1311585 九、發明說明： 【發明所屬之技術領域】 本發明係關於水性光阻剝離液組成物其能夠剝離一已 熟成之光阻劑（cured resist)，特別是水性光阻剝離液組成物 5 其能夠將光阻劑自其所塗覆之基板，如一彩色濾光片（color filter substrate)或一薄模電晶體基板（TFT substrate)，上剝 離而再生一基板。_ 1 【先前技術】 10 通常，製成一彩色薄膜電晶體液晶顯示器（TFT-LCD) 包含數個生成步驟，在一透明基板如玻璃上，一彩色濾光 片生成一黑色矩陣樹脂（black matrix resin)及一畫素（pixel) 其包含紅色（R)、綠色（G)和藍色（B);在彩色濾光片上以濺 鍍法（sputtering method)生成一透明導電膜（transparent 15 conducting film)以作為一電極；在透明導電膜上生成一配 向膜（alignment layer);及填充液晶於液晶顯示器中。 ; 光阻劑被廣泛運用於生成彩色薄膜電晶體液晶顯示器 之配置物上，如一保護膜（overcoat)、一感光間隔材（photo spacer)、一彩色濾光片、一黑色矩陣等。然而，當光阻劑 20 以光或熱熟成之後，就無法只將錯誤配置之光阻劑從基板 去除。特別是，很難去除各種光阻劑，如環氧基（epoxy-based) 、' 環氧丙 稀瘦基 （epoxy acrylate- based) 、 丙烯 酸基紫 外線保護膜（acrylate-based UV overcoat)和_熱保護膜 (thermal overcoat)、一感光間隔材光阻、一彩色濾光片光 1311585 阻，一黑色矩陣樹脂及使用於異丙醇（IPA)和多區域垂直配 向（MVA)模式之光阻劑。如上所述，習知光阻剝離液組成 物具有一缺失’即錯誤配置之不良彩色濾光片或不良薄膜 電晶體基板沒有經過如修復與再生等再生程序就被棄置， 因為其缺乏能夠從基板上有效脫除大量熟成光阻劑之溶 劑。 為了解決上述問題，因而出現許多相關的研究。在美 國專利第5,059,500號中，揭露一些經熟成之彩色光阻可在 Ό 10毫米托耳（mmtorr)之真空及50瓦（W)工作電流（operating 10 current)的條件下以電漿脫除。但是此使用電漿之方法卻 有使用高真空、高電力、有毒氣體及設僥昂貴等缺點。 美國專利第5,756,239號中，揭露一些經熟成之彩色光 阻被小規模脫除，但是此方法並不適於應用在大規模的玻 璃基板上。 15 美國專利第5,091，103號、第 5,308,745號、第 5,102,777 號及第5，597,678號揭露一光阻剝離液其包括N-曱基石比嗔酮 (N-methylpyrrolidone)、伸烧基乙二醇醚（alkylene glycol / ether)及 1，3-二甲基-2-口米0坐琳酮（1,3-dimethyl-2-imidazo-• lidinone)以剝離一交聯之光阻薄膜（cross- linked photoresist 20 film)。然而，此剝離劑具有其可溶性不足以脫除彩色濾光 片之缺點。 韓國專利公開第2003-2664號揭露一彩色濾光片之水 性剝離液組成物其包括：（a)由無機驗性氫氧化物 (inorganic alkaline hydroxide)、 一烧基銨氫氧化物 1311585 (alkylammonium hydroxide)、烧基芳香基I安氳氧化物 (alkylarylammonium hydroxide)所組成之群族，（b)伸炫基 乙二醇醚（alkylene glycol ether) ’（c)水性胺（aqueous amine compound)，及（d)水。然而，此水性剝離液之缺點在於其修 5 復過程的時間增長，其原因在於其對熱保護膜的剝離速率 緩慢。 【發明内容】 J 因此，本發明係為解決上述先前技術之缺失而產生， 10 故本發明之一目的在提供水性光阻剝離液組成物以輕鬆脫 除各種在薄膜電晶體液晶顯示器製造過程中所產生而不易 經由習知方法脫除之光阻劑，該光阻劑係選自於環氧基、 環氧丙烯酸基、丙烯酸基紫外線保護膜和熱保護膜、一感 光間隔材光阻、一彩色濾光片光阻，一黑色矩陣樹脂及使 15 用於異丙醇（IPA)和多區域垂直配向（MVA)模式之族群者， 且本發明可以將剝離過程中下層金屬層和玻璃基板的受腐 蝕程度降到最低，將剝離液之替換週期增至最大，因為其 蒸氣損失率低且其大規模再生彩色基板和薄膜電晶體基板 的剝離速率高。 20 為達成上述目的，本發明提供水性光阻剝離液組成 物，其根據組成物之總重，包括0.3至15重量百分比之無機 驗性化合物；0.1至12重量百分比之四烧基銨氫氧化物化合 (tetraalkylammonium hydroxide compound) ； 0.1 至 40 重量 百分比之水溶性有機溶劑；及33至99.5重量百分比之水。 1311585 【實施方式】 以下，將詳細說明本發明之較佳實施例。 本發明之水性光阻剝離液組成物包括一無機鹼性化合 物。該無機鹼性化合物的作用在於減弱鍵結成份和/或組成 5 剝離液組成物之經熟成之多功用單體之間的鍵結力而可容 易將一光阻劑自一玻璃表面脫除。無機驗性化合物之一例 子可以包括，但不限定於’碳酸納（sodium carbonate)、礙 酸钟（potassium carbonate)、石夕酸納（sodium silicate)、石夕酸 鉀(potassium silicate)、氫氡化鈉（sodium hydroxide)、氫氧 10 化鉀(P〇tassium hydroxide)等，只要其具有上述作用即可。 其中較佳為使用氫氧化鈉或氫氧化卸。 本發明中’根據剝離液組成物之總重，該無機鹼性化 合物之含量為0.3至15重量百分比。該無機鹼性化合物含量 若低於0.3重量百分比，會有剝離性不良之缺失，而其含量 15若超過15重量百分比，則會有因水分蒸發及有機溶劑的關 係而使一有機鹽和一無機鹼性化合物沈澱成固狀的缺失， 、一進而造成玻璃基板嚴重的損傷。無機鹼性化合物較佳含量 為1至7重量百分比。 四.烧基兹氧化物化合物（tetraaikyiammonium 20 hydroxide comP〇und) ’其包含於本發明之水性光阻剝離液 組成物中，如下列化學式1所示： 【化學式1】 13115851311585 IX. Description of the Invention: [Technical Field] The present invention relates to an aqueous photoresist stripper composition capable of peeling off a cured resist, in particular an aqueous photoresist stripper composition 5 The substrate can be regenerated by stripping the photoresist from a substrate to which it is applied, such as a color filter substrate or a thin film substrate. _ 1 [Prior Art] 10 Generally, a color thin film transistor liquid crystal display (TFT-LCD) is formed by a plurality of generating steps. On a transparent substrate such as glass, a color filter generates a black matrix resin (black matrix). And a pixel containing red (R), green (G), and blue (B); a transparent conductive film is formed on a color filter by a sputtering method (transparent 15 The film is used as an electrode; an alignment layer is formed on the transparent conductive film; and the liquid crystal is filled in the liquid crystal display. Photoresists are widely used in the formation of color thin film transistor liquid crystal display devices, such as an overcoat, a photo spacer, a color filter, a black matrix, and the like. However, when the photoresist 20 is cooked by light or heat, it is impossible to remove only the misconfigured photoresist from the substrate. In particular, it