TW200303430A

TW200303430A - Semi-transmission type color filter, radiation sensitive component and color liquid crystal display device

Info

Publication number: TW200303430A
Application number: TW092103146A
Authority: TW
Inventors: Yasukyo Shinyama; Tomio Nagatsuka; Kinyasu Sano
Original assignee: Jsr Corp
Priority date: 2002-02-15
Filing date: 2003-02-14
Publication date: 2003-09-01
Also published as: KR20030069083A

Abstract

The present invention provides a semi-transmission type color filter to make it possible to reduce the protrusions in the optical reflection area and in the light-transmission area, so that the color purity during the backlight usage and reflection mode usage are about the same, and to increase the color purity during the backlight usage. This color filter is formed of a protrusion part and coloring part on the substrate. The protrusion part has an optical reflection layer, and the coloring part covers the protrusion part and the residual substrate surface. The protrusions in the optical reflection area of the coloring layer and in the light-transmission area are below 0.1 μ m, for example.

Description

200303430 (1) 玖、發明說明【發明所屬之技術領域】本發明係有關半透射型濾色片，於形成該半透射型爐色片之著色層時所用的放射線敏感性組成物及具備該半透 ^ 射型濾色片而成的彩色液晶顯示元件。 ^ 【先前技術】液晶顯示器係長久以來爲確保均勻的晝面亮度，以具 · 備背光者爲主流’惟隨著近年之行動型終端機的普及，各需要另外的光源之反射型液晶顯示器正增加著。然而，此等的液晶顯不器其可使用的環境乃各自受限著。亦即，已具備背光之液晶顯示器，雖然適於室內或夜間之使用，然而若在來自日間之室外等的外界之光線較多的場所使用時 ’變成較難觀看晝面’另一方面反射型之液晶顯示器，雖然適於在來自日間之室外等的外界之光線足夠的場所使用，然而在室內或夜間未能獲得足夠的亮度，畫面變成依然馨較難看淸楚。針對此點，近年因應使用環境，至於可提供適度的畫面亮度之液晶顯示器的方式，在陰暗處所藉由背光可確保人亮度，同時亦在有足夠光源之環境作用成反射型顯示器之 | 所謂「半透射型」之液晶顯示器乃被提出著。然而’對於半透射型之液晶顯示器，使用背光時，爲使用作利用來自外界之光源的反射型時，有所謂晝面之亮度或色純度不同的問題，可解決此種問題之濾色片’製造 -6- (2) (2)200303430 各該濾色片之方法、及可較合適的使用於該等之放射線硬化型著色組成物則尙未爲人所知的。又，使用半透射型液晶顯示器於數位相機等時，在室外的拍攝等，通常若拍攝對象之構圖可予確認時，則足夠，故色純度方面並不成爲問題，雖成爲亮度重視，但在觀看所拍攝的影像之際，在室內較常使用發光，即成爲較拍攝時被要求較高的色純度。因此，若亦考慮此種情形時，則保持晝面之売度或色純度於約略相同水準以外，在使用背光時及使用作反射型時之間，可任意調整色純度等，尤其成爲欲提高使用背光時之色純度一事而被要求著。然而，在習用的半透射型之液晶顯示器方面，此種要求亦未能充分達成。【發明內容】發明之掲示本發明之目的係提供使著色層於光反射領域之突出値 [I]及光透射領域之突出値[II]減少成爲可能，使用背光時及使用作反射型時之間可將色純度作成約略相同，尤其可提高使用背光時之色純度的半透射型濾色片。本發明之另一目的係提供於本發明之半透射型濾色片的突起部之形成所用的放射線敏感性組成物。本發明之再另一目的，係提供於本發明之半透射型濾色片的著色層之形成所用的放射線敏感性組成物。本發明之再另一目的係提供於本發明之半透射型濾色 (3) (3)200303430 片而成的彩色液晶顯示元件。本發明之再另一目的及優點，由以下的說明或可顯而得知。若依本發明時，前述目的係第一藉由以半透射型濾色片予以達成，此半透射型濾色片係以於基板上形成突起部及著色層而成，該突起部具有光反射層且該著色層係予以形成立被覆該突起部及殘存的基板之表面爲特徵。若依本發明時，前述目的係第二藉由申請專利範圍第 H 1項至第3項中任一項之於半透射型濾色片形成突起部所用的放射線敏感性組成物予以達成，此放射線敏感性組成物係以由 (甲）含有（a 1)不飽和羧酸及/或不飽和多元羧酸酐與含有環氧基之不飽和單體與前述以外的不飽和單體間之共聚物，及 (b 1 ) 1，2 -醌二疊氮化合物之放射線敏感性組成物，與 ® (乙）由含有（a2)不飽和羧酸及/或不飽和多元羧酸酐與含有環氧基之不飽和單體與前述以外的不飽和單體間之共聚物，及 (b2)放射線敏感性聚合引發劑與（c2)不飽和單體之放射線敏感性組成物之群體選出的至少一種而成爲特徵。若依本發明時，前述目的係第三藉由於前述半透射型濾色片形成著色層所用的放射線敏感性組成物予以達成， -8- (4) (4)200303430 此放射線敏感性組成物係以含有（A )著色層、（B )驗可溶性樹脂、（C)多官能性單體、（D)光聚合引發劑及（E)溶劑爲特徵。若依本發明時’前述目的係第四藉由彩色液晶顯示元件予以達成，此彩色液晶顯示元件係具備以於基板上形成突起部及著色層而成，該突起部係具有光反射層且該著色層係予以形成至被覆該突起部及殘存的基板之表面爲特徵之半透射型濾色片而成。【實施方式】以下詳細說明本發明。於本發明之半透射型濾色片，於突起部之光反射層係可形成於該突起部之表面，亦可形成於底部（亦即突起部及基板之間）。光反射層經予形成於突起部之表面時，各該突起部可爲透明，半透明或不透明之任一種，惟對光反射層經予形成於突起部之底部時，各該突起部須爲透明。又，著色層係予以形成至被覆突起部且被覆已形成該突起部的領域以外之基板表面。突起用放射線敏感性組成物至於本發明之半透射型濾色片的形成突起部所使用的材料（以下稱作「突起用放射線敏感性組成物」），以與基板間之附著性、強度、耐熱性、耐溶解性、形狀之控制等優越，且形成著色層時突起部不致潤膨及變形者係爲人 -9- (5) (5)200303430 所期待的。至於其較宜的例子，可舉出：（甲）含有（al) 不飽和羧酸及/或不飽和多元羧酸酐與含有環氧基之不飽和單體與前述以外的不飽和單體間之共聚物，及（b 1 ) 1 ，2 -醌二疊氮化合物之放射線敏感性組成物（以下稱作「突起用放射線敏感性組成物（甲）」、與（乙）由含有（a2)不飽和羧酸及/或不飽和多元羧酸酐與含有環氧基之不飽和單體與前述以外的不飽和單體間之共聚物，及 (b2)放射線敏感性聚合引發劑與（c：2)不飽和單體之放射線敏感性組成物（以下稱作「突起用放射線敏感性組成物（乙）」）。又亦可使用後述的著色放射線敏感性組成物於突起部之形成。此等放射線性組成物係亦可使用於突起部之形成。此等放射線敏感性組成物可單獨或混合二種以上使用。以下說明突起用放射線敏感性組成物（甲）及突起用放射線敏感性組成物（乙）。 -突起用放射線敏感性組成物（甲）- 至於突起用放射線敏感性組成物（甲）之（al)不飽和羧酸及/或不飽和多元羧酸酐及含有環氧基之不飽和化合物與前述以外的烯烴系不飽和化合物之共聚物（以下稱作「共聚物a 1」），其中不飽和羧酸，可舉出例如：（甲基）丙烯酸、巴豆酸等不飽和單羧酸類；順丁烯二酸、反丁烯二酸、順甲基丁烯二酸、反甲基丁烯二酸、伊康酸等不飽和二羧酸等。此等二飽和羧酸係可單獨或混合二種 -10- (6) (6)200303430 以上使用。又至於不飽和多元羧酸酐，例如可舉出：順丁烯二酐、順甲基丁烯二酐、伊康酐等。此等不飽和多元羧酸酐係可單獨或混合二種以上使用。至於共聚物（a 1)之不飽和羧酸及不飽和多元羧酸酐，以丙烯酸、甲基丙烯酸、順丁烯二酐由共聚合反應性，對鹼顯影液之溶解性及容易到手的觀點係較宜的。於共聚物（al)，由不飽和羧酸及/或不飽和多元羧酸酐而成的構成單位之含有率，宜有5〜40重量％，尤宜爲1 0〜3 0重量％。此時，該構成單位之含有率未滿5 重量％，所得的共聚物對鹼顯微液之溶解性有降低的傾向，另一方面若超過40重量％時，則所得的共聚物對鹼顯影液之溶解性有變成過大的傾向。又，至於含有環氧基之不飽和單體，例如可舉出：（甲基）丙烯酸縮水甘油酯、α ·乙基丙烯酸縮水甘油酯、 ^ -正丙基丙烯酸縮水甘油基酯、α -正丁丙烯酸縮水甘油基酯、（甲基）丙烯酸3，4 -環氧基丁酯、（甲基）丙烯酸 6，7 -環氧基庚酯、α -乙基丙烯酸6，7 -環氧基庚酯、（甲基）丙烯酸-/3 -甲基縮水甘油基酯、（甲基）丙烯酸-/3 -乙基縮水甘油基酯、（甲基）丙烯酸-/3·丙基縮水甘油基酯、α -乙基丙烯酸-/3 -甲基縮水甘油基酯、（甲基）丙烯酸-3 -甲基-3，4 -環氧基丁基酯、（甲基）丙烯酸-3-乙基-3，4-環氧基丁基酯、（甲基）丙烯酸-4-甲基-4，5-環氧基戊酯、（ -11 - (7) (7)200303430 甲基）丙烯酸-5 -甲基-5，6-環氧基己酯、3 -乙基_ 氮雜環丁烷基（甲基）丙烯酸酯、鄰-乙烯基苄基縮水甘油基醚、間乙烯基苄基縮水甘油基醚、對乙烯基縮水甘油基醚等。此等含有環氧基不飽和單體係可單獨或混合二種以上使用。至於共聚物（al)之含有環氧基不飽和單體，由共聚合反應性，所得的突起部之強度等的觀點，宜爲（甲基）丙烯酸縮水甘油基酯、甲基丙烯酸-6，7 -環氧基庚酯、鄰乙烯基苄基縮水甘油基醚、間乙烯基苄基縮水甘油基醚、對乙烯基苄縮水甘油基醚等。於共聚物（a 1)，由含有環氧基之不飽和單體而成的構成單位之含有率，宜爲10〜70重量％，尤宜爲20〜 6 〇重量％。此時，該構成單位之含有率未滿]〇重量％時，所得的突起部之強度有降低的傾向，另一方面若超過 7 0重量％時，則所得的共聚物之保有安定性有降低的傾向。又’至於前述以外的不飽和單體（以下稱作「其他的不飽和單體」）’例如可舉出：（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、（甲基）丙烯酸正丙醋、（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）丙烯酸正十二基酯等 (甲基）丙烯酸烷基酯類；（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 ] 癸院-8-基、（甲基）丙烯酸2_三環（5.2.丨，6)癸 -12- (8) (8)200303430 烷-8 -基氧基乙基酯、（甲基）丙烯酸異佛爾酮基等（甲基 )丙烯酸環狀醚類；（甲基）丙烯酸苯基酯、（甲基）丙烯酸苄基酯等的（甲基）丙烯酸芳香酯類；（甲基）丙烯酸2 — 羥基酯、（甲基）丙烯酸2 -羥基丙酯等（甲基）丙烯酸羥烷基酯類；順丁烯二酸二酯、反丁烯二酸二乙酯、伊康酸二乙酯等不飽和二羧酸二酯類；苯乙烯、鄰甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、對-甲氧基苯乙烯、（甲基）丙烯腈、氯乙烯、偏二氯乙烯、（甲基）丙烯醯胺、 · 醋酸乙烯基酯、1，3- 丁二烯、異戊二烯、2，3-二甲基-1，3 · 丁二烯、N-苯基順丁烯二醯胺、環己基順丁烯二醯胺、N-苄基順丁烯二醯胺、N-琥珀醯亞胺基-3 -順丁烯二醯亞胺苯甲酸酯、N-琥珀醯亞胺基-4-順丁烯二醯亞胺丁酯、N-琥珀醯亞胺基-6-順丁烯二醯亞胺己酯、N-琥珀醯亞胺基-3 -順丁烯醯亞胺丙酯、N-(9-吖啶基）順丁烯二醯亞胺等。此等的其他不飽和單體係可單獨或混合2種以上使用。 # 至於共聚物（al)之其他的不飽和單體，由共聚合反應性、共聚物（a 1 )對鹼顯影液之溶解性等觀點宜爲甲基丙烯酸第三丁基酯、甲基丙烯酸三環[5.2.1.02’6]癸烷-8 -基、甲基丙烯酸正十二基酯、N-環己基順丁烯二醯亞胺、丙烯酸2-甲基環己酯、苯乙烯、對甲氧基苯乙烯、1，3 - 丁二烯等。於共聚物（a 1)，由其他不飽和單體而成的構成單位之含有率，宜爲1〇〜70重量％，尤宜爲20〜50重量％ -13- 200303430 Ο) 。此時在該構成單位之含有率爲1 〇重量％時’所得的共聚物之保存安定性有降低的傾向，另一方面若超過7〇重量％時，則所得的共聚物對鹼顯影液之溶解性有降低的傾向。至於突起用放射線敏感性組成物（甲）之共聚物 (a 1)之較宜例子，可舉出：甲基丙烯酸/甲基丙烯酸縮水甘油基酯/苯乙烯/甲基丙烯酸二環戊烷基共聚物、甲基丙烯酸/甲基丙烯酸縮水甘油基酯/對乙烯基苄基縮水甘油基醚/甲基丙烯酸二環戊烷基/苯乙烯共聚物、甲基丙烯酸/甲基丙烯酸縮水甘油基/苯乙烯/甲基丙烯酸二環戊烷基/1， 3 - 丁二烯/N-環己基順丁烯二醯亞胺共聚物、甲基丙烯酸/甲基丙烯酸縮水甘油基/對乙烯基苄基縮水甘油基醚/甲基丙烯酸二環戊烷基/甲基丙烯酸正十二烷基酯共聚物、甲基丙烯酸/甲基丙烯酸縮水甘油基酯/苯乙烯/ I，3 - 丁二烯/甲基丙烯酸二環戊烷基共聚物。又至於更宜者，可舉出甲基丙烯酸/甲基丙烯酸縮水甘油基酯/苯乙烯/甲基丙烯酸二環戊烷基共聚物、甲基丙烯酸/甲基丙烯酸縮水甘油基酯/對乙烯基苄基縮水甘油基醚/甲基丙烯酸二環戊烷基酯/苯乙烯共聚物 '甲基丙烯酸/甲基丙烯酸縮水甘油基酯/ 對乙烯基苄基縮水甘油基醚/甲基丙烯酸二環戊烷基酯/甲基丙烯酸正十二烷基酯共聚物。共聚物（al)之聚苯乙烯換算重量平均分子量（以下稱作「Mw」，宜爲2，000〜1〇〇，〇〇〇，較宜爲5，000〜 5 03 0 00。此時，共聚物（al)之Mw未滿2，000，組成物 (10) (10)200303430 之顯影性、圖案形狀有殘膜率降低，又所得的突起部之耐熱性有降低的傾向，另一方面若超過1 〇〇，〇〇〇時，則有形成突起之際的靈敏度、圖案形狀等降低的傾向。其次，至於1，2 -醌二疊氮化合物（b 1 )，例如可舉出1，2-苯並醌二疊氮磺酸酯、1，2-萘醌二疊氮磺酸酯、1，2-苯並醌二疊氮磺醯酯、1，2-萘醌二疊氮磺醯酯等，具體而言可舉出：2，3，4-三羥基苯二苯甲酮-1，2-萘醌疊氮-4-磺酸醌、2，3，4-三羥基二苯甲酮-1，2-萘酮二疊氮-5-磺酸酯、2，4，6-三羥基二苯甲酮-1，2-萘醌二疊氮-4-磺酸酯、2，4，6-三羥基二苯甲酮-1，2-萘醌疊氮· 4-磺酸酯、2，3，-三羥基二苯甲酮-1，2-萘醌二疊氮-5-磺酸酯、2，4，6-三羥基二苯甲酮-1，2-萘醌二疊氮-4-磺酸酯、2，4， 6-三羥基二苯甲酮-1，2-萘醌二疊氮-5-磺酸酯等三羥基二苯甲酮之1，2-萘醌二疊氮磺酸酯類； 2，2 ’，4，4 ’ -四羥基二苯甲酮-1，2-萘醌二疊氮-4-磺酸酯、2，2’，4，4、四羥基二苯甲酮· 1，2-萘醌二疊氮 -5 -磺酸酯、2，3，4，3 ’ -四羥基二苯甲酮-1 ，2-萘醌二疊氮-4-磺酸酯、2，3，4，3、四羥基二苯甲酮-1，2-萘醌二疊氮-5-磺酸酯、2，3，4，4、四羥基二苯甲酮-1，2-萘醌二疊氮-4-磺酸酯、2，3， 4，4、四羥基二苯甲酮· 1，2-萘醌二疊氮-5-磺酸酯、2，3，4，25 - 四羥基-4 ’ -甲基二苯甲酮-1，2 · 萘醌二疊氮-4-磺酸酯、2，3，4，2、四羥基-4、甲基二 -15 - (11) (11)200303430 苯甲酮-1，2-萘醌二疊氮-5-磺酸酯、2，3，4，4、四羥基-3、甲氧基二苯甲酮-1，2-萘醌二疊氮-4-磺酸酯、2，3，4，25-四羥基-4、甲基苯二甲酮-1，2-蔡醌二疊氮-5 -磺酸酯、2，3，4，2 四羥基-4 ’ -甲基苯二甲酮-1，2-萘醌二疊氮-4-磺酸酯、2，3，4， 4’-四羥基-3、甲氧基二苯曱酮-1，2-萘醌二疊氮-5-磺酸酯等的四羥基二苯甲酮之1，2-萘醌二疊氮磺酸酯類； ⑩ 2，3，4，2’，6’-五羥基二苯甲酮-1，2-萘醌二疊氮-4-磺酸酯、2，3，4，2，，6 ’ -五羥基二苯甲酮-1， 2-萘醌二疊氮-5-磺酸酯等五羥基二苯甲酮之I，2-萘醌二疊氮磺酸酯；2，4，6，3 5，4 ’，5、六羥基二苯甲酮-1，2-萘醌二疊氮-4-磺酸酯、2，4，6，3,，4,， 5 5 -六羥基二苯甲酮-1，2-萘醌二疊氮-5-磺酸酯、3 ，4，5，3 ’，4 ’，5 5 -六羥基二苯曱酮-1，2 -萘醌二疊氮-4 -磺酸酯、3，4，5，3 ’，4 ’，5 ’ ·六羥基二苯甲酮- · 1，2-萘醌二疊氮-5-磺酸酯等的六羥基二苯甲酮之1， 2-萘醌二疊氮磺酸酯類；雙（2，4-二羥基苯基）甲烷-1，2-萘醌二疊氮-4-磺酸酯、雙（2，4-二羥基苯基）甲烷-1，2-萘醌二疊氮-5-磺酸酯、雙（對羥基苯基）甲烷-1，2_萘醌二疊氮-4-磺酸酯、雙（對羥基苯基）甲烷-1，2-萘醌二疊氮-5-磺酸酯、三（對羥基苯基）甲烷-1，2_萘醌二疊氮-4-磺酸酯、三（對羥基苯基）甲烷-1，2-萘醌 -16- (12) (12)200303430 二疊氮-5 -磺酸酯、1，1，卜三（對羥基苯基）己烷-1 ，2-萘醌二疊氮-4-磺酸酯、1，1，1-三（對羥基苯基）己烷-1，2-萘醌二疊氮-5-磺酸酯、雙（2，3，4-三羥基苯基）甲烷-]，2-萘醌二疊氮-4-磺酸酯、雙 (2，3，4-三羥基苯基）甲烷-1，2-萘醌二疊氮-5-磺酸酯、2，2-雙（2，3，4-三羥基苯基）丙烷-1，2-萘醌二疊氮-4-磺酸酯、2，2-雙（2，3，4-三羥基苯基）丙烷-1，2-萘醌二疊氮-5-磺酸酯、1，1，3-參 (2，5-二甲基-4-羥基苯基）-3-苯基丙烷-1，2-萘醌二疊氮· 4-磺酸酯， 1，1，3-參（2，5-二曱基-4-經基苯基）-3-苯基丙烷-1，2-萘醌二疊氮 -5-磺酸酯、4，4、 [1- [4- [1- [4-羥基苯基]-1-甲基乙基]苯基]次乙]雙酚-1，2-萘醌二疊氮-4-磺酸酯、4，4、 [1- [4- [1- [4-羥基苯基]-1-甲基乙基]苯基]次乙]雙酚-]， 2-萘醌二疊氮-5-磺酸酯、雙（2，5-二甲基· 4-羥苯基）-2-羥基苯基甲烷-1，2-萘醌二疊氮-4-磺酸酯、雙（2，5-二甲基-4-羥基苯基）-2-羥基苯基甲烷-1，2-萘醌二疊氮-5-磺酸酯、3，3，3’，3、四甲基-1，1 5 -螺雙茚-5，6，7，5 ’，6 ’，75 -己醇-1，2_ 萘醌二疊氮-4-磺酸酯、3，3，3’，3’-四甲基-1，1、螺雙茚-5，6，7，5，，6，，7、己醇-1，2 -萘醌二疊氮-5-磺酸酯、2，2，4-三甲基-7，2’，45-三羥基黃烷-1，2-萘醌二疊氮-4-磺酸酯、2，2，4-三甲基-7，2’ -17- (13) (13)200303430 ，45-三羥基黃烷-1，2-萘醌二疊氮-5-磺酸酯等的（聚羥基苯基）烷之1，2 -萘醌二疊氮磺酸酯類等。至於1，2 -醌二疊氮化合物（b 1 )之較宜者，可舉出1，2-萘醌二疊氮磺酸酯。更宜可舉出1，2-萘醌二疊氮-5-磺酸酯。具體而言可舉出：2，3，4-三羥基二苯甲酮-1，2 -萘醌二疊氮-5 -磺酸酯、2，3，4，4 ’ -四羥基二苯甲酮-1，2-萘醌二疊氮-5-磺酸酯、1，1， 3-參（2，5-二甲基-4-羥基苯基）-3-苯基丙烷-1， 2-萘醌二疊氮-5-磺酸酯、4，4’- [1- [4- [1- [4-羥基苯基]-1-甲基乙基]苯基]次乙]雙酚-1，2-萘醌二疊氮-5-磺酸酯、2，6-雙 {雙（4-羥基-3-甲基苯基）甲烷} - 4-甲基酚-1，2-萘醌二疊氮-5-磺酸酯爲較宜的化合物。此等的1，2-醌二疊氮化合物（b 1 )係可單獨使用或混合二種以上使用。至於突起用放射線敏感性組成物（甲）之1，2-醌二疊氮化合物（bl)之使用量，對共聚物（al) 1〇〇重量份，宜爲5〜1〇〇重量份，尤宜爲10〜50重量份。此時1 ’ 2-醒一疊氮化合物（bl)之使用量未滿5重量份時，由曝光生成的酸之量變少，曝光部及未曝光部間對鹼顯影液的溶解度之差小，形成圖案變成困難，與環氧基之反應有關的酸之量變小，有較難獲得足夠的耐熱性及耐溶劑性之傾向，另一方面若超過1 0 0重量份時，曝光時間較短時，未反應的〗，2 -醌二疊氮化合物之殘有量變多，曝光 -18- (14) (14)200303430 部對鹼顯影液之溶解性降低，有顯影較困難之顧慮。再者’於突起用放射線敏感性組成物內，可配合感熱性酸生成化合物、聚合性不飽和單體（ci)，特定三聚氰胺化合物、環氧樹脂、接著助劑、界面活性劑等。前述感熱性酸生成化合物，係具有再使突起部之耐熱性或硬度提高的作用者，至於其具體例，可舉出氟化銻類，至於市售品可舉出 Sunaid SI- L80，Sunaid SI- L110、 SunaidSI-L150(以上，三新化學工業（股）製造）等。於突起用放射線敏感性組成物，感熱性酸生成化合物之使用量，對共聚物（a 1) 1 0 0重量份，宜爲2 0重量份以下，較宜爲5重量份以下。此時，感熱性酸生成化合物之使用量若超過2 0重量份時，則析出物變成容易發生，有圖案形成成爲困難之顧慮。又，至於前述聚合性不飽和單體（cl)，例如宜爲單官能（甲基）丙烯酸酯類、二官能（甲基）丙烯酸酯類或三官能以上的（甲基）丙烯酸酯類。至於前述單官能（甲基）丙烯酸酯類、例如（甲基）丙烯酸2 -羥乙酯、（甲基）丙烯酸卡必醇酯、（甲基）丙烯酸異冰片醇酯、（甲基）丙烯酸3 -甲氧丁酯、對苯二甲酸2-(甲基）丙烯醯氧基乙基-2- 2-羥丙基酯等，至於市售品，例如可舉出All Μ- 1 01，Alio nix Μ- 1 1 1 、Allonix Μ- 1 14 (以上，東亞合成（股）製造）、ΚΑΥΑ RADTC- 1 ] OS，KAYARADTC- 120S (以上日本化藥（股）製造），Biskote- 158、Biskote 23 1 1 (以上，大阪有機化 (15) (15)200303430 學工業（股）製造）等。又’至於則述二官能（甲基）丙烯酸酯類、例如可舉出（甲基）丙烯酸乙二醇酯、二（甲基）丙烯酸1，6_ 己二醇酯、二（甲基）丙烯酸1，9 -壬二醇酯、二（甲基）丙烯酸多元丙二醇酯、二（甲基）丙烯酸四乙二醇酯、二丙燒酸雙苯氧乙醇芴酯等。至於市售品，例如可舉出 Allonix M- 210、Allonix M- 240、Allonix M- 6200 (以上’東亞合成（股）製造），KAYARADHDDA、 KAYARAD HX- 220、KAYARAD R· 604 (以上，日本化藥 (股）製造）、Biskote 260、Biskote 3 12、Biskote 3 3 5HP (以上，大阪有機化學工業（股）製造）等。又至於前述三官能以上的（甲基）丙烯酸酯，例如可舉出三（甲基）丙烯酸三羥甲基丙烷酯、三（甲基）丙烯酸異戊四醇酯、四（甲基）丙烯酸異戊四醇酯、五（甲基）丙烯酸二異戊四醇酯、六（甲基）丙烯酸二異戊四醇酯、磷酸三[(甲基）丙烯醯氧乙基]酯等，或至於市售品，例如可舉出 Allonix M- 3 09、Allonix M- 400、 Allonix Μ- 4 0 5、Allonix Μ - 4 5 0、Allonix Μ- 7100、200303430 (1) Description of the invention [Technical field to which the invention belongs] The present invention relates to a semi-transmissive color filter, a radiation-sensitive composition used in forming a coloring layer of the semi-transmissive furnace color sheet, and the semi-transmissive color filter. A color liquid crystal display element made of a transmissive color filter. ^ [Prior technology] For a long time, liquid crystal displays have been used to ensure uniform day-to-day brightness, and those with backlights have become the mainstream. However, with the popularization of mobile terminals in recent years, reflective liquid crystal displays that require additional light sources are Increasing. However, the environment in which these liquid crystal displays can be used is limited. That is, a liquid crystal display that has a backlight is suitable for indoor or night use. However, if it is used in a place where there is a lot of outside light, such as daytime and outdoor, it becomes 'difficult to see the daytime surface.' Although the liquid crystal display is suitable for use in places where there is sufficient light from the outside, such as during the day and outdoors, it does not get enough brightness indoors or at night, and the picture becomes ugly. In view of this, in recent years, in accordance with the use environment, as for a liquid crystal display that can provide moderate screen brightness, backlight can ensure human brightness in a dark place, and it also acts as a reflective display in an environment with sufficient light sources | "Semi-transmissive" liquid crystal displays have been proposed. However, 'for transflective liquid crystal displays, when using a backlight, in order to use a reflective type that uses a light source from the outside, there are so-called problems with the brightness or color purity of the daylight surface, which can solve this problem' The method of manufacturing -6- (2) (2) 200303430 each of the color filters, and a radiation-curable coloring composition that can be suitably used for these are unknown. In addition, when a transflective liquid crystal display is used in a digital camera or the like, it is usually sufficient if the composition of the subject can be confirmed when shooting outdoors. Therefore, color purity is not a problem. Although brightness is important, When viewing the captured image, light is more commonly used indoors, which means that it requires higher color purity than when shooting. Therefore, if such a situation is also taken into consideration, it is necessary to maintain the degree of daylight or the color purity at approximately the same level, and when the backlight is used and when it is used as a reflective type, the color purity can be arbitrarily adjusted. Color purity is required when using a backlight. However, in the conventional semi-transmissive liquid crystal display, such requirements have not been fully fulfilled. [Summary of the invention] The purpose of the present invention is to provide a reduction in the coloring layer in the light reflection field [I] and the light transmission field [II] reduction is possible, when using backlight and when using as a reflective type The color purity can be made approximately the same, and the transflective color filter can improve the color purity when using a backlight. Another object of the present invention is to provide a radiation-sensitive composition for forming protrusions of the transflective color filter of the present invention. Still another object of the present invention is to provide a radiation-sensitive composition for forming a colored layer of a transflective color filter of the present invention. Still another object of the present invention is to provide a color liquid crystal display element including the transflective color filter (3) and (3) 200303430 pieces of the present invention. Still another object and advantages of the present invention will be apparent from the following description. According to the present invention, the foregoing object is achieved first by using a semi-transmissive color filter, which is formed by forming a protrusion portion and a coloring layer on a substrate, and the protrusion portion has light reflection. And the colored layer is characterized by forming a surface that covers the protruding portion and the remaining substrate. According to the present invention, the foregoing object is achieved by the second application of the radiation-sensitive composition for forming protrusions on a transflective color filter in any one of the scope of claims H1 to 3 of the patent application. The radiation-sensitive composition is a copolymer of (a) containing (a 1) an unsaturated carboxylic acid and / or an unsaturated polycarboxylic acid anhydride, an unsaturated monomer containing an epoxy group, and an unsaturated monomer other than the foregoing. , And (b 1) 1,2-quinonediazide radiation-sensitive composition, and ® (B) consisting of (a2) unsaturated carboxylic acid and / or unsaturated polycarboxylic anhydride and epoxy containing It is characterized by a copolymer selected from unsaturated monomers and unsaturated monomers other than the foregoing, and at least one selected from the group of (b2) a radiation-sensitive polymerization initiator and (c2) a radiation-sensitive composition of an unsaturated monomer. . According to the present invention, the foregoing object is achieved by the third radiation-sensitive composition used for forming the colored layer of the transflective color filter. -8- (4) (4) 200303430 This radiation-sensitive composition system It is characterized by containing (A) a colored layer, (B) a soluble resin, (C) a polyfunctional monomer, (D) a photopolymerization initiator, and (E) a solvent. According to the present invention, the foregoing object is achieved by a fourth color liquid crystal display element. The color liquid crystal display element is provided with a projection portion and a coloring layer formed on a substrate. The projection portion has a light reflecting layer and the The colored layer is formed by forming a semi-transmissive color filter that covers the surface of the protrusion and the remaining substrate. [Embodiment] The present invention will be described in detail below. In the transflective color filter of the present invention, the light reflection layer on the protrusion may be formed on the surface of the protrusion, or may be formed on the bottom (that is, between the protrusion and the substrate). When the light reflection layer is formed on the surface of the protrusion, each of the protrusions may be transparent, translucent, or opaque. However, when the light reflection layer is formed on the bottom of the protrusion, each of the protrusions must be Transparent. The colored layer is formed on the surface of the substrate other than the area where the protruding portion is covered and the protruding portion is formed. Radiation-sensitive composition for protrusion As for the material used to form the protrusion of the transflective color filter of the present invention (hereinafter referred to as "radiation-sensitive composition for protrusion"), the adhesion to the substrate, the strength, Those who are superior in heat resistance, solubility resistance, shape control, etc., and whose protrusions do not swell or deform when forming a colored layer, are expected by people-9- (5) (5) 200303430. As for a preferable example, (a) the unsaturated monomer containing (al) an unsaturated carboxylic acid and / or an unsaturated polycarboxylic acid, an unsaturated monomer containing an epoxy group, and an unsaturated monomer other than the foregoing Copolymer, and (b 1) 1,2-quinonediazide compound radiation-sensitive composition (hereinafter referred to as "radiation-sensitive composition for protrusion (A)") and (B) containing (a2) Copolymers of saturated carboxylic acids and / or unsaturated polycarboxylic anhydrides, unsaturated monomers containing epoxy groups and unsaturated monomers other than the foregoing, and (b2) a radiation-sensitive polymerization initiator and (c: 2) Radiation-sensitive composition of unsaturated monomer (hereinafter referred to as "radiation-sensitive composition for protrusions (B)"). A colored radiation-sensitive composition to be described later may also be used to form protrusions. These radiations The composition system can also be used for the formation of protrusions. These radiation-sensitive compositions can be used alone or as a mixture of two or more. The radiation-sensitive composition for protrusions (a) and the radiation-sensitive composition for protrusions (the ).-Radiation sensitive composition (A) for protrusions-(al) unsaturated carboxylic acid and / or unsaturated polycarboxylic acid anhydride and unsaturated compound containing epoxy group for radiation sensitive composition (A) for protrusions Copolymers with olefin-based unsaturated compounds other than the above (hereinafter referred to as "copolymer a 1"). Examples of the unsaturated carboxylic acid include unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic acid, fumaric acid, itaconic acid, etc. These di-saturated carboxylic acids can be used alone or in combination Two kinds of -10- (6) (6) 200303430 or more are used. As for the unsaturated polycarboxylic acid anhydride, for example, maleic anhydride, maleic anhydride, itaconic anhydride, etc. The saturated polycarboxylic acid anhydrides can be used alone or as a mixture of two or more. As for the unsaturated carboxylic acid and unsaturated polycarboxylic acid anhydride of the copolymer (a 1), acrylic acid, methacrylic acid, and maleic anhydride can be copolymerized and reacted. The viewpoint of the solubility of alkali developer and its easy access In the copolymer (al), the content rate of the constituent unit composed of unsaturated carboxylic acid and / or unsaturated polycarboxylic anhydride is preferably 5 to 40% by weight, and particularly preferably 10 to 30% by weight. At this time, the content of the constituent unit is less than 5% by weight, and the solubility of the obtained copolymer in the alkali microfluid tends to decrease. On the other hand, if it exceeds 40% by weight, the obtained copolymer is resistant to alkali. The solubility of the developer tends to become too large. Examples of the unsaturated monomer containing an epoxy group include glycidyl (meth) acrylate, glycidyl α-ethylacrylate, and ^ -n Glycidyl acrylate, α-glycidyl n-butyrate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, α- 6,7-epoxyheptyl ethacrylate, 3 / 3-methyl glycidyl (meth) acrylate, 3/3 ethyl glycidyl (meth) acrylate, (meth) acrylic acid -/ 3 · propyl glycidyl ester, α-ethyl acrylic acid- / 3-methyl glycidyl ester, ( (Meth) acrylic acid 3-methyl-3,4-epoxybutyl ester, (meth) acrylic acid 3-ethyl-3,4-epoxybutyl ester, (meth) acrylic acid 4- Methyl-4,5-epoxypentyl ester, (-11-(7) (7) 200303430 meth) acrylic acid 5-methyl-5,6-epoxyhexyl ester, 3-ethyl_nitrogen Heterocycloalkyl (meth) acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinyl glycidyl ether, and the like. These epoxy-containing unsaturated monosystems can be used alone or in combination of two or more. From the viewpoints of copolymerization (al) containing epoxy-based unsaturated monomers, copolymerization reactivity, strength of the obtained protrusions, etc., it is preferably (meth) glycidyl acrylate, methacrylic acid-6, 7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like. In the copolymer (a 1), the content rate of a constituent unit made of an unsaturated monomer containing an epoxy group is preferably 10 to 70% by weight, and particularly preferably 20 to 60% by weight. At this time, when the content rate of the constituent unit is less than 0% by weight, the strength of the obtained protrusions tends to decrease. On the other hand, when it exceeds 70% by weight, the stability of the obtained copolymer is reduced. Propensity. As for the "unsaturated monomers other than the above (hereinafter referred to as" other unsaturated monomers "), for example, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid may be mentioned. N-propyl ester, n-propyl methacrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, n-dodecyl (meth) acrylate (Meth) acrylic acid alkyl esters; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclic methacrylic acid [5.2. 1. 02 '6] decyl Yuan-8-yl, 2-tricyclic (meth) acrylic acid (5.2. 丨, 6) dec-12- (8) (8) 200303430 alkyl-8-yloxyethyl ester, (meth) acrylic acid isopropyl (Meth) acrylic cyclic ethers such as furfuryl; aromatic (meth) acrylic esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; (meth) acrylic acid 2 — Hydroxyl esters, 2-hydroxypropyl (meth) acrylate, and other hydroxyalkyl (meth) acrylates; maleic acid diesters, diethyl fumarate Unsaturated dicarboxylic acid diesters such as diethyl iconate; styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, (meth) propylene Nitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3, butadiene Diene, N-phenyl-cis-butene-diamine, cyclohexyl-cis-butenedi-amidamine, N-benzyl-cis-butenedi-amidamine, N-succinimide-imino-3 -cis-butenedi-fluorene Aminobenzoate, N-succinimidylimide-4-cis-butenedifluorene butylimide, N-succinimidylimino-6-cis-butenedifluorene iminohexyl ester, N-succinimidine Imino-3 -cis-butenefluorenimine propyl, N- (9-acridyl) cis-butenedifluorenimide and the like. These other unsaturated monomers can be used alone or in combination of two or more. # As for the other unsaturated monomers of the copolymer (al), from the viewpoints of copolymerization reactivity and the solubility of the copolymer (a 1) in an alkali developing solution, the third butyl methacrylate and methacrylic acid are preferred. Tricyclo [5.2.1.02'6] decane-8-yl, n-dodecyl methacrylate, N-cyclohexylcis-butenediamidoimide, 2-methylcyclohexyl acrylate, styrene, para- Methoxystyrene, 1,3-butadiene, etc. In the copolymer (a 1), the content rate of the constituent units made of other unsaturated monomers is preferably 10 to 70% by weight, and more preferably 20 to 50% by weight (-13 to 200303430). At this time, when the content rate of the constituent unit is 10% by weight, the storage stability of the obtained copolymer tends to decrease. On the other hand, when the content exceeds 70% by weight, the obtained copolymer is resistant to the alkali developer. The solubility tends to decrease. Preferred examples of the copolymer (a 1) of the radiation-sensitive composition (a) for protrusions include methacrylic acid / glycidyl methacrylate / styrene / dicyclopentyl methacrylate Copolymer, methacrylic acid / glycidyl methacrylate / p-vinylbenzyl glycidyl ether / dicyclopentyl methacrylate / styrene copolymer, methacrylic acid / glycidyl methacrylate / Styrene / dicyclopentyl methacrylate / 1,3-butadiene / N-cyclohexyl cis butylene diimide copolymer, methacrylic acid / glycidyl methacrylate / p-vinylbenzyl Glycidyl ether / dicyclopentyl methacrylate / n-dodecyl methacrylate copolymer, methacrylic acid / glycidyl methacrylate / styrene / I, 3-butadiene / methyl Acrylic acid dicyclopentyl copolymer. More suitable ones include methacrylic acid / glycidyl methacrylate / styrene / dicyclopentyl methacrylate copolymer, methacrylic acid / glycidyl methacrylate / p-vinyl Benzyl glycidyl ether / dicyclopentyl methacrylate / styrene copolymer 'methacrylic acid / glycidyl methacrylate / p-vinyl benzyl glycidyl ether / dicyclopentyl methacrylate Alkyl ester / n-dodecyl methacrylate copolymer. The polystyrene-equivalent weight average molecular weight of the copolymer (al) (hereinafter referred to as "Mw") is preferably 2,000 to 10,000, and more preferably 5,000 to 5 03 00. At this time, The Mw of the copolymer (al) is less than 2,000, the developability and pattern shape of the composition (10) (10) 200303430 are reduced, and the heat resistance of the obtained protrusions tends to decrease. When it exceeds 100,000, there is a tendency that sensitivity, pattern shape, etc., at the time of forming a protrusion are lowered. Next, as for the 1,2-quinonediazide compound (b 1), for example, 1, 2-benzoquinonediazidesulfonate, 1,2-naphthoquinonediazidesulfonate, 1,2-benzoquinonediazidesulfonyl ester, 1,2-naphthoquinonediazidesulfonium Examples of the esters include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azide-4-sulfonic acid quinone, and 2,3,4-trihydroxybenzophenone. Keto-1,2-naphthone diazide-5-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,4 1,6-trihydroxybenzophenone-1,2-naphthoquinone azide 4-sulfonate, 2,3, -trihydroxybenzophenone-1 2-naphthoquinonediazide-5-sulfonate, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,4,6-tris 1,2-naphthoquinonediazide sulfonates such as hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate; 2,2 ', 4, 4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,2 ', 4,4, tetrahydroxybenzophenone Nitrogen-5 -sulfonate, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,3, tetrahydroxy Benzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4, tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid Ester, 2,3,4,4, tetrahydroxybenzophenone, 1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,25-tetrahydroxy-4'-methyldi Benzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,2, tetrahydroxy-4, methyldi-15-(11) (11) 200303430 Benzophenone- 1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4, tetrahydroxy-3, methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonate Acid ester, 2,3,4,25-tetrahydroxy-4, methylbenzophenone-1,2-caequinonediazide-5 -sulfonate, 2,3,4,2 tetrahydroxy-4'-methyl Benzophenone-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,4'-tetrahydroxy-3, methoxybenzophenone-1,2-naphthoquinone 1,2-naphthoquinonediazide sulfonates such as diazide-5-sulfonate; ⑩ 2,3,4,2 ', 6'-pentahydroxybenzophenone Keto-1,2-naphthoquinonediazide-4-sulfonate, 2,3,4,2,, 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate 1,2-naphthoquinonediazide sulfonates such as pentahydroxybenzophenone; 2,4,6,3 5,4 ', 5, hexahydroxybenzophenone-1,2-naphthoquinone Diazide-4-sulfonate, 2,4,6,3,, 4,, 5 5-Hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 3, 4,5,3 ', 4', 5 5 -Hexahydroxybenzophenone-1,2-naphthoquinonediazide-4 -sulfonate, 3,4,5,3 ', 4', 5 ' · Hexahydroxybenzophenone-· 1,2-naphthoquinonediazide-5-sulfonate, such as 1,2-naphthoquinonediazide, bis (2 , 4-Dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5 -Sulfonate, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5 -Sulfonate, tris (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonate, tris (p-hydroxyphenyl) methane-1,2-naphthoquinone-16- (12 ) (12) 200303430 Diazide-5 -sulfonate, 1,1,3-tris (p-hydroxyphenyl) hexane-1,2-naphthoquinonediazide-4-sulfonate, 1,1, 1-tri (p-hydroxyphenyl) hexane-1,2-naphthoquinonediazide-5-sulfonate, bis (2,3,4-trihydroxyphenyl) methane-], 2-naphthoquinonedi Azide-4-sulfonate, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonate, 2,2-bis (2,3, 4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonate, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinone Diazide-5-sulfonate, 1,1,3-ginseng (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone di Nitrogen 4-sulfonate, 1,1,3-ginseng (2,5-diamidino-4-merylphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5- Sulfonate, 4,4, [1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol-1,2-naphthoquinonediazide -4-sulfonate, 4,4, [1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol-], 2-naphthoquinone Diazide-5-sulfonate, bis (2,5-dimethyl · 4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonate, Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonate, 3,3,3 ', 3,4 Methyl-1,1 5 -spirobisindene-5,6,7,5 ', 6', 75-hexanol-1,2-naphthoquinonediazide-4-sulfonate, 3,3,3 ' , 3'-tetramethyl-1,1, spirobisindene-5,6,7,5,6,7, hexanol-1,2-naphthoquinonediazide-5-sulfonate, 2 , 2,4-trimethyl-7,2 ', 45-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonate, 2,2,4-trimethyl-7,2 '-17- (13) (13) 200303430, 45-trihydroxyflavane-1,2-naphthoquinonediazide-5-sulfonate, etc. ( Hydroxyphenyl) alkane of 1,2 - naphthoquinone diazide sulfonate esters and the like. As a preferable one of the 1,2-quinonediazide compounds (b 1), 1,2-naphthoquinonediazide sulfonate can be mentioned. More preferably, 1,2-naphthoquinonediazide-5-sulfonate is mentioned. Specific examples include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone Keto-1,2-naphthoquinonediazide-5-sulfonate, 1,1,3-ginseng (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1, 2 -Naphthoquinonediazide-5-sulfonate, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylene] bisphenol 1,2-naphthoquinonediazide-5-sulfonate, 2,6-bis {bis (4-hydroxy-3-methylphenyl) methane}-4-methylphenol-1,2-naphthalene Quinonediazide-5-sulfonate is a preferred compound. These 1,2-quinonediazide compounds (b 1) can be used alone or in combination of two or more. As for the usage amount of the 1,2-quinonediazide compound (bl) of the radiation-sensitive composition (a) for protrusions, it is preferably 100 parts by weight to the copolymer (al), and preferably 5 to 100 parts by weight. It is particularly preferably 10 to 50 parts by weight. At this time, when the amount of 1 ′ 2-azide compound (bl) is less than 5 parts by weight, the amount of acid generated by exposure will decrease, and the difference in solubility between the exposed and unexposed parts to the alkali developer will be small. It becomes difficult to form a pattern, the amount of the acid related to the reaction of the epoxy group becomes small, and it is difficult to obtain sufficient heat resistance and solvent resistance. On the other hand, if it exceeds 100 parts by weight, the exposure time is short. Unreacted, the residual amount of the 2-quinonediazide compound increases, and the solubility of the alkali developing solution is lowered by exposure -18- (14) (14) 200303430, which may cause difficulty in development. Furthermore, in the radiation-sensitive composition for protrusions, a thermo-acid generating compound, a polymerizable unsaturated monomer (ci), a specific melamine compound, an epoxy resin, an adhesive, a surfactant, and the like can be blended. The above-mentioned thermosensitive acid generating compound has the effect of further increasing the heat resistance or hardness of the protrusions. Specific examples thereof include antimony fluoride, and commercially available products include Sunaid SI-L80 and Sunaid SI. -L110, SunaidSI-L150 (above, manufactured by Sanxin Chemical Industry Co., Ltd.), etc. The amount of the radiation-sensitive composition for the protrusion and the thermo-acid-forming compound is 100 parts by weight of the copolymer (a 1), preferably 20 parts by weight or less, and more preferably 5 parts by weight or less. At this time, if the amount of the thermo-acid-generating compound used exceeds 20 parts by weight, precipitates tend to occur, and there is a concern that pattern formation becomes difficult. The polymerizable unsaturated monomer (cl) is preferably, for example, a monofunctional (meth) acrylate, a difunctional (meth) acrylate, or a trifunctional or higher (meth) acrylate. As for the aforementioned monofunctional (meth) acrylates, for example, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3 (meth) acrylate -Methoxybutyl ester, 2- (meth) acryloxyethyl-2- 2-hydroxypropyl terephthalate, etc. As for commercially available products, for example, All M-1 01, Alio nix Μ-1 1 1, Allonix Μ-1 14 (above, manufactured by Toa Kosei Co., Ltd.), ΚΑΥΑ RADTC- 1] OS, KAYARADTC- 120S (above manufactured by Nippon Kayaku Co., Ltd.), Biskote- 158, Biskote 23 1 1 (above, Osaka Organic Chemicals (15) (15) 200303430, Manufacturing by Industrial Co., Ltd.), etc. As for the difunctional (meth) acrylates, for example, ethylene glycol (meth) acrylate, hexamethylene di (meth) acrylate, and di (meth) acrylic acid 1 may be mentioned. , 9-nonanediol, poly (propylene) di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol dipropionate, and the like. As for commercially available products, for example, Allonix M-210, Allonix M-240, Allonix M- 6200 (above 'East Asia Synthetic Co., Ltd.'), KAYARADHDDA, KAYARAD HX- 220, KAYARAD R · 604 (above, Japanese Pharmaceutical (stock) manufacturing), Biskote 260, Biskote 3 12, 12, Biskote 3 3 5HP (above, manufactured by Osaka Organic Chemical Industry (Stock)), etc. As for the trifunctional or higher (meth) acrylate, for example, trimethylolpropane tri (meth) acrylate, isopentaerythritol tri (meth) acrylate, and iso (tetra (meth) acrylate) Pentaerythritol ester, diisopentaerythritol penta (meth) acrylate, diisopentaerythritol (meth) acrylate, tri [(meth) acryloxyethyl] phosphate, etc., or as Examples of the product include Allonix M-3 09, Allonix M-400, Allonix Μ-405, Allonix Μ-4450, Allonix Μ-7100,

