TW574619B - Photosensitive resin, photoresist for color filters, and process for producing color filter - Google Patents
Photosensitive resin, photoresist for color filters, and process for producing color filter Download PDFInfo
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- TW574619B TW574619B TW90107186A TW90107186A TW574619B TW 574619 B TW574619 B TW 574619B TW 90107186 A TW90107186 A TW 90107186A TW 90107186 A TW90107186 A TW 90107186A TW 574619 B TW574619 B TW 574619B
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574619 五、發明説明(1 ) 技術領域 本發明係關於感光性樹脂組成物,濾色片用感光性抗蝕 劑,以及濾色片之製法。具體而言,於塗料、印刷油墨、 及使用此等材料之著色顯示板’或在護色等基板上形成著 色圖像之物,尤指彩色液晶顯示器、彩色掃描器,固體攝 像元件等所用濾色片,經顯像等圖案形成步驟後,適於要 求的耐久性用途之感光性樹脂組成物,耐久性優良之濾色 片用感光性抗蝕劑,以及濾色片之製法。 背景技術 向來已知,利用感光性樹脂組成物改良硬化塗膜之耐久 性時,除藉乙烯性不飽和雙鍵之交聯構造外,還可引進藉 其他官能基之交聯構造。 於此目的,設想利用環氧基爲其他官能基。環氧基可以 本身單獨聚合,或與具有胺基、羥基、羧基等之化合物進 行交聯反應,可有效導入交聯構造。然而,由於環氧基的 反應性高,含有環氧基的感光性樹脂組成物,保存安定性 不佳,難以單液化。 針對此問題,日本專利特開平4- 1 753 59號公報提倡一 種熱固型樹脂組成物,所含化合物具有2-氧-1,3-二噚茂 烷-4-基,可得耐酸性、耐候性、平滑性均優之塗膜。然而 ,此組成物不具有乙烯性不飽和雙鍵,幾乎不會發生光硬 化反應,用非加熱系無法硬化,在塗膜耐久性方面有問題。 感光性樹脂特別在近年,隨著用途廣闊,做爲圖案形成 材料之位置也提高。其中鹼顯像型圖案形成材料必須可溶 574619 A7 B7 i、發明說明(2) 於鹼性水溶液,故一般使用樹脂組成物所含化合物,係含 有羧基。可是在最終用途上,具有羧基等官能基,則成爲 耐水性、耐藥品性等不良肇因。 於此,如特開昭60-21 7230或特開平6-192389號公報 ’提議具有羧基之化合物,可倂用具有可與羧基反應的環 氧基之化合物,利用羧基與環氧基之反應消耗羧酸,再導 入該反應所生交聯構造,以改善耐熱性或機械特性。 尤其是使用同一分子中兼具環氧基和羧基之化合物時, 最後可由環氧基/羧基形成交聯構造,具有提升耐久性的 效果。 可是,使用此化合物時,因環氧基與羧基之反應性高, 含此化合物之感光性樹脂組成物,在製造和保存方面的安 定性都不佳,難以單液化,結果造成鹼顯像性降低的問題。 向來已知感光性樹脂組成物爲使用顏料、染料等著色劑 的感光性樹脂組成物之一,是在使用合成樹脂和分散劑等 ’把顏料加以分散之樹脂組成物,添加光聚合性,光聚合 引發劑而成。 已知著色像素之製法,是將此組成物塗在基材上乾燥, 使用具有像素圖案之光罩,進行曝光顯像,形成像素圖案 後,加熱將該像素圖案固定。 尤其是感光性抗蝕劑利用領域之一,是使用彩色液晶顯 示器、彩色掃描器,固體攝像元件等之濾色片。 濾色片所用材料,必須滿足彩色液晶顯示器製造步驟致 使之特性,故使用著色劑以顏料爲主。 -4- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) | * ---I I I I I 訂1111111· 經濟部智慧財產局員工消費合作社印製 574619 五、發明説明(3 ) 近年來,爲兼顧良好耐溶劑性、耐熱性等塗膜物性和鹼 顯像性,並改進感光性樹脂組成物之性能,據報已有種種 方法。例如特開平1 0-3 1 672 1號公報提議,在黏合劑樹脂 導入酯環式環氧基,與羧基反應,最後把不要的羧酸消耗 ,再導入該反應生成的交聯構造,以改進耐溶劑性或耐熱 性。 可是,此等感光性抗蝕劑,確實硬化的像素部塗膜物性 良好,但因環氧基與羧基的反應性高,做爲抗蝕劑時,在 製造和保存方面之安定性不足,結果造成鹼顯像性降低的 問題。 另外,特開平5-39336號公報提議一種活性能射線硬化 型樹脂組成物,包含有2-氧-1,3-二噚茂烷-4-基之化合物 ’可得耐水性、耐溶劑性、耐藥品性、耐熱性和硬化性優 良之塗膜。可是此等組成物,其樹脂骨架是以環氧樹脂爲 主體,在組成物中含有顏料時’顏料分散性不足,造成透 明性降低的問題。 發明槪要 本發明所要解決之目的,即在於提供耐熱性、耐水性、 耐溶劑性及耐藥品性優良,且在步驟中顏料的分散性極佳 ’而透明性不會降低之感光性樹脂組成物,濾色片用感光 性抗蝕劑,和濾色片之製法。 本發明人等有鑑於上述習知技術的缺點,就耐熱性、耐 水性、耐溶劑性及耐藥品性優良,且顏料之分散安定性佳 ’透光性不降低之感光性樹脂組成物,一再潛心硏究結果, 574619 五、發明説明(4 ) ,透光性不降低之感光性樹脂組成物,一再潛心硏究結果, 發現使用在分子中兼具有至少一個2-氧-1,3 -二噚茂烷-4-基和至少一個羧基之乙烯基聚合物,以及分子中至少有二 個乙烯性不飽和雙鍵之化合物的感光性樹脂組成物,即可 解決習知技術之缺點,而完成本發明。 即,本發明提供的感光性樹脂組成物,包括在分子中兼 具有至少一個2-氧-1,3-二噚茂烷-4-基和至少一個羧基的 乙烯基聚合物(A)[以下稱乙烯基聚合物(A)],以及在分子 中具有至少二個乙烯性不飽和雙鍵的化合物(B)爲主要成 份。另外提供濾色片用感光性抗蝕劑,包括在分子中具有 至少一個2-氧-1,3-二噚茂烷-4-基(以下稱環碳酸根)和至少 一個羧基的乙烯基聚合物(A),以及分子中具有至少二個 乙烯性不飽和雙鍵的化合物(B)和著色齊!J (C)爲主成份。本 發明又提供使用上述濾色片用感光性抗蝕劑之濾色片製法。 較佳具體例之詳細說明 茲就本發明感光性樹脂組成物詳加說明。 首先關於乙烯基聚合物(A)可說明如下。 乙烯基聚合物(A)中的環碳酸根基,如下通式所示 574619 A7 R7 、發明說明(5 ) R1 R2 R3 •C—c-574619 V. Description of the Invention (1) Technical Field The present invention relates to a photosensitive resin composition, a photosensitive resist for a color filter, and a method for manufacturing a color filter. Specifically, paints, printing inks, and colored display panels using such materials, or objects that form colored images on substrates such as color protection, especially filters for color liquid crystal displays, color scanners, and solid-state imaging elements After the color sheet is subjected to a pattern forming step such as development, a photosensitive resin composition suitable for the required durable use, a photosensitive resist for a color filter with excellent durability, and a method for producing a color filter. BACKGROUND ART Conventionally, when using a photosensitive resin composition to improve the durability of a cured coating film, in addition to a crosslinked structure of an ethylenically unsaturated double bond, a crosslinked structure of another functional group may be introduced. For this purpose, the use of epoxy groups as other functional groups is envisaged. The epoxy group can be polymerized by itself, or a cross-linking reaction with a compound having an amine group, a hydroxyl group, a carboxyl group, or the like, can effectively introduce a cross-linking structure. However, since the epoxy group has high reactivity, the photosensitive resin composition containing an epoxy group has poor storage stability and is difficult to be single-liquid. In view of this problem, Japanese Patent Laid-Open No. 4- 1 753 59 advocates a thermosetting resin composition containing a compound having 2-oxo-1,3-diphosphorane-4-yl group, which can obtain acid resistance, Coating with excellent weather resistance and smoothness. However, this composition does not have an ethylenically unsaturated double bond, hardly undergoes a photohardening reaction, cannot be hardened by a non-heating system, and has a problem in durability of the coating film. Especially in recent years, the photosensitive resin has been used widely, and its position as a pattern forming material has also increased. Among them, the alkali-developing pattern-forming material must be soluble. 574619 A7 B7 i. Description of the invention (2) In an alkaline aqueous solution, a compound contained in a resin composition is generally used, which contains a carboxyl group. However, in the end use, having functional groups such as a carboxyl group can cause problems such as water resistance and chemical resistance. Here, for example, JP-A-Sho 60-21 7230 or JP-A No. 6-192389 proposes a compound having a carboxyl group, a compound having an epoxy group capable of reacting with a carboxyl group can be used, and a reaction between the carboxyl group and the epoxy group can be used. Carboxylic acid is introduced into the crosslinked structure produced by the reaction to improve heat resistance or mechanical properties. In particular, when a compound having both an epoxy group and a carboxyl group in the same molecule is used, a crosslinked structure can be finally formed from the epoxy group / carboxyl group, which has the effect of improving durability. However, when this compound is used, the sensitivity of the photosensitive resin composition containing the compound due to the high reactivity of the epoxy group and the carboxyl group is not good in terms of production and storage, and it is difficult to be singly liquefied, resulting in alkali developability. Reduced problems. The photosensitive resin composition has been known to be one of the photosensitive resin compositions using colorants such as pigments and dyes. It is a resin composition in which pigments are dispersed using synthetic resins and dispersants, etc. Polymerization initiator. A known method for producing a colored pixel is to coat the composition on a substrate and dry it, use a photomask with a pixel pattern, perform exposure and development, and form the pixel pattern, and then heat the pixel pattern to fix it. In particular, one of the fields of use of photosensitive resists is the use of color filters such as color liquid crystal displays, color scanners, and solid-state imaging devices. The material used for the color filter must meet the characteristics caused by the manufacturing steps of the color liquid crystal display. Therefore, the colorant is mainly pigment. -4- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) | * --- IIIII Order 1111111 · Intellectual Property Office Staff, Ministry of Economic Affairs Printed by a consumer cooperative 574619 V. Description of the invention (3) In recent years, various methods have been reported in order to balance the physical properties of coating films such as good solvent resistance and heat resistance with alkali developability, and to improve the performance of photosensitive resin compositions. . For example, Japanese Unexamined Patent Publication No. 1 0-3 1 672 1 proposes to introduce an ester cyclic epoxy group into a binder resin, react with a carboxyl group, and finally consume unnecessary carboxylic acid, and then introduce a cross-linked structure generated by the reaction to improve Solvent or heat resistance. However, these photosensitive resists have good physical properties of the cured pixel film. However, because of the high reactivity of epoxy groups and carboxyl groups, when used as a resist, the stability in manufacturing and storage is insufficient. As a result, This causes the problem of reduced alkali developability. In addition, Japanese Patent Application Laid-Open No. 5-39336 proposes an active energy ray-curable resin composition containing a compound of 2-oxo-1,3-difluorenyl-4-yl group, which can obtain water resistance, solvent resistance, Coating with excellent chemical resistance, heat resistance and hardening properties. However, in these compositions, the resin skeleton is mainly composed of epoxy resin, and when pigments are contained in the composition, the pigment dispersibility is insufficient, resulting in a problem of lowering transparency. The object of the present invention is to provide a photosensitive resin composition that is excellent in heat resistance, water resistance, solvent resistance, and chemical resistance, and has excellent dispersibility of pigments in the step, and does not reduce transparency. Material, a color resist for a photoresist, and a method for producing a color filter. In view of the shortcomings of the conventional techniques, the present inventors have repeatedly described a photosensitive resin composition that is excellent in heat resistance, water resistance, solvent resistance, and chemical resistance, and has good dispersion stability of pigments. Intensive research results, 574619 V. Description of the invention (4): The photosensitive resin composition that does not reduce light transmittance has been intensively researched and found that it has at least one 2-oxo-1,3-in the molecule. Vinyl polymers of bisphosphorane-4-yl and at least one carboxyl group, and photosensitive resin compositions of compounds having at least two ethylenically unsaturated double bonds in the molecule can solve the shortcomings of the conventional technology, and The present invention has been completed. That is, the photosensitive resin composition provided by the present invention includes a vinyl polymer (A) having at least one 2-oxo-1,3-difluorenyl-4-yl group and at least one carboxyl group in the molecule [ Hereinafter, the vinyl polymer (A)] and the compound (B) having at least two ethylenically unsaturated double bonds in the molecule are main components. In addition, a photoresist for a color filter is provided, which includes a vinyl polymer having at least one 2-oxo-1,3-diphosphone-4-yl group (hereinafter referred to as a cyclic carbonate) and at least one carboxyl group in a molecule. (A), and the compound (B) having at least two ethylenically unsaturated double bonds in the molecule, and the coloring! J (C) are the main components. The present invention also provides a method for producing a color filter using the photosensitive resist for a color filter. DETAILED DESCRIPTION OF THE PREFERRED SPECIFIC EXAMPLES The photosensitive resin composition of the present invention will be described in detail. First, the vinyl polymer (A) can be explained as follows. The cyclic carbonate group in the vinyl polymer (A) is represented by the following general formula: 574619 A7 R7, description of the invention (5) R1 R2 R3 • C—c-
〇 式中R ’ R2,R3可相同或不同,分別代表氫原子或Cl_C4 烷基。 乙烯基聚合物(A)係以分子中具有至少一個環碳酸根基 和乙烯性不飽和雙鍵的單體(下稱具有環碳酸根和乙烯性 不飽和雙鍵之單體,以及分子中具有至少一個羧基和乙烯 性不飽和雙鍵的單體(以下稱具有羧基和乙烯性不飽和雙 鍵之單體),做爲必要成份共聚合而得。 具有環碳酸根基和·乙烯性不飽和雙鍵之單體,有如下通 式所示化合物In the formula, R ', R2, and R3 may be the same or different, and each represents a hydrogen atom or a Cl_C4 alkyl group. The vinyl polymer (A) is a monomer having at least one cyclic carbonate group and an ethylenically unsaturated double bond in the molecule (hereinafter referred to as a monomer having a cyclic carbonate and an ethylenically unsaturated double bond, and a monomer having at least one A monomer having a carboxyl group and an ethylenically unsaturated double bond (hereinafter referred to as a monomer having a carboxyl group and an ethylenically unsaturated double bond) is obtained by copolymerizing as an essential component. It has a cyclic carbonate group and an ethylenically unsaturated double bond. Monomers, compounds of the following formula