is difficult to remove various photoresists such as epoxy-based, epoxy acrylate-based, acrylate-based UV overcoat and heat. Thermal overcoat, a photo spacer photoresist, a color filter light 1311585, a black matrix resin and a photoresist used in isopropyl alcohol (IPA) and multi-region vertical alignment (MVA) mode. As described above, the conventional photoresist stripping liquid composition has a defective 'that is, a misconfigured bad color filter or a poor thin film transistor substrate is discarded without undergoing a regeneration process such as repair and regeneration because its lack can be effective from the substrate. Remove a large amount of solvent from the mature photoresist. In order to solve the above problems, many related studies have appeared. In U.S. Patent No. 5,059,500, it is disclosed that some of the matured color resists can be removed by plasma under the conditions of a vacuum of 毫米10 mm (mmtorr) and an operating current of 50 watts (W). However, the method of using plasma has the disadvantages of using high vacuum, high power, toxic gas and expensive installation. In U.S. Patent No. 5,756,239, it is disclosed that some of the matured color resists are removed on a small scale, but this method is not suitable for use on large-scale glass substrates. U.S. Patent Nos. 5,091,103, 5,308,745, 5,102,777, and 5,597,678 disclose a photoresist stripping solution comprising N-methylpyrrolidone, an extended alkyl glycol ether. (alkylene glycol / ether) and 1,3-dimethyl-2-imidazo-• lidinone to strip a cross-linked photoresist film (cross-linked) Photoresist 20 film). However, this release agent has the disadvantage that its solubility is insufficient to remove the color filter. Korean Patent Publication No. 2003-2664 discloses an aqueous stripping liquid composition of a color filter comprising: (a) an inorganic alkaline hydroxide, an alkyl ammonium hydroxide 1311585 (alkylammonium hydroxide) ), a group consisting of alkylarylammonium hydroxide, (b) alkylene glycol ether '(c) aqueous amine compound, and d) water. However, this aqueous stripping solution has a drawback in that the time for the repair process is increased because of the slow rate of peeling off the heat protective film. SUMMARY OF THE INVENTION Therefore, the present invention has been made to solve the above-mentioned shortcomings of the prior art, and it is therefore an object of the present invention to provide an aqueous photoresist stripping liquid composition for easy removal of various thin film transistor liquid crystal display manufacturing processes. a photoresist which is produced and is not easily removed by a conventional method, and is selected from the group consisting of epoxy groups, epoxy acrylate groups, acrylic-based ultraviolet protective films and thermal protective films, and photosensitive spacer photoresists. Color filter photoresist, a black matrix resin and a group of 15 for isopropyl alcohol (IPA) and multi-region vertical alignment (MVA) modes, and the present invention can be used for the lower metal layer and the glass substrate during the stripping process. The degree of corrosion is minimized, and the replacement cycle of the stripper is maximized because of its low vapor loss rate and high peeling rate of the large-scale regenerated color substrate and thin film transistor substrate. In order to achieve the above object, the present invention provides an aqueous photoresist stripping liquid composition comprising 0.3 to 15% by weight of an inorganic compound according to the total weight of the composition; 0.1 to 12% by weight of a tetraalkylammonium hydroxide Tetraalkylammonium hydroxide compound; 0.1 to 40% by weight of a water-soluble organic solvent; and 33 to 99.5% by weight of water. [Embodiment] Hereinafter, preferred embodiments of the present invention will be described in detail. The aqueous photoresist stripper composition of the present invention comprises an inorganic basic