TW200540565A - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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Publication number
TW200540565A
TW200540565A TW094116842A TW94116842A TW200540565A TW 200540565 A TW200540565 A TW 200540565A TW 094116842 A TW094116842 A TW 094116842A TW 94116842 A TW94116842 A TW 94116842A TW 200540565 A TW200540565 A TW 200540565A
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Taiwan
Prior art keywords
photosensitive resin
compound
item
group
resin composition
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TW094116842A
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Chinese (zh)
Inventor
Kazuo Takebe
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Sumitomo Chemical Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • G03F7/027—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
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G03F7/0295—Photolytic halogen compounds
    • 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
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

Abstract

A photosensitive resin composition comprising (A) a binder resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator and (D) a solvent, wherein the binder resin (A) is a copolymer obtained by copolymerizing the following (A1), (A2) and (A4) to obtain a copolymer 1, reacting the resulted copolymer 1 and (A3) at a site derived from (A4) of the copolymer 1 to obtain a copolymer 2, further, reacting the resulted copolymer 2 and (A5) to a hydroxyl group produced by reaction of (A4) and (A3) of the copolymer 1, and the photopolymerization initiator (C) is at least one compound selected from the group consisting of acetophenone-based compounds, biimidazole-based compounds, oxime-based compounds and triazine-based compounds: (A1): a compound having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and dicyclopentadiene skeleton, and an unsaturated bond in one molecule, (A2): a compound having an unsaturated bond copolymerizable with (A1) and (A4), (A3): a carboxylic acid having an unsaturated group, (A4): a compound having an unsaturated bond and an epoxy group in one molecule, (A5): an acid anhydride, wherein, (A1) to (A5) are not identical.

Description

20054罐 c 九、發明說明： 【發明所屬之技術領域】 本發明涉及一種光敏樹脂組合物。 【先前技術】 在構成諸如液晶顯示器和觸板等顯示器的渡色器和陣 列基板之間，設置有使兩基板保持間隔的隔離物(spacer)。 作為該隔離物，通常使用諸如玻璃珠、塑膠珠等的球形顆 粒0 • 但是，使用球形顆粒時，TFT元件、電極等會由於它 們在玻璃基板上的隨機散佈而受損，並且當其存在於可透 過的圖元部位時，液晶顯示元件的對比度有時會因入射光 的散射而降低。因此，作為對散佈的球形顆粒的替代，人 們提出了使用光敏性樹脂來形成隔離物。通過這種方法， 可以在任意位置形成隔離物，從而可以使上述的問題得到 解決。作為這種光敏樹脂組合物，已知的是一種含有輕射 敏感固化樹脂的隔離物形成組合物，所述輻射敏感固化樹 脂帶有（曱基）丙烯醯基和羧基（JP-A No. 2002-20442， * 第2頁左欄第2行至第3頁左欄第6行）。 但是，在輻射敏感固化樹脂中使用了異氰酸酯化合物 來引入（曱基）丙烯醯基，而在處理所得到的輻射敏感固 化樹脂及使用該樹脂的隔離物形成組合物的過程中，存在 著由異氰酸酯化合物引起的臭氣問題。 另外’當採用含有所述輻射敏感固化樹脂的樹脂組合 物形成諸如光隔離物(photo spacer)的結構時，還存在著而才 溶劑性差的問題。 7 20054賴 c 【發明内容】 本發明的目的是提供一種可形成具有優異耐溶劑性的 結構的光敏樹脂組合物。 本發明人已經通過研究發現了一種可解決上述問題的 光敏樹脂組合物，並因此發現含有一種樹脂和一種光聚合 引發劑的光敏樹脂組合物能夠解決上述的問題，而完成的 本發明。 也就是說，本發明提供以下的[1]至[14]。 [1] 一種包含（A)粘結劑樹脂，（B)可光聚合的化 合物，（C)光聚合引發劑和（D)溶劑的光敏樹脂組合物， 其中（A)是以下述方法獲得的共聚物：將下述的（A1)、 (A2)和（A4)進行共聚形成共聚物1，使得到的共聚物 1以其源自（A4)的部位與（A3)進行反應形成聚合物2， 再將得到的共聚物2和（A5)與共聚物1的（A3)及（A4) 反應形成的羥基進行反應，光聚合引發劑（C)為選自苯 乙酮基化合物、雙味嗤基(biimidazole_based)化合物、將基 (oxime-based)化合物和三嗪基(triazine-based)化合物中的 至少一種： ❿ (A1):帶有選自三環癸院骨架（tricyclodecane skeleton)和雙環戊二烯骨架（dicyclopentadiene skeleton)中 至少一種骨架的化合物’且單個分子中含有不飽和鍵’ (A2) ··帶有可與（A1)和（A4)進行共聚的不飽 和鍵的化合物， (A3) ··帶有不飽和基團的叛酸， 8 2005405ρ65〇 (A4):在單個分子中帶有不飽和鍵及環氧基的化合 物， (A5):酸酐， 其中，（A1)至（A5)是不相同的。 .20054 can c IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a photosensitive resin composition. [Prior Art] A spacer that keeps a distance between the two substrates is provided between a color filter and an array substrate constituting a display such as a liquid crystal display and a touch panel. As the separator, spherical particles such as glass beads, plastic beads, etc. are usually used. However, when spherical particles are used, TFT elements, electrodes, etc. are damaged due to their random dispersion on a glass substrate, and when they are present in When the image element is transparent, the contrast of the liquid crystal display element may decrease due to the scattering of incident light. Therefore, as an alternative to scattered spherical particles, it has been proposed to use a photosensitive resin to form a spacer. In this way, spacers can be formed at arbitrary positions, so that the problems described above can be solved. As such a photosensitive resin composition, a separator-forming composition containing a light-sensitive curing resin having a (fluorenyl) acrylic fluorenyl group and a carboxyl group (JP-A No. 2002) is known. -20442, * left line 2 on page 2 to left line 6 on page 3). However, an isocyanate compound is used in the radiation-sensitive curable resin to introduce a (fluorenyl) propenylfluorene group, and in the process of processing the obtained radiation-sensitive curable resin and a spacer-forming composition using the resin, there is an isocyanate Odor problems caused by compounds. In addition, when a resin composition containing the radiation-sensitive curable resin is used to form a structure such as a photo spacer, there is a problem that the solvent is poor. 7 20054 赖 c [Summary of the Invention] An object of the present invention is to provide a photosensitive resin composition capable of forming a structure having excellent solvent resistance. The present inventors have found a photosensitive resin composition that can solve the above problems through research, and therefore found that the photosensitive resin composition containing a resin and a photopolymerization initiator can solve the above problems, and completed the present invention. That is, the present invention provides the following [1] to [14]. [1] A photosensitive resin composition comprising (A) a binder resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a solvent, wherein (A) is obtained by the following method Copolymer: The following (A1), (A2), and (A4) are copolymerized to form copolymer 1, so that the obtained copolymer 1 reacts with (A3) to form a polymer 2 at a site derived from (A4) Then, the obtained copolymers 2 and (A5) are reacted with the hydroxyl groups formed by the reaction of (A3) and (A4) of the copolymer 1. The photopolymerization initiator (C) is selected from the group consisting of acetophenone-based compounds and diisocyanine. At least one of a biimidazole-based compound, an oxime-based compound, and a triazine-based compound: ❿ (A1): with a tricyclodecane skeleton and dicyclopentane selected from the group consisting of tricyclodecane skeleton A compound of at least one skeleton in a dicyclopentadiene skeleton, and containing an unsaturated bond in a single molecule; (A2) a compound having an unsaturated bond that can be copolymerized with (A1) and (A4), (A3 ) ·· Any acid with unsaturated group, 8 2005405ρ65〇 (A4): in a single molecule Unsaturated bond and an epoxy group-compound, (A5): acid anhydride, wherein, (A1) to (A5) is not the same. .

