TW200535461A

TW200535461A - Color filter used light-sensitive resin composite

Info

Publication number: TW200535461A
Application number: TW93110919A
Authority: TW
Inventors: bo-yi Xu
Original assignee: Chi Mei Corp
Priority date: 2004-04-20
Filing date: 2004-04-20
Publication date: 2005-11-01
Also published as: TWI232317B

Abstract

A color filter used light-sensitive resin composite with the following advantages is introduced. Its advantages are: (1) less residue on the unexposed and black matrix of the substrate after coating, exposing and developing; (2) pixel with good heat-resist and base-resist after developing and post baking; (3) small ITO resistance of LCD. The composite consists of a base dissolvable resin (A), a chemical compound contained unsaturated ethane radicals (B), a photo initiator(C), organic solvent (D), pigment (E) and a compound in which one molecular includes at least two epoxide radicals (F). The hydro value of the base dissolvable resin (A) is between 0.1 to 20 KOHmg/g and the TG of 5 weight percentage (%) is larger than 300 degrees of centigrade tested by TGA. Based on the bass dissolvable resin (A) as 100 weight portion, the usage of the compound, in which one molecular there includes at least two epoxide radicals, is 0.1 to 30 weight portion.

Description

200535461 五、發明說明（1) 【發明所屬之技術領域】本發明係關於一種應用在液晶顯示器之彩色滤光片上的感光性樹脂組成物。特別是提供一種經由塗佈、曝光、顯影後’在基板上未曝光之部分及遮光層（black matr 1X) 上之殘渣量少，且顯影、後烤後，晝素之耐熱性、耐鹼性佳’液晶顯示器之I T 0透明電極層阻抗值小，且可以驗性顯影液顯影之彩色濾光片用感光性樹脂組成物。【先前技術】200535461 V. Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to a photosensitive resin composition applied to a color filter of a liquid crystal display. In particular, after coating, exposure, and development, the amount of residue on the unexposed portion of the substrate and the light-shielding layer (black matr 1X) is small, and after development and post-baking, the heat resistance and alkali resistance of daylight The photosensitive resin composition for color filter of IT's transparent electrode layer of Jia's liquid crystal display has a small resistance value and can be developed by a developing developer. [Prior art]

在液晶顯示器（LCD)的技術領域中，一般係先將感光性樹脂組成物塗佈於基板上並進行乾燥（預烤），透過光罩施行紫外線曝光、硬化，再藉鹼性顯影液顯影形成圖案後，最後對此進行熱處理（後烤）。具體而言，如彩色濾光片中之紅、藍、綠之晝素（P 1 x e 1 )、樹脂黑色矩陣（b 1 ack ma t r i x )、保護膜或層間絕緣膜等硬化膜’皆是利用該製程加以完成。In the technical field of liquid crystal display (LCD), generally, a photosensitive resin composition is first coated on a substrate and dried (pre-baked), and then exposed to light through a photomask and cured, and then developed by an alkaline developer. After patterning, this is finally heat treated (post-baked). Specifically, hardened films such as red, blue, and green daytime pigments (P 1 xe 1), resin black matrices (b 1 ack ma trix), protective films, or interlayer insulating films in color filters are used. The process is completed.

但上述各種用途之硪化膜，其形成過程或形成後之加工過程，硬化膜一般皆須曝露於2 2 0 °c以上高溫或強鹼、強酸之環境，故該硬化腺皆需具備較佳之耐高溫、耐酸、鹼等特性。例如目前在製造彩色濾光片之紅、藍、綠之晝素（p i X e 1 )時，當書素上形成I T 〇透明電極時，必須處於高溫（2 3 0。(3 )，其次，進行透明電極之低阻抗化的流程中，亦須施以2 3 0。(：至2 6 0 之尚溫處理。針對上述之要求，將曱基丙稀酸單體作為共聚成分所共聚合而得之共聚物來作為感光性樹脂用黏結劑之相關報However, the hardened film of the various uses of the above-mentioned various applications, in the formation process or the post-formation process, generally need to be exposed to a temperature of more than 220 ° c or a strong alkali, strong acid environment, so the hardened glands need to have better High temperature, acid and alkali resistance. For example, when manufacturing red, blue, and green daytime pigments (pi X e 1) of color filters, when IT 〇 transparent electrodes are formed on the substrates, they must be at a high temperature (2 3 0. (3), secondly, In the process of reducing the resistance of the transparent electrode, it is also necessary to apply a temperature treatment of 2 3 0. (: to a temperature of 2 6 0. In response to the above requirements, the fluorenyl acrylic acid monomer is copolymerized as a copolymerization component and Related reports of copolymers obtained as adhesives for photosensitive resins

第5頁 200535461 五、發明說明（2) 告，已被揭露。此類型之專利如日本公開特許之特開平1 -1 5 2449號公報、特開平9-31 1210號公報。但此類型專利中所使用之共聚物經2 2 0 °C之熱處理後，有I T0阻抗值增加之缺點存在。另，前述彩色濾光片之紅、藍、綠之晝素（p i X e 1 )之製法中，以往是以染色法為主，其方法乃是將染色可能之樹脂（如天然之明膠、酪朊等）先行圖案化，其次再以染料染色而得紅、藍、綠之畫素。但以染色法所製得之畫素，因材料之限制，一般皆存在有耐熱性不佳之問題。最近，為改善該耐熱性之問題，乃改採以使用顏料分散法之感光材料為主。顏料分散法具有製法簡單、壽命長等優點。但因紅、藍、綠晝素之製造過程中，需重覆施行曝光、顯影等步驟。往往紅、藍、綠晝素形成後，未曝光部分之感光性樹脂未能完全除去，基板上將有殘渣殘留之問題。因此，顯影後，仍需以稀薄之顯影液或高壓水液進行洗淨之工作，如此，易使彩色濾光片之製造工序數目複雜化。【發明内容】本發明之目的在於提供一種液晶顯示器之彩色濾光片用感光性樹脂組成物。特別是提供一種經由塗佈、曝光、顯;景彡後，在基板上未曝光之部分及遮光層（b 1 a c k m a t r i X ) 上之殘渣量少，且顯影、後烤後，畫素之耐熱性、耐鹼性佳，液晶顯示器之I T0透明電極層阻抗值小，且可以鹼性顯影液顯影之彩色濾光片用感光性樹脂組成物。該組成物包括：驗可溶性樹脂（A )、含乙稀性不飽和Page 5 200535461 V. Description of Invention (2) The notice has been disclosed. This type of patent is disclosed in Japanese Patent Application Laid-Open No. 1-1 5 2449 and Japanese Patent Application Laid-Open No. 9-31 1210. However, the copolymer used in this type of patent has the disadvantage of an increased I T0 resistance after heat treatment at 220 ° C. In addition, the red, blue, and green diurnal (pi X e 1) manufacturing method of the aforementioned color filter was mainly based on the dyeing method. The method is to dye the resin (such as natural gelatin, casein, etc.).朊, etc.) patterned first, and then dyed with dye to obtain red, blue, and green pixels. However, the pixels produced by the dyeing method generally have the problem of poor heat resistance due to material limitations. Recently, in order to improve the heat resistance, a photosensitive material using a pigment dispersion method has been used instead. The pigment dispersion method has the advantages of simple preparation method and long life. However, during the manufacturing process of red, blue and green pigments, it is necessary to repeat the steps of exposure and development. After the formation of red, blue, and green pigments, the photosensitive resin in the unexposed portion is not completely removed, and there is a problem that residues remain on the substrate. Therefore, after development, it is still necessary to perform washing with a thin developing solution or high-pressure water solution. In this way, it is easy to complicate the number of manufacturing processes of color filters. SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive resin composition for a color filter of a liquid crystal display. In particular, it provides a small amount of residue on the unexposed portion of the substrate and the light-shielding layer (b 1 ackmatri X) after coating, exposure, and display; and the heat resistance of the pixels after development and post-baking. 2. A photosensitive resin composition for color filters with good alkali resistance, a small resistance value of the I T0 transparent electrode layer of the liquid crystal display, and development with an alkaline developer. The composition includes: soluble resin (A), ethylenic unsaturated

第6頁 200535461 五、發明說明（3) 基之化合物（B )、光起始劑（C )、有機溶劑（D )、顏料（E ) 及1分子中至少含有2個環氧基之化合物（F );其中，該鹼可溶性樹脂（A)之羥值介於〇. 1〜20 KOHmg/g，且以熱減重分析儀（TGA)測定其5重量％之熱減重溫度為30 0 °C以上；且基於鹼可溶性樹脂（A) 1 〇〇重量份，1分子中至少含有2個環氧基之化合物（F)的使用量為〇·ι〜3〇重量份。以下逐一對本發明各組成做詳細的說明：鹼可溶性樹脂（A ) 本發明之驗可溶性樹脂（A)係由含羥基之乙烯性不飽合單體（a - 1 )(以下簡稱為含有羥基之不飽和單體）、具有 # 一個或一個以上之羧基的乙烯性不飽合單體（a_ 2 )(以下簡稱為含有叛基之不飽和單體）與其他可共聚合之乙烯性不飽和單體（a— 3 )(以下簡稱為其他不飽和單體）共聚合而成〇上述含有羥基之不飽和單體（a—；l)乃例如：丙烯酸-2-沒基乙醋、甲基丙烯酸—2 -羥基乙酯、丙烯酸—2-羥基丙酯、曱基丙烯酸-2 -羥基丙酯、丙烯酸—3 —羥基丙酯、甲基丙稀酸-3-經基丙酯、丙烯酸_ 2_羥基丁酯、曱基丙烯酸_2-經基丁酯、丙烯酸-羥基丁酯、曱基丙烯酸一3 —羥基丁酯•齡、丙烯酸-4-羥基丁酯、甲基·、丙烯酸—4_羥基丁酯、N-鄰-羥基苯基馬來醯亞胺、N -間-羥基苯基馬來醯亞胺、n -對-爹里基笨基馬來醯亞胺、N —羥乙基丙烯醯胺、n -羥乙基曱基丙烯―胺、一丙二醇丙稀酸酯（dipropylene glycol acrylate)、一丙二醇甲基丙稀酸酯（dipr〇pyiene giyC〇iPage 6 200535461 V. Description of the invention (3) -based compound (B), photoinitiator (C), organic solvent (D), pigment (E) and compound containing at least 2 epoxy groups in one molecule ( F); wherein the hydroxyl value of the alkali-soluble resin (A) is between 0.1 and 20 KOHmg / g, and the thermal weight loss temperature of 5% by weight measured by a thermal weight loss analyzer (TGA) is 300 ° C or more; and based on 100 parts by weight of the alkali-soluble resin (A), the amount of the compound (F) containing at least two epoxy groups in one molecule is 0.00 to 30 parts by weight. The following is a detailed description of each composition of the present invention: Alkali soluble resin (A) The soluble resin (A) of the present invention is composed of a hydroxyl-containing ethylenically unsaturated monomer (a-1) (hereinafter referred to as a hydroxyl-containing resin). Unsaturated monomers), ethylenically unsaturated monomers (a_ 2) with one or more carboxyl groups (hereinafter referred to as unsaturated monomers containing treasonous groups) and other copolymerizable ethylenically unsaturated monomers (A-3) (hereinafter referred to as other unsaturated monomers) by copolymerization. The above-mentioned hydroxyl-containing unsaturated monomers (a-; l) are, for example: acrylic acid 2-methyl ethyl acetate, methacrylic acid —2 -Hydroxyethyl, 2-Hydroxypropyl Acrylic Acid, 2-Hydroxypropyl Acrylic Acid, 3-Hydroxypropyl Acrylic Acid, 3-Hydroxypropyl Methacrylic Acid, Acrylic Acid_ 2_ Hydroxybutyl ester, fluorenyl acrylic acid 2-hydroxypropyl butyl, acrylic acid-hydroxybutyl acrylate, fluorenyl acrylic acid 3-hydroxybutyl acrylate • age, 4-hydroxybutyl acrylate, methyl ·, acrylic acid — 4-hydroxy Butyl ester, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, n-p-daddy Methylbenzyl maleimide, N-hydroxyethylpropenylamine, n-hydroxyethylpropenyl-amine, dipropylene glycol acrylate, monopropylene glycol methyl acrylate ( dipr〇pyiene giyC〇i

