TW201202280A

TW201202280A - Addition copolymers, photosensitive resin compositions and color filters

Info

Publication number: TW201202280A
Application number: TW100112326A
Authority: TW
Inventors: Takehiro Kinoshita; Yasuhiro Komori; Yasuaki Kawaguchi
Original assignee: Showa Denko Kk
Priority date: 2010-04-13
Filing date: 2011-04-08
Publication date: 2012-01-16
Also published as: KR101405765B1; CN102844712B; JP5588503B2; TWI520975B; WO2011129182A1; JPWO2011129182A1; KR20120125511A; CN102844712A

Abstract

Disclosed is a photosensitive resin composition which is characterized by containing a solvent (B) and an addition copolymer (A) that is obtained by adding a monomer (a-4) having a hydroxyl group to a copolymer that is obtained by copolymerizing 2-60% by mole of a monomer (a-1) that has a bridged cyclic hydrocarbon group having 10-20 carbon atoms and/or a monomer (a-1') that is represented by general formula (1), 30-88% by mole of an unsaturated polybasic acid anhydride (a-2) and 10-68% by mole of a copolymerizable monomer (a-3) that is other than the components (a-1), (a-1') and (a-2). The photosensitive resin composition is capable of providing a color pattern that exhibits good sensitivity and developability, while having excellent thermal decomposition resistance and solvent resistance. (In general formula (1), X and Y each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1-4 carbon atoms; R1 and R2 each independently represents a hydrogen atom, a hydrocarbon group having 1-20 carbon atoms or a carboxyl group; and R1 and R2 may combine together to form a cyclic structure.)

Description

201202280 六、發明說明【發明所屬之技術領域】本發明關於一種加成共聚物、感光性樹脂組成物及彩色濾光器，特別是關於一種加成共聚物及感光性樹脂組成物，係使用於有機EL顯示器、液晶顯示裝置 '固態攝影元件內建的彩色濾光器之製造；以及使用該等該加成共聚物及感光性樹脂組成物所製造之彩色濾光器。【先前技術】近年來，從省資源或省能源的觀點考量，在各種塗敷、印刷、塗料、黏著劑等領域之中，正廣泛利用可藉由紫外線或電子束等活性能量射線而硬化的感光性樹脂組成物。另外，在印刷電路板等電子材料的領域中，阻焊劑或彩色濾光器用光阻等亦採用藉由活性能量射線而硬化的感光性樹脂組成物。彩色濾光器一般是由：玻璃基板等透明基板；形成於透明基板上的紅（R)、綠（G)及藍（B)之畫素：形成於畫素的交界之黑色矩陣；與形成於畫素及黑色矩陣上之保護膜所構成。具有這種構成的彩色濾光器，通常藉由在透明基板上依序形成黑色矩陣、畫素及保護膜而製造出來。就畫素及黑色矩陣（以下將畫素及黑色矩陣稱爲「著色圖型」）之形成方法而言，已有文獻提出各種製造方法，而使用感光性樹脂組成物作爲光阻，重覆進行塗佈、曝光、顯像及烘烤之光蝕刻法，可產生耐光性或耐熱性等耐久性優異、 -5- 201202280 小孔等缺陷少的著色圖型，因此逐漸成爲目前的主流。一般而言，光蝕刻法所使用的感光性樹脂組成物，含有鹼可溶性樹脂、反應性稀釋劑、光聚合起始劑、著色劑及溶劑。作爲鹼可溶性樹脂，曾經有文獻提出採用使含羧基的不飽和單體、馬來酸酐、與含羧基的不飽和單體及馬來酸酐以外之可共聚合的不飽和單體以既定比率進行共聚合而得之物（參照例如專利文獻1)。另外還有文獻提出採用在由馬來酸酐以及可與馬來酸酐共聚合的單體所得到的共聚物，加成含羥基的化合物而得之物（參照例如專利文獻2〜5)。 [先前技術文獻] [專利文獻] 專利文獻1:日本特開2005-148720號公報專利文獻2:日本特開平10-293402號公報專利文獻3:日本特開2007-79294號公報專利文獻4:日本特開2007-133032號公報專利文獻5:日本特開2009-223127號公報【發明內容】 [發明所欲解決之課題] 然而，以往的感光性樹脂組成物會有靈敏度或顯像性不足的情形，或無法得到耐熱分解性及耐溶劑性優異的著色圖型的情形。所以，本發明爲了解決上述這些課題而完成，目的爲201202280 VI. Description of the Invention [Technical Field] The present invention relates to an addition copolymer, a photosensitive resin composition, and a color filter, and more particularly to an addition copolymer and a photosensitive resin composition, which are used in An organic EL display, a liquid crystal display device, a color filter built in a solid-state image sensor, and a color filter manufactured using the additive copolymer and the photosensitive resin composition. [Prior Art] In recent years, from the viewpoints of saving resources or energy saving, in various fields such as coating, printing, coating, and adhesives, it is widely used to be hardened by active energy rays such as ultraviolet rays or electron beams. A photosensitive resin composition. Further, in the field of electronic materials such as printed circuit boards, a photoresist composition for a solder resist or a color filter or the like is also used as a photosensitive resin composition which is cured by active energy rays. The color filter is generally composed of a transparent substrate such as a glass substrate; red (R), green (G), and blue (B) pixels formed on the transparent substrate: a black matrix formed at the boundary of the pixels; and formation It consists of a protective film on the pixels and the black matrix. A color filter having such a configuration is usually produced by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate. In the method of forming a pixel and a black matrix (hereinafter referred to as a "coloring pattern" for a pixel and a black matrix), various manufacturing methods have been proposed in the literature, and a photosensitive resin composition is used as a photoresist and repeated. The photolithography method of coating, exposure, development, and baking can produce a color pattern with excellent durability such as light resistance and heat resistance, and a small defect such as -5-201202280, which has gradually become the mainstream. In general, the photosensitive resin composition used in the photolithography method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. As an alkali-soluble resin, it has been proposed in the literature to use a carboxyl group-containing unsaturated monomer, maleic anhydride, a carboxyl group-containing unsaturated monomer, and a copolymerizable unsaturated monomer other than maleic anhydride at a predetermined ratio. Polymerized product (see, for example, Patent Document 1). Further, there has been proposed a copolymer obtained by adding a hydroxyl group-containing compound to a copolymer obtained by maleic anhydride and a monomer copolymerizable with maleic anhydride (see, for example, Patent Documents 2 to 5). [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Problem to be Solved by the Invention] However, the conventional photosensitive resin composition may have insufficient sensitivity or developability. Or, a color pattern of excellent heat decomposition resistance and solvent resistance cannot be obtained. Therefore, the present invention has been made to solve the above problems, and the object is

S -6- 201202280 提供一種感光性樹脂組成物，可產生靈敏度或顯像性良好，同時耐熱分解性及耐溶劑性優異的著色圖型。另外’ 本發明目的爲提供一種鹼可溶性樹脂（加成共聚物）’係使用於可產生靈敏度或顯像性良好，同時耐熱分解性及耐溶劑性優異的著色圖型之感光性樹脂組成物。進一步而言’ 本發明目的爲提供一種彩色濾光器，係具有耐熱分解性及耐溶劑性優異的著色圖型。 [用於解決課題之方法] 本發明人等爲了解決上述這些課題而潛心檢討，結果發現’特定的加成共聚物最適合作爲感光性樹脂組成物所使用的鹼可溶性樹脂，而完成了本發明。亦即，本發明爲以下第[1 ]〜[1 3 ]項。 [1] 一種感光性樹脂組成物，其特徵爲含有加成共聚物（A)與溶劑（B) ’該加成共聚物（A)，係在使具有碳數 10〜20之架橋環式烴基之單體（a_i)及/或下述一般式（1)所表示之單體（a-l')2〜60莫耳％ [化1]S -6- 201202280 A photosensitive resin composition that produces a color pattern with excellent sensitivity or developability and excellent heat decomposition resistance and solvent resistance. Further, the object of the present invention is to provide an alkali-soluble resin (addition copolymer) which is used in a coloring pattern of a photosensitive resin composition which is excellent in sensitivity and developability, and which is excellent in thermal decomposition resistance and solvent resistance. Further, the object of the present invention is to provide a color filter which is a color pattern having excellent heat decomposition resistance and solvent resistance. [Means for Solving the Problem] The present inventors have intensively reviewed the above-mentioned problems, and as a result, it has been found that the specific addition copolymer is most suitable as an alkali-soluble resin used for a photosensitive resin composition, and the present invention has been completed. . That is, the present invention is the following items [1] to [1 3]. [1] A photosensitive resin composition comprising an addition copolymer (A) and a solvent (B) 'the addition copolymer (A), which is a bridged cyclic hydrocarbon group having a carbon number of 10 to 20 Monomer (a_i) and/or monomer (a-1') represented by the following general formula (1) 2 to 60 mol% [Chemical 1]

(式中’ X及Y各自獨立，表示氫原子、或碳數1〜4之直鏈或支鏈之烴基；R1及R2各自獨立，表示氫原子、碳數 1〜20之烴基或羧基；R1及R2可形成連結的環狀構造） 201202280 、不飽和多元酸酐（a-2)30〜88莫耳％、以及（a-l)、（a-l·) 及（a-2)以外之可共聚合的單體（a_3)10〜68莫耳％進行共聚合而得之共聚物，加成具有羥基的單體（a-4)。 [2] 如第[1 ]項所記載之感光性樹脂組成物’…其中前述單體（a-Ι)係二環戊基甲基丙烯酸酯。 [3] 如第[1]或[2]項所記載之感光性樹脂組成物，其中前述不飽和多元酸酐（a-2)係馬來酸酐。 [4] 如第[1 ]〜[3 ]項中任一項所記載之感光性樹脂組成物’其中前述單體（a-3)含有乙烯基甲苯10〜40莫耳 %。 [5] 如第Π]〜[4]項中任一項所記載之感光性樹脂組成物’其中前述單體（a-4)係由（甲基）丙烯酸2-羥乙酯、 (甲基）丙烯酸2-羥丙酯、三羥甲基丙烷二（甲基）丙烯酸酯及季戊四醇三丙烯酸酯所構成之群中所選出之丨種以上。 [6] 如第Π]〜[5]項中任一項所記載之感光性樹脂組成物，其中進一步含有由反應性稀釋劑（C)、光聚合起始劑（D)及著色劑（E)所構成之群中所選出之！種以上。 [7] 如第[6]項所記載之感光性樹脂組成物，.其中前述著色劑（E)含有染料。 [8] —種加成共聚物（A)，其特徵爲：具有碳數1〇〜 20之架橋環式烴基之單體（a_l)及/或下述一般式（1)所表示之-單體（a-l')2〜60莫耳％(wherein X and Y are each independently represented by a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms; and R1 and R2 are each independently represented by a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a carboxyl group; And R2 can form a linked cyclic structure) 201202280, unsaturated polybasic acid anhydride (a-2) 30 to 88% by mole, and (al), (al·) and (a-2) other than the copolymerizable single The copolymer (a-3) is a copolymer obtained by copolymerization of 10 to 68 mol%, and a monomer (a-4) having a hydroxyl group is added. [2] The photosensitive resin composition as described in the item [1], wherein the monomer (a-oxime) is a dicyclopentyl methacrylate. [3] The photosensitive resin composition according to [1] or [2] wherein the unsaturated polybasic acid anhydride (a-2) is maleic anhydride. [4] The photosensitive resin composition according to any one of [1] to [3] wherein the monomer (a-3) contains 10 to 40 mol% of vinyl toluene. [5] The photosensitive resin composition as described in any one of the items [4], wherein the monomer (a-4) is 2-hydroxyethyl (meth)acrylate, (methyl) Any of the selected species selected from the group consisting of 2-hydroxypropyl acrylate, trimethylolpropane di(meth) acrylate, and pentaerythritol triacrylate. [6] The photosensitive resin composition according to any one of [5], which further comprises a reactive diluent (C), a photopolymerization initiator (D), and a color former (E) ) selected among the groups formed! More than one species. [7] The photosensitive resin composition according to [6], wherein the colorant (E) contains a dye. [8] An addition copolymer (A) characterized by a monomer (a-1) having a bridged cyclic hydrocarbon group having a carbon number of 1 to 20 and/or a single represented by the following general formula (1) Body (a-l') 2~60 mol%

S -8 " 201202280 [化2]S -8 " 201202280 [Chemical 2]

(式中，X及Y各自獨立，表示氫原子、或碳數1〜4之直鏈或支鏈之烴基；R1及R2各自獨立，表示氫原子、碳數 1〜20之烴基或羧基；R1及R2可形成連結的環狀構造）、不飽和多元酸酐（a-2)30〜88莫耳％、以及（a-l)、（a-Γ) 及（a-2)以外之可共聚合的單體（a-3)l〇〜68莫耳％進行共聚合而得之共聚物，加成具有羥基的單體（a-4)。 [9] 如第[8]項所記載之加成共聚物（A)，其中前述單體（a-1)係二環戊基甲基丙烯酸酯。 [10] 如第[8]或[9]項所記載之加成共聚物（A)，其中前述不飽和多元酸酐（a-2)係馬來酸酐。 [11] 如第[8]〜[10]項中任一項所記載之加成共聚物 (A) ’其中前述單體（a-3)含有乙烯基甲苯1〇〜40莫耳％。 [12] 如第[8]〜[1 1]項中任一項所記載之加成共聚物 (A) ’其中前述單體（a-4)係由（甲基）丙烯酸2-羥乙酯、（甲基）丙烯酸2-羥丙酯、三羥甲基丙烷二（甲基）丙烯酸酯及季戊四醇三丙烯酸酯所構成之群中所選出之1種以上。 [13] —種彩色濾光器，其特徵爲：具有由如第[1]〜 [7]項中任一項所記載之感光性樹脂組成物所形成的著色圖型。 201202280 [發明之效果] 依據本發明可提供一種感光性樹脂組成物，可產生靈敏度或顯像性良好，同時耐熱分解性及耐溶劑性優異的著色圖型。另外，依據本發明可提供一種鹼可溶性樹脂（加成共聚物），係使用於可產生靈敏度或顯像性良好，同時耐熱分解性及耐溶劑性優異的著色圖型之感光性樹脂組成 .物。進一步而言，依據本發明還可提供一種彩色濾光器，係具有耐熱分解性及耐溶劑性優異的著色圖型。【實施方式】實施形態1 . 本實施形態之加成共聚物（A)，係藉由在使具有碳數 10〜20之架橋環式烴基之單體（a_ 1)及/或下述一般式（1)所表示之單體（a_l’） [化3](wherein X and Y each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms; and R1 and R2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a carboxyl group; And R2 can form a linked cyclic structure), unsaturated polybasic acid anhydride (a-2) 30 to 88% by mole, and (al), (a-Γ) and (a-2) other than the copolymerizable single The copolymer (a-3) is a copolymer obtained by copolymerization, and a monomer (a-4) having a hydroxyl group is added. [9] The addition copolymer (A) according to the item [8], wherein the monomer (a-1) is a dicyclopentyl methacrylate. [10] The addition copolymer (A) according to [8] or [9] wherein the unsaturated polybasic acid anhydride (a-2) is maleic anhydride. [11] The addition copolymer (A)' according to any one of [8] to [10] wherein the monomer (a-3) contains vinyl toluene in an amount of from 1 to 40 mol%. [12] The addition copolymer (A) as described in any one of [8] to [1], wherein the aforementioned monomer (a-4) is 2-hydroxyethyl (meth)acrylate One or more selected from the group consisting of 2-hydroxypropyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol triacrylate. [13] A color filter having a coloring pattern formed by the photosensitive resin composition according to any one of [1] to [7]. [Embodiment of the Invention] According to the present invention, it is possible to provide a photosensitive resin composition which is excellent in sensitivity and developability, and which is excellent in thermal decomposition resistance and solvent resistance. Further, according to the present invention, it is possible to provide an alkali-soluble resin (addition copolymer) which is used in a photosensitive resin composition which is excellent in sensitivity and developability, and which is excellent in thermal decomposition resistance and solvent resistance. . Further, according to the present invention, it is also possible to provide a color filter having a coloring pattern excellent in heat decomposition resistance and solvent resistance. [Embodiment] Embodiment 1 The addition copolymer (A) of the present embodiment is a monomer (a-1) having a bridged cyclic hydrocarbon group having a carbon number of 10 to 20 and/or the following general formula. (1) The monomer represented (a_l') [Chemical 3]

