TW574604B - A remover solution composition and process using the same - Google Patents
A remover solution composition and process using the same Download PDFInfo
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- TW574604B TW574604B TW91104523A TW91104523A TW574604B TW 574604 B TW574604 B TW 574604B TW 91104523 A TW91104523 A TW 91104523A TW 91104523 A TW91104523 A TW 91104523A TW 574604 B TW574604 B TW 574604B
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574604 五、發明說明（l) 【發明領域】 本發明是關於一種清洗液的組成物，使其運用在彩色 液晶裝置或彩色濾光片（以下簡稱LCD)之領域上，且用來 清洗基板周邊不必要光阻劑之清洗液的組成物。 【先前技術】 ，通常 在基板 即該基 中，位 一，而 及背面 。就光 以及背 光阻劑 離成小 物之原 沾附於 故 像之前 起部13 曰本特 加以清 glycol 般而言，光阻劑欲塗佈於矽晶圓或者玻璃基板上時 係以迴轉的方式，藉由遠心力使光阻劑擴散而塗佈 的表面，其塗佈後之膜厚橫截面如第一圖所示者， 板11頂面、周邊、邊緣、背面皆附著有光阻劑，其 在基板11頂面中心部位之中心部塗佈層丨2的厚薄均 位於頂面周緣形成一周緣突起部丨3，在基板丨丨側緣 則各別附著形成一邊緣附著部14或一背面附著部15 阻劑之功用而言，該周緣突起部13、邊緣附著部Μ 面附著部15並非預期形〜成之塗佈部位，此等邻位之 在預烤熱處理之後會變脆，容易在基板搬運過程剝 鱗片狀，上述剝離之小鱗片光阻劑將成為裝置 因，並導致LCD製造上良率下降，或於曝光過程中、 光罩上，使光罩之清洗頻率提高，降低產能。 一般為了改善前述缺失，在光阻劑塗佈後，眼 皆會先將基板週邊之突起部清除。為了清除^ 、邊緣附著部14及背面附著部15等不要的光,大 開昭刪號發明公^報中揭露，= 除，所述溶劑乃例如：乙_ | y & ^ , S予早乙基醚（ethylene monoethyl ether)、乙二醇單乙醚醋酸醋574604 V. Description of the invention (l) [Field of the invention] The present invention relates to a composition of a cleaning liquid, which is used in the field of color liquid crystal devices or color filters (hereinafter referred to as LCD), and is used to clean the periphery of the substrate The composition of the cleaning solution of the photoresist is unnecessary. [Prior art], usually in the substrate, that is, the base, one, and the back. As far as the light and the backlight resist are separated into small objects, they are attached to the original part. As described in the previous section 13, Ben Gol added clear glycol. When the photoresist is to be coated on a silicon wafer or a glass substrate, it is rotated. The surface coated with the photoresist diffused by the telecentric force, and the cross-section of the film thickness after coating is as shown in the first figure. The photoresist is attached to the top surface, periphery, edges, and back of the plate 11, The thickness of the central coating layer 2 on the central portion of the top surface of the substrate 11 is located at the periphery of the top surface to form a peripheral edge protrusion 3, and the edge of the substrate 丨 is attached to form an edge attachment 14 or a back surface. Attachment 15 The function of the resist is that the peripheral protrusions 13, the edge attachments M, and the surface attachments 15 are not intended to be shaped coatings. These adjacent positions will become brittle after the pre-baking heat treatment, and it is easy to The scale is peeled off during the substrate transportation process. The peeled small scale photoresist will become a device factor and cause the yield of LCD manufacturing to decrease. Or during the exposure process, the photomask will increase the cleaning frequency of the photomask and reduce the production capacity. Generally, in order to improve the aforementioned defects, after the photoresist is applied, the eyes will first remove the protrusions around the substrate. In order to remove unnecessary light such as ^, edge-attached portion 14 and back-side attached portion 15, it is disclosed in the Dakaizhao No. Invention Publication ^, except that the solvent is, for example: B_ | y & ^, Syozai Ethylene ether (ethylene monoethyl ether), ethylene glycol monoethyl ether acetate