R h2c=c R1 R2 R3 r---111 I --------^--------- (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製R h2c = c R1 R2 R3 r --- 111 I -------- ^ --------- (Please read the precautions on the back before filling this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives
C—〇· -C—c- CHC—〇 · -C—c- CH
〇 式中R代表氫原子或甲基,R1,R2’ R3可相同或不同, 分別代表氫原子或烷基,η爲1〜6之整數。 具體例有2,3-碳酸根丙基(甲基)丙烯酸酯、2-甲基-2,3_ 碳酸根丙基(甲基)丙烯酸酯、3,4-碳酸根丁基(甲基)丙_酸 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 574619 經濟部智慧財產局員工消費合作社印製 A7 B7 ___ 五、發明說明(6 ) 酯、3-甲基-3,4-碳酸根丁基(甲基)丙烯酸酯、4-甲基-3,4-碳酸根丁基(甲基)丙烯酸酯、6,7-碳酸根己基(甲基)丙烯酸 酯、5-乙基-5,6_碳酸根己基(甲基)丙烯酸酯、7,8-碳酸根 辛基(甲基)丙烯酸酯等(甲基)丙烯酸酯類;2,3-碳酸根丙基 乙烯醚、甲基-2,3-碳酸根丙基順丁烯二酸酯、或甲基-2,3-碳酸根丙基丁烯酸酯等。具有此等環碳酸根基和乙烯性不 飽和雙鍵之單體,可以一種或二種以上組合使用。 另外,具有羧基和乙烯性不飽和雙鍵之單體,有例如丙 烯酸、甲基丙烯酸、苯并呋喃酸、伊康酸、順丁烯二酸、 反丁烯二酸等乙烯性不飽和單和二羧酸類;順丁二烯二酸 單烷基酯、反丁烯二酸單烷基酯,或伊康酸單烷基酯;另 於含羥基化合物附加苯二甲酐、丁二酐或偏苯三酐等酐所 得物等。 乙烯基聚合物(A),可由上述具有環碳酸根和乙烯性不 飽和雙鍵的單體,以及具有羧基和乙烯性不飽和雙鍵的單 體,再以具有與此等單體共聚性的其他乙烯性不飽和雙鍵 的單體(以下稱具有共聚性乙烯性不飽和雙鍵之單體),經 共聚合而得。 具有共聚性乙烯性不飽和雙鍵之單體,有例如、 (1)丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁 酯、丙烯酸己酯、丙烯酸庚酯、丙烯酸辛酯、丙烯酸壬酯 、丙烯酸癸酯、丙烯酸十二烷酯,丙烯酸十四烷酯、丙烯 酸十六烷酯、丙烯酸硬脂酯、丙烯酸十八烷酯、丙烯酸二 十二烷酯等具有(:!-(:22烷基之丙烯酸酯,以及具有上述同 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注咅?事項再填寫本頁) -I --------訂---------- 574619 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明(7) 樣烷基之甲基丙烯酸酯等; (2) 丙烯酸環己酯、丙烯酸異冰片酯、丙烯酸二環戊酯 、丙烯酸二環戊基氧乙酯等具有脂環式烷基之丙烯酸酯, 另具有上述同樣脂環式烷基之甲基丙烯酸酯等,或四氫糠 醇與ε -己內酯附加物之丙烯酸酯或甲基丙烯酸酯等, (3) 丙烯酸苯甲醯基氧乙酯、丙烯酸苄酯、丙烯酸苯乙 酯、丙烯酸苯氧基乙酯、丙烯酸苯氧基二乙二醇酯、丙烯 酸2-羥基-3-苯氧基丙酯等具有芳族環之丙烯酸酯,以及 具有上述同樣芳族環之甲基丙烯酸酯等, (4) 丙烯酸羥乙酯、丙烯酸羥丙酯、丙烯酸甘油酯等具 有羥烷基之丙烯酸酯,或具有上述同樣羥烷之甲基丙烯酸 酯、內酯改質之丙烯酸羥乙酯或甲基丙烯酸羥乙酯,或丙 烯酸聚乙二醇、丙烯酸聚丙二醇等具有聚烷二醇基之丙烯 酸酯,以及具有上述同樣聚烷二醇基之甲基丙烯酸酯等, (5) 丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、α -乙 基丙烯酸縮水甘油酯、α -正丙基丙烯酸縮水甘油酯、α -正丁基丙烯酸縮水甘油酯、丙烯酸-3,4-環氧基丁酯、甲基 丙烯酸-3,4-環氧基丁酯、甲基丙烯酸_4,5-環氧基戊酯、丙 烯酸-6,7·環氧基戊酯、甲基丙烯酸_6,7_環氧基戊酯、α _ 乙基丙烯酸-6,7-環氧基戊酯等;丙烯酸-3,4-環氧基己酯、 甲基丙烯酸-3,4-環氧基環己酯、內酯改質丙烯酸_3,4_環氧 基環己酯、內酯改質甲基丙烯酸-3,4-環氧基環己酯、乙烯 基環氧己烷等脂環式環氧化合物,以及分子中具有至少二 個以上脂環式環氧基的化合物,與分子中具有至少一個乙 -9- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) : ?----r I ^--------^--------- (請先閱讀背面之注音^事項再填寫本頁) 574619 Α7 Β7 經濟部智慧財產局員工消費合作社印製 五、發明說明( 烯性不飽和雙鍵和一個脂環式環氧基呈反應性基之化合物 ,反應所得在分子中具有縮水甘油基和乙烯性不飽和雙鍵 之化合物;下列通式所示具有縮水甘油基和乙烯性不飽和 雙鍵之化合物。 R4 h2c=c C——〇· // 〇 ch2- R5In the formula, R represents a hydrogen atom or a methyl group, R1, R2 'and R3 may be the same or different, and each represents a hydrogen atom or an alkyl group, and η is an integer of 1 to 6. Specific examples are 2,3-carbonate propyl (meth) acrylate, 2-methyl-2,3_ carbonate propyl (meth) acrylate, 3,4-carbonate butyl (meth) acrylate _Acid paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 574619 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 ___ 5. Description of the invention (6) Ester, 3-methyl-3 , 4-carbonate butyl (meth) acrylate, 4-methyl-3,4-carbonate butyl (meth) acrylate, 6,7-carbonate hexyl (meth) acrylate, 5- (Meth) acrylates such as ethyl-5,6-carbonate hexyl (meth) acrylate, 7,8-carbonate octyl (meth) acrylate; 2,3-carbonate propyl vinyl ether , Methyl-2,3-carbonate propyl maleate, or methyl-2,3-carbonate propyl butyrate, and the like. The monomer having such a cyclic carbonate group and an ethylenically unsaturated double bond may be used singly or in combination of two or more kinds. In addition, monomers having a carboxyl group and an ethylenically unsaturated double bond include, for example, ethylenic unsaturated monomers such as acrylic acid, methacrylic acid, benzofuranic acid, itaconic acid, maleic acid, and fumaric acid. Dicarboxylic acids; maleic acid monoalkyl esters, fumaric acid monoalkyl esters, or itaconic acid monoalkyl esters; phthalic anhydride, succinic anhydride, or meta Anhydride products such as trimellitic anhydride. The vinyl polymer (A) may be composed of the monomers having a cyclic carbonate and an ethylenically unsaturated double bond, and the monomers having a carboxyl group and an ethylenically unsaturated double bond. Other monomers having ethylenically unsaturated double bonds (hereinafter referred to as monomers having copolymerizable ethylenically unsaturated double bonds) are obtained by copolymerization. Monomers having copolymerizable ethylenically unsaturated double bonds include, for example, (1) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, and nonyl acrylate , Decyl acrylate, dodecyl acrylate, tetradecyl acrylate, cetyl acrylate, stearyl acrylate, stearyl acrylate, behenyl acrylate, etc. have (:!-(: 22 alkane) Base acrylic esters, and those with the same paper size as the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back? Matters before filling out this page) -I ----- --- Order ---------- 574619 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (7) Methacrylic acid esters like alkyl; (2) Cycloacrylate Acrylates having alicyclic alkyl groups such as esters, isobornyl acrylate, dicyclopentyl acrylate, dicyclopentyloxyethyl acrylate, etc., and methacrylates having the same alicyclic alkyl groups as above, or the like Acrylic esters of hydrogen furfuryl alcohol and epsilon-caprolactone Acrylate, etc., (3) Benzoyloxyethyl acrylate, benzyl acrylate, phenethyl acrylate, phenoxyethyl acrylate, phenoxy diethylene glycol acrylate, 2-hydroxy-3-acrylate Acrylates having aromatic rings such as phenoxypropyl esters, and methacrylates having the same aromatic rings as described above. (4) Hydroxyalkyl acrylates such as hydroxyethyl acrylate, hydroxypropyl acrylate, and glyceryl acrylate. Acrylic acid ester, or methacrylic acid ester or lactone modified hydroxyethyl acrylate or hydroxyethyl methacrylate with the same hydroxyalkane, or acrylic acid polyethylene glycol, acrylic acid polypropylene glycol, etc. Acrylic esters, and methacrylic esters having the same polyalkylene glycol group as described above, (5) glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate, α-n-propyl acrylate Glyceryl ester, α-n-butyl glycidyl acrylate, -3,4-epoxybutyl acrylate, -3,4-epoxybutyl methacrylate, _4,5-epoxy methacrylate Pentyl ester, acrylic acid-6,7 _6,7_ epoxypentyl acrylate, α_ethyl acrylate-6,7-epoxypentyl acrylate, etc .; -3,4-epoxyhexyl acrylate, -3,4-cyclomethacrylate Oxycyclohexyl ester, lactone modified acrylic acid _3,4_ epoxy cyclohexyl ester, lactone modified methacrylic acid 3,4-epoxy cyclohexyl ester, vinyl epoxy hexane and other lipids Cyclic epoxy compounds, and compounds with at least two alicyclic epoxy groups in the molecule, and at least one B-9 in the molecule- This paper is in accordance with China National Standard (CNS) A4 (210 X 297) Li):? ---- r I ^ -------- ^ --------- (Please read the note on the back ^ before filling out this page) 574619 Α7 Β7 Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives 5. Description of the invention (Ethylene unsaturated double bond and an alicyclic epoxy group are reactive groups, and the compound obtained by the reaction has a glycidyl group and an ethylenically unsaturated double bond in the molecule ; A compound having a glycidyl group and an ethylenically unsaturated double bond represented by the following general formula. R4 h2c = c C——〇 · // 〇 ch2- R5
•C-CH2 V (式中R4爲氫原子或甲基,115爲CrCs烷基,η爲1〜6之 整數),例如R4爲氫或甲基,R5低級烷基爲甲基、丙基、 異丙基、異丁基、戊基等之丙烯酸酯或甲基丙烯酸酯等, (6) 氟乙烯、二氟乙烯、三氟乙烯、氯三氟乙烯.、溴三 氟乙烯、五氟丙烯、六氟丙烯等含氟α-烯烴類;三氟甲 基三氟乙烯醚、五氟乙基三氟乙烯醚、或七氟丙基三氟乙 烯醚等(全)氟烷基之Ci-Cu(全)氟烷基全氟乙烯醚類; 2,2,2-三氟乙基(甲基)丙烯酸酯、2,2,3,3-四氟丙基(甲基) 丙烯酸酯、1H,1H,5H-八氟戊基(甲基)丙烯酸酯、ΙΗ,ΙΗ, 2Η,1Η-十七氟癸基(甲基)丙烯酸酯、或全氟乙氧基乙基(甲 基)丙烯酸酯等(全)氟烷基之C ! ^ 8(全)氟烷基(甲基)丙烯酸 酯類等具有氟原子和乙烯性不飽和雙鍵之化合物等, (7) 7 -甲基丙烯醯氧基丙基三甲氧基矽烷等含矽烷基之( 甲基)丙烯酸酯, (8) Ν,Ν-二甲基胺乙基(甲基)丙烯酸酯、Ν,Ν-二乙基胺乙 基(甲基)丙烯酸酯,或Ν,Ν-二乙基胺丙基(甲基)丙烯酸酯 -10- (請先閱讀背面之注咅?事項再填寫本頁) -裝--------訂--------· 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 574619 A7 ________B7__ 五、發明說明(9 ) 等Ν,Ν-二烷基胺烷基(甲基)丙烯酸酯, (9) 丙烯膪,甲基丙烯腈等, (請先閱讀背面之注意事項再填寫本頁) (10) 丙烯醯胺或其酸醇樹脂取代醯胺等, (11) 反丁烯二酸二甲酯、反丁烯二酸二乙酯、反丁烯二 酸二丁酯、伊康酸二甲酯、伊康酸二丁酯、反丁烯二酸甲 乙酯、反丁烯二酸甲丁酯、伊康酸甲乙酯等不飽和二羧酸 酯, (12) 苯乙烯,α -甲基苯乙烯、氯苯乙烯等苯乙烯衍生物 等, (13) 丁二烯、異戊間二烯、戊間二烯、二甲基丁二烯等 二烯系化合物, (14) 甲基乙烯酮、丁基乙烯酮等不飽和酮, (15) 甲基乙烯醚、丁基乙烯醚等乙烯醚等等。 上述具有共聚性乙烯性不飽和雙鍵之單體當中,就顏料 的分散性觀點言,以具有芳族環的(甲基)丙烯酸酯爲佳, 而以(甲基)丙烯酸苄酯尤佳。 另外,具有共聚性乙烯性不飽和雙鍵之單體,可以一種 或二種以上組合使用。 經濟部智慧財產局員工消費合作社印製 乙烯基聚合物(Α),係在具有環碳酸根基和乙烯性不飽 和雙鍵的單體,具有羧基和乙烯性不飽和雙鍵的單體,以 及具有共聚性乙烯性不飽和雙鍵的單體當中,以具有(甲 基)丙烯醯基的單體爲主成份,必要時與其他具有乙烯性 不飽和雙鍵的單體共聚所得之丙烯酸系樹脂,在耐熱性、 耐光性、透明性等方面較佳。 -11 - ^紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)~' Α7• C-CH2 V (where R4 is a hydrogen atom or a methyl group, 115 is a CrCs alkyl group, and η is an integer from 1 to 6), for example, R4 is hydrogen or methyl group, and R5 lower alkyl group is methyl group, propyl group, Isopropyl, isobutyl, pentyl, etc. acrylates or methacrylates, etc. (6) Ethylene fluoride, difluoroethylene, trifluoroethylene, chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene, Ci-Cu (Fluoro-α-olefins such as hexafluoropropylene; Ci-Cu (per) fluoroalkyl groups such as trifluoromethyl trifluoroethylene ether, pentafluoroethyl trifluoroethylene ether, or heptafluoropropyl trifluoroethylene ether Perfluorofluoroalkyl perfluoroethylene ethers; 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H , 5H-octafluoropentyl (meth) acrylate, 1Η, 1Η, 2Η, 1Η-heptadecafluorodecyl (meth) acrylate, or perfluoroethoxyethyl (meth) acrylate, etc. ( Perfluorofluoroalkyl C! ^ 8 (per) fluoroalkyl (meth) acrylates and other compounds having a fluorine atom and an ethylenically unsaturated double bond, etc., (7) 7-Methacryloxypropane Trimethoxysilane and other silyl-containing (methyl Acrylate, (8) Ν, Ν-dimethylaminoethyl (meth) acrylate, Ν, Ν-diethylaminoethyl (meth) acrylate, or Ν, Ν-diethylaminepropyl (Meth) acrylate-10- (Please read the note on the back? Matters before filling out this page) -Installation -------- Order -------- · This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 574619 A7 ________B7__ 5. Description of the invention (9) and other N, N-dialkylamine alkyl (meth) acrylates, (9) Acrylic acid, methyl Acrylonitrile, etc. (Please read the precautions on the back before filling out this page) (10) Acrylamidine or its acid-alcohol resin replaces amidine, etc., (11) Dimethyl fumarate, fumaric acid Diethyl ester, dibutyl fumarate, dimethyl iconate, dibutyl iconate, ethyl fumarate, methyl fumarate, methyl econate Unsaturated dicarboxylic acid esters such as esters, (12) styrene derivatives such as styrene, α-methylstyrene, chlorostyrene, etc., (13) butadiene, isoprene, pentadiene, Diene compounds such as dimethyl butadiene, (14) Group vinyl ketone, butyl vinyl ketone, unsaturated ketone, (15) methyl vinyl ether, butyl vinyl ether, vinyl ether and the like. Among the above monomers having a copolymerizable ethylenically unsaturated double bond, from the viewpoint of dispersibility of the pigment, a (meth) acrylate having an aromatic ring is preferred, and a benzyl (meth) acrylate is particularly preferred. The monomer having a copolymerizable ethylenically unsaturated double bond may be used singly or in combination of two or more kinds. Vinyl polymer (A) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is a monomer having a cyclic carbonate group and an ethylenically unsaturated double bond, a monomer having a carboxyl group and an ethylenically unsaturated double bond, and Acrylic resin obtained by copolymerizing a monomer having a (meth) acrylfluorenyl group as a main component among monomers having a copolymerizable ethylenically unsaturated double bond, and if necessary, copolymerizing with other monomers having an ethylenically unsaturated double bond, It is preferable in terms of heat resistance, light resistance, transparency, and the like. -11-^ Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ~ 'Α7
