TWI351581B

TWI351581B - Photosensitive resin composition and color filter

Info

Publication number: TWI351581B
Application number: TW093123169A
Authority: TW
Inventors: Manabu Higashi; Masahiro Tsuchiya; Masanori Kono
Original assignee: Nippon Steel Chemical Co
Priority date: 2003-08-28
Filing date: 2004-08-03
Publication date: 2011-11-01
Also published as: JP4437651B2; TWI447523B; TW200508799A; TW201142502A; KR101077077B1; JP2005077451A; KR20050021902A

Description

1351581 九、發明說明：【發明所屬之技術領域】本發明乃關於光硬化性組成物及採用該光硬化性組成物的彩色濾光片，更詳細而言，乃關於適用於彩色遽光片用油墨之感光性樹脂組成物。 " 【先前技術】：彩色液晶顯示裝置是以控制光的穿透量或是反射量的液晶部及彩色濾光片為構成要素。該彩色濾光片的製造方法一般為於玻璃或塑膠片等透明基板的表面上形成黑色矩籲陣（black matrix)，接下來以長條狀或是馬赛克狀等顏色圖案，依序形成紅、綠、藍等不同色相的方法。圖案尺寸因彩色濾光片的用途及各個顏色的不同而不同，隨著紅、綠、藍的晝素從200至300 "!!1往100"m，黑色矩陣由2〇"m 往10 /z m薄線化，因而更進一步要求能夠達到高精密尺寸的感光性樹脂材料。最近幾年，於液晶電視、液晶顯示器、彩色液晶手機等領域中’採用彩色液晶顯示裝置。彩色滤光片為決定彩籲色液晶顯示裝置的視覺性的重要元件之一，視覺性的提升亦即為了獲得更為鮮盤的晝像，構成彩色滤光片之紅、綠、藍等晝素必須達到比目前更高的色純度，以及黑色矩陣的冋遮光f生’因而必須於感光性樹脂組成物當中添加較以往更多的著色劑。圖案的形成乃利用光反應性樹脂與光聚合起始劑的反應所產生的光硬化仙，且主要以為水銀燈紐頻譜之一 316123 6 1351581 的i線（365nm)做為使顏料分散系列負型彩色光阻層硬化的曝光波長。紅、綠、藍及黑色的感光性樹脂組成物（亦稱·> 為油墨）中’著色劑本身吸收紫外線，且由於著色劑在感光 v 性樹脂組成物中所占的比例高，因此，基於下述理由，感光性樹脂組成物的光硬化性及顯像性惡化，而難以獲得圖〜案尺寸女疋性、顯像圖框、圖案密著性、及圖案輪廊之形狀皆良好之彩色濾光片。（1)於曝光部分上，在膜厚方向上的交聯密度產生差距，即使於塗膜表面上達到足夠的光硬化，於基板底面上亦難以進行光硬化，（2)曝光部分及未曝· 光部分中的交聯密度難以達到差距，（3)由於添加多量不溶, 於顯像液中的不溶性著色劑，因而使顯像性顯著下降。而這些問題尤其在感光性樹脂組成物的分光特性上，及遮光感光性樹脂組成物中更為顯著。再者’最近幾年，為了提升生產效率及降低成本，彩色濾光片生產線上的母玻璃基板有逐年增大的趨勢，甚至於製造出超過lm的母玻璃基板。此外，為了降低作業時間及提升生產效率，於曝光製程中要求較短的曝光時間，亦即，要求可採用低曝光量來進行光硬化之彩色濾光片用感光性樹脂組成物。由於如上述期求可使著色劑之含有比率高且光硬化困難之彩色遽光片用感光性樹脂脂組成物於低曝光量下，獲得圖案尺寸安定性、圖案密著性及圖案輪廓之形狀之清晰 f白良好且顯像圖框寬之圖案，所以感光性樹脂組成物的南感度為不可或缺。 316123 7 1351581 [專利文獻1]日本特開平1·152449號公報 [專利文獻2]曰本特開平7_278214號公報 [專利文獻3]日本特開2〇〇1_26453〇號公報 [專利文獻4]曰本特開2〇〇2_323762號公報 [專利文獻5]曰本特開2〇〇3_96ii8號公報 [專利文獻6]日本特開平7_3122號公報 * 於專利文獻1 _，提示為了提升顏料濃度而達到優良的顏色再現性並防止感度降低，採用_甲基。惡二唾系列化合物及鹵曱基-S-三啡系列化合物來做為高感度光聚合起鲁始劑之例子。然而，這些化合物雖然藉由抑制因氧引起之反應而使表面平坦性降低的情形改善’但是就圖案尺寸的精密度而言，仍無法達到令人滿意的程度。此外，於專利文獻2 i 5等中揭示於感光性樹脂組成物中採用汚醋 (Oxime ester)系列的光聚合起始劑，來做為高感度光聚合起始劑，但尚未達到令人滿意的程度。於專利文獻6中揭示採用含不飽和基的驗可溶性樹脂化合物之彩色滤光片用感光性樹脂組成物。攀【發明内容】因此，為了解決上述問題，本發明的目的在於提供可形成圖案尺寸的安定性優良，顯像圖框寬，以及圖案密著 ,及圖案輪廓之形狀之清晰度良好之圖案之彩色遽光片用感光性树脂組成物。此外，其他目的在於提供採用此彩色濾光片用感光性樹脂組成物所形成的塗膜及彩色濾光片。本發明者為了解決上述課題而探討之後的結果發現， 8 316123 1351581 將衍生自雙酚（bisphenol)的芳香族環氧化合物與（甲基）丙烯酸的反應物，再與多元羧酸或是多元羧酸酐進行反&應，1351581 IX. The invention relates to a photocurable composition and a color filter using the same, and more particularly to a color calender A photosensitive resin composition of an ink. <Prior Art: A color liquid crystal display device is a constituent element that controls a light penetration amount or a reflection amount of a liquid crystal portion and a color filter. The method for manufacturing the color filter generally comprises forming a black matrix on a surface of a transparent substrate such as a glass or a plastic sheet, and then forming a red color in a color pattern such as a strip or a mosaic. A method of different hue such as green and blue. The size of the pattern varies depending on the purpose of the color filter and the color of each color. As the red, green and blue elements are from 200 to 300 "!!1 to 100"m, the black matrix is from 2〇"m The thinning of 10 /zm further requires a photosensitive resin material capable of achieving high precision. In recent years, color liquid crystal display devices have been employed in the fields of liquid crystal televisions, liquid crystal displays, color liquid crystal mobile phones, and the like. The color filter is one of the important components for determining the visuality of the color-recalling liquid crystal display device. The visual enhancement is to obtain the image of the fresh disk, and the red, green, blue, etc. of the color filter are formed. It is necessary to achieve a higher color purity than the current one, and the black matrix of the black matrix, and thus it is necessary to add more color formers to the photosensitive resin composition. The pattern is formed by the photohardening reaction of the photoreactive resin and the photopolymerization initiator, and is mainly used as the i-line (365 nm) of one of the mercury lamp spectrums of 316123 6 1351581 as the pigment dispersion series negative color. The exposure wavelength at which the photoresist layer is hardened. In the photosensitive resin composition of red, green, blue, and black (also referred to as > ink), the coloring agent itself absorbs ultraviolet rays, and since the coloring agent accounts for a high proportion in the photosensitive v-resin composition, The photocurability and developability of the photosensitive resin composition are deteriorated for the following reasons, and it is difficult to obtain the shape of the figure, the size of the image frame, the pattern adhesion, and the shape of the pattern wheel. Color filter. (1) On the exposed portion, the crosslink density in the film thickness direction causes a difference, and even if sufficient light hardening is achieved on the surface of the coating film, it is difficult to perform photohardening on the bottom surface of the substrate, and (2) the exposed portion is not exposed. The crosslink density in the light portion is difficult to reach the difference, and (3) the insoluble colorant is added to the developing solution due to the addition of a large amount of insoluble matter, so that the developability is remarkably lowered. These problems are particularly remarkable in the spectral characteristics of the photosensitive resin composition and in the light-shielding photosensitive resin composition. Furthermore, in recent years, in order to increase production efficiency and reduce costs, the mother glass substrate on the color filter production line has been increasing year by year, and even the mother glass substrate exceeding lm has been manufactured. Further, in order to reduce the working time and increase the production efficiency, a short exposure time is required in the exposure process, that is, a photosensitive resin composition for a color filter which is photohardened by a low exposure amount is required. The pattern size stability, the pattern adhesion, and the shape of the pattern outline are obtained at a low exposure amount because the photosensitive resin composition for a color calender sheet having a high content ratio of the colorant and difficulty in photohardening is obtained as described above. The sharpness of white is good and the pattern is wide, so the south sensitivity of the photosensitive resin composition is indispensable. 。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Color reproducibility and prevention of sensitivity reduction, using _methyl. The diterpene series compound and the halo-based-S-trimorphine series compound are examples of high-sensitivity photopolymerization initiation agents. However, these compounds are improved in the case where the surface flatness is lowered by suppressing the reaction due to oxygen. However, in terms of the precision of the pattern size, a satisfactory degree cannot be obtained. Further, in Patent Document 2 i 5 or the like, a photopolymerization initiator of an Oxime ester series is used as a high-sensitivity photopolymerization initiator in a photosensitive resin composition, but it has not yet reached satisfactory. Degree. Patent Document 6 discloses a photosensitive resin composition for a color filter using an unsaturated group-containing soluble resin compound. SUMMARY OF THE INVENTION Therefore, in order to solve the above problems, an object of the present invention is to provide a pattern which is excellent in stability in pattern size, wide in image frame width, and in which the pattern is dense, and the shape of the pattern outline is good in definition. The color glazing sheet is made of a photosensitive resin composition. Further, another object is to provide a coating film and a color filter formed using the photosensitive resin composition for a color filter. In order to solve the above problems, the inventors of the present invention have found that 8 316 123 1351581 is a reaction product of an aromatic epoxy compound derived from bisphenol and (meth)acrylic acid, and a polycarboxylic acid or a polycarboxylic acid. The anhydride is reversed and should,

得到含不飽和基的化合物，於包含此含不飽和基的化合物的感光性樹脂組成物的光聚合起始劑中，若添加具有特定化學構造之0-醯基肟（〇-aCyl〇xime)系列光聚合起始劑，將' 可解決上述問題點，因而完成本發明。 I 本發明為一種彩色濾光片用感光性樹脂組成物，乃以下列（A)至（D)成份為必需成份：（A)將具有衍生自雙酚 (bisphenol)類之2個縮水甘油醚基之環氧化合物與（^基）# 丙烯酸的反應物，再與多元羧酸或多元羧酸酐反應所得^到· 之含不飽和基的鹼可溶性樹脂化合物，（B)具有至少〗個以上的乙烯性不飽和鍵結之光聚合性單體，（c)光聚合起始劑，（D)著色劑；其特徵為，（A)成份與（B)成份的重量比例 (A)/(B)為20/80至90/10;相對於（A)成份與（B)成份合計1〇〇重量份，（C)成份之含量為2至30重量份；且以下列通式 ⑴所表示的化合物做為成份光聚合起始劑：【化學式1】 ’A compound containing an unsaturated group is obtained, and a photopolymerization initiator containing a photosensitive resin composition of the unsaturated group-containing compound is added with a specific chemical structure of 0-fluorenylpyrene (〇-aCyl〇xime). A series of photopolymerization initiators will solve the above problems and thus complete the present invention. I The present invention is a photosensitive resin composition for a color filter, which has the following components (A) to (D) as essential components: (A) will have two glycidyl ethers derived from bisphenols. (B) having at least one or more of the unsaturated group-containing alkali-soluble resin compound obtained by reacting a reaction product of an epoxy compound with (meth) #acrylic acid with a polycarboxylic acid or a polycarboxylic acid anhydride An ethylenically unsaturated bonded photopolymerizable monomer, (c) a photopolymerization initiator, (D) a colorant; characterized by a weight ratio of the component (A) to the component (B) (A)/(B ) is 20/80 to 90/10; the content of the component (C) is 2 to 30 parts by weight based on 1 part by weight of the component (A) and the component (B); and is represented by the following formula (1) Compound as a photopolymerization initiator: [Chemical Formula 1] '

