystal display device which does not easily cause screen defects or screen formation obstacles is provided. Furthermore, it is possible to provide a photohardenable composition suitable for a color filter which is most suitable for a development boundary or a high development latitude and excellent developmental suitability, and provides a high degree of resistance to screen defects or obstacles to screen formation. Liquid crystal display device for chromaticity picture. [Schematic description]: Μ 〇 «η ,, -57-

Claims (1)

y >J2齡1 %! > 口 "Τ"Ίy > J2age 1%! > 口 " Τ " Ί 一^>Φ請專利範 1 ·一種光硬化性組成物，其包括（a)著色劑，（b)鹼可溶性樹 脂，（C)感光性聚合成分，（d)光聚合起始劑，及（e)溶劑， 其中該（b)鹼可溶性樹脂方面含有 U)酸成分單體， (η)以下述通式（1)或（2)所表示之烷基聚氧化乙烯•聚 氧化丙烯（甲基）丙烯酸酯， Ri[(OC2H4)m(OC3H6)n]OCOCR2 = CHR3 (1) Ri[(OC2H4)m(〇C3H6)n]〇COC(CH3) = CHR3 (2) φ (iii)由具有碳-碳不飽和鍵的選自下述族群I之丙烯酸 酯類、苯乙烯類及乙烯酯類之至少1種化合物所構成之 丙烯酸系共聚物A ; 其中， Ri表示1〜20碳數之直鏈或分枝之烷基； R2表示氫原子或甲基； R1表示氫原子、甲基或乙基； 爪及η係各爲2〜20之整數、m/n係30/70〜80/20; 但是，於上述通式（1)及通式（2)中，對於氧化乙烯基 (QC2H4)及氧化丙烯基（OC3h6)之鍵結順序並無限制，非 限定於上述表記者； I族群： @基）丙烯酸苄酯、（甲基）丙烯酸苯酯、（甲基）丙烯酸辛 1旨 '(甲基）丙烯酸環己酯、（甲基）丙烯酸甲基環己酯、（甲 基）丙烯酸己酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸正丁 -58- 1245164 酯、（甲基）丙烯酸異丁酯、苯乙烯、甲基苯乙烯、二甲 基苯乙烯、甲氧基苯乙烯、環己基苯乙烯、乙酸乙烯酯、 丙酸乙烯酯。 2 ·如申請專利範圍第1項之光硬化性組成物，其中該（i)酸 成分單體爲至少1種選自順式丁烯二酸酐、丙烯酸、甲 基丙烯酸及富馬酸之酸成分單體。 3 ·如申請專利範圍第1或2項之光硬化性組成物，其更含 有非該丙烯酸系共聚物A之丙烯酸系共聚物B作爲該（b) 鹼可溶性樹脂。 4 ·如申請專利範圍第1或2項之光硬化性組成物，其中在 已除去該（e)溶劑之光硬化性組成物中，該（a)著色劑含有 率爲30〜70質量％。 5 .如申請專利範圍第3項之光硬化性組成物，其中在已除 去該（e)溶劑之光硬化性組成物中，該（a)著色劑含有率爲 30〜70質量％。 6. 如申請專利範圍第1或2項之光硬化性組成物，其中該 (b)鹼可溶性樹脂中之⑴酸成分單體、（ii)烷基聚氧化乙烯 •聚氧化丙烯（甲基）丙烯酸酯及I族群化合物之組成質量 比爲10〜25/5〜25/50〜85，而且聚苯乙燦換算質量平均分 子量（Mw)爲 3,000 〜50,000 ° 7. 如申請專利範圍第3項之光硬化性組成物，其中該（b)鹼 可溶性樹脂中之（i)酸成分單體、（Π)烷基聚氧化乙烯•聚 氧化丙烯（甲基）丙烯酸酯、及I族群化合物之組成質量比 爲10〜25/5〜25/50〜85，而且聚苯乙烯換算質量平均分子 量（Mw)爲 3,000〜50,000。 -59- 1245164 8 .如申請專利範圍第4項之光硬化性組成物，其中該（b)鹼 可溶性樹脂中之（i)酸成分單體、（i i)烷基聚氧化乙烯•聚 氧化丙烯（甲基）丙烯酸酯及I族群化合物之組成質量比爲 10〜25/5〜25/50〜85，而且聚苯乙烯換算質量平均分子量 (Mw)爲 3,0 00 〜50,〇〇〇 〇 9·如申請專利範圍第5項之光硬化性組成物，其中該（b)鹼 可溶性樹脂中之（i)酸成分單體、（ii)烷基聚氧化乙烯•聚 氧化丙烯（甲基）丙烯酸酯、及（iii)I族群化合物之組成質 量比爲10〜2 5/5〜25/50〜85,而且聚苯乙烯換算質量平均 分子量（]\4^¥)爲 3,000〜50,000。 I 〇 ·如申請專利範圍第1或2項之光硬化性組成物，其中該 (a)著色劑爲碳黑。 II ·如申請專利範圍第3項之光硬化性組成物，其中該（a) 著色劑爲碳黑。 1 2 .如申請專利範圍第4項之光硬化性組成物，其中該（a) 著色劑爲碳黑。 13·如申請專利範圍第5項之光硬化性組成物，其中該（a) 著色劑爲碳黑。 1 4.如申請專利範圍第6項之光硬化性組成物，其中該（a) 著色劑爲碳黑。 1 5 ·如申請專利範圍第7項之光硬化性組成物，其中該（a) 著色劑爲碳黑。 1 6 ·如申請專利範圍第8項之光硬化性組成物，其；中該（a) 著色劑爲碳黑。 1 7·如申請專利範圍第9項之光硬化性組成物，其中該（a) -60- 1245164 著色劑爲碳黑。 1 8 . —種濾色片，其係由塗佈如申請專利範圍第1至1 7項 中任一項之光硬化性組成物於基板上，乾燥後，進行圖 案曝光、鹼性顯像而得。 1 9 . 一種液晶顯示裝置，其中具有由直接形成於如申請專利 範圍第1 8項之濾色片層上之光硬化性（甲基）丙烯酸系樹 脂組成物所構成之罩面層。^ ≫ Φ Patent Claim 1 · A photocurable composition comprising (a) a colorant, (b) an alkali-soluble resin, (C) a photosensitive polymerization component, (d) a photopolymerization initiator, and (E) a solvent, wherein the (b) alkali-soluble resin contains U) an acid component monomer, and (η) an alkylpolyoxyethylene • polyoxypropylene (formaldehyde) represented by the following general formula (1) or (2) Group) acrylate, Ri [(OC2H4) m (OC3H6) n] OCOCR2 = CHR3 (1) Ri [(OC2H4) m (〇C3H6) n] 〇COC (CH3) = CHR3 (2) φ (iii) by Acrylic copolymer A consisting of at least one compound selected from the group consisting of acrylates, styrenes, and vinyl esters of carbon-carbon unsaturated bonds; wherein Ri represents a straight number of 1 to 20 carbons A chain or branched alkyl group; R2 represents a hydrogen atom or a methyl group; R1 represents a hydrogen atom, a methyl group, or an ethyl group; claw and η are each an integer of 2 to 20, and m / n is 30/70 to 80/20 However, in the above general formula (1) and general formula (2), there is no limitation on the bonding order of the oxyethylene group (QC2H4) and propylene oxide group (OC3h6), and it is not limited to the reporter of the above table; Group I: @ 基） 丙Benzyl acid, phenyl (meth) acrylate, octyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, hexyl (meth) acrylate, ( Amyl (meth) acrylate, n-butyl (58) -1245164 (meth) acrylate, isobutyl (meth) acrylate, styrene, methylstyrene, dimethylstyrene, methoxystyrene, cyclic Hexylstyrene, vinyl acetate, vinyl propionate. 