TW201635024A - 著色感光性樹脂組合物 - Google Patents
著色感光性樹脂組合物 Download PDFInfo
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- TW201635024A TW201635024A TW105102561A TW105102561A TW201635024A TW 201635024 A TW201635024 A TW 201635024A TW 105102561 A TW105102561 A TW 105102561A TW 105102561 A TW105102561 A TW 105102561A TW 201635024 A TW201635024 A TW 201635024A
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- photosensitive resin
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Landscapes
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Abstract
本發明提供一種著色感光性樹脂組合物,其係未曝光部於顯影液中之溶解性良好,可製作明確之圖案形狀,可提供雖為薄膜但具有較高亮度之高精細彩色濾光片。
本發明之著色感光性樹脂組合物之特徵在於:其包含著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D),且包含C.I.顏料綠58、C.I.顏料黃185及C.I.顏料黃138作為上述著色劑(A)。
Description
本發明係關於一種綠色之著色感光性樹脂組合物,尤其是關於一種含有C.I.顏料綠58、C.I.顏料黃185及C.I.顏料黃138作為著色劑(A)之著色感光性樹脂組合物。
近年來,為了擴大顯示器可顯示之色彩再現區域而正在進行開發,作為其一環,亦要求彩色濾光片之顏色更濃。為了滿足該要求,可列舉提高彩色濾光片中之色料濃度之方法,但若色料濃度上升,則圖案形狀劣化等,作為著色感光性樹脂組合物之性能劣化,故而欠佳。又,為了具有目標顏色特性,必須以厚膜之方式製作彩色濾光片,但於應用於液晶顯示裝置之情形時,產生與鄰接像素之光之混色,因此厚膜化亦欠佳。
於專利文獻1中,為了設計濃色之綠色彩色濾光片而記載有如下綠色感光性樹脂組合物,其包含:含有C.I.顏料綠58、C.I.顏料藍15:3及C.I.顏料黃150等之著色劑,樹脂,聚合性單體,光聚合起始劑及溶劑。
[專利文獻1]日本專利特開2012-247539號公報
本發明之課題在於提供一種著色感光性樹脂組合物,其係未曝光部於顯影液中之溶解性良好,可製作明確之圖案形狀,可提供雖為薄膜但具有較高亮度之高精細彩色濾光片。
本發明者等人反覆銳意研究,結果發現可獲得可解決上述課題之著色感光性樹脂組合物,從而完成了本發明。
即,本案係揭示以下之發明。
[1]一種著色感光性樹脂組合物,其特徵在於:包含著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D),且包含C.I.顏料綠58、C.I.顏料黃185及C.I.顏料黃138作為上述著色劑(A)。
[2]如[1]記載之著色感光性樹脂組合物,其中C.I.顏料黃185具有粒徑100nm以上之粒子為5質量%以下之粒度分佈。
[3]如[1]或[2]記載之著色感光性樹脂組合物,其中於著色感光性樹脂組合物之固形物成分100質量%中,著色劑(A)之合計量為20~50質量%。
[4]如[1]至[3]中任一項記載之著色感光性樹脂組合物,其進而包含硫醇化合物(T)。
[5]如[1]至[4]中任一項記載之著色感光性樹脂組合物,其中上述聚合起始劑(D)為選自由O-醯基肟化合物、苯烷基酮化合物、聯咪唑化合物、三化合物、及醯基氧化膦化合物所組成之群中之2種以上。
[6]如[1]至[5]中任一項記載之著色感光性樹脂組合物,其中上述樹脂(B)為包含源自具有碳數2~4之環狀醚結構與乙烯性不飽和鍵之單體(b)之結構單元的共聚物。
[7]一種塗膜,其係由如[1]至[6]中任一項記載之著色感光性樹脂
組合物所形成。
[8]一種彩色濾光片,其係由如[1]至[6]中任一項記載之著色感光性樹脂組合物所形成。
[9]一種顯示裝置,其包含如[8]記載之彩色濾光片。
根據本發明,可取得一種著色感光性樹脂組合物,其係未曝光部於顯影液中之溶解性良好,可製作明確之圖案形狀,可提供雖為薄膜但具有較高亮度之高精細彩色濾光片。
本發明之著色感光性樹脂組合物之特徵在於:包含著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D),且包含綠色顏料之C.I.顏料綠58、與黃色顏料之C.I.顏料黃185及C.I.顏料黃138作為上述著色劑(A)。
又,本發明之著色感光性樹脂組合物較佳為進而包含溶劑(E)。
又,本發明之著色感光性樹脂組合物較佳為進而包含硫醇化合物(T)。
又,本發明之著色感光性樹脂組合物較佳為進而包含調平劑(F)。
再者,關於本說明書中作為各成分而例示之化合物,只要無特別說明,則可單獨使用或組合使用複數種。
本發明之著色感光性樹脂組合物包含作為綠色顏料之C.I.顏料綠58、作為黃色顏料之C.I.顏料黃185及C.I.顏料黃138。
於著色感光性樹脂組合物中,C.I.顏料黃185較佳為具有粒徑100
nm以上之粒子為5質量%以下之粒度分佈。若粒徑100nm以上之粒子之含有率為上述範圍內,則可獲得相位差之值較低之良好塗膜。粒徑100nm以上之粒子更佳為4質量%以下,進而較佳為3.5質量%以下,尤佳為3質量%以下,最佳為2.5質量%以下。
上述顏料之粒徑可藉由對顏料施加機械強度而變小。例如,可藉由於有機溶劑中攪拌顏料而對顏料施加機械強度。若使用珠磨機攪拌顏料,則可簡單地調整該粒徑。為了製備顯示出上述粒度分佈之顏料所必需之攪拌時間可藉由進行下述粒度分佈之測定而決定。較佳之攪拌時間係根據顏料之量或種類等而不同,通常可藉由延長攪拌時間而使粒徑變得更小。除此以外,可藉由提高攪拌速度而高效率地對顏料施加機械強度。
再者,C.I.顏料黃185之粒徑及粒度分佈例如可利用下述所示之方法求出。
1)將丙二醇單甲醚乙酸酯、丙烯酸系顏料分散劑及C.I.顏料黃185混合,利用珠磨機充分進行攪拌,藉此使該C.I.顏料黃185分散。混合分散液中之C.I.顏料黃185之濃度係設為5質量%,丙烯酸系顏料分散劑之濃度係設為3.5質量%。
2)利用丙二醇單甲醚乙酸酯將所獲得之混合分散液稀釋至50倍後,藉由動態光散射測定裝置(Zetasizer Nano ZS;Malvern製造)於25℃下進行測定,根據散射強度算出顏料之粒徑及粒度分佈。標準物質係使用聚苯乙烯乳液。
關於C.I.顏料綠58與C.I.顏料黃185之含有比率(C.I.顏料黃185/C.I.顏料綠58),以質量比計,較佳為1%以上,更佳為3%以上,進而較佳為5%以上,且較佳為30%以下,更佳為25%以下,進而較佳為20%以下。
關於C.I.顏料綠58與C.I.顏料黃138之含有比率(C.I.顏料黃138/C.I.
顏料綠58),以質量比計,較佳為1%以上,更佳為1.5%以上,進而較佳為2%以上,且較佳為70%以下,更佳為65%以下,進而較佳為60%以下。
於著色劑(A)之合計100質量%中,C.I.顏料綠58之含量通常較佳為40質量%以上,更佳為50質量%以上,進而較佳為60質量%以上,且較佳為98質量%以下,更佳為90質量%以下,進而較佳為85質量%以下。
於著色劑(A)之合計100質量%中,C.I.顏料黃185之含量通常較佳為1質量%以上,更佳為2質量%以上,進而較佳為3質量%以上,且較佳為20質量%以下,更佳為18質量%以下,進而較佳為16質量%以下。
於著色劑(A)之合計100質量%中,C.I.顏料黃138之含量通常較佳為0.3質量%以上,更佳為1質量%以上,進而較佳為1.5質量%以上,且較佳為40質量%以下,更佳為38質量%以下,進而較佳為35質量%以下。
再者,著色劑(A)之合計係將上限設為100質量%。
於組合物中之固形物成分100質量%中,C.I.顏料綠58之含量通常較佳為10質量%以上,更佳為20質量%以上,進而較佳為24質量%以上,且較佳為45質量%以下,更佳為40質量%以下,進而較佳為35質量%以下。
於組合物中之固形物成分100質量%中,C.I.顏料黃185之含量通常為0.5質量%以上,更佳為1質量%以上,進而較佳為2質量%以上,且較佳為25質量%以下,更佳為20質量%以下,進而較佳為10質量%以下。
於組合物中之固形物成分100質量%中,C.I.顏料黃138之含量通常為0.1質量%以上,更佳為0.3質量%以上,進而較佳為0.5質量%以
上,且較佳為30質量%以下,更佳為25質量%以下,進而較佳為20質量%以下。
於將C.I.顏料黃185及C.I.顏料黃138之合計量設為100質量%時,C.I.顏料黃185較佳為10質量%以上且90質量%以下。於C.I.顏料黃185之含量處於該範圍內時,顯影類型良好。
本說明書中所謂「固形物成分之總量」,係指自本發明之著色感光性樹脂組合物中去掉溶劑(E)所得之成分之合計量。固形物成分之總量及各成分相對於其之含量例如可利用液相層析法或氣相層析法等公知之分析手段進行測定。
C.I.顏料綠58、C.I.顏料黃185及C.I.顏料黃138均可視需要而實施以下處理:松香處理、使用導入有酸性基或鹼性基之顏料衍生物等之表面處理、利用高分子化合物等之對顏料表面之接枝處理、利用硫酸微粒化法等之微粒化處理、或用以去除雜質之利用有機溶劑或水等之洗淨處理、利用離子交換法等之離子性雜質之去除處理等。
本發明中,上述顏料較佳為以顏料於溶劑中均勻分散之顏料分散液之狀態使用。顏料分散液可藉由將顏料於溶劑中進行混合而獲得。顏料分散液中,視需要亦可混合顏料分散劑。於混合中,C.I.顏料綠58、C.I.顏料黃185及C.I.顏料黃138可分別單獨混合,亦可將該等組合而混合。