(式中’ X及Y各自獨立，表示氫原子、或碳數1〜4之直鏈或支鏈之烴基；R1及R2各自獨立，表示氫原子、碳數 1〜20之烴基或羧基；Ri及R2可形成連結的環狀構造）、不飽和多元酸酐（a-2)、以及（a-l)、（a-i，）及（a-2)以外之可共聚合的單體（a-3)進行共聚合而得之共聚物，加成具有羥基的單體（a-4)所得到之物》(wherein X and Y are each independently represented by a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms; and R1 and R2 are each independently and represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a carboxyl group; And R2 may form a linked cyclic structure), an unsaturated polybasic acid anhydride (a-2), and a copolymerizable monomer (a-3) other than (al), (ai,) and (a-2). a copolymer obtained by copolymerization and addition of a monomer having a hydroxyl group (a-4)

S -10- 201202280 單體（a_l)只要具有碳數10〜2〇之架橋環式烴基，則並未受到特別限定。此處，架橋環式烴意指以金剛烷、降莰烷爲代表，而具有下述一般式（2)或（3)所示構造之物質’架橋環式烴基意指相當於除去該構造中一部分的氫之後所殘餘的部分之基團》 [化4]S -10- 201202280 The monomer (a-1) is not particularly limited as long as it has a bridged cyclic hydrocarbon group having 10 to 2 carbon atoms. Here, the bridged cyclic hydrocarbon means a substance represented by adamantane or norbornane, and a substance having a structure represented by the following general formula (2) or (3) 'bridged cyclic hydrocarbon group means equivalent to removing the structure a part of the group remaining after the hydrogen" [Chemical 4]

[化5] Η Α({>2 ⑶ R4 一般式（2)中，Α1及Β1相同或相異皆可，分別表示直鏈或分支伸烷基（包括環式）；R3表示氫原子或甲基。另外，A1及B1之分支可彼此鍵結而成爲環狀。另外，一般式（3)中，A2、B2及L相同或相異皆可，分別表示直鏈或分支伸烷基（包括環式）；R4表示氫原子或甲基。另外， A2、B2及L的分支亦可彼此結合成爲環狀。單體（a-Ι)的例子，可列舉二環戊烯基（甲基）丙烯酸酯、二環戊基（甲基）丙烯酸酯、（甲基）丙烯酸異莰酯、（甲基）丙烯酸金剛烷酯等。在該等之中，係以耐熱分解性、密著性、顯像性等觀點看來二環戊基甲基丙烯酸酯爲佳。 -11 - 201202280 該等可單獨使用或組合兩種以上。單體（a-Γ)只要具有上述一般式（1)所表示之化學構造，則並未受到特別限定》在一般式（1)之中，表示碳數1 〜4之直鏈或支鏈之烴基之X及Y的例子，可列舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基等。另外，表示碳數1〜20之烴基之R1及R2的例子，可列舉甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、第三戊基、硬脂醯基、月桂基、2-乙基己基等直鏈或支鏈之烷基；苯基等芳香基；環己基、第三丁基環己基、二環戊二烯基、三環癸基、異冰片基、金剛烷基、2-甲基-2-金剛烷基等脂環式基；1-甲氧基乙基、1-乙氧基乙基等經烷氧基取代之烷基；經苄基等芳香基取代之烷基等。具有一般式（1)所表示之化學構造之單體（a-Γ)的例子，可列舉降莰烯（雙環[2 ·2·1]庚-2-烯）、5-甲基雙環 [2·2_1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、四環 [4.4 · 0.1 2 ’5 · 1 7 ’1 0 ]十二-3 -烯、8 -甲基四環[4 · 4.0.1 2 ’5 · 1 7 ’1 0 ] 十二-3-烯、8-乙基四環[4.4.0.12’5.l7’10]十二-3-烯、二環戊二烯、三環[5.2.1.02’6]癸-8-烯、三環[5.2.1.02’6]癸-3-烯、三環[4.4.0.12’5]十一-3-烯、三環[6.2.1.01^+-9-烯、三環[6.2.1.01，8]十一-4-烯、四環[HO.lU.lUQ.O1，6] 十二-3-烯、8-甲基四環[4_4.0.12’5.17’1().01，6]十二-3-烯、 8-亞乙基四環[4.4.0.12’5.17’12]十二-3-烯、8-亞乙基四環 [4.4.0.12’5.17’1。.01’6]十二-3-烯、五環[6.5.1.13,6.02’7.09，13] 十五-4-烯、五環[7.4.0.12’5.19’12.〇8’13]十五-3-烯、5-降莰化 Α ({>2 (3) R4 In general formula (2), Α1 and Β1 are the same or different, respectively representing a straight or branched alkyl group (including a ring); R3 represents a hydrogen atom or Further, the branches of A1 and B1 may be bonded to each other to form a ring. Further, in the general formula (3), A2, B2 and L may be the same or different, and each represents a linear or branched alkyl group ( R4 represents a hydrogen atom or a methyl group. Further, the branches of A2, B2 and L may be bonded to each other to form a ring. Examples of the monomer (a-fluorene) include dicyclopentenyl (methyl) Acrylate, dicyclopentyl (meth) acrylate, isodecyl (meth) acrylate, adamantyl (meth) acrylate, etc. Among these, heat decomposition resistance, adhesion, Dicyclopentyl methacrylate is preferred from the viewpoints of development, etc. -11 - 201202280 These may be used alone or in combination of two or more. The monomer (a-Γ) is represented by the above general formula (1). The chemical structure is not particularly limited. In the general formula (1), X and Y of a linear or branched hydrocarbon group having a carbon number of 1 to 4 are represented. Examples of the group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, etc. Further, examples of R1 and R2 which represent a hydrocarbon group having 1 to 20 carbon atoms may be mentioned. Listed as straight chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, third amyl, stearyl, lauryl, 2-ethylhexyl or Branched alkyl; aryl group such as phenyl; cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, 2-methyl-2-gold An alicyclic group such as an alkyl group; an alkyl group substituted by an alkoxy group such as a 1-methoxyethyl group or a 1-ethoxyethyl group; an alkyl group substituted with an aryl group or the like; and the like. Examples of the chemically-organic monomer (a-Γ) represented by the invention include norbornene (bicyclo[2·2·1]hept-2-ene), 5-methylbicyclo[2·2_1]heptane- 2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4 ·0.1 2 '5 · 1 7 '1 0 ]dode-3-ene, 8-methyltetracyclo[ 4 · 4.0.1 2 '5 · 1 7 '1 0 ] Dodec-3-ene, 8-ethyltetracyclo[4.4.0.12'5.l7'10]dodec-3-ene, dicyclopentane Alkene, tricyclo[5.2.1.0''6]non-8-ene, tricyclo[5.2.1.02'6]non-3-ene, tricyclo[4.4.0.12'5]undec-3-ene, tricyclic [6.2.1.01^+-9-ene, tricyclo[6.2.1.01,8]und-4-ene, tetracyclo[HO.lU.lUQ.O1,6] dodeca-3-ene, 8-a Tetracyclic ring [4_4.0.12'5.17'1().01,6]dodec-3-ene, 8-ethylenetetracyclo[4.4.0.12'5.17'12]dodec-3-ene, 8- Ethylene tetracycline [4.4.0.12'5.17'1. .01'6]Dode-3-ene, pentacyclic [6.5.1.13, 6.02'7.09,13] fifteen-4-ene, pentacyclic [7.4.0.12'5.19'12.〇8'13] fifteen 3-ene, 5-northene

S -12- 201202280 烯-2-羧酸、5-降莰烯-2,3-二羧酸、5-降莰烯-2,3-二羧酸酐等。在該等之中，從耐熱分解性、密著性、顯像特性等觀點看來，係以降莰烯、二環戊二烯、5-降莰烯-2,3-二殘酸酐爲佳。該等可單獨使用或組合兩種以上。單體U-1)及/或單體（a-Ι’）的摻合比例，在將單體（a·1) 及/或單體（a-1，）、不飽和多元酸酐（a-2)以及單體（a-3)之合計定爲100莫耳％的情況下爲2〜60莫耳％，宜爲5〜20 莫耳％。單體（a-l)及/或單體（a-Γ)的摻合比例若未達2莫耳％，則無法得到所希望的耐熱分解性。另一方面，該摻合比例若超過60莫耳％，則不飽和多元酸酐（a-2)的摻合比例變少，而無法得到所希望的靈敏度或顯像性。不飽和多元酸酐（a-2)並未受到特別限定，可採用在該技術領域所周知的物質。不飽和多元酸酐（a-2)的例子，可列舉馬來酸酐、伊康酸酐、檸康酸酐等。在該等之中，從容易取得、聚合性、反應性等觀點看來，以馬來酸酐爲佳。不飽和多元酸酐（a-2)的摻合比例，在將單體（a_l)及/ 或單體（a-1·)、不飽和多元酸酐（a-2)以及單體（a-3)之合計定爲100莫耳％的情況下爲30〜88莫耳％ ’宜爲35〜7〇莫耳％。不飽和多元酸酐（a-2)的摻合比例若未達30莫耳 %，則在加成共聚物（A)中的雙鍵量變少’而無法得到所希望的靈敏度。另一方面，該摻合比例若超過88莫耳 %，則未反應不飽和多元酸酐（a-2)的殘存會變多。單體（a-3)只要是（a-1)、（a-1，）及（a-2)以外的可共聚合 -13- 201202280 物質，則並未受到特別限定。單體（a-3)—般而言，係具有乙烯性不飽和基之自由基聚合性化合物，其例子可列舉丁二烯、2,3-二甲基丁二烯、異戊二烯、氯丁二烯等二烯類；（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸正丙酯、（甲基）丙烯酸異丙酯、（甲基）丙烯酸正丁酯、 (甲基）丙烯酸第二丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸第三丁酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸新戊酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸異戊酯、（甲基）丙烯酸己酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸月桂酯、（甲基）丙烯酸十二烷酯、（甲基）丙烯酸環戊酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸甲基環己酯、（甲基）丙烯酸乙基環己醋、1，4-環己院二甲醇單（甲基）丙嫌酸酯、（甲基）丙烯酸松香酯、（甲基）丙烯酸降莰酯、（甲基）丙烯酸5 -甲基降莰酯、（甲基）丙烯酸5-乙基降莰酯、（甲基）丙烯酸烯丙酯、（甲基）丙烯酸炔丙酯、（甲基）丙烯酸胡椒酯、（甲基）丙烯酸水楊酯、（甲基）丙烯酸呋喃酯、（甲基）丙烯酸呋喃甲酯、（甲基）丙烯酸四氫呋喃甲酯、（甲基）丙烯酸吡喃酯、（甲基）丙烯酸苯乙酯、（甲基）丙烯酸甲苯酚酯、（甲基）丙烯酸三氟乙酯、（甲基）丙烯酸全氟乙酯、（甲基）丙烯酸全氟正丙酯、（甲基）丙烯酸全氟異丙酯、三苯基甲基（甲基）丙烯酸酯、（甲基）丙烯酸異丙苯酯、（甲基）丙烯酸3-(N，N-二甲胺基）丙酯、甘油單（甲基）丙烯酸酯、丁三醇單（甲基）丙烯酸酯、戊三醇單（甲基）丙烯酸酯、（甲基）丙烯酸萘酯、（甲基）丙烯酸蒽酯等（甲基）丙烯酸酯類；（甲S -12- 201202280 Alkene-2-carboxylic acid, 5-northene-2,3-dicarboxylic acid, 5-northene-2,3-dicarboxylic anhydride, and the like. Among these, from the viewpoints of heat decomposition resistance, adhesion, development characteristics and the like, it is preferably decene, dicyclopentadiene or 5-northene-2,3-dicarboxylic acid anhydride. These may be used alone or in combination of two or more. The blending ratio of the monomer U-1) and/or the monomer (a-Ι') in the monomer (a·1) and/or the monomer (a-1,), the unsaturated polybasic acid anhydride (a- 2) When the total of the monomers (a-3) is 100 mol%, it is 2 to 60 mol%, preferably 5 to 20 mol%. When the blending ratio of the monomer (a-1) and/or the monomer (a-ruthenium) is less than 2 mol%, the desired thermal decomposition resistance cannot be obtained. On the other hand, when the blending ratio exceeds 60 mol%, the blending ratio of the unsaturated polybasic acid anhydride (a-2) becomes small, and the desired sensitivity or developability cannot be obtained. The unsaturated polybasic acid anhydride (a-2) is not particularly limited, and those known in the art can be used. Examples of the unsaturated polybasic acid anhydride (a-2) include maleic anhydride, itaconic anhydride, and citraconic anhydride. Among these, maleic anhydride is preferred from the viewpoints of easy availability, polymerizability, reactivity, and the like. The blending ratio of the unsaturated polybasic acid anhydride (a-2) is such that the monomer (a-1) and/or the monomer (a-1·), the unsaturated polybasic acid anhydride (a-2), and the monomer (a-3) The total amount is set to 100% by mole in the case of 30 to 88% by mole % of which is preferably 35 to 7 〇% by mole. When the blending ratio of the unsaturated polybasic acid anhydride (a-2) is less than 30 mol%, the amount of double bonds in the addition copolymer (A) becomes small, and the desired sensitivity cannot be obtained. On the other hand, when the blending ratio exceeds 88 mol%, the residual of the unreacted unsaturated polybasic acid anhydride (a-2) increases. The monomer (a-3) is not particularly limited as long as it is a copolymerizable substance other than (a-1), (a-1,), and (a-2) -13-201202280. The monomer (a-3) is generally a radical polymerizable compound having an ethylenically unsaturated group, and examples thereof include butadiene, 2,3-dimethylbutadiene, and isoprene. Diene such as chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate Ester, second butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, (a) Benzyl acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, 12 (meth)acrylate Alkyl ester, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexanyl (meth)acrylate, 1,4-cyclohexyl Dimethanol mono(methyl)propionic acid ester, (meth)acrylic acid rosin ester, (meth)acrylic acid methyl ester, (methyl 5-methylnorbornyl acrylate, 5-ethylnorphthyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, piperonyl (meth)acrylate, (A) Base) Salicyl acrylate, furyl (meth) acrylate, furan methyl (meth) acrylate, tetrahydrofuran methyl (meth) acrylate, pyryl (meth) acrylate, phenethyl (meth) acrylate , cresyl (meth) acrylate, trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro- n-propyl (meth) acrylate, perfluoroisopropyl (meth) acrylate Ester, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3-(N, N-dimethylamino) propyl (meth) acrylate, glycerol mono (methyl) (meth) acrylates such as acrylate, butyl triol mono(meth) acrylate, pentyl triol mono (meth) acrylate, naphthyl (meth) acrylate, decyl (meth) acrylate; A