[2] [1]中所述的組合物，其中（A1)為選自（曱基） 丙烯酸雙環戊 S旨（dicyclopentanyl(meth)acrylate)、（曱基） 丙烯酸雙環戊烯酯(dicyclopentenyl(meth)acrylate)、（曱基） 丙 烯酸雙 環戊基 氧乙酯 ((11。>^1〇卩61^&11)4〇乂}^11}4(11^11)&(；7以6)和（曱基）丙烯酸 雙環戊烯基氧乙酯（dicyclopentenyloxyethyl(meth)acrylate) 中至少一種的化合物。 [3] [1]或[2]中所述的組合物，其中（A2)為選自苯乙 烯、甲基）丙烯酸苄酯和N-取代的順丁烯醯亞胺 (N-substituted maleimide)化合物中至少一種的化合物。 [4] [1]至[3]中任一項所述的組合物，其中（A3)為選 自丙稀酸和甲基丙烯酸中至少一種的化合物。 [5] [1]至[4]中任一項所述的組合物，其中（A4)為選 自丙烯酸縮水甘油酯(glycidyl aery late)和曱基丙烯酸縮水 甘油醋中至少一種的化合物。 [6] [1]至[5]中任一項所述的組合物，其中（A5)為選 自順丁 稀酸酐（maleic anhydride)、琥拍酸酐（Sllccinic anhydride)、衣康酸酐(itaconic anhydride)、鄰笨二曱酸針 (phthalic anhydride)、四氫化鄰苯二曱酸酐 (tetrahydrophthalic anhydride)、六氫化鄰苯二曱酸釺 9 20054 娜 (hexahydrophthalic anhydride)、甲基内亞甲基四氫化鄰苯二 甲酸酐 （methylendomethylenetetrahydrophthalic anhydride) 甲基四氫化鄰苯二甲酸酐 (methyltetrahydrophthalicanhydride)和偏苯三*甲酸酐 (trimelliticanhydride)中至少一種的化合物。 [7] [1]至[6]中任一項所述的組合物，其中通過（A4) 和（A3)進行反應形成的組成單元與全部組成單元的比值 為30-60摩爾％。 • [8]使用[1]至[7]中任一項所述的組合物形成的固化 樹脂結構。 [9] [8]中所述的固化樹脂結構，其中的結構為光隔離 物0 [10] [8]中所述的固化樹脂結構，其中的結構為絕緣 m ° ' [11] [8]中所述的固化樹脂結構，其中的結構為覆膜 (over coat) 〇 φ [12] [8]中所述的固化樹脂結構，其中的結構為用於液 晶取向控制的突出部分。 [13] 含有[8]至[12]中任一項所述固化樹脂結構的渡 色器。 “ [14] 安裝有[13]中所述濾色器的液晶顯示器。 以下將對本發明進行詳細說明。 在本發明的光敏樹脂組合物中，粘結劑樹脂（Α)、 可光聚合的化合物（Β)光聚合引發劑（C)及另外任選的 20054淑蛛 其他添加劑被溶解或分散在溶劑（D)中。 枯結劑樹脂（A)具有對光和熱作用的反應性，以及 域溶性。用於本發明的光敏樹脂組合物中的粘結劑樹脂 (A)疋以下述方法獲得的共聚物：將下述的（a〗）、（A2) 和（A4)進行共聚形成共聚物1，使得到的共聚物1以其 源自（A4)的部位與（A3)進行反應形成聚合物2，再將 得到的共聚物2和（A5)與共聚物！的（A3)及（A4) 反應形成的羥基進行反應： • (A1):帶有選自三環癸烷骨架和雙環戊二烯骨架中 至少一種骨架的化合物，且單個分子中含有不飽和鍵， (A2):帶有可與（A1)和（A4)進行共聚的不飽 和鍵的化合物， (A3):帶有不飽和基團的羧酸， (A4):在單個分子中帶有不飽和鍵及環氧基的化合 物， (A5):酸酐， φ 其中，（A1)至（A5)是不相同的。 化合物（A1)為帶有選自三環癸烷骨架和雙環戊二烯 骨架中至少一種骨架且單個分子中含有不飽和鍵的化合 物’特別要提到的是（曱基）丙烯酸雙環戊酯、（甲基） 丙稀酸雙環戊烯酯、（甲基）丙烯酸雙環戊基氧乙酯和（甲 基）、内烯酸雙環戊烯基氧乙酯等。這些化合物可以單獨使 用或組合使用。在這裏，本說明書中所述的（甲基）丙烯 曰是指丙烯酸酯和/或曱基丙烯酸酯。 20054^1 化合物（A2)帶有可與（A1)和（A4)進行共聚的 不飽和鍵’特別要提到的是不飽和羧酸的未取代或被取代 烷基酯，例如（曱基）丙烯酸甲酯、（甲基）丙烯酸乙酯、 (曱基）丙烯酸丁酯、（曱基）丙烯酸2-羥乙酯：（曱基） 丙烯酸氨乙酯； 不飽和羧酸的含脂環基(alicydie group)酯化合物，例 如（曱基）丙烯酸環戊酯、（甲基）丙烯酸環己酯、（甲 基）丙稀酸甲基環己酷、（甲基）丙稀酸環庚酯、（甲基） 丙烯酸環辛酯、（曱基）丙烯酸薄荷酯 (menthyl(meth)acrylate)、（曱基）丙烯酸環戊烯酯、（曱 基）丙烯酸環己烯酯、（曱基）丙烯酸環庚烯酯、（曱基） 丙烯酸環辛烯酯、（曱基）丙烯酸薄荷二烯酯、（甲基） 丙烯酸異冰片酯如〇1)〇111^1(11^1;11)&(^7以6)、（曱基）丙烯酸 蒎酯（pinanyl(meth)acrylate)、（曱基）丙烯酸金剛酯 (adamantly(meth)acrylate)、（甲基）丙烯酸降冰片烯酯 (norbornenyl(meth)acrylate)、（甲基）丙烯酸蒎烯酯 (pinenyl(meth)acrylate)； 乙二醇的單飽和羧酸酯化合物，例如（甲基）丙烯酸 低聚乙二醇单烧基醋（oligoethylene glycol monoalkyl(meth)acrylate)； 不飽和羧酸的含芳環酯化合物，例如（曱基）丙晞酸 苄酯（benzyl(meth)acrylate)、（曱基）丙烯酸笨氧酯 (phenoxy(meth)acrylate)； 芳族乙烯基化合物，例如苯乙烯(styrene)、α-曱基苯乙 12 20054Q縱 烯(a_methylstyrene)、α·苯基苯乙烯(a_phenylstyrene)、乙烯 基曱苯(vinyltoluene);[2] The composition described in [1], wherein (A1) is selected from the group consisting of (fluorenyl) dicyclopentanyl (meth) acrylate, (fluorenyl) dicyclopentenyl (meth ) acrylate), (fluorenyl) dicyclopentyloxyethyl acrylate ((11. > ^ 1〇 卩 61 ^ & 11) 4〇 乂) ^ 11} 4 (11 ^ 11) &(; 7 to 6) A compound of at least one of dicyclopentenyloxyethyl (meth) acrylate and (fluorenyl) acrylate. [3] The composition described in [1] or [2], wherein (A2) is A compound selected from at least one of styrene, benzyl methacrylate, and N-substituted maleimide compounds. [4] The composition according to any one of [1] to [3], wherein (A3) is a compound selected from at least one of acrylic acid and methacrylic acid. [5] The composition according to any one of [1] to [4], wherein (A4) is a compound selected from at least one of glycidyl aery late and glycidyl acrylate. [6] The composition according to any one of [1] to [5], wherein (A5) is selected from the group consisting of maleic anhydride, Sllccinic anhydride, and itaconic anhydride ), Phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic acid 9 20054 hexahydrophthalic anhydride, methylmethylenetetrahydrophthalic anhydride A compound of at least one of methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalicanhydride and trimelliticanhydride. [7] The composition according to any one of [1] to [6], wherein the ratio of the constituent units formed by the reaction of (A4) and (A3) to all the constituent units is 30 to 60 mol%. [8] A cured resin structure formed using the composition according to any one of [1] to [7]. [9] The cured resin structure described in [8], wherein the structure is a photo-isolator 0 [10] The cured resin structure described in [8], wherein the structure is an insulating m ° '[11] [8] The cured resin structure described in the above, wherein the structure is an overcoat θφ [12] [8], wherein the structure is a protruding portion used for liquid crystal alignment control. [13] A color filter containing the cured resin structure according to any one of [8] to [12]. "[14] A liquid crystal display equipped with the color filter described in [13]. The present invention will be described in detail below. In the photosensitive resin composition of the present invention, a binder resin (A), a photopolymerizable compound (B) The photopolymerization initiator (C) and other optional 20054 spider spider additives are dissolved or dispersed in the solvent (D). The deadening agent resin (A) has reactivity to light and heat, and domains Solubility. The binder resin (A) used in the photosensitive resin composition of the present invention is a copolymer obtained by: copolymerizing the following (a), (A2), and (A4) to form a copolymer 1, so that the obtained copolymer 1 reacts with (A3) to form polymer 2 at a position derived from (A4), and then the obtained copolymer 2 and (A5) and (A3) and (A4) of the copolymer! ) The hydroxyl group formed by the reaction proceeds: • (A1): a compound having at least one skeleton selected from a tricyclodecane skeleton and a dicyclopentadiene skeleton, and a single molecule contains an unsaturated bond, (A2): Compounds with unsaturated bonds that can be copolymerized with (A1) and (A4), (A3): with unsaturated groups Carboxylic acid, (A4): a compound having an unsaturated bond and an epoxy group in a single molecule, (A5): an acid anhydride, φ wherein (A1) to (A5) are different. Compound (A1) is Compounds having at least one skeleton selected from the group consisting of a tricyclodecane skeleton and a dicyclopentadiene skeleton and having an unsaturated bond in a single molecule 'are to be mentioned in particular: (fluorenyl) dicyclopentyl acrylate, (meth) propane Dicyclopentenyl dilute acid, dicyclopentyloxyethyl (meth) acrylate and (meth), dicyclopentenyloxyethyl lactone, etc. These compounds can be used alone or in combination. Here, this specification The (meth) acrylic acid in the description refers to acrylates and / or fluorenyl acrylates. 20054 ^ 1 Compound (A2) has an unsaturated bond that can be copolymerized with (A1) and (A4). Unsubstituted or substituted alkyl esters of unsaturated carboxylic acids, such as methyl (fluorenyl) acrylate, ethyl (meth) acrylate, butyl (fluorenyl) acrylate, 2-hydroxy (fluorenyl) acrylate Ethyl ester: (fluorenyl) aminoethyl acrylate; alicylic group containing unsaturated carboxylic acid (alicy die group) ester compounds such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, ( (Methyl) cyclooctyl acrylate, (menthyl (meth) acrylate), (menthyl) cyclopentenyl acrylate, (fluorenyl) cyclohexenyl acrylate, (fluorenyl) cycloheptyl acrylate Enol, (octyl) cyclooctenyl acrylate, (fluorenyl) menthyl diacrylate, isobornyl (meth) acrylate such as 〇1) 〇111 ^ 1 (11 ^ 1; 11) & (^ 7) 6), pinanyl (meth) acrylate, adamantly (meth) acrylate, norbornenyl (meth) acrylate ), Pinenyl (meth) acrylate; monosaturated carboxylic acid ester compounds of ethylene glycol, such as (oligoethylene glycol monoalkyl (meth) acrylate ) acrylate); aromatic ring-containing ester compounds of unsaturated carboxylic acids, such as (benzyl) benzyl propionate (benzyl (met h) acrylate), phenoxy (meth) acrylate; aromatic vinyl compounds, such as styrene, α-methylphenyl 12 20054Q a_methylstyrene, α · Phenylstyrene (a_phenylstyrene), vinyltoluene;

叛酸乙稀醋（carboxylic acid vinyl esters)，例如醋酸乙 稀酉旨（vinyl acetate)、丙酸乙醋（vinyl propionate) ;A 乙晞基氰化合物(vinyl cyanide compounds)，例如（曱 基）丙烯腈（(meth)acrylonitrile)、α-氣代丙烯腈 (α-chloroacrylonitrile)； N-取代順丁烯醯亞胺化合物（N-substituted maleimide)，例如 N-環己基順丁烯醯亞胺 (N-cyclohexylmaleimide)、N_ 苯基順丁浠醯亞胺 (N-phenylmaleimide) 、N-苄基順丁烯醯亞胺 (N-benzylmaleimide)等0 這些化合物可以單獨或組合使用。 作為帶有不飽和基團的羧酸（A3)，可特別提到的是 丙烯酸和甲基丙烯酸。丙烯酸和曱基丙烯酸可以單獨或組 合使用。除了丙烯酸和甲基丙烯酸，也可以使用帶有不飽 和基團的其他羧酸。作為帶有不飽和基團的其他羧酸，例 如有巴豆酸(crotonic acid)、衣康酸、順丁浠二酸(maleic acid)、反丁烯二酸(fumaric acid)等。也可以同時使用帶有 不飽和基團且在單個分子中含有經基和叛基的叛酸，例如 α-(經甲基）丙烯酸(a-(hydroxymethyl)acrylic acid)。 作為在單個分子中帶有不飽和鍵和環氧基的化合物 (A4)，可列舉（曱基）丙烯酸縮水甘油酯、（曱基）丙 烯酸β-甲基縮水甘油酯、（甲基）丙烯酸β-甲基縮水甘油 13 20054Ω5Μ 酯、（甲基）丙烯酸β_乙基縮水甘油酯、（甲基）丙烯酸 Ρ-丙基縮水甘油酯、α-乙基丙烯酸卜甲基縮水甘油酯、 基）酸3-甲基-3,4-環氧丁酯、（甲基）丙烯酸夂乙基 _3,4-裱氧丁酯、（曱基）丙烯酸4_曱基_4,5_環氧戊酯、（曱 基）丙烯酸5-甲基-5,6-環氧己酯、縮水甘油乙烯基醚等， 幸乂佳的疋（甲基）丙婦酸縮水甘油酯。Carboxylic acid vinyl esters, such as vinyl acetate, vinyl propionate; A vinyl cyanide compounds, such as (fluorenyl) propylene (Meth) acrylonitrile, α-chloroacrylonitrile; N-substituted maleimide, such as N-cyclohexyl maleimide (N -cyclohexylmaleimide), N-phenylmaleimide, N-benzylmaleimide, etc. These compounds can be used alone or in combination. As the carboxylic acid (A3) having an unsaturated group, acrylic acid and methacrylic acid can be particularly mentioned. Acrylic acid and fluorenyl acrylic acid may be used alone or in combination. In addition to acrylic and methacrylic acids, other carboxylic acids with unsaturated groups can also be used. Examples of the other carboxylic acid having an unsaturated group include crotonic acid, itaconic acid, maleic acid, fumaric acid, and the like. It is also possible to use a metabotropic acid having an unsaturated group and containing a cationic group and a cationic group in a single molecule, such as α- (hydroxymethyl) acrylic acid. Examples of the compound (A4) having an unsaturated bond and an epoxy group in a single molecule include (fluorenyl) glycidyl acrylate, (fluorenyl) β-methylglycidyl acrylate, and (meth) acrylic acid β -Methylglycidyl 13 20054Ω5M ester, β-ethylglycidyl (meth) acrylate, P-propylglycidyl (meth) acrylate, methylglycidyl-ethyl acrylate Methyl-3,4-butylene oxide, ethyl ethyl methacrylate (3,4-methyl acrylate), methyl ethyl acrylate (4-methyl acrylate) 4,5-epoxy pentyl acrylate, ( Fluorenyl) 5-methyl-5,6-epoxyhexyl acrylate, glycidyl vinyl ether, etc., and fortunately fluorene (meth) glycidyl glycidyl ester.