574604 五、發明說明（2) (ethylene glycol monoethyl ether acetate)、丙二酉享 烧 *_Kpropylene glycol alkyl ether)、丙二醇烧基 _ 醋酸酯（propylene glycol alkyl ether acetate)之醇類 衍生物，酮（ketone)系之丙酮（acetone)、曱乙酮（methyl ethyl ketone)、環己酮（cyclohexanone)、甲丁酮 (methyl butyl ketone)等或如日本特許番號2 95040 7號發 明公開公報中揭示之二丙二醇單乙基_(dipr〇pylene glycol monoe thy 1 ether)以及乳酸曱酯、乳酸乙酯、醋 酸甲酯、醋酸乙酯、醋酸丁酯等之酸類，前述溶劑可單獨 或合併使用。 但 殘渣， 且二丙 酮等酮 今 使用上 缺失加 【發明 因此， 毒性低 泡性、 【發明 於 不必要 其中乙 二醇單 類有引 本案發 具有上 以改良 目的】 本發明 ’對環 膨潤性 概要】 是，本 的光（1 且 二醇衍 乙基酉迷 火點偏 明人乃 述缺失 之目的 境污染 低之清 發明之 劑，該 於光阻劑的洗淨效果不佳，容易生成 生系溶劑更有毒性及環境污染等問題 為毒性高的有機溶劑，而丙酮或甲乙 低及環境污染等缺失。 有鑒於習知用於清除光阻劑之溶劑在 ，乃本著精益求精之精神，針對上述 係在提供一種洗淨效果佳、殘渣少、 少，並可進一步增進清洗液本身之消 洗液的組成物。 清洗液組成物用來清洗LCD基板周邊 組成物包括··一種清洗液之組成物，574604 V. Description of the invention (2) (ethylene glycol monoethyl ether acetate), propylene glycol alkyl ether *, alcohol derivatives of propylene glycol alkyl ether acetate, ketone ) Is acetone, methyl ethyl ketone, cyclohexanone, methyl butyl ketone, etc. or as disclosed in Japanese Patent Publication No. 2 95040 7 Dipropylene glycol monoe thy 1 ether and acids such as ethyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate and the like can be used alone or in combination. But the residues, and ketones such as diacetone are missing today. [Invention, therefore, low toxicity, [Invention is unnecessary, where the ethylene glycol single class is cited. This case has the purpose of improving.] The present invention 'ring swelling Characteristic summary] Yes, the light (1 and diol-derived ethyl hydrazine has a fire point that is too clear for humans is the agent of the Qing invention with low pollution and a lack of purpose. The cleaning effect of the photoresist is not good and it is easy. The generation of bio-based solvents is more toxic and environmentally polluting. Highly toxic organic solvents are lacking, while acetone or methyl ethyl is low and environmental pollution is missing. In view of the conventional solvents used to remove photoresist, it is in the spirit of excellence. In view of the above, it is to provide a composition for a cleaning solution with good cleaning effect, less residue and less, and can further enhance the cleaning liquid itself. The cleaning liquid composition for cleaning the periphery of the LCD substrate includes a cleaning liquid. Composition
第5頁 574604Page 5 574604
光阻劑，該組 五、發明說明（3) 係用於清洗彩色濾光片之基板週邊不必要的 成物包括： (A ) 9 9 · 4〜8 0重量％之水； (B ) 0 · 5〜1 5重量％之氫氧四級銨基鹽類化合物； (C) 0.1〜10重量％之醇胺（alkanolamine)類几人 硕化合物； (D) 0 · 〇 0 0 1〜0 · 1重量％之氟系界面活性劑； 且該組成物在25°C之表面張力為60 dyne/cmi^下 以下針對本發明所使用各組成成份（A)〜（D、彳1 Ώ ν作具體謂 (A)水： 一般而言，清洗液係以水來作為分散媒，以水為分散 媒之清洗液，具有低毒性、不具引火性，以及管理容易政 廢液處理簡便及成本低廉等優點。 ' (B )氫氧四級銨基鹽類化ρ物： 對於使用丙烯酸酯（aery late)系樹脂作為感光性樹脂 的黏結劑（binder)而言，本發明所使用之氫氧四級銨基^ 類化合物乃以有機氫氧四級銨基鹽類化合物所製配之鹼^ 水溶液為較佳。其中又以氫氧四曱銨（tetramethy i ammonium hydroxide)、2-經基-氫氧三甲銨（2 — hydr〇xyl trimethyl ammonium hydroxide)為較佳。