第7頁 200535461 五、發明說明（4) m e t h a c r y 1 a t e )、丁二醇丙稀酸SI、丁二醇甲基丙烯酸醋、聚乙二醇甲基丙烯酸酯（polyethylene glycol methacrylate) 、丙二酉享丙稀 S踅醋（P〇 1 y propy 1 en e glycol acrylate)、聚丙二醇甲基丙烯酸醋（ polypropylene glycol methacrylate)、聚乙二醇-聚丙二酉享甲基丙烯酉曼醋（polyethylene glycol—polypropylene glycol methacrylate)、聚乙二醇-1，4- 丁二醇甲基丙稀酸酯（polyethylene glycol-1，4-butanediol methacrylate)、2 -丙烯醯氧基乙醇-2-羥基乙醇鄰苯二酸酯（2-acryloxy ethyl-2-hydroxy ethyl phthalate)、己内酯改質丙稀酸酯（caprolactone modified acrylate)、己内S旨改質甲基丙稀酸g旨（caprolactone modified methacrylate)、丙烯酸-2-羥基-3-苯氧基丙酯（2-hydr〇xy-3-phenoxy-propy 1 acry 1 ate，東亞合成公司製之ARONIX M-5700)等。其中所列舉者乃以2—丙烯醯氧基乙醇-2~經基乙醇鄰苯二酸酯、丙稀酸—2 —經基_3—苯氧基丙酯、丙烯酸-2-羥基丙酯、甲基丙烯酸—2—羥基丙酯、丙烯酸-2-羥基乙酯、曱基丙烯酸_2_羥基乙酯較佳。該等含有羥基之不飽和單體可單獨使用，或者混合兩種以上併用。上述含有敌基之不飽和單體（a〜2 )乃例如：丙烯酸：、曱基丙烯酸、丁烯酸、α-氣丙烯酸、乙基丙烯酸及肉桂酸 =不飽和一元羧酸類；馬來酸、馬來酸酐、富馬酸、衣康衣康酸酐、檸康酸、檸康酸酐等不飽和二元羧酸（酐）類，3價以上之不飽和多價羧酸（酐）類等等。Page 7 200535461 V. Description of the invention (4) methacry 1 ate), butanediol acrylic acid SI, butanediol methacrylic acid vinegar, polyethylene glycol methacrylate, propylene glycol Polypropylene glycol methacrylate (polypropylene glycol methacrylate), polypropylene glycol methacrylate, polyethylene glycol-polypropylene glycol methacrylate), polyethylene glycol-1,4-butanediol methacrylate, polyethylene glycol-1,4-butanediol methacrylate, 2-propenyloxyethanol-2-hydroxyethanol phthalate 2-acryloxy ethyl-2-hydroxy ethyl phthalate, caprolactone modified acrylate, caprolactone modified methacrylate, caprolactone modified methacrylate, acrylic acid- 2-Hydroxy-3-phenoxypropyl ester (2-hydroxy-3-phenoxy-propy 1 acry 1 ate, ARONIX M-5700 manufactured by Toa Synthetic Corporation) and the like. Among them are 2-propenyloxyethanol-2 ~ lauryl alcohol phthalate, acrylic acid-2-lauryl-3-phenoxypropyl ester, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate are preferred. These unsaturated monomers containing a hydroxyl group can be used alone or in combination of two or more kinds. The aforementioned unsaturated monomers (a ~ 2) containing enemy groups are, for example: acrylic acid: fluorenyl acrylic acid, butenoic acid, α-gas acrylic acid, ethyl acrylic acid, and cinnamic acid = unsaturated monocarboxylic acids; maleic acid, Unsaturated dicarboxylic acids (anhydrides) such as maleic anhydride, fumaric acid, itaconic acid anhydride, citraconic acid, citraconic anhydride, unsaturated polyvalent carboxylic acids (anhydrides) having a valence of 3 or more, and the like.

200535461 五、發明說明（5) 其中所列舉者乃以丙烯酸、甲基丙烯酸為較佳。該等含有羧基之不飽和單體可單獨或混合複數種使用。前述其他不飽和單體（a - 3 )乃例如：苯乙烯、α -甲基苯乙烯、乙烯基甲苯、氯乙烯、甲氧基苯乙烯等之芳香族乙烯基化合物；丙烯酸苯曱酯、曱基丙烯酸笨曱酯、丙烯酸苯酯、甲基丙烯酸苯酯等之含芳香族官能基之不飽和羧酸酯類；Ν -苯基馬來醯亞胺、Ν -鄰-甲基苯基馬來醯亞胺、Ν -間-曱基苯基馬來醯亞胺、Ν -對-甲基苯基馬來醯亞胺、Ν -鄰-曱氧基笨基馬來醯亞胺、Ν -間-甲氧基苯基馬來醯亞胺、Ν-對-曱氧基苯基馬來醯亞胺、Ν-環己基馬來醯亞胺等馬來醯亞胺類；丙烯酸甲酯、甲基丙烯酸曱酯、丙烯酸乙醋、甲基丙烯酸乙醋、丙烯酸正丙S旨、曱基丙稀酸正丙酯、丙烯酸異丙酯、甲基丙烯酸異.丙酯、丙烯酸正丁酯、曱基丙烯酸正丁酯、丙烯酸異丁酯、曱基丙烯酸異丁酯、丙烯酸第二丁酯、甲基丙烯酸第二丁酯、丙烯酸第三丁酯、甲基丙烯酸第三丁酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丙烯酸三乙二醇甲氧酯（methoxy triethylene glycol acrylate)、甲基丙烯酸三乙二醇甲氧S旨（methoxy triethylene glycol methacrylate)、甲基丙稀酸十二烧基酯（lauryl .methacrylate)、甲基丙稀酸十四烧基酯（ tertadecyl methacrylate)、甲基丙稀酸十六烧基·醋（ cetyl methacrylate)、曱基丙稀酸十八烧基酯（ octadecyl methacrylate)、甲基丙烯酸二十烧基醋（ eicosyl methacrylate)、甲基丙烯酸二十二烧基酯（200535461 V. Description of the invention (5) Among them, acrylic acid and methacrylic acid are preferred. These unsaturated monomers containing a carboxyl group can be used alone or in combination. The aforementioned other unsaturated monomers (a-3) are, for example, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, vinyl chloride, methoxystyrene, and the like; Unsaturated functional carboxylic acid esters containing aromatic functional groups such as benzyl acrylate, phenyl acrylate, phenyl methacrylate, etc .; N-phenylmaleimide, N-o-methylphenylmaleate Fluorenimine, N-m-fluorenylphenylmaleimide, N-p-methylphenylmaleimide, N-o-o-methoxybenzylmaleimide, N-m-imino -Methoxyphenylmaleimide, N-p-methoxyphenylmaleimide, N-cyclohexylmaleimide and other maleimides; methyl acrylate, methyl Acrylic acid acrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl acrylate, isopropyl acrylate, isopropyl methacrylate, propyl acrylate, n-butyl acrylate, methacrylic acid N-butyl, isobutyl acrylate, isobutyl acrylate, second butyl acrylate, second butyl methacrylate, third butyl acrylate, methyl Tert-butyl acrylate, allyl acrylate, allyl methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate ), Lauryl .methacrylate, tertadecyl methacrylate, cetyl methacrylate, 曱Octadecyl methacrylate, eicosyl methacrylate, methacrylic acid methacrylate

第9頁 200535461 五、發明說明（6) do cosyl methacrylate)等之不飽和竣酸酯類；丙稀酸-2-氨乙酯、甲基丙烯酸-2-氨乙S旨、丙稀酸-2-氨丙S旨、曱基丙烯酸-2 -氨丙酯、丙烯酸-3 -氨丙酯、甲基丙烯酸-3-氨丙酯等不飽和羧酸氨烷酯類；丙烯酸環氧丙基酯、甲基丙烯酸環氧丙基酯等不飽和羧酸環氧丙基酯類；乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯等之羧酸乙烯酯類；乙烯基甲醚、乙烯基乙醚、烯丙基環氧丙基醚、甲代烯丙基環氧丙基醚等不飽和醚類；丙烯腈、甲基丙烯腈、α-氯丙烯腈、氰化亞乙烯等之氰化乙烯基化合物；丙烯醯胺、甲基丙烯醯胺、α-氯丙烯醯胺等之不飽和醯胺；1，3 - 丁二烯、異丙· 烯、氣丙烯等之脂肪族共軛二烯類。其中所列舉者乃以苯乙烯、丙烯酸笨曱酯、曱基丙烯酸苯曱酯、Ν -苯基馬來醯亞胺、丙烯酸曱酯、甲基丙烯酸曱酯較佳。該等其他不飽和單體可單獨或混合複數種使用〇本發明之鹼可溶性樹脂（A )，其共聚合用單體之使用量，基於其共聚合用單體（a-1 )、（a-2)、（a-3)三者合計 1 0 0重量份，如以下所示。含有經基之不飽和單體（a - 1 )的使用量較佳為1〜3 5重|| 量份，更佳為2〜32重量份，最佳為3〜30重量份。含有羧基之不飽和單體（a - 2 )的使用量較佳為1〜3 0重量份，更佳為2〜25重量份，最佳為3〜20重量份；其他不飽和單體（ a-3)的使用量較佳為35〜98重量份，更佳為43〜96重量份，最佳為50〜94重量份。Page 9 200535461 V. Description of the invention (6) do cosyl methacrylate) and other unsaturated esters; acrylic acid-2-aminoethyl ester, methacrylic acid-2-aminoethyl S, and acrylic acid-2 -Unsaturated amino acid alkyl esters such as aminopropyl S, 2-aminopropyl acrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, and 3-aminopropyl methacrylate; epoxypropyl acrylate, Unsaturated carboxylic acid glycidyl esters such as glycidyl methacrylate; vinyl carboxylic acid esters such as vinyl acetate, vinyl propionate, vinyl butyrate; vinyl methyl ether, vinyl ether, Unsaturated ethers such as allyl glycidyl ether, methallyl glycidyl ether; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinyl cyanide compounds, etc. ; Unsaturated fluorenamines such as acrylamide, methacrylamide, α-chloropropenamide; and aliphatic conjugated dienes such as 1,3-butadiene, isopropylene, and acrylamide. Among them, styrene, benzyl acrylate, benzyl methacrylate, N-phenylmaleimide, methacrylate, and methacrylate are preferred. These other unsaturated monomers may be used singly or in combination. The alkali-soluble resin (A) of the present invention is used in an amount of the copolymerization monomer based on the copolymerization monomers (a-1), (a -2) and (a-3) are 100 parts by weight in total, as shown below. The amount of the unsaturated monomer (a-1) containing a warp group is preferably 1 to 3 5 parts by weight, more preferably 2 to 32 parts by weight, and most preferably 3 to 30 parts by weight. The amount of the unsaturated monomer (a-2) containing a carboxyl group is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, and most preferably 3 to 20 parts by weight; other unsaturated monomers (a -3) The use amount is preferably 35 to 98 parts by weight, more preferably 43 to 96 parts by weight, and most preferably 50 to 94 parts by weight.

第10頁 200535461 五、發明說明（7) 本發明鹼可溶性樹脂（A )之羥值較佳介於〇 . 1〜2 〇 KOHmg/g，更佳為介於〇·3〜is K〇Hmg/g，最佳為介於〇·5 〜10 KOHmg/g 〇本發明的鹼可溶性樹脂（A)之羥值可由習知的羥值測定方法測定而得，單位以叫K0H/g p〇ly〇l表示。羥值的疋義為經由乙酸化可與1克多醇物結合之酸酐的氫氧化鉀中和之笔克數，此測定方法記載的文獻例如w〇〇ds， G.， T h e I C I Ρ ο 1 y u r e t h a n e s B 〇〇 k，第 2 版（I C I Polyurethanes’ Netherlands， 1 9 9 0 )。本發明的鹼可溶性樹脂（A)之羥值即是以上述習知的滴定方法測定而得的，即，將本發明之鹼可溶性樹脂（A)以氫氧化鉀溶液滴定，可得到驗可溶性樹脂（A)中原有的酸中和滴定所需之氫氧化鉀毫克數（X);再將鹼可溶性樹脂（A)在吡啶存在下與醋酸酐進行乙醯化，則鹼可溶性樹脂（A)中之羥基盥醋酸、酐反應形成醋酸，然後再以氫氧化鉀溶液滴定，所測得之數值為鹼可溶性樹脂（A)中原有的酸及羥基在乙醯化後形成之醋酸二者中和滴定所需之氫氧化鉀總毫克數，則 (y) —(X)所得到的差值即為本發明鹼可溶性樹脂之鞞值。工 t本發明之鹼可溶性樹脂（A)之羥值可藉由鹼可·、溶性榈脂（A )之聚合過程中，含有羥基之不飽和單體（& — 1 及使用量等加以控制。本發明驗可溶性樹脂（A)以熱減重分析儀測定，其5 量％之熱減重溫度較佳為30 0 t以上，更佳為3〇5艽以^Page 10 200535461 V. Description of the invention (7) The hydroxyl value of the alkali-soluble resin (A) of the present invention is preferably between 0.1 ~ 2 〇KOHmg / g, more preferably between 0.3 · is ~ KOHmg / g The optimal value is between 0.5 and 10 KOHmg / g. The hydroxyl value of the alkali-soluble resin (A) of the present invention can be determined by a conventional hydroxyl value measurement method. The unit is called KOH / gp〇ly〇l. . The meaning of the hydroxyl value is the number of grams neutralized by potassium hydroxide of an acid anhydride which can be combined with 1 gram of polyol by acetic acid. Literatures described in this measurement method include, for example, WOODS, G., T he ICI ρ ο 1 yurethanes B 00k, 2nd edition (ICI Polyurethanes' Netherlands, 199 0). The hydroxyl value of the alkali-soluble resin (A) of the present invention is measured by the above-mentioned conventional titration method, that is, the alkali-soluble resin (A) of the present invention is titrated with a potassium hydroxide solution to obtain a test-soluble resin. The number of milligrams of potassium hydroxide (X) required for the neutralization and titration of the original acid in (A); and then the alkali-soluble resin (A) is acetylated with acetic anhydride in the presence of pyridine. The hydroxy acetic acid and anhydride react to form acetic acid, and then titrate with potassium hydroxide solution. The measured value is the neutralization titration of the original acid and the acetic acid formed by the hydroxylation in the alkali-soluble resin (A). The total number of milligrams of potassium hydroxide required, then the difference between (y) and (X) is the threshold value of the alkali-soluble resin of the present invention. The hydroxyl value of the alkali-soluble resin (A) of the present invention can be controlled by the unsaturated monomer (& — 1 and the amount used) containing hydroxyl groups during the polymerization of alkali-soluble and soluble palm resin (A). The soluble resin (A) of the present invention is measured by a thermal weight loss analyzer, and its thermal weight loss temperature of 5% by weight is preferably 300 t or more, and more preferably 305 ° to ^

