TWI289577B

TWI289577B - Photopolymerization composition and color filter using the same

Info

Publication number: TWI289577B
Application number: TW92125645A
Authority: TW
Inventors: Shigeo Tsuji
Original assignee: Mitsubishi Chem Corp
Priority date: 2002-10-28
Filing date: 2003-09-17
Publication date: 2007-11-11
Also published as: TW200413461A

Abstract

This invention provides a photopolymerization composition comprising (a) a black color material, (b) an organic binder, (c) a photopolymerization initiator and (d) a photopolymerization monomer, in which (b) is an epoxy acrylate resin having carboxylic group and (c) is a specific urethane compound. The invented photopolymerization composition has high light shielding property in film and also has excellent photosensitivity and resolution so that a resin black matrix (BM) with low cost and high quality can be formed. A color filter using the invented resin BM has excellent precision, smoothness and durability and thus the display quality of liquid crystal element can be increased. Moreover, there is no harmful material contained in the manufacturing steps or the color filter so that danger to human body is low and environmental safety can be increased.

Description

(1) 1289577 玖、發明說明【發明所屬之技術領域】本發明係關於彩色電視、液晶顯示元件、固件、照相機等所使用之光學濾色器製造所使用之光聚合性組成物及由該組成物所得濾色器、詳言明係關於在具高遮光性同時高感度且解像性優異質（Black Matrix。以下、簡稱爲 BM。）製造合之濾色器用光聚合性組成物及具有高精度、高樹脂BM之濾色器。【先前技術】濾色器、通常係在玻璃、塑膠薄片等透明基成黒色基質、接著、依順序將紅、綠、藍等3種之色相、以條紋狀或鑲嵌（πι 〇 s a i c )狀等之色樣樣大小因濾色器用途及各種色而有不同，爲5〜右又、重疊（superposition )之位置精度爲 μιη、可由尺寸精度高的微細加工技術來製造。濾色器之代表性的製造方法有' 染色法、印料分散法、電解澱積法等。該等之中、尤其是、材料之光聚合性組成物、塗敷於透明基板上、光、顯像、並依需要予以重複硬化之，以形成濾之顔料分散法、因濾色器畫素位置、膜厚等精度性耐熱性等耐久性優異、故針孔（pin hole 少、而廣受採用。體攝影元濾色器用之、本發之黑色基上爲極適遮光性之 :板表面形 :以上不同形成。色 7 0 0 μ m 左數〜數十刷法、顔將含有色使畫像曝色器畫像局、耐光 )等缺陷 -4 - (2) 1289577 BM在、紅、綠、藍色樣間配置成格子狀、條紋狀或鑲嵌狀爲一般、對因各色間混色抑制所致對比之提高或對光漏所致薄fl旲電晶體（Thin Film Transistor : TFT)誤動作之防止，有其作用。因此、對B Μ則要求要有高度遮光性。習知之Β Μ係由鉻等金屬膜所形成方法爲一般。此方法係在透明基板上將鉻等金屬予以蒸鍍、經由照相石板步驟將鉻層予以蝕刻處理、故在薄的膜厚下高遮光性可在高精度下獲得。相反的、因爲係製造步驟長且生産性低之方法，需高成本、又、會有因蝕刻處理之廢棄液等引起的環境問題等。因此、以使遮光性顔料、染料分散之感光性樹脂，來形成低成本、無公害之樹脂ΒΜ之形成方法被全力的硏究著。但是、樹脂ΒΜ因會有後述等問題、故在目前並無法實用化。在樹脂ΒΜ中、爲了顯現鉻等金屬膜所致與ΒΜ 有同等遮光性（光學濃度）、則可使遮光性之顔料、染料等含有量變多、或者、有必要使膜厚變厚。在使膜厚變厚之方法中、受到ΒΜ凹凸之影響、會損及其上所形成RGB着色畫素之平坦性。因此、會引起液晶晶胞間隔（c e 11 g a p )之不均勻化或液晶定向之紊亂，造成顯示能力降低。又、亦會有設於濾色器上之透明電極 I TO (銦錫氧化物）膜之斷線（平面狀膜之破損）等之問題產生。又、在使遮光性顔料、染料含有量變多之方法中、會有感光性樹脂（黑色抗蝕劑）感度、顯像性、解像性、密 -5- (3) 1289577 接性等悪化之問題、不僅生産性降低而且濾色器所要求之精度、信頼性亦無法獲得。亦即、在薄膜、高遮光性之條件下因可發揮感度、解像性之感光材料無法被實現，故阻礙了樹脂B Μ之實用化。(1) 1289577 发明Inventive Description [Technical Field] The present invention relates to a photopolymerizable composition used in the manufacture of optical color filters used in color televisions, liquid crystal display elements, firmware, cameras, and the like, and the like. The color filter obtained by the object is a photopolymerizable composition for a color filter which is manufactured by a black matrix (hereinafter, abbreviated as BM) with high light-shielding property and high resolution and high resolution. , high resin BM color filter. [Prior Art] A color filter is usually formed by forming a transparent substrate such as glass or a plastic sheet into a ochre substrate, followed by three kinds of hue of red, green, and blue in a sequence, such as a stripe or a mosaic (πι 〇 saic). The color sample size varies depending on the purpose of the color filter and various colors, and the positional accuracy of 5 to right and superposition is μιη, and can be manufactured by a microfabrication technique with high dimensional accuracy. Representative production methods of the color filter include 'dyeing method, printing dispersion method, electrolytic deposition method, and the like. Among these, in particular, a photopolymerizable composition of a material, coated on a transparent substrate, light, developed, and repeatedly hardened as needed to form a filtered pigment dispersion method, due to a color filter pixel Excellent durability such as position, film thickness, and other precision heat resistance, so pinholes are small and widely used. For the photographic element color filter, the black base of the present invention is extremely suitable for light shielding: the surface of the plate Shape: The above is different. Color 7 0 0 μ m Left to tens of brushing, color will contain color to make the image of the imager, lightfast, etc. -4 - (2) 1289577 BM in, red, green, The blue sample is arranged in a lattice shape, a stripe shape or a mosaic shape, and the contrast is improved by the color mixture suppression between the colors, or the thin film transistor (TFT) is prevented from being malfunctioned by the light leakage. Has its role. Therefore, for B 要求, it is required to have a high degree of opacity. Conventional methods The method of forming a metal film such as chromium is general. In this method, a metal such as chromium is vapor-deposited on a transparent substrate, and the chromium layer is etched by a lithographic step. Therefore, high light-shielding properties can be obtained with high precision at a thin film thickness. On the contrary, because of the long manufacturing process and low productivity, high cost, environmental problems due to etching treatment, and the like are required. Therefore, a method of forming a low-cost, pollution-free resin crucible by using a light-blocking pigment or a photosensitive resin in which a dye is dispersed is fully studied. However, since the resin has problems such as those described later, it is currently not practical. In the resin crucible, in order to exhibit a light-shielding property (optical density) similar to that of ruthenium in order to exhibit a metal film such as chromium, it is possible to increase the content of the light-blocking pigment or dye, or to increase the film thickness. In the method of making the film thickness thick, it is affected by the unevenness of the ridge, and the flatness of the RGB coloring pixels formed thereon is damaged. Therefore, the unevenness of the liquid crystal cell spacing (c e 11 g a p ) or the disorder of the liquid crystal orientation may be caused, resulting in a decrease in display ability. Further, there is a problem that the transparent electrode I TO (indium tin oxide) film provided on the color filter is broken (damage of the planar film). In addition, in the method of increasing the amount of the light-shielding pigment or the dye, the photosensitive resin (black resist) sensitivity, developability, resolution, and adhesion - 5 - (3) 1289577 bondability may be deteriorated. The problem, not only the decrease in productivity, but also the accuracy and reliability required for the color filter is not available. In other words, in the case of a film or a high light-shielding property, a photosensitive material capable of exhibiting sensitivity and resolution cannot be realized, which hinders the practical use of the resin B.

習知之一般的感光性樹脂、或者、濾色器用之着色感光性組成物等具有一定光透過性之感光性樹脂中，就改善感度、解像性性能的方法爲周知。例如、作爲使顔料分散之濾色器用着色組成物則有黏合劑樹脂、多官能丙烯單體、含有三哄化合物所成引發劑之感光性組成物爲周知 (請參照專利文獻1〜4 )。又、在同樣組成中引發劑爲雙咪唑爲周知（請參照專利文獻5〜6 )、在該等所揭示之組成物之場合、在空氣中曝光之情況受到因氧所致之聚合阻礙、故實用上無法獲得感度。A method for improving the sensitivity and the resolution performance of a photosensitive resin having a light transmittance such as a photosensitive resin or a coloring photosensitive composition for a color filter is known. For example, a photosensitive composition for a color filter for dispersing a pigment is known as a binder resin, a polyfunctional propylene monomer, and a photosensitive composition containing an initiator of a triterpene compound (see Patent Documents 1 to 4). Further, in the same composition, the initiator is known as diimidazole (see Patent Documents 5 to 6), and in the case of the disclosed compositions, exposure to air is inhibited by polymerization due to oxygen. Sensitivity is not available in practice.

如樹脂Β Μ般在光之全波長領域中有要求遮光能力之情形、（1 )曝光部分與未曝光部分中要使交聯密度有所差別極爲困難、（2 )即使在被曝光之部分，相對於膜厚方向之交聯密度有所差別、就是說、在光照射面即使予以充分硬化、在基底面仍然不會硬化、（3 )在顯像液配合有不溶性的多量黒色色材，造成顯像性顯著降低等、則在賦予感光特性上造成障礙。尤其是、上述（1 )與（2 )之顯像爲相反、若使曝光部分更爲硬化之組成、則膜厚方向之之硬化密度差變大，造成解像力降低。又、當曝光部/未曝光部之交聯密度差與曝光部之硬化密度無法均勻化時，溶解力強的顯像液之 (4) 1289577 使用亦顯困難，造成顯像性之改良亦爲困難。周知之樹脂 BM形成用感光性組成物（例如、請參照日本專利文獻7 〜8 )、可避免此等狀況、但並非形成與金屬BM相同程度之遮光樹脂BM、而是使某種程度之光透過以獲得感光能力，但其遮光能力顯著降低並無法實際使用。因此、既然高膜厚、低遮光性之樹脂 BM —旦形成後在固化 (cure )步驟中予以膜收縮、得以獲得在薄膜具有高遮光度之樹脂BM被提案出（請參照專利文獻9 )、但步驟變得複雑、故因膜收縮時之變形（strain )蓄積使得密接性降低等之問題，實用化亦有困難。這樣的話、所謂遮光、則會與原來與光反應相反之條件下產生光反應，如此乍見之下實在相當矛盾、因此要實現樹脂BM之實用化有其困難。又、作爲光聚合引發劑，使用特定之肟酯化合物之技術爲周知（請參照專利文獻1 〇 )、習知之樹脂B Μ所使用之引發劑（例如、雙咪唑或三I]井系引發劑）、若只是取代該肟化合物、則無法改善樹脂Β Μ所要求之畫像特性、亦即無法改善感度或解像性。【專利文獻1】日本特開平1-152449號公報【專利文獻2】日本特開平1-254918號公報【專利文獻3】日本特開平2-153353號公報【專利文獻4】日本特開平2 _ 8 〇 4號公報【專利文獻5】日本特開平6 - 7 5 3 7 2號公報【專利文獻6】日本特開平6 - 7 5 3 7 3號公報 (5) 1289577 【專利文獻7】日本特開平6 - 5 1 4 9 9號公報【專利文獻8】日本特開平6 - 3 5 1 8號公報【專利文獻9】日本特開平8-44〇5()號公報【專利文獻1 〇】日本特開2 0 0 0 - 8 0 0 6 8號公報【發明內容】〔發明欲解決課題〕本發明係爲解決上述問題，提供一種使具有薄膜、高遮光性之圖案以照相平版法（photo lithography )更容易形成、擁有充分之感度、解像性之抗蝕劑材料、使得濾色器之樹脂BM可在高精度、低成本下製造。又使用如此方式製造之濾、色器的液晶顯示裝置，其對比等之顯示能力優異。又、藉由BM之樹脂化可衡量濾色器之高畫質化、無公害化。〔解決課題之手段〕本發明人等經努力硏究結果、發現作爲光聚合引發劑，係使特定之肟酯化合物、且作爲有機結合劑，係使具有羧基之環氧丙烯酸酯樹脂加以組合所含有之光聚合性組成物來加以使用、而可達成上述目的，因而完成本發明。亦即、本發明之要旨、係在含有（a )黒色色材、 (b )有機結合材及（c )光聚合引發劑之光聚合性組成物中、（b )爲具有羧基之環氧丙烯酸酯樹脂、（c )爲肟酯系化合物，爲其特徵之前述光聚合性組成物。 -8- (6) 1289577 又、本發明之上述光聚合性組成物、進而含有（d ) 光聚合性單體，爲其特徴之光聚合性組成物。又、本發明中上述光聚合性組成物、進而含有（e ) 具鹼性官能基之高分子分散劑，爲其特徴之光聚合性組成物。又、本發明係、在基板上具有上述光聚合性組成物所形成之B Μ，爲其特徴之濾色器、及使用如此方式製造出之濾色器來製造之液晶顯示裝置。〔發明之効果〕本發明之光聚合性組成物、在薄膜中有高遮光性，同時感度、解像性優異、故可在低成本形成高品質之樹脂 ΒΜ。使用本發明之樹脂 ΒΜ之濾色器，在精度、平坦性、耐久性均優異、故可提高液晶元件顯示品質。又、製造步驟及濾色器本身亦不含有害物質、故對於人體之危險性可予減低並提高環境安全性。〔實施發明之最佳形態〕 (a )黒色色材本發明之黒色色材、可使用單獨黒色色材、或紅、綠、藍色等混合所致之黒色色材。該等黒色色材、可自無機或者有機之顔料、染料之中適宜選擇、亦可單獨使用或多種混合使用。In the case of resin Β 有, there is a requirement for shading ability in the full wavelength range of light, (1) it is extremely difficult to make the difference in crosslink density between the exposed portion and the unexposed portion, and (2) even in the exposed portion, The crosslink density differs from the film thickness direction, that is, even if it is sufficiently cured on the light-irradiated surface, it does not harden on the base surface, and (3) a large amount of indigo color material is blended in the developing liquid, resulting in When the developing property is remarkably lowered, the photosensitive property is impeded. In particular, when the development of the above (1) and (2) is reversed and the composition of the exposed portion is hardened, the difference in hardening density in the film thickness direction is increased, resulting in a decrease in the resolution. Further, when the difference in the crosslink density between the exposed portion and the unexposed portion and the hardening density of the exposed portion are not uniformized, the use of the developing liquid having a strong dissolving power (4) 1289577 is also difficult, and the improvement in development is also difficult. A photosensitive composition for forming a resin BM is known (for example, refer to Japanese Patent Laid-Open Nos. 7-8), and it is possible to avoid such a situation, but it is not a light-shielding resin BM which is formed to the same extent as the metal BM, but a certain degree of light. Through the ability to obtain photosensitivity, but its shading ability is significantly reduced and can not be used. Therefore, since the resin BM having a high film thickness and a low light-shielding property is formed by shrinking the film in the cure step after the formation, a resin BM having a high light-shielding property in the film is proposed (refer to Patent Document 9). However, since the steps are re-examined, problems such as a decrease in the adhesion due to the accumulation of strain during film shrinkage are difficult to put into practical use. In this case, the so-called shading causes a photoreaction under the condition that the original reaction with the light is opposite, so that it is quite contradictory in view of this, so it is difficult to realize the practical use of the resin BM. Further, as a photopolymerization initiator, a technique using a specific oxime ester compound is known (refer to Patent Document 1), and an initiator (for example, a diimidazole or a tri-I] well initiator used in a conventional resin B Μ If the ruthenium compound is merely substituted, the image characteristics required for the resin 无法无法 cannot be improved, that is, the sensitivity or the resolution cannot be improved. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 6-75. [Patent Document 8] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION In order to solve the above problems, the present invention provides a photolithography method for a film having a film and a high light-shielding property. It is easier to form a resist material having sufficient sensitivity and resolution, and the resin BM of the color filter can be manufactured with high precision and low cost. Further, a liquid crystal display device using a filter and a color filter manufactured in such a manner is excellent in display capability such as contrast. Moreover, the resin of BM can measure the high image quality and pollution-free color of the color filter. [Means for Solving the Problem] The inventors of the present invention have found that a specific oxime ester compound and an organic binder are combined with an epoxy acrylate resin having a carboxyl group as a photopolymerization initiator. The above object can be attained by using a photopolymerizable composition contained therein, and thus the present invention has been completed. That is, the gist of the present invention is a photopolymerizable composition containing (a) a ochre color material, (b) an organic binder, and (c) a photopolymerization initiator, and (b) an epoxy acrylate having a carboxyl group. The ester resin and (c) are oxime ester-based compounds, and the photopolymerizable composition is characterized by the above. -8- (6) 1289577 Further, the photopolymerizable composition of the present invention further contains (d) a photopolymerizable monomer, which is a photopolymerizable composition. Further, in the present invention, the photopolymerizable composition further contains (e) a polymer dispersing agent having a basic functional group as a photopolymerizable composition. Further, the present invention relates to a liquid crystal display device comprising the above-mentioned photopolymerizable composition, B Μ formed by the above-mentioned photopolymerizable composition, a special color filter thereof, and a color filter manufactured in this manner. [Effect of the Invention] The photopolymerizable composition of the present invention has high light-shielding property in a film and is excellent in sensitivity and resolution, so that a high-quality resin can be formed at low cost. The color filter of the resin of the present invention is excellent in accuracy, flatness, and durability, so that the display quality of the liquid crystal element can be improved. Moreover, the manufacturing steps and the color filter itself do not contain harmful substances, so the danger to the human body can be reduced and the environmental safety can be improved. [Best Mode for Carrying Out the Invention] (a) Twilight Color Material The green color material of the present invention may be a single color material or a red color material obtained by mixing red, green, blue or the like. These ochre color materials, which may be selected from inorganic or organic pigments and dyes, may be used singly or in combination.