其使用量為〇·5 〜15重量％，較佳為〇· 75〜1〇重量％ ’更佳為丨· 〇〜6重量％ (C) 醇胺類化合物： 一般清洗液之組成物中之鹼性化合物，雖然單獨使用Photoresistant, this group V. Description of the invention (3) The unnecessary products for cleaning the periphery of the substrate of the color filter include: (A) 9 9 · 4 ~ 80 0% by weight of water; (B) 0 5 to 15% by weight of quaternary ammonium hydroxide compounds; (C) 0.1 to 10% by weight of several alkanolamine compounds; (D) 0 · 〇0 0 1 ~ 0 · 1% by weight of a fluorine-based surfactant; and the surface tension of the composition at 25 ° C is 60 dyne / cmi ^ The following is specific for each component (A) ~ (D, 彳 1 Ώ ν) used in the present invention That (A) water: Generally speaking, the cleaning liquid is water as the dispersing medium, and the water is the dispersing medium. It has the advantages of low toxicity, no pyrophoricity, easy management, simple waste disposal, and low cost. "(B) Hydroxyl quaternary ammonium salt type ρ: For a binder using an aery late resin as a photosensitive resin, the quaternary ammonium hydroxide used in the present invention The basic compound is preferably a basic aqueous solution prepared by using organic hydroxide quaternary ammonium salt compounds. Among them, hydrogen hydroxide Ammonium (tetramethy i ammonium hydroxide) and 2-hydroxyxyl trimethyl ammonium hydroxide are preferred. The amount used is from 0.5 to 15% by weight, preferably from 0.75 to 75. 10% by weight 'more preferably 丨 · 〇 ~ 6% by weight (C) Alcohol amine compounds: Basic compounds in the composition of general cleaning liquids, although used alone
574604 五、發明說明（4) 時其效果亦佳，但因其清洗之光阻之差異，常搭配不同種 類及比例之醇胺類化合物以提高其清洗能力；本發明之醇 胺類化合物的具體例子有：單乙醇胺（mon〇ethan〇lamine) 、二乙醇胺（diethanolamine)、三乙醇胺 (triethanolamine) 、2-(2 —氨基乙氧基）乙面享 (2-(2-aminoethoxy)ethanol)、單異丙醇胺 (mono i sopropano 1 am i ne )、二異丙醇胺 (diisopropanolamine)、三異丙醇胺 (triisopropanolamine)、正乙基乙醇胺（N — ethyl ethanolanune)及正丁基乙醇胺（N-butyl ethan〇Umine) 等化合物之至少一種或兩種以上之混合物。本發明之醇胺 類化合物之使用量為〇· 1〜1〇重量％，較佳為〇· 2〜7重旦〇/ ，更佳為0· 4〜5重量。/。。 里0 (D)氟系界面活性劑： 本發明中所使用之氟系界面活性劑並無特別限 為非離子性、陽離子性、陰離子性或兩性之任何界 σ 劑。在陰離子性及兩性界面活性劑中，因為含於=性 j金屬離子’ *造成半導體或液晶之污染’因此本：： 界面活性劑以非離子性及陽離子性較好，特別9 3之 有較好之殘渣去除能力。本發明之氟系界面活：：：：性 水性基例如氟烷基（Π uoroa 1 ky 1)、氟烯基 ^、 疏 (fluoroaikenyl)、氟炔基（flu〇r〇alkynyl) 烷基較佳。這些氟化碳素基一般為氟八烷基、，/、中以氟 (fluorooctyl)、氟十烧基（fiu〇r〇deCyi)、氣 + 一 — 丁 ~燒基574604 V. Description of the invention (4) The effect is also good, but because of the difference in photoresist for cleaning, different types and ratios of alcohol amine compounds are often used to improve its cleaning ability; Examples are: monoethanolamine, diethanolamine, triethanolamine, 2- (2-aminoethoxy) ethanol, monoethanolamine Isopropanolamine (mono i sopropano 1 am i ne), diisopropanolamine, triisopropanolamine, n-ethyl ethanolanune, and n-butyl ethanolamine (N- At least one or a mixture of two or more compounds such as butyl ethan〇Umine). The use amount of the alcohol amine compound of the present invention is from 0.1 to 10% by weight, preferably from 0.2 to 7 weights, and more preferably from 0.4 to 5 weight. /. . Li (D) fluorine-based surfactant: The fluorine-based surfactant used in the present invention is not particularly limited to any non-ionic, cationic, anionic or amphoteric σ agent. Among the anionic and amphoteric surfactants, because they are contained in the metal ions of 'sexuality', * contamination of semiconductors or liquid crystals', so this :: Surfactants are better non-ionic and cationic, especially 9 3 Good residue removal ability. The fluorine-based interfacial activity of the present invention: ::: Aqueous water-based groups such as fluoroalkyl (Πuoroa 1 ky 1), fluoroalkenyl ^, fluoroaikenyl, and fluroalkynyl alkyl are preferred. . These fluorinated carbon groups are generally fluorooctyl groups, fluorooctyl groups, fluorooctyl groups, fluorodecyl groups, and fluorooctyl groups.