於通式⑴中，Ri表示苯基（可被碳數1至ό的烷基、 316123 9 1351581 苯基或崮素原子取代），碳數丨至2〇的烷基（可被丨個以上羥基取代，且烷基鏈中間可具有丨個以上氧原子），碳數5 至8的環烷基，碳數2至20的烷醯基或苯甲醯基（可被碳數1至6的烷基或苯基取代）；化表示碳數2至12的烷醯基（可被1個以上的鹵素原子或氰基取代），雙鐽與羰基非呈共軛之碳數4至6的烯醯基，苯甲醯基（可被碳數丨至6 的烷基、鹵素原子或氰基取代），碳數2至6的烷氧基羰基或苯氧基羰基（可被1個以上碳數丨至6的烷基或齒素原子取代）；R3、R4、R5、R6、r7、r8、化及Riq相互獨立各表示氫原子’鹵素原子’碳數1至12的烷基，環戊基環己基，苯基，笨甲基，苯甲醯基，碳數2至12的烷醯基，石厌數2至12的烷氧基羰基（烷氧基的碳數為2至丨丨的情況，主鏈碳原子間可具有丨個以上氧原子，且上經基取彳mm録。本發明之彩色濾光片用感光性樹脂組成物中，具備有衍生自雙酚類的2個縮水甘油醚基的環氧化合物為以下列通式（II)所表示的環氧化合物：【化學式2】 -Λιι ΟΒ,-ΟΗ-Μ,Ο--^^·1In the formula (1), Ri represents a phenyl group (which may be substituted by an alkyl group having 1 to 10 carbon atoms, a phenyl group of 316123 9 1351581 phenyl or a halogen atom), and an alkyl group having a carbon number of 2 to 2 Å (more than one hydroxy group may be used) Substituted, and the alkyl chain may have more than one oxygen atom in the middle), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzhydryl group (an alkane having 1 to 6 carbon atoms) Substituted or substituted by phenyl); represents an alkanoyl group having 2 to 12 carbon atoms (which may be substituted by one or more halogen atoms or a cyano group), and an olefin having a carbon number of 4 to 6 which is not conjugated to a carbonyl group a benzylidene group (which may be substituted by an alkyl group having a carbon number of 丨6, a halogen atom or a cyano group), an alkoxycarbonyl group having 2 to 6 carbon atoms or a phenoxycarbonyl group (having a carbon number of 1 or more) Alkyla or dentate atom substituted to 6); R3, R4, R5, R6, r7, r8, and Riq each independently represent a hydrogen atom 'halogen atom' of an alkyl group having 1 to 12 carbon atoms, a cyclopentyl ring a hexyl group, a phenyl group, a methyl group, a benzamidine group, an alkanoyl group having 2 to 12 carbon atoms, and an alkoxycarbonyl group having 2 to 12 anthracene (the alkoxy group has a carbon number of 2 to fluorene). There may be 丨 between the main chain carbon atoms In the photosensitive resin composition for a color filter of the present invention, the epoxy compound having two glycidyl ether groups derived from bisphenol is selected from the following. Epoxy compound represented by the formula (II): [Chemical Formula 2] - Λιι ΟΒ, -ΟΗ-Μ, Ο--^^·1

OCH,-CH-CH,0 I » OH R丨： Ru (D)OCH,-CH-CH,0 I » OH R丨: Ru (D)

Rn Ria Y 316123 10 1351581 於通式（Π)中，Rn及心相互獨立碳數1至5的焓其主合表不虱原子， Μ基或鹵素原子；χ表以〇· ， (3)2- * 'Si(CH3)2- , _ch2- » -C(CH ) π (―)或不存在;一至1〇=:〇- 成份(。)光二1明之节色濾光片用感光性樹脂組成物中，【化起始劑為以下列通_)所表示的化合物：Rn Ria Y 316123 10 1351581 In the general formula (Π), Rn and the core are independent of each other. The carbon number of the ruthenium is 1 to 5, and the main combination thereof is an atom, a sulfhydryl group or a halogen atom; - * 'Si(CH3)2- , _ch2- » -C(CH ) π (-) or non-existent; one to one 〇 =: 〇- component (.) Light II 1 color filter is composed of photosensitive resin In the case of the compound represented by the following:

On)On)

^本&明之彩色;慮光片用感光性樹脂組成物中，成份（D)著Μ為遮紐分散純。再者，本發明之彩色滤光片用感光性樹脂組成物中，遮光性分散顏料為碳黑分散體。此外’本發明為使上述彩色遽光片用感光性樹脂也成物硬化而形成之塗膜。再者’本發明為彩色濾光片盆且備藉由於透明基板上塗佈上述彩色渡光片用感光性樹脂组成物’前供烤之後，以紫外㈣光裝置進行曝《，用驗性水溶液進行顯像，以及進行後烘烤而製作出之畫素或是黑色矩陣（black matrix)。以下詳細說明本發明。本發明的彩色濾光片用感光性樹脂組成物（以下亦僅稱為組成物），乃以（A)至（D)成份為必須成份，關於（B)成份及（D)成份及因應必要所加入的溶 316123 1351581 劑及其他成份記載於專利文獻1至6中，可從其中加以選擇使用。因此，簡單說明（A)成份及（C)成份之外的成份，並詳細說明（A)成份及（〇成份。 (A)成伤之含不飽和基的化合物，乃藉由（曱基）丙稀酸 (此意味丙烯酸及/或甲基丙烯酸），與具有衍生自雙酚類的 2個縮水甘油醚基的環氧化合物進行反應，然後將所獲得之具羥基（hydroxy)的化合物與多元羧酸或多元羧酸酐進行反應，而獲得環氧（甲基）丙烯酸酯加成物。該加成物的化學式及製法的一例，記载於專利文獻6。所謂衍生自雙酚類的環氧化合物係指使雙酚類與表鹵醇（epihal〇hydrin) 反應所獲得的環氧化合物或是與環氧化合物同等的化合物由於為（A)成伤之含不飽和基的化合物同時具有稀性不飽和雙鍵讀基，因此可賦予彩色滤光片用感光性樹脂組成物優良的光硬化性、良好顯像性、圖案特性，並提升遮光膜的物性。 (A)成伤即含不餘和基的化合物，較佳衍生自通 :表示的環氧化合物。此環氧化合物射自雙_卜由於措由說明雙酚類可明瞭含不飽和基的化合物，因此藉由雙紛類來說明較佳具體例。於通式（11)中，^及心相互獨^本&明色色; The light-sensitive sheet is made of a photosensitive resin composition, and the component (D) is dispersed and pure. Further, in the photosensitive resin composition for a color filter of the present invention, the light-shielding dispersible pigment is a carbon black dispersion. Further, the present invention is a coating film formed by curing a photosensitive resin for a color calender sheet as described above. In addition, the present invention is a color filter basin and is prepared by baking a photosensitive resin composition for a color light-passing sheet on a transparent substrate, and then exposed by an ultraviolet (four) optical device. The development is performed, and the pixels produced by post-baking are either black matrix or black matrix. The invention is described in detail below. The photosensitive resin composition for a color filter of the present invention (hereinafter also referred to simply as a composition) has components (A) to (D) as essential components, and (B) component and (D) component and necessary The added 316123 1351581 agent and other components are described in Patent Documents 1 to 6, and can be selectively used therefrom. Therefore, the components other than (A) and (C) are briefly described, and (A) and (〇) are described in detail. (A) A compound containing an unsaturated group in a wound is made by (sulfenyl) Acrylic acid (which means acrylic acid and/or methacrylic acid) is reacted with an epoxy compound having two glycidyl ether groups derived from bisphenols, and then the obtained compound having a hydroxy group and a plurality of The carboxylic acid or the polycarboxylic acid anhydride is reacted to obtain an epoxy (meth) acrylate adduct. An example of the chemical formula and the production method of the adduct is described in Patent Document 6. The epoxy derived from bisphenols The compound is an epoxy compound obtained by reacting a bisphenol with an epihalohydrin or a compound equivalent to an epoxy compound because it is (A) a compound containing an unsaturated group and has a thinness. Since the saturated double bond read group is provided, it is excellent in photocurability, good developability, and pattern characteristics of the photosensitive resin composition for a color filter, and the physical properties of the light-shielding film are improved. Base compound, preferably自自通: The epoxy compound represented. This epoxy compound is shot from the double bis, because the bisphenols can explain the unsaturated group-containing compound, so the preferred examples are illustrated by the double categorization. In the formula (11), ^ and the heart are independent

丁氫原子，奴數1至5的烷基或是鹵素原子，X =^S〇2 ’ C(CF3)2〜Si(CH3)2_、CH2〜C(CH3)2·，難敫/基或是不存在’以9,9_苟基為較佳。是f佳為G或是平均值在之間的範圍。，勿基疋指以下列化學式所表示的基。 316123 12 1351581 【化學式4】Butane hydrogen atom, alkyl group of 1 to 5 or halogen atom, X =^S〇2 'C(CF3)2~Si(CH3)2_, CH2~C(CH3)2·, difficult/base or It is not present that '9,9_ 苟 is preferred. Is the range between f or G or the average. , 疋基疋 refers to the group represented by the following chemical formula. 316123 12 1351581 [Chemical Formula 4]

做為供應較理想的含不飽和基的化合物之雙紛類，有下列化合物。包含，雙（4_羥基笨基）酮、雙（4_羥基_3,5_二甲基笨基）_、雙（4,基_3,5_二氣苯基）酮、雙（㈣基笨基楓、雙（4-沒基_3,5_二甲基笨基）楓、雙（4_經基_3,5_二氣笨基）碉、雙（4-羥基苯基）六氟丙烷、 _二As a mixture of desirable unsaturated group-containing compounds, the following compounds are available. Containing, bis(4-hydroxyphenyl) ketone, bis(4-hydroxy-3,5-dimethylphenyl)-, bis(4,yl-3,5-diphenyl)one, bis((iv) Stupid base maple, double (4-diyl_3,5-dimethyl stupyl) maple, double (4_base 3), bis(4-hydroxyphenyl) Hexafluoropropane, _two