574619 五、發明說明(1〇) 如上所述,乙烯基聚合物(A)係由具有環碳酸根基和乙 烯性不飽和雙鍵的單體,具有羧基和乙烯性不飽和雙鍵的 單體,以及具有共聚性乙烯性不飽和雙鍵的單體,共聚合 所得。此等共聚合形態雖無特別限制,但在例如觸媒(聚 合引發齊!I)存在下,可利用自由基聚合法製造。共聚合方 法可用塊狀聚合法、溶液聚合法、懸浮聚合法、乳化聚合 法等公知方法。所得乙烯基聚合物(A)凡無規共聚物、嵌 段共聚物、接枝共聚物等均可。‘ 於此,溶液聚合法等所用溶劑,有例如: (1) 丙酮、丁酮、甲基正丙酮、甲基異丙、甲基正丁 酮、甲基異丁酮、甲基正戊酮、甲基正己酮、二乙酮、乙 基正丁酮、二正丙酮、二異丁酮,環己酮、佛酮等酮系溶 劑; (2) 乙醚、異丙醚、正丁醚、二異戊醚、乙二醇二甲醚 、乙二醇二乙醚、二乙二醇二甲醚、二乙二醇、二噚烷、 四氫呋喃等醚系溶劑; (3) 甲酸乙酯、甲酸丙酯、甲酸正丁酯、乙酸乙酯、乙 酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸正戊酯、乙二 醇單甲醚乙酸酯、乙二醇單乙醚乙酸酯、二乙二醇單甲醚 乙酸酯、二乙二醇單乙醚乙酸酯、丙二醇單甲醚乙酸酯、 3-乙氧基丙酸乙酯等酯系溶劑等。 觸媒可用公知自由基聚合引發劑。自由基聚合引發劑有 例如2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2,4-二甲基戊腈)、 2,2’-偶氮雙(4_甲氧基-2,4·二甲基戊腈)等偶氮化合物,過 -12- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注咅?事項再填寫本頁) · I-----—訂---------· 經濟部智慧財產局員工消費合作社印製 574619 五、發明説明(11 ) 氧化苯甲醯,過氧化月桂醯、三級丁基過氧三甲基乙酸酯 、1,Γ-雙(三級丁基過氧)環己烷、三級戊基過氧-2-乙基己 酸酯、三級己基過-2-乙基己酸酯等有機過氧化物,以及過 氧化氫等。 自由基聚合引發劑使用有過氧化物時,可於有機過氧化 物倂用還原劑,做爲氧化還原型引發劑。 乙烯基聚合物(Α)的環碳酸根基量,換算成上述具有環 碳酸根基和乙烯性不飽和雙鍵之單體量時,其數値以1〜 50重量%爲佳,而以2〜40重量%最好。環碳酸根基在1 重量%以下時,具有環碳酸根基和乙烯性不飽和雙鍵的單 體量,無法期待交聯反應的效果。另方面,用量超過50 重量%時,環碳酸根基彼此分子間的相互作用轉強,對溶 劑的溶解性降低,以致顏料分散性下降,故不佳。 乙烯基聚合物(Α)的羧基量,換算成上述具有羧基和乙 烯性不飽和雙鍵之單體量時,其數値以3〜40重量%爲佳 ,而以5〜30重量%最好。在3重量%下時,具有羧基和 乙烯性不飽和雙鍵之單體對鹼性水溶液之溶解性不足。另 方面,用量超過4〇重量%時,對鹼性水溶液的溶解性太高 ,塗膜之圖案形成難,故此等方面不佳。 乙烯基聚合物(Α)的酸値(在試料1克中存在的酸份,按 規定方法中和所需氫氧化鈣毫克數),可視塗膜形成之目 的而選擇。在利用鹼性水溶液可以顯像之條件下,酸値無 特別限制’惟以2〇〜250ngKOH/g範圍爲佳。 另外,乙烯基聚合物(A)以在分子中具有乙烯性不飽和 -13- 574619 五、發明説明(12 ) 雙鍵爲佳。於乙烯基聚合物(A)內導入乙烯性不飽和雙鍵 ,可使乙烯基聚合物(A)本身具有活性能射線硬化性。所 導入的乙烯性不飽和雙鍵和聚合性化合物(B)間,因進行 父聯反應’可改進光硬化敏感度。 乙烯基聚合物(A),以具有羥基爲佳。具有羥基的乙烯 基聚合物(A),可由具有環碳酸根基和乙稀性不飽和雙鍵 的單體,與具有羧基和乙烯性不飽和雙鍵的單體,與具有 殘基和乙稀性不飽和雙鍵的單體,以及分子中具有至少一 個羥基和乙烯性不飽和雙鍵的單體,經共聚合而得。使用 具有羥基的乙烯基聚合物(A),可改進對鹼性水溶液的溶 解性,不會有顯像殘餘,可得形成敏銳像素圖案之塗膜。 乙烯基聚合物(A)的分子量雖無特別限制,但爲維持塗 膜性能等,以苯乙烯換算的數平均分子量(以下稱Μη)以 2,000以上爲佳。其中又以3,500〜50,000最好。數平均分 子量不到2,000時,難以形成均勻塗膜和賦予各種塗膜性 能。而數平均分子量超過5 0, 〇〇〇時,樹脂黏度高,利用 塗裝方法之塗裝作業性等不良。 而重量平均分子量(以下稱Mw)與Μη之比(Mw/Μη:分子 量分佈)無特別限制’但以6.0以下爲佳,又以5.0以下最 好。Mw/Mn超過6.0時’和上述分子量時同樣難以形成均 勻塗膜,又因樹脂黏度高,利用塗裝方法之塗裝作業性有 惡化傾向,而且顯像之際’對鹼性水溶液的溶解性有惡化傾 向。 此分子量可視所形成塗膜厚,塗佈方法等形成塗膜之目 -14- 574619 A7 ____ B7 五、發明說明(13) 的或條件,加以適當選擇。 其次,就分子中具有至少二個乙烯性不飽和雙鍵之化合 物[以下稱聚合性化合物(B)]加以說明。 聚合性化合物(B)有例如三羥甲基乙烷三丙烯酸酯、三 羥甲基丙烷三丙烯酸酯、三羥甲基丙烷二丙烯酸酯、新戊 二醇二(甲基)丙烯酸酯、異戊四醇四(甲基)丙烯酸酯、異 戊四醇三(甲基)丙烯酸酯、二異戊四醇六(甲基)丙烯酸酯 、二異戊四醇五(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸 酯、三羥甲基丙烷三(丙烯醯氧基丙基)醚、三(丙烯醯氧基 乙基)異三聚氰酸酯、丙三醇三(甲基)丙烯酸酯、環氧基( 甲基)丙烯酸酯[例如酚•酚醛型環氧樹脂、甲酚•酚醛型環 氧樹脂、雙酚A型環氧樹脂等環氧樹脂與(甲基)丙烯酸酯 之反應物等], (甲基)丙烯酸胺基甲酸乙酯{例如乙二醇、聚乙二醇、 聚丙二醇、聚丁二醇、雙酚A之聚乙氧基二醇、聚酯多醇 、聚丁二烯多醇、聚碳酸根多醇等多醇類,與有機聚異氰 酸酯類(例如甲苯二異氰酸酯,二甲苯二異氰酸酯,異佛 酮二異氰酸酯、六亞甲基二異氰酯等),及含羥基(甲基)丙 烯酸酯[例如2-羥乙基(甲基)丙烯酸酯、2-羥丙基(甲基)丙 烯酸酯、1,4·丁二醇單(甲基)丙烯酸酯等]之反應物等}, 聚酯(甲基)丙烯酸酯[例如多元酸化合物及其酐(例如順丁 烯二酸、丁二酸、己二酸、異苯二甲酸、苯二甲酸、對苯 二甲酸、四氫苯二甲酸、六氫苯二甲酸,及其酐等),與 多醇類(例如乙二醇、丙二醇、3-甲基-1,5-戊二醇、新戊 -15- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) "~ (請先閱讀背面之注意事項再填寫本頁) --------訂---------. 經濟部智慧財產局員工消費合作社印製 574619 五、發明説明(14 ) 等聚酯多醇類與(甲基)丙烯酸之反應物等]等。 此等聚合性化合物(B)中,以三羥甲基丙烷三(甲基)丙烯 酸酯、異戊四醇四(甲基)丙烯酸酯、二異戊四醇六(甲基) 丙烯酸酯、二異戊四醇五(甲基)丙烯酸酯,在光硬化感度 方面最好。 聚合性化合物(B)之使用比例,佔本發明感光性樹脂組 成物的樹脂成份中之5〜90重量%範圍。聚合性化合物(B) 可以上述具體化合物一種或二種以上組合使用。尤其是本 發明感光性樹脂組成物做爲濾色片用感光性抗蝕劑使用, 必須具有圖案形成特性時,以10〜70重量%使用爲佳。此 時聚合性化合物(B)超過70重量%時,本發明目的之鹼溶 解性也會降低。另方面,在1 〇重量%以下時’難以獲得具 有所需塗膜物性之硬化塗膜,且圖案形成困難,故不佳。 本發明感光性樹脂組成物原狀即可用做感光性塗料,黏 著劑,圖案形成材料。於此感光性樹脂阻成’可含有適宜顏 料、染料等之著色劑,含著色劑之感光性樹脂組成物,宜 用做塗料、印刷油墨、抗蝕劑’尤其是濾色片用感光性抗 蝕劑。 又,乙烯基聚合物(A)中的環碳酸根基,係具有極性之 官能基,有進一步改進顏料分散性的效果。 爲了將環碳酸根基開環,以促進交聯反應,可用開環觸 開環觸媒有環碳酸根基之開瓌觸媒或環氧基之開環觸媒 。具體例有四甲基溴化銨、三甲基苄基氫氧化銨、2-羥基 吡啶、三甲基苄基甲氧化銨、苯基三甲基氯化銨、苯基三 -16- 574619 A7 B7 五、發明說明(15) 甲基溴化銨、苯基三甲基氫氧化銨、苯基三甲基碘化銨、 膽鹼磷酸氯化鈉鹽、硬脂基溴化銨、四正戊基碘化銨、四 正丁基溴化銨、四正甲基氫氧化銨、四正丁基磷酸銨、四 正癸基三氯化銨、四乙基氫氧化銨、四乙基四氟硼酸銨。 乙醯基膽鹼溴化物、烷基二甲基苄基氯化銨、苄基膽鹼 溴化物、苄基正丁基溴化銨、恭菜鹼、丁基氯、雙(四正 丁基銨)二氯化物,或三甲基乙烯基溴化銨等四級銨鹽類 、烯丙基三苯基氯化鱗、正戊基三苯基溴化鱗、苄基三苯 基氯化鳞、溴甲基三苯基溴化鳞、2-二甲基胺乙基三苯基 溴化鱗、乙氧基羰基溴化鱗、正庚基三苯基溴化鳞、甲基 三苯基溴化鳞、肆(羥甲基)硫酸錢、或四苯基溴化錢等鳞 鹽類;磷酸、對甲苯磺酸、或二甲基硫酸等酸觸媒;以及 碳酸錫等碳酸鹽。 本發明感光性樹脂組成物使用光等活性能射線硬化時, 可使用光聚合引發劑,以開始利用光進行聚合反應。 光聚合引發劑可用公知的光聚合引發劑。公知光聚合引 發劑有例如: (1) 二苯甲酮、3,3·二甲基-4·甲氧基二苯甲酮、4,4’·雙 二甲胺基二苯甲酮、4,4’-雙二甲胺基二苯甲酮、4,4-二氯 二苯甲酮、米其勒酮、3,3’,4,4’-四(三級丁基過氧羰基) 二苯甲酮等二苯甲酮類, (2) _酮、硫口山酮、2-甲基硫卩山酮、2-異丙基硫卩山酮、2-氯化硫_酮、2,4-二乙基硫卩山酮、2,4-二甲基硫_酮、硫 口山酮_4_磺酸等pilj酮、硫_酮類, -17- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) _~ " (請先閱讀背面之注意事項再填寫本頁) -丨裝 ----訂---------. 經濟部智慧財產局員工消費合作社印製 574619 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(16) (3) 苯偶姻、苯偶姻甲醚、苯偶姻乙醚、苯偶姻異丙醚 、苯偶姻正丁醚、苯偶姻異丁醚、苯偶姻丁醚等苯偶姻類’ (4) 苄基、二乙醯基等α-二酮類, (5) 四甲基秋蘭姆單硫化物、四甲基秋蘭姆二硫化物、 對甲苯醯二硫化物等硫化物類, (6) 4-甲胺基安息香酸、4-二甲胺基安息香酸甲酯、4-二 甲胺基安息香酸乙酯、4-二甲胺基安息香酸丁酯、4-二甲 胺基安息香酸-2-乙基己酯、4-二甲胺基安息香酸-2-異戊 酯等安息香酸類, 此外還有3,3’-羰基雙(7-二乙胺基)薰草素、1-羥基環己 基苯酮、2,2-二甲氧基-1,2-二苯乙烷-1-酮、2-甲基-1-[4-( 甲硫基)苯基]-2-嗎啉并丙烷-1-酮、2-苄基-2-二甲胺基-ΙΟ-嗎啉并苯基 )-丁烷-1-酮、 2-羥基 甲基-1· 苯基丙烷-1-酮|、2,4,6 -二甲基平基一苯膦氧化物、1-[4-(2 -羥基乙氧基) 苯基]-2·羥基-2-甲基-1·丙烷-1-酮,1-(4-異丙基苯基)-2-羥 基-2-甲基丙烷-1-酮、1-(4-十二烷基苯基)-2-羥基-2-甲基 丙烷-1-酮、4-苯甲醯基-4’-甲基二甲基硫化物, 乙氧基乙縮醛、1-苯基-1,2-丙二酮-3-(鄰乙氧基羰基)肟 、2-苯基-1,2-丁二酮-2-(鄰甲氧基羰基)肟、;ι,3-二苯基丙 二酮-2-(鄰乙氧基鑛基)汚、1-苯基-3-乙氧基丙三酮- 2- (鄰 苯甲醯基)亏、鄰苯甲酸基安息香酸甲酯、雙(4 -二甲胺基 苯基)酮、對二甲胺基苯乙酮、α,α -二氯苯氧基苯乙 酮、4-二甲胺基苯甲酸戊酯, 2,2’-雙(2-氯苯基)-4,4’,5,5’-肆(4-乙氧基鑛基苯基)_ -18- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) — ILIII-llll· I ----丨丨 I I 訂·-------- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 574619 A7 —一 B7 五、發明說明(17) 1,2’-二咪唑、2,2、雙(2-溴苯基)、4,4’,5,5’-肆(4-乙氧基羰 基苯基)-1,2’-二咪唑、2,2,-雙(2,4-二氯苯基-4,4,’5,5、四 苯基-1,2’-二咪唑、2,2,-雙(2,4-二溴苯基)-4,4,,,5,5’-四苯 基·1,2,-二咪唑、2,2,-雙(2,4,6-三溴苯基)-4,4’,5,5’-四苯 基·1,2’-二咪唑等二咪唑類; 對二甲胺基苯乙酮、α,α -二氯-4-苯氧基苯乙酮、4-二 甲胺苯甲酸戊酯、2,4-雙三氯甲基-6-[二-(乙氧基羰基甲基) 胺基]苯基-S-三畊、2,4-雙三氯甲基-6-(4-乙氧基)苯基-S-三哄、2,4-雙三氯甲基-6-(3-溴-4-乙氧基)苯基三哄蒽醌 、2-三級丁基蒽醌、2-戊基蒽醌、氯蒽醌、苯并蒽酮、 二苯并環庚環、亞甲蒽酮、4-疊氮基卡基苯乙酮、2,6-雙( 對疊氮基亞苄基)環己烷、2,6-雙(對疊氮基亞苄基)-4-甲基 環己酮、萘磺醯氯、喹啉磺醯氯、正苯基硫吖叮酮、4,4-偶氮雙異丁腈、二苯二硫、苯并噻唑二硫化、三苯膦、四 溴化碳、三溴苯楓、過氧化苯偶姻、曙紅、亞甲藍等光還 原性色素,與抗壞血酸、三乙醇胺等還原劑之組合等。 另外,光聚合引發劑有Irgaure系列184,149,261, 369 , 500 , 651 , 784 , 819 , 907 , 1116 , 1664 , 1700 , 1 800,1 850,2959,4043,Darocurll73(汽巴特殊化學公 司製品),Lucirin TPO(BASF 公司製品),KAYACURE 系 歹ij DETX,MBP,DMBI,EPA,OA(日本化藥公司製品), VICURE 系歹ij 1〇,55(STAUFFER 公司製品),TRIGONAL Ρ1(ΑΚΖΟ 公司製品),SANDORY1 000(SANDOZ 公司製品) ,DEOP(APJ〇HX 公司製品),QUANTAX URE 系歹[]PDO, -19- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---r ---— l· Aw I --------訂--------- (請先閱讀背面之注音心事項再填寫本頁) 574619 A7 B7 五、發明說明(18) ITX,EPO(WARO BLEKINSOP 公司製品)等。 上述光聚合引發劑可倂用光增感劑。 光增感劑可用公知光增感劑。公知光增感劑有例如胺類 、尿素類、含硫化合物、含磷化合物、含氯化合物,以及 腈類,或其他含氮化合物。 光聚合引發劑和光增感劑可一種或二種組合使用。使用 量無特別限制,以相對於聚合性化合物(B)的0· 1〜20重量 %爲佳,而以0.5〜10重量%尤佳。在〇·1重量%以下時, 光感度會降低,而超過20重量%時,會引起結晶析出,塗 膜物性之劣化等,故不佳。 本發明感光性樹脂組成物,必要時在不悖本發明目的, 可保持貯藏安定性、耐水性、耐藥品性和耐熱性等條件下 ,可含有其他成份。 其他成份有例如反應性稀釋劑、硬化觸媒、有機溶劑、 偶合劑或抗氧化劑、紫外線吸收劑等安定劑,矽酮系、氟 系、丙烯酸系等各種勻化劑。爲改善本發明感光性樹脂組 成物之鹼顯像性和熱硬化性,可添加多元酸及酐爲其他成 份。且爲改善熱硬化性,可添加環氧化合物等。 反應性稀釋劑有例如丁氧基乙基(甲基)丙烯酸酯、正氧 基乙二醇(曱基)丙烯酸酯、2-羥乙基(甲基)丙烯酸酯、2-羥 丙基(甲基)丙烯酸酯、2-乙基己基(甲基)丙烯酸酯、N-乙 烯基四氫吡咯酮、1-乙烯基咪唑、異冰片基(甲基)丙烯酸 酯、四氫糠基(甲基)丙烯酸酯、卡必醇(甲基)丙烯酸酯、 苯氧基乙基(甲基)丙烯酸酯、環戊二烯(甲基)丙烯酸酯、 -20- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) I --------訂---------AWI · 經濟部智慧財產局員工消費合作社印製 574619 A7 B7 五、發明說明(19) N-乙烯基甲醯胺、N-乙烯基乙醯胺、N-乙烯基嗎啉等。凡 此可一種或二種以上組合使用。 (請先閱讀背面之注意事項再填寫本頁) 偶合劑有例如矽烷偶合劑,鈦偶合劑、鋁偶合劑等。 其中就各種材料而言,尤其是在優良平滑性、黏著性、 耐水性和耐溶劑性各方面而言,以矽烷偶合劑爲佳。 矽烷偶合劑有例如r -(2-胺乙基)胺丙基三甲氧基矽烷、 r-(2-胺乙基)胺丙基甲基二甲氧基矽烷、r-甲基丙烷氧 基丙基三甲氧基矽烷、7-縮水甘油基丙基三甲氧基矽烷 、/3 -(3,4-環氧基環己基)乙基三甲氧基矽烷、7-氫硫基丙 基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三甲基 矽烷、三甲氧基甲矽烷基安息香酸、r -異氰根丙基三甲 氧基矽烷等,以及此等矽烷偶合劑製成之寡聚物或聚合物 類。 上述矽烷偶合劑當中,以7 -縮水甘油基丙基三甲氧基 矽烷、/3 -(3,4-環氧基環己基)乙基三甲氧基矽烷等具有環 氧基的矽烷偶合劑爲佳。 此等偶合劑可一種或二種組合使用。 經濟部智慧財產局員工消費合作社印製 乙烯基聚合物(A)每100重量份,偶合劑混配量以0.1〜 30重量份範圍爲佳,而以0.5〜20重量份更好。偶合劑混 配量在0.1重量份以下時,所形成塗膜之平滑性,以及與 基體之黏著劑、耐水性和耐溶劑性不足,而超過30重量 份時,不但不能期待改進黏著性,所形成塗膜之硬化性還 會降低,故不宜。 本發明感光性樹脂組成物,可由上述成份均勻混合而得 -21- 本紙張尺度適用中國國家標準(CNS)A4規格(21^< 297公釐) 574619 A7 B7 i、發明說明(、 。混合方法可將此等成份溶於適當溶劑,再加以混合之溶 劑混合法。此等溶劑只要可將上述各成份溶解,且不發生 反應即可,無特別限制。 此溶劑可原狀使用上述乙烯基聚合物(A)製造之際所列 各種溶劑。 本發明感光性樹脂組成物利用溶劑混合法調製時之混合 順序’無特別限定。例如可將全部成份同時溶於溶劑,以 調配本發明感光性樹脂組成物之溶液。亦可將各成份分別 溶於相同或不同溶劑,成爲二種以上的溶液,再將此等溶 液混合,而調配本發明感光性樹脂組成物之溶液。 由上述調製之本發明感光性樹脂組成物,可原狀用做塗 料、黏著劑、圖案形成材料等。將此等感光性樹脂組成物 塗佈於基材,即可形成耐熱性、耐水性、耐溶劑性及耐藥 品性之硬化塗膜。 本發明感光性樹脂組成物用做塗料時,可把乙烯基聚合 物(A)和聚合性化合物(B)當做黏合劑樹脂,混配著色劑和 添加劑等,即可用做UV硬化型塗料,熱固型塗料等。 本發明感光性樹脂組成物用做印刷油墨時,可以乙烯基 聚合物(A)、聚合性化合物(B)和溶劑等,做爲媒液組成份 ,混配著色劑和助劑等,即可用做UV硬化型油墨等。 其次,說明本發明濾色片用感光性抗蝕劑。 本發明濾色片用感光性抗蝕劑,係含有乙烯基聚合物(A) 、環碳酸根基(B)和著色劑(C)爲必要成份所得。 此乙烯基聚合物(A)和聚合性化合物(B)已知上述。 -22- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注咅心事項再填寫本頁) -1 --------訂----I----· 經濟部智慧財產局員工消費合作社印製 574619 A7 B7 i、發明說明(21) 著色劑(C)則有顏料、染料,及其他色料。 顏料包含有機顏料和無機顏料。有機顏料有例如CiI.9號 紅色顏料、C.1.97號紅色顏料、C. 1.1 22號紅色顏料、 C.I.123號紅色顏料、C.L149號紅色顏料、c.1.168號紅色 顏料、C.I.177號紅色顏料、C.i.180號紅色顏料、c.1.192 號紅色顏料、C.I.215號紅色顏料、C.I.216號紅色顏料、 C.1.217號紅色顏料、C.L22〇號紅色顏料、c.1.223號紅色 顏料、C.I.224號紅色顏料、C.L226號紅色顏料、C.1.227 號紅色顏料、C.I.228號紅色顏料、C.I.240號紅色顏料、 C. 1.254號紅色顏料、。丄48:1號紅色顏料等紅色顏料, C-I,7號綠色顏料、(:丄36號綠色顏料等綠色顏料,c.l.15 號藍色顏料、C.1.15:6號藍色顏料、C.I.22號藍色顏料、 C.I.60號藍色顏料、αι·64號藍色顏料等藍色顏料; C.I.19號紫色顏料、c.lu號紫色顏料、c.i.29號紫色顏 料、C.I.30號紫色顏料、c.1.37號紫色顏料、C.1.40號紫 色顏料、C.I.50號紫色顏料等紫色f ; C.I.20號黃色顏料 、C.I.24號黃色顏料、C.L83號黃色顏料、c.l.86號黃色 顏料、C.1.93號黃色顏料、c.m 09號黃色顏料、c. 1.1 1〇 號頁色顏料、C · I · 1 1 7號黃色顏料、c · 1.1 2 5號黃色顏料、 C.I.137號黃色顏料、c.uw號黃色顏料、C.L139號黃色 顏料、C.I.147號黃色顏料、c.1.148號黃色顏料、C.I.150 號黃色顏料、C.I· 153號黃色顏料、cj·:! 54號黃色顏料、 C.I.166號黃色顏料、C.I168號黃色顏料、C.I.185號黃色 顏料等黃色F ; C.I.7號黑色顏料等黑色顏料。利用電子顯 -23- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁)574619 V. Description of the invention (10) As mentioned above, the vinyl polymer (A) is composed of a monomer having a cyclic carbonate group and an ethylenically unsaturated double bond, and a monomer having a carboxyl group and an ethylenically unsaturated double bond. And a monomer having a copolymerizable ethylenically unsaturated double bond is obtained by copolymerization. Although these copolymerization forms are not particularly limited, they can be produced by a radical polymerization method in the presence of, for example, a catalyst (polymerization initiation! I). As the copolymerization method, known methods such as a block polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be used. The obtained vinyl polymer (A) may be any random copolymer, block copolymer, graft copolymer, or the like. '' Here, the solvents used in the solution polymerization method include, for example: (1) acetone, methyl ethyl ketone, methyl n-acetone, methyl isopropyl, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-pentanone, Ketone solvents such as methyl-n-hexanone, diethylketone, ethyl-n-butanone, di-n-acetone, diisobutanone, cyclohexanone, phorone; (2) ether, isopropyl ether, n-butyl ether, diiso Ether solvents such as pentyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol, dioxane, tetrahydrofuran; (3) ethyl formate, propyl formate, N-butyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethyl acetate Ester-based solvents such as glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and ethyl 3-ethoxypropionate. As the catalyst, a known radical polymerization initiator can be used. Free radical polymerization initiators include, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4_ Methoxy-2,4 · dimethylvaleronitrile) and other azo compounds, over -12- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back first) Please fill in this page for matters) · I -----— Order --------- · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 574619 V. Description of the invention (11) Benzozone oxide, over Laurel oxide, tertiary butyl peroxy trimethyl acetate, 1, Γ-bis (tertiary butyl peroxy) cyclohexane, tertiary pentyl peroxy-2-ethylhexanoate, tri Organic peroxides such as hexylper-2-ethylhexanoate, and hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, a reducing agent can be used as a redox initiator in organic peroxides. When the amount of the cyclic carbonate group of the vinyl polymer (A) is converted into the above-mentioned amount of the monomer having a cyclic carbonate group and an ethylenically unsaturated double bond, the number 値 is preferably 1 to 50% by weight, and 2 to 40 % By weight is best. When the cyclic carbonate group is 1% by weight or less, the monomer has an amount of monomers of a cyclic carbonate group and an ethylenically unsaturated double bond, and the effect of a crosslinking reaction cannot be expected. On the other hand, when the amount exceeds 50% by weight, the molecular interaction between the cyclic carbonate groups becomes stronger, and the solubility in the solvent is lowered, so that the pigment dispersibility is lowered, which is not good. When the amount of the carboxyl group of the vinyl polymer (A) is converted into the amount of the monomer having a carboxyl group and an ethylenically unsaturated double bond, the number 値 is preferably 3 to 40% by weight, and most preferably 5 to 30% by weight. . At 3% by weight, the monomer having a carboxyl group and an ethylenically unsaturated double bond has insufficient solubility in an alkaline aqueous solution. On the other hand, when the amount exceeds 40% by weight, the solubility in an alkaline aqueous solution is too high, and pattern formation of a coating film is difficult, so it is not good in these respects. The acid base of the vinyl polymer (A) (the acid content present in 1 g of the sample is neutralized