單獨之黒色色材、有例如碳黑、乙炔黑、燈黑（lamP -9- (7) 1289577 b 1 a c k )、骨黑（b ο n e b 1 a c k )、黒錯、鐵黒、苯胺黑、花青黑（cyan in black )等。該等中、尤其是碳黑就遮光率、畫像特性之觀點言之較佳。相關碳黑之市售品之例、有以下等之品牌。三菱化學公司製：MA7、MA8、MA 11、MA 100、MA 220、MA 23 0、#52、井 50、井 47、井 45、井 2700、井 265 0、井 2200、井 1 000、井 990、#900 等〇Separate color materials, such as carbon black, acetylene black, lamp black (lamP -9- (7) 1289577 b 1 ack ), bone black (b ο neb 1 ack ), error, iron sputum, nigrosine, flowers Cyan in black and so on. Among these, in particular, carbon black is preferred in terms of light blocking rate and image characteristics. Examples of commercial products related to carbon black, such as the following brands. Mitsubishi Chemical Corporation: MA7, MA8, MA 11, MA 100, MA 220, MA 23 0, #52, well 50, well 47, well 45, well 2700, well 265 0, well 2200, well 1 000, well 990 , #900, etc.

Degussa 公司製：Printex 95、Printex 90、Printex 85、Printex 75、Print ex 55、Printex 45、P r i n t e x 40、 Printex 30、Printex 3、Printex A、Printex G、Special Black 5 5 0、Special Black 3 5 0 Special Black 2 5 0、 Special B lack 1 00 等 °Degussa company: Printex 95, Printex 90, Printex 85, Printex 75, Print ex 55, Printex 45, Printex 40, Printex 30, Printex 3, Printex A, Printex G, Special Black 5 5 0, Special Black 3 5 0 Special Black 2 5 0, Special B lack 1 00 etc.

Cabot 公司製：Monarch 460、Monarch 430、Monarch 2 8 0、Monarch 120、 Monarch 8 0 0 、 Monarch 463 0、Cabot company: Monarch 460, Monarch 430, Monarch 2 8 0, Monarch 120, Monarch 8000, Monarch 463 0,

REGAL 99、REGAL 99R、REGAL 415、REGAL 415R、 REGAL 25 0 、 REGAL 25 0R 、 REGAL 3 3 0 、 BLACK PEARLS 480、P EARLS 130REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 25 0 , REGAL 25 0R , REGAL 3 3 0 , BLACK PEARLS 480, P EARLS 130

Columbian Carbon 公司製：RAVEN 11 、RAVEN 15、 RAVEN 30 、 RAVEN 35 > RAVEN 40、 RAVEN 410、 RAVEN 42 0、 RAVEN 45 0、 RAVEN 5 00、 RAVEN 7 8 0、 RAVEN 8 5 0、 RAVEN 8 90H、RAVEN 1 000、 RAVEN 1 020、RAVEN 1 04 0 等。其次、就混合所致之黒色色材加以説明。作爲混合基質（base )之色材之具體例、有維多利亞純藍 -10- (8) 1289577 (42595)、金色胺（auramine) Ο ( 41000) 、Kachii.on 華麗黃色素（briliant flavin )(基色 13 )、若丹明 (rhodamine) 6 G C P ( 4 5 1 6 0 )、若丹明 B ( rhodamine B) ( 4 5 1 7 0 )、藏紅（safranine) OK7 0: 1 00 ( 5 024 0 )、羊毛罌紅（erioglaucine) ( 42080) 、NO，120 /李奧黃 (rionol yellow ) (21090)、李奧黃- GRO(21090)、西姆拉堅牢黃（shim la fast yellow) -8GF ( 21105)、聯苯胺黃-4T-5 64D ( 2 1 095 )、西姆拉堅牢紅 4015Columbian Carbon Company: RAVEN 11, RAVEN 15, RAVEN 30, RAVEN 35 > RAVEN 40, RAVEN 410, RAVEN 42 0, RAVEN 45 0, RAVEN 5 00, RAVEN 7 8 0, RAVEN 8 5 0, RAVEN 8 90H, RAVEN 1 000, RAVEN 1 020, RAVEN 1 04 0, etc. Next, the description will be made on the color of the ochre material. Specific examples of the color material of the mixed base include Victoria Pure Blue-10-(8) 1289577 (42595), auramine Ο (41000), and Kachii.on Brilliant flavin (primary color) 13), rhodamine 6 GCP ( 4 5 1 6 0 ), rhodamine B ( 4 5 1 7 0 ), safranine OK7 0: 1 00 ( 5 024 0 ) , erioglaucine ( 42080) , NO , 120 / rionol yellow (21090), Li Ao Huang - GRO (21090), Shim la fast yellow -8GF ( 21105 ), benzidine yellow-4T-5 64D ( 2 1 095 ), Shimla fast red 4015

( 12355)、李奧紅 7B4401 ( 1 5 8 5 0 ) 、Fastgen 藍- TGR-L (74160)、李奧藍- SM(26150)、李奧藍-ES (色素藍· 15:6) 、Ri〇n〇gen 紅 GD(色素紅 168)、李奧綠 2YS (色素綠（pigment green) 36)等（又、上述之（）内之數字、係指比色指數（C . I ·))。又、進而其他可混合使用之顔料，若以C. I .數字表示、貝U有例如、C . I.黄色顔料 2 0，2 4，8 6，9 3，1 〇 9， 110， 117， 125， 137， 138， 147， 148， 153， 154， 166、 C.I·橘色顔料 36，43，51，55，59，61、c.l.紅色顔料 9，97，1 22，123，1 49，1 68，1 77，1 80，1 92，215， 216 ， 217 ， 220 ， 223 ， 224 ， 226 ， 227 ， 228 ， 240 、 C.I. 紫顔料 19，23，29，30，37，40，50、C.;[•藍色顔料 15，15:1，15:4，22，60，64、C.I·綠色顔料 7、C.I·棕色顔料2 3，2 5，2 6等。又、上述碳黑、可與其他黒色或有色之無機、有機顔料倂用。其他之顔料、因比碳黑之遮光性或畫像特性爲 -11 - (9) 1289577 低，故本身之混合比率有其限制。 (b )有機結合材本發明中作爲（b )有機結合材、係使用具有羧基之環氧丙烯酸酯樹脂。(12355), Li Aohong 7B4401 (1 5 8 5 0 ), Fastgen Blue - TGR-L (74160), Leo Blue-SM (26150), Leo Blue-ES (Pigment Blue 15:6), Ri 〇n〇gen red GD (pigment red 168), Leo green 2YS (pigment green 36), etc. (again, the number in the above () refers to the colorimetric index (C.I ·)). Further, other pigments which can be used in combination, if expressed by C.I., have, for example, C. I. yellow pigments 2 0, 2 4, 8 6, 9 3, 1 〇 9, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI·orange pigment 36, 43, 51, 55, 59, 61, cl red pigment 9,97,1 22,123,1 49,1 68 , 1 77,1 80,1 92,215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI violet pigments 19, 23, 29, 30, 37, 40, 50, C.; [• Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, CI · green pigment 7, CI · brown pigment 2 3, 2 5, 2 6 and so on. Moreover, the above carbon black can be used together with other inorganic or organic pigments of colored or colored. Other pigments, due to the light-shielding or image characteristics of carbon black, are -11 - (9) 1289577, so the mixing ratio of itself is limited. (b) Organic binder In the present invention, as the (b) organic binder, an epoxy acrylate resin having a carboxyl group is used.

上述環氧丙烯酸酯樹脂、係將α，β —不飽和單羧酸或在酯部分具羧基之a，β —不飽和單羧酸酯予以加成至環氧樹脂、進而、與多鹼式酸酐反應來合成。此等反應生成物在化學構造上、實質上不具有環氧基、且並非限定於「丙烯酸酯」、但環氧樹脂爲原料、且「丙烯酸酯」係代表性之例、故依慣用方式如此命名而已。The above epoxy acrylate resin is obtained by adding an α,β-unsaturated monocarboxylic acid or an a,β-unsaturated monocarboxylic acid having a carboxyl group in an ester moiety to an epoxy resin, and further, to a polybasic acid anhydride. The reaction is synthesized. These reaction products are chemically structurally substantially free of epoxy groups, and are not limited to "acrylates", but epoxy resins are used as raw materials, and "acrylates" are representative examples. Name it.