基）六說丙烧、雙（4.經基.3,5•二氣苯基）六氟丙烧、雙; 羥基苯基）二甲基石找、雙⑷經基Μ•二甲基苯基）二甲基矽烷、雙（4-說基-3,5-二氣苯基）二甲基石夕烧、雙（4_經基笨基）甲烷、雙（4-沒基-3,5·二氣苯基）甲烧、雙（4_經基-3,5 二漠苯基）曱院、2,2-雙（4_經基苯基）丙烧、2,2_雙（4•經基 ¥二曱基苯基）丙烧、2,2_雙（4·窥基·V•二氣苯基^ 烷2,2-雙（4·說基-3-曱基苯基）丙燒、2,2雙（4_經基j氣笨基)丙烷、雙(4-羥基苯基)喊、雙(4游3,5•二甲基苯美域、雙（4-經基·3’5-二氣苯基）驗等化合物；及χ為上述的 9,9_苟基之9,9-雙（4_經基苯基）苟、9,9雙（4經基·3_甲部，基-3-氣苯基)场、9,9_雙(4·經基 =9,雙(4-經基_3·氟苯基)苟、”雙㈣基基苟、9,9-雙㈣基_3,5·二甲基苯基）苟、9,9 經土-3,5·二氯苯基）¾ ' 9,9,4nm 苯 ^ 316123 13 1351581 等，此外，亦可舉出4,4’-雙酚類及3,3’·雙酚類等。此含不飽和基的化合物，雖可由上述衍生自雙紛類的環氧化合物獲得，但亦可使用除了含有該環氧化合物之外，亦含顯著量紛系盼經樹脂型環氧化合物及甲驗系驗酸樹脂型（Cresylic Novolak)環氧化合物等具有2個縮水甘油謎基的化合物。此外，將雙齡類予以縮水甘油醚化之際，若以寡聚物单位混入’即通式（II)中的η的平均值為〇至 10(以0至2為較佳），則本樹脂組成物的功能將無任何問題。此外，與「環氧化合物與（甲基）丙烯酸反應所獲得之 (曱基）丙烯酸環氧酯之羥基」反應之多元羧酸或多元羧酸酐，例如有，順丁烯二酸、琥拍酸、衣康酸、苯二曱酸、四氫苯二曱酸（tetrahydrophthalic acid)、六氫苯二曱酸 (hexahydrophthalic acid)、曱基内亞曱基四氫苯二甲酸 (methylendomethylene tetrahydrophthalic acid)，六氣内亞-曱基四氫苯二曱酸（chlorendic acid)、曱基四氫苯二曱酸 (methyl tetrahydrophthalic acid)、偏苯三曱酸（trimellitic acid) ’苯均四甲酸（pyromellitic Acid)等，及這些化合物的酸酐類；再者’二苯曱嗣四鲮酸（benz〇phen〇ne tetracarboxylic acid)、聚苯四羧酸、二苯驗四叛酸 (diphenylether tetracarboxylic acid)等芳香族多元羧酸及這些酸的二酸酐類等。關於酸酐類及二醆酐類的使用^例，可選擇適於在因驗性液顯像操作時形成精密圖案之比例。關於（A)成份之含不飽和基的化合物，可僅使用1種， 316123 14 種以上的混合物。此外，使環氧化合物與(T ^丙烯:反應’獲得的⑽）丙料環氧㈣多频酸或 = : 應’以製造㈧成份的含不飽和基的化合物 =法，錢職定，例如可採用下财法製造。亦即， ==9,9-雙（4-經基苯基巧與表氯醇㈣咖⑽反二、口成以下列通式（IV)所表示的雙紛努型環氧化合物，二:使該通切V)表示的雙_型環氧化合物與下列通式丁的（曱基）丙婦酸進行反應，獲得以下列通式（νι)表不的㈣酸雙㈣型環氧醋’接下來於丙二醇單甲驗溶劑 =匕於加熱之下使通式（VI)表示的丙烯酸雙酚芴型環氧酯 H與上述多元竣酸或多元幾酸的酸酐類進行反應，而出為目標之含不飽和基的化合物。於通式（ιν)至（νι) 中’R〗1及R12與上述相同，R13為Η或ch3。【化學式5】Base) six said propane burned, double (4. trans. 3,5 • di-phenyl) hexafluoropropane, bis; hydroxyphenyl) dimethyl stone, bis (4) quinone dimethyl benzene Methyl) dimethyl decane, bis(4-indolyl-3,5-diphenyl) dimethyl sulphur, bis (4 _ phenyl) methane, bis (4-diyl-3, 5. Dioxinyl phenyl)methyst, bis(4_carbyl-3,5 dimethyl phenyl) brothel, 2,2-bis(4-cyanophenyl)propane, 2,2_bis ( 4•Phenyl-di-decylphenyl)propane, 2,2_bis (4·Pyracyl·V•di-phenylene 2,2-bis(4·?-3-ylphenyl) )propane burned, 2,2 double (4_ via base j gas base) propane, bis (4-hydroxyphenyl) shout, double (4 swim 3,5 • dimethylbenzene beautiful domain, double (4- a 3·5-diphenyl group) test compound; and χ is 9,9-bis(4-phenylphenyl)anthracene, 9,9-bis (4-mercapto) · 3_甲甲,基-3-气phenyl) field, 9,9_double (4·carbyl=9, bis(4-carbazyl-3-fluorophenyl) fluorene,” bis(tetra)yl fluorene , 9,9-bis(tetra)yl_3,5·dimethylphenyl)anthracene, 9,9, 3,5,2,dichlorophenyl) 3⁄4 ' 9,9,4 nm benzene ^ 316123 13 1351581, etc. In addition, 4, 4 can also be cited. - bisphenols, 3,3', bisphenols, etc. The unsaturated group-containing compound may be obtained from the above-mentioned epoxy compound derived from a mixture, but may be used in addition to the epoxy compound. There are also a significant amount of compounds which have two glycidyl groups, such as a resin type epoxy compound and a Creslic Novolak epoxy compound. In addition, glycosyl etherification of the double age class is also required. In the case where the average of η in the formula (II) is 〇 to 10 (preferably 0 to 2), the function of the present resin composition is not problematic. a polycarboxylic acid or a polycarboxylic acid anhydride which reacts with a "hydroxy group of a (meth)acrylic acid epoxy ester obtained by reacting an epoxy compound with (meth)acrylic acid, for example, maleic acid, succinic acid, Itaconic acid, benzoic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylene tetrahydrophthalic acid, six gases Neya-mercaptotetrahydrobenzoquinone (chlorendic acid), methyl tetrahydrophthalic acid, trimellitic acid 'pyromellitic acid, etc., and anhydrides of these compounds; An aromatic polycarboxylic acid such as benz〇phen〇ne tetracarboxylic acid, polyphenylenetetracarboxylic acid, diphenylether tetracarboxylic acid, or a dianhydride of these acids. Regarding the use of an acid anhydride and a dicarboxylic anhydride, a ratio suitable for forming a precise pattern at the time of the developer liquid imaging operation can be selected. As the unsaturated group-containing compound of the component (A), only one type of 316,123 or more of a mixture of 14 or more types may be used. Further, an epoxy compound is obtained by reacting an epoxy compound with (T^ propylene: (a) obtained by reacting (10)) propylene (4) polyfluorinated acid or =: to produce an unsaturated group-containing compound of the (eight) component, It can be manufactured by the following financial method. That is, ==9,9-bis(4-pyridylphenyl) and epichlorohydrin (iv) coffee (10), and the double-formed epoxy compound represented by the following general formula (IV), two: The bis-epoxy compound represented by the pass-through V) is reacted with (mercapto)g-butanoic acid of the following formula to obtain a (tetra) acid bis(tetra) type epoxy vinegar represented by the following formula (νι) Next, the propylene glycol monomethyl solvent = hydrazine is heated to react the bisphenol oxime epoxy ester H represented by the general formula (VI) with the above-mentioned polybasic decanoic acid or polybasic acid anhydride. A compound containing an unsaturated group. In the general formulae (ιν) to (νι), 'R' 1 and R12 are the same as above, and R13 is Η or ch3. [Chemical Formula 5]