酸酐（Α5)是分子中含有酸酐基團的化合物，特別列 f順丁？酸酐、琥珀酸酐、衣康酸酐、鄰苯二甲酸酐、四 氮，鄰笨二甲贿、六氫化鄰笨二甲酸Sf、甲基内亞甲基 四氯化鄰笨二甲酸肝、曱基四氫化鄰笨二甲酸if和偏笨^ 甲酸酐等，較佳的是四氫化鄰笨二甲gH — 本發明中使用的粘結劑樹脂（A)是〆種通過以下方 式獲得的絲物：將（A1)、（A2)和（A4)進行共聚 形成聚合物1，將得到的共聚物1與（a3)反應形成共聚 物2，將得到的共聚物2與（A5)進行反應。 …首先，為了獲得共聚物i，將（ai)、（A2)和（A4) 進仃共聚。這種共聚是在常規條 的。例 以度計、回*冷:器'滴液漏斗上 20:心入土、（ U、（A2)和（A4)總量為〇.5至 倍的輔，並將燒瓶巾Μ氛由空氣變為氮氣。之 ^冬洛劑加熱到40至_，然後加入特定量的（A1)、 (=)和（A4)、基於（A1)、（a2)和（μ)總量為 〇旦重量倍的溶劑、基於(A1)、（A2)*(a4)總 置為0.1 S10m〇1〇/〇的聚合引發劑，例如偶氮二異丁腈、過 14 20054α 麻 入$|1_、. ·、，8小時的時間内將該溶液從滴液漏斗中加 小時。述燒瓶中’再將混合物在40^14(rc下授掉i到10 到，可將部分的或所有的聚合引發劑加入 ，瓶中或將部分的或所有的（Α1)、（Α2)和（Α4)The acid anhydride (Α5) is a compound containing an acid anhydride group in the molecule, and is particularly listed as f-cis-butyl? Acid anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrazine, o-dimethylbenzene, hexahydro-o-benzenedicarboxylic acid Sf, methylmethylenetetrachloride, o-benzenedicarboxylic acid, fluorenyl tetra Hydrogenated o-benzyl dicarboxylic acid if and meta-benzyl formic anhydride, etc., preferably tetrahydro-o-benzyl dicarboxylic acid gH — the binder resin (A) used in the present invention is a silk material obtained by: (A1), (A2), and (A4) are copolymerized to form polymer 1, the obtained copolymer 1 is reacted with (a3) to form copolymer 2, and the obtained copolymer 2 is reacted with (A5). ... First, in order to obtain copolymer i, (ai), (A2), and (A4) were copolymerized. This copolymerization is conventional. For example, in degrees, return to the cold: device 'dropping funnel 20: heart into the soil, (U, (A2) and (A4) total amount of 0.5 to times the auxiliary, and change the flask towel M atmosphere from air It is nitrogen. The dongluo agent is heated to 40 to _, and then a specific amount of (A1), (=), and (A4) is added, based on the total amount of (A1), (a2), and (μ). Solvent, based on (A1), (A2) * (a4) polymerization initiators with a total set of 0.1 S10m0 / 0, such as azobisisobutyronitrile, over 14 20054α hemp into $ | 1 _, ..., Add the solution from the dropping funnel to the hour within 8 hours. In the flask, 'add the mixture at 40 ^ 14 (rc to i to 10 to, and you can add some or all of the polymerization initiator, (A1), (Α2) and (Α4) in or in the bottle

二:j?瓶：：為了控制分子量或分子量分佈，可以使用 朴7 1本乙稀—聚體或縣化合物作為鏈轉移劑。α-甲基 :曰烯二聚體或絲化合物_量基於（Α1)爿（α3)的 =為G.GG5_5%重量。關於聚合條件，可以根據生產設備 Λ s發熱量等對加料方法和反應溫度進行適當調節。 關於源自各化合物的組成單元，基於組成上述共聚物 1的組成單域摩爾數的以下是較佳的摩爾分率。 源自（Α1)的組成單元：2至4〇m〇1% 源自（A2)的組成單元：2至95m〇1% 源自（A4)的組成單元：3至65m〇1% 上述組成單元的以下摩爾分率是更優選的。 源自（A1)的組成單元：5至35m〇1% 源自（A2)的組成單元：5至8〇m〇1〇/〇 源自（A4 )的組成單元·· 1 $至6〇m〇i% 當上述構成比處於上述範圍内時，柔順性和耐熱性優 良，且可獲得更好的主鏈聚合物。 接著’將（A3)添加到上述共聚物1中以賦予粘結劑 树月曰（A)以光/熱固化性能。 15 20054iQ5i^^c 共聚物1與（A3)的反應可在曰本專 No. 2001-咖中描述的條件下進行。具體=開=) 中的氣氛從空氣變為氮氣，將次將粍瓶 總量為_至5%重量的用概基和環 乳基的反應催化劑’例如三二甲基氨基㈣、和用量基於Two: j? Bottle :: In order to control molecular weight or molecular weight distribution, you can use Park 7 1 ethylene-polymer or county compound as a chain transfer agent. α-methyl: ene dimer or silk compound. The amount based on (A1) 爿 (α3) = G.GG5_5% by weight. Regarding the polymerization conditions, the feeding method and the reaction temperature can be appropriately adjusted according to the amount of heat generated by the production equipment Λ s. Regarding the constituent units derived from each compound, the following molar ratios based on the number of moles of the single domain of the composition constituting the above-mentioned copolymer 1 are preferable. Component units derived from (Α1): 2 to 40 〇1% Component units derived from (A2): 2 to 95 〇1% Component units derived from (A4): 3 to 65 〇1% The following molar fractions are more preferred. Component unit derived from (A1): 5 to 35 m〇1% Component unit derived from (A2): 5 to 80 m〇1〇 / 〇 Component unit derived from (A4) · 1 $ to 60 m 〇i% When the above composition ratio is within the above range, excellent flexibility and heat resistance are obtained, and a better main chain polymer can be obtained. Next, (A3) is added to the above-mentioned copolymer 1 to give the binder Shu Yue Yue (A) with light / heat curing properties. 15 20054iQ5i ^^ c The reaction of copolymer 1 and (A3) can be performed under the conditions described in Japanese Patent No. 2001-Ka. The specific = on =) atmosphere changes from air to nitrogen, and the flask will be used for a total amount of _ to 5% by weight of the reaction catalyst based on the radical and the emulsion, such as tridimethylaminofluorene, and the amount is based on

女(A1)到（Μ)總量為〇._至5〇%重量的阻聚劑，例如 ，虱酿加入到燒瓶中，在6〇至13(rc下反應i到ι〇小時， 從而使上述共聚物丨可與（A3)進行反應。對於聚合條件， 可以根據生產设備和聚合發熱量等對加料方法和反應溫度 進行適當調節。 (A3)的添加量為5」〇〇m〇1%，優選為1〇 95m〇i%， ，於由（Al)、（A2)和（A4)共聚所形成樹脂中的環 氧基（源自A4組分）。 得足夠的光固化和熱固化性能，以及獲得優異的可靠性。 接著’使上述的共聚物物2與（A5)進行反應以賦予 枯結劑樹脂（A)以域溶性。 共聚物2與（A5)的反應可在JP-A No· 2001_89533 當（A4)的組成比處於上述範圍内時，可更可取地獲 中描述的條件下進行。具體來說，將燒瓶中的氣氛從空氣 、炎為氮氣’將用量基於上述共聚物2中源自（A3)的組成 單元為5至l〇〇mol〇/〇摩爾分率的（A5)、用量基於（A1) 到（A4)總量為〇〇1至5%重量的反應催化劑，例如三乙 胺加入到燒瓶中，在60至130°C下反應1到10小時，從 2005m^c 而使上述共聚物2可與（A5)進行反應 可以根據生產設備和聚合發熱量等對;料=聚合條件， 進行適當調節。 卞石法和反應溫度 (A5)的添加量為5-1〇〇m〇1%， 基於共聚物2中的_基（源自A3組^為1祕_%， 上述粘結劑樹脂（A)基於聚苯 :子量優選為3，_至晴，更優=重句The total amount of female (A1) to (M) is from .0 to 50% by weight of the polymerization inhibitor. For example, lice brew is added to the flask, and the reaction is performed at 60 to 13 (rc for i to ι0 hours, so that The above copolymer 丨 can react with (A3). For the polymerization conditions, the feeding method and reaction temperature can be appropriately adjusted according to the production equipment and the amount of heat of polymerization, etc. (A3) The addition amount is 5 ″ 〇〇〇〇〇 %, Preferably 1095 moi%, of epoxy groups (derived from A4 component) in the resin formed by copolymerization of (Al), (A2), and (A4). Sufficient photo-curing and heat-curing Performance, and obtain excellent reliability. Next, the above-mentioned copolymer 2 and (A5) are reacted to impart domain solubility to the curative resin (A). The reaction of copolymer 2 and (A5) can be performed in JP- A No. 2001_89533 When the composition ratio of (A4) is within the above range, it is more preferable to perform under the conditions described in the above. Specifically, the atmosphere in the flask is changed from air, inflammation to nitrogen, and the amount is based on the above copolymerization. The component unit derived from (A3) in (2) is (A5) in a molar fraction of 5 to 100 mol / 0, and the amount is based on (A1) to (A 4) A reaction catalyst with a total amount of 0.001 to 5% by weight, for example, triethylamine is added to the flask, and the reaction is performed at 60 to 130 ° C for 1 to 10 hours, so that the above copolymer 2 can be reacted with (A5) The reaction can be performed according to the production equipment, the amount of heat generated during polymerization, etc .; material = polymerization conditions, which can be appropriately adjusted. The addition of the vermiculite method and the reaction temperature (A5) is 5 to 100%, based on copolymer 2 _ Group (derived from the A3 group ^ is 1% _%, the above-mentioned binder resin (A) is based on polybenzene: preferably the amount is 3, _ to sunny, more excellent = heavy sentence