爲原料之環氧樹脂可恰當的使用、（鄰，間，對-) 甲酚粉醛淸漆型環氧樹脂、酚粉醛淸漆型環氧樹脂、雙酉分 Α型環氧樹脂、雙酚F型環氧樹脂、三酚甲烷型環氧樹脂、下述[化4 ]所示環氧樹脂等（請參照專利第2 8 7 8 4 8 6 號公報）。環氧樹脂之分子量、以GP C測定之重量平均分子量、通常在200〜20万、較佳爲300〜1000 00之範圍。分子量未滿上述範圍時在皮膜形成性方面有很多問題會產生、相反的、超過上述範圍之樹脂則在α，β —不飽和單羧酸之加成反應時很容易引起膠化，而有難以製造之虞。 -12- (10) 1289577Epoxy resin for raw materials can be used properly, (o-, m-, p-) cresol aldehyde enamel lacquer epoxy resin, phenolic aldehyde enamel lacquer epoxy resin, double bismuth bifurcated epoxy resin, double A phenol F type epoxy resin, a trisphenol methane type epoxy resin, an epoxy resin represented by the following [Chemical Formula 4], etc. (refer to Japanese Patent No. 2 8 7 8 4 8 6). The molecular weight of the epoxy resin and the weight average molecular weight measured by GP C are usually in the range of 200 to 200,000, preferably 300 to 1,000. When the molecular weight is less than the above range, there are many problems in film formability, and the opposite, the resin exceeding the above range is liable to cause gelation in the addition reaction of α,β-unsaturated monocarboxylic acid, which is difficult. Manufacturing flaws. -12- (10) 1289577

α，β —不飽和單羧酸、有衣康酸、八豆酸、桂皮酸、丙燒酸、異丁燃酸等、較佳爲、丙烯酸及異丁烯酸、尤其是丙烯酸反應性良好故較佳。在酯部分具有羧基之a，β — 不飽和單殘酸酯、有丙烯酸一 2-琥珀醯基氧乙酯、丙烯酸一 2 -馬來醯基氧乙酯、丙烯酸一 2 -酞醯基氧乙酯、丙嫌酸-2-六氫酞醯基氧乙酯、異丁烯酸琥珀醯基氧乙醋、異丁烯酸一 2 -馬來醯基氧乙酯、異丁烯酸一 2_酞醯基氧乙酯、異丁烯酸-2-六氫酞醯基氧乙酯、八豆酸-2-琥拍醯基氧乙醋等、較佳爲、丙烯酸-2 _馬來醯基氧乙酯及丙嫌酸-2-駄醯基氧乙酯、尤其是丙烯酸馬來醯基氧乙醋較佳。 a ’ β —不飽和單羧酸或其酯與環氧樹脂之加成反應、可使用公知方法、例如、可在酯化觸媒存在下、於 5 〇〜1 5 0 °C之温度下反應。酯化觸媒可使用三乙胺、三甲胺、节基二甲胺、苄基二乙胺等之3級胺、氯化四甲基錢、氯化四乙基銨、氯化十二基三甲基銨等之4級銨鹽等。 •13- (11) 1289577 a，β —不飽和單羧酸或其酯之使用量、相對於原料環氧樹脂之環氧基1當量以0.5〜1 · 2當量之範圍較佳、更佳者爲在0.7〜1.1當量之範圍，a，β —不飽和單羧酸或其酯之使用量若少則不飽和基之導入量不足、接著與多鹼式酸酐之反應亦不充分。又、多量環氧基之殘存亦非有利。一方面、該使用量若大，則α，β —不飽和單羧酸或其酯則以未反應物方式殘存。在任一之情形均被認爲會使硬化特性傾向於悪化。在附加a，β —不飽和羧酸或其酯之環氧樹脂、進而予以附加之鹼式酸酐、有馬來酸酐、琥珀酸酐、衣康酸酐、酞酸酐、四氫酞酸酐、六氫酞酸酐、均苯四甲酸酐、偏苯三酸酐、二苯基酮四羧酸二酐、甲基六氫酞酸酐、端亞甲基四氫酿酸酐、氯菌酸（chlorendic)酐、甲基四氫酞酸酐、聯苯基四羧酸二酐等、較佳爲、有馬來酸酐、琥珀酸酐、衣康酸酐、酞酸酐、四氫酞酸酐、六氫酞酸酐、均苯四甲酸酐、偏苯三酸酐、聯苯基四羧酸二酐、最佳之化合物爲、四氫酞酸酐及聯苯基四羧酸二酐。關於多驗式酸酐之附加反應亦可使用公知之手法、在與a，β —不飽和羧酸或其酯之附加反應相同條件下繼續反應之而可獲得。多鹼酸酐之附加量、以生成之環氧丙烯酸酯樹脂之酸値爲10〜150mg KOH/g之範圍較佳、進而以2 0〜140m g KOH/g特佳。樹脂酸値在上述範圍以下時則缺乏鹼顯像性、又、超過上述範圍時被認爲硬化性能傾向於劣化。 -14 - (12) 1289577 (c)光聚合引發劑劑則含有 ,合物。本發明之光聚合性組成物、作爲光聚合引: 肟酯系化合物。較佳之肟酯系化合物、有一般式（2 )所示【化5】α,β—unsaturated monocarboxylic acid, itaconic acid, crotonic acid, cinnamic acid, propionic acid, isobutyric acid, etc., preferably, acrylic acid and methacrylic acid, especially acrylic acid, are preferably reactive. . a, β-unsaturated mono-residue having a carboxyl group in the ester moiety, 2-non-succinyloxyethyl acrylate, 2-a-maleyloxyethyl acrylate, 2-nonyloxyethyl acrylate Ester, alkanoic acid-2-hexahydroindenyloxyethyl ester, methacrylate succinyl oxyacetate, methacrylic acid 2- 2-maleyl oxyethyl ester, methacrylic acid 2- 2 decyl oxyethyl ester , methacrylic acid-2-hexahydroindenyloxyethyl ester, octadecanoic acid-2-sodium decyl oxyacetate, etc., preferably, acrylic acid-2 _maleyl oxyethyl ester and acrylic acid - 2-Mercaptooxyethyl ester, especially acrylic acid maleic oxyacetate, is preferred. a 'β-addition reaction of an unsaturated monocarboxylic acid or an ester thereof with an epoxy resin, and a known method, for example, in the presence of an esterification catalyst, at a temperature of 5 Torr to 150 ° C . As the esterification catalyst, a tertiary amine such as triethylamine, trimethylamine, benzyl dimethylamine or benzyldiethylamine, tetramethylammonium chloride, tetraethylammonium chloride or decyl chloride can be used. A grade 4 ammonium salt such as methylammonium or the like. • 13-(11) 1289577 a, the amount of β-unsaturated monocarboxylic acid or its ester used is preferably in the range of 0.5 to 1 · 2 equivalents per 1 equivalent of the epoxy group of the starting epoxy resin. When the amount of the a,β-unsaturated monocarboxylic acid or an ester thereof is small in the range of 0.7 to 1.1 equivalents, the amount of introduction of the unsaturated group is insufficient, and then the reaction with the polybasic acid anhydride is insufficient. Moreover, the residual amount of a large amount of epoxy groups is also not advantageous. On the one hand, if the amount used is large, the α,β-unsaturated monocarboxylic acid or the ester thereof remains as an unreacted product. In either case, it is considered that the hardening characteristics tend to degenerate. An epoxy resin to which an a, β-unsaturated carboxylic acid or an ester thereof is added, and further a basic acid anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Pyromellitic anhydride, trimellitic anhydride, diphenyl ketone tetracarboxylic dianhydride, methyl hexahydrophthalic anhydride, terminal methylene tetrahydro fulgic anhydride, chlorendic anhydride, methyl tetrahydrofurfuric anhydride, Phenyltetracarboxylic dianhydride or the like, preferably, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, biphenyltetracarboxylic acid The acid dianhydride, the most preferred compound, is tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride. The additional reaction with respect to the multi-test acid anhydride can also be obtained by continuing the reaction under the same conditions as the additional reaction of the a, β-unsaturated carboxylic acid or its ester by a known method. The additional amount of the polybasic acid anhydride is preferably in the range of 10 to 150 mg KOH/g, and more preferably 20 to 140 m KOH/g. When the resin strontium silicate is less than the above range, it lacks alkali developability, and when it exceeds the above range, it is considered that the hardenability is degraded. -14 - (12) 1289577 (c) Photopolymerization initiator Contains a compound. The photopolymerizable composition of the present invention is used as a photopolymerization: an oxime ester compound. A preferred oxime ester compound is represented by the general formula (2).

(式中、R1、爲可各自取代之苯基、碳數1〜1〇碳數5〜8之環烷基、碳數2〜20之烷醯基、苯碳數2〜12之烷氧羰基、苯氧羰基、醯胺基或爲、可各自取代之碳數2〜12之烷醯基、碳數‘ 醯基（alkenoyl)、苯甲醯基、碳數2〜6之烷氧氧羰基、R3、R4、R5、r6及R7爲、互相獨立之鹵原子、可各自取代之碳數1〜12之烷基、碳數院氧基、碳數 5〜8之環烷基、苯基、苄基、苯碳數2〜12之烷醯基、碳數2〜12之烷氧羰基、或、-OR8、-SR9、-SOR9、-S02R9 或者-NR】0R R3、R4、R5、r6及R7之至少一個、表示·〇Κ8、 ΝϊΐΉ。但R8爲、氫原子、可各自取代之碳數之烷基、甲醯基、硝基、R2 •〜6之烯羯基或苯氫原子、 1〜1 2之甲醯基、苯氧羰基 Η、且、 -SR9 或， 1〜1 2之 -15- (14) 1289577 之組合以一覧表顯不則如表1所示。又、表1所無記載之 R3，R6，R7則均爲氫原子。在表1化合物中以2〗號及2 2 號之化合物較佳、尤其是2 1號之化合物更佳。【表1】化合物 ago. C3 R1 - R2- R4- R5- 1 C2H5— CH3CO — H CHqS — 2 C2H5 — c6h5co - H ch3s— 3 C2H5 - ch3co— H 1，4-氧氮雜- 4 C2H5— c6h5co— H 1，4-氧氮雜- 5 c2h5— CH3CO— CH3O- ch3o- 6 C2H5— ΟβΗβΟΟ 一 ch3o— ch3o— 7 C6Hs- CH3CO — H CH3S — 8 c2h5— CH3CO— H ch3o— 9 c2h5— C6H5CO — H CH30 — 10 c2h5— CH3CO — H C6H5S— 11 C2H5— C6H5CO- H c6H5s— 12 C2H5 — 2,4f6-(CH3)3C6H2CO- H CH3S— 13 CH3 — C6H5C〇一 H 「CH3S - 14 n — C6H13 — CH3CO— .H ch3s- 15 n — C6H13 — C6H5CO — H ch3s- 16 (CHa) aCCH2CH (CH3)- c6h5c〇一 H ch3s- 17 (CH3) 3CCH2CH (CH3) — CH3CO— H ch3s一 18 π 一 C6H13 一 4-CH3C6H4CO~ H c6H5s— 19 n — C6H13 — 4 一 CIC6H4CO— H c6H5s— 20 η — C6H13 — 3 — CH3C6H4CO — H c6H5s- 21 η — C6H13 — C6H5CO - H c6H6s- 22 η—C3H7 — CHgCO — H ch3s— 23 n — C3H7 — CH3CO— H 06H5S- 24 n —C3H广 c6H5co - H CH3S— -17- (15) 1289577 其他之肟酯系化合物、則有下述一般式（3 ) 、 ( 4 ) 及（5 )所示化合物。【化6】(wherein, R1 is a phenyl group which may be substituted each, a cycloalkyl group having 1 to 1 carbon number, 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms, and an alkoxycarbonyl group having 2 to 12 carbon atoms; a phenoxycarbonyl group, a decylamino group or an alkanoyl group having a carbon number of 2 to 12, a carbon number 'alkenoyl group, a benzamidine group, an alkoxycarbonyl group having 2 to 6 carbon atoms, each of which may be substituted, R3, R4, R5, r6 and R7 are mutually independent halogen atoms, each of which may be substituted with an alkyl group having 1 to 12 carbon atoms, a carbon number of a group of alkoxy groups, a cycloalkyl group having a carbon number of 5 to 8, a phenyl group, and a benzyl group. Alkyl fluorenyl group having 2 to 12 carbon atoms, alkoxycarbonyl group having 2 to 12 carbon atoms, or -OR8, -SR9, -SOR9, -S02R9 or -NR) 0R R3, R4, R5, r6 and R7 At least one of them represents 〇Κ8, ΝϊΐΉ. However, R8 is a hydrogen atom, an alkyl group which may be substituted by a carbon number, a fluorenyl group, a nitro group, an olefin group of R2 • 1-6 or a benzene hydrogen atom, 1~ The combination of 1 2 methyl thiol, phenoxycarbonyl hydrazine, and -SR9 or 1 to 1 2 -15- (14) 1289577 is shown in Table 1. However, Table 1 does not. The recited R3, R6, and R7 are all hydrogen atoms. In the compound of Table 1, the number is 2 The compound of No. 2 is preferably, especially the compound of No. 21. [Table 1] Compound ago. C3 R1 - R2- R4- R5- 1 C2H5-CH3CO — H CHqS — 2 C2H5 — c6h5co - H ch3s— 3 C2H5 - ch3co- H 1,4-oxaza- 4 C2H5— c6h5co— H 1,4-oxazepine-5 c2h5—CH3CO—CH3O- ch3o- 6 C2H5—ΟβΗβΟΟ a ch3o— ch3o— 7 C6Hs- CH3CO — H CH3S — 8 c2h5— CH3CO— H ch3o— 9 c2h5— C6H5CO — H CH30 — 10 c2h5— CH3CO — H C6H5S— 11 C2H5— C6H5CO- H c6H5s— 12 C2H5 — 2,4f6-(CH3)3C6H2CO- H CH3S — 13 CH3 — C6H5C〇一H “CH3S - 14 n — C6H13 — CH3CO— .H ch3s- 15 n — C6H13 — C6H5CO — H ch3s- 16 (CHa) aCCH2CH (CH3)- c6h5c〇H Ch3s- 17 (CH3 3CCH2CH (CH3) - CH3CO - H ch3s - 18 π - C6H13 - 4-CH3C6H4CO~ H c6H5s - 19 n - C6H13 - 4 - CIC6H4CO - H c6H5s - 20 η - C6H13 - 3 - CH3C6H4CO - H c6H5s - 21 η - C6H13 — C6H5CO - H c6H6s- 22 η—C3H7 — CHgCO — H ch3s— 23 n — C3H7 — CH3CO— H 06H5S- 24 n C3H wide c6H5co - H CH3S- -17- (15) 1289577 oxime ester compounds of the other, there is the following general formula (3), (4) and (5) a compound shown. 【化6】

⑶(3)

(5) (式中、R1、R2、R3、R4、R5、R6及R7係與前述一般式 (2 )中之定義相同、R4〜R6爲互相鍵結可形成環構造。又、Μ係表示、C; - C, 2烯烴基、環烯烴基、亞苯基基、- -! 8 - (18) 1289577 上^@旨系化合物中、較佳之化合物之取代基如示0 RI ·'Γη* •口」取代之碳數1〜1 0之烷基、例如甲基、乙丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基較佳爲碳數1〜6、更佳爲碳數1〜3、特佳爲甲基。 R2 :可取代之碳數2〜1 0之烷醯基、例如乙醢基醯基、丁醯基、戊醯基、己醯基、庚醯基、辛醯基、基、癸醯基等。較佳爲碳數2〜5者、更佳爲碳數者、特佳爲乙醯基。 R 1 G :可取代之碳數1〜1 2之烷基、例如甲基、乙丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基一基、十二基等。較佳爲碳數2〜8者、更佳爲碳數者、特佳爲乙基。(5) (wherein, R1, R2, R3, R4, R5, R6 and R7 are the same as defined in the above general formula (2), and R4 to R6 are bonded to each other to form a ring structure. , C; - C, 2 olefinic group, cycloalkenyl group, phenylene group, - - 8 - (18) 1289577 The substituent of the preferred compound is shown as 0 RI · 'Γη* The alkyl group having a carbon number of 1 to 10, such as a methyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group, is preferably a carbon number of 1 to 6 More preferably, it has a carbon number of 1 to 3, particularly preferably a methyl group. R2: an alkylene group having 2 to 10 carbon atoms which may be substituted, such as an ethyl fluorenyl group, a butyl group, a pentyl group, a hexyl group, and a fluorene group. Mercapto, octyl, hydrazino, fluorenyl, etc., preferably having a carbon number of 2 to 5, more preferably a carbon number, particularly preferably an ethylene group. R 1 G : a carbon number which can be substituted 1 to 1 2 An alkyl group, such as methyl, ethyl propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl-based, dodecyl, etc. preferably having a carbon number of 2 to 8, preferably It is a carbon number and is particularly preferably an ethyl group.