compound. The inorganic basic compound functions to reduce the bonding force between the bonding component and/or the matured monomer of the composition of the composition 5 to facilitate the removal of a photoresist from a glass surface. An example of an inorganic test compound may include, but is not limited to, 'sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, hydroquinone Sodium hydroxide, P〇tassium hydroxide, etc., as long as they have the above effects. Among them, it is preferred to use sodium hydroxide or hydroxide to discharge. In the present invention, the inorganic basic compound is contained in an amount of from 0.3 to 15% by weight based on the total mass of the peeling liquid composition. If the content of the inorganic basic compound is less than 0.3% by weight, there is a lack of peeling property, and if the content of 15 is more than 15% by weight, an organic salt and an inorganic substance may be caused by evaporation of water and an organic solvent. The alkaline compound precipitates into a solid form, which in turn causes severe damage to the glass substrate. The inorganic basic compound is preferably contained in an amount of from 1 to 7 % by weight. 4. The tetrakiykilium oxide compound (tetraaikyiammonium 20 hydroxide comPundund) is contained in the composition of the aqueous photoresist stripper of the present invention, as shown in the following Chemical Formula 1: [Chemical Formula 1] 1311585
RR
OH R2-n+-r4 r3 其中，心至^係獨立地為可被取代的烷基或不可被取 代的烷基。不可被取代的烷基包括具有1至4個碳原子之烷 基，其係選自由曱基（methyl group)、乙基（ethyl group)、n-5 丙基（n-propyl group)、n-丁基（n-butyl group)等之基團所組 成者。而可被取代的烷基較佳為一具1至4個碳原子烷基， 該烷基中之氫原子可以被羥基、烷氧基或羥烷基 (hydroxyalkyl)取代，可被取代的烧基的例子包括2-羧乙基 (2-hydroxy ethyl group) 、 3-經丙基（3-hydroxy propyl 10 group)、4-經丁基（4-hydroxy butyl group)、2-甲氧基乙基 (2-methoxyethyl group) 、 2-(2-經乙.氧）乙基 (2-(2-hydroxyethoxy) ethyl group)等。四烧基铵氫氧化物化 合物(tetraalkylammonium hydroxide compound)的例子包 括四甲基銨氫氧化物（tetramethyl ammonium hydroxide)、 13 四乙基銨氫氧化物（tetraethylammonium hydroxide)、四正丙 基銨氳氧化物（tetra n-propylammonium hydroxide)、四正丁 基銨氳氧化物（tetra n-butylammonium hydroxide)、四（2-經 乙基）銨氫氧化物（tetra(2- hydroxyethyl)ammonium hydroxide)、三曱基（2-經乙基）敍氫氧化物 20 (trimethyl(2-hydroxyethyl) ammonium hydroxide)、三曱基 2-(2-經乙氧）乙基銨氫氧化物（trimethyl2-(2-hydroxy ethoxy)ethylammonium hydroxide)、二曱基二乙基錄氫氧化 1311585 物（dimethyldiethylammonium hydroxide)等。上述化合物可 以單獨使用也可以混和使用。 四烷基銨氫氧化物，其主要作用在於將紅、綠、藍光 之彩色光阻自彩色濾光片上移除，其含量依據本發明水性 5 光阻剝離液組成物之總重，而為〇. 1至12重量百分比且較佳 的為0.1至8重量百分比。四烧基錄氫氧化物的含量若低於 0 · 1重量百分比，則其具有不良的光阻劑剝離性，而其含量 若超過12重量百分比，雖然其具有能輕鬆剝離光阻劑的優 點，但是卻會造成玻璃基板的腐#。 10 本發明之水性光阻剝離液組成物包括一水溶性有機溶 劑。該水溶性有機溶劑只膨脹光阻劑中被熟成的部分，故 可有效地將該經熟成的部分從基板上剝離，且其可特別有 效運用於熱保護膜之脫除。 該水溶性有機溶劑包括氨類（amides)如二甲基亞硬 15 (dimethylsulfoxide)、N-曱基-2- °比口各 _ (N-methyl-2-pyrrolidinone)、N-乙基 2-°比洛酮.(N-ethyl-2-pyrrolidinone)、 / N-丙基-2-0比洛酮（N-propyl-2-pyrrolidinone)、.N-經甲基-2- 0比 口各酮（N-hydroxymethyl-2-pyrrolidinone)、N-經-2-乙基 °比 洛酮（N-hydroxyethyl-2-pyrrolidinone)、N-曱基曱醯胺 2〇 (N-methylformamide)、N，N-二曱基曱醯胺（N，N-dimethyl -formamide)、N-甲基乙醯胺（N-methylacetamide)、N-二曱 基乙醯胺（N-dimethylacetamide)、N，N、-二曱基乙醯胺 (Ν,Ν-dimethyl acetamide) 、 Ν,Ν-二乙基乙酿胺 (Ν,Ν-diethylacetamide)等；諷類（sulfones)如二甲颯 10 1311585 (dimethylsulfone)、二乙颯（diethyl- sulfone)、雙（2-經乙基） 石風(bis(2-hydroxyethyl)sulfone)、四亞曱 基石風 (tetramethylenesulfone)等；醇類如甲醇（methylalcohol)、乙 醇（ethyl alcohol)、丙醇（propylalcohol)、丁醇（butyl 5 alcohol)、戊醇（pentylalcohol)、己醇（hexyl alcohol)、異丙 醇（isopropylalcohol)、異丁醇（isobutylalcohol)等及其衍生 物。以上化合物可獨立使用或混和使用。 上述水溶性有機溶劑之含量，依據水性剝離液組成物 一 j 的總重，而為0.1至40重量百分比，且較佳的為1至3〇重量百 10 分比。該水溶性有機溶劑之含量若少於〇. 1重量百分比，則 對光阻劑的膨脹效果不良因而造成其剝離性不良，而該水 溶性有機溶劑的含量若超過40重量百分比，其雖然會顯現 出絕佳的光阻劑膨脹效果’但是卻會有因組成物穩定性降 低而使用時間增長之不良剝離性。 15 本發明之水性光阻剝離液組成物中，水可以作為一溶 劑，因其係一環保溶劑且其具有穩定及抗易燃之剝離性等 )特性。使用於本發明水性光阻剝離液組成物之水較佳為純 水或超純水（ultra pure water)如離子交換水（i〇n_exchanged water)、蒸餾水等，且其含量依本發明組成物之總重，而為 20 33至99.5重量百分比。 同時’ 一胺化合物或一含伸烷基乙二醇基（alkylene glycol-based)之有機溶劑更可以添加以增進本發明水性光 阻剝離液組成物之剝離性。由於鈦（Ti)和鋁（A1)的腐蝕性， 該複合胺較佳為在251：的水溶液中具有酸分解常數（acid 11 1311585 dissociation constant, pH)7.5至 13.5之負對數。