2. The photocurable composition according to item 1 of the scope of the patent application, wherein the (i) acid component monomer is at least one acid component selected from the group consisting of maleic anhydride, acrylic acid, methacrylic acid, and fumaric acid. monomer. 3. If the photocurable composition according to item 1 or 2 of the patent application scope, it further contains an acrylic copolymer B other than the acrylic copolymer A as the (b) alkali-soluble resin. 4. The photocurable composition according to item 1 or 2 of the scope of patent application, wherein in the photocurable composition from which the (e) solvent has been removed, the content of the (a) colorant is 30 to 70% by mass. 5. The photocurable composition according to item 3 of the scope of patent application, wherein in the photocurable composition from which the (e) solvent has been removed, the (a) colorant content is 30 to 70% by mass. 6. The photocurable composition according to item 1 or 2 of the scope of patent application, wherein (b) the monomer of the gallic acid component in the alkali-soluble resin, (ii) the alkyl polyoxyethylene • polyoxypropylene (methyl) The composition and mass ratio of the acrylate and the group I compound is 10 to 25/5 to 25/50 to 85, and the polystyrene-equivalent mass average molecular weight (Mw) is 3,000 to 50,000 °. Photocurable composition, wherein (b) the component mass of (i) an acid component monomer, (Π) an alkyl polyoxyethylene • polyoxypropylene (meth) acrylate, and a group I compound in the alkali-soluble resin The ratio is 10 to 25/5 to 25/50 to 85, and the polystyrene-equivalent mass average molecular weight (Mw) is 3,000 to 50,000. -59- 1245164 8. The photocurable composition according to item 4 of the scope of patent application, wherein (i) the acid component monomer and (ii) the alkyl polyoxyethylene and polyoxypropylene in the (b) alkali-soluble resin The composition-to-mass ratio of the (meth) acrylate and the group I compound is 10 to 25/5 to 25/50 to 85, and the polystyrene-equivalent mass average molecular weight (Mw) is 3,000 to 50,000. 9. The photocurable composition according to item 5 of the scope of the patent application, wherein (i) an acid component monomer and (ii) an alkyl polyoxyethylene and a polyoxypropylene (methyl) in the (b) alkali-soluble resin The composition and mass ratio of the acrylate and the (iii) group I compound is 10 to 2 5/5 to 25/50 to 85, and the polystyrene-equivalent mass average molecular weight (] \ 4 ^ ¥) is 3,000 to 50,000. I 〇 The photocurable composition according to item 1 or 2 of the patent application scope, wherein the (a) colorant is carbon black. II. The photocurable composition according to item 3 of the application, wherein (a) the colorant is carbon black. 12. The photocurable composition according to item 4 of the scope of patent application, wherein the (a) colorant is carbon black. 13. The photocurable composition according to item 5 of the application, wherein the (a) colorant is carbon black. 1 4. The photocurable composition according to item 6 of the application, wherein the (a) colorant is carbon black. 15 · The photocurable composition according to item 7 of the scope of patent application, wherein the (a) colorant is carbon black. 16 · If the photocurable composition according to item 8 of the patent application scope, wherein (a) the colorant is carbon black. 17. The light-curable composition according to item 9 of the scope of patent application, wherein (a) -60-1245164 colorant is carbon black. 18. A color filter, which is formed by coating a photocurable composition such as any one of claims 1 to 17 on a substrate, applying a pattern exposure and alkaline development after drying. Got. 19. A liquid crystal display device having a cover layer composed of a photocurable (meth) acrylic resin composition formed directly on a color filter layer as described in claim 18 of the scope of patent application. -61 --61-
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