第11頁 200535461 五、發明說明（8) 最佳為3 1 0 °C以上。該熱減重溫度可藉由鹼可溶性樹脂（A ) 之聚合過程中，單體與起始劑之種類及使用量、單體與起始劑之入料方式、反應溫度以及驗可溶性樹脂（A)以貧溶媒處理等加以控制。本發明之鹼可溶性樹脂（A)在製造時所使用的溶劑，一般較常用者為乙二醇曱醚、乙二醇乙醚、二甘醇曱醚、二甘醇乙醚、二甘醇正丙醚、二甘醇正丁醚、三甘醇甲醚、三甘醇乙醚、丙二醇甲醚、丙二醇乙醚、一縮二丙二醇曱醚、一縮二丙二醇乙醚、一縮二丙二醇正丙醚、一縮二丙二醇正丁醚、二縮三丙二醇曱醚（tripropylene glycol ⑩ mono methyl ether)、二乡宿三丙二酉享乙醚（tripropylene glycol mono ethyl ether)等之（聚）亞烧基二醇單院醚類 ;乙二醇甲醚醋酸酯、乙二醇乙醚醋酸酯、丙二醇曱醚醋酸酯、丙二醇乙醚醋酸酯等（聚）亞烷基二醇單烷醚醋酸酯類；二甘醇二甲醚、二甘醇甲乙醚、二甘醇二乙醚、四氫呋喃等其他醚類；甲乙酮、環己酮、2 -庚酮、3 -庚酮等酮類；2 -羥基丙酸曱酯、2 -羥基丙酸乙酯等乳酸烷酯類；2 -羥基-2 -曱基丙酸甲酯、2 -羥基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3 -乙氧基丙酸甲酯、3- || 乙氧基丙：酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙酯、2 -羥基-3-甲基丁酸甲酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸乙酯、乙酸正丁酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸正戊酯、乙酸異戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯Page 11 200535461 V. Description of the invention (8) The best temperature is above 3 10 ° C. The thermal weight loss temperature can be determined by the type and amount of the monomer and the initiator, the way of feeding the monomer and the initiator, the reaction temperature, and the solubility of the soluble resin (A) during the polymerization of the alkali-soluble resin (A). ) Controlled by lean solvent treatment, etc. Generally, the solvents used in the production of the alkali-soluble resin (A) of the present invention are ethylene glycol ether, ethylene glycol ether, diethylene glycol ether, diethylene glycol ether, diethylene glycol n-propyl ether, Diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ether, propylene glycol methyl ether, propylene glycol ether, dipropylene glycol ether, dipropylene glycol ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether Butyl ether, tripropylene glycol ⑩ mono methyl ether, dixiangsu tripropylene glycol mono ethyl ether, and other (poly) arylene glycol mono-academic ethers; B (Poly) alkylene glycol monoalkyl ether acetates, such as glycol methyl ether acetate, ethylene glycol ether acetate, propylene glycol ether ether acetate, propylene glycol ether ether acetate; diglyme, diglyme Methyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; 2-hydroxypropionate, 2-hydroxypropionate, etc. Alkyl lactates; 2-hydroxy-2 -methyl methylpropionate, 2-hydroxy- Ethyl 2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- || ethoxypropionate: ethyl acetate Ester, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3- Methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, propionic acid N-butyl ester, ethyl butyrate, n-propyl butyrate

第12頁 200535461 五、發明說明（9) 、丁酸異丙酯、丁酸正丁酯、丙@同酸甲酯、丙酮酸乙酯、丙酮酸正丙酷、乙醯乙酸曱醋、乙醯乙酸乙醋、2一氧基丁酸乙酯等其他酷類；曱笨、二曱笨等芳香族碳氫化合物類，N-曱基吡咯烷鲖、N，N_:甲基曱醯胺、n，n一二甲基乙醯胺等羧酸醯胺類等等。該等溶劑可單獨使用，亦可混合2 種以上使用。前述溶劑中係以丙二醇曱醚醋酸酯、3—乙氧基丙酸乙醋較佳。驗可溶性樹脂（A)製造時所使用之起始劑，一般為自由基形聚合起始劑，例如2，2 ’ -偶氮雙異丁膳（2，2，-&2〇1)13 13〇1)1^71'〇1^1：1^16)、2,2’-偶氮雙（2,4-二甲基戊腈）[2,2’％〇1^-（2,4-(^11161:1^1¥&161'〇1^1：1^16)]、2,2, 〜偶氮雙（4-甲氧基-2,4-二甲基戊腈）[2,2，-&2〇1^3-(4-methoxy-Z，4-dimethylvaleronitri le)]、2，2’ -偶氮雙 -2 〜曱基丁腈（2, 2’ -az〇bis-2-methyl butyronitrile)等偶 ll(azo)化合物；過氧化二苯曱酸（benzoylperoxide)等之過氧化合物。其中，以2, 2’-偶氮雙-2_甲基丁腈較佳。本發明之驗可溶性樹脂（A )以凝膠滲透色譜法（G P C ; 溶出溶媒四氫呋喃）測定，換算聚笨乙烯之重量平均分子量較佳為3,0 0 0至5 0,0 0 0，更佳為4,00 0至40,00 0，最佳為 4，5 0 0至3 5，0 0 0。重量平均分子量在前述範圍時，可獲得較佳顯影性之感光性樹脂組成物，藉此所形成之圖案邊緣較鮮明。含乙烯性不飽和基之化合物（B) 基於鹼可溶性樹脂(A) 1 0 0重量份，本發明含乙烯性不Page 12 200535461 V. Description of the invention (9), isopropyl butyrate, n-butyl butyrate, propyl @ isoacid methyl ester, ethyl pyruvate, n-propyl pyruvate, ethyl acetate, acetic acid, ethyl acetate Ethyl acetate, ethyl 2-monooxybutyrate, and other cool compounds; aromatic hydrocarbons such as benzyl and dibenzyl, N-fluorenylpyrrolidine, N, N_: methylamidamine, n , N-dimethylacetamide and other carboxylic acid amines and the like. These solvents can be used alone or in combination of two or more. Among the aforementioned solvents, propylene glycol ether ether acetate and ethyl 3-ethoxypropionate are preferred. The initiator used in the manufacture of the soluble resin (A) is generally a radical-type polymerization initiator, such as 2,2'-azobisisobutylate (2,2,-& 2〇1) 13 13〇1) 1 ^ 71'〇1 ^ 1: 1 ^ 16), 2,2'-azobis (2,4-dimethylvaleronitrile) [2,2 '% 〇1 ^-(2, 4-(^ 11161: 1 ^ 1 ¥ & 161'〇1 ^ 1: 1 ^ 16)], 2,2, ~ Azobis (4-methoxy-2,4-dimethylvaleronitrile) [2,2,-& 2〇1 ^ 3- (4-methoxy-Z, 4-dimethylvaleronitri le)], 2,2'-azobis-2 to fluorenylbutyronitrile (2, 2 '-az 〇bis-2-methyl butyronitrile) and other peroxo compounds; benzoylperoxide and other peroxy compounds. Among them, 2, 2'-azobis-2_methylbutyronitrile The soluble resin (A) of the present invention is determined by gel permeation chromatography (GPC; dissolution solvent tetrahydrofuran), and the weight average molecular weight of the converted polystyrene is preferably 3,0 0 to 5 0,0 0, More preferably, it is 4,000 to 40,000, and most preferably 4,500 to 35,000. When the weight average molecular weight is in the foregoing range, a photosensitive resin composition having better developability can be obtained. The picture formed by this The edge of the case is sharper. The ethylenically unsaturated group-containing compound (B) is based on 100 parts by weight of the alkali-soluble resin (A).

第13頁 200535461 五、發明說明（10) 飽和基之化合物（B )的使用量較佳為5〜2 2 0重量份，更佳為50〜160重量份，最佳為70〜140重量份。上述含乙烯性不飽和基之化合物（B)乃具有至少一個乙烯性不飽和基之乙稀性不飽和化合物。其中具有一個乙烯性不飽和基之化合物之具體例有：丙烯醯胺、（甲基）丙烯醯嗎啉、（甲基）丙烯酸-7 -氨基-3， 7-二甲基辛酯、異丁氧基甲基（甲基）丙烯醯胺、（甲基）丙烯酸異冰片基氧乙酯、（甲基）丙烯酸異冰片酯、（甲基）丙烯酸-2 -乙基己酯、乙基二甘醇（甲基）丙烯酸酯、第三辛基（曱基）丙烯醯胺、二丙酮（曱基）丙烯醯胺、（甲基）丙烯酸二曱氨基酯、（曱基）丙烯酸十二烷基酯、（甲基）丙烯酸二環戊烯氧乙酯、（甲基）丙烯酸二環戊烯酯、N，N-二甲基 (甲基）丙烯醯胺、（甲基）丙烯酸四氯苯酯、（甲基）丙烯酸 -2-四氯苯氧基乙酯、（曱基）丙烯酸四氫糠酯、（甲基）丙烯酸四溴苯酯、（甲基）丙烯酸-2-四溴苯氧基乙酯、（甲基 )丙烯酸-2 -三氣苯氧基乙酯、（甲基）丙烯酸三溴苯酯、（曱基）丙烯酸-2-三溴苯氧基乙酯、（甲基）丙烯酸-2-羥乙醋、（甲基）丙烯酸-2 -羥丙酯、乙烯基己内醯胺、N -乙烯基皮酪烷酮、（甲基）丙烯酸苯氧基乙酯、（甲基）丙烯酸五氯笨酯、（曱基）丙烯酸五溴苯酯、聚單（甲基）丙烯酸乙二醇酯、聚單（曱基）丙烯酸丙二醇酯、（曱基）丙烯酸冰片〇具有2個或2個以上乙烯性不飽和基之乙烯性不飽和化合物之具體例如下：乙二醇二（曱基）丙烯酸酯、二（甲基）Page 13 200535461 V. Description of the invention (10) The amount of the saturated compound (B) used is preferably 5 to 220 parts by weight, more preferably 50 to 160 parts by weight, and most preferably 70 to 140 parts by weight. The ethylenically unsaturated group-containing compound (B) is an ethylenically unsaturated compound having at least one ethylenically unsaturated group. Specific examples of the compound having one ethylenically unsaturated group are: acrylamide, (meth) acrylic morpholine, (meth) acrylic acid 7-amino-3, 7-dimethyloctyl ester, isobutyl Oxymethyl (meth) acrylamide, isobornyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol Alcohol (meth) acrylate, tertiary octyl (fluorenyl) allylamine, diacetone (fluorenyl) allylamine, dimethylamino (meth) acrylate, dodecyl acrylate , Dicyclopentenyl ethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (fluorenyl) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate Ester, 2-trifluorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (fluorenyl) acrylate 2-Hydroxyethyl (meth) acrylate, 2-Hydroxypropyl (meth) acrylate, Vinyl caprolactam, N-Vinyl tyrosinone, Phenoxyethyl (meth) acrylate , Pentachlorobenzyl (meth) acrylate, Pentabromophenyl (fluorenyl) acrylate, Polyethylene glycol mono (meth) acrylate, Polypropylene glycol mono (fluorenyl) acrylate, Borneol (fluorenyl) acrylic acid. Specific examples of the ethylenically unsaturated compound having two or more ethylenically unsaturated groups are as follows: ethylene glycol di (fluorenyl) acrylate, di (methyl)

第14頁 200535461 五、發明說明（11) 丙烯酸二環戊烯酯、三甘醇二丙烯酸酯、四甘醇二（甲基）丙烯酸酯、三（2 -羥乙基）異氰酸酯二（甲基）丙烯酸酯、三 (2 -羥乙基）異氰酸酯三（甲基）丙烯酸酯、己内酯改質之三 (2 -羥乙基）異氰酸酯三（曱基）丙烯酸酯、三（曱基）丙烯酸三羥曱基丙酯、環氧乙烷（以下簡稱E0)改質之三（甲基）丙烯酸三羥甲基丙酯、環氧丙烷（以下簡稱P0 )改質之三（甲基）丙烯酸三羥曱基丙酯、三甘醇二（甲基）丙烯酸酯、新戊二醇二（甲基）丙烯酸酯、1，4 - 丁二醇二（甲基）丙烯酸酯、1，6-己二醇二（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、季戊四醇四（曱基）丙烯酸酯、聚酯二（曱基）丙烯酸酯、聚乙二醇二（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、二季戊四醇四（曱基）丙烯酸酯、己内酯改質之二季戊四醇六（甲基）丙烯酸酯、己内酯改質之二季戊四醇五（甲基）丙烯酸酯、四（曱基）丙烯酸二三羥曱基丙酯、E0改質之雙酚A二（曱基）丙烯酸酯、P0改質之雙酚A二（甲基）丙烯酸酯、E0改質之氫化雙酚A二（曱基）丙烯酸酯、P0改質之氫化雙酚A二（曱基）丙烯酸酯、P0改質之甘油三丙酸酯、E0改質之雙酚F二（甲基）丙稀酸酯、S分酸聚縮水甘油醚（甲基）丙烯酸S旨等等。 & :前述乙烯性不飽和化合物中，較佳者為三丙烯酸三羥甲基丙酯、E 0改質之三丙烯酸三羥曱基丙酯、P 0改質之三丙烯酸三經甲基丙醋、季戊四醇三丙稀酸S旨、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇四丙烯酸酯、己内酯改質之二季戊四醇六Page 14 200535461 V. Description of the invention (11) Dicyclopentenyl acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, tris (2-hydroxyethyl) isocyanate di (methyl) Acrylate, tris (2-hydroxyethyl) isocyanate tris (meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanate tris (fluorenyl) acrylate, tris (fluorenyl) acrylic acid Modified hydroxymethyl propyl ester, ethylene oxide (hereinafter referred to as E0) trimethylol methacrylate (trimethylmethacrylate), modified propylene oxide (hereinafter referred to as P0) trihydroxy (meth) acrylate trihydroxy Fluorenyl propyl ester, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (fluorenyl) acrylate, polyester di (fluorenyl) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythr Alcohol tetra (fluorenyl) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (tetramethyl) acrylate, tetra (fluorenyl) ditriol Ethyl propyl ester, E0 modified bisphenol A di (fluorenyl) acrylate, P0 modified bisphenol A di (meth) acrylate, E0 modified bisphenol A di (fluorenyl) acrylate , P0 modified hydrogenated bisphenol A di (fluorenyl) acrylate, P0 modified glycerol tripropionate, E0 modified bisphenol F di (methyl) acrylic acid ester, S polyacid glycidol Ether (meth) acrylic acid and so on. &: Among the aforementioned ethylenically unsaturated compounds, trimethylol propyl triacrylate, trimethylol propyl triacrylate modified by E 0, and trimethyl propyl triacrylate modified by P 0 are preferred. Vinegar, pentaerythritol tripropionic acid S, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexa

第15頁 200535461 五、發明說明（12) 丙烯酸酯、四丙烯酸二三經曱基丙酯、P0改質之甘油三丙酸酯。光起始劑（C) 基於含乙烯性不飽和基之化合物（B ) 1 0 0重量份，本發明光起始劑（C )之使用量較佳為2 0〜1 2 0重量份，更佳為3 0 〜100重量份，最佳為40〜80重量份。上述光起始劑（C)之具體例為：苯乙酮系化合物（ acetophenone)或二咪唑系化合物（biimidazole)。其中笨乙酮系化合物如：對二甲胺苯乙酮（ρ - dimethylamino-acetophenone)、α，α’ -二甲氧基氧化偶氮苯乙酮（a，aJ -dimethoxyazoxyacetophenone)、2, 2’ -二曱基-2 -苯基苯乙酮（2,2’ -dimethy卜2-phenyl acetophenone)、對甲氧基苯乙酮（p-methoxyacetophenone)、2-甲基-1-(4-甲基硫代苯基）-2-嗎啉代-1-丙嗣（2-1116111乂1-1-(4-1116七1^11:1^〇011611丫1)-2-morpholino-propane-1-on)、2 - ▼基- 2- N，N -二甲胺 -1-(4 -嗎啉代笨基）-1- 丁嗣（2-benzyl-2-N，N-dimethylamino-1 —(4 —morph〇lino phenyl) — 1一butanone) o 而二口米峻系化合物（b i i m i d a z o 1 e )如：2，2 ’ -雙（鄰-氣笨基）-4,4’，5,5’-四苯基二咪.唆[2,2’-1^3(〇-chlorophenyl)-4，4’，5，5’ -tetraphenyl-biimidazole]、 2, 2，-雙（鄰-氟苯基）-4，4，，5, 5, -四苯基二咪唑[2, 2, - bis (o-fluorophenyl)-4, 4’，5，5’ - tetraphenylbiimidazole] 、2, 2’ -雙（鄰-甲基苯基）-4, 4’，5, 5’ -四苯基二咪唑[2, 2’Page 15 200535461 V. Description of the invention (12) Acrylic acid ester, ditrimethylene propyl tetramethacrylate, glycerol tripropionate modified by P0. The photoinitiator (C) is based on 100 parts by weight of the ethylenically unsaturated group-containing compound (B). The use amount of the photoinitiator (C) in the present invention is preferably 20 to 120 parts by weight, more It is preferably 30 to 100 parts by weight, and most preferably 40 to 80 parts by weight. Specific examples of the photo-initiator (C) are: acetophenone-based compounds (acetophenone) or biimidazole-based compounds (biimidazole). Among them, acetophenone-based compounds such as: p-dimethylamino-acetophenone, α, α'-dimethoxyazoxyacetophenone, 2, 2 ' -Difluorenyl-2 -phenylacetophenone (2,2 '-dimethy 2-phenyl acetophenone), p-methoxyacetophenone (p-methoxyacetophenone), 2-methyl-1- (4-methyl Thiophenyl) -2-morpholino-1-propane (2-1116111 乂 1-1- (4-1116 seven 1 ^ 11: 1 ^ 〇011611 丫 1) -2-morpholino-propane-1 -on), 2-▼-2 -N, N -dimethylamine-1- (4-morpholinobenzyl) -1-butanidine (2-benzyl-2-N, N-dimethylamino-1 — (4 —morph〇lino phenyl) — 1-butanone) o And biimidazo 1 e compounds such as: 2,2'-bis (o-o-benzyl) -4,4 ', 5,5 '-Tetraphenyldiimide. 唆 [2,2'-1 ^ 3 (〇-chlorophenyl) -4,4', 5,5 '-tetraphenyl-biimidazole], 2, 2, -bis (o-fluorobenzene ) -4,4,5,5,5 -tetraphenylbiimidazole [2, 2,-bis (o-fluorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole], 2, 2 '-bis (O-methylphenyl) -4, 4 ', 5, 5 ’-tetraphenyldiimidazole [2, 2’

第16頁 200535461 五、發明說明（13) -bis(〇-methyl phenyl)-4， 4’ ， 5， 5’ -tetraphenyl biimidazole]、2, 2’-雙（鄰甲氧基苯基）-4, 4’，5, 5’ -四笨基二 _、^[2，2’-bis(o-methoxyphenyl)-4,4’，5,5’-tetraphenyl biimidazole]、2, 2’-雙（對曱氧基笨基）-4, 4’，5，5’ -四笨基二口米唾[2，2’ -bis(p-meth〇xyphenyl)-4， 4’，5, 5’-tetraphenyl biimidazole]、2, 2’-雙（2, 2，，4， 4’ -四甲氧基苯基）-4, 4’，5, 5’ -四苯基二咪唑[2, 2, -bis(2 ，2’，4，4, -tetramethoxyphenyl)-4，4,，5, 5, - tetraphenyl -biimidazole]、2, 2’-雙（2 -氯苯基）-4，4’，5, 5’ -四苯基二口米嗤[2，2’ -bis(2-chlorophenyl)-4，4’，5，5’ -tetraphenyl biimidazole]、2,2’-雙（2,4-二氣苯基）-4, 4’，5，5’ -四苯基：^^[2，2’-bis(2，4-dichlorophenyl)-4,4’，5, 5’ -tetraphenyl biimidazole]等。其中以2 -卞基- 2- N，N-二甲胺-l-(4 -嗎琳代苯基）-1-丁酮、2, 2’ -雙（2-氣苯基）-4, 4’，5, 5’ -四笨基二咪唑併用之光起始劑效果較佳。本發明之彩色濾光片用感光性樹脂組成物中，可進一步添加二苯甲酮（benzophenone)系化合物為光起始劑，如噻il_(thioxanthone)、2，4-二乙基噻°頓酮（2，4 -diethylthioxanthanone)、噻噸酮-4-碾（thioxanthone-, 4一sulfone)、二苯甲酮（benzophenone) 、 4，4’一雙（二甲胺 )二苯曱酮[4，4’ -bis(dimethylamino)benzophenone]、4, 4’ -雙（二乙胺）二苯甲酮[4, 4’ -bis( diethyl ami no) benzophenone ] ^ 〇Page 16 200535461 V. Description of the invention (13) -bis (〇-methyl phenyl) -4, 4 ', 5, 5' -tetraphenyl biimidazole], 2, 2'-bis (o-methoxyphenyl) -4 , 4 ', 5, 5' -tetrabenzyl di_, ^ [2,2'-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenyl biimidazole], 2, 2'-bis ( P-Methoxybenzyl) -4, 4 ', 5,5' -tetrabenzyl glutamyl [2,2 '-bis (p-methoxylphenyl) -4, 4', 5,5'- tetraphenyl biimidazole], 2, 2'-bis (2, 2, 4, 4, 4'-tetramethoxyphenyl) -4, 4 ', 5, 5'-tetraphenyl diimidazole [2, 2,- bis (2,2 ', 4,4, -tetramethoxyphenyl) -4,4,5,5, -tetraphenyl-biimidazole], 2,2'-bis (2-chlorophenyl) -4,4', 5 , 5 '-tetraphenyl bimethyl [2,2' -bis (2-chlorophenyl) -4,4 ', 5,5' -tetraphenyl biimidazole], 2,2'-bis (2,4-bis Gas phenyl) -4, 4 ', 5,5'-tetraphenyl: ^^ [2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl biimidazole], etc. . Among them, 2-fluorenyl-2-N, N-dimethylamine-l- (4-morpholinophenyl) -1-butanone, 2, 2'-bis (2-aminophenyl) -4, 4 ', 5,5'-tetrabenzylimidazole is a better photoinitiator. In the photosensitive resin composition for a color filter of the present invention, a benzophenone-based compound may be further added as a photoinitiator, such as thioxanthone, 2,4-diethylthiton. Ketone (2,4-diethylthioxanthanone), thioxanthone-4-, (4-sulfone), benzophenone (benzophenone), 4,4'-bis (dimethylamine) benzophenone [4 ， 4 '-bis (dimethylamino) benzophenone], 4, 4' -bis (diethylamine) benzophenone [4, 4 '-bis (diethyl ami no) benzophenone] ^ 〇

第17頁 200535461 五、發明說明（14) 其他尚有苯偶醯（benzil)、乙醯基（acetyl)等之α -二酮（a-diketone)類，二笨乙醇酮（benzoin)等之_醇（ acyloin)類；二笨乙醇酮甲醚（benzoin methylether)、二笨乙醇S同乙醚（benzoin ethylether)、二苯乙醇酮異丙 &l(benzoin isopropyl ether)等之酉同商享 S^(acyl〇 in ether)類；2, 4，6-三甲基苯醯二苯基膦氧化物（2, 4, 6-trimethyl-benzoyl diphenylphosphineoxide)、雙-(2,6 -二甲氧基苯醯）-2,4,4-三甲基苯基膦氧化物[bis-(2,6-diπlethoxy-benzoyl)-2,4,4-trimethyl benzyl phosphineoxide]等之醯膦氧化物（acylphosphineoxide) 類·’蒽 i 昆（a n t h r a q u i η ο n e )、1，4 -萘酿（1，4 -naphthoquinone)等之醌（qUinone)類；笨醯甲基氯（ phenacyl chloride)、三、;臭甲基苯楓（tribromomethyl phenylsulfone)、三（三氯曱基）-s-三嗪[tris( trichloromethyl)-s-triazine]等之 i 化物；二-第三丁基過氧化物（di-tertbutylperoxide)等之過氧化物。其中以二苯曱酮（benzophenone)系化合物最佳，尤以 4, 4’-雙（二乙胺）二笨甲酮效果最佳。有機溶劑（D) 本發明彩色濾光片用感光性樹脂組成物係以前述鹼可溶性樹脂（A )、含乙烯性不飽和基之化合物（B )，以及光起始劑（C )及後述之顏料（E )為必要成分，必要時可加入後述之添加物成分。通常’將顏料（E)以外的各成分溶解於適當之有機溶Page 17 200535461 V. Description of the invention (14) Other α-diketones such as benzil, acetyl, etc., and benzoin, etc. Alcohols; benzoin methylether, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether & benzoin isopropyl ether (acyl〇in ether); 2,4,6-trimethyl-benzoyl diphenylphosphine oxide, bis- (2,6-dimethoxybenzene醯) Acetylphosphine oxides such as bis- (2,6-diπlethoxy-benzoyl) -2,4,4-trimethyl benzyl phosphineoxide · Anthraqui quinone (anthraqui η ο ne), 1,4-naphthoquinone (1,4-naphthoquinone) and other quinones (qUinone); Benzene methyl chloride (phenacyl chloride), tris; Maple (tribromomethyl phenylsulfone), tris (trichloromethyl) -s-triazine [tris (trichloromethyl) -s-triazine] and other compounds; di-tertbutylp eroxide) and other peroxides. Among them, benzophenone compounds are the best, and 4, 4′-bis (diethylamine) dibenzylone is the best. Organic solvent (D) The photosensitive resin composition for a color filter of the present invention is composed of the alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), and a photoinitiator (C). The pigment (E) is an essential component, and an additive component to be described later may be added if necessary. In general, the components other than the pigment (E) are dissolved in a suitable organic solvent

第18頁 200535461 五、發明說明（15) 劑（D )中，調製成液狀組成物。前述有機溶劑（D )之選擇上，需選擇可溶解鹼可溶性樹脂（A )、含乙烯性不飽和基之化合物（B )，以及光起始劑（c )，且不與該等成分相互反腐，並具有適當的揮發性者。乃〜、基於鹼可溶性樹脂（A ) 1 〇 0重量份，本發用感光性樹脂組成物之有機溶劑（以） y /思Page 18 200535461 V. Description of the invention (15) In the agent (D), a liquid composition is prepared. In the selection of the aforementioned organic solvent (D), it is necessary to select a soluble alkali-soluble resin (A), an ethylenically unsaturated group-containing compound (B), and a photoinitiator (c). And have appropriate volatility. Is based on 100 parts by weight of the alkali-soluble resin (A), the organic solvent (in) of the photosensitive resin composition for use in the present invention.