S -14 - 201202280 基）丙烯醯胺、（甲基）丙烯酸N-N-二甲基醯胺、（甲基）丙烯酸N，N-二乙基醯胺、（甲基）丙烯酸N，N-二丙醯胺、（甲基）丙烯酸N，N-二異丙醯胺、（甲基）丙烯酸蒽醯胺等（甲基）丙烯醯胺；（甲基）丙烯酸苯胺、（甲基）丙烯醯腈、丙烯醛、氯乙烯、偏二氯乙烯、氟乙烯' 偏二氟乙烯、N-乙烯基吡咯烷酮、乙烯基吡啶、醋酸乙烯酯、乙烯基甲苯等乙烯基化合物；苯乙烯、苯乙烯在α位、鄰位、間位、對位的烷基、硝基、氰基、醯胺之衍生物；檸康酸二乙酯、馬來酸二乙酯、富馬酸二乙酯、伊康酸二乙基等不飽和二羧酸二酯：Ν-苯基馬來醯亞胺、Ν-環己基馬來醯亞胺、Ν-月桂基馬來醯亞胺、Ν-(4-羥苯基）馬來醯亞胺等單馬來醯亞胺類；Ν-(甲基）丙烯醯基酞醯亞胺、（甲基）丙烯酸、巴豆酸、桂皮酸等具有羧基之化合物等。該等可單獨使用或組合兩種以上。特別是在不飽和多元酸酐（a-2)採用馬來酸酐的情況下，馬來酸酐爲電子接受性強的化合物，因此單體（a-3)係以電子供予性單體爲佳。藉由使用這種電子供予性單體，與馬來酸酐等之間發生交互共聚，各個單元更隨機配置的結果，可提升顯像性或靈敏度等’同時可形成耐熱分解性優異的著色圖型。電子供予性單體可列舉乙烯基醚類、乙烯基硫類、苯乙烯類等。在該等之中’從共聚合性的觀點看來，係以苯乙烯類爲佳，從耐分解性的觀點看來，係以乙烯基甲苯爲較佳。另外，在使用乙烯基甲苯的情況下，藉著倂用（甲基）丙烯酸酯類，能夠更進一步提升顯像性。 -15- 201202280 單體（a-3)的摻合比例，在將單體（a-l)及/或單體（a_ 1·)、不飽和多元酸酐（a-2)以及單體U-3)之合計定爲1〇〇莫耳％的情況下爲10〜68莫耳％，宜爲20〜50莫耳％。單體（a-3)的摻合比例若未達10莫耳％，則無法取得耐熱分解性或顯像性的平衡。另一方面，該摻合比例若超過 68莫耳％，則靈敏度或耐熱性降低。特別是在單體（a-3)採用乙烯基甲苯的情況下，在將單體（a-l)及/或單體（a-l’）、不飽和多元酸酐（a-2)以及單體 (a-3)之合計定爲1〇〇莫耳％的情況下，單體（a-3)係以含有 10〜40莫耳％的乙烯基甲苯爲佳。使用單體（a-l)及/或單體（a-i·)、不飽和多元酸酐（3-2) 以及單體（a_ 3)作爲原料的共聚合反應，可依照該技術領域之中周知的自由基聚合方法而進行。例如使單體（a-l)及/ 或單體（a-l·)、不飽和多元酸酐（a-2)以及單體（a-3)溶於溶劑之後，在該溶液添加聚合起始劑，使其在50〜1301反應1〜2 0小時即可。該共聚合反應所能夠使用的溶劑並未受到特別限定，而可列舉例如丙二醇單甲醚、丙二醇單甲醚醋酸酯等二醇酸系溶劑；甲苯、二甲苯等烴系溶劑、醋酸乙酯等不具有反應性官能基的溶劑。該等可單獨使用或組合兩種以上。另外，在該等之中，係以二醇醚系溶劑爲佳。溶劑的摻合量只要能夠使原料溶解，則並未受到特別限定，然而在將單體（a-l)及/或單體（a-l')、不飽和多元酸無酐（a-2)以及單體（a-3)之合計定爲100質量份的情況S -14 - 201202280 base acrylamide, NN-dimethyl decyl (meth) acrylate, N,N-diethyl decyl (meth) acrylate, N, N-dipropyl (meth) acrylate (Methyl) acrylamide such as decylamine, N,N-diisopropyl hydrazine (meth) acrylate, decyl (meth) acrylate, aniline (meth) acrylate, (meth) acrylonitrile, Acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinyl pyrrolidone, vinyl pyridine, vinyl acetate, vinyl toluene, etc.; styrene, styrene in the alpha position, Ortho-, meta-, para-alkyl, nitro, cyano, decylamine derivatives; diethyl citrate, diethyl maleate, diethyl fumarate, diconazole Iso-unsaturated dicarboxylic acid diester: Ν-phenyl maleimide, Ν-cyclohexylmaleimide, Ν-lauryl maleimide, Ν-(4-hydroxyphenyl) horse A monomaleimide such as quinone imine; a compound having a carboxyl group such as fluorene-(meth)acrylonitrile quinone imine, (meth)acrylic acid, crotonic acid or cinnamic acid. These may be used alone or in combination of two or more. In particular, when maleic anhydride is used as the unsaturated polybasic acid anhydride (a-2), maleic anhydride is a compound having high electron acceptability, and therefore, the monomer (a-3) is preferably an electron-donating monomer. By using such an electron-donating monomer, it is interactively copolymerized with maleic anhydride or the like, and the results of more random arrangement of the respective units can improve the development performance, sensitivity, etc., and form a color map excellent in thermal decomposition resistance. type. Examples of the electron donating monomer include vinyl ethers, vinyl sulfides, and styrenes. Among these, 'styrene is preferred from the viewpoint of copolymerizability, and vinyltoluene is preferred from the viewpoint of decomposition resistance. Further, in the case of using vinyl toluene, the development property can be further improved by using (meth) acrylate. -15- 201202280 The blending ratio of monomer (a-3), in the monomer (al) and / or monomer (a-1), unsaturated polybasic acid anhydride (a-2) and monomer U-3) The total amount is 10 to 68 mol% in the case of 1 mol%, preferably 20 to 50 mol%. When the blending ratio of the monomer (a-3) is less than 10 mol%, the balance between heat decomposition resistance and developing ability cannot be obtained. On the other hand, if the blending ratio exceeds 68 mol%, the sensitivity or heat resistance is lowered. Particularly in the case where the monomer (a-3) is a vinyl toluene, the monomer (al) and/or the monomer (a-1'), the unsaturated polybasic acid anhydride (a-2), and the monomer ( In the case where the total of a-3) is 1% by mole, the monomer (a-3) is preferably a vinyl toluene containing 10 to 40% by mole. The copolymerization reaction using a monomer (al) and/or a monomer (ai·), an unsaturated polybasic acid anhydride (3-2), and a monomer (a-3) as a raw material may be a free radical known in the art. The polymerization method is carried out. For example, after dissolving a monomer (al) and/or a monomer (al·), an unsaturated polybasic acid anhydride (a-2), and a monomer (a-3) in a solvent, a polymerization initiator is added to the solution to cause a polymerization initiator to be added thereto. The reaction can be carried out in 50~1301 for 1~2 0 hours. The solvent which can be used for the copolymerization reaction is not particularly limited, and examples thereof include glycolic acid solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; hydrocarbon solvents such as toluene and xylene; and ethyl acetate. A solvent that does not have a reactive functional group. These may be used alone or in combination of two or more. Further, among these, a glycol ether solvent is preferred. The amount of the solvent to be blended is not particularly limited as long as the raw material can be dissolved. However, the monomer (al) and/or the monomer (a-1') and the unsaturated polybasic acid (a-2) and the unsaturated polybasic acid are not particularly limited. When the total of the monomers (a-3) is 100 parts by mass

S • 16 - 201202280 下，一般而言爲30〜1000質量份，宜爲 50〜800質量份。特別是將溶劑摻合量定爲1 000質量份以下，並藉由鏈轉移作用，可抑制共聚物分子量降低，且可將共聚物的黏度控制在適當的範圍。另外，藉著將溶劑的摻合量定爲 30質量份以上，可防止異常的聚合反應，而使聚合反應安定地進行，同時還可防止共聚物的著色或膠化。另外，該共聚合反應所能夠使用的聚合起始劑並未受到特別限定，而可列舉例如偶氮雙異丁腈、偶氮雙異纈草腈、過氧化苯甲醯基、過氧化2-乙基已酸第三丁酯等《該等可單獨使用或組合兩種以上。聚合起始劑的摻合量，在將單體（a-Ι)及/或單體（a-1’）、不飽和多元酸酐（a_2)以及單體（a_3)之合計定爲1〇〇質量份的情況下，一般而言，爲0.5〜20質量份，宜爲 1.0〜1 0質量份。另外，亦可不使用有機溶劑，而使用單體（a-1)及/或單體（a-1’）、不飽和多元酸酐（a-2)以及單體（a-3)與聚合起始劑進行塊狀聚合。上述共聚物反應所得到的共聚物，係藉由加成具有羥基的單體（a-4)，而在共聚物的側鏈導入羧基及雙鍵。藉此可提升感光性樹脂組成物的靈敏度或顯像性。單體（a-4)的例子，可列舉2-羥乙基（甲基）丙烯酸酯、 (甲基）丙烯酸2-羥丙酯、（甲基）丙烯酸2-羥基丁酯、（甲基）丙烯酸2,3-二羥丙酯、甘油二甲基丙烯酸酯、（甲基）丙烯酸2_羥基-3-丙烯醯氧基丙酯、2-丙烯醯氧基乙基-2-羥 -17- 201202280 乙基-苯二甲酸、三羥甲基丙烷二（甲基）丙烯酸酯、季戊四醇三丙烯酸酯等。該等可單獨使用，或組合兩種以上。特別是在考慮到與共聚物中的酸酐基之反應性的情況下，單體（a-4)係以具有1級羥基爲佳。另外，在考慮到感光性樹脂組成物靈敏度的情況下，單體（a-4)由於會使加成共聚物（A)中雙鍵的量變多，因此係以分子量小的物質或多官能之（甲基）丙烯酸酯爲佳。滿足該等條件的單體，可列舉（甲基）丙烯酸2-羥乙酯、（甲基）丙烯酸2-羥丙酯、三羥甲基丙烷二（甲基）丙烯酸酯、季戊四醇三丙烯酸酯等。單體（a_4)相對於共聚物中酸酐基的加成比例係以10 〜100%爲佳。爲了進行這種單體（a-4)的加成反應，在將共聚物的酸酐基莫耳當量定爲1時，只要添加單體（a-4)使單體（a-4)中的羥基莫耳當量在0.1〜1的範圍而使其反應即可。加成比例若未達1 〇%，則在共聚物的側鏈所導入的羧基及雙鍵的量變得太少，而無法得到所希望的靈敏度或顯像性。單體（a-4)對於共聚物中的酸酐基之加成反應.，只要在共聚物中添加單體（a-4)、聚合禁止劑及觸媒，並在50〜 15 0°C (宜爲80〜130°C )進行反應即可。另外，在該加成反應中，即使含有共聚合反應所使用的溶劑，也不會特別產生問題，因此在共聚合反應結束之後，不需要將溶劑除去也能進行加成反應。此處添加聚合禁止劑是爲了防止共聚物的聚合造成膠化。聚合禁止劑並未受到特別限定，而可列舉例如氫醌、S 16 - 201202280, generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass. In particular, the solvent blending amount is set to 1,000,000 parts by mass or less, and by chain transfer, the molecular weight of the copolymer can be suppressed from decreasing, and the viscosity of the copolymer can be controlled to an appropriate range. In addition, by setting the blending amount of the solvent to 30 parts by mass or more, an abnormal polymerization reaction can be prevented, and the polymerization reaction can be carried out stably, and the coloring or gelation of the copolymer can be prevented. Further, the polymerization initiator which can be used in the copolymerization reaction is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisohumamonitrile, benzoyl peroxide, and peroxide 2- "Ethyl hexanoate, etc." These may be used alone or in combination of two or more. The blending amount of the polymerization initiator is set to 1 in a total of the monomer (a-fluorene) and/or the monomer (a-1'), the unsaturated polybasic acid anhydride (a_2), and the monomer (a-3). In the case of a part by mass, it is usually 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass. Alternatively, the monomer (a-1) and/or the monomer (a-1'), the unsaturated polybasic acid anhydride (a-2), and the monomer (a-3) may be used without the use of an organic solvent. The agent is subjected to bulk polymerization. The copolymer obtained by the above copolymer reaction is a carboxyl group and a double bond introduced into the side chain of the copolymer by addition of a monomer (a-4) having a hydroxyl group. Thereby, the sensitivity or developability of the photosensitive resin composition can be improved. Examples of the monomer (a-4) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and (methyl) 2,3-dihydroxypropyl acrylate, glycerol dimethacrylate, 2-hydroxy-3-propenyloxypropyl (meth)acrylate, 2-propenyloxyethyl-2-hydroxy-17- 201202280 Ethyl-phthalic acid, trimethylolpropane di(meth)acrylate, pentaerythritol triacrylate, and the like. These may be used alone or in combination of two or more. In particular, in consideration of reactivity with an acid anhydride group in the copolymer, the monomer (a-4) is preferably a hydroxyl group having a first order. Further, in consideration of the sensitivity of the photosensitive resin composition, since the monomer (a-4) increases the amount of double bonds in the addition copolymer (A), it is a substance having a small molecular weight or a polyfunctional one. (Meth) acrylate is preferred. Examples of the monomer satisfying these conditions include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol triacrylate, and the like. . The addition ratio of the monomer (a-4) to the acid anhydride group in the copolymer is preferably from 10 to 100%. In order to carry out the addition reaction of the monomer (a-4), when the acid anhydride molar equivalent of the copolymer is set to 1, the monomer (a-4) is added to the monomer (a-4). The hydroxy molar equivalent may be in the range of 0.1 to 1, and may be reacted. If the addition ratio is less than 1%, the amount of the carboxyl group and the double bond introduced into the side chain of the copolymer becomes too small, and the desired sensitivity or developability cannot be obtained. The addition reaction of the monomer (a-4) to the acid anhydride group in the copolymer, as long as the monomer (a-4), the polymerization inhibiting agent and the catalyst are added to the copolymer at 50 to 150 ° C ( It is preferred to carry out the reaction at 80 to 130 ° C. Further, in the addition reaction, even if the solvent used in the copolymerization reaction is contained, no problem is particularly caused. Therefore, after the completion of the copolymerization reaction, the addition reaction can be carried out without removing the solvent. The polymerization inhibitor is added here to prevent gelation of the copolymer. The polymerization inhibiting agent is not particularly limited, and examples thereof include hydroquinone.