作為上述顏料分散劑,可為陽離子系、陰離子系、非離子系及兩性中之任一種分散劑,可列舉聚酯系、聚胺系、丙烯酸系等之顏料分散劑等。
該等顏料分散劑可單獨使用,亦可組合使用2種以上。作為顏料分散劑,以商品名可列舉:KP(信越化學工業(股)製造)、Flowlen(共榮社化學(股)製造)、Solsperse(Zeneca(股)製造)、EFKA(BASF公司製造)、Ajisper(Ajinomoto Fine-Techno(股)製造)、Disperbyk(BYK-
Chemie公司製造)等。
於使用顏料分散劑之情形時,相對於顏料100質量份,其使用量較佳為100質量份以下,更佳為5質量份以上且50質量份以下。若顏料分散劑之使用量處於上述範圍內,則存在可獲得顏料於溶劑中均勻地分散之顏料分散液之傾向。
作為上述溶劑,並無特別限定,可列舉與本發明之著色感光性樹脂組合物中之溶劑(E)相同之溶劑(詳細內容將於後述)。其中,較佳為丙二醇單甲醚乙酸酯、二丙二醇甲醚乙酸酯、乳酸乙酯、丙二醇單甲醚、3-乙氧基丙酸乙酯、乙二醇單甲醚、二乙二醇單甲醚、二乙二醇單乙醚、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、4-羥基-4-甲基-2-戊酮、N,N-二甲基甲醯胺等,更佳為丙二醇單甲醚乙酸酯、丙二醇單甲醚、二丙二醇甲醚乙酸酯、乳酸乙酯、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、3-乙氧基丙酸乙酯等。
溶劑之使用量並無特別限定,溶劑可以如下方式使用:可將顏料分散液中之固形物成分濃度調整為3~20質量%、更佳為5~18質量%。
顏料分散液之製備方法並無特別限定,(i)可藉由將C.I.顏料綠58、C.I.顏料黃185及C.I.顏料黃138各自於溶劑中混合,而製成C.I.顏料綠58之顏料分散液、C.I.顏料黃185之顏料分散液、C.I.顏料黃138之顏料分散液;(ii)亦可藉由將C.I.顏料綠58、C.I.顏料黃185及C.I.顏料黃138全部於溶劑中混合,而製成包含C.I.顏料綠58、C.I.顏料黃185及C.I.顏料黃138三種之顏料分散液。
再者,作為著色劑(A),除上述C.I.顏料綠58、C.I.顏料黃185及C.I.顏料黃138以外,亦可使用公知之顏料及染料。本發明中,於著色劑(A)100質量%中,C.I.顏料綠58、C.I.顏料黃185及C.I.顏料黃138之使用量之合計較佳為50質量%以上,更佳為60質量%以上,進而較佳
為70質量%以上,尤佳為80質量%以上,進而更佳為90質量%以上,最佳為100質量%。
於著色感光性樹脂組合物之固形物成分100質量%中,著色劑(A)之合計量較佳為20~50質量%,更佳為25~47質量%,進而較佳為35~45質量%。
作為樹脂(B),並無特別限定,較佳為鹼溶性樹脂。作為樹脂(B),可列舉以下之樹脂[K1]~[K6]等。
樹脂[K1]選自由不飽和羧酸及不飽和羧酸酐所組成之群中之至少1種(a)(以下有稱為「(a)」之情形)、與具有碳數2~4之環狀醚結構與乙烯性不飽和鍵之單體(b)(以下有稱為「(b)」之情形)之共聚物。
樹脂[K2](a)與(b)與可和(a)共聚合之單體(c)(其中,與(a)及(b)不同)(以下有稱為「(c)」之情形)之共聚物。
樹脂[K3](a)與(c)之共聚物。
樹脂[K4]使(b)與(a)和(c)之共聚物反應而獲得之樹脂。
樹脂[K5]使(a)與(b)和(c)之共聚物反應而獲得之樹脂。
樹脂[K6]使(a)與(b)和(c)之共聚物反應,進而使羧酸酐反應而獲得之樹脂。
作為(a),具體而言,例如可列舉:丙烯酸、甲基丙烯酸、丁烯酸、鄰乙烯基苯甲酸、間乙烯基苯甲酸、對乙烯基苯甲酸等不飽和單羧酸類;馬來酸、富馬酸、檸康酸、中康酸、伊康酸、3-乙烯基鄰苯二甲酸、4-乙烯基鄰苯二甲酸、3,4,5,6-四氫鄰苯二甲酸、1,2,3,6-四氫鄰苯二甲酸、二甲基四氫鄰苯二甲酸、1,4-環己烯二羧酸等不飽和二羧酸類;甲基-5-降烯-2,3-二羧酸、5-羧基二環[2.2.1]庚-2-烯、5,6-二羧
基二環[2.2.1]庚-2-烯、5-羧基-5-甲基二環[2.2.1]庚-2-烯、5-羧基-5-乙基二環[2.2.1]庚-2-烯、5-羧基-6-甲基二環[2.2.1]庚-2-烯、5-羧基-6-乙基二環[2.2.1]庚-2-烯等含有羧基之二環不飽和化合物類;馬來酸酐、檸康酸酐、伊康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐、5,6-二羧基二環[2.2.1]庚-2-烯酐(雙環庚烯二甲酸酐)等不飽和二羧酸酐類;琥珀酸單[2-(甲基)丙烯醯氧基乙基]酯、鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]酯等2元以上之多元羧酸之不飽和單[(甲基)丙烯醯氧基烷基]酯類;如α-(羥甲基)丙烯酸般之於同一分子中含有羥基及羧基之丙烯酸等。
該等中,就共聚合反應性之方面或於鹼性水溶液中之溶解性之方面而言,較佳為丙烯酸、甲基丙烯酸、馬來酸酐等。
(b)例如係指具有碳數2~4之環狀醚結構(例如選自由氧雜環丙烷環、氧雜環丁烷環及四氫呋喃環(氧雜環戊烷環)所組成之群中之至少1種)與乙烯性不飽和鍵之聚合性化合物。(b)較佳為具有碳數2~4之環狀醚與(甲基)丙烯醯氧基之單體。
再者,於本說明書中,所謂「(甲基)丙烯酸」,表示選自由丙烯酸及甲基丙烯酸所組成之群中之至少1種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等表述亦具有相同之含義。
作為(b),例如可列舉:具有氧雜環丙基與乙烯性不飽和鍵之單體(b1)(以下有稱為「(b1)」之情形)、具有氧雜環丁基與乙烯性不飽和鍵之單體(b2)(以下有稱為「(b2)」之情形)、具有四氫呋喃基與乙烯性不飽和鍵之單體(b3)(以下有稱為「(b3)」之情形)等。
(b1)例如可列舉:具有將不飽和脂肪族烴加以環氧化而成之結構
之單體(b1-1)(以下有稱為「(b1-1)」之情形)、具有將不飽和脂環式烴加以環氧化而成之結構之單體(b1-2)(以下有稱為「(b1-2)」之情形)。
作為(b1-1),可列舉:(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸β-甲基縮水甘油酯、(甲基)丙烯酸β-乙基縮水甘油酯、縮水甘油基乙烯醚、鄰乙烯基苄基縮水甘油醚、間乙烯基苄基縮水甘油醚、對乙烯基苄基縮水甘油醚、α-甲基-鄰乙烯基苄基縮水甘油醚、α-甲基-間乙烯基苄基縮水甘油醚、α-甲基-對乙烯基苄基縮水甘油醚、2,3-雙(縮水甘油氧基甲基)苯乙烯、2,4-雙(縮水甘油氧基甲基)苯乙烯、2,5-雙(縮水甘油氧基甲基)苯乙烯、2,6-雙(縮水甘油氧基甲基)苯乙烯、2,3,4-三(縮水甘油氧基甲基)苯乙烯、2,3,5-三(縮水甘油氧基甲基)苯乙烯、2,3,6-三(縮水甘油氧基甲基)苯乙烯、3,4,5-三(縮水甘油氧基甲基)苯乙烯、2,4,6-三(縮水甘油氧基甲基)苯乙烯等。
作為(b1-2),可列舉:一氧化環己烯乙烯、1,2-環氧-4-乙烯基環己烷(例如Celloxide 2000;Daicel化學工業(股)製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(例如Cyclomer A400;Daicel化學工業(股)製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(例如CyclomerM100;Daicel化學工業(股)製造)、式(I)所表示之化合物及式(II)所表示之化合物等。
[式(I)及式(II)中,Ra及Rb彼此獨立地表示氫原子、或碳數1~4之烷基,該烷基所含之氫原子亦可經羥基取代。
X1及X2彼此獨立地表示單鍵、*-Rc-、*-Rc-O-、*-Rc-S-、*-Rc-NH-。
Rc表示碳數1~6之烷二基。
*表示與O之結合鍵]。
作為碳數1~4之烷基,可列舉:甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基等。
作為氫原子經羥基取代之烷基,可列舉:羥基甲基、1-羥基乙基、2-羥基乙基、1-羥基丙基、2-羥基丙基、3-羥基丙基、1-羥基-1-甲基乙基、2-羥基-1-甲基乙基、1-羥基丁基、2-羥基丁基、3-羥基丁基、4-羥基丁基等。
作為Ra及Rb,較佳可列舉氫原子、甲基、羥基甲基、1-羥基乙基、2-羥基乙基,更佳可列舉氫原子、甲基。
作為烷二基,可列舉:亞甲基、伸乙基、丙烷-1,2-二基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基等。
作為X1及X2,較佳可列舉單鍵、亞甲基、伸乙基、*-CH2-O-(*表示與O之結合鍵)基、*-CH2CH2-O-基,更佳可列舉單鍵、*-CH2CH2-O-基。
作為式(I)所表示之化合物,可列舉式(I-1)~式(I-15)所表示之化合物等。較佳可列舉式(I-1)、式(I-3)、式(I-5)、式(I-7)、式(I-9)、式(I-11)~式(I-15)。更佳可列舉式(I-1)、式(I-7)、式(I-9)、式(I-15)。
[化2]
作為式(II)所表示之化合物,可列舉式(II-1)~式(II-15)所表示之化合物等。較佳可列舉式(II-1)、式(II-3)、式(II-5)、式(II-7)、式(II-9)、式(II-11)~式(II-15)。更佳可列舉式(II-1)、式(II-7)、式(II-9)、式(II-15)。
[化4]
式(I)所表示之化合物及式(II)所表示之化合物可分別單獨使用。又,可將該等以任意之比率混合。於混合之情形時,其混合比率以莫耳比計,較佳為式(I):式(II)為5:95~95:5,更佳為10:90~90:10,進而較佳為20:80~80:20。