第7頁 574604 五、發明說明（5) (fluorolauryl)等碳素5〜20，特別是6〜18之直鏈或分歧鏈 狀為佳。越高度氟化其去除殘渣的能力越高，因此全氣化 物更佳。疏水基及親水基之結合部位可為酯、_或酮等無 特別的限制。Page 7 574604 V. Description of the invention (5) Carbons such as (fluorolauryl) 5 to 20, especially 6 to 18, are preferably straight or branched. The higher the degree of fluorination, the higher its ability to remove residues and therefore the better the total gasification. The binding site of the hydrophobic group and the hydrophilic group may be an ester, ketone, or ketone, and the like is not particularly limited.
適合於本發明中所使用之氟系界面活性劑之舉例，非 離子性者有全氟烧基環氧乙院胺（perflu〇rC)alkyi amine ethyleneoxide)附加物、全氟烷基環氧乙烷 (perfluoroalkyl ethyleneoxide)附加物、丙烯酸全氟烷 基 S旨寡聚物（perfiuoroaikyl acrylate 〇lig0mer)等；陽 離子性者有磷酸全氟烷基酯（perf 1 uoroaIky 1 phosphate) 、全氟烷基銨鹽（perfluoroalkyl ammonium salt)等。其 中’以全氟烷基錄鹽的殘渣去除能力最強，其構成之陰離 子並黑特別限制，可為氯、氟、溴、碘等鹵離子，硝酸離 子或碟酸離子等。這泰，化合物構成之氟系界面活性劑之商 口口 ’例如公司製之 Fluorad FC-135、F-4430 及F - 430、 大曰本印墨化學工業之F-475等。 上本發明之氟系界面活性劑使用量為〇· 0 0 0丨〜〇. 1重量％ 旦，佳為0 . 〇 〇 〇 5〜〇 · 〇 5重量％。當氟系界面活性劑之使用Examples of fluorine-based surfactants suitable for use in the present invention include non-fluorinated perfluoroalkoxyamine (perfluorc) alkyi amine ethylene oxide, and perfluoroalkyl ethylene oxide. (perfluoroalkyl ethyleneoxide) add-on, acrylic perfluoroalkyl S oligomer (perfiuoroaikyl acrylate 0lig0mer), etc .; cationic ones include perf 1 uoroaIky 1 phosphate, perfluoroalkyl ammonium salt ( perfluoroalkyl ammonium salt). Among them, the salt removal of perfluoroalkyl salt is the strongest. The anion ions of its composition are particularly restricted, and can be halogen ions such as chlorine, fluorine, bromine, and iodine, nitric acid ions, or dish acid ions. In this industry, fluorinated surfactants composed of compounds are commercially available, such as Fluorad FC-135, F-4430, and F-430 manufactured by the company, and F-475 from Daikimoto Ink Chemical Industry. The use amount of the fluorine-based surfactant of the present invention is from 0.00% to 0.1% by weight, preferably from 0.00% to 5% to 0.5% by weight. When the use of fluorine-based surfactants
里而於0 · 1重量％時’其清洗液的消泡性變差，操作使用性 不良。 本發明之清洗液組成物中，當氫氧四級銨基鹽類化合 物使用量為0 · 5〜1 5重量％、醇胺類化合物使用量為〇. 1〜 1 〇重置％及氟系界面活性劑使用量為0 · 0 0 0 1〜0 · 1重量°/〇， 且組成物25 °C之表面張力為6〇 dyne/cm以下時，清洗液之When the weight is 0.1% by weight, the defoaming property of the cleaning solution is deteriorated, and the workability is poor. In the cleaning liquid composition of the present invention, when the used amount of the quaternary ammonium hydroxide compound is 0.5 to 15% by weight, the used amount of the alcohol amine compound is 0.1 to 10 and the fluorine is used. When the amount of surfactant is 0 · 0 0 0 1 ~ 0 · 1 weight ° / 〇, and the surface tension of the composition at 25 ° C is 60 dyne / cm or less,