胺化合物之 一例子包括燒醇胺類（alkanol amines)如經胺 (hydroxylamine)、乙酵胺（monoethanolamine)、二乙醇胺 (diethanolamine)、三乙醇胺（triethanolamine)、2-(2-氨基乙 5 氧基）乙醇（2-(2-(aminoethoxy)ethanol)、Ν,Ν-二曱基乙基胺 (Ν,Ν-dimethylethylamine) 、 Ν,Ν-二乙 基醇胺 (Ν,Ν-diethylethanolamine) 、 Ν,Ν-二丁 基醇胺 (Ν,Ν-dibutylethanolamine) 、 Ν- 曱 基醇胺 w (N-methylethanolamine) 、 N- 乙 基醇胺 10 (N-ethylethanolamine)、N-丁 基醇胺（N-butylethanolamine)、 N-甲基二乙醇胺（N-methyl diethanolamine)、單異丙醇胺 (monoisopropanol- amine)、三異丙醇月安（triisopropanolamine) 等；聚伸燒基多胺類（polyalkylene polyamines)如二伸乙烧. 三胺 （diethylenetriamine)、.三伸 乙 烧.四.胺 15 (triethylenetetraamine)、伸丙二胺（propylene- diamine)、Ν,Ν-二乙基伸乙二胺（N，N-diethyl ethylenediamine)、Ν,Ν’-二乙 基伸乙二胺（N，N’-diethylethylenediamine)、1，4- 丁二胺 (1,4-butanediamine) 、N-乙基伸乙二胺（N-ethyl-ethylenediamine)、1,2-丙二胺（l，2-propane- diamine)、1,3-20 丙二胺（l，3-propanediamine) 、 1,6-己二胺 (l，6-hexanediamide)等；脂肪胺基類（aliphatic amines)如 2-乙基己胺（2-ethyl- hexylamine)、二辛基胺.(dioctylamine)、 三丁胺（tributylamine)、三丙胺（tripropylamine)、庚胺 (heptylamine)、環己胺（cyclohexyl amine)等；芳香胺類 12 1311585 -: (aromatic amines)如苯甲胺（benzyl_ amine)、二苯胺 (diphenylamine)等’環形胺（叮化^ amines)如派嗓 (piperazine)、N-甲基哌嗪（N_ methyl_piperazine)、曱基哌嗪 (methyl- piperazine)、羥基乙基哌嗓(hydroxylethyl_ 5 piperazine)等。上述化合物中最佳為使用單乙醇胺、2_(2_ 氨基乙氧基）乙醇、二伸乙三胺、三伸乙四胺、環己胺及哌 嗪。該胺化合物之含量根據組成物之總重及其穩定性與剝 離性可為1至30重量百分比。 — 此外，含伸烷基乙二醇基之有機溶劑包括，但不限定 10 於’一二甘醇（carbitols)有機溶劑如甲基二甘醇 (methylcarbitol)、乙基二甘醇（ethylcarbitol)、丁基二甘醇 (butyl carbitol); — 多元醇（polyhydric alcohols)之乙二醇有 機溶劑如乙二醇（ethylene glycol)、乙二醇甲醚（ethylene glycol monomethyl ether)、乙二醇乙醚（ethylene glycol 15 monoethyl ether)、乙二醇 丁 _ (ethylene glycol monobutyl ether)、乙二醇甲謎醋酸醋（ethylene glycol monome.thyl ether acetate) 、. 乙 二 醇.乙 躂 醋.酸 西旨 " (ethyleneglycolethyletheracetate) 、.二 甘 醇 . (diethyleneglycol)、二乙二醇甲醚（diethylene glycol 2〇 monomethyl ether)、二乙二醇乙醚（diethylene glycol monoethyl ether)、二乙二醇丁醚（diethylene glycol monobutyl ether);及其衍生物。其可以單獨使用或混合使 用。根據組成物之總重，該伸烷基乙二醇基之有機溶劑之 含量依其剝離性和水容性可為1至45重量百分比。 13 1311585 且，一界面活性劑（surfactant)可以添加以便更有效地 移除光阻劑成分。界面活性劑之作用在於降低光阻薄膜與 玻璃基板之間的相互作用力’因而降低表面能（surface energy)以讓一驗性化合物和一有機溶劑可滲透入一光阻塗 5 覆薄膜，最後提供玻璃基板優良之剝離性。此外，界面活 性劑可以避免讓已經剝離之光阻劑成分再次依附於玻璃基 板上，並且也可以避免水性剝離液因氧化作用而被漂白， 即使長時間使用亦然。界面活性劑並無特別限定，只要其 j 能夠使用於水性光阻剝離液即可。例如，界面活性劑包括 .... _ 10 亞礙基（sulfoxide-based)或羧基（carboxy-based)陽子界面活 性劑（cationic surfactant)如烧基苯續酸鹽（alkylbenzene sulfonate)、烧基硫酸鹽（alkyl-sulfate)、聚氧烧基鱗硫酸鹽 (polyoxyalkyl-ethersulfate)、烧烴磺酸（alkansulfonate)、聚 氧化乙烯烧基趟叛酸甲_醋（polyoxyethylene alkylether 15 methylcarboxylate)、烧基填酸酯（alkyl-phosphate)、烧基確 基琥 ίό 酸醋（alkylsulfo- succinate)、稀烴確酸 (olefinsulfonate)、艾斯基醯胺烧基硫酸酯（aceylamidoalkyl sulfate)、艾斯基肉胺酸醋（aceylsarcosinate)、.萘確酸納福馬 林濃縮物（sodium naphthalene sulfonate formalin condensate) 20 等’或具5至20重量百分比環氧乙烧加成物（ethylene oxide adduct)之非離子界面活性劑，其可以單獨使用或混合使 用。根據組成物之總重，界面活性劑之含量依其添加物之 效果和水性剝離液處理後之水洗特性較佳為〇.〇5至10重量 百分比。 14 1311585 本發明之水性光阻剝離液組成物顯現一優良之剝離 性’一下層基板之極低腐蝕度，及一低蒸發和熟成特性。 本水性剝離液組成物亦允許玻璃基板之大量製造，因其對 環境污染低，且’如上所述’使用水作為組成物之一溶劑 5 而在此範疇中能夠保持穩定地作用。因此，不像習知彩色 慮光片或薄膜電晶體基板因錯誤的組裝而造成浪費，本發 明水性光阻剝離液組成物所得之彩色瀘光片或薄膜電晶體 基板可以有效地脫除在彩色濾光片和薄膜電晶體基板上大 v $的各種光阻劑，因而使彩色濾光片和薄膜電晶體基板可 10 被再利用。 此後，將配合圖表說明本發明之較佳實施例。在說明 之别’應瞭解說明書及申請專利範圍中所使用之專有名詞 並非限疋於般的或字面的意義，而是依本發明之技術範 15 20 圍相關之思思與觀點詮釋，故創作人可對該專有名詞作最 適切的全釋與^義。因&，以下的說明僅係為了方便說明 而舉例而已，而非限定本專利之範圍，其他相同或經修改 而不離本發明之精神與範圍者，亦可包含在本發明之專利 範圍内。 f施例】-1 6 無機 … 化σ物、水、一四烷基銨氫氧化物及一水 溶性有椽溶劑依下# 下表1所列之ΐ添加入一配有攪拌器之容 、。。而《所得之混合物在室溫下以轉速至_啊授摔 違0.5至3小時1取得水㈣㈣組成物。 【表1】 15 1311585 亲1 離劑組成物（重量百分比） 無機鹼性 四烷基敍 水溶性有 伸烷基乙 水性脂肪 界面活 化 氫 機 二醇基之 胺 水 性 合物 氧化物 溶劑 有機溶劑 化合物 劑 實驗例1 KOH TMAH NMP - - 69 - 1 10 20 - - - 實驗例2 NaOH TMAH NMP - - 71 - 9 5 15 - - - 實驗例3 KOH TEAH NMP - - 63 - 1 11 25 - - - 實驗例4 KOH TPAH NMP - - 53 - 5 12 30 - - — 實驗例5 KOH TMAH NMP - - 73 - 9 3 15 - - 一 實驗例6 KOH TMAH DMAC - - 75 - 9 1 15 - - - 實驗例7 KOH TMAH BzOH - - 72 - 11 2 15 - - - 實驗例8 KOH TMAH DMSO - - 68 - 7 10 15 - - - 實驗例9 KOH TMAH 異丙醇 - - 68 - 7 10 15 - - - 實驗例 KOH TMAH 丁醇 - - 68 - 10 7 10 15 - - - 實驗例 KOH TMAH NMP EC - 63 11 7 10 10 10 - - 實驗例8 KOH TMAH NMP BDG - 63 - 7 10 10 10 - - 實驗例 KOH TMAH NMP - HDA 63 - 12 7 10 10 - 10 - 實驗例 KOH TMAH NMP - MEA 63 - 13 7 10 10 - 10 - 實'驗例 KOH TMAH NMP EC MEA 53 - 14 7 10 10 10 10 - 實驗例 KOH TMAH NMP EC MEA 54 K-290 15 7 8 10 10 10 1 實驗例 KOH TMAH NMP EC MEA 54 OP-10 16 7 8 10 10 10 1 比較例1-3 以備製上述實施例1 -16之方法備製水性光阻剝離液組 成物，唯其係依據下列表2之成分與含量備製而成。 