316123 1351581 就該反應而言’較佳以環氧丙烯酸酯樹脂的OH基1 莫耳與酸肝類1/2莫耳進行定量反應為佳，反應溫度以9〇 °C至130°C為較佳’以95。〇至i25〇c為更佳。於此反應當中’關於具備通式（I)的單位構造的化合物，全體均相同。做為（B)成份之具有至少1個以上乙烯性不飽和鍵結之光聚合性單體，例如有，（曱基）丙烯酸2_羥基乙酯、（曱基）丙稀酸2-經基丙酯、（曱基）丙烯酸2_乙基己酯等具備羥基的單體，及乙二醇二（甲基）丙烯酸酯、二乙二醇二（曱基）丙烯酸酯、三乙二醇二（曱基）丙烯酸酯、四乙二醇二（甲基）丙稀酸醋、1，4-丁二醇二（曱基）丙烯酸酯、三羥甲基丙烷 (trimethylol propane)三（曱基）丙烯酸酯、三羥曱基乙烷三 (曱基）丙烯酸酯、季戊四醇二（甲基）丙烯酸酯、季戊四醇三 (甲基）丙烯酸醋、季戊四醇四（曱基）丙烯酸酯、季戊四醇四 (甲基）丙烯酸酯、雙季戊四醇六（曱基）丙烯酸酯、甘油 (glycerol)(曱基）丙烯酸酯等（曱基）丙烯酸酯類，這些化合物可單獨採用1種，亦可併用2種以上。這些（A)成份與（B)成份的重量調配比例（a)/(B)為 20/80至90/10，以40/60至80/20為較佳。（A)成份的調配比例若少於20/80，由於光硬化後的硬化物容易變脆，且未曝光部分中塗膜的酸價會降低，因此對鹼性顯像液的溶解性會降低，使圖案輪廓產生鋸齒狀，而發生「不清晰」的問題；此外’若多於9〇/1 〇，由於光反應性官能基在樹脂中所占的比例較少’無法形成足夠的交聯構造，且樹脂成份中的酸價度將過高’曝光部份對鹼性顯像液的溶解性 16 316123 1351581 會過高，因此使所形成的圖案線寬比希望的線寬度細，容易產生圖案缺陷的問題。 · 做為（C)成份的光聚合起始劑，以上述通式⑴表示的化合物做為必須成份，藉由紫外線光等的照射而產生自由基 (Radical) ’此等自由基與光聚合性的化合物進行加成反應而引發自由基聚合，並硬化組成物。其中，於通式⑴中，， Ri表示苯基（可被碳數1至6的烷基、苯基或鹵素原子取代）’碳數1至20的烷基（可被1個以上羥基取代，烷基鏈的中可具有1個以上的氧原子，亦可具有羥基與氧原子兩籲者），碳數5至8的環院基，碳數2至20的烧酿基或是苯甲醯基（可被碳數1至6的烷基或苯基取代）。化表示碳數 2至12的烷醯基（可被1個以上的鹵素原子或氰基取代），雙鏈與幾基非為共軛的碳數4至6的烷醯基、苯曱醯基（可被碳數1至6的烷基、齒素原子或氰基取代），碳數2至6 的烷氧羰基或笨氧羰基（可被1個以上的碳數1至6的烧基、苯基或鹵素原子取代），此等基總稱為醯基（acyl)。R3、 R4、R5、R6、R7、R8、R9及R1Q相互獨立，各表示氫原子，函素原子，碳數1至12的烷基，環戊基，環己基，苯基，笨甲基，苯甲酿基’碳數2至12的烷醯基，碳數2至12 的烷氧基羰基（烷氧基的碳數為2至11的情況，該院氧基 (於主鏈碳原子間可具有1個以上氧原子及/或被丨個以^ 羥基取代）或是苯氧基羰基。該化合物的製造係參照專利文獻4記載的類似的化合物的製造方法。於本發明中之以通式⑴表示的光聚合起二 316123 17 1351581 劑中，以上述通式（III)表示的化合物為較佳。此外，於本發明令，可與通式⑴表示的光聚合起始劑可與1種以上的其他光聚合起始劑或是感光劑（Sensit㈣併用。上述其他光聚合起始劑或是感光劑，例如有苯乙酮、2,2-二乙氧基苯乙酮、對二甲基笨乙酮、對二甲基胺，基苯丙酮、二氣苯乙_、三氣苯乙綱、對·第三丁基苯乙酮. 等苯乙酮類，及二苯甲酮（benz〇phen〇ne)、2氯二苯曱酮、 P，P’-雙二甲基胺基二苯甲酮等二笨甲酮類；苯偶醯 (benzil);苯偶因（benzoin)、苯偶因甲基醚、苯偶因異丙基φ 醚、苯偶因異丁基醚等苯偶因醚類；2_(鄰氯苯基）_4,5_二苯基聯嘴嗤（2-(0-chl〇rophenyl)-4,5_diphenylbiimidaz〇le)、 2-(鄰氯笨基）-4,5-一（間甲氧基苯基）聯嘧唾、2_(鄰氟苯基）_4,5_二苯基聯嘧唑、2-(鄰甲氧基苯基）_4,5_二笨基聯嘧 <»坐、2，4，5-二方香基聯喊哇等聯嘴唾系列化合物，2_三氣曱基-5-苯乙烯基-1，3,4-噁二唑、2-三氯甲基_5_(對氰基苯乙烯基）-1，3,4-噁二唑、2-三氣甲基_5_(對甲氧基苯乙烯春基）-l，3,4-w惡一哇等il曱基π坐化合物類；2,4,6-三（三氣曱基）-1,3,5-三畊、2，-甲基-4,6-雙（三氣甲基）_ι，3,5-三畊、2,-苯基-4,6-雙（二氣曱基）-1,3,5-三啡、2-(4-氯苯基）-4,6-雙（三氯甲基-二D井、2-(4-曱氧基苯基）-4,6-雙（三氣曱基）-1，3,5-三哄、2-(4-曱氧基萘基）_4,6_雙（三氣曱基）_1，3,5-三哄、2-(4-曱氧基苯乙烯基）_4,6·雙（三氣曱基）_ι，3,5-三畊、2-(3,4,5-三甲氧基苯乙烯基）_4,6_雙（三氣曱基pi%% 三畊、2-(4-曱基硫笨乙烯基）_4,6-雙（三氣曱基）-l，3,5-三哄 1S 316123 1351581 等鹵甲基-S-三哄系列化合物類；l-[4-(苯硫基）苯基]-2-(0-笨曱醯肟）-辛-1，2-二酮、1-(4-苯硫基苯基）丁-1，2-二酮-2-時-0-苯曱酸醋（l-(4-phenylsulfanylphenyl)butane-l，2-dione -2-oxime-0-benzoate)、1-(4-曱硫基苯基）丁-1，2-二酮-2-月亏 •0-乙酸酯、1-(4-甲硫基苯基）丁-1-酮肟-〇-乙酸酯等上述通式⑴未包含的範圍中之0-醯基后系列化合物類；二甲醇縮笨曱酮（benzyl dimethyl ketal);硫口山酮（thioxanthone)、2-氣硫灿酮、2,4-二乙基硫口山酮、2-曱基硫口山酮、2_異丙基硫口山酮等硫化合物；2-乙基蒽醌、八甲基蒽醌、L2-苯并蒽醌、2,3-二苯基蒽醌等蒽醌類；偶氮雙異丁腈（az〇 bis-isobutylnitrile)、苯曱醯過氧化物、異丙苯（cumene)過氧化物等有機過氧化物；2-硫醇基苯并咪唑、2_硫醇基苯并喔唾、2-硫醇基苯并噻唑等硫醇化合物等。這些光聚合起始劑或是感光劑，可採用單獨丨種，亦可併用2種以上。此外，可以添加本身雖無光聚合起始劑或是感光劑之作用’但可藉由與上述化合物的組合，而可增加光聚合起始劑或是感光劑能力的化合物。此等化人 :算例f為若與二苯甲洞組合使用將可發揮效果的三乙醇胺等二級胺。316123 1351581 For the reaction, it is preferred to carry out quantitative reaction with OH group 1 molar of epoxy acrylate resin and acid liver 1/2 molar, and the reaction temperature is 9 ° C to 130 ° C. Good' to 95. 〇 to i25〇c is better. In the present reaction, the compounds having the unit structure of the general formula (I) are all the same. The photopolymerizable monomer having at least one or more ethylenically unsaturated bonds as the component (B), for example, 2-hydroxyethyl (meth) acrylate or 2- thiol (meth) acrylate a monomer having a hydroxyl group such as propyl ester or 2-ethylhexyl acrylate, and ethylene glycol di(meth)acrylate, diethylene glycol bis(indenyl)acrylate, and triethylene glycol (fluorenyl) acrylate, tetraethylene glycol di(meth) acrylate vinegar, 1,4-butanediol bis(indenyl) acrylate, trimethylol propane tris(fluorenyl) Acrylate, trihydroxydecylethane tri(indenyl)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tris(meth)acrylate vinegar, pentaerythritol tetrakis(meth)acrylate, pentaerythritol tetra(methyl) (Alkyl) acrylates such as acrylate, dipentaerythritol hexa(meth) acrylate, glycerol (mercapto) acrylate, and the like. These compounds may be used alone or in combination of two or more. The weight ratio (a)/(B) of these (A) component to (B) component is 20/80 to 90/10, preferably 40/60 to 80/20. (A) If the proportion of the components is less than 20/80, the cured product after photohardening tends to become brittle, and the acid value of the coating film in the unexposed portion is lowered, so the solubility in the alkaline developing solution is lowered. To make the outline of the pattern jagged, and the problem of "unclear" occurs; in addition, if it is more than 9 〇/1 〇, the proportion of photoreactive functional groups in the resin is small, and sufficient cross-linking cannot be formed. The structure and the acidity of the resin component will be too high. The solubility of the exposed portion to the alkaline developing solution is too high. Therefore, the formed line width is thinner than the desired line width, which is easy to produce. The problem of pattern defects. In the photopolymerization initiator of the component (C), a compound represented by the above formula (1) is used as an essential component, and radicals are generated by irradiation of ultraviolet light or the like. [The radicals and photopolymerization properties. The compound undergoes an addition reaction to initiate radical polymerization and hardens the composition. In the formula (1), Ri represents a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom) and an alkyl group having 1 to 20 carbon atoms (which may be substituted by one or more hydroxyl groups, The alkyl chain may have more than one oxygen atom, and may have both a hydroxyl group and an oxygen atom, a ring of 5 to 8 carbon atoms, a carbon number of 2 to 20, or benzamidine. A group (which may be substituted by an alkyl group having 1 to 6 carbon atoms or a phenyl group). An alkanoyl group having 2 to 12 carbon atoms (which may be substituted by one or more halogen atoms or a cyano group), a double-chain and a non-conjugated carbon alkene group having 4 to 6 carbon atoms, a benzoinyl group (Substitutable by an alkyl group having 1 to 6 carbon atoms, a dentate atom or a cyano group), an alkoxycarbonyl group having 2 to 6 carbon atoms or an alkoxycarbonyl group (having one or more alkyl groups having 1 to 6 carbon atoms, The phenyl or halogen atom is substituted), and these groups are collectively referred to as acyl. R3, R4, R5, R6, R7, R8, R9 and R1Q are independent of each other, each represents a hydrogen atom, a functional atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a stupid methyl group, Benzoyl alcoholic group 2 to 12 alkyl alkoxy group, alkoxycarbonyl group having 2 to 12 carbons (the alkoxy group has a carbon number of 2 to 11, the alkoxy group (between the main chain carbon atoms) It may have one or more oxygen atoms and/or may be substituted by a hydroxyl group or a phenoxycarbonyl group. The production of the compound is referred to a method for producing a similar compound described in Patent Document 4. The photopolymerization represented by the formula (1) is preferably a compound represented by the above formula (III) in the 316123 17 1351581 agent. Further, in the present invention, the photopolymerization initiator represented by the formula (1) may be used. The above other photopolymerization initiators or sensitizers (Sensit (4) are used together. The above other photopolymerization initiators or sensitizers, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylene Benzophenone, p-dimethylamine, phenylacetonate, diphenophene _, trigas benzene, p-tert-butyl acetophenone, etc. Ketones, and benzophenone (benz〇phen〇ne), 2 chlorinated benzophenone, P, P'-bisdimethylaminobenzophenone, etc.; benzoin (benzil) ); benzoin, benzoin methyl ether, benzoin isopropyl φ ether, benzoin isobutyl ether and other benzoin ethers; 2_(o-chlorophenyl)_4,5_ Diphenyl hydrazine (2-(0-chl〇rophenyl)-4,5_diphenylbiimidaz〇le), 2-(o-chlorophenyl)-4,5-mono(m-methoxyphenyl)-pyrimidine, 2_(o-fluorophenyl)_4,5-diphenyl thiazolidine, 2-(o-methoxyphenyl)_4,5-diphenyl-pyrimidine<», 2,4,5-diaryl Joint shouting wow and other joints, 2_trimethylsulfonyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl_5_(p-cyanostyryl)- 1,3,4-oxadiazole, 2-trimethylmethyl_5_(p-methoxystyrene), l,3,4-w, acetonide, etc. 4,6-three (three gas sulfhydryl)-1,3,5-three tillage, 2,-methyl-4,6-bis (trimethyl)methyl,3,5-three tillage, 2,- Phenyl-4,6-bis(dioxamethyl)-1,3,5-trimorphine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl-di D well, 2 - (4-methoxyphenyl)-4,6-bis(trimethylsulfonyl)-1,3,5-triazine, 2-(4-decyloxynaphthyl)_4,6-bis (three gases)曱)),3,5-triterpene, 2-(4-decyloxystyryl)_4,6·bis (trioxanyl)_ι,3,5-three tillage, 2-(3,4 ,5-trimethoxystyryl)_4,6_bis (three gas sulfhydryl pi%% three tillage, 2-(4-mercaptothiophenyl)_4,6-bis (trioxanyl)- l,3,5-triterpenoid 1S 316123 1351581 isohalomethyl-S-triterpene series of compounds; l-[4-(phenylthio)phenyl]-2-(0-alum)-octane -1,2-dione, 1-(4-phenylthiophenyl)butane-1,2-dione-2-oxo-benzoic acid vinegar (l-(4-phenylsulfanylphenyl)butane-l, 2-dione -2-oxime-0-benzoate), 1-(4-decylthiophenyl)butane-1,2-dione-2-month-deficient 0-acetate, 1-(4-A Benzyl dimethyl ketal; sulfur in the range not included in the above formula (1), such as thiophenyl)butan-1-one oxime-indole-acetate; Sulfur compounds such as thioxanthone, 2-oxothione, 2,4-diethylthioxanthone, 2-mercaptothioxanthone, 2-isopropylthioxanthone; Ethyl hydrazine Anthraquinone, octamethyl hydrazine, L2-benzopyrene, 2,3-diphenyl hydrazine and the like; azobisisobutyronitrile, benzoquinone peroxide, An organic peroxide such as cumene peroxide; a thiol compound such as 2-thiolbenzimidazole, 2-thiolbenzopyrene, or 2-thiolbenzothiazole. These photopolymerization initiators or sensitizers may be used alone or in combination of two or more. Further, a compound which itself has no photopolymerization initiator or a sensitizer, but which can increase the photopolymerization initiator or the sensitizer ability by a combination with the above compound, can be added. Such a person: Example f is a secondary amine such as triethanolamine which can exert an effect when used in combination with a benzophenone.