Allonix Μ- 8030、Allonix Μ· 8060 (以上，東亞合成（股 ) 製）， KAYARADTMPTA ， KAYARADDPHA 、 KAYARADDPCA- 20 、 KAYARADDPCΑ- 30 、 KAYARADDPCA- 60、 KAYARADDPCΑ- 120 (以上，日本化藥（股）製），Biskote 295、Biskote 300、Biskote 3 60、Biskote GPT，Biskote 3PA、Biskote 400 (以上，大 (16) 200303430 阪有機化學工業（股）製造）等。此等聚合性不飽和單體（c 1 )可單獨或混合2種以上使用。於突起用放射線敏感性組成物（甲），聚合性不飽和單體（cl)之使用量，對共聚物（ai) 100重量份，宜爲 5 〇重量份以下，較宜爲3 0重量份以下。藉由以此量使用聚合性不飽和單體，可更使所得的突起部之耐熱性、強度等提高。 .於突起用放射線敏感性組成物（甲），再者可含有一種以上以下式（1)或下式（2)表示的化合物（以下稱作「特定三聚氰胺衍生物」）。Allonix M-8030, Allonix M · 8060 (above, manufactured by East Asia Synthesis), KAYARADTMPTA, KAYARADDPHA, KAYARADDPCA-20, KAYARADDPCΑ-30, KAYARADDPCA-60, KAYARADDPCΑ-120 (above, manufactured by Nippon Kayaku Co., Ltd.) , Biskote 295, Biskote 300, Biskote 3 60, Biskote GPT, Biskote 3PA, Biskote 400 (above, large (16) 200303430 manufactured by Hankoku Chemical Industry Co., Ltd.), etc. These polymerizable unsaturated monomers (c 1) can be used singly or in combination of two or more kinds. The amount of the radiation-sensitive composition (a) for the protrusion and the polymerizable unsaturated monomer (cl) is 100 parts by weight of the copolymer (ai), preferably 50 parts by weight or less, and more preferably 30 parts by weight the following. By using the polymerizable unsaturated monomer in this amount, the heat resistance, strength, and the like of the obtained protrusion can be further improved. The radiation-sensitive composition (a) for protrusions may further contain one or more compounds represented by the following formula (1) or formula (2) (hereinafter referred to as "specific melamine derivatives").

(式內’ R1〜R6係表示相互獨立的氫原子或基_CH2〇r φ R表示氫原子或碳數1〜6之直鏈狀或枝鏈狀的烷基）(In the formula, 'R1 to R6 represent mutually independent hydrogen atoms or groups —CH2〇r φ R represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms]

，R7〜RlG係表示相互獨立的氫原子或基 R表不氫原子或碳數〗〜6之直鏈狀或枝鏈狀的, R7 ~ RlG represent independent hydrogen atoms or radicals. R represents a hydrogen atom or a carbon number. Straight chain or branched chain of ∼6.