==八严聚苯乙稀校準基準的重均分Γ量 處於上相_時’制性優異，在顯影中膜不易發生縮 二取:非曝光部分在顯影中呈現出極好的透明性，這是更 枯結劑樹脂（A)的分子量分佈[重均分子量（Mw) / 數均分：量(Μη)]優選為L5至6.0,更優選為J 8至4〇。 當分子量分佈處於上述範圍内時，顯影性極好，這是更可 取的。 本發明中光敏樹脂組合物中所使用的粘結劑樹脂（A) 的含：!：通常為5-90wt%，優選為10-70wt%的重量分率，基 於光敏樹脂組合物中的固體組分。當粘結劑樹脂（A)的 含量處於上述範圍内時，在顯影劑中的溶解性充足，在非 曝光部分的基板上不易產生顯影殘渣，在顯影中膜不易發 生縮小’並且有助於非曝光部分在顯影中呈現出極好的透 明性，這是更可取的。 本發明中使用的粘結劑樹脂在主鏈上沒有羧基，在側 鏈上帶有（曱基）丙烯酸基，其溶液粘度低，易於操作。 17 200540)5 故 本發明的光敏樹脂組合物中所使用的可光聚合化合物 (B)包括單官能性單體、雙官能性單體或其他多官能性 單體。 單B此性單體的具體例子包括丙稀酸壬基笨基卡必醇 酯、丙烯酸2-羥基苯氧基丙酯、丙烯酸2_乙基己基卡必 醇酯、丙烯酸2_羥乙酯、N-乙烯基吡咯烷酮等。 雙官能性單體的具體例子包括二（甲基）丙烯酸丨，^ 己一醇酯、二（甲基）丙烯酸乙二醇酯、二（甲基）丙烯 修 酸新戊二醇酉旨、二（甲基）丙稀酸三甘醇酯、雙齡A的雙 (丙烯醯氧乙基）醚、二（甲基）丙烯酸3_曱基戊二醇酯 等。 其他多官能性單體的具體例子包括三（甲基）丙烯酸 二經甲基丙烧酯、三（甲基）丙烯酸季戊四醇酯、四（甲 基）丙烯酸季戊四醇酯、五（曱基）丙烯酸二季戊四醇酯、 六（曱基）丙烯酸二季戊四醇酯、三（曱基）丙烯酸季戊 四醇酯與酸酐的反應產物、五（甲基）丙烯酸二季戊四醇 φ 酯與酸酐的反應產物等。其中，雙官能性或更多官能性的 單體是優選的。 可光聚合化合物（B)的含量優選為1至70重量份， 更優選為5至60重量份，基於光敏樹脂組合物中粘結劑樹 脂（A)和可光聚合的化合物（B)的總量100重量份。當 可光聚合的化合物（B)的含量處於上述範圍内時，圖元 部位的強度、平滑性和可靠性趨向於是優異的，這是更可 取的。 200541½^ 作為本發明中含有的光聚合引發劑（c)，優選使用 的是苯乙酮基、雙咪唑基、肟基、三嗪基引發劑及其混合 物。通過組合使用上述的光聚合引發劑和光聚合引發助劑 (c-l)，光敏樹脂組合物具有更高的敏感性，並且提高了 使用違組合物形成結構的生產率，這是更可取的。但是， 當光聚合引發助劑（c_l)的吸收波長位於比光聚合引發劑 (C)吸收波長更長的一侧時，所形成膜呈現出更低的透 射性，因而可以按不損害本發明效果的量進行使用。 • 上述苯乙酮基化合物包括二乙氧基苯乙酮、2_羥基 甲基-1-苯基丙烷_1_酮、苄基二甲縮醛苯乙酮、2_羥基 -l-[4-(2-羥乙氧基)笨基]_2_甲基丙烷β1_酮、丨_羥基環己基苯 基酮、2-曱基曱基苯硫基)-2-嗎啉代丙烷-1-酮、2-苄 基二甲氨基小(4-嗎啉代笨基)丁烧小_，特別要提到的 是以下化合物的低聚物： 2_(2_甲基节基>2-二甲氨基小(4_嗎啉代苯基>丁酮、 2-(3·曱基节基)_2•二甲氨基小(心嗎啉代苯基>丁酮、 φ 1♦甲基节基)-1-二甲氨基小(4-嗎啉代苯基)_ 丁酮、 2-(2-乙基节基)_2-二甲氨基小(4_嗎啉代苯基)_丁酮、 2_(2_丙基节基)_1二甲氨基小(4·嗎啉代苯基)-丁酮、 2-(2-丁基苄基)-2-二甲氨基_丨_(4_嗎啉代苯基> 丁酮、 2_(1,3-二甲基苄基)-2-二曱氨基-1_(4-嗎啉代苯基)-丁 酮、 19 1 _(2,4-二甲基苄基)-2-二甲氨基-1-(4-嗎啉代苯基)-丁 酉同、 20054Q 狐 2-(2-氯代节基)-2-二甲氨基-1-(4-嗎琳代苯基)-丁嗣、 2-(2-溴代苄基)-2-二曱氨基小(4-嗎啉代苯基)·丁酮、 2-(3•氣代节基)-2-二曱氨基-1-(4•嗎琳代苯基)-丁 S同、 2_(4_氣代苄基)-2-二曱氨基小(4-嗎啉代苯基)丁酮、 2-(3-溴代苄基)-2-二甲氨基-1-(4-嗎啉代苯基)-丁酮、 2-(4->臭代节基)-2-二甲氨基-1-(4-嗎琳代苯基)-丁嗣、 2·(2-甲氧基节基)-2-二曱氨基-1 -(4•嗎琳代苯基)-丁 酮、 鲁 2-(3-曱氧基节基)-2-二曱氨基-1-(4-嗎淋代苯基)-丁 酮、 2-(4-甲氧基节基)-2-二曱氨基· 1 -(4-嗎琳代苯基)-丁 酮、 2-(2-曱基-4-曱氧基节基)-2-二曱氨基-1 -(4-嗎琳代苯 基)-丁酮、 2-(2-曱基-4-溴代苄基)-2-二曱氨基-1-(4-嗎啉代苯基)-丁酮、 $ 2-(2溴_4_曱氧基苄基)-2-二曱氨基小(4-嗎啉代苯基)- 丁酮、 2-羥基-2-曱基-l-[4-(l-曱基乙烯基)苯基]丙烷-1-酮等。 上述聯咪唑化合物包括2,2’-雙(2-氯代苯基)_4,4’，5,5’_ 四苯基聯咪唑、2,2’-雙(2,3_二氯代苯基)-4,4’，5,5’_四苯基聯 咪唑（參見，例如 JP_A No· 6-75372、JP-A No· 6-75374 等）、 2,2’-雙(2-氯代苯基)-4,4’，5,5’_四苯基聯咪唑、2,2’-雙(2_氣 代苯基)_4,4’，5,5’四(烷氧基苯基)聯咪唑、2,2’-雙(2-氯代苯 2005495^ 基M’4 ,5,5 -四（二炫氧基苯基)聯咪唑、2,2，_雙(2_氯代苯 基）4’4 ’5’5 _四(二烧氧基苯基)聯0米唾（參見，例如jp_B N〇. 48-38403、爪A N。62_1742()4 等）、其中 4,4，，5,5、位苯基 被烷氧羰基取代的聯咪唑（參見，例如JP-A Να 7-10913 等）等，優選提到的是2,2，·雙(2-氣代苯基)-4,4，，5,5，-四苯 基聯咪姊2,2，_雙(2,3_二滅苯基)_4,4，，5,5，_四苯基聯喃 口坐〇 上述職合物包括0_乙氧減_α_氧亞氨基·^苯基-丙 烧-1·酮、式u)的化合物和式⑻的化合物等。== The weight-averaged weighting of the Ba-Yan polystyrene calibration standard is superior when the amount is in the upper phase, and the film is not easy to shrink during development: the non-exposed part shows excellent transparency during development. This is the molecular weight distribution [weight average molecular weight (Mw) / number average: amount (Mn)] of the more deadening agent resin (A), preferably from L5 to 6.0, and more preferably from J 8 to 40. When the molecular weight distribution is within the above range, developability is excellent, which is more preferable. The binder resin (A) used in the photosensitive resin composition of the present invention contains:!: Usually a weight fraction of 5-90 wt%, preferably 10-70 wt%, based on the solid group in the photosensitive resin composition Minute. When the content of the binder resin (A) is within the above range, the solubility in the developer is sufficient, the development residue is not easily generated on the substrate of the non-exposed portion, and the film is not easily reduced during development. The exposed portion exhibits excellent transparency during development, which is more preferable. The binder resin used in the present invention has no carboxyl group on the main chain and (fluorenyl) acrylic group on the side chain, and its solution viscosity is low and easy to handle. 17 200540) 5 Therefore, the photopolymerizable compound (B) used in the photosensitive resin composition of the present invention includes a monofunctional monomer, a difunctional monomer, or another polyfunctional monomer. Specific examples of the mono-B monomer include nonylbenzylcarbitol acrylate, 2-hydroxyphenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like. Specific examples of the difunctional monomer include di (meth) acrylic acid, hexyl alcohol ester, ethylene glycol di (meth) acrylate, di (meth) acrylic acid neopentyl glycol, and Triethylene glycol (meth) acrylic acid, bis (acryloxyethyl) ether of age A, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of other polyfunctional monomers include diacrylic acid tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. Ester, dipentaerythritol hexa (fluorenyl) acrylate, reaction product of pentaerythritol tri (fluorenyl) acrylate and anhydride, reaction product of dipentaerythritol penta (meth) acrylate and anhydride, etc. Of these, difunctional or more functional monomers are preferred. The content of the photopolymerizable compound (B) is preferably 1 to 70 parts by weight, and more preferably 5 to 60 parts by weight, based on the total of the binder resin (A) and the photopolymerizable compound (B) in the photosensitive resin composition. The amount is 100 parts by weight. When the content of the photopolymerizable compound (B) is within the above range, the strength, smoothness, and reliability of the picture element portion tend to be excellent, which is more preferable. 200541½ ^ As the photopolymerization initiator (c) contained in the present invention, acetophenone-based, bisimidazolyl-based, oxime-based, triazine-based initiators, and mixtures thereof are preferably used. By using the above-mentioned photopolymerization initiator and photopolymerization initiation aid (c-1) in combination, the photosensitive resin composition has higher sensitivity, and the productivity of forming a structure using the composition is improved, which is more preferable. However, when the absorption wavelength of the photopolymerization initiation aid (c_l) is located on a side longer than the absorption wavelength of the photopolymerization initiator (C), the formed film exhibits lower transmittance, so that the present invention may not be impaired. The amount of effect is used. • The above acetophenone-based compounds include diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropane_1_one, benzyldimethylacetal acetophenone, 2-hydroxy-l- [4 -(2-hydroxyethoxy) benzyl] -2-methylpropane β1_one, 丨 _hydroxycyclohexylphenyl ketone, 2-fluorenylfluorenylphenylthio) -2-morpholinopropane-1- Ketones, 2-benzyldimethylamino-small (4-morpholino-benzyl) butyrate, especially the oligomers of the following compounds: 2- (2-methylbenzyl)> 2-di Methylamino small (4-morpholinophenyl) butanone, 2- (3.fluorenylbenzyl) _2 • dimethylamino small (cardiomorpholinophenyl) butanone, φ 1 ) -1-dimethylamino small (4-morpholinophenyl) _butanone, 2- (2-ethylbenzyl) _2-dimethylamino small (4-morpholinophenyl) _butanone , 2- (2-propylbenzyl) _1dimethylamino small (4-morpholinophenyl) -butanone, 2- (2-butylbenzyl) -2-dimethylamino_ 丨 _ (4_ Morpholinophenyl> butanone, 2- (1,3-dimethylbenzyl) -2-diamidoamino-1_ (4-morpholinophenyl) -butanone, 19 1_ (2,4 -Dimethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 20054Q fox 2- (2-chlorobenzyl) -2-dimethylamino-1- (4- Morinyl phenyl) -butyridine, 2- (2-bromobenzyl) -2-diamidoamino small (4-morpholinophenyl), butanone, 2- (3, azabenzyl) 2-Diamidoamino-1- (4 • morpholinophenyl) -butane-S, 2- (4- 4-aminobenzyl) -2-diamidoamino (4-morpholinophenyl) butanone , 2- (3-bromobenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2- (4- > benzyl) -2-dimethyl Amino-1- (4-morpholinophenyl) -butane, 2 (2-methoxybenzyl) -2-difluorenamino-1-(4-morpholinophenyl) -butanone, 2- (3-Methoxybenzyl) -2-difluorenylamino-1- (4-morpholinophenyl) -butanone, 2- (4-methoxybenzyl) -2-difluorenylamino 1- (4-morpholinophenyl) -butanone, 2- (2-fluorenyl-4-methoxybenzyl) -2-diamidoamino-1-(4-morpholinophenyl) -Butanone, 2- (2-fluorenyl-4-bromobenzyl) -2-diamidoamino-1- (4-morpholinophenyl) -butanone, $ 2- (2bromo_4_ (Methoxybenzyl) -2-diamidoamino small (4-morpholinophenyl) -butanone, 2-hydroxy-2-amidino-l- [4- (l-fluorenylvinyl) phenyl ] Propane-1-one, etc. The above biimidazole compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'_tetraphenylbiimidazole, 2,2'-bis ( 2,3_ Chlorophenyl) -4,4 ', 5,5'_tetraphenylbiimidazole (see, for example, JP_A No. 6-75372, JP-A No. 6-75374, etc.), 2,2'-bis ( 2-Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2_airophenyl) _4,4', 5,5'tetra (alkane) Oxyphenyl) biimidazole, 2,2'-bis (2-chlorobenzene 2005495 ^ yl M'4,5,5-tetrakis (dihydroxyoxyphenyl) biimidazole, 2,2, _bis ( 2-Chlorophenyl) 4'4'5'5_tetrakis (dialkyloxyphenyl) diamine (see, for example, jp_B No. 48-38403, Claw AN). 62_1742 () 4, etc.), in which 4,4,5,5, biphenylazoles in which the phenyl group is substituted with an alkoxycarbonyl group (see, for example, JP-A Να 7-10913, etc.), etc., preferably 2, 2, · bis (2-Arophenyl) -4,4,5,5, -tetraphenylbiimide 2,2, _bis (2,3_difenyl) -4,4 ,, 5,5, _tetraphenyl hydrazine. The above compounds include 0_ethoxyminus_α_oxyimino. ^ Phenyl-propan-1.one, a compound of formula u), and Compounds etc.

苯基Μ 3 5 i 括2,4-雙(三氯甲基)-6-(4_甲氧基 基H 3 5, i #二嗪、2,4_雙（三氣曱基）-6-(4-曱氧基萘 雙(三，4_雙(三氣甲基外胡椒基-1，3,5·三嗪、2,4_ 氯曱Μ ^)_6私甲氧基苯乙稀基)_U，5·三嗪、2,4·雙(三 雙(三ϋ(5_甲基外_2_取代)乙烯基H，3,5-三嗓、2,4· 雙(三氣甲夫喃取代）乙婦基]-1,3,5_三。秦、2,4-三嗪、2 4土雄rf_(4·二乙氨基_2_甲基苯基）乙烯基]_1，3,5· 基H，3,5^嗪等二。氣甲基)-6·[2·(3,4·二甲氧基笨基）乙稀 的光聚二丨：：知害本發明效果的量同時使用本領域常用 "’例如可提到諸如安息香基化合物、苯曱 21 20〇54_1 酮基化合物、噻噸酮基化合物、蒽基化合物等的光聚合引 發劑。Phenyl M 3 5 i includes 2,4-bis (trichloromethyl) -6- (4-methoxyl H 3 5, i #diazine, 2,4_bis (trifluoromethyl) -6 -(4-Methoxynaphthalene bis (tri, 4-bis (tris-methylmethylpiperinyl-1,3,5 · triazine, 2,4-chlorochloromethyl ^) _ 6) ) _U, 5 · triazine, 2,4 · bis (tris (bis (tris (5_methylex_2_2 substituted) vinyl H, 3,5-tris, 2,4 · bis (trifluoromethyl Furan substitution) ethynyl] -1,3,5_tri. Qin, 2,4-triazine, 2 4 androgen rf_ (4 · diethylamino_2_methylphenyl) vinyl] _1, 3,5 · group H, 3,5 ^ azine and other two. Gas methyl) -6 · [2 · (3,4 · dimethoxybenzyl) ethene photopolymerization 丨 :: harm the present invention The amount of the effect is concurrently used with "" 'for example, a photopolymerization initiator such as a benzoin compound, a benzophenone 21 2054_1 ketone compound, a thioxanthone compound, an anthracene compound, and the like can be mentioned.