S •18- 201202280 甲基氫醌、氫醌單甲醚等。另外，觸媒亦並未受到特定，而可列舉例如三乙胺般的三級胺、三乙基苄基氯般的四級銨鹽、三苯膦般的磷化合物、鉻的螯合化等。在該等之中，從酸酐與羥基的反應方面看來，宜三乙胺、三乙烯二胺、4 _二甲胺基吡啶、甲基丙烯酸胺基乙酯等三級胺。如上述方式所得到加成共聚物（A)的酸價，宜爲 400KOHmg/g、較佳爲 150 〜300KOHmg/g。此酸價若 50KOHmg/g，則會有感光性樹脂組成物之顯像性降低形。另一方面，此酸價若超過400KOHmg/g，則會有部分（光硬化部分）變得容易溶於鹼顯像液的情形。另外，加成共聚物（A)的分子量（聚苯乙烯換算之平均分子量）宜爲1000〜40000，較佳爲3000〜20000 分子量若未達1 000，則會有在顯像後容易發生著色缺損的情形。另一方面，此分子量若超過40000，則顯像時間變得太長而缺乏實用性的情形。本實施形態的加成共聚物（A)最適合作爲感光性組成物所使用的鹼可溶性樹脂，能夠製造出可產生靈或顯像性良好，同時耐熱分解性及耐溶劑性優異的著型之感光性樹脂組成物。實施形態2 . 本實施形態之感光性樹脂組成物，係含有實施形的加成共聚物（A)與溶劑（B)。別限化銨合物採用二甲 50〜未達的情曝光重量。此圖型會有樹脂敏度色圖態1 -19- 201202280 溶劑（B)只要是不與加成共聚物（A)發生反應的非活性溶劑，則並未受到特別限定。溶劑（B)可採用與製造加成共聚物（A)時（共聚合反應）的使甩·的溶劑相同的物質。具體而言，溶劑（B)的例子，可列舉丙二醇單甲醚、丙二醇單甲醚醋酸酯、二丙二醇單甲醚醋酸酯、醋酸乙酯、醋酸丁酯、醋酸異丙酯、丙二醇單甲醚、二丙二醇單甲醚、三丙二醇單甲醚、乙二醇單甲醚、二乙二醇單甲醚、甲基乙基酮、甲基異丁酮、環己酮、乙二醇單乙醚醋酸酯、二乙二醇乙醚醋酸酯等。該等可單獨使用，或組合兩種以上。另外，在該等之中，係以在製造加成共聚物（A)時（共聚合反應）所使用的丙二醇單甲醚、丙二醇單甲醚醋酸酯等·二醇·醜系溶劑爲佳。本實施形態之感光性樹脂組成物中的溶劑（B)摻合量，相對於感光性樹脂組成物中之固體成分（亦即溶劑以外的成分）100質量份而言，一般爲30〜1 000質量份，宜爲50〜800質量份，較佳爲1〇〇〜700質量份。只要摻合量在此範圍，即可成爲具有適當黏度的感光性樹脂組成物。本實施形態之感光性樹脂組成物，在上述成分之外，還可含有反應性稀釋劑（C)、光聚合起始劑（D)及著色劑 (E)。反應性稀釋劑（C)只要能夠與加成共衆物（A)發生反應，則並未受到特別限定。反應稀釋劑的例子，可列舉苯乙烯、α-甲基苯乙烯、氯甲基苯乙烯、乙烯基甲苯、S •18- 201202280 Methylhydroquinone, hydroquinone monomethyl ether, etc. Further, the catalyst is not particularly limited, and examples thereof include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzyl chloride, phosphorus compounds such as triphenylphosphine, and chelation of chromium. . Among these, a tertiary amine such as triethylamine, triethylenediamine, 4-dimethylaminopyridine or aminoethyl methacrylate is preferable from the viewpoint of the reaction of the acid anhydride with the hydroxyl group. The acid value of the addition copolymer (A) obtained as described above is preferably 400 KOHmg/g, preferably 150 to 300 KOHmg/g. When the acid value is 50 KOHmg/g, the development property of the photosensitive resin composition is lowered. On the other hand, when the acid value exceeds 400 KOHmg/g, a part (photohardenable portion) may be easily dissolved in the alkali developing solution. Further, the molecular weight (average molecular weight in terms of polystyrene) of the addition copolymer (A) is preferably from 1,000 to 40,000, preferably from 3,000 to 20,000. If the molecular weight is less than 1,000, coloration defects are likely to occur after development. The situation. On the other hand, if the molecular weight exceeds 40,000, the development time becomes too long and the practicality is lacking. The addition copolymer (A) of the present embodiment is most suitable as an alkali-soluble resin used as a photosensitive composition, and can produce a shape which is excellent in reproducibility and development, and excellent in heat decomposition resistance and solvent resistance. A photosensitive resin composition. (Embodiment 2) The photosensitive resin composition of the present embodiment contains the addition copolymer (A) and the solvent (B) of the embodiment. Do not limit the ammonium compound to use dimethyl 50 ~ not reached the exposure weight. This pattern has a resin sensitivity. Color pattern 1 -19-201202280 The solvent (B) is not particularly limited as long as it is an inert solvent which does not react with the addition copolymer (A). The solvent (B) can be the same as the solvent of the oxime when the addition copolymer (A) is produced (copolymerization). Specific examples of the solvent (B) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, and propylene glycol monomethyl ether. , dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate Ester, diethylene glycol diethyl ether acetate, and the like. These may be used alone or in combination of two or more. In addition, among these, a diol/ugly solvent such as propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate used in the production of the addition copolymer (A) (copolymerization reaction) is preferred. The blending amount of the solvent (B) in the photosensitive resin composition of the present embodiment is generally 30 to 1,000 with respect to 100 parts by mass of the solid content (that is, a component other than the solvent) in the photosensitive resin composition. The mass part is preferably 50 to 800 parts by mass, preferably 1 to 700 parts by mass. As long as the blending amount is within this range, it becomes a photosensitive resin composition having an appropriate viscosity. The photosensitive resin composition of the present embodiment may further contain a reactive diluent (C), a photopolymerization initiator (D), and a color former (E) in addition to the above components. The reactive diluent (C) is not particularly limited as long as it can react with the addition co-organism (A). Examples of the reactive diluent include styrene, α-methylstyrene, chloromethylstyrene, and vinyltoluene.

S -20- 201202280 二乙烯基苯、酞酸二烯丙酯、苯膦酸二烯丙酯等芳香族乙烯基系單體類；醋酸乙烯酯、己二酸乙烯酯等多元酸單體類；（甲基）丙烯酸甲酯 '(甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸/9-羥乙酯、 (甲基）丙烯酸羥丙酯、乙二醇二（甲基）丙烯酸酯、二乙二醇二（甲基）丙烯酸酯、丙二醇二（甲基）丙烯酸酯、乙二醇二（甲基）丙烯酸酯、三羥甲基丙烷二（甲基）丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、參（羥乙基）異氰尿酸酯之三（甲基）丙烯酸酯等（甲基）丙烯酸系單體；三烯丙基氰尿酸酯等。該等可單獨使用，或組合兩種以上。本實施形態之感光性樹脂組成物中的反應性稀釋劑（C) 摻合量，相對於感光性樹脂組成物中的固體成分（亦即溶劑以外的成分）1 〇〇質量份而言，一般爲10〜90質量份，宜爲20〜80質量份，較佳爲25〜70質量份。只要摻合量在此範圍，即可成爲具有適當的光硬化性及黏度的感光性樹脂組成物。光聚合起始劑（D)並未受到特別限定，而可列舉例如安息香、安息香甲醚、安息香乙醚等安息香與其烷醚類；苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、1，1-二氯苯乙酮、 4-U-第三丁基二氧基-1-甲基乙基）苯乙酮等苯乙酮類；2-甲基蒽醌、2-戊基蒽醌、2-第三丁基蒽醌、1-氯蒽醌等蒽醌類；2,4-二甲基噻噸酮、2,4-二異丙基噻噸酮、2·氯噻噸酮等噻噸酮類；苯乙酮二甲基縮酮、苄基二甲基縮酮等 -21 - 201202280 縮酮類；二苯酮、4-(1-第三丁基二氧基-1-甲基乙基）二苯酮、3,3’，4，f-肆（第三丁基二氧基羰基）二苯酮等二苯酮類：2-甲基-1_[4-(甲基硫代）苯基]-2_嗎啉基-丙-1-酮：2-苄基-2-二甲胺基-1-(4-嗎啉基苯基）丁酮-1 ;氧化醯膦類；及咕噸酮類等。該等可單獨使用，或組合兩種以上。本實施形態之感光性樹脂組成物中的光聚合起始劑（D) 摻合量，相對於感光性樹脂組成物中的固體成分（亦即溶劑以外的成分）100質量份而言，一般爲0.1〜30質量份，宜爲0.5〜20質量份，較佳爲1〜10質量份。只要摻合量在此範圍，即可成爲具有適當的光硬化性的感光性樹脂組成物。著色劑（E)只要是可溶於溶劑（B)的物質，則並未受到特別限定，可列舉例如染料或顏料等。特別是在以往的感光性樹脂組成物中，若採用染料，則可得到輝度高的著色圖型，然而與採用顏料的情況相比，會有著色圖型的耐熱性變低的問題。相對於此，在本實施形態之感光性樹脂組成物中，染料的親和性良好，因此即使採用染料也能夠得到耐熱性優異的著色圖型。就染料而言，從對於溶劑（B)或鹼顯像液的溶解性、與感光性樹脂組成物中其他成分的交互作用、耐熱性等觀點看來，宜採用羧酸等具有酸性基團的酸性染料、酸性染料與氮化合物之鹽、酸性染料之磺醯胺體等。這種染料的例子可列舉 acid alizarin violet N ; acid black 1、2、 24 、 48 ; acid blue 1 、 7 、 9 、 25 、 29 、 40 、 45 、 62 、 70 、 s -22- 201202280 74、80 83 ' 90 、 92 ' 112' 113' 120 、129 、1 47 ；acid chrome violet K ♦ acid Fuchsin ; acid green 1 ' 3 丨、5、 25 ' 27 % 5 0 ； acid orange 6 、7、8、1 0、12 、50 '51' 52、56 、 63、 74 、 95 ； acid red 1 、 4 、 8、14 、17 '18' 26、27 、 29、 3 1 、 34、 35 ' 37 ' 42 ' 44 > 50 、5 1 、52 > 57、69 73 ' 80 87、 88、9 1 、 92 、 94 、97、 103、 111' 114、 129 、13 3、 134、 138、 143 、 145 、 150、 15 1、 158、 176、 183 、198、 2 11' 2 15、 216、 217、 249、 25 2 ' 25 7、 260 、 266 、274 ； acid violet 6 B ' 7 ' 9、17 、19 ；acid yellow 1 ' 3、 9 > 11' 17、 23 、 25 、 29 、 34 、36 、42、 54、72 ' 73、 7 6 > 79 ' 98 ' 99 、 111、 112、 114、 116； food yellow 3及該等衍生物等。在該等之中，係以偶氮系、咕噸系、蒽醌系或酞青素系之酸性染料爲佳。該等可因應於目標之畫素顔色而單獨使用或組合兩種以上。顔料的例子，可列舉 C.I. Pigment Yellow 1、3、 12、13、14、15、16、17、20、24、31、53、83、86、 93、94、109、110、117、125、128、137、138、139、 147、 148 ' 150、 153、 154、 166 ' 173、 194、 214 等黃色顏料；C.I. Pigment Orange 1 3、3 1、3 6、3 8、4 0、4 2、 43、51、55、59、61、64、65、71、73 等橘色顏料；C.I. Pigment Red 9 、 97 、 105 、 122 、 123 、 144 、 149 、 166 、 168 > 176、 177、 180、 192、 209、 215、 216、 224、 242、 254、25 5、264、265 等紅色顏料；C.I. Pigment Blue 15、15: 3' 15: 4、156: 6' 60 等藍色顏料；C.I· -23- 201202280S -20- 201202280 aromatic vinyl monomers such as divinylbenzene, diallyl phthalate, diallyl phenylphosphonate; polybasic acid monomers such as vinyl acetate and vinyl adipate; Methyl (meth) acrylate 'ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate / 9- hydroxyethyl ester, hydroxy (meth) acrylate Propyl ester, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylol Propane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, cis (hydroxyethyl)isocyanurate A (meth)acrylic monomer such as an ester tris(meth)acrylate; a triallyl cyanurate or the like. These may be used alone or in combination of two or more. The amount of the reactive diluent (C) blended in the photosensitive resin composition of the present embodiment is generally 1 part by mass based on the solid content (that is, the component other than the solvent) in the photosensitive resin composition. It is preferably 10 to 90 parts by mass, preferably 20 to 80 parts by mass, preferably 25 to 70 parts by mass. When the blending amount is within this range, it becomes a photosensitive resin composition having appropriate photocurability and viscosity. The photopolymerization initiator (D) is not particularly limited, and examples thereof include benzoin such as benzoin, benzoin methyl ether, and benzoin ethyl ether, and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenyl group; Acetophenones such as acetophenone, 1,1-dichloroacetophenone, 4-U-t-butyldioxy-1-methylethyl)acetophenone; 2-methylindole, 2 - anthraquinone such as amyl hydrazine, 2-tert-butyl fluorene, 1-chloroindole; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2· Thiophenones such as chlorothioxanthone; acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.-21 - 201202280 ketals; benzophenone, 4-(1-tert-butyldioxane Benzophenones such as keto-1-methylethyl)benzophenone, 3,3',4,f-fluorene (t-butyldioxycarbonyl)benzophenone: 2-methyl-1_[4 -(methylthio)phenyl]-2_morpholinyl-propan-1-one: 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1 ; bismuth oxide phosphine; and xanthone ketones. These may be used alone or in combination of two or more. The amount of the photopolymerization initiator (D) blended in the photosensitive resin composition of the present embodiment is generally 100 parts by mass based on 100 parts by mass of the solid component (that is, a component other than the solvent) in the photosensitive resin composition. 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass. When the blending amount is within this range, it becomes a photosensitive resin composition having appropriate photocurability. The coloring agent (E) is not particularly limited as long as it is soluble in the solvent (B), and examples thereof include a dye and a pigment. In particular, in the conventional photosensitive resin composition, when a dye is used, a color pattern having a high luminance can be obtained, but the heat resistance of the color pattern is lowered as compared with the case of using a pigment. On the other hand, in the photosensitive resin composition of the present embodiment, since the affinity of the dye is good, a coloring pattern excellent in heat resistance can be obtained even if a dye is used. In terms of the solubility of the solvent (B) or the alkali developing solution, the interaction with other components in the photosensitive resin composition, heat resistance, etc., it is preferred to use an acidic group such as a carboxylic acid. Acid dyes, salts of acid dyes and nitrogen compounds, sulfonamides of acid dyes, and the like. Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1 , 7 , 9 , 25 , 29 , 40 , 45 , 62 , 70 , s -22- 201202280 74, 80 83 ' 90 , 92 ' 112 ' 113 ' 120 , 129 , 1 47 ; acid chrome violet K ♦ acid Fuchsin ; acid green 1 ' 3 丨, 5, 25 ' 27 % 5 0 ; acid orange 6 , 7, 8, 1 0, 12, 50 '51' 52, 56, 63, 74, 95; acid red 1 , 4 , 8, 14 , 17 '18' 26, 27, 29, 3 1 , 34, 35 ' 37 ' 42 ' 44 > 50 , 5 1 , 52 > 57, 69 73 ' 80 87, 88, 9 1 , 92 , 94 , 97 , 103 , 111 ' 114 , 129 , 13 3 , 134 , 138 , 143 , 145 , 150 , 15 1, 158, 176, 183, 198, 2 11' 2 15, 216, 217, 249, 25 2 ' 25 7, 260, 266, 274; acid violet 6 B ' 7 ' 9, 17, 19; acid yellow 1 ' 3, 9 > 11' 17, 23, 25, 29, 34, 36, 42, 54, 72 '73, 7 6 > 79 ' 98 ' 99 , 111 , 112 , 114 , 116 ; food yellow 3 And such derivatives and the like. Among these, an acid dye of an azo type, a xanthene type, an anthraquinone type or an anthraquinone type is preferable. These may be used alone or in combination of two or more depending on the pixel color of the target. Examples of the pigment include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128. Yellow pigments such as 137, 138, 139, 147, 148 '150, 153, 154, 166 '173, 194, 214; CI Pigment Orange 1 3, 3 1 , 3 6 , 3 8 , 4 0 , 4 2 , 43 , orange pigments such as 51, 55, 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168 > 176, 177, 180, 192 , red pigments such as 209, 215, 216, 224, 242, 254, 25 5, 264, 265; CI Pigment Blue 15, 15: 3' 15: 4, 156: 6' 60 and other blue pigments; CI · -23 - 201202280