(式內，R7〜R -CH2〇R， -21 - (17) (17)200303430 烷基）。至於特定三聚氰胺衍生物，例如可舉出：六甲氧基羥甲基三聚氰胺、六正丁氧基羥曱基三聚氰胺、以二者之合計甲氧基羥甲基及正丁氧基羥甲基間之雙方具有六個的六烷氧基三聚氰胺類；將屬於前述六烷氧基羥甲基三聚氰胺類化合物中的烷氧基羥甲基之一部分取代成羥甲基的化合物；將屬於前述六烷氧基羥甲基三聚氰胺類之化合物中的烷氧基羥甲基之一部分取代成氫原子的化合物；四甲氧基羥甲基苯胍，將四甲氧基羥甲基苯胍等甲氧基羥甲基之一部分取代成羥甲基的化合物；將四甲氧基羥甲基苯胍等甲氧基羥甲基之一部分取代成氫原子的化合物等。又，至於特定三聚氰胺衍生物之市售品，例如可舉出 Cy mel 300、301、303、370、325 > 327、701、266、267 、238、 1141、 272' 202、 1156、 1158、 1123、 ]17〇、 1 174、UFR 65、3 00 (以上，三井氰胺（股）製造）、(In the formula, R7 ~ R-CH2OR, -21- (17) (17) 200303430 alkyl). As for the specific melamine derivative, for example, hexamethoxymethylol melamine, hexa-n-butoxyhydroxymethyl melamine, a total of methoxymethylol and n-butoxymethylol may be mentioned. A compound having six hexaalkoxymelamines on both sides; a compound in which one part of the alkoxymethylol group in the aforementioned hexaalkoxymethylolmelamine compound is partially replaced with a methylol group; the compound belonging to the aforementioned hexaalkoxy A compound in which a part of an alkoxymethylol group in a methylolmelamine compound is partially substituted with a hydrogen atom; a tetramethoxymethylol benzoguanidine, or a methoxymethylol such as a tetramethoxymethylol benzoguanidine Compounds in which one part of a group is substituted into a methylol group; compounds in which one part of a methoxymethylol group such as tetramethoxyhydroxymethylbenzoguanidine is replaced with a hydrogen atom, and the like. As for the commercially available products of specific melamine derivatives, for example, Cy mel 300, 301, 303, 370, 325 > 327, 701, 266, 267, 238, 1141, 272 '202, 1156, 1158, 1123 ,] 17〇, 1 174, UFR 65, 3 00 (above, made by Mitsui Cyanoamide (stock)),

Nikalac Mx- 750、- 032、- 706、· 708、- 40、 31'Nikalac Mx- 750,-032,-706, · 708,-40, 31 '

Nilcalac Ms- 11、Nikalac Mw- 30 (以上’（股）二和化學公司製造）等。此等特定三聚氰胺衍生物，係可單獨或混合=種以上使用。於突起用放射線敏感性組成物，特定三聚氰胺衍生物之使用量，對共聚物（a 1) 1 0 0重量份，宜爲1〜〗〇〇重量份，尤宜爲5〜5 0重量份。藉由將特定三聚氰胺衍生物之使用量設成此範圍，可形成良好的形狀之突起部，可 -22- (18) (18)200303430 得表示出對鹼顯影液之適當的溶解性之突起用放射線敏感性組成物（甲）。又，至於前述之環氧樹脂，若爲可與突起用放射線敏感性組成物（甲）中的其他構成成分相溶時，則未予特別限制者。宜爲可舉出雙酚A型環氧樹脂、酚酚醛淸漆型環氧樹脂、甲酚酚醛型環氧樹脂、環狀脂肪族環氧樹脂、縮水甘油基酯型環氧樹脂、縮水甘油基胺型環氧樹脂、雜環式環氧基樹脂、已共聚合甲基丙烯酸縮水甘油基酯的樹脂等。此等環氧樹脂係可單獨或混合二種以上使用。前述環氧樹脂之中，宜爲雙酚A型環氧樹脂、甲酚酚醛淸漆型環氧樹脂、縮水甘油基酯型環氧樹脂等。於突起用放射線敏感性組成物（甲）、環氧樹脂之使用量，對共聚物（a〗）100重量份，宜爲30重量份以下。藉由以此量含有環氧樹脂，可再使由各該突起用放射線敏感性組成物（甲）而得的突起部之耐熱性、強度等提高。又，至於前述接著助劑，例如可舉出具有羧基、甲基丙烯醯基、異氰酸酯基、環氧基等反應性官能基之矽烷偶合劑，至於其具體例，可舉出三甲氧基甲矽基安息香酸、甲基丙烯氧基丙基三甲氧基矽烷。乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、r -異氰酸基丙基三乙氧基矽烷、r -縮水丙氧基丙基三甲氧基矽烷、/3 - (3，c環氧基環己基）乙基三甲氧基矽烷等。此等矽烷偶合劑係可單獨或混合二種以上使用。於突起用放射線敏感性組成物（甲），接著助劑之使 - 23- (19) (19)200303430 用量’對共聚物（a 1 ) 1 0 0重量份，宜爲2 0重量份以下，尤宜爲1 〇重量份以下。此時，接著助劑之使用量若超過 20重量份時，則有顯影殘存成爲容易生成的傾向。再者’前述界面活性劑，係具有再使突起用放射線敏感性組成物（甲）之塗布性提高的作用之成分，至於其例，可舉出氟系界面活性劑及矽氧系界面活性劑。至於前述氟系界面活性劑，宜爲於終端、主鏈及側鏈之至少任一部位上具有氟烷基或氟伸烷基之化合物。至於其具體例，可舉出：1，1，2，2-四氟辛基（1，1，2, 2_四氟丙基）醚、1，1，2，2-四氟辛基己基醚、八乙二醇二（1，1，2，2-四氟丁基）醚、六乙二醇（〗，；! ，2，2，3，3 -六氟戊基）醚、八丙二醇二（1，1，2， 2-四氟丁基）醚、六丙二醇二（1，1，2，2，3，3-六氟戊基）醚、全氟十二烷基磺酸鈉、1，1，2，2，8，8， 9，9，10，10-十氟十二烷、1，1，2，2，3，3-六氟癸烷、氟烷基苯磺酸鈉、氟烷基磺酸鈉、氟烷基羧酸鈉、氟烷基聚環氧乙烷醚、二丙三醇肆（氟烷基聚環氧乙烷醚）、碘化氟烷基銨' 氟烷基甜菜鹼、氟烷基聚環氧乙烷醚、全氟烷基聚氧基乙醇、全氟烷基烷氧鹽、氟系烷基酯等。又’至於細；系界面活性劑Z巾售品，例如可舉出： BM- 1000、BM- 1100 (以上，BM化學公司製造）、Nilcalac Ms-11, Nikalac Mw- 30 (above the '(share) manufactured by Erwa Chemical Co., Ltd.), etc. These specific melamine derivatives can be used alone or in combination. For the radiation-sensitive composition for protrusions, the specific amount of the melamine derivative to be used is 100 parts by weight of the copolymer (a 1), preferably 1 to 〖00 〇, and particularly preferably 5 to 50 parts by weight. By setting the amount of the specific melamine derivative to be in this range, a protrusion having a good shape can be formed. The protrusion can be used for -22- (18) (18) 200303430 to show the proper solubility of the alkali developer. Radiation-sensitive composition (a). The epoxy resin is not particularly limited as long as it is compatible with other constituents in the radiation-sensitive composition (A) for protrusions. Preferable examples include bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, and glycidyl group. Amine-type epoxy resins, heterocyclic epoxy resins, resins copolymerized with glycidyl methacrylate, and the like. These epoxy resins can be used alone or in combination of two or more. Among the aforementioned epoxy resins, bisphenol A type epoxy resin, cresol novolac type epoxy resin, glycidyl ester type epoxy resin and the like are preferred. The amount of the radiation-sensitive composition (a) and epoxy resin used for the protrusion is preferably 30 parts by weight or less based on 100 parts by weight of the copolymer (a). By containing the epoxy resin in such an amount, the heat resistance, strength, and the like of the protrusions obtained from the radiation-sensitive composition (a) for each protrusion can be further improved. Moreover, as said adhesive agent, the silane coupling agent which has reactive functional groups, such as a carboxyl group, a methacryl group, an isocyanate group, and an epoxy group, is mentioned, for example, Trimethoxysilyl is mentioned as a specific example. Benzoic acid, methacryloxypropyltrimethoxysilane. Vinyltriethoxysilane, vinyltrimethoxysilane, r-isocyanatopropyltriethoxysilane, r-glycidoxypropyltrimethoxysilane, / 3-(3, c ring Oxycyclohexyl) ethyltrimethoxysilane and the like. These silane coupling agents can be used alone or in combination of two or more. The radiation-sensitive composition (a) for the protrusions, followed by the amount of the additive-23- (19) (19) 200303430 The amount of the copolymer (a 1) is 100 parts by weight, preferably 20 parts by weight or less, It is particularly preferably 10 parts by weight or less. At this time, if the amount of the adjuvant used exceeds 20 parts by weight, the development residue tends to be easily formed. It is to be noted that the aforementioned surfactant is a component having the effect of further improving the coatability of the radiation-sensitive composition (a) for protrusions, and examples thereof include fluorine-based surfactants and silicone-based surfactants. . As the aforementioned fluorine-based surfactant, a compound having a fluoroalkyl group or a fluoroalkylene group on at least one of the terminal, the main chain and the side chain is preferred. Specific examples include: 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl Ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (〗,;!, 2, 2, 3, 3-hexafluoropentyl) ether, octapropylene glycol Bis (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol bis (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkylbenzenesulfonate , Sodium fluoroalkyl sulfonate, sodium fluoroalkyl carboxylate, fluoroalkyl polyethylene oxide ether, diglycerol (fluoroalkyl polyethylene oxide ether), fluoroalkyl ammonium iodide 'fluorine Alkyl betaines, fluoroalkyl polyethylene oxide ethers, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxy salts, fluorine-based alkyl esters, and the like. As for the fineness, the products of the surfactant Z towel are, for example, BM-1000, BM-1100 (above, manufactured by BM Chemical Co., Ltd.),

Megafac F142D、Megafac F]72、Megafac F173、Megafac F183、Megafac F178、Megafac F191、Megafac F47]、Megafac F142D, Megafac F] 72, Megafac F173, Megafac F183, Megafac F178, Megafac F191, Megafac F47],

Megafac F4 76 (以上，大日本.油墨化學工業（股）製造） (20) 200303430 。Floard FC 170C、FC- 171、FC- 430、FC- 43 1 (以上，住友 3M (股）製）、Surflon S- 112、Surflon S-I13、 Surflon S-131、Surflon S-141、Surflon S-145、Surflon S-3 82、 Surflon S-101、Surflon S-102、 Surflon S-103、Megafac F4 76 (above, manufactured by Dainippon. Ink Chemical Industry Co., Ltd.) (20) 200303430. Floard FC 170C, FC- 171, FC- 430, FC- 43 1 (above, made by Sumitomo 3M (Stock)), Surflon S- 112, Surflon S-I13, Surflon S-131, Surflon S-141, Surflon S- 145, Surflon S-3 82, Surflon S-101, Surflon S-102, Surflon S-103,

Surflon S-104、Surflon S-105、Surflon S-106 (以上，旭玻璃（股）製造）、EFTOP EF301、EFTOP 3 03、EFTOP 3 5 2 (以上，新秋田化成（股）製造）、Futagent FT- 100 、Futagent FT-110 、 Futagent FT-140A 、 Futagent FT-150 、Futagent FT-250、 Futagent FT-251、 Futagent FTX-251 、Futagent FTX-218、 Futagent FT-300、 Futagent FT-310 、Futagent FT-400S (以上，（股）Neos 製造）等。至於前述矽氧系界面活性劑，市售品例如可舉出 Toray Silicone DC3PA、Toray Silicone DC7PA、SH11PA 、SH21PA、SH28PA、SH29PA、SH30PA、SH- 190、SH-193、SZ- 6032、SF- 8428、DC- 57、DC- 190 (以上 Toray Dow Corning Silicone (股）製造）、TSF- 4440、TSF-43 00、TSF- 444 5、TSF- 4446、TSF- 4460、TSF- 44 5 2 ( 以上GE東芝Silicone (股）製造）等。再者，除氟系界面活性劑及矽氧系界面活性劑以外，例如亦可使用聚環氧乙烷月桂基醚、聚環氧乙烷硬脂基醚、聚環氧乙烷油基醚等聚環氧乙烷烷基醚類；聚環氧乙烷辛基苯基醚、聚環氧乙烷壬苯基醚等聚環氧乙烷芳香基醚類；聚環氧乙烷二月桂基酯、聚環氧乙烷二硬脂酸酯等聚環氧乙烷二烷基酯類等的非離子系界面活性劑、或市售品 -25- (21) (21)200303430 之KP341 (信越化學工業（股）製造），Polyflow No.57,Surflon S-104, Surflon S-105, Surflon S-106 (above, manufactured by Asahi Glass Co., Ltd.), EFTOP EF301, EFTOP 3 03, EFTOP 3 5 2 (above, manufactured by Shin Akita Chemical Co., Ltd.), Futagent FT -100, Futagent FT-110, Futagent FT-140A, Futagent FT-150, Futagent FT-250, Futagent FT-251, Futagent FTX-251, Futagent FTX-218, Futagent FT-300, Futagent FT-310, Futagent FT -400S (above, manufactured by (shares) Neos), etc. As for the aforementioned silicone-based surfactants, commercially available products include Toray Silicone DC3PA, Toray Silicone DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above manufactured by Toray Dow Corning Silicone), TSF-4440, TSF-43 00, TSF-444 5, TSF-4446, TSF-4460, TSF-44 5 2 (above GE Toshiba Silicone (stock)). Furthermore, in addition to a fluorine-based surfactant and a silicone-based surfactant, for example, polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, and polyethylene oxide oleyl ether can be used. Polyethylene oxide alkyl ethers; Polyethylene oxide octylphenyl ether, polyethylene oxide nonphenyl ether and other polyethylene oxide aryl ethers; polyethylene oxide dilauryl ester , Non-ionic surfactants such as polyethylene oxide distearate, polyethylene oxide dialkyl esters, etc., or commercially available KP341 (Shin-Etsu Chemical Co., Ltd.-25- (21) (21) 200303430) Industrial (Stock) Manufacturing), Polyflow No.57,

PolyflowNo. 95(以上，共榮公司化學（股）製造）等。此等界面活性劑係可單獨或混合二種以上使用。於突起用放射線敏感性組成物（甲），界面活性劑之使用量，對共聚物（a 1 ) 1 0 0重量份，宜爲5重量份以下，較宜爲2重量份以下。此時，界面活性劑之使用量若超過5重量份時，則有塗布時之塗膜容易生成粗糙的傾向。 -突起用放射線敏感性組成物（乙）- 於突起用放射線敏感性組成物（乙）之（a 2)不飽和羧酸及/或不飽和多元羧酸酐及含有環氧基之不飽和單體與前述以外的不飽和單體（以下稱作·「其他的不飽和單體」）之共聚物（以下，稱作「共聚物（a2)」），至於不飽和羧酸，不飽和多元羧酸酐，含有環氧基之不飽和單體及其他不飽和單體，例如可舉出前述共聚物（al)例示的各自不飽和羧酸，不飽和多元羧酸酐，含有環氧基之不飽和單體及其他不飽和單體相同者。至於共聚物（a2)之不飽和羧酸及不飽和多元羧酸酐，由共聚合反應性，對鹼顯影液之溶解性及容易到手的觀點，宜爲甲基丙烯酸、順丁烯二酐等。於共聚物（a2)，由不飽和羧酸及/或不飽和羧酸酐而成的構成單位之含有率，宜爲5〜50重量％，尤宜爲 1 〇〜4 0重量％。此時，該構成單位之含有未滿5重量％時，則所得的突起部之耐熱性、耐藥品性、表面硬度等有 -26- (22) (22)200303430 降低的傾向，另一方面若超過5 0重量％時，則所得的共聚物之保有安定性有降低的傾向。又至於共聚物（a2)之含有環氧基之不飽和單體，由其聚合反應性，所得的突起部之強度等的觀點，宜爲例如 (甲基）丙烯酸縮水甘油基酯、甲基丙烯酸· 6，7-環氧基庚酯、鄰-乙烯基苄基縮水甘油基醚、間-乙烯基苄酯縮水甘油基醚、對-乙烯基苄基縮水甘油基醚、甲基丙烯酸-沒-甲基縮水甘油基酯等。 φ 於共聚物（a2)，由含有環氧基之不飽和單體而成的構成單位之含有率，宜爲10〜70重量％，尤宜爲20〜 60重量％。此時，該構成單位之含有率未滿1 0重量％，所得的突起部之耐熱性、耐藥品性等有降低的傾向，另一方面若超過70重量％時，則所得的共聚物之保存安定性有降低的傾向。又’至於共聚物（a2)之其他不飽和單體，由共聚合反應性之觀點宜爲甲基丙烯酸第三丁酯、甲基丙烯酸正丁 φ 酯、甲基丙烯酸二環戊基酯、甲基丙烯酸苄酯、曱基丙烯酸2-羥乙基酯、丙烯酸2-甲基環己酯、苯乙烯、對-曱氧基苯乙烯、1，3 - 丁二烯、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺等，尤宜爲甲基丙烯酸二環戊基酯、甲基丙烯酸苄酯、甲基丙烯酸2-羥乙酯、苯乙烯、1，3 - 丁二烯、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺等。於共聚物（a2)，由其他不飽和單體而成的構成單位 -27- (23) (23)200303430 之含有率，宜爲1〇〜80重量％，尤宜爲30〜70重量％。此時，該構成單位之含有率未滿1 〇重量％時，所得的共聚物之保存安定性有降低的傾向，另一方面若超過8 0 重量％時，則所得的共聚物對鹼顯影液之溶解性有降低的傾向。共聚物（a2)之Mw宜爲2，000〜100，000，較宜爲 5,0 0 0〜50，000。此時共聚物（a2) 之Mw未滿2，000時，則所得的突起部之耐熱性、表面硬度等有降低的傾向，另一方面若超過100, 〇〇〇時，則對鹼顯影液之溶解性有降低的傾向。於突起用放射線敏感性組成物（乙），共聚物（a2) 係可單獨或混合二種以上使用。· 至於突起用放射線敏感性組成物（乙）之共聚物 (a2)之較宜者，例如可舉出苯乙烯/甲基丙烯酸/甲基丙烯酸縮水甘油基酯共聚物、1，3 - 丁二烯/苯乙烯/甲基丙烯酸/甲基丙烯酸縮水甘油基酯共聚物、苯乙烯/甲基丙烯酸/ 甲基丙烯酸縮水甘油基酯/甲基丙烯酸二環戊基酯共聚物、1 ’ 3 - 丁一燒/本乙烯/甲基丙燒酸/甲基丙;(:希酸縮水甘油基酯/甲基丙烯酸二環戊基酯共聚物、苯乙烯/甲基丙儲酸/ 甲基丙烯酸縮水甘油基酯/對乙烯基苄基縮水甘油基醚/甲基丙烯酸二環戊基酯共聚物、苯乙烯/甲基丙烯酸/甲基丙烯酸縮水甘油基酯/環己基順丁烯二醯亞胺共聚物、苯乙少希/甲基丙細酸/甲基丙細酸縮水甘油基醋/甲基丙條酸二環戊基酯/環己基順丁烯一醯亞胺共聚物、苯乙烯/甲基丙烯 -28- (24) (24)200303430 酸/甲基丙烯酸縮水甘油基酯/甲基丙烯酸二環戊基酯/苯基順丁烯二醯亞胺共聚物，此等之中尤宜爲苯乙烯/甲基丙烯酸/甲基丙烯酸縮水甘油酯/甲基丙烯酸二環戊基酯共聚物、苯乙烯/甲基丙烯酸/曱基丙烯酸縮水甘油基酯/環己基順丁烯乙醯亞胺共聚物、1，3 - 丁二烯/苯乙烯/甲基丙烯酸/甲基丙烯酸縮水甘油酯/甲基丙烯酸二環戊基酯共聚物、苯乙烯/甲基丙烯酸/甲基丙烯酸縮水甘油基酯/對-乙烯基苄基縮水甘油基醚/甲基丙烯酸二環戊基酯共聚物、苯乙烯/甲基丙烯酸/甲基丙烯酸縮水甘油酯/甲基丙烯酸二環戊基酯/苯基順丁烯二醯亞胺共聚物。於突起用放射線敏感性組成物（乙）之放射線敏感性聚合引發劑（b2)，係藉由可見光、紫外線、遠紫外線、電子射束、X射線等的曝光，可發生能聚合前述不飽和單體（c 2 )之活性種的化合物而成。至於此種放射線敏感性組成物（b2)，例如可舉出： ;基、二乙醯基等的α -二酮類；苯偶因等偶姻類；苯偶因甲醚 '苯偶因乙醚 '苯偶因丙醚等的偶姻醚類；二苯並硫喃、2，4 -二乙基二苯並硫喃、二苯並硫喃-4 -磺酸、二苯並甲酮、4，4’-雙（二甲基胺基）二苯基甲酮、4 ’ 4 5 -雙（二乙基胺基）二苯並甲酮等的二苯並甲酮類；本乙酮、對二甲基胺基苯乙酮、α ，α’-二甲氧基乙氧基二苯並甲酮、2，2，_二甲氧基-2-苯基苯乙酮、對甲氧基苯乙酮、2 -甲基 [4 - (甲基硫代）苯基]-2 -嗎啉基-1-丙酮、2-苄基-2-二甲基胺基-(4_嗎啉基 -29- (25) 200303430 苯基）-丁烷-1 -酮等苯乙酮類；蒽醌、1，4_萘醌等醌類；氯化苯醯甲基、三溴甲基苯基硕、參（三氯甲基） -S-三畊等鹵化合物；氧化2，4，6-三甲基苯甲醯二苯基膦、氧化雙（2，6-二甲氧基苯甲醯基）-2，4，4-三甲基-戊基膦、氧化雙（2，4，6·三甲基苯甲醯基）苯基膦等氧化醯基膦；及過氧化二第三丁基等的過氧化物Polyflow No. 95 (above, manufactured by Kyoei Chemical Co., Ltd.), etc. These surfactants can be used alone or in combination of two or more. The amount of the radiation-sensitive composition (a) for the protrusion and the amount of the surfactant is preferably 100 parts by weight of the copolymer (a 1), preferably 5 parts by weight or less, and more preferably 2 parts by weight or less. In this case, if the amount of the surfactant used exceeds 5 parts by weight, the coating film tends to be rough when coated. -Radiation-sensitive composition (B) for protrusions-(a 2) unsaturated carboxylic acid and / or unsaturated polycarboxylic acid anhydride and unsaturated monomer containing epoxy group in radiation-sensitive composition (B) for protrusions Copolymers with unsaturated monomers other than the above (hereinafter referred to as "other unsaturated monomers") (hereinafter, referred to as "copolymer (a2)"), and unsaturated carboxylic acids, unsaturated polycarboxylic acid anhydrides The unsaturated monomers containing epoxy groups and other unsaturated monomers include, for example, the respective unsaturated carboxylic acids, unsaturated polycarboxylic acid anhydrides, and unsaturated monomers containing epoxy groups as exemplified by the aforementioned copolymer (al). And other unsaturated monomers are the same. As for the unsaturated carboxylic acid and unsaturated polycarboxylic acid anhydride of the copolymer (a2), methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity, solubility in an alkali developing solution, and easy accessibility. In the copolymer (a2), the content rate of the constituent units made of unsaturated carboxylic acid and / or unsaturated carboxylic anhydride is preferably 5 to 50% by weight, and particularly preferably 10 to 40% by weight. At this time, when the content of the constituent unit is less than 5% by weight, the heat resistance, chemical resistance, surface hardness, and the like of the obtained protrusions tend to decrease. (26) (22) (22) 200303430 When it exceeds 50% by weight, the stability of the obtained copolymer tends to decrease. As for the unsaturated monomer containing an epoxy group in the copolymer (a2), from the viewpoints of polymerization reactivity and strength of the obtained protrusions, for example, glycidyl (meth) acrylate, methacrylic acid, etc. are preferred. · 6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, methacrylic acid-but- Methyl glycidyl ester and the like. The content of φ in the copolymer (a2), which is a constituent unit made of an unsaturated monomer containing an epoxy group, is preferably 10 to 70% by weight, and particularly preferably 20 to 60% by weight. At this time, the content of the constituent unit is less than 10% by weight, and the heat resistance and chemical resistance of the obtained protrusions tend to decrease. On the other hand, if it exceeds 70% by weight, the obtained copolymer is stored. Stability tends to decrease. As for the other unsaturated monomers of the copolymer (a2), from the viewpoint of copolymerization reactivity, the third butyl methacrylate, n-butyl methacrylate, dicyclopentyl methacrylate, and methyl Benzyl acrylate, 2-hydroxyethyl methacrylate, 2-methylcyclohexyl acrylate, styrene, p-methyloxystyrene, 1,3-butadiene, N-phenylcis-butene Difluorene imine, N-cyclohexyl cis butene difluorene imine, etc., especially dicyclopentyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, styrene, 1, 3-butadiene, N-phenyl-cis-butene-diimine, N-cyclohexyl-cis-butene-diimine, and the like. In the copolymer (a2), the constituent unit made of other unsaturated monomers is -27- (23) (23) 200303430, and the content rate is preferably 10 to 80% by weight, and particularly preferably 30 to 70% by weight. At this time, when the content rate of the constituent unit is less than 10% by weight, the storage stability of the obtained copolymer tends to decrease. On the other hand, when it exceeds 80% by weight, the obtained copolymer is resistant to an alkali developer. The solubility tends to decrease. The Mw of the copolymer (a2) is preferably 2,000 to 100,000, and more preferably 5,000 to 50,000. At this time, when the Mw of the copolymer (a2) is less than 2,000, the heat resistance and surface hardness of the obtained protrusions tend to decrease. On the other hand, if it exceeds 100, 000, the alkali developing solution is used. The solubility tends to decrease. For the radiation-sensitive composition (B) for the protrusion, the copolymer (a2) can be used alone or as a mixture of two or more. · As a preferable copolymer (a2) of the radiation-sensitive composition (B) for protrusions, for example, styrene / methacrylic acid / glycidyl methacrylate copolymer, 1,3-butane Olefin / styrene / methacrylic acid / glycidyl methacrylate copolymer, styrene / methacrylic acid / glycidyl methacrylate / dicyclopentyl methacrylate copolymer, 1 '3-butane 1-burner / ethylene / methacrylic acid / methacrylic acid; (: glycidyl glycidate / dicyclopentyl methacrylate copolymer, styrene / methacrylic acid / glycidyl methacrylate Ester / p-vinylbenzyl glycidyl ether / dicyclopentyl methacrylate copolymer, styrene / methacrylic acid / glycidyl methacrylate / cyclohexyl cis butylene diimide copolymer , Styrene / Methylpropionic acid / Glycidyl glycidyl vinegar / Dicyclopentyl methylpropionate / Cyclohexyl butene monoimide copolymer, Styrene / methyl Propylene-28- (24) (24) 200303430 acid / glycidyl methacrylate / dicyclopentyl methacrylate / phenyl Copolymers of butene difluorene imine, especially among these are styrene / methacrylic acid / glycidyl methacrylate / dicyclopentyl methacrylate copolymer, styrene / methacrylic acid / fluorenyl Glycidyl acrylate / cyclohexyl cis butene ethyleneimine copolymer, 1,3-butadiene / styrene / methacrylic acid / glycidyl methacrylate / dicyclopentyl methacrylate copolymer Styrene / methacrylic acid / glycidyl methacrylate / p-vinylbenzyl glycidyl ether / dicyclopentyl methacrylate copolymer, styrene / methacrylic acid / glycidyl methacrylate Ester / Dicyclopentyl Methacrylate / Phenyl Butene Diimine Copolymer. The radiation-sensitive polymerization initiator (b2) of the radiation-sensitive composition (B) for protrusions is based on visible light, Exposure to ultraviolet rays, extreme ultraviolet rays, electron beams, X-rays, and the like may be produced by polymerizing the active species of the unsaturated monomer (c 2). As for such a radiation-sensitive composition (b2), for example, Examples:; radical, diethenyl, etc. α-Diketones; Marriages such as benzoin; Benzoin methyl ether 'Phenyl ether ether' Benzoin propyl ether; Dibenzosulfan, 2,4-diethyl Dibenzosulfan, dibenzosulfan-4 -sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) diphenylmethanone, 4 '4 5 -bis (di Ethylamino) benzophenones such as benzophenone; Benzophenone, p-dimethylaminoacetophenone, α, α'-dimethoxyethoxydibenzophenone , 2,2, _dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4-(methylthio) phenyl] -2 -morpholinyl- Acetophenones such as 1-acetone, 2-benzyl-2-dimethylamino- (4-morpholinyl-29- (25) 200303430 phenyl) -butane-1 -one; anthraquinone, 1 Quinones such as 4, naphthoquinone; halogenated compounds such as benzamidine methyl chloride, tribromomethylphenyl sulfonate, ginseng (trichloromethyl) -S-Sangen; oxidation of 2,4,6-trimethyl Benzamidinediphenylphosphine, bis (2,6-dimethoxybenzylidene) -2,4,4-trimethyl-pentylphosphine, bis (2,4,6 · trimethyl oxide) Benzyl amidino) fluorenyl oxide such as phenylphosphine ; Tert-butyl peroxide and other peroxides

至於此等放射線敏感性自由基引發劑之市售品，例如可舉出 IRGACURE- 184、369、500、651、907、1700、 819、 124、 1 000、 29 5 9、 149、 1 800、 1 8 5 0 ， Darocur-As for commercially available products of these radiation-sensitive free radical initiators, for example, IRGACURE- 184, 369, 500, 651, 907, 1700, 819, 124, 1 000, 29 5 9, 149, 1 800, 1 8 5 0, Darocur-