成伤（C)光聚合起始劑的借用旦，—B 成份合計Η)。重乂是以(A)成份與(B) 重置伤為基準，則較佳為2至3〇旦更佳為5至20沾舌的重里份，目丨丄，的重置伤。若（C)成份的添加比例未滿2 則光聚合的诘疮料阻0 β 列禾/雨2 ’ 重量份，降低’另—方面，若超過30 則感度過強，圖案線寬將比圖案光罩寬，而無法 316123 1351581 忠實地重現光罩的線寬，此外，圖案輪廓呈鋸齒狀，恐產生不清晰的問題。成份（c)光聚合起始劑以通式⑴所表示的光聚合起始劑為必需成份，其之用量，於未添加其他（C) 成份時’只要在可單獨發揮光聚合起始劑之作用之量以上即可，該劑量，以（A)成份與（B)成份合計100重量份為基準時，較佳為2至30重量份’更佳為3至15重量份。成份（D)著色劑之色調並未特別限定，可依彩色遽光片的用途而適當的選定，顏料染料及天然色素均可。由於彩色濾光片要求高精密的顏色顯現及耐熱性，因此一般乃採籲用顏料，尤其較為理想者為採用有機顏料及碳黑。關於上述有機顏料，就紅色顏料言之，可採用單一的紅色顏料系列’亦可於紅色顏料系列之中混合黃色顏料系列來進行調色。關於紅色顏料’例如有蒽醌（anthraquinone)系列顏料、喹吖啶酮系列顏料’二酮基吡咯系列顏料、祐加:細）系列顏料# ’以二酮卩比洛并卩比洛紅（Diket〇 pyrr〇i〇加… ^幻⑷丄顏料紅254)及蒽醌紅（c〗·顏料紅η?)等為尤佳。此外’關於黃色的顏料，例如有，異養啉黃（is。— Yell〇w)(C丄顏料黃139)、鎳偶氮黃㈤加丨Az〇 ah⑽狀丄，料θ 150)、雙芳香酿苯胺黃⑼㈣也训⑽)i顏料黃83)等。這些紅色顏料系列及黃色顏料系列各可混合2 =上來使用。此外’於混合使用紅色顏料系列及黃色顏 =列的：況’，於紅色顏料系列與黃色顏料系列的總里00重里份，頁色顏料系列以為90重量份以下為較佳。關於綠色的顏料可採用單一的綠色顏料系列，亦可混合黃 316123 20 1351581 色顏料系列於綠色顏料系列之中來進行調色。關於綠色的顏料，例如有，氯化献菁綠（chlorophthal〇cyaninegreen)顏料（C.I.顏料綠7)、溴化酞綠顏料（C I顏料綠3幻等。此外，關於！色的顏料，例如有異吲哚啉黃（C I.顏料黃13巧、雙芳香醯苯胺頁（C.I.顏料黃83)等。這些綠色顏料系列及黃色顏料系列各可混合2種以上來使用。此外，於混合使用綠色顏料系列及黃色顏料系列而使用的情況，相對於綠色顏料系列與黃色顏料系列的總量為100重量份，黃色顏料系列較佳為90重量份以下。關於藍色的顏料可採用單一的藍色顏料系列，亦可現合紫色顏料系列於藍色顏料系列之中來進行調色。關於藍色的顏料，例如有，_系_料、陰丹士林（Indanthrene)系列顏料等，尤其是較為理想者為 ε 型酞菁藍（Phthalocyanine Blue)顏料（c.I.顏料藍 15 . 6) 等。此夕卜，關於紫色的顏料，例如有，二喔哄紫 %⑻(C.!.顏料紫23)，這些藍色顏料系列及紫色顏料系列各可混合2種以上來使用。此外，於混合使用藍色顏料系列及紫色顏料㈣的情況，相對於藍色顏料㈣及紫料系列的總量100重量份1色顏料系列的重量份為：〇以下。Injury (C) photopolymerization initiator borrowed, -B component total Η). The weight is based on the (A) component and (B) the replacement injury. It is preferably 2 to 3 旦. More preferably, it is 5 to 20 cc. If the addition ratio of (C) component is less than 2, the photopolymerized acne resistance is 0 β 禾 / rain 2 ' parts by weight, lowering 'other', if more than 30, the sensitivity is too strong, the pattern line width will be more than the pattern The mask is wide, and it is impossible to 316123 1351581 faithfully reproduce the line width of the mask. In addition, the outline of the pattern is jagged, which may cause unclear problems. Component (c) Photopolymerization initiator The photopolymerization initiator represented by the formula (1) is an essential component, and the amount thereof is used when no other component (C) is added, as long as the photopolymerization initiator can be used alone. The amount of the action may be more than 2 to 30 parts by weight, more preferably 3 to 15 parts by weight, based on 100 parts by weight of the total of the component (A) and the component (B). The color tone of the component (D) coloring agent is not particularly limited, and may be appropriately selected depending on the use of the color calendering film, and both the pigment dye and the natural pigment may be used. Since color filters require high-precision color development and heat resistance, pigments are generally used, and in particular, organic pigments and carbon black are preferred. Regarding the above organic pigment, in the case of a red pigment, a single red pigment series can be used, and a yellow pigment series can also be mixed among the red pigment series for color adjustment. About red pigments such as anthraquinone series pigments, quinacridone series pigments 'diketopiprrole series pigments, yuga: fine) series of pigments # 'diketone 卩洛洛卩卩洛 ( ( (Diket〇 Pyrr〇i〇加... ^ Magic (4) 丄 Pigment Red 254) and blush (c〗·Pigment Red η?) are especially preferred. In addition, 'yellow pigments, for example, isoflavone yellow (is. - Yell〇w) (C丄 pigment yellow 139), nickel azo yellow (five) plus Az〇ah (10) 丄, material θ 150), double aroma Stuffed aniline yellow (9) (four) also training (10)) i pigment yellow 83) and so on. These red pigment series and yellow pigment series can each be mixed 2 = used up. Further, in the case of mixing the red pigment series and the yellow color = column: the case, the total amount of the red pigment series and the yellow pigment series is 00 parts by weight, and the page color pigment series is preferably 90 parts by weight or less. For the green pigment, a single green pigment series can be used, or the yellow 316123 20 1351581 color pigment series can be mixed with the green pigment series for coloring. For the green pigment, for example, chlorophthalocyanine green pigment (CI pigment green 7), cesium bromide green pigment (CI pigment green 3 illusion, etc. Porphyrin yellow (C I. Pigment Yellow 13 bis, diaryl aniline page (CI Pigment Yellow 83), etc. These green pigment series and yellow pigment series can be used in combination of two or more. In addition, green pigment is used in combination. When the series and the yellow pigment series are used, the total amount of the green pigment series and the yellow pigment series is 100 parts by weight, and the yellow pigment series is preferably 90 parts by weight or less. For the blue pigment, a single blue pigment may be used. The series can also be blended with the purple pigment series in the blue pigment series. For the blue pigments, for example, _ _ _ materials, Indanthrene series of pigments, etc., especially ideal It is ε-type Phthalocyanine Blue pigment (cI pigment blue 15.6), etc. Further, regarding the purple pigment, for example, bismuth violet (8) (C.!. Pigment Violet 23), These blue The pigment series and the purple pigment series may be used in combination of two or more kinds. In addition, when the blue pigment series and the purple pigment (four) are used in combination, the total amount of the blue pigment (four) and the purple material series is 100 parts by weight of the one color pigment. The weight of the series is: 〇 below.

此外，關於遮光性分散_例如有黑色有機色有機顏料或是遮光材料等，關於黑色有機顏料 L 比黑、花青素（c—ne)黑等。關於黑色有機顏料，例從紅、藍、綠、紫、黃、花青素、洋紅當中採用 2種以上的顏料來混而而成為近似黑色者。： 316123 21 =例如有’碳黑、氧化鉻、氧化鐵鈦黑、苯胺二、花青素黑等’亦可適當地選擇2種以上來採用，在這 Γΐ丄較為理想者為具備良好的遮光性，表面平滑性及分政女疋f生且與樹脂具相容性（compatabi脚)之碳黑。此外’著色劑視需要，可與分散劑合用。關於此等分散劑’例如有陽離子系列'陰離子系列、非離子系列、兩 i·系歹J石夕_系列、氟系列等界面活性劑。關於上述界面活性劑的具體例，例如有聚氧伸乙基十二烷基醚、聚氧伸乙基硬脂基醚等聚氧伸乙基烷基醚。本發明中之成份（D)的色素的使用量，若是以（A)成份 ”（B)成伤合计1〇〇重量份為基準則以⑽至“ο重量份為較佳，以50至23〇重量份為更佳。若未滿3〇重量份，則不具足夠的顏色純度及遮光性，為了獲得所希望的對比而必須增加膜厚’因而難以獲得具備平滑面的彩色滤光片，相對的，若超過280重量份，則包含（D)成份的彩色濾光片用感光性樹脂組成物的分散安定性下降，此外，由於原先做為黏結劑的感光性樹脂的含量降低，因此可能產生可能損及顯像特性並可能損及膜形成能力之問題。於本發明的彩色滤光片用感光性樹脂組成物當中，較理心除了上述（A)至（D)成份之外’亦採用溶劑。關於溶劑，例如有，甲醇、乙醇、正丙醇、異丙醇、乙二醇、丙二醇等醇類，或是点-松油醇（terpineol)等萜類（terpene)、丙酉同、丁酮、環己酮、N_甲基_2_吡咯烷酮 (N-Methyl-2-Pyrr〇iid〇ne)等酮類；甲笨、二曱苯、四曱基 316123 22 1351581 本·#务香知奴氫化合物類；赛璐素（cell〇s〇lve)、乙二醇單曱醚（methyl cellosolve)、乙二醇單乙醚（ethyl celi〇solve)、卡必醇（carbitol)、曱基卡必醇、乙基卡必醇、丁基卡必醇、丙二醇單甲基醚、丙二醇單乙基醚、二丙二醇單甲基醚、一丙一醇單乙基醚、三丙二醇單甲基趟、三乙二醇單乙基崎等二元醇醚類；醋酸乙酯、醋酸丁酯、乙二醇單醋酸酯 (Cellosolve Acetate)、乙二醇單乙醚單醋酸酯、乙二醇單丁醚單醋酸酯、卡必醇醋酸酯、乙基卡必醇醋酸酯、丁基卡必醇醋酸酯、丙二醇單曱基醚乙酸酯、丙二醇單乙基醚乙酸酯等醋酸酯類，藉由溶解並混合這些化合物，可製作均一的溶液狀組成物。此外’於本發明的彩色濾光片用感光性樹脂組成物中’可視需要添加硬化促進劑、熱聚合禁止劑、可塑劑、填充材料、勻染劑、消泡劑等添加劑。關於熱聚合禁止劑，例如有對苯二朌（hydroquinone)、對苯二酚單甲基醚、焦掊酚（pyrogallol)、第三級丁基鄰苯二酚（tert_ butylcatech〇1)、啡噻畊（phenothiazine)等；關於可塑劑，例如有鄰苯二曱酸二丁酯（dibutyl phthalate)、鄰苯二曱酸二辛酯（di〇ctyl phthalate)、甲酚混合物（tricresol，鄰曱酚、間曱酚及對曱酚之混合物）等；關於填充材，例如有玻璃纖維、矽膠、雲母、氧化鋁等；此外’關於消泡劑及勻染劑，例如有石夕系列、氟系列、丙烯酸系列化合物。此外’本發明彩色滤'光片用感光性樹脂組成物以上述 (A)至（D)成份或者（A)至（D)成份與溶劑為主成份。於去除 316123 23 1351581Further, the light-shielding dispersion is, for example, a black organic color organic pigment or a light-shielding material, and the black organic pigment L is black, anthocyanin (c-ne) black or the like. Regarding the black organic pigment, two or more kinds of pigments are mixed from red, blue, green, purple, yellow, anthocyanin, and magenta to form a black color. : 316123 21 = For example, 'carbon black, chromium oxide, iron oxide titanium black, aniline II, anthocyanin black, etc.' can be appropriately selected from two or more types, and it is preferable to have good shading. Sex, surface smoothness and carbon black of the virginity and compatibility with the resin (compatabi foot). Further, the coloring agent may be used in combination with a dispersing agent as needed. Examples of such dispersing agents are surfactants such as a cationic series 'anion series, a non-ionic series, two i-systems, a series, and a fluorine series. Specific examples of the above surfactants include polyoxyethylene ethyl ethers such as polyoxyethylene ethyl lauryl ether and polyoxyethylene ethyl stearyl ether. The amount of the pigment used in the component (D) in the present invention is preferably from (10) to "o parts by weight, based on 1 part by weight of the component (B). 〇 The weight is better. If it is less than 3 parts by weight, it does not have sufficient color purity and light-shielding property, and it is necessary to increase the film thickness in order to obtain a desired contrast. Therefore, it is difficult to obtain a color filter having a smooth surface, and if it exceeds 280 parts by weight In addition, the dispersion stability of the photosensitive resin composition for the color filter containing the component (D) is lowered, and since the content of the photosensitive resin originally used as the binder is lowered, there is a possibility that the development characteristics may be impaired. It may damage the film forming ability. Among the photosensitive resin compositions for color filters of the present invention, a solvent is used in addition to the above components (A) to (D). The solvent may, for example, be an alcohol such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol or propylene glycol, or a terpene such as terpineol, propyl ketone or butanone. , ketones such as cyclohexanone, N-methyl-2-pyrrolidine (N-Methyl-2-Pyrr〇iid〇ne); methyl stupid, diterpene benzene, tetradecyl 316123 22 1351581 Hydrogens; cell 〇s璐lve, methyl cellosolve, ethyl celi〇solve, carbitol, decyl carbitol , ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, monopropanol monoethyl ether, tripropylene glycol monomethyl hydrazine, triethyl Glycol monoethyl ether and other glycol ethers; ethyl acetate, butyl acetate, ethylene glycol monoacetate (Cellosolve Acetate), ethylene glycol monoethyl ether monoacetate, ethylene glycol monobutyl ether monoacetate , carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monodecyl ether acetate, propylene glycol monoethyl ether acetate, etc. Esters, by mixing and dissolving these compounds in a solution state can be made uniform composition. Further, in the photosensitive resin composition for a color filter of the present invention, an additive such as a curing accelerator, a thermal polymerization inhibiting agent, a plasticizer, a filler, a leveling agent, or an antifoaming agent may be added as needed. Regarding thermal polymerization inhibiting agents, for example, hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol (tert_butylcatech〇1), thiophene Phenothiazine, etc.; for plasticizers, for example, dibutyl phthalate, dioctyl phthalate, cresol mixture (tricolsol, o-nonylphenol, For the filler, for example, glass fiber, silicone rubber, mica, alumina, etc.; and 'for defoaming agents and leveling agents, for example, Shi Xi series, fluorine series, acrylic acid Series of compounds. Further, the photosensitive resin composition for a color filter of the present invention contains the above components (A) to (D) or (A) to (D) and a solvent as a main component. For removal 316123 23 1351581

