TW200830043A - Radiation sensitive resin composition and color filter - Google Patents

Radiation sensitive resin composition and color filter Download PDF

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Publication number
TW200830043A
TW200830043A TW096136333A TW96136333A TW200830043A TW 200830043 A TW200830043 A TW 200830043A TW 096136333 A TW096136333 A TW 096136333A TW 96136333 A TW96136333 A TW 96136333A TW 200830043 A TW200830043 A TW 200830043A
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Taiwan
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group
meth
carbon atoms
methyl
radiation
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TW096136333A
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Chinese (zh)
Inventor
Tatsuyoshi Kawamoto
Tsukasa Toyoshima
Masashi Arai
Ryu Matsumoto
Tomio Nagatsuka
Isamu Makihira
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Jsr Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Optical Filters (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A radiation sensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer and (D) a radiation sensitive radical generator, wherein the component (B) comprises a resin having a group represented by the following formula (i) or (ii) at one terminal and the component (D) comprises a compound of the following formula (1) and/or a compound of the following formula (2): (Z1 and Z2 are each a hydrogen atom, chlorine atom, alkyl group or alkoxyl group) (R3 is a (cyclo) alkyl group or phenyl group, R4 and R5 are each a hydrogen atom or (cyclo) alkyl group, R6 is a monovalent heterocyclic group, R7 is a hydrogen atom or (cyclo) alkyl group, n=1 to 5, m=0 to 5, (n+m) ≤5, and p=0 to 6.). The composition is a radiation sensitive resin composition which can provide a color filter free from "burning" and has high sensitivity, and its dried coating film has high solubility in a solvent.

Description

200830043 九、發明說明 【發明所屬之技術領域】 本發明係有關可用於製造供透射型及反射型彩色液晶 裝置及彩色攝影裝置使用之濾光片的輻射敏感性樹脂組成 物、製備該輻射敏感性樹脂組成物之方法、自該輻射敏感 性樹脂組成物形成之濾光片及包含該濾光片之彩色液晶顯 示裝置。 【先前技術】 作爲自彩色輻射敏感性樹脂組成物形成濾光片之方式 ，已知有一種方法，其中於基板或包含具有所需圖案之遮 光層的基板上形成彩色輻射敏感性樹脂組成物之塗膜，經 由具有所需圖案形狀之光罩曝照輻射（以下稱爲「曝光」 )，使用鹼顯影劑顯影以溶解並移除未曝光部分，及於無 塵爐中或於熱板上後烘烤，以得到彩色像素（參考 JP-A 2000-329929) 〇 因爲用以形成濾光片之基板的尺寸愈來愈大，施加輻 射敏感性樹脂組成物之方式也由旋塗法（藉著將組成物滴 於基板中心）轉變成扁狀噴嘴塗覆法（使用小直徑液體噴 射部分以施加輻射敏感性樹脂組成物）。後一種扁狀噴嘴 塗覆法中，因爲液體噴射部分之直徑小（狹窄），故輻射 敏感性樹脂組成物經常在塗覆之後殘留於噴嘴末端周圍。 當樹脂組成物變乾時，掉落於濾光片上，於後續塗覆時成 爲乾燥之外來物質，大幅降低濾光片之品質。因此，通常 -6 - 200830043 在塗覆之前於噴嘴末端施加清潔溶劑噴流以進行清洗。然 而，仍無法有效防止濾光片因爲乾燥外來物質所需之品質 降低，因而大幅降低產品良率。 爲克服此項問題，現在需要一種對清洗溶劑具有清洗 性（也就是即使乾燥後，仍於清洗溶劑中具有高度溶解度 ^ )之濾光片用輻射敏感性樹脂組成物。 包含濾光片之液晶顯示裝置現在需要長使用壽命，且 濾光片對於防止影像烙痕（burning )之能力的需求愈來愈 高。 術語「烙痕」係爲液晶顯示裝置之一種顯示故障，爲 一種將不應顯示之影像顯示於螢幕上或在應顯示之影像上 顯示黑或白「霧」之現象。認爲此種現象之原因如下即 ，液晶中所含之帶電雜質擴散進入液晶內，而無法在特定 時間週期間保持用以使液晶分子配向之電位差。最近已發 現該等雜質不僅在製造液晶分子時產生，亦自所形成之濾 I 光片內部產生。如JP-A 2000-329929所揭示，已知藉由增 加顏料之純度可有效地防止「影像烙痕」。然而，因爲雜 質可能來自輻射敏感性樹脂組成物中所含之除顏料以外的 % 組份，故增加顏料純度未必可完全防止前述現象。 戶 因此，極需要發展一種等合高產品良率之要求且在製 造濾光片時不會有「烙痕」之濾光片用輻射敏感性樹脂組 成物。 【發明內容】 200830043 本發明之目的係提供一種輻射敏感性樹脂組成物，其 可在高產品良率下提供不會有「烙痕」之濾光片、具有高 敏感性且即使乾燥仍於清洗溶劑中具有高溶解度。 本發明另一項目的係提供一種製備前述輻射敏感性樹 脂組成物之方法。 本發明另一項目的係提供一種自前述本發明輻射敏感 性樹脂組成物形成之濾光片及一種包含該濾光片之彩色液 晶顯7K裝置。 由以下描述可明瞭本發明之其他目的及優點。 根據本發明，首先，前述本發明目的及優點可由一種 輻射敏感性樹脂組成物達成，該組成物包含（A )著色劑 ’ （B )鹼可溶性樹脂，（C )多官能性單體及（D )輻射 敏感性自由基生成劑，其中 該鹼可溶性樹脂（B )係包含在其聚合物鏈之至少~ 末端具有下式（i)或（ii)所示之基團的樹脂且輻射敏感 性自由基生成劑（D )係包含下式（1 )之化合物及/或下 式（2 )之化合物：200830043 IX. Description of the Invention [Technical Field] The present invention relates to a radiation-sensitive resin composition which can be used for manufacturing a filter for use in a transmissive and reflective type color liquid crystal device and a color photographic device, and which is prepared for the radiation sensitivity A method of forming a resin composition, a filter formed from the radiation-sensitive resin composition, and a color liquid crystal display device including the filter. [Prior Art] As a method of forming a filter from a color radiation-sensitive resin composition, a method is known in which a color radiation-sensitive resin composition is formed on a substrate or a substrate including a light-shielding layer having a desired pattern. The coating film is irradiated with a reticle having a desired pattern shape (hereinafter referred to as "exposure"), developed with an alkali developer to dissolve and remove the unexposed portion, and in a dust-free furnace or on a hot plate. Baking to obtain color pixels (refer to JP-A 2000-329929) 〇Because the size of the substrate for forming the filter is getting larger and larger, the method of applying the radiation-sensitive resin composition is also by spin coating (by means of spin coating) The composition was dropped on the center of the substrate to be converted into a flat nozzle coating method (using a small-diameter liquid ejecting portion to apply a radiation-sensitive resin composition). In the latter flat nozzle coating method, since the diameter of the liquid ejecting portion is small (narrow), the radiation-sensitive resin composition often remains around the nozzle end after coating. When the resin composition dries, it falls on the filter and becomes a dry foreign matter upon subsequent coating, which greatly reduces the quality of the filter. Therefore, usually -6 - 200830043 applies a cleaning solvent jet at the end of the nozzle for cleaning prior to coating. However, it is still impossible to effectively prevent the filter from deteriorating the quality required for drying foreign matter, thereby greatly reducing the yield of the product. In order to overcome this problem, there is a need for a radiation-sensitive resin composition for a filter which is washable to a cleaning solvent (i.e., has a high solubility in a cleaning solvent even after drying). Liquid crystal display devices including filters now require a long life, and the need for filters to prevent image burns is increasing. The term "glue" is a display failure of a liquid crystal display device, which is a phenomenon in which an image that should not be displayed is displayed on a screen or a black or white "fog" is displayed on an image to be displayed. The reason for this phenomenon is considered to be that the charged impurities contained in the liquid crystal diffuse into the liquid crystal, and the potential difference for aligning the liquid crystal molecules cannot be maintained for a certain period of time. It has recently been found that these impurities are generated not only in the production of liquid crystal molecules but also from the inside of the formed filter. As disclosed in JP-A No. 2000-329929, it is known that the "image mark" can be effectively prevented by increasing the purity of the pigment. However, since the impurities may come from the % component other than the pigment contained in the radiation-sensitive resin composition, increasing the purity of the pigment does not necessarily completely prevent the aforementioned phenomenon. Therefore, it is highly desirable to develop a radiation-sensitive resin composition for a filter that does not have a "glue" when manufacturing a filter. SUMMARY OF THE INVENTION 200830043 The object of the present invention is to provide a radiation-sensitive resin composition which can provide a filter which does not have a "marking" at a high product yield, has high sensitivity and is cleaned even when dried. High solubility in solvents. Another aspect of the present invention provides a method of preparing the aforementioned radiation-sensitive resin composition. Another item of the present invention provides a filter formed from the above-described radiation-sensitive resin composition of the present invention and a color liquid crystal 7K device comprising the filter. Other objects and advantages of the invention will be apparent from the description. According to the present invention, first, the foregoing objects and advantages of the present invention can be attained by a radiation-sensitive resin composition comprising (A) a colorant '(B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a radiation-sensitive radical generating agent, wherein the alkali-soluble resin (B) contains a resin having a group represented by the following formula (i) or (ii) at least to the terminal of the polymer chain and is free from radiation sensitivity The base generator (D) is a compound of the following formula (1) and/or a compound of the following formula (2):

SHO SHC- I I s SSHO SHC- I I s S

[式（i)及（ii)中，Z1及Z2各獨立地爲氫原子、氯原子 、殘基、氰基、具有1至20個碳原子之烷基、具有6至 20個碳原子之單價芳族烴基、由碳原子及雜原子所組成之 -8 - 200830043 具有3至20個原子的單價雜環基、-OR1、-SR1、-OC( =0 ) R1 ^ -NCR1) ( R2 ) ' -C ( =0 ) OR1 > -C ( =0 ) N ( R1) ( R2 ) 、-P(=0) (0R1)2、-P(=0) (R1):或具 有聚合物鏈之單價基團，…及r2各係獨立地爲具有1至 18個碳原子之烷基、具有2至18個碳原子之烯基、具有 6至18個碳原子之單價芳族烴基或由碳原子及雜原子組成 之具有3至18個原子之單價雜環基，其附帶條件爲具有1 至20個碳原子之烷基、具有6至20個碳原子之單價芳族 烴基、由碳原子及雜原子所組成之具有3至20個原子的 單價雜環基、R1及R2可經取代]。[In the formulae (i) and (ii), Z1 and Z2 are each independently a hydrogen atom, a chlorine atom, a residue, a cyano group, an alkyl group having 1 to 20 carbon atoms, and a unit price of 6 to 20 carbon atoms. An aromatic hydrocarbon group consisting of a carbon atom and a hetero atom -8 - 200830043 A monovalent heterocyclic group having 3 to 20 atoms, -OR1, -SR1, -OC( =0 ) R1 ^ -NCR1) ( R2 ) ' -C ( =0 ) OR1 > -C ( =0 ) N ( R1 ) ( R2 ) , -P (=0) (0R1) 2, -P (=0) (R1): or have a polymer chain The monovalent groups, ... and r2 are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a carbon atom. And a hetero atom-constituting monovalent heterocyclic group having 3 to 18 atoms, which is conditioned by an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a carbon atom and a hetero A monovalent heterocyclic group having 3 to 20 atoms consisting of atoms, R1 and R2 may be substituted].