25 0 0重量份，更佳為4〇〇〜22〇〇㈤=敉仏為3UU 重量份。里h ，取佳為5 0 0〜2 0 0 0 上述有機溶劑（D )可選自前述給程中所使用之溶劑，在此不贅述。μ脂（A)聚合過或將2種或2種以上混合使用。上述洛劑可單獨使用，醇甲醚醋酸酯、3 -乙 " 前述有機溶劑（D)中，亦以内氧基丙酸乙酯較佳。顏料（E) 基於驗可溶性樹脂（A)丨〇〇重量之使用量較佳為2 〇〜5 〇〇重量份，77」本發明之顏料（E ) 最佳為80〜3 〇〇重量份。炅佳為50〜400重量份，鐵、鈷、鋁鋼本發明之顏料（E)係可使用迄枓或有機顏料。無機顏料可舉例所公知之各種無機顏鹽等等之金屬化合物，具體而言，·金屬氧化物、金屬錯、+、人鈦、鎂、鉻、亞鉛、銻等夕人Γ 奶以至屬之複合氧化物為例。至屬氧化物有機顏料可舉例如下： • 1 ·顏料黃 1，3，1 1， 1 2， 1 3 . ^ ，14，15，16，17, 叙、. A, 如 ·错、丄、如、顧J、以及前250,000 parts by weight, more preferably 400 to 2200. ㈤ = 敉仏 is 3UU parts by weight. Here, h is preferably 500 to 2000. The above organic solvent (D) may be selected from the solvents used in the foregoing process, and will not be repeated here. The μ fat (A) is polymerized or two or more kinds are mixed and used. The above-mentioned agent can be used alone, and among the aforementioned organic solvents (D), ethyl oxypropionate is also preferred. The pigment (E) is preferably used in an amount of 200 to 5000 parts by weight based on the weight of the soluble resin (A). The pigment (E) of the present invention is preferably 80 to 300 parts by weight. It is preferably 50 to 400 parts by weight. Iron, cobalt, aluminum, and steel. The pigment (E) of the present invention can be conventionally used, or organic pigments. Inorganic pigments can be exemplified by various well-known metal compounds such as inorganic salts, and specifically, metal oxides, metal oxides, +, human titanium, magnesium, chromium, lead, antimony, and the like. An example is a composite oxide. Examples of organic oxide organic pigments are as follows: • 1 · Pigment Yellow 1, 3, 1 1, 1, 2, 1 3. ^, 14, 15, 16, 17, A, such as · 丄, 丄, such as Gu Gu, and Ex

200535461 五、發明說明（16) 20， 24， 31， 53, 55， 60， 61， 65， 71， 73, 74， 81， 83， 93， 95， 97, 98， 99， 100， 101，1 04， 106，1 08， 109, 110， 113, 114, 116 ,117 \ 119, 120 ，126, 127, 128, 129 ，138， 139， 150, 151， 152， 153, 154， 155， 156, 166 ，167， 168， 175 〇 C· I. 顏料橙1 ，5， 13， 14, 1 6，17, 24, 34，36， 38， 40， 43， 46, 49， 51， 61， 63， 64, 71， 73 〇 C. I. 顏料紅1 ，2， 3，4 ，5， 6，7， 8，9， 10， 11， 12， 14， 15， 16, 17， 18， 19， 21， 22, 23, 30，31， 32， 37， 38， 40, 41， 42， 48:1, 48:2, 48: 3，48 : 4， 49 : 1 ，49 :2，5 0 : 1，52 :1， 53:1, 57，57:1， 57:2, 58:2, 58 :4, 6 0:1, 63 :1， 63:2, 64:1, 81 : 1，83, 88， 90:1 ，97 ，101， 102， 104, 105, 106， 108, 112， 113， 114, 122 ，123， 144， 146, 149, 150， 151， 155， 166， 168, 170 ，171， 172， 174, 175, 176， 177, 178， 179， 180, 185 ，187， 188， 190, 193, 194， 2 02, 2 06， 20 7， 208, 209 ，215， 216， 2 2 0, 224, 2 26， 242, 2 43， 24 5， 254, 255 ，2 64， 2 6 5 ° C. I. 顏料紫1 ，19, 23, 29， 32，36 ，38 ，39 ° C. I. 顏料藍1 ，2， 15， 15:3, 15:4, 15: 6，16，, 22， 60， 6 6 ° C. I. 顏料綠7， 36, 37 〇 C. I.顏料棕23，25，28。 C. I.顏料黑1， 7。200535461 V. Description of the invention (16) 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 99, 100, 101, 1 04 , 106, 1 08, 109, 110, 113, 114, 116, 117 \ 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175 ° C.I. Pigment Orange 1, 5, 13, 13, 14, 6, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71 , 73 〇CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 5 0: 1, 52: 1, 53: 1 , 57, 57: 1, 57: 2, 58: 2, 58: 4, 6 0: 1, 63: 1, 63: 2, 64: 1, 81: 1,83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 2 02, 2 06, 20 7, 208, 209, 215, 216, 2 2 0, 224, 2 26, 242, 2 43, 24 5, 254, 255, 2 64, 2 6 5 ° CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, 39 ° CI Pigment Blue 1, 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 6 6 ° CI Pigment Green 7, 36, 37 ° CI Pigment Brown 23, 25, 28. C. I. Pigment Black 1, 7.

第20頁 200535461 五、發明說明（17) 前述顏料可單獨或混合2種以上使用。於本發明中著色劑（E )’依據所期望者，亦可伴隨使用分散劑。此等分散劑可舉陽離子系、陰離子系、非離子系、兩性、聚石夕氧院系、氟系等之界面活性劑為例。其中界面活性劑舉例而言有：聚環氧乙烷十二烷基_ 、聚環氧乙烷硬脂醯醚、聚環氧乙烷油醚等之聚環氧乙烧烧基騎類；聚環氧乙炫辛基苯、聚環氧乙烧壬基笨_等之聚環氧乙烧烧基笨醚類，聚乙二醇二月桂酸醋、聚乙二醇一硬脂酸酯等之聚乙二醇二酯類；山梨糖醇酐脂肪酸酯類；脂肪酸改質之聚酯類；3級胺改質之聚胺基甲酸酯類 ;以下為商品名：ΚΡ(信越化學工業製）、SF_84 27 (T〇ray Dow Corning Silicon 製）、普利弗隆（ρ〇ΐγ【ι〇ψ，共榮社油脂化學工業製）、愛夫多普[F-Top，得克姆普洛大庫茲製（Tochem Products Co. , Ltd.)]、美卡夫克（Megafac ，大曰本印墨化學工業製）、弗洛多（Fiuorade，住友3M製）、阿魏卡多（Asahi Guard)、薩弗隆（surfl〇n，旭硝子製）等等。此等界面活性劑可單獨或混合複數種以上使用。 1分子中至少含有2個環氧基之化合物（F ) 基於鹼可溶性樹脂（A) 1 0 0重量份，1分子中至少含有2 個環氧基之化合物（F )的使用量較佳為〇 . 1〜3 0重量份，更佳為1〜25重量份，最佳為2〜20重量份。本發明之1分子中至少含有2個環氧基之化合物（F )之具體例如·雙 A型環氧樹脂（b i s p h e η ο 1 A t y p e e ρ ο X y r e s i n，例如：油化s h e 1 1 E p〇x y公司製，商品名E p i k o t ePage 20 200535461 V. Description of the invention (17) The aforementioned pigments can be used alone or in combination of two or more. In the present invention, the colorant (E) 'may be accompanied by the use of a dispersant, as desired. Such dispersants can be exemplified by cationic, anionic, nonionic, amphoteric, polyisocyanate, fluorine-based surfactants, and the like. Among the surfactants are, for example, polyethylene oxide dodecyl_, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether, etc., polyethylene oxide fired bases; Ethylene oxide octylbenzene, polyethylene oxide nonyl benzyl ether, etc. Polyethylene oxide benzyl ethers, polyethylene glycol dilaurate, polyethylene glycol monostearate, etc. Polyethylene glycol diesters; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes; the following are trade names: Κ (made by Shin-Etsu Chemical Industries), SF_84 27 (manufactured by Toray Dow Corning Silicon), preflon (ρ〇ΐγ [ι〇ψ, manufactured by Kyoeisha Olefin Chemical Industry), Evdorp [F-Top, Tkampulo (Tochem Products Co., Ltd.)], Megafac (made by Daimon Ink Chemical Industry), Frodo (made by Sumitomo 3M), Asahi Guard (Asahi Guard), Saffron (Surflon, made by Asahi Glass) and so on. These surfactants can be used alone or in combination of a plurality of kinds. The compound (F) containing at least two epoxy groups in one molecule is based on 100 parts by weight of the alkali-soluble resin (A). The amount of the compound (F) containing at least two epoxy groups in one molecule is preferably 0. 1 to 30 parts by weight, more preferably 1 to 25 parts by weight, and most preferably 2 to 20 parts by weight. Specific examples of the compound (F) containing at least two epoxy groups in one molecule of the present invention are, for example, a double-A epoxy resin (bisphe η ο 1 A typee ρ ο X yresin, for example, oiled she 1 1 E p〇 xy company, trade name E pikote

第21頁 200535461 五、發明說明（18) 828 、Epik〇te 1001 、Epik〇te 1002 、Epik〇te 1004 等）、雙酚A型環氧樹脂之醇型羥基（aic〇h〇l ic hydroxyl )與環氧氣丙烷（6口化111〇]：〇1^(1]^11)反應而得之環氧樹脂（例如：曰本化藥公司製，商品名NER- 1 3 0 2，環氧當量3 2 3，軟化點 76°C)、雙酚F 型環氧樹脂（bisphenol F type epoxy resin，例如：油化Shel 1 Epoxy公司製，商品名Epikote 807 、Epikote 4001 、Epikote 4002 、Epik〇te 4004 等）、雙酚F型環氧樹脂之醇型羥基與環氧氣丙烷反應而得之環氧樹脂（例如··日本化藥公司製，商品名NER- 74 0 6，環氧當量35 0，軟化點66°C)、雙酚S型環氧樹脂（bisphenol S type epoxy resin)、二苯基縮水甘油醚（biphenyl glycidyl ether ’例如：油化Shell Epoxy公司製，商品名Epikote YX40 0 0 )、（苯）酚醛型環氧樹脂（phen〇i Novolac type epoxy resin ，例如：日本化藥公司製，商品名EPPN-201、油化Shell Epoxy公司製，商品名Epikote 1 5 2、E p i k 〇 t e 1 5 4、E p i k 〇 t e 1 5 7 S 6 5、E p i k 〇 t e 1 5 7 S 7 0、陶氏化學公司製，商品名DEN-43 8 )、甲（苯）酚醛型環氧樹月旨（cresol Novo 1 ac type epoxy resin ，例如:日本化藥公司製，商品名EOCN-102S 、 EOCN-1020 、 EOCN-104S)、三縮水甘油異氰尿酸酯（t r i g 1 y c i d y 1 i s 〇 c y a n u r a t e，例如 •曰產化學公司製，商品名T E P I C )、三盼甲烧型環氧樹脂 (trisphenol me thane type epoxy resin ， Ϊ列士口：曰本 J 匕藥公司製，商品名EPPN-501 、EPPN-502、EPPN-503)、苟環氧核十月旨（f 1 uor ene epoxy resin ， Ϊ列女口：新曰鐵4匕學公Page 21 200535461 V. Description of the invention (18) 828, Epik〇te 1001, Epik〇te 1002, Epik〇te 1004, etc.), alcoholic hydroxyl groups (aic〇h〇l ic hydroxyl) of bisphenol A epoxy resin An epoxy resin obtained by reacting with epoxy propane (6 alkylates 111〇): 〇1 ^ (1) ^ 11 (for example: manufactured by Yueben Chemical Co., Ltd., trade name NER- 1 3 02, epoxy equivalent 3 2 3, softening point 76 ° C), bisphenol F type epoxy resin (for example: oily Shel 1 Epoxy company, trade names Epikote 807, Epikote 4001, Epikote 4002, Epik〇te 4004 Etc.), epoxy resin obtained by reacting the alcoholic hydroxyl group of bisphenol F-type epoxy resin with epoxy propane (for example, made by Nippon Kayaku Co., Ltd., trade name NER-74 0 6, epoxy equivalent 35 0, softened Point 66 ° C), bisphenol S type epoxy resin, biphenyl glycidyl ether 'for example: manufactured by Petrochemical Shell Epoxy, trade name Epikote YX40 0 0), ( Benzene) phenol novolac type epoxy resin (phen〇i Novolac type epoxy resin, for example: made by Nippon Kayaku Co., Ltd. Product name EPPN-201, manufactured by Petrochemical Shell Epoxy, trade name Epikote 1 5 2, E pik 〇te 1 5 4, E pik 〇te 1 5 7 S 6 5, E pik 〇te 1 5 7 S 7 0, pottery DEN-43 8), cresol Novo 1 ac type epoxy resin (produced by Nippon Kayaku Co., Ltd., trade names EOCN-102S, EOCN-1020) , EOCN-104S), triglycidyl isocyanurate (trig 1 ycidy 1 is 〇cyanurate, for example, • manufactured by Japan Chemical Company, trade name TEPIC), trisphenol me thane type epoxy resin Resin, Ϊ 列士口: Made by J.J. Pharmaceutical Co., Ltd., trade names EPPN-501, EPPN-502, EPPN-503), October epoxy purpose (f 1 uor ene epoxy resin, Ϊ 列女口): Xin Yue Iron 4 Dagger School

第22頁 200535461 五、發明說明（19) 司製’商品名E S F - 3 0 0 )、脂壞式壞氣樹脂（例如：d a i c e 1 化學工業公司製’商品名Celloxide 2021P、Celloxide EHPE)及％氧化聚丁一細樹脂（epoxidized polybutadiene ，例如：Dai cel化學工業公司製，商品名Epolead PB3 6 0 0 )等。本發明之1分子中至少含有2個環氧基之化合物（F )中 ’以（苯）酚醛型環氧樹脂及環氧化聚丁二烯樹脂更佳。該等1分子中至少含有2個環氧基之化合物可單獨使用，亦可 2種或2種以上混合使用。Page 22 200535461 V. Description of the invention (19) The company's product name ESF-3 0 0), greasy gas resin (for example: Daice 1 Chemical Industry Company's product name Celloxide 2021P, Celloxide EHPE) and% oxidation Polybutadiene (epoxidized polybutadiene, for example: Daicel Chemical Industry Co., Ltd., trade name Epolead PB3600). Among the compounds (F) containing at least two epoxy groups in one molecule of the present invention, (benzene) novolac epoxy resin and epoxidized polybutadiene resin are more preferred. These compounds containing at least two epoxy groups in one molecule may be used alone or in combination of two or more kinds.