by the prescribed method in milligrams of calcium hydroxide) can be selected according to the purpose of forming a coating film. Under the condition that development can be performed using an alkaline aqueous solution, the acid is not particularly limited ', but it is preferably in the range of 20 to 250 ngKOH / g. In addition, the vinyl polymer (A) preferably has ethylenic unsaturation in the molecule -13- 574619 V. Description of the invention (12) Double bond is preferred. The introduction of an ethylenically unsaturated double bond in the vinyl polymer (A) can make the vinyl polymer (A) itself have active energy ray-hardenability. The sensitization between the introduced ethylenically unsaturated double bond and the polymerizable compound (B) can be improved due to the paternity reaction '. The vinyl polymer (A) preferably has a hydroxyl group. The vinyl polymer (A) having a hydroxyl group can be composed of a monomer having a cyclic carbonate group and an ethylenically unsaturated double bond, a monomer having a carboxyl group and an ethylenically unsaturated double bond, and a monomer having a residue and ethylenicity. An unsaturated double bond monomer and a monomer having at least one hydroxyl group and an ethylenically unsaturated double bond in the molecule are obtained by copolymerization. By using a vinyl polymer (A) having a hydroxyl group, the solubility in an alkaline aqueous solution can be improved without developing residues, and a coating film forming a sharp pixel pattern can be obtained. Although the molecular weight of the vinyl polymer (A) is not particularly limited, in order to maintain the coating film properties and the like, the number average molecular weight (hereinafter referred to as Mη) in terms of styrene is preferably 2,000 or more. Among them, 3,500 ~ 50,000 is the best. When the number average molecular weight is less than 2,000, it is difficult to form a uniform coating film and impart various coating film properties. When the number average molecular weight exceeds 50,000, the resin has a high viscosity and the coating workability by the coating method is poor. The ratio of the weight average molecular weight (hereinafter referred to as Mw) to Mη (Mw / Mη: molecular weight distribution) is not particularly limited ', but is preferably 6.0 or less, and most preferably 5.0 or less. When Mw / Mn exceeds 6.0, it is difficult to form a uniform coating film as well as the above molecular weight, and because the resin viscosity is high, the coating workability by the coating method tends to deteriorate, and the solubility in alkaline aqueous solutions during development There is a tendency to worsen. This molecular weight can be appropriately selected according to the thickness of the coating film to be formed, the coating method, etc. -14- 574619 A7 ____ B7 V. The description or condition of the invention (13), can be appropriately selected. Next, a compound [hereinafter referred to as a polymerizable compound (B)] having at least two ethylenically unsaturated double bonds in the molecule will be described. Examples of the polymerizable compound (B) include trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, and isopentyl. Tetraol tetra (meth) acrylate, isopentaerythritol tri (meth) acrylate, diisopentaerythritol hexa (meth) acrylate, diisopentaerythritol penta (meth) acrylate, hexamethylene Alcohol di (meth) acrylate, trimethylolpropane tri (acryloxypropyl) ether, tris (propyleneamyloxyethyl) isotricyanate, glycerol tri (meth) acrylic acid Esters, epoxy (meth) acrylates [e.g. the reaction of epoxy resins such as phenol-phenolic epoxy resin, cresol-phenolic epoxy resin, bisphenol A epoxy resin and (meth) acrylate Materials], urethane (meth) acrylate {such as ethylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, polyethoxy glycol of bisphenol A, polyester polyol, poly Polyols such as butadiene polyols, polycarbonate polyols, and organic polyisocyanates (such as toluene diisocyanate, Toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc.), and hydroxyl-containing (meth) acrylates [eg, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( (Meth) acrylates, 1,4 · butanediol mono (meth) acrylates, etc.], etc.}, polyester (meth) acrylates [such as polybasic acid compounds and their anhydrides (such as maleic acid Acids, succinic acid, adipic acid, isophthalic acid, phthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and their anhydrides, etc., and polyols (such as ethylene glycol Alcohol, propylene glycol, 3-methyl-1,5-pentanediol, neopentyl-15- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) " ~ (Please read the back Please fill in this page for attention) -------- Order ---------. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 574619 V. Description of Invention (14) Polyester Polyols Reactants with (meth) acrylic acid, etc.] etc. Among these polymerizable compounds (B), trimethylolpropane tri (meth) acrylate, isopentaerythritol tetra ( Base) acrylate, diisopentaerythritol hexa (meth) acrylate, and diisopentaerythritol penta (meth) acrylate are the best in terms of light curing sensitivity. The proportion of polymerizable compound (B) used is The range of 5 to 90% by weight of the resin component of the photosensitive resin composition of the present invention. The polymerizable compound (B) may be used in combination of one or two or more of the specific compounds described above. In particular, the photosensitive resin composition of the present invention is used as a color filter. When a photosensitive resist for a sheet is used, when it is necessary to have a pattern forming property, it is preferably used in an amount of 10 to 70% by weight. In this case, when the polymerizable compound (B) exceeds 70% by weight, the alkali solubility of the object of the present invention is also reduced. On the other hand, when it is 10% by weight or less, it is difficult to obtain a hardened coating film having desired coating film physical properties, and it is difficult to form a pattern, which is not preferable. The photosensitive resin composition of the present invention can be used as a photosensitive coating, an adhesive, and a pattern forming material as it is. Here, the photosensitive resin is blocked to include a coloring agent suitable for pigments, dyes, and the like, and a photosensitive resin composition containing a colorant is suitable for coatings, printing inks, and resists, and particularly to photosensitive resistance for color filters. Etchant. In addition, the cyclic carbonate group in the vinyl polymer (A) is a polar functional group and has the effect of further improving the dispersibility of the pigment. In order to ring-open the cyclic carbonate group to promote the cross-linking reaction, the ring-opening catalyst can be used as a ring-opening catalyst having a cyclic carbonate group or an epoxy-based ring-opening catalyst. Specific examples include tetramethylammonium bromide, trimethylbenzyl ammonium hydroxide, 2-hydroxypyridine, trimethylbenzyl ammonium methoate, phenyltrimethylammonium chloride, and phenyltri-16-574619 A7. B7 V. Description of the invention (15) Methyl ammonium bromide, phenyltrimethylammonium hydroxide, phenyltrimethylammonium iodide, choline phosphate sodium chloride, stearyl ammonium bromide, tetra-n-pentyl Ammonium iodide, tetra-n-butylammonium bromide, tetra-n-methylammonium hydroxide, tetra-n-butylammonium phosphate, tetra-n-decylammonium trichloride, tetraethylammonium hydroxide, tetraethyltetrafluoroborate Ammonium. Ethylcholine bromide, alkyldimethylbenzyl ammonium chloride, benzylcholine bromide, benzyl-n-butylammonium bromide, carmenine, butyl chloride, bis (tetra-n-butylammonium) ) Dichloride, or quaternary ammonium salts such as trimethyl vinyl ammonium bromide, allyl triphenyl chloride scale, n-pentyl triphenyl scale scale, benzyl triphenyl scale scale, Bromomethyl triphenyl bromide scale, 2-dimethylamine ethyl triphenyl bromide scale, ethoxycarbonyl bromide scale, n-heptyl triphenyl bromide scale, methyl triphenyl bromide Scale salts such as scales, methyl (hydroxymethyl) sulfate, or tetraphenyl bromide; acid catalysts such as phosphoric acid, p-toluenesulfonic acid, or dimethylsulfuric acid; and carbonates such as tin carbonate. When the photosensitive resin composition of the present invention is cured using active energy rays such as light, a photopolymerization initiator may be used to start the polymerization reaction using light. As the photopolymerization initiator, a known photopolymerization initiator can be used. Known photopolymerization initiators include, for example: (1) benzophenone, 3,3 · dimethyl-4 · methoxybenzophenone, 4,4 '· bisdimethylaminobenzophenone, 4 , 4'-bisdimethylaminobenzophenone, 4,4-dichlorobenzophenone, Michelin, 3,3 ', 4,4'-tetrakis (tertiary butyl peroxycarbonyl) Benzophenones such as benzophenone, (2) ketone, thioketone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-sulfanyl chloride, 2 Pilj ketones, thio_ketones, such as 1,4-diethylthioxanthone, 2,4-dimethylthioketone, thioketone_4_sulfonic acid, -17- This paper size applies to Chinese national standards (CNS) A4 specifications (210 X 297 mm) _ ~ " (Please read the precautions on the back before filling out this page)-丨 Installation ---- Order ---------. Ministry of Economy Wisdom Printed by the Consumer Cooperative of the Property Bureau 574619 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (16) (3) Benzoin, Benzoin Methyl Ether, Benzoin Ether, Benzoin Isopropyl Ethers, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether and other benzoin groups' (4) α-diketones such as benzyl and diethylfluorenyl, (5) Sulfides such as methylthiuram monosulfide, tetramethylthiuram disulfide, p-toluene disulfide, (6) 4-methylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl ester Ester, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid butyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester, 4-dimethylaminobenzoic acid-2 -Isoamyl esters and other benzoic acids, in addition to 3,3'-carbonylbis (7-diethylamino) -humulin, 1-hydroxycyclohexyl phenone, 2,2-dimethoxy-1,2 -Diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamine -IO-morpholinophenyl) -butane-1-one, 2-hydroxymethyl-1 · phenylpropane-1-one |, 2,4,6-dimethylpentyl monophenylphosphine oxidation Compound, 1- [4- (2-hydroxyethoxy) phenyl] -2 · hydroxy-2-methyl-1 · propane-1-one, 1- (4-isopropylphenyl) -2- Hydroxy-2-methylpropane-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1-one, 4-benzylidene-4'-form Dimethyl sulfide, ethoxyacetal, 1-phenyl-1,2-propanedione-3- (o-ethoxycarbonyl) Oxime, 2-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, ι, 3-diphenylpropanedione-2- (o-ethoxymine), 1-phenyl-3-ethoxyglycerone- 2- (o-benzylfluorenyl) benzene, o-benzoic acid methyl benzoate, bis (4-dimethylaminophenyl) ketone, p-dimethylene Aminoacetophenone, α, α-Dichlorophenoxyacetophenone, Amyl 4-dimethylaminobenzoate, 2,2'-bis (2-chlorophenyl) -4,4 ', 5 , 5'- 肆 (4-ethoxymine-based phenyl) _ -18- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) — ILIII-llll · I ---- 丨丨 Order II -------- (Please read the precautions on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economy, Employee Consumer Cooperative 574619 A7 —One B7 V. Description of Invention (17) 1, 2 '-Diimidazole, 2,2, bis (2-bromophenyl), 4,4', 5,5 '-(4-ethoxycarbonylphenyl) -1,2'-diimidazole, 2 ,, 2, -bis (2,4-dichlorophenyl-4,4, '5,5, tetraphenyl-1,2'-diimidazole, 2,2, -bis (2,4-dibromophenyl) ) -4,4 ,,, 5,5'-tetraphenyl · 1,2, -diimidazole, 2,2, -bis (2 , 4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl · 1,2, -diimidazole and other diimidazoles; p-dimethylaminoacetophenone, α, α- Dichloro-4-phenoxyacetophenone, 4-dimethylamine benzoic acid amyl ester, 2,4-bistrichloromethyl-6- [di- (ethoxycarbonylmethyl) amino] phenyl -S-Sanken, 2,4-bistrichloromethyl-6- (4-ethoxy) phenyl-S-trioxine, 2,4-bistrichloromethyl-6- (3-bromo- 4-ethoxy) phenyltrianthraquinone, 2-tert-butylanthraquinone, 2-pentylanthraquinone, chloroanthraquinone, benzoxanthone, dibenzocycloheptane, methylene anthrone, 4-azidocarbylacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexyl Ketones, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, n-phenylthioazetone, 