[式（1)及（2)中，R3各獨立地爲具有1至2〇個碳原子 之烷基、具有3至8個碳原子之環烷基或苯基，R4及R5 各獨立地爲氫原子、具有1至20個碳原子之烷基、具有3 -9 - 200830043 至8個碳原子之環烷基、可經取代之苯基或具有7至20 個碳原子之單價脂環族基團（不包括前述環烷基），R6各 係獨立地爲具有4至20個碳原子之單價含氧雜環基、具 有4至20個碳原子之單價含氮雜環基或具有4至20個碳 原子之單價含硫雜環基，R7各獨立地爲氫原子、具有1至 12個碳原子之烷基、具有3至8個碳原子之環烷基、具有 1至12個碳原子之烷氧基或具有3至8個碳原子之環烷氧 基，η各獨立地爲1至5之整數，m各獨立地爲0至5之 整數，其附帶條件爲（n + m) ^5，且p係爲0至6之整數 ]° 根據本發明，其次，前述本發明目的及優點係由一種 製備前述輻射敏感性樹脂組成物之方法達成，該方法包含 將一顏料分散液與（B )鹼可溶性樹脂，（C )單官能性單 體及（D )輻射敏感性自由基生成劑混合，該顏料分散液 係藉由於分散劑存在下邊碾磨邊於溶劑中混合且分散作爲 著色劑（A )之顏料而製得。 根據本發明，第三，前述本發明目的及優點係由使用 於濾光片之前述輻射敏感性樹脂組成物達成（以下稱爲「 濾光片用輻射敏感性樹脂組成物」）。 根據本發明，第四，前述本發明目的及優點係由該濾 光片用輻射敏感性樹脂組成物所形成之濾光片達成。 根據本發明，第五，前述本發明目的及優點係由包含 前述濾光片之彩色液晶顯示裝置達成。 -10- 200830043 【實施方式】 較佳具體實施態樣之詳述 以下詳細描述本發明。 輻射敏感性樹脂組成物 -(A )著色劑- 雖然本發明著色劑不特別限定，但因爲顯現高純度及 高透明性色彩（或遮蔽性）及耐熱性係濾光片所需，故以 顏料較佳，而有機顏料或碳黑尤佳。 前述有機顏料之實例有根據比色指數歸類爲一組顏料 的化合物，尤其是具有以下比色指數（C.I.)編號之化合 物： C.I·顏料黃12、C.I·顏料黃13、C.I.顏料黃14、C.I. 顏料黃1 7、C · I.顏料黃2 0、C · I ·顏料黃2 4、C · I ·顏料黃3 1 、C.I.顏料黃55、C.I·顏料黃83、C.I.顏料黃93、C.I.顏 料黃1 0 9、C · I.顏料黃1 1 0、C · I ·顏料黃1 3 8、C · I ·顏料黃 139、C.I·顏料黃 150、C.I·顏料黃 i53、C.I.顏料黃 154、 C.I·顏料黃155、C.I.顏料黃166、C.I.顏料黃168及C.I. 顏料黃2 1 1 ; C · I.顏料橙5、C · I.顏料橙1 3、C · I ·顏料橙1 4、C · I ·顏 料橙2 4、C · I ·顏料橙3 4、C · I.顏料橙3 6、C · I.顏料橙3 8、 C.I·顏料橙40、C.I.顏料橙43、C.I.顏料橙46、C.I.顏料 橙49、C.I·顏料橙61、C.I·顏料橙64、C.I.顏料橙68、 C.I·顏料橙70、C.I·顏料橙71、C.I.顏料橙72、C.I·顏料 -11 - 200830043 橙7 3及C · I ·顏料橙7 4 ; C · I.顏料紅1、C · I ·顏料紅2、C . I ·顏料紅5、C · I ·顏料 紅1 7、C · I.顏料紅3 1、C · I ·顏料紅3 2、C · I ·顏料紅4 1、 C . I.顏料紅1 2 2、C · I ·顏料紅1 2 3、C . I ·顏料紅1 4 4、C · I ·顏 料紅1 4 9、C . I ·顏料紅1 6 6、C · I.顏料紅1 6 8、C · I ·顏料紅 1 7 0、C . I.顏料紅 1 7 1、C . I.顏料紅 1 7 5、C · I.顏料紅 1 7 6、 C . I ·顏料紅1 7 7、C · I ·顏料紅1 7 8、C . I ·顏料紅1 7 9、C . I ·顏 料紅1 8 0、C · I.顏料紅1 8 5、C · I ·顏料紅1 8 7、C · I ·顏料紅 2 0 2、C . I ·顏料紅 2 0 6、C · I ·顏料紅 2 0 7、C · I ·顏料紅 2 0 9、 C . I.顏料紅2 1 4、C · I ·顏料紅2 2 0、C · I ·顏料紅2 2 1、C · I ·顏 料紅2 2 4、C · I ·顏料紅2 4 2、C · I ·顏料紅2 4 3、C · I.顏料紅 25 4、C.I.顏料紅2 5 5、C.I·顏料紅262、C.I·顏料紅264及 C.I.顏料紅272 ; C.I.顏料紫1、C.I.顏料紫19、C.I·顏料紫23、C.I.顏 料紫29、C.I.顏料紫32、C.I.顏料紫36及C.I·顏料紫38 ( . C . I.顏料藍1 5、C _ I ·顏料藍1 5 : 3、c · I ·顏料藍1 5 : 4 、C.I.顏料藍15 : 6、C.I·顏料藍60及C.I·顏料藍80 ; 羲 C . I.顏料綠7及C . I.顏料綠3 6 ; # C.I.顏料棕23及C.I.顏料棕25 ;及 C.I.顏料黑1及C.I.顏料黑7。 此等有機顏料中，以C.I.顏料黃83、C.I.顏料黃139 、C . I.顏料黃 1 3 8、C · I ·顏料黃 1 5 0、C · I ·顏料黃 1 8 0、c ·1 · 顏料紅1 7 7、C · I ·顏料紅2 5 4、C · I ·顏料藍1 5 : 3、C · I ·顏料 -12- 200830043 藍1 5 : 4、C · I ·顏料藍1 5 : 6、C · I.顏料綠7、C · I ·顏料綠 36、C.I.顏料紫23、c·；[•顏料藍6〇及c.i·顏料藍8〇較佳 〇 前述有機顏料可單獨或二或更多種組合使用，亦可使 用有機顏料與碳黑之混合物。 本發明中，當輻射敏感性樹脂組成物之著色劑係顏料 時’較佳係於分散劑存在下藉珠磨機或輥磨機碾磨而混合 且分散於溶劑中，以製備顏料分散液，此分散液隨後與組 份（B ) 、（ C )及（D )且視情況與附加之溶劑及其他描 述於下文之添加劑混合，以製備輻射敏感性樹脂組成物。 Μ ^用以製備前述顏料分散液之分散劑可爲陽離子性 、陰離子性、非離子性或兩性分散劑。其中，具有胺基甲 酸酯鍵結之化合物（以下稱爲「以胺基甲酸酯爲主之分散 劑」）較佳。 前述胺基甲酸酯鍵結通常係以通式R-NH-COO-R·表示 (R及R’各爲脂族、脂環族或芳族單價或多價有機基團， 該多價有機基團另外鍵結於具有另一個胺基甲酸酯鍵結之 基團或另一個基團）且可存在於該以胺基甲酸酯爲主之分 散劑的親脂性基團及/或親水性基團中或於該以胺基甲酸 酯爲主之分散劑的主鏈及/或側鏈中，且該以胺基甲酸酯 爲主之分散劑中可存在一或多個胺基甲酸酯鍵結。當該以 胺基甲酸酯爲主之分散劑中存有二或更多個胺基甲酸酯鍵 結時，其可相同或相異。 該以胺基甲酸酯爲主之分散劑係爲例如二異氰酸酯及 -13- 200830043 /或三異氰酸酯與一末端具有羥基之聚酯及/或兩末端皆具 有羥基之聚酯的反應產物。 二異氰酸酯之實例係包括苯二異氰酸酯，諸如苯-1，3-二異氰酸酯及苯-1，4 -二異氰酸酯；甲苯二異氰酸酯，諸如 甲苯-2,4 -二異氰酸酯、甲苯- 2,5 -二異氰酸酯、甲苯-2,6-二異氰酸酯及甲苯-3,5 -二異氰酸酯；及其他芳族二異氰酸 酯，諸如甲苯二異氰酸酯，包括1，2 -二甲苯-3,5 -二異氰酸 酯、1，2-二甲苯-3,6-二異氰酸酯、1，3-二甲苯-2,4·二異氰 酸酯、1，3-二甲苯-2,5-二異氰酸酯、1，3-二甲苯-4,6_二異 氰酸酯、1,4-二甲苯-2,5-二異氰酸酯及1,4-二甲苯-2,6-二 異氰酸酯。 前述三異氰酸酯之實例係包括苯三異氰酸酯，諸如 苯-1，2,4-三異氰酸酯及苯-1，3,5-三異氰酸酯；甲苯三異氰 酸酯，諸如甲苯-2,3,5-三異氰酸酯、甲苯-2,3,6-三異氰酸 酯、甲苯-2，4,5 -三異氰酸酯及甲苯-2,4,6 -三異氰酸酯；及 其他芳族三異氰酸酯，諸如甲苯二異氰酸酯，包括^-二 甲苯-3，4,5 -三異氰酸酯、1，2-二甲苯-3,4,6 -三異氰酸酯、 1，3-二甲苯-2,4,5-三異氰酸酯、1,3-二甲苯-2,4,6-三異氰 酸酯、1，3-二甲苯-4,5,6-三異氰酸酯及1，4-二甲苯·2,3,5· 三異氰酸酯。 此等二異氰酸酯及三異氰酸酯可單獨或二或更多種組 合使用。 於一末端具有羥基之聚酯及兩末端皆具有羥基之聚酯 的實例係包括於一末端或兩末端皆具有羥基之聚內酯，於 -14- 200830043 一末端或兩末端皆具有羥基之聚己內酯、於一末 端皆具有羥基之聚戊內酯及於一末端或兩末端皆 之聚丙內酯；及於一末端或兩末端皆具有羥基之 酯，諸如於一末端或兩末端皆具有羥基之聚對苯 二酯及於一末端或兩末端皆具有羥基之聚對苯二 酯。 此等於一末端具有羥基之聚酯及此等於兩末 羥基之聚酯可單獨或二或更多種組合使用。 本發明以胺基甲酸酯爲主之分散劑較佳係爲 氰酸酯與於一末端具有羥基之聚內酯及/或於兩 有羥基之聚內酯的反應產物，尤其是甲苯二異氰 一末端具有羥基之聚己內酯及/或於兩末端皆具 聚己內酯的反應產物。 以胺基甲酸酯爲主之分散劑的實例 Disperbyk 16 1 及 Disperbyk 170 ( B YK-Chemie ( 、EFKA ( EFKA Chemicals BV ( EFKA ))及 D Kusumoto Chemicals Ltd.) o 本發明以胺基甲酸酯爲主之分散劑的重量平 (Mw )較佳係爲5,000至5 0,000，更佳爲7,0 00 〇 前述以胺基甲酸酯爲主之分散劑可單獨或二 組合使用。 由（甲基）丙烯酸單體之（共）聚合物組成 )丙烯酸分散劑亦爲較佳分散劑。 端或兩末 具有羥基 之縮聚聚 二甲酸乙 甲酸丁二 端皆具有 芳族二異 末端皆具 酸酯與於 有羥基之 係包括 B YK )) isparon ( 均分子量 至 20,000 或更多種 之（甲基 -15- 200830043 (甲基）丙烯酸分散劑的實例係包括Disperbyk 2000 及 Disperbyk 200 1 ( B YK-Chemie ( B YK ))。 前述（甲基）丙烯酸分散劑可單獨或二或更多種組合 使用。 用以製備含有顏料或碳黑之顏料分散液的分散劑之量 以10 0重量份數顏料計，較佳係爲1〇〇重量份數或更低， 更佳係爲〇·5至100重量份數，再更佳係1至7〇重量份 數，尤其是10至50重量份數。當分散劑之量大於1〇〇重 量份數時，破壞顯影性。 用以製備顏料分散液的溶劑可與用以製備下文所述之 液體輻射敏感性樹脂組成物所用溶劑相同。 用以製備顏料分散液之溶劑的量以1 〇〇重量份數顏料 計，較佳爲5 00至1，〇〇〇重量份數，更佳爲70〇至900重 量份數。 使用珠磨機製備顏料分散液時，使用直徑約〇 . 5至1 〇 毫米之玻璃珠粒、二氧化駄珠粒或諸如此類者混合且分散 包含顏料、溶劑及分散劑之顏料混合溶液，較佳係同時以 冷卻水或諸如此類者進行冷卻。 此情況下，珠粒之裝塡率較佳係爲磨機容量之5 0至 80%，而顏料混合溶液之注射量較佳係爲磨機容量之約2〇 至5 0%。處理時間較佳係爲2至5 0小時，更佳係爲2至 25小時。 輥磨機製備顏料分散液時，使用三輥磨機、雙輥磨機 或諸如此類者混合且分散該混合有顏料之溶液，較佳係同 -16- 200830043 時以冷卻水或諸如此類者冷卻。 此情況下’輥間之間隔較佳係爲1 0微米或更小，且 剪切力較佳係爲約1 〇8達因/秒。處理時間較佳係爲2至 5 0小時，更佳2至2 5小時。 -(B )鹼可溶性樹脂- 本發明鹼可溶性樹脂係包含在其聚合物鏈之至少一末 端具有前式（i )或（ii )所示之基團的樹脂（以下稱爲「 樹脂（B )」）。 式（i)或（ii)中由Z1及Z2所表示之具有1至20 個碳原子的烷基實例係包括甲基、乙基、正丙基、異丙基 、正丁基、異丁基、第二丁基、第三丁基、正戊基、正己 基、正庚基、正辛基、正壬基、正癸基、正十二碳基、正 十四碳基、正十六碳基、正十八碳基及正二十碳基。 由Z1及Z2所表示之具有6至20個碳原子的單價芳 族烴基實例係包括苯基、1-萘基、2-萘基、1-蒽基、9-蒽 基、苄基及苯乙基。 由Z1及Z2所表示之由碳原子及雜原子組成而具有3 至20個原子之單價雜環基實例係包括環氧乙烷基、氮 基、2-呋喃基、3-呋喃基、2-四氫呋喃基、3-四氫呋喃基 、1 -吡咯基、2 -吡咯基、3 -吡咯基、1 _吡咯啶基、2 -吡咯 啶基、3 -吡略啶基、1 -吡唑基、2 -四氫哌喃基、3 -四氫哌 喃基、4-四氫哌喃基、2-噻烷基、3-噻烷基、4-噻烷基、 2 -吡啶基、3 -吡啶基、4 -吡啶基、2 -哌啶基、3 -哌啶基、 -17- 200830043 4 -哌啶基、2 ·嗎啉基及3 -嗎啉基。 由 Z1 及 Z2 所表示之- OR1、-SR1、-0C(=0) R1、-N (R1 ) (R2) ^ -C ( =0 ) OR1 > _C ( =0 ) NCR1) (r2) 、-P(=0) (〇Ι^)2&-Ρ(=0) 表示之具有1至18個碳原子之烷基、具有6至18個碳原 子之單價芳族烴基及由碳原子及雜原子組成之具有3至1 8 個原子之單價雜環基的實例個別係爲Z 1及Z2所列示之選 自具有1至20個碳原子之烷基、具有6至20個碳原子之 單價芳族烴基及由碳原子及雜原子組成之具有3至20個I 原子之單價雜環基的具有18或更少碳原子之基團。 由R1及R2所表示之具有2至18個碳原子的烯基之 實例係包括乙烯基、1-丙烯基、2-丙烯基、1-丁烯基、2_ 丁烯基、3 -丁烯基、1-戊烯基、2 -戊烯基、3 -戊烯基、4-戊烯基、1-己烯基、2 -己烯基、3 -己烯基、4 -己烯基及5_ 己烯基。 具有1至20個碳原子之烷基、具有6至20個碳原子 之單價芳族烴基、由碳原子及雜原子所組成之具有3至20 個原子的單價雜環基、R1及R2可經取代，且此等基團之 取代基可適當地選自氯原子；羧基；氰基；R1及R2所列 之具有1至18個碳原子之烷基、具有6至18個碳原子之 單價芳族烴基、由碳原子及雜原子組成之具有3至18個 原子之單價雜環基及具有2至18個碳原子之烯基；及Z1 及 Z2 所歹 ij 之 _〇Ri、_SRi、_OC (=0) R1 ^ -NCR1) ( R2 ) > -C ( =0) OR1 ^ -C ( =0) NCR1) ( R2 ) 、-p(=〇)( -18- 200830043 〇1^)2及-?(=〇) (R1) 2。取代基中可 同種類或不同種類之取代基。經取代基團 原子總數（若爲雜環基）應不多於20個爲 z1及z2所表示之具有聚合物鏈的單 括具有自至少一種選自以下化合物之不飽 加成聚合聚合物鏈的單價基團：α -烯烴 烯；芳族乙烯基化合物，諸如苯乙烯或α 乙烯鹵，諸如乙烯氟、乙烯氯或偏二氟乙 諸如乙烯醇或烯丙基醇；不飽和醇之酯， 或乙酸烯丙酯；不飽和羧酸，諸如（甲塞 乙烯基苯甲酸；（甲基）丙烯酸酯，諸如 甲酯、（甲基）丙烯酸乙酯、（甲基）丙 甲基）丙烯酸異丙酯、（甲基）丙烯酸正 丙烯酸第三丁酯、（甲基）丙烯酸正己酯 酸環己酯；（甲基）丙烯醯胺，諸如（甲 Ν，Ν-二甲基（甲基）丙烯醯胺；不飽和腈 丙烯腈或亞乙烯基二氰；或共軛二烯，諸 間二烯；及具有加成聚合聚合物鏈或縮合 單價基團，諸如聚醚、聚酯、聚醯胺或聚I 式（i)中之Ζ1及式（ii)中之ζ2各 20個碳原子之烷基、由碳原子及雜原子| 20個原子的單價雜環基、-OR1或_N ( R1 係甲基、乙基、1 -吡咯基、1 -吡唑基、甲 二甲基胺基或二乙基胺基。 存在一或多個相 中碳原子總數或 佳。 價基團實例係包 和化合物形成之 ，諸如乙烯或丙 -甲基苯乙烯； 烯；不飽和醇， 諸如乙酸乙烯酯 B )丙烯酸或對-(甲基）丙烯酸 烯酸正丙酯、（ 丁酯、（甲基） 或（甲基）丙烯 基）丙烯醯胺或 ，諸如（甲基） 如丁二烯或異戊 聚合聚合物鏈之 驢亞胺。 較佳爲具有1至 Ϊ成之具有3至 )(R2)，特佳 氧基、乙氧基、 -19- 200830043 樹脂（B )若可作爲著色劑（A )所用之黏合劑且於顯 影劑（較佳係製造濾光片之顯影步驟中所使用的鹼顯影劑 )中具有溶解度，則不特別限制。樹脂（B )係爲例如由 加聚作用、加成聚合及縮合聚合所製備之具有酸官能基（ 諸如羧基、羧酸酐基或酚羥基）及/或醇羥基（該酸官能 基及醇羥基以下通稱爲「鹼可溶性官能基」）的樹脂。 本發明中，樹脂（B )較佳係爲經由可聚合之不飽和 化合物之聚合而製得的具有鹼可溶性官能基之樹脂（以下 稱爲「樹脂（B1 )」），詳言之，係爲使用下式（3 )所 示之二硫化物化合物（以下稱爲「二硫化物化合物（3 ) 」）作爲分子量控制劑將可聚合之不飽和化合物聚合所製 得的具有鹼可溶性官能基之樹脂。[In the formulae (1) and (2), R3 is each independently an alkyl group having 1 to 2 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, and R4 and R5 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 -9 to 200830043 to 8 carbon atoms, a substituted phenyl group or a monovalent alicyclic group having 7 to 20 carbon atoms a group (excluding the aforementioned cycloalkyl group), each of which is independently a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or having 4 to 20 The monovalent sulfur-containing heterocyclic group of one carbon atom, each of which is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and having 1 to 12 carbon atoms. Alkoxy or cycloalkoxy having 3 to 8 carbon atoms, η each independently an integer of 1 to 5, m each independently an integer of 0 to 5, with the condition of (n + m) ^5 And p is an integer of 0 to 6]. According to the present invention, the foregoing objects and advantages of the present invention are achieved by a method for preparing the aforementioned radiation-sensitive resin composition, which method comprises The pigment dispersion is mixed with (B) an alkali-soluble resin, (C) a monofunctional monomer, and (D) a radiation-sensitive radical generating agent, which is mixed in a solvent by grinding in the presence of a dispersing agent. And it is prepared by dispersing as a pigment of the coloring agent (A). According to the present invention, the third object of the present invention is achieved by the above-mentioned radiation-sensitive resin composition for use in a filter (hereinafter referred to as "radiation-sensitive resin composition for a filter"). According to the present invention, fourth, the objects and advantages of the present invention described above are attained by the filter formed of the radiation-sensitive resin composition of the filter. According to the present invention, fifth, the above objects and advantages of the present invention are achieved by a color liquid crystal display device including the above-described filter. -10- 200830043 [Embodiment] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is described in detail below. Radiation-sensitive resin composition-(A) colorant - Although the coloring agent of the present invention is not particularly limited, it is pigmented because it exhibits high purity and high transparency color (or shielding) and heat-resistant filter. Preferably, organic pigments or carbon black are preferred. Examples of the foregoing organic pigments are compounds classified as a group of pigments according to a colorimetric index, particularly compounds having the following color index (CI) number: CI·Pigment Yellow 12, CI·Pig Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 1 7 , C · I. Pigment Yellow 2 0, C · I · Pigment Yellow 2 4, C · I · Pigment Yellow 3 1 , CI Pigment Yellow 55, CI·Pig Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 1 0 9 , C · I. Pigment Yellow 1 1 0, C · I · Pigment Yellow 1 3 8 , C · I · Pigment Yellow 139, CI·Pigment Yellow 150, CI·Pigment Yellow i53, CI Pigment Yellow 154 , CI·Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168 and CI Pigment Yellow 2 1 1 ; C · I. Pigment Orange 5, C · I. Pigment Orange 1 3, C · I · Pigment Orange 1 4, C · I · Pigment Orange 2 4, C · I · Pigment Orange 3 4, C · I. Pigment Orange 3 6 , C · I. Pigment Orange 3 8 , CI · Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI·Pigment Orange 61, CI·Pigment Orange 64, CI Pigment Orange 68, CI·Pigment Orange 70, CI·Pigment Orange 71, CI Pigment Orange 72, CI·Pigment-11 - 200830043 Orange 7 3 and C · I · Pigment Orange 7 4 ; C · I. Pigment Red 1, C · I · Pigment Red 2, C. I · Pigment Red 5, C · I · Pigment Red 1 7 , C · I. Pigment Red 3 1 , C · I · Pigment Red 3 2. C · I · Pigment Red 4 1 , C . I. Pigment Red 1 2 2, C · I · Pigment Red 1 2 3, C . I · Pigment Red 1 4 4, C · I · Pigment Red 1 4 9 , C I · Pigment Red 166, C · I. Pigment Red 168, C · I · Pigment Red 1.7, C. I. Pigment Red 1 7 1 , C. I. Pigment Red 1 7 5, C · I. Pigment Red 1 7 6 , C · I · Pigment Red 1 7 7 , C · I · Pigment Red 1 7 8 , C . I · Pigment Red 1 7 9 , C . I · Pigment Red 1 8 0, C · I. Pigment Red 1 8 5, C · I · Pigment Red 1 8 7 , C · I · Pigment Red 2 0 2, C . I · Pigment Red 2 0 6 , C · I · Pigment Red 2 0 7 , C · I · Pigment Red 2 0 9 , C . I. Pigment Red 2 1 4, C · I · Pigment Red 2 2 0, C · I · Pigment Red 2 2 1 , C · I · Pigment Red 2 2 4, C · I · Pigment Red 2 4 2, C · I · Pigment Red 2 4 3, C · I. Pigment Red 25 4, CI Pigment Red 2 5 5, CI·Pigment Red 262, CI·Pigment Red 264, and CI Pigment Red 272 ; CI Pigment Violet 1, CI Pigment Violet 19, CI·Pigment Violet 23, CI Pigment Violet 29 CI Pigment Violet 32, CI Pigment Violet 36 and CI·Pigment Violet 38 ( . C . I. Pigment Blue 1 5, C _ I · Pigment Blue 1 5 : 3, c · I · Pigment Blue 1 5 : 4 , CI Pigment Blue 15: 6, CI·Pigment Blue 60 and CI·Pigment Blue 80; 羲C. I. Pigment Green 7 and C. I. Pigment Green 3 6 ; # CI Pigment Brown 23 and CI Pigment Brown 25; and CI Pigment Black 1 and CI Pigment Black 7. Among these organic pigments, CI Pigment Yellow 83, CI Pigment Yellow 139, C. I. Pigment Yellow 1 3 8 , C · I · Pigment Yellow 1 50, C · I · Pigment Yellow 1 800, c ·1 · Pigment Red 1 7 7 , C · I · Pigment Red 2 5 4, C · I · Pigment Blue 1 5 : 3, C · I · Pigment-12 - 200830043 Blue 1 5 : 4, C · I · Pigment Blue 1 5: 6, C · I. Pigment Green 7, C · I · Pigment Green 36, CI Pigment Violet 23, c ·; [• Pigment Blue 6〇 and ci·Pigment Blue 8〇 Preferably, the aforementioned organic pigments may be used alone or A mixture of an organic pigment and carbon black may also be used in combination of two or more. In the present invention, when the coloring agent of the radiation-sensitive resin composition is a pigment, it is preferably mixed and dispersed in a solvent by grinding in a bead mill or a roll mill in the presence of a dispersing agent to prepare a pigment dispersion liquid. This dispersion is then mixed with components (B), (C) and (D) and optionally with additional solvents and other additives described below to prepare a radiation-sensitive resin composition. The dispersant used to prepare the aforementioned pigment dispersion may be a cationic, anionic, nonionic or amphoteric dispersant. Among them, a compound having an urethane bond (hereinafter referred to as "a urethane-based dispersant") is preferred. The aforementioned urethane linkage is usually represented by the general formula R-NH-COO-R· (R and R' are each an aliphatic, alicyclic or aromatic monovalent or polyvalent organic group, the multivalent organic a group which is additionally bonded to a group having another urethane-bonded group or another group) and which may be present in the urethane-based dispersing agent and/or hydrophilic Or in the main chain and/or side chain of the urethane-based dispersing agent, and one or more amine groups may be present in the urethane-based dispersing agent. Formate bonding. When the urethane-based dispersant contains two or more urethane linkages, they may be the same or different. The urethane-based dispersing agent is a reaction product of, for example, diisocyanate and -13-200830043 / or a triisocyanate with a polyester having a hydroxyl group at one terminal and/or a polyester having a hydroxyl group at both terminals. Examples of diisocyanates include phenyl diisocyanates such as benzene-1,3-diisocyanate and benzene-1,4-diisocyanate; toluene diisocyanate such as toluene-2,4-diisocyanate, toluene-2,5-di Isocyanate, toluene-2,6-diisocyanate and toluene-3,5-diisocyanate; and other aromatic diisocyanates such as toluene diisocyanate, including 1,2-xylene-3,5-diisocyanate, 1,2 -xylene-3,6-diisocyanate, 1,3-xylene-2,4.diisocyanate, 1,3-xylene-2,5-diisocyanate, 1,3-xylene-4,6_ Diisocyanate, 1,4-xylene-2,5-diisocyanate and 1,4-xylene-2,6-diisocyanate. Examples of the aforementioned triisocyanate include benzene triisocyanate such as benzene-1,2,4-triisocyanate and benzene-1,3,5-triisocyanate; toluene triisocyanate such as toluene-2,3,5-triisocyanate, Toluene-2,3,6-triisocyanate, toluene-2,4,5-triisocyanate and toluene-2,4,6-triisocyanate; and other aromatic triisocyanates such as toluene diisocyanate, including x-xylene -3,4,5-triisocyanate, 1,2-xylene-3,4,6-triisocyanate, 1,3-xylene-2,4,5-triisocyanate, 1,3-xylene-2 4,6-triisocyanate, 1,3-xylene-4,5,6-triisocyanate and 1,4-xylene·2,3,5·triisocyanate. These diisocyanates and triisocyanates may be used singly or in combination of two or more. Examples of the polyester having a hydroxyl group at one end and the polyester having a hydroxyl group at both ends include a polylactone having a hydroxyl group at one end or both ends, and having a hydroxyl group at one end or both ends of-14-200830043 Caprolactone, polyvalerolactone having a hydroxyl group at one end, and polypropiolactone at one or both ends; and an ester having a hydroxyl group at one or both ends, such as at one end or both ends A poly(p-phenylene terephthalate) having a hydroxyl group and a polyparaphenylene ester having a hydroxyl group at one or both ends. The polyester which is equal to one end having a hydroxyl group and the polyester which is equal to the two terminal hydroxyl groups may be used singly or in combination of two or more. The urethane-based dispersing agent of the present invention is preferably a reaction product of a cyanate ester with a polylactone having a hydroxyl group at one end and/or a polylactone having two hydroxyl groups, especially toluene. A polycaprolactone having a hydroxyl group at one end of the cyanide and/or a reaction product of polycaprolactone at both ends. Examples of urethane-based dispersing agents Disperbyk 16 1 and Disperbyk 170 (B YK-Chemie ( , EFKA (Efficient BV ( EFKA )) and D Kusumoto Chemicals Ltd.) o Amino carboxylic acid The ester-based dispersing agent preferably has a weight (Mw) of 5,000 to 50,000, more preferably 7,000 Å. The aforementioned urethane-based dispersing agent may be used singly or in combination. The (co)polymer composition of the (meth)acrylic monomer) acrylic dispersant is also a preferred dispersant. The polycondensed polydicarboxylate having a hydroxyl group at the terminal or both ends has an aromatic diisomeric end with an acid ester and a hydroxyl group including B YK )) isparon (average molecular weight to 20,000 or more) Examples of the methyl-15-200830043 (meth)acrylic dispersant include Disperbyk 2000 and Disperbyk 200 1 (B YK-Chemie (B YK )). The aforementioned (meth)acrylic dispersant may be used alone or in two or more. The amount of the dispersant used to prepare the pigment dispersion containing the pigment or carbon black is, in terms of 100 parts by weight of the pigment, preferably 1 part by weight or less, more preferably 〇·5. To 100 parts by weight, more preferably 1 to 7 parts by weight, especially 10 to 50 parts by weight. When the amount of the dispersant is more than 1 part by weight, the developability is deteriorated. The solvent of the liquid may be the same as the solvent used to prepare the liquid radiation-sensitive resin composition described below. The amount of the solvent used to prepare the pigment dispersion is 1 part by weight of the pigment, preferably 500 to 1 , 〇〇〇 part by weight, more preferably 70〇 to 90 0 parts by weight. When preparing a pigment dispersion using a bead mill, glass beads having a diameter of about 0.5 to 1 mm, ceria beads or the like are mixed and dispersed with a pigment containing a pigment, a solvent and a dispersant. The mixed solution is preferably cooled simultaneously with cooling water or the like. In this case, the beading rate of the beads is preferably from 50 to 80% of the mill capacity, and the injection amount of the pigment mixed solution is preferably It is about 2 to 50% of the mill capacity. The treatment time is preferably 2 to 50 hours, more preferably 2 to 25 hours. When the roller mill prepares the pigment dispersion, a three-roll mill is used. A roller mill or the like mixes and disperses the pigment-mixed solution, preferably cooled with cooling water or the like when it is -16-200830043. In this case, the interval between the rolls is preferably 10 μm or more. Small, and the shearing force is preferably about 1 〇 8 dynes/second. The treatment time is preferably from 2 to 50 hours, more preferably from 2 to 25 hours. - (B) alkali-soluble resin - the base of the present invention The soluble resin is contained in at least one end of its polymer chain having the formula (i) Or a resin of the group shown in (ii) (hereinafter referred to as "resin (B)"). An alkyl group having 1 to 20 carbon atoms represented by Z1 and Z2 in the formula (i) or (ii) It includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, Sulfhydryl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-octadecyl. 6 to 20 carbons represented by Z1 and Z2 Examples of the monovalent aromatic hydrocarbon group of the atom include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 9-fluorenyl group, a benzyl group, and a phenethyl group. Examples of the monovalent heterocyclic group represented by Z1 and Z2 which are composed of a carbon atom and a hetero atom and have 3 to 20 atoms include an oxiranyl group, a nitrogen group, a 2-furyl group, a 3-furyl group, and 2 Tetrahydrofuranyl, 3-tetrahydrofuranyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyridolidinyl, 1-pyrazolyl, 2- Tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-thylalkyl, 3-thiaalkyl, 4-thiaalkyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-piperidinyl, 3-piperidinyl, -17-200830043 4-piperidinyl, 2-morpholinyl and 3-morpholinyl. -Z1 and Z2 - OR1, -SR1, -0C (=0) R1, -N (R1) (R2) ^ -C ( =0 ) OR1 > _C ( =0 ) NCR1) (r2) , -P(=0)(〇Ι^)2&-Ρ(=0) represents an alkyl group having 1 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and a carbon atom and a hetero Examples of the monovalent heterocyclic group having an atomic composition of 3 to 18 atoms are each a unit selected from Z 1 and Z 2 selected from an alkyl group having 1 to 20 carbon atoms and having a carbon number of 6 to 20 carbon atoms. An aromatic hydrocarbon group and a group having a carbon atom and a hetero atom having a monovalent heterocyclic group of 3 to 20 I atoms and having 18 or less carbon atoms. Examples of the alkenyl group having 2 to 18 carbon atoms represented by R1 and R2 include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group. , 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl and 5_ Hexenyl. An alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 atoms consisting of a carbon atom and a hetero atom, and R1 and R2 may be Substituted, and the substituents of such groups may be suitably selected from a chlorine atom; a carboxyl group; a cyano group; an alkyl group having 1 to 18 carbon atoms listed in R1 and R2, and a monovalent aromatic group having 6 to 18 carbon atoms. a hydrocarbon group, a monovalent heterocyclic group having 3 to 18 atoms composed of a carbon atom and a hetero atom, and an alkenyl group having 2 to 18 carbon atoms; and _Ri, _SRi, _OC of Z1 and Z2 =0) R1 ^ -NCR1) ( R2 ) > -C ( =0) OR1 ^ -C ( =0) NCR1) ( R2 ) , -p(=〇)( -18- 200830043 〇1^) 2 and -?(=〇) (R1) 2. Substituents of the same or different kinds in the substituents. The total number of atoms of the substituent group (if a heterocyclic group) should be no more than 20, and the polymer chain having a polymer chain represented by z1 and z2 has a polymerizable polymer chain derived from at least one compound selected from the following compounds. Monovalent group: an α-olefin alkene; an aromatic vinyl compound such as styrene or an α-ethylene halide such as ethylene fluoride, ethylene chloride or difluoroethane such as vinyl alcohol or allyl alcohol; an ester of an unsaturated alcohol, Or allyl acetate; unsaturated carboxylic acid, such as (methicillinbenzoic acid; (meth) acrylate, such as methyl ester, ethyl (meth) acrylate, (methyl) propylmethyl) isopropyl acrylate Ester, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexyl (meth) acrylate, such as (methyl hydrazine, hydrazine-dimethyl (meth) propylene hydride An amine; an unsaturated nitrile acrylonitrile or vinylidene dicyanohydroxide; or a conjugated diene, an inter-diene; and an addition polymerized polymer chain or a condensed monovalent group such as a polyether, a polyester, a polyamide or Poly(I) is a carbon atom of Ζ1 in formula (i) and ζ2 in formula (ii) a carbon atom and a hetero atom | 20 atomic monovalent heterocyclic group, -OR1 or _N (R1 is methyl, ethyl, 1-pyrrolyl, 1-pyrazolyl, methyldimethylamino or Diethylamino group. The total number of carbon atoms in one or more phases is preferably or better. Examples of valence groups are formed by coatings and compounds, such as ethylene or propyl-methyl styrene; olefins; unsaturated alcohols, such as vinyl acetate B) acrylic acid or n-propyl (meth) acrylate, (butyl ester, (meth) or (meth) propylene) acrylamide or, such as (methyl) such as butadiene or isoprene a ruthenium imine of a polymerized polymer chain. It preferably has 3 to) (R2), a particularly preferred oxy group, an ethoxy group, and a -19-200830043 resin (B) if it can be used as a coloring agent (A). The binder to be used and solubility in a developer (preferably an alkali developer used in the development step of producing a filter) is not particularly limited. The resin (B) is, for example, an acid functional group (such as a carboxyl group, a carboxylic anhydride group or a phenolic hydroxyl group) and/or an alcoholic hydroxyl group (for example, an acid functional group and an alcoholic hydroxyl group) prepared by addition polymerization, addition polymerization, and condensation polymerization. A resin commonly referred to as "alkali-soluble functional group"). In the present invention, the resin (B) is preferably a resin having an alkali-soluble functional group (hereinafter referred to as "resin (B1)") obtained by polymerization of a polymerizable unsaturated compound, and in detail, A resin having an alkali-soluble functional group obtained by polymerizing a polymerizable unsaturated compound using a disulfide compound represented by the following formula (3) (hereinafter referred to as "disulfide compound (3)") as a molecular weight controlling agent .