第8頁 574604 五、發明說明（6) 洗淨效果好，殘渣少，且膨潤性及消泡性佳。 當清洗液組成物之表面張力高於60 dyne/cm時，濕潤 效果不佳，洗淨效果變差。 本發明之清洗液特別適合使用在含有著色劑之著色感 光性樹脂，上述感光性樹脂並無特別的限制，其可為正型 或負型之感光性樹脂組成物，在彩色感光性樹脂組成物方 面，其通常包含有：有機或無機之顏料（著色劑）、驗可溶 性之黏結樹脂（b i n d e r r e s i η )、感光性化合物、光起始劑 及溶劑等成份；上述鹼可溶性之黏結樹脂可為：熱塑性盼 酸樹脂（Ν ο ν ο 1 a c r e s i η )、丙烯酸酯系樹脂（a c r y 1 a t e resin)、順丁 稀二酐（Maleic anhydride)或其半酯（half ester)之聚合物、聚經基苯（polyhydroxy styrene)等， 其中以丙烯酸酯系樹脂為佳；而前述丙烯酸酯系樹脂係指 以（甲基）丙稀酸酯[(meth)acrylate]及/或（甲基）丙稀酸 [(meth)acrylic acid]為主要成份，其具體例子有： (1) 甲基丙烯酸甲酯（methyl methacrylate) /經基笨 (hydroxy styrene) / 苯乙稀（styrene)/ 甲基丙稀酸 (me thacry 1 i c acid)共聚物。 (2) 甲基丙稀酸苯曱酯（benzyl methacrylate)/曱基丙歸 酸（methacrylic acid) / 笨乙稀（styrene)共聚物。 (3) 甲基丙烯酸曱酯（methyl methacrylate) /甲基丙烯酸 (methacrylic acid) / 笨乙稀（styrene)共聚物。 (4) 甲基丙稀酸笨曱酯（benzyl methacrylate)/曱基丙埽 酸（methacrylic acid) /苯乙烯巨大單體Page 8 574604 V. Description of the invention (6) Good cleaning effect, less residue, and good swelling and defoaming properties. When the surface tension of the cleaning liquid composition is higher than 60 dyne / cm, the wetting effect is not good and the cleaning effect becomes poor. The cleaning liquid of the present invention is particularly suitable for use in a coloring photosensitive resin containing a colorant. The above-mentioned photosensitive resin is not particularly limited, and may be a positive or negative photosensitive resin composition. On the one hand, it usually contains: organic or inorganic pigments (colorants), soluble binder resin (binderresi η), photosensitive compounds, photoinitiators, and solvents; the alkali-soluble binder resin can be: thermoplastic Polymers of acid resin (N ο ν ο 1 acresi η), acrylic resin (acry 1 ate resin), maleic anhydride (maleic anhydride) or polymer of half ester thereof, polybasic benzene ( polyhydroxy styrene), etc., among which acrylate resin is preferred; and the aforementioned acrylate resin refers to (meth) acrylate [(meth) acrylate] and / or (meth) acrylate [(meth) ) acrylic acid] is the main component, and specific examples are: (1) methyl methacrylate / hydroxy styrene / styrene / styrene / methyl acrylic acid (m e thacry 1 i c acid) copolymer. (2) benzyl methacrylate / methacrylic acid / styrene copolymer. (3) Copolymer of methyl methacrylate / methacrylic acid / styrene. (4) benzyl methacrylate / methacrylic acid / styrene macromonomer