本舍明之彩色滤光片用感光性樹脂組成物中，當（1 ) 鹼可溶性樹脂（A)之羥值介於〇·丨〜2〇 K〇Hmg/g、（2)鹼可 f性樹脂（A。）以熱減重分析儀（TGA)測定其5重量％之熱減重 /孤^_為3 0 0 C以上及（3 )基於驗可溶性樹脂（a ) 1 〇〇重量份， 1分子1中&至^少含有2個環氧基之化合物（F)的使用量為1〜 3 0重里，等條件滿足時，則感光性樹脂組成物經由塗佈、曝光·、顯影後，在基板上未曝光之部分及遮光層（bUck 上之殘渣量少，且顯影、後烤後，晝素之耐熱性跃生仏且液晶顯示器之I 丁〇透明電極層阻抗值降低In the photosensitive resin composition for a color filter of Ben Summing, when (1) the alkali-soluble resin (A) has a hydroxyl value between 〇 · 丨 ~ 2〇KOmg / g, and (2) an alkali-soluble resin (A.) 5% by weight with a thermal weight loss analyzer (TGA) for a thermal weight loss / solarity of 300 ° C or more and (3) based on 100 parts by weight of soluble resin (a), 1 The amount of the compound (F) containing at least 2 epoxy groups in the molecule 1 is 1 to 30 weights. When the conditions are satisfied, the photosensitive resin composition is subjected to coating, exposure, and development. The unexposed part on the substrate and the light-shielding layer (bUck have a small amount of residue, and after development and post-baking, the heat resistance of daylight suddenly rises and the resistance value of the transparent electrode layer of the liquid crystal display is reduced.

本七明感光性樹脂組成物中為提高塗佈性，並可伴I =界面活性劑。基於鹼可溶性樹脂(A) 100重量份，本， ~ ^面^活性劑_之使用量較佳介於0〜6重量份，更佳介於C 里伤’取佳介於〇〜4重量份，上述界面活性劑之舉例同丽述顏料中所使用之界面活性劑。In the present Qiming photosensitive resin composition, in order to improve the coating property, it may be accompanied by I = surfactant. Based on 100 parts by weight of the alkali-soluble resin (A), the use amount of ~~ ^^^ active agent is preferably between 0 ~ 6 parts by weight, more preferably between C and C ', preferably between 0 ~ 4 parts by weight, the above interface Examples of the active agent are the same as those used in Lishu pigments.

第23頁 200535461 五、發明說明（20) 此外，本發明之感光性樹脂組成物中，必要時可調合各種添加物，例如填充劑、驗可溶性樹脂（A )以外之高分子化合物、密著促進劑、抗氧化劑、紫外線吸收劑、防凝集劑等。基於鹼可溶性樹脂（A ) 1 0 0重量份，本發明添加物之使用量較佳介於0〜1 0重量份，更加介於0〜6重量份，最佳介於0〜3重量份。此等添加物之具體例有：玻璃、鋁之填充劑；聚乙烯醇、聚丙烯酸、聚乙二醇單烷基醚、聚氟丙烯酸烷酯等之鹼可溶性樹脂（A)以外的高分子化合物；乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基三（2-甲氧乙氧基）矽烷、N-(2 -氨基乙基）-3-氨基丙基甲基二甲氧基矽烷、N-( 氨基乙基）-3 -氨基丙基三曱氧基石夕烧、3 -氨基丙基三乙氧基矽烷、3 -環氧丙醇丙基三曱氧基矽烷、3 -環氧丙醇丙基甲基二甲氧基矽烷、2-(3, 4-環氧環己基）乙基三甲氧基石夕烧、3 -氯丙基甲基二甲氧基石夕烧、3_氯丙基三曱氧基石夕烷、3-甲基丙烯氧基丙基三甲氧基矽烷、3 -硫醇基丙基三甲氧基矽烷等密著促進劑；2, 2 -硫代雙（4-甲基-6-第三丁基苯盼）、2，6 -二-第三丁基苯S分等之抗氧化劑；2-(3-第三丁基-5-曱基-2 -羥基苯基）-5-氣苯基疊氮、烷氧基苯酮等紫外線吸收劑；及聚丙烯酸鈉等防凝集劑。、本發明之彩色濾光片用感光性樹脂組成物係將上述成分（A)〜（F )於攪拌器中均勻混合成溶液狀態，必要時可加入界面活性劑、密著助劑等其他添加劑。本發明之感光性樹脂組成物，係藉由迴轉塗佈、流延Page 23 200535461 V. Description of the invention (20) In addition, various additives such as fillers, polymer compounds other than soluble resin (A), and adhesion promotion can be blended into the photosensitive resin composition of the present invention as necessary. Agents, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc. Based on 100 parts by weight of the alkali-soluble resin (A), the amount of the additive of the present invention is preferably between 0 and 10 parts by weight, more preferably between 0 and 6 parts by weight, and most preferably between 0 and 3 parts by weight. Specific examples of such additives include glass and aluminum fillers; polymer compounds other than alkali-soluble resins (A) such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylates. ; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silyl, N- (aminoethyl) -3 -aminopropyltrimethoxysilane, 3 -aminopropyltriethoxysilane, 3 -glycidylpropyltrimethoxysilane, 3- Glycidyl propylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxylithium, 3-chloropropylmethyldimethoxysilyl, 3_ Adhesion promoters such as chloropropyltrimethoxyxanthane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane; 2, 2-thiobis (4 -Methyl-6-tert-butylphenyl), 2,6-di-tert-butylbenzene S grade antioxidant; 2- (3-tert-butyl-5-fluorenyl-2-hydroxyl Phenyl) -5-oxyphenyl azide, alkoxybenzophenone and other UV absorbers Agents; and anti-coagulant such as sodium polyacrylate. The photosensitive resin composition for a color filter of the present invention is a mixture of the above-mentioned components (A) to (F) in a stirrer to form a solution state, and other additives such as a surfactant, an adhesion aid, etc. may be added if necessary. . The photosensitive resin composition of the present invention is formed by spin coating and casting.

第24頁 200535461 五、發明說明（21) ' -塗佈或W塗佈等、塗佈方式將組成物塗佈在基Page 24 200535461 V. Description of the invention (21) '-Coating or W coating, etc. The coating method is to apply the composition to the substrate.

後，以預烤（prebake)方式將溶劑去除而形成I 層。本發明所述之基板，舉伽t m _ ^ , . J而言有用於液晶之無鹼玻璃、鈉鈣玻璃、硬暂 „ „ ^ ll ^ ^ 更貝坡璃（派勒斯玻拜埚及於此專玻璃上附著透明逡穿蹩々上不h v電膜者，或用於置寺之先電變換裝置基板（如危彻# π十斤h _=b_ 士 /基板）寻寻。此係形成隔離各晝素之黑色脫犋。預烤之條件，依各成分之㈤人,μ安在7〇〜90。。溫度下進行)分鐘#八’-；比气性樹脂組成物層介於所指定刀、’里、' ^ c '皿度下浸潰於顯影液3〇秒〜5八 I丨、分除去而形成圖案。瞧刀紅進订頒衫’ 等之f外岭Α *先使用之光線，以g線. 寺（^、外線為㊣，而紫外線函素燈。置可為（起）局水再者，顯影液係使用如& — 、碳酸氫鈉、碳酸鉀、碳酸卜化鈉、氫氧化氨水、乙胺、-7… 乳鉀、矽酸鈉、甲一 G月女、二甲苴氧化四乙銨、膽鹼、_ 土乙醇胺、氫氧化、〇) —7-十一烯等鹼性化合物、哌啶、1，8_二氮雜 10重量％，更佳為0 0 0 5〜”、、員影液之濃度較ί 構成之鹼性水溶液。〜b重量％，最佳為〇· 01 使用此等鹼性水溶液像後再以水洗淨。盆名、β構成之顯影液時，乂壓縮空氣或壓縮氮氣板上。塗佈 ^光性樹脂顯示裝置等 ο、石英破固體攝影裝荨基板一般而異，通常 I，該感光⑯ 光，於2 3 ± 2 不要之部 k h線、i線銀燈及金屬鉀、碳酸鈉基石夕酸納、四甲銨、氫二環-(5, 4，f L為0· 00 1〜〜1重量％所一般係於顯將圖案風乾Then, the solvent is removed in a prebake manner to form an I layer. The substrates described in the present invention are, for example, tm _ ^,. For J, there are alkali-free glass, soda-lime glass, and hard-temporary glass for liquid crystals. ^ ^ Ll ^ ^ The transparent glass is attached to this special glass, and the person who does not have the HV electrical film, or the substrate of the first electrical conversion device (such as Wei Toru # π 十斤 h _ = b_ taxi / substrate) is used to find. This system is formed Isolate the black exfoliation of each day. Pre-baking conditions, depending on the ingredients of each ingredient, μ Ann at 70 ~ 90 ... temperature) minutes # 八 '-; the specific resin composition layer is between The pattern is formed by immersing in a developing solution for 30 seconds to 58 minutes at a specified degree of knife, lining, and ^ c 'to form a pattern. Look at the knife red into the order shirt, and so on, the f outer ridge * * The first light to use is g line. Temple (^, outside line is ㊣, and ultraviolet letter lamp. Set can be (from) the local water and then develop The liquid system uses such as & —, sodium bicarbonate, potassium carbonate, sodium bicarbonate, ammonia hydroxide, ethylamine, -7 ... potassium lactate, sodium silicate, formaldehyde, tetramethylammonium oxide , Choline, triethanolamine, hydroxide, 0) — 7-undecene and other basic compounds, piperidine, 1,8-diaza 10% by weight, more preferably 0 0 0 5 ~ ", The concentration of the film solution is higher than that of an alkaline aqueous solution composed of ί. ~ B% by weight, the best is 0.01. After using these alkaline aqueous solutions, wash them with water. When the developer solution is composed of a basin name and β, pressurized air Or compressed nitrogen gas plate. Coating photoresist display devices, etc. Quartz broken solid photographic mounting substrates generally vary, usually I, the photosensitive light is on 2 3 ± 2 unnecessary parts kh line, i line silver Lamps and metallic potassium, sodium carbonate-based sodium oxalate, tetramethylammonium, and hydrogen bicyclo- (5, 4, f L is 0. 00 1 to 1% by weight are generally shown in the map Air-dry