更具體來說，下面提到的化合物，這些化合物可以單 獨或組合使用。 A 上述安息香基化合物的例子包括安息香、安息香甲基 醚、安息香乙基醚、安息香異丙基醚、安息香異丁基醚等。 上述苯曱酮基化合物的例子包括苯甲酮、〇-苯曱醯苯 甲酸甲酯、4-苯基苯甲酮、硫化4-苯曱醯-4，·曱基聯苯、 3,3’，4,4’-四(叔丁基過氧羰基)苯曱酮、2,4,6-三曱基苯曱酮 等。 上述噻噸酮基化合物的例子包括2-異丙基ϋ塞噸酮、4-異丙基噻噸酮、2,4-二氯代噻噸酮、2,4_二乙基噻噸酮、卜 氣-2_丙氧基嘆嘲酮等。 上述蒽基化合物包括9,10-二曱氧基蒽、2-乙基-9，1〇-二曱氧基蒽、9，10-二乙氧基蒽、2-乙基-9，10-二乙氧基蒽等。 另外’可以同時使用2,4,6-三曱基苯曱醯聯苯膦氧化 ^ 丁基2乳°丫 σ疋嗣、2·乙基葱酿、聯苯酿、9,1 〇-菲酿、 ^月祕b、甲基笨基乙_、二茂鈦化合物等作為光聚合引 發劑。 使用Γϋ有可引起鍵轉移的基團的光聚合引發劑’可以 劑。那』^田述在日本專利公開ν〇· 2〇02-544205中的引發 可以具有可弓丨起鍵轉移的基團的上述光聚合引發劑’ lJ ’例如下式（2)至（7) 的那些化合物。 22 2〇〇54_i H^COOC Hz C·More specifically, the compounds mentioned below can be used alone or in combination. A Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like. Examples of the benzophenone-based compound include benzophenone, 0-benzophenone benzoate, 4-phenylbenzophenone, 4-benzopyrene-4, fluorenylbiphenyl, 3,3 ' , 4,4'-tetrakis (t-butylperoxycarbonyl) benzophenone, 2,4,6-trifluorenylbenzophenone and the like. Examples of the above-mentioned thioxanthone-based compounds include 2-isopropylxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, Buqi-2_propoxy sigmazone and so on. The anthracene-based compound includes 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10- Diethoxyanthracene and the like. In addition, you can use 2,4,6-trimethylphenylphenyl biphenylphosphine oxidation at the same time butyl 2 milk ° σ σ 疋 嗣, 2 ethyl onion, biphenyl, 9, 10-phenanthrene As a photo-polymerization initiator, yttrium b, methylbenzyl ethyl, titanium diocene compound, and the like. A photopolymerization initiator ' which has a group capable of causing a bond transfer in? Is used. That is, the above-mentioned photopolymerization initiator '1J', which is initiated in Japanese Patent Laying-Open No. 002.02-544205, which may have a group capable of bond transfer, for example, the following formulae (2) to (7) Of those compounds. 22 2〇〇54_i H ^ COOC Hz C ·

H C4He—5—CHz —CHr» CH3 HVL—-〇XpN: C4H9—3—CHZ H CHaH C4He—5—CHz —CHr »CH3 HVL—-〇XpN: C4H9—3—CHZ H CHa

Ha\/=(Ha \ / = (

-S-S

CHa ch3 一〒一 f CHa (S)CHa ch3 one by one f CHa (S)

h3cooc _c_ h2 ⑹ CHa CHah3cooc _c_ h2 ⑹ CHa CHa

H^\ c-c- H3COOC Hz S-fCH女s—卜 j/ 1 i忾、CH， (7) 上述具有可引起鏈轉移的基團的光聚合引發劑可以用 作共聚物1的構成成分（A2) 1 (A2)獲得触結劑樹 脂（A)可以被組合用於本發明的枯結劑樹脂中。 使用還==丨發助劑(c_1)與光聚合引發劑組合 ΪΓ 劑，胺化合物和叛酸化合物是優 1 ’作接化合物，純化合物 ===(叫的吸收波長位於比光聚合二劑二 收波長更長的，時，所形賴呈現出更低的透射性， 23 20054Q縱 因而可以扣不損害本發明效果的量進行使用。 一光$合引發助劑的具體例子包括諸如三乙醇胺、甲基 二乙醇胺、三異丙醇胺等的脂肪胺化合物、和諸如私二$ 氨基苯甲酸甲酯、4-二甲氨基苯甲酸乙酉旨、4·二 甲酸異戊醋、4-二甲氨基苯甲酸2_乙基己醋、苯甲：:: 甲氨基乙酯、N，N-二甲基對甲苯胺、4,4，_雙（二甲氨美^ 苯曱嗣（類名，·米希勒酮）、4,雙(二乙氨基)笨甲^ 芳胺化合物。 ' • 作為上述的羧酸化合物，可提到芳雜乙酸，例如苯基 硫代乙酸、甲苯基硫代乙酸、乙苯基硫代乙酸、甲基乙^ 基硫，乙酸、二甲基苯基硫代乙酸、甲氧基苯基硫代乙酸、 一甲氧基苯基硫代乙酸、氯代苯基硫代乙酸、二氯代苯基 硫代乙酸、N-苯基甘氨酸、苯氧基乙酸、萘基硫代乙酸、 N-萘基甘氨酸、萘氧基乙酸等。 光聚合引發劑（C)的含量優選為oj-40重量份，更 優選為1-30重量份，基於粘結劑樹脂（A)和可光聚合化 合物（B)總量的1〇〇重量份。 當使用光聚合引發助劑（C-1)時，其含量優選為01-50 重量份，更優選為0.1-40重量份，基於上述基準。 當光聚合引發劑（C)的含量處於上述範圍内時，光 敏樹脂組合物具有高敏感性，由上述光敏樹脂組合物形成 的圖元部位的強度和上述圖元表面的平滑性和可靠性趨向 於是優異的，這是更可取的。除了上述的條件，當光聚合 引發劑（C-1 )的量處於上述範圍内時，所得到的光敏樹脂 24 20〇54Q^c ΐίί具有高㈣性’並且有麟仙上述光敏樹脂組合 ^結構基板的生產率得到提高，這是更可取的。 本發明的光敏樹脂組合物含有溶劑⑼。作為溶劑 溶劑。’可以使用絲樹餘合物領域巾使_洛種有機 、 等； 子包括乙二醇單絲轉，例如乙二醇單甲基 -醇單乙細、乙二醇單丙基㈣、乙二醇單丁基鍵H ^ \ cc- H3COOC Hz S-fCH Female s—Buj / 1 i 忾, CH, (7) The above-mentioned photopolymerization initiator having a group capable of causing chain transfer can be used as a constituent of copolymer 1 (A2 ) 1 (A2) Obtaining a caking agent resin (A) can be used in combination in the caking agent resin of the present invention. Use also == 丨 hair auxiliaries (c_1) combined with photopolymerization initiator ΪΓ agent, amine compounds and acid acid compounds are excellent 1 'as the compound, pure compounds === (called absorption wavelength is located in the photopolymerization two agents When the second harvest wavelength is longer, it has a lower transmission, so it can be used in an amount that does not impair the effect of the present invention. Specific examples of the photoinitiator include triethanolamine , Fatty amine compounds such as methyldiethanolamine, triisopropanolamine, etc., and methyl diaminobenzoate, 4-dimethylaminobenzoate ethyl acetate, isoamyl diacetate, 4-dimethylformate Aminobenzoic acid 2-ethylhexyl vinegar, benzyl ::: methylaminoethyl, N, N-dimethyl-p-toluidine, 4,4, _bis (dimethylaminomethanil ^ phenylhydrazone (class name, · Michler's ketone), 4, bis (diethylamino) benzylamine compounds. '• As the carboxylic acid compounds mentioned above, aromatic acetic acids such as phenylthioacetic acid and tolylthioacetic acid can be mentioned. , Ethylphenyl thioacetic acid, methyl ethyl thiosulfate, acetic acid, dimethylphenyl thioacetic acid, methoxyphenyl thioacetic acid Monomethoxyphenyl thioacetic acid, chlorophenyl thioacetic acid, dichlorophenyl thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, Naphthyloxyacetic acid, etc. The content of the photopolymerization initiator (C) is preferably oj-40 parts by weight, more preferably 1-30 parts by weight, based on the total amount of the binder resin (A) and the photopolymerizable compound (B) When using the photopolymerization initiation aid (C-1), its content is preferably from 01 to 50 parts by weight, more preferably from 0.1 to 40 parts by weight, based on the above criteria. When the photopolymerization initiator ( When the content of C) is within the above range, the photosensitive resin composition has high sensitivity, and the strength of the graphic element portion formed from the photosensitive resin composition and the smoothness and reliability of the surface of the graphic element tend to be excellent, which is More preferable. In addition to the above conditions, when the amount of the photopolymerization initiator (C-1) is within the above range, the obtained photosensitive resin 24 20〇54Q ^ c ΐίί has the above-mentioned photosensitive properties of Linxian The productivity of the resin combination ^ structural substrate is improved, which is more possible The photosensitive resin composition of the present invention contains a solvent ⑼. As a solvent solvent. 'You can use silk tree residues in the field to make organic organic, etc .; including ethylene glycol monofilament, such as ethylene glycol monomethyl -Alcohol monoethyl ether, ethylene glycol monopropyl hydrazone, ethylene glycol monobutyl bond

醇n、二乙二醇二丙基醚、二乙二醇二丁細等； 溶纖劑：：乙酸醋，例如甲基溶纖軸^ r、=擇二醇絲鍵乙酸酯，例如丙二醇單甲基鱗乙酸 “氧；ϋ早乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、乙 甲乳丁酉日、乙酸甲氧戊酯等； 芳烴，例如苯、甲苯、二甲苯、均三甲苯·Alcohol n, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc .; Cellosolve: acetic acid vinegar, such as methyl cellulose fiber axis ^ r, = selective glycol silk bond acetate, such as propylene glycol Monomethylphosphonic acid "oxygen; Isotaya ethyl ether acetate, propylene glycol monopropyl ether acetate, methyl ethyl butyl butyrate, methoxypentyl acetate, etc .; aromatic hydrocarbons, such as benzene, toluene, xylene, Xylene