4,4-azobisisobutyronitrile, diphenyldisulfide, benzothiazole disulfide, triphenylphosphine, tetrabromide A combination of carbon, tribromophenanthrene, benzoin peroxide, eosin, methylene blue and other photoreductive pigments, ascorbic acid, triethanolamine and other reducing agents. In addition, photopolymerization initiators include Irgaure series 184, 149, 261, 369, 500, 651, 784, 819, 907, 1116, 1664, 1700, 1 800, 1 850, 2959, 4043, Darocurll 73 (Ciba Specialty Chemicals) Products), Lucirin TPO (manufactured by BASF), KAYACURE series 歹 ij DETX, MBP, DMBI, EPA, OA (manufactured by Nippon Kayaku Co., Ltd.), VICURE series 歹 ij 10, 55 (manufactured by STAUFFER), TRIGONAL P1 (ΑΚΚΟ) (Product of the company), SANDORY1 000 (product of the company SANDOZ), DEOP (product of the company APJ〇HX), QUANTAX URE system [] PDO, -19- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) --- r ----- l · Aw I -------- Order --------- (Please read the phonetic notes on the back before filling this page) 574619 A7 B7 V. Description of the invention (18) ITX, EPO (made by WARO BLEKINSOP) and so on. As the photopolymerization initiator, a photosensitizer can be used. As the photosensitizer, a known photosensitizer can be used. Known photosensitizers include, for example, amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, and nitriles, or other nitrogen-containing compounds. The photopolymerization initiator and the photosensitizer can be used singly or in combination. The amount used is not particularly limited, but it is preferably from 0.1 to 20% by weight relative to the polymerizable compound (B), and more preferably from 0.5 to 10% by weight. When the content is less than 0.1% by weight, the photosensitivity is reduced, and when it exceeds 20% by weight, crystal precipitation and deterioration of the coating film physical properties are not preferred. The photosensitive resin composition of the present invention may contain other ingredients, if necessary, without preserving storage stability, water resistance, chemical resistance, heat resistance, and the like, without departing from the purpose of the present invention. Other ingredients include stabilizers such as reactive diluents, hardening catalysts, organic solvents, coupling agents, antioxidants, and ultraviolet absorbers, and various homogenizers such as silicone, fluorine, and acrylic. In order to improve alkali developability and thermosetting property of the photosensitive resin composition of the present invention, a polybasic acid and an anhydride may be added as other components. In order to improve the thermosetting property, an epoxy compound or the like may be added. Reactive diluents include, for example, butoxyethyl (meth) acrylate, n-oxyethylene glycol (fluorenyl) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (methyl Base) acrylate, 2-ethylhexyl (meth) acrylate, N-vinyltetrahydropyrrolidone, 1-vinylimidazole, isobornyl (meth) acrylate, tetrahydrofurfuryl (methyl) Acrylate, carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, cyclopentadiene (meth) acrylate, -20- This paper size applies to Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) (Please read the notes on the back before filling out this page) I -------- Order --------- AWI Printing 574619 A7 B7 5. Description of the invention (19) N-vinylformamide, N-vinylacetamide, N-vinylmorpholine, etc. These can be used singly or in combination of two or more kinds. (Please read the precautions on the back before filling out this page) Coupling agents include, for example, silane coupling agents, titanium coupling agents, and aluminum coupling agents. Among these materials, a silane coupling agent is preferred in terms of excellent smoothness, adhesion, water resistance, and solvent resistance. Examples of the silane coupling agent include r- (2-aminoethyl) aminopropyltrimethoxysilane, r- (2-aminoethyl) aminopropylmethyldimethoxysilane, and r-methylpropaneoxypropyl Trimethoxysilane, 7-glycidylpropyltrimethoxysilane, / 3-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 7-hydrothiopropyltrimethoxysilane , Vinyltriethoxysilane, vinyltrimethylsilane, trimethoxysilylbenzoic acid, r-isocyanatopropyltrimethoxysilane, etc., and oligomers made from these silane coupling agents Materials or polymers. Among the above-mentioned silane coupling agents, silane coupling agents having an epoxy group such as 7-glycidylpropyltrimethoxysilane and / 3- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are preferred. . These coupling agents may be used singly or in combination. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. For each 100 parts by weight of vinyl polymer (A), the blending amount of the coupling agent is preferably in the range of 0.1 to 30 parts by weight, and more preferably 0.5 to 20 parts by weight. When the blending amount of the coupling agent is less than 0.1 part by weight, the smoothness of the coating film formed, and the adhesive, water resistance and solvent resistance with the substrate are insufficient, and when it exceeds 30 parts by weight, not only can the improvement of adhesion not be expected. It is not suitable to form a coating film with reduced hardenability. The photosensitive resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components. -21- The paper size is applicable to the Chinese National Standard (CNS) A4 (21 ^ < 297 mm) 574619 A7 B7 i. Description of the invention (,. Mixing The method is a solvent mixing method in which these components are dissolved in an appropriate solvent and then mixed. These solvents are not particularly limited as long as they can dissolve the above components without reacting. This solvent can be used as it is for the above-mentioned vinyl polymerization. Various solvents listed at the time of production of the substance (A). The mixing order of the photosensitive resin composition of the present invention when prepared by the solvent mixing method is not particularly limited. For example, all the components can be dissolved in the solvent at the same time to prepare the photosensitive resin of the present invention The solution of the composition. The components can also be dissolved in the same or different solvents to form two or more kinds of solutions, and then these solutions are mixed to prepare the solution of the photosensitive resin composition of the present invention. The present invention prepared from the above The photosensitive resin composition can be used as it is as a paint, an adhesive, a pattern forming material, etc. The photosensitive resin composition is coated on a substrate That is, a hardened coating film having heat resistance, water resistance, solvent resistance, and chemical resistance can be formed. When the photosensitive resin composition of the present invention is used as a coating material, the vinyl polymer (A) and the polymerizable compound (B) can be regarded as The binder resin can be used as a UV-curable coating, a thermosetting coating, etc. by mixing colorants and additives. When the photosensitive resin composition of the present invention is used as a printing ink, it can be vinyl polymer (A), polymerizable The compound (B), the solvent, etc., can be used as a component of the medium, and can be used as a UV-curable ink by mixing a colorant and an auxiliary agent. Next, the photosensitive resist for a color filter of the present invention will be described. A photosensitive resist for a color filter is obtained by containing a vinyl polymer (A), a cyclic carbonate group (B), and a colorant (C) as essential components. This vinyl polymer (A) and a polymerizable compound ( B) The above is known. -22- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back before filling this page) -1 ----- --- Order ---- I ---- · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 574619 A7 B7 i. Description of the invention (21) The colorant (C) includes pigments, dyes, and other colorants. Pigments include organic pigments and inorganic pigments. Organic pigments include, for example, CiI.9 red pigment and C.1.97 red Pigment, C. 1.1 No. 22 Red Pigment, CI123 No. Red Pigment, C.L149 No. Red Pigment, c.1.168 No. Red Pigment, CI177 No. Red Pigment, Ci180 No. Red Pigment, No. c.1.192 Red Pigment, CI Red pigment No. 215, red pigment No. CI216, red pigment No. C.1.217, red pigment No. C.L22, red pigment No. c.1.223, red pigment No. CI224, red pigment No. C.L226, no. C.1.227 Red pigment, CI228 red pigment, CI240 red pigment, C. 1.254 red pigment.丄 48: Red pigments such as No. 1 red pigment, CI, No. 7 green pigments, (: No. 36 green pigments such as green pigment, cl15 blue pigment, C.1.15: No. 6 blue pigment, CI22 blue Blue pigments, blue pigments such as CI60 blue pigment, αι · 64 blue pigment, etc .; CI19 purple pigment, c.lu purple pigment, ci29 purple pigment, CI30 purple pigment, c.1.37 No. purple pigment, C.1.40 purple pigment, CI50 purple pigment and other purple f; CI20 yellow pigment, CI24 yellow pigment, C.L83 yellow pigment, cl86 yellow pigment, C.1.93 yellow Pigment, cm 09 yellow pigment, c. 1.1 10 page pigment, C · I · 11 1 7 yellow pigment, c · 1.1 2 5 yellow pigment, CI137 yellow pigment, c.uw yellow pigment , C.L139 yellow pigment, CI147 yellow pigment, c.1.148 yellow pigment, CI150 yellow pigment, CI · 153 yellow pigment, cj · :! No. 54 yellow pigment, CI166 yellow pigment, C Yellow pigments such as I168 yellow pigment and CI185 yellow pigment; black pigments such as CI7 black pigment. Electronic display -23- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)
-I I I I 1T--------- 經濟部智慧財產局員工消費合作社印製 574619 經濟部智慧財產局員工消費合作社印製 A7 B7 了 22 1、發明說明() 微照片以習用顏料無法觀察,但可觀構成凝集體的各個顏 料一次粒子。本發明顏料一次粒子平均粒徑在〇.〇〗〜〇.;!〇 // m者,前期分散性良好。另外,顏料一次粒子之平均粒 徑,可藉顏料以超音波分散於溶劑,而利用透射型電子顯 微鏡或掃描型電子顯微鏡測量。本發明中顏料一次粒子的 平均粒徑,以掃描型電子顯微鏡JEM-2〇10(日本電子公司 製品)拍攝視域內之顏料,構成二次元圖像上的凝集體之 顏料一次粒各50個,分別求出其縱長方向的直徑(長徑), 得平均値。 而無機顏料有例如硫酸鋇、硫酸鉛、氧化鈦、黃丹、紅 丹、氧化鉻、碳黑等。 染料有各種各樣可用,例如 <<染料便覽 >>(有機合成化 學協會編,1970),<<色材工業手冊 >>(色材協會編,朝倉 書店,1 989),<<工業用色素技術和市場〉>(CMC,1 983) ,《化學便覽應用化學編〉>(日本化學會編,九善書店, 1986)所載均可用。具體例有偶氮染料、金屬鏈鹽偶氮染 料、吡唑嘮偶氮染料、萘醌染料、蒽醌染料、酞花青染料 、碳染料、醌亞胺染料、次甲基染料、喳啉藍染料、靛染 料、喹啉染料、硝基系染料、二苯并哌喃染料、噻畊染料 、畊染料、噚畊染料、斯克歐理恩色素等。 此等顏料、染料等可以一種或二種以上混合使用。 上述顏料、染料之外、著色劑可用無機色素。無機色素 有例如碳系、鈦系、鉅系、鋁系、鈣系、鐵系、鉛系、鈷 系等無機色素。 -24- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) " ---_----1---Γ Aw I ^--------訂---------AWI (請先閱讀背面之注意事項再填寫本頁) 574619 A7 __ B7 五、發明說明(23) 著色劑在耐熱性、耐光性方面,以顏料爲佳。 本發明感光性樹脂組成物中的著色劑含有率爲5〜8 0重 ° (請先閱讀背面之注意事項再填寫本頁) 又,可用分散劑使顏料分散於濾色片用感光性抗蝕劑中 。於此,分散劑無特別限制,有例如顏料中間體,染料中 間體,聚醯胺系化合物或聚胺酯系化合物之類的樹脂型分 散劑。 此樹脂型分散劑市售品,有例如油斯巴-匹克系列1 30, 1 61,1 63,1 70耶福卡系列46,47,索路斯比斯等。另外 ’丙儲酸系、聚乙燒系等樹脂型分散劑等亦可用。 顏料分散之際可用分散機,此分散機有輥筒製粉機、球 磨粉機、珠粒磨粉機、磨碎機、分散攪拌機等。 經濟部智慧財產局員工消費合作社印製 此顏料在分散之際,使用溶劑。溶劑無特別限制。例如 甲苯或二甲苯、甲氧基苯等芳族系溶劑,乙酸乙酯或乙酸 丁酯、丙二醇單甲醚乙酸酯、丙二醇單乙醚乙酸酯等乙酸 酯系溶劑、乙氧基乙基丙酸酯等丙酸酯系溶劑,甲醇、乙 醇等醇系溶劑,丁基纖維素、丙二醇單甲醚、二乙二醇乙 醚、二乙二醇二甲醚等醚系溶劑,丁酮、甲基異丁酮、環 己酮等酮系溶劑,己烷等脂族烴系溶劑,N,N-二甲基甲醯 胺、7 -丁內酯、N-甲基-2-四氫吡咯酮、苯胺、吡啶等氮 化合物系溶劑,r -丁內酯等內酯系溶劑,胺基甲醇甲酯 和胺基甲酸乙酯48:52混合物之類的胺基甲酸酯,水等。 本發明濾色片用感光性抗蝕劑,除上述著色劑和分散劑 外’和上述感光性樹脂組成物同樣,可添加環碳酸根基之 -25- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 574619 經濟部智慧財產局員工消費合作社印製 A7 B7 i、發明說明(24) 開環觸媒、光聚合引發劑、光增感劑、反應性稀釋劑、硬 化觸媒、有機溶劑、偶合劑或抗氧化劑、紫外線吸收劑等 安定劑,勻化劑等。 本發明濾色片用感光性抗蝕劑中,乙烯基聚合物(A)之 環碳酸根基和羧基,在常溫和預熱所暴露溫度,可抑制二 官能基彼此間的反應,到顯像之像素部形成步驟爲止,可 維持安定性。像素部形成後的加熱步驟中,使環碳酸根基 與羧基反應,在像素部導入交聯構造,可改進像素部的耐 溶劑性、耐熱性或機械特性等。在最後加熱步驟中,由於 環碳酸根基與羧基反應,消耗羧基,可對羧基引起的塗膜 耐水性、耐藥品性等降低有所改善。 其次,詳述本發明濾色片之製法。 本發明濾色片之製法,是在使用本發明濾色片用感光性 抗蝕劑之透明基板上形成抗蝕劑層,通過設有濾色片用像 素圖案的光罩,對該抗蝕劑層曝光,使該抗蝕劑層光硬化 ’將該抗蝕劑層顯像,形成像素部,再將該像素部加熱, 使該像素部熱硬化。 在此製法中,感光性抗蝕劑中含有溶劑時,在形成抗蝕 劑層後,爲除去抗蝕劑層中的溶劑,可在50〜15(TC預熱 1〜1 5分鐘左右。 濾色片主要包括透明基板,和透明基板上所設稱爲黑色 基材的遮光性像素部,以及配在遮光薄膜上,由紅、綠、 藍三原色構成之透光性像素部。 在上述濾色片製法中’形成紅、綠、藍三原色之像素部 -26- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) -裝--------訂---------AWI · 574619 五、 發明說明( 25、 ’必須重複實施三次:形成抗蝕劑層、抗蝕劑層曝光、顯 像、加熱之步驟。 透明基板有例如玻璃板或透明塑膠板等。 在透明基板表面形成本發明感光性抗蝕劑層之方法,並 無特別限制。例如塗佈、轉印等均可。塗佈可以例如印刷 法、噴塗法、輥塗法、旋塗法等各種方法進行,轉印則可 在薄膜基材上預塗感光性抗蝕劑,再將此感光性抗蝕劑轉 印於玻璃基板,而在玻璃基板上形成感光性抗蝕劑層。 曝光是對透明基板上所形感光性抗蝕劑層,通過具有濾 色片用像素圖案的光罩,利用高壓水銀燈等進行。利用此 曝光,可使感光性抗蝕劑層光硬化。 顯像是令感光性抗蝕劑層與顯像液接觸爲之。利用此顯 像,在未曝光部的羧基可利用鹼性水溶液中而溶化,除去 該未曝光部。顯像方法有滿液法、浸液法、噴液法等。 顯像後,再進行流水洗淨,以壓縮空氣或壓縮氮氣風乾 ,把不要的未曝光部完全除去,形成像素部。 顯像液可用鹼性水溶液。鹼性水溶液有例如氫氧化鈉、 氫氧化鉀、碳酸鈉、矽酸鈉、氨水、乙胺、正丙胺、二乙 胺、二正丙胺、三乙胺、甲基二乙胺、二甲基乙醇胺、二 乙醇胺、三乙醇胺、四甲基氫氧化銨、四乙基氫氧化銨、 四丁基氬氧化錢、吡略、吡陡、1,8-重氮二環[5.4·0]-7-十 一碳烯、1,5-重氮二環[4·3·0]-5-壬烷等水溶液。