1173、1116、2959、1664、4043 (以上，Ciba Specialty Chemicals公司-汽巴特用化學品公司製造），， KAYACURE- DETX、MBP、DMBI、EPA、OA (以上，日本化學（股）製造），LUCIRIN TPO (BASF Co. LTD 製造），VIICURE- 10、同 55 (以上，STAUFFER Co. LTD 製造），TRIGONALPI (AKZO Co. LTD 製造）， TRIGONALPI (AKZO Co. LTD 製造），S ANDORAY 1000 (SANDOZ Co. LTD 製造）、DEAP (APJOHN Co. LTD 製造），QUANTACURE- PDO，同 ITX、同 EPD (以上， W ARD BLEKINSOP Co. LTD 製造）等。再者，至於前述以外的放射線敏感性聚合引發劑，亦可使用4-疊氮苯醛、疊氮芘、氧化雙（2，6-二甲氧基苯甲醯基）-2，4，4-三甲基戊基膦、N-苯基硫代吖啶酮、三苯基吡啶鏺過氯鹽等。 -30- (26) (26)200303430 此等放射線敏感性聚合引發劑（b 2 )，係可單獨使用或混合二種以上使用。至於放射線敏感性聚合引發劑（b2)之較宜者，可舉出二苯並甲酮類及苯乙酮類，該等之中尤宜爲2，4-二乙基二苯並硫喃、2 - 單基 [4 -(甲基硫代）苯基]—2 -嗎啉基· 1-丙院、及2-;基· 2-二甲基胺基-1- (4- 嗎啉基苯基）-丁烷-酮。於突起用放射線敏感性組成物（乙），放射線敏感性聚合引發劑（b2)之使用量，對聚合物（a2) 100重量份，宜爲1〜50重量份，尤宜爲5〜35重量份。此時，放射線敏感性聚合引發劑之使用量未滿1重量份，所得的突起部在顯影時引起塗膜減少，又有強度降低的顧慮，另一方面超過5 0重量份時，則所得的突起部之電壓保持率有不足的顧慮。再者，於突起用放射線敏感性組成物（乙），與前述放射線敏感性聚合引發劑（b2)同時可合倂使用增感劑、硬化促進劑、高分子光交聯增感劑等一種以上。至於前述增感劑，例如可舉出4 -二乙基胺基苯乙酮、4-二甲基胺基苯丙酮、4-二甲基胺基安息香酸乙酯、 4_二甲基胺基安息香酸2·乙己基酯、2，5-雙（4_二乙基胺基苯西甲）環己酮、7-二乙基胺基-3- (4-二乙基胺基苯甲醯基）香豆素、4-(二乙基胺基）查酮等，此等增感劑係可單獨使用或混合二種以上使用。又，至於前述硬化促進劑，例如可舉出2 -酼基苯並 -31 - (27) (27)200303430 咪唑、2 -锍基苯並噻唑' 2 -锍基苯並腭唑、2，5 -二疏基-1，3，4 -噻二Π坐、2 -疏基-4 ’ 6 - 一甲基胺基吼啶等鏈轉移劑，此等硬化促進劑’可單獨或混合二種以上使用。又前述高分子光交聯、增感劑’係於主鏈及/或側鏈中具有由於曝光可作用交聯劑及/或增感劑之至少一種官能基的高分子化合物，至於其例，可舉出4-疊氮苯醛及聚乙烯醇之縮合物、4-疊氮苯醛及酚酚醛淸漆樹脂之縮 · 合物、桂皮酸4-丙烯醯苯基之（共）聚物、1，4-聚丁二烯、1，2-聚丁二烯等。此等高分子光交聯、增感劑係可單獨或混合二種以上使用。於突起用放射線敏感性組成物（乙）、增感劑、硬化促進劑及高分子光交聯、增感劑之合計使用量，對放射線敏感性聚合引發劑1 0 0重量份，宜爲3 0 0重量份以下，較宜爲5〜200重量份，更宜爲〜1〇〇重量份。 φ 其次’至於突起用放射線敏感性組成物（乙）之不飽和單體（c2)，宜爲二官能或三官能以上的（甲基）丙烯酸酯類。至於上述二官能（甲基）丙烯酸酯類，例如可舉出·· 乙二醇（甲基）丙烯酸酯、二（甲基）丙烯酸〗，6 -己二醇酯、一（甲基）丙烯酸1，9 _壬二醇酯、二（甲基）丙烯酸聚丙二醇酯、二（甲基）丙烯酸四乙二醇酯、二丙烯酸雙苯氧基乙醇芴酯等。至於其市售品，例如ΑΠ 〇n ix M- -32- (28) (28)200303430 210、Μ- 240、Μ- 6200 (以上，東亞合成（股）製造）， K AYARAD HDD A、ΗΧ- 220、R- 6 04 (以上，曰本化學（股）製造）、Biskote 260、3 12、3 3 5 HP (以上，大阪有機化學工業（股）製造）等。至於上述三官能以上的（甲基）丙烯酸酯，例如可舉出：三（甲基）丙烯酸三羥甲丙烷酯、三（甲基）丙烯酸季戊四醇酯、磷酸三（（甲基）丙烯醯氧乙基）酯、四 (甲基）丙烯酸季戊四醇酯、五（甲基）丙烯酸二季戊四醇酯、六（甲基）丙烯酸二季戊四醇酯等。至於其市售品，例如可舉出 Allonix M- 309、M- 400、M- 402、M- 405 ' Μ- 450、Μ - 7100、Μ- 8030、Μ- 8060、Μ- 1310、Τ0_ 1 4 5 0、Μ- 1 6 00、Μ- I 960 ' Μ - 8 1 00、Μ· 8 5 3 0 - Μ- 8 5 60 、Μ- 9050 (以上，東亞合成（股）製造），KAYARAD TMPTA、DPHA、DP C A- 20、DP C A- 30、DPCA- 60、 DPCA· 120、MAX- 3510 (以上，日本化學（股）製造），Biskote 29 5、300、360、GPT、3PA、400 (以上，大阪有機化學工業（股）製造）等。此等一吕目自或二官能以上的（甲基）丙烯酸酯，係可單獨或組合使用。至於不飽和單體（C2)之較宜者，可舉出：四（甲基 )丙烯酸季戊四醇酯、五（甲基）丙烯酸二季戊四醇酯、六（甲基）丙烯酸二季戊四醇酉旨。於突起用放射線敏感性組成物（乙），不飽和單體 (c2)之使用重:對共聚物（a2) 1〇〇重量份，宜爲go〜200 (29) (29)200303430 重量份，尤宜爲5 0〜140重量份。此時，聚合性不飽和單體（c2)之使用量未滿3 0重量份時’所得的突起部在顯影時會引起塗膜減量，且有強度降低的顧慮，另一方面若超過2 0 0重量份時，則與所得的突起部之基板間的附著性有降低的傾向。突起用放射線敏感性組成物（乙），更宜爲含有以對突起用放射線敏感性組成物（甲）記載的前式（1 )或前述（2)表示的特定三聚氰胺衍生物一種以上。鲁於突起用放射線敏感性組成物（乙），特定三聚氰胺衍生物之使用量，對共聚物（a2) 100重量份，宜爲1〜 100重量份，尤宜爲5〜50重量份。藉由將特定三聚氰胺衍生物之使用量設成此範圍時，可形成良好的形狀之突起部，可得顯示出對鹼顯影液之適當的溶解性之突起用放射線敏感性組成物（乙）。再者，於突起用放射線敏感性組成物（乙）內，可配合接著助劑、界面活性劑等。 · 至於前述接著助劑及界面活性劑，例如可舉出與已例示作前述突起用放射線敏感性組成物（甲）之配合成份的接著助劑及界面活性劑相同者。於突起用放射線敏感性組成物（乙），接著助劑之使用量，對共聚物（a2) 100重量份，宜爲200重量份以下，尤宜爲1 〇重量份以下。此時，接著助劑之使用量若超過20重量份時，則有殘存顯影變成容易生成的傾向。又，界面活性劑之使用量，對共聚物（a2) 100重量 -34- (30) (30)200303430 份，宜爲0.2重量份以下，尤宜爲0.0 5重量份以下。此時，界面活性劑之使用量若超過〇 . 2重量份時’則塗布定向膜時有容易生成彈濺的現象之傾向。 -突起用組成物溶液- 突起用放射線敏感性組成物，在使用之際’通常將構成該組成物之各成份溶解於適當的溶劑後，宜爲例如藉由孔徑0.2 // m程度之過濾器過濾，經予製備成突起用組成物溶液。至於製備突起用組成物溶液時所用的溶劑，只要是可均勻的溶解構成突起用放射線敏感性組成物之各成份，與各成份不反應且具有適當的揮發性者，可適當選擇並予使用。至於此種溶劑，例如可舉出：甲醇、乙醇等的醇類；四氫呋喃等醚類；乙二醇單甲醚、乙二醇單乙醚等的二醇醚類；甲氧基乙醇乙酸酯、乙氧基乙醇乙酸酯等的乙二醇烷基醚乙酸酯類；二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇二甲醚等二乙二醇類；丙二醇甲醚、丙二醇乙醚、丙二醇丙醚、丙二醇丁醚等丙二醇單烷醚類；丙二醇甲醚乙酸酯、丙二醇乙醚乙酸酯、円二醇丙醚乙酸酯、丙二醇丁醚乙酸酯等的丙二醇烷醚乙酸酯類；丙二醇甲醚丙酸酯、丙二醇乙醚丙酸酯、丙二醇丙醚丙酸酯、丙二醇丁醚丙酸酯等丙二醇烷醚乙酸酯類；甲苯、二甲苯等的芳香族烴類；甲乙酮、環己酮、4 -羥 -35- (31) (31)200303430 基-4-甲基-2-戊酮等酮類；乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、羥基乙酸甲酯' 羥基乙酸乙酯、羥基乙酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3 -羥基丙酸甲酯、3 -羥基丙酸乙酯、3 -羥基丙酸丙酯、3 -羥基丙酸丁酯、2-羥基-3-甲基丁酸甲酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基醋酸丙酯、甲氧基醋酸丁酯、乙氧基醋酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸丙酯、丙氧基乙酸乙酯、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、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-甲氧基丙酸丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、2-乙氧基丙酸丁酯、2- 丁氧基丙酸甲酯、2- 丁氧基丙禮乙酯、2 - 丁氧基丙酸丙酯、2 „ 丁氧基丙酸丁酯、3 -甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、 3~甲氧基丙酸丁酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸丙酯、3-乙氧基丙酸丁酯、3-丙氧基丙酸甲酯、3-丙氧基丙酸乙酯、3-丙氧基丙酸丙醋、3 -丙氧基丙酸丁酯、3 - 丁氧基丙酸甲酯、3 - 丁氧基丙酸乙酯、3 - 丁氧基丙酸丙酯、3 - 丁氧基丙酸丁酯等其他酯類等。此等溶劑係可單獨或混合二種以上使用。 -36- (32) (32)200303430 製備突起用組成物溶液（甲）及（乙）之時所用的溶劑之較宜者，由溶解性、與各成份間之反應性及塗膜之形成的容易度，較宜使用二醇醚類、乙二醇烷基醚乙酸酯類、二乙二醇類及其他酯類。再者’與前述溶劑同時亦可合倂使用高沸點溶劑。至於高沸點溶劑，例如可舉出N -甲基甲醯胺、N， N-二甲基甲醯胺、N-甲基甲醯胺、N-甲基甲醯苯胺、 Ν·甲基乙醯胺、N，N-二甲基乙醯胺、N-甲基批咯烷酮、二甲基亞硕、苄基乙基醚、二己基醚、乙腈丙酮、異佛爾酮、己酸、辛酸、1 -辛醇、^壬醇、苄基醇、醋酸卡基酯、安息香酸乙酯、草酸二乙酯、順丁烯二酸二乙酯、r - 丁內酯、碳酸乙烯酯、碳酸丙烯酯、乙苯基乙醇乙酸酯等。此等高沸點溶劑係可單獨或混合二種以上使用。著色放射線敏感性組成物本發明之形成半透射型濾色片的著色層所用的放射線敏感性組成物（以下，稱作「著色放射線敏感性組成物」 )係由含有（A)著色層，（B)鹼可溶性樹脂，（C) 多官能性單體，（D)放射線敏感性聚合引發劑及（E) ί谷劑者而成。以下說明構成著色放射線敏感性組成物之各成份。 -(Α)著色層- 於著色放射線敏感性組成物之著色劑，係色調未予特 -37- (33) (33)200303430 別限定者，因應所得的濾色片之用途可予適當選擇，又有機顏料、無機顏料、染料或天然色素之任一者亦可。於濾色片方面由被要求需高精密的發色及耐熱性，於本發明之著色劑，係宜爲採用發色性高且耐熱性高的著色劑，尤宜爲耐熱分解性較高的著色劑，尤宜爲採用有機顏料。至於前述有機顏料，例如可舉出於C. I. (Color Index:染料及顏料學會公司發行）之顏料所分類的化合物’具體而言，可舉出附有下述的C[.號碼者： C· I· Pigment yellow (顏料黃）12、C. I.顏料黃-13 、C.I.顏料黃-14、C.I.顏料黃-17、C.I·顏料黃-20 、（：.I.顏料黃-2 4、C . I ·顏料黃-3 1、C . I.顏料黃-5 5 、（:.1..顏料黃-83、C. I.顏料黃、93、C· I.顏料黃-]09、C· I·顏料黃-110、C·〗·顏料黃-；[38、c.；[.顏料黃-139、C. I.顏料黃· 150、C· I.顏料黃-153、C. I. 顏料黃-1 5 4、C . I ·顏料黃-1 5 5、C . I.顏料黃-1 6 6、C . I.顏料黃' 1 6 8、C _ I.顏料黃-1 8 0、C . I.顏料黃-1 8 5 、C . I ·顏料黃-2 1 1 ; C. I·顏料橙36、C. 1.顏料橙43、C. I.顏料橙51 、C .I. 顏料橙6 1 、C. I. 顏料橙7 1 ; C. I. 顏料紅 9、 C. 1.顏料紅 97、C. I. 顏料紅 122 > C. I. 顏料紅 1 23 、C .I.顏料紅 149、C. I. 顏料紅 168 、C. I. 顏料紅 176 、C .I.顏料紅 177、C. I· 顏料紅 1 80 、C· I. 顏料紅 209 、C .I.顏料紅 215、C. I. 顏料紅 224 、C . I. 顏料紅 242 、C .I.顏料紅 2 5 4; (34) 200303430 I，顏料紫19、C.；[ 顏料紫2 3、C 1 ·顔料藍1 5、c _ I 顏料藍6 0、C 顔料藍-15: 4、C. 1.顏料藍1 5 : 1.顏料綠7、c. I 顏料綠3 6、C . C . 1.顏料綠2 1 〇 ; 顏料紫2 9 ; II料藍1 5 : 彦頁料綠1 3 6 C . 1.顏料褐2 3、C .][.顏料褐2 5 ; c. L顏料黑1、C. 顏料黑7。、溶劑淸此等有機顏料係可單獨或混合二種以上使用又則述有機顏料，例如藉由硫酸再結晶法洗法或此等的組合精製可予使用。，可舉出二氧化鈦、、黃色鉛、鲜黃、紅、氧化鉻綠、銘綠、又，至於前述無機顏料之具體例硫酸鋇、碳酸鈣、二氧化鋅、硫酸鉛色氧化鐵（III)、鎘紅、普魯土藍琥珀、鈦黑、合成鐵黑、碳黑等。此等無機顏料，可單獨或混合二種以上使用。於本發明，前述各顏料，視所期待的，可使用以聚合物改質其粒子表面。至於改質顏料之粒子表面的聚合物，例如可舉出日本特開平8 - 2 5 9 8 7 6號公報等所記載的聚合物、或市售的各種顏料分散用之聚合物或寡聚物等。又’於著色放射線敏感性組成物，著色劑依可依所期待的與分散劑同時使用。至於前述分散劑，例如可舉出：陽離子系、陰離子系、非離子系、兩性、矽氧系、氟系等界面活性劑。至於前述界面活性劑之具體例，可舉出：聚環氧乙烷 -39- (35) (35)200303430 月桂基醚、聚環氧乙烷硬脂基醚、聚環氧乙烷油基醚等聚環氧乙烷烷基醚類；聚環氧乙烷正辛基苯基醚、聚環氧乙烷正壬基苯基醚等聚環氧乙烷烷基苯基醚類；聚環氧乙院二月桂基酯、聚乙二醇二硬脂酸酯等聚乙二醇二酯類；山梨糖醇酐脂肪酸酯類；脂肪酸改質聚酯類；三級胺改質聚胺酯類；聚乙亞胺類、或市售品之KP (售越化學工業（股）製造），Polyflow (共榮社化學（股）製造）， EFTOP (Tochem Product 公司製造），Megafac (大日本油墨化學工業（股）製造），Flowlard (住友3M (股）製造 )，Asahiguard、Surflon (以上，旭玻璃（股）製造）， Disperbyk- 101、103、107、110、111、115、130、160' 161、 162、 163、 164、 165、 166、 170、 180、 182、 2000 、2001、BYK- 165 (以上，Bykchemie Japan (股）製造），Solsperse S 5 000、S 1 2000 ' S 1 3 240 > S 1 3 940 > S 1 7000、 S 2 0 0 0 0 ^ S22000、S24000、S24000GR、S26000、S27000 、S28000 (以上，Avisia (股）製造）、EFKA46、47、48 、745 、 4540 、 4550 、 6750 、 EFKA LP4008 、 4009 、 4010 、401 5、4050、405 5、4 560、4800、EFKA Polymer 400、 401、402、403、450、451、453 (以上 EFKA Chemicals ( 股）製造）等。此等界面活性劑，係可單獨或混合二種以上使用。於著色放射線敏感性組成物，顏料分散劑之使用量，附著色劑100重量份，宜爲1〜50重量份，較宜爲3〜30 重量份。此時，顏料分散劑之使用量未滿1重量份時，顏 -40- (36) (36)200303430 料之分散性有降低的傾向，另一方面若超過5 0重量份時，則對鹼顯影液之溶解性有降低的傾向。 -(B)鹼可溶性樹脂- 其次，至於著色放射線敏感性組成物之鹼可溶性樹脂 ’對著色劑作用或黏合劑，且限於製造濾色片時之顯影處理步驟所用的鹼顯影液內爲可溶性，可使用適當的樹脂。至於此種鹼可溶性樹脂，例如可舉出會有羧基、酚性馨羥基等酸性官能基之樹脂。鹼可溶性樹脂之中，至於含有羧基之鹼可溶性樹脂，例如可舉出具有一個以上的羧基之乙烯性不飽和單體（以下單單稱作「含有羧基之不飽和，單體」之（共）聚物。至於含有前述羧基之不飽和單體之（共）聚物，尤宜爲由含有羧基之不飽和單體及其他可共聚合的不飽和單體 (以下單口稱作「其他不飽和單體」）而成之單體混合物之共聚物（以稱作「含有羧基之共聚物（/S )」。鲁至於前述含有羧基之不飽和單體，例如可舉出丙烯酸、甲基丙烯酸、巴豆酸、α -氯丙烯酸、桂皮酸等不飽和單羧酸類、順丁烯二酸、順丁烯二酸酐、順丁烯二酸、伊康酸、伊康酸酐、順式甲基丁烯二酸、順式甲基丁烯二酐、反式甲基丁烯二酸等不飽和二羧酸（酐）類；三價以上的不飽和多元羧酸（酐）類；琥珀酸單（2-丙烯醯氧基乙基）酯、琥珀酸單（2-甲基丙烯醯氧基乙基）酯、苯二甲酸單（2-丙烯醯氧基乙基）酯、苯二甲酸單（2- -41 - (37) (37)200303430 甲基丙烯醯氧基乙基）酯等非聚合性二羧酸之單[2-(甲基）丙燃醯氧基乙基]酯類、ω -殘基聚己內酯單丙燒酸酯、ω -羧基聚己內酯單甲基丙烯酸酯等。此等含有羧基之不飽和單體，可單獨或混合二種以上使用。且，琥珀酸單（2-丙烯醯氧基乙基）酯及苯二甲酸單（2·丙烯醯氧基乙基）酯，係各以Μ· 5 3 0 0及Μ_ 54〇〇之商品名（東西合成（股）製造）正予上市著。又，至於其他的不飽和單體，例如可舉出：苯乙烯、甲基苯乙烯、鄰乙烯基甲苯、間乙烯基甲苯、對乙烯基甲苯、鄰氯苯乙烯、間氯苯乙烯、對氯苯乙烯、鄰甲氧基苯乙烯、間甲氧基苯乙烯、對甲氧基苯乙烯、鄰乙烯基爷基甲醚、間乙烯基爷基甲醚、對乙烯基爷基甲基醚、鄰乙烯基苄基縮水甘油基醚、間乙烯基苄基縮水甘油基醚、芳香族乙烯基化合物；茚.I -甲基茚等茚類： (甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、（甲基）丙烯酸異丙基酯、（甲基）丙焼酸正丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸第二丁酯、（甲基）丙烯酸第三丁酯 '(甲基）丙燒酸2 -羥乙酯、（甲基）丙烯酸2-羥丙酯、（甲基）丙烯酸3_羥丙酯、（甲基）丙烯酸2 -羥丁酯、（甲基）丙烯酸3 -羥丁酯、（甲基）丙烯酸4-羥丁酯、（甲基）丙烯酸烯丙酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸苯酯、（甲基）丙烯酸2·甲氧基乙酯、（甲基）丙烯酸2-苯 -42- (38) (38)200303430 氧基乙酯、（甲基）丙烯酸異佛爾酮基酯、（甲基）丙烯酸二環戊基酯、（甲基）丙烯酸2-羥基-3-苯氧基丙酯、甲氧基二乙二醇（甲基）丙烯酸酯、甲氧基三乙二醇（甲基）丙烯酸酯、甲氧基丙二醇（甲基）丙烯酸酯、甲氧基丙二醇（甲基）丙烯酸酯、丙三醇單（甲基）丙烯酸酯等的不飽和羧酸酯類； (甲基）丙烯酸-2-胺基乙酯、（甲基）丙烯酸-2· 一甲基S女基乙酉曰、（甲基）丙儲酸-2-胺基丙醋、（甲基）丙烯酸-2-二甲基胺基丙酯、（甲基）丙烯酸·3-胺基丙酯、（甲基）丙烯酸-3 -胺基丙酯、（甲基）丙烯酸-3 -二甲基胺基丙酯等不飽和羧酸胺基烷基酯類； (甲基）丙烯酸縮水甘油基酯等不飽和羧酸縮水甘油基酯類；醋酸乙烯基酯、丙酸乙烯基酯、酪酸乙烯基酯、安息香酸乙烯基酯等羧酸乙烯基酯類；乙烯基甲基醚、乙烯基乙基醚、烯丙基縮水甘油基醚、甲基丙烯縮水甘油基醚等不飽和醚類； (曱基）丙烯腈、α -氯丙烯腈、氰化亞乙基等氰化乙烯基化合物； (甲基）丙烯醯胺、α -氯丙烯醯胺、Ν - (2 -羥基乙基）（甲基）丙烯醯胺、Ν-羥甲基（甲基）丙烯醯胺等不飽和醯胺類；順丁烯二醯亞胺、Ν-環己基順丁烯二醯亞胺、Ν-苯基順丁烯二醯亞胺等的不飽和醯亞胺類； -43- (39) (39)200303430 1，3 - 丁二烯、異戊二烯、氯平等的脂肪族共軛二烯類；聚苯乙烯、聚丙烯酸甲基酯、聚甲基丙烯酸甲酯、聚丙烯酸正丁基、聚矽氧烷等的聚合物分子鏈之終端上具有單丙烯醯基或單甲基丙烯醯基之巨單體類。此等其他的不飽和單體，係可單獨或混合二種以上使用。至於含有竣基之共聚物（y?)，宜爲①以丙烯酸及/ 或甲基丙烯酸爲必須，視情況，再含有琥珀酸單（2 -丙燃醯氧基乙基）酯、琥珀酸單（2-甲基丙烯醯氧基乙基）酯、ω-羧基聚己內酯單丙烯酸酯及羧基聚己內酯單甲基丙烯酸酯之群體選出的至少一種之含有竣基之不飽和單體，②與由苯乙烯、（甲基）丙烯酸甲酯、（甲基）丙烯酸2 -羥乙酯、（甲基）丙烯酸烯丙酯、（甲基）丙烯酸节酯、丙二醇單（甲基）丙烯酸酯、Ν -苯基順丁烯二醯亞胺、聚苯乙烯巨單體及聚甲基丙烯酸甲酯巨單體之群體選出的至少一種不飽和單體間之共聚物（以下稱作含有羧基之共聚物（/3-1))。至於含有羧基之共聚物（万-〗）之具體例，可舉出： (甲基）丙烯酸/甲基丙烯酸甲酯共聚物， (甲基）丙烯酸./(甲基）丙烯酸苄酯共聚物， (甲基）丙烯酸/苯乙烯/(曱基）丙烯酸甲酯共聚物， (甲基）丙烯酸/苯乙烯/(甲基）丙烯酸苄酯共聚物， (甲基）丙烯酸/(甲基）丙烯酸甲酯/聚苯乙烯巨單體 -44- (40) (40)200303430 共聚物， (甲基）丙烯酸/(甲基）丙烯酸甲酯/聚甲基丙烯酸甲酯巨單體共聚物， (甲基）丙烯酸/(甲基）丙烯酸2-羥乙酯/(甲基）丙烯酸苄酯基聚物， (甲基）丙烯酸/(甲基）丙烯酸苄酯/聚苯乙烯巨單體共聚物， (甲基）丙烯酸/(甲基）丙烯酸苄酯/聚甲基丙烯酸甲酯巨單體共聚物， (甲基）丙烯酸/(甲基）丙烯酸2-羥乙酯/(甲基）丙烯酸苄酯/聚苯乙烯巨單體共聚物， (甲基）丙烯酸/(甲基）丙烯酸2-羥乙酯/(甲基）丙烯酸苄酯/聚甲基丙烯酸甲酯巨單體共聚物， (甲基）丙烯酸/苯乙烯/ (甲基）丙烯酸苄酯/N_苯基順丁烯二醯亞胺共聚物， (甲基）丙烯酸/苯乙烯/(甲基）丙烯酸苄酯/單（甲基）丙烯酸丙三醇酯/N-苯基順丁烯二醯亞胺共聚物， (甲基）丙烯酸/琥珀酸單[2-甲基]丙烯醯氧基乙基]酯/苯乙烯/(甲基）丙烯酸苄酯/N-苯基順丁烯二醯亞胺共聚物， (甲基）丙烯酸/琥珀酸單[2-甲基]丙烯醯氧基乙基]酯/苯乙烯/(甲基）丙烯酸烯丙酯/N-苯基順丁烯二醯亞胺共聚物， (甲基）丙烯酸/單（甲基）丙烯酸ω -羧基聚己內 (41) (41)200303430 酯/苯乙烯/ (甲基）丙烯酸苄酯/單（甲基）丙烯酸丙三醇酯/N-苯基順丁烯二醯亞胺共聚物， (甲基）丙烯酸/琥珀酸單[2·(甲基）丙烯醯氧基乙基]酯/單（甲基）丙烯酸羧基聚己內酯/苯乙烯/ (甲基）丙丨希:卡基臨/單（甲基）丙燒酸丙三醇酉旨/Ν_苯基順丁烯二醯亞胺共聚物， (甲基）丙烯酸/琥珀酸單[2-(甲基）丙烯醯氧基乙基]酯/單（甲基）丙烯酸ω -羧基聚己內酯/苯乙烯/ φ (甲基）丙烯酸苄酯/單（甲基）丙烯酸丙三醇酯/N-苯基順丁烯二醯亞胺共聚物， (甲基）丙烯酸/琥珀酸單[2-(甲基）丙烯醯氧基乙基]酯/單（甲基）丙烯酸ω -羧基聚己內酯/苯乙烯/ (甲基）丙烯酸苄基酯/單（甲基）丙烯酸丙三醇_/Ν-苯基順丁烯二醯亞胺共聚物， (甲基）丙烯酸/琥珀酸單[2-(甲基）丙烯醯氧基乙基]酉曰/單（甲基）丙烯酸ω·殘基聚己內酯/苯乙儀/ 馨 (甲基）丙烯酸烯丙酯/單（甲基）丙烯酸丙三醇酯/ Ν-苯基順丁烯二醯亞胺共聚物。此等含有竣基之共聚物1)之中，尤宜爲甲基丙烯酸/甲基丙烯酸苄基酯共聚物、甲基丙烯酸/曱基两_ 酸2 -羥乙酯/甲基丙烯酸苄酯共聚物、甲基丙烯酸/甲基丙烯酸苄基酯/聚苯乙烯巨單體共聚物、甲基丙燦酸/甲基丙烯酸苄酯/聚甲基丙烯酸甲酯巨單體共聚物、甲基丙烯酸/苯乙烯/甲基丙烯酸苄基酯/N-苯基順丁烯二酸亞胺共 -46- (42) (42)200303430 聚物、甲基丙烯酸/甲基丙烯酸2-羥乙酯/甲基丙烯酸苄基I曰/聚本乙；(：希巨單體共聚物、甲基丙燦酸/甲基丙酸羥乙酯/甲基丙烯酸苄酯/聚甲基丙烯酸甲酯巨單體共聚物、甲基丙烯酸/苯乙烯/甲基丙烯酸苄基酯/單甲基丙烯酸丙三醇酯1 N_苯基順丁烯二醯亞胺共聚物、甲基丙烯酸/琥拍酸單（2-丙烯醯氧基乙基）酯/苯乙烯/甲基丙烯酸苄基酯/N-苯基順丁烯二醯亞胺共聚物、甲基丙烯酸/琥珀酸單（2-丙烯醯氧基乙基）酯/苯乙烯/甲基丙烯酸苄基 φ 酯/N-苯基順丁烯二醯亞胺共聚物等。含有羧基之不飽和單體於含有羧基之共聚物（Θ)中的共聚合比率，宜爲5〜50重量％，較宜爲10〜40重量％。此時，含有羧基之不飽和單體之共聚合比率未滿 5重量％時，則所得的組成物對鹼顯影液之溶解性有降低的傾向，另一方面若超過5 0重量。/〇時，則於利用鹼顯影液顯影時，則有容易引起所形成的像元之由基板的脫落像元表面之塗膜粗糙的傾向。 φ 其前述特定的共聚合比率含有含羧基之不飽和單體之含有羧基的共聚物（)，對鹼顯影液具有優越的溶解性者’已使用各該共聚物作黏合劑之著色放射線敏感性組成物，於利用鹼顯影液顯影後殘存有未溶解物係極少的，形成基板上的像元之部份以外的領域較難發生基材污垢、塗膜殘存’而且由該組成物而得的像元係不過量的溶解於鹼顯影液，對基板具有優越的附著性，成爲亦無束自基板脫落之虞者。 -47- (43) (43)200303430 鹼可溶性樹脂之Mw，宜爲3，〇〇〇〜300，〇〇〇，更宜爲 5，000〜8 0，000。又鹼可溶性樹脂之凝膠滲透色譜 (GPC)而得的數目平均分子量（以下稱作「Μη」），宜爲1，500〜60，000，更宜爲3，000〜25，000，尤宜爲 5，000〜20,000。此時鹼可溶性樹脂之Mw或Μη愈高時，則著色層之平坦性愈有提高的傾向，Mw以設成1 0，〇〇〇以上或Μη設成5，000以上爲佳。惟，鹼可溶性樹脂之 Mw若超過300，000，又Μη若超過60，000時，則所得的組成物之塗布性有降低的傾向。於著色放射線敏感性組成物，鹼可溶性樹脂之使用量對著色劑100重量份，宜爲1〇〜1，〇〇〇重量份，較宜爲 20〜5 00重量份。此時鹼可溶性樹脂之使用量未滿10重量份時，例如鹼顯影性有降低，又在像元經予形成的部份以外之領域的基材污染或塗膜殘存發生的顧慮，另一方面若超過1，〇〇〇重量份時，則相對的著色劑濃度降低，欲達成薄膜目的之色濃度即成爲困難的情形。 -(C)多官能單體- 其次，於著色放射線敏感性組成物之多官能性單體，係具有二個以上的聚合性不飽和鍵結之化合物。至於多官能性單體，例如可舉出：乙二醇、丙二醇等的伸烷二醇之二（甲基）丙烯酸酯類；聚乙二醇、聚丙二醇等的聚伸烷二醇之二（甲基）丙烯酸酯類；丙三醇、三羥甲基丙烷、季戊四醇-二季戊四醇等三價以上的多元醇 -48- (44) (44)200303430 之a (甲基）丙烯酸酯類或該等的二羧酸改質物；聚酯、必氧樹月曰月安酉曰樹脂、醇酸樹脂、砂氧樹脂、螺院樹脂等的寡羥基（甲基）丙烯酸酯類；兩終端羥基聚丨，厂丁一細、兩終端聚異戊二烯、兩終端羥基聚己內酯等的兩終端羥基化聚合物之二（甲基）丙烯酸酯類、或參（I (甲基）丙烯醯氧基乙基）磷酸酯等。此等的多官能性單體係可單獨或混合二種以上使用。前述多官能性單體之中，三價以上的多元醇之聚（甲 φ 基）丙嫌酸酯類或該等的二羧酸改質物，具體而言，宜爲二（甲基）丙烯酸二羥甲基丙烷酯、三（甲基）丙烯酸季戊四醇酯、四（甲基）丙烯酸季戊四醇酯、五（甲基）丙烯酸二季戊四醇酯、三（甲基）丙烯酸季戊四醇酯之琥拍酸改質物等，像元之強度及表面平滑性優越且未曝光部之基板及遮光層上以較難發生基材污染、塗膜殘存等的觀點，尤宜爲三丙烯酸三羥甲基丙烷醇、三丙烯酸季戊四醇酯及六丙烯酸二季戊四醇酯。修於著色放射線敏感性組成物，多官能性單體之使用量，對鹼可溶性樹脂1 〇〇重量份，宜爲5〜5 0 0重量份，較宜爲50〜300重量份，尤宜爲100〜300重量份。此時，多官能性單體之使用量愈多則著色層之平坦性愈有提高的傾向，宜爲使用5 0重量份以上。惟多官性單體之使用量若超過5 00重量份時，則鹼顯影性有降低，又未曝光部之基板上或遮光層上有容易發生基底污染、塗膜殘存等的傾向0 -49- (45) (45)200303430 又，於著色放射線敏感性組成物，可以具有一個聚合性不飽和鍵結之單官能性單體取代多官能性單體之一部份〇至於前述單官能性單體，例如前述鹼可溶性樹脂已例示的含有羧基之不飽和單體，其他的不飽和單體之外，可舉出N-乙烯基丁二醯亞胺、N-乙烯基吡咯烷酮、N-乙烯基苯二甲醯亞胺-N-乙烯基-2-薄荷儲酮、N-乙烯基-ε -己內醯胺、Ν-乙烯基吡咯、Ν-乙烯基咪唑鲁、Ν-乙烯基咪唑畊、Ν-乙烯基吲哚、Ν-乙烯基吲哚滿、Ν-乙；基苯并咪唑、Ν-乙燦基咔唑、Ν-乙燒基四氫吡啶、Ν-乙烯基哌啶' Ν-乙烯基嗎啉、Ν-乙烯基苯氧口等哄等Ν-乙烯基衍生物類；Ν·(甲基）丙烯醯基嗎啉、或市售品之Μ- 5300、Μ- 5400、5600 (商品名，東亞合成（股）製造）等。此等單官能性單體，係可單獨或混合二種以上使用。單官能性單體之使用比例，對多官能性單體及單官能鲁性單體之合計，宜爲9〇重量％以下，較宜爲5〇重量％以下。此時，單官能性單體之使用比例若超過90重量％時，則像元之強度或表面平滑性有降低的傾向。 -(D)放射線敏感性聚合引發劑- 其次’於著色放射線敏感性組成物之放射線敏感性聚合引發；=ι!ΐ ’係葙由可具光、紫外線、遠紫外線、電子射束、X射線等之曝光’由可發生能開始前述多官能性單體及 -50- (46) (46)200303430 視情形所使用的單官能性單體之聚合的活性種之化合物而成。至於此種放射線敏感性聚合引發劑，例如可舉出雙咪唑系化合物、苯偶因系化合物、苯乙酮系化合物、二苯酮系化合物、α -二酮系化合物、多核醌系化合物、二苯並硫喃系化合物、重氮系化合物、三啡系化合物等。至於前述雙咪唑系化合物之具體例，可舉出： 2’ 2 -雙（2·氣苯基）—4，4’，5，5’-肆（4_ 乙氧基類基苯基）-1，2、聯咪唑、2，2，-雙（2，4-二氯苯基）-4，4，，5，5、四苯基-1，2，-聯咪唑、2, 2’-雙（2，4，6-三氯苯基）—4，4，，5，5，-四苯基-1 ，2、聯咪唑、2，2，-雙（2-溴苯基）—4，4,，5，5、肆（4-乙氧基羯基苯基）-1，2’-聯咪Ρ坐、2，2，-雙 (2，4-二溴苯基）-4，4’，5，5’-四苯基-1，2，-聯咪唑、2，2’-雙（2，4，6·二溴苯基）一 4，4，，5，5，-四苯基· 1，2、聯咪唑等。此等聯咪唑系化合物，係對溶劑之溶解性優越，不生成未溶解物、析出物等異物，而且靈敏度高，藉由較少的能量之曝光，可使硬化反應充分進行，同時對比較高，於未曝光部不生成硬化反應，故曝光後之塗膜對鹼顯影液，可予明確的區分成不溶性的硬化部份及對鹼顯影液具有較高的溶解性之未硬化部份，可形成圖案之缺損，欠缺或無倒角之優越的濾色片。又’至於前述苯偶因系化合物，例如可舉出苯偶因、 -51 - (47) (47)200303430 苯偶因甲基醚、苯偶因乙醚、苯偶因異丙醚、苯偶因異丁基醚、甲基-2 -苯甲醯基苯甲酸酯等。至於前述苯乙酮系化合物，例如可舉出：2，2-二甲氧基-2-苯基苯乙酮、1-苯基-2-羥基-2-甲基丙烷-卜酮、卜（4-異丙基苯基）-2-羥基-2-甲基丙烷-1-酮、4- (2-羥基乙氧基）苯基-2-(羥基-2-丙基）酮、 2，2- 二甲氧基苯乙酮、2，2-二乙氧基苯乙酮、2-甲基-(4_甲基硫代苯基）-2-嗎啉基-1-丙烷-卜酮、鲁 1- (4-嗎啉基苯基）-2-苄基-2-二甲基胺基丁烷-卜酮、1-羥基環己基苯基酮、4-疊氮苯乙酮、4-疊氮苯醛基苯乙酮等。至於前述二苯酮系化合物，例如可舉出：二苯酮、4 ，4’-雙（二甲基胺基）二苯酮、4，4’-雙（二乙基胺基）二苯酮'3，3’-二甲基-4-甲氧基二苯酮等。至於前述α -二酮系化合物，例如可舉出二乙醯基、二苯甲醯基、甲基苯甲醯基甲酸酯等。 Φ 至於前述多核醌系化合物，例如可舉出二苯並硫喃、咕噸酮' 2，4-二乙基二苯並硫喃、2-氯二苯並硫喃等〇至於前述重氮系化合物，例如可舉出4-重氮二苯基胺、4-重氮-45-甲氧基二苯基胺、4-重氮-3-甲氧基二苯基胺等。至於前述三畊系化合物，例如可舉出2- (2-呋喃基亞乙烯基）-4，6-雙（三氯甲基）-S-三畊、2- (3，4- -52- (48) (48)200303430 一甲氧基苯乙；)#基）-4，6-雙（三氯甲基）-S-三D井、 2-(4-甲氧基萘基）-4，6-雙（三氯甲基）-S-三畊、 2-(2-溴-4-甲基苯基）-4，6、雙（三氯甲基）-S-三畊、2 - (2 -噻嗯基亞乙烯基）—4，6 -雙（三氯甲基）-S -三畊等。再者，至於前述以外的光聚合引發劑，可使用4 -疊氮苯醛、疊氮芘、雙（2，6-二甲氧基苯甲醯基）—2，4 ，4-三甲戊基膦氧化物、N-苯基硫代吖啶酮、三苯基吡喃鏺過氯酸鹽等。此等放射線敏感性聚合引發劑，可單獨或混合二種以於著色放射線敏感性組成物，放射線敏感性聚合引發劑之使用量，對多官能性單體及視情形所使用的單官能性單體之合計100重量份，宜爲〇.〇1〜200重量份，較宜爲 2 0〜1 0 0重量份，尤宜爲4 0〜7 0重量份。此時，放射線敏感性聚合引發劑之使用愈多則著色層之平坦性有愈提高的傾向，宜爲設成2 0重量份以上。惟，放射線敏感性聚合引發劑之使用量若超過200重量份時，則所形成的著色層有顯影時變成容易由基板脫落的傾向。再者，於著色放射線敏感性組成物，與前述放射線敏感性聚合引發劑，同時亦可使用增感劑、氧化促進劑、高分子光交聯、增感劑一種以上。至於前述增感劑，例如可舉出：4-二乙基胺基苯基乙酮、4-二甲基胺基苯丙酮、4-二甲基胺基安息香酸乙 -53- (49) (49)200303430 酯、4-二甲基胺基安息香酸2-乙己酯、2，5-雙（4-二乙基胺基苯醛基）環己酮、7-二乙基胺基-3- (4-二乙基胺基苯甲醯基）香豆素、4-(二乙基胺基）查酮等。此等的增感劑係可單獨或混合二種以上使用。又，至於前述硬化促進劑，例如可舉出2- 1¾基苯并咪唑、2- 1¾基苯並噻Π坐、2 - 酼基苯幷卩坐、2，5 - 二疏基-1，3，4 -噻二唑、2- St基-4，6-二甲基吡啶等鏈轉移劑。此等硬化促進劑，可單獨或混合二種以上使用。又，前述高分子光交換、增感劑，係藉由曝光於主鏈及/或側鏈中具有可用作交聯劑及/或增感劑之至少一種官能基的高分子化合物。至於其例，可舉出：4 -疊氮苯醛及聚乙烯醇之縮合物、4-疊氮苯醛及酚酚醛樹脂之縮合物、桂皮酸4-丙烯醯基苯其酯之（共）聚物、1，4-聚丁二烯、1，2 -聚丁二烯等。此等高分子光交聯、增感劑係可單獨或混合二種以上使用。於著色放射線敏感性組成物、增感劑、硬化促進劑及高分子光交聯、增感劑之合計使用量，對放射線敏感性聚合引發劑100重量份，宜爲3 00重量份以下，較宜爲5〜 200重量份，更宜爲10〜100重量份。 -(E)溶劑· 至於著色放射線敏感性組成物之溶劑’係可適當選擇均勻的分散或溶解構成各該組成物之各成份，與各成份不 -54- (50) (50)200303430 反應’且沸點較2 0 0 °C低者（以下稱作「低沸點溶劑」）並予使用。至於低沸點溶劑，例如可舉出：乙二醇甲基醚、乙二醇單乙基醚、乙二醇單正丙基醚、乙二醇單正丁基醚等二醇醚類；乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單正丙基醚乙酸酯、乙二醇單正丁基醚乙酸酯等乙二醇單烷基醚乙酸酯類； φ 二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單正丙基醚、二乙二醇單正丁基醚等二乙二醇單烷基醚類；丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯等丙二醇單烷基醚乙酸酯類；二乙二醇二甲基醚、二乙二醇二乙基醚、四氫呋喃等的其他醚類；甲基乙基酮、甲異丁基酮、2-庚酮、3-庚酮 '環己酮等酮類； φ 2-羥丙酸甲酯、2-羥丙酸乙酯等的乳酸烷基酯類； 2 ·羥基· 2 -甲基丙酸乙酯、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、乙氧基醋酸乙酯、羥基醋酸乙酯、2-羥基· 3 -甲基丁酸甲酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3 -甲氧基丁基丙酸酯、醋酸乙酯、醋酸正丙酯、醋酸正丁酯、醋酸異丁酯、蟻酸正戊酯、醋酸異戊酯、丙酸正丁酯、酪酸乙酯、酪酸正丙酯、酪酸異丙酯、酪酸正丁 -55- (51) (51)200303430 酯、丙酮甲酸甲酯、丙酸甲酸乙酯、两酸酸正丙酯、乙g盘醋酸甲酯、乙醯醋酸乙酯、2-氮丁烷酸乙酯等的其他酯類；甲苯、二甲苯等芳香族烴類等，此等低沸點溶劑係可單獨或混合二種以上使用。再者於著色放射線敏感性組成物，宜爲使用沸點200 °C以上的溶劑（以下稱作「高沸點溶劑」），由而可使著色層之平坦性提高。至於高沸點溶劑，例如可舉出：二苄基醚、二苯基醚、二正己基醚、二正庚基醚、二正辛基醚、二正十二烷基醚、苄基正十二烷基醚等的醚類 Λ ;異佛爾酮、苯基丙酮、苯丙酮、苯丁酮、苯戊酮等酮類 ;己酸、辛酸等的羧酸類；I -辛醇、1 -壬醇、苄基醇等醇類；安息香酸乙酯、蘋果酸二丙基酯、順丁烯二酸二乙酯、r - 丁內酯等酯類或內酯類；碳酸乙烯酯、碳酸丙烯酯等碳酸伸烷基類；二乙二醇單正丁基醚、二乙二醇單苯基醚、二丙二醇單正丁基醚等的（聚）伸烷二醇單烷基醚或（聚）伸烷二醇單芳香基醚類；二乙二醇單乙基醚乙酸酯、二乙二醇單正丁基醚乙酸酯、二乙二醇單苯基醚乙酸酯、二丙二醇單乙基醚乙酸酯等的（聚）伸烷二醇單烷基醚乙酸酯或（聚）伸烷二醇單芳香醚乙酸酯類。此等高沸點溶劑可單獨或混合二種以上使用。於著色放射線敏感性組成物，高沸點溶劑之使用比例，對全部溶劑，宜爲40重量％以下，更宜爲3 0重量％ -56- (52) (52)200303430 以下，尤宜爲1〜2 0重量％。此時，高沸點溶劑之使用比率若愈高則著色層之平坦性愈提高，惟若超過40重量 %時，則組成物在塗布後之乾燥成爲稍微困難，欲得像元圖案依指定的排列予以配置的像元陣列一事即成爲較困難的顧慮。又，於著色放射線敏感性組成物，溶劑之使用量，對驗可溶性樹脂1 0 0重量份，宜爲1 〇〇〜1 〇，〇 0 0重量份，較宜爲500〜5，00重量份。 φ 添加劑再者，於著色放射線敏感性組成物內，可配合各種添加劑。至於前述添加劑，例如可舉出：玻璃、氧化鋁等塡充劑；聚乙烯醇、聚乙二醇單烷基醚類、聚（氟烷基丙烯酸酯）等高分子化合物；非離子系界面活性劑、陽離子系界面活性劑、陰離子系界面活性劑等之界面活性劑；乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、N- (2-胺基乙修基）-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_胺基丙基乙氧基矽烷、 3-縮水丙氧基丙基三甲氧基砂院、3·縮水丙氧基丙基甲基二甲氧基矽烷、2- (3，4-環氧基環己基）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 -锍基丙基三甲氧基矽烷等附著促進劑；2，2 -硫代雙（4 -甲基-6-第三丁基酚）、2，6-二-第三丁基酚等抗氧化 -57- (53) (53)200303430 劑；2 - (3 -第三丁基-5 -甲基-2 -羥基苯基）-5 -氯苯並三唑、烷氧基二苯酮類等紫外線吸收劑；聚丙烯酸鈉等防止凝集劑等。著色放射線敏感性組成物，在其使用之際，通常分散或溶解構成該組成物之各成份後，宜爲利用例如孔徑2 A m程度之過濾器予以過濾，予以製備著色液狀組成物。於著色放射線敏感性組成物，由可得平坦性優越的著色層之觀點，宜爲可使①需提高鹼可溶性樹脂之分子量， ②需增加多官能性單體之使用量，③需增加放射線敏感性聚合引發劑之使用量，或④使用低沸點溶劑及高沸點溶劑之混合溶劑之至少一個條件滿足。半透射型濾色片之形成方法其次，說明本發明之半透射型濾色片之形成法。半透射型滤色片之形成方法，基本上於基板之表面上，視必要時形成遮光層至使能分劃出形成著色層之部份後 ’於此基板上，形成突起部，同時於該突起部之表面或底部上形成光反射層，其次由形成著色層至使被覆該突起部及殘餘的基板表面而成。以下，具體的說明突起部及著色層之形成方法。至於形成半透射型濾色片之際所使用的基板，例如可舉出玻璃、矽、聚碳酸酯、聚酯、芳香族聚醯胺、聚醯胺醯亞胺、聚醯亞胺等。於此等基板上，視所期待的，亦可先施以利用矽烷偶合劑等之藥品處理、電漿處理、離子植 -58- (54) (54)200303430 入、濺鍍、氣相反應法、真空蒸鍍等適當的前處理。首先，於基板上塗布突起用組成物溶液後，進行後烘烤使溶劑蒸發，形成塗膜。於塗布突起用組成物溶液至基板之際，例如可採用旋塗、流展塗布、輥塗、噴塗等適當的塗布法。塗布厚度係以乾燥後的膜厚計，宜爲0.5〜5.0 // m，較宜爲1.0〜3.5//m，尤宜爲1.5〜3.0//m。其後，於此塗膜上介由光罩使放射線曝光後，採用鹼顯影液並予顯影，溶解去除塗膜之未曝光部，其後因應必要藉由後烘烤，形成突起部。至於形成突起部之際所使用的放射線，例如可使用可具光、紫外線、遠紫外線、電子射束、X射線等。波長爲 1 9 0〜4 5 0 n m之範圍的放射線較宜，尤以含有波長3 6 5 n m 之紫外線的放射線爲尤宜。放射線之曝光量，宜爲400〜9，000J/m2，較宜爲 600 〜4， 500J/m2 〇又，至於前述鹼顯影液，宜爲碳酸鈉、氫氧化鈉、氫氧化鉀、氫氧化四甲基銨、膽鹼、1，8-二氮雜環-[5.4.0] - 7-十一烯、1，5-二氮雜雙聯環· [4.3.0] - 5- 壬烯等的水溶液。鹼顯影液之pH，宜爲10.0〜13.0，又於鹼顯影液內 ’例如亦可適量添加甲醇、乙醇等水溶性有機溶劑或界面活性劑等。至於顯影處理法，例如可適用淋浴顯影法、噴佈顯影 -59- (55) (55)200303430 法、浸漬顯影法、槳葉顯影法等。顯影條件係在常溫宜爲 1 0〜1 8 0秒程度。且，鹼顯影後，宜爲水洗。如此所形成的突起部之形狀，係縱截面形狀基本上以底面爲平面的凸透鏡狀，由上面觀察的平面形狀爲圓形或略圓形，突起部之平面形狀的直徑宜爲1〜30//m，較宜爲5〜20//m。又，突起部之高度（由基板表面至突起部之頂點爲止至基板表面垂直的距離），宜爲〇. 1〜5 // m ’ 更宜爲0.2〜3//m。 · 其次，於突起部之表面上例如藉由金屬蒸鍍，形成指定的光反射層。且，光反射層係依情況亦可形成於突起部之底部與基板之間。至於光反射層所用的金屬，例如可舉出鋁、銀或此等金屬之合金寺。其次，例如塗布含有紅色的著色劑之著色放射線敏感性組成物後，進行預烘烤並使溶劑蒸發，形成塗膜。其後於此塗膜上介由光罩使放射線曝光後，採用鹼顯影液顯影 ® ，溶解去除塗膜之未曝光部，其後視必要時藉由後烘烤，形成紅色之像元圖案以指定的排列配置的像元陣列。又，採用含有綠色或藍色的著色劑之各著色放射線敏感性組成物，與前述同法，進行塗布、預烘烤、曝光及顯影。其後視必要時進行後烘烤，藉由在同一基板上形成綠色的像元陣列及藍色的像元陣列，可得紅色、綠色及藍色之三原色的像元陣列而成之著色層經予配置於基板上的濾色片。惟，形成著色層之際之各色的像元圖案之形成順序 - 60- (56) (56)200303430 ，並非受前述所限定者。塗布著色放射線敏感性組成物於基板之際，例如可採用旋塗、輥塗、噴塗等適當的塗布法。塗布厚度以乾燥後的膜厚計，宜爲〇. 1〜1 0 # m，較宜爲0.2〜5.0//m，尤宜爲0.2〜3.0//m。至於形成著色層之際所使用的放射線，例如可使用可見光、紫外線、遠紫外線、電子射束、X射線等。宜爲波長在190〜45 Onm之範圍內的放射線。 __ 放射線之曝光量宜爲10〜10，000 J/m2。又’至於前述鹼顯影液，例如宜爲碳酸鈉、氫氧化鈉、氫氧化鉀、氫氧化四甲基銨、膽鹼、1，2-二氮雜聯環-[5.4.0] — 7-十一烯、1，5-二氮雜聯環-[4·3·0] -5 -壬烯等的水溶液。前述鹼顯影液之pH宜爲10.0〜13.0。於前述鹼顯影液內，例如可適量添加例如甲醇、乙醇等水溶性有機溶劑或界面活性劑等。馨至於顯影處理法，例如可適用淋浴顯影法、噴布顯影法、浸漬顯影法、槳葉顯影法等。顯影條件係在常溫宜爲 5〜3 00秒。且，鹼顯影後，宜爲用水洗。如此所形成的著色層之縱截面形狀，係雖然不可避免的於位於突起部之上方的光反射領域的某種程度突出於上方’又在突起部不存在的光透射領域的某種程度突出於下部，然而本發明之半透射型濾色片如下述般係具有所謂可減少此等的突起寬幅（突出値）之特徵。 -61 - (57) (57)200303430 半透射型濾色片其次，再具體的說明本發明之半透射型濾色片之特性〇本發明之半透射型濾色片，係於著色層之光反射領域的突出値 [I]，宜爲0.1//Π1以下，更宜爲0.07/zm以下，尤宜爲0.05// m以下。又於光透過領域之突出値[II] ，宜爲〇.l//m以下，更宜爲0.07//m以下，尤宜爲0.05 // m以下。在此，至於「著色層之光反射領域之突出値 [I]」及「著色層之光透射領域之突出値 [II]」，採用第11 圖予以說明。於第1圖，1爲基板、2爲突起部、3爲光反射層、4爲著色層。「於著色層之光反射領域的突出値 [I]」，係意指如第1圖所示，於突起部之上方的光反射領域5的著色層之縱截面，與著色層之平坦的側面接近的平面7係由該側面離開的上方之位置a及該著色層之頂部之間之與基板表面垂直的距離。又「於著色層之光透射領域的突出値 [II]」，係意指如第1圖所示，於突起部不存在的光透射領域6之著色面的縱截面，與位於突起部之上方的著色層之側面相接近的平面7係由該側面離開的下方之位置b 及該著色層之底部之間之與基板表面垂直的距離。本發明之半透射型濾色片，係突出値 Π]及突出値 [II]由於滿足前述條件，在使用背光時及使用作反射型 (58) (58)200303430 時之間可將色純度設成約略同等，尤其提高背光使用時之色純度即成爲可能的。又，本發明之半透射型濾色片’係於著色層之光反射領域的膜厚。宜爲〇。2〜2.0//m，更宜爲0.3〜1·5//ιώ，尤宜爲0.5〜且著色層於光透射領域之膜厚Dt’ 宜爲0.3〜6.0/zm，更宜爲0.5〜4.0//m，尤宜爲1.0〜 2.5 // m 〇在此，「著色層於光反射領域之膜厚」，係意指著色 φ 層於通過突起部及其上方的光反射領域之縱截面，與突起部之頂部（惟形成光反射層於突起部表面時，係該光反射層之表面）及著色層之頂部之間的基板表面成垂直的距離，「著色層於光透射領域之膜厚」係意指著色層於突起部不存在的光透射領域之縱截面，著色層之底部及基板表面之間之與基板表面垂直的距離。又，著色層之膜厚Dt及膜厚Dr之比（Dt/D〇，宜爲1.5〜6.0，更宜爲2.0〜5.0。 Φ 本發明之半透射型濾色片，例如除一般的彩色液晶顯示裝置外，亦於彩色攝影管元件、彩色偵檢器等方面係極其有用的。以下，舉實施例，更具體的說明本發明之實施形態。惟本發明並非受此等實施例所限制者。在此，份及％係重量基準。【實施方式】 -63- (59) 200303430 (顔料分散槳液之製備）調合下述的顏料'顔料，用砂磨器進行分散化處埋、顔料分散助劑及溶劑色顏料分散漿液。衣蒲綠色顏料分散槳液及藍綠色顏料分散漿液 •顏料（份） (10) (5) · (4) (1) (80) C · 1.顏料綠3 6 C ♦ 1.顏料黃1 5 0 •顏料分散劑（份）1173, 1116, 2959, 1664, 4043 (above, manufactured by Ciba Specialty Chemicals-Ciba Specialty Chemicals), KAYACURE- DETX, MBP, DMBI, EPA, OA (above, manufactured by Japan Chemical (Stock)), LUCIRIN TPO (BASF Co. LTD), VIICURE-10, same as 55 (above, STAUFFER Co. LTD), TRIGONALPI (AKZO Co. LTD), TRIGONALPI (AKZO Co. LTD), S ANDORAY 1000 (SANDOZ Co. LTD), DEP (APJOHN Co. Ltd.), QUANTACURE- PDO, same as ITX, same EPD (above, WARD BLEKINSOP Co. LTD)). In addition, as the radiation-sensitive polymerization initiator other than the foregoing, 4-azidobenzoaldehyde, azidofluorene, and bis (2,6-dimethoxybenzylidene) -2,4,4 may be used. -Trimethylpentylphosphine, N-phenylthioacridone, triphenylpyridinium perchlorate and the like. -30- (26) (26) 200303430 These radiation-sensitive polymerization initiators (b 2) can be used alone or in combination of two or more. As the preferred radiation-sensitive polymerization initiator (b2), benzophenones and acetophenones may be mentioned. Among these, 2,4-diethyldibenzosulfan, 2-Monoyl [4- (methylthio) phenyl] -2-morpholinyl · 1-propanyl, and 2-; yl 2-dimethylamino-1- (4-morpholinyl Phenyl) -butane-one. The amount of the radiation-sensitive composition (B) for the protrusion and the radiation-sensitive polymerization initiator (b2) is 100 parts by weight of the polymer (a2), preferably 1 to 50 parts by weight, and particularly preferably 5 to 35 parts by weight. Serving. At this time, the amount of the radiation-sensitive polymerization initiator used is less than 1 part by weight, and the resulting protrusions may cause a decrease in the coating film during development, and there is a concern that the strength may decrease. On the other hand, when the amount exceeds 50 parts by weight, the obtained There is a concern that the voltage holding ratio of the protrusions is insufficient. Furthermore, the radiation-sensitive composition (B) for protrusions can be used in combination with the radiation-sensitive polymerization initiator (b2) in combination with one or more sensitizers, hardening accelerators, and polymer photocrosslinking sensitizers. . Examples of the sensitizer include 4-diethylaminoacetophenone, 4-dimethylaminophenylacetone, 4-dimethylaminobenzoic acid ethyl ester, and 4-dimethylamino group. 2.Ethylhexyl benzoate, 2,5-bis (4-diethylaminophenylmethanine) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzyl) ) Coumarin, 4- (diethylamino) chalconone, etc. These sensitizers can be used alone or in combination of two or more. As the hardening accelerator, for example, 2-fluorenylbenzo-31-(27) (27) 200303430 imidazole, 2-fluorenylbenzothiazole '2 -fluorenylbenzoxazole, 2,5 -Dithiol-1,3,4-thiadihydrazine, 2-thio-4 '6-monomethylaminopyridine, and other chain transfer agents. These hardening accelerators can be used alone or in combination of two or more kinds. use. In addition, the aforementioned polymer photocrosslinking and sensitizers are polymer compounds having at least one functional group of the crosslinker and / or sensitizer in the main chain and / or side chain due to exposure. As for the examples, Examples include the condensate of 4-azidobenzaldehyde and polyvinyl alcohol, the condensate and condensate of 4-azidobenzaldehyde and phenol novolac resin, the (co) polymer of 4-propenylphenyl cinnamate, 1,4-polybutadiene, 1,2-polybutadiene, and the like. These polymer photocrosslinkers and sensitizers can be used alone or in combination of two or more. The total amount of the radiation-sensitive composition (B), sensitizer, hardening accelerator, and polymer photocrosslinking and sensitizer for protrusions is 100 parts by weight of the radiation-sensitive polymerization initiator, preferably 3 The content is less than or equal to 0 parts by weight, more preferably 5 to 200 parts by weight, and even more preferably 100 parts by weight. φ Secondly, as for the unsaturated monomer (c2) of the radiation-sensitive composition (B) for protrusions, difunctional or trifunctional or higher (meth) acrylates are preferred. As for the above-mentioned difunctional (meth) acrylates, for example, ethylene glycol (meth) acrylate, di (meth) acrylic acid, 6-hexanediol, mono (meth) acrylic acid 1 9-nonanediol ester, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol fluorenyl diacrylate, and the like. As for its commercially available products, for example, ΑΠ〇n ix M- -32- (28) (28) 200303430 210, M-240, M-6200 (above, manufactured by Toa Synthetic Co., Ltd.), K AYARAD HDD A, YX- 220, R-6 04 (above, manufactured by Yoshimoto Chemicals Co., Ltd.), Biskote 260, 3 12, 3 3 5 HP (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc. Examples of the trifunctional or higher (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and tri ((meth) acrylic acid ethoxylate) phosphate. Ester), pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. As for the commercially available products, for example, Allonix M-309, M-400, M-402, M-405 'M-450, M-7100, M-8030, M-8060, M-1310, T0_ 1 4 50, M-1 600, M-I 960 'M-8100, M · 8 5 3 0-M-8560, M-9050 (above, manufactured by East Asia Synthetic), KAYARAD TMPTA, DPHA, DP C A-20, DP C A-30, DPCA-60, DPCA · 120, MAX-3510 (above, manufactured by Nippon Chemical Co., Ltd.), Biskote 29 5, 300, 360, GPT, 3PA, 400 ( Above, manufactured by Osaka Organic Chemical Industry Co., Ltd.). These (meth) acrylic acid esters of two or more functional groups can be used alone or in combination. As for the preferable of the unsaturated monomer (C2), pentaerythritol tetrakis (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate can be mentioned. Radiation-sensitive composition (B) for protrusions, unsaturated monomer (c2) weight: 100 parts by weight of copolymer (a2), preferably go ~ 200 (29) (29) 200303430 parts by weight, It is particularly preferably 50 to 140 parts by weight. At this time, when the amount of the polymerizable unsaturated monomer (c2) is less than 30 parts by weight, the resulting protrusions may cause a decrease in the coating film during development, and there is a concern that the strength may decrease. On the other hand, if it exceeds 20, At 0 parts by weight, the adhesion to the substrate of the obtained protrusion tends to decrease. The radiation-sensitive composition (B) for protrusions is more preferably one or more kinds of specific melamine derivatives containing the radiation-sensitive composition (A) for protrusions as described in the above formula (1) or (2). The amount of the radiation-sensitive composition (B) used for protrusions and the specific amount of the melamine derivative is 100 parts by weight of the copolymer (a2), preferably 1 to 100 parts by weight, and particularly preferably 5 to 50 parts by weight. By setting the amount of the specific melamine derivative to be in this range, a projection having a good shape can be formed, and a radiation-sensitive composition (B) for projection that exhibits an appropriate solubility in an alkali developer can be obtained. In addition, a radiation-sensitive composition (B) for protrusions may be compounded with a bonding aid, a surfactant, and the like. As the aforesaid bonding aid and surfactant, for example, the same as the bonding aid and surfactant which have been exemplified as the compounding components of the radiation-sensitive composition (a) for the protrusion described above. The amount of the radiation-sensitive composition (B) for the protrusion, followed by the amount of the adjuvant is 100 parts by weight of the copolymer (a2), preferably 200 parts by weight or less, and particularly preferably 10 parts by weight or less. In this case, if the amount of the adjuvant used exceeds 20 parts by weight, the residual development tends to be easily generated. In addition, the amount of surfactant used, for the copolymer (a2) 100 weight -34- (30) (30) 200303430 parts, preferably 0. 