作為具有氧雜環丁基與乙烯性不飽和鍵之單體(b2),更佳為具有氧雜環丁基與(甲基)丙烯醯氧基之單體。作為(b2),可列舉:3-甲基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-甲基-3-丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-丙烯醯
氧基甲基氧雜環丁烷、3-甲基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-甲基-3-丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基乙基氧雜環丁烷、3-乙基-3-丙烯醯氧基乙基氧雜環丁烷等。
作為具有四氫呋喃基與乙烯性不飽和鍵之單體(b3),更佳為具有四氫呋喃基與(甲基)丙烯醯氧基之單體。作為(b3),具體而言可列舉丙烯酸四氫糠酯(例如Viscoat V#150,大阪有機化學工業(股)製造)、甲基丙烯酸四氫糠酯等。
作為(c),例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲基環己酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烷-8-基酯(於該技術領域中,以慣用名而稱為「(甲基)丙烯酸雙環戊酯」。又,有稱為「(甲基)丙烯酸三環癸酯」之情形)、(甲基)丙烯酸三環[5.2.1.02,6]癸烯-8-基酯(於該技術領域中,以慣用名而稱為「(甲基)丙烯酸雙環戊烯酯」)、(甲基)丙烯酸雙環戊氧基乙酯、(甲基)丙烯酸異基酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸酯類;(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯等含羥基之(甲基)丙烯酸酯類;馬來酸二乙酯、富馬酸二乙酯、伊康酸二乙酯等二羧酸二酯;二環[2.2.1]庚-2-烯、5-甲基二環[2.2.1]庚-2-烯、5-乙基二環[2.2.1]庚-2-烯、5-羥基二環[2.2.1]庚-2-烯、5-羥基甲基二環[2.2.1]庚-2-烯、5-(2'-羥基乙基)二環[2.2.1]庚-2-烯、5-甲氧基二環[2.2.1]庚-2-烯、5-乙氧基二環[2.2.1]庚-2-烯、5,6-二羥基二環[2.2.1]庚-2-烯、5,6-
二(羥基甲基)二環[2.2.1]庚-2-烯、5,6-二(2'-羥基乙基)二環[2.2.1]庚-2-烯、5,6-二甲氧基二環[2.2.1]庚-2-烯、5,6-二乙氧基二環[2.2.1]庚-2-烯、5-羥基-5-甲基二環[2.2.1]庚-2-烯、5-羥基-5-乙基二環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基二環[2.2.1]庚-2-烯、5-第三丁氧基羰基二環[2.2.1]庚-2-烯、5-環己氧基羰基二環[2.2.1]庚-2-烯、5-苯氧基羰基二環[2.2.1]庚-2-烯、5,6-雙(第三丁氧基羰基)二環[2.2.1]庚-2-烯、5,6-雙(環己氧基羰基)二環[2.2.1]庚-2-烯等二環不飽和化合物類;N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、N-丁二醯亞胺基-3-馬來醯亞胺苯甲酸酯、N-丁二醯亞胺基-4-馬來醯亞胺丁酸酯、N-丁二醯亞胺基-6-馬來醯亞胺己酸酯、N-丁二醯亞胺基-3-馬來醯亞胺丙酸酯、N-(9-吖啶基)馬來醯亞胺等二羰基醯亞胺衍生物類;苯乙烯、α-甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、乙烯基甲苯、對甲氧基苯乙烯、丙烯腈、甲基丙烯腈、氯乙烯、偏二氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯、1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等。
該等中,就共聚合反應性及耐熱性之方面而言,較佳為(甲基)丙烯酸苄酯、(甲基)丙烯酸三環癸酯、苯乙烯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、二環[2.2.1]庚-2-烯等。又,就圖案形成時之顯影性優異之方面而言,更佳為(甲基)丙烯酸苄酯、(甲基)丙烯酸三環癸酯。
樹脂[K1]中,關於源自(a)及(b)之結構單元之比率,較佳為於構成樹脂[K1]之所有結構單元中處於以下範圍內。
源自(a)之結構單元;2~50莫耳%(更佳為10~45莫耳%)
源自(b)之結構單元;50~98莫耳%(更佳為55~90莫耳%)
若樹脂[K1]之結構單元之比率處於上述範圍內,則存在保存穩定
性、顯影性、所獲得之圖案之耐溶劑性優異之傾向。
樹脂[K1]例如可參考文獻「高分子合成之實驗法」(大津隆行著發行單位 化學同人(股)第1版第1印 1972年3月1日發行)所記載之方法及該文獻中記載之引用文獻而製造。
具體而言可列舉如下方法:將(a)及(b)之特定量、聚合起始劑及溶劑等添加於反應容器中,於脫氧環境下進行攪拌、加熱、保溫。再者,此處所使用之聚合起始劑及溶劑等並無特別限定,可使用該領域中通常所使用之任意者。例如作為聚合起始劑,可列舉偶氮化合物(2,2'-偶氮二異丁腈、2,2'-偶氮二(2,4-二甲基戊腈)等)或有機過氧化物(過氧化苯甲醯等),作為溶劑,只要將各單體溶解即可,可使用下文中作為著色感光性樹脂組合物之溶劑而描述之溶劑(E)等。
再者,所獲得之共聚物可直接使用反應後之溶液,亦可使用經濃縮或稀釋之溶液,亦可使用藉由再沈澱等方法以固體(粉體)之形式取出者。尤其藉由於該聚合時使用下述溶劑(E)作為溶劑,可直接使用反應後之溶液,從而可使製造步驟簡化。
樹脂[K2]中,關於源自(a)、(b)及(c)之結構單元之比率,較佳為於構成樹脂[K2]之所有結構單元中處於以下範圍內。
源自(a)之結構單元;4~45莫耳%(更佳為10~30莫耳%)
源自(b)之結構單元;2~95莫耳%(更佳為5~80莫耳%)
源自(c)之結構單元;1~65莫耳%(更佳為5~60莫耳%)
若樹脂[K2]之結構單元之比率處於上述範圍內,則存在保存穩定性、顯影性、所獲得之圖案之耐溶劑性、耐熱性及機械強度優異之傾向。
樹脂[K2]例如可與作為樹脂[K1]之製造方法所記載之方法同樣地製造。
具體而言可列舉如下方法:將(a)、(b)及(c)之特定量、聚合起始
劑及溶劑添加於反應容器中,於脫氧環境下進行攪拌、加熱、保溫。所獲得之共聚物可直接使用反應後之溶液,亦可使用經濃縮或稀釋之溶液,亦可使用藉由再沈澱等方法以固體(粉體)之形式取出者。
樹脂[K3]中,關於源自(a)、(c)之結構單元之比率,較佳為於構成樹脂[K3]之所有結構單元中處於以下範圍內。
(a)2~55莫耳%,更佳為10~50莫耳%
(c)45~98莫耳%,更佳為50~90莫耳%
樹脂[K3]例如以與作為樹脂[K1]之製造方法所記載之方法同樣地製造。
樹脂[K4]可藉由如下方式製造:獲得(a)與(c)之共聚物,使(b)所具有之碳數2~4之環狀醚加成於(a)所具有之羧酸及/或羧酸酐上。
首先,與作為樹脂[K1]之製造方法所記載之方法同樣地製造(a)與(c)之共聚物。於該情形時,關於源自(a)及(c)之結構單元之比率,較佳為於構成(a)與(c)之共聚物之所有結構單元中處於以下範圍內。
(a)5~50莫耳%,更佳為10~45莫耳%
(c)50~95莫耳%,更佳為55~90莫耳%
繼而,使(b)所具有之碳數2~4之環狀醚與上述共聚物中之源自(a)之羧酸及/或羧酸酐之一部分反應。
製造(a)與(c)之共聚物後,將燒瓶內環境由氮氣置換為空氣,將(b)、羧酸或羧酸酐與環狀醚之反應觸媒(例如三(二甲基胺基甲基)苯酚等)及聚合抑制劑(例如對苯二酚等)等裝入燒瓶內,例如於60~130℃下反應1~10小時,藉此可獲得樹脂[K4]。
相對於(a)100莫耳,(b)之使用量較佳為5~80莫耳,更佳為10~75莫耳。藉由設為該範圍,而存在保存穩定性、顯影性、耐溶劑性、耐熱性、機械強度及感度之平衡變良好之傾向。就環狀醚之反應性較高、不易殘留未反應之(b)之方面而言,作為樹脂[K4]中所使用之
(b),較佳為(b1),進而較佳為(b1-1)。
相對於(a)、(b)及(c)之合計量,上述反應觸媒之使用量較佳為0.001~5質量%。相對於(a)、(b)及(c)之合計量,上述聚合抑制劑之使用量較佳為0.001~5質量%。
添加方法、反應溫度及時間等反應條件可考慮製造設備或聚合之發熱量等而適當調整。再者,與聚合條件同樣地,可考慮製造設備或聚合之發熱量等而適當調整添加方法或反應溫度。
關於樹脂[K5],作為第一階段,與上述樹脂[K1]之製造方法同樣地獲得(b)與(c)之共聚物。與上述同樣地,所獲得之共聚物可直接使用反應後之溶液,亦可使用經濃縮或稀釋之溶液,亦可使用藉由再沈澱等方法以固體(粉體)之形式取出者。
關於源自(b)及(c)之結構單元之比率,較佳為相對於構成上述之共聚物之所有結構單元之合計莫耳數而處於以下範圍內。
源自(b)之結構單元;5~95莫耳%(更佳為10~90莫耳%)
源自(c)之結構單元;5~95莫耳%(更佳為10~90莫耳%)
進而,可於與樹脂[K4]之製造方法相同之條件下,使(a)所具有之羧酸或羧酸酐與(b)和(c)之共聚物所具有之源自(b)之環狀醚反應,藉此獲得樹脂[K5]。
相對於(b)100莫耳,與上述共聚物反應之(a)之使用量較佳為5~80莫耳。就環狀醚之反應性較高、不易殘留未反應之(b)之方面而言,作為樹脂[K5]中所使用之(b),較佳為(b1),進而較佳為(b1-1)。
樹脂[K6]係進而使羧酸酐與樹脂[K5]反應而獲得之樹脂。使羧酸酐與藉由環狀醚與羧酸或羧酸酐之反應而產生之羥基反應。