5 【表2】 彔丨. 離劑組成物（重量百分比） KOH TMAH NMP ' DI 比較例1 - 15 30 55 比較例2 20 - 30 50 16 1311585OH R2-n+-r4 r3 wherein the heart is independently an alkyl group which may be substituted or an alkyl group which may not be substituted. The alkyl group which may not be substituted includes an alkyl group having 1 to 4 carbon atoms selected from a methyl group, an ethyl group, an n-5 propyl group, n- A group consisting of a group such as an n-butyl group. The alkyl group which may be substituted is preferably an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom in the alkyl group may be substituted by a hydroxy group, an alkoxy group or a hydroxyalkyl group, and a substituted alkyl group may be substituted. Examples include 2-hydroxy ethyl group, 3-hydroxy propyl 10 group, 4-hydroxy butyl group, 2-methoxyethyl group. (2-methoxyethyl group), 2-(2-hydroxyethoxy) ethyl group, and the like. Examples of the tetraalkylammonium hydroxide compound include tetramethyl ammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide (tetra n-propylammonium hydroxide), tetra n-butylammonium hydroxide, tetra(2-hydroxyethyl)ammonium hydroxide, triterpene (2-ethylethyl) ammonium hydroxide, trimethyl 2-(2-ethoxy ethoxy) Ethylammonium hydroxide, dimethyldiethylammonium hydroxide, and the like. The above compounds may be used singly or in combination. a tetraalkylammonium hydroxide whose main function is to remove the color resist of red, green and blue light from the color filter according to the total weight of the aqueous 5 photoresist stripper composition of the present invention. 1. 1 to 12% by weight and preferably 0.1 to 8% by weight. If the content of the four-burning hydroxide is less than 0.1% by weight, it has poor photoresist stripping property, and if the content exceeds 12% by weight, although it has the advantage of easily peeling off the photoresist, But it will cause the rot of the glass substrate #. The aqueous photoresist stripper composition of the present invention comprises a water-soluble organic solvent. The water-soluble organic solvent swells only the matured portion of the photoresist, so that the matured portion can be effectively peeled off from the substrate, and it can be particularly effectively used for the removal of the thermal protective film. The water-soluble organic solvent includes amides such as dimethylsulfoxide, N-methyl-2-pyrrolidinone, N-ethyl 2- °N-ethyl-2-pyrrolidinone, / N-propyl-2-0 pirenone (N-propyl-2-pyrrolidinone), .N-methyl-2-0 ratio N-hydroxymethyl-2-pyrrolidinone, N-hydroxyethyl-2-pyrrolidinone, N-methylformamide, N, N-N-dimethyl-formamide, N-methylacetamide, N-dimethylacetamide, N, N, - Dimethyl acetamide, hydrazine, hydrazine-diethylacetamide, etc.; sulfones such as dimethylhydrazine 10 1311585 (dimethylsulfone), two Diethyl-sulfone, bis(2-ethylethyl)sulfone, tetramethylenesulfone, etc.; alcohols such as methylalcohol, ethyl alcohol ), propylalcohol, butanol (butyl 5 alcohol) , pentemylcohol, hexyl alcohol, isopropylalcohol, isobutylalcohol, and the like, and derivatives thereof. The above compounds can be used independently or in combination. The content of the above water-soluble organic solvent is from 0.1 to 40% by weight, based on the total weight of the aqueous stripper composition, and preferably from 1 to 3 parts by weight. If the content of the water-soluble organic solvent is less than 0.1% by weight, the effect of swelling the photoresist is poor, thereby causing poor peelability, and if the content of the water-soluble organic solvent exceeds 40% by weight, it may appear. An excellent photoresist expansion effect is produced, but there is a poor peeling property due to a decrease in the stability of the composition and a prolonged use time. In the composition of the aqueous