Rl2 R14及R15:氫原子 R13:可取代之苯甲醯基、較佳爲甲苯醯基、特佳甲苯醯基。上述一般式（3) 、（4) 、（5)及（6)所示化亦爲相同，其本身爲周知之化合物、例如、曰本 2 0 00- 8 0068號公報所記載之一連串化合物之一種。又、本發明之光聚合引發劑，可單獨使用上述肟化合物、亦可與其他之光聚合引發劑倂用、而可期待所致之高感度化。例如、可列舉下述之化合物。 2- (4-甲氧基苯基）-4，6-雙（三氯甲基）-s-三 2- (4 -甲氧基萘基）-4，6 -雙（三氯甲基）-s -三畊下所基、等。、丙壬醯 2〜3 基、、十 2〜6 爲鄰合物特開酯系併用畊、 -21 - 、2- -(4- (19) 1289577 (4-乙氧基萘基）-4，6-雙（三氯甲基）-s-三畊、2 乙氧基羰基萘基）-4，6-雙（三氯甲基）-s-三畊等之基化三畊衍生物、2 -三氯甲基-5 - ( 2 ’ -苯並呋喃基） 3，4-氧二氮茂、2-三氯甲基-5-〔 β- ( 2’-苯並呋喃基烯基〕-1，3，4-氧二氮茂、2-三氯甲基- 5-〔β-(2'_ 苯並呋喃基）乙烯基）〕-1，3，4-氧二氮茂、2-三基-5-呋喃基-1，3，4-氧二氮茂等之鹵甲基化氧二氮生物、2- (2’-氯苯基）-4，5-二苯基咪唑二聚物、2-氯苯基）-4，5 -雙（3 甲氧基苯基）咪唑二聚物 (2’-氟苯基）-4，5 -二苯基咪唑二聚物、2- (2’-甲氧基）-4，5-二苯基咪唑二聚物、（4'-甲氧基苯基）-4 二苯基咪唑二聚物等之咪唑衍生物、安息香基甲基醚息香基苯基醚、安息香基異丁基醚、安息香基異丙基之安息香基（benzoin)烷醚類、2-甲基蔥醌，2-乙醌，2 -第三丁基蔥醌、1 -氯蔥醌等之蔥醌衍生物、苯酮（ben zan throne) 衍生物、二苯基酮、米] (Michler’s ketone) 、2 -甲基二苯基酮1、3 -甲基二苯 4-甲基二苯基酮、2-氯二苯基酮、4-溴二苯基酮、2-二苯基酮等之二苯基酮衍生物、2，2-二甲氧基-2-苯醯苯、2，2 -二甲氧基乙醯苯、1-羥基環己基苯酮、基-2 -甲基苯基丙酮、1-羥基-1-甲基乙基-(P-異丙基）酮、1-羥基-1-(P-十二苯基）酮、2-甲基- (4'-基硫代）苯基）-2 -嗎啉代（m ο 1· p h ο 1 i η 〇 ) - 1 -丙酮、 1，]-三氯甲基-(ρ-丁基苯基）酮等之乙醯苯衍生物鹵甲 -1 ? )乙 ( 6 - 氯甲茂衍 (2，-、2- 基苯，5- 、安醚等基蔥并蒽 S酮基酮羧基基乙 a-羥基苯 (甲 1，、噻 -22 ‘ (20) 1289577 噸酮（thioxanthone ) 、2-乙基噻噸酮、2-異丙基噻噸酮I、 2 -氯噻噸酮、2 · 4 -二甲基噻噸酮、2、4 -二乙基噻噸酮、 2，4 ·二異丙基噻噸酮等之噻d頓酮衍生物、p -二甲基胺基苯甲酸乙酯、P -二乙基胺基苯甲酸乙酯等之苯甲酸酯衍生物、9-苯基吖啶（acridine ) 、9 -(對甲氧基苯基）吖啶等之吖啶衍生物、9 ， 1 〇 _二甲基苯并吩嗪 (benzphenazine )等之吩嗪衍生物、雙-環戊二烯二氯化物、雙-環戊二烯-Ti〜雙-苯基、雙-環戊二烯1丨_雙· (2，3，4，5，6-五氟苯、^基）、雙-環戊二烯-Ti-雙· (2，3，5，6-四氟苯-1-基）、雙-環戊二烯-Ti-雙_(2， 4，6-三氟苯-1-基）、雙·環戊二烯-Ti_2，6-二-氟苯q· 基、雙-環戊二烯- Ti-2’ 4 -二-氟苯-丨_基、雙-甲基環戊二烯- Ti-雙-(2，3，4，5，6〜五氟苯_卜基）、雙·甲基環戊二烯- Ti-雙_ ( 2，6-二-氟苯·卜基）、雙-環戊二烯- Ti-2， 6-二-氟-3-(吡咯（pyrryl ) 基）_苯-卜基等之二茂鈦 (t i t a η 〇 c e n e )衍生物等。本發明之光聚合性組成物、除了上述引發劑成分以外’進而可添加増感色素（sensitizing dye)。在高遮光下谷人產生光Ικ合反應、則添加増感色素較佳。此等増感色素、有例如日本特開平3 -239703號公報、日本特開平5_ 2 8 93 3 5號公報所記載之具有雜環之香豆素（⑶⑽““）化合物、日本特開昭63 -22 1 1]〇號公報記載之3_苯并二氫咲喃酮（ket〇Coumarin)化合物、日本特開平4·22ΐ 95 8號公報、日本特開平4_2 ：1975 6號公報記載之二苯駢哌喃 (21) 1289577 (xanthene)色素、日本特開平6-19240號公報記載之甲撐舭略（pyrro met hen e)色素、日本特開昭47-2528號公報、日本特開昭 5 4- 1 5 5 292號公報、日本特開昭 56-]66 1 5 4號公報、日本特開昭5 9- 5 64 0 3號公報記載之（對二烷基胺基亞苄基（benzylidene ))酮、苯乙烯基系色素、日本特開平 6-2 9 5 06 1號公報記載之具有杜烯 (durolidyl)基之増感色素、日本特開平1-326624號公報記載之二胺基苯化合物等。該等増感色素中特佳爲含胺基之増感色素及二苯駢哌喃色素。 (d )光聚合性單體本發明之光聚合性單體、係使用具有乙烯性不飽和基一個以上之化合物（以下、稱爲乙烯性化合物）。具體而言、有脂肪族（聚）羥基化合物與不飽和羧酸之酯、芳香族（聚）羥基化合物與不飽和羧酸之酯、不飽和羧酸與多價羧酸與脂肪族聚羥基化合物所得之酯、芳香族聚羥基化合物之環氧乙烷、環氧丙烷加成物與不飽和羧酸之酯化反應物、脂肪族聚羥基化合物之環氧乙烷、環氧丙烷加成物與不飽和羧酸之酯化反應物、已內酯變性多價醇與不飽和殘酸之醋、多價醇與多價異氰酸酯與不飽和羧酸之反應物、苯乙稀基末端化合物、含憐酸不飽和化合物、聚環氧基與不飽和羧酸之加成物等該等之中、脂肪族聚經基化合物與不飽和殘酸之醋， -24 - (24) 1289577 溶劑方面、可使構成組成物之各成分予以溶解或分散、選擇沸點爲100〜200 °C範圍之物較佳。更佳爲具有 1 2 0〜1 7 0 °C沸點者。此等溶劑有、例如、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、乙二醇單丁基醚丙二醇單甲基醚、丙二醇第三丁基醚、二乙二醇單甲基醚二乙二醇單乙基醚、甲氧基甲基戊醇、丙二醇單乙基醚、二丙二醇單乙基醚、二丙二醇單甲基醚、3-甲基-3-甲氧基丁醇、三丙二醇甲基醚等之乙二醇單烷基醚類；乙二醇二甲醚、乙二醇二***、二乙二醇二甲醚、二乙二醇二 ***、二乙二醇二丙醚、二乙二醇二丁醚等之乙二醇二烷基醚類；乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、甲氧基丁基乙酸酯、甲氧基戊基乙酸酯、二丙二醇單甲醚乙酸酯、3-甲基-3-甲氧基丁基乙酸酯等之乙二醇烷基醚乙酸酯類；二***、二丙醚、二異丙醚、丁醚、二戊烷基醚、乙基異丁基酸、一·己基酸等之釀類；丙酮、甲基乙基酮、甲基戊烷基酮、甲基異丙基酮、甲基異戊烷基酮、二異丁基酮、甲基異丙基酮、環己酮、乙基戊烷基酮、甲基丁基酮、甲基己基酮、甲基壬基酮等之酮類；乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二 -27- (25) 1289577 醇、二乙二醇、二丙二醇、甘油等之丨價或多儐醇類；正戊烷、正辛烷、二異丁烯、正己烷、己烷、異戊二 _、二戊烯、十二烷等之脂肪族烴類；己ί元、甲基ϊ哀己院、甲基環己嫌、二環己基等之脂環式烴類；本、甲苯、一甲苯、枯稀（cumene)等之芳香族烴類；甲酸戊醋（amyl formate)、甲酸乙酯、乙酸乙醋、乙酸丁酯、乙酸丙酯、乙酸戊酯、乙二醇乙酸酯、乙基丙酸酯、丙基丙酸酯、丁酸丁酯、丁酸異丙酯、異丁酸甲酯、乙基辛酸酯、丙基硬脂酸酯、乙基苯甲酸酯、3 -乙氧基丙酸甲酯、3 -乙氧基丙酸乙酯、3 -甲氧基丙酸甲酯、3 _乙氧基丙酸乙酯、3 -甲氧基丙酸甲酯、3 -甲氧基丙酸乙酯、3 _ 甲氧基丙酸丙酯、3 -甲氧基丙酸丁酯、γ-丁內酯等之鏈狀或環狀酯類； 3 -甲氧基丙酸、3 -乙氧基丙酸等之烷氧基羧酸類；丁基氯、戊基氯等之鹵烴類；甲氧基甲基戊酮等之醚酮類；乙腈、苄腈等之腈類；該當於上述之溶劑有、礦油精（m i n e r a 1 s p i r i t )、 Barsol #2、APCO #18 Solvent、APCO 稀釋齊!l ( thinner) Solcal 溶齊！1 No.l 及 Ν0·2、Solbeso #150、Shell TS28 溶齊!J 、卡比醇、乙基卡比醇、丁基卡比醇（carbital )、甲基溶纖劑、乙基溶纖劑、乙基溶纖劑乙酸酯、Diglyme等商品 -28- (26) 1289577 名之市售品。該等之溶劑、可單獨或數種混合使用。而本發明之光聚合性組成物、係使用該等之溶劑、使固形成分濃度爲5 〜5 0重量％、較佳爲！〇〜3 〇重量％之範圍之調液爲所望。在本發明此等必須成分（a ) 、（ b )及（c )、可因應需要添加任意成分（d )、除此以外可恰當的添加顔料分散劑、密接提高劑、塗敷性提高劑、顯像改良劑等。尤其是、在本發明之組成物係將黒色色材微細地分散、且、使其分散狀態穩定化，在品質安定上爲重要者，故配合顔料分散劑爲所望。顔料分散劑、係（a )黒色色材及（b )有機結合材之双方具有親和性者、有非離子、陽離子、陰離子等之界面活性劑、高分子分散劑等、其中、以高分子分散劑較佳、尤其是一級、二級、或三級胺基、吡啶、喃啶、吡嗪 (pyrazine)等之含氮雜環等之（e)具有鹼性官能基之高分子分散劑可有利地使用。 (e )作爲具有鹼性官能基之高分子分散劑若欲具體的例示較佳化學構造、例如、聚異氰酸酯化合物、分子内具有1個或2個羥基之化合物及同一分子内具有活性氫與 3級胺基之化合物予以反應所得分散樹脂等。上述聚異氰酸酯化合物之例、有對亞苯基二異氰酸酯、 2，4 -亞苄基異氰酸酯、2，6 -亞苄基二異氰酸酯、4，V-二苯基甲烷二異氰酸酯、萘基-1，5 -二異氰酸酯、聯甲苯胺（t ο 1 i d i n e )二異氰酸酯等之芳香族二異氰酸酯、亞己 -29- (29) 1289577 醇、苯二甲基乙二醇、雙羥基乙氧基苯等之芳香 N-甲基二乙醇胺等之N-烷基二烷醇胺等）予以得者、例如聚乙烯己二酸酯、聚丁烯己二酸酯、一酸醋、聚乙；(¾ /丙儲己一酸酯等、或前述二醇类j 〜2 5之1價醇作爲引發劑使用所得之聚內酯二醋單醇、例如聚己內酯二醇、聚甲基 (valerolactone)及該等之2種以上混合物。聚佳爲聚己內酯二醇或碳數1〜2 5之作爲引發劑酯。聚碳酸酯二醇、有聚（1，6 -亞己基）碳 (3 -甲基-1，5 -亞戊基）碳酸酯等、聚稀烴二醇烯二醇、氫添加型聚丁二烯二醇、氫添加型聚異 (isoprene)二醇等。在同一分子内具有i個或化合物之數平均分子量爲300〜1〇, 〇〇〇、較佳 6,000、更佳爲 1，000 〜4,000。本發明所用在同一分子内具有活性氫與3級合物加以説明。活性氫、亦即、與氧原子、氮原原子直接鍵結之氫原子、有羥基、胺基、硫醇（等之官能基中之氫原子、其中以胺基、尤其是1 氫原子較佳。3級胺基並無特別限定。又、3級具有碳數1〜4之烷基之胺基、或雜環構造、之、有咪唑環或***環。此等同一分子内具有活性氫與3級胺基之化如下、N，N-二甲基·1，3-丙烷二胺、N，N-二乙族二醇、縮聚合所聚己烯己 I或碳數1 醇或聚內戊內酯酯二醇最之聚己內酸酯、聚有聚丁二戊間二燒 2個羥基爲 5 0 0〜胺基之化子或硫磺 thiol )基級胺基之胺基、爲更具體言合物例示基-1 ， 3- -32- (30) 1289577 丙烷二胺、N，N -二丙基-1，3-丙烷二胺、n，N -二丁基_ 1，3-丙烷二胺、N，N -二甲基乙二胺、n， N -二乙基乙二胺、N，N-二丙基乙二胺、N，N-二丁基乙二胺、N，N-一甲基-1 ’ 4-丁一胺、Ν’ Ν -二乙基-1，4 -丁二胺、ν， Ν-二丙基-1，4-丁二胺、Ν，Ν·二丁基 q，4· 丁二胺等。又、三級胺基爲含氮雜環、則有吡唑（pyraz〇le ) 環、咪坐環、三坐環、四D坐環、吲哚環、昨口坐 (carbazole )環、吲唑（indazole )環、苯并咪π坐環、苯并***環、苯并噁唑環、苯並噻唑環、苯并噻二哗環等之含Ν雜5貝環、卩比卩疋1哀、噠嗦（p y r丨d a z i n e )環、嘧u定環、三嗪環、D奎啉（quinoline )環、吖啶環、異喧啉環、等之含N雜6員環。該等之含氮雜環，較佳爲咪唑環或 ***環。該等之具有咪唑環與胺基之化合物，具體例示之、則有1- ( 3-胺基丙基）咪唑、組織胺（histizine) 、2-胺基咪唑、1 - ( 2 -胺基乙基）咪唑等。又、具有***環與胺基之化合物，具體例示則有、3 -胺基-1，2，4 -***、5 - ( 2 -胺基-5-氯苯基）-3 -苯基-1H-1，2，4 -三卩坐、4 -胺基-4H-1，2，4 -*** _3，5 —二醇、3 -胺基-5-苯基-1H-1，3，4 -三唑、5 -胺基-1，4 -二苯基-1，2，3-***、3 -胺基-1-苄基-1 Η - 2，4 -***等。其中、Ν，Ν -二甲基-1，3 -丙二胺、Ν，Ν -二乙基-1， 3-丙二胺、1- ( 3-胺基丙基）咪唑、3-胺基-1，2，4-*** 較佳。分散劑原料之較佳配合比率爲相對於聚異氰酸酯化 -33- (31) 1289577 合物100重量份、在同一分子内具有1個或2個羥基之數平均分子量300〜10, 〇〇〇之化合物爲1〇〜200重量份、較佳爲20〜190重量份、更佳爲30〜180重量份、在同一分子内具有活性氫與3級胺基之化合物爲〇 . 2〜2 5重量份、較佳爲0.3〜24重量份。 (e)具有鹼基官能基之高分子分散劑之GPC換算重量平均分子量爲 15000〜200,000、較佳爲 2,000〜 100,000、更佳爲3,〇〇〇〜50,000之範圍。分子量1,000以下分散性及分散安定性差、在2 0 0，0 0 0以上溶解性降低，且分散性差同時反應之控制困難，而高分子分散劑之製造係依照聚胺基甲酸乙酯樹脂製造之公知之方法進行。製造之際之溶媒、通常、使用丙酮、甲基乙基酮、甲基異丁基酮、環戊酮、環己酮、異氟爾酮等之酮類、乙酸乙酯、乙酸丁酯、乙酸溶纖劑等之酯類、苯、甲苯、二甲苯、己烷等之烴類、雙丙酮醇、異丙醇、第二丁醇、第三丁醇等一部之醇類、二氯甲院（methylene chloride)、三氯甲院等之氯化物、四氫呋喃、二乙基醚等之醚類、二甲基甲醯胺、N-甲基吡咯烷酮、二甲基亞颯等之非質子性極性溶媒在上述製造之際、通常、係使用胺基甲酸乙酯化反應觸媒。例如、二丁基錫二月桂酸鹽、二辛基錫二月桂酸鹽、二丁基錫辛酸鹽、亞錫辛酸鹽等之錫系、鐵乙醯基乙酸酯、氯化鐵等之鐵系、三乙基胺、三亞乙基二胺等之三級胺系等。 -34- (32) 1289577 在同一分子内具有活性氫與三級胺基之化量，於反應後之胺價1〜l〇〇mg KOH/g之範圍佳。更佳爲5〜9 5mg KOH/g之範圍。胺價、基酸來中和滴定之、而以對應於酸値之KOH 表示之値。胺價在上述範圍以下時分散能力傾又、若超過上述範圍時顯像性易於降低。又、應使異氰酸酯基殘存於高分子分散劑之場合，或胺化合物使異氰酸酯基壓碎時，則生成物之變高爲佳。又、使用高分子分散劑之場合、其對於（a )黒色色材以〇. 1〜3 0重量％較佳、j 2 5重量％較佳。其次說明本發明之光聚合性組成物之製造發明中、通常黒色色材、係預先使用塗I (paint c ο n d i t i ο n e r )、砂濾器、球磨機、輥機、噴射式磨機、均質機等進行分散處理較佳處理使黒色色材微粒子化，而可達成抗蝕劑之高及塗布特性之提高，在分散處理中具有黒色色材與溶劑或分散結合劑、或者前述顔料分散劑進而予以倂用之以處理較佳尤其是使用高分子分散劑時，因安定性優異故較佳。又、以抗蝕劑液配合之全時在混合液下之分散處理、在分散時所產生發反應性之成分有變性之虞並不佳。在以砂濾器（sand grinder)分散之場合合物之導入予以控制較係使鹼性胺之 m g數來向於降低、在以上之反進而、以醇經時安定性使用比率相 :其是0.5〜方法。在本調節裝置磨機、石磨。藉由分散遮光能力提機能之有機系統中，予經時之分散成分予以同熱，會使高、可恰當的 (33) 1289577Rl2 R14 and R15: a hydrogen atom R13: a substituted benzamidine group, preferably a toluene group, and a particularly preferred toluene group. The above general formulas (3), (4), (5), and (6) are also the same, and are themselves a well-known compound, for example, a series of compounds described in Japanese Patent Publication No. 2000-80068. One. Further, the photopolymerization initiator of the present invention can be used alone or in combination with other photopolymerization initiators, and can be expected to have high sensitivity. For example, the following compounds are mentioned. 2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris-2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) -s - Three ploughs under the foundation, and so on. , propylene 2~3 base, and twentieth 6~6 are conjugates of conjugates, -21 - , 2- -(4- (19) 1289577 (4-ethoxynaphthyl)-4 , 6-bis(trichloromethyl)-s-three-pill, 2 ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-three tillage, etc. 2-trichloromethyl-5-( 2 '-benzofuranyl) 3,4-oxadiazepine, 2-trichloromethyl-5-[β-( 2'-benzofuranylalkenyl) -1,3,4-oxadiazoene, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl)]-1,3,4-oxadiazepine, 2 - Halomethylated oxadiazepines such as tris-5-furyl-1,3,4-oxadiazepine, 2-(2'-chlorophenyl)-4,5-diphenylimidazolium Polymer, 2-chlorophenyl)-4,5-bis(3 methoxyphenyl)imidazole dimer (2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2- (2'-Methoxy)-4,5-diphenylimidazole dimer, imidazole derivative of (4'-methoxyphenyl)-4 diphenylimidazole dimer, benzoin methyl Ethyl pyridyl phenyl ether, benzoin isobutyl ether, benzoin isopropyl benzoin Benzoin alkyl ether, 2-methyl onion, 2-acetamidine, 2-tert-butyl onion, 1-chloropurine and other onion derivatives, benzone (ben zan throne) derivatives, Phenyl ketone, rice] (Michler's ketone), 2-methyldiphenyl ketone 1, 3-methyldiphenyl 4-methyldiphenyl ketone, 2-chlorodiphenyl ketone, 4-bromodiphenyl Diphenyl ketone derivatives such as ketone and 2-diphenyl ketone, 2,2-dimethoxy-2-phenyl benzene, 2,2-dimethoxy acetophenone, 1-hydroxycyclohexyl benzene Ketone, -2-methylphenylacetone, 1-hydroxy-1-methylethyl-(P-isopropyl) ketone, 1-hydroxy-1-(P-dodecyl) ketone, 2- Methyl-(4'-ylthio)phenyl)-2 -morpholino (m ο 1 · ph ο 1 i η 〇) - 1 -acetone, 1,]-trichloromethyl-(ρ-butyl Ethyl benzene derivative such as phenyl phenyl ketone, halo-1 -? B (6-chloromethane derivative (2,-, 2-ylbenzene, 5-, ethene, etc.) Carboxylethyl a-hydroxybenzene (methyl 1, thio-22 ' (20) 1289577 ton ketone (thioxanthone), 2-ethyl thioxanthone, 2-isopropyl thioxanthone I, 2-chlorothioxanthone , 2 · 4 - dimethyl thioxanthone, 2, 4 - two a thiodonone derivative such as ethyl thioxanthone or 2,4 diisopropyl thioxanthone, ethyl p-dimethylaminobenzoate, ethyl P-diethylaminobenzoate, or the like a benzoate derivative, acridine derivative of 9-phenyl acridine, 9-(p-methoxyphenyl) acridine, etc., 9 , 1 〇 dimethyl benzophenazine ( Benzophenazine derivatives, bis-cyclopentadiene dichloride, bis-cyclopentadiene-Ti~bis-phenyl, bis-cyclopentadiene 1 丨 bis (2,3,4 , 5,6-pentafluorobenzene, benzyl), bis-cyclopentadiene-Ti-bis(2,3,5,6-tetrafluorophenyl-1-yl), bis-cyclopentadiene-Ti -bis-(2,4,6-trifluorophenyl-1-yl), bis-cyclopentadiene-Ti_2,6-di-fluorobenzene q-yl, bis-cyclopentadiene-Ti-2' 4 -difluorobenzene-indole-yl, bis-methylcyclopentadiene-Ti-bis-(2,3,4,5,6-pentafluorophenyl-bu), bis-methylcyclopentadiene - Ti-bis-(2,6-di-fluorophenyl)yl, bis-cyclopentadiene-Ti-2,6-di-fluoro-3-(pyrryl)-phenyl-bu-based Etc. Titanium (tita η 〇cene) derivatives and the like. In addition to the above-mentioned initiator component, the photopolymerizable composition of the present invention may further contain a sensitizing dye. It is preferred to add a sensitizing dye to the glutinous glutinous reaction of the gluten in the high light-shielding. For example, the coumarin having a heterocyclic ring ((3) (10) "") compound described in JP-A-H03-239703, JP-A No. Hei. -22 1 1] 3_benzoxanthone (ket〇Coumarin) compound described in the 〇公报、、、日本 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 记载记载记载记载记载记载记载记载记载记载记载记载Pyromethene (21) 1289577 (xanthene) dye, pyrro methene pigment described in JP-A-6-19240, JP-A-47-2528, and JP-A-2014 - 1 5 5 292, Japanese Patent Laid-Open No. 56-] No. 66 1 5 4, and Japanese Patent Laid-Open Publication No. 5 9- 5 64 0 (p-dialkylaminobenzylidene) a ketone, a styrene-based dye, and a diuryl phenyl compound described in JP-A No. 1-326624, which is described in the Japanese Patent Publication No. Hei. Wait. Among these sensitizing dyes, an amine group-containing sensitizing dye and a diphenyl sulfonium pigment are particularly preferred. (d) Photopolymerizable monomer The photopolymerizable monomer of the present invention is one or more compounds having an ethylenically unsaturated group (hereinafter referred to as an ethylenic compound). Specifically, there are esters of aliphatic (poly)hydroxy compounds and unsaturated carboxylic acids, esters of aromatic (poly)hydroxy compounds and unsaturated carboxylic acids, unsaturated carboxylic acids and polyvalent carboxylic acids, and aliphatic polyhydroxy compounds. The obtained ester, an ethylene oxide of an aromatic polyhydroxy compound, an esterification reaction of a propylene oxide adduct with an unsaturated carboxylic acid, an ethylene oxide or a propylene oxide adduct of an aliphatic polyhydroxy compound, Esterification reactant of unsaturated carboxylic acid, vinegar modified with lactone polyvalent alcohol and unsaturated residual acid, reaction of polyvalent alcohol with polyvalent isocyanate and unsaturated carboxylic acid, styrene terminal compound, pity An acid-unsaturated compound, an adduct of a polyepoxy group and an unsaturated carboxylic acid, or the like, an aliphatic poly-based compound and an unsaturated residual acid vinegar, -24 - (24) 1289577 It is preferred that the components constituting the composition are dissolved or dispersed to have a boiling point of from 100 to 200 °C. More preferably, it has a boiling point of 1 2 0 to 1 70 °C. Such solvents are, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether propylene glycol monomethyl Ether, propylene glycol, tert-butyl ether, diethylene glycol monomethyl ether diethylene glycol monoethyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Ethylene glycol monoalkyl ethers such as methyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol Ethylene glycol dialkyl ethers such as dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, dipropylene glycol Ethylene glycol acetate, 3-methyl-3-methoxybutyl acetate, etc.; ethylene glycol alkyl ether acetate; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentane Alkyl ether, ethyl Butic acid, monohexyl acid, etc.; acetone, methyl ethyl ketone, methyl pentanyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisobutyl ketone, A Ketones such as isopropyl ketone, cyclohexanone, ethylpentanone, methyl butyl ketone, methyl ketone ketone, methyl decyl ketone, etc.; ethanol, propanol, butanol, hexanol, ring a valence or polyterpene alcohol such as hexanol, ethylene glycol, or propylene dihydrogen -27-(25) 1289577 alcohol, diethylene glycol, dipropylene glycol, glycerin, etc.; n-pentane, n-octane, diisobutylene, n-hexane Aliphatic hydrocarbons such as hexane, isoprene, dipentene, and dodecane; alicyclic hydrocarbons such as hexane, methyl oxime, methylcyclohexyl, dicyclohexyl, etc. ; aromatic hydrocarbons such as toluene, monomethylbenzene, cumene, etc.; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, ethylene Alcohol acetate, ethyl propionate, propyl propionate, butyl butyrate, isopropyl butyrate, methyl isobutyrate, ethyl octanoate, propyl stearate, ethyl benzene Formate, 3-ethoxyl Methyl propionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-methoxypropionate, 3-methoxy a chain or cyclic ester of ethyl propionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone; 3-methoxypropionic acid, 3- An alkoxycarboxylic acid such as ethoxypropionic acid; a halogenated hydrocarbon such as butyl chloride or pentyl chloride; an ether ketone such as methoxymethylpentanone; a nitrile such as acetonitrile or benzonitrile; The above solvents are, mineral oil (minera 1 spirit), Barsol #2, APCO #18 Solvent, APCO diluted! l (thinner) Solcal dissolve! 1 No.l and Ν0·2, Solbeso #150, Shell TS28 are dissolved! J, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve , Ethyl cellosolve acetate, Diglyme and other commodities -28- (26) 1289577 commercial products. These solvents may be used singly or in combination of several. Further, the photopolymerizable composition of the present invention uses such a solvent to have a solid content concentration of 5 to 50% by weight, preferably!调~3 〇% by weight of the solution is expected. In the above-mentioned essential components (a), (b), and (c), the optional component (d) may be added as needed, and a pigment dispersant, an adhesion improver, a coatability improver, or the like may be appropriately added. Imaging improver, etc. In particular, in the composition of the present invention, the ochre color material is finely dispersed and stabilized in a dispersed state, which is important in quality stability. Therefore, it is desirable to blend a pigment dispersant. a pigment dispersant, a (a) ochre color material, and (b) an organic binder, both having affinity, a nonionic, cationic, anionic surfactant, a polymer dispersant, etc., wherein the polymer is dispersed The agent is preferably, in particular, a nitrogen-containing heterocyclic ring such as a primary, secondary or tertiary amine group, a pyridine, a pyridinium or a pyrazine, etc. (e) a polymeric dispersant having a basic functional group may be advantageous Use. (e) As a polymer dispersing agent having a basic functional group, a preferred chemical structure, for example, a polyisocyanate compound, a compound having one or two hydroxyl groups in the molecule, and an active hydrogen in the same molecule and 3 are specifically exemplified. A dispersion resin or the like obtained by reacting a compound of the amino group. Examples of the above polyisocyanate compound include p-phenylene diisocyanate, 2,4-benzylidene isocyanate, 2,6-benzylidene diisocyanate, 4,V-diphenylmethane diisocyanate, naphthyl-1, An aromatic diisocyanate such as 5-diisocyanate or toluidine (t ο 1 idine ) diisocyanate, or hexylene-29-(29) 1289577 alcohol, benzodimethyl glycol, bishydroxyethoxybenzene or the like An N-alkyl dialkanolamine such as aromatic N-methyldiethanolamine, etc.), such as polyethylene adipate, polybutylene adipate, mono-acid vinegar, polyethyl; (3⁄4 / propyl) The polylactone diacetal monool, such as polycaprolactone diol, polymethyl (valerolactone), and the like, which are used as an initiator, or a monovalent alcohol of the above-mentioned diols j to 2 5 as an initiator Two or more kinds of mixtures, such as polycaprolactone diol or carbon number 1 to 2 5 as an initiator ester. Polycarbonate diol, poly(1,6-hexylene) carbon (3-A) Poly-1,5-pentylene)carbonate, polydiene glycol diol diol, hydrogen addition type polybutadiene diol, hydrogen addition type isoprene diol, and the like. The number average molecular weight of i or a compound in the same molecule is 300 to 1 Å, 〇〇〇, preferably 6,000, more preferably 1,000 to 4,000. The present invention has active hydrogen in the same molecule and 3 levels. The active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom or a nitrogen atom, a hydroxyl group, an amine group, a thiol (such as a hydrogen atom in a functional group, wherein an amine group, especially 1) The hydrogen atom is preferred. The third-stage amine group is not particularly limited, and is an amine group having a C 1 to 4 alkyl group or a heterocyclic ring structure, and an imidazole ring or a triazole ring. The active hydrogen and the tertiary amine group are as follows, N,N-dimethyl-1,3-propanediamine, N,N-diethanediol, polycondensed polyhexene I or carbon number 1 alcohol or poly-n-lactone lactone diol is the most polycaprolactone, polybutadienyl di-sintered two hydroxyl groups are 500~ amine group or sulfur thiol)-based amine group Amine, as a more specific example, exemplified by -1, 3- -32- (30) 1289577 propanediamine, N,N-dipropyl-1,3-propanediamine, n,N-dibutyl _ 1,3-propanediamine, N,N-dimethylethylenediamine, n,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylene Amine, N,N-monomethyl-1 '4-butanamine, Ν' Ν-diethyl-1,4-butanediamine, ν, Ν-dipropyl-1,4-butanediamine, Ν,Ν·dibutyl q,4·butylenediamine, etc. Further, the tertiary amino group is a nitrogen-containing heterocyclic ring, and there are pyrazole (pyraz〇le) rings, microphone rings, three rings, and four D seats. Ring, anthracycline, carbazole ring, indazole ring, benzopyrene π ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazine环5,5卩, 卩1卩疋, pyrpydazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoporphyrin Rings, etc. contain N hetero 6-member rings. The nitrogen-containing heterocyclic ring is preferably an imidazole ring or a triazole ring. Such compounds having an imidazole ring and an amine group, specifically exemplified are 1-(3-aminopropyl)imidazole, histizine, 2-aminoimidazole, 1-(2-aminoethyl) Base) imidazole and the like. Further, a compound having a triazole ring and an amine group, and specifically exemplified is 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl -1H-1,2,4-triterpenoid, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1, 3,4-triazole, 5-amino-1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1-indole-2,4-triazole, and the like. Wherein, hydrazine, hydrazine-dimethyl-1,3-propanediamine, hydrazine, hydrazine-diethyl-1, 3-propanediamine, 1-(3-aminopropyl)imidazole, 3-amino group -1,2,4-triazole is preferred. The preferred blending ratio of the dispersant raw material is 100 to 10 parts by weight of the polyisocyanate-33-(31) 1289577 compound, and has an average molecular weight of 300 to 10 in one molecule or two hydroxyl groups in the same molecule. The compound is from 1 to 200 parts by weight, preferably from 20 to 190 parts by weight, more preferably from 30 to 180 parts by weight, and the compound having active hydrogen and a tertiary amino group in the same molecule is 2 to 2 parts by weight. Preferably, it is 0.3 to 24 parts by weight. (e) The polymer-dispersing polymer having a base functional group has a GPC-equivalent weight average molecular weight of from 15,000 to 200,000, preferably from 2,000 to 100,000, more preferably from 3 to 50,000. When the molecular weight is 1,000 or less, the dispersibility and the dispersion stability are inferior, the solubility is lowered at 2000 or more, and the dispersibility is poor, and the control of the reaction is difficult. The production of the polymer dispersant is made of a polyurethane resin. A known method is carried out. A solvent for the production, usually, a ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone or isophorone, ethyl acetate, butyl acetate, acetic acid An ester such as a cellosolve, a hydrocarbon such as benzene, toluene, xylene or hexane, an alcohol such as diacetone alcohol, isopropanol, a second butanol or a third butanol, or a dichlorocarbyl (methylene chloride), a chloride such as trichloromethane, an ether such as tetrahydrofuran or diethyl ether, an aprotic polar solvent such as dimethylformamide, N-methylpyrrolidone or dimethyl alum. In the above production, a urethane reaction catalyst is usually used. For example, tin-based, di-butyltin dilaurate, dibutyltin octoate, stannous octoate, tin-based, iron-ethyl acetate, iron chloride, etc. A tertiary amine such as a base amine or triethylenediamine. -34- (32) 1289577 The amount of active hydrogen and tertiary amine group in the same molecule is preferably in the range of 1 to 10 mg KOH/g of the amine after the reaction. More preferably, it is in the range of 5 to 9 5 mg KOH/g. The amine valence, the base acid is used to neutralize the titration, and the KOH is represented by the KOH corresponding to the acid hydrazine. When the amine value is less than the above range, the dispersibility is lowered, and when it exceeds the above range, the developing property is liable to lower. Further, when the isocyanate group remains in the polymer dispersant, or when the amine compound crushes the isocyanate group, the product becomes high. Further, in the case of using a polymer dispersant, it is preferable that the (a) ochre color material is preferably from 1 to 30% by weight, and preferably from 2 to 5% by weight. Next, in the invention for producing a photopolymerizable composition of the present invention, usually a ochre color material is used, and a coating I (paint c nd rit ner ), a sand filter, a ball mill, a roll mill, a jet mill, a homogenizer, etc. are used in advance. Preferably, the dispersing treatment is performed to finely pulverize the ochre color material, thereby achieving high resist and improvement in coating properties, and having a ochre color material, a solvent or a dispersing binder, or the pigment dispersing agent in the dispersion treatment. It is preferred to use it for treatment, especially when a polymer dispersant is used, because it is excellent in stability. Further, it is not preferable that the resist liquid is uniformly dispersed in the mixed solution at the time of the dispersion, and the component which is reactive at the time of dispersion is denatured. In the case of dispersing with a sand grinder, the introduction of the compound is controlled so that the number of mg of the basic amine is decreased, and the ratio of the above is further reversed, and the ratio of the alcohol is used for stability: it is 0.5~ method. In this adjustment device mill, stone grinding. In an organic system that disperses the ability to dissipate light, the dispersing components of the time are given the same heat, which is high and appropriate (33) 1289577