作為羧酸酐,可列舉:馬來酸酐、檸康酸酐、伊康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐、5,6-二羧
基二環[2.2.1]庚-2-烯酐(雙環庚烯二甲酸酐)等。
作為樹脂(B),具體而言可列舉:(甲基)丙烯酸3,4-環氧環己基甲酯/(甲基)丙烯酸共聚物、丙烯酸3,4-環氧三環[5.2.1.02,6]癸酯/(甲基)丙烯酸共聚物等樹脂[K1];(甲基)丙烯酸縮水甘油酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸縮水甘油酯/苯乙烯/(甲基)丙烯酸共聚物、丙烯酸3,4-環氧三環[5.2.1.02,6]癸酯/(甲基)丙烯酸/N-環己基馬來醯亞胺共聚物、3-甲基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷/(甲基)丙烯酸/苯乙烯共聚物等樹脂[K2];(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物、苯乙烯/(甲基)丙烯酸共聚物、(甲基)丙烯酸苄酯/(甲基)丙烯酸三環癸酯/(甲基)丙烯酸共聚物等樹脂[K3];於(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物上加成(甲基)丙烯酸縮水甘油酯而成之樹脂、於(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸共聚物上加成(甲基)丙烯酸縮水甘油酯而成之樹脂、於(甲基)丙烯酸三環癸酯/(甲基)丙烯酸苄酯/(甲基)丙烯酸共聚物上加成(甲基)丙烯酸縮水甘油酯而成之樹脂等樹脂[K4];使(甲基)丙烯酸與(甲基)丙烯酸三環癸酯/(甲基)丙烯酸縮水甘油酯之共聚物反應而成之樹脂、使(甲基)丙烯酸與(甲基)丙烯酸三環癸酯/苯乙烯/(甲基)丙烯酸縮水甘油酯之共聚物反應而成之樹脂等樹脂[K5];進而使四氫鄰苯二甲酸酐與使(甲基)丙烯酸與(甲基)丙烯酸三環癸酯/(甲基)丙烯酸縮水甘油酯之共聚物反應而成之樹脂進行反應而成的樹脂等樹脂[K6]等,其中較佳為樹脂[K1]。
該等樹脂可單獨使用,亦可併用2種以上。
樹脂(B)之聚苯乙烯換算之重量平均分子量較佳為3,000~100,000,更佳為5,000~50,000,進而較佳為5,000~30,000。若分子量處於上述範圍內,則存在未曝光部於顯影液中之溶解性較高、所獲得之圖案之殘膜率或硬度亦較高之傾向。
樹脂(B)之分子量分佈[重量平均分子量(Mw)/數量平均分子量
(Mn)]較佳為1.1~6,更佳為1.2~4。
樹脂(B)之溶液酸值較佳為5~180mg-KOH/g,更佳為10~100mg-KOH/g,進而較佳為12~50mg-KOH/g。此處,溶液酸值係以將樹脂1g中和所必需之氫氧化鉀之量(mg)的形式所測得之值,例如可藉由使用氫氧化鉀水溶液進行滴定而求出。
於著色感光性樹脂組合物之固形物成分100質量%中,樹脂(B)之含量較佳為7~65質量%,更佳為13~60質量%,進而較佳為17~55質量%。若樹脂(B)之含量處於上述範圍內,則存在未曝光部於顯影液中之溶解性較高之傾向。
聚合性化合物(C)只要為可藉由活性自由基等進行聚合之化合物,則無特別限定,上述活性自由基係藉由照射光而由聚合起始劑(D)產生,聚合性化合物(C)例如可列舉具有聚合性之乙烯性不飽和鍵之化合物等。聚合性化合物(C)之重量平均分子量例如較佳為3,000以下。
其中,作為聚合性化合物(C),較佳為具有3個以上之乙烯性不飽和鍵之光聚合性化合物,例如可列舉:三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三季戊四醇八(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯、四季戊四醇十(甲基)丙烯酸酯、四季戊四醇九(甲基)丙烯酸酯、異氰尿酸三(2-(甲基)丙烯醯氧基乙基)酯、乙二醇改性季戊四醇四(甲基)丙烯酸酯、乙二醇改性二季戊四醇六(甲基)丙烯酸酯、丙二醇改性季戊四醇四(甲基)丙烯酸酯、丙二醇改性二季戊四醇六(甲基)丙烯酸酯、己內酯改性季戊四醇四(甲基)丙烯酸酯、己內酯改性二季戊四醇六(甲基)丙烯酸酯等。其中,可列舉二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲
基)丙烯酸酯等。
相對於著色感光性樹脂組合物中之樹脂(B)100質量份,聚合性化合物(C)之含量較佳為20~150質量份,更佳為25~120質量份。
聚合起始劑(D)只要為藉由光或熱之作用而產生活性自由基、酸等從而可引發聚合之化合物,則無特別限定,可使用公知之聚合起始劑。
作為聚合起始劑(D),可列舉:O-醯基肟化合物、苯烷基酮化合物、聯咪唑化合物、三化合物、及醯基氧化膦化合物。
上述O-醯基肟化合物係具有式(d1)所表示之結構之化合物。以下,*表示結合鍵。
作為上述O-醯基肟化合物,例如可列舉:N-苯甲醯氧基-1-(4-苯基巰基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基巰基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基巰基苯基)-3-環戊基丙烷-1-酮-2-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-{2-甲基-4-(3,3-二甲基-2,4-二氧雜環戊基甲氧基)苯甲醯基}-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-亞胺、N-苯甲醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-酮-2-亞胺等。亦可使用Irgacure(註冊商標)OXE01、OXE02(以上為BASF公司製造)、N-1919(ADEKA公司製造)等市售
品。其中,O-醯基肟化合物較佳為選自由N-苯甲醯氧基-1-(4-苯基巰基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯基巰基苯基)辛烷-1-酮-2-亞胺及N-苯甲醯氧基-1-(4-苯基巰基苯基)-3-環戊基丙烷-1-酮-2-亞胺所組成之群中之至少1種,更佳為N-苯甲醯氧基-1-(4-苯基巰基苯基)辛烷-1-酮-2-亞胺。若為該等O-醯基肟化合物,則存在可獲得高亮度之彩色濾光片之傾向。
上述苯烷基酮化合物係具有式(d2)所表示之部分結構或式(d3)所表示之部分結構之化合物。該等部分結構中,苯環亦可具有取代基。
作為具有式(d2)所表示之結構之化合物,可列舉:2-甲基-2-啉基-1-(4-甲基巰基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-啉基苯基)-2-苄基丁烷-1-酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-啉基)苯基]丁烷-1-酮等。亦可使用Irgacure369、907、379(以上為BASF公司製造)等市售品。
作為具有式(d3)所表示之結構之化合物,可列舉:2-羥基-2-甲基-1-苯基丙烷-1-酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)苯基]丙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-(4-異丙烯基苯基)丙烷-1-酮之低聚物、α,α-二乙氧基苯乙酮、苯偶醯二甲基縮酮等。
於感度之方面而言,作為苯烷基酮化合物,較佳為具有式(d2)所表示之結構之化合物。
作為上述聯咪唑化合物,可列舉式(d5)所表示之化合物等。
[式(d5)中,R13~R18表示可具有取代基之碳數6~10之芳基]。
作為碳數6~10之芳基,可列舉苯基、甲苯甲醯基、二甲苯基、乙基苯基及萘基等,較佳為苯基。
作為取代基,可列舉鹵素原子、碳數1~4之烷氧基等。作為鹵素原子,可列舉氟原子、氯原子、溴原子、碘原子等,較佳為氯原子。作為碳數1~4之烷氧基,可列舉甲氧基、乙氧基、丙氧基、丁氧基等,較佳為甲氧基。
作為聯咪唑化合物,可列舉:2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2,3-二氯苯基)-4,4',5,5'-四苯基聯咪唑(例如,參照日本專利特開平6-75372號公報、日本專利特開平6-75373號公報等)、2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(二烷氧基苯基)聯咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四(三烷氧基苯基)聯咪唑(例如,參照日本專利特公昭48-38403號公報、日本專利特開昭62-174204號公報等)、4,4',5,5'-位之苯基經碳烷氧基取代之咪唑化合物(例如,參照日本專利特開平7-10913號公報等)等。其中,較佳為下述式所表示之化合物及該等之混合物。
[化9]
作為上述三化合物,可列舉:2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三、2,4-雙(三氯甲基)-6-向日葵基-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(4-二乙基胺基-2-甲基苯基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三等。
作為上述醯基氧化膦化合物,可列舉2,4,6-三甲基苯甲醯基二苯基氧化膦等。