photoresist stripping liquid of the present invention, water can be used as a solvent because it is an environmentally friendly solvent and has stable and antiflammable peeling properties. The water used in the composition of the aqueous photoresist stripper of the present invention is preferably pure water or ultra pure water such as ion exchanged water, distilled water, etc., and the content thereof is according to the composition of the present invention. The total weight is 20 33 to 99.5 weight percent. Meanwhile, an 'monoamine compound or an alkylene glycol-based organic solvent may be added to enhance the releasability of the aqueous resist stripper composition of the present invention. Due to the corrosive nature of titanium (Ti) and aluminum (A1), the composite amine preferably has a negative logarithm of an acid decomposition constant (pH 11 7.5585 dissociation constant, pH) of 7.5 to 13.5 in an aqueous solution of 251:. Examples of the amine compound include alkanol amines such as a hydroxylamine, a monoethanolamine, a diethanolamine, a triethanolamine, and a 2-(2-aminoethyl-5-oxyl group). Ethanol (2-(amino)ethanol), hydrazine, hydrazine-dimethylethylamine, hydrazine, hydrazine-diethylethanolamine, hydrazine , Ν-dibutylethanolamine, --mercaptoethanolamine, N-ethylethanolamine, N-butyl alcoholamine (N-butyl alcoholamine) -butylethanolamine), N-methyl diethanolamine, monoisopropanol-amine, triisopropanolamine, etc.; polyalkylene polyamines For example, diethylenetriamine, triethylenetetramine, tetraethylenetetraamine, propylene-diamine, hydrazine, hydrazine-diethylethylenediamine (N, N) -diethyl ethylenediamine), Ν,Ν'-diethylethylenediamine (N,N'-diethylethylened Iamine), 1,4-butanediamine, N-ethyl-ethylenediamine, 1,2-propane-diamine, 1, 3-propanediamine, 1,6-hexanediamide, etc.; adiphatic amines such as 2-ethylhexylamine (2- Ethyl-hexylamine, dioctylamine, tributylamine, tripropylamine, heptylamine, cyclohexyl amine, etc.; aromatic amines 12 1311585 -: ( Aromatic amines) such as benzylamine, diphenylamine, etc. 'ring amines such as piperazine, N-methyl piperazine, decylpiperazine Methyl-piperazine), hydroxyethylethylhydrazine (hydroxylethyl_ 5 piperazine), and the like. Among the above compounds, monoethanolamine, 2-(2-aminoethoxy)ethanol, diethylenetriamine, triethylenetetramine, cyclohexylamine and piperazine are preferably used. The content of the amine compound may be from 1 to 30% by weight based on the total weight of the composition and its stability and peeling property. — In addition, the organic solvent containing an alkylene glycol group includes, but is not limited to, 10 carbitols organic solvents such as methylcarbitol, ethylcarbitol, Butyl carbitol; — glycolic organic solvents such as ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol ether (ethylene) Glycol 15 monoethyl ether), ethylene glycol monobutyl ether, ethylene glycol monome.thyl ether acetate, ethylene glycol, ethyl vinegar, acid Ethyleneglycolethyletheracetate), diethyleneglycol, diethylene glycol 2〇monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether ); and its derivatives. They can be used alone or in combination. The content of the alkyl glycol group-containing organic solvent may be from 1 to 45% by weight, based on the total weight of the composition, depending on the peelability and water solubility. 13 1311585 Also, a surfactant can be added to more effectively remove the photoresist component. The role of the surfactant is to reduce the interaction between the photoresist film and the glass substrate, thus reducing the surface energy to allow an organic compound and an organic solvent to penetrate into a photoresist film. Provide excellent peelability of the glass substrate. In addition, the surfactant prevents the stripped photoresist component from being attached to the glass substrate again, and also prevents the aqueous stripper from being bleached by oxidation, even when used for a long period of