2 parts by weight or less, particularly preferably 0. 0 5 parts by weight or less. At this time, if the amount of the surfactant used exceeds 0. When it is 2 parts by weight, there is a tendency that a splashing phenomenon tends to occur when the alignment film is applied. -Composition solution for protrusions-The radiation-sensitive composition for protrusions, when used, is generally prepared by dissolving the components constituting the composition in an appropriate solvent, for example, by a pore diameter of 0. It is filtered by a filter with a degree of 2 // m, and is prepared into a composition solution for protrusions. As for the solvent used in the preparation of the composition solution for protrusions, as long as the components constituting the radiation-sensitive composition for protrusions are uniformly dissolved, and do not react with each component and have appropriate volatility, they can be appropriately selected and used. Examples of such solvents include: alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methoxyethanol acetate, Ethylene glycol alkyl ether acetates such as ethoxyethanol acetate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, and other diethylene glycol; propylene glycol a Propylene glycol monoalkyl ethers such as ether, propylene glycol ether, propylene glycol propyl ether, propylene glycol butyl ether; propylene glycol methyl ether acetate, propylene glycol ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, and other propylene glycol Alkyl ether acetates; propylene glycol methyl ether propionate, propylene glycol ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate and other propylene glycol alkyl ether acetates; aromatic hydrocarbons such as toluene and xylene ; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-35- (31) (31) 200303430 methyl-4-methyl-2-pentanone; methyl acetate, ethyl acetate, propyl acetate, butyl acetate , Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, hydroxy Methyl acetate ', ethyl glycolate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, 3-hydroxy Propyl propionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, methoxyl Butyl acetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, butoxyacetate Methyl ester, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate. ,2·. Ethyl methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2- Propyl ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2 „ Butyl butoxy propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, 3- Ethyl propoxy propionate, 3-propoxy propionate propionate, 3-propoxy propionate butyl ester, 3-butoxy propionate methyl ester, 3-butoxy propionate ethyl ester, 3- Other esters such as propyl butoxy propionate, butyl 3-butoxy propionate, etc. These solvents can be used alone or in combination of two or more. -36- (32) (32) 200303430 Composition for preparing protrusions The solvents used in the physical solution (A) and (B) are more suitable because of the solubility, the reactivity with each component, and the ease of formation of the coating film. Glycol ethers, glycol alkyl ether acetates, diethylene glycols, and other esters. Furthermore, high-boiling-point solvents can be used in combination with the aforementioned solvents. Examples of high-boiling-point solvents include N-methylformamide, N, N-dimethylformamide, N-methylformamide, N-methylformanilide, N · methylacetamide, N, N-dimethyl Acetylamine, N-methylpyrrolidone, dimethylasco, benzylethyl ether, dihexyl ether, acetonitrile, acetone, isophorone, hexanoic acid, caprylic acid, 1-octanol, ^ nonanol , Benzyl alcohol, carbyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, r-butyrolactone, ethylene carbonate, propylene carbonate, ethylphenylethanol acetate Etc. These high-boiling-point solvents can be used singly or in combination of two or more kinds. Coloring radiation-sensitive composition The radiation-sensitive composition (hereinafter, referred to as "coloring") used in the colored layer forming the transflective color filter of the present invention The radiation-sensitive composition ") is composed of (A) a colored layer, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) radiation Sensitivity of a polymerization initiator and (E) ί valley formed by agent. Hereinafter, each component which comprises a colored radiation sensitive composition is demonstrated. -(Α) Coloring layer- The coloring agent for coloring radiation-sensitive composition, the color tone is not specified. -37- (33) (33) 200303430 If you limit it, you can choose appropriately according to the use of the obtained color filter. Any of organic pigments, inorganic pigments, dyes, and natural pigments may be used. In terms of color filters, high-precision color development and heat resistance are required. The coloring agent of the present invention is preferably a coloring agent with high color development and high heat resistance, and more preferably a high thermal decomposition resistance. The colorant is particularly preferably an organic pigment. As for the aforementioned organic pigment, for example, C. I. Specifically, the compounds classified by pigments (Color Index: issued by the Institute of Dyestuffs and Pigments) are exemplified by the following C [. Number: C · I · Pigment yellow (Pigment Yellow) 12, C. I. Pigment Yellow-13, C. I. Pigment Yellow-14, C. I. Pigment Yellow-17, C. I · Pigment Yellow-20, (:. I. Pigment Yellow-2 4, C. I Pigment Yellow-3 1.C. I. Pigment Yellow-5 5, (:. 1. . Pigment Yellow-83, C. I. Pigment Yellow, 93, C.I. Pigment Yellow-] 09, C · I · Pigment Yellow-110, C ·〗 · Pigment Yellow-; [38, c. ; [. Pigment Yellow-139, C. I. Pigment Yellow150, C.I. Pigment Yellow-153, C. I. Pigment Yellow-1 5 4, C. I Pigment Yellow-1 5 5, C. I. Pigment Yellow-1 6 6, C. I. Pigment Yellow '1 6 8, C _ I. Pigment Yellow-1 8 0, C. I. Pigment Yellow-1 8 5, C. I. Pigment Yellow-2 1 1; C. I. Pigment Orange 36, C. 1. Pigment Orange 43, C. I. Pigment Orange 51, C. I. Pigment Orange 61, C. I. Pigment Orange 7 1; C. I. Pigment Red 9, C. 1. Pigment Red 97, C. I. Pigment Red 122 > C. I. Pigment Red 1 23 、 C. I. Pigment Red 149, C. I. Pigment Red 168, C. I. Pigment Red 176, C. I. Pigment Red 177, C. I. Pigment Red 1 80, C.I. Pigment Red 209, C. I. Pigment Red 215, C. I. Pigment Red 224, C. I. Pigment Red 242, C. I. Pigment Red 2 5 4; (34) 200303430 I, Pigment Violet 19, C. ; [Pigment Violet 2 3, C 1 · Pigment Blue 1 5, c _ I Pigment Blue 6 0, C Pigment Blue -15: 4, C. 1. Pigment Blue 1 5: 1. Pigment Green 7, c. I Pigment Green 3 6, C. C. 1. Pigment Green 2 10; Pigment Violet 2 9; II Material Blue 15: Yan Page Material Green 1 3 6 C. 1. Pigment Brown 2 3, C. ] [. Pigment Brown 2 5; c. L pigment black 1, C. Pigment Black 7. Solvents These organic pigments can be used alone or as a mixture of two or more organic pigments. For example, the organic pigments can be used after being purified by a sulfuric acid recrystallization method or a combination of these. Examples include titanium dioxide, yellow lead, bright yellow, red, chrome oxide green, Ming green, and specific examples of the aforementioned inorganic pigments. Barium sulfate, calcium carbonate, zinc dioxide, lead sulfate-colored iron (III) oxide, Cadmium red, Prolu blue amber, titanium black, synthetic iron black, carbon black, etc. These inorganic pigments can be used alone or in combination of two or more. In the present invention, each of the aforementioned pigments can be modified with a polymer to modify the particle surface as desired. As for the polymer on the particle surface of the modified pigment, for example, the polymers described in Japanese Patent Application Laid-Open No. 8-2 5 9 8 7 6 or the commercially available polymers or oligomers for dispersing various pigments can be mentioned. Wait. In the case of coloring a radiation-sensitive composition, the colorant may be used together with a dispersant as desired. Examples of the dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants. As specific examples of the aforementioned surfactants, polyethylene oxide-39- (35) (35) 200303430 lauryl ether, polyethylene oxide stearyl ether, and polyethylene oxide oleyl ether can be mentioned. And other polyethylene oxide alkyl ethers; polyethylene oxide n-octyl phenyl ether, polyethylene oxide n-nonyl phenyl ether and other polyethylene oxide alkyl phenyl ethers; poly epoxy Yiyuan Institute polyethylene glycol diesters such as dilauryl ester, polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes; polyethylene Imine or KP (sold by Kyoei Chemical Industry Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Product), Megafac )), Flowlard (manufactured by Sumitomo 3M), Asahiguard, Surflon (above, manufactured by Asahi Glass), Disperbyk- 101, 103, 107, 110, 111, 115, 130, 160 '161, 162, 163, 164, 165, 166, 170, 180, 182, 2000, 2001, BYK-165 (above, manufactured by Bykchemie Japan (stock)), So lsperse S 5 000, S 1 2000 'S 1 3 240 > S 1 3 940 > S 1 7000, S 2 0 0 0 0 ^ S22000, S24000, S24000GR, S26000, S27000, S28000 (above, Avia (shares) Manufacturing), EFKA46, 47, 48, 745, 4540, 4550, 6750, EFKA LP4008, 4009, 4010, 401 5, 4050, 405 5, 4 560, 4800, EFKA Polymer 400, 401, 402, 403, 450, 451 453 (manufactured by EFKA Chemicals) These surfactants can be used singly or in combination of two or more kinds. For the coloring radiation-sensitive composition and the amount of pigment dispersant used, 100 parts by weight of the attached colorant, preferably 1 to 50 parts by weight, and more preferably 3 to 30 parts by weight. At this time, when the amount of pigment dispersant is less than 1 part by weight, the dispersibility of Yan-40- (36) (36) 200303430 tends to decrease. On the other hand, if it exceeds 50 parts by weight, the The solubility of the developer tends to decrease. -(B) Alkali-soluble resin-Secondly, the alkali-soluble resin 'coloring radiation-sensitive composition' acts on a colorant or a binder, and is limited to being soluble in an alkali developing solution used in a developing process step when manufacturing a color filter, Appropriate resins can be used. Examples of the alkali-soluble resin include resins having acidic functional groups such as a carboxyl group and a phenolic hydroxyl group. Among the alkali-soluble resins, as for the alkali-soluble resin containing a carboxyl group, for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to simply as "copolymer-containing unsaturated, monomer" (co) polymerization) As for the (co) polymer of the unsaturated monomer containing the aforementioned carboxyl group, it is particularly preferred that the unsaturated monomer containing a carboxyl group and other copolymerizable unsaturated monomer (hereinafter referred to as "other unsaturated monomer" ") Is a copolymer of monomer mixtures (referred to as" carboxyl-containing copolymer (/ S) ". Examples of the unsaturated monomer containing a carboxyl group include acrylic acid, methacrylic acid, and crotonic acid. , Unsaturated monocarboxylic acids such as α-chloroacrylic acid and cinnamic acid, maleic acid, maleic anhydride, maleic acid, itaconic acid, itaconic anhydride, maleic acid, Unsaturated dicarboxylic acids (anhydrides) such as cis methylbutene dianhydride, trans methylbutenedioic acid, etc .; unsaturated polycarboxylic acids (anhydrides) of three or more valences; succinic acid mono (2-propene) Oxyethyl) ester, succinate mono (2-methylpropane) Ethoxyethyl) ester, phthalic acid mono (2-propylene ethoxyethyl) ester, phthalic acid mono (2- -41-(37) (37) 200303430 methacrylic ethoxyethyl) Mono- [2- (methyl) propanyloxyethyl] esters of non-polymerizable dicarboxylic acids such as esters, ω-residue polycaprolactone monopropionate, ω-carboxy polycaprolactone mono Methacrylic esters, etc. These unsaturated monomers containing a carboxyl group can be used alone or in combination of two or more. In addition, succinic acid mono (2-propenyloxyethyl) ester and phthalic acid mono (2 · propylene) Ethoxyethyl) esters are being marketed under the trade names of M. 5300 and M_ 5400 (manufactured by East-West Synthetic Co., Ltd.). As for other unsaturated monomers, for example, Examples: styrene, methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methyl Oxystyrene, p-methoxystyrene, o-vinyl methyl ethyl ether, m-vinyl methyl ethyl ether, p-vinyl methyl ethyl ether, o-vinyl benzyl glycidyl Ether, m-vinylbenzyl glycidyl ether, an aromatic vinyl compound; indene. I-indenes such as methylindene: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid N-butyl acid, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate '(meth) propionic acid 2-hydroxyethyl ester, (methyl ) 2-hydroxypropyl acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Ester, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2.methoxyethyl (meth) acrylate, ( 2-benzene-42- (meth) acrylate (38) (38) 200303430 oxyethyl, isophorone (meth) acrylate, dicyclopentyl (meth) acrylate, (meth) acrylic acid 2-hydroxy-3-phenoxypropyl ester, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (methyl Unsaturated carboxylic acid esters such as acrylate, methoxypropylene glycol (meth) acrylate, glycerol mono (meth) acrylate, etc .; 2-aminoethyl (meth) acrylate, (meth) Acrylic-2 · Monomethyl Acetyl Acetate, (Meth) propane-2-aminopropionate, (Meth) -2-dimethylaminopropyl Acrylate, (Meth) Acrylic · Unsaturated carboxylic acid amino alkyl esters such as 3-aminopropyl ester, 3-aminopropyl (meth) acrylate, and 3-dimethylaminopropyl (meth) acrylate; (methyl ) Glycidyl esters of unsaturated carboxylic acids, such as glycidyl acrylate; Vinyl carboxylates, such as vinyl acetate, vinyl propionate, vinyl caseinate, and vinyl benzoate; vinyl methyl Unsaturated ethers such as ether, vinyl ethyl ether, allyl glycidyl ether, methacryl glycidyl ether; (fluorenyl) acrylonitrile, α-chloroacrylonitrile, ethylene cyanide, etc. Vinyl compounds; (meth) acrylamide, α-chloroacrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N-hydroxymethyl Unsaturated fluorenes such as methyl) acrylamide; unsaturated fluorenes such as maleimide diimide, N-cyclohexyl maleimide diimide, N-phenyl maleimide diimide Amines; -43- (39) (39) 200303430 1,3-Butadiene, isoprene, chlorinated aliphatic conjugated diene; polystyrene, polymethyl acrylate, polymethyl Macromonomers having monoacrylfluorene or monomethacrylfluorene groups at the terminals of polymer molecular chains such as methyl acrylate, polybutyl acrylate, and polysiloxane. These other unsaturated monomers can be used alone or in combination of two or more. As for the copolymer (y?) Containing the end group, it is preferred that ① acrylic and / or methacrylic acid is necessary, and as appropriate, succinic acid mono (2-propanefluorenyloxyethyl) ester and succinic acid monomer are further included. (2-methacryloxyethyl) ester, ω-carboxy polycaprolactone monoacrylate, and carboxy polycaprolactone monomethacrylate selected from the group of unsaturated monomers containing at least one unsaturated group ② with styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, and propylene glycol mono (meth) acrylic acid Copolymers of at least one unsaturated monomer selected from the group of esters, N-phenylcis butylene diimide, polystyrene macromonomers, and polymethyl methacrylate macromonomers (hereinafter referred to as containing carboxyl groups) Copolymer (/ 3-1)). As for specific examples of carboxyl-containing copolymers (million-〗), examples include: (meth) acrylic acid / methyl methacrylate copolymer, (meth) acrylic acid. / (Meth) acrylic acid benzyl copolymer, (meth) acrylic acid / styrene / (fluorenyl) methyl acrylate copolymer, (meth) acrylic acid / styrene / (meth) acrylic acid benzyl copolymer, ( (Meth) acrylic acid / (meth) acrylic acid / polystyrene macromonomer-44- (40) (40) 200303430 copolymer, (meth) acrylic acid / (meth) acrylic acid methyl ester / polymethacrylic acid Methyl ester macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate-based polymer, (meth) acrylic acid / benzyl (meth) acrylate / Polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / (meth) acrylic acid 2-hydroxyethyl Ester / (meth) acrylic acid benzyl ester / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / (meth) benzyl acrylate / polymethyl methacrylate Macromonomer copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylcis butylene diimide copolymer, (meth) acrylic acid / styrene / (Benzyl) (meth) acrylate / glycerol mono (meth) acrylate / N-phenyl maleene diimide copolymer, (meth) acrylic acid / succinic mono [2-methyl] propylene Ethoxyethyl] ester / styrene / benzyl (meth) acrylate / N-phenylcis butylene diimide copolymer, (meth) acrylic acid / succinic acid mono [2-methyl] acrylic acid Oxyethyl] ester / styrene / allyl (meth) acrylate / N-phenylmaleimide diimide copolymer, (meth) acrylic acid / mono (meth) acrylic omega-carboxy polyhexylene (41) (41) 200303430 ester / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylcis butylene diimide copolymer, (methyl) Acrylic acid / succinic acid mono [2 · (meth) acryloxyethyl] ester / mono (meth) acrylic carboxy polycaprolactone / styrene / (meth) acrylic acid: Cargill Pro / mono ( Methyl) glycerol glycerol / N-phenyl maleene diimide copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) propenyloxyethyl] ester / Mono (meth) acrylic omega-carboxy polycaprolactone / styrene / φ (meth) acrylic acid Acid benzyl ester / glycerol mono (meth) acrylate / N-phenylcis butylene difluorene imine copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acrylic acid oxyethyl [Ethyl] ester / ω-carboxypolycaprolactone / styrene (styrene) / benzyl (meth) acrylate / glycerol mono (meth) acrylate_ / N-phenylmaleic acid Imine copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloxyethyl]] / mono (meth) acrylic acid ω · residual polycaprolactone / acetophenone / Allyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylcis butylene diimide copolymer. Among these copolymers 1) containing a radical, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / fluorenyl bis-acid 2-hydroxyethyl ester / benzyl methacrylate copolymer Polymer, methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / Styrene / benzyl methacrylate / N-phenylmaleic acid imine co-46- (42) (42) 200303430 polymer, methacrylic acid / 2-hydroxyethyl methacrylate / methyl Benzyl acrylate I / polyethylene; (: Greek macromonomer copolymer, methacrylic acid / hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer Methacrylic acid / styrene / benzyl methacrylate / glycerol monomethacrylate 1 N-phenylcis butylene diimide copolymer, methacrylic acid / succinic acid mono (2-propylene Ethoxyethyl) ester / styrene / benzyl methacrylate / N-phenylcis butylene diimide copolymer, methacrylic acid / succinic acid mono (2-propenyloxyethyl) ester / Ethylene / benzyl φ methacrylate / N-phenylcis butylene diimide copolymer, etc. The copolymerization ratio of the unsaturated monomer containing a carboxyl group to the copolymer (Θ) containing a carboxyl group is preferably 5 ~ 50% by weight, more preferably 10 ~ 40% by weight. At this time, when the copolymerization ratio of the unsaturated monomer containing a carboxyl group is less than 5% by weight, the solubility of the obtained composition in the alkali developer is reduced. On the other hand, if it exceeds 50% by weight, when it is developed with an alkaline developer, there is a tendency that the formed film may be roughened by the falling off of the surface of the pixel from the substrate. Φ its The above-mentioned specific copolymerization ratio contains a carboxyl group-containing unsaturated monomer and a carboxyl group-containing copolymer (), which has excellent solubility in an alkali developer, and has used each of the copolymers as a binder for a colored radiation-sensitive composition After the development with an alkaline developer, there are very few undissolved substances remaining, and it is more difficult to produce substrate dirt and coating film residues in areas other than the pixels forming the substrate on the substrate, and the pixels obtained from the composition Not excessively soluble in The developing solution has excellent adhesion to the substrate, and there is no risk that the bundle will fall off the substrate. -47- (43) (43) 200303430 The Mw of the alkali-soluble resin is preferably 3,000-300,00. 〇, more preferably 5,000 to 8,000. The number-average molecular weight (hereinafter referred to as "Μη") obtained by gel permeation chromatography (GPC) of an alkali-soluble resin is preferably 1,500 to 60,000. , More preferably 3,000 to 25,000, especially 5,000 to 20,000. At this time, the higher the Mw or Mη of the alkali-soluble resin, the flatness of the colored layer tends to be improved, and Mw is set to 10,000 or more or Mn is preferably set to 5,000 or more. However, if the Mw of the alkali-soluble resin exceeds 300,000 and the Mη exceeds 60,000, the coatability of the obtained composition tends to decrease. For coloring radiation-sensitive compositions, the amount of alkali-soluble resin used is preferably 100 to 1,000,000 parts by weight, and more preferably 20 to 5,000 parts by weight, based on 100 parts by weight of the colorant. At this time, when the amount of the alkali-soluble resin is less than 10 parts by weight, for example, the alkali developability is reduced, and there is a concern that the substrate is contaminated or the coating film remains in areas other than the area where the pixels are formed, on the other hand If it exceeds 1,000 parts by weight, the relative concentration of the toner decreases and it becomes difficult to achieve the color concentration of the film. -(C) Polyfunctional monomer-Second, the polyfunctional monomer in the colored radiation sensitive composition is a compound having two or more polymerizable unsaturated bonds. Examples of the polyfunctional monomer include di (meth) acrylates of butanediols such as ethylene glycol and propylene glycol; and two of poly (alkylene glycols) such as polyethylene glycol and polypropylene glycol ( (Meth) acrylates; glycerol, trimethylolpropane, pentaerythritol-dipentaerythritol and more than trivalent polyhydric alcohols-48- (44) (44) 200303430 a (meth) acrylates or these Modified products of dicarboxylic acids; polyesters, bismuth resins, alkyd resins, sand oxygen resins, snail resins, and other oligohydroxy (meth) acrylates; two terminal hydroxyl poly, Two (meth) acrylic acid esters of a two-terminal hydroxylated polymer, such as a plant, two-terminal polyisoprene, two-terminal hydroxypolycaprolactone, or ginseng (I (meth) acrylic acid) Ethyl) phosphate and the like. These polyfunctional monosystems can be used alone or in combination of two or more. Among the above-mentioned polyfunctional monomers, poly (methylφ) propionic acid esters of trivalent or higher polyhydric alcohols or dicarboxylic acid modified products thereof, specifically, di (meth) acrylic acid Methylolpropane ester, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, modified succinic acid of pentaerythritol tri (meth) acrylate, etc., The pixel has excellent strength and surface smoothness, and the substrate and the light-shielding layer of the unexposed part are more difficult to cause contamination of the substrate and the remaining of the coating film. Trimethylolpropane triacrylate and pentaerythritol triacrylate are particularly preferred. And dipentaerythritol hexaacrylate. Modified for coloring radiation-sensitive composition, the amount of polyfunctional monomer used is 1,000 parts by weight of alkali-soluble resin, preferably 5 to 500 parts by weight, more preferably 50 to 300 parts by weight, and particularly preferably 100 to 300 parts by weight. In this case, the more the amount of the polyfunctional monomer used, the flatness of the colored layer tends to be improved, and it is preferable to use 50 parts by weight or more. However, if the amount of the polyfunctional monomer exceeds 5000 parts by weight, the alkali developability will be reduced, and the substrate on the unexposed area or the light-shielding layer will tend to cause substrate contamination and residual coating film. 0 -49 -(45) (45) 200303430 In the colored radiation sensitive composition, a polymerizable unsaturated bond may be used to replace a part of the polyfunctional monomer with a monofunctional monomer. As for the aforementioned monofunctional monomer, For example, the unsaturated monomer containing a carboxyl group as exemplified in the aforementioned alkali-soluble resin, and other unsaturated monomers include N-vinyl succinimide, N-vinyl pyrrolidone, and N-vinyl Xylyleneimine-N-vinyl-2-menthol, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylimidazole, N-vinylimidazole, N-vinylindole, N-vinylindole, N-ethyl; benzimidazole, N-ethanylcarbazole, N-ethylenyltetrahydropyridine, N-vinylpiperidine 'Ν- Vinylmorpholine, N-vinylphenoxy, and other N-vinyl derivatives; N · (meth) acrylfluorenylmorpholine, or commercially available products Μ- 5300, Μ- 5400,5600 (trade name, East Asia synthesis (shares)) and the like. These monofunctional monomers may be used alone or in combination of two or more. The use ratio of the monofunctional monomer is preferably 90% by weight or less, and more preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the use ratio of the monofunctional monomer exceeds 90% by weight, the strength of the pixel and the surface smoothness tend to decrease. -(D) Radiation-sensitive polymerization initiator-Secondly, it is initiated by radiation-sensitive polymerization of colored radiation-sensitive composition; = ι! Ϊ́ '系葙 is composed of light, ultraviolet, far ultraviolet, electron beam, X-ray Etc. 