作為聚合起始劑(D),進而可列舉:安息香、安息香甲醚、安息香乙醚、安息香異丙醚、安息香異丁醚等安息香化合物;二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4'-甲基二苯硫醚、3,3',4,4'-四(第三丁基過氧化羰基)二苯甲酮、2,4,6-三甲基二苯甲酮等二苯甲酮化合物;9,10-菲醌、2-乙基蒽醌、樟腦醌等醌化合物;10-丁基-2-氯吖啶酮、苯偶醯、苯基乙醛酸甲酯、二茂鈦化合物等。該等較佳為與下述聚合起始助劑(D1)(尤其是胺類)組合使用。
本發明之著色感光性樹脂組合物更佳為包含選自由O-醯基肟化合物、苯烷基酮化合物及聯咪唑化合物所組成之群中之至少2種以上作為聚合起始劑(D),進而較佳為包含O-醯基肟化合物及聯咪唑化合物作為聚合起始劑(D)。
於包含O-醯基肟化合物及聯咪唑化合物作為聚合起始劑(D)之情形時,相對於聚合起始劑(D)之總量,O-醯基肟化合物與聯咪唑化合物之合計含量較佳為40質量%以上,更佳為50質量%以上,進而較佳為60質量%以上,尤佳為80質量%以上,最佳為100質量%。
於使用選自由聚合起始劑(D)與硫醇化合物(T)所組成之化合物群中之至少2種以上之情形時,第1主成分(含有比率最高之化合物)與第2主成分(含有比率與第1主成分相同,或含有比率第2高之化合物)之含量比以質量基準計,較佳為1:9~9:1,更佳為2:8~8:2,進而較佳為4:6~6:4。
相對於樹脂(B)(固形物成分量)及聚合性化合物(C)之合計量100質量份,聚合起始劑(D)之含量較佳為0.1~30質量份,更佳為1~20質量份,進而較佳為2~10質量份。若聚合起始劑(D)之含量處於上述範圍內,則存在高感度化而縮短曝光時間之傾向,因此彩色濾光片之生產性提高。
聚合起始助劑(D1)係用於促進藉由聚合起始劑而引發聚合之聚合性化合物的聚合之化合物、或增感劑。於包含聚合起始助劑(D1)之情形時,通常與聚合起始劑(D)組合使用。
作為聚合起始助劑(D1),可列舉:胺化合物、烷氧基蒽化合物、9-氧硫化合物及羧酸化合物等。
作為上述胺化合物,可列舉:三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸2-二甲基胺基乙酯、4-二甲基胺基苯甲酸2-乙基己酯、N,N-二甲基對甲苯胺、4,4'-雙(二甲基胺基)二苯甲酮(通稱米其勒酮)、4,4'-雙(二乙基胺基)二苯甲酮、4,4'-雙(乙基甲基胺基)二苯甲酮等,其中較佳為4,4'-雙(二乙基胺基)二苯甲酮。亦可使
用EAB-F(保土谷化學工業(股)製造)等市售品。
作為上述烷氧基蒽化合物,可列舉:9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二乙氧基蒽、9,10-二丁氧基蒽、2-乙基-9,10-二丁氧基蒽等。
作為上述9-氧硫化合物,可列舉:2-異丙基9-氧硫、4-異丙基9-氧硫、2,4-二乙基9-氧硫、2,4-二氯9-氧硫、1-氯-4-丙氧基9-氧硫等。
作為上述羧酸化合物,可列舉:苯基巰基乙酸、甲基苯基巰基乙酸、乙基苯基巰基乙酸、甲基乙基苯基巰基乙酸、二甲基苯基巰基乙酸、甲氧基苯基巰基乙酸、二甲氧基苯基巰基乙酸、氯苯基巰基乙酸、二氯苯基巰基乙酸、N-苯基甘胺酸、苯氧基乙酸、萘硫基乙酸、N-萘基甘胺酸、萘氧基乙酸等。
作為聚合起始助劑(D1),較佳為9-氧硫化合物。
於使用該等聚合起始助劑(D1)之情形時,相對於樹脂(B)及聚合性化合物(C)之合計量100質量份,其含量較佳為0.1~30質量份,更佳為1~20質量份。若聚合起始助劑(D1)之量處於該範圍內,則存在可進一步以高感度形成著色圖案、彩色濾光片之生產性提高之傾向。
硫醇化合物(T)係於分子內具有巰基(-SH)之化合物。
作為分子內具有1個巰基之化合物,例如可列舉:2-巰基唑、2-巰基噻唑、2-巰基苯并咪唑、2-巰基苯并噻唑、2-巰基苯并唑、2-巰基煙鹼酸、2-巰基吡啶、2-巰基吡啶-3-醇、2-巰基吡啶-N-氧化物、4-胺基-6-羥基-2-巰基嘧啶、4-胺基-6-羥基-2-巰基嘧啶、4-胺基-2-巰基嘧啶、6-胺基-5-亞硝基-2-硫尿嘧啶、4,5-二胺基-6-羥基-2-巰基嘧啶、4,6-二胺基-2-巰基嘧啶、2,4-二胺基-6-巰基嘧啶、4,6-二羥基-2-巰基嘧啶、4,6-二甲基-2-巰基嘧啶、4-羥基-2-巰基-6-甲基嘧
啶、4-羥基-2-巰基-6-丙基嘧啶、2-巰基-4-甲基嘧啶、2-巰基嘧啶、2-硫尿嘧啶、3,4,5,6-四氫嘧啶-2-硫醇、4,5-二苯咪唑-2-硫醇、2-巰基咪唑、2-巰基-1-甲基咪唑、4-胺基-3-肼基-5-巰基-1,2,4-三唑、3-胺基-5-巰基-1,2,4-三唑、2-甲基-4H-1,2,4-三唑-3-硫醇、4-甲基-4H-1,2,4-三唑-3-硫醇、3-巰基-1H-1,2,4-三唑-3-硫醇、2-胺基-5-巰基-1,3,4-噻二唑、5-胺基-1,3,4-噻二唑-2-硫醇、2,5-二巰基-1,3,4-噻二唑、(呋喃-2-基)甲硫醇、2-巰基-5-四氫噻唑、2-巰基噻唑啉、2-巰基-4(3H)-喹唑啉酮、1-苯基-1H-四唑-5-硫醇、2-喹啉硫醇、2-巰基-5-甲基苯并咪唑、2-巰基-5-硝基苯并咪唑、6-胺基-2-巰基苯并噻唑、5-氯-2-巰基苯并噻唑、6-乙氧基-2-巰基苯并噻唑、6-硝基-2-巰基苯并噻唑、2-巰基萘并咪唑、2-巰基萘并唑、3-巰基-1,2,4-三唑、4-胺基-6-巰基吡唑并[2,4-d]吡啶、2-胺基-6-嘌呤硫醇、6-巰基嘌昤、4-巰基-1H-吡唑并[2,4-d]嘧啶等。
作為分子內具有2個以上之巰基之化合物,可列舉:己二硫醇、癸二硫醇、1,4-雙(甲基巰基)苯、丁二醇雙(3-巰基丙酸酯)、丁二醇雙(3-巰基乙酸酯)、乙二醇雙(3-巰基乙酸酯)、三羥甲基丙烷三(3-巰基乙酸酯)、丁二醇雙(3-巰基丙酸酯)、三羥甲基丙烷三(3-巰基丙酸酯)、三羥甲基丙烷三(3-巰基乙酸酯)、季戊四醇四(3-巰基丙酸酯)、季戊四醇四(3-巰基乙酸酯)、三羥基乙基三(3-巰基丙酸酯)、季戊四醇四(3-巰基丁酸酯)、1,4-雙(3-巰基丁氧基)丁烷等。
相對於聚合起始劑(D)100質量份,硫醇化合物(T)之含量較佳為0.5~50質量份,更佳為5~45質量份,進而較佳為10~40質量份。若硫醇化合物(T)之含量處於該範圍內,則存在感度變高、且顯影性變良好之傾向。
本發明之著色感光性樹脂組合物較佳為包含溶劑(E)。溶劑(E)並
無特別限定,可使用該領域中通常使用之溶劑。例如可自酯溶劑(含有-COO-之溶劑)、酯溶劑以外之醚溶劑(含有-O-之溶劑)、醚酯溶劑(含有-COO-與-O-之溶劑)、酯溶劑以外之酮溶劑(含有-CO-之溶劑)、醇溶劑、芳香族烴溶劑、醯胺溶劑、二甲基亞碸等中選擇而使用。
作為酯溶劑,可列舉:乳酸甲酯、乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、乙酸乙酯、乙酸正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、環己二醇乙酸酯、γ-丁內酯等。
作為醚溶劑,可列舉:乙二醇單甲醚、乙二醇單乙醚、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單乙醚、丙二醇單丙醚、丙二醇單丁醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、四氫呋喃、四氫吡喃、1,4-二烷、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲基乙基醚、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚、苯乙醚、甲基苯甲醚等。
作為醚酯溶劑,可列舉:甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯、二丙二醇甲醚乙酸酯等。
作為酮溶劑,可列舉:4-羥基-4-甲基-2-戊酮、丙酮、2-丁酮、2-
庚酮、3-庚酮、4-庚酮、4-甲基-2-戊酮、環戊酮、環己酮、異佛爾酮等。
作為醇溶劑,可列舉:甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇、甘油等。
作為芳香族烴溶劑,可列舉苯、甲苯、二甲苯、均三甲苯等。
作為醯胺溶劑,可列舉N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮等。
該等溶劑可單獨使用,亦可併用2種以上。
上述溶劑中,就塗佈性、乾燥性之方面而言,較佳為1atm下之沸點為120℃以上且180℃以下之有機溶劑。其中,較佳為丙二醇單甲醚乙酸酯、二丙二醇甲醚乙酸酯、乳酸乙酯、丙二醇單甲醚、3-乙氧基丙酸乙酯、乙二醇單甲醚、二乙二醇單甲醚、二乙二醇單乙醚、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、4-羥基-4-甲基-2-戊酮、N,N-二甲基甲醯胺等,更佳為丙二醇單甲醚乙酸酯、丙二醇單甲醚、二丙二醇甲醚乙酸酯、乳酸乙酯、3-甲氧基丁基乙酸酯、3-甲氧基-1-丁醇、3-乙氧基丙酸乙酯等。
於著色感光性樹脂組合物中,溶劑(E)之含量較佳為70~95質量%,更佳為75~92質量%。換言之,著色感光性樹脂組合物之固形物成分較佳為5~30質量%,更佳為8~25質量%。若溶劑(E)之含量處於上述範圍內,則存在塗佈時之平坦性變良好、且形成彩色濾光片時色濃度不會不足故顯示特性變良好之傾向。
作為調平劑(F),可列舉聚矽氧系界面活性劑、氟系界面活性劑等。該等亦可於側鏈中具有聚合性基。
作為聚矽氧系界面活性劑,可列舉分子內具有矽氧烷鍵之界面活性劑等。具體而言可列舉:Toray Silicone DC3PA、Toray Silicone
SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone SH8400(商品名:Toray-Dow Corning(股)製造);KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業(股)製造);TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF-4446、TSF4452及TSF4460(日本邁圖高新材料(Momentive Performance Materials Japan)有限公司製造)等。