使用〇 . 1〜8 m m徑之玻璃珠（b e a d )或錐氧（z i ι· c ο n i a )珠。使分散之條件、通常、温度爲〇°C至l〇〇t、較佳爲、室温至8 0 °C之範圍。分散時間會因油墨之組成（黒色色材、溶劑、分散劑）及砂磨機之裝置尺寸等因適正時間之不同而可適宜調節，控制油墨之光澤使抗蝕劑之2 0度光澤値在1 〇〇〜2 0 0之範圍，分散之目標。在抗餓劑光澤降低時分散處理並非充分多有粗的顔料粒子之殘存、就顯像性、密接性、解像性等之點而言並不充分。又、進行分散處理時使光澤値超過上述範圍爲止，因超微粒子多數產生，反而易於損及分散安定性。其次上述分散處理所得黒色油墨與抗蝕劑成分，可添加、混合必要的上述其他成分成爲均勻之溶液。在製造步驟中因微細的灰塵多混在於感光液、故所得抗蝕劑感光液藉由過濾器等來進行濾過處理爲所望。接著、就使用本發明光聚合性組成物之濾色器之製造方法加以説明。Use 玻璃. 1 to 8 m m glass beads (b e a d ) or cone oxygen (z i ι· c ο n i a ) beads. The conditions for dispersion, usually, the temperature are in the range of 〇 ° C to l 〇〇 t, preferably, room temperature to 80 ° C. The dispersion time can be adjusted according to the composition of the ink (green color material, solvent, dispersant) and the size of the sander, etc., and the gloss of the ink can be adjusted to make the gloss of the resist 1 〇〇 ~ 2 0 0 range, the goal of dispersion. When the gloss of the anti-hungry agent is lowered, the dispersion treatment is not sufficient, and the remaining pigment particles remain insufficient, and are not sufficient in terms of developability, adhesion, and resolution. Further, when the dispersing treatment is carried out, the gloss 値 exceeds the above range, and most of the ultrafine particles are generated, and the dispersion stability is easily impaired. Next, the ochre ink and the resist component obtained by the above dispersion treatment can be added and mixed with the above-mentioned other components to form a homogeneous solution. In the manufacturing step, fine dust is often mixed in the photosensitive liquid, so that the resulting resist photosensitive liquid is subjected to filtration treatment by a filter or the like. Next, a method of producing a color filter using the photopolymerizable composition of the present invention will be described.