'and the like are formed from compounds capable of initiating polymerization of the aforementioned polyfunctional monomer and -50- (46) (46) 200303430, as appropriate, of the monofunctional monomer used. Examples of such radiation-sensitive polymerization initiators include bisimidazole-based compounds, benzoin-based compounds, acetophenone-based compounds, benzophenone-based compounds, α-diketone-based compounds, polynuclear quinone-based compounds, Benzosulfan-based compounds, diazonium-based compounds, trimorphine-based compounds, and the like. As specific examples of the aforementioned bisimidazole-based compound, 2 '2 -bis (2 · phenylphenyl) -4,4', 5,5 '-(4_ethoxy-based phenyl) -1 2,2, biimidazole, 2,2, -bis (2,4-dichlorophenyl) -4,4,5,5, tetraphenyl-1,2, -biimidazole, 2, 2'-bis (2,4,6-trichlorophenyl) -4,4,5,5,5-tetraphenyl-1,2, biimidazole, 2,2, -bis (2-bromophenyl) -4, 4,, 5,5, 4- (4-ethoxyfluorenylphenyl) -1,2'-bipyrimidine, 2,2, -bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2, -biimidazole, 2,2'-bis (2,4,6 · dibromophenyl) -4,4,5,5, -tetrabenzene Base · 1, 2, biimidazole and the like. These biimidazole-based compounds have excellent solubility in solvents, do not generate foreign matters such as undissolved matter and precipitates, and have high sensitivity. With less energy exposure, the hardening reaction can be fully carried out, and the contrast is high. There is no hardening reaction in the unexposed part, so the coating film after exposure can be clearly distinguished into the insoluble hardened part and the unhardened part with higher solubility to the alkali developing solution. Excellent color filter for forming defects, lacking or no chamfering. As for the aforementioned benzoin-based compound, for example, benzoin, -51-(47) (47) 200303430 benzoin methyl ether, benzoin ether, benzoin isopropyl ether, and benzoin Isobutyl ether, methyl-2-benzylidene benzoate, and the like. Examples of the aforementioned acetophenone-based compounds include 2,2-dimethoxy-2-phenylacetophenone, 1-phenyl-2-hydroxy-2-methylpropane-butanone, and ( 4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) one, 2, 2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2-methyl- (4-methylthiophenyl) -2-morpholinyl-1-propane-butanone 1- (4-morpholinylphenyl) -2-benzyl-2-dimethylaminobutane-butanone, 1-hydroxycyclohexylphenyl ketone, 4-azidoacetophenone, 4 -Azidobenzophenone and the like. Examples of the benzophenone-based compound include benzophenone, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis (diethylamino) benzophenone. '3,3'-dimethyl-4-methoxybenzophenone and the like. As the α-diketone-based compound, for example, diethylfluorenyl, dibenzofluorenyl, methylbenzylmethyl formate and the like can be mentioned. Φ As for the aforementioned polynuclear quinone-based compound, for example, dibenzosulfan, gurtanone '2,4-diethyldibenzosulfan, 2-chlorodibenzosulfan, etc. are mentioned. Examples of the compound include 4-diazodiphenylamine, 4-diazo-45-methoxydiphenylamine, 4-diazo-3-methoxydiphenylamine, and the like. Examples of the three-tillage compounds include 2- (2-furanylvinylene) -4,6-bis (trichloromethyl) -S-three-tillage, 2- (3,4- -52- (48) (48) 200303430 monomethoxyphenethyl;) #yl) -4,6-bis (trichloromethyl) -S-tri-D, 2- (4-methoxynaphthyl) -4 , 6-Bis (trichloromethyl) -S-Sangen, 2- (2-Bromo-4-methylphenyl) -4,6, Bis (trichloromethyl) -S-Sangen, 2- (2-thienyl vinylidene) -4,6-bis (trichloromethyl) -S-Sangen, etc. In addition, as for the photopolymerization initiator other than the foregoing, 4-azidobenzaldehyde, azide, and bis (2,6-dimethoxybenzyl) -2,4,4-trimethylpentyl can be used. Phosphine oxide, N-phenylthioacridone, triphenylpyranonium perchlorate, and the like. These radiation-sensitive polymerization initiators can be used alone or as a mixture of two types of radiation-sensitive polymerization initiators, the amount of radiation-sensitive polymerization initiators used, and polyfunctional monomers and monofunctional monomers as appropriate. The total body is 100 parts by weight, preferably 0. 〇1 ~ 200 parts by weight, more preferably 20 ~ 100 parts by weight, particularly preferably 40 ~ 70 parts by weight. At this time, the more the radiation-sensitive polymerization initiator is used, the more the flatness of the colored layer tends to be improved, and it is preferably set to 20 parts by weight or more. However, when the amount of the radiation-sensitive polymerization initiator used exceeds 200 parts by weight, the colored layer formed tends to be easily peeled off from the substrate during development. Furthermore, in the colored radiation-sensitive composition, the radiation-sensitive polymerization initiator may be used in combination with one or more of a sensitizer, an oxidation accelerator, a high-molecular photocrosslinking agent, and a sensitizer. Examples of the sensitizer include 4-diethylaminophenylethyl ketone, 4-dimethylaminophenylacetone, and 4-dimethylaminobenzoic acid ethyl-53- (49) ( 49) 200303430 ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 2,5-bis (4-diethylaminobenzyl) cyclohexanone, 7-diethylamino-3- (4-Diethylaminobenzyl) coumarin, 4- (diethylamino) chalconone, and the like. These sensitizers can be used individually or in mixture of 2 or more types. As the hardening accelerator, for example, 2- 12-benzylbenzimidazole, 2- 12-benzylbenzothiazine, 2-fluorenylbenzofluorene, and 2,5-bissulfanyl-1,3 are mentioned. , 4-thiadiazole, 2-Styl-4,6-dimethylpyridine and other chain transfer agents. These hardening accelerators can be used alone or in combination of two or more. The polymer light exchange and sensitizer are polymer compounds having at least one functional group that can be used as a cross-linking agent and / or a sensitizer by being exposed to the main chain and / or the side chain. As examples thereof, there may be mentioned: a condensate of 4-azidobenzaldehyde and polyvinyl alcohol, a condensate of 4-azidobenzaldehyde and a phenol novolac resin, and (co) of 4-propenylbenzyl cinnamate Polymers, 1,4-polybutadiene, 1,2-polybutadiene, and the like. These polymer photocrosslinkers and sensitizers can be used alone or in combination of two or more. Based on the total amount of colored radiation-sensitive composition, sensitizer, hardening accelerator, and high-molecular photocrosslinking and sensitizer, 100 parts by weight of the radiation-sensitive polymerization initiator is preferably 300 parts by weight or less. It is preferably 5 to 200 parts by weight, and more preferably 10 to 100 parts by weight. -(E) Solvent · As for the solvent of the colored radiation-sensitive composition, 'The components constituting each composition can be uniformly dispersed or dissolved appropriately, and react with the components not in the range of -54- (50) (50) 200303430' And the boiling point is lower than 200 ° C (hereinafter referred to as "low boiling point solvent") and used. As for the low boiling point solvent, for example, glycol ethers such as ethylene glycol methyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol mono-n-butyl ether; Ethylene glycol monoalkyl such as alcohol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate Ether acetates; φ diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, and other diethylene glycol monoalkanes Ethers; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran And other ethers; methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 3-heptanone 'cyclohexanone and other ketones; φ methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate Lactic acid alkyl esters such as esters; 2-hydroxy-2-methylpropionate, 3-methoxypropionate methyl ester, 3-methoxypropionate ethyl ester, and 3.ethoxypropionate methyl ester Ester, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, hydroxy Ethyl acetate, 2-hydroxy3-methylbutanoic acid methyl ester, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, acetic acid Ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyrate D-55- (51) (51) 200303430 ester, methyl acetone formate, ethyl propionate, n-propyl diacetate, ethyl acetate, ethyl acetate, 2-nitrobutanoic acid Other esters such as ethyl ester; aromatic hydrocarbons such as toluene and xylene, etc. These low boiling point solvents can be used alone or as a mixture of two or more. Furthermore, for colored radiation-sensitive compositions, it is preferable to use a solvent having a boiling point of 200 ° C or higher (hereinafter referred to as "high boiling point solvent"), so that the flatness of the colored layer can be improved. As for the high boiling point solvent, for example, dibenzyl ether, diphenyl ether, di-n-hexyl ether, di-n-heptyl ether, di-n-octyl ether, di-n-dodecyl ether, benzyl-n-dodecyl Ethers such as alkyl ethers; ketones such as isophorone, phenylacetone, phenylacetone, phenone ketone, phenvalerone; carboxylic acids such as hexanoic acid, octanoic acid; I-octanol, 1-nonanol , Alcohols such as benzyl alcohol; ethyl benzoate, dipropyl malate, diethyl maleate, r-butyrolactone and other esters or lactones; ethylene carbonate, propylene carbonate, etc. Alkyl carbonates; (poly) alkylene glycol monoalkyl ethers or (poly) ethylene glycols such as diethylene glycol mono-n-butyl ether, diethylene glycol monophenyl ether, and dipropylene glycol mono-n-butyl ether Alkanediol monoaryl ethers; diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monophenyl ether acetate, dipropylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ether acetates and (Poly) alkylene glycol monoaromatic ether acetates, such as alkyl ether acetates. These high boiling point solvents can be used alone or in combination of two or more. For colored radiation-sensitive compositions, the proportion of high boiling point solvents used is preferably 40% by weight or less, more preferably 30% by weight of all solvents, -56- (52) (52) 200303430 or less, particularly preferably 1 to 20% by weight. At this time, the higher the use ratio of the high-boiling-point solvent, the higher the flatness of the colored layer. However, if it exceeds 40% by weight, it becomes slightly more difficult to dry the composition after coating. Arranging a cell array becomes a more difficult concern. In addition, the amount of solvent used in the colored radiation-sensitive composition and the solvent is 100 parts by weight of the soluble resin, preferably 1,000 to 10,000 parts by weight, and more preferably 500 to 5,000 parts by weight. . φ Additives Various additives can be added to the colored radiation sensitive composition. Examples of the aforementioned additives include: fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, and poly (fluoroalkyl acrylate); and nonionic interface activity Surfactants, cationic surfactants, anionic surfactants, etc .; vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethoxy) -3-amine Propylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropylethoxysilane, 3-glycidoxypropane Trimethoxysilane, 3 · propoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Adhesion promoters such as dimethoxysilane-3-chloropropyltrimethoxysilane '3-methacryloxypropyltrimethoxysilane, 3-methylpropyltrimethoxysilane; 2, 2- Anti-oxidants such as thiobis (4-methyl-6-tert-butylphenol) and 2,6-di-tert-butylphenol-57- (53) (53) 200303430; 2-(3- Tributyl-5 -methyl-2 -hydroxyl Yl) -5 - chlorobenzotriazole, alkoxy benzophenone ultraviolet absorbers and the like; sodium polyacrylate and the like to prevent aggregation. The colored radiation-sensitive composition is usually prepared by dispersing or dissolving the components constituting the composition, and then filtering the colored radiation-sensitive composition by using a filter having a pore size of about 2 A m, for example. From the viewpoint of obtaining a coloring layer with excellent flatness from the viewpoint of obtaining a coloring layer with excellent flatness, it is desirable to make it necessary to increase the molecular weight of the alkali-soluble resin, ② increase the amount of polyfunctional monomers, ③ increase radiation sensitivity At least one of the conditions of the amount of the polymerization initiator used or ④ the use of a mixed solvent of a low boiling point solvent and a high boiling point solvent is satisfied. Method for forming transflective color filter Next, a method for forming the transflective color filter of the present invention will be described. The method for forming a semi-transmissive color filter is basically on the surface of the substrate. If necessary, a light-shielding layer is formed to enable the portion where the colored layer is formed to be divided. A light reflecting layer is formed on the surface or bottom of the protrusion, and the second step is to form a colored layer to cover the protrusion and the surface of the remaining substrate. Hereinafter, a method for forming the protrusions and the colored layer will be specifically described. Examples of the substrate used in forming the transflective color filter include glass, silicon, polycarbonate, polyester, aromatic polyimide, polyimide, imine, and polyimide. On these substrates, depending on expectations, chemical treatment using plasma coupling agent, plasma treatment, ion implantation, -58- (54) (54) 200303430 injection, sputtering, gas phase reaction method can also be applied first. , Vacuum evaporation and other appropriate pretreatment. First, after applying the composition solution for protrusions on a substrate, post-baking is performed to evaporate the solvent to form a coating film. When applying the composition solution for a protrusion to a substrate, a suitable coating method such as spin coating, flow coating, roll coating, or spray coating can be used. Coating thickness is based on the film thickness after drying, preferably 0. 5 ~ 5. 0 // m, preferably 1. 0 ~ 3. 5 // m, especially 1. 5 ~ 3. 0 // m. Thereafter, after the radiation is exposed through a photomask on this coating film, an alkali developing solution is used and developed to dissolve and remove the unexposed portion of the coating film. Thereafter, it is necessary to form a protruding portion by post-baking. As the radiation to be used when forming the protrusions, for example, light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used. Radiation having a wavelength in the range of 190 to 450 nm is more suitable, and radiation containing ultraviolet rays having a wavelength of 365 nm is particularly suitable. The amount of radiation exposure is preferably 400 to 9,000 J / m2, more preferably 600 to 4,500 J / m2. As for the aforementioned alkali developing solution, sodium carbonate, sodium hydroxide, potassium hydroxide, and tetrahydroxide are preferred. Methyl ammonium, choline, 1,8-diazepine- [5. 4. 0]-7-undecene, 1,5-diazabicyclo [4. 3. 0]-Aqueous solution such as 5-nonene. The pH of the alkaline developer is preferably 10. 0 ~ 13. 0, and in an alkaline developer, for example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added. As the development processing method, for example, a shower development method, a spray development method, a -59- (55) (55) 200303430 method, an immersion development method, and a paddle development method can be applied. The developing conditions should be about 10 to 180 seconds at normal temperature. After alkali development, washing with water is preferred. The shape of the protruding portion formed in this way is a convex lens shape whose longitudinal cross-sectional shape is basically a plane on the bottom surface, and the planar shape viewed from above is circular or slightly circular. The diameter of the planar shape of the protruding portion is preferably 1 to 30 / / m, more preferably 5 to 20 // m. In addition, the height of the protrusion (the vertical distance from the substrate surface to the apex of the protrusion to the substrate surface) is preferably 0. 1 ~ 5 // m ′ is more preferably 0. 2 ~ 3 // m. · Next, a predetermined light reflecting layer is formed on the surface of the protrusion, for example, by metal evaporation. In addition, the light reflecting layer may be formed between the bottom of the protruding portion and the substrate as appropriate. As the metal used in the light reflection layer, for example, aluminum, silver, or an alloy of these metals can be mentioned. Next, for example, after a colored radiation-sensitive composition containing a red coloring agent is applied, pre-baking is performed and the solvent is evaporated to form a coating film. Then, after the radiation is exposed through a photomask on this coating film, it is developed with an alkali developer to dissolve and remove the unexposed part of the coating film. Afterwards, if necessary, a red pixel pattern is formed by post-baking to form The cell array of the specified arrangement. Further, each colored radiation-sensitive composition containing a green or blue coloring agent was applied, pre-baked, exposed, and developed in the same manner as described above. Afterwards, if necessary, post-baking is performed. By forming a green pixel array and a blue pixel array on the same substrate, a coloring layer formed by a pixel array of three primary colors of red, green, and blue can be obtained. A color filter pre-arranged on the substrate. However, the order of formation of the pixel patterns of each color when forming the colored layer-60- (56) (56) 200303430 is not limited by the foregoing. When applying a colored radiation-sensitive composition to a substrate, a suitable coating method such as spin coating, roll coating, or spray coating can be used. The coating thickness is based on the film thickness after drying, preferably 0. 1 ~ 1 0 # m, preferably 0. 2 ~ 5. 0 // m, especially 0. 2 ~ 3. 0 // m. As the radiation used in forming the coloring layer, for example, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used. It should be radiation with a wavelength in the range of 190 to 45 Onm. __ The radiation exposure should be 10 ~ 10,000 J / m2. And as for the aforementioned alkali developing solution, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,2-diazabicyclo- [5. 4. 0] — 7-undecene, 1,5-diazabicyclo- [4 · 3 · 0] -5 -nonene and other aqueous solutions. The pH of the aforementioned alkaline developer is preferably 10. 0 ~ 13. 0. For example, a suitable amount of a water-soluble organic solvent such as methanol, ethanol, or a surfactant may be added to the alkali developing solution. As the development treatment method, for example, a shower development method, a spray development method, a dip development method, a paddle development method, and the like can be applied. The developing conditions are preferably 5 to 300 seconds at room temperature. After alkali development, washing with water is preferred. The longitudinal cross-sectional shape of the coloring layer formed in this way is unavoidable to protrude to a certain extent in the light reflection area above the protrusions, and to a certain extent in the light transmission area where the protrusions do not exist The lower part, however, the transflective color filter of the present invention has a feature of reducing so-called protrusion width (protrusion) as described below. -61-(57) (57) 200303430 Semi-transmissive color filter Secondly, the characteristics of the semi-transmissive color filter of the present invention will be described in detail. The semi-transmissive color filter of the present invention is based on the light of the colored layer. The prominent 値 [I] in the reflection field should be 0. Below 1 // Π1, more preferably 0. Below 07 / zm, especially 0. 05 // m or less. Also prominent in the field of light transmission 値 [II], preferably 〇. l // m or less, more preferably 0. Below 07 // m, especially 0. 05 // m or less. Here, as for the "prominence in the light reflection area of the colored layer [I]" and "the prominence in the light transmission area of the colored layer [II]", description is made with reference to FIG. 11. In Fig. 1, 1 is a substrate, 2 is a protrusion, 3 is a light reflecting layer, and 4 is a colored layer. "Protrusion in the light reflection area of the colored layer [I]" means the longitudinal section of the colored layer in the light reflection area 5 above the protrusions as shown in Fig. 1, and the flat side of the colored layer The approaching plane 7 is the distance perpendicular to the substrate surface between the upper position a which is separated from the side surface and the top of the colored layer. Also, "prominence in the light-transmitting area of the colored layer [II]" means a longitudinal section of the colored surface of the light-transmitting area 6 that does not exist in the protrusion as shown in Fig. 1, and is located above the protrusion. The plane 7 on which the side surfaces of the colored layer are close to each other is the distance perpendicular to the substrate surface between the bottom position b left from the side surface and the bottom of the colored layer. The semi-transmissive color filter of the present invention is a protrusion 値 Π] and a protrusion 値 [II]. Because the aforementioned conditions are satisfied, the color purity can be set between using a backlight and using a reflective type (58) (58) 200303430. It is almost equal, and especially it is possible to improve the color purity when the backlight is used. The transflective color filter of the present invention is a film thickness in the light reflection field of the colored layer. Should be 0. 2 ~ 2. 0 // m, more preferably 0. 3 ~ 1 · 5 // ιώ, especially 0. 5 ～， The film thickness Dt ’of the colored layer in the light transmission field should be 0. 3 ~ 6. 0 / zm, more preferably 0. 5 ~ 4. 0 // m, especially 1. 0 ~ 2. 5 // m 〇 Here, the "film thickness of the colored layer in the light reflection area" means the longitudinal section of the colored φ layer in the light reflection area passing through and above the protrusion, and the top of the protrusion (only forming light When the reflective layer is on the surface of the protrusion, the surface of the substrate is perpendicular to the top of the colored layer). The "film thickness of the colored layer in the light transmission area" means that the colored layer is on the protrusion. The vertical cross-section of the non-existent light transmission area, the distance between the bottom of the colored layer and the surface of the substrate perpendicular to the substrate surface. In addition, the ratio of the film thickness Dt and the film thickness Dr of the colored layer (Dt / D0, preferably 1. 5 ~ 6. 0, more preferably 2. 0 ~ 5. 0. Φ The transflective color filter of the present invention is extremely useful in, for example, color photographic tube elements, color detectors, etc., in addition to general color liquid crystal display devices. Hereinafter, examples will be used to more specifically describe the embodiments of the present invention. However, the present invention is not limited by these embodiments. Here, parts and% are based on weight. [Embodiment] -63- (59) 200303430 (Preparation of pigment dispersion paddle liquid) The following pigments' pigments were blended and dispersed with a sand mill, pigment dispersion aids and solvent-colored pigment dispersion slurry. Ipomo green pigment dispersion liquid and blue-green pigment dispersion slurry • Pigment (parts) (10) (5) · (4) (1) (80) C · 1. Pigment Green 3 6 C ♦ 1. Pigment yellow 1 5 0 • Pigment dispersant (parts)