溶劑的固形成份中，（A)至（d)成份合計為70wt%以上，較佳為80wt%以上，更佳為9〇wt%以上。溶劑的量乃因目標 · 黏度的不同而改變，較佳為20至80wt%。本發明的彩色濾光片用感光性樹脂組成物雖適合用於黑色及r、G、B 用光阻層（油墨），但更適合用於黑色用光阻層（遮光用油‘ 墨）。 - 接下來說明採用感光性樹脂組成物的彩色濾光片的製造方法。首先，視需要，於基板表面上形成用於區隔形成晝素之部分之遮光層，於此基板上塗佈例如分散有紅色的鲁顏料的感光性樹脂組成物的液狀組成物，之後進行前烘烤使溶劑蒸發形成塗膜。接下來於此塗膜上通過光罩來曝光，之後採用鹼性顯像液顯像，溶解以去除塗膜的未曝光部分之後’藉由後供烤，形成紅色晝素圖案按預定排列而配置的畫素陣列（array)。之後，採用分散有綠色或藍色顏料的感光性樹脂組成物的液狀組成物，進行與上述相同之各個液狀組成物的塗佈、前烘烤、曝光、顯像及後供烤，以於同I板上依序形成綠色的晝素陣列及藍色的畫素陣# 列’藉此獲得紅色、綠色及藍色的晝素陣列被配置於基上的彩色遽光片。於基板上塗佈感光性樹脂組成物的液狀組成物之際，除了可採用眾所皆知的溶液浸泡法及喷濃法之外，亦可採用依據滾輪塗佈機，圓盤塗佈機及旋床（spinner)之方法等。根據這些方法，於塗佈所希望的厚度之後，去除溶前供烤）而形成覆膜。前供烤可藉由烤箱、加熱板等來進行。 316123 24 1351581 刖烘烤中的加熱溫度及加埶時間，可;田μ 而滴m γ ”、、㈣了視所使用的溶劑種類、擇，例如於80至120°c的溫度進行】至10分鐘。用可=製Π色濾光片之際所使用的放射線’例如可使先、紫外線、遠紫外線、電子束、χ射線等，較佳 :波長25〇s 450mM|圍内的放射線。此外，關於適用於 4驗=顯像的顯像液，例如有驗金屬及驗土金屬之碳酸鹽的水溶液’驗金屬氫氧化物水溶液等，其中，以採用包含〇’〇5至1〇重量％的碳酸鈉、碳酸妈、碳酸鐘等碳酸鹽之弱鹼m讀’於2G i贼下顯像為佳並㈣市:上所販賣的顯像機及超音波洗淨機，而可精密的形成纖細的晝像。於驗性顯像讀’進行清洗。關於顯像處理法，例如可適用沖淋顯像法、喷灑顯像法、浸泡（浸液）顯像法、攪拌顯像法等。顯像條件較佳為於常溫下進行10至丨20 秒。如此顯像之後，可於180至250。〇的溫度及2〇至1〇〇分鐘的條件下進行熱處理（後烘烤）。進行後烘烤的目的為提升形成圖案後的塗膜與基板之間的密著性。後供烤與前烘烤相同’可藉由烤箱、加熱板等來進行。本發明之形成圖案後的塗膜’乃經由依據上述光微影（ph〇t〇Hth〇graphy) 製程法之各個步驟而形成。此外，黑色矩陣（black matrix)可採用遮光感光性樹脂組成物’並以與上述晝素陣列相同之方式形成。形成具有晝素及/或黑色基質之彩色濾光片之際所使用的基板’例如為於玻璃或透明薄膜（例如聚碳酸酯、聚對 316123 25 丄乃1581 ，一甲酸丁 —酯（po】yethylene terephthalate)、聚醚碉等）上為錢ITO、金等透明電極或鍍上圖案等者。此外，可視需要預先於這些基板上，適當地施以矽烷偶合處理劑等藥二處理、電漿處理、離子蒸鍍、減鑛、氣相反應法、真空蒸鑛等前處理。 [發明之效果] 本發明的彩色濾光片用感光性樹脂組成物可以形成圖案尺寸女疋性優異’且顯像圖框（margin)、圖案密著性及圖案之輪廓形狀良好的圖案，因此，本發明的彩色濾光片鲁用感光性樹脂組成物，可適當的用做彩色液晶顯示裝置、彩色傳真機、影像感測器等各種多色彩顯示器及光學機器等之彩色濾光片用的著色油墨，又，藉由該感光樹脂組成物形成之具有黑色基質之彩色濾光片適合用於電視、視訊顯示器、或是電腦的顯示器等。此外，如此獲得的彩色濾光片極適合用於例如穿透型或是反射型的彩色液晶顯示裝置、彩色影像管元件及色彩感測器等。【實施方式】籲以下根據實施例及比較例’具體說明本發明，但是本發明並不限定於此。其中，於實施例及比較例的彩色濾光片的製造中所採用的原料及省略符號如下所述。 (A)-1 .具備芴骨架的環氧丙烯酸酯的酸酐類聚縮合物的丙二醇單曱基醚乙酸酯溶液（樹脂固形成份濃度=56.1重量％ ’日本新日鐵化學公司製造，商品名稱為V259me) ⑷七Mw8800’酸價130的Ν·苯基醯亞胺/曱基丙烯 316123 26 1351581 西文/甲基丙稀酸苯甲酯共聚合物的丙二醇單甲基醚乙酸酯溶液（樹脂固形成份濃度=37·9重量％)(N苯基醯亞胺：甲基丙烯酸：曱基丙烯酸苯甲酯=26 : 34 ·· 4〇莫耳 ^ (A)_3 : Mwl60000，酸價95的N-苯基醯亞胺/甲基丙烯1/曱基丙烯酸卞酯共聚合物的丙二醇單甲基醚乙酸酯溶液（樹脂固形成份濃度=381重量％)(队苯基醯亞胺：甲基丙稀酸··甲基丙烯酸T酯=36 : 25 : 39莫耳％) (B) 又季戊四醇六丙烯酸酯及雙季戊四醇五丙浠酸酯的混合物(日本化葯公司製造，商品名稱為DpHA) (C) 1 ·上述通式⑴所表示的化合物 (C)-2 : p，p’_雙乙基胺基二苯曱酮一（）3 . 2·(4-甲氧基苯乙烯基）_4,6_雙（三氣甲基三哄 ’ ’ ()笨曱基-2_二甲基胺基-1-(4-嗎啉基笨基）丁 (C)-5 : (C)-6 : 酮（化學式如甲基-1-[4-(甲基硫）苯基]_2·嗎啉基丙_丨_酮 M4-(苯硫基）苯基]_2-(〇_苯甲醯月亏）_辛_12_二下） ?In the solid content of the solvent, the total of the components (A) to (d) is 70% by weight or more, preferably 80% by weight or more, more preferably 9% by weight or more. The amount of the solvent varies depending on the target and viscosity, and is preferably from 20 to 80% by weight. The photosensitive resin composition for a color filter of the present invention is suitably used for a photoresist layer (ink) for black and r, G, and B, but is more suitably used for a photoresist layer for black (an ink for light-shielding). - Next, a method of manufacturing a color filter using a photosensitive resin composition will be described. First, a light-shielding layer for partitioning a portion where a halogen element is formed is formed on a surface of a substrate, and a liquid composition of a photosensitive resin composition in which a red pigment is dispersed is applied onto the substrate, followed by The pre-baking causes the solvent to evaporate to form a coating film. Next, the film is exposed through a mask, and then imaged by an alkaline developing solution, dissolved to remove the unexposed portion of the film, and then baked, and the red halogen pattern is arranged in a predetermined arrangement. The array of pixels. Thereafter, the liquid composition of the photosensitive resin composition in which the green or blue pigment is dispersed is applied, and the same liquid composition as described above is applied, pre-baked, exposed, developed, and post-baked. A green halogen array and a blue pixel array # column are sequentially formed on the same I plate, thereby obtaining a color light sheet in which a red, green, and blue pixel array is disposed on the substrate. When the liquid composition of the photosensitive resin composition is coated on the substrate, in addition to the well-known solution soaking method and the spray concentration method, a roller coating machine or a disc coater may be used. And the method of a spinner. According to these methods, after coating a desired thickness, the pre-dissolution bake is removed to form a film. The front grilling can be carried out by an oven, a heating plate or the like. 316123 24 1351581 The heating temperature and the twisting time during baking can be made; the field μ drops m γ ”, and (4) depending on the type of solvent used, for example, at a temperature of 80 to 120 ° C] to 10 The radiation used in the case of the color filter can be used, for example, ultraviolet light, far ultraviolet light, electron beam, xenon ray, etc., preferably: radiation at a wavelength of 25 〇s 450 mM. For a developing solution suitable for 4 test = development, for example, an aqueous solution of a metal hydroxide and a metal hydroxide of a soil test metal, etc., wherein the use of 〇'〇5 to 1% by weight is included. The sodium carbonate, carbonic acid mother, carbonic acid clock and other carbonates of the weak base m read 'in 2G i thief under the image is better and (four) city: the video camera and ultrasonic cleaning machine sold, but can be precisely formed Slim image. Read on the inspection image for cleaning. For the development method, for example, shower imaging, spray imaging, soaking (immersion) imaging, stirring imaging, etc. The development condition is preferably 10 to 丨 20 seconds at normal temperature. After such development, it can be 1 80 to 250. The heat treatment (post-baking) is carried out under the conditions of 〇 and 2 Torr to 1 Torr. The purpose of post-baking is to improve the adhesion between the coating film and the substrate after patterning. The same as the pre-baking can be performed by an oven, a hot plate, etc. The patterned film of the present invention is subjected to various steps in accordance with the above-described photolithography process. Further, a black matrix may be formed by using a light-shielding photosensitive resin composition' in the same manner as the above-described halogen matrix. When a color filter having a halogen and/or a black matrix is formed, it is used. The substrate 'is, for example, a transparent electrode such as ITO or gold on a glass or a transparent film (for example, polycarbonate, polypair 316123 25 丄 1581, yethylene terephthalate, polyether oxime, etc.). Or plating a pattern, etc. Further, as needed, a decane coupling treatment agent or the like may be appropriately applied to the substrate, a plasma treatment, an ion deposition, an ore reduction, a gas phase reaction method, a vacuum distillation, or the like. Front [Effects of the Invention] The photosensitive resin composition for a color filter of the present invention can form a pattern having excellent pattern size and excellent virginity, and a texture frame, a pattern adhesion, and a contour shape of the pattern. Therefore, the color filter of the present invention uses a photosensitive resin composition, and can be suitably used as a color filter such as a color liquid crystal display device, a color facsimile machine, an image sensor, or the like, and a color filter such as an optical device. The coloring ink used, and the color filter having a black matrix formed by the photosensitive resin composition is suitable for use in a television, a video display, or a display of a computer, etc. Further, the color filter thus obtained is extremely suitable It is used for, for example, a transmissive or reflective type color liquid crystal display device, a color image tube element, a color sensor, and the like. [Embodiment] The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited thereto. Here, the raw materials and the omission symbols used in the production of the color filters of the examples and the comparative examples are as follows. (A)-1. A propylene glycol monodecyl ether acetate solution of an acid anhydride-based polycondensate of an epoxy acrylate having an anthracene skeleton (resin solid content concentration = 56.1% by weight) manufactured by Nippon Steel Chemical Co., Ltd., trade name is V259me) (4) Seven Mw8800' acid valence Ν phenyl phenyl imidate / mercapto propylene 316123 26 1351581 Western / methacrylic acid benzyl ester copolymer propylene glycol monomethyl ether acetate solution (resin Solid component concentration=37·9 wt%) (N-phenyl quinone imine: methacrylic acid: benzyl methacrylate = 26: 34 · · 4 〇 Mo Er ^ (A) _3 : Mwl60000, acid value 95 Propylene glycol monomethyl ether acetate solution of N-phenyl quinone imine / methacryl 1 / decyl decyl acrylate copolymer (resin solid content concentration = 381% by weight) (team phenyl quinone imine: A Acrylic acid · T-ester of methacrylate = 36 : 25 : 39 mole %) (B) Mixture of pentaerythritol hexaacrylate and dipentaerythritol penta-propionate (manufactured by Nippon Kayaku Co., Ltd., trade name DpHA (C) 1 - Compound (C)-2 represented by the above formula (1): p,p'-diethylaminodibenzophenone-(3). 2·(4-methoxystyryl)_4,6_bis(trioxanemethyltrimium ' ' () alkalyl-2-dimethylamino-1-(4-morpholinyl) ) butyl (C)-5 : (C)-6 : ketone (chemical formula such as methyl-1-[4-(methylthio)phenyl]_2·morpholinylpropan-1-one M4-(phenylthio) ) phenyl]_2-(〇_苯甲醯月亏)_辛_12_二下) ?