⑶ [式（3)中，21及Z2個別與式（i)中之ζι及式（ii)中 之Z2相同]。 本發明中，樹脂（B 1 )較佳係爲具有鹼可溶性官能基 之可聚合不飽和化合物與另一種可共聚不飽和化合物之共 聚物（以下稱爲「鹼可溶性共聚物」）。 驗可溶性共聚物特佳係爲（b 1 )不飽和羧酸及/或不 飽和竣酸酐（以下稱爲「不飽和化合物（b i )」）與（b2 )至少一種選自芳族乙烯基化合物、茚、N-取代順丁烯二 醯亞胺 '於聚合物分子鏈之一末端具有（甲基）丙烯醯基 之巨單體、不飽和羧酸酯、不飽和羧酸胺基烷酯、不飽和 -20- 200830043 羧酸縮水甘油酯、羧酸乙烯酯、不飽和醚、不飽和醯胺及 脂族共軛二烯之可共聚不飽和化合物（以下稱爲「不飽和 化合物（b2 )」）之共聚物（以下稱爲「鹼可溶性共聚物 (I) j ) ° % 不飽和化合物（b 1 )之實例係包括不飽和單羧酸，諸 • 如（甲基）丙烯酸、巴豆酸、^ -氯丙烯酸及肉桂酸；不 飽和二羧酸及其酐，諸如順丁烯二酸、順丁烯二酸酐、反 :丁烯二酸、依康酸、依康酸酐、檸康酸、檸康酸酐及中康 酸·，具有三或更多個羧基之不飽和多羧酸及其酐；具有二 或更多個羧基之多羧酸的單[(甲基）丙烯醯氧烷基]酯， 諸如琥珀酸單[2-(甲基）丙烯醯氧乙基]酯及苯二甲酸單 [2-(甲基）丙烯醯氧乙基]酯；及於兩末端具有羧基及羥 基之聚合物的單（甲基）丙烯酸酯，諸如羧基聚己內 酯單（甲基）丙烯酸酯。 此等不飽和化合物（b 1 )中，（甲基）丙烯酸、琥珀 % 酸單[2-(甲基）丙細醯氧乙基]酯及〇 -錢基聚己內酯單（ 甲基）丙烯酸酯特佳。 • 前述不飽和化合物（b 1 )可單獨或二或更多種組合使 用。 不飽和化合物（b2 )之實例係包栝芳族乙烯基化合物 ，諸如苯乙烯、α -甲基苯乙烯、鄰-羥基苯乙烯、間-羥基 苯乙嫌、對-經基苯乙熥、鄰-羥基-α -甲基苯乙嫌、間-經 基-α-甲基苯乙燒、對-經基-α-甲基苯乙烯、對-苯乙烯 磺酸、鄰-乙儲基甲苯、間-乙;(¾基甲苯、對-乙嫌基甲苯、 -21 - 200830043 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-乙烯基苄基甲基醚、間-乙烯基苄基甲 基醚、對-乙烯基苄基甲基醚、鄰-乙烯基苄基縮水甘油基 醚、間-乙烯基苄基縮水甘油基醚及對-乙烯基苄基縮水甘 油基醚；茚，諸如茚及1 -甲基茚；N -取代順丁烯二醯亞胺 ，諸如N-環己基順丁烯二醯亞胺及N-(經取代）_芳基順 丁烯二醯亞胺，諸如N-苯基順丁烯二醯亞胺、N-鄰-羥基 苯基順丁烯二醯亞胺、N-間-羥基苯基順丁烯二醯亞胺、 N-對-羥基苯基順丁烯二醯亞胺、N-鄰-甲基苯基順丁烯二 醯亞胺、N-間-甲基苯基順丁烯二醯亞胺、N-對-甲基苯基 順丁烯二醯亞胺、N-鄰-甲氧基苯基順丁烯二醯亞胺、N-間-甲氧基苯基順丁烯二醯亞胺及[對-甲氧基苯基順丁烯 二醯亞胺；於聚合物分子鏈之一末端具有（甲基）丙烯醯 基之巨單體（以下簡稱爲「巨單體」），諸如聚苯乙烯、 聚（甲基）丙烯酸甲酯、聚（甲基）丙烯酸正丁酯及聚矽 氧烷；不飽和羧酸酯，諸如（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 異丙酯、（曱基）丙烯酸正丁酯、（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）丙烯酸2 -羥基乙酯、（甲基）丙烯酸2 -羥基丙酯 、（甲基）丙儲酸3 -經基丙酯、（甲基）丙燃酸2 -羥基丁 酯、（甲基）丙烯酸3 -羥基丁酯、（甲基）丙烯酸4 -羥基 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 -22- 200830043 烯酸2-甲氧基乙酯、（甲基）丙烯酸2-苯氧基乙酯、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、甲氧基二丙 二醇（甲基）丙烯酸酯、（甲基）丙烯酸異萡酯、（甲基 )丙烯酸三環[5·2·1·02,6]癸-8-酯、（甲基）丙烯酸2-羥 基-3-苯氧基丙酯及甘油（甲基）丙j：希酸酯；不飽和羧酸胺 基烷基酯，諸如（甲基）丙烯酸2-胺基乙酯、（甲基）丙 烯酸2-二甲基胺基乙酯、（甲基）丙烯酸2-胺基丙酯、（ 甲基）丙烯酸2-二甲基胺基丙酯、（甲基）丙烯酸3-胺基 丙酯及（甲基）丙烯酸3 -二甲基胺基丙酯；不飽和羧酸縮 水甘油酯，諸如（甲基）丙烯酸縮水甘油酯；羧酸乙烯酯 ，諸如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯及苯甲酸乙 烯酯；不飽和醚，諸如乙烯基甲基醚、乙烯基乙基醚及烯 丙基縮水甘油醚；乙烯基氰化合物，諸如（甲基）丙烯腈 、α-氯丙烯腈及亞乙烯基二氰；不飽和醯胺，諸如（甲 基）丙烯醯胺、α-氯丙烯醯胺及Ν-2-羥基乙基（甲基） 丙烯醯胺；及脂族共軛二烯，諸如1，3-丁二烯、異戊間二 烯、氯丁二烯及異戊間二烯磺酸。 此等不飽和化合物（b2 )中，苯乙烯、巨單體、Ν-取 代順丁烯二醯亞胺、（甲基）丙烯酸甲酯、（甲基）丙烯 酸2-羥基乙酯、（甲基）丙烯酸烯丙酯、（甲基）丙烯酸 苄酯、（甲基）丙烯酸苯酯及甘油單（甲基）丙烯酸酯較 佳。巨單體中，聚苯乙烯巨單體及聚（甲基）丙烯酸甲酯 巨單體特佳，而N-取代順丁烯二醯亞胺中，N-苯基順丁 -23- 200830043 烯二醯亞胺及N-環己基順丁烯二醯亞胺特佳。 前述不飽和化合物（b 2 )可單獨或二或更多種組合使 用。 本發明中’鹼可溶性共聚物（I )較佳係爲（bl )至 少一種選自（甲基）丙烯酸、琥拍酸單[2-(甲基）丙烯醯 氧乙基]酯及ω-羧基聚己內酯單（甲基）丙烯酸酯之不飽 和化合物及（b2)至少一種選自聚苯乙烯巨單體、聚（甲 基）丙烯酸甲酯巨單體、N-苯基順丁烯二醯亞胺、環己 基順丁烯二醯亞胺、（甲基）丙儲酸2 -羥基乙酯、（甲基 )丙烯酸苄酯及甘油單（甲基）丙烯酸酯之不飽和化合物 及視情況存在之（b2)至少一種選自苯乙嫌、（甲基）丙 烯酸甲酯、（甲基）丙烯酸烯丙酯及（甲基）丙烯酸苯酯 之不飽和化合物的單體混合物之共聚物（以下稱爲「含殘 基共聚物（1-1 )」）。 該含羧基共聚物（1-1)更佳係爲係爲（bl)含有（甲 基）丙燃酸作爲必要組份且視情況含有、號班酸單[2 -(甲 基）丙烯醯氧乙基]酯之不飽和化合物及（b2)至少一種 選自聚苯乙烯巨單體、聚（甲基）丙烯酸甲酯巨單體、N_ 苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、（甲基 )丙烯酸2-羥基乙酯、（甲基）丙烯酸苄酯及甘油單（甲 基）丙烯酸酯之不飽和化合物及視情況存在之（b2 )至少 一種選自苯乙烯、（甲基）丙烯酸甲酯、（甲基）丙嫌酸 烯丙酯及（甲基）丙烯酸苯酯之不飽和化合物的單體混合 物之共聚物（以下稱爲「含羧基共聚物（1-2)」）。 -24- 200830043 含羧基共聚物（I - 2 )之特定實例係包括（甲基）丙烯 酸與（甲基）丙烯酸2 -羥基乙酯之共聚物、（甲基）丙烯 酸、聚苯乙嫌巨單體與（甲基）丙烯酸节酯之共聚物、（ 甲基）丙烯酸、聚（甲基）丙烯酸甲酯巨單體與（甲基） 丙烯酸苄酯之共聚物、（甲基）丙烯酸、、（甲基）丙烯 酸苄酯與甘油單（甲基）丙烯酸酯之共聚物、（甲基）丙 烯酸、（甲基）丙烯酸2-羥基乙酯與（甲基）丙烯酸苯酯 之共聚物、（甲基）丙烯酸、（甲基）丙烯酸2-羥基乙酯 與苯乙烯之共聚物、（甲基）丙烯酸、（甲基）丙烯酸苄 酯與甘油單（甲基）丙烯酸酯之共聚物、（甲基）丙烯酸 、（甲基）丙烯酸2 -羥基乙酯與（甲基）丙烯酸苄酯之共 聚物、（甲基）丙烯酸、聚苯乙烯巨單體、（甲基）丙烯 酸2-羥基乙酯與（甲基）丙烯酸苄酯之共聚物、（甲基） 丙烯酸、聚（甲基）丙烯酸甲酯巨單體、（甲基）丙烯酸 2 -羥基乙酯與（甲基）丙烯酸苄酯之共聚物、（甲基）丙 烯酸、N -苯基順丁烯二醯亞胺、（甲基）丙烯酸烯丙酯與 苯乙烯之共聚物、（甲基）丙烯酸、N -苯基順丁烯二醯亞 胺、（甲基）丙烯酸苄酯與苯乙烯之共聚物、（甲基）丙 烯酸、N -環己基順丁烯二醯亞胺、（甲基）丙烯酸烯丙酯 與苯乙烯之共聚物、（甲基）丙烯酸、N-環己基順丁烯二 醯亞胺、（甲基）丙烯酸苄酯與苯乙烯之共聚物、（甲基 )丙烯酸、N_苯基順丁烯二醯亞胺、（甲基）丙烯酸苄酯 、甘油單（甲基）丙烯酸酯與苯乙烯之共聚物、（甲基） 丙烯酸、琥珀酸單[2-(甲基）丙烯醯氧乙基]酯、（甲基 -25- 200830043 )丙烯酸苄酯及甘油單（甲基）丙烯酸酯之共聚物、（甲 基）丙烯酸、琥珀酸單[2-(甲基）丙烯醯氧乙基]酯、N-苯基順丁烯二醯亞胺、（甲基）丙烯酸烯丙酯及苯乙烯之 共聚物、（甲基）丙烯酸、琥珀酸單[2_(甲基）丙烯醸氧 乙基]酯、N-苯基順丁烯二醯亞胺、（甲基）丙烯酸苄酯 及苯乙烯之共聚物、（甲基）丙烯酸、琥珀酸單[2-(甲基 )丙烯醯氧乙基]酯、N -環己基順丁烯二醯亞胺、（甲基 )丙烯酸烯丙酯及苯乙烯之共聚物、（甲基）丙烯酸、號 Ϊ白酸單[2-(甲基）丙烯醯氧乙基]酯、N -環己基順丁烯二 醯亞胺、（甲基）丙烯酸苄酯及苯乙烯之共聚物及（甲基 )丙烯酸、琥珀酸單[2-(甲基）丙烯醯氧乙基]酯、N-苯 基順丁烯二醯亞胺、（甲基）丙烯酸苄酯、甘油單（甲基 )丙烯酸酯及苯乙烯之共聚物。 含羧基共聚物（I -1 )之特定實例係包括（甲基）丙烯 酸、ω-羧基聚己內酯單（甲基）丙烯酸酯、N -苯基順丁 烯二醯亞胺、（甲基）丙烯酸苄酯、甘油單（甲基）丙烯 酸酯及苯乙烯之共聚物、（甲基）丙烯酸、ω-羧基聚Β 內酯單（甲基）丙烯酸酯及（甲基）丙烯酸2-羥基乙酯之 共聚物、（甲基）丙烯酸、羧基聚己內酯單（甲基） 丙烯酸酯、聚苯乙烯巨單體及（甲基）丙烯酸苄酯之共聚 物、（甲基）丙烯酸、ω-羧基聚己內酯單（甲基）丙烯 酸酯、聚（甲基）丙烯酸甲酯巨單體及（甲基）丙烯酸苄 酯之共聚物、（甲基）丙烯酸、ω-羧基聚己內酯單（甲 基）丙烯酸酯、（甲基）丙烯酸苄酯及甘油單（甲基）丙 -26- 200830043 烯酸酯之共聚物、（甲基）丙烯酸、ω-羧基聚己內酯單 (甲基）丙烯酸酯、（甲基）丙烯酸2-羥基乙酯及（甲基 )丙烯酸苯酯之共聚物、（甲基）丙烯酸、ω-羧基聚己 內酯單（甲基）丙烯酸酯、（甲基）丙烯酸2-羥基乙酯及 ^ 苯乙烯之共聚物、（甲基）丙烯酸、ω-羧基聚己內酯單 ^ (甲基）丙烯酸酯、（甲基）丙烯酸苄酯及甘油單（甲基 )丙烯酸酯之共聚物、（甲基）丙烯酸、ω-羧基聚己內 ： 酯單（甲基）丙烯酸酯、（甲基）丙烯酸2-羥基乙酯及（ 甲基）丙烯酸苄酯之共聚物、（甲基）丙烯酸、ω -羧基 聚己內酯單（甲基）丙烯酸酯、聚苯乙烯巨單體、（甲基 )丙烯酸2-羥基乙酯及（甲基）丙烯酸苄酯之共聚物、（ 甲基）丙烯酸、ω-羧基聚己內酯單（甲基）丙烯酸酯、 聚（甲基）丙烯酸甲酯巨單體、（甲基）丙烯酸2-羥基乙 酯及（甲基）丙烯酸苄酯之共聚物、（甲基）丙烯酸、 ω -羧基聚己內酯單（甲基）丙烯酸酯、Ν-苯基順丁烯二 ί 醯亞胺、（甲基）丙烯酸烯丙酯及苯乙烯之共聚物、（甲 基）丙烯酸、ω-羧基聚己內酯單（甲基）丙烯酸酯、Ν-苯基順丁烯二醯亞胺、（甲基）丙烯酸苄酯及苯乙烯之共 聚物、（甲基）丙烯酸、ω -羧基聚己內酯單（甲基）丙 ’ 烯酸酯、Ν-環己基順丁烯二醯亞胺、（甲基）丙烯酸烯丙 酯及苯乙烯之共聚物、（甲基）丙烯酸、ω -羧基聚己內 酯單（甲基）丙烯酸酯、Ν-環己基順丁烯二醯亞胺、（甲 基）丙烯酸苄酯及苯乙烯之共聚物、（甲基）丙烯酸、 ω -羧基聚己內酯單（甲基）丙烯酸酯、Ν-苯基順丁烯二 -27- 200830043 醯亞胺、（甲基）丙烯酸苄酯、甘油單（甲基）丙烯 及苯乙烯之共聚物、（甲基）丙烯酸、ω-羧基聚己 單（甲基）丙烯酸酯、琥珀酸單[2-(甲基）丙烯醯氧 ]酯、（甲基）丙烯酸苄酯及甘油單（甲基）丙烯酸 共聚物、（甲基）丙烯酸、ω-羧基聚己內酯單（甲 丙烯酸酯、琥珀酸單[2-(甲基）丙烯醯氧乙基]酯、 基順丁烯二醯亞胺、（甲基）丙烯酸烯丙酯及苯乙烯 聚物、（甲基）丙烯酸、ω -羧基聚己內酯單（甲基 烯酸酯、琥珀酸單[2-(甲基）丙烯醯氧乙基]酯、Ν-順丁烯二醯亞胺、（甲基）丙烯酸苄酯及苯乙烯之共 、（甲基）丙烯酸、ω-羧基聚己內酯單（甲基）丙 酯、琥珀酸單[2-(甲基）丙烯醯氧乙基]酯、Ν-環己 丁烯二醯亞胺、（甲基）丙烯酸烯丙酯及苯乙烯之共 、（甲基）丙烯酸、ω-羧基聚己內酯單（甲基）丙 酯、琥珀酸單[2-(甲基）丙烯醯氧乙基]酯、Ν-環己 丁烯二醯亞胺、（甲基）丙烯酸苄酯及苯乙烯之共聚 (甲基）丙烯酸、ω-竣基聚己內酯單（甲基）丙嫌 、琥珀酸單[2-(甲基）丙烯醯氧乙基]酯、Ν_苯基順 二醯亞胺、（甲基）丙烯酸苄酯、甘油單（甲基）丙 酯及苯乙烯之共聚物。 樹脂（Β 1 )中具有鹼可溶性官能基之可聚合不飽 合物的聚合比例以所有不飽和化合物之總重计較丨土係 至1 0 0重量％，更佳係爲5至3 0重量％ ’特別是10 重量％。當具有鹼可溶性官能基之可聚合不飽和化合 酸酯 內酯 乙基 酯之 基） Ν-苯 之共 )丙 苯基 聚物 烯酸 基順 聚物 烯酸 基順 物及 酸酯 丁烯 烯酸 和化 爲1 至30 物的 -28- 200830043 聚合比例低於1重量％時’所得樹脂於鹼顯影劑中之溶解 度可能降低。 鹼可溶性共聚物中具有鹼可溶性官能基之可聚合不飽 和化合物的共聚比例以所有不飽和化合物之總量計較佳係 爲1至40重量％，更佳係爲5至30重量％，尤其是10至 3 0重量％。當具有鹼可溶性官能基之可聚合不飽和化合物 的共聚比例低於1重量°/。時’所得之鹼可溶性共聚物於鹼 顯影劑中之溶解度可能降低’當共聚比例高於4 0重量°/。時 ，所得之鹼可溶性共聚物於鹼顯影劑中之溶解度變得太高 ，而可能傷害圖案形狀。 下文描述用以製造樹脂（B1)之聚合。 構成樹脂（B 1 )之可聚合不飽和化合物係於自由基聚 合起始劑及二硫化物化合物（3 )存在下於溶劑中聚合。 藉以將前式（i )或（Π )所示之基團導入所形成之聚合物 鏈的至少一末端。 可聚合不飽和化合物於二硫化物化合物（3 )存在下 之聚合可爲在聚合物鏈之生長末端具有活性自由基之活性 自由基聚合。 當前述聚合係爲活性自由基聚合且使用具有可能使活 性自由基失活之官能基（諸如羧基）之化合物作爲可聚合 不飽和化合物時，可在視情況於藉著酯化保護該官能基以 防止生長末端失活下進行聚合之後，將不飽和化合物中所 含之官能基脫保護而製得樹脂（B 1 )。 前述自由基聚合起始劑係根據所使用之可聚合不飽和 -29 - 200830043 化合物種類及可使用之一般已知自由基聚合起始劑而適當 地選擇。自由基聚合起始劑之實例係包括偶氮基化合物’ 諸如2,2，-偶氮基雙異丁腈、2,2f-偶氮基雙（2,4-二甲基戊 腈）及2,2’-偶氮基雙（4-甲氧-2,4-二甲基戊腈）；有機過 氧化物，諸如苯甲醯化過氧、月桂醯化過氧、1，^-雙（第 三丁基過氧）環己烷及過氧特戊酸第三丁酯；過氧化氫； 及由此等過氧化物及還原劑組成之氧化還原起始劑。 此等自由基聚合起始劑中，偶氮基化合物諸如2,2’-偶 氣基雙異丁騰及2,2^偶氣基雙（2,4 - 一甲基戊膳）較佳， 因其幾乎不因氧產生副反應產物。 前述自由基聚合起始劑可單獨或二或更多種組合使用 〇 表不二硫化物化合物（3 )之式（3 )中由Z1及Z2所 表示而具有1至2 0個碳原子的未經取代或經取代烷基的 實例係如同前述式（i)中之ζι及前述式（ϋ)中之z2所 表示的具有1至2〇個碳原子之未經取代或經取代烷基所 列基團’由Z及z2所表示而具有6至2〇個碳原子的未 經取代或經取代單價芳族烴基的實例係如同前述式（i )(3) [In the formula (3), 21 and Z2 are individually the same as those in the formula (i) and Z2 in the formula (ii)]. In the present invention, the resin (B 1 ) is preferably a copolymer of a polymerizable unsaturated compound having an alkali-soluble functional group and another copolymerizable unsaturated compound (hereinafter referred to as "alkali-soluble copolymer"). The soluble copolymer is particularly preferably (b 1 ) an unsaturated carboxylic acid and/or an unsaturated phthalic anhydride (hereinafter referred to as "unsaturated compound (bi )") and (b2) at least one selected from the group consisting of aromatic vinyl compounds,茚, N-substituted maleimide, a macromonomer having a (meth) acrylonitrile group at one end of a polymer molecular chain, an unsaturated carboxylic acid ester, an aminoalkyl ester of an unsaturated carboxylic acid, Saturated -20- 200830043 A copolymerizable unsaturated compound of glycidyl carboxylate, vinyl carboxylate, unsaturated ether, unsaturated decylamine and aliphatic conjugated diene (hereinafter referred to as "unsaturated compound (b2)") Copolymer (hereinafter referred to as "alkali-soluble copolymer (I) j ) ° % Examples of the unsaturated compound (b 1 ) include unsaturated monocarboxylic acids, such as (meth)acrylic acid, crotonic acid, ^ - Chloroacrylic acid and cinnamic acid; unsaturated dicarboxylic acid and its anhydride, such as maleic acid, maleic anhydride, trans: butenedioic acid, isaconic acid, isaconic anhydride, citraconic acid, citraconic anhydride And mesaconic acid, an unsaturated polycarboxylic acid having three or more carboxyl groups and an anhydride thereof; Mono[(meth)acryloxyalkyl]esters of polycarboxylates of multiple carboxyl groups, such as mono[2-(methyl)propenyloxyethyl] succinate and monophthalic acid [2-(A) a methacrylic acid ethyl ester; and a mono(meth) acrylate having a carboxyl group and a hydroxyl group polymer at both terminals, such as carboxypolycaprolactone mono(meth) acrylate. In b 1 ), (meth)acrylic acid, amber % acid mono [2-(methyl)propionyloxyethyl] ester and hydrazine-co-polycaprolactone mono(meth)acrylate are particularly preferred. The foregoing unsaturated compound (b 1 ) may be used singly or in combination of two or more. Examples of the unsaturated compound (b2) are an aromatic vinyl compound such as styrene, α-methylstyrene, ortho-hydroxyl group. Styrene, m-hydroxyphenylethyl, p-parabenzidine, o-hydroxy-α-methylphenylethyl, m-carbo-α-methylphenyrene, p-carbazyl-α- Methylstyrene, p-styrenesulfonic acid, o-ethyl storage toluene, m-B; (3⁄4-methyltoluene, p-ethyl-toluene, -21 - 200830043 p-chlorostyrene, o-methoxy Styrene M-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinyl Benzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether; hydrazine, such as hydrazine and 1-methyl hydrazine; N-substituted maleimide , such as N-cyclohexyl maleimide and N-(substituted)-aryl maleimide, such as N-phenyl maleimide, N-o-hydroxybenzene Isobutyleneimine, N-m-hydroxyphenyl maleimide, N-p-hydroxyphenyl maleimide, N-o-methylphenyl-butene Diquinone imine, N-m-methylphenyl maleimide, N-p-methylphenyl maleimide, N-o-methoxyphenyl-butene Yttrium imine, N-m-methoxyphenyl maleimide and [p-methoxyphenyl maleimide]; having (methyl) at one end of the polymer molecular chain A macromonomer of acrylonitrile (hereinafter referred to as "macrocell"), such as polystyrene, poly(methyl) Methyl acrylate, n-butyl poly(meth) acrylate and polyoxy siloxane; unsaturated carboxylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate Ester, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, ( 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 3-methyl propyl acrylate, 2-hydroxybutyl (meth) propyl ketone, (A) 3-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, (methyl) Phenyl acrylate, (methyl) propyl-22-200830043 2-methoxyethyl acrylate, 2-phenoxyethyl (meth) acrylate, methoxy diethylene glycol (meth) acrylate, Methoxy triethylene glycol (meth) acrylate, methoxy propylene glycol (meth) acrylate, methoxy dipropylene glycol (methyl Acrylate, isodecyl (meth)acrylate, tricyclo[5·2·1·02,6]癸-8-ester, 2-hydroxy-3-phenoxy (meth)acrylate Propyl propyl ester and glycerol (methyl) propyl j: oxalate; aminoalkyl ester of unsaturated carboxylic acid, such as 2-aminoethyl (meth) acrylate, 2-dimethylamine (meth) acrylate Ethyl ethyl ester, 2-aminopropyl (meth)acrylate, 2-dimethylaminopropyl (meth)acrylate, 3-aminopropyl (meth)acrylate, and (meth)acrylic acid 3- Dimethylaminopropyl ester; unsaturated glycidyl carboxylate such as glycidyl (meth)acrylate; vinyl carboxylate such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; vinyl cyanide compounds such as (meth)acrylonitrile, α-chloroacrylonitrile and vinylidene dicyandiamide; Unsaturated guanamines such as (meth) acrylamide, α-chloropropenylamine and oxime-2-hydroxyethyl (meth) acrylamide; and aliphatic conjugated dienes, Such as 1,3-butadiene, isopentyl inter-diene, chloroprene, and isoprene sulfonic acid. Among these unsaturated compounds (b2), styrene, macromonomer, fluorene-substituted maleimide, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (methyl) Allyl acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate and glycerol mono (meth) acrylate are preferred. Among the macromonomers, polystyrene macromonomers and poly(methyl) acrylate macromonomers are particularly preferred, while N-substituted maleimide, N-phenyl cis-butane-23-200830043 ene Diimine and N-cyclohexylmethyleneimine are particularly preferred. The aforementioned unsaturated compound (b 2 ) may be used singly or in combination of two or more. In the present invention, the 'alkali-soluble copolymer (I) is preferably (bl) at least one selected from the group consisting of (meth)acrylic acid, succinic acid mono [2-(methyl) propylene oxiranyl] ester, and ω-carboxyl group. a polycaprolactone mono(meth)acrylate unsaturated compound and (b2) at least one selected from the group consisting of polystyrene macromonomers, poly(methyl) methacrylate macromonomers, N-phenylhhenene An imine, a cyclohexyl maleimide, a 2-hydroxyethyl (meth)propionate, a benzyl (meth)acrylate, and an glycerol mono(meth)acrylate unsaturated compound, as appropriate (b2) a copolymer of at least one monomer mixture selected from the group consisting of phenethyl, methyl (meth) acrylate, allyl (meth) acrylate and phenyl (meth) acrylate It is called "residual copolymer (1-1)"). More preferably, the carboxyl group-containing copolymer (1-1) is (bl) containing (meth)propionic acid as an essential component and, if necessary, a benzoic acid mono[2-(methyl)propene oxime An ethyl ester ester unsaturated compound and (b2) at least one selected from the group consisting of polystyrene macromonomers, polymethyl (meth) acrylate macromonomers, N-phenyl maleimide, N-cyclohexyl At least one selected from the group consisting of maleimide, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, and glycerol mono(meth)acrylate unsaturated compounds, and optionally (b2) a copolymer of a monomer mixture of styrene, methyl (meth) acrylate, (meth) propyl methacrylate and phenyl (meth) acrylate unsaturated compound (hereinafter referred to as "carboxyl-containing copolymer" (1-2)"). -24- 200830043 Specific examples of the carboxyl group-containing copolymer (I - 2 ) include a copolymer of (meth)acrylic acid and 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid, polystyrene-butadiene Copolymer of (meth) acrylate, (meth)acrylic acid, copolymer of poly(methyl) methacrylate macromonomer and benzyl (meth) acrylate, (meth)acrylic acid, ( Copolymer of benzyl methacrylate with glycerol mono(meth) acrylate, (meth)acrylic acid, copolymer of 2-hydroxyethyl (meth) acrylate and phenyl (meth) acrylate, (methyl) Acrylic acid, copolymer of 2-hydroxyethyl (meth)acrylate and styrene, (meth)acrylic acid, copolymer of benzyl (meth)acrylate and glycerol mono(meth)acrylate, (methyl) Acrylic acid, copolymer of 2-hydroxyethyl (meth)acrylate and benzyl (meth)acrylate, (meth)acrylic acid, polystyrene macromonomer, 2-hydroxyethyl (meth)acrylate and (A) Copolymer of benzyl acrylate, (meth) propyl Acid, polymethyl (meth) acrylate macromonomer, copolymer of 2-hydroxyethyl (meth) acrylate and benzyl (meth) acrylate, (meth) acrylic acid, N-phenyl butylene Copolymer of ruthenium imine, allyl (meth) acrylate and styrene, (meth)acrylic acid, N-phenyl maleimide, benzyl (meth) acrylate and styrene , (meth)acrylic acid, N-cyclohexylmethyleneimine, copolymer of allyl (meth)acrylate and styrene, (meth)acrylic acid, N-cyclohexylbutylene Amine, copolymer of benzyl (meth) acrylate and styrene, (meth)acrylic acid, N-phenyl maleimide, benzyl (meth) acrylate, glycerol mono (meth) acrylate Copolymer with styrene, (meth)acrylic acid, succinic acid mono [2-(methyl) propylene oxiranyl] ester, (methyl-25-200830043) benzyl acrylate and glycerol mono(meth)acrylic acid Copolymer of ester, (meth)acrylic acid, mono[2-(methyl)acryloyloxyethyl] succinate, N-phenyl-butenylene Copolymer of ruthenium imine, allyl (meth) acrylate and styrene, (meth)acrylic acid, mono[2-(methyl) propylene oxyethyl] succinate, N-phenyl s-butene Copolymer of ruthenium imine, benzyl (meth) acrylate and styrene, (meth)acrylic acid, mono[2-(methyl) propylene oxyethyl] succinate, N-cyclohexyl cis-butene Copolymer of sulfimine, allyl (meth) acrylate and styrene, (meth)acrylic acid, mono [2-(methyl) propylene oxyethyl] phthalate, N-cyclohexyl cis Copolymer of butylene diimine, benzyl (meth) acrylate and styrene and (meth)acrylic acid, succinic acid mono [2-(methyl) propylene oxiranyl] ester, N-phenyl cis Copolymer of butylene diimine, benzyl (meth) acrylate, glycerol mono (meth) acrylate and styrene. Specific examples of the carboxyl group-containing copolymer (I-1) include (meth)acrylic acid, ω-carboxypolycaprolactone mono(meth)acrylate, N-phenylbutyleneimine, (methyl) Benzyl acrylate, copolymer of glycerol mono(meth)acrylate and styrene, (meth)acrylic acid, ω-carboxypolydecalactone mono(meth)acrylate and 2-hydroxyethyl (meth)acrylate Copolymer of ester, (meth)acrylic acid, carboxypolycaprolactone mono(meth)acrylate, copolymer of polystyrene macromonomer and benzyl (meth)acrylate, (meth)acrylic acid, ω- Copolymer of carboxypolycaprolactone mono(meth)acrylate, poly(methyl) methacrylate macromonomer and benzyl (meth)acrylate, (meth)acrylic acid, ω-carboxypolycaprolactone (Meth) acrylate, benzyl (meth) acrylate and glycerol mono(methyl) propyl-26- 200830043 copolymer of enoate, (meth)acrylic acid, ω-carboxypolycaprolactone mono (methyl a copolymer of acrylate, 2-hydroxyethyl (meth)acrylate and phenyl (meth)acrylate (meth)acrylic acid, ω-carboxypolycaprolactone mono(meth)acrylate, 2-hydroxyethyl (meth)acrylate and copolymer of styrene, (meth)acrylic acid, ω-carboxypoly a copolymer of lactone mono(meth)acrylate, benzyl (meth)acrylate and glycerol mono(meth)acrylate, (meth)acrylic acid, ω-carboxy polycaprolide: ester mono(methyl) Acrylate, copolymer of 2-hydroxyethyl (meth)acrylate and benzyl (meth)acrylate, (meth)acrylic acid, ω-carboxypolycaprolactone mono(meth)acrylate, polystyrene Monomer, copolymer of 2-hydroxyethyl (meth)acrylate and benzyl (meth)acrylate, (meth)acrylic acid, ω-carboxypolycaprolactone mono(meth)acrylate, poly(methyl) a copolymer of methyl acrylate macromonomer, 2-hydroxyethyl (meth)acrylate and benzyl (meth)acrylate, (meth)acrylic acid, ω-carboxypolycaprolactone mono(meth)acrylate , a total of Ν-phenyl cis-butenylene, allyl (meth) acrylate and styrene , (meth)acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate, fluorene-phenyl maleimide, benzyl (meth) acrylate and styrene copolymer, ( a copolymer of methyl)acrylic acid, ω-carboxypolycaprolactone mono(methyl)propionate, fluorene-cyclohexylmethyleneimine, allyl (meth)acrylate and styrene, Copolymer of (meth)acrylic acid, ω-carboxypolycaprolactone mono(meth)acrylate, fluorene-cyclohexylmethyleneimine, benzyl (meth)acrylate and styrene, (methyl) Acrylic acid, ω-carboxypolycaprolactone mono(meth)acrylate, fluorenyl-phenyl-butylene -27-200830043 quinone imine, benzyl (meth) acrylate, glycerol mono(meth) propylene and Copolymer of styrene, (meth)acrylic acid, ω-carboxypolyhexyl (meth) acrylate, succinic acid mono [2-(methyl) propylene oxime] ester, benzyl (meth) acrylate and glycerin Mono(meth)acrylic acid copolymer, (meth)acrylic acid, ω-carboxypolycaprolactone mono (methacrylate, succinic acid single [2-( Methyl)propenyloxyethyl]ester, cis-butenylenediamine, allyl (meth)acrylate and styrene, (meth)acrylic acid, ω-carboxypolycaprolactone single (A) Alkyl methacrylate, succinic acid mono [2-(methyl) propylene oxiranyl] ester, hydrazine-m-butylene imidate, benzyl (meth) acrylate and styrene (meth) Acrylic acid, ω-carboxypolycaprolactone mono(methyl)propyl ester, succinic acid mono [2-(methyl) propylene oxiranyl] ester, Ν-cyclohexamethylene diimide, (methyl) Alkyl acrylate and styrene, (meth)acrylic acid, ω-carboxypolycaprolactone mono(methyl)propyl ester, succinic acid mono [2-(methyl) propylene oxiranyl] ester, hydrazine - cyclohexamethylene diimide, copolymerization of benzyl (meth) acrylate and styrene (meth)acrylic acid, ω-mercapto polycaprolactone mono(methyl) propyl, succinic acid single [2- Copolymer of (meth)acryloyloxyethyl]ester, fluorene-phenyl cis-diimine, benzyl (meth) acrylate, glycerol mono(methyl) propyl ester and styrene. The polymerization ratio of the polymerizable unsaturated group having an alkali-soluble functional group in the resin (Β 1 ) is from 1 to 10% by weight, more preferably from 5 to 30% by weight based on the total weight of all the unsaturated compounds. % 'especially 10% by weight. a base of a polymerizable unsaturated acid ester lactone having an alkali-soluble functional group) a fluorene-phenyl olefinic acid cis olefinic acid acyl ester and an acid ester butene When the polymerization ratio is less than 1% by weight, the solubility of the obtained resin in the alkali developer may be lowered. The copolymerization ratio of the polymerizable unsaturated compound having an alkali-soluble functional group in the alkali-soluble copolymer is preferably from 1 to 40% by weight, more preferably from 5 to 30% by weight, especially 10, based on the total of all the unsaturated compounds. Up to 30% by weight. When the copolymerizable unsaturated compound having an alkali-soluble functional group has a copolymerization ratio of less than 1% by weight. The solubility of the resulting alkali-soluble copolymer in the alkali developer may be lowered when the copolymerization ratio is higher than 40% by weight. At this time, the solubility of the resulting alkali-soluble copolymer in the alkali developer becomes too high, which may damage the pattern shape. The polymerization for producing the resin (B1) is described below. The polymerizable unsaturated compound constituting the resin (B 1 ) is polymerized in a solvent in the presence of a radical polymerization initiator and a disulfide compound (3). The group represented by the formula (i) or (Π) is introduced into at least one end of the formed polymer chain. The polymerization of the polymerizable unsaturated compound in the presence of the disulfide compound (3) may be an active radical polymerization having an active radical at the growth end of the polymer chain. When the aforementioned polymerization is living radical polymerization and a compound having a functional group (such as a carboxyl group) which may inactivate the living radical is used as the polymerizable unsaturated compound, the functional group may be protected by esterification as appropriate. After the polymerization is terminated under the inactivation of the growth end, the functional group contained in the unsaturated compound is deprotected to obtain a resin (B 1 ). The above-mentioned radical polymerization initiator is appropriately selected depending on the kind of the polymerizable unsaturated -29 - 200830043 compound to be used and a generally known radical polymerization initiator which can be used. Examples of the radical polymerization initiator include azo compounds such as 2,2,-azobisisobutyronitrile, 2,2f-azobis(2,4-dimethylvaleronitrile), and 2 , 2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); organic peroxides such as benzamidine peroxygen, lauryl peroxide, 1,^-double ( Tert-butylperoxy)cyclohexane and tert-butyl peroxypivalate; hydrogen peroxide; and redox initiators composed of such peroxides and reducing agents. Among these radical polymerization initiators, an azo compound such as 2,2'-isopropanyl diisobutan and 2,2^oxyl bis(2,4-methylamyl) is preferred. Because it produces little side reaction products due to oxygen. The above-mentioned radical polymerization initiator may be used alone or in combination of two or more, in the formula (3), which is represented by Z1 and Z2 and has 1 to 20 carbon atoms in the formula (3). Examples of the substituted or substituted alkyl group are as shown in the above formula (i) and the unsubstituted or substituted alkyl group having 1 to 2 carbon atoms represented by z2 in the above formula (ϋ). Examples of the group 'unsubstituted or substituted monovalent aromatic hydrocarbon group represented by Z and z2 and having 6 to 2 carbon atoms are as in the above formula (i)