Pigment Violet 1、19、23、29、32、36、38 等紫色顏料；C.I. Pigment Green7、36、58 等綠色顏料；〇：.1· P i g m e n t B r o w n 2 3、2 5 等褐色顏料；.C . I · P i g m e n t B1 a c k 1、7、碳黑、鈦黑、氧化鐵等黑色顏料等。該等可因應於目標之畫素顏色而單獨使用或組合兩種以上。另外還可因應於目標之畫素顏色，而將上述染料及顏料組合使用。本實施形態之感光性樹脂組成物中的著色劑（E)摻合量，相對於感光性樹脂組成物中的固體成分（亦即溶劑以外的成分）1〇〇質量份而言，一般爲5〜80質量份，宜爲5 〜7〇質量份，較佳爲1〇〜60質量份。在著色劑（E)採用顏料的情況下，從提升顔料分散性的觀點考量，亦可將周知的分散劑摻合至感光性樹脂組成物。分散劑宜採用長時間之分散安定性優異的高分子分散劑。高分子分散劑的例子，可列舉胺甲酸乙酯系分散劑、聚乙烯亞胺系分散劑、聚氧乙烯烷醚系分散劑、聚氧乙二醇二酯系分散劑、去水山梨醇脂肪酸酯系分散劑、變性脂肪酸酯系分散劑等》這樣的高分子分散劑亦可採用以 EFKA(Efka Chemicals B.V.(EFKA)公司製）、 Disperbyk(Byk Chemie 公司製）、DISPARLON(楠本化成股份有限公司製）、SOLSPERSE(Zeneca公司製）等的商品名市售之物品。本實施形態之感光性樹脂組成物中的分散劑摻合量，只要因應於所使用的顏料等的種類適當地設定即可。Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments; CI Pigment Green 7, 36, 58 and other green pigments; 〇: .1· P igment B rown 2 3, 2 5 and other brown pigments; I · P igment B1 ack 1, 7, black pigment such as carbon black, titanium black, iron oxide, etc. These may be used alone or in combination of two or more depending on the pixel color of the target. In addition, the above dyes and pigments can be used in combination depending on the color of the target. The blending amount of the coloring agent (E) in the photosensitive resin composition of the present embodiment is generally 5 parts by mass based on 1 part by mass of the solid content (that is, a component other than the solvent) in the photosensitive resin composition. It is preferably from 5 to 7 parts by mass, preferably from 1 to 60 parts by mass, to 80 parts by mass. In the case where a pigment is used as the colorant (E), a known dispersant may be blended into the photosensitive resin composition from the viewpoint of improving the dispersibility of the pigment. The dispersing agent is preferably a polymer dispersing agent excellent in dispersion stability for a long period of time. Examples of the polymer dispersant include an urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, and a sorbitan fat. As a polymer dispersing agent such as an acid ester dispersing agent or a modified fatty acid ester dispersing agent, EFKA (Efka Chemicals BV (EFKA)), Disperbyk (Byk Chemie), and DISPARLON (Nanben Chemical Co., Ltd.) may be used. The product name of the product, such as the company's product), SOLSPERSE (made by Zeneca). The amount of the dispersant to be blended in the photosensitive resin composition of the present embodiment may be appropriately set depending on the type of the pigment to be used or the like.

S -24- 201202280 本實施形態之感光性樹脂組成物’在上述成分之外’ 還可爲了賦予既定特性而摻合周知的偶合劑、均勻劑、熱聚合禁止劑等周知的添加劑。該等添加劑的摻合量’只要在不阻礙本發明效果的範圍內，則不受特別限定。本實施形態之感光性樹脂組成物，可藉由利用周知的混合裝置將上述成分混合而製造出來。如上述方式所得到本實施形態之感光性樹脂組成物係具有鹼顯像性，因此可藉由利用鹼水溶液輕易地進行顯像。特別是本實施形態之感光性樹脂組成物，可產生靈敏度或顯像性優異，同時耐熱分解性及耐溶劑性優異的著色圖型。因此，本實施形態之感光性樹脂組成物適合使用作爲各種光阻，尤其是用於製造有機EL顯示器、液晶顯示裝置、固態攝影元件內建的彩色濾光器所使用的光阻。另外，本實施形態之感光性樹脂組成物，會產生耐熱分解性及耐溶劑性等這些特性優異的硬化膜，因此亦可使用於各種塗敷、黏著劑、印刷油墨用黏結劑等。、實施形態3. 本實施形態之彩色濾光器具有由上述感光性樹脂組成物所得到的著色圖型。以下針對本實施形態之彩色濾光器，使用圖式進行說明。S-24-201202280 The photosensitive resin composition of the present embodiment is in addition to the above-mentioned components, and a well-known additive such as a known coupling agent, a homogenizer, or a thermal polymerization inhibitor can be blended in order to impart a predetermined characteristic. The blending amount of the additives is not particularly limited as long as it does not inhibit the effects of the present invention. The photosensitive resin composition of the present embodiment can be produced by mixing the above components by a known mixing device. Since the photosensitive resin composition of the present embodiment obtained as described above has alkali developability, it can be easily imaged by using an aqueous alkali solution. In particular, the photosensitive resin composition of the present embodiment is excellent in sensitivity and development properties, and is excellent in color resistance pattern which is excellent in thermal decomposition resistance and solvent resistance. Therefore, the photosensitive resin composition of the present embodiment is suitably used as a photoresist for use in various types of photoresists, particularly for manufacturing color filters built in organic EL displays, liquid crystal display devices, and solid-state imaging devices. Further, since the photosensitive resin composition of the present embodiment has a cured film excellent in such properties as thermal decomposition resistance and solvent resistance, it can be used in various coatings, adhesives, and binders for printing inks. (Embodiment 3.) The color filter of this embodiment has a color pattern obtained from the above-mentioned photosensitive resin composition. Hereinafter, the color filter of this embodiment will be described using a drawing.

圖1係本實施形態之彩色濾光器之剖面圖。在圖1之中，彩色濾光器，係由：基板1 ;形成於基板1上之RGB -25- 201202280 畫素2及形成於畫素2的交界之黑色矩陣3;形成於畫素 2及黑色矩陣3上之保護膜4所構成。在此構成之中，除了畫素2及黑色矩陣3(著色圖型）係使用上述感光性樹脂組成物所形成之外，其他的構成可採用周知的物質。另外，圖1所示的彩色濾光器爲其中一例，不受此構成所侷限。接下來，針對本實施形態之彩色濾光器之製造方法作說明。首先，在基材1上形成著色圖型。具體而言，在基材 1上依序形成黑色矩陣3及畫素2。此處的基材1並未受到特別限定，而可採用玻璃基板、矽基板、聚碳酸酯基板、聚酯基板、聚醯胺基板、聚醯胺醯亞胺基板、聚醯亞胺基板、鋁基板、印刷電路板、陣列基板等。著色圖型可藉由光蝕刻法而形成。具體而言，將上述感光性樹脂組成物塗佈在基板1上形成塗佈膜之後，隔著既定圖型的光罩使塗佈膜曝光，而使曝光部分發生光硬化。然後，以鹼水溶液使未曝光部分顯像之後，藉由烘烤，可形成既定圖型。感光性樹脂組成物之塗佈方法並未受到特別限定，而可採用絲網印刷法、輥式塗佈法、簾式塗佈法、噴霧塗佈法、旋轉塗佈法等。另外，感光性樹脂組成物之塗佈後，亦可因應必要利用循環式烘箱、紅外線加熱器、熱板等加熱手段進行加熱，藉此使溶劑（B)揮發。加熱條件並未受到特別限定，只要因應於所使用的感光性樹脂組成物種類Fig. 1 is a cross-sectional view showing a color filter of the embodiment. In FIG. 1, the color filter is composed of: a substrate 1; RGB -25 - 201202280 pixels 2 formed on the substrate 1 and a black matrix 3 formed at the boundary of the pixel 2; formed in the pixel 2 and The protective film 4 on the black matrix 3 is composed of. In this configuration, except that the pixel 2 and the black matrix 3 (colored pattern) are formed using the photosensitive resin composition described above, other known structures can be used. Further, the color filter shown in Fig. 1 is an example thereof and is not limited to this configuration. Next, a method of manufacturing the color filter of the present embodiment will be described. First, a color pattern is formed on the substrate 1. Specifically, the black matrix 3 and the pixel 2 are sequentially formed on the substrate 1. The substrate 1 herein is not particularly limited, and a glass substrate, a ruthenium substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyimide substrate, a polyimide substrate, or an aluminum may be used. Substrate, printed circuit board, array substrate, and the like. The coloring pattern can be formed by photolithography. Specifically, after the photosensitive resin composition is applied onto the substrate 1 to form a coating film, the coating film is exposed through a mask of a predetermined pattern, and the exposed portion is photohardened. Then, after the unexposed portion is developed with an aqueous alkali solution, a predetermined pattern can be formed by baking. The coating method of the photosensitive resin composition is not particularly limited, and a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, or the like can be employed. Further, after the application of the photosensitive resin composition, the solvent (B) may be volatilized by heating by means of a heating means such as a circulating oven, an infrared heater or a hot plate. The heating conditions are not particularly limited as long as it depends on the type of photosensitive resin composition used.