作為上述氟系界面活性劑,可列舉分子內具有氟碳鏈之界面活性劑等。具體而言可列舉:Fluorad(註冊商標)FC430、Fluorad FC431(Sumitomo 3M(股)製造);Megafac(註冊商標)F142D、Megafac F171、Megafac F172、Megafac F173、Megafac F177、Megafac F183、Megafac F554、Megafac R30、Megafac RS-718-K(DIC(股)製造);Eftop(註冊商標)EF301、Eftop EF303、Eftop EF351、Eftop EF352(三菱綜合材料電子化成(股)製造);Surflon(註冊商標)S381、Surflon S382、Surflon SC101、Surflon SC105(旭硝子(股)製造)及E5844(Daikin Fine Chemical研究所(股)製造)等。
作為聚矽氧系界面活性劑,可列舉進而具有氟原子之聚矽氧系界面活性劑。作為具有氟原子之聚矽氧系界面活性劑,具體而言可列舉:Megafac(註冊商標)R08、Megafac BL20、Megafac F475、Megafac F477及Megafac F443(DIC(股)製造)等。
於著色感光性樹脂組合物之總量中,調平劑(F)之含量較佳為0.001質量%以上且0.2質量%以下,較佳為0.002質量%以上且0.1質量%以下,更佳為0.01質量%以上且0.05質量%以下。再者,於該含量中不包括上述顏料分散劑之含量。
就提高著色劑之耐熱性及耐光性之觀點而言,較佳為單獨使用
或組合使用2種以上之抗氧化劑。作為抗氧化劑,只要為工業上通常使用之抗氧化劑,則無特別限定,可使用酚系抗氧化劑、磷系抗氧化劑及硫系抗氧化劑等。
作為上述酚系抗氧化劑,可列舉:Irganox 1010(Irganox 1010:季戊四醇四[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯],BASF(股)製造)、Irganox 1076(Irganox 1076:3-(3,5-二-第三丁基-4-羥基苯基)丙酸十八烷基酯,BASF(股)製造)、Irganox 1330(Irganox 1330:3,3',3",5,5',5"-六-第三丁基-a,a',a"-(均三甲苯-2,4,6-三基)三-對甲酚,BASF(股)製造)、Irganox 3114(Irganox 3114:1,3,5-三(3,5-二-第三丁基-4-羥基苄基)-1,3,5-三-2,4,6(1H,3H,5H)-三酮,BASF(股)製造)、Irganox 3790(Irganox 3790:1,3,5-三((4-第三丁基-3-羥基-2,6-二甲苯基)甲基)-1,3,5-三-2,4,6(1H,3H,5H)-三酮,BASF(股)製造)、Irganox 1035(Irganox 1035:硫代二伸乙基雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯],BASF(股)製造)、Irganox 1135(Irganox 1135:苯丙酸-3,5-雙(1,1-二甲基乙基)-4-羥基-C7-C9側鏈烷基酯,BASF(股)製造)、Irganox 1520L(Irganox 1520L:4,6-雙(辛硫基甲基)-鄰甲酚,BASF(股)製造)、Irganox 3125(Irganox 3125,BASF(股)製造)、Irganox 565(Irganox 565:2,4-雙(正辛硫基)-6-(4-羥基3',5'-二-第三丁基苯胺基)-1,3,5-三,BASF(股)製造)、Adekastab AO-80(Adekastab AO-80:3,9-雙(2-(3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基)-1,1-二甲基乙基)-2,4,8,10-四氧雜螺(5,5)十一烷,ADEKA(股)製造)、Sumilizer BHT(Sumilizer BHT,住友化學(股)製造)、Sumilizer GA-80(Sumilizer GA-80,住友化學(股)製造)、Sumilizer GS(Sumilizer GS,住友化學(股)製造)、Cyanox 1790(Cyanox 1790,Cytec(股)製造)及維生素E(Eisai(股)製造)等。
作為上述磷系抗氧化劑,可列舉:Irgafos 168(Irgafos 168:亞磷
酸三(2,4-二-第三丁基苯基)酯,BASF(股)製造)、Irgafos 12(Irgafos 12:三[2-[[2,4,8,10-四-第三丁基二苯并[d,f][1,3,2]二氧雜膦-6-基]氧基]乙基]胺,BASF(股)製造)、Irgafos 38(Irgafos 38:雙(2,4-雙(1,1-二甲基乙基)-6-甲基苯基)乙酯亞磷酸,BASF(股)製造)、Adekastab 329K(ADEKA(股)製造)、Adekastab PEP36(ADEKA(股)製造)、Adekastab PEP-8(ADEKA(股)製造)、Sandstab P-EPQ(Clariant公司製造)、Weston 618(Weston 618,GE公司製造)、Weston 619G(Weston 619G,GE公司製造)、Ultranox 626(Ultranox 626,GE公司製造)及Sumilizer GP(Sumilizer GP:6-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙氧基]-2,4,8,10-四-第三丁基二苯并[d,f][1.3.2]二氧雜磷雜環庚烯)(住友化學(股)製造)等。
作為上述硫系抗氧化劑,例如可列舉:硫代二丙酸二月桂酯、硫代二丙酸二肉豆蔻酯或硫代二丙酸二硬脂酯等硫代二丙酸二烷基酯化合物及四[亞甲基(3-十二烷硫基)丙酸酯]甲烷等多元醇之β-烷基巰基丙酸酯化合物等。
於本發明之著色感光性樹脂組合物中,視需要亦可併用填充劑、樹脂(B)以外之高分子化合物、密接促進劑、紫外線吸收劑、抗凝聚劑、有機酸、有機胺化合物、硬化劑等添加劑。
作為上述填充劑,具體而言可例示玻璃、二氧化矽、氧化鋁等。
作為上述樹脂(B)以外之高分子化合物,例如可列舉聚乙烯醇、聚丙烯酸、聚乙二醇單烷基醚、聚氟烷基丙烯酸酯等。
作為上述密接促進劑,具體而言可列舉:乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三(2-甲氧基乙氧基)矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基
三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷等。
作為上述紫外線吸收劑,例如可列舉:2-(2-羥基-3-第三丁基-5-甲基苯基)-5-氯苯并三唑等苯并三唑系化合物;2-羥基-4-辛氧基二苯甲酮等二苯甲酮系化合物;2,4-二-第三丁基苯基-3,5-二-第三丁基-4-羥基苯甲酸酯等苯甲酸酯系化合物;2-(4,6-二苯基-1,3,5-三-2-基)-5-己氧基苯酚等三系化合物等。
又,作為抗凝聚劑,具體而言可列舉聚丙烯酸鈉等。
上述有機酸可用於調整顯影性,具體而言可列舉:甲酸、乙酸、丙酸、丁酸、戊酸、三甲基乙酸、己酸、二乙基乙酸、庚酸、辛酸等脂肪族單羧酸;草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十三烷二酸、甲基丙二酸、乙基丙二酸、二甲基丙二酸、甲基琥珀酸、四甲基琥珀酸、環己烷二羧酸、伊康酸、檸康酸、馬來酸、富馬酸、中康酸等脂肪族二羧酸;三胺甲酸、烏頭酸、降三酸等脂肪族三羧酸;苯甲酸、甲苯甲酸、小茴香酸、2,3-二甲基苯甲酸、3,5-二甲基苯甲酸等芳香族單羧酸;鄰苯二甲酸、間苯二甲酸、對苯二甲酸等芳香族二羧酸;偏苯三甲酸、均苯三甲酸、1,2,3,5-苯四甲酸、均苯四甲酸等芳香族多羧酸等。
作為上述有機胺化合物,例如可列舉:正丙基胺、異丙基胺、正丁基胺、異丁基胺、第二丁基胺、第
三丁基胺、正戊基胺、正己基胺、正庚基胺、正辛基胺、正壬基胺、正癸基胺、正十一烷基胺、正十二烷基胺等單烷基胺;環己基胺、2-甲基環己基胺、3-甲基環己基胺、4-甲基環己基胺等單環烷基胺;甲基乙基胺、二乙基胺、甲基正丙基胺、乙基正丙基胺、二-正丙基胺、二異丙基胺、二-正丁基胺、二異丁基胺、二-第二丁基胺、二-第三丁基胺、二-正戊基胺、二-正己基胺等二烷基胺;甲基環己基胺、乙基環己基胺等單烷基單環烷基胺;二環己基胺等二環烷基胺;二甲基乙基胺、甲基二乙基胺、三乙基胺、二甲基-正丙基胺、二乙基-正丙基胺、甲基二-正丙基胺、乙基二-正丙基胺、三-正丙基胺、三異丙基胺、三-正丁基胺、三異丁基胺、三-第二丁基胺、三-第三丁基胺、三-正戊基胺、三-正己基胺等三烷基胺;二甲基環己基胺、二乙基環己基胺等二烷基單環烷基胺;甲基二環己基胺、乙基二環己基胺、三環己基胺等單烷基二環烷基胺;2-胺基乙醇、3-胺基-1-丙醇、1-胺基-2-丙醇、4-胺基-1-丁醇、5-胺基-1-戊醇、6-胺基-1-己醇等單烷醇胺;4-胺基-1-環己醇等單環烷醇胺;二乙醇胺、二-正丙醇胺、二異丙醇胺、二-正丁醇胺、二異丁醇胺、二-正戊醇胺、二-正己醇胺等二烷醇胺;二(4-環己醇)胺等二環烷醇胺;三乙醇胺、三-正丙醇胺、三異丙醇胺、三-正丁醇胺、三異丁醇胺、三-正戊醇胺、三-正己醇胺等三烷醇胺;三(4-環己醇)胺等三環烷醇胺;3-胺基-1,2-丙二醇、2-胺基-1,3-丙二醇、4-胺基-1,2-丁二醇、4-