首先、在透明基板上、藉由旋轉器，盤條（Wire bar )，淋塗機（flow coater )，模塗敷機，輥塗敷機，噴灑器等之塗敷裝置將本發明之光聚合性組成物予以塗敷乾燥後、在該試料上放置光罩（P h 〇 t 〇 m a s k )、藉由該光罩使畫像曝光，顯像，並因應需要藉由熱硬化或光硬化形成遮光用BM畫像、進而使此操作就RGB3色予以各自重複進行、以形成濾色器畫像。又、使用本發明之光聚合性組成物來形成濾色器畫素之情形、因爲有非常高感度、高解像力、故不設置聚乙烯 ^35- (34) 1289577 醇等之氧遮斷層就可進行曝光、顯像以用之透明基板、係濾色器用透明基板、定、例如、聚對苯二甲酸乙二酯等之聚烯等之聚烯烴等、聚碳酸酯、聚甲基甲等之熱可塑性塑膠薄片、環氧樹脂、聚烯酸酯樹脂等之熱硬化性塑膠薄片、或其是、就耐熱性之點而言以使用玻璃；佳。在此等透明基板、爲改良表面之接先進行電暈放電處理、臭氧處理、砂院乙酯聚合物等之各種聚合物之薄膜處理特別限定、塗敷、乾燥後之樹脂黑色基 2 μ m、較佳爲 0 · 1〜1 . 5 μ m、更佳爲〇 . 1 本發明之濾色器、就遮光性之點言之於度爲3 · 0以上較佳。又、以顔料等固型指標、貝(J BM20度光澤値爲1〇〇〜200較在乾燥時可使用熱板、IR火: (convection oven )等、較佳爲乾燥條燥時間1 0秒〜6 0分之範圍。又、曝光氙氣燈、鹵素燈、鎢燈、高壓水銀燈、屬鹵素燈、中壓水銀燈、低壓水銀燈等射、YAG雷射、激態原子（excimer ) 雷射光源等。在僅使用特定照射光波長學過濾器。形成畫像。在此所其材質並無特別限酯或聚丙烯、聚乙基丙烯酸酯、聚颯酯樹脂、聚甲基丙各種玻璃板等。尤板、耐熱性塑膠較着性等物性、可預偶合劑或胺基甲酸等。塗敷方法並無質之fe厚爲0.1〜〜1 μ m範圍。又、膜厚Ιμηι、光學濃成分之分散狀態爲 :爲有利。考爐、對流烤爐件 4 0〜1 5 0 °C、乾所用光源、例如、超高壓水銀燈、金燈光源或氬離子雷雷射、氮雷射等之之情形則可利用光 (35) 1289577 顯像處理、若爲使未曝光部之抗蝕劑膜有溶解能力之溶劑則無受特別限制。例如可使用丙酮、二氯乙烯、三氯乙烯（trichlene )、環己酮等有機溶劑。但是、因有機溶劑多具有環境汚染性、對人體有害性、火災危險性等、使用此等無危險性之鹼性顯像液較好。此等鹼性顯像液、有例如、碳酸鈉、碳酸鉀、矽酸鈉、矽酸鉀、氫氧化鈉、氫氧化鉀等無機鹼性劑、或者二乙醇胺、三乙醇胺、羥基化四烷基銨鹽等之含有有機鹼性劑水溶液。在鹼性顯像液、可因應必要、含有界面活性劑、水溶性之有機溶劑、具羥基或羧基之低分子化合物等。尤其是、界面活性劑相對於顯像性、解像性、質地汚染等多具有改良効果，故添加較佳。例如、顯像液用之界面活性劑、則有萘基磺酸鈉基、苯基磺酸鈉基之陰離子性界面活性劑、聚烷基氧基之非離子性界面活性劑、具四烷基銨基之陽離子性界面活性劑等。在顯像處理方法方面並無特別限制、通常、在1 〇〜 5 〇 °C、較佳是以15〜45 °c之顯像温度、澄淸顯像、噴灑顯像、刷毛（brush )顯像、超音波顯像等方法來進行。其次、就本發明之液晶顯示裝置（面板）加以説明。本發明之液晶顯示裝置、係使用前述之濾色器所成爲其特徵者。因此、可以下述方式製造。首先、在濾色器上形成定向膜、在此定向膜上配置隔件後、與對向基板貼合形成液晶晶胞。接著、在所形成之 '液晶晶胞注入液晶、與對向電極結線而完成。 (36) 1289577 定向膜、以聚醯胺等之樹脂膜爲恰當。定向膜之形成、通常、係採用照相凹版（gravure )印刷法或苯胺 (flexography )印刷法、通常、使定向膜之厚度爲 1 0〜1 0 0 η m。在進行熱煅燒所致之定向膜硬化處理後、藉由紫外線照射或磨光（lapping )塗敷處理所致之表面處理、在可調節液晶傾斜之表面狀態予以加工。隔件係使用於因應與對向基板之間隔（cap )(間隙）大小、通常2〜8 μη者爲恰當。在濾色器之基板上、藉由照相石板法（photolithography )法來形成透明樹脂膜之光隔件（p h 〇 t 〇 s p a c e r ) ( P S )、可以此來取代隔件加以活用。對向基板、通常、係使用（陣列）基板、尤其是TFT (薄膜電晶體）基板爲恰當。與對向基板貼合之間隔、因液晶顯示裝置之用途而異、通常選擇2〜8 μπι之範圍。與對向基板貼合後、在液晶注入以外部分、被環氧樹脂等之密封材料所密封。密封材料係藉由 UV照射及/或加熱使之硬化、並在液晶晶胞周邊被密封。周邊被密封之液晶晶胞、以面板切斷後、在真空反應室内減壓、將上述之液晶注入口浸漬於液晶後、藉由反應室内之漏出、在液晶晶胞内注入液晶。液晶晶胞内之減壓度、通常爲1 XI 〇_2〜1 xl(T7Pa、較佳爲1 X ι〇·3〜J χ 1 (Γ6 P a。又、在減壓時使液晶晶胞加溫較佳、加温溫度、通常爲3 0〜1 0 0 °C、較佳爲5 0〜9 0 °C，減壓時之加溫保持、通常在1 〇〜6 0分之範圍、其後浸漬於液晶中。在已 -39- (37) 1289577 注入液晶之液晶晶胞、錯由U V硬化樹脂之硬化、可使液晶注入口密封、而完成液晶顯示裝置（面板）。液晶種類、並無特別限制、可爲芳香族系、脂肪族系、多環狀化合物等、習知公知之液晶、液向性 (1 y 〇 t r 〇 p i c )液晶、熱向性液晶等任一均可。在熱向性 (t h e r m a 11 r 〇 p i c )液晶中，以向列相（n e m a t i c )液晶、距列相（s m e c t i c )液晶、膽固醇相（c h o r e s t e r i c )液晶等爲周知、而該等之中可任擇一種。【實施方式】〔實施例〕以下參照實施例及比較例更詳細說明本發明、但本發明在不超越要旨之範圍內，並非只限定於以下之實施例。合成例-1 (高分子分散劑溶液調製）亞苄基二異氰酸酯之三聚物（三菱化學公司製、 MytecGP75 0A、樹脂固形成分50重量％、乙酸丁酯溶液） 3 2 g與爲觸媒之二丁基錫二月桂酸鹽〇.〇2g在丙二醇單甲醚乙酸酯（P G Μ E A ) 4 7 g下稀釋溶解。在攪拌下、使其一方末端爲甲氧基之數平均分子量丨，000之聚乙二醇（曰本油脂公司製、UNIOXM- 1 000 ) Μ·4 g與數平均分子量 15〇〇〇之聚丙二醇（三洋化成工業公司製、3111^11^1^-1 0 0 0 ) 9.6 g之混合物予以滴定後、於7 0 °C進而使反應3 小時。接著、添加N，N-二甲基胺基，％丙二胺、於 ^40 - (38) 1289577 4 〇 °C進而反應1小時。如此所得之含有高分子分散劑之溶液之胺價藉由中和滴定來求得其値爲14mg KOH/g。又、藉由乾燥法（dry up )來求得樹脂含有量（1501：，30分鐘、在熱板上除去溶劑，依重量變化量來算出樹脂濃度）而爲4 0重量。/〇。合成例-2 (有機結合材之合成）環氧當量200g/eq、軟化點6 5°C之鄰甲酚粉醛淸漆環氧樹脂200g、丙烯酸72g、對甲氧基酚0.2 g、十二基三甲基銨氯化物0.2 g、PGMEA 2 72g裝入燒瓶，在l〇〇°C 温度下反應8小時（相對於環氧基1當量、使丙烯酸1當量反應）。進而、添加四氫酞酸酐42g於80°C下反應3 小時。將此反應液再沈殿於水、使真空乾燥，得到具羧基之粉醛淸漆環氧丙烯酸酯樹脂。藉由KOH來進行中和滴定時樹脂之酸値爲50mg KOH/g。合成例-3 (有機結合材之合成）除了四氫酞酸酐之添加量爲63 g以外，其他則與合成例-2同樣進行反應。所得之樹脂酸値爲70mg KOH/g。 (碳黑之分散）以顏色用碳黑（三菱化學公司製、MA-220 ) 5 0重量份、合成例-1所示高分子分散劑爲固形成分之5重量份之比率、且固形成分濃度爲5 0重量％之方式添加碳黑、高 -41 - (39) 1289577 分子分散劑溶液及PGMEA。分散液之全重量爲50g。使其藉由攪拌機加以攪拌，來進行預混（P r e m i X i n g )。接著、藉由塗料攪拌器（paint shaker)在25〜45°C 範圍進行6小時分散處理。小珠係使用0.5 mm 0之銷氧珠、添加與分散液同樣的重量。分散完成後、藉由過濾器使小珠與分散液分離。實施例1〜3及比較例1〜3 (1 )抗蝕劑液之調合使用上述之碳黑分散油墨，添加各成分（a )、 (b ) 、( c ) 、( d ) 、( e )、有機溶劑及界面活性劑使作爲固形成分成爲下述之配合比率、藉由攪拌機 (s t i r r e r s )攪拌、溶解、來調整黑色抗蝕劑感光液。 (a )黒色色材碳黑（三菱化學公司製、ΜΑ-220) 50g (b )有機結合劑 (表2所記載） 30g (d )光聚合性單體··乙烯性化合物二新戊四醇六丙烯酸酯 10g (c)光聚合引發劑 (表2所記載）有機溶劑丙二醇單甲基醚乙酸酯 300g (e)高分子分散劑（合成例-1) 5g -42 - (40) 1289577 界面活性劑（住友3M公司製、FC-4 3 0) ΙΟΟρρηι (2)抗蝕劑之評價First, the photopolymerization of the present invention is carried out on a transparent substrate by a coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, a sprayer or the like. After the composition is applied and dried, a mask (P h 〇t 〇 mask ) is placed on the sample, and the image is exposed, developed, and formed by heat hardening or light hardening as needed. The BM image is further reproduced in this manner by RGB3 colors to form a color filter image. Further, in the case where the photopolymerizable composition of the present invention is used to form a color filter pixel, since it has a very high sensitivity and a high resolution, it is not necessary to provide an oxygen barrier layer such as polyethylene 35-(34) 1289577 alcohol. a transparent substrate for exposure and development, a transparent substrate for a color filter, a polyolefin such as a polyene such as polyethylene terephthalate, a polycarbonate, a polymethyl group or the like. A thermosetting plastic sheet such as a thermoplastic plastic sheet, an epoxy resin, a polyacrylate resin, or the like, or a glass for use in terms of heat resistance; In these transparent substrates, the surface treatment of various polymers such as corona discharge treatment, ozone treatment, and sand-based ethyl ester polymer for the improvement of the surface is particularly limited, coated, and dried after the resin black base 2 μ m Preferably, it is 0. 1 to 1. 5 μ m, more preferably 〇. 1 The color filter of the present invention is preferably at least 3.0 in terms of the light-shielding property. In addition, a solid type index such as a pigment, a shell (J BM 20 degree gloss 値 is 1 〇〇 to 200, a hot plate can be used for drying, an IR convection oven, etc., preferably a drying time of 10 seconds) ~60 ° range. Also, exposed xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, halogen lamp, medium pressure mercury lamp, low pressure mercury lamp, YAG laser, excimer laser source. The filter is formed using only a specific wavelength of the illuminating light. The image is formed here. The material is not particularly limited to ester or polypropylene, polyethyl acrylate, polydecyl acrylate resin, polymethyl acrylate glass, etc. , heat-resistant plastics, etc., pre-coupling agent or urethane, etc. The coating method is not in the range of 0.1 to 〜1 μm, and the film thickness Ιμηι, the dispersion state of the optically concentrated component For the benefit of the test furnace, convection oven parts 40 ~ 1 50 ° C, dry source, for example, ultra-high pressure mercury lamp, gold light source or argon ion laser, nitrogen laser, etc. Use light (35) 1289577 development processing, if not exposed The solvent having a dissolving ability of the resist film is not particularly limited. For example, an organic solvent such as acetone, dichloroethylene, tricholene or cyclohexanone can be used. However, organic solvents are more environmentally polluting. It is good for the use of such non-hazardous alkaline imaging liquids, such as sodium carbonate, potassium carbonate, sodium citrate, potassium citrate. An inorganic alkaline agent such as sodium hydroxide or potassium hydroxide, or an aqueous solution containing an organic alkaline agent such as diethanolamine, triethanolamine or a hydroxylated tetraalkylammonium salt. In an alkaline developing solution, it may be necessary to contain an interface. An active agent, a water-soluble organic solvent, a low molecular compound having a hydroxyl group or a carboxyl group, etc. In particular, the surfactant has an improved effect with respect to development, resolution, texture contamination, etc., so that it is preferably added. a surfactant for a developing solution, an anionic surfactant having a sodium naphthalenesulfonate group, a sodium phenylsulfonate group, a nonionic surfactant having a polyalkyloxy group, and a tetraalkylammonium group. Sun away a surfactant, etc. There is no particular limitation on the development method, and usually, a development temperature of 1 〇 5 5 ° C, preferably 15 to 45 ° C, a sputum imaging, a spray imaging Next, the liquid crystal display device (panel) of the present invention will be described. The liquid crystal display device of the present invention is characterized by using the above-described color filter. Therefore, it can be manufactured in the following manner. First, an alignment film is formed on a color filter, and a spacer is disposed on the alignment film, and then bonded to the opposite substrate to form a liquid crystal cell. Next, the formed liquid crystal The cell is injected into the liquid crystal and is completed by bonding to the opposite electrode. (36) 1289577 The alignment film and the resin film such as polyamine are suitable. The formation of the alignment film is usually carried out by a gravure printing method or a flexography printing method, and usually, the thickness of the alignment film is 10 to 1 0 0 η m. After the orientation film hardening treatment by the thermal calcination, the surface treatment by the ultraviolet irradiation or the lapping coating treatment is performed, and the surface of the liquid crystal is tilted to be processed. The spacer is preferably used in accordance with the size (cap) of the opposing substrate (interval), usually 2 to 8 μη. The optical spacer (p h 〇 t 〇 s p a c e r ) ( P S ) of the transparent resin film is formed on the substrate of the color filter by a photolithography method, and the spacer can be used instead. It is appropriate to use the (array) substrate, especially the TFT (thin film transistor) substrate, for the counter substrate. The interval to be bonded to the counter substrate is different depending on the use of the liquid crystal display device, and a range of 2 to 8 μm is usually selected. After bonding to the counter substrate, the portion other than the liquid crystal injection is sealed with a sealing material such as an epoxy resin. The sealing material is hardened by UV irradiation and/or heating and sealed at the periphery of the liquid crystal cell. The liquid crystal cell sealed in the periphery is cut by a panel, decompressed in a vacuum reaction chamber, and the liquid crystal injection port is immersed in a liquid crystal, and then leaked through the reaction chamber to inject liquid crystal into the liquid crystal cell. The degree of pressure reduction in the liquid crystal cell is usually 1 XI 〇 2 to 1 x 1 (T7Pa, preferably 1 X ι 〇 3~J χ 1 (Γ6 P a. Further, the liquid crystal cell is made under reduced pressure) The heating temperature is preferably a heating temperature, usually 30 to 1 0 0 ° C, preferably 5 0 to 90 ° C, and the temperature is maintained under reduced pressure, usually in the range of 1 〇 to 60 °, Thereafter, it is immersed in a liquid crystal. The liquid crystal cell in which liquid crystal is injected at -39-(37) 1289577 is cured by UV curing resin, and the liquid crystal injection port can be sealed to complete the liquid crystal display device (panel). The liquid crystal, the liquid crystal (1 y 〇tr 〇pic) liquid crystal, the thermal liquid crystal, or the like which are known in the art, such as an aromatic system, an aliphatic system, or a polycyclic compound, may be used. In the thermotropic (therma 11 r 〇pic) liquid crystal, nematic liquid crystal, smectic liquid crystal, choresteric liquid crystal, etc. are known, and one of them may be selected. [Embodiment] [Examples] Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. The present invention is not limited to the following examples. Synthesis Example-1 (Preparation of polymer dispersant solution) Terpolymer of benzylidene diisocyanate (Mitsubishi Chemical Co., Ltd., Mytec GP75 0A, resin solid) 50% by weight of the component, butyl acetate solution) 3 2 g and dibutyltin dilaurate as a catalyst, 〇 2g diluted in propylene glycol monomethyl ether acetate (PG Μ EA ) 4 7 g dissolved. A polyethylene glycol having a number average molecular weight of 丨, 000 at one end (manufactured by Sakamoto Oil Co., Ltd., UNIOXM-1 000) Μ·4 g and a polypropylene glycol having a number average molecular weight of 15 Å ( A mixture of 3111^11^1^-1 0 0 0 ) 9.6 g manufactured by Sanyo Chemical Industry Co., Ltd. was titrated and further reacted at 70 ° C for 3 hours. Then, N,N-dimethylamino group was added. % propylenediamine was further reacted for 1 hour at 40 ° (38) 1289577 4 ° C. The amine valence of the solution containing the polymer dispersant thus obtained was determined by neutralization titration to obtain a hydrazine of 14 mg KOH/g. Again, the resin content was determined by dry up (1501:, 30 minutes, at The solvent was removed from the plate, and the resin concentration was calculated according to the amount of change in weight. The weight was 40%. /〇. Synthesis Example-2 (Synthesis of organic binder) Ethylene equivalent of 200 g/eq, softening point of 65 °C Phenol aldehyde enamel paint epoxy resin 200g, acrylic acid 72g, p-methoxyphenol 0.2 g, dodecyl trimethyl ammonium chloride 0.2 g, PGMEA 2 72g into the flask, reaction at 10 ° C temperature 8 Hour (1 equivalent of acrylic acid is reacted with 1 equivalent of acrylic acid). Further, 42 g of tetrahydrophthalic anhydride was added and reacted at 80 ° C for 3 hours. The reaction solution was again poured into water and dried under vacuum to obtain a powdery aldehyde lacquer epoxy acrylate resin. The acid hydrazine of the resin was neutralized by KOH to be 50 mg KOH/g. Synthesis Example-3 (Synthesis of Organic Bonding Material) The reaction was carried out in the same manner as in Synthesis Example 2 except that the amount of tetrahydrophthalic anhydride added was 63 g. The obtained resin strontium was 70 mg KOH/g. (Dispersion of carbon black) 50 parts by weight of carbon black (manufactured by Mitsubishi Chemical Corporation, MA-220) and a polymer dispersant represented by Synthesis Example-1 as a ratio of 5 parts by weight of solid content, and solid content concentration Carbon black, high-41 - (39) 1289577 molecular dispersant solution and PGMEA were added in a manner of 50% by weight. The total weight of the dispersion was 50 g. Premixing (P r e m i X i n g ) was carried out by stirring with a stirrer. Next, dispersion treatment was carried out for 6 hours in the range of 25 to 45 ° C by a paint shaker. The beads were made of 0.5 mm 0 of oxygen beads and added to the same weight as the dispersion. After the dispersion is completed, the beads are separated from the dispersion by a filter. Examples 1 to 3 and Comparative Examples 1 to 3 (1) Combination of resist liquids Using the carbon black dispersion ink described above, each component (a), (b), (c), (d), (e) was added. The organic solvent and the surfactant were adjusted to have a solid content as a blending ratio described below, and stirred and dissolved by a stirrer to adjust the black resist photosensitive liquid. (a) Green color carbon black (manufactured by Mitsubishi Chemical Corporation, ΜΑ-220) 50 g (b) Organic binder (described in Table 2) 30 g (d) Photopolymerizable monomer··Ethylene compound dipentaerythritol Hexaacrylate 10g (c) Photopolymerization initiator (described in Table 2) Organic solvent propylene glycol monomethyl ether acetate 300g (e) Polymer dispersant (Synthesis Example-1) 5g -42 - (40) 1289577 Interface Active agent (made by Sumitomo 3M Co., Ltd., FC-4 3 0) ΙΟΟρρηι (2) Evaluation of resist