time. The surfactant is not particularly limited as long as it can be used for the aqueous photoresist stripping solution. For example, surfactants include .... _ 10 sulfoxide-based or carboxy-based cationic surfactants such as alkylbenzene sulfonate, sulphur-based sulphuric acid Alkaline-sulfate, polyoxyalkyl-ethersulfate, alkansulfonate, polyoxyethylene alkylether 15 methylcarboxylate, burnt acid Alkyl-phosphate, alkylsulfo-succinate, olefinsulfonate, aceylamidoalkyl sulfate, eskesidine vinegar (aceylsarcosinate), sodium naphthalene sulfonate formalin condensate 20 or the like or a nonionic surfactant having 5 to 20 weight percent ethylene oxide adduct Can be used alone or in combination. Depending on the total weight of the composition, the surfactant content is preferably from 5% to 10% by weight, based on the effect of the additive and the water wash characteristics after treatment with the aqueous stripper. 14 1311585 The aqueous photoresist stripper composition of the present invention exhibits an excellent peelability 'very low corrosion of the underlying substrate, and a low evaporation and ripening characteristics. The aqueous stripper composition also allows for the mass production of a glass substrate because it is low in environmental pollution, and the use of water as one of the solvents 5 as described above can maintain a stable action in this category. Therefore, unlike the conventional color light-receiving sheet or the thin film transistor substrate, which is wasteful due to erroneous assembly, the color light-receiving sheet or the thin film transistor substrate obtained by the composition of the aqueous photoresist stripping liquid of the present invention can be effectively removed in color. Various photoresists of large v $ on the filter and the thin film transistor substrate, thereby allowing the color filter and the thin film transistor substrate 10 to be reused. Hereinafter, preferred embodiments of the present invention will be described in conjunction with the drawings. In the description, the proper nouns used in the description and the scope of the patent application are not limited to the meaning of the general or the literal, but are based on the thinking and viewpoints of the technical scope of the invention. The creator can make the most appropriate full interpretation of the proper noun. The following descriptions are intended to be illustrative only, and not to limit the scope of the invention, and the scope of the invention may be included in the scope of the invention. fExample]-1 6 Inorganic... Sigma, water, tetraalkylammonium hydroxide and a water-soluble hydrazine solvent. # The following Table 1 is added to a tank equipped with a stirrer. . . And the mixture obtained at room temperature at a speed of _ ah owed off 0.5 to 3 hours 1 to obtain water (4) (four) composition. [Table 1] 15 1311585 Pro- 1 agent composition (% by weight) Inorganic alkaline tetraalkyl water-soluble alkylene glycol aqueous fat interface activated hydrogen diol-based amine water-based compound oxide solvent organic solvent compound Experimental Example 1 KOH TMAH NMP - - 69 - 1 10 20 - - - Experimental Example 2 NaOH TMAH NMP - - 71 - 9 5 15 - - - Experimental Example 3 KOH TEAH NMP - - 63 - 1 11 25 - - - Experiment Example 4 KOH TPAH NMP - - 53 - 5 12 30 - - - Experimental Example 5 KOH TMAH NMP - - 73 - 9 3 15 - - Experimental Example 6 KOH TMAH DMAC - - 75 - 9 1 15 - - - Experimental Example 7 KOH TMAH BzOH - - 72 - 11 2 15 - - - Experimental Example 8 KOH TMAH DMSO - - 68 - 7 10 15 - - - Experimental Example 9 KOH TMAH Isopropanol - - 68 - 7 10 15 - - - Experimental Example KOH TMAH Butanol - - 68 - 10 7 10 15 - - - Experimental Example KOH TMAH NMP EC - 63 11 7 10 10 10 - - Experimental Example 8 KOH TMAH NMP BDG - 63 - 7 10 10 10 - - Experimental Example KOH TMAH NMP - HDA 63 - 12 7 10 10 - 10 - Experimental example KOH TMAH NMP - MEA 63 - 13 7 10 10 - 10 - Real test case KOH TMAH NMP EC MEA 53 - 14 7 10 1 0 10 10 - Experimental example KOH TMAH NMP EC MEA 54 K-290 15 7 8 10 10 10 1 Experimental example KOH TMAH NMP EC MEA 54 OP-10 16 7 8 10 10 10 1 Comparative Example 1-3 In order to prepare the above implementation The method of Example 1-16 prepares the composition of the aqueous photoresist stripper, which is prepared according to the composition and content of Table 2 below. 5 [Table 2] 离. Offset composition (% by weight) KOH TMAH NMP ' DI Comparative Example 1 - 15 30 55 Comparative Example 2 20 - 30 50 16 1311585