胺基-1,3-丁二醇、3-二甲基胺基-1,2-丙二醇、3-二乙基胺基-1,2-丙二醇、2-二甲基胺基-1,3-丙二醇、2-二乙基胺基-1,3-丙二醇等胺基烷二醇;4-胺基-1,2-環己二醇、4-胺基-1,3-環己二醇等胺基環烷二醇;1-胺基環戊酮甲醇、4-胺基環戊酮甲醇等含胺基之環烷酮甲醇;1-胺基環己酮甲醇、4-胺基環己酮甲醇、4-二甲基胺基環戊烷甲醇、4-二乙基胺基環戊烷甲醇、4-二甲基胺基環己烷甲醇、4-二乙基胺基環己烷甲醇等含胺基之環烷烴甲醇;β-丙胺酸、2-胺基丁酸、3-胺基丁酸、4-胺基丁酸、2-胺基異丁酸、3-胺基異丁酸、2-胺基戊酸、5-胺基戊酸、6-胺基己酸、1-胺基環丙烷羧酸、1-胺基環己烷羧酸、4-胺基環己烷羧酸等胺基羧酸;苯胺、鄰甲基苯胺、間甲基苯胺、對甲基苯胺、對乙基苯胺、對正丙基苯胺、對異丙基苯胺、對正丁基苯胺、對第三丁基苯胺、1-萘胺、2-萘胺、N,N-二甲基苯胺、N,N-二乙基苯胺、對甲基-N,N-二甲基苯胺等芳香族胺;鄰胺基苄醇、間胺基苄醇、對胺基苄醇、對二甲胺基苄醇、對二乙基胺基苄醇等胺基苄醇;鄰胺基苯酚、間胺基苯酚、對胺基苯酚、對二甲胺基苯酚、對二乙基胺基苯酚等胺基苯酚;間胺基苯甲酸、對胺基苯甲酸、對二甲基胺基苯甲酸、對二乙基胺基苯甲酸等胺基苯甲酸等。
作為上述硬化劑,可列舉:可藉由加熱而與樹脂(B)中之羧基反應從而將樹脂(B)交聯之化合物、可單獨聚合而使著色圖案硬化之化合物等。作為上述化合物,可列舉環氧化合物、氧雜環丁烷化合物等。
此處,作為環氧化合物,可列舉:雙酚A系環氧樹脂、氫化雙酚
A系環氧樹脂、雙酚F系環氧樹脂、氫化雙酚F系環氧樹脂、酚醛清漆型環氧樹脂、其他芳香族系環氧樹脂、脂環族系環氧樹脂、雜環式環氧樹脂、縮水甘油酯系樹脂、縮水甘油胺系樹脂、環氧化油等環氧樹脂、或者該等環氧樹脂之溴化衍生物、環氧樹脂及其溴化衍生物以外之脂肪族或脂環族或芳香族之環氧化合物、丁二烯之(共)聚物之環氧化物、異戊二烯之(共)聚物之環氧化物、(甲基)丙烯酸縮水甘油酯之(共)聚物、異氰尿酸三縮水甘油酯等。
作為環氧樹脂之市售品,可列舉鄰甲酚酚醛清漆型環氧樹脂、「Sumiepoxy(註冊商標)ESCN-195XL-80」(住友化學(股)製造)等。
作為上述氧雜環丁烷化合物,例如可列舉:碳酸酯二氧雜環丁烷、苯二甲基二氧雜環丁烷、己二酸酯二氧雜環丁烷、對苯二甲酸酯二氧雜環丁烷、環己烷二羧酸二氧雜環丁烷等。
於本發明之著色感光性樹脂組合物含有環氧化合物、氧雜環丁烷化合物等作為硬化劑之情形時,亦可包含可使環氧化合物之環氧基、氧雜環丁烷化合物之氧雜環丁烷骨架進行開環聚合之化合物。作為該化合物,例如可列舉多元羧酸、多元羧酸酐、酸產生劑等。
作為上述多元羧酸,可列舉:鄰苯二甲酸、3,4-二甲基鄰苯二甲酸、間苯二甲酸、對苯二甲酸、均苯四甲酸、偏苯三甲酸、1,4,5,8-萘四羧酸、3,3',4,4'-二苯甲酮四羧酸等芳香族多元羧酸;琥珀酸、戊二酸、己二酸、1,2,3,4-丁烷四羧酸、馬來酸、富馬酸、伊康酸等脂肪族多元羧酸;六氫鄰苯二甲酸、3,4-二甲基四氫鄰苯二甲酸、六氫間苯二甲酸、六氫對苯二甲酸、1,2,4-環戊烷三羧酸、1,2,4-環己烷三羧酸、環戊烷四羧酸、1,2,4,5-環己烷四羧酸等脂環式多元羧酸等。
作為上述多元羧酸酐,可列舉:
鄰苯二甲酸酐、均苯四甲酸酐、偏苯三甲酸酐、3,3',4,4'-二苯甲酮四羧酸二酐等芳香族多元羧酸酐;伊康酸酐、琥珀酸酐、檸康酸酐、十二烯基琥珀酸酐、1,2,3-丙三甲酸酐、馬來酸酐、1,2,3,4-丁烷四羧酸二酐等脂肪族多元羧酸酐;六氫鄰苯二甲酸酐、3,4-二甲基四氫鄰苯二甲酸酐、1,2,4-環戊烷三羧酸酐、1,2,4-環己烷三羧酸酐、環戊烷四羧酸二酐、1,2,4,5-環己烷四羧酸二酐、雙環庚烯二甲酸酐、3,6-亞甲基四氫鄰苯二甲酸酐等脂環式多元羧酸酐;乙二醇雙偏苯三甲酸、甘油三偏苯三甲酸酐等含酯基之羧酸酐;等。
作為上述羧酸酐,亦可使用作為環氧樹脂硬化劑而市售者。作為上述環氧樹脂硬化劑,可列舉:商品名「Adeka Hardener(註冊商標)EH-700」(ADEKA(股)製造)、商品名「RIKACID(註冊商標)HH」(新日本理化(股)製造)、商品名「MH-700」(新日本理化(股)製造)等。
作為酸產生劑,可列舉:4-羥基苯基二甲基鋶對甲苯磺酸鹽、4-羥基苯基二甲基鋶六氟銻酸鹽、4-乙醯氧基苯基二甲基鋶對甲苯磺酸鹽、4-乙醯氧基苯基-甲基-苄基鋶六氟銻酸鹽、三苯基鋶對甲苯磺酸鹽、三苯基鋶六氟銻酸鹽、二苯基錪對甲苯磺酸鹽、二苯基錪六氟銻酸鹽等鎓鹽類,或硝基苄基甲苯磺酸鹽類,安息香甲苯磺酸鹽類等。
上述硬化劑可單獨使用,亦可組合使用2種以上。
本發明之著色感光性樹脂組合物可藉由將著色劑(A)、樹脂(B)、聚合性化合物(C)、聚合起始劑(D)、以及視需要使用之溶劑(E)、硫醇化合物(T)、調平劑(F)、聚合起始助劑(D1)、抗氧化劑(J)、及其他成
分混合而製備。
作為由本發明之著色感光性樹脂組合物製造著色圖案之方法,可列舉光微影法、噴墨法、印刷法等。其中,較佳為光微影法。光微影法係將上述著色感光性樹脂組合物塗佈於基板上,進行乾燥而形成著色組合物層,隔著光罩對該著色組合物層進行曝光並進行顯影之方法。於光微影法中,藉由於曝光時不使用光罩及/或不進行顯影,可形成作為上述著色組合物層之硬化物之著色塗膜。以上述方式形成之著色圖案或著色塗膜為本發明之彩色濾光片。
作為基板,可使用:石英玻璃、硼矽酸玻璃、鋁硼矽酸鹽玻璃、表面上塗佈有二氧化矽之鈉鈣玻璃等之玻璃板,或聚碳酸酯、聚甲基丙烯酸甲酯、聚對苯二甲酸乙二酯等之樹脂板,於矽、上述基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。亦可於該等基板上形成有另一彩色濾光片層、樹脂層、電晶體、電路等。
利用光微影法之各色像素之形成可利用公知或慣用之裝置或條件進行。例如可以下述方式進行製作。
首先,將著色感光性樹脂組合物塗佈於基板上,進行加熱乾燥(預烘烤)及/或減壓乾燥,藉此將溶劑等揮發成分去除並加以乾燥,獲得平滑之著色組合物層。
作為塗佈方法,可列舉旋轉塗佈法、狹縫式塗佈法、狹縫及旋轉塗佈法等。
於進行加熱乾燥之情形時之溫度較佳為30~120℃,更佳為50~110℃。又,作為加熱時間,較佳為10秒鐘~5分鐘,更佳為30秒鐘~3分鐘。
於進行減壓乾燥之情形時,較佳為於50~150Pa之壓力下於20~25℃之溫度範圍內進行。
著色組合物層之膜厚並無特別限定,只要根據目標彩色濾光片之膜厚而適當選擇即可。
繼而,隔著用以形成目標著色圖案之光罩對著色組合物層進行曝光。該光罩上之圖案並無特別限定,可使用與目標用途相對應之圖案。
作為曝光所使用之光源,較佳為產生250~450nm之波長之光的光源。例如亦可對未達350nm之光使用截止該波長區域之濾波器加以截止,或者對436nm附近、408nm附近、365nm附近之光使用擷取該等波長區域之帶通濾波器選擇性地擷取。具體而言,作為光源,可列舉水銀燈、發光二極體、金屬鹵化物燈、鹵素燈等。
較佳為使用光罩對準曝光機及步進式曝光機等曝光裝置,其原因在於:可對曝光面整個面均勻地照射平行光線,或者進行光罩與形成有著色組合物層之基板之準確對位。
藉由使曝光後之著色組合物層與顯影液接觸進行顯影,而於基板上形成著色圖案。藉由顯影,著色組合物層之未曝光部溶解於顯影液中而被去除。作為顯影液,例如較佳為氫氧化鉀、碳酸氫鈉、碳酸鈉、氫氧化四甲基銨等鹼性化合物之水溶液。該等鹼性化合物之水溶液中之濃度較佳為0.01~10質量%,更佳為0.03~5質量%。進而,顯影液亦可包含界面活性劑。
顯影方法可為覆液法、浸漬法及噴霧法等之任一種方法。進而亦可於顯影時使基板傾斜至任意之角度。
顯影後較佳為進行水洗。
較佳為進而對所獲得之著色圖案進行後烘烤處理。後烘烤處理溫度較佳為150~250℃,更佳為160~235℃。後烘烤處理時間較佳為1~120分鐘,更佳為10~60分鐘。
關於所獲得之塗膜之膜厚,就影響鄰接像素之方面而言,較佳
為塗膜儘可能薄。尤其於成為厚膜之情形時,存在於製作液晶面板時,光源之光通過2色以上之像素而漏出之情況,而於斜向觀察面板之情形時,有喪失顏色之鮮豔度之虞。後烘烤處理後之塗膜較佳為3.5μm以下,更佳為3.2μm以下。塗膜之下限並無特別限定,通常為1μm以上,亦可為1.5μm以上。
又,塗膜之亮度越高越佳,較佳為45以上,更佳為47以上,上限並無特別限定,通常為70以下,亦可為58以下。
又,塗膜較佳為於下述所示之對比度評價中顯示較高之值,具體而言,通常為1000以上,較佳為5000以上,更佳為5500以上,上限並無特別限定,通常為35000以下。
[對比度評價]
對塗膜使用對比度計(CT-1:壺阪電機(TSUBOSAKA ELECTRIC)(股),色彩色差計BM-5A:TOPCON公司製造,光源:F-10,偏光膜:壺阪電機(TSUBOSAKA ELECTRIC)(股)),於不隔著塗膜進行測定之情形時,以成為50000之方式進行測定。
又,塗膜較佳為於下述所示之相位差評價中顯示較低之值,具體而言,通常為70nm以下,較佳為50nm以下,更佳為40nm以下,下限通常為1nm以上,亦可為3nm以上。
[相位差評價]
對塗膜使用相位差測定裝置(橢圓偏光計;日本分光公司製造)於測定波長為550nm、折射率為1.5之條件下進行測定。作為相位差之Rth係由下述式算出。
Rth={(Nx+Ny)/2-Nz}×d
由本發明之著色感光性樹脂組合物形成之著色塗膜及著色圖案可用作彩色濾光片。該彩色濾光片可用作顯示裝置(例如液晶顯示裝置、有機EL(Electroluminescence,電致發光)裝置、電子紙等)及固體
攝像元件所使用之彩色濾光片。
以下,列舉實施例對本發明更具體地進行說明,但本發明當然不受下述實施例之限制,當然亦可於可適合上述及下述宗旨之範圍內適當地加以變更而實施,該等均包含於本發明之技術範圍內。再者,以下只要無特別說明,則「份」意指「質量份」,「%」意指「質量%」。
合成例1