【化學式6J[Chemical Formula 6J

15 : 6)濃度 13.7 316123 27 1351581 重量％，高分子分散劑濃度5.4重量％的丙二醇單曱基醚乙酸酯分散液（固形成份19.1%) (D)-2:溴氣化駄菁綠顏料（C.I.顏料綠36)濃度15.1重量％，高分子分散劑濃度4.0重量％的丙二醇單曱基醚乙酸酯分散液（固形成份19.1%) * (D)_3 :二酮基吡咯并吡咯紅顏料（C.I.顏料紅254)濃度 15.0重量％ ’高分子分散劑濃度5.3重量％的丙二醇單曱基醚乙酸酯分散液（固形成份18.3%) (D)-4.鎳偶氮黃顏料（c.l.顏料黃15〇)濃度13.3重量馨 % ’高分子分散劑濃度4.4重量％的丙二醇單曱基醚乙酸酯分散液（固形成份17.7%) (D) -5 :碳黑濃度20重量％，高分子分散劑濃度5重量％的丙二醇單曱基醚乙酸酯分散液（固形成份25.0%) (E) -l :丙二醇單甲基醚乙酸酯 (E) -2 .乳酸乙醋（ethyi lactate) (F) ·環氧樹脂（曰本環氧樹脂公司（japan Ep0Xy Resin) _ 製造，商品名稱為γΧ4〇〇〇Η) (G) :矽烷（Siiane)偶合劑 (H) :界面活性劑 [實施例] 按第1表所記載的比例來添加上述添加成份，而調製出貫知例1至8的組成物。於表中所謂的P/B，係顯示（分散液中的顏料重量）/((A)、（B)、（F)成份中的固形成份合計重量）。 28 316123 ⑶丄581 [第1表]15 : 6) Concentration 13.7 316123 27 1351581% by weight, polymer dispersant concentration 5.4% by weight of propylene glycol monodecyl ether acetate dispersion (solid content 19.1%) (D)-2: brominated gasified phthalocyanine green pigment (CI Pigment Green 36) Concentration of 15.1% by weight, polymer dispersant concentration of 4.0% by weight of propylene glycol monodecyl ether acetate dispersion (solid content 19.1%) * (D)_3 : Diketopyrrolopyrrole red pigment (CI Pigment Red 254) Concentration 15.0% by weight 'Polymer dispersant concentration 5.3% by weight of propylene glycol monodecyl ether acetate dispersion (solid content 18.3%) (D)-4. Nickel azo yellow pigment (cl pigment Yellow 15 〇) concentration 13.3 weight%% 'polymer dispersant concentration 4.4% by weight of propylene glycol monodecyl ether acetate dispersion (solid content 17.7%) (D) -5: carbon black concentration 20% by weight, polymer Dispersant concentration: 5% by weight of propylene glycol monodecyl ether acetate dispersion (solid content 25.0%) (E) -l : propylene glycol monomethyl ether acetate (E) -2 . Ethyl lactate (ethyi lactate) (F) · Epoxy resin (japan Ep0Xy Resin) _ Manufactured under the trade name γΧ4〇〇〇 ) (G): Silane (Siiane) coupling agent (H): surfactant [Example] by the ratio of the first table according to add the additive ingredients, to prepare a consistent composition known in Examples 1 to 8. The so-called P/B in the table shows (the weight of the pigment in the dispersion) / (the total weight of the solid components in the components (A), (B), and (F)). 28 316123 (3)丄581 [Table 1]