第25頁Page 25

200535461 五、發明說明（22) 〇之後再以熱板或烘箱等加熱裝置作最後之加熱處理。所疋加熱’孤度為1 5 0〜2 5 〇，使用熱板時加熱時間為5分鐘〜6 0义麵’使用烘箱加熱時之加熱時間為3 〇分鐘〜9 〇分鐘。各色（主要包括紅、綠、藍三色）重覆上述步驟，便可製作彩色〉慮光片之畫素。其次，在畫素上以2 2 Q °c至2 5 0 〇C 程度之真空下形成I T 0蒸鍍膜，必要時，對I τ 〇膜施行蝕刻暨佈線之後，再塗佈液晶配向膜用聚醯亞胺，進而燒成之，即可作為液晶顯示器用之彩色濾光片。丨_ 【實施方式】本發明之前述以及其他技術内容、特點與功效，在以下配合實施例及比較例的說明，將可清楚的明白。〔驗可溶性樹脂（A )之合成例〕合成例A - 1 在一容積1000毫升之四頸錐瓶上設置氮氣入口、攪拌器、加熱器、冷凝管及溫度計，並導入氮氣。其聚合方式乃先將溶劑3 -乙氧基丙酸乙酯（以下簡稱EEP) 2 0 0重量份加入四頸錐瓶中，加以攪拌，油浴之溫度被提升至8 5 °C後，φ 再加入表一所述之單體混合物。該單體混合物之入料方式為連續添加，添加方式為將丙烯酸-2 -羥基-3-苯氧基丙酯（以下簡稱Μ-5700)5重量份、甲基丙烯酸單體（以下簡稱M A A ) 1 5重量份、甲基丙稀酸苯甲酯單體（以下簡稱BZ MA) 75重量份、丙烯酸甲酯單體（200535461 V. Description of the invention (22) 〇 Then use a heating device such as a hot plate or an oven for the final heating treatment. The heating degree is 1500 to 2500, and the heating time is 5 minutes to 60 minutes when using a hot plate. The heating time is 30 minutes to 90 minutes when using an oven. Repeat the above steps for each color (mainly including three colors of red, green, and blue), and then you can make pixels of color> light-resistant film. Secondly, IT 0 vapor-deposited film is formed on the pixels under a vacuum of 2 2 Q ° c to 2 500 ° C. If necessary, the I τ 〇 film is etched and wired, and then a polycrystalline film for alignment film is coated. Perylene imine, which can be further fired, can be used as a color filter for liquid crystal displays.丨 _ [Embodiments] The foregoing and other technical contents, features, and effects of the present invention will be clearly understood from the following description of the examples and comparative examples. [Synthesis example of soluble resin (A)] Synthesis example A-1 A four-necked conical flask with a volume of 1000 ml was provided with a nitrogen inlet, a stirrer, a heater, a condenser tube, and a thermometer, and nitrogen was introduced. In the polymerization method, 200 parts by weight of ethyl 3-ethoxypropionate (hereinafter referred to as EEP) is first added to a four-necked conical flask and stirred. After the temperature of the oil bath is raised to 8 5 ° C, φ Add the monomer mixture described in Table 1. The feeding method of the monomer mixture is continuous addition. The adding method is to add 5 parts by weight of acrylic acid 2-hydroxy-3-phenoxypropyl ester (hereinafter referred to as M-5700) and methacrylic monomer (hereinafter referred to as MAA). 15 parts by weight, 75 parts by weight of benzyl methacrylate monomer (hereinafter referred to as BZ MA), methyl acrylate monomer (

第26頁 200535461 五、發明說明（23) ' ----- 以下簡稱Μ A ) 5重量份之單體混人*产 / 。 Ό物在油浴之溫度被提升至 90 C後之5小時内，連續添加’且油浴之溫度被提升至⑽ C後，依表一所示將聚合用起始劑2, 2, _偶氮雙_2_ 腈（以下簡稱AMBNH重量份溶於右嬙_ + ,Page 26 200535461 V. Description of the invention (23) '----- Hereinafter referred to as Μ A) 5 parts by weight of monomers are mixed and produced. Within 5 hours after the temperature of the oil bath is increased to 90 C, the temperature of the oil bath is continuously added, and after the temperature of the oil bath is increased to ⑽ C, the polymerization initiator 2, 2, _ couple is shown in Table 1. Nitrobis_2_2 nitrile (hereinafter referred to as AMBNH)

/分々、頁機溶劑EEP中，並將AMRN/ Tiller, pager solvent EEP, and AMRN

與EEP的溶液分成五等份，以每 =AMBN 加在四頸錐瓶中。母…間隔添聚合過程的反應溫度維持90 t，聚合時間6小時。合完成後，該聚合物溶液中，加入2〇〇重量份之甲笨（媒）加以攪拌洗滌，聚合物析出，再經離心過， Φ 可溶性樹脂A-1。双合成例A - 2〜a - 5 ^ 同合成例A- 1之操作方法，不同之處係改變聚合用單，之種類、混合用量、反應溫度、及貧溶媒洗滌過程中甲笨（負/谷媒）之使用量及洗滌次數，其配方及反應條件载於表一。 ' 合成例A - 6〜a - 7 同合成例A -1之操作方法，不同之處係改變聚合用單體之種類、混合用量、反應溫度，其配方及反應條件裁於表一。 ' 合成例A - 8 在一容積1 0 0 0毫升之四頸錐瓶上設置氮氣入口、授掉為、加熱器、冷凝管及溫度計，並導入氮氣且依表—所示用量加入進料組成物，上述進料組成物包括：甲基丙歸酸 —2 -經基乙酯（以下簡稱hema)15重量份、MAA 10重量份、Divide the solution with EEP into five equal portions and add each to AMBN in a four-necked conical flask. Master ... interval addition The reaction temperature during the polymerization was maintained at 90 t, and the polymerization time was 6 hours. After the completion of the synthesis, 200 parts by weight of methylbenzyl (methane) was added to the polymer solution, and the mixture was stirred and washed. The polymer was precipitated, and then centrifuged. Φ Soluble resin A-1. Double Synthesis Example A-2 ~ a-5 ^ The operation method is the same as that of Synthesis Example A-1, except that the type of polymerization used is changed, the type, mixing amount, reaction temperature, and methylbenzene (negative / The amount of cereals and the number of washing times, the formula and reaction conditions are shown in Table 1. 'Synthesis Example A-6 ~ a-7 The operation method is the same as that of Synthesis Example A -1, except that the type, mixing amount and reaction temperature of the monomers used for polymerization are changed. The formula and reaction conditions are shown in Table 1. '' Synthesis Example A-8 A four-necked conical flask with a volume of 1000 ml was provided with a nitrogen inlet, a discharge tube, a heater, a condensing tube, and a thermometer, and introduced nitrogen and added the feed composition according to the amount shown in the table— The above feed composition includes: 15 parts by weight of methylpropionate-2-hydroxyethyl (hereinafter referred to as hema), 10 parts by weight of MAA,

第27頁 200535461 五、發明說明（24)Page 27 200535461 V. Description of the Invention (24)

BzMA 70重量份、MA 5重量份，以及溶劑EEP 2 0 0重量份。其中’早體 '心合物之入料方式為/次全部添加。當四頸錐瓶之内容物被攪拌時，油浴之溫度被提升至 95 °C，然後依表一所示將聚合用起始劑AMBN 4重量份溶於有機溶劑EEP中，並將AMBN與EEP的溶液分成五等份，以每小日守一寺份之里間1¾添加在四頸錐瓶中。聚合過程的反應溫度維持9 5 〇c，聚合時間6小時。聚合完成後，將聚合產物自四頸錐瓶中取出，將溶劑脫揮，可得驗可溶性樹脂A - 8。70 parts by weight of BzMA, 5 parts by weight of MA, and 200 parts by weight of the solvent EEP. The feeding method of the 'early body' heart compound is to add all at once. When the contents of the four-necked conical flask were stirred, the temperature of the oil bath was raised to 95 ° C, and then 4 parts by weight of the polymerization initiator AMBN was dissolved in the organic solvent EEP as shown in Table 1, and the AMBN and The solution of EEP was divided into five equal parts and added to a four-necked conical flask at a rate of 1¾ each in a small temple. The reaction temperature during the polymerization was maintained at 95 ° C, and the polymerization time was 6 hours. After the polymerization was completed, the polymerization product was taken out from the four-necked conical flask, and the solvent was devolatilized to obtain soluble resin A-8.

合成例A-9〜A-1 1 W 同合成例A - 8之操作方法，不同之處係改變聚合用單月豆之種類、混合用量、聚合用起始劑A Μ B N之用量及反應溫度，其配方及反應條件載於表一。 [感光性樹脂組成物之實施例及比較例] 貫施例1 使用前述合成例所得之鹼可溶性樹脂Α-1 1 〇〇重量份（Synthesis Example A-9 ~ A-1 1 W The operation method is the same as that of Synthesis Example A-8, except that the type, mixing amount, amount of polymerization initiator A M BN, and reaction temperature of the polymerization month beans are changed. The formula and reaction conditions are shown in Table 1. [Examples and Comparative Examples of Photosensitive Resin Compositions] Example 1 The alkali-soluble resin A-1 1 100 parts by weight (

固形份），與表二所示之二季戊四醇六丙烯酸酯1 0 0重量份、2 -苄基-2-Ν，Ν -二甲胺一卜（4_嗎啉代苯基）一1— 丁酮4〇重，份、4, 4’-雙（二乙胺）二笨曱酮5重量份、2, 2，-雙（2 -氣笨基）-4，4 ’，5，5 ’ -四笨基二咪唑5重量份、顏料c I 2 5 4 1 6 0 重量份及（苯）紛醛型環氧樹脂（油化SHELL Epoxy公司製，商。口名E p i k 〇 t e 1 5 7 S 7 0 ) 3重量份之混合物，加入溶劑丙二醇甲鍵醋酸(以下簡稱PGMEA)1 70重量份及EEP 83 0重量 ^後’以搖動式攪拌器，加以溶解混合，即可調製而得彩(Solid content), and dipentaerythritol hexaacrylate of 100 parts by weight, 2-benzyl-2-N, N-dimethylamine-b (4-morpholinophenyl) -1-butane Ketone 40 parts by weight, 4, 4'-bis (diethylamine) dibenzinonone 5 parts by weight, 2, 2, 2-bis (2-airbenzyl) -4,4 ', 5,5'- 5 parts by weight of tetrabenzyldiimidazole, c I 2 5 4 1 6 0 parts by weight of pigment and (benzene) aldehyde aldehyde epoxy resin (manufactured by SHELL Epoxy Corporation, trade name. E pik 〇te 1 5 7 S 7 0) 3 parts by weight of the mixture, adding 1 70 parts by weight of the solvent propylene glycol methyl bond acetic acid (hereinafter referred to as PGMEA) and EEP 83 0 by weight ^ 'After mixing with a shaker, dissolve and mix, you can prepare and color

第28頁 200535461Page 28 200535461

該感光性樹脂組成物以下所得結果如表二所示。色遽光片用感光性樹脂組成物吕己之各測疋评價方式進行評價【評價方式】一、經值Table 2 shows the results obtained with this photosensitive resin composition. Photosensitive resin composition for color photo film Lu Jizhi's evaluation methods for each test [Evaluation method] 1. Economic value

將本發明之鹼可溶性樹脂（A)以氫氧化鉀溶液滴定，可得到鹼可溶性樹脂（A)中原有的酸中和滴定所需之氫氧化鉀笔克數（X );再將鹼可溶性樹脂（A )在吡啶存在下與醋酸酐進行乙醯化，則鹼可溶性樹脂（A)中之羥基與醋酸酐反應形成醋酸，然後再以氫氧化鉀溶液滴定，所測得之數值為驗可溶性樹脂（A)中原有的酸及羥基在乙醯化後形成之醋酸一者中和滴定所需之氫氧化鉀總毫克數（y )，貝彳（y ) 一（X)所彳寸到的差值即為本發明驗可溶性樹脂（A )之經值。二、驗可溶性樹脂（A)之5重量％之熱減重溫度在氮氣存在下，將所製得之鹼可溶性樹脂（A)丨〇毫克置於熱減重分析儀（間稱TGA，ΤΑ公司製型號Thermal Analyst 2100)，先升溫至i〇〇°c並持續1〇分鐘去除水份，再以1 0 °C /分鐘的速率升溫，當試料的重量減少5重量％時，測定當時的溫度，即為5重量％之熱減重溫度。The alkali-soluble resin (A) of the present invention is titrated with a potassium hydroxide solution to obtain the number of grams of potassium hydroxide pen (X) required for neutralization and titration of the original acid in the alkali-soluble resin (A); (A) Acetate with acetic anhydride in the presence of pyridine, the hydroxyl groups in the alkali-soluble resin (A) react with acetic anhydride to form acetic acid, and then titrate with a potassium hydroxide solution. The measured value is the soluble resin. The difference between the total number of milligrams of potassium hydroxide (y) required for neutralization and titration of one of the original acid and hydroxyl group formed by acetic acid in (A), and the difference between acetic acid (y) and (X). The value is the historical value of the soluble resin (A). 2. Test the thermal weight loss temperature of 5% by weight of the soluble resin (A). In the presence of nitrogen, place the prepared alkali-soluble resin (A). 0 mg in a thermal weight loss analyzer (sometimes called TGA, TA company). Thermal Analyst 2100), first raise the temperature to 100 ° C and remove the water for 10 minutes, and then raise the temperature at a rate of 10 ° C / minute. When the weight of the sample is reduced by 5% by weight, the temperature at that time is measured. , Which is the thermal weight loss temperature of 5% by weight.

三、耐熱性將所製得之感光性樹脂組成物以旋轉塗佈方式，塗布在1 0公分X 1 0公分玻璃基板上，可得到約8 μ m之塗膜，在 8 5 °C下預烤5分鐘。然後將該塗膜以紫外光（曝光機Can on PLA-501F) 2 0 0mJ/cm2照射，之後浸潰於23。(：之顯影液2分鐘顯影，以純水洗淨，再以2 0 0 °C後烤4 0分鐘，即可在玻璃3. Heat resistance The prepared photosensitive resin composition is spin-coated on a glass substrate of 10 cm × 10 cm to obtain a coating film of about 8 μm. Bake for 5 minutes. Then, the coating film was irradiated with ultraviolet light (exposure machine Can on PLA-501F) at 200 mJ / cm2, and then immersed in 23. (: The developing solution is developed for 2 minutes, washed with pure water, and then baked at 200 ° C for 40 minutes.