S -26- 201202280 適當地設定即可。一般而言，在50 °C〜120 °C的溫度加熱 30秒鐘〜30分鐘即可。曝光所使用的光源並未受到特別限定，而可採用低壓水銀燈、中壓水銀燈、高壓水銀燈、氙燈、金屬齒素燈等。另外’曝光量亦並未受到特別限定，只要因應於所使用的感光性樹脂組成物種類適當地調整即可。顯像所使用的鹼水溶液並未受到特別限定，而可採用碳酸鈉、碳酸鉀、碳酸鈣、氫氧化鈉、氫氧化鉀等水溶液：乙胺、二乙胺、二甲基乙醇胺等胺系化合物之水溶液；3-甲基-4-胺基-Ν,Ν-二乙基苯胺、3-甲基-4-胺基-N-乙基-N-万-羥乙基苯胺、3 -甲基-4-胺基-Ν -乙基-Ν-/3-甲烷磺醯胺乙基苯胺、3 -甲基-4 -胺基-Ν -乙基-N-/S-甲氧基乙基苯胺及該等硫酸鹽、鹽酸鹽或對甲苯磺酸鹽等對苯二胺系化合物之水溶液等。在該等之中，宜採用對苯二胺系化合物之水溶液。另外，在該等水溶液中，還可因應必要添加消泡劑或界面活性劑。此外，藉由上述鹼水溶液顯像之後，宜進行水洗並使其乾燥。烘烤的條件並未受到特別限定，只要因應於所使用的感光性樹脂組成物種類進行加熱處理即可。一般而言，只要在130 °C〜250 °C加熱10〜60分鐘即可。藉由使用黑色矩陣3用的感光性樹脂組成物及畫素2 用的感光性樹脂組成物，並依序重覆如上述般的塗佈、曝光、顯像及烘烤，可形成所希望的著色圖型。另外，上述內容說明了藉由光硬化進行的著色圖型之 -27- 201202280 形成方法’然而以代替光聚合起始劑（D)，只要使用摻合了硬化促進劑及周知的環氧樹脂之感光性樹脂組成物，即可在藉由噴墨法進行塗佈之後，藉由加熱形成所希望的著色圖型。接下來’在著色圖型（畫素2及黑色矩陣3)上形成保護膜4。保護膜4並未受到特別限定，只要使用周知的物質形成即可。以這種方式製造出來的彩色濾光器，係使用可產生靈敏度或顯像性優異，同時耐熱分解性及耐溶劑性優異的著色圖型之感光性樹脂組成物所製造，因此具有耐熱分解性及耐溶劑性優異的著色圖型。 [實施例] 以下參照實施例對本發明作詳細說明，而本發明不受該等實施例限定。另外，在本實施例之中只要沒有特別解釋，份及百分比皆以質量爲基準。 <感光性樹脂組成物之調製> 在具備攪拌裝置、滴液漏斗、冷凝管、溫度計及氣體導入管的燒瓶加入426.1g的丙二醇單甲醚醋酸酯（溶劑1) 及176.4g的馬來酸酐（a-2)之後，進行氮氣置換，同時加以攪拌，並昇溫至12〇°C。接下來，在由66.0g的二環戊基甲基丙烯酸酯（a-Ι)及l〇6.2g的乙烯基甲苯（a-3)所構成的單體混合物添加24.4g的過氧化2·乙基已酸第三丁酯S -26- 201202280 It can be set as appropriate. Generally, it is heated at a temperature of 50 ° C to 120 ° C for 30 seconds to 30 minutes. The light source used for the exposure is not particularly limited, and a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal guillo lamp, or the like can be used. Further, the amount of exposure is not particularly limited, and may be appropriately adjusted depending on the type of photosensitive resin composition to be used. The aqueous alkali solution used for development is not particularly limited, and an aqueous solution such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide or potassium hydroxide may be used: an amine compound such as ethylamine, diethylamine or dimethylethanolamine. Aqueous solution; 3-methyl-4-amino-indole, fluorene-diethylaniline, 3-methyl-4-amino-N-ethyl-N-wan-hydroxyethylaniline, 3-methyl 4-amino-indole-ethyl-indole-/3-methanesulfonamide ethylaniline, 3-methyl-4-amino-indole-ethyl-N-/S-methoxyethylaniline And an aqueous solution of a p-phenylenediamine compound such as a sulfate, a hydrochloride or a p-toluenesulfonate. Among these, an aqueous solution of a p-phenylenediamine compound is preferably used. Further, in such aqueous solutions, an antifoaming agent or a surfactant may be added as necessary. Further, after development by the above aqueous alkali solution, it is preferably washed with water and dried. The baking conditions are not particularly limited as long as they are heat-treated in accordance with the type of the photosensitive resin composition to be used. In general, it is only necessary to heat at 130 °C to 250 °C for 10 to 60 minutes. By using the photosensitive resin composition for the black matrix 3 and the photosensitive resin composition for the pixel 2, and sequentially coating, exposing, developing, and baking as described above, it is possible to form a desired one. Coloring pattern. In addition, the above description illustrates the coloring pattern of photohardening -27-201202280 formation method 'however, instead of photopolymerization initiator (D), as long as a hardening accelerator and a well-known epoxy resin are blended. The photosensitive resin composition can be formed into a desired color pattern by heating after coating by an inkjet method. Next, the protective film 4 is formed on the coloring pattern (pixel 2 and black matrix 3). The protective film 4 is not particularly limited as long as it is formed using a well-known substance. The color filter manufactured in this manner is produced by using a photosensitive resin composition which is excellent in sensitivity and developability and is excellent in thermal decomposition resistance and solvent resistance, and thus has thermal decomposition resistance. A coloring pattern with excellent solvent resistance. [Examples] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples. In addition, in the present embodiment, the parts and percentages are based on mass unless otherwise specified. <Preparation of photosensitive resin composition> In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 426.1 g of propylene glycol monomethyl ether acetate (solvent 1) and 176.4 g of Malay were placed. After the acid anhydride (a-2), nitrogen substitution was carried out while stirring, and the temperature was raised to 12 °C. Next, 24.4 g of peroxide 2·B was added to a monomer mixture composed of 66.0 g of dicyclopentyl methacrylate (a-fluorene) and 〇6.2 g of vinyltoluene (a-3). Tert-butyl acid

S -28- 201202280 (聚合起始劑）’將所得之物由滴液漏斗滴A前述燒瓶中。滴入結束後’在120°C攪拌2小時進行共聚合反應，而產生共聚物。接下來’將則述燒瓶內的氣體置換爲空氣之後，加入 139.2g的丙燃酸2 -經乙醋（a-4)、1.5g的三乙胺（觸媒）及 1.5g的甲基氫醌（聚合禁止劑），在12〇°C進行加成反應6 小時，而產生加成共聚物（A)。接下來，在該加成共聚物（A)中加入3〇5.6g的丙二醇單甲醚（溶劑2)，得到感光性樹脂組成物（試樣no. 1)。除了改變原料的種類及量以外，係以與上述同樣的方式，調製出數種感光性樹脂組成物（試樣No.2〜19)。將調製感光性樹脂組成物（試樣No.l〜19)所使用的原料及其摻合量揭示於表1。 201202280 【I Μ (ΜΙΛΙ) 冪士芬 o s 〇 i o CM CO o o 〇 s 〇〇 00 〇 LO in s 00 O s CO 0 1 1 io 〇〇) l〇〇 s o 00 in 〇 σ> <D o s 〇> i in 〇 CO tr> O s σ> 備考） DCPMA :二環戊基甲基丙烯酸酯、NOR :降纖、ΜΑ :馬來酸酐、VT :乙烯基甲苯、SM :苯乙烯、AA :丙烯酸、 BZMA :甲基丙烯酸苄酯、MAA :甲基丙烯酸、THFMA :甲基丙烯酸四氫呋喃甲酯、HEA :丙烯酸2·羥乙酯、 HEMA :甲基丙烯酸2-羥乙酯、PTA :季戊四醇三丙烯酸酯、GMA :甲基丙烯酸縮水甘油酯、TEA :三乙胺、 DMMA :甲某丙烯醉二甲胺某乙酯 |S 趙 g CM g CVJ 〇 CM w r^· 00 Cvl co 〇> CM 00 00 〇> CM CO a 00 co CM C>J C*l r— CNJ CM <〇 in s Ln 00 00 cs· m % aft i〇 8 CO <〇 l〇 § QO S CO CM CO CO <〇〇> csi eg CM C4 CO CO CM a> o 另 00 eo l〇 oj K p 寸 co s § C3 〇> w s T~ 一 σ> CM O) g s CD »— CD in 寸卜· to CM 5 i m Si % T- Φ CM 5 CM 5 co CM 寸 <D C4 § CO CM* 0» CO 5 CO (〇 CO s to tn co 5 卜 o 5 <o s C9 OJ (O 2 00 CO 5 in 1 csj <〇 C*J i § 駿 < S o < < S5 H S5 H h- S5 H g 55 1- iS 1- g 1 >2 gg ^~N 9 C>J 〇» CO 〇»«<. O a) CO o N_^ (D m r— § CO in co ¥^\ § CM 〇> CO ,^Ν a> co >-✓ r~ «<—s o CM σ> co If? •S O) i 00 § § 〇 /—s 0 CM 01 eo ^—s« o eg σ> co s o CM σ> CO 8 CO <n <〇 <*"S S CM CO ?; 8 <〇〇> (O o m _ X S5 X < Έ UJ X i 0. IS X if X X X 工 2 X S5 X 2i X S5 X I S5 X X 25 X X σ S ! JO S§ 〇—s w CM g co ci cd o s ci g 8 eg g «#—«» o q 严n 兮<〇· ιο i»> in #—s o o CS 甘eg id co co寸 NmX m co « CO ui 5 CQ I g s ii g T— g» CQ CO CO σ> to CO w « ss cs 5S co ^s 3 CD GO 1 1 y-N ^-N 00 o Si5 <〇 oo 〇·对· o in C^J T- m 郷 % < H l Ϊ < < 2 5 s备 c5 1 JO 8¾¾ g I «g. (O Vm^ o—V s CO § (O s 呀 CO s 兮 (O § CM CO 00 1 00 s 00 m 04 (O CO f (O Y— (O 芩 (O r— § to >r- O-N s 寸 y—S § 寸 CD s 00 CO in 3 CO 一 CO CM § CO 00 in 1 媒 W < s < < < < < < < s < < < Έ < < < < < S < S < 1 | (a — 1 ), (a—1 ’）逛s gH W 6¾¾ /—s o <d CO o o to CO «•-s CD (D rf—·V o CO CO I 量 (D S o cd a> co ci co Q ci CO T·— >^y CD <〇 «"-n o to Φ g» s_o, CO <〇 ΰ T~ i 1 >-««· <D <D »— i /—V s o cd Si s eg co m limll 卿 < Q. 〇 Q < l o < Έ 〇〇 < S a O o < s CL 〇〇 i 0. o a < a. o a i 0. 〇 < S a a a Q < S 〇 < l 〇 Q；〇 Z i 0. 〇 Q 1 < s 0. o o < S o o < S 0. o Q < 0. o Q ΜΛ/ CM CO LA CD P- 00 O) o T~ r— y^· oj r· co 寸 lO CD r- r- co σ> -30- 201202280 在表1之中，（a-l)、（a-i，）、（a_2)及（a-3)各原料的莫耳％ ’意指在將原料（a-1)、（a-i，）、（a_2)及（a-3)的合計定爲1〇〇莫耳％時，各原料的莫耳％。另外，（a-4)的莫耳當量意指共聚物的酸酐基莫耳當量定爲1時，單體U-4)的羥基莫耳當量。另外，酸價意指依照JIS K690 1 5.3所測得的加成共聚物（A)的酸價，且爲中和加成共聚物（A)lg中所含的酸性成分所需的氫氧化鉀毫克數。另外，分子量（Mw) 意指藉由凝膠滲透層析，採用以下的條件下所測得的標準聚苯乙烯換算重量平均分子量。 <分子量測定條件> 管柱：Shodex LF-804 + LF-804(昭和電工股份有限公司製）S -28-201202280 (Polymerization Initiator) The obtained product was dropped from the dropping flask into the flask. After the completion of the dropwise addition, the copolymerization was carried out by stirring at 120 ° C for 2 hours to produce a copolymer. Next, after replacing the gas in the flask with air, 139.2 g of propionic acid 2 - ethyl acetate (a-4), 1.5 g of triethylamine (catalyst) and 1.5 g of methyl hydrogen were added.醌 (polymerization inhibiting agent), an addition reaction was carried out at 12 ° C for 6 hours to produce an addition copolymer (A). Next, 3 5.6 g of propylene glycol monomethyl ether (solvent 2) was added to the addition copolymer (A) to obtain a photosensitive resin composition (sample No. 1). Several kinds of photosensitive resin compositions (sample Nos. 2 to 19) were prepared in the same manner as above except that the type and amount of the raw materials were changed. The raw materials used for preparing the photosensitive resin compositions (Sample Nos. 1 to 19) and the blending amounts thereof are shown in Table 1. 201202280 [I Μ (ΜΙΛΙ) 士士芬os 〇io CM CO oo 〇s 〇〇00 〇LO in s 00 O s CO 0 1 1 io 〇〇) l〇〇so 00 in 〇σ><D os 〇 > i in 〇CO tr> O s σ> Remarks DCPMA: Dicyclopentyl methacrylate, NOR: defibration, hydrazine: maleic anhydride, VT: vinyl toluene, SM: styrene, AA: acrylic acid , BZMA: benzyl methacrylate, MAA: methacrylic acid, THFMA: tetrahydrofuran methyl methacrylate, HEA: 2·hydroxyethyl acrylate, HEMA: 2-hydroxyethyl methacrylate, PTA: pentaerythritol triacrylate GMA: glycidyl methacrylate, TEA: triethylamine, DMMA: a certain ethyl ester of propylene dimethyl dimethylamine|S Zhao g CM g CVJ 〇CM wr^· 00 Cvl co 〇> CM 00 00 〇 > CM CO a 00 co CM C>JC*lr- CNJ CM <〇in s Ln 00 00 cs· m % aft i〇8 CO <〇l〇§ QO S CO CM CO CO <〇〇&gt Csi eg CM C4 CO CO CM a> o another 00 eo l〇oj K p inch co s § C3 〇> ws T~ a σ> CM O) gs CD »— CD in 寸 · to CM 5 im Si % T- Φ CM 5 CM 5 co CM Inch <D C4 § CO CM* 0» CO 5 CO (〇CO s to tn co 5 卜o 5 <os C9 OJ (O 2 00 CO 5 in 1 csj <〇C*J i § 骏< S o << S5 H S5 H h- S5 H g 55 1- iS 1- g 1 > 2 gg ^~N 9 C>J 〇» CO 〇»«<. O a) CO o N_^ (D mr— § CO in co ¥^\ § CM 〇> CO ,^Ν a> co >-✓ r~ «<-so CM σ> co If? •SO) i 00 § § 〇/- s 0 CM 01 eo ^—s« o eg σ> co so CM σ> CO 8 CO <n <〇<*"SS CM CO ?; 8 <〇〇> (O om _ X S5 X < Έ UJ X i 0. IS X if XXX 2 X S5 X 2i X S5 XI S5 XX 25 XX σ S ! JO S§ 〇—sw CM g co ci cd os ci g 8 eg g «#—« » oq 严n 兮<〇· ιο i»> in #-soo CS 甘eg id co co inch NmX m co « CO ui 5 CQ I gs ii g T- g» CQ CO CO σ> to CO w « Ss cs 5S co ^s 3 CD GO 1 1 yN ^-N 00 o Si5 <〇oo 〇·对· o in C^J T- m 郷% < H l Ϊ << 2 5 s preparation c5 1 JO 83⁄43⁄4 g I «g. (O Vm^ o-V s CO § (O s 呀 CO s 兮 (O § CM CO 00 1 00 s 00 m 04 (O CO f (OY—(O 芩(O r— § to >r- ON s inch y-S § inch CD s 00 CO in 3 CO-CO CM § CO 00 in 1 media W < s &lt ; <<<<<<<<<<<<<<<<<< S < S < 1 | (a - 1 ), (a-1' ) s gH W 63⁄43⁄4 /—so <d CO oo to CO «•-s CD (D rf—·V o CO CO I amount (DS o cd a> co ci co Q ci CO T· — >^ y CD <〇«"-no to Φ g» s_o, CO <〇ΰ T~ i 1 >-««· <D <D »- i /—V so cd Si s eg co m Limll 卿< Q. 〇Q < lo < Έ 〇〇< S a O o < s CL 〇〇i 0. oa < a. oai 0. 〇< S aaa Q < S 〇< l 〇Q; 〇Z i 0. 〇Q 1 < s 0. oo < S oo < S 0. o Q < 0. o Q ΜΛ/ CM CO LA CD P- 00 O) o T~ R— y^· oj r· co inch lO CD r- r- co σ> -30- 201202280 In Table 1, (al), (ai,), (a_2), and (a-3) "Mor%" means that when the total of the raw materials (a-1), (ai,), (a_2), and (a-3) is set to 1% mol%, Mole% of raw materials. Further, the molar amount of (a-4) means the hydroxyl group equivalent of the monomer U-4) when the acid anhydride molar equivalent of the copolymer is set to 1. Further, the acid value means the acid value of the addition copolymer (A) measured in accordance with JIS K690 1 5.3, and is required to neutralize the acidic component contained in the addition copolymer (A) lg. The number of milligrams. Further, the molecular weight (Mw) means a weight average molecular weight converted by standard polystyrene measured by gel permeation chromatography under the following conditions. <Molecular weight measurement conditions> Column: Shodex LF-804 + LF-804 (manufactured by Showa Denko Co., Ltd.)