第9頁 574604 五、發明說明（7) (polystyrene macro monomer) ^ ° (5) 曱基丙烯酸甲酯（methyl methacrylate)/甲基丙稀酸 (methacrylic acid) / 苯乙烯巨大單體（polystyrene macro monomer)共聚物 ° (6) 曱基丙稀酸曱酯（methyl methacrylate)/曱基丙稀酸 苯甲酯（benzyl methacrylate)/甲基丙稀酸 (methacrylic acid)共聚物。 (7) 甲基丙稀酸（methylacrylic acid)/甲基丙嫦酸笨甲 酯（benzyl methacrylate)共聚物。 (8) 甲基丙稀酸（methylacrylic acid)/曱基丙稀酸笨曱 酯（benzyl methacrylate)/2 -經基乙基丙稀酸甲酯 (2-hydroxy ethyl methacrylate)共聚物。 【清洗液之評價方式】 一、洗淨效果：在'LCD基板上，以迴轉方式藉遠心力將光 阻劑擴散塗佈後，在基板之邊緣部份以清洗液浸潰i 〇 秒鐘，再以水沖洗，然後以目視觀察基板邊緣之光阻 劑層經過洗淨後是否為直線。 〇 直 線性 佳 Δ 直 線性 差 X 洗 邊不 良 、殘 渣 ·· 以50 倍之顯 微鏡觀察上述LCD玻璃基板上經洗 淨 後 之 洗淨 部位是 否有殘渣。 〇 • 鉦 殘渣 X I 有 殘渣Page 9 574604 V. Description of the invention (7) (polystyrene macro monomer) ^ ° (5) methyl methacrylate / methacrylic acid / polystyrene macro monomer ) Copolymer ° (6) Copolymer of methyl methacrylate / benzyl methacrylate / methacrylic acid. (7) Copolymer of methylacrylic acid / benzyl methacrylate. (8) methylacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer. [Evaluation method of cleaning liquid] I. Cleaning effect: After the photoresist is spread and coated by the telecentric force on the LCD substrate in a rotary manner, the edge of the substrate is immersed in the cleaning liquid for 〇 seconds. Rinse with water, and then visually observe whether the photoresist layer on the edge of the substrate is straight after cleaning. 〇 Straight linear good Δ straight linear poor X poor washing edge, residue ··· Using a microscope with a magnification of 50 times, observe whether there is residue on the cleaned part of the LCD glass substrate after washing. 〇 • 钲 Residue X I Yes Residue
第10頁 574604 五、發明說明（8) 三、 膨潤性：以觸針式段差測定器（Tenc〇r α -500 surf ace scan)測定，計算其清洗斷面膜庳和内側膜 厚之膜厚增加率。 〇：膜厚增加率< 5%以下 X :膜厚增加率> 5%以上 四、 消泡性：以100ml量筒盛裝所製得之清洗浪20c· c.， 並以垂直式搖盪機在適當頻率下搖盪3 〇分鐘，之後靜 置一小時後量其泡沫高度，再根據泡沫高度以如下之 基準評價： 〇：1 c m以下 X = 1 c m以上 【較佳實施例之說明】 [實施例1 ] 在4英吋之玻璃基板上，以迴轉方式藉遠心力將下述-彩色光阻劑分散塗佈在基板後，以10-2 torr真空乾燥1〇 秒後，即可形成預備形成圖像之基材；將此尚未曝光之基 材的邊緣部份浸潰於清洗液中約1 〇秒鐘，清洗基板週邊之 突起物，然後以水洗淨，洗淨後之物性如表一所示。即以 顯微鏡觀察基板邊緣，可知其洗淨效果佳、無殘渣，且清 洗液本身之消泡性及膨潤性均佳。上述清洗液之組成包含 :94. 39重量％之水、5重量％之氫氧四曱銨（tetramethyl ammonium hydroxide，以下簡稱TMAH)、0.6 重量％ 之單乙 醇胺（monoethanolamine)，以及0.01重量％之敗系界面活 性劑（3 Μ公司製之F 1 u〇r a d F C - 1 3 5 )。Page 10 574604 V. Description of the invention (8) III. Swellability: Measured with a stylus-type step difference measuring device (Tencor α-500 surf ace scan) to calculate the increase in film thickness of the cleansing mask 庳 and the inner film thickness rate. 〇: Film thickness increase rate < 5% or less X: Film thickness increase rate > 5% or more 4. Defoaming property: The cleaning wave 20c · c. Prepared in a 100ml graduated cylinder was filled with a vertical shaker at Shake for 30 minutes at an appropriate frequency, and then measure the foam height based on the foam height after standing for one hour, and then evaluate it as follows: 〇: 1 cm or less X = 1 cm or more [Description of the preferred embodiment] [Example 1] On a 4-inch glass substrate, apply the following-color photoresist to the substrate in a rotating manner by telecentric force, and then dry it at 10-2 torr for 10 seconds in a vacuum to prepare a pre-form. Imaged