環二例如甲乙明、丙明、甲基“甲基異丁基明、 例如乙醇、丙醇、丁醇、已醇、環己醇、乙二醇、 甘油等； ，’例如3-乙氧丙酸乙酯、3-甲氧丙酸甲酯等； 環酯，例如γ-丁内酯等。 從塗布性和乾燥性的觀點來看，在上述溶劑中，優選 提到的是沸點在··20(Γ(：的有機溶劑，更優選提到的是 25 20054曝。c 烷撐二醇烷基醚乙酸酯、酮和諸如3-乙氧丙酸乙醋及3 甲氧丙酸甲酯的酯，特別優選提到的是丙二醇單曱美鱗乙 酸酯、丙二醇單乙基醚乙酸酯、環己酮、3_乙氧丙酸 和3-甲氧丙酸甲酯。 我 這些溶劑（D)可以單獨或組合使用。 在本發明的光敏樹脂組合物中，溶劑（D)的含旦、 常為60-90wt%，優選為70_85wt。/。的重量分率，美二=通 樹脂組合物。當溶劑⑼的含量處於上述範圍二時^ 使用塗布設備進行塗敷時的塗布性趨向是優異的 布設備為例如旋塗機、旋縫塗布機、縫塗機 ^ 模塗機、幕簾流動塗布機）、喷墨器等。另于也％為 如果需要’在本發明的光敏樹脂組合物中還可以 使用添加劑㈤，例如填料、其他聚合物化合物、= ^性f、枯接促進劑、抗氧劑、紫外線吸收劑、防凝 料、凝結劑、鏈轉移劑等。 方疑…材 ，為填料’例如有破璃、二氧化梦、氧化 他聚合物化合物的例子包括产押 酿胺亞胺等的固化樹脂、孰^^日、順丁歸 聚氨酯等。 心聚丙烯酸氟代烷基酯、聚酯、 如可:生：可2用可商購的表面活性劑’例 離子美、主、、知基、陽離子基、陰離子基、非 上述^ m、面活性劑等’它們可以單獨或組合使用。 上述表面活性劑的例子包括聚氧乙稀燒細、聚氧乙烯炫 26 200540^ 基苯基醚、聚乙二醇二酯、脫水山梨醇脂肪酸酯、脂肪酸 改性的聚酯、叔胺改性的聚氨酯、聚乙烯亞胺等，還有商 品名為 KP(由 Shin_Etsu Chemical Co· Ltd·製造）、Polyflow (由 Kyoei Kagaku Κ· Κ·製造）、Eftop(由 Tochem Products Κ· Κ·製造）、Magafac (由 Dainippon Ink & Chemical Inc· 製造）、Fluorad (由 Sumitomo 3M 製造）、Asahiguard、 Surflon(由 Asahi Glass Co· Ltd·製造）、Solsperse(由 Zeneca 製造）、EFKA (由 EFKA CHEMICALS 製造）、PB821 (由AjimonotoCo.Inc·製造）等的產品。 粘接促進劑的具體例子包括乙烯基三曱氧基矽烷、乙 烯基三乙氧基矽烷、乙烯基三(2_甲氧基乙氧基)矽烷、Ν-(2· 氨乙基)-3-氨丙基曱基二曱氧基矽烷、ν·(2-氨乙基)-3-氨丙 基二曱乳基石夕烧、3-氣丙基三乙氧基石夕烧、3-環氧丙氧丙 基三甲氧基矽烷、3-環氧丙氧丙基甲基二曱氧基矽烷、 2-(3,4-環氧環己基）乙基三甲氧基矽烷、3-氣丙基甲基二曱 氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯基丙基 三甲氧基矽烷、3-酼丙基三曱氧基矽烷等。 抗氧劑的具體例子包括2,2，-硫雙(4-曱基-6-叔丁基笨 盼）、2,6-二叔丁基-4_曱基苯基等。 紫外線吸收劑的具體例子包括2-(3-叔丁基-2-羥基_5-曱基苯基)_5_氣代苯並三唑、烷氧基苯甲酮等。 凝結劑的具體例子包括聚丙烯酸鈉等。 鏈轉移劑包括十二烷硫醇、2,4-二苯基-4-曱基-1-戊稀 等0 27 20054〇m 本發明的光敏樹脂組合物貯存後的粘度與貯存前的枯 度相比變化小，這是更可取的。 本發明的光敏樹脂組合物可以通過例如混合上述的 (A) _ (D)進行製備，如果需要，可以按任意^的順序混 合。 、作Cyclodi, such as methyl ethyl amine, propyl amine, methyl "methyl isobutyl amine, such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, etc .; 'e.g. ethyl 3-ethoxypropionate Esters, methyl 3-methoxypropionate, etc .; cyclic esters, such as γ-butyrolactone, etc. From the viewpoints of coating properties and drying properties, among the solvents mentioned above, it is preferable to mention a boiling point of ·· 20 ( Γ (: organic solvent, more preferably mentioned is 25 20054 exposure. C alkylene glycol alkyl ether acetates, ketones and esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate Of particular mention are propylene glycol monoammonium acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionic acid and methyl 3-methoxypropionate. These solvents (D ) Can be used singly or in combination. In the photosensitive resin composition of the present invention, the solvent (D) contains denier, usually 60-90 wt%, preferably 70-85 wt%. When the content of the solvent ⑼ is in the above-mentioned range II ^ The coatability when coating with a coating device tends to be excellent The cloth equipment is, for example, a spin coater, a spin coat Machine, slit coater ^ die coater, curtain flow coater), inkjet, etc. In addition, it is also possible to use additives ㈤, such as fillers, other polymerization, in the photosensitive resin composition of the present invention if necessary. Chemical compounds, organic compounds, anti-fouling accelerators, antioxidants, ultraviolet absorbers, anti-coagulants, coagulants, chain transfer agents, etc. It is suspected that ... materials, such as fillers, have broken glass, dioxide dreams, Examples of oxidized polymer compounds include cured resins such as imine and imine, urethane, polybutadiene polyurethane, etc. Heart polyfluoroalkyl acrylates, polyesters, such as: raw: can be used for two purposes Commercially available surfactants, such as ionic beauty, main, amine, cationic, anionic, non-mentioned, surfactants, etc., can be used alone or in combination. Examples of the above-mentioned surfactants include polyoxygen Ethylene burned fine, polyoxyethylene fluorinated 26 200540 ^ phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, polyethyleneimine, etc. , And the trade name is KP (by Shin_Etsu Chemical Co. Ltd.), Polyflow (manufactured by Kyoei Kagaku K · K ·), Eftop (manufactured by Tochem Products K · K ·), Magafac (manufactured by Dainippon Ink & Chemical Inc ·), Fluorad (manufactured by Sumitomo 3M) ), Asahiguard, Surflon (manufactured by Asahi Glass Co. Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by EFKA CHEMICALS), PB821 (manufactured by AjimonotoCo. Inc.), etc. Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, N- (2.aminoethyl) -3 -Aminopropylfluorenyldimethoxysilane, ν · (2-aminoethyl) -3-aminopropyldifluorene lactate, 3-aminopropylethoxylate, 3-epoxy Propoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidylmethyl Didimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacrylpropylpropyltrimethoxysilane, 3-methylpropyltrimethoxysilane, and the like. Specific examples of the antioxidant include 2,2, -thiobis (4-fluorenyl-6-tert-butylbenzyl), 2,6-di-tert-butyl-4-fluorenylphenyl, and the like. Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy_5-fluorenylphenyl) _5-gasobenzotriazole, alkoxybenzophenone, and the like. Specific examples of the coagulant include sodium polyacrylate and the like. The chain transfer agent includes dodecanethiol, 2,4-diphenyl-4-fluorenyl-1-pentane, etc. 0 27 20054 0 m The viscosity and the dryness before storage of the photosensitive resin composition of the present invention This is more desirable than small changes. The photosensitive resin composition of the present invention can be prepared by, for example, mixing the above (A) to (D), and if necessary, can be mixed in any order. For

光敏樹脂組合物可以例如被塗布在下述基材上，並進 行固化和顯影而形成結構。首先，將該組合物塗布在基板 (通常為玻璃）或由先前形成的光敏樹脂組合物固體成分 所製成的層上。塗布是用諸如旋塗機、縫塗機、幕簾流動 塗布機、棒塗機的已知設備來實施的。 、所塗敷的光敏樹脂組合物可以進行預烘以除去揮發性 成分、’例如溶劑等，形成一種平滑的塗布膜。在這種情況 下’塗布膜的厚度通常為約。將這樣得到的 通過掩模進行紫外線轄照，形成預期的結構。在這種操作 ^優牛選束酿㈣曝光料錄職如掩模校 ^ 4的設備，以使得掩模和基板能夠正確定位。 ΐ H t % ^ ^ _布膜與驗性水溶液進行接觸以溶解未 影以獲得預期的結構。作為顯影方法， g，η Ϊ法、浸潰法、伽法等巾的任何一種。 n/r巾基板可轉任何肖度制。顯影後，水洗 在形成結構的曝光後所 劑通常是含有鹼性化合物和 進行的顯影中，所使用的 表面活性劑的水溶液。 顯影 28 20〇54 峨 鹼性化合物可以是任何有機或無機的鹼性化合物。無 機鹼性化合物的具體例子包括氫氧化鈉、氫氧化鉀、磷酸 氫二納、構酸二氫納、虱一錢、碟酸二氫銨、填酸二 氫鉀、矽酸鈉、矽酸鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳 酸氫鉀、棚酸納、棚酸鉀、氨水等。 有機鹼性化合物的具體例子包括氫氧化四甲基銨、氫 氧化2-經乙基三甲基銨、單甲胺、二曱胺、三曱胺、單乙 胺、二乙胺、三乙胺、單異丙基胺、二異丙胺、乙醇胺等。 鲁這些有機和無機的鹼性化合物可以單獨或組合使用。鹼性 化合物在顯影劑中的浪度優選為O.OMOwt%，更優選為 〇.〇3-5wt%。 鹼性顯影劑中的表面活性劑可以是離子性表面活性 劑、陰離子表面活性劑和陽離子表面活性劑中的任何表面 活性劑。 非離子表面活性劑的具體例子為聚氧乙烯烷基醚、聚 氣乙浠芳基&|、聚氧乙烯烧基芳基_、其他的聚氧乙稀衍 鲁 生物、氧化乙婦/氧化丙烯搬段共聚物、山梨糖醇酐脂肪酸 醋、聚氧乙烯山梨糖醇酐脂肪酸酯、聚氧乙烯山梨糖醇脂 肪酸酯、甘油脂肪酸酯、聚氧乙烯脂肪酸酯、聚氧乙烯烷 基胺等。 陰離子表面活性劑的具體例子包括諸如十二烷醇硫酸 酯鈉鹽、油醇硫酸酯鈉鹽的高級醇硫酸酯鹽、諸如十二烷 基硫酸鈉和十二烷基硫酸銨的烷基硫酸鹽、諸如十二烧基 苯磺酸鈉和十二烷基萘磺酸鈉的烷基芳基磺酸鹽等。 29 20054曝i, 故些表面活性劑可以單獨或組合使用。 π m 面活性劑在鹼性顯影劑中的濃度通常為 wt/〇 ’ 優選為 〇.〇5-8wt%，更優選為 〇 uwt〇/〇。 可以通過以下操作在基板或濾色器基板上形成固化的 ^脂結構··例如按上述方法塗布和乾燥光敏樹脂液體，在 付到，乾紐布膜上騎形成結構轉光，進行顯影。 忒固化樹脂結構可作為光隔離物而用於液晶顯示器 上。在液晶顯示器中，顯示出改善的視角的MVA (多疇 垂直對齊）液晶顯示器具有通過在取向膜面上設置構造而 形，的突出物，並且作為該構造，可以使用作本發明的光 敏树知組合物形成的結構。在乾燥的塗布膜上進行形成結 才冓的曝光中，如·果使用形成孔沿的光掩模，可以形成孔洞， 这可以用作絕緣膜内層。另外，在對乾燥塗布膜進行曝光 中，可以通過不使用光掩模的曝光和熱固化或僅僅是熱固 化來形成樹脂膜，該樹脂膜可用作覆膜。 、 在使用本發明的光敏樹脂組合物製成的濾色器中，濾 色恭中膜厚的差別小，例如當膜厚度為〇1_6μιη時，面内 厚度差別或能是〇·15μιη或更小，更進一步為〇·〇5μπι或更 小。因此’這樣獲得的濾色器在平滑性上極好，並且通過 將其引入彩色液晶顯示器，可以以高產率製造極高品質的 液晶顯示器。 為讓本發明之上述和其他目的、特徵和優點能更明顯 20054Q^ic 易懂，下文特舉實施例，作詳細說明如下。 【實施方式】The photosensitive resin composition can be applied, for example, to a substrate described below, and cured and developed to form a structure. First, the composition is coated on a substrate (usually glass) or a layer made of a solid content of a previously formed photosensitive resin composition. The coating is performed using known equipment such as a spin coater, a slit coater, a curtain flow coater, and a bar coater. The applied photosensitive resin composition may be pre-baked to remove volatile components, such as solvents, etc., to form a smooth coating film. In this case, the thickness of the 'coated film is usually about. The thus obtained ultraviolet light was irradiated through a mask to form a desired structure. In this operation, you can use exposure equipment such as mask calibration equipment to enable the mask and substrate to be positioned correctly. ΐ H t% ^ ^ _ The cloth film was contacted with a test aqueous solution to dissolve the shadow to obtain the desired structure. As the developing method, any of g, η Ϊ method, dipping method, and gamma method is used. The n / r towel substrate can be transferred to any shaw system. After development, washing with water After the structure-forming exposure, the solvent is usually an aqueous solution containing a basic compound and a surfactant used in the development. Development 28 2054 A The basic compound may be any organic or inorganic basic compound. Specific examples of the inorganic basic compound include sodium hydroxide, potassium hydroxide, dibasic sodium phosphate, dibasic acid dihydrogen, diamidine, ammonium dihydrogenate, potassium dihydrogenate, sodium silicate, potassium silicate , Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium shed, potassium shed, ammonia, etc. Specific examples of the organic basic compound include tetramethylammonium hydroxide, 2-triethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, and triethylamine , Monoisopropylamine, diisopropylamine, ethanolamine, etc. These organic and inorganic basic compounds can be used alone or in combination. The waviness of the basic compound in the developer is preferably 0.03 wt%, more preferably 0.003-5 wt%. The surfactant in the alkaline developer may be any of an ionic surfactant, an anionic surfactant, and a cationic surfactant. Specific examples of non-ionic surfactants are polyoxyethylene alkyl ethers, polyoxyethyl aryl & |, polyoxyethylene aryl aryl, other polyoxyethylene derivatives, ethoxylated / oxidized Polypropylene copolymer, sorbitan fatty acid vinegar, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkane Amines, etc. Specific examples of the anionic surfactant include higher alcohol sulfate salts such as dodecanol sulfate sodium salt, oleyl alcohol sulfate sodium salt, and alkyl sulfate salts such as sodium dodecyl sulfate and ammonium dodecyl sulfate , Alkylaryl sulfonates such as sodium dodecylbenzenesulfonate and sodium dodecylnaphthalenesulfonate. 29 20054 exposure, so these surfactants can be used alone or in combination. The concentration of the π m surfactant in the alkaline developer is usually wt / 0 ', preferably 0.05 to 8 wt%, and more preferably 0 uwt 0 / 〇. The following operations can be used to form a cured grease structure on a substrate or a color filter substrate. For example, a photosensitive resin liquid can be applied and dried as described above, and the structure can be light-transformed on a dry button cloth for development. The fluorene-cured resin structure can be used as an optical spacer for a liquid crystal display. In a liquid crystal display, an MVA (Multi-domain Vertical Alignment) liquid crystal display showing an improved viewing angle has protrusions shaped by providing a structure on an alignment film surface, and as the structure, a photosensitive tree known as the present invention can be used. Structure formed by the composition. In the exposure for forming a junction on a dried coating film, if a photomask forming a hole edge is used, a hole can be formed, which can be used as an inner layer of an insulating film. In addition, in exposing a dry coating film, a resin film can be formed by exposure and thermal curing without using a photomask or only thermal curing, and this resin film can be used as a film. In a color filter made using the photosensitive resin composition of the present invention, the difference in film thickness between the color filters is small. For example, when the film thickness is 0-16 μm, the difference in in-plane thickness may be 0.15 μm or less. , And even more 0.05 μm or less. Therefore, the color filter thus obtained is excellent in smoothness, and by introducing it into a color liquid crystal display, an extremely high-quality liquid crystal display can be manufactured at a high yield. In order to make the above and other objects, features, and advantages of the present invention more obvious, 20054Q ^ ic is easy to understand, the following specific examples are given below for detailed description. [Embodiment]