而上述化 合物凡對水難溶性者,可將甲醇、乙醇、異丙醇等有機溶 劑之溶解液’用水稀釋成水溶液使用。 -27- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) ----------------I · 經濟部智慧財產局員工消費合作社印製 574619 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(26) 像素部形成後’此像素部可利用熱板、烘箱等加熱裝置 ,在預定溫度,例如100〜250°c,加熱預定時間,使像素 部熱硬化。經此熱硬化,即可形成耐熱性、透明性、硬度 等耐久性優良之像素部。 本發明方法所得濾色片具有耐久性,可用做例如彩色液 晶顯示器、彩色掃描器、固體攝像元件等。 實施例 其次,利用實施例詳細說.明本發明,惟本發明不受此等 實施例之限制。以下凡「份」和「%」若無特別提明,槪 以重量爲基準,關於所製成塗膜的性能試驗,採用下述方 法。 件能試驗之測定方法和評定基進 保存安定性 將後述實施例之感光性樹脂組成物25克,移至密封之 玻璃容器,在40t保存24小時,測量黏度,相對於初期 黏度之變化率在1 0%以下時爲Ο,1 0%以上者爲X。關於 後述實施例的感光性抗蝕劑,進行和上述同樣的操作。黏 度測量採用(特奇美克)公司製E型黏度計進行。 顯像特性 將後述實施例的感光性樹脂組成物,使用旋塗機在玻璃 板上,以lOOOrpm轉數旋塗9秒鐘後,於6(TC預乾5分 鐘,形成塗膜。於上述塗膜使用具有設定圖案之光罩,以 高壓水銀燈200mJ/cm2曝光後,在30°C的1·〇重量%碳酸 水溶液中顯像後,再用純水洗淨。經此操作,評定線寬20 -28- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -裝--------訂---------^_wi (請先閱讀背面之注意事項再填寫本頁) 574619 Α7 Β7 1、發明說明(27) V m圖案(殘留)之可能性。後述實施例的感光性抗鈾劑, 亦進行上述同樣操作。可圖案化者爲〇,不可爲X。 透明件 將後述實施例之感光性樹脂組成物,使用旋塗機在玻璃 板上,以lOOOrpm轉數旋塗9秒鐘後,在60°C預乾5分 鐘,形成塗膜。於上述塗膜以高壓水銀燈200mJ/cm2曝光 後,在23 °C進行加墊15分鐘,使塗膜硬化。形成硬化塗 膜的玻璃板吸收光譜,以所用玻璃板爲基準,測量在 400nm〜800nm範圍之光透射率。後述實施例的感光性抗 蝕劑,進行上述同樣操作。光透射率在95%以上者爲〇, 95%以下爲X。 耐熱件-1 上述透明性試驗所得硬化塗膜的色度(以下稱Y値),以 奧林帕斯公司製品顯微分光測定裝置OSP-SP200測量(此 時Y値爲Y1),其次,上述硬化塗膜於28(TC加熱30分鐘 後,使用上述裝置測量硬化塗膜之Y値(此時Y値爲Y2) 。由Y1和Y2之差△ Y,評定硬化塗膜之耐熱性。此△ γ 在0.5以下時爲〇,〇.5以上時爲X。 耐熱性-2 上述透明性試驗所得硬化塗膜最大光線透射率,使用上 述裝置測量。其次,上述硬化塗膜在28(TC加熱30分鐘後 ’使用上述裝置測量硬化塗膜最大光線透射率。由加熱前 硬化塗膜最大光線透射率値(A)與加熱後硬化塗膜最大光 線透射率値(B)之變化率{[(Α-Β)/Α]χ100},評定硬化塗膜 -29- 本紙張尺度適用中國國家標準(CNS)A4規袼(210 X 297公釐) (請先閱讀背面之注音?事項再填寫本頁) 一 ---------訂---------· 經濟部智慧財產局員工消費合作社印製 574619 五、發明説明(28 ) 耐熱性。此變化率在5%以下時爲〇,在5%以上時爲X。 上述最大光線透射率之測量,使用上述OSP-SP200爲之。 耐藥品忡-1 於上述透明性試驗所得硬化塗膜,在23°CN-甲基-2-四 氫吡咯酮中浸泡30分鐘。觀察浸泡後的硬化塗膜受到浸 泡部的界限面,界線可用目視確認時爲X,不可時爲〇。 耐藥品件-2 將上述透明性試驗所得硬化塗膜,使用摩擦試驗機(太 平理化工業公司製品),於25 t條件,以〇.5公斤負荷, 用丙酮摩擦,評定達到下方玻璃基板爲止之摩擦次數。此 時的摩擦次數在100次以下時爲X,100以上到300以下 時爲△,300次以上到500次以下時爲〇,而500次以上 爲◎。 製造例1 :調製乙烯某聚合物(A) 於設有溫度計、回流冷卻管、攪拌機和氮氣進入管的四 口燒瓶,塡充丙二醇單甲醚乙酸酯(以下稱PGMAc)425.0 份,攪拌中升溫到90°C爲止,在1小時內滴加2,3-碳酸根 丙基甲基丙烯酸酯(以下稱CPMA)82.0份,甲基丙綠酸酯( 以下稱ΜΜΑ)38·0份,甲基丙烯酸苄酯(以下稱BZMA)210.0份 ,PGMAC97.0份’和三級丁基過氧-2-乙基己酸酯(以下稱 P-0)16.5份之混合溶解物。滴加結束後,在90°C保持2 小時,然後加P-01.7份,再於同溫度反應7小時,得樹 脂固體份的酸價(在試料1克中存在的酚份,根據規定方 法中和所需氫氧化鈉毫克數)爲7 5 m g Κ Ο H / g之乙烯基聚合 -30- 經濟部智慧財產局員工消費合作社印製 574619 A7 B7 29 五、發明說明() 物(A-1)。所得樹脂溶液的不揮發份(在l〇7.5°C乾燥1小時 後的殘餘樹脂重量%)爲40.7%,Gardner黏度爲T〜U,苯 乙烯換算之數平均分子量爲5300, Mw/Mn爲2.29。 製浩例2 :同上 在製造例1中,把MAA3 8.0份改爲76.0份,BZMA 210.0份改爲BZMA122.0份,甲基丙烯酸-2-羥乙酯(以下 稱HEMA) 17.0份和苯乙烯33.0份,另外聚合引發劑把 P-Ο改爲2,2’-偶氮雙(2,4-二甲基戊腈(以下稱ADVN), P-016.5 份改用 ADVN19.8 份,P-01.7 份改用 ADVN1.7 份 ,再將反應溫度90°C改爲80°C,混合溶解物滴加時間1 小時改爲2小時,其餘和製造例1同樣,得樹脂固體份酸 價爲150mgKOH/g之乙烯基聚合物(A-2)。所得樹脂溶液 的不揮發份爲41.0%,Gandner黏度爲X〜Y,其數平均分 子量爲 3700,Mw/Mn 爲 3.55。 製浩例3 :同上 在製造例1中,把CPMA82.5份改爲3,4-碳酸根丁基丙 烯酸酯25·0份,MAA3 8.0份改爲49.5份,BZMA209.5份 改爲甲基丙烯酸甲酯255.5份,所用聚合引發劑P-Ο改爲 三級戊基過氧-2-乙基己酸酯(以下稱ΤΑΕΗ),把Ρ-0 16.5份改爲ΤΑΕΗ3.5份,其餘和製造例1同樣,得樹脂 固體份酸價98mgKOH/g之乙烯基聚合物(Α-3)。所得樹脂 溶液之不揮發份爲41.2%,Gandner黏度爲Z22〜Z3,其 數平均分子量爲1 1 500,Mw/Mn爲2.65。 製造例3 :調製比較用共聚物 -31- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 丨丨—丨-1丨丨丨1- ·丨丨丨丨丨丨丨訂.丨丨丨丨丨! · (請先閱讀背面之注意事項再填寫本頁) 574619 五、發明説明(3G ) 在製造例1中,滴加的混合溶解物中不用CPMA,而 BZMA210.0份改爲292.0份,其餘和製造例1同樣,得樹 脂固體份酸價爲75mgKOH/g之比較用共聚物(H-1)。所得 樹脂溶液的不揮發份爲40.7%,Gandnen黏度爲Η,其數 平均分子量爲4800,分散度Mw/Mn爲2.40。 製造例4 :同上 在製造例1同樣的反應器,充塡PGMAC400.0份,攪拌 中升溫到80°C,在1小時內滴加甲基丙烯酸66.4份, MMA196.9份,甲基丙烯酸縮水甘油酯113.9和P-022.6 份之混合溶解物。滴完後,在80°C保持1小時,加P-0 0.34份,再於同溫度反應。但在單體滴完後約3小時反應 中增黏,以致最後凝膠化,得不到比較用共聚物(H-2)。 製造例5 :同上 在製造例1中,除滴加混合溶解物中的2,3-碳酸根丙基 甲基丙烯酸酯,改爲環氧基環己基甲基丙烯酸酯[戴西爾 化學工業公司製品(塞克羅)100],爲防止聚合時的凝膠 化反應,把反應溫度從90t改爲80°C外,其餘和製造例1 同樣進行反應。追加P-0,2小時後的Gandner黏度均爲 Z1〜Z2,此時數平均分子量爲1 1 700,Mw/Mn爲6.8 6。 然後追加P-0,使反應溶液徐徐增黏,經5小時停止反應 ,得樹脂固體份酸價爲75mgKOH/g之比較用聚合物(H-3) 。所得樹脂溶液的不揮發份爲40.7%,Gandner黏度爲Z4 〜Z5,數平均分子量爲12700,Mw/Mn爲25.59,成爲分 子量分佈更廣之聚合物。 -32- 574619 A7 B7 五、發明說明(31) 製造例6_ :同上 (請先閱讀背面之注咅?事項再填寫本頁) 在設有溫度計、回流冷卻管和攬拌機的燒瓶,充塡環氧 當量187之雙酚A型環氧樹脂187份,丙烯酸72份, 三苯膦12份,攪拌中升溫至11 〇。(:,在此溫度反應至酸價 在3以下爲止。其次,加四氫苯二甲酐152份,在100°C 進行反應至酸價137爲止,得兼有羧基和不飽和雙鍵之化 合物(H-4)。 在設有溫度計、回流冷卻管和攪拌機的燒瓶,充塡丙三 醇-α ·單氯醇11 〇份,二甲基甲醯胺1 〇〇份,碳酸氫鈉 120份,攪拌中升溫至100°C,在此溫度反應2小時,然 後除去不溶份和溶劑,得羥甲基伸乙基碳酸酯黏稠液。 其次,於設有溫度計、攪拌機、冷凝器之燒瓶,充塡此 羥甲基伸乙基碳酸酯1 1 8份,攪拌中升溫到60t,在1小 時在小心發熱中添加六亞甲基二異氰酸酯之異三聚氰酸酯 型聚異氰酸酯(NCO% = 23.8%)165份,進行反應。反應1 小時,利用紅外線吸收光譜確認異氰酸酯基吸收已消滅, 得標的環碳酸根基之化合物(H-5)。 實施例1 經濟部智慧財產局員工消費合作社印製 製造例1所得乙烯基聚合物(A-l)lOO.O份,用PGMAc 220.0份稀釋後,秤量二異戊四醇六丙烯酸酯(以下稱 DPHA)40.0份,和Irgacunel84(汽巴特殊化學公司製品) 1.2份,攬拌混合到均勻爲止。以孔徑0.2 // m的濾材過濾 ,得本發明感光性樹脂組成物。評估此組成物之保存安定 性。結果如表1所示。 -33- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 574619 五、發明説明(32 ) 所得溶液,使用旋塗機在玻璃板上,以lOOOrpm轉數旋 塗9秒後,在60°C預乾5分鐘,形成預乾塗膜。 上述預乾塗膜以高壓水銀燈曝光200mJ/cm2後,於 23(TC加熱處理1 5分鐘,使塗膜硬化,評估塗膜透明性、 耐熱性和耐藥品性。評估結果如表1所示。 於上述預乾塗膜,通過具有預定圖案之光罩,以高壓水 銀燈曝光200mJ/cm2後,在30°C的1·0重量%碳酸鈉水溶 液中顯像後,就純水進一步洗淨之際,線寬2 0 // m g[案 (殘餘)之可能性(顯像特性)加以評估。結果如表1 m 。 其次,將上述圖案塗膜,以熱板,於23(TC加熱處理15 分鐘,加以硬化。 實施例2-5和比較例1-4 除改用表1所示物質外,進行實施例1同樣操作,得横f 脂組成物後,進行各種試驗。其塗膜性能如表1 & #。 -34- 574619 發 五 比較例 : 寸 1 ' 1 ' 1 § S 导, 280 (N 1—Η 1 1 〇 X 〇 1 〇 良好 〇 〇 1 1 1 1 〇 1 1 1—H 穿· | 220 | CN r-H 1 雇 X X 〇 1 〇 良好 〇 〇 (N 凝膠化 O 1 1 1 〇 1 1 1 1—H 导· 220 (N i—H 1 1 〇 〇 〇 1 X 微小波肌 〇 〇 實施例 § 二 1 _ , r—H 导· 220 (N r-H 1 1 〇 〇 〇 1 〇 良好 〇 〇 寸 1 〇 1 1 1 1 1 〇 220 (N 1 1 〇 〇 〇 1 〇 良好 〇 〇 cn 〇 1 1 1 1 1 1 r—1 • ? 220 <N 1—H 1 着 〇 〇 〇 1 〇 良好 〇 〇 (N 〇 1 1 1 1 1 1 H 导· 220 (N T-H (N o ο (Ν 〇 〇 〇 1 〇 良好 〇 ◎ 〇 1 1 1 1 1 1 T—( 220 (N T-H 1 1 〇 〇 〇 1 〇 良好 〇 〇 < < < HJJ 锭锲锲锲锲 ι!Λ U.X ΜΛ Ttr\ <V 齡鏃齡齡齡鈕飪 _ _ _稍_鬆鬆 N3 ^ K) 1¾ N3 DPHA PETA PGMAc r-H =tt W) | Vh 四丁基溴化銨 r -甲基丙烯醯氧基丙基三甲 氧基矽烷 保存安定性 顯像特性 透明性 耐熱性-1 耐熱性-2 耐熱試驗後之塗膜外觀 耐藥品性-1 耐藥品性-2 -35- 574619 五、發明説明(34 ) 實施例6 使用五十嵐機械工廠製造的高速分散機TSG-6H,將製 造例1調製之乙烯基聚合物(A-1)溶液25.0份,C.I.254號 紅色顏料(一次粒徑80nm以下)8.0份,迪斯巴一匹克161( 樹脂型分散劑)2·5份PGMAC64.5份所組成分散液,以 氧化鍩粒,藉2000rpm進行分散8小時,得紅色 顏料分散液。其次,相對於上述所得紅色顏料分散液1〇〇 份,添加DPHA7.0份,Irgacune369(汽巴特殊化學公司製 品)0·3份混合,經孔徑1 ·〇 # m之濾材過濾,得本發明感 光性抗蝕劑。 其次,將所得感光性抗蝕劑25克,移至密閉玻璃容器 中,在4〇°C保存24小時,評估保存安定性。 所得感光性抗蝕劑,使用旋塗機在玻璃板上,以 lOOOrpm轉數旋塗9秒鐘後,在6(TC預乾5分鐘,形成預 乾塗膜。 上述預乾塗膜以高壓水銀燈曝光2G0mJ/Cm2後,於 23 0°C加熱處理15分鐘,使塗膜硬化,評估塗膜的透明性 、耐熱性和耐藥品性。評估結果如表2所示。 於上述預乾塗膜,使用具有預定濾色片用像素圖案之光 罩,以高壓水銀燈曝光lOOmJ/cm2後,在30°C的0.5重量 %碳酸鈉水溶液中顯像後,用純水再洗淨之際,就線寬 20μπι圖案(殘餘)之可能性(顯像特性)加以評估。 其次,將上述所得像素部,以230°C加熱處理15分鐘 ,加以硬化。 -36- 574619 五、發明説明(35 ) 比較例5-6 除改用表2所示物質外,進行實施例6同樣操作,調製 紅色顏料分散液後,得感光性抗蝕劑。再進行同樣各種試 驗,其諸性能綜合如表2。 表2 實方ί g例 比較例 6 5 6 7 乙烯基聚合物溶液A-1 25 - - - 乙烯基聚合物溶液A-2 - - - - 乙烯基聚合物溶液A-3 - - - - 乙烯基聚合物溶液H_1 - 25 - - 感 乙烯基聚合物溶液H-2 - - - - 光 乙烯基聚合物溶液H-3 - - 25 - 抗 化合物溶液 H-4 - - - 10 蝕 化合物溶液 H-5 - - - 7 劑 C.1.254號紅色顏料 8 8 8 8 2.5 2.5 2.5 2.5 DPHA 7 7 7 - PGMAc 64.5 64.5 64.5 79.5 Irg#369 0.3 0.3 0.3 0.3 保存安定性 〇 〇 X X 顯像特性 〇 〇 X X 透明性 〇 〇 〇 X 塗 耐熱性-1 〇 X 〇 〇 膜 耐熱性-2 〇 X 〇 〇 性 耐熱試驗後之塗膜外觀 良好 微小波肌 良好 良好 能 耐藥品性-1 〇 〇 〇 〇 耐藥品性-2 〇 〇 〇 〇 -37- 574619 A7 ___B7_ 五、發明說明(36) 產業上利用價値 本發明感光性樹脂組成物因含有環碳酸根基和羧基之乙 烯基聚合物,保存安定性良,透明性優,最後由環碳酸根 基與羧基反應,導入交聯構造,即可得耐熱性和耐藥品性 均優之塗膜,可用於塗料、印刷油墨、抗蝕劑等,尤其是 濾色片用感光性抗蝕劑。 交聯構造濾色片用感光性抗蝕劑,因係包括具有環碳酸 根基和羧基的乙烯基聚合物,以及具有乙烯性不飽和雙鍵 之化合物,可在濾色片像素部利用光硬化和熱硬化導入交 聯構造,可用於形成耐久性濾色片像素部。 本發明濾色片之製法,由於使用上述濾色片用感光性抗 蝕劑,可用來製造耐久性之濾色片。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)-IIII 1T --------- Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 574619 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 However, it can be seen that each pigment primary particle that constitutes the aggregate. If the average particle diameter of the primary particles of the pigment of the present invention is in the range of 〇〗 ~ 〇 .;! 〇 // m, the early dispersibility is good. In addition, the average particle diameter of the primary particles of the pigment can be measured by using a transmission electron microscope or a scanning electron microscope by dispersing the pigment in a solvent by ultrasonic waves. In the present invention, the average particle diameter of the primary pigment particles is photographed with a scanning electron microscope JEM-2010 (manufactured by Japan Electronics Co., Ltd.), and each of the primary pigment particles constituting the aggregate on the secondary image is 50 particles. , Respectively, to obtain the diameter (long diameter) in the longitudinal direction, and obtain the average 値. The inorganic pigments include, for example, barium sulfate, lead sulfate, titanium oxide, Huang Dan, Hong Dan, chromium oxide, carbon black, and the like. Various dyes are available, such as < < Dye Guide > > (organic synthetic chemistry association, 1970), < < color material industry manual > > (color material association, asakura bookstore, 1 989), < < Industrial Pigment Technology and Markets > (CMC, 1 983), "Chemistry Fact Sheet Applied Chemistry" > (edited by the Chemical Society of Japan, Jiusen Bookstore, 1986) are available. Specific examples include azo dyes, metal chain salt azo dyes, pyrazolium azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbon dyes, quinone imine dyes, methine dyes, perylene blue Dyes, indigo dyes, quinoline dyes, nitro-based dyes, dibenzopiperan dyes, thienol dyes, tiller dyes, tiller dyes, Skorion dyes, and the like. These pigments, dyes, and the like may be used in combination of one kind or two or more kinds. In addition to the pigments and dyes, inorganic pigments can be used as colorants. The inorganic pigments include, for example, inorganic pigments such as carbon-based, titanium-based, macro-based, aluminum-based, calcium-based, iron-based, lead-based, and cobalt-based. -24- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) " ---_---- 1 --- Γ Aw I ^ -------- Order- -------- AWI (Please read the precautions on the back before filling in this page) 574619 A7 __ B7 V. Description of the invention (23) Pigments are preferred in terms of heat resistance and light resistance. The coloring agent content in the photosensitive resin composition of the present invention is 5 to 80% by weight (please read the precautions on the back before filling in this page). The dispersant can be used to disperse the pigment in the photosensitive resist for color filters. Agent. Here, the dispersant is not particularly limited, and examples thereof include resin-based dispersants such as pigment intermediates, dye intermediates, polyamine compounds or polyurethane compounds. Commercially available products of this resin-based dispersant include, for example, oil spa-pic series 1 30, 1 61, 1 63, 1 70 Jefka series 46, 47, Solusbis and the like. In addition, resin-based dispersants such as' acrylic acid-based and polyethylene fired-based systems can also be used. When dispersing the pigment, a dispersing machine can be used. The dispersing machine includes a roller mill, a ball mill, a bead mill, a pulverizer, and a dispersion mixer. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This pigment uses a solvent when it is dispersed. The solvent is not particularly limited. For example, aromatic solvents such as toluene or xylene, methoxybenzene, ethyl acetate or butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and other acetic acid solvents, ethoxyethyl Propionate solvents such as propionate, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellulose, propylene glycol monomethyl ether, diethylene glycol ether, and diethylene glycol dimethyl ether, methyl ethyl ketone, methyl formaldehyde Ketone solvents such as isobutyl ketone and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; N, N-dimethylformamide, 7-butyrolactone, N-methyl-2-tetrahydropyrrolidone , Nitrogen compound solvents such as aniline and pyridine, lactone solvents such as r-butyrolactone, carbamates such as 48:52 mixtures of aminomethyl methyl esters and urethanes, water and the like. Except for the above colorant and dispersant, the photosensitive resist for a color filter of the present invention can be added with a cyclic carbonate group of -25 as with the above-mentioned photosensitive resin composition.