中之Z 及前述式（ii )Z in the middle and the above formula (ii)

中之Z 所表示的具有6至20個碳 原子之未經取代或經取代單價芳族烴基所列基團。由z 及Z2所表不之由碳原子及其他原子組成而具有3至20個The group represented by the unsubstituted or substituted monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by Z. 3 to 20 by carbon and other atoms represented by z and Z2

其他原子組成而具有 代單價雜環基的實例係如同前述式 ()中之Z2所表示之由碳原子及 至20個原子之未經取代或經取代 -30- 200830043 單價雜環基所列基團。由z1及z2所表示之-OR1、-oc ( =〇 ) R1、_N ( R1 ) ( R2 )、-c ( =0) ORi、· )NCR1) (R2)、-P(=0) (ORi)2 及 PbOMR1 同前述式（i)中之Z1及前述式（ii)中之z2所表 經取代或經取代對應基團。此外，由Z1及Z2所表 有聚合物鏈的單價基團之實例係如同前述式（i ) d 及前述式（ii )中之Z2所表示的具有聚合物鏈之單 所列基團。 就與可聚合之不飽和化合物的反應性之觀點而 (3)中，Z1及Z2各爲具有1至20個碳原子之烷 中式（1)中硫代鑛基（c = s)係共價鍵結於相異原 如Z1及Z2中之氮原子或氧原子）的基團、尤其較 碳原子及其他原子組成之具有3至20個碳原子的 環基、-OR1或-N ( R1 ) ( R2)，特佳爲甲基、乙基 咯基、1 -吡唑基、甲氧基、乙氧基、二甲基胺基或 胺基。 本發明中，二硫化物化合物（3 )可單獨或二 種組合使用。 就前述聚合而言，該二硫化物化合物（3 )可 一種其他分子量控制劑（諸如^ -甲基苯乙儲二聚 三十二碳基硫醇）組合使用。 使用於前述聚合之溶劑不特別限制。溶劑之實 丙二醇單烷基醚，諸如丙二醇單甲基醚及丙二醇單 ；(聚）烷二醇單烷基醚乙酸酯，諸如乙二醇單甲 SR1、- c ( =〇 )2係如 示之未 示之具 〕之Z1 價基團 言，式 基、其 子（諸 佳爲由 單價雜 、1 - D比 二乙基 或更多 與至少 物或第 例包括 乙基醚 基醚乙 -31 - 200830043 酸酯、乙二醇單乙基醚乙酸酯、二乙二醇單甲基醚乙酸酯 、二乙二醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙 二醇單乙基醚乙酸酯、二丙二醇單甲基醚乙酸酯及二丙二 醇單乙基醚乙酸酯；（聚）烷二醇二烷基醚，諸如二乙二 醇二甲基醚、二乙二醇甲基乙基醚、二乙二醇二乙基醚、 二丙二醇二甲基醚、二丙二醇甲基乙基醚及二丙二醇二乙 基醚；其他醚類，諸如四氫呋喃；酮類，諸如甲基乙基酮 、環己酮、2-庚酮及3-庚酮；酮醇類，諸如雙丙酮醇（即 ，4-羥基-4-甲基戊-2-酮）及4-羥基-4-甲基己-2-酮；乳酸 烷酯，諸如乳酸甲酯及乳酸乙酯；其他酯類，諸如2-羥 基-2-甲基丙酸乙酯、羥基乙酸乙酯、2-羥基-3-甲基丁酸 甲酯、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、乙氧基乙酸乙酯、3 -甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸 乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁 酯、甲酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、 丁酸正丙酯 丁酸異丙酯、丁酸正丁酯、丙酮酸甲酯、丙 酮酸乙酯、丙酮酸正丙酯、乙醯基乙酸甲酯、乙醯基乙酸 乙酯及2 -合氧基丁酸乙酯；芳族烴類，諸如甲苯及二甲苯 ;及醯胺類，諸如N -甲基吡咯啶酮、N，N -二甲基曱醯胺 及N，N-二甲基乙醯胺。 因爲活性自由基不會在活性自由基聚合期間失活，且 就各組份之溶解度、顏料分散性及輻射敏感性樹脂組成物 之塗覆性的觀點而言，此等溶劑中，丙二醇單甲基醚、乙 -32- 200830043 二醇單甲基醚乙酸酯、二乙二醇單甲基醚乙酸酯、二乙二 醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙 基醚乙酸酯、二丙二醇單甲基醚乙酸酯、二乙二醇二甲基 醚、二乙二醇甲基乙基醚、二丙二醇二甲基醚、環己酮、 2-庚酮、3-庚酮、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯 ^ 、3-乙氧基丙酸乙酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸 正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、丙酸正 " 丁酯、丁酸乙酯、丁酸異丙酯、丁酸正丁酯及丙酮酸乙酯 較佳。 前述溶劑可單獨或二或更多種組合使用。 前述聚合中所使用之自由基聚合起始劑的量以1 〇〇重 量份數所有不飽和化合物之總量計，較佳係爲0.1至50 重量份數，更佳爲0.1至20重量份數。 二硫化物化合物（1 )之量以1 00重量份數所有不飽 和化合物之總量計，較佳係〇 . 1至5 0重量份，更佳爲0 · 2 ί 至16重量份數，尤其佳是0.4至8重量份數。當二硫化 物化合物（1 )之量低於〇 · 1重量份數時，控制分子量及 分子量分布之效果可能降低，當該量高於5 0重量份數時 ，可能優先形成低分子量組份。 ' 其他分子量控制劑之量以1 0 0重量份數所有分子量控 制劑之總量計，較佳係爲6 0重量份數或更低’更佳係爲 40重量份數或更低。當其他分子量控制劑之量高於60重 量份數時，可能破壞本發明預期效果。 溶劑之量以1 〇〇重量份數所有不飽和化合物之總量計 -33- 200830043 ，較佳係爲50至1，000重量份數’更佳係爲100至500 重量份數。 聚合溫度較佳係爲0至1 5 0 °C ’更佳係爲5 0至1 2 0 °c 。聚合時間較佳係爲1 〇分鐘至20小時，更佳係爲3 0分 鐘至6小時。 樹脂（B )之Mw ( Mw係爲藉凝膠滲透層析（GPC ) 測量以聚苯乙烯計之重量平均分子量）較佳係爲1，〇〇〇至 45,000，更佳爲 3,000 至 20,000，尤其是 4,000 至 10,000 〇 樹脂（B )之Mw/Mn ( Μη係爲藉凝膠滲透層析（GPC )測量以聚苯乙烯計之數量平均分子量）較佳係爲1至 2.0，更佳係爲1至1.4。 使用具有前述特定 Mw (較佳爲前述特定 Μη及 Mw/Mn )之樹脂（Β )製得具有優異顯影性之輻射敏感性 樹脂組成物，可形成具有明確圖案邊緣之像素，顯影時幾 乎不會在未曝光部分之基板或遮光層上產生殘留物、沾染 或薄膜殘留物，因爲有機溶劑之高度清洗性，故製造濾光 片時可得到高產物良率，而不產生乾燥之外來物，有效地 防止濾光片之「影像烙痕」。 樹脂（B )可單獨或二或更多種組合使用。 本發明中，樹脂（B )可與至少一種其他鹼可溶性樹 脂組合使用。 本發明中，樹脂（B)之量以100重量份數著色劑（A )計，較佳係爲10至1，000重量份數，更佳爲20至500 -34- 200830043 重量份數。當樹脂（B )之量低於1 〇重量份數時，鹼顯影 性可能降低’或未曝光部分之基板或遮光層上可能產生沾 染或薄膜殘留物，當該量高於1，〇〇〇重量份數時，顏料之 濃度變得相對低，而難以達到薄膜之目標色彩密度。 其他鹼可溶性樹脂之量以所有鹼可溶性樹脂之總量計 ，較佳爲5 0重量％或更低，更佳爲2 0重量％或更低。當 其他鹼可溶性樹脂之量高於50重量％時，可能破壞本發明 預期效果。 -(C )多官能性單體- 本發明多官能性單體係爲具有二或更多個可聚合之不 飽和鍵結之單體。 該多官能性單體之實例係包括烷二醇，諸如乙二醇及 丙二醇之二（甲基）丙烯酸酯；聚烷二醇，諸如聚合度爲 2或更大之聚乙二醇及聚合度爲2或更大之聚丙二醇的二 (甲基）丙烯酸酯；具有3或更多個羥基之多羥基醇及其 經二羧酸修飾之產物諸如甘油、三羥甲基丙烷、異戊四醇 及二異戊四醇的多（甲基）丙烯酸酯；聚酯、環氧樹脂、 胺基甲酸酯樹脂、醇酸樹脂、聚矽酮樹脂及螺烷樹脂之寡 (甲基）丙烯酸酯；於兩末端皆具有羥基之聚合物諸如於 兩末端皆具有羥基之聚-1，3 -丁二烯、於兩末端皆具有羥基 之聚異戊間二烯及於兩末端皆具有羥基之聚己內酯的二（ 甲基）丙烯酸酯；及磷酸三[2-(甲基）丙烯醯氧基乙基] 酯。 -35- 200830043 此等多官能性單體中，具有3或更多個羥基之多羥基 醇及其經二羧酸修飾之產物的多（甲基）丙烯酸酯較佳， 實例有三羥甲基丙烷三（甲基）丙烯酸酯、異戊四醇三（ 甲基）丙烯酸酯、異戊四醇四（甲基）丙烯酸酯、二異戊 四醇五（甲基）丙烯酸酯及二異戊四醇六（甲基）丙烯酸 酯。此等化合物中，三羥甲基丙烷三丙烯酸酯、異戊四醇 三丙烯酸酯及二異戊四醇六丙烯酸酯特佳，因其提供具有 高強度及優異之表面光滑性的像素，且極少於未曝光部分 之基板或遮光層上產生沾染或薄膜殘留物。 本發明中，前述多官能性單體可單獨使用或二或更多 種組合使用。 本發明多官能性單體之量以1 00重量份數該鹼可溶性 樹脂（B )計較佳係爲5至5 00重量份數，更佳係爲20至 3 〇〇重量份數。當該多官能性單體之量低於5重量份數時 ，像素之強度及表面光滑性可能降低，而當該量高於500 重量份數時，驗顯影性可能降低，或未曝光部分之基板或 遮光層上可能產生沾染或薄膜殘留物。 本發明中，多官能性單體可與具有單一個可聚合不飽 和鍵結之單官能性單體組合使用。 前述單官能性單體之實例係包括前述鹼可溶性共聚物 (I)所列舉之不飽和單體（bl)及不飽和單體（b2)、 N_乙烯基含氮雜環化合物諸如N -乙烯基琥珀醯亞胺、N-乙烯基吡咯啶酮、N -乙烯基苯二甲醯亞胺、N -乙烯基- 2-哌啶酮、N -乙烯基_ ε -己內醯胺、N -乙烯基吡咯、n -乙烯 -36- 200830043 基吡咯啶、N -乙烯基咪唑、N -乙烯基咪唑啶 哚、N-乙烯基吲哚啉、N-乙烯基苯并咪唑、 、N-乙烯基哌啶、N-乙烯基哌嗪、N-乙烯3 烯基吩噁嗪；及N -(甲基）丙烯醯嗎啉； 諸如 M-5300、M-5400 及 M-5600 ( Toagosei 此等單官能性單體可單獨使用或二或更 〇 該單官能性單體之量以多官能性單體及 之總量計較佳係爲9 0重量％或更低，更佳 低。當該單官能性單體之量高於9 0重量％時 的強度及表面光滑性可能降低。 -(D )輻射敏感性自由基生成劑 - 本發明輻射敏感性自由基生成劑（以下 基生成劑（D)」）係包含前式（1)化合物 肟型自由基生成劑（1)」）及/或前式（2 以下稱爲「肟型自由基生成劑（2 )」）且 諸如可見光輻射、紫外線輻射、遠紫外線輻 或X -輻射之輻射時形成自由基，該自由基 官能性單體（C )及視情況使用之單官能性 組份。 式（1)及（2)中，R3所示之具有1 3 的烷基之實例係包括甲基、乙基、正两基、 基、第二丁基、第三丁基、正戊基、正己基 、N-乙烯基吲 N-乙烯基咔唑 I嗎啉及N-乙 及市售產物， C 〇 ·，Ltd ·)。 多種組合使用 單官能性單體 50重量％或更 ，所得之像素 簡稱爲「自由 (以下稱爲^ )之化合物（ 係爲可在曝照 射、電子輻射 可起始前述多 單體的聚合之 [20個碳原子 異丙基、正丁 、正庚基、正 -37- 200830043 辛基、正壬基、正癸基、正十一碳基及正十二碳基。 R3所示之具有3至8個碳原子的環烷基之實例係包括 環戊基及環己基。 式（1)及（2)中，R3較佳係爲甲基或乙基。 式（1)及（2)中，R4及R5所示之具有1至20個碳 原子的烷基之實例係包括曱基、乙基、正丙基、異丙基、 正丁基、第二丁基、第三丁基、正戊基、正己基、正庚基 、正辛基、正壬基、正癸基、正'碳基及正十二碳基。 R4及R5所示之具有3至8個碳原子的環烷基之實例 係包括環戊基及環己基。 R4及R5所示之苯基的取代基實例係包括具有1至6 個碳原子之烷基，諸如甲基、乙基、正丙基、異丙基、正 丁基、第二丁基、第三丁基、正戊基及正己基；具有3至 6個碳原子之環烷基，諸如環戊基及環己基；具有1至6 個碳原子之烷氧基，諸如甲氧基、乙氧基、正丙氧基、異 丙氧基、正丁氧基及第三丁氧基；具有3至6個碳原子之 環烷氧基，諸如環戊氧基及環己氧基；苯基；及鹵原子， 諸如氟原子及氯原子。 R4及R5所示之具有7至20個碳原子的單價脂環族基 團（不包括前述環烷基）之實例係包括具有1 -烷基環烷結 構之基團、具有雙環烷結構之基團、具有三環烷結構之基 團、具有螺烷結構之基團、具有萜結構之基團及具有金剛 烷結構之基團。 式（1)及（2)中，R4及R5較佳各係氫原子、甲基 -38- 200830043 或乙基。 式（1)及（2)中，R6所示之具有4至20個碳原子 的單價含氧雜環基、具有4至20個碳原子之單價含氮雜 環基及具有4至20個碳原子之單價含硫雜環基係包括硫 基（thioranyl )、氮雜環庚烯基、二氫氮雜環庚烯基、 二氧戊環基、三嗪基、氧硫環己烷基、噻唑基、噁二嗪基 、二氧雜氫節基、dihyangphthalenyl、呋喃基、噻吩基、 吡咯基、噁唑基、異噁唑基、噻唑基、異噻唑基、吡唑基 、呋咱基、哌喃基、吡啶基、嗒嗪基、嘧啶基、吡嗪基、 口比咯啉基、morphonyl、卩质嗪基、喂U定基、D引哄基、異口引 哚基、苯并呋喃基、苯并噻吩基、吲哚嗪基、色烯基、喹 啉基、異喹啉基、嘌呤基、喹唑啉基、啐啉基、酞嗪基、 嗓卩疋基、味嗤基、卩丫 D定基、非卩定基、嚷囉基、吩曉基、吩 噻嗪基、氧硫雜蒽基、吩噁嗪基、噻嗯基、四氫呋喃基及 四氫哌喃基。 式（1)及（2)中，R6較佳係爲四氫呋喃基或四氫哌 喃基。 式（1)及（2)中，R7所示之具有1至12個碳原子 的烷基之實例係包括甲基、乙基、正丙基、異丙基、正丁 基、第二丁基、第三丁基、正戊基、正己基、正庚基、正 辛基、正壬基、正癸基、正十一碳基及正十二碳基。 R7所不之具有3至8個碳原子的環院基之實例係包括 環戊基及環己基。 R7所示之具有1至1 2個碳原子之烷氧基的實例係包 -39 - 200830043 括甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第 三丁氧基、正戊氧基、正己氧基、正庚氧基、正辛氧基、 正壬氧基、正癸氧基、正十一碳氧基及正十二碳氧基。 R7所示之具有3至8個碳原子的環烷氧基之實例係包 括環戊氧基及環己氧基。 式（1)及（2)中，R7較佳係爲甲基、乙基、正丙基 、異丙基、正丁基、甲氧基或乙基。 式（1 )及（2 )中，η較佳係爲1，m較佳係爲〇、1 或2，特佳係爲1，且P較佳係爲〇、1或2，特佳係爲1 〇 肟型自由基生成劑（1)之特定實例係包括乙酮- l-[9-乙基_6_ (2 -甲基-2-四氫呋喃基苯甲醯基）-9·Η· -咔唑-3-基 ]-卜（0-乙醯肟）、乙酮-1·[9-乙基-6- ( 2-甲基-2-四氫哌 喃基苯甲醯基）-9·Η·-咔唑-3-基]-1-(0-乙醯肟）、乙酮-1-[9-乙基-6- ( 2-甲基-3-四氫呋喃基苯甲醯基）咔 唑-3-基]-1- ( 〇-乙醯肟）、乙酮- 乙基-6- ( 2-甲基-3 - 四氫哌喃基苯甲醯基）-9·Η·-咔唑-3-基]-1- ( 〇-乙醯肟） 、乙酮乙基-6-(2-甲基-4-四氫呋喃基苯甲醯基）-9.H. -咔唑-3-基]-l-(〇 -乙醯肟）、乙酮- l- [9 -乙基- 6-(2-甲基-4-四氫哌喃基苯甲醯基）-9·H·-咔唑-3-基]-l-(0-乙 醯脂）、乙酮- l- [9 -乙基-6- (2 -甲基-5-四氫呋喃基苯甲醯 基）-9·Η·-咔唑-3-基]-1-(0-乙醯肟）、乙酮- l-[9-乙基-6- ( 2 -甲基-5-四氫哌喃基苯甲醯基）-9·Η· -咔唑-3-基]-1-(0 -乙醯肟）、乙酮-1-[9 -乙基- 6-( 2_甲基-2-四氫呋喃基 -40- 200830043 苯甲醯基）-9·Η· -咔唑-3-基]-1- ( 0 -苯甲醯基乙醯肟）、 乙酮-1-[9 -乙基-6- (2 -甲基-2 -四氫哌喃基苯甲醯基）-9.Η·-咔唑-3-基]-1- ( 0-苯甲醯基乙醯肟）、乙酮-1-[9-乙 基-6- (2 -甲基-3-四氫呋喃基苯甲醯基）-9.Η. -咔唑-3-基]-1- ( 0-苯甲醯基乙醯肟）、乙酮-1-[9-乙基-6- ( 2-甲基- 3-四氫哌喃基苯甲醯基）-9·Η·-咔唑-3-基]-1- ( 0-苯甲醯基 乙醯肟）、乙酮-1-[9-乙基-6- (2-甲基-4-四氫呋喃基苯甲 醯基）-9·Η·-咔唑-3-基]-1-(0-苯甲醯基乙醯肟）、乙酮- 1 - [ 9 -乙基-6- ( 2 -甲基-4-四氣派喃基本甲釀基）-9 · Η ·-味 唑-3-基]-1- ( 0-苯甲醯基乙醯肟）、乙酮-1-[9·乙基-6-( 2 -甲基-5-四氫呋喃基苯甲醯基）-9.Η. -咔唑-3-基]-1- ( 0-苯甲醯基乙醯肟）、乙酮-1-[9-乙基-6- (2·甲基-5-四氫哌 喃基苯甲醯基）-9.Η. -咔唑-3-基]-1- ( 0 -苯甲醯基乙醯肟 )及乙酮-1-[9-乙基-6- ( 2-甲基-4- ( 2,2-二甲基-1，3-二氧 戊環基）苯甲醯基）-9.Η·-咔唑-3-基]-1-(0 -乙醯肟）。 此等肟型自由基生成劑（1 )可單獨或二或更多種組 合使用。 肟型自由基生成劑（2)之特定實例係包括乙酮-1-[9-乙基-6- (2 -甲基-2-四氫呋喃基氧基苯甲醯基）咔 唑-3-基]-1- ( 0-乙醯肟）、乙酮- l-[9-乙基-6- ( 2-甲基- 2-四氫哌喃基氧基苯甲醯基）-9.H.-咔唑-3-基]-1-(0-乙醯 肟）、乙酮- l-[9-乙基-6- (2-甲基-2-四氫呋喃基甲氧基苯 甲醯基）-9·Η·-咔唑-3-基]-1- ( 0-乙醯肟）、乙酮-1-[9-乙 基-6- (2 -甲基-2 -四氫哌喃基甲氧基苯甲醯基）-9.Η·-咔 -41 - 200830043 唑-3-基]-1- ( 0 -乙醯肟）、乙酮- l- [9 -乙基-6- ( 2 -甲基- 3- 四氫呋喃基氧基苯甲醯基）咔唑-3-基]-1- ( 0-乙醯 肟）、乙酮-l-[9-乙基-6- ( 2-甲基-3-四氫哌喃基氧基苯甲 醯基）-9·Η·-咔唑-3·基]-1-(0-乙醯肟）、乙酮- l-[9-乙 基-6- (2 -甲基-3-四氫呋喃基甲氧基苯甲醯基）-9.H.-咔 唑-3-基]-1- ( 0-乙醯肟）、乙酮- l-[9-乙基-6- ( 2-甲基- 3· 四氫哌喃基甲氧基苯甲醯基）-9·Η· -咔唑-3-基]-1- ( 0 -乙 醯肟）、乙酮-1-[9-乙基-6- ( 2-甲基-4-四氫呋喃基氧基苯 甲醯基）-9·Η·-咔唑-3-基]-1-(0-乙醯肟）、乙酮- l-[9-乙 基-6- (2 -甲基-4-四氫哌喃基氧基苯甲醯基）-9.H.-咔唑- 3-基]-1- ( 〇-乙醯肟）、乙酮- l-[9-乙基-6- ( 2-甲基-4-四氫 呋喃基甲氧基苯甲醯基）-9.H·-咔唑-3-基]-1-(0 -乙醯肟 )、乙酮- 乙基-6- (2-甲基-4-四氫暖喃基甲氧基苯甲 醯基）咔唑-3-基]-1- ( 0-乙醯肟）、乙酮- l-[9-乙 基-6- ( 2 -甲基-5-四氫呋喃基氧基苯甲醯基）-9.H.-咔唑- 3-基]-卜（〇-乙醯肟）、乙酮-1-[9-乙基-6-(2-甲基-5-四氫 哌喃基氧基苯甲醯基）-9·Η·-咔唑-3-基]-1- ( 0-乙醯肟） 、乙酮-1-[9-乙基-6- (2-甲基-5-四氫呋喃基甲氧基苯甲醯 基）-9.Η·-咔唑-3-基]-1- ( 0-乙醯肟）、乙酮-1-[9-乙基-6- (2 -甲基-5-四氫哌喃基甲氧基苯甲醯基）-9.Η·-咔唑- 3-基]-卜（0-乙醯肟）、乙酮-1-[9-乙基-6- ( 2-甲基-2-四氫 呋喃基氧基苯甲醯基）-9.HL -咔唑-3-基]-1- ( 0 -苯甲醯基 乙醯肟）、乙酮乙基-6-(2-甲基-2-四氫哌喃基氧基 苯甲醯基）-9·Η· -咔唑-3-基]-1- ( 0 -苯甲醯基乙醯肟）、 -42- 200830043 乙酮- l- [9 -乙基-6- (2 -甲基-2-四氫呋喃基甲氧基苯甲醯基 )·9.Η·-咔唑-3-基]-1-(0-苯甲醯基乙醯肟）、乙酮- l-[9-乙基-6- (2 -甲基-2 -四氫哌喃基甲氧基苯甲釀基）-9·Η· -味 唑-3-基]-1- ( 0 -苯甲醯基乙醯肟）、乙酮-1-[9 -乙基-6-( 2 -甲基-3-四氫呋喃基氧基苯甲醯基）-9.Η.-咔唑-3-基]-1-(0-苯甲醯基乙醯肟）、乙酮-1-[9-乙基-6- ( 2-甲基-3-四 氫哌喃基氧基苯甲醯基）-9.Η.-咔唑-3-基]-1-(0 -苯甲醯 基乙醯肟）、乙酮_1-[9 -乙基-6- ( 2 -甲基-3-四氫呋喃基甲 氧基苯甲醯基）-9·Η·-咔唑-3_基]-1-(〇-苯甲醯基乙醯肟 )、乙酮-1-[9 -乙基-6- (2 -甲基-3-四氫哌喃基甲氧基苯甲 醯基）-9.Η.-咔唑-3-基]-1-(〇-苯甲醯基乙醯肟）、乙酮-1-[9·乙基-6- ( 2 -甲基-4-四氫呋喃基氧基苯甲醯基）-9.H.-咔唑-3-基]-1-(0 -苯甲醯基乙醯肟）、乙酮- l- [9 -乙基- 6-(2 -甲基-4-四氫哌喃基氧基苯甲醯基）-9.η·-咔唑-3-基]-1-(0 -苯甲醯基乙醯肟）、乙酮- l- [9 -乙基- 6-(2-甲基·4-四氫呋喃基甲氧基苯甲醯基）-9·H·-咔唑-3-基]-l-(0-苯 甲醯基乙醯肟）、乙酮- l- [9 -乙基-6- ( 2 -甲基-4-四氫哌喃 基甲氧基苯甲醯基）-9.H·-咔唑-3-基]-1-(0 -苯甲醯基乙 醯肟）、乙酮- -乙基_6_ ( 2 -甲基-5_四氫呋喃基氧基苯 甲醯基）-9·Η· -咔唑-3-基]-l-(〇 -苯甲醯基乙醯肟）、乙 酮- -乙基-6- (2 -甲基-5-四氫哌喃基氧基苯甲醯基）_ 9·Η· -咔唑-3-基]-1-(〇·苯甲醯基乙醯肟）、乙酮- l- [9 -乙 基_6-(2-甲基-5-四氫呋喃基甲氧基苯甲醯基）-9.11.-咔 唑-3-基]-1- ( 0 -苯甲醯基乙醯肟）、乙酮-1·[9 -乙基-6-( -43- 200830043 2- 甲基-5-四氫哌喃基甲氧基苯甲醯基）-9.η·_味嗤_3_基]_ 1-(〇-苯甲醯基乙醯肟）及乙酮-1_[9-乙基_6_[2_甲基_4_( 2,2-—甲基-1,3 -一氧戊環基）甲氧基苯甲酿基]_9.η·-昨哇_ 3- 基]-1- ( 0-乙醯肟）。 此等聘型自由基生成劑（2)可單獨或二或更多種組 合使用。 本發明自由基生成劑（D)較佳係至少含有勝型自由 基生成劑（2)，尤其是至少一種選自乙酮_1-[9_乙基_6_ (2-甲基-4-四氫呋喃基甲氧基苯甲醯基）-9H-味唑_3_基 ]-1· ( 0 -乙醯膀）、乙酮- -乙基-6- ( 2 -甲基-4 -四氫峨 喃基甲氧基苯甲醯基）-9.H.-咔唑-3-基卜1- ( 〇_乙醯聘） 、乙酮- l- [9 -乙基-6- (2 -甲基-5-四氫呋喃基甲氧基苯甲醯 基）-9·Η· -咔唑-3 -基]-l_(〇 -乙醯肟）、乙酮- i- [9 -乙基-6- ( 2-甲基-5-四氫哌喃基甲氧基苯甲醯基）_9.η.-咔唑- 3-基]-1- ( 〇 -乙醯肟）及乙酮- l- [9 -乙基- 6- [2 -甲基-4- ( 2,2-二甲基-1，3·二氧戊環基）甲氧基苯甲醯基]咔唑-3-基]-1-(0 -乙醯膀）者。 本發明中，另一種輻射敏感性自由基生成劑（以下簡 稱爲「另一種自由基生成劑」）可與肟型自由基生成劑（ 1 )及肟型自由基生成劑（2 )組合使用。 該另一種自由基生成劑之實例係包括除肟型自由基生 成劑（1 )及肟型自由基生成劑（2 )以外之肟型自由基生 成劑（以下稱爲「其他肟型自由基生成劑」）。 該其他肟型自由基生成劑係包括 L2-辛二酮-l-[4-( -44- 200830043 苯硫基）苯基]_2-(〇 -苯甲醯肟）、1，2 -丁二酮-1-[4-(苯 硫基）苯基]-2- ( 〇 -苯甲醯肟）、1,2 -丁二酮(苯硫 基）苯基]-2-(0-乙醯肟）、1，2-辛二酮_1β[4-(甲硫基） 苯基]-2- ( 〇 -苯甲醯肟）及ι，2 -辛二酮- ΐ_[4-(苯硫基）苯 基]-2- ( 0- ( 4-甲基苯甲醯肟））。 其中，1，2 -半一*酬-1-[4-(苯硫基）苯基卜2-(0 -苯甲 醯肟）特佳。 除該其他肟型自由基生成劑以外之自由基生成劑有例 如具有至少一種由下式（4-1) 、（4-2)或（4-3)所示之 主要結構的以聯咪唑爲主之化合物，以安息香爲主之化合 物，以乙醯苯爲主之化合物，以二苯甲酮爲主之化合物， 以α -二酮爲主之化合物，以多環醌爲主之化合物，以咕噸 酮爲主之化合物，以膦爲主之化合物或以三嗪爲主之化合 物。Examples of other atomic constituents having a monovalent heterocyclic group are as defined by Z2 in the above formula (), and are represented by a carbon atom and up to 20 atoms of unsubstituted or substituted -30-200830043 monovalent heterocyclic group. . -OR1, -oc ( =〇) R1, _N ( R1 ) ( R2 ), -c ( =0) ORi, · ) NCR1) (R2), -P(=0) (ORi) represented by z1 and z2 And 2 and PbOMR1 are substituted or substituted corresponding groups represented by Z1 in the above formula (i) and z2 in the above formula (ii). Further, examples of the monovalent group having a polymer chain represented by Z1 and Z2 are the groups listed as the polymer chain represented by the above formula (i) d and Z2 in the above formula (ii). In view of the reactivity with the polymerizable unsaturated compound, (3), Z1 and Z2 are each an alkane having 1 to 20 carbon atoms, and the thione group (c = s) in the formula (1) is covalently a group bonded to a nitrogen atom or an oxygen atom in a different original such as Z1 and Z2, especially a ring group having 3 to 20 carbon atoms, -OR1 or -N (R1), which is composed of a carbon atom and other atoms. (R2) is particularly preferably a methyl group, an ethyl aryl group, a 1-pyrazolyl group, a methoxy group, an ethoxy group, a dimethylamino group or an amine group. In the present invention, the disulfide compound (3) may be used singly or in combination of two or more. For the aforesaid polymerization, the disulfide compound (3) can be used in combination with another molecular weight controlling agent such as 2-methylphenylethyl dimercaptotridecyl mercaptan. The solvent used in the aforementioned polymerization is not particularly limited. a solvent of propylene glycol monoalkyl ether, such as propylene glycol monomethyl ether and propylene glycol mono; (poly) alkanediol monoalkyl ether acetate, such as ethylene glycol monomethyl SR1, -c (=〇) 2 series The Z1 valence group, which is not shown, has a formula, a group thereof, and a subunit, which is composed of a monovalent impurity, a 1-D ratio of diethyl or more, and at least an object or a first example, including ethyl ether ether. -31 - 200830043 Acid ester, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate , propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate and dipropylene glycol monoethyl ether acetate; (poly) alkanediol dialkyl ether, such as diethylene glycol dimethyl ether , diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether and dipropylene glycol diethyl ether; other ethers such as tetrahydrofuran; ketone Classes such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; ketone alcohols such as diacetone alcohol (ie 4-hydroxy-4-methylpentan-2-one) and 4 -hydroxy-4-methylhexan-2-one; alkyl lactate such as methyl lactate and ethyl lactate; other esters such as ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, 2 -methyl hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate Ester, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, Isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyric acid Butyl ester, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoxyacetate, ethyl acetoacetate and ethyl 2- oxybutyrate; aromatic hydrocarbons such as toluene And xylene; and guanamines such as N-methylpyrrolidone, N,N-dimethyldecylamine and N,N-dimethylacetamide. Because active free radicals do not act on active free radicals Inactivation during polymerization, and solubility and pigment dispersibility of each component From the viewpoint of the coatability of the photosensitive resin composition, among these solvents, propylene glycol monomethyl ether, B-32-200830043 diol monomethyl ether acetate, diethylene glycol monomethyl ether B Acid ester, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl Ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl ester ^, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, Propionate "butyl ester, ethyl butyrate, isopropyl butyrate, n-butyl butyrate and ethyl pyruvate are preferred. The foregoing solvents may be used singly or in combination of two or more. The amount of the radical polymerization initiator used in the above polymerization is preferably from 0.1 to 50 parts by weight, more preferably from 0.1 to 20 parts by weight, based on 1 part by weight of the total of all the unsaturated compounds. . The amount of the disulfide compound (1) is preferably from 1 to 50 parts by weight, more preferably from 0 to 2 ί to 16 parts by weight, based on 100 parts by total of the total of all the unsaturated compounds. Preferably, it is from 0.4 to 8 parts by weight. When the amount of the disulfide compound (1) is less than 0.1 part by weight, the effect of controlling the molecular weight and the molecular weight distribution may be lowered, and when the amount is more than 50 parts by weight, a low molecular weight component may be preferentially formed. The amount of the other molecular weight controlling agent is preferably 60 parts by weight or less based on the total amount of all molecular weight controlling agents of 100 parts by weight, more preferably 40 parts by weight or less. When the amount of the other molecular weight controlling agent is more than 60 parts by weight, the intended effects of the present invention may be impaired. The amount of the solvent is from -33 to 200830043, preferably from 50 to 1,000 parts by weight, more preferably from 100 to 500 parts by weight, based on 1 part by weight of the total of all the unsaturated compounds. The polymerization temperature is preferably from 0 to 150 ° C. More preferably from 50 to 1 20 °c. The polymerization time is preferably from 1 minute to 20 hours, more preferably from 30 minutes to 6 hours. The Mw of the resin (B) (the Mw is a weight average molecular weight measured by gel permeation chromatography (GPC) in terms of polystyrene) is preferably 1, 1 to 45,000, more preferably 3,000 to 20,000, especially It is Mw/Mn of 4,000 to 10,000 Å resin (B) (the Μη is a number average molecular weight measured by gel permeation chromatography (GPC) in terms of polystyrene), preferably 1 to 2.0, more preferably 1 To 1.4. A radiation-sensitive resin composition having excellent developability can be obtained by using a resin (Β) having the specific Mw (preferably the aforementioned specific Μ and Mw/Mn) to form a pixel having a clear pattern edge, which is hardly developed during development. Residues, contamination, or film residues are generated on the unexposed portion of the substrate or the light-shielding layer. Because of the high cleaning properties of the organic solvent, high yields can be obtained when the filter is manufactured without producing dry matter, which is effective. Prevent the "image mark" of the filter. The resin (B) may be used singly or in combination of two or more. In the present invention, the resin (B) can be used in combination with at least one other alkali-soluble resin. In the present invention, the amount of the resin (B) is preferably from 10 to 1,000 parts by weight, more preferably from 20 to 500 to 34 to 200830043 parts by weight, based on 100 parts by weight of the coloring agent (A). When the amount of the resin (B) is less than 1 part by weight, the alkali developability may be lowered or the