管柱溫度：4 0 °C 試樣：加成共聚物（A)之0.2%四氫呋喃溶液展開溶劑：四氫呋喃偵測器：示差折射計（Shodex RI-71S)(昭和電工股份有限公司製）流速：lmL/分鐘使用試樣No. 1〜1 9的感光性樹脂組成物，調製出透明光阻、彩色光阻（顏料型）及彩色光阻（染料型）。 <透明光阻之調製> 相對於試樣No. 1〜1 9的感光性樹脂組成物的固體成分1〇〇質量份而言，添加季戊四醇四丙烯酸酯（反應性稀 -31 - 201202280 釋劑）30質量份' 2,2-二甲氧基-2-苯基苯乙酮（光聚合起始劑）4質量份，調製出透明光阻（實施例1〜1 4及比較例1 〜5) 〇 <利用透明光阻進行的硬化塗膜之形成> 將所調製出的透明光阻旋轉塗佈於邊長5cm的方形玻璃基板（無鹼玻璃基板）上，使最終硬化塗膜厚度爲 2.5μιη，然後在 90 °C加熱3 0分鐘以使溶劑揮發。接下來，對於所得到塗膜的整個表面實施曝光（曝光量 50mJ/cm2)使其光硬化之後，進一步在230°C烘烤30分鐘，而得到硬化塗膜。 <由透明光阻所形成的硬化塗膜之評估> 對於由透明光阻所形成的硬化塗膜，評估耐熱分解性、透明性及密著性。 (1) 耐熱分解性的評估耐熱分解性的評估，係藉由使用由透明光阻所形成的硬化塗膜切出的試樣進行熱重量分析（TGA)而進行。在此分析中，求得此試樣與將試樣加熱至220 °C並保持2小時後的試樣之間的重量變化率。這項評估的基準如以下所述。〇：未達-2.0% X : - 2.0 % 以上 (2) 透明性的評估Column temperature: 40 °C Sample: 0.2% tetrahydrofuran solution of addition copolymer (A) Development solvent: Tetrahydrofuran detector: Differential refractometer (Shodex RI-71S) (manufactured by Showa Denko Co., Ltd.) Flow rate: The photosensitive resin composition of the sample No. 1 to 19 was used for lmL/min to prepare a transparent photoresist, a color resist (pigment type), and a color resist (dye type). <Preparation of Transparent Photoresist> Pentaerythritol tetraacrylate was added to 1 part by mass of the solid content of the photosensitive resin composition of Sample Nos. 1 to 19 (reactive rare -31 - 201202280) For example, 4 parts by mass of '2,2-dimethoxy-2-phenylacetophenone (photopolymerization initiator), 4 parts by mass, to prepare a transparent photoresist (Examples 1 to 14 and Comparative Example 1) 5) 〇 <Formation of hardened coating film by transparent photoresist> The prepared transparent photoresist was spin-coated on a square glass substrate (alkali-free glass substrate) having a side length of 5 cm to form a final hardened coating film. The thickness was 2.5 μm, and then heated at 90 ° C for 30 minutes to evaporate the solvent. Next, the entire surface of the obtained coating film was exposed to light (exposure amount: 50 mJ/cm2) to be photohardened, and then further baked at 230 ° C for 30 minutes to obtain a cured coating film. <Evaluation of the cured coating film formed of the transparent photoresist> The heat-resistant decomposition property, transparency, and adhesion were evaluated for the cured coating film formed of the transparent photoresist. (1) Evaluation of thermal decomposition resistance The evaluation of thermal decomposition resistance was carried out by thermogravimetric analysis (TGA) using a sample cut out from a cured coating film formed of a transparent photoresist. In this analysis, the rate of change in weight between the sample and the sample after heating the sample to 220 ° C for 2 hours was determined. The basis for this assessment is as follows. 〇: Less than -2.0% X : - 2.0 % or more (2) Evaluation of transparency

S -32- 201202280 透明性的評估，係對於由透明光阻所形成的硬化塗膜，與將此硬化塗膜在乾燥機中加熱至230 °C並放置1小時所得之物，藉由分光光度計測定400nm的光線透過率，調查其透過率的變化率而進行。這項評估的基準如以下所述。〇：透過率的變化率未達1 % X :透過率的變化率在1 %以上 (3)密著性的評估密著性的評估，係藉由以JIS K5400爲基準，對於由透明光阻所形成的硬化塗膜進行棋盤格測試，並以目視觀察1 00個棋盤格的剝離狀態而進行。這項評估的基準如以下所述。〇：完全沒有觀察到剝離 X :觀察到剝離將上述耐熱分解性、透明性及密著性的評估結果胃# 於表2。 ί：： -33- 201202280 [表2] 所使用的感光性樹脂組成物耐熱分解性透明性密著性重麗變化率(％) 評估實;ά例1 No. 1 -1.4 〇〇 0 實施例2 No. 2 -1.7 〇 0 〇實施鈿3 No. 3 -1.4 〇 0 0 實施例4 No. 4 -1.8 〇 0 0 實施例5 No. 5 -1.4 〇〇〇實施例6 No. 6 -1.4 0 0 0 實施術 No. 7 -1.4 〇 0 0 實施例8 No. 8 -1.8 〇 0 0 實施例9 No. 9 -1.7 〇〇〇實施例10 No. 10 -1.4 0 0 〇一實施例11 No. 11 -1.4 〇〇〇實施例12 No. 12 -1.9 〇〇〇實施例13 No. 13 -1.4 〇〇〇實施例14 No. 14 -1.4 〇〇〇比較例1 No. 15 -2.1 X X 〇比較例2 No. 16 -2.2 X 〇〇 _比較例3 No. 17 -1.8 〇 X 0 比較例4 No. 18 -2.3 X 〇 X 比較例5 No. 19 -2.5 X 0 0 由表2的結果可知，實施例1〜14的透明光阻會產生耐熱分解性、透明性及密著性全部皆優異的硬化塗膜，相對於此，比較例1〜5的透明光阻會產生耐熱分解性、透明性、密著性的任一者皆不足的硬化塗膜。 <彩色光阻（顏料型）的調製> 藉由在塡充有直徑〇.5mm锆珠180質量份的SUS容器，加入 10.00 質量份的 C.I Pigment Green36、33.75 質量份的PGMEA(溶劑）及6.25質量份的分散劑（Byk Chemie Japan股份有限公司製Disperbyk-161)，並以塗料搖動器混合3小時而使其分散，而得到綠色顏料分散液。S -32- 201202280 The evaluation of transparency is performed on a hardened coating film formed of a transparent photoresist, and the cured coating film is heated to 230 ° C in a dryer and left for 1 hour, by spectrophotometry. The light transmittance at 400 nm was measured, and the rate of change in transmittance was examined. The basis for this assessment is as described below. 〇: The rate of change of transmittance is less than 1% X: The rate of change of transmittance is more than 1%. (3) Evaluation of adhesion The adhesion is evaluated by JIS K5400, for transparent photoresist The formed hardened coating film was subjected to a checkerboard test and visually observed to observe the peeling state of 100 checkerboards. The basis for this assessment is as described below. 〇: Peeling was not observed at all X: Peeling was observed The results of evaluation of the above-mentioned heat-resistant decomposability, transparency, and adhesion were shown in Table 2. ::: -33- 201202280 [Table 2] Photosensitive resin composition used, heat-resistant decomposition transparency, density change rate (%) Evaluation; Example 1 No. 1 -1.4 〇〇0 Example 2 No. 2 -1.7 〇0 〇Implementation No3 No. 3 -1.4 〇0 0 Example 4 No. 4 -1.8 〇0 0 Example 5 No. 5 -1.4 〇〇〇Example 6 No. 6 -1.4 0 0 0 Implementation No. 7 -1.4 〇0 0 Example 8 No. 8 -1.8 〇0 0 Example 9 No. 9 -1.7 〇〇〇Example 10 No. 10 -1.4 0 0 Example 11 No. 11 -1.4 〇〇〇 Example 12 No. 12 -1.9 〇〇〇 Example 13 No. 13 -1.4 〇〇〇 Example 14 No. 14 -1.4 〇〇〇 Comparative Example 1 No. 15 - 2.1 XX 〇Comparative Example 2 No. 16 -2.2 X 〇〇_Comparative Example 3 No. 17 -1.8 〇X 0 Comparative Example 4 No. 18 -2.3 X 〇X Comparative Example 5 No. 19 -2.5 X 0 0 From Table 2 As a result, it was found that the transparent photoresists of Examples 1 to 14 produced a cured coating film which was excellent in thermal decomposition resistance, transparency, and adhesion. On the other hand, the transparent photoresists of Comparative Examples 1 to 5 exhibited heat decomposition resistance. Transparency, adhesion Either by key inadequate hardening coating. <Preparation of color resist (pigment type)> 1,000,000 parts by mass of CI Pigment Green 36, 33.75 parts by mass of PGMEA (solvent) and 1 part by mass of SUS container filled with 180 parts by mass of zirconium beads having a diameter of 55 mm 6.25 parts by mass of a dispersant (Disperbyk-161, manufactured by Byk Chemie Japan Co., Ltd.) was dispersed by a paint shaker for 3 hours to obtain a green pigment dispersion.

S -34- 201202280 接下來’藉由將所調製出的綠色顏料分散液、試樣 No. 1〜1 9的感光性樹脂組成物及其他成分加以混合，而調製出彩色光阻（顏料型）（實施例15〜28及比較例6〜 10)。將此彩色光阻（顔料型）的配方成分及其摻合量揭示於表3。 [表3] 配方成分摻合量 (質量份）綠色顏料分散液 50 感光性樹脂組成物 8.03 三羥甲基丙烷三丙烯酸酯 (反應性稀釋劑） 6.5 Irgacure 907 (光聚合起始劑，Chiba Specialty Chemicals 製） 1.66 Hicure ΑΒΡ (光聚合起始劑，川口藥品製） 0.83 丙二醇單甲醚醋酸酯 (溶劑） 52.6 合計 119.62 <利用彩色光阻（顏料型）進行的圖型形成> 將所調製出的彩色光阻（顏料型）旋轉塗佈於5cm角玻璃基板（無鹼玻璃基板）上’使乾燥時厚度成爲2.2 μηι，然後在80 °C加熱3分鐘使溶劑揮發，並使其乾燥。接下來’在距離塗佈膜1〇0μιη之處設置既定圖型的光罩’隔著此光罩使塗佈膜曝光（曝光量i50mJ/cm2)，而使曝光部分光硬化。接下來，藉由在23。(：的溫度及 -35- 201202280 0.3MPa的壓力下，將含有0.1質量％碳酸鈉的水溶液加以噴霧，以使未曝光部分溶解而顯像，然後在23 〇°C $丨考30 分鐘，而形成既定圖型。 <彩色光阻（顏料型）及圖型的評估> 對於彩色光阻（顏料型）及圖型，進行鹼顯像性 '靈敏度及耐溶劑性的評估。 (4)鹼顯像性的評估鹼顯像性係藉由鹼顯像時間、鹼顯像後的殘澄及顯像形態進行評估。鹼顯像時間係藉由使用上述噴霧的鹼顯像，而測(定完全無法辨別圖型時的時間。鹼顯像後的殘渣，係藉由使用電子顯微鏡觀察鹼顯像後的其圖型進行評估。這項評估的基準如以下所述。〇：無殘渣 X :有殘渣顯像形態，係藉由目視評估鹼顯像時未曝光部分的去除情形。此處，負型光阻的顯像步驟之中，未硬化的未曝光部分會被鹼顯像液溶解，並逐漸由基板上脫離，而就其顯像形態而言，已知有逐漸脫離的部分爲主，變成大的積塊而剝落的剝離型，與徐緩溶解及擴散的溶解型》前者的剝離型，由於積塊會成爲異物而殘留在系統內，容易污染其他顏色的畫素，故爲不佳。亦即以後者的溶解型爲佳，. 因此這項評估的基準如以下所述。S -34- 201202280 Next, a color resist (pigment type) is prepared by mixing the prepared green pigment dispersion liquid, the photosensitive resin composition of sample No. 1 to 19, and other components. (Examples 15 to 28 and Comparative Examples 6 to 10). The formulation of the color resist (pigment type) and the blending amount thereof are shown in Table 3. [Table 3] Formulation component blending amount (parts by mass) Green pigment dispersion 50 Photosensitive resin composition 8.03 Trimethylolpropane triacrylate (reactive diluent) 6.5 Irgacure 907 (Photopolymerization initiator, Chiba Specialty Chemicals) 1.66 Hicure ΑΒΡ (Photopolymerization initiator, manufactured by Kawaguchi Pharmaceuticals) 0.83 Propylene glycol monomethyl ether acetate (solvent) 52.6 Total 119.62 <Form formation by color resist (pigment type)> The colored resist (pigment type) was spin-coated on a 5 cm-angle glass substrate (alkali-free glass substrate) to have a thickness of 2.2 μm when dried, and then heated at 80 ° C for 3 minutes to volatilize the solvent and dry it. Next, a mask having a predetermined pattern is placed at a distance of 1 〇 0 μm from the coating film. The coating film is exposed (the exposure amount i50 mJ/cm 2 ) through the mask, and the exposed portion is photo-cured. Next, by at 23. (: The temperature and the pressure of -35-201202280 0.3MPa, spray an aqueous solution containing 0.1% by mass of sodium carbonate to dissolve the unexposed part and develop the image, and then test for 30 minutes at 23 °C Forming a predetermined pattern. <Evaluation of color resist (pigment type) and pattern> For color resist (pigment type) and pattern, alkali sensitivity 'sensitivity and solvent resistance are evaluated. (4) Evaluation of alkali imaging The alkali imaging was evaluated by the time of alkali imaging, the residue after alkali imaging, and the imaging morphology. The alkali imaging time was measured by alkali imaging using the above spray ( The time when the pattern was completely unrecognizable. The residue after alkali imaging was evaluated by observing the pattern after alkali imaging using an electron microscope. The basis of this evaluation is as follows. 〇: No residue X : Residual imaging morphology is obtained by visually evaluating the removal of unexposed portions during alkali imaging. Here, in the imaging step of negative photoresist, the unhardened unexposed portion is dissolved by the alkali imaging solution. And gradually detached from the substrate, and in terms of its imaging morphology In other words, it is known that there is a detached part mainly, a peeling type which becomes a large block and peels off, and a peeling type which dissolves and diffuses slowly. The peeling type of the former is a foreign matter and remains in the system. It is not good to contaminate the pixels of other colors. That is, the solubility of the latter is better. Therefore, the benchmark for this evaluation is as follows.