-This paper size applies to Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) 574619 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 i. Invention Description (24) Ring-opening catalyst, photopolymerization initiator, photosensitizer, reactive diluent, hardened contact Solvents, organic solvents, coupling agents or stabilizers such as antioxidants, UV absorbers, homogenizers, etc. In the photoresist for a color filter of the present invention, the cyclic carbonate group and carboxyl group of the vinyl polymer (A) can inhibit the reaction between the difunctional groups at normal temperature and the temperature exposed by preheating to the time of development. Stability can be maintained up to the pixel portion formation step. In the heating step after the pixel portion is formed, a cyclic carbonate group is reacted with a carboxyl group, and a crosslinked structure is introduced into the pixel portion, which can improve the solvent resistance, heat resistance, and mechanical characteristics of the pixel portion. In the last heating step, the cyclic carbonate group reacts with the carboxyl group and consumes the carboxyl group, which can improve the decrease in water resistance and chemical resistance of the coating film caused by the carboxyl group. Next, the manufacturing method of the color filter of the present invention will be described in detail. The color filter of the present invention is produced by forming a resist layer on a transparent substrate using the photosensitive resist for the color filter of the present invention, and providing the resist with a photomask provided with a pixel pattern for the color filter. Layer exposure, photo-curing the resist layer, developing the resist layer, forming a pixel portion, and heating the pixel portion to thermally harden the pixel portion. In this manufacturing method, when a solvent is contained in the photosensitive resist, after the resist layer is formed, in order to remove the solvent in the resist layer, it may be preheated at 50 to 15 (TC for about 1 to 15 minutes.) The color chip mainly includes a transparent substrate, a light-shielding pixel portion called a black substrate provided on the transparent substrate, and a light-transmitting pixel portion composed of three primary colors of red, green, and blue arranged on the light-shielding film. In the film method, the pixels forming the three primary colors of red, green, and blue are -26- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page)- -------- Order --------- AWI · 574619 V. Description of the invention (25, 'must be repeated three times: forming a resist layer, exposing the resist layer, developing, The step of heating. The transparent substrate includes, for example, a glass plate or a transparent plastic plate. The method for forming the photosensitive resist layer of the present invention on the surface of the transparent substrate is not particularly limited. For example, coating, transfer, etc. may be applied. For example, printing method, spraying method, roll coating method, spin coating method, etc. For printing, a photoresist can be pre-coated on a thin film substrate, and then transferred to a glass substrate to form a photoresist layer on the glass substrate. Exposure is applied to a transparent substrate. The shape of the photosensitive resist layer is performed by using a mask having a pixel pattern for a color filter, using a high-pressure mercury lamp, etc. With this exposure, the photosensitive resist layer is light-cured. The development is to make the photosensitive resist The layer is in contact with the developing solution. With this developing method, the carboxyl group in the unexposed portion can be dissolved in an alkaline aqueous solution to remove the unexposed portion. The developing method includes a full liquid method, an immersion method, and a liquid spray method. After development, rinse with running water and air dry with compressed air or compressed nitrogen to completely remove unnecessary unexposed parts to form pixel parts. The developing solution can be alkaline aqueous solution. The basic aqueous solution includes, for example, sodium hydroxide, Potassium hydroxide, sodium carbonate, sodium silicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, diethanolamine, triethanolamine, tetramethyl Ammonium hydroxide, tetraethyl Ammonium hydroxide, tetrabutyl argon oxide, pyridine, pyridine, 1,8-diazobicyclo [5.4 · 0] -7-undecene, 1,5-diazobicyclo [4 · 3 · 0] -5-nonane and other aqueous solutions. Where the above compounds are insoluble in water, the solution of organic solvents such as methanol, ethanol, isopropanol, etc. can be diluted with water to form an aqueous solution. -27- This paper size applies to China National Standard (CNS) A4 Specification (210 X 297 mm) (Please read the precautions on the back before filling this page) ---------------- I · Bureau of Intellectual Property, Ministry of Economic Affairs Printed by the employee consumer cooperative 574619 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperative A7 B7 V. Description of the invention (26) After the pixel unit is formed, this pixel unit can use heating devices such as hot plates and ovens at a predetermined temperature, such as 100 ~ 250 ° C, heating for a predetermined time to thermally harden the pixel portion. By this heat curing, a pixel portion having excellent durability such as heat resistance, transparency, and hardness can be formed. The color filter obtained by the method of the present invention has durability and can be used as, for example, a color liquid crystal display, a color scanner, a solid-state imaging element, and the like. Examples Next, the present invention will be explained in detail using examples, but the present invention is not limited by these examples. Unless otherwise specified, the following "parts" and "%" are based on weight. For the performance test of the finished coating film, the following method is used. Measurement method and evaluation basis of component performance test Storage stability The 25 g of the photosensitive resin composition of the examples described below was transferred to a sealed glass container and stored at 40t for 24 hours. The viscosity was measured. The change rate from the initial viscosity was 0 is below 10%, and X is above 10%. Regarding the photosensitive resist in the examples described later, the same operations as described above were performed. Viscosity measurement was performed using an E-type viscometer manufactured by (Tequico). Development characteristics The photosensitive resin composition of the examples described later was spin-coated on a glass plate with a spin coater at 1,000 rpm for 9 seconds, and then dried at 6 ° C. for 5 minutes to form a coating film. The film was exposed with a high-pressure mercury lamp 200mJ / cm2 using a photomask with a set pattern, and developed in a 1.0 wt% carbonic acid aqueous solution at 30 ° C, and then washed with pure water. After this operation, the line width was evaluated to 20 -28- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)-installed -------- order --------- ^ _ wi (Please read the Please fill in this page again for attention) 574619 Α7 Β7 1. Description of the invention (27) Possibility of Vm pattern (residual). The same operation is also performed for the photosensitive uranium anti-oxidant of the examples described later. The patternable is 0, It cannot be X. The transparent resin is coated with the photosensitive resin composition of the following examples on a glass plate using a spin coater at 1000 rpm for 9 seconds, and then dried at 60 ° C for 5 minutes to form a coating film. After the above coating film was exposed with a high-pressure mercury lamp 200 mJ / cm2, padding was performed at 23 ° C for 15 minutes to harden the coating film. A hardened coating was formed. The absorption spectrum of the glass plate was measured based on the glass plate used, and the light transmittance in the range of 400 nm to 800 nm was measured. The photosensitive resist in the examples described later was performed in the same manner as above. The light transmittance of 95% or more was 0. 95% or less is X. Heat-resistance-1 The chromaticity (hereinafter referred to as Y 所得) of the hardened coating film obtained in the above-mentioned transparency test is measured by OSP-SP200, a micro-spectrophotometer manufactured by Olympus Corporation (At this time, Y 値 is Y1), secondly, the hardened coating film was heated at 28 (after 30 minutes of TC heating, the Y 値 of the hardened coating film was measured using the above device (Y 此时 is Y2 at this time). The hardened coating film was evaluated from the difference ΔY between Y1 and Y2 Heat resistance. This △ γ is 0.5 when it is 0.5 or less, and X when it is 0.5 or more. Heat resistance-2 The maximum light transmittance of the cured coating film obtained in the above-mentioned transparency test is measured using the above device. Second, the above cured coating film At 28 ° C after heating for 30 minutes, use the above device to measure the maximum light transmittance of the cured coating film. From the maximum light transmittance of the cured coating film before heating 値 (A) and the maximum light transmittance of the cured coating film after heating 値 (B) Change rate {[(Α-Β) / Α] χ100}, comment Hardened coating film-29- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the phonetic on the back? Matters before filling out this page) I --------- Order --------- · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 574619 V. Description of the invention (28) Heat resistance. This change rate is 0 when it is less than 5% and X when it is more than 5% For the measurement of the above maximum light transmittance, use the OSP-SP200 as described above. Chemical resistance 忡 -1 The cured coating film obtained in the transparency test described above was immersed in 23 ° CN-methyl-2-tetrahydropyrrolidone for 30 minutes. The boundary surface of the cured coating film after immersion was observed, and the boundary line was X when visual confirmation, and 0 when not possible. Chemical resistance part-2 The hardened coating film obtained by the above-mentioned transparency test was rubbed with a acetone under a condition of 25 t under a load of 0.5 kg by using a friction tester (product of Taiping Ricoh Chemical Industry Co., Ltd.), and it was evaluated that it reached the lower glass substrate. Number of frictions. The number of frictions at this time is X for 100 times or less, Δ for 100 to 300 times, 0 for 300 to 500 times, and ◎ for 500 or more times. Production Example 1: Preparation of a certain polymer (A) of ethylene In a four-necked flask equipped with a thermometer, a reflux cooling tube, a stirrer, and a nitrogen inlet tube, 425.0 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) was charged, while stirring The temperature was raised to 90 ° C, and 82.0 parts of 2,3-carbonate propyl methacrylate (hereinafter referred to as CPMA) and 38.0 parts of methylpropionate (hereinafter referred to as MMA) were added dropwise within 1 hour. A mixed solution of 210.0 parts of benzyl acrylate (hereinafter referred to as BZMA), 97.0 parts of PGMAC 'and 16.5 parts of tertiary butyl peroxy-2-ethylhexanoate (hereinafter referred to as P-0). After the dropwise addition, keep at 90 ° C for 2 hours, then add P-01.7 parts, and then react at the same temperature for 7 hours to obtain the acid value of the resin solids (phenol content in 1 g of the sample, according to the prescribed method And the required number of milligrams of sodium hydroxide) is 7 5 mg Κ Ο H / g of vinyl polymerization -30-printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 574619 A7 B7 29 V. Description of the invention () Object (A-1 ). The nonvolatile matter (residual resin weight% after drying at 107.5 ° C for 1 hour) of the obtained resin solution was 40.7%, the Gardner viscosity was T ~ U, the number average molecular weight in terms of styrene was 5300, and Mw / Mn was 2.29 . System Example 2: Ibid. In Production Example 1, 8.0 parts of MAA3 was changed to 76.0 parts, 210.0 parts of BZMA was changed to 122.0 parts of BZMA, 17.0 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA) and styrene 33.0 parts. In addition, the polymerization initiator changed P-O to 2,2'-azobis (2,4-dimethylvaleronitrile (hereinafter referred to as ADVN)), P-016.5 parts to ADVN 19.8 parts, and P- 01.7 parts was changed to 1.7 parts of ADVN, and the reaction temperature was changed from 90 ° C to 80 ° C. The mixed solution was added dropwise for 1 hour to 2 hours. The rest was the same as in Production Example 1. The acid value of the resin solids was 150 mgKOH. / g of vinyl polymer (A-2). The obtained resin solution has a nonvolatile content of 41.0%, a Gandner viscosity of X to Y, a number average molecular weight of 3700, and a Mw / Mn of 3.55. Production Example 3: Ibid. In Manufacturing Example 1, 82.5 parts of CPMA was changed to 25.0 parts of 3,4-carbonate butyl acrylate, 8.0 parts of MAA3 was changed to 49.5 parts, and 209.5 parts of BZMA was changed to 255.5 parts of methyl methacrylate. The polymerization initiator P-0 was changed to tertiary pentylperoxy-2-ethylhexanoate (hereinafter referred to as TAE), and 16.5 parts of P-0 was changed to 3.5 parts of TAE. The rest was the same as in Production Example 1. Resin solids A vinyl polymer (A-3) with a valence of 98 mgKOH / g. The obtained resin solution had a nonvolatile content of 41.2%, a Gandner viscosity of Z22 to Z3, a number average molecular weight of 1 1 500, and a Mw / Mn of 2.65. Production Examples 3: Copolymer for modulation and comparison-31- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 丨 丨 —— 丨 -1 丨 丨 1-1- 丨 丨 丨 丨 丨 丨 丨 Order.