於具備回流冷凝器、滴液漏斗及攪拌機之1L之燒瓶內流通適量之氮氣而置換成氮氣環境,添加丙二醇單甲醚乙酸酯280質量份,一面攪拌一面加熱至80℃。繼而,歷時5小時滴加丙烯酸38質量份、丙烯酸3,4-環氧三環[5.2.1.02,6]癸烷-8及/或9-基酯之混合物289質量份、丙二醇單甲醚乙酸酯125質量份之混合溶液。另一方面,歷時6小時,滴加使2,2-偶氮雙(2,4-二甲基戊腈)33質量份溶解於丙二醇單甲醚乙酸酯235質量份中而成之混合溶液。滴加結束後,於相同溫度下保持4小時後,冷卻至室溫,獲得B型黏度(23℃)125mPa‧s、固形物成分37.0重量%、溶液酸值27mg-KOH/g之共聚物。所產生之共聚物之重量平均分子量Mw為9200、分散度為2.08。
關於上述合成例中所獲得之樹脂之聚苯乙烯換算重量平均分子量Mw之測定,使用GPC法於以下條件下進行。
裝置;HLC-8120GPC(Tosoh(股)製造)
管柱;TSK-GELG2000HXL
管柱溫度;40℃
溶劑;THF
流速;1.0mL/min
受檢液固形物成分濃度;0.001~0.01質量%
注入量;50μL
檢測器;RI
校正用標準物質;TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500(Tosoh(股)製造)
[顏料分散液(A-1)之製備]
將以上成分混合,使用珠磨機攪拌顏料直至測定顏料之粒度分佈結果具有100nm以上之粒徑的粒子成為總體之22%為止,藉此獲得顏料分散液(A-1)。
[顏料分散液(A-2)之製備]
將以上成分混合,使用珠磨機攪拌顏料直至測定顏料之粒度分佈結果具有100nm以上之粒徑的粒子成為總體之1%為止,藉此獲得顏料分散液(A-2)。
[顏料分散液(A-3)之製備]
將以上成分混合,使用珠磨機攪拌顏料直至測定顏料之粒度分佈結果具有100nm以上之粒徑的粒子成為總體之7%為止,藉此獲得顏料分散液(A-3)。用以製備顏料分散液(A-3)之攪拌時間係較顏料分散液(A-2)短之時間。
[顏料分散液(A-4)之製備]
將以上成分混合,使用珠磨機攪拌顏料直至測定顏料之粒度分佈結果具有100nm以上之粒徑的粒子成為總體之8%為止,藉此獲得顏料分散液(A-4)。
[顏料分散液(A-5)之製備]
將以上成分混合,使用珠磨機攪拌顏料直至測定顏料之粒度分佈結果具有100nm以上之粒徑的粒子成為總體之11%為止,藉此獲得顏料分散液(A-5)。
[顏料分散液(A-6)之製備]
將以上成分混合,使用珠磨機攪拌顏料直至測定顏料之粒度分佈結果具有100nm以上之粒徑的粒子成為總體之42%為止,藉此獲得顏料分散液(A-6)。
於上述顏料分散液之製備中,按以下順序進行顏料之粒徑及粒度分佈之測定:利用丙二醇單甲醚乙酸酯將所獲得之顏料分散液稀釋至50倍後,藉由動態光散射測定裝置(Zetasizer Nano ZS;Malvern製造)於25℃下進行測定,根據散射強度算出顏料之粒徑及粒度分佈。標準物質係使用聚苯乙烯乳液。
[著色感光性樹脂組合物之製備]
實施例1~4及比較例1~3
將表1記載之成分混合而獲得著色感光性樹脂組合物。再者,以著色感光性樹脂組合物之固形物成分成為表1之「固形物成分(%)」之方式混合丙二醇單甲醚乙酸酯。
於表1中,各成分係如下所示。
著色分散液(A1);上述所獲得之顏料分散液(A-1)
著色分散液(A2);上述所獲得之顏料分散液(A-2)
著色分散液(A3);上述所獲得之顏料分散液(A-3)
著色分散液(A4);上述所獲得之顏料分散液(A-4)
著色分散液(A5);上述所獲得之顏料分散液(A-5)
著色分散液(A6);上述所獲得之顏料分散液(A-6)
樹脂溶液(B1);合成例1中所獲得之共聚物
聚合性化合物(C1);二季戊四醇六丙烯酸酯(KAYARADDPHA;日本化藥(股)製造)
聚合起始劑(D1);N-苯甲醯氧基-1-(4-苯基巰基苯基)辛烷-1-酮-2-亞胺(Irgacure OXE01;BASF公司製造;O-醯基肟化合物)
聚合起始劑(D2);下述式所表示之化合物之混合物(CHEMCURE-TCDM;Cambridge公司製造;聯咪唑化合物)
硫醇化合物(T1);2-巰基苯并噻唑(Soxinol M;住友化學(股)製造;下述式所表示之化合物)
調平劑(F1);聚醚改性聚矽氧油(SH8400;Dow Corning Toray股份有限公司製造)
[塗膜之製作]
使用實施例1~4及比較例1~3之著色感光性樹脂組合物,按下述順序製作塗膜。
製作順序:利用旋轉塗佈法將著色感光性樹脂組合物塗佈於2吋見方之玻璃基板(Eagle XG;Corning公司製造)上後,於100℃下預烘烤3分鐘。冷卻後,使用曝光機(TME-150RSK;TOPCON(股)製造),於大氣環境下以150mJ/cm2之曝光量(365nm標準)對該塗佈有著色感光性樹脂組合物之基板進行光照射。光照射後,於24℃下將所獲得之膜於包含非離子系界面活性劑0.12%與氫氧化鉀0.04%之水系顯影液中浸漬60秒鐘,藉此進行顯影,水洗後,於烘箱中於230℃下進行30分鐘之後烘烤,獲得綠色之塗膜。
[膜厚測定]
對由實施例1~4及比較例1~3之著色感光性樹脂組合物獲得之塗膜使用膜厚測定裝置(DEKTAK3;日本真空技術(股)製造)測定膜厚FT(μm)。將結果示於表2。
[色度評價]
對由實施例1~4及比較例1~3之著色感光性樹脂組合物獲得之各塗膜使用測色機(OSP-SP-200;Olympus(股)製造)測定光譜,使用F10光源之特性函數,測定CIE之XYZ表色系統中之xy色度座標(x,y)與亮度Y。
反覆進行塗膜製作與色度評價,調整塗佈著色感光性樹脂組合物時之旋轉塗佈之轉速,藉此獲得色度座標中x=0.29且y=0.66之塗膜。將所獲得之塗膜之顏色特性之結果示於表2。
[對比度評價]
對由實施例1~3及比較例1之著色感光性樹脂組合物獲得之各塗膜使用對比度計(CT-1:壺阪電機(TSUBOSAKA ELECTRIC)(股),色
彩色差計BM-5A:TOPCON公司製造,光源:F-10,偏光膜:壺阪電機(TSUBOSAKA ELECTRIC)(股))測定對比度。再者,測定時之空白值為50000。將結果示於表3。
[相位差評價]
對由實施例1~3及比較例1之著色感光性樹脂組合物獲得之塗膜使用相位差測定裝置(橢圓偏光計;日本分光公司製造)於測定波長為550nm、折射率1.5為之條件下進行測定。將結果示於表3。
[圖案之製作]
使用實施例1~4及比較例1~3之各著色感光性樹脂組合物,按以下順序製作圖案。
製作順序:利用旋轉塗佈法將著色感光性樹脂組合物以成為表2所示之膜厚之方式塗佈於2吋見方之玻璃基板(Eagle XG;Corning公司製造)上,利用減壓乾燥機進行減壓乾燥直至130Pa。其後,將該塗佈有著色感光性樹脂組合物之基板與具有圖案之石英玻璃製光罩的間隔設為100μm,使用曝光機(TME-150RSK;TOPCON(股)製造),於大氣環境下以150mJ/cm2之曝光量(365nm標準)進行光照射。再者,作為光罩,使用形成有50μm線與間隙圖案之遮罩。光照射後,於24℃下將上述塗膜於包含非離子系界面活性劑0.12%與氫氧化鉀0.04%之水系顯影液中浸漬60秒鐘而進行顯影,水洗後,於烘箱中於230℃下進行30分鐘之後烘烤,製作圖案。
[顯影類型]
上述圖案製作中,於浸漬於顯影液中時,對未曝光部於顯影液中之溶解性進行確認。於溶解於顯影液中之情形時記作「○」,於伴有剝離片而確認到自玻璃基板剝離之固形物之情形時記作「×」而進行評價。將結果示於表2。
[可否製作圖案]
於藉由與上述[圖案之製作]中記載之方法相同之方法而製作之線與間隙圖案中,於獲得了30μm之圖案之情形時記作「○」,於曝光部剝離、或溶解、或而未殘留30μm之圖案之情形時記作「×」而進行評價。將結果示於表2。
確認到由實施例1~4之著色感光性樹脂組合物可形成膜厚處於適當之範圍內、且亮度優異之塗膜。又,亦確認到於形成圖案時,亦未產生剝離片而於顯影液中之溶解性良好,顯影性良好。進而確認到實施例1~3之著色感光性樹脂組合物可形成相位差較低,對比度較高之塗膜。
另一方面,關於由比較例1~3之著色感光性樹脂組合物獲得之塗膜,確認到於形成圖案時,未曝光部中產生剝離片,於顯影液中之溶解性欠佳。由比較例1之著色感光性樹脂組合物獲得之塗膜未獲得實用之相位差或對比度。由比較例2及3之各著色感光性樹脂組合物獲得之塗膜由於膜厚超過3.5μm故而實用性較低。而且,由該等著色感光性樹脂組合物製作圖案,結果由於產生曝光部之剝離或溶解故而無
法形成圖案。
根據本發明之著色感光性樹脂組合物,未曝光部於顯影液中之溶解性良好,可製作形狀良好之圖案,進而可製造雖為薄膜但具有高亮度之高精細彩色濾光片。
Claims (9)
- 一種著色感光性樹脂組合物,其特徵在於:包含著色劑(A)、樹脂(B)、聚合性化合物(C)及聚合起始劑(D),且包含C.I.顏料綠58、C.I.顏料黃185及C.I.顏料黃138作為上述著色劑(A)。
- 如請求項1之著色感光性樹脂組合物,其中C.I.顏料黃185具有粒徑100nm以上之粒子為5質量%以下之粒度分佈。
- 如請求項1或2之著色感光性樹脂組合物,其中於著色感光性樹脂組合物之固形物成分100質量%中,著色劑(A)之合計量為20~50質量%。
- 如請求項1至3中任一項之著色感光性樹脂組合物,其進而包含硫醇化合物(T)。
- 如請求項1至4中任一項之著色感光性樹脂組合物,其中上述聚合起始劑(D)為選自O-醯基肟化合物、苯烷基酮化合物、聯咪唑化合物、三化合物、及醯基氧化膦化合物中之2種以上。
- 如請求項1至5中任一項之著色感光性樹脂組合物,其中上述樹脂(B)為包含源自具有碳數2~4之環狀醚結構與乙烯性不飽和鍵之單體(b)之結構單元的共聚物。
- 一種塗膜,其係由如請求項1至6中任一項之著色感光性樹脂組合物所形成。
- 一種彩色濾光片,其係由如請求項1至6中任一項之著色感光性樹脂組合物所形成。
- 一種顯示裝置,其包含如請求項8之彩色濾光片。
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