contamination or film residue may be generated on the substrate or the light-shielding layer of the unexposed portion, when the amount is higher than 1, 〇〇〇 At the parts by weight, the concentration of the pigment becomes relatively low, and it is difficult to attain the target color density of the film. The amount of the other alkali-soluble resin is preferably 50% by weight or less, more preferably 20% by weight or less, based on the total of all the alkali-soluble resins. When the amount of the other alkali-soluble resin is more than 50% by weight, the intended effects of the present invention may be impaired. - (C) Polyfunctional Monomer - The polyfunctional single system of the present invention is a monomer having two or more polymerizable unsaturated bonds. Examples of the polyfunctional monomer include alkanediols such as di(meth)acrylates of ethylene glycol and propylene glycol; polyalkylene glycols such as polyethylene glycol having a degree of polymerization of 2 or more and degree of polymerization a di(meth) acrylate of 2 or more polypropylene glycol; a polyhydric alcohol having 3 or more hydroxyl groups and a product modified by the dicarboxylic acid such as glycerin, trimethylolpropane, and isoamyl alcohol And poly(meth) acrylate of diisopentyl alcohol; oligo(meth) acrylate of polyester, epoxy resin, urethane resin, alkyd resin, polyketone resin and spiro resin; A polymer having a hydroxyl group at both ends, such as poly-1,3-butadiene having a hydroxyl group at both ends, polyisoprene having a hydroxyl group at both ends, and a polyhydroxy group having a hydroxyl group at both ends a di(meth)acrylate of a lactone; and a tris[2-(methyl)propenyloxyethyl]phosphate. -35- 200830043 Among these polyfunctional monomers, a polyhydric alcohol having 3 or more hydroxyl groups and a poly(meth) acrylate thereof modified by a dicarboxylic acid are preferred, and an example is trimethylolpropane. Tris(meth)acrylate, pentaerythritol tris(meth)acrylate, pentaerythritol tetra(meth)acrylate, diisopentaerythritol penta(meth)acrylate, and diisopentaerythritol Hexa(meth)acrylate. Among these compounds, trimethylolpropane triacrylate, pentaerythritol triacrylate and diisopentaerythritol hexaacrylate are particularly preferred because they provide pixels with high strength and excellent surface smoothness, and rarely A stain or film residue is formed on the unexposed portion of the substrate or light-shielding layer. In the present invention, the aforementioned polyfunctional monomers may be used singly or in combination of two or more. The amount of the polyfunctional monomer of the present invention is preferably from 5 to 500 parts by weight, more preferably from 20 to 3 parts by weight, based on 100 parts by weight of the alkali-soluble resin (B). When the amount of the polyfunctional monomer is less than 5 parts by weight, the strength and surface smoothness of the pixel may be lowered, and when the amount is more than 500 parts by weight, the developability may be lowered, or the unexposed portion may be Contamination or film residue may form on the substrate or light-shielding layer. In the present invention, the polyfunctional monomer can be used in combination with a monofunctional monomer having a single polymerizable unsaturated bond. Examples of the aforementioned monofunctional monomer include the unsaturated monomer (bl) and the unsaturated monomer (b2) exemplified in the aforementioned alkali-soluble copolymer (I), and N-vinyl nitrogen-containing heterocyclic compound such as N-ethylene. Alkyl iminoimine, N-vinylpyrrolidone, N-vinylphthalimide, N-vinyl-2-piperidone, N-vinyl_ε-caprolactam, N- Vinylpyrrole, n-ethylene-36- 200830043 pyrrolidine, N-vinylimidazole, N-vinylimidazolium, N-vinylporphyrin, N-vinylbenzimidazole, N-vinyl Piperidine, N-vinylpiperazine, N-ethylene 3 alkenyl phenoxazine; and N-(methyl) propylene morpholine; such as M-5300, M-5400 and M-5600 (Toagosei such monofunctional) The monomer may be used alone or in an amount of two or more monofunctional monomers, preferably in a total amount of 90% by weight or less, more preferably in terms of the polyfunctional monomer and the total amount. When the amount of the monomer is more than 90% by weight, the strength and surface smoothness may be lowered. - (D) Radiation-sensitive radical generating agent - Radiation-sensitive radical generating agent of the present invention (D)") includes a quinone type radical generating agent (1)") of the compound of the above formula (1) and/or a former formula (hereinafter referred to as "a quinoid type radical generating agent (2)") and such as visible light radiation. , ultraviolet radiation, far ultraviolet radiation or X-radiation radiation forms free radicals, the free radical functional monomer (C) and optionally monofunctional components. In the formulae (1) and (2), examples of the alkyl group having 1 3 represented by R3 include a methyl group, an ethyl group, a n-butyl group, a group, a second butyl group, a tert-butyl group, a n-pentyl group, n-Hexyl, N-vinylindole N-vinylcarbazole Imorpholine and N-B and commercially available products, C 〇·, Ltd.). In a plurality of combinations, a monofunctional monomer is used in an amount of 50% by weight or more, and the obtained pixel is simply referred to as a "free (hereinafter referred to as ^) compound (which can initiate polymerization of the aforementioned multi-monomer under exposure, electron irradiation [ 20 carbon atoms isopropyl, n-butyl, n-heptyl, n-37-200830043 octyl, n-decyl, n-decyl, n-undecyl and n-dodecyl. R3 has 3 to Examples of the cycloalkyl group of 8 carbon atoms include a cyclopentyl group and a cyclohexyl group. In the formulae (1) and (2), R3 is preferably a methyl group or an ethyl group. In the formulae (1) and (2), Examples of the alkyl group having 1 to 20 carbon atoms represented by R4 and R5 include an anthracenyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a tert-butyl group, and a n-pentyl group. Base, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-carbon and n-dodecyl. R4 and R5 are cycloalkyl having 3 to 8 carbon atoms. Examples include cyclopentyl and cyclohexyl. Examples of the substituent of the phenyl group represented by R4 and R5 include an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, positive Base, second butyl, tert-butyl, n-pentyl and n-hexyl; cycloalkyl having 3 to 6 carbon atoms, such as cyclopentyl and cyclohexyl; alkoxy having 1 to 6 carbon atoms , such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and tert-butoxy; cycloalkoxy having 3 to 6 carbon atoms, such as cyclopentyloxy and a cyclohexyloxy group; a phenyl group; and a halogen atom such as a fluorine atom and a chlorine atom. Examples of a monovalent alicyclic group having 7 to 20 carbon atoms represented by R4 and R5 (excluding the aforementioned cycloalkyl group) are The invention includes a group having a 1-alkylcycloalkane structure, a group having a bicycloalkane structure, a group having a tricycloalkane structure, a group having a spiro structure, a group having a fluorene structure, and an adamantane structure. In the formulae (1) and (2), R4 and R5 are preferably each a hydrogen atom, a methyl group -38-200830043 or an ethyl group. In the formulae (1) and (2), R6 has a 4 to Monovalent oxygen-containing heterocyclic group of 20 carbon atoms, monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, and monovalent sulfur-containing heterocyclic group having 4 to 20 carbon atoms including sulfur group Thioranyl), azetidinyl, dihydroazepine, dioxolanyl, triazinyl, oxathiocyclohexane, thiazolyl, oxadiazine, dioxahydrogen , dihyangphthalenyl, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, furazolyl, piperidyl, pyridyl, pyridazinyl, pyrimidinyl, Pyrazinyl, phenanthroline, morphonyl, phthalazine group, urethane group, D fluorenyl group, iso-indolyl group, benzofuranyl group, benzothienyl group, pyridazinyl group, leucoyl group , quinolyl, isoquinolyl, fluorenyl, quinazolinyl, porphyrinyl, pyridazinyl, fluorenyl, hydrazino, hydrazide D, undecided, fluorenyl, phenanthrene Base, phenothiazine, oxathiazide, phenoxazinyl, thienyl, tetrahydrofuranyl and tetrahydropyranyl. In the formulae (1) and (2), R6 is preferably a tetrahydrofuranyl group or a tetrahydropyridyl group. In the formulae (1) and (2), examples of the alkyl group having 1 to 12 carbon atoms represented by R7 include methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups. , tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, n-undecyl and n-dodecyl. Examples of ring-backed groups having 3 to 8 carbon atoms which R7 does not include cyclopentyl and cyclohexyl. An example of an alkoxy group having 1 to 12 carbon atoms represented by R7 is -39 - 200830043 comprising methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, third Butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-decyloxy, n-decyloxy, n-undecyloxy and n-dodecyloxy. Examples of the cycloalkoxy group having 3 to 8 carbon atoms represented by R7 include a cyclopentyloxy group and a cyclohexyloxy group. In the formulae (1) and (2), R7 is preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a methoxy group or an ethyl group. In the formulas (1) and (2), η is preferably 1, m is preferably 〇, 1 or 2, particularly preferably 1, and P is preferably 〇, 1 or 2, and particularly preferably Specific examples of the quinoid type radical generating agent (1) include ethyl ketone-l-[9-ethyl_6_(2-methyl-2-tetrahydrofuranylbenzylidene)-9·Η·-咔Zyrid-3-yl]-bu (0-acetamidine), ethyl ketone-1·[9-ethyl-6-(2-methyl-2-tetrahydropyranylbenzylidene)-9· Η·-carbazol-3-yl]-1-(0-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-3-tetrahydrofuranylbenzylidene) hydrazine Zyrid-3-yl]-1-(indo-acetamidine), ethyl ketone-ethyl-6-(2-methyl-3-tetrahydropyranylbenzylidene)-9·Η·-咔Zyridin-3-yl]-1-(indo-acetamidine), ethyl ketone ethyl-6-(2-methyl-4-tetrahydrofuranylbenzylidene)-9.H.-carbazole-3- Base]-l-(〇-acetamidine), ethyl ketone-l-[9-ethyl-6-(2-methyl-4-tetrahydropiperidylbenzylidene)-9·H·- Oxazol-3-yl]-l-(0-ethyl oxime), ethyl ketone-l-[9-ethyl-6-(2-methyl-5-tetrahydrofurylbenzoguanidino)-9·Η ·-oxazol-3-yl]-1-(0-acetamidine), ethyl ketone-l-[9-ethyl-6-(2-methyl-5-tetrahydropyran Benzyl hydrazino)-9·Η·-oxazol-3-yl]-1-(0-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-2- Tetrahydrofuranyl-40-200830043 benzhydryl)-9·Η·-oxazol-3-yl]-1-( 0-benzylidene acetyl), ethyl ketone-1-[9-ethyl- 6-(2-Methyl-2-tetrahydropiperidylbenzylidene)-9.Η·-carbazol-3-yl]-1-(0-benzylideneacetin), ethyl ketone -1-[9-ethyl-6-(2-methyl-3-tetrahydrofuranylbenzylidene)-9.Η.-carbazol-3-yl]-1-(0-benzhydryl B醯肟), Ethyl Ketone-1-[9-Ethyl-6-(2-methyl-3-trihydropiperidylbenzylidene)-9·Η·-carbazol-3-yl]-1 - (0-benzylidene acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzylidene)-9·Η·-carbazole- 3-yl]-1-(0-benzylideneacetin), ethyl ketone-1 - [9-ethyl-6-(2-methyl-4-tetrapentanyl) · Η ·- oxazol-3-yl]-1-( 0-benzylidene acetyl), ethyl ketone-1-[9·ethyl-6-( 2 -methyl-5-tetrahydrofuranylbenzene Mercapto)-9.Η.-carbazol-3-yl]-1-(0-benzylideneacetyl), ethyl ketone-1-[9-ethyl-6- (2.methyl -5-tetrahydropyranylbenzene Mercapto)-9.Η.-carbazol-3-yl]-1-(0-benzylideneacetin) and ethyl ketone-1-[9-ethyl-6-(2-methyl -4- ( 2,2-Dimethyl-1,3-dioxolanyl)benzylidene)-9.Η·-carbazol-3-yl]-1-(0-acetyl) . These quinoid type radical generating agents (1) may be used singly or in combination of two or more. Specific examples of the quinoid type radical generating agent (2) include ethyl ketone-1-[9-ethyl-6-(2-methyl-2-tetrahydrofuranyloxybenzylidene) oxazol-3-yl ]-1-(0-acetamidine), ethyl ketone-l-[9-ethyl-6-(2-methyl-2-tetrahydropyranyloxybenzylidene)-9.H. -oxazol-3-yl]-1-(0-acetamidine), ethyl ketone-l-[9-ethyl-6-(2-methyl-2-tetrahydrofurylmethoxybenzylidene) -9·Η·-oxazol-3-yl]-1-(0-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-2-tetrahydropyranyl) Methoxybenzylidene)-9.Η·-咔-41 - 200830043 Zyrid-3-yl]-1-(0-acetamidine), ethyl ketone-l- [9-ethyl-6- ( 2-methyl-3-(tetrahydrofuranyloxybenzimidyl)oxazol-3-yl]-1-(0-acetamidine), ethyl ketone-l-[9-ethyl-6- (2- Methyl-3-tetrahydropyranyloxybenzhydryl)-9·Η·-carbazole-3·yl]-1-(0-acetamidine), ethyl ketone-l-[9-B -6-(2-methyl-3-tetrahydrofuranylmethoxybenzylidene)-9.H.-carbazol-3-yl]-1-(0-acetamidine), ethyl ketone-l -[9-ethyl-6-(2-methyl-3·tetrahydropyranylmethoxybenzylidene)-9·Η·-oxazol-3-yl]-1-(0-B醯Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuryloxybenzylidene)-9·Η·-carbazol-3-yl]-1-(0) -ethyl hydrazine), ethyl ketone - l-[9-ethyl-6-(2-methyl-4-tetrahydropyranyloxybenzhydryl)-9.H.-carbazole-3- 1,-1-(anthracene-ethene), ethyl ketone-l-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9.H-- Oxazol-3-yl]-1-(0-acetamidine), ethyl ketone-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzylidene) oxazole- 3-yl]-1-(0-acetamidine), ethyl ketone-l-[9-ethyl-6-(2-methyl-5-tetrahydrofuranyloxybenzylidene)-9.H. -carbazole-3-yl]-b (〇-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranyloxybenzylidene) )-9·Η·-carbazol-3-yl]-1-(0-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxy Benzobenzhydryl)-9.Η·-carbazol-3-yl]-1-(0-acetamidine), ethyl ketone-1-[9-ethyl-6- (2-methyl-5 -tetrahydropyranomethoxymethoxybenzylidene)-9.Η·-carbazole-3-yl]-b (0-acetamidine), ethyl ketone-1-[9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzene Mercapto)-9.HL-carbazol-3-yl]-1-(0-benzylideneacetyl), ethyl ketone ethyl-6-(2-methyl-2-tetrahydropyranyl Oxylbenzylidene)-9·Η·-oxazol-3-yl]-1-( 0-benzylidene acetyl), -42- 200830043 ethyl ketone - l- [9 -ethyl- 6-(2-Methyl-2-tetrahydrofurylmethoxybenzylidene)·9.Η·-carbazol-3-yl]-1-(0-benzylidene acetyl), ethyl ketone - l-[9-Ethyl-6-(2-methyl-2-tetrahydropyranylmethoxybenzyl)-9·Η·-oxazol-3-yl]-1-(0 -benzimidylacetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-3-tetrahydrofuranyloxybenzylidene)-9.Η.-carbazole-3 -yl]-1-(0-benzylideneacetyl), ethyl ketone-1-[9-ethyl-6-(2-methyl-3-tetrahydropyranyloxybenzylidene) )-9.Η.-oxazol-3-yl]-1-(0-benzylidene acetyl), ethyl ketone-1-[9-ethyl-6-(2-methyl-3- Tetrahydrofuranylmethoxybenzylidene)-9·Η·-carbazole-3-yl]-1-(indolyl-benzhydrylacetin), ethyl ketone-1-[9-ethyl-6 - (2-methyl-3-tetrahydropyranylmethoxybenzylidene)-9.Η.-carbazol-3-yl]-1-(indolyl-benzoylaminopurine), Ethyl ketone-1-[9 Ethyl-6-(2-methyl-4-tetrahydrofuranyloxybenzhydryl)-9.H.-carbazol-3-yl]-1-(0-benzylidene acetyl) Ethylketone- l-[9-ethyl-6-(2-methyl-4-tetrahydropyranyloxybenzhydryl)-9.η·-carbazol-3-yl]-1- (0-benzimidylacetamidine), ethyl ketone-l-[9-ethyl-6-(2-methyl·4-tetrahydrofurylmethoxybenzylidene)-9·H·-咔Zyrid-3-yl]-l-(0-benzylidene acetyl), ethyl ketone- l-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxy) Benzyl hydrazino)-9.H--oxazol-3-yl]-1-(0-benzylidene acetyl), ethyl ketone - ethyl _6_ (2-methyl-5-tetrahydrofuran Benzyl benzhydryl)-9·Η·-oxazol-3-yl]-l-(〇-benzylidene acetyl), ethyl ketone-ethyl-6- (2-methyl -5-tetrahydropyranoyloxybenzhydryl)_ 9·Η·-oxazol-3-yl]-1-(indolyl benzoyl oxime), ethyl ketone - l- [9 -ethyl_6-(2-methyl-5-tetrahydrofuranylmethoxybenzylidene)-9.11.-carbazol-3-yl]-1-(0-benzylidene acetyl), Ethylketone-1·[9-ethyl-6-(-43-200830043 2-methyl-5-tetrahydropyranylmethoxybenzylidene)-9.η·_ Miso _3_基]_ 1-(〇-benzylidene acetyl) and ethyl ketone-1_[9-ethyl_6_[2_methyl_4_( 2,2--methyl-1 , 3-methoxypentayl)methoxybenzyl ketone]_9.η·- yesterday wow_3-base]-1-(0-acetamidine). These liberated radical generating agents (2) may be used singly or in combination of two or more. The radical generating agent (D) of the present invention preferably contains at least a radical radical generating agent (2), especially at least one selected from the group consisting of ethyl ketone-1-[9-ethyl_6_(2-methyl-4- Tetrahydrofuranylmethoxybenzylidene)-9H-isoxazole_3_yl]-1· (0-acetamidine), ethyl ketone-ethyl-6-(2-methyl-4-tetrahydrogen峨 基 methoxybenzyl hydrazino)-9.H.-carbazole-3-yl b 1- ( 〇 _ 醯 醯 ), ethyl ketone - l- [9 - ethyl-6- (2 - Methyl-5-tetrahydrofuranylmethoxybenzylidene)-9·Η·-carbazole-3-yl]-l_(〇-acetamidine), ethyl ketone-i- [9-ethyl-6 - (2-Methyl-5-tetrahydropyranylmethoxybenzylidene)_9.η.-carbazole-3-yl]-1-(indolyl) and ethyl ketone-l- [9-Ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene]oxazol-3-yl] -1- (0 - B.). In the present invention, another radiation-sensitive radical generating agent (hereinafter simply referred to as "another radical generating agent") may be used in combination with the quinoid type radical generating agent (1) and the quinoid type radical generating agent (2). Examples of the other radical generating agent include a quinoid type radical generating agent other than the quinoid type radical generating agent (1) and the quinoid type radical generating agent (2) (hereinafter referred to as "other hydrazine type radical generating" Agent"). The other quinoid type free radical generating agent includes L2-octanedione-l-[4-(-44-200830043 phenylthio)phenyl]_2-(〇-benzothymidine), 1,2-butadiene Keto-1-[4-(phenylthio)phenyl]-2-(indolyl-benzamide), 1,2-butanedione (phenylthio)phenyl]-2-(0-acetamidine)肟), 1,2-octanedione-1-β[4-(methylthio)phenyl]-2-(indole-benzamide) and iota,2-dienedionone-ΐ_[4-(phenylsulfonate) Phenyl]-2-(0-(4-methylbenzhydrazide)). Among them, 1,2-half-one-retal-1-[4-(phenylthio)phenyl-2-(0-benzoquinone) is particularly preferred. The radical generating agent other than the other quinoid type radical generating agent is, for example, biimidazole having at least one main structure represented by the following formula (4-1), (4-2) or (4-3) The main compound, a compound based on benzoin, a compound mainly composed of acetophenone, a compound mainly composed of benzophenone, a compound mainly composed of α-diketone, and a compound mainly composed of polycyclic guanidine. A compound based on xanthone, a phosphine-based compound or a triazine-based compound.