、以y將結合實施例對本發明進行詳細說明，但是無需 說明的是，本發明並不局限於這些實施例。A 貫施例1，實施例2和對比實施例1中所使用的粘結 劑樹脂的構造等示於式（x)，式（γ)和表i中。在表i 中，a至h代表摩爾比。 由於枯結劑樹脂中不使用異氰酸酯化合物，不存在由 • 異氰酸酯化合物導致的特殊臭氣。The invention will be described in detail with reference to the embodiments in y, but needless to say, the invention is not limited to these embodiments. A The structure and the like of the binder resin used in Example 1, Example 2 and Comparative Example 1 are shown in Formula (x), Formula (γ) and Table i. In Table i, a to h represent molar ratios. Since isocyanate compounds are not used in the caulking resin, there is no special odor caused by isocyanate compounds.

c=oc = o

A 組成單元的解釋 a ·共聚物1中源自（A1 )的組成單元 b :共聚物1中源自（A2)的組成單元 c由共^^物1中源自（A4 )的組成單元與（A3 )反 31 20〇54Q5^5〇c 應所形成的組成單元 d :由共聚物2中源自（A3)的部位與（A5)反應所 形成的組成單元 e ·由（Al )、（ A2)和（A3)反應所形成的共聚物 中源自（A1)的組成單元 f :由（Al)、（A2)和（a3)反應所形成的共聚物 中源自（A2 )的組成單元 g :由（Al)、（A2)和（A3)反應所形成的共聚物 中源自（A3)的組成單元 h:由源自（A4)的組成單元與由（A1)、（A2)和 (A3)反應所形成的共聚物中源自（a3)的組成單元反應 所形成的組成單元 表1 樹脂A 樹脂B 樹脂c a 0.25 0.25 b 0.25 0.25 c 0.15 0.15 d 0.35 0.35 e 0.10 f 0.54 g _ 0.21 h 0.15 Ri H ch3 ch3 Mw 18,000 18,000 15,000 M>ln 2.2 2.2 2.1 上述粘結聚合物的基於聚苯乙烯校準基準的重均分子 量（Mw)和數均分子量（Μη)是採用GPC法在以下條件 下測定的。 32 2〇〇54p^oc 儀 : HLC-8120GPC (TosohCorp·製造） 柱：TSK-GELG 4000 HXL + TSK-GELG 2000 HXL(串 聯） 柱溫：40°C ^A Explanation of the constituent units a. The constituent unit derived from (A1) in the copolymer 1 b: The constituent unit derived from (A2) in the copolymer 1 c is composed of the constituent unit derived from (A4) in the copolymer 1 and (A3) Constituent unit d formed by reaction 31 20〇54Q5 ^ 50c: A constituent unit e formed by the reaction of the site derived from (A3) in copolymer 2 with (A5) e. (Al), ( A2) and (A3) the copolymer derived from the (A1) -derived unit f: the copolymer formed from the (Al), (A2), and (a3) reaction-derived unit from the (A2) g: the component unit derived from (A3) in the copolymer formed by the reaction of (Al), (A2) and (A3) h: the component unit derived from (A4) and (A1), (A2) and (A3) In the copolymer formed by the reaction, the constituent units derived from the reaction of the constituent units derived from (a3) Table 1 Resin A Resin B Resin ca 0.25 0.25 b 0.25 0.25 c 0.15 0.15 d 0.35 0.35 e 0.10 f 0.54 g _ 0.21 h 0.15 Ri H ch3 ch3 Mw 18,000 18,000 15,000 M &ln; 2.2 2.2 2.1 The weight average molecular weight (Mw) and number average of the above-mentioned adhesive polymers based on polystyrene calibration standards Amount (Μη) is measured under the following conditions using a GPC method. 32 2〇54p ^ oc instrument: HLC-8120GPC (manufactured by TosohCorp) Column: TSK-GELG 4000 HXL + TSK-GELG 2000 HXL (series) Column temperature: 40 ° C ^

流率：l.Oml/min 注入量：50μ1 檢測器·· RI 測定樣品濃度：〇.6wt% (溶劑·· THF) 校準基準物質·· TSK標準聚苯乙烯F-40、F-4、F-卜 A-2500、A-500 (由 TosohCorp·製造） 以上得到的重均分子量與數均分子量的比值用作分子 量分佈（Mw/Mn)。 實施例和對比實施例中的混合成分示於表2中。表2 中的數值代表重量份。 表2 實施例1 實施例2 對比實施例1 粘結劑樹脂（A) 樹脂A 50 樹脂B 50 樹脂C 50 可光聚合化合物 (B) 六丙埽酸二季戊四醇酯（KAYARAD DPHA ;由 Nippon Kayaku Co·，Ltd.製造） 50 50 50 光聚合引發劑 (C) 2-苄基-2-二曱氨基嗎啉代苯基> 丁酮 (Irgacure 369 ;由 Ciba Specialty Chemicals 製造） 3 3 3 光聚合引發助劑 (C-1) 4,4，·二(N，N-二乙氨基苯曱酮（EAB-F，由 Hodogaya Chemical Co.，Ltd.製造） 1 1 1 溶劑 丙二醇單曱基醚乙酸酯 38 38 38 (D) 丙酸3-乙氧基乙酯 24 24 24 其他化合物 環氧樹脂（ESCN-195XL ;由 Sumitomo Chemical C〇.，Ltd 製造） 5 5 5 33 200540cSs^f5〇c 依次用中性洗滌劑、水和酒精洗滌2平方英寸的玻璃 基板（Corning製造，#1737)，然後進行乾燥。、在該玻璃 基板上旋塗上光敏樹驗合物（表2)並使得經過曝光量 為100mJ/cm2的曝光（365nm)、顯影、水洗々後洪烤後 膜厚為4·7μιη，然後在清潔的烘箱中和1〇〇。〇^預烘烤3 分鐘。冷卻後，在該基板上塗布光敏樹脂組合物並以 的間隔安裝石英玻璃光掩模（帶有圖案，圖案中邊長為 20μιη的方塊與空白部分的比為ι:2)，再在空氣中用超 高壓水銀燈（USH-250D，Ushiolnc.製造）以 i00mJ/cm^ 的曝光量進行輻照，之後，將上述塗布膜浸入含有〇.丨2 ^ t % 非離子表面活性劑和〇.〇5wt%氫氧化鉀的水性顯影劑中經 過80秒，同時在23°C攪拌（300rpm，使用磁力搜拌器^ 顯影劑進行顯影，再用水洗滌該膜並在220°C下後块烤^3() 分鐘，得到固化樹脂結構。 所得到的固化樹脂結構在以下專案上的測定結果示於 表3中。 、、 表3 實施例1 實施例2 對比實施例] 耐NMP性 102% 102% 105%^〜- 平滑性 〇 0 ~〇~^^— 粒狀雜質 〇 0 "〇~' - 線寬（pm) 30.8 30.9 "282~- 形 S _ ----- 正向錐形 正向錐形 正向錐形 恢復係數（〇/0) 70 71 "67^—— 102 102 1〇2~^^-- 34Flow rate: 1.0ml / min Injection volume: 50μ1 Detector ·· RI Measurement sample concentration: 0.6wt% (solvent ·· THF) Calibration reference substance ·· TSK standard polystyrene F-40, F-4, F -A-2500, A-500 (manufactured by Tosoh Corp.) The ratio of the weight average molecular weight to the number average molecular weight obtained above is used as the molecular weight distribution (Mw / Mn). The mixing ingredients in the examples and comparative examples are shown in Table 2. The values in Table 2 represent parts by weight. Table 2 Example 1 Example 2 Comparative Example 1 Binder resin (A) resin A 50 resin B 50 resin C 50 photopolymerizable compound (B) dipentaerythritol hexapropionate (KAYARAD DPHA; by Nippon Kayaku Co ·, Ltd.) 50 50 50 Photopolymerization initiator (C) 2-benzyl-2-diamidinoaminomorpholinophenyl> Butanone (Irgacure 369; manufactured by Ciba Specialty Chemicals) 3 3 3 Photopolymerization Initiation aid (C-1) 4,4, · bis (N, N-diethylaminobenzophenone (EAB-F, manufactured by Hodogaya Chemical Co., Ltd.) 1 1 1 Solvent propylene glycol monofluorenyl ether ethyl Ester 38 38 38 (D) 3-ethoxyethyl propionate 24 24 24 Other compounds epoxy resin (ESCN-195XL; manufactured by Sumitomo Chemical Co., Ltd) 5 5 5 33 200540 cSs ^ f50 A 2-square-inch glass substrate (manufactured by Corning, # 1737) was washed with neutral detergent, water, and alcohol, and then dried. The glass substrate was spin-coated with a photosensitive tree test compound (Table 2) and exposed to light. 100mJ / cm2 exposure (365nm), development, water washing, flooding and baking after film thickness is 4 · 7μιη, and then clean The oven was neutralized with 100. ^ pre-baking for 3 minutes. After cooling, the substrate was coated with a photosensitive resin composition and a quartz glass photomask (with a pattern, a square with a side length of 20 μm in the pattern) was installed at intervals. The ratio to the blank portion is ι: 2), and then irradiated with an ultrahigh-pressure mercury lamp (USH-250D, manufactured by Ushiolnc.) In the air at an exposure amount of i00mJ / cm ^, and then the above coating film was immersed in a solution containing 0.丨 2 ^ t% non-ionic surfactant and 0.05% by weight potassium hydroxide in aqueous developer after 80 seconds, while stirring at 23 ° C (300rpm, using a magnetic mixer ^ developer for development, and then water The film was washed and baked at 220 ° C for ^ 3 () minutes to obtain a cured resin structure. The measured results of the obtained cured resin structure on the following projects are shown in Table 3. Table 3 Example 1 Implementation Example 2 Comparative Example] NMP resistance 102% 102% 105% ^ ~-smoothness 〇0 ~ 〇 ~ ^^ — granular impurities 〇0 " 〇 ~ '-line width (pm) 30.8 30.9 " 282 ~ -Shape S _ ----- Forward taper Forward taper Forward taper recovery coefficient (〇 / 0) 70 71 " 67 ^ ---- 102 102 1〇2 ~ ^^-34