將黑色抗蝕劑感光液在旋轉塗膜機予以塗敷於玻璃基板（Corning公司製、7 0 5 9 )、在熱板乾燥80°C、1分鐘。乾燥後之抗蝕劑膜厚以觸針式膜厚計（TenC01·公司製、a-步驟）測定則爲1 μηι。接著、將此樣本透過掩罩以高壓水銀燈改變曝光量予以像曝光。使用温度2 5 °C、濃度〇 · 8 %之碳酸鈉水溶液藉由噴灑顯像而獲得抗蝕劑圖案。感度、解像力及遮光性係以下述基準評價、得到表2 結果。 1.感度The black resist photosensitive liquid was applied onto a glass substrate (manufactured by Corning Co., Ltd., 7059) in a spin coater, and dried on a hot plate at 80 ° C for 1 minute. The thickness of the resist film after drying was 1 μm by a stylus film thickness meter (manufactured by TenC01·Company, a-step). Then, the sample is exposed to the image by masking the exposure amount with a high pressure mercury lamp. A resist pattern was obtained by spray development using a sodium carbonate aqueous solution having a temperature of 2 5 ° C and a concentration of 8%. The sensitivity, the resolution, and the light-shielding property were evaluated by the following criteria, and the results of Table 2 were obtained. Sensitivity