前述以聯咪唑爲主之化合物之實例係包括2,2’-雙（2- -45- 200830043 氯苯基）-必^^^’-四彳仁乙氧基羰基苯基丨—丨义-聯咪唑 、2,2’-雙（2-溴苯基）-4,4’，5,5’-四（4-乙氧基羰基苯基 )-1，2’-聯咪唑、2,2’-雙（2-氯苯基）_4,4’，5,5’-四苯基-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'-四苯基-1，2’-聯咪唑、2,2’-雙（2,4-二溴苯基）-4,4’，5,5’-四苯基-1，2’聯 咪唑及2,2’ -雙（2,4,6 -三溴苯基）-4,4，，5,5’ -四苯基-1，2·-聯咪唑。 -氫供體- 當使用以聯咪唑爲主之化合物作爲本發明自由基生成 劑（D )時，其較佳係與以下氫供體組合使用，以進一步 改善敏感性。 本發明所使用之術語「氫供體」係表示可在曝光時提 供氫原子給自該以聯咪唑爲主之化合物所形成之自由基的 化合物。 該氫供體較佳係爲下文所定義之以硫醇爲主之化合物 或以胺爲主之化合物。 前述以硫醇爲主之化合物係爲具有作爲母核之苯環或 雜環及1或多個，較佳1至3個，更佳1或2個直接鍵結 於母核之氫硫基的化合物（以下稱爲「以硫醇爲主之氫供 體」）。 前述以胺爲主之化合物係爲具有作爲母核之苯環或雜 -46 - 200830043 環及1或多個，較佳1至3個，更佳1或2個直接鍵結於 母核之胺基的化合物（以下稱爲「以胺爲主之氫供體」） 〇 此等氫供體可同時具有氫硫基及胺基。 以下詳細描述此等氫供體。 以硫醇爲主之氫供體可具有至少一個苯環或雜環或兩 者。當其具有二或更多個該等環時，可形成稠合環。 當該以硫醇爲主之氫供體具有二或更多個氫硫基時， 只要保留至少一個游離氫硫基，則其他氫硫基中至少一個 可經烷基、芳烷基或芳基所取代。此外，只要保留至少一 個游離氫硫基，該以硫醇爲主之氫供體可具有其中兩硫原 子係藉二價有機基團（諸如伸烷基）鍵合之結構單元或其 中兩硫原子係以二硫醚形式鍵合之結構單元。 此外，該以硫醇爲主之氫供體在氫硫基（等）以外之 位置上可經以下基團所取代：羧基、經取代或未經取代之 烷氧羰基、經取代或未經取代之苯氧基羰基或腈基。 此等以硫醇爲主之氫供體之實例係包括2 -氫硫基苯并: 噻嗤、2 -氫硫基苯并H惡哗、2 -氫硫基苯并咪Π坐、2,5 -二氫 硫基-1，3,4-噻二唑及2-氫硫基-2,5-二甲基胺基吡啶。 此等以硫醇爲主之氫供體中，2 -氫硫基苯并噻π坐及2 _ 氫硫基苯并噁唑較佳，且2-氫硫基苯并噻唑特佳。 以胺爲主之氫供體可具有至少一個苯環或雜環或胃# 。當其具有二或更多個該等環時，可形成稠合環。 該以胺爲主之氫供體之至少一個胺基可經烷基或,經耳又 -47- 200830043 代之院基所取代。該以胺爲主之氫供體在除胺基（等）以 外之位置上可經以下基團所取代：羧基、經取代或未經取 代之烷氧羰基、經取代或未經取代之苯氧基羰基或腈基。 前述以胺爲主之氫供體之實例係包括4，4，-雙（二甲基 胺基）二苯甲酮、4,4’ -雙（二乙基胺基）二苯甲酮、4 -二 乙基胺基乙醯基苯、4-二甲基胺基丙醯基苯、乙基-4-二甲 基胺基苯甲酸酯、異戊基-4 -二甲基胺基苯甲酸酯、4 -二甲 基胺基苯甲酸及4-二甲基胺基苄腈。 此等以胺爲主之氫供體中，4,4^雙（二甲基胺基）二 苯甲酮及4,4’-雙（二乙基胺基）二苯甲酮較佳，且4,4’-雙（二乙基胺基）二苯甲酮特佳。4,4’-雙（二甲基胺基） 二苯甲酮及4,4’-雙（二乙基胺基）二苯甲酮本身可作爲感 光自由基起始劑，即使以聯咪唑爲主之化合物不存在亦然 〇 本發明中，前述氫供體可單獨使用或二或更多種組合 使用。較佳係使用至少一種以硫醇爲主之氫供體及至少一 種以胺爲主之氫供體之組合物，因爲所形成之彩色層在顯 影期間幾乎不會自基板脫落且具有高強度及敏感性。 該以硫醇爲主之氫供體及該以胺爲主之氫供體之組合 物的較佳實例係包括2-氫硫基苯并噻唑及4,4’-雙（二甲 基胺基）二苯甲酮之組合物、2-氫硫基苯并噻唑及4,4’-雙 (二乙基胺基）二苯甲酮之組合物、2 -氫硫基苯并噁唑及 4,4’-雙（二甲基胺基）二苯甲酮之組合物及2_氫硫基苯并 噁唑及4，4 ’ -雙（二乙基胺基）二苯甲酮之組合物。此等組 -48- 200830043 合物中，2-氫硫基苯并噻唑及4,4’-雙（二乙基胺基 甲酮之組合物及2-氫硫基苯并噁唑及4，4’ -雙（二 基）二苯甲酮之化合物較佳，且2-氫硫基苯并 4,4’-雙（二乙基胺基）二苯甲酮之組合物特佳。 該以硫醇爲主之氫供體及該以胺爲主之氫供體 物中，以硫醇爲主之氫供體相對於以胺爲主之氫供 量比較佳係爲1 : 1至1 : 4，更佳1 : 1至1 : 3。 前述以安息香爲主化合物之實例係包括安息香 香甲基醚、安息香乙基醚、安息香異丙基醚、安息 基醚及2-安息香苯甲酸甲酯。 前述以乙醯基苯爲主化合物之實例係包括2,2-基乙醯苯、2，2-二乙氧基乙醯苯、2，2-二甲氧_2_苯 醯苯、2-羥基-2-甲基-1-苯基丙-1-酮、1- (4·異丙 )-2-羥基-2-甲基丙-1-酮、2-甲基-(4-甲基噻吩基 啉-1-丙-1-酮、4-(2-經基乙氧基）苯基-2-(經基· )酮、2-苄基-2-二甲基胺基-1-(4-嗎啉苯基）丁 _ 卜羥基環己基苯基酮及2,2-二甲氧基-1，2-二苯基乙· 前述以二苯基甲酮爲主化合物之實例係包括4， 二甲基胺基）二苯基甲酮及4，4’-雙（二乙基胺基） 甲酮。 前述以α -二酮爲主化合物之實例係包括二乙 二苯甲醯基及甲基苯甲醯基甲酸酯。 前述以多纟哀酿爲主化合物之貫例係包括蒽醌、 蒽醌、2-第三丁基蒽醌及1，4-萘醌。 )二苯 乙基胺 噻唑及 之組合 體之重 、安息 香異丁Examples of the aforementioned biimidazole-based compound include 2,2'-bis(2--45-200830043 chlorophenyl)-bis^^^-tetraterpine ethoxycarbonylphenyl hydrazine-deutero- Biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2 '-Bis(2-chlorophenyl)_4,4',5,5'-tetraphenyl-1,2'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,·tetraphenyl -1, 2, biimidazole, 2, 2, bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis ( 2,4-Dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'biimidazole and 2,2'-bis(2,4,6-tribromophenyl)- 4,4,,5,5'-tetraphenyl-1,2·-biimidazole. - Hydrogen donor - When a compound mainly composed of biimidazole is used as the radical generator (D) of the present invention, it is preferably used in combination with the following hydrogen donor to further improve the sensitivity. The term "hydrogen donor" as used in the present invention means a compound which can supply a hydrogen atom to a radical formed from the biimidazole-based compound upon exposure. The hydrogen donor is preferably a thiol-based compound or an amine-based compound as defined hereinafter. The above-mentioned thiol-based compound is a benzene ring or a heterocyclic ring as a mother nucleus and one or more, preferably 1 to 3, more preferably 1 or 2 thiol groups directly bonded to the nucleus of the mother nucleus. Compound (hereinafter referred to as "thiol-based hydrogen donor"). The above amine-based compound is a ring having a benzene ring or a hetero-46 - 200830043 ring as a mother nucleus and one or more, preferably 1 to 3, more preferably 1 or 2 amines directly bonded to the mother nucleus. A compound of the group (hereinafter referred to as "an amine-based hydrogen donor"). These hydrogen donors may have both a hydrogenthio group and an amine group. These hydrogen donors are described in detail below. The thiol-based hydrogen donor may have at least one benzene ring or a heterocyclic ring or both. When it has two or more of such rings, a fused ring can be formed. When the thiol-based hydrogen donor has two or more thiol groups, at least one of the other thio groups may be alkyl, aralkyl or aryl as long as at least one free thiol group is retained. Replaced. Further, as long as at least one free thiol group is retained, the thiol-based hydrogen donor may have a structural unit in which two sulfur atoms are bonded via a divalent organic group (such as an alkylene group) or two of the sulfur atoms therein. A structural unit bonded in the form of a disulfide. Further, the thiol-based hydrogen donor may be substituted at a position other than the thiol group (etc.) by a carboxy group, a substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted. a phenoxycarbonyl or nitrile group. Examples of such thiol-based hydrogen donors include 2-hydrothiobenzone: thiazide, 2-hydrothiobenzoH oxime, 2-hydrothiobenzopyrene, 2, 5-Dihydrothio-1,3,4-thiadiazole and 2-hydrothio-2,5-dimethylaminopyridine. Among these thiol-based hydrogen donors, 2-hydrothiobenzothiazolidine and 2 _hydrothiobenzoxazole are preferred, and 2-hydrothiobenzothiazole is particularly preferred. The amine-based hydrogen donor may have at least one benzene ring or heterocyclic ring or stomach #. When it has two or more of such rings, a fused ring can be formed. At least one amine group of the amine-based hydrogen donor may be substituted with an alkyl group or an amphoteric group of -47-200830043. The amine-based hydrogen donor may be substituted at a position other than the amine group (etc.) by a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted phenoxy group. A carbonyl or nitrile group. Examples of the aforementioned amine-based hydrogen donor include 4,4,-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4 -diethylaminoethenylbenzene, 4-dimethylaminopropionylbenzene, ethyl-4-dimethylaminobenzoate, isoamyl-4-dimethylaminobenzene Formate, 4-dimethylaminobenzoic acid and 4-dimethylaminobenzonitrile. Among these amine-based hydrogen donors, 4,4 bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone are preferred, and 4,4'-bis(diethylamino)benzophenone is particularly preferred. 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone can be used as photoinitiator as photoinitiator, even with diimidazole The main compound is not present. Also in the present invention, the aforementioned hydrogen donor may be used singly or in combination of two or more. Preferably, at least one composition of a thiol-based hydrogen donor and at least one amine-based hydrogen donor is used because the formed color layer hardly falls off from the substrate during development and has high strength and Sensitivity. Preferred examples of the thiol-based hydrogen donor and the amine-based hydrogen donor include 2-hydrothiobenzothiazole and 4,4'-bis(dimethylamino). a composition of benzophenone, a composition of 2-hydrothiobenzothiazole and 4,4'-bis(diethylamino)benzophenone, 2-hydrothiobenzoxazole and 4 Composition of 4'-bis(dimethylamino)benzophenone and composition of 2-hydrothiobenzoxazole and 4,4 '-bis(diethylamino)benzophenone . In the group -48-200830043, a composition of 2-hydrothiobenzothiazole and 4,4'-bis(diethylaminomethanone and 2-hydrothiobenzoxazole and 4, A compound of 4'-bis(diyl)benzophenone is preferred, and a composition of 2-hydrothiobenzo-4,4'-bis(diethylamino)benzophenone is particularly preferred. In the thiol-based hydrogen donor and the amine-based hydrogen donor, the thiol-based hydrogen donor is preferably 1:1 to 1: relative to the amine-based hydrogen supply. 4, more preferably 1: 1 to 1: 3. Examples of the aforementioned benzoin-based compounds include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin ether and 2-benzoin benzoate methyl ester Examples of the above-mentioned acetaminobenzene-based compound include 2,2-ylethyl benzene, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl benzene, 2 -hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4.isopropyl)-2-hydroxy-2-methylpropan-1-one, 2-methyl-(4-methyl Thiophenanthrhen-1-propan-1-one, 4-(2-carbylethoxy)phenyl-2-(yl)-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinylphenyl) butyl _ Hydroxycyclohexyl phenyl ketone and 2,2-dimethoxy-1,2-diphenylethyl · The foregoing examples of the main compound of diphenyl ketone include 4, dimethylamino) diphenyl Ketone and 4,4'-bis(diethylamino)methanone. Examples of the above-mentioned α-diketone-based compound include diethyldibenzyl and methyl benzhydrazide. The above-mentioned examples of the compounds which are mainly composed of sputum, sputum, 2-tert-butyl fluorene and 1,4-naphthoquinone are the weights of the combination of diphenylethylamine thiazole and the combination thereof. Benzoin

基苯基 )-2-嗎 -2-丙基 1-酮、 .1 -酮。 4·-雙（ 二苯基 醯基、 2-乙基 -49- 200830043 前述以咕噸酮爲主化合物之實例係包括咕噸酮、噻噸 酮及2-氯咕噸酮。 前述以膦爲主化合物之實例係包括氧化雙（2,4,6-三 甲基苯甲醯基）苯基膦及氧化2，4,6 -三甲基苯甲醯基二苯 基膦。 前述以三嗪爲主化合物之實例係包括具有鹵甲基之三 嗪化合物，諸如2,4,6-三（三氯甲基）-3-三嗪、2-甲基· 4.6- 雙（三氯甲基）^-三嗪、2-[2-(呋喃-2-基）乙烯基]- 4.6- 雙（三氯甲基）-s-三嗪、2-[2-(5-甲基呋喃-2-基）乙 烯基]-4,6-雙（三氯甲基）-s-三嗪、2-[2· ( 4-二乙基胺基-2-甲基苯基）乙烯基]-4,6-雙（三氯甲基）-3-三嗪、2-[2- (3,4-二甲氧基苯基）乙烯基]-4,6-雙（三氯甲基）-s—三 嗪、2-(4-甲氧基苯基）-4,6-雙（三氯甲基）-s-三嗪、2-(4-乙氧基苯乙烯基）-4,6-雙（三氯甲基）-s-三嗪、2-( 4-正丁氧基苯基）-4,6-雙（三氯甲基）-s-三嗪及下式（5 )及（6 )所示之化合物Phenyl phenyl)-2- -2-propyl 1-ketone, .1-ketone. 4·-bis(diphenylfluorenyl, 2-ethyl-49-200830043 The above examples of xanthone-based compounds include xanthone, thioxanthone and 2-chloroxanthone. Examples of the main compound include bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide and 2,4,6-trimethylbenzhydryldiphenylphosphine oxide. Examples of the main compound include a triazine compound having a halomethyl group such as 2,4,6-tris(trichloromethyl)-3-triazine, 2-methyl·4.6-bis(trichloromethyl). ^-Triazine, 2-[2-(furan-2-yl)vinyl]-4.6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2- Vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2·(4-diethylamino-2-methylphenyl)vinyl]-4, 6-bis(trichloromethyl)-3-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s- Triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-double (trichloromethyl)-s-triazine, 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine and Compounds of formula (5) and (6)