substrate; immerse the edge of this unexposed substrate in the cleaning solution for about 10 seconds, clean the protrusions around the substrate, and then wash with water. The physical properties after cleaning are as shown in Table 1. Show. That is, when the edge of the substrate is observed with a microscope, it can be seen that the cleaning effect is good, there is no residue, and the cleaning liquid itself has good defoaming and swelling properties. The composition of the above cleaning liquid includes: 94.39% by weight of water, 5% by weight of tetramethyl ammonium hydroxide (hereinafter referred to as TMAH), 0.6% by weight of monoethanolamine, and 0.01% by weight of failure It is a surfactant (F 1 urad FC-1 3 5 manufactured by 3M).
第11頁 574604 五、發明說明（9) 上述光阻劑組成物的成份及使用量如下表所示： 組成份 成份的具體例子 使用量 黏結劑 甲基丙烯酸-甲基丙烯酸笨甲酯共聚物 (methacrylic acid/benzyl methacrylate copolymer) S.40公克 感光性化 合物 二季戊四醇六（甲基)丙烯酸酯 (dipentaen^tluitol hexa aciylate) 〇·24公克 光起始劑 2_T基-2·氮，氮-二甲胺_1(4·嗎n林代笨基)1_ 丁圃 [2 -b enz>Tl-2 -N - dimethylaniino -1 - (4 -moipholino -phenyl) -1 -butaiione] 0.14公克 4，-雙(二匕胺)二笨甲P] [4?45-bis(diethylamine)benzophenone] 0-04公克 有機溶劑 丙二醇甲基醚醋酸酯 (Propyleneglycol methyl ether acetate) 9.54公克 顏枓 PR177(汽巴嘉基，商品名Re(lA2B) 4Ό0公克Page 11 574604 V. Description of the invention (9) The composition and usage amount of the above photoresist composition are shown in the following table: Specific examples of the component ingredients The amount used is a binder methacrylic acid-benzyl methacrylate copolymer ( methacrylic acid / benzyl methacrylate copolymer) S. 40 grams of photosensitive compound dipentaen ^ tluitol hexa aciylate 〇24 grams of photoinitiator 2_T group-2 nitrogen, nitrogen-dimethylamine _1 (4 · 吗 n 林 代 笨 基) 1_ Ding Pu [2 -b enz> Tl-2 -N-dimethylaniino -1-(4 -moipholino -phenyl) -1 -butaiione] 0.14 g 4, -double ( Dimethylamine) Dibenzyl P] [4? 45-bis (diethylamine) benzophenone] 0-04 grams of organic solvent Propyleneglycol methyl ether acetate 9.54 grams Yan Yan PR177 (Ciba Jiaji, commodity Name Re (lA2B) 4Ό0g
前述各成份以搖動式攪拌器混合。 [實施例2〜4及比較例1〜1 0 ] 同實施例Γ之操作方式，不同之處係將清洗液的組成 改變如表一所示，洗淨後之結果載於表一。 惟以上所述僅為本發明數較佳可行實施例，舉凡熟習 此項技藝人仕，其依本發明精神範疇所作之修飾或變更， 均理應包含在本案申請專利範圍内。The aforementioned ingredients are mixed with a shaker. [Examples 2 to 4 and Comparative Examples 1 to 10] The method of operation is the same as that of Example Γ, except that the composition of the cleaning liquid is changed as shown in Table 1, and the results after cleaning are shown in Table 1. However, the above are only a few of the preferred embodiments of the present invention. For those skilled in the art, modifications or changes made within the spirit and scope of the present invention should be included in the scope of patent application for this case.