Solsperse S24000 •顏料分散助劑（份）Solsperse S24000 • Pigment dispersion aid (parts)

Solsperse S 5 000 •溶劑（份）甲氧基丙基乙酸酯藍色顏料分散發液 •顏料（份） C . 1.顏料藍1 5 : 6 •顏料分散劑（份） BYK- 165 •顏料分散助劑（份） Solsperse S 5 0 0 0 •溶劑（份）3*乙氧基丙基乙酯 (15) (4)Solsperse S 5 000 • Solvent (parts) methoxypropyl acetate blue pigment dispersion hair • Pigment (parts) C. 1. Pigment blue 15: 6 • Pigment dispersant (parts) BYK- 165 • Pigments Dispersion aid (parts) Solsperse S 5 0 0 0 • Solvent (parts) 3 * ethoxypropyl ethyl ester (15) (4)

(8〇)(8〇)

-64- (60) 200303430 (著色放射線敏感性組成物之製備）採用前述各顏料分散漿液，製備以下的者色放射線敏感性組成物。 -綠色放射線敏感性組成物（i)- (A) 前述綠色顏料分散漿液 60份-64- (60) 200303430 (Preparation of colored radiation-sensitive composition) Using the aforementioned pigment dispersion slurry, the following color-radiation-sensitive composition was prepared. -Green radiation sensitive composition (i)-(A) 60 parts of the aforementioned green pigment dispersion slurry

(B) 鹼可溶性樹脂 •甲基丙烯酸/N-苯基順丁烯二醯亞胺/苯乙烯/ 甲基丙細酸节基酯共聚物（共聚合重量比=15/15/25/45，(B) Alkali-soluble resin