前述其他自由基生成劑可單獨或二或更多種組合使用 -50- 200830043 在本發明中，該其他自由基生成劑之量以所有自由基 生成劑（D )之總量圍較佳係爲5 0重量％或更低，更佳爲 1至30重量％。當其他自由基生成劑之量高於50重量％時 ，可能傷害本發明預期之效果。 本發明中，自由基生成劑（D)之量以100重量份數 之多官能性單體（C )或多官能性單體及單官能性單體之 總量計較佳係爲〇 . 〇 1至2 0 0重量份數，更佳1至1 2 0重 量份數，尤其是1至100重量份數。當該自由基生成劑（ D)之量低於0.01重量份數時，藉由曝光進行之固化不完 全，可能難以得到具有預定像素圖案或黑色基質圖案的圖 案陣列。而當該量高於200重量份數時，所形成之彩色層 可能在顯影時脫離基板或可能在未曝光部分之基板或遮光 層上產生沾染或膜殘留物。 本發明中，自由基生成劑（D )可視情況與至少一種 敏化劑、固化加速劑及聚合物感光交聯及增敏劑組合使用 -其他添加劑- 本發明輻射敏感性樹脂組成物係含有作爲必要組份之 前述組份（A )至（D )且可視需要另外含有其他添加劑 前述其他添加劑係包括塡充劑，諸如玻璃或氧化鋁； 聚合物化合物，諸如聚乙烯醇或聚（丙烯酸氟烷酯）；界 -51 - 200830043 面活性劑，諸如非離子性、陽離子性或陰離子性界面活性 劑；黏著加速劑’諸如乙烯基三甲氧基矽烷、乙烯基三乙 氧基砂院、乙嫌基二（2 -甲氧基乙_基）砍丨兀、N-(2 -胺 基乙基）-3-胺基丙基·甲基·二甲氧基矽烷、N-(2-胺基 乙基）-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽 烷、3 -縮水甘油氧基丙基三甲氧基矽烷、3 -縮水甘油氧基 丙基·甲基·二甲氧基矽烷、2-(3,4-環氧基環己基）乙 基三甲氧基石夕院、3 -氯丙基.甲基·一甲氧基砂院、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 或3-氫硫基丙基三甲氧基矽烷；抗氧化劑，諸如2,2-硫基 雙（4-甲基-6-第三丁基酚）或2,6-二-第三丁基酚；紫外 光吸收劑，諸如2- ( 3-第三丁基-5-甲基-2-羥基苯基）-5-氯苯并***或烷氧基二苯基甲酮；及黏結抑制劑，諸如聚 丙烯酸鈉。 液體組成物之製備 本發明輻射敏感性樹脂組成物通常與溶劑混合以製備 成液體組成物。 適當之溶劑只要分散或溶解構成該輻射敏感性樹脂組 成物之組份（A )至（D )及其他添加劑、不與此等組份 反應且具有適當之揮發性，則皆可選擇使用。 溶劑之實例包括丙二醇單烷基醚，諸如丙二醇單甲基 醚及丙二醇單乙基醚；（聚）烷二醇單烷基醚乙酸酯，諸 如乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、二乙 -52- 200830043 二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、丙二醇 單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、二丙二醇單甲 基醚乙酸酯及二丙二醇單乙基醚乙酸酯；（聚）烷二醇二 烷基醚，諸如二乙二醇二甲基醚、二乙二醇甲基乙基醚、 二乙二醇二乙基醚、二丙二醇二甲基醚、二丙二醇甲基乙 基醚及二丙二醇二乙基醚；其他醚類，諸如四氫呋喃；酮 類，諸如甲基乙基酮、環己酮、2 -庚酮及3 -庚酮；酮醇類 ，諸如雙丙酮醇（即，4-羥基-4-甲基戊-2-酮）及4-羥基-4-甲基己-2-酮；乳酸烷酯，諸如乳酸甲酯及乳酸乙酯；其 他酯類，諸如2-羥基-2-甲基丙酸乙酯、羥基乙酸乙酯、 2-羥基-3-甲基丁酸甲酯、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 乙酸乙酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧 基丁基丙酸酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙 酸正丁酯、乙酸異丁酯、甲酸正戊酯、乙酸異戊酯、丙酸 正丁酯、丁酸乙酯、丁酸正丙酯 丁酸異丙酯、丁酸正丁 酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙醯基乙 酸甲酯、乙醯基乙酸乙酯及2-合氧基丁酸乙酯；芳族烴類 ，諸如甲苯及二甲苯；及醯胺類，諸如N-甲基吡咯啶酮 、N，N-二甲基甲醯胺及N，N•二甲基乙醯胺。 就溶解度、顏料分散性及塗覆性的觀點而言，此等溶 劑中，丙二醇單甲基醚、乙二醇單甲基醚乙酸酯、二乙二 醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、丙二醇單 甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、二丙二醇單甲基 -53- 200830043 醚乙酸酯、二乙二醇二甲基醚、二乙二醇甲基乙基醚 丙二醇二甲基醚、環己酮、2 -庚酮、3 -庚酮、3 -甲氧 酸乙酯、3 -乙氧基丙酸甲酯、3 -乙氧基丙酸乙酯、3-1 3 -甲氧基丁基丙酸酯、乙酸正丁酯、乙酸異丁酯、甲 戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸異 、丁酸正丁酯及丙酮酸乙酯特佳。 前述溶劑可單獨或二或更多種組合使用。 此外，高沸點溶劑諸如苄基乙基醚、二-正己基 丙酮基丙酮、異佛爾酮、己酸、辛酸、1-辛醇、1-壬 苄醇、乙酸苄酯、苯甲酸乙酯、草酸二乙酯、順丁烯 二乙酯、r-丁內酯、碳酸乙二酯、碳酸丙二酯或乙 單苯基醚乙酸酯可與前述溶劑結合使用。 此等高沸點溶劑可單獨或二或更多種組合使用。 溶劑之量不特別限制，但就所得之液體組成物的 及安定性而言，期望係爲確定組成物所有組份（不包 劑）之總量變成較佳5至5 0重量％ (尤其是1 〇至4 0 % )之値。 濾光片形成方法 以下描述自本發明輻射敏感性樹脂組成物形成本 濾光片之方法。 形成濾光片之方法係至少包含以下步驟（1)至 (1 )於基板上形成本發明濾光片用輻射敏感性 基丙 戸基- 酸正 丙酯 醚、 醇、 二酸 二醇 塗覆 括溶 重量 發明 (4) 樹脂 -54- 200830043 組成物的塗膜； (2 )使該塗膜至少部分曝照輻射； (3 )使曝光後之塗膜顯影；及 (4 )加熱顯影之後的塗膜（以下稱 〇 前述步驟各描述於下文。 -步驟（1 )- 視情況於基板表面上形成遮光層，以 素之部分，之後將含有例如紅色顏料之濾 性樹脂組成物施加於該基板上，預烘烤以 塗膜。 此步驟所使用之基板係由玻璃、矽、 、芳族聚醯胺、聚醯胺-醯亞胺、聚醯亞 烯烴之開環聚合物或其氫化產物所製得。 該基板可視情況進行適當之預處理， 合劑進行化學處理、電漿處理、離子電鍍 應或真空沈積。 作爲將液體組成物施加於基板之方式 塗覆技術，諸如旋轉塗覆法（旋塗法）、 塗法或扁狀噴嘴塗覆法。因爲本發明輻射 物即使於乾燥後仍於清洗溶劑中具有高度 噴嘴塗覆法較佳。 至於預烘烤條件，塗膜較佳係於70 3 爲「後烘烤」） 界定用以形成像 光片用輻射敏感 蒸發溶劑，形成 聚碳酸酯、聚酯 胺、聚醚 、環 諸如使用矽烷偶 、濺鍍、氣相反 ，可採用適當之 鑄造塗覆法、桿 敏感性樹脂組成 溶解度，故扁狀 i 1 1 〇 °c預烘烤約 -55- 200830043 2至4分鐘。 移除溶劑後所形成之塗膜的厚度較佳係爲〇」至1() 微米’更佳爲0.2至8.0微米，特佳係0.2至6.0微米。 -步驟（2 )- 之後，所形成之塗膜至少一部分曝照輻射。爲使塗膜 之一部分曝光，較佳係經由具有適當圖案之光罩曝光。 使用於此步驟之輻射係選自可見光輻射、紫外線輻射 、遠紫外線輻射、電子輻射及X -輻射。具有1 9 〇至4 5 0 奈米波長之輻射較佳。 輻射劑量較佳係約10至1 0,000焦耳/米2。 -步驟（3 )- 之後，塗膜以較佳驗顯影劑顯影，溶解並移除塗膜未 曝光部分，以形成圖案。 則述顯影劑較佳係爲碳酸鈉、氫氧化鈉、氫氧化鉀、 氫氧化四甲基銨、膽鹼、1,8 -二氮雜雙環-[5·4·0]-7 -十一 碳烯或1，5-二氮雜雙環-[4.3·0]-5-壬烯之水溶液。 可將適量之水溶性有機溶劑（諸如甲醇或乙醇）或界 面活性劑添加於前述鹼顯影劑中。塗膜通常在鹼顯影之後 加以潤洗。 可採用噴淋式顯影、噴霧式顯影、沾浸（浸泡）式顯 影或攪煉顯影。 至於顯影條件，塗膜較佳係於常溫顯影約5至3 00秒 -56- 200830043 -步驟（4 )- 藉由後烘烤經顯影之塗膜’可得到具有由該輻射敏感 性樹脂組成物之固化產物所構成的預定像素圖案之基板。 至於後烘烤條件，塗膜較佳係於180至23 0°C加熱約 20至40分鐘。 如前文所述般形成之像素薄膜的厚度較佳係〇·5至 5.0微米，更佳係爲1.5至3.0微米。 使用含有綠色及藍色顏料之濾光片用液體輻射敏感性 樹脂組成物重複前述步驟（1 )至（4 )，可於同一基板上 形成綠色及藍色像素圖案，可形成在基板上具預定紅色、 綠色及藍色像素圖案之彩色層。本發明中，形成此等彩色 像素圖案之順序不特別限制。 濾光片 本發明濾光片係自本發明濾光片用輻射敏感性樹脂組 成物形成。 本發明濾光片極適用於透射型及反射型彩色液晶顯示 裝置、彩色攝影裝置、彩色感測器等。 彩色液晶顯示裝置 本發明彩色液晶顯示裝置係包含本發明濾光片。 本發明彩色液晶顯示裝置可具有適當之結構。例如， -57- 200830043 其可具有以下結構：在與具有薄膜電晶體（TFT )之驅動 基板分隔的基板上形成濾光片，該驅動基板與具有濾光片 之基板之間夾置液晶層且彼此相對。或者，藉著於具有薄 膜電晶體（TFT )之驅動基板表面上形成濾光片所製得之 基板及具有ITO (摻雜錫之氧化銦）之基板在中間夾置液 晶層下彼此相對。後一種結構可大幅改善隙孔，而可得到 明亮之高明晰度液晶顯示裝置。 本發明輻射敏感性樹脂組成物可於高產物良率下提供 不具有「影像烙痕」之濾光片，具有高敏感性，即使曝光 量低亦不會有像素圖案之缺角或側蝕，即使乾燥後亦於清 洗溶劑中具有高溶解度且適用於扁狀噴嘴塗覆。 實施例 以下實施例係用以進一步說明本發明，但不構成限制 〇 以下各合成例中所製得之樹脂的Mw及Μη係藉由基 於以下規格之凝膠滲透層析（GPC )測量。 裝置：GPC-101 ( Showa Denko K.K.) 管柱:組合 GPC-KF-801 、 GPC-KF-802 、 GPC-KF-803 及 GPC-KF-804 。 傳送相：含有〇 . 5重量％磷酸之四氫呋喃 合成例1 將重量份數2,2，-偶氮基雙異丁腈及400重量份數 -58- 200830043 二丙二醇二甲基醚送入裝置有冷卻管及攪拌器之燒瓶中， 之後將20重量份數甲基丙烯酸、31.2重量份數N-苯基順 丁烯二醯亞胺、30重量份數甲基丙烯酸苄酯、18.8重量 份數苯乙烯及10重量份數α -甲基苯乙烯二聚物（分子量 控制劑）送入燒瓶內，燒瓶內以氮置換，所得反應溶液在 溫和攪拌下於80 °C加熱，藉由保持該溫度進行聚合3小時 。反應溶液隨之於100°C加熱，添加2重量份數2,2’-偶氮 基雙異丁腈，進一步持續聚合1小時，以得到樹脂溶液（ 固體含量20.1重量％)。此樹脂具有5,000之Mw及3.6 之Mw/Mn。此樹脂稱爲樹脂（点-1 )。 合成例2 將2.5重量份數2,2’-偶氮基雙異丁腈及200重量份數 二丙二醇二甲基醚送入裝置有冷卻管及攪拌器之燒瓶中， 之後將20重量份數甲基丙烯酸、31.2重量份數N-苯基順 丁烯二醯亞胺、30重量份數甲基丙烯酸苄酯、18.8重量 份數苯乙烯及3重量份數α -甲基苯乙烯二聚物（分子量 控制劑）送入燒瓶內，燒瓶內以氮置換，所得反應溶液在 溫和攪拌下於80°C加熱，藉由保持該溫度進行聚合3小時 。反應溶液隨之於l〇〇°C加熱，添加0.5重量份數2,2’-偶 氮基雙異丁腈，進一步持續聚合1小時，以得到樹脂溶液 (固體含量33.2重量％ )。此樹脂具有14,000之Mw及 2.1之Mw/Mn。此樹脂稱爲樹脂（/3-2)。 -59- 200830043 合成例3 將3重量份數2,2’-偶氮基雙異丁腈、4重量份數四乙 基秋蘭姆化二硫（分子量控制劑）及200重量份數二丙二 醇二甲基醚送入裝置有冷卻管及攪拌器之燒瓶中’之後將 20重量份數甲基丙烯酸、31.2重量份數N -苯基順丁烯二 醯亞胺、30重量份數甲基丙烯酸苄酯及18.8重量份數苯 乙烯送入燒瓶內，燒瓶內以氮置換，所得反應溶液在溫和 攪拌下於80 °C加熱，藉由保持該溫度進行聚合3小時。反 應溶液隨之於1〇〇。(：加熱，添加2重量份數2,2’-偶氮基雙 異丁腈，進一步持續聚合1小時，以得到樹脂溶液（固體 含量33.0重量％ )。此樹脂具有5, 〇〇〇之Mw及1.7之 Mw/Mn。此樹脂稱爲樹脂（B-1 )。 浸泡試驗 對照例1 40重量份數作爲顏料（A)之C.I·顏料紅254與C.I· 顏料黃1 3 9重量比5 0/5 0混合物、1 〇重量份數作爲分散劑 之Disperbyk 2001及100重量份數作爲溶劑之3-乙氧基丙 酸乙酯藉 Diamond Fine Mill (商標，Mitsubishi Materials Corporation提供之珠磨機（珠粒直徑1·〇毫米））混合並 分散1 2小時，以製備顏料分散液。 之後，混合1 〇 〇重量份數此顏料分散液、7 0重量份數 作爲鹼可溶性樹脂之樹脂（0 -1 )、80重量份數作爲多官 能性單體（C )之二異戊四醇六丙烯酸酯、5重量份數作 -60- 200830043 爲自由基生成劑（D)之1-[9-乙基-6-[2-甲基-4- ( 2,2-甲 基-1,3-二氧戊環基）甲氧苄醯基]咔唑-3-基M-(〇-乙醯肟）及1，〇〇〇重量份數作爲溶劑之丙二醇單甲基醚乙 酸酯，以製備液體組成物（r-Ι)。 之後，以旋塗器將液體組成物（r-1 )施加於4-英吋 直徑之鈉玻璃基板上（該基板之表面上具有Si02膜以防 止鈉離子溶離）於無塵室中在23 °C留置1 2小時，以乾燥 形成塗膜。 之後，當此基板於100毫升丙二醇單甲基醚乙酸酯中 浸泡2分鐘時，塗膜完全溶解。 對照例2 以如同對照例1之方式製備液體組成物（r-2 )，不同 處係使用70重量份數樹脂（0 -2 )取代樹脂（/3 -1 )，以 於鈉玻璃基板上形成塗膜。 當此基板於100毫升丙二醇單甲基醚乙酸酯中浸泡2 分鐘時，塗膜未完全溶解，溶液中見到大量外來物。 實施例1 以如同對照例1之方式製備液體組成物（n ，$ 同處係使用70重量份數樹脂（B-l )取代樹脂（a q )， 以於鈉玻璃基板上形成塗膜。 當此基板於100毫升丙二醇單甲基醚乙酸酯中浸泡2 分鐘時，塗膜完全溶解。 -61 - 200830043 塗覆性之評估 對照例3 使用濾光片用TR632 1 0S-CL扁狀噴嘴施加裝置（商 標，Tokyo Ohka Kogyo Co·，Ltd·製造）將對照例1所製備 之液體組成物（r-1 )施加於表面上具有Si02膜以防止鈉 離子溶離之鈉玻璃基板上，留置於常溫經1小時，以乾燥 形成塗膜。 在噴射丙二醇單甲基醚乙酸酯清洗該扁狀噴嘴後，以 TR63 2 1 0S-CL將液體組成物（r-Ι)施加於新的鈉玻璃基 板上時，所形成之塗膜上未產生外來物。 對照例4 依如同對照例3之方式評估塗覆性，不同處係以對照 例2製備之液體組成物（r-2)取代液體組成物（r-l)， 所形成之塗膜上產生外來物，故無法形成令人滿意之塗膜 實施例2 依如同對照例3之方式評估塗覆性，不同處係以實施 例1製備之液體組成物（R-1 )取代液體組成物（r-1 )， 所形成之塗膜上未產生外來物。 電壓保持比之評估 -62- 200830043 對照例5 以旋塗器將對照例1所製備之液體組成物（r-1 )施加 於表面上具有Si02膜以防止鈉離子溶離及沈積成預定形 狀之ITO (氧化銦錫合金）電極的鈉玻璃基板上，於90 °C 在無塵爐中預烘烤1〇分鐘，以形成2.0微米厚塗膜。 之後，該塗膜在不使用光罩下以高壓汞燈曝照具有 365奈米、405奈米及436奈米波長之5,000 J/m2輻射。 此基板隨後於23 °C浸入由0.04重量％氫氧化鉀水溶液所 組成之顯影溶液中1分鐘，以進行顯影，以超純水潤洗， 風乾且於2 5 0 °C進一步後烘烤3 0分鐘，將塗膜固化，於基 板上形成紅色像素。像素膜厚爲1.60微米。 之後，將具有此等像素之基板及已沈積預定形狀之 ITO電極的基板藉含有0.8毫米玻璃珠粒之密封劑接合， 於此等基板之間的空間內注射 MLC 6 608液晶（商標， Merck Ltd.製造）以製得液晶構件。 該液晶構件隨後置入60°C恆溫槽中，以使用VHR-1A 液晶電壓保持比測量系統（商標，Toyo Corporation製造 )測量其電壓保持比。施加電壓爲5.5伏特矩形波，測量 頻率爲60赫茲。電壓保持比係爲液晶構件在16.7毫秒後 之電位差除以在〇毫秒時所施加之電壓所得的値。電壓保 持比係爲45%。 當液晶構件之電壓保持比爲90%或更低時，液晶構件 無法將施加電壓保持於預定位準歷經1 6.7秒’無法使液 晶完全配向。因此，包含自液體組成物（r-1 )所形成之濾 -63- 200830043 光片的液晶顯示裝置極可能產生「影像烙痕」。 對照例6 依如同對照例5之方式測量液晶構件之電壓保持比， 不同處係以對照例2中所製備之液體組成物（r-2 )取代液 體組成物（r-Ι )，其係92%。因此，包含自液體組成物（ r-2 )所形成之濾光片的液晶顯示裝置產生「影像烙痕」之 可能性極低。 實施例3 依如同對照例5之方式測量液晶構件之電壓保持比， 不同處係以實施例1所製備之液體組成物（R-1 )取代液 體組成物（r-Ι )，其係92%。因此，包含自液體組成物（ R-1 )所形成之濾光片的液晶顯示裝置產生「影像烙痕」 之可能性極低。 敏感性評估 對照例7 依如同對照例i之方式製備液體組成物（r-3 )，不同 處係對照例1所製備之液體組成物（r-1 )的自由基生成劑 (D)係變成50重量份數2-甲基-(4-甲基噻吩基）-2-嗎 啉-1 -丙-1 -酮。 以旋塗器將液體組成物（r-3 )施加於表面上具有 Si02膜以防止鈉離子溶離的鈉玻璃基板上，於90 °C熱板 -64- 200830043 上預烘烤2分鐘，以形成1.7微米厚塗膜。 之後，將基板冷卻至室溫，塗膜在經由光罩（狹縫寬 度30微米）以高壓汞燈曝照具有365奈米、405奈米及 43 6奈米波長之紫外線輻射。此時之曝光量爲400 J/m2。 此基板隨後於23t浸入〇.〇4重量％氫氧化鉀水溶液中1 分鐘進行顯影，以超純水潤洗並風乾。之後，基板於220 °C在無塵爐中後烘烤3 0分鐘，形成具有條狀圖案之紅色 像素陣列。經由光學顯微鏡觀察基板上之像素陣列時，發 現像素圖案邊緣缺角。經由掃描式電子顯微鏡（SEM )觀 察基板上之像素陣列時，發現側蝕。 對照例8 依如同對照例2之方式製備液體組成物（r-4 )，不同 處係對照例2所製備之液體組成物（r-2 )的自由基生成劑 (D)係變成50重量份數2-甲基-(4-甲基噻吩基）-2-嗎 啉-1 -丙-1 -酿|。 依如同對照例7之方式形成具有條狀圖案之紅色像素 陣列，不同處係使用液體組成物（r-4 )取代液體組成物（ r- 3 )。經由光學顯微鏡觀察基板上之像素陣列時，發現像 素圖案邊緣缺角。經由掃描式電子顯微鏡（S EM )觀察像 素陣列剖面時，發現側蝕。 實施例4 依如同對照例7之方式形成具有條狀圖案之紅色像素 -65- 200830043 陣列，不同處係使用實施例1所製備之液體組成物（R- 1 )取代液體組成物（r-3 )。經由光學顯微鏡觀察基板上之 像素陣列時，未發現像素圖案邊緣缺角。經由掃描式電子 顯微鏡（SEM )觀察像素陣列剖面時，未發現側飩。 前述評估結果係連同輻射敏感性樹脂組成物之主要構 成組份一起顯示於表1及表2中。雖然此處係評估包含紅 色顏料之輻射敏感性樹脂組成物，但包含藍色、綠色、黃 色及黑色顏料之輻射敏感性樹脂組成物亦得到相同結果。 表1及表2中之自由基生成劑係列示如下。 D-1 :乙酮- l-[9-乙基- 6-[2-甲基-4- ( 2,2-二甲基-1,3-二氧戊環基）甲氧基苯甲醯基]咔唑-3-基]-1- ( 〇-乙 醯肟） 5-1: 2 -甲基-(4 -甲噻吩基）-2 -嗎啉-1-丙·卜酮 表1 樹脂 自由基生成劑 浸泡試驗 塗覆性 電壓保持比 對照例1/3/5 /3-1 D-1 〇 〇 X (45%) 對照例2/4/61 /5-2 D-1 X(產生外來物） X(產生外來物） Ο (92%) 實施例1/2/3 B-1 D-1 〇 〇 〇（92%) 表2 樹脂 自由基生成劑 敏感性 對照例7 β-l 5-1 X 對照例8 β"2 5-1 X 實施例4 B-1 D-1 〇 表1及表2中，於浸泡試驗、塗覆性評估、電壓保持 比評估及敏感性評估中’〇表示輻射敏感性樹脂組成物令 -66 - 200830043 人滿意且χ係示輻射敏感性樹脂組成物無法令人滿意 -67-The foregoing other radical generating agents may be used singly or in combination of two or more. In the present invention, the amount of the other radical generating agent is preferably in the total amount of all the radical generating agents (D). 50% by weight or less, more preferably 1 to 30% by weight. When the amount of other radical generating agent is more than 50% by weight, the intended effect of the present invention may be impaired. In the present invention, the amount of the radical generating agent (D) is preferably 〇. 〇1 based on 100 parts by weight of the polyfunctional monomer (C) or the total amount of the polyfunctional monomer and the monofunctional monomer. Up to 200 parts by weight, more preferably 1 to 12,000 parts by weight, especially 1 to 100 parts by weight. When the amount of the radical generating agent (D) is less than 0.01 part by weight, the curing by exposure is incomplete, and it may be difficult to obtain a pattern array having a predetermined pixel pattern or a black matrix pattern. When the amount is more than 200 parts by weight, the formed color layer may be detached from the substrate during development or may cause contamination or film residue on the substrate or the light-shielding layer of the unexposed portion. In the present invention, the radical generating agent (D) may optionally be used in combination with at least one sensitizer, curing accelerator, and polymer photosensitive cross-linking agent and a sensitizer - other additives - the radiation-sensitive resin composition of the present invention contains The aforementioned components (A) to (D) of the necessary components may additionally contain other additives as needed. The other additives include a chelating agent such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkane acrylate) Ester); boundary -51 - 200830043 Surfactant, such as nonionic, cationic or anionic surfactant; adhesion accelerator 'such as vinyl trimethoxy decane, vinyl triethoxy sand, B. Bis(2-methoxyethyl-yl) chopped, N-(2-aminoethyl)-3-aminopropylmethyl-dimethoxydecane, N-(2-amino-ethyl 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyl Dimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxylate , 3-chloropropyl.methyl·monomethoxy sand, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane or 3-hydrothiopropyl Trimethoxy decane; an antioxidant such as 2,2-thiobis(4-methyl-6-tert-butylphenol) or 2,6-di-t-butylphenol; an ultraviolet light absorber such as 2 - (3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole or alkoxydiphenyl ketone; and a binding inhibitor such as sodium polyacrylate. Preparation of Liquid Composition The radiation-sensitive resin composition of the present invention is usually mixed with a solvent to prepare a liquid composition. A suitable solvent may be used as long as it disperses or dissolves the components (A) to (D) and other additives constituting the radiation-sensitive resin composition, does not react with the components, and has appropriate volatility. Examples of the solvent include propylene glycol monoalkyl ether such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetate such as ethylene glycol monomethyl ether acetate, Glycol monoethyl ether acetate, diethyl-52- 200830043 diol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol single B Ethyl ether acetate, dipropylene glycol monomethyl ether acetate and dipropylene glycol monoethyl ether acetate; (poly)alkylene glycol dialkyl ether, such as diethylene glycol dimethyl ether, diethylene Alcohol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether and dipropylene glycol diethyl ether; other ethers such as tetrahydrofuran; ketones, such as Ketoethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; keto alcohols such as diacetone alcohol (ie, 4-hydroxy-4-methylpentan-2-one) and 4-hydroxy-4 -methylhexan-2-one; alkyl lactate such as methyl lactate and ethyl lactate; other esters such as ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, 2-hydroxy-3 - Methyl butyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxyacetic acid Ethyl ester, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, acetic acid N-butyl ester, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, acetone Ester, ethyl pyruvate, n-propyl pyruvate, methyl acetoxyacetate, ethyl acetoxyacetate and ethyl 2-oxybutyrate; aromatic hydrocarbons such as toluene and xylene; Amines such as N-methylpyrrolidone, N,N-dimethylformamide and N,N•dimethylacetamide. From the viewpoints of solubility, pigment dispersibility, and coatability, among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, and Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl-53- 200830043 ether acetate, diethylene glycol dimethyl Ether, diethylene glycol methyl ethyl ether propylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 3-methoxylate, methyl 3-ethoxypropionate, 3 -ethyl ethoxypropionate, 3- 13 -methoxybutyl propionate, n-butyl acetate, isobutyl acetate, methyl amyl ester, isoamyl acetate, n-butyl propionate, butyric acid Ethyl ester, butyric acid, n-butyl butyrate and ethyl pyruvate are particularly preferred. The foregoing solvents may be used singly or in combination of two or more. In addition, high boiling solvents such as benzyl ethyl ether, di-n-hexylidene acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-indolyl benzyl alcohol, benzyl acetate, ethyl benzoate, Diethyl oxalate, maleic acid diethyl ester, r-butyrolactone, ethylene carbonate, propylene carbonate or ethyl monophenyl ether acetate can be used in combination with the aforementioned solvents. These high boiling solvents may be used singly or in combination of two or more. The amount of the solvent is not particularly limited, but in terms of the stability and stability of the obtained liquid composition, it is desirable to determine that the total amount of all components (non-encapsulated) of the composition becomes preferably 5 to 50% by weight (especially 1 〇 to 40%). Filter Forming Method A method of forming the present filter from the radiation-sensitive resin composition of the present invention is described below. The method of forming a filter comprises at least the following steps (1) to (1) forming a filter of the present invention on a substrate, which is coated with a radiation-sensitive propyl acrylate-n-propyl ester, an alcohol, a diacid diol. The invention discloses a coating film of the composition (4) Resin-54-200830043; (2) at least partially exposing the coating film; (3) developing the coating film after exposure; and (4) after heating and developing Coating film (hereinafter referred to as the foregoing steps are each described below.) - Step (1) - a light-shielding layer is formed on the surface of the substrate as a case, and a portion of the element is applied, and then a filter resin composition containing, for example, a red pigment is applied to the substrate Pre-baked to coat the film. The substrate used in this step is made of glass, ruthenium, aromatic polyamine, polyamine-imide, open-loop polymer of polyfluorene or its hydrogenated product. The substrate may be suitably pretreated, and the mixture may be subjected to chemical treatment, plasma treatment, ion plating or vacuum deposition. As a method of applying a liquid composition to a substrate, such as a spin coating method Coating method, coating method or flat Nozzle coating method. Because the radiation of the present invention has a high nozzle coating method in the cleaning solvent even after drying. As for the prebaking conditions, the coating film is preferably defined as "post-baking" at 70 3 For forming a radiation-sensitive evaporating solvent for a light sheet, forming a polycarbonate, a polyesteramine, a polyether, a ring such as a decane couple, sputtering, and gas, instead, a suitable casting coating method or a rod-sensitive resin may be used. Solubility, so flat i 1 1 〇 °c pre-bake about -55- 200830043 2 to 4 minutes. The thickness of the coating film formed after removing the solvent is preferably from 〇" to 1 () μ', more preferably from 0.2 to 8.0 μm, particularly preferably from 0.2 to 6.0 μm. - Step (2) - Thereafter, at least a portion of the formed coating film is exposed to radiation. In order to expose a portion of the coating film, it is preferably exposed through a photomask having an appropriate pattern. The radiation used in this step is selected from the group consisting of visible radiation, ultraviolet radiation, far ultraviolet radiation, electron radiation, and X-radiation. Radiation having a wavelength of from 1 9 4 to 450 nm is preferred. The radiation dose is preferably from about 10 to 10,000 joules per square meter. - Step (3) - Thereafter, the coating film is developed with a preferred developer to dissolve and remove the unexposed portion of the coating film to form a pattern. The developer is preferably sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5·4·0]-7 - eleven An aqueous solution of a carbene or 1,5-diazabicyclo-[4.3.0]-5-pinene. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or an interfacing agent may be added to the aforementioned alkali developer. The coating film is usually rinsed after alkali development. Spray development, spray development, dip-immersion or smelting development can be used. As for the development conditions, the coating film is preferably developed at room temperature for about 5 to 300 seconds - 56 - 200830043 - step (4) - by post-baking the developed coating film - to obtain a composition having the radiation-sensitive resin A substrate of a predetermined pixel pattern formed by the cured product. As for the post-baking conditions, the coating film is preferably heated at 180 to 23 ° C for about 20 to 40 minutes. The thickness of the pixel film formed as described above is preferably from 5 to 5.0 μm, more preferably from 1.5 to 3.0 μm. Repeating the above steps (1) to (4) with a liquid radiation sensitive resin composition using a filter containing green and blue pigments, green and blue pixel patterns can be formed on the same substrate, and can be formed on the substrate. A layer of red, green, and blue pixel patterns. In the present invention, the order in which these color pixel patterns are formed is not particularly limited. Filter The filter of the present invention is formed from the radiation sensitive resin composition of the filter of the present invention. The filter of the present invention is extremely suitable for a transmissive and reflective type color liquid crystal display device, a color photographing device, a color sensor, and the like. Color Liquid Crystal Display Device The color liquid crystal display device of the present invention comprises the filter of the present invention. The color liquid crystal display device of the present invention can have a suitable structure. For example, -57-200830043 may have a structure in which a filter is formed on a substrate separated from a driving substrate having a thin film transistor (TFT), and a liquid crystal layer is interposed between the driving substrate and the substrate having the filter and Opposite each other. Alternatively, the substrate obtained by forming a filter on the surface of the driving substrate having a thin film transistor (TFT) and the substrate having ITO (tin-doped indium oxide) are opposed to each other under the intermediate liquid crystal layer. The latter structure can greatly improve the aperture, and a bright, high-definition liquid crystal display device can be obtained. The radiation-sensitive resin composition of the invention can provide a filter without "image mark" at high product yield, has high sensitivity, and has no corner or side etching of the pixel pattern even if the exposure amount is low. It has high solubility in the cleaning solvent even after drying and is suitable for flat nozzle coating. EXAMPLES The following examples are intended to further illustrate the invention, but are not to be construed as limiting. The Mw and Μη of the resins obtained in the following synthesis examples are measured by gel permeation chromatography (GPC) based on the following specifications. Device: GPC-101 (Showa Denko K.K.) Column: Combination GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804. Transport phase: tetrahydrofuran containing 〇. 5 wt% phosphoric acid Synthesis Example 1 parts by weight of 2,2,-azobisisobutyronitrile and 400 parts by weight -58-200830043 dipropylene glycol dimethyl ether fed to the device In a cooling tube and a stirrer flask, 20 parts by weight of methacrylic acid, 31.2 parts by weight of N-phenyl maleimide, 30 parts by weight of benzyl methacrylate, and 18.8 parts by weight of benzene are then added. Ethylene and 10 parts by weight of α-methylstyrene dimer (molecular weight controlling agent) were fed into a flask, and the flask was replaced with nitrogen, and the resulting reaction solution was heated at 80 ° C with gentle stirring, by maintaining the temperature. Polymerization for 3 hours. The reaction solution was then heated at 100 ° C, 2 parts by weight of 2,2'-azobisisobutyronitrile was added, and polymerization was further continued for 1 hour to obtain a resin solution (solid content: 20.1% by weight). This resin has a Mw of 5,000 and a Mw/Mn of 3.6. This resin is called a resin (dot-1). Synthesis Example 2 2.5 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of dipropylene glycol dimethyl ether were fed into a flask equipped with a cooling tube and a stirrer, and then 20 parts by weight Methacrylic acid, 31.2 parts by weight of N-phenyl maleimide, 30 parts by weight of benzyl methacrylate, 18.8 parts by weight of styrene and 3 parts by weight of α-methylstyrene dimer (Molecular weight control agent) was placed in a flask, and the inside of the flask was replaced with nitrogen, and the resulting reaction solution was heated at 80 ° C with gentle stirring, and polymerization was carried out for 3 hours while maintaining the temperature. The reaction solution was then heated at 10 ° C, 0.5 parts by weight of 2,2'-azobisisobutyronitrile was added, and polymerization was further continued for 1 hour to obtain a resin solution (solid content: 33.2% by weight). This resin has a Mw of 14,000 and a Mw/Mn of 2.1. This resin is called a resin (/3-2). -59- 200830043 Synthesis Example 3 3 parts by weight of 2,2'-azobisisobutyronitrile, 4 parts by weight of tetraethyl thiuram disulfide (molecular weight controlling agent), and 200 parts by weight of dipropylene glycol The dimethyl ether feeding device is equipped with a cooling tube and a stirrer flask. After that, 20 parts by weight of methacrylic acid, 31.2 parts by weight of N-phenyl maleimide, and 30 parts by weight of methacrylic acid are added. The benzyl ester and 18.8 parts by weight of styrene were fed into a flask, and the flask was replaced with nitrogen. The resulting reaction solution was heated at 80 ° C with gentle stirring, and polymerization was carried out for 3 hours while maintaining the temperature. The reaction solution is followed by 1 〇〇. (: Heating, adding 2 parts by weight of 2,2'-azobisisobutyronitrile, and further continuing the polymerization for 1 hour to obtain a resin solution (solid content: 33.0% by weight). This resin has 5, Mw of Mw And Mw/Mn of 1.7. This resin is called resin (B-1). Immersion test Comparative Example 1 40 parts by weight as pigment (A) CI·Pigment Red 254 and CI·Pigment Yellow 1 3 9 by weight 5 0 /5 0 mixture, 1 part by weight of Disperbyk 2001 as a dispersing agent and 100 parts by weight of solvent as ethyl 3-ethoxypropionate as a solvent by Diamond Fine Mill (trademark, bead mill supplied by Mitsubishi Materials Corporation) The particle diameter is 1·〇 mm)) mixed and dispersed for 12 hours to prepare a pigment dispersion. Thereafter, 1 part by weight of the pigment dispersion, 70 parts by weight of the resin as an alkali-soluble resin (0 -1) is mixed. 80 parts by weight as the polyfunctional monomer (C) of diisopentyl alcohol hexaacrylate, 5 parts by weight as -60-200830043 is a radical generating agent (D) 1-[9-ethyl -6-[2-methyl-4-(2,2-methyl-1,3-dioxolanyl)methoxybenzyl] oxazol-3-yl M-(〇-B肟) and 1, 〇〇〇 by weight of propylene glycol monomethyl ether acetate as a solvent to prepare a liquid composition (r-Ι). Thereafter, the liquid composition (r-1) is applied by a spin coater. On a 4-inch diameter sodium glass substrate (the surface of the substrate has a SiO 2 film to prevent sodium ion elution), it is left in a clean room at 23 ° C for 12 hours to form a coating film by drying. When the substrate was immersed in 100 ml of propylene glycol monomethyl ether acetate for 2 minutes, the coating film was completely dissolved. Comparative Example 2 A liquid composition (r-2) was prepared in the same manner as in Comparative Example 1, and 70 parts by weight were used in the different portions. The resin (0 -2 ) is substituted for the resin (/3 -1 ) to form a coating film on the soda glass substrate. When the substrate is immersed in 100 ml of propylene glycol monomethyl ether acetate for 2 minutes, the coating film is not completely Dissolved, a large amount of foreign matter was observed in the solution. Example 1 A liquid composition was prepared in the same manner as in Comparative Example 1 (n, $ was replaced with 70 parts by weight of the resin (Bl) in place of the resin (aq) to the soda glass. A coating film is formed on the substrate. When the substrate is in 100 ml of propylene glycol monomethyl ether When the ester was immersed for 2 minutes, the coating film was completely dissolved. -61 - 200830043 Evaluation of coating property Comparative Example 3 Using a filter with a TR632 1 0S-CL flat nozzle application device (trademark, Tokyo Ohka Kogyo Co., Ltd. The liquid composition (r-1) prepared in Comparative Example 1 was applied to a soda glass substrate having a SiO 2 film on the surface to prevent sodium ions from being dissolved, and left to stand at normal temperature for 1 hour to form a coating film by drying. After the propylene glycol monomethyl ether acetate was sprayed to clean the flat nozzle, the liquid composition (r-Ι) was applied to the new soda glass substrate with TR63 2 1 0S-CL, and the formed coating film was not formed. Produce foreign objects. Comparative Example 4 The coating property was evaluated in the same manner as in Comparative Example 3, except that the liquid composition (r-2) prepared in Comparative Example 2 was substituted for the liquid composition (rl), and a foreign matter was formed on the formed coating film. Therefore, a satisfactory coating film could not be formed. Example 2 The coating property was evaluated in the same manner as in Comparative Example 3, except that the liquid composition (R-1) prepared in Example 1 was substituted for the liquid composition (r-1). No foreign matter was formed on the formed coating film. Evaluation of voltage holding ratio - 62 - 200830043 Comparative Example 5 The liquid composition (r-1) prepared in Comparative Example 1 was applied to a ITO having a SiO 2 film on the surface to prevent sodium ions from being dissolved and deposited into a predetermined shape by a spin coater. The (indium tin oxide alloy) electrode was prebaked on a soda glass substrate at 90 ° C for 1 minute in a dust-free oven to form a 2.0 μm thick coating film. Thereafter, the coating film was exposed to 5,000 J/m2 of a wavelength of 365 nm, 405 nm, and 436 nm with a high pressure mercury lamp without using a mask. The substrate was then immersed in a developing solution consisting of 0.04% by weight aqueous potassium hydroxide solution at 23 ° C for 1 minute for development, rinsed with ultrapure water, air dried and further post-baked at 250 ° C. In minutes, the coating film was cured to form red pixels on the substrate. The pixel film thickness was 1.60 microns. Thereafter, the substrate having the pixels and the substrate on which the ITO electrode of a predetermined shape has been deposited are bonded by a sealant containing 0.8 mm glass beads, and MLC 6 608 liquid crystal is injected into the space between the substrates (Trademark, Merck Ltd) Manufacturing) to produce a liquid crystal member. The liquid crystal member was then placed in a 60 ° C thermostat to measure its voltage holding ratio using a VHR-1A liquid crystal voltage retention ratio measuring system (trademark, manufactured by Toyo Corporation). A rectangular wave with a voltage of 5.5 volts was applied and the measurement frequency was 60 Hz. The voltage holding ratio is obtained by dividing the potential difference of the liquid crystal member after 16.7 milliseconds by the voltage applied at 〇 milliseconds. The voltage holding ratio is 45%. When the voltage holding ratio of the liquid crystal member is 90% or less, the liquid crystal member cannot maintain the applied voltage at the predetermined level for 1 6.7 seconds', and the liquid crystal is not completely aligned. Therefore, the liquid crystal display device including the filter of the -63-200830043 formed from the liquid composition (r-1) is highly likely to produce an "image mark". Comparative Example 6 The voltage holding ratio of the liquid crystal member was measured in the same manner as in Comparative Example 5, except that the liquid composition (r-2) prepared in Comparative Example 2 was substituted for the liquid composition (r-Ι), which was 92. %. Therefore, the liquid crystal display device including the filter formed from the liquid composition (r-2) is extremely unlikely to generate an "image mark". Example 3 The voltage holding ratio of the liquid crystal member was measured in the same manner as in Comparative Example 5, except that the liquid composition (R-1) prepared in Example 1 was substituted for the liquid composition (r-Ι), which was 92%. . Therefore, the liquid crystal display device including the filter formed from the liquid composition (R-1) is extremely unlikely to generate an "image mark". Sensitivity Evaluation Comparative Example 7 A liquid composition (r-3) was prepared in the same manner as in Comparative Example i, except that the radical generating agent (D) of the liquid composition (r-1) prepared in Comparative Example 1 was changed. 50 parts by weight of 2-methyl-(4-methylthienyl)-2-morpholine-1-propan-1-one. The liquid composition (r-3) was applied to a soda glass substrate having a SiO 2 film on the surface to prevent sodium ions from being dissolved by a spin coater, and prebaked on a hot plate of -64-200830043 at 90 ° C for 2 minutes to form 1.7 micron thick film. Thereafter, the substrate was cooled to room temperature, and the coating film was irradiated with ultraviolet rays having wavelengths of 365 nm, 405 nm, and 43 6 nm through a reticle (slit width: 30 μm) with a high pressure mercury lamp. The exposure amount at this time is 400 J/m2. This substrate was then developed by immersing it in a 4 wt% potassium hydroxide aqueous solution at 23 t for 1 minute, rinsing with ultrapure water, and air drying. Thereafter, the substrate was post-baked in a dust-free oven at 220 ° C for 30 minutes to form a red pixel array having a stripe pattern. When the pixel array on the substrate was observed through an optical microscope, the edge of the pixel pattern was found to be missing. When the pixel array on the substrate was observed via a scanning electron microscope (SEM), side etching was found. Comparative Example 8 A liquid composition (r-4) was prepared in the same manner as in Comparative Example 2, except that the radical generating agent (D) of the liquid composition (r-2) prepared in Comparative Example 2 was changed to 50 parts by weight. Number 2-methyl-(4-methylthienyl)-2-morpholine-1 -propan-1 - Stuffed | A red pixel array having a stripe pattern was formed in the same manner as in Comparative Example 7, except that the liquid composition (r-4) was used instead of the liquid composition (r-3). When the pixel array on the substrate was observed through an optical microscope, the edge of the pixel pattern was found to be missing. Lateral etching was observed when the pixel array profile was observed via a scanning electron microscope (S EM ). Example 4 An array of red pixels-65-200830043 having a strip pattern was formed in the same manner as in Comparative Example 7, except that the liquid composition (R-1) prepared in Example 1 was used instead of the liquid composition (r-3). ). When the pixel array on the substrate was observed through an optical microscope, no corners of the pixel pattern were found. When the cross section of the pixel array was observed by a scanning electron microscope (SEM), no side defects were found. The foregoing evaluation results are shown in Tables 1 and 2 together with the main constituent components of the radiation-sensitive resin composition. Although the radiation-sensitive resin composition containing the red pigment was evaluated here, the radiation-sensitive resin composition containing the blue, green, yellow, and black pigments gave the same result. The series of radical generating agents in Tables 1 and 2 are shown below. D-1: Ethylketone-l-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzidine咔 咔 -3--3-yl]-1-( 〇-acetamidine) 5-1: 2 -methyl-(4-methylthienyl)-2 -morpholin-1-propanthone Table 1 Resin The free radical generator immersion test coating voltage was maintained compared to the control 1/3/5 /3-1 D-1 〇〇X (45%) Comparative Example 2/4/61 /5-2 D-1 X (produced Exogenous) X (produces foreign matter) Ο (92%) Example 1/2/3 B-1 D-1 〇〇〇 (92%) Table 2 Resin radical generating agent sensitivity Comparative Example 7 β-l 5 -1 X Comparative Example 8 β"2 5-1 X Example 4 B-1 D-1 In Tables 1 and 2, in the immersion test, coating evaluation, voltage holding ratio evaluation, and sensitivity evaluation Indicates that the radiation-sensitive resin composition is satisfactory to -66 - 200830043 and that the lanthanide-induced radiation-sensitive resin composition is unsatisfactory -67-