第12頁 574604Page 12 574604
第13頁Page 13
Φ 574604 表一本發明各實施例及比較例之各清洗液的組成比率與實驗結果 項 a 清洗液組成(重量％) 性能 溶媒 氫氧四級銨基 鹽類化合物 醇胺類 化合物 界面活性 劑 洗淨 效果 殘渣 膨潤 性 消泡 性 表面張力 (dyne/cm) 有機溶劑 水 實 施 例 1 94.39 TMAH(5) ΜΕΑ(0·6) FC-135 (0.01) 〇 〇 〇 〇 35.2 * 2 92.79 TMAH(4.5) DEA(2.7) FC-135 (0.01) 〇 〇 〇 〇 34.4 、 3 95.88 TMAH(3.5) MEA(0.6) F-475 (0.02) 〇 〇 〇 〇 32.1 4 89.19 TMAH(4.5) TEA(6.3) FC-135 (0.05) Δ 〇 〇 〇 34.6 比 較 例 1 99.2 TMAH(O.l) MEA(0.6) FC-135 (0.1) X X 〇 〇 40·應 2 81.6 TMAH(17.5) MEA(0.7) FC-135 (0.2) X 〇 〇 X ▼ 33.2 3 95.4 TMAH(4.5) 一 FC-135 (0.1) X X X 〇 45.6 4 96.8 TMAH(3.2) — — X X X 〇 68.5 5 95.4 TMAH(2.1) DEA(2.3) — X 〇 X 〇 72.5 6 87.8 TMAH(O.l) MEA(12) FC-135 (0.1) X 〇 X 〇 32 7 醋酸甲酯 (95.8) — TMAH(3.5) MEA(0.6) FC-135 (0.1) X X X 〇 28.6 8 環己酮 (95.8) — TMAH(3.5) MEA(0.6) FC-135 (0.1) 〇 〇 X 〇 34 9 甲乙酮 (95.8) — TMAH(3.5) MEA(0.6) FC-135 (0.1) X X X 〇 24.6 10 95.8 TMAH(3.5) MEA(0.6) 十八烧基 苯磺酸鈉 (0.1) 〇 〇 〇 X Φ 54.3 11 醋酸甲酯 (95.9) 一 TMAH(3.5) MEA(0.6) — X X X 〇 42Φ 574604 Table 1 Composition ratios and experimental results of the cleaning solutions of the examples and comparative examples of the present invention Item a Cleaning solution composition (% by weight) Performance solvent Hydroxide quaternary ammonium salt compounds Alcohol amine compounds Surfactants Net effect Residue Swelling defoaming surface tension (dyne / cm) Organic solvent water Example 1 94.39 TMAH (5) MEA (0.6) FC-135 (0.01) 〇〇〇〇35.2 * 2 92.79 TMAH (4.5) DEA (2.7) FC-135 (0.01) 0.0030.0, 3 95.88 TMAH (3.5) MEA (0.6) F-475 (0.02) 0.0032.1 4 89.19 TMAH (4.5) TEA (6.3) FC-135 (0.05) Δ 〇〇〇34.6 Comparative Example 1 99.2 TMAH (Ol) MEA (0.6) FC-135 (0.1) XX 〇〇40 · 2 81.6 TMAH (17.5) MEA (0.7) FC-135 (0.2) X 〇 〇X ▼ 33.2 3 95.4 TMAH (4.5)-FC-135 (0.1) XXX 〇45.6 4 96.8 TMAH (3.2) — — XXX 〇68.5 5 95.4 TMAH (2.1) DEA (2.3) — X 〇X 〇72.5 6 87.8 TMAH (Ol) MEA (12) FC-135 (0.1) X 〇X 〇32 7 methyl acetate (95.8) — TMAH (3.5) MEA (0.6) FC-135 (0.1) XXX 〇28.6 8 cyclohexanone (95.8)— TMAH (3.5) MEA (0.6) FC-135 (0.1) 〇〇 × 〇34 9 Methyl ethyl ketone (95.8) — TMAH (3.5) MEA (0.6) FC-135 (0.1) XXX 〇24.6 10 95.8 TMAH (3.5) MEA (0.6) Sodium octadecylbenzenesulfonate (0.1) 〇〇X Φ 54.3 11 methyl acetate (95.9)-TMAH (3.5) MEA (0.6) — XXX 〇42
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