2 0 μηι之掩罩圖案係以按照尺寸來形成之適正曝光量 (mj/cm2 )來表示。亦即、曝光量少的抗蝕劑在低曝光量可使畫像形成，故顯示爲高感度。 2 ·解像力在可使2 0 μηι掩罩圖案忠實再現之曝光量中，以可解像之抗蝕劑最小圖案尺寸於200倍倍率的顕微鏡觀察最小圖案尺寸爲1 以下，解像力超過〇、1 Ομηι者以X表示0 3 .遮光性 -43 - (42) 1289577 【化8】The mask pattern of 20 μm is expressed by a suitable amount of exposure (mj/cm 2 ) formed in accordance with the size. In other words, since the resist having a small exposure amount can form an image at a low exposure amount, it is displayed as high sensitivity. 2 · The resolution is in the exposure amount that can faithfully reproduce the 20 μηι mask pattern, and the minimum pattern size is 1 or less with a minimum mirror size of the solvable resist at a magnification of 200, and the resolution exceeds 〇, 1 Ομηι It is represented by X as 0 3 . opacity -43 - (42) 1289577 [Chemical 8]

c-2:4-(間溴對甲氧基苯基）-2，6-二（三氯甲基）-s-三嗪.........（5 g ) c-3:2，2’一雙（鄰氯苯基）-4，V 5，5’-s四苯基二咪唑 (2g)十4，4·-雙（二乙基胺）二苯基酮（lg)十2-氫硫基苯并噻唑（1 g )C-2: 4-(m-bromo-p-methoxyphenyl)-2,6-bis(trichloromethyl)-s-triazine (5 g ) c-3: 2,2'-double (o-chlorophenyl)-4,V 5,5'-s tetraphenyldiimidazole (2g) tetra- 4,4-bis(diethylamine)diphenyl ketone (lg) Tetrahydrothiobenzothiazole (1 g )

c-4:光聚合引發劑（千葉特用化學品公司製、CGI- 242 ) ......... ( 5 g ) 【化9】C-4: Photopolymerization initiator (manufactured by Chiba Special Chemicals Co., Ltd., CGI-242) (5 g ) [Chem. 9]

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Claims

1289577 拾、申請專利範圍第921 25645號專利申請案中文申請專利範圍修正本民國96年8月1〇曰修正 1 · 一種光聚合性組成物，其特徵爲含有（a )黒色色材、（b)有機結合材’ （c)光聚合引發劑及（e)具有鹼性官能基之高分子分散劑，之光聚合性組成物中、 (b)有機結合材爲具竣基之環氧丙烯酸酯樹脂，（〇)光聚合引發劑係下述一般式（6 )所示之膀酯系化合物，【化1】1289577 Pickup, Patent Application No. 921 25645 Patent Application Revision of Chinese Patent Application Revision of the Republic of China, August 1, 1 rev. 1 · A photopolymerizable composition characterized by (a) ochre color material, (b (organic binder) (c) photopolymerization initiator and (e) polymer dispersant having a basic functional group, a photopolymerizable composition, (b) the organic binder is a thiol-based epoxy acrylate The resin (〇) photopolymerization initiator is a compound of the following formula (6), which is a compound of the following formula (6).

(式中、R1爲可取代之碳數丨〜⑺之烷基，r2爲各自可取代之碳數2〜10之院醯基、碳數7〜2〇之苯甲醯基， R10爲互相獨立之氫原子、各自可取代之碳數丨〜丨〗之烷基、碳數2〜4之羥烷基、碳數3〜5之鏈烯基或碳數6〜 20之苯基，R1Q爲藉由有Ri〇鍵結之氮原子而鍵結之芳香族環双方或一方之進而與取代基或芳香族環之碳原子之其一鍵結來形成環構造’ R12、 R13、Ri4及Ri5可互爲獨立，表不氫原子、各自可取代之碳數6〜2〇之苯基、碳數 1289577 1〜10之烷基、碳數5〜8之環烷基、碳數2〜20之烷醯基、碳數7〜20之苯甲醯基、碳數2〜12之烷氧羰基、碳數7〜20之苯氧羰基、碳數1〜20之醯胺基或硝基）。 2 ·如申請專利範圍第1項之光聚合性組成物，其中光聚合性組成物更含有（d )光聚合性單體。 3 .如申請專利範圍第1或2項之光聚合性組成物，其中，（b )有機結合材係在環氧樹脂加成α，々·不飽合單羧酸，或在酯部份加成具有羧基之α，/5-不飽合單羧酸酯，進而藉由使多鹼式酸酐反應而合成之環氧基丙烯酸酯樹脂。 4·如申請專利範圍第1或2項之光聚合性組成物，其中（b )有機結合材係在酚醛清漆型環氧樹脂及/或下述式 (7)所示環氧樹脂與（甲基）丙烯酸之反應生成物，使多鹼式酸酐反應所得之環氧丙烯酸酯樹脂者。(wherein R1 is an alkyl group having a carbon number of 丨~(7) which may be substituted, and r2 is a fluorenyl group having a carbon number of 2 to 10, and a benzoyl group having a carbon number of 7 to 2, and R10 is independent of each other. a hydrogen atom, an alkyl group each having a carbon number of 丨~丨, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or a phenyl group having 6 to 20 carbon atoms, R1Q is borrowed The ring structure 'R12, R13, Ri4, and Ri5' may be mutually bonded by one or both of the aromatic rings bonded by the nitrogen atom bonded to the Ri bond, and further bonded to the carbon atom of the substituent or the aromatic ring. Independently, it is a hydrogen atom, a phenyl group having a carbon number of 6 to 2 Å, an alkyl group having a carbon number of 1,289,577 to 10, a cycloalkyl group having a carbon number of 5 to 8, and an alkane having a carbon number of 2 to 20. A benzoyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, a phenoxycarbonyl group having 7 to 20 carbon atoms, a decylamino group having 1 to 20 carbon atoms or a nitro group. 2. The photopolymerizable composition according to claim 1, wherein the photopolymerizable composition further contains (d) a photopolymerizable monomer. 3. The photopolymerizable composition according to claim 1 or 2, wherein (b) the organic binder is added to the epoxy resin α, 々· unsaturated monocarboxylic acid, or added to the ester moiety An epoxy acrylate resin synthesized by reacting a polybasic acid anhydride with an α,/5-unsaturated monocarboxylic acid ester having a carboxyl group. 4. The photopolymerizable composition according to claim 1 or 2, wherein (b) the organic binder is a novolac type epoxy resin and/or an epoxy resin represented by the following formula (7) The epoxy acrylate resin obtained by reacting a polybasic acid anhydride with a reaction product of acrylic acid.

5 · —種濾色器，其係在透明基板上，具有申請專利範圍第1〜4項中任一項記載之光聚合性組成物所形成之黑色基質者。 6 ·如申請專利範圍第5項之濾色器，其係使用該濾色器而形成液晶顯示裝置者 -2-A color filter comprising a photopolymerizable composition according to any one of claims 1 to 4, which is a color filter. 6) The color filter of claim 5, which uses the color filter to form a liquid crystal display device -2-