200540)5 命 5C (表3的解釋） 耐NMP性·· 用於實施例相同的工藝製備塗布膜，除了在曝光時不 使用。光掩模。將得到的塗布膜浸入N-曱基°比.略烧酮中 ( = Cx3〇分鐘），並測定浸泡前後的厚度。當浸泡前後 的厚度變化卜（浸泡後的厚度（μηι)/浸泡前的厚度（μιη)) χ1〇〇)為103%或更小時，評價是◦，當超過1〇3%時，評 價是χ。 φ 表面平滑性： 關於表面平滑性的標準，用目視觀察，光滑而用〇表 示，白濁（不透明）用χ表示。 粒狀雜質（顆粒）： 目視觀察表面，無雜質時用〇表示，有雜質時用χ表 示。 線寬： 用 SEM (型號：S_4000，Hitachi c〇rp·製造）測定結 構底部兩側的尺寸，計算所得到的兩個值的平均值。 9 形狀： 用同樣的SEM觀察垂直於結構基板的橫斷面。 恢復係數： 使用動態超精細硬度測試儀（DUH-W201S，Shimadzu Corp·製造）、在以下條件下測定總位移量（μπ1)和彈性 位移量（μηι)，然後由所測得的數值計算恢復係數。 測試模式：載入和卸載測試 35 20054(½^ 測試力：5 gf (SI單元降低值：0.049N) 載入速度：〇.45g/秒（SI單元降低值：q 〇〇44n/秒） 保持時間：5秒 壓頭··截錐形壓頭（直徑：50ππηΦ) 恢復係數(％Μ彈性位移量（μηι)/總位移量（μιη )) χ ；[ 〇〇 貯存穩定性： 按照下式計算在23°C下貯存3個月前後的枯度變化 率。 • 粘度變化率（％)=[(貯存後粘度）/(貯存前粘度）] X100 由於實施例1和實施例2的光敏樹脂組合物中含有本 發明的粘結劑樹脂，因而獲得了耐NMP性、表面平滑性、 結構形狀和恢復係數均優異的結構和塗布膜，而由於對比 實施例的光敏樹脂組合物中不含本發明的粘結劑樹脂，因 而耐NMP性差。 本發明的光敏樹脂組合物沒有特別的臭味，並且所形 φ 成的塗布膜和結構具有優異的耐NMP性和表面平滑性， 不存在由粒狀雜質導致的塗布缺陷，可以提供具有高達 3-50μιη的高解析度的結構，具有良好透明性和適合於作為 諸如光隔離物的結構。 、一本發明的光敏樹脂組合物可以用於形成液晶顯示器的 光隔離物，另外，還可以用於形成絕緣膜（形成接觸孔）、 覆膜（展平膜）和用於控制液晶取向的突出物。另外，也 可能用作對其進行粘接的膠粘劑。 36 20054iQ)5|^.5)c 雖然本發明已以實施例揭露如上，然其並非用以限定 本發明，任何熟習此技藝者，在不脫離本發明之精神和範 圍内，當可作些許之更動與潤飾，因此本發明之保護範圍 當視後附之申請專利範圍所界定者為準。 . 【圖式簡單說明】 無。 【主要元件符號說明】 無。 37200540) 5C 5C (explanation in Table 3) NMP resistance. The coating was used in the same process as in the example to prepare a coating film, except that it was not used during exposure. Photomask. The obtained coating film was immersed in N-fluorenyl ° ratio slightly burned ketone (= Cx30 minutes), and the thickness before and after immersion was measured. When the thickness change before and after soaking (thickness after soaking (μηι) / thickness before soaking (μιη)) χ 100) is 103% or less, the evaluation is ◦, and when it exceeds 103%, the evaluation is χ . φ Surface smoothness: Standards for surface smoothness are visually observed, smooth and expressed as 0, and opaque (opaque) as χ. Granular impurities (particles): Visually observe the surface. When there are no impurities, they are represented by 0, and when there are impurities, they are represented by χ. Line width: The dimensions of the two sides of the bottom of the structure were measured by SEM (Model: S_4000, manufactured by Hitachi Corp ·), and the average of the two values obtained was calculated. 9 Shape: Observe the cross section perpendicular to the structural substrate with the same SEM. Recovery coefficient: Using a dynamic ultra-fine hardness tester (DUH-W201S, manufactured by Shimadzu Corp.), the total displacement (μπ1) and elastic displacement (μηι) were measured under the following conditions, and then the recovery coefficient was calculated from the measured values . Test mode: Load and unload test 35 20054 (½ ^ Test force: 5 gf (SI unit reduction value: 0.049N) Loading speed: 0.45 g / s (SI unit reduction value: q 〇〇44n / s) Hold Time: 5 seconds indenter · · truncated cone indenter (diameter: 50ππηΦ) recovery factor (% M elastic displacement (μηι) / total displacement (μιη)) χ; [〇〇Storage stability: Calculated according to the following formula Change rate of dryness before and after storage at 23 ° C for 3 months. • Viscosity change rate (%) = [(viscosity after storage) / (viscosity before storage)] X100 Because of the photosensitive resin combination of Examples 1 and 2 The binder resin of the present invention is contained therein, and thus a structure and a coating film having excellent NMP resistance, surface smoothness, structural shape, and recovery coefficient are obtained, and the photosensitive resin composition of the comparative example does not contain the present invention. The binder resin has poor NMP resistance. The photosensitive resin composition of the present invention has no special odor, and the coating film and structure formed by φ have excellent NMP resistance and surface smoothness, and there is no granularity. Coating defects caused by impurities can provide A high-resolution structure up to 3-50 μιη, which has good transparency and is suitable for use as a structure such as a photo-isolator. The photosensitive resin composition of the present invention can be used to form a photo-isolator for a liquid crystal display. It is used to form an insulating film (to form a contact hole), a cover film (flattening film), and a protrusion for controlling the orientation of a liquid crystal. In addition, it may be used as an adhesive for bonding it. 36 20054iQ) 5 | ^ .5) c Although the present invention has been disclosed as above by way of example, it is not intended to limit the present invention. Any person skilled in the art can make some modifications and retouching without departing from the spirit and scope of the present invention. The scope of protection shall be determined by the scope of the attached patent application. [Schematic description] None. [Description of main component symbols] None. 37

Claims (1)

(Α5):酸酐， 其中’ （Α1)至（Α5)是不相同的。 20054獅 5〇, 十、申請專利範圍： 1.一種光敏樹脂組合物，包含（A)粘結劑樹脂’（B) 可光聚合的化合物，（C)光聚合弓丨發劑和（D)溶劑的， 其中粘結劑樹脂（八）是通過下述方法獲得的丼聚物：將 下述的（Al)、（A2)和（A4)進行共聚形成共聚物1， 使得到的共聚物1以其源自（A4)的部位與（A3)進行反 應形成聚合物2，再將得到的共聚物2和（A5)與共聚物 1的（A3)及（A4)反應形成的羥基進行反應，光聚合引 《X知彳（C )為選自笨乙嗣基化合物、雙咪α坐基化合物、月亏 基化合物和三嗪基化合物中的至少一種： (Α1):帶有選自三環癸烷骨架和雙環戊二烯骨架中 至少一種骨架的化合物，且單個分子中含有不飽和鍵， (Α2):帶有可與（Α1)和（Α4)進行共聚的不飽 和鍵的化合物， (A3):帶有不飽和基團的羧酸， (Α4):在單個分子中帶有不飽和鍵及環氧基的化合 物， 2·如申叫專利範圍第J項所述之光敏樹脂組合物，其 中（A1)為選自（甲基）丙烯酸雙環戊S旨、（曱基）丙烯 酸it戊，、（甲基）丙烯酸雙環戊基氧乙醋和（甲基） 丙烯酉夂雙喊歸基氧乙g旨中至少—種的化合物。 3.士申#專利_第1項或第2項所述之光敏樹脂組 38 20054Q縱 。物’、其中（A2)為選自苯乙烯、（曱基）丙烯酸节酉旨和 N-取代的順丁稀酿亞胺化合物中至少一種的化合物。 人4·如申請專利範圍第1項或第2項所述之光敏樹脂組 δ物其中（A3)為選自丙稀酸和甲基丙稀酸中*至少一種 的化合物。 威 人5·如申請專利範圍第1項或第2項所述之光敏樹脂組 一 八中（)為選自丙烯酸縮水甘油g旨和曱基丙烯酸 縮水甘油醋中至少一種的化合物。 籲 ^ 6·如申晴專利範圍第1項或第2項所述之光敏樹脂組 合物’其中（A5)為選自順丁稀酸酐、琥拍酸酐、衣康酸 if、鄰苯二曱酸酐、四氫化鄰苯二曱酸酐、六氫化鄰苯二 曱酸針、曱基内亞甲基四氫化鄰苯二曱酸針、曱基四氫化 鄰苯二甲酸酐和偏苯三曱酸酐中至少一種的化合物。 7·如申請專利範圍第1項或第2項所述之光敏樹脂組 合物’其中通過（A4)和（A3)進行反應形成的組成單元 與全部組成單元的比值為30-60摩爾％。 φ 8·—種使用專利範圍第1項所述之光敏樹脂組合物形 成的固化樹脂結構(pattern)。 9·如申請專利範圍第8項所述之使用專利範圍第1項 所述之光敏樹脂組合物形成的固化樹脂結構，其中的結構 為光隔離物(photo spacer)。 10·如申請專利範圍第8項所述之使用專利範圍第1項 所述之光敏樹脂組合物形成的固化樹脂結構，其中的結構 為絕緣膜。 39 20054^65 11=申請專利範固第8項所述之使用專利 = 光敏樹脂組合物形成的固化樹脂結構，】 為覆膜(over coat)。 〜構 12.如申請專利範圍第8項所述之使用專利氮圍 所述之光敏樹脂組合物形成的固化樹脂結構，其备 為用於液晶取向控制的突出部。 13·—種含有專利範圍第8項至第12項任一項 化樹脂結構的濾色器。 、&口(Α5): acid anhydride, in which (A1) to (A5) are different. 20054 Lion 50, 10. Application patent scope: 1. A photosensitive resin composition comprising (A) a binder resin ', (B) a photopolymerizable compound, (C) a photopolymerizable bow, and (D) The solvent, wherein the binder resin (8) is an oligomer obtained by: copolymerizing the following (Al), (A2), and (A4) to form a copolymer 1 such that the obtained copolymer 1 The polymer derived from (A4) is reacted with (A3) to form polymer 2, and the obtained copolymer 2 and (A5) are reacted with the hydroxyl groups formed by the reaction of (A3) and (A4) of copolymer 1, Photopolymerization "X knows that (C) is at least one selected from the group consisting of acetofluorenyl compounds, bis-imide α-group-based compounds, lunyl compounds, and triazine-based compounds: (Α1): with a tricyclic ring A compound having at least one of a decane skeleton and a dicyclopentadiene skeleton, and a single molecule containing an unsaturated bond, (Α2): a compound having an unsaturated bond that can be copolymerized with (Α1) and (Α4), ( A3): carboxylic acid with unsaturated group, (Α4): compound with unsaturated bond and epoxy group in a single molecule 2. The photosensitive resin composition as described in item J of the patent application, wherein (A1) is selected from the group consisting of (meth) acrylic acid dicyclopentyl S, (fluorenyl) acrylic acid it, and (meth) At least one of the compounds of dicyclopentyloxyethyl acrylate and (meth) acrylic acid. 3. Shishen #patent_photosensitive resin group described in item 1 or 2 38 20054Q vertical. A substance ', in which (A2) is a compound selected from at least one of styrene, (fluorenyl) acrylic acid, and N-substituted cis-butylimine compound. Human 4. The photosensitive resin group δ according to item 1 or 2 of the scope of the patent application, wherein (A3) is a compound selected from at least one of acrylic acid and methyl acrylic acid. Weiren 5. The photosensitive resin group described in item 1 or 2 of the scope of the patent application (18) () is a compound selected from at least one of glycidyl acrylic acid and glycidyl acrylic acid glycidyl vinegar. ^^ 6. The photosensitive resin composition as described in item 1 or item 2 of Shen Qing's patent scope, wherein (A5) is selected from the group consisting of maleic anhydride, succinic anhydride, itaconic acid if, and phthalic anhydride , Tetrahydrophthalic anhydride, hexahydrophthalic acid needle, fluorenylmethylenetetrahydrophthalic acid needle, fluorenyltetrahydrophthalic acid anhydride, and trimellitic anhydride A compound. 7. The photosensitive resin composition according to item 1 or item 2 of the scope of the patent application, wherein the ratio of the constituent units formed by the reaction of (A4) and (A3) to all constituent units is 30-60 mol%. φ 8-A cured resin pattern formed using the photosensitive resin composition described in item 1 of the patent scope. 9. The cured resin structure formed by using the photosensitive resin composition described in the patent scope item 1 described in the patent scope item 8, wherein the structure is a photo spacer. 10. The cured resin structure formed by using the photosensitive resin composition described in the patent scope item 1 as described in the patent scope item 8, wherein the structure is an insulating film. 39 20054 ^ 65 11 = Using the patent described in the patent application No. 8 = the cured resin structure formed by the photosensitive resin composition,] is an over coat. ~ Structure 12. The cured resin structure formed using the photosensitive resin composition described in the patent application No. 8 of the patent application scope is prepared as a protrusion for liquid crystal alignment control. 13. · A color filter containing any one of the patented items 8 to 12 with a resin structure. , &Amp; mouth 14·一種安裝有專利範圍第13項所述濾色器的液晶顯 示器。 ” 2〇〇5條么 • Ψ 七、 指定代表圖： (一） 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明： 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。14. A liquid crystal display having a color filter according to item 13 of the patent scope. “Article 2005 • Ψ 7. Designated Representative Map: (1) The designated representative map in this case is: None. (2) The component symbols of this representative map are simply explained: None. * 8. If there is a chemical formula in this case, please Reveal the chemical formula that best characterizes the invention: None. 66
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US8822110B2 (en) 2011-12-02 2014-09-02 Cheil Industries Inc. Photosensitive resin composition for color filter and color filter including the same
TWI473821B (en) * 2011-12-02 2015-02-21 Cheil Ind Inc Photosensitive resin composition for color filter and color filter using the same
US9334399B2 (en) 2012-12-12 2016-05-10 Cheil Industries Inc. Photosensitive resin composition and black spacer using the same

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CN1707358A (en) 2005-12-14

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