丨 丨 丨 丨 丨! · (Please read the precautions on the back before filling this page) 574619 V. Description of the Invention (3G) In Manufacturing Example 1, CPMA is not used in the mixed solution added dropwise, but 210.0 parts of BZMA is modified. It was 292.0 parts, and the rest was the same as in Production Example 1. A comparative copolymer (H-1) having an acid value of 75 mgKOH / g as the solid content of the resin was obtained. The non-volatile content of the obtained resin solution was 40.7%, and the Gandnen viscosity was Η The average molecular weight is 4800 and the dispersion Mw / Mn is 2.40. Production Example 4: The same reactor as in Production Example 1 was filled with 400.0 parts of PGMAC, heated to 80 ° C while stirring, and methyl was added dropwise within 1 hour. 66.4 parts of acrylic acid, 196.9 parts of MMA, 113.9 parts of glycidyl methacrylate and P-022.6 parts of mixed dissolved matter. , Hold at 80 ° C for 1 hour, add 0.34 parts of P-0, and then react at the same temperature. However, the reaction will thicken in about 3 hours after the monomer is dripped, so that it will finally gel and no comparative copolymer will be obtained. (H-2). Production Example 5: Same as in Production Example 1, except that 2,3-carbonate propyl methacrylate in the mixed solution was added dropwise to epoxy cyclohexyl methacrylate [Daisil Chemical Industry Co., Ltd. Product (Secero) 100]. In order to prevent the gelation reaction during polymerization, the reaction temperature was changed from 90t to 80 ° C, and the rest were reacted in the same manner as in Production Example 1. After adding P-0, the Gandner viscosity after 2 hours were all Z1 to Z2. At this time, the number average molecular weight was 1 1 700, and the Mw / Mn was 6.86. Then, P-0 was added to gradually increase the viscosity of the reaction solution, and the reaction was stopped after 5 hours to obtain a comparative polymer (H-3) having a resin solid acid value of 75 mgKOH / g. The obtained resin solution had a nonvolatile content of 40.7%, a Gandner viscosity of Z4 to Z5, a number average molecular weight of 12,700, and a Mw / Mn of 25.59, which became a polymer with a wider molecular weight distribution. -32- 574619 A7 B7 V. Description of the invention (31) Manufacturing example 6_: same as above (please read the note on the back? Matters before filling out this page) Fill the flask equipped with a thermometer, reflux cooling tube and stirrer. 187 parts of epoxy equivalent 187 parts of bisphenol A type epoxy resin, 72 parts of acrylic acid, 12 parts of triphenylphosphine, and the temperature was raised to 110 ° C while stirring. (: Reaction at this temperature until the acid value is 3 or less. Next, 152 parts of tetrahydrophthalic anhydride is added, and the reaction is performed at 100 ° C until the acid value is 137 to obtain a compound having both a carboxyl group and an unsaturated double bond. (H-4). A flask equipped with a thermometer, a reflux cooling tube, and a stirrer was filled with 110 parts of glycerol-α · monochlorohydrin, 1,000 parts of dimethylformamide, and 120 parts of sodium bicarbonate. During the stirring, the temperature was raised to 100 ° C, and the reaction was carried out at this temperature for 2 hours, and then the insoluble matter and the solvent were removed to obtain a viscous liquid of methylol-ethyl carbonate. Next, a flask equipped with a thermometer, a stirrer and a condenser was charged.塡 This is 1 18 parts of hydroxymethyl ethylene carbonate, and the temperature is raised to 60t during stirring, and the hexamethylene diisocyanate isotricyanate-type polyisocyanate (NCO% = 23.8) is added in a careful heating for 1 hour. %) 165 parts, and reacted. After 1 hour of reaction, it was confirmed by infrared absorption spectrum that the isocyanate group absorption was eliminated, and the target cyclic carbonate-based compound (H-5) was obtained. Example 1 Printed and manufactured by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs The vinyl polymer (Al) 100.O obtained in Example 1 After diluting with 220.0 parts of PGMAc, measure 40.0 parts of diisopentaerythritol hexaacrylate (hereinafter referred to as DPHA) and 1.2 parts of Irgacunel 84 (product of Ciba Specialty Chemicals Co., Ltd.). The filter material of m was filtered to obtain the photosensitive resin composition of the present invention. The storage stability of the composition was evaluated. The results are shown in Table 1. -33- This paper size is applicable to China National Standard (CNS) A4 (210 X 297) (Centi) 574619 V. Description of the invention (32) The solution obtained was spin-coated on a glass plate using a spin coater at 1000 rpm for 9 seconds, and then pre-dried at 60 ° C for 5 minutes to form a pre-dried coating film. After the coating film was exposed to 200 mJ / cm2 with a high-pressure mercury lamp, the coating film was hardened at 23 ° C for 15 minutes to evaluate the transparency, heat resistance, and chemical resistance of the coating film. The evaluation results are shown in Table 1. The dry coating film was exposed to 200mJ / cm2 with a high-pressure mercury lamp through a mask with a predetermined pattern, and then developed in a 1.0% by weight sodium carbonate aqueous solution at 30 ° C, and then washed with pure water. 2 0 // mg [case (residual) possibility (imaging features The results are shown in Table 1 m. Next, the pattern coating film was heated with a hot plate at 23 ° C for 15 minutes and cured. Examples 2-5 and Comparative Examples 1-4 were changed to tables Except for the substance shown in Example 1, the same operation as in Example 1 was performed to obtain a horizontal lipid composition, and then various tests were performed. The coating film properties are shown in Table 1 &#. -34- 574619 Five Comparative Examples: Inch 1 '1' 1 § S Guide, 280 (N 1-Η 1 1 〇X 〇1 〇 Good 〇〇1 1 1 1 〇1 1 1-H wear · | 220 | CN rH 1 hire XX 〇1 〇 Good 〇 (N condensed Gelled O 1 1 1 〇1 1 1 1-H guide · 220 (N i-H 1 1 〇OO1 X Microwave muscle 〇〇 Example § 2 _, r-H guide · 220 (N rH 1 1 〇〇〇〇 〇 Good 〇〇 inch 1 〇1 1 1 1 1 〇220 (N 1 1 〇〇〇〇〇 Good 〇〇cn 〇1 1 1 1 1 1 r—1 •? 220 < N 1- H 1 〇 〇 〇 〇 〇 〇 good 〇 〇 (N 〇 1 1 1 1 1 1 H guide · 220 (N TH (N o ο (N 〇 〇 〇 〇 〇 good 〇 ◎ 1 1 1 1 1 1 T- (220 (N TH 1 1 0 0 1 0 good 0 0 < < < HJJ 锲 锲 锲 锲 锲 锲 锲 锲 ι! Λ UX ΜΛ Ttr \ < V 镞 镞 龄 龄 龄 饪 _ _ _ slightly_ loose pine N3 ^ K) 1¾ N3 DPHA PETA PGMAc rH = tt W) | Vh Tetrabutylammonium bromide r-Methacryloxypropyltrimethoxysilane Storage stability Development characteristics Transparent heat resistance-1 Heat resistance-2 Coating film appearance after heat resistance test Chemical resistance-1 Chemical resistance Property-2 -35- 574619 V. Description of the Invention (34) Example 6 Using a high-speed disperser TSG-6H manufactured by Igarashi Machinery Factory, 25.0 parts of the vinyl polymer (A-1) solution prepared in Manufacturing Example 1 was used. CI 8.0 parts of No. 254 red pigment (primary particle size below 80nm), 8.0 parts of Dispar one 161 (resin-based dispersant) 2.5 parts of PGMAC, 64.5 parts of PGMAC dispersion, dispersed with oxidized particles, and dispersed at 2000 rpm for 8 hours To obtain a red pigment dispersion. Next, with respect to 100 parts of the red pigment dispersion liquid obtained above, 7.0 parts of DPHA was added, 0.3 parts of Irgacune 369 (manufactured by Ciba Specialty Chemicals Co., Ltd.) was mixed and filtered through a filter material having a pore size of 1.0 mm, to obtain the present invention. Photoresist. Next, 25 g of the obtained photosensitive resist was transferred to a closed glass container, and stored at 40 ° C. for 24 hours to evaluate storage stability. The obtained photosensitive resist was spin-coated on a glass plate using a spin coater at 1000 rpm for 9 seconds, and then pre-dried at 6 ° C. for 5 minutes to form a pre-dried coating film. The high-pressure mercury lamp was used for the pre-dried coating film. After exposure to 2G0mJ / Cm2, heat treatment was performed at 23 ° C for 15 minutes to harden the coating film, and evaluate the transparency, heat resistance and chemical resistance of the coating film. The evaluation results are shown in Table 2. For the above pre-dried coating film, Using a mask with a pixel pattern for a predetermined color filter, exposed to 100 mJ / cm2 with a high-pressure mercury lamp, and developed in a 0.5% by weight sodium carbonate aqueous solution at 30 ° C, and then washed with pure water to obtain a line width. The possibility (developing characteristics) of a 20 μm pattern (residual) was evaluated. Next, the obtained pixel portion was heat-treated at 230 ° C for 15 minutes and hardened. -36- 574619 V. Description of the Invention (35) Comparative Example 5 -6 Except that the materials shown in Table 2 were used instead, the same operation as in Example 6 was carried out, and a red pigment dispersion liquid was prepared to obtain a photosensitive resist. The same various tests were performed, and their properties are summarized in Table 2. Table 2 Fang g Example Comparative Example 6 5 6 7 Vinyl polymer solution A-1 25---Vinyl polymer solution A-2----Vinyl polymer solution A-3----Vinyl polymer solution H_1-25--Sensitive vinyl polymer solution H-2--- -Photovinyl polymer solution H-3--25-Anti-compound solution H-4---10 Etching compound solution H-5---7 agents C.1.254 red pigment 8 8 8 8 2.5 2.5 2.5 2.5 DPHA 7 7 7-PGMAc 64.5 64.5 64.5 79.5 Irg # 369 0.3 0.3 0.3 0.3 Storage stability 〇XX Development characteristics 〇XX Transparency 〇〇〇X Coating heat resistance-1 〇X 〇〇 Film heat resistance-2 〇X 〇〇 After heat resistance test, the appearance of the coating film is good. Microwave muscle is good. Good chemical resistance -1 〇〇〇〇 Chemical resistance-2 〇〇〇-37- 574619 A7 ___B7_ V. Description of the invention (36) Industrial use Valence Since the photosensitive resin composition of the present invention contains a cyclic carbonate group and a carboxyl group-based vinyl polymer, it has good storage stability and excellent transparency. Finally, the cyclic carbonate group and the carboxyl group are reacted to introduce a crosslinked structure to obtain heat resistance and heat resistance. Coating with excellent chemical resistance. It is used in coatings, printing inks, resists, etc., especially for color filters. Photoresist for cross-linked structure color filters, because it contains vinyl polymers with cyclic carbonate groups and carboxyl groups. As well as compounds having ethylenically unsaturated double bonds, a crosslinked structure can be introduced in the pixel portion of the color filter by light curing and thermal curing, and can be used to form a durable color filter pixel portion. The method for producing a color filter of the present invention can be used to produce a durable color filter by using the above-mentioned photosensitive resist for a color filter. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)
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JP27208099A JP2001089511A (en) | 1999-09-27 | 1999-09-27 | Active energy ray curable resin composition |
JP27422699A JP2001100413A (en) | 1999-09-28 | 1999-09-28 | Photosensitive colored composition and color filter using same |
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TWI460237B (en) * | 2010-07-05 | 2014-11-11 | Chi Mei Corp | A pattern forming ink composition, a light guide plate, a light emitting unit, and a liquid crystal display element having the light emitting unit |
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