S -36- 201202280 〇·_溶解型 X :剝離型 (5) 靈敏度的評估靈敏度係採用上述噴霧的鹼顯像進行30秒鐘’測定鹼顯像前後的圖型厚度減少量。此圖型厚度的減少量愈少，則可說是靈敏度愈良好，因此這項評估的基準如以下所述。〇··未達〇.20μιη X: 0.20μιη 以上 (6) 耐溶劑性的評估耐溶劑性的測定’除了不使用光罩而對整個表面曝光以外，係以與上述同樣的方式使其光硬化’使用所形成的圖型試樣，容量500mL的附蓋玻璃瓶加入200mL的正甲基-2 -吡咯烷酮，將圖型試樣浸漬於其中’然後後在23 °C 以色差計測定6 0分鐘後的顏色變化。這項評估的基準如以下所述。〇：△ E*ab未達0.3 X: △Ehb爲0.3以上將上述鹼顯像性、靈敏度及耐溶劑性的評估結果揭示於表4。 -37- 201202280 [表4]S -36- 201202280 〇·_dissolved type X: peeling type (5) Evaluation of sensitivity The sensitivity was measured by alkali imaging of the above spray for 30 seconds'. The thickness reduction of the pattern before and after alkali imaging was measured. The less the thickness reduction of this pattern, the better the sensitivity, so the benchmark for this evaluation is as follows. 〇··未达〇.20μιη X: 0.20μηη or more (6) Evaluation of solvent resistance Determination of solvent resistance 'The light is hardened in the same manner as above except that the entire surface is exposed without using a photomask. 'Using the formed pattern sample, a 500 mL capped glass vial was added to 200 mL of n-methyl-2-pyrrolidone, and the pattern sample was immersed therein. Then, the color difference meter was measured at 23 ° C for 60 minutes. After the color changes. The basis for this assessment is as follows. 〇: △ E*ab is less than 0.3 X: ΔEhb is 0.3 or more The evaluation results of the above-described alkali developability, sensitivity, and solvent resistance are shown in Table 4. -37- 201202280 [Table 4]

所使用的感光性樹脂組成物鹼顯像時間 (秒鐘）鹼顯像後的殘渣顯像形態靈敏度耐溶劑性 m 評估實施例15 No. 1 14 〇〇 0.14 〇〇實施例16 No. 2 14 〇〇 0.16 〇〇實施例17 No. 3 17 〇〇 0.17 〇 0 實施例18 No. 4 20 〇〇 0.09 0 〇實施例19 No. 5 12 〇〇 0.15 0 〇實施例20 No. 6 11 〇〇 0.16 〇 0 實施例21 No. 7 45 〇〇 0.18 〇〇實施例22 No. 8 14 〇〇 0.15 0 〇實施例23 No. 9 12 〇〇 0.12 0 0 實施例24 No. 10 11 〇 0 0.12 0 0 實施例25 No. 11 38 〇〇 0.18 0 〇實施例26 No. 12 13 〇〇 0.13 〇〇實施例27 No. 13 12 〇〇 0.14 0 〇實施例28 No. 14 12 〇〇 0.14 〇〇比較例6 No. 15 13 〇 0 0.15 〇 X 比較例7 No. 16 59 X 〇 0.28 X X 比較例8 No. 17 9 X X .0.12 I Ο 〇比較例9 No. 18 62 〇 X 0.26 X X 比較例10 No. 19 45 〇〇 0.30 X X 由表4的結果可知，實施例15〜28的彩色光阻（顏料型）會產生鹼顯像性及靈敏度良好，耐溶劑性優異的圖型，相對於此，比較例6〜10的彩色光阻（顔料型）會產生鹼顯像性或靈敏度不良或耐溶劑性不足的圖型。 <彩色光阻（染料型）的調製> 藉由將染料（acid green3)、試樣No.l〜19的感光性樹脂組成物及其他成分加以混合，而調製出彩色光阻（染料型）（實施例29〜42及比較例11〜is)。將此彩色光阻 (染料型）的配方成分及其摻合量掲示於表5。Photosensitive resin composition used for alkali development time (seconds) Residue development after alkali development Morphology sensitivity Solvent resistance m Evaluation Example 15 No. 1 14 〇〇0.14 〇〇Example 16 No. 2 14 〇〇0.16 〇〇Example 17 No. 3 17 〇〇0.17 〇0 Example 18 No. 4 20 〇〇0.09 0 〇Example 19 No. 5 12 〇〇0.15 0 〇Example 20 No. 6 11 〇〇 0.16 〇0 Example 21 No. 7 45 〇〇0.18 〇〇Example 22 No. 8 14 〇〇0.15 0 〇Example 23 No. 9 12 〇〇0.12 0 0 Example 24 No. 10 11 〇0 0.12 0 0 Example 25 No. 11 38 〇〇0.18 0 〇Example 26 No. 12 13 〇〇0.13 〇〇Example 27 No. 13 12 〇〇0.14 0 〇Example 28 No. 14 12 〇〇0.14 〇〇Comparison Example 6 No. 15 13 〇0 0.15 〇X Comparative Example 7 No. 16 59 X 〇0.28 XX Comparative Example 8 No. 17 9 XX .0.12 I Ο 〇 Comparative Example 9 No. 18 62 〇X 0.26 XX Comparative Example 10 No 19 45 〇〇0.30 XX From the results of Table 4, it is known that the color resists (pigment type) of Examples 15 to 28 produce alkali imaging. In contrast, the color resist (pigment type) of Comparative Examples 6 to 10 exhibited a pattern of alkali developability, poor sensitivity, or insufficient solvent resistance. <Preparation of color resist (dye type)> A color resist (dye type) was prepared by mixing a dye (acid green 3), a photosensitive resin composition of samples No. 1 to 19, and other components. (Examples 29 to 42 and Comparative Examples 11 to is). The formulation of the color resist (dye type) and the blending amount thereof are shown in Table 5.

S -38- 201202280 表5] 配方成分摻合量 (質量份） acid green3 5.2 感光性樹脂組成物 32.5 三羥甲基丙烷三丙烯酸酯 (反應性稀釋劑） 15.6 Irgacure 907 (光聚合起始劑、Chiba Specialty Chemicals 製） 1.3 丙二醇單甲醚 (溶劑） 45.4 合計 100.0 <利用彩色光阻（染料型）進行的圖型形成> 除了採用彩色光阻（染料型）以外，係以與利用彩色光阻（顏料型）進行的圖型形成同樣的方式形成既定圖型。 <彩色光阻（染料型）及圖型的評估〉 (顏料型）同樣的方法，評估鹼顯像性、靈敏度及耐溶劑性。將_t述驗顯像性、靈敏度及耐溶劑性的評估結果揭示於表6。 -39- 201202280 [表6]S -38- 201202280 Table 5] Formulation ingredients (parts by mass) acid green3 5.2 Photosensitive resin composition 32.5 Trimethylolpropane triacrylate (reactive diluent) 15.6 Irgacure 907 (Photopolymerization initiator, Chiba Specialty Chemicals 1.3) Propylene glycol monomethyl ether (solvent) 45.4 Total 100.0 <Form formation by color resist (dye type)> In addition to color resist (dye type), color light is used The pattern formed by the resistance (pigment type) forms the same pattern in the same manner. <Evaluation of color resist (dye type) and pattern> (Pigment type) The alkali-developability, sensitivity, and solvent resistance were evaluated in the same manner. The evaluation results of _t test imaging, sensitivity, and solvent resistance are shown in Table 6. -39- 201202280 [Table 6]

所使用的感光性樹脂鹏物鹸顯像時間 cm) 鹼顯像後之殘渣靈敏度耐溶劑性顯像形態減少量 (Urn) 實施例29 No. 1 13 ο ο 0.13 ο ο 實施例30 No. 2 11 ο 0 0.14 ο ο 實施例31 No. 3 12 ο ο 0.16 ο Ο 實施例32 No. 4 15 0 0 0.10 ο 0 實施例33 No. 5 11 0 0 0.16 0 Ο 實施卿 No. 6 9 ο ο 0.15 ο Ο 實施例35 No. 7 43 ο 0 0.18 ο ο 實施例36 No. 8 31 ο ο 0.17 ο 〇實施例37 No. 9 10 ο 0 0.13 ο ο 實施例38 No. 10 12 ο ο 0.13 ο ο 實施例39 No. 11 22 ο 0 0.18 ο ο 實施例40 No. 12 10 ο 0 0.13 ο ο 實施例41 No. 13 M ο 0 0.13 ο ο 實施例42 No. 14 10 ο 0 0.12 ο 0 比較例11 No. 15 14 X 0 0.14 ο X 比較例12 No. 16 60 X 0 0.30 X X 比較例13 No. 17 8 X X 0.13 ο 0 比較例14 No. 18 93 ο X 0.28 X X 比較例15 No. 19 46 ο 0 0.32 X X 由表6的結果可知，實施例29〜42的彩色光阻（染料型）會產生鹼顯像性及靈敏度良好、耐溶劑性優異的圖型，相對於此’比較例Η〜15的彩色光阻（染料型），會產生鹼顯像性或靈敏度不良或耐溶劑性不足的圖型。以上的結果可知，依據本發明可提供一種鹼可溶性樹脂（加成共聚物）’用於製造可產生靈敏度或顯像性良好，同時耐熱分解性及耐溶劑性優異的著色圖型之感光性樹脂組成物。另外依據本發明可提供一種感光性樹脂組成物，可產生靈敏度或顯像性良好’同時耐熱分解性及耐溶劑性優異的著色圖型。進一步而言’依據本發明可提供一種彩色濾光器，係具有耐熱分解性及耐溶劑性優異的著色Photosensitive resin used for imaging time cm) Residue sensitivity after alkali development Solvent-resistant development pattern reduction amount (Urn) Example 29 No. 1 13 ο ο 0.13 ο ο Example 30 No. 2 11 ο 0 0.14 ο ο 实施 31 31 31 31 31 31 31 31 31 31 31 31 31 0.15 ο 实施 Example 35 No. 7 43 ο 0 0.18 ο ο Example 36 No. 8 31 ο ο 0.17 ο 〇 Example 37 No. 9 10 ο 0 0.13 ο ο Example 38 No. 10 12 ο ο 0.13 ο o Example 39 No. 11 22 ο 0 0.18 ο 实施 Example 40 No. 12 10 ο 0 0.13 ο ο Example 41 No. 13 M ο 0 0.13 ο ο Example 42 No. 14 10 ο 0 0.12 ο 0 Comparison Example 11 No. 15 14 X 0 0.14 ο X Comparative Example 12 No. 16 60 X 0 0.30 XX Comparative Example 13 No. 17 8 XX 0.13 ο 0 Comparative Example 14 No. 18 93 ο X 0.28 XX Comparative Example 15 No. 19 46 ο 0 0.32 XX From the results of Table 6, it is understood that the color resists (dye type) of Examples 29 to 42 have a pattern of excellent alkali developability, sensitivity, and solvent resistance. This' color resist of Comparative Example Η~15 (dye), will have adverse alkaline developer solvent resistance or insufficient sensitivity pattern. As a result of the above, according to the present invention, it is possible to provide an alkali-soluble resin (addition copolymer) for producing a photosensitive resin which is excellent in sensitivity or development, and which is excellent in thermal decomposition resistance and solvent resistance. Composition. Further, according to the present invention, it is possible to provide a photosensitive resin composition which is excellent in sensitivity and developability, and has a coloring pattern excellent in heat decomposition resistance and solvent resistance. Further, according to the present invention, it is possible to provide a color filter which is excellent in thermal decomposition resistance and solvent resistance.

S -40- 201202280 圖型。 2010年4月13日所申請的日號而主張優先權，並將該日本此國際申請。另外，此國際申請基於本特許出願第2010-092286 專利申請案的全內容援用至【圖式簡單說明】色濾光器之剖面圖。圖1係實施形態3之彩【主要元件符號說明】 1 :基板 2 : RGB畫素 3 :黑色矩陣 4 :保護膜 -41 -S -40- 201202280 Pattern. Priority is claimed on the date of application on April 13, 2010, and this international application will be made in Japan. In addition, this international application is based on the entire contents of the Patent Application No. 2010-092286, the entire contents of which are incorporated herein by reference. 1 is a color of Embodiment 3 [Description of main component symbols] 1 : Substrate 2 : RGB pixels 3 : Black matrix 4 : Protective film - 41 -

Claims

201202280 VII. Patent application scope 1. A photosensitive resin composition characterized by comprising an addition copolymer (A) and a solvent (B), the addition copolymer (A) having a carbon number of 10 〜 20 bridged cyclic hydrocarbon group monomer (a-1) and/or monomer (a-1) represented by the following general formula (1) 2 to 60 mol%, [Chem. 6]

(wherein X and Y are each independently represented by a hydrogen atom or a linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R1 and R2 are each independently and represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a carboxyl group 'R1 And R2 can form a linked cyclic structure), unsaturated polybasic acid anhydride (a-2) 30 to 88 mol%, and (al), (a-1,) and (a-2) other than copolymerizable The copolymer obtained by copolymerization of the monomer (a-3) 10 to 68 mol% is added to the monomer (a-4) having a hydroxyl group. 2. The photosensitive resin composition of claim 1, wherein the monomer (a-1) is dicyclopentyl methacrylate. 3. The photosensitive resin composition according to claim 1 or 2, wherein the unsaturated polybasic acid anhydride (a_2) is maleic anhydride. The photosensitive resin composition as described in any one of claims 1 to 3 wherein the monomer (a-3) contains vinyl toluene in an amount of from 1 to 40 mol%. The photosensitive resin composition of any one of claims 1 to 4 wherein the aforementioned monomer (a-4) is 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate. One or more selected from the group consisting of trimethylolpropane di(meth)acrylate S-42-201202280 and pentaerythritol triacrylate. The photosensitive resin composition according to any one of claims 1 to 5, which further comprises a reactive diluent (C), a photopolymerization initiator (D), and a color former (E). One or more selected from the group. 7. The photosensitive resin composition of claim 6, wherein the colorant (E) contains a dye. 8. An addition copolymer (A) characterized by a monomer (al) having a bridged cyclic hydrocarbon group having a carbon number of 10 to 20 and/or a monomer represented by the following general formula (1) (a-l') 2 to 60 mol % '[7] x-Vfy (1) R1 V (wherein X and Y are each independently, and represent a hydrogen atom or a linear or branched carbon number of 1 to 4; a hydrocarbon group, R1 and R2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a carboxyl group, R1 and R2 may form a linked cyclic structure, and an unsaturated polybasic acid anhydride (a-2) 30 to 88 mol%. And a copolymer obtained by copolymerizing a copolymerizable monomer (a-3) other than (a-1), (a-1·) and (a-2) at 10 to 68 mol%, and the addition has The monomer (a-4) of the hydroxy group. The addition copolymer (A) according to item 8 of the patent application, wherein the aforementioned monomer (a-fluorene) is a dicyclopentyl methacrylate. The addition copolymer (A) according to claim 8 or 9, wherein the unsaturated polybasic acid anhydride (a-2) is maleic anhydride. 1 1 · Addition copolymerization-43-201202280 (A) according to any one of claims 8 to 10, wherein the aforementioned monomer (a-3) contains vinyl toluene 10 to 40 mol% » The addition copolymer (A) according to any one of claims 8 to 11, wherein the monomer (a-4) is 2-hydroxyethyl (meth)acrylate, (A) A group selected from the group consisting of 2-hydroxypropyl acrylate, trimethylolpropane di(meth) acrylate, and pentaerythritol triacrylate. A color filter having a coloring pattern formed by the photosensitive resin composition according to any one of claims 1 to 7. S -44 -