Claims (1)

200830043 十、申請專利範圍 1 · 一種輻射敏感性樹脂組成物，其包含（A )著色劑 ，（B )鹼可溶性樹脂，（C )多官能性單體及（D )輻射 敏感性自由基生成劑，其中 該鹼可溶性樹脂（B )係包含在其聚合物鏈之至少一 末端具有下式（i)或（ii)所示之基團的樹脂且該輻射敏 感性自由基生成劑（D )係包含下式（1 )所示之化合物及 /或下式（2)所示之化合物： S —s—c—Z1 ⑴ S —S—C—Z2 (ii) [式（i)及（ii)中，Z1及Z2各獨立地爲氫原子、氯原子 、羧基、氰基、具有1至20個碳原子之烷基、具有6至 20個碳原子之單價芳族烴基、由碳原子及雜原子所組成之 具有3至20個原子的單價雜環基、-OR^-SRl-OCC =0 ) R1、-N ( R1) ( R2 ) 、-C ( =0) OR1、-C ( =0) N ( R1 ) ( R2 ) 、-P(=〇) ( OR1 ) 2、-P ( =0 ) (R1)〗或具 有聚合物鏈之單價基團，R1及R2各係獨立地爲具有1至 18個碳原子之烷基、具有2至18個碳原子之烯基、具有 6至1 8個碳原子之單價芳族烴基或由碳原子及雜原子組成 之具有3至18個原子之單價雜環基’其附帶條件爲具有1 至20個碳原子之烷基、具有6至20個碳原子之單價芳族 烴基、由碳原子及雜原子所組成之具有3至2〇個原子的 -68- 200830043 單價雜環基、R1及R2可經取代];200830043 X. Patent Application No. 1 · A radiation-sensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a radiation-sensitive radical generating agent Wherein the alkali-soluble resin (B) is a resin having a group represented by the following formula (i) or (ii) at least one terminal of a polymer chain thereof and the radiation-sensitive radical generating agent (D) is A compound represented by the following formula (1) and/or a compound represented by the following formula (2): S - s - c - Z1 (1) S - S - C - Z2 (ii) [Formula (i) and (ii) Wherein Z1 and Z2 are each independently a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a carbon atom and a hetero atom. a monovalent heterocyclic group having 3 to 20 atoms, -OR^-SRl-OCC =0) R1, -N ( R1) ( R2 ) , -C ( =0) OR1, -C ( =0) N ( R1 ) ( R2 ) , -P (=〇) ( OR1 ) 2, -P ( =0 ) (R1) or a monovalent group having a polymer chain, each of R 1 and R 2 independently having 1 to 18 carbon atoms in the alkyl group, with 2 to 18 An alkenyl group of a carbon atom, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a monovalent heterocyclic group having 3 to 18 atoms consisting of a carbon atom and a hetero atom, with the proviso having 1 to 20 carbons An alkyl group of an atom, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a -68-200830043 monovalent heterocyclic group having 3 to 2 atomic atoms composed of a carbon atom and a hetero atom, and R1 and R2 may be substituted ]; [式（1)及（2)中，R3各獨立地爲具有1至20個碳原子 之烷基、具有3至8個碳原子之環烷基或苯基，R4及R5 各獨立地爲氫原子、具有1至20個碳原子之烷基、具有3 至8個碳原子之環烷基、可經取代之苯基或具有7至20 個碳原子之單價脂環族基團（不包括前述環烷基），R6各 係獨立地爲具有4至20個碳原子之單價含氧雜環基、具 有4至20個碳原子之單價含氮雜環基或具有4至20個碳 原子之單價含硫雜環基，R7各獨立地爲氫原子、具有1至 12個碳原子之烷基、具有3至8個碳原子之環烷基、具有 1至12個碳原子之烷氧基或具有3至8個碳原子之環烷氧 基，η各獨立地爲1至5之整數，m各獨立地爲0至5之 整數，其附帶條件爲（n + m )^5，且p係爲〇至6之整數 •69- 200830043 2 ·如申請專利範圍第1項之輻射敏感性樹脂組成物’ 其中Z1及Z2各爲由碳原子及雜原子組成之具有3至20 個原子的單價雜環基、-0Ri或-N(Ri) (R2) (R1及R2 係個別如同式（i)中之 Z1及式（ii)中之Z2的R1及R2 )° 3 ·如申請專利範圍第1或2項之輻射敏感性樹脂組成 物，其中該鹼可溶性樹脂（B )係爲使用下式（3 )所示之 二硫化物化合物作爲分子量控制劑將可聚合之不飽和化合 物聚合所製得的樹脂： S S z1—c—s—s—c—Z2 (3) [式（3)中，Z1及Z2個別與式（i)中之Z1及式（ii)中 之Z2相同]。 4 ·如申請專利範圍第3項之輻射敏感性樹脂組成物， 其中用以製造鹼可溶性樹脂（B )之可聚合不飽和化合物 的聚合係爲活性自由基聚合。 5 ·如申請專利範圍第丨或2項之輻射敏感性樹脂組成 物’其中該鹼可溶性樹脂（B )係爲（b 1 )不飽和羧酸及/ 或不飽和羧酸酐與（b2 )至少一種選自芳族乙烯基化合物 、茚、N-取代順丁烯二醯亞胺、於聚合物分子鏈之一末端 具有（甲基）丙烯醯基之巨單體、不飽和羧酸酯、不飽和 羧酸胺基烷酯、不飽和羧酸縮水甘油酯、羧酸乙烯酯、不 飽和醚、不飽和醯胺及脂族共軛二烯之可共聚不飽和化合 -70- 200830043 物之單體混合物的共聚物。 6 ·如申請專利範圍第1或2項之輻射敏感 物，其中該鹼可溶性樹脂（B )係具有1，〇〇〇 3 Mw ( Mw係爲藉凝膠滲透層析（GPC )測量以 之重量平均分子量）。 7.如申請專利範圍第1或2項之輻射敏感 物，其中該鹼可溶性樹脂（B )係具有1至2J (Μη係爲藉凝膠滲透層析（GPC )測量以聚 數量平均分子量）。 8 · —種製備如申請專利範圍第1至7項中 射敏感性樹脂組成物的方法，其包含將一顏料 B )鹼可溶性樹脂，（C )多官能性單體及（D 性自由基生成劑混合，該顏料分散液係藉由於 下邊碾磨邊於溶劑中混合且分散作爲著色劑（ 而製得。 9.如申請專利範圍第1或2項之輻射敏感 物，其係用於濾光片。 1 0 . —種由申請專利範圍第9項之輻射敏 成物形成之濾光片。 1 1 . 一種彩色液晶顯示裝置，其包含申請 1 0項之濾光片。 性樹脂組成 E 45,000 之 聚苯乙烯計 性樹脂組成 0 之 Mw/Mn 苯乙嫌計之 任一項之輻 分散液與（ )輻射敏感 分散劑存在 A )之顏料 性樹脂組成 感性樹脂組 專利範圍第 -71 - 200830043 七 明 說 單 簡 號 符 表 為代 圖件 表元 代之 定圖 指表 :案代 @0本本 表' ， ^ xly 定I二 ^ (( 無 無 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無[In the formulae (1) and (2), R3 is each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms or a phenyl group, and R4 and R5 are each independently hydrogen. An atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group which may be substituted or a monovalent alicyclic group having 7 to 20 carbon atoms (excluding the foregoing a cycloalkyl group, each of which is independently a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a monovalent nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or a monovalent having 4 to 20 carbon atoms. a sulfur-containing heterocyclic group, each independently being a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or having a cycloalkoxy group of 3 to 8 carbon atoms, η each independently an integer of 1 to 5, and m each independently an integer of 0 to 5, with the attached condition being (n + m )^5, and the p-system is 〇 to the integer of 6 • 69- 200830043 2 • Radiation-sensitive resin composition as in the scope of claim 1 wherein Z1 and Z2 are each a single crystal having 3 to 20 atoms consisting of carbon atoms and hetero atoms Avalent heterocyclic group, -0Ri or -N(Ri) (R2) (R1 and R2 are each as Z1 in the formula (i) and R1 and R2 in the Z2 in the formula (ii) ° 3 · as claimed The radiation-sensitive resin composition of the first or second aspect, wherein the alkali-soluble resin (B) is produced by polymerizing a polymerizable unsaturated compound using a disulfide compound represented by the following formula (3) as a molecular weight controlling agent. Resin obtained: SS z1 - c - s - s - c - Z2 (3) [In the formula (3), Z1 and Z2 are individually the same as Z1 in the formula (i) and Z2 in the formula (ii)]. 4. The radiation-sensitive resin composition of claim 3, wherein the polymerization of the polymerizable unsaturated compound for producing the alkali-soluble resin (B) is living radical polymerization. 5. The radiation-sensitive resin composition of claim 2 or 2 wherein the alkali-soluble resin (B) is (b 1 ) an unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride and at least one of (b2) An aromatic vinyl compound, an anthracene, an N-substituted maleimide, a macromonomer having a (meth)acrylinyl group at one end of a polymer molecular chain, an unsaturated carboxylic acid ester, or an unsaturated group Monomer mixture of copolymerizable unsaturated compound of aminoalkyl carboxylate, unsaturated carboxylic acid glycidyl ester, vinyl carboxylate, unsaturated ether, unsaturated decylamine and aliphatic conjugated diene-70-200830043 Copolymer. 6. The radiation sensitive substance according to claim 1 or 2, wherein the alkali-soluble resin (B) has 1, 〇〇〇3 Mw (Mw is measured by gel permeation chromatography (GPC) Average molecular weight). 7. The radiation sensitive substance according to claim 1 or 2, wherein the alkali-soluble resin (B) has 1 to 2 J (the Μη system is measured by gel permeation chromatography (GPC) to aggregate the number average molecular weight). 8 - A method for preparing a radiation-sensitive resin composition as claimed in claims 1 to 7, which comprises a pigment B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D-radical generation Mixing, the pigment dispersion is prepared by mixing and dispersing in a solvent as a coloring agent by grinding underneath. 9. The radiation sensitive substance according to claim 1 or 2 is used for filtering A filter formed by a radiation sensitive substance of claim 9 of the patent application. 1 1. A color liquid crystal display device comprising the filter of claim 10. The resin composition E 45,000 The polystyrene resin consists of 0% of the Mw/Mn benzene benzene and the radiation-sensitive dispersant (A) of the pigmented resin composition of the inductive resin group patent range -71 - 200830043 Explain that the single-character table is the map of the generation of the map. The table represents the case: @0本本表', ^ xly 定I二^ ((No no eight, if there is a chemical formula in this case, please reveal the best display) Chemical formula of the inventive feature: none
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JP4923496B2 (en) * 2005-02-18 2012-04-25 Ｊｓｒ株式会社 Radiation sensitive resin composition for color filter and color filter

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