採用旋轉塗佈機，將混合這些組成物所得到的彩色濾光片用感光性樹脂組成物’以使前烘烤後的膜厚成為1.0 或是l 5//m之方式，來塗佈於i25mmx l25mm的玻璃基板上，於90t下前烘烤2分鐘。之後，調整曝光間距為80/zm’於乾燥塗膜上方配置線/空間為2〇"m/2〇# m ’ 100# m/lOOy m的負型光罩，以ϊ線明度3〇mW/cm2 的超高壓水銀燈照射1 〇〇mj/ cm2的紫外線，而進行感光部分的光硬化反應。接下來，以0.04%的氫氧化鉀水溶液，於23°C以lkgf/ cm2壓力沖淋曝光後的塗膜板5〇秒或8〇秒以使之顯像’並進行1 kgf/ cm2壓力的喷灑水洗，去除塗 316123 29 1351581 膜的未曝光部分後’於玻璃基板上形成畫素圖案，之後才采用熱烘乾機’於進行230t的熱後烘烤30分鐘之後，評估圖案線寬、圖案直線性及塗膜表面粗糙度。再者’於121°C、100%RH、2atm、24小時的條件下，對後烘烤後的圖案形成後的基板實施) Cooker Test，高壓水氣測試），並於20/zm的圖案部上面. 貼附玻璃紙膠帶（Cellophane Tape)，藉由進行剝落試驗來評估圖案密著性。實施例、比較例中的圖案畫素之圖案評估項目及方法籲如下所述。公司膜厚·採用觸針式高度差形狀測定器（美商科磊 (KLA-Tencor)製造，商品名稱為p_1〇)來測定。站圖案線寬：採用長度測定顯微鏡（日本尼康（耻叫公司製造，商品名稱為XD_20)，對於紅、綠、黃色感光性樹 ^组成物，光罩寬度為_心，對於黑色感光性樹脂组成物，光罩寬度為20/zm，若是峻官' 右疋線見率未超過± 10%之際為〇(良好）’超過± 10%之際為χ (不良）。圖案直線性：以顯微鏡觀察顯像後的晝素圖案觀察到從基板剝落及圖荦輪麻 '、好），若觀察到從基板剝落及阓宏為〇（良 X (不良)。及圖案邊緣部分呈鋸齒狀，則為塗膜表面粗链度·顯像、度（Ra)之值，若未滿15〇 Α， A，則為χ (不良）。熱燒結之後的塗膜表面粗糙則為〇（良好），若超過150 316123 30 1351581 將結果示於第2表中。於第2矣击 „ 弟2表中，各個實施例的左欄為顯像間5 〇秒的例子，六總支# J 右襴為顯像時間80秒的例子的結果。如第2表所示，均為良好。 [第2表] 膜厚（// m) 實施例 1.5 實施例2 1.5 線寬（// m) 線粗率(％) 判定圖案直線性表面粗鏠度 Ra(A) ~备著性~ 106.4 1W] 106.8 5.48 108.3 ~fjr\ 107.4 ~6^89~ 一 102.3 — 〇 ~0~ (60) 〇 ~〇~ (76) 〇 ~〇~~ (75) 〇 (83) 〇— (106) 〇〇〇〇 -v / 〇 L例3 實施例4 .5 1.5 98.6 105.3 103.2 -1.42 5.03 3.10 〇〇〇 —〇〇〇〇〇〇 (110) (80) (92) 〇〇〇實施例5 實施例6 實施例7 實施例8 膜厚（A m) 1.0 1 •0 1.0 1.0 線寬（// m) 20.32 18.98 20.89 19.50 21.67 19.67 21.80 20.78 線粗率(％) 1.57 -5.88 4.26 -2.56 7.71 -1.68 8.26 3.75 判定〇〇〇〇〇〇〇〇圖案直線性〇〇〇〇〇〇〇〇表面凹凸〇〇〇〇〇〇〇〇 Ra(A) (94) (110) (93) (100) (86) (93) (83) (80) 密著性〇〇〇〇〇〇〇〇比較例1 關於（C)成份’除了（C)-4變更為〇.3重量份及（C)-6變更為1.5重量份之外，其他以與實施例1相同的條件來形成畫素圖案’評估之後’觀察到圖案輪廓呈鋸齒狀，因此圖案直線性為不良（X )。比較例除了將（A)成份變更為（A)-2之外，其他以與實施例3 31 3J6123 1351581 相同的條件製造畫素圖案並進行評估，確認於9〇秒顯像下，線寬變細10%以上，因此線寬判定為不良（>< 此外，圖案直線性及密著性判定亦為不良（x)。 _比較例3 除將（C)成份變更為2.〇重量份之（c)_3之外，其他以與實施例4相同的條件製造畫素圖案，評估之後，觀察到圖案直線性不良（X )，此外，被認為是（(：>3的不溶物之異物’以點狀存在於塗膜表面上。比較例4 除了將（A)成份變更為（a)-2之外，其他以與實施例5 相同的條件製造成晝素圖案，評估之後，確認於8〇秒顯像下，由於感度不足而使圖案產生缺陷，因而判定為不良 (X )。比較例5 除了將（C)成份變更為丨8重量份之（c)_6之外，其他以與實施例5相同的條件製造畫素圖案，評估之後，確認於 90秒顯像下，線寬變細10%以上，因此線寬判定為不良 (X )。此外，圖案直線性亦不良（X )。比較例6 除了將（C)成份的添加量變更為〇」重量份之外，其他以與實施例5相同的條件製造畫素圖案，評估之後，確認於5 0秒顯像下，線寬變細1 〇 %以上，因此線寬判定為不良（X )。此外，圖案直線性及密著性判定亦為不良（χ )，表面粗糙度為250人’亦為不良（χ)。 316123 32 1351581 比較例7 除將（A)成份的種類變更為（A)-3之外，其他以與實施例8相同的條件製造晝素圖案，評估之後，圖案直線性及密著性均判定為不良（X )。气一》 316123The color filter obtained by mixing these components is applied to the photosensitive resin composition by a spin coater so that the film thickness after the prebaking is 1.0 or 15/m. On the i25mmx l25mm glass substrate, bake for 2 minutes at 90t. After that, adjust the exposure interval to 80/zm' to arrange a negative mask with a line/space of 2〇"m/2〇# m ' 100# m/lOOy m above the dry coating film, with a line brightness of 3〇mW The ultra-high pressure mercury lamp of /cm2 is irradiated with ultraviolet rays of 1 〇〇mj/cm2 to carry out photohardening reaction of the photosensitive portion. Next, the exposed coated film was sprayed with a 0.04% potassium hydroxide aqueous solution at a pressure of lkgf/cm 2 at 23 ° C for 5 sec or 8 sec to visualize ' and carry out a pressure of 1 kgf / cm 2 After spraying with water, removing the unexposed portion of the film of 316123 29 1351581, 'forming a pixel pattern on the glass substrate, and then using a hot dryer' to perform post-heat baking for 230 minutes for 30 minutes, the pattern line width was evaluated. Pattern linearity and coating surface roughness. In addition, under the conditions of 121 ° C, 100% RH, 2 atm, and 24 hours, the substrate after pattern formation after post-baking was performed) Cooker Test, high pressure water gas test), and the pattern portion at 20/zm Above. Attach a cellophane tape (Cellophane Tape) and evaluate the pattern adhesion by performing a peeling test. The pattern evaluation items and methods of the pattern pixels in the examples and comparative examples are as follows. The company's film thickness was measured using a stylus type height difference shape measuring device (manufactured by KLA-Tencor, trade name p_1〇). Station pattern line width: using a length measuring microscope (manufactured by Nikon, Japan (trade name: XD_20), for red, green, and yellow photosensitive tree composition, the mask width is _ heart, for black photosensitive resin composition The width of the mask is 20/zm. If the peak of the right ridge is not more than ± 10%, it is 〇 (good) 超过超过 (bad) when it exceeds ± 10%. Pattern linearity: with microscope After observing the image, the alizarin pattern was observed to peel off from the substrate and the pattern was fine, and if it was observed to peel off from the substrate and the 阓 macro was 〇 (good X (bad). and the edge portion of the pattern was jagged, then The value of the surface roughness, development, and (Ra) of the coating film is χ (poor) if it is less than 15 〇Α, A. The surface roughness of the coating film after thermal sintering is 〇 (good). More than 150 316123 30 1351581 The results are shown in the second table. In the second sniper „ brother 2 table, the left column of each embodiment is an example of 5 〇 seconds between the developments, the six total branch # J right 襕 is obvious The result of the example like the time of 80 seconds is as good as shown in the second table. [Table 2] Film thickness (// m) Example 1.5 Example 2 1.5 Line width (// m) Line roughness (%) Determination pattern Linear surface roughness Ra(A) ~ Readiness ~ 106.4 1W] 106.8 5.48 108.3 ~fjr\ 107.4 ~6 ^89~一102.3 — 〇~0~ (60) 〇~〇~ (76) 〇~〇~~ (75) 〇(83) 〇—(106) 〇〇〇〇-v / 〇L Example 3 Example 4 .5 1.5 98.6 105.3 103.2 -1.42 5.03 3.10 〇〇〇-〇〇〇〇〇〇 (110) (80) (92) 〇〇〇 Example 5 Example 6 Example 7 Example 8 Film thickness (A m ) 1.0 1 •0 1.0 1.0 Line width (// m) 20.32 18.98 20.89 19.50 21.67 19.67 21.80 20.78 Line roughness (%) 1.57 -5.88 4.26 -2.56 7.71 -1.68 8.26 3.75 Determining the linearity of the pattern 〇〇〇〇〇〇〇〇 Surface 〇〇〇〇〇〇〇〇 Ra(A) (94) (110) (93) (100) (86) (93) (83) (80) Adhesion 〇〇〇〇〇〇〇〇Comparative Example 1 The component (C) was the same as in Example 1 except that (C)-4 was changed to 〇.3 parts by weight and (C)-6 was changed to 1.5 parts by weight. Condition to form a pixel map 'After evaluating' jagged pattern profile was observed, thus the linearity of the pattern is poor (X). In the comparative example, except that the component (A) was changed to (A)-2, the pixel pattern was produced and evaluated under the same conditions as in the example 3 31 3J6123 1351581, and it was confirmed that the line width was changed under the 9-second imaging. When the thickness is 10% or more, the line width is judged to be defective (><>, and the pattern linearity and adhesion determination are also defective (x). _Comparative Example 3 except that the component (C) is changed to 2. Other than (c)_3, the pixel pattern was produced under the same conditions as in Example 4. After the evaluation, the pattern linearity defect (X) was observed, and further, it was considered to be ((:>3 insoluble matter). The foreign matter 'appears on the surface of the coating film in a dot shape. Comparative Example 4 A halogen pattern was produced under the same conditions as in Example 5 except that the component (A) was changed to (a)-2, and after the evaluation, it was confirmed. In the case of 8 sec development, the pattern was defective due to insufficient sensitivity, and thus it was judged to be defective (X). Comparative Example 5 In addition to changing the component (C) to 8 parts by weight of (c)_6, The pixel pattern was produced under the same conditions as in Example 5, and after evaluation, it was confirmed that the line width was 90 seconds. When the thickness is 10% or more, the line width is judged to be defective (X). Further, the pattern linearity is also poor (X). Comparative Example 6 In addition to changing the amount of the component (C) to 〇" by weight, The pixel pattern was produced under the same conditions as in Example 5. After the evaluation, it was confirmed that the line width was reduced by 1% or more under the 50 second development, and therefore the line width was judged to be defective (X). Further, the pattern was linear and dense. The judgment was also bad (χ), and the surface roughness was 250. It was also bad (χ). 316123 32 1351581 Comparative Example 7 In addition to changing the type of (A) component to (A)-3, The alizarin pattern was produced under the same conditions as in Example 8. After the evaluation, the pattern linearity and the adhesion were judged to be poor (X). Gas No. 316123

Claims

1 351 581 351 93 月曰 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 93 The photosensitive resin composition for sheets is an ink for R, G, and B, and the following components (A) to (D) are essential components: (A) an epoxy having two glycidyl ether groups derived from bisphenols. a reaction product of a compound with (mercapto)acrylic acid, an unsaturated group-containing soluble resin compound obtained by reacting with a polybasic carboxylic acid or a multi-polyphenolic acid needle, and (B) having at least one ethylene (ethylenic) unsaturatedly bonded photopolymerizable monomer, (C) photopolymerization initiator, (D) colorant (excluding black color); characterized by: - (A) component and (B) The weight ratio (A)/(B) of the component is 20/80 to 90/10, and the content of the component (C) is 2 to 30 parts by weight based on 100 parts by weight of the component (A) and the component (B). And using the compound represented by the following general formula (I) as a component (C) photopolymerization initiator: [Chemical Formula 1] 】

(I)

In the formula (1), the core represents a phenyl group (which may be substituted by an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (which may be substituted by one or more hydroxyl groups, and 34 316123 ( Revised version) I35l58l February vi-day correction replacement page · Patent application No. 93123169, August 26, pp., correction, replacement of the page-burning chain, which may have more than one oxygen atom in the middle, and a carbon number of 5 to 8, An alkanoyl group having 2 to 20 carbon atoms or a benzoquinone group (which may be substituted by a carbon group having 1 to 6 carbon atoms or a phenyl group); and R2 represents an alkylene group having 2 to 12 carbon atoms (may be one or more) a halogen atom or a cyano group substituted), a double bond and a carbonyl group which are not conjugated with a carbon number of 4 to 6 olefin groups, a benzene group having a carbon number of 1 to 6 or a sulfanyl group or a cyano group , an alkoxycarbonyl group having 2 to 6 carbon atoms or a phenoxycarbonyl group (which may be substituted by one or more alkyl groups having 1 to 6 carbon atoms or a halogen atom); R3, R4, R5, R6, R7, R8, and a ruler; 9 and Rl〇 are independent of each other, each represents _ a hydrogen atom 'dentate atom', an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group 'phenyl' benzyl group, a benzoquinone group having a carbon number of 2 to 12 alkyl alkene, carbon Alkoxycarbonyl group of 2 to 12 (when the number of carbon atoms of the alkyl group constituting the alkoxy group is 2 or more, the alkyl group may be substituted by one or more groups, and the alkyl chain may have one or more oxygen atoms in the middle. Or phenoxycarbonyl. 2. The photosensitive resin composition for a color filter according to the first aspect of the invention, wherein the epoxy compound having two glycidyl ether groups derived from bisphenols is represented by the following formula (π) Epoxy compound: · [Chemical Formula 2]

316123 (Revised Edition) 35 1351581 Month H曰Revision Replacement Page No. 93123169 Patent Application 100 August 26 Revision Correction Page [In general formula (II), Rll and r12 are independent of each other, each having a carbon number of 1 to 5 Alkyl or halogen atom; X represents _c〇_, _s〇2·, -C(CF3)2-, -Si(CH3)2-, -CH2-, -C(Ch3)2_,·〇·,9 9 seedlings or absent; η is an integer from 0 to 1〇]. The photosensitive resin composition for a color light-passing sheet according to the first aspect of the invention, wherein the component (c) photopolymerization initiator is a compound represented by the following formula (πι): [Chemical Formula 3]

(m) 4. The photosensitive resin composition for a color filter according to the second aspect of the invention, wherein the component (c) photopolymerization initiator is a compound represented by the following formula (ΙΠ):

(m) The coating film is obtained by curing the photosensitive resin composition of the coloring calender sheet according to any one of claims 1 to 4. A color filter' is characterized in that it is provided by a transparent substrate coated with 6.36 316123 (revision) 1351581 (Room Μ曰 Amendment Replacement Page No. 93123169, Patent Application, August 26, pp. The photosensitive resin composition for a color filter according to any one of the first to fourth aspects of the invention, which is subjected to pre-baking, exposed to an ultraviolet exposure apparatus, developed with an alkaline aqueous solution, and post-baked. Baked and made into a vegetarian meal. 37 316123 (Revised Edition)