第29頁 200535461 五、發明說明（26) 基板上形成感光性樹脂層。將所製得之玻璃基板上之感光性樹脂層，以4 0 0〜7 0 0 nm波長之光測定其光透過率，然後於2 5 0 °C中放置6 0分鐘後，再以4 0 0〜7 0 0 nm波長之光測定其光透過率，根據其光透過率變化比例以如下之基準評價。〇：透過率變化5 %以下 △:透過率變化5〜1 〇 % X :透過率變化1 0 %以上四、耐驗性Page 29 200535461 V. Description of the invention (26) A photosensitive resin layer is formed on the substrate. Measure the light transmittance of the photosensitive resin layer on the prepared glass substrate with light having a wavelength of 400 to 700 nm, and then place it at 250 ° C for 60 minutes, and then take 40 The light transmittance of light with a wavelength of 0 to 7 0 nm was measured, and evaluated based on the change ratio of the light transmittance according to the following criteria. 〇: Transmittance change less than 5% △: Transmittance change 5 ~ 1 〇% X: Transmittance change 10% or more 4. Test resistance

將所製得之玻璃基板上之感光性樹脂層，以4〇〇〜7〇〇 nm波長之光測定其光透過率，然後於2% 中放置1 〇分釦後，再以4 0 0〜7 0 0 nm波長之光測定其光透過率，並根據其光透過率變化比例以如下之基準評價。〇：透過率變化5 %以下 △:透過率變化5〜10% X :透過率變化10%以上五、ITO透明電極層阻抗值 w Λ述Λ製f之感光性樹脂層形成後，於樹脂層上^The light transmittance of the photosensitive resin layer on the prepared glass substrate was measured with light having a wavelength of 4,000 to 7000 nm, and then a 10-minute deduction was placed in 2%, and then 40,000 to 4,000. Light with a wavelength of 700 nm was measured for its light transmittance, and evaluated based on the ratio of change in light transmittance on the following basis. 〇: Transmittance change 5% or less △: Transmittance change 5 ~ 10% X: Transmittance change 10% or more 5. ITO transparent electrode layer resistance value w Λ The Λ made of photosensitive resin layer f is formed on the resin layer Up ^

該條件，錢1TG膜形成透明電極層^ 儀器分別曰二。再以三菱化工製，型腑-T6 :測其阻抗值，取其平均值。單位Ω。 200535461 五仏、發明說明（27) — ' ⑽C下預烤5 >分鐘。然後將掩膜圖案（ma s k )貼緊該預烤塗膜’以紫外光（曝光機Can〇n PLA_5〇1F)3〇〇mJ/cm2照射，之 $浸潰於2 3 C之顯影液2分鐘顯影，在基板上未曝光之部分$去後’以純水洗淨，再以2〇〇它後烤4〇分鐘，即可在，璃基板上形成所要之感光性樹脂圖案，以電祭，確定表面是否有殘渣存在。、U奴嬈Under these conditions, the Qian 1TG film forms a transparent electrode layer. Then use Mitsubishi Chemical, Model 腑 -T6: Measure the impedance value and take the average value. The unit is Ω. 200535461 Five 仏, description of the invention (27) — 'Pre-bake at ⑽C for 5 > minutes. Then, a mask pattern (ma sk) is adhered to the pre-baking coating film, and is irradiated with ultraviolet light (exposure machine CanOn PLA_50F) at 300mJ / cm2, and the developer solution immersed in 2 3 C 2 Develop in minutes, remove the unexposed portion on the substrate, wash it with pure water, and then bake it for 200 minutes. Then, you can form the desired photosensitive resin pattern on the glass substrate. To determine if there are residues on the surface. U slave

〇 Δ X 一無殘渣 Φ 少許殘渣殘渣很多貫施例2〜5及比較例1〜8 同實施例1之操作方法，不同之處係改變鹼可溶性樹〇 Δ X No residue Φ A little residue A lot of residues The same method as in Example 1 was used in Examples 2 to 5 and Comparative Examples 1 to 8, except that the alkali-soluble tree was changed.

月曰（A )、顏料（E )及1分子中至少含右2個王-〆贫 )夕接相β田曰久1刀千中至乂 3有2個％氧基之化合物（F )之種類及用I，其配方及評價結果載於表二。〜惟t Γ述者，•為本發明 < 較佳實施例而。，當不月匕以此限疋本發明實施之範圍，即大凡依主範圍及發明說明蚩內六所你夕1 w Μ斤 ‘月申岣專利 ^ L , 曰内谷所作之間早的等效變化與修飾，皆怎仍屬本舍明專利涵蓋之範圍内。【附表說明】表-：=明驗可溶性樹脂（A)合成例的組成比例及評價 •、结果。、表二：本發明實施例及比較例的組成比例及其評價結果。Yue Yue (A), pigment (E), and at least two right-wang wangs in one molecule), followed by β Tian Yuejiu 1 knife Qianzhong to 乂 3 compound (F) with 2% oxygen Kind and use I, its formulation and evaluation results are shown in Table 2. ~ 惟 t Γ As described, • This is a < preferred embodiment of the present invention. When the month is limited, the scope of implementation of the present invention is limited, that is, according to the main scope and the description of the invention. How the effect changes and modifications are still within the scope of this Schering patent. [Description of attached table] Table-: = Composition ratio and evaluation of the synthetic examples of soluble resin (A). • Results. Table 2: Composition ratios and evaluation results of the examples and comparative examples of the present invention.

第31頁 200535461 五、發明說明（28)Page 31, 200535461 V. Description of the invention (28)

雲 Μ丨57Q0 ΗΕΜΑ ΜΑΑ BzMA SM ΜΑ AMBN EEP ③茹箨-2-菡一.-3-舛！1^溫竭&及幕琛-2-菡_(>爵碼&及幕琛舛-S爵郫鷂^£s ③莓漭f謊啷鷂 2,2' -¾ 11^-2--¾御7-舔 3—6^&a漭nsl CNOlh^lrox^lsIOhenox^lOroOy一 2—hydroxyethyl methsrylate methacrylic acid benzyl methacrylate styr*rDnrDnl〇n〇3n5r methyl acrylate 2,2* —azobis—2—nlethyl butyronitri le ethyl 3leth〇xyiDr〇plionate A-ll 1 > 1 CO > oo > 1 CD >- cn > 1 OO > 1 DO > t 樹脂 CsD cn to - CJ-Ϊ on M-5700 (a-1) 共聚合用單體組成物（重量份） oo CD cn IS DO CnD HEMA cn cn 〇> CD CnD CT) cn cn - - cn 1 (a-2) 1 CD ΟΊ CJD ΟΊ cn cn oo CD cn> cn cn cn cm BzMA (a-3) cn cn CO CJl g cn cn OO CJl cn 5 1 > \ > i 1 |連續添加 I連續添加1 連續添加連續添加連續添加連續添加連續添加入料方式 1① AMBN 起始劑 g o g CD g CD g CD g CD g CD g ο g ◦ IND Ο Q ro ο <z? CD Μ 溶劑 CO cn Is CO cn CO cn CO cn s CO cr> CO CTi CO cn CO cn CO c? n 反應溫度 l〇 l〇 l〇 ICD 运 o ◦ g g II <〇 ◦ 1(重量份）| 曱笨貧溶媒貧溶媒洗滌 l〇 l〇 l〇 l〇一一一 ICO loo - [(A)—」洗滌次數 CD CD CO 15.7 OO CD oo CD oo CX) CD CD cn 1 mg/g 經值 loo Is CO CO CJ1 CO oo CD CO CO DO CO OO CJl CO C\〇 CO CO oo o° 熱減重溫度 >—'^^^>li^s0\)^L^^^s:^^rrb^^t2;f^>Cloud Μ 丨 57Q0 ΗΕΜΑ ΜΑΑ BzMA SM ΜΑ AMBN EEP ③Ru 箨 -2- 菡一 .-3- 舛! 1 ^ 温竭 & 和幕琛 -2- 琛 _ (> Jue Ma & and Mu Chen 舛 -S 郫鹞 ^^ s ③berry 漭 f 漭 2,2 '-¾ 11 ^ -2 --¾ 御 7-lick 3-6 ^ & a 漭 nsl CNOlh ^ lrox ^ lsIOhenox ^ lOroOy-1 2-hydroxyethyl methsrylate methacrylic acid benzyl methacrylate styr * rDnrDnl0n〇3n5r methyl acrylate 2,2 * —azobis—2— nlethyl butyronitri le ethyl 3leth〇xyiDr〇plionate A-ll 1 > 1 CO > oo > 1 CD >-cn > 1 OO > 1 DO > t resin CsD cn to-CJ-Ϊ on M- 5700 (a-1) Copolymerization monomer composition (parts by weight) oo CD cn IS DO CnD HEMA cn cn 〇 > CD CnD CT) cn cn--cn 1 (a-2) 1 CD ΟΊ CJD ΟΊ cn cn oo CD cn > cn cn cn cm BzMA (a-3) cn cn CO CJl g cn cn OO CJl cn 5 1 > \ > i 1 | Continuous addition I Continuous addition 1 Continuous addition Continuous addition Continuous addition Continuous addition continuous Adding method 1① AMBN initiator gog CD g CD g CD g CD g CD g CD g ο g ◦ IND 〇 Q ro ο < z? CD Μ solvent CO cn Is CO cn CO cn CO cn CO cn CO CO > CO CTi CO cn CO cn CO c? n Reaction temperature l010l〇l〇ICD operation o ◦ gg II < 〇◦ 1 (parts by weight) | [(A) — ”Number of washing cycles CD CD CO 15.7 OO CD oo CD oo CX) CD CD cn 1 mg / g Value loo Is CO CO CJ1 CO oo CD CO CO DO CO OO CJl CO C \ 〇CO CO oo o ° Thermal weight loss temperature >-'^^^ > li ^ s0 \) ^ L ^^^ s: ^^ rrb ^^ t2; f ^ >

A 第32頁 200535461 五、發明說明（29)A Page 32 200535461 V. Description of Invention (29)

.:1^^3-¾^^奚黑器 2丨：讲-2-N, N-卜洵漭-1-( 4-屝奏方舛4YTT 1 4,4·-席(1(>弟)卜沭-ffls 2,2_-礞(2-|1艿轳丫4,4',5,5‘-@识咖卜去异 ^.τ-δι-δ&|蹂漭盎 3 丨Γ*ιι:&^^6溫湓韋Ci254 ^5iG3G ¾¾B15:6 itsHELL EPPVY^3^^^0<»Epikote 157S7S ^^^>^τ-=-^(γ>£ιο'€1>>°!)^,^^^εροο3<:1 PB3G00) dipentaerythritol hexaacrylate 2—benzy 1—2—z, Mid i me thy 1 as i no丨一 I (tlllorpho 1 i nophenyi ) 11—bu tanone 4, 4· lbis(diethylamino)benzophenone 2, 2· -bis(2-chlorophenylr4,4- ,5, 5- -tetraphenylbiiniidazole propylene glycol methyl ether acetate Ethyl 3-ethoxypropionate /Mli(E) (ftf;) 齐啟东迻(ο (啉t^) (Β) (its 雰^科 ti^^(A) (一一:岑) _ ^'^•fi F-2.: 1 ^^ 3-¾ ^^ 奚黑器 2 丨: Speaking 2-N, N-Bu 洵漭 -1- (4- 屝琴方舛 4YTT 1 4,4 · -seat (1 (> (Brother) Bu 沭 -ffls 2,2_- 礞 (2- | 1 艿轳丫 4,4 ', 5,5'-@ 识咖卜去异 ^ .τ-δι-δ & | 蹂漭 Angle 3 丨 Γ * ιι: & ^^ 6 温湓韦 Ci254 ^ 5iG3G ¾¾B15: 6 itsHELL EPPVY ^ 3 ^^^ 0 < »Epikote 157S7S ^^^ > ^ τ-=-^ (γ > £ ιο '€ 1 > >; °!) ^, ^^^ εροο3 <: 1 PB3G00) dipentaerythritol hexaacrylate 2—benzy 1—2—z, Mid i me thy 1 as i no 丨 I (tlllorpho 1 i nophenyi) 11—bu tanone 4, 4 Lbis (diethylamino) benzophenone 2, 2 · -bis (2-chlorophenylr4,4-, 5, 5- -tetraphenylbiiniidazole propylene glycol methyl ether acetate Ethyl 3-ethoxypropionate / Mli (E) (ftf;) Qi Qidongyi (ο (phyrin t ^) (Β) (its ^^ 科 ti ^^ (A) (一一: 岑) _ ^ '^ • fi F-2

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S 100 100 160 0030 170 έ 100 100 tt^玄尜涔 160 so 170 έ 100 100 160 830 170 40 100 1G0 〇 1¾ s 160 CO30 170 40 100 100 第33頁 200535461 圖式簡單說明第34頁S 100 100 160 0030 170 έ 100 100 tt ^ 玄尜涔 160 so 170 100 100 100 160 830 170 40 40 100 1G0 〇 1¾ s 160 CO30 170 40 100 100 Page 33 200535461 Simple illustration of the page Page 34

Claims

200535461 VI. Scope of Patent Application " 1 · A kind of photosensitive resin composition for color filters. The products include: (A) soluble resin; (B) compounds containing ethylenically unsaturated groups; (C) light on (D) an organic solvent; (E) a pigment; and (F) a compound having at least two epoxy groups in one molecule; wherein the longitude of the soluble resin (A) is between 0.1 and 2 〇KOHmg / g 'and its thermal weight loss temperature of 5% by weight measured by a thermal weight loss analyzer (TGA) is 300 C or more; and based on 100 parts by weight of the alkali-soluble resin (A), at least 1 molecule The amount of the compound (F) containing two epoxy groups is from 0.1 to 30 parts by weight. 〇

Page 35 200535461 VI. Designated Representative Map (I) The representative map in this case is: Figure ________ (II). Brief description of the component representative symbols of the representative map in this case II iiiii Page 3