Mw= 9, 000，Mn= 4, 000) 75份 (C) 多官能單體 •六丙烯酸二季戊四醇酯 75份 (D) 光聚合引發劑 • 1-(4-嗎咐、基苯基）-^苄基-2· 二甲基胺基丁烷-1 - 酮 25份 •2，2’-雙（2-氯苯基4，4，， 5，5、肆 (4-乙氧基鐵基苯基）-1，2’-聯咪口坐 2份 • 4，45-雙（二乙基胺基）二苯酮 2份 • 2 -锍基二苯酮 1份 (E) 溶劑 • 3 -乙氧基丙酸乙酯 700份 •環己酮 100份 •二乙二醇單正丁基醚乙酸酯 100份 -65- (61) (61)200303430 -綠色放射線敏感性組成物（ii) - (A) 前述綠色顏料分散漿液 90份 (B) 鹼可溶性樹脂 •甲基丙烯酸/甲基丙烯酸2 -羥乙酯/甲基丙烯酸苄基酯共聚物（共聚合重量比=15/15/70，Mw= 9，000 ，Mn=4，000) 75 份 (C) 多官能單體 · •六丙烯酸二季戊四醇酯 7 5份 (D) 光聚合引發劑 • 1-(4 -嗎啉基苯基）-1-苄基-2-二甲基胺基丁烷-1 -酮 2 5份 •2，2’-雙（2-氯苯基）-4，4，，5，5、肆 (4-乙氧基羰基苯基）-1，25-聯咪唑 2份 • 4，42-雙（二乙基胺基）二苯酮 2份 • 2-疏基二苯酮 1份 · (E) 溶劑 • 3 -乙氧基丙酸乙酯 7 〇〇份 •環己酮 1 〇〇份 •二乙二醇單正丁基醚乙酸酯 1 〇〇份 -綠色放射線敏感性組成物（iii) - (A) 前述綠色顏料分散漿液 15〇份 (B) 鹼可溶性樹脂 -66 - (62) (62)200303430 •甲基丙烯酸/甲基丙烯酸2 -羥乙酯/甲基丙烯酸苄基酯共聚物（共聚合重量比=1 5/1 5/70，Mw= 9，000 ，Mn=4,000) 75 份 (C) 多官能單體 •六丙烯酸二季戊四醇酯 7 5份 (D) 光聚合引發劑 • 1-(4-嗎啉基苯基）-卜苄基-2-二甲基胺基丁烷-1 -酮 2 5份 •2，2’·雙（2-氯苯基）-4，4’，5，5、肆 (4-乙氧基羰基苯基）-1，25-聯咪唑 2份 • 4，4’-雙（二乙基胺基）二苯酮 2份 • 2 -酼基二苯酮 1份 (E) 溶劑 • 3 -乙氧基丙酸乙酯 8 0 0份 •環己酮 1 0 0份 -綠色放射線敏感性組成物（i V)- (A) 前述綠色顏料分散漿液 90份 (B) 鹼可溶性樹脂 •甲基丙烯酸/甲基丙烯酸2 -羥乙酯/甲基丙烯酸苄基酯共聚物（共聚合重量比=1 5/1 5/70，Mw= 9，000 ，Mn=4，0 00) 75 份 (C )多官能單體 •六丙烯酸二季戊四醇酯 1 5 0份 •67- (63) (63)200303430 (D) 光聚合引發劑 • 1-(4-嗎啉基苯基）-1-苄基-2-二甲基胺基丁烷-1 -酮 2 5份 •2，2\ 雙（2-氯苯基）-4，45，5，55-肆 (4-乙氧基羰基苯基）-1，25-聯咪唑 2份 • 4，4’-雙（二乙基胺基）二苯酮 2份 • 2 -毓基二苯酮 1份 (E) 溶劑钃| • 3-乙氧基丙酸乙酯 8 00份 •環己酮 1 0 0份 -綠色放射線敏感性組成物（V)- (A) 前述綠色顏料分散漿液 90份 (B) 鹼可溶性樹脂 •甲基丙烯酸/甲基丙烯酸2-羥乙酯/甲基丙烯酸苄基酯共聚物（共聚合重量比=15/15/70，Mw= 9，000 · ，Mn=4，000) 75 份 (C) 多官能單體 •六丙烯酸二季戊四醇酯 7 5份 (D) 光聚合引發劑 • 1-(4-嗎啉基苯基）-1-苄基-2-二甲基胺基丁烷-1 -酮 5 0份 •2，2，-雙（2-氯苯基）-4，4，，5，55-肆 (4-乙氧基羰基苯基）-1，2'聯咪唑 2份 -68 - (64)200303430 • 4，45-雙（二乙基胺基）二苯酮 2份 • 2 -毓基二苯酮 1份 (E)溶劑 • 3-乙氧基丙酸乙酯 8 00份 •環己酮 1〇〇份 -綠色放射線敏感性組成物（vi) -Mw = 9, 000, Mn = 4, 000) 75 parts (C) polyfunctional monomer • 75 parts of dipentaerythritol hexaacrylate (D) photopolymerization initiator • 1- (4-manganyl, phenyl)- ^ 25 parts of benzyl-2 · dimethylaminobutane-1 -one · 2,2'-bis (2-chlorophenyl 4,4,5,5,4 (4-ethoxy iron Phenyl) -1,2'-bimidazoline 2 parts • 4,45-bis (diethylamino) benzophenone 2 parts • 2-fluorenylbenzophenone 1 part (E) Solvents • 3- 700 parts of ethyl ethoxypropionate 100 parts of cyclohexanone 100 parts of diethylene glycol mono-n-butyl ether acetate -65- (61) (61) 200303430-Green radiation sensitive composition (ii) -(A) 90 parts of the aforementioned green pigment dispersion slurry (B) Alkali-soluble resin • Methacrylic acid / 2-methacrylic acid / benzyl methacrylate copolymer (copolymerization weight ratio = 15/15/70 , Mw = 9,000, Mn = 4,000) 75 parts (C) polyfunctional monomer • • dipentaerythritol hexaacrylate 7 5 parts (D) photopolymerization initiator • 1- (4-morpholinylphenyl) ) -1-Benzyl-2-dimethylaminobutane-1 -one 2 5 parts • 2,2'-bis (2-chlorophenyl) -4,4 2,5,4 (4-ethoxycarbonylphenyl) -1,25-biimidazole 2 parts • 4,42-bis (diethylamino) benzophenone 2 parts • 2-sulfobiphenyl 1 part of ketone · (E) Solvent • 3 000-ethoxypropionate • 1,000 parts of cyclohexanone • 1,000 parts of diethylene glycol mono-n-butyl ether acetate-green radiation Sensitive composition (iii)-(A) 150 parts of the aforementioned green pigment dispersion slurry (B) Alkali-soluble resin -66-(62) (62) 200303430 • Methacrylic acid / methacrylic acid 2-hydroxyethyl ester / formaldehyde Copolymer of benzyl acrylate (copolymerization weight ratio = 1 5/1 5/70, Mw = 9,000, Mn = 4,000) 75 parts (C) polyfunctional monomer • dipentaerythritol hexaacrylate 7 5 parts ( D) Photopolymerization initiator • 1- (4-morpholinylphenyl) -benzyl-2-dimethylaminobutane-1 -one 2 5 parts • 2,2 '· bis (2-chlorophenyl ) -4,4 ', 5,5, 2 (4-ethoxycarbonylphenyl) -1,25-biimidazole • 2 parts of 4,4'-bis (diethylamino) benzophenone • 2-fluorenyl benzophenone 1 part (E) solvent • 3-ethyl ethoxypropionate 800 0 part • cyclohexanone 100 part-green radiation sensitive Sensitive composition (i V)-(A) 90 parts of the aforementioned green pigment dispersion slurry (B) Alkali-soluble resin • methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymerized weight) Ratio = 1 5/1 5/70, Mw = 9,000, Mn = 4, 00) 75 parts (C) polyfunctional monomer • dipentaerythritol hexaacrylate 150 parts • 67- (63) (63 ) 200303430 (D) Photoinitiator • 1- (4-morpholinylphenyl) -1-benzyl-2-dimethylaminobutane-1 -one 2 5 parts • 2, 2 \ bis ( 2-Chlorophenyl) -4,45,5,55-Di (4-ethoxycarbonylphenyl) -1,25-biimidazole 2 parts • 4,4'-bis (diethylamino) di 2 parts of benzophenone • 1 part of 2-benzyl benzophenone (E) Solvent 钃 | • 800 parts of ethyl 3-ethoxypropionate • 100 parts of cyclohexanone-green radiation-sensitive composition (V )-(A) 90 parts of the aforementioned green pigment dispersion slurry (B) Alkali soluble resin • methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymerization weight ratio = 15/15 / 70, Mw = 9,000 ·, Mn = 4,000) 75 parts (C) polyfunctional monomer • dipentaerythritol hexaacrylate 7 5 parts ( D) Photopolymerization initiator • 1- (4-morpholinylphenyl) -1-benzyl-2-dimethylaminobutane-1 -one 50 parts • 2,2, -bis (2- (Chlorophenyl) -4,4,5,55- (4-ethoxycarbonylphenyl) -1,2'biimidazole -2 -68-(64) 200303430 • 4,45-bis (diethyl 2 amino groups) benzophenone • 2-1-benzyl benzophenone (E) solvent • 3-ethoxypropionate 8,000 parts • cyclohexanone 100 parts-green radiation sensitive composition (Vi)-

(A) 前述綠色顏料分散漿液 90份 (B) 鹼可溶性樹脂 •甲基丙烯酸/甲基丙烯酸2 -羥乙酯/甲基丙烯酸苄基酯共聚物（共聚合重量比=15/15/70，Mw= 9，000 ，Μ η = 13，0 00) 7 5 份 (C) 多官能單體 •六丙烯酸二季戊四醇酯 7 5份 (D) 光聚合引發劑(A) 90 parts of the aforementioned green pigment dispersion slurry (B) Alkali soluble resin • methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymerization weight ratio = 15/15/70, Mw = 9,000, M η = 13,000) 7 5 parts (C) polyfunctional monomer • dipentaerythritol hexaacrylate 7 5 parts (D) photopolymerization initiator

• 1-(4-嗎啉基苯基）-卜苄基-2-二甲基胺基丁烷-1 -酮 2 5份 •2，2、雙（2-氯苯基）-4，4，，5，5、肆 (4-乙氧基羰基苯基）-1，25-聯咪唑 2份 • 4，45-雙（二乙基胺基）二苯酮 2份 • 2 -毓基二苯酮 1份 (E) 溶劑 • 3-乙氧基丙酸乙酯 8 00份 •環己酮 1 〇〇份 -69- (65) (65)200303430 -綠色放射線敏感性組成物（vii) - (A) 前述綠色顏料分散漿液 90份 (B) 鹼可溶性樹脂 •甲基丙烯酸/甲基丙烯酸2 -羥乙酯/甲基丙烯酸苄基酯共聚物（共聚合重量比=15/15/70，Mw= 9，000 ，Mn=4，000) 75 份 (C) 多官能單體 φ •六丙烯酸二季戊四醇酯 7 5份 (D) 光聚合引發劑 • 1-(4-嗎啉基苯基）-1-苄基-2-二甲基胺基丁烷· 1-酮 25份 •2，2、雙（2-氯苯基）-4，4，，5，5、肆 (4-乙氧基羰基苯基）-]，2’-聯咪唑 2份 • 4，45-雙（二乙基胺基）二苯酮 2份 • 2 -巯基二苯酮 1份 _ (E) 溶劑 • 3 -乙氧基丙酸乙酯 8 0 0份 •環己酮 1 〇〇份 -藍色放射線敏感性組成物（i) - (A)前述藍色顏料分散漿液 140份 (B )鹼可溶性樹脂 -70- (66) 200303430 •甲基丙烯酸/甲基丙烯酸2_羥乙基酯/曱基丙烯酸节基酯共聚物（共聚合重量比=i5/15/70，Mw = 75份二甲基胺基 25份 9，000，Mn= 4，〇〇〇) (C)多官能單體 •四丙烯酸二季戊四醇酯 (D )光聚合引發劑 • 1-(4-嗎啉基苯基）—2-苄基-2_ 丁烷-1 -酮 (4 - 2’2 -雙（2-氯苯基）_ 4，4, 乙_基^基苯基）—1，2 聯咪唑，5 ， 5，-肆 2份 • 4，4，_雙（二乙基胺基） • 2 _疏基二苯酮二苯酮 2份 1份 (E)溶劑 •丙二醇單甲醚乙酸酯 •環己酮 700份 100份• 1- (4-morpholinylphenyl) -benzyl-2-dimethylaminobutane-1 -one 2 5 parts • 2, 2, bis (2-chlorophenyl) -4, 4 ,, 5,5, 2 (4-ethoxycarbonylphenyl) -1,25-biimidazole • 2,45-bis (diethylamino) benzophenone • 2-fluorenyl benzophenone 1 part (E) Solvent • 800 parts of ethyl 3-ethoxypropionate • 1,000 parts of cyclohexanone-69- (65) (65) 200303430-Green radiation sensitive composition (vii)-(A ) 90 parts of the aforementioned green pigment dispersion slurry (B) Alkali soluble resin • methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymerization weight ratio = 15/15/70, Mw = 9,000 Mn = 4,000) 75 parts (C) polyfunctional monomer φ • dipentaerythritol hexaacrylate 7 5 parts (D) photopolymerization initiator • 1- (4-morpholinylphenyl) -1 -Benzyl-2-dimethylaminobutane · 1-ketone 25 parts · 2,2, bis (2-chlorophenyl) -4,4,5,5, (4-ethoxycarbonyl) Phenyl)-], 2'-biimidazole 2 parts • 4,45-bis (diethylamino) benzophenone 2 parts • 2-mercaptobenzophenone 1 part_ (E) Solvents • 3 -Ethoxy Ethyl propionate Ester 800 parts • Cyclohexanone 1,000 parts-Blue radiation sensitive composition (i)-(A) 140 parts of the aforementioned blue pigment dispersion slurry (B) Alkali soluble resin-70- (66) 200303430 • Copolymer of methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate (copolymerization weight ratio = i5 / 15/70, Mw = 75 parts dimethylamine group 25 parts 9,000, Mn = 4,000) (C) Polyfunctional monomer • Dipentaerythritol tetraacrylate (D) Photopolymerization initiator • 1- (4-morpholinylphenyl) -2-benzyl-2_butane-1 -Ketone (4-2'2-bis (2-chlorophenyl) _4,4, ethyl-yl ^ ylphenyl) -1,2 biimidazole, 5, 5,-2 parts • 4, 4, _Bis (diethylamino) • 2 _Sulfobenzophenone benzophenone 2 parts 1 part (E) Solvents • Propylene glycol monomethyl ether acetate • 700 parts of cyclohexanone 100 parts

正丁基醚乙酸酯 100份 (突起用組成物溶液之製備） σ共Μ物（a 1)之甲基丙烯酸/甲基丙烯酸縮水甘油基醒/苯乙燒共聚物（共聚合重量比=2 5/50/2 5, Mw= 25，000) 100 份及 1，2_ 酿二疊氮之 4，4，_ [卜[4_ [卜 [4_羥基本基]-1-甲基乙基]苯基]亞乙]雙酚（1莫耳）及1，2-萘醌二疊氮_ 5_磺酸氯化物（2莫耳）之縮合物3 〇份，溶解於二乙二醇二甲基醚內至固形份濃度成3 2%後，以孔徑0.2 A m之過濾器過濾，製備突起用 -71 - (67) 200303430 組成物溶液。 (基板1之製作）採用旋塗器塗布前述突起用組成物溶液於玻璃基板（商品名Corning #丨73 7)上後，在90 Ό之熱板上進行3 分鐘預烘烤，形成塗膜。其次採用指定的光罩，照射波長3 6 5 nm之強度 1 00W/m2之紫外線至所得的塗膜5秒鐘。其後，利用氫氧化四甲基錢0.2%水溶液在25 。(：進行淋浴顯影90秒鐘後’以純水沖水淸洗1分鐘。其後，以波長3 65 nm之強度100W /m2之紫外線對全面曝光3〇秒鐘後，在]2〇之熱板上加熱2分鐘，再於2 2 0 °C之烘箱中加熱6 0分鐘使其硬化’製作具有高度1 . 5 // m之突起部的基板1。 (基板2之製作）製作具有高度2.0//m之突起部的基與基板 1同法板2 〇 (基板3之製作）製作具有高度2.5//m之突起部的基與基板 1同法板3。實施例實施例1 -72 - (68) (68)200303430 採用旋塗器塗布綠色放射線敏感性組成物（ii)於基板1上後，在8 0 °C之乾淨烘箱內進行1 〇分鐘預烘烤，形成塗膜。其次，採用含有365nm、405nm及436nm之各波長的咼壓水銀燈，以5 0 0 J / m 2之曝光量曝光於基板全面上。其後，以超純水稀釋GASR (股）製造的濃縮鹼顯影液CD-15 OCR (商品名）成 1〇〇倍的顯影液，在 25 °C 進行淋浴顯影60秒鐘後，使純水吐出並予淸洗。其後，在220 t 之乾淨烘箱內進行3 0分鐘後烘烤，而得綠色著色層。以掃瞄型電子顯微鏡觀察所得的綠色著色層時，於光反射領域之突出値 [I]爲〇.〇6 // m，於光透射領域之突出値[II]爲 0.07//m。又，該綠色著色層之膜厚Dt爲2.19// m，膜厚Dr爲 1 · 0 0 // m 〇另外，採用旋塗器塗布綠色放射線敏感性組成物 (ϋ)於基板2後，與前述同法進行評估時，綠色著色層於光反射領域之突出値（I)爲〇.〇7 // m，於光透射領域之突出値 [II]爲0.07 // m。又，該綠色著色層之膜厚Dt爲2.87//m，膜厚Dr爲 1 . 0 0 // m 〇以上的結果，即使已形成於基板上的突起部之高度改變時，亦可確認出突出値 Π]及突出値 [II]係可予抑制的。 -73- (69) 200303430 實施例2 採用旋塗器塗布綠色放射線敏感性組成物（i)於基板2上後，與實施例1同法進行評估時，綠色著色層時於光反射領域之突出値[I]爲0.05 // m，於光透射領域之突出値 [II] 爲0.04 // m。又，該綠色著色層之膜厚Dt爲3. 12 // m，膜厚Dr爲 1.4 5 // m 〇100 parts of n-butyl ether acetate (preparation of the composition solution for protrusions) σ acrylic copolymer (a 1) of a methacrylic acid / glycidyl methacrylate / styrene copolymer (copolymerization weight ratio = 2 5/50/2 5, Mw = 25,000) 100 parts and 1,2_ Diazide 4,4, _ [Bu [4_ [卜 [4_hydroxybenzyl] -1-methylethyl 30 parts of condensate of [phenyl] ethylene] bisphenol (1 mole) and 1,2-naphthoquinonediazide-5_sulfonic acid chloride (2 mole), dissolved in diethylene glycol di After the methyl ether had a solid content concentration of 32%, it was filtered through a filter with a pore size of 0.2 A m to prepare a composition solution for protrusions -71-(67) 200303430. (Fabrication of Substrate 1) After applying the composition solution for protrusions on a glass substrate (trade name: Corning # 丨 73 7) using a spin coater, pre-baking was performed on a 90 ° hot plate for 3 minutes to form a coating film. Next, a designated photomask was used, and an ultraviolet light having a wavelength of 3,65 nm and an intensity of 100 W / m2 was irradiated to the obtained coating film for 5 seconds. Thereafter, a 0.2% aqueous solution of tetramethylsulfonium hydroxide was used at 25 ° C. (: After developing for 90 seconds in a shower, rinse with pure water for 1 minute. Then, expose it to UV light with a wavelength of 3 65 nm and an intensity of 100 W / m2 for 30 seconds. The board was heated for 2 minutes, and then heated in an oven at 220 ° C for 60 minutes to make it harden. 'Make substrate 1 with protrusions with a height of 1.5 // m. (Production of substrate 2) Manufacture with a height of 2.0 The base of the // m protrusion is the same as the base plate 1 of the substrate 1 (production of the base plate 3) The base and the base 1 having the protrusion of 2.5 // m is the same as the base plate 3. Example 1 -72- (68) (68) 200303430 The green radiation-sensitive composition (ii) was coated on the substrate 1 by a spin coater, and then pre-baked in a clean oven at 80 ° C for 10 minutes to form a coating film. Next, Using a pressurized mercury lamp with wavelengths of 365 nm, 405 nm, and 436 nm, the entire surface of the substrate was exposed at an exposure of 500 J / m 2. Thereafter, the concentrated alkaline developer made by GASR (stock) was diluted with ultrapure water. CD-15 OCR (trade name) was developed at a magnification of 100 times. After shower development at 25 ° C for 60 seconds, pure water was spit out. Pre-washing. After that, bake in a clean oven of 220 t for 30 minutes to obtain a green colored layer. When the obtained green colored layer was observed with a scanning electron microscope, it protruded in the area of light reflection. I] is 0.06 // m, and the highlight in the field of light transmission [II] is 0.07 // m. In addition, the film thickness Dt of the green colored layer is 2.19 // m, and the film thickness Dr is 1 · 0. 0 // m 〇 In addition, after applying the green radiation-sensitive composition (ϋ) to the substrate 2 by using a spin coater, when evaluated in the same manner as described above, the protrusion 绿色 (I) of the green colored layer in the light reflection field is 〇. 〇7 // m, the highlight in the light transmission field [II] is 0.07 // m. In addition, the film thickness Dt of the green colored layer is 2.87 // m, and the film thickness Dr is 1. 0 0 // m 〇 As a result, even when the height of the protrusions formed on the substrate is changed, it can be confirmed that the protrusion 値 Π] and the protrusion 値 [II] can be suppressed. -73- (69) 200303430 Example 2 After the applicator was coated with the green radiation-sensitive composition (i) on the substrate 2 and evaluated in the same manner as in Example 1, the green colored layer was used in the light reflection field. The protrusion 値 [I] is 0.05 // m, and the protrusion 値 [II] in the light transmission field is 0.04 // m. In addition, the film thickness Dt of the green colored layer is 3. 12 // m, and the film thickness Dr is 1.4. 5 // m 〇

另外，採用旋塗器塗布綠色放射線敏感性組成物 (iii)於基板2上後，與前述同法進行評估時，綠色著色層於光反射領域之突出値（I)爲0.07 // m，於光透射領域之突出値 [11 ] 爲〇 . 0 6 // m。又，該綠色著色層之膜厚Dt爲1.84//m，膜厚Dr爲 0 · 6 4 // m 〇In addition, after applying the green radiation-sensitive composition (iii) on the substrate 2 by using a spin coater, when the same method as described above was used for evaluation, the protrusion of the green colored layer in the light reflection field (I) was 0.07 // m, at The prominent 値 [11] in the field of light transmission is 0.06 // m. The film thickness Dt of the green colored layer is 1.84 // m, and the film thickness Dr is 0 · 6 4 // m 〇

由以上的結果及採用實施例1之綠色放射線敏感性組成物（Π)之結果，著色放射線敏感性組成物中的顏料濃度即使改變，亦可確認出突出値 [I]及突出値 [II]係可予抑制的。實施例3 採用旋塗器塗布綠色放射線敏感性組成物（i)於基板2上後，與實施例1同法進行評估時，藍色著色層於光反射領域之突出値 [I]爲0.04 // m，於光透射領域之突出値[11 ]爲〇 . 〇 6 // m。又，該藍色著色層之膜厚Dt爲2.36//m，膜厚Dr爲 • 74- (70) (70)200303430 1 . 0 0 // m 〇實施例4 採用旋塗器塗布（C)多官能性單體之使用量較多的綠色放射線敏感性組成物（iv)於基板2上後’與實施例 1同法進行評估時，綠色著色層時於光反射領域之突出値 [I]爲0.03 // m，於光透射領域之突出値[Π]爲0.04//From the above results and the results of using the green radiation-sensitive composition (Π) of Example 1, even if the pigment concentration in the colored radiation-sensitive composition was changed, the protrusion 値 [I] and the protrusion 値 [II] Department can be suppressed. Example 3 After applying a green radiation-sensitive composition (i) on a substrate 2 using a spin coater, the same method as in Example 1 was used to evaluate the blue coloring layer in the light reflection field. [I] was 0.04 / m, which stands out in the field of light transmission [11] is 0.06 // m. In addition, the film thickness Dt of the blue colored layer was 2.36 // m, and the film thickness Dr was • 74- (70) (70) 200303430 1. 0 0 // m 〇 Example 4 Coating using a spinner (C) The green radiation sensitive composition (iv) with a large amount of polyfunctional monomers (iv) on the substrate 2 was evaluated in the same manner as in Example 1. The green colored layer was prominent in the light reflection field. [I] 0.03 // m, which stands out in the field of light transmission [Π] is 0.04 //

又，該綠色著色層之膜厚Dt爲2.25 // m，膜厚Dr爲 1 . 0 0 // m 0 實施例5 採用旋塗器塗布（D)放射線敏感性聚合引發劑之使用量較多的綠色放射線敏感性組成物（v)於基板2上後，與實施例1同法進行評估時，綠色著色層於光反射領域之突出値 [I]爲0.05 // m，於光透射領域之突出値 [II] 爲 0.0 4 " m。又，該綠色著色層之膜厚Dt爲2.3 6// m，膜厚Dr爲 1 · 0 0 " m 〇實施例6 採用旋塗器塗布（B)鹼可溶性樹脂之分子量較大的綠色放射線敏感性組成物（vi)於基板2上後，與實施例 1同法進行評估時，綠色著色層時於光反射領域之突出値 -75- (71) (71)200303430 [I]爲〇.〇3//m，於光透射領域之突出値[II]爲0.05 β m 〇又，該綠色著色層之膜厚Dt爲2.33//m，膜厚Dr爲 1 . 0 0 // m 〇實施例7 採用旋塗器塗布綠色放射線敏感性組成物（νΠ)於基板2上後，與實施例1同法進行評估時，綠色著色層時於光反射領域之突出値 Π]爲0.18 // m，於光反射領域之突出値 [II]爲〇.20//m。又，該綠色著色層之膜厚Dt爲2.71/zm，膜厚Dr爲 1 . 0 0 // m 0 本發明之半透射型濾色片，係欲降低著色層於光反射領域之突出値 [I]及於光透射領域之突出値 [Π] —事係可能的，在使用背光時及使用作反射型時之間可將色純度設成約略同等，尤其可提高使用背光時的色純度。【圖式之簡單說明】第]圖係說明突出値[I]及突出値[Π]之評估步驟的圖。元件對照表 1 :基板 2 :突起部 -76- (72) (72)200303430 3 :光反射層 4 :著色層 5 :光反射領域 6 :光透射領域 7 :與著色層之平坦的側面接近的平面In addition, the film thickness Dt of the green colored layer is 2.25 // m, and the film thickness Dr is 1. 0 0 // m 0 Example 5 A spin coater is used to apply a larger amount of (D) radiation-sensitive polymerization initiator. After the green radiation sensitive composition (v) on the substrate 2 was evaluated in the same manner as in Example 1, the green coloring layer was prominent in the light reflection field. [I] is 0.05 // m, Prominent 値 [II] is 0.0 4 " m. The film thickness Dt of the green colored layer was 2.3 6 // m, and the film thickness Dr was 1. 0 0 " m 〇 Example 6 The spin coater was used to coat (B) a green radiation having a large molecular weight of an alkali-soluble resin. After the sensitive composition (vi) was evaluated on the substrate 2 in the same manner as in Example 1, the green colored layer was prominent in the light reflection field when 値 -75- (71) (71) 200303430 [I] was 0. 〇3 // m, the highlight in the field of light transmission [II] is 0.05 β m 〇 Also, the film thickness Dt of the green colored layer is 2.33 // m, and the film thickness Dr is 1. 0 0 // m 〇 Implementation Example 7 After applying a green radiation-sensitive composition (νΠ) to a substrate 2 by using a spin coater, when evaluated in the same manner as in Example 1, the protrusion of the green colored layer in the light reflection field (値 Π) is 0.18 // m The prominent [II] in the field of light reflection is 0.20 // m. In addition, the film thickness Dt of the green colored layer is 2.71 / zm, and the film thickness Dr is 1. 0 0 // m 0 The transflective color filter of the present invention is intended to reduce the protrusion of the colored layer in the light reflection field. I] and the highlight in the field of light transmission [Π] — It is possible. The color purity can be set to approximately the same when using the backlight and when it is used as a reflective type, especially the color purity can be improved when using the backlight. [Brief description of the drawings] The first figure is a diagram illustrating the evaluation steps of the prominence 値 [I] and the prominence 値 [Π]. Component comparison table 1: Substrate 2: Projection -76- (72) (72) 200303430 3: Light reflection layer 4: Colored layer 5: Light reflection area 6: Light transmission area 7: Close to the flat side of the colored layer flat

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Claims

200303430 ⑴ Pickup, patent application scope 1 · A semi-transmissive color filter, which is characterized by a raised portion and a coloring layer on the substrate, the protruding portion has a light reflecting layer, and the coating is formed to cover the protruding portion and the remaining The surface of the substrate. 2. If the semi-transmissive color filter color layer in the patent application scope item 1 has a protrusion 値 [I] of less than 0.1 // m, the protrusion 値 [II] of the transmission area is 0.1 / / m or less. 3 · Semi-transmissive color filter according to item 1 of the patent application. The film thickness of the color layer in the light reflection field is 0.2 ~ 2.0 // m, and the film thickness in the color transmission field is 0.3 ~ 6.0 // m. 4. A radiation sensitivity used in the formation of the projections of the radiation-type color filter according to any one of claims 1 to 3, characterized in that (a) contains (a 1) an unsaturated carboxylic acid And / or unsaturated multivalent and unsaturated monomers containing epoxy groups and unsaturated monocopolymers other than the foregoing, and (b 1) a radiation composition of a 1,2-quinonediazide compound, and (B) by Containing (a2) an unsaturated carboxylic acid and / or an unsaturated polyanhydride, an unsaturated monomer containing an epoxy group and an unsaturated copolymer other than the foregoing, and (b2) a radiation-sensitive polymerization initiator to cleave the unsaturated monomer The radiation-sensitive composition is selected by the group of 0.5. —The radiation-sensitive group used to form the coloring layer of any of the semi-transmissive color filters in the scope of application patents Nos. 3 to 3 forms a burst layer system , Attached to light, attached to the light-permeable semi-transparent composition, the sensitive carboxylic acid monomer between the carboxylic acid anhydrides, I (C2), one of which is less than one, which is-78- (2) 200303430 Features It contains (A) a colored layer, (B) an alkali-soluble resin, and (C ) A polyfunctional monomer, (D) a photopolymerization initiator, and (E) a solvent. 6. A kind of color liquid crystal display element, which is provided with a transflective color filter according to any one of claims 1 to 3. 7. A color liquid crystal display element, which is a transflective color filter having a coloring layer formed of a radiation-sensitive composition formed by a radiation-sensitive composition according to item 4, . -79-