- 比較例 3 1 20 I 15 1 - 1 65 I 在表 1 和表 2 中 ’ KOH為氫氧化 If (potassium hydroxide)， TMAH為四曱基錢氫氧化物 （tetramethyl- ammonium hydroxide) ， TEAH為四乙基録氫氧化物 (tetraethylmmonium hydroxide)，TP AH 為四丙基敍氫氧化物 5 (tetrapropylammonium hydroxide)，NMP為 N-曱基n比口各烧酮 (N-methyl pyrrolidone)，DMSO 為二甲亞石風（dimethyl sulfoxide)，BzOH為苯甲醇（benzyl alcohol)，BDG為二丁二 醇（butyldiglycol)，EC為乙基二甘醇（ethylcarbitol)，HDA為 i 經胺 （hydroxyl amine)· ， MEA 為單乙醇胺 10 (monoethanolamine)，DMAC 為 N，N -二甲基乙醯胺 (N，N-dimethyl- acetamide)，DI為超純水，K-290 為陽子界面 活性劑其得自於漢儂化學公司（Hannong Chemicals Inc.)， 及ΡΟ-ΙΟ為非離子界面活性劑其得自於漢儂化學公司 (Hannong Chemicals Inc.)。 15 上述方法備製之實施例與比較例之水性光阻剝離液組 成物測試以其剝離性、腐蝕性與蒸發率，如下： \ . . <剝離性評估〉- Comparative Example 3 1 20 I 15 1 - 1 65 I In Tables 1 and 2, 'KOH is oxidized If (potassium hydroxide), TMAH is tetramethyl- ammonium hydroxide, TEAH is four Tetraethylmmonium hydroxide, TP AH is tetrapropylammonium hydroxide, NMP is N-methyl pyrrolidone, DMSO is dimethyl Dimethyl sulfoxide, BzOH is benzyl alcohol, BDG is butyldiglycol, EC is ethylcarbitol, HDA is iyl amine, MEA It is monoethanolamine, DMAC is N,N-dimethyl-acetamide, DI is ultrapure water, and K-290 is a proton surfactant. It is obtained from Hanyu. Hannong Chemicals Inc., and ΡΟ-ΙΟ are nonionic surfactants available from Hannong Chemicals Inc. The composition of the above-mentioned method and the aqueous photoresist stripping liquid of the comparative example were tested for peelability, corrosivity and evaporation rate as follows: \ . . < peelability evaluation>
組成物A係由一黑色矩陣樹脂、一彩色濾光片、一紫外 線保護膜及一感光間隔材光阻所組成，而組成物B與組成物 20 A相同，只是以一熱保護膜取代紫外線保護膜。對組成物A 及B進行其剝離性之評估。以實施例及比較例所備製之水性 剝離液組成物保持在55°C的溫度下，然後在10分鐘、15分 鐘及20分鐘時各以超音波清洗（ultrasonic cleaning)調查測 試樣本之剝離程度。評估標準如下： 17 1311585 ◎:在15分鐘内完全去除。 〇：在15到20分鐘内完全去除。 X .:在20分鐘後仍未去除。 <腐钱性評估> 上述剝離性評估所使用之測試樣本亦同時被用來進行 水性剝離液組成物之腐蝕性測試。以實施例及比較例所備 製之水性剝離劑組成物保持在551的溫度下，將組成物浸 入經鉻黑色矩陣（Cr black matrix)處理過之有機基質中為時 25分鐘，然後以超純水洗淨。經此處理的鉻黑色矩陣以一 蚀刻劑去除’然後測量玻璃基板上受損部分與鉻黑色矩陣 剩餘的部分之間的差值以取得玻璃基板的腐蝕程度值。 〇：鉻黑色矩陣與玻璃基板幾乎受到腐银。 △:絡黑色矩陣與玻璃基板部分受到腐勉。 X :鉻黑色矩陣與玻璃基板受相當顯著之腐餘。 15 <蒸發率評估> 在一玻璃燒杯中加入100克之水性剝離液，將其保持在The composition A is composed of a black matrix resin, a color filter, an ultraviolet protective film and a photosensitive spacer photoresist, and the composition B is the same as the composition 20 A except that the thermal protection film is substituted for the ultraviolet protection. membrane. Compositions A and B were evaluated for their peelability. The aqueous stripping solution compositions prepared in the examples and comparative examples were maintained at a temperature of 55 ° C, and then the ultrasonic cleaning was used to investigate the peeling degree of the test samples at 10 minutes, 15 minutes, and 20 minutes. . The evaluation criteria are as follows: 17 1311585 ◎: Completely removed within 15 minutes. 〇: Completely removed within 15 to 20 minutes. X .: Not removed after 20 minutes. <Corrugation Evaluation> The test samples used in the above peelability evaluation were also used for the corrosivity test of the aqueous stripper composition. The aqueous stripper composition prepared in the examples and the comparative examples was kept at a temperature of 551, and the composition was immersed in an organic matrix treated with a Cr black matrix for 25 minutes, and then ultrapure. Washed with water. The thus treated chrome black matrix is removed by an etchant' and then the difference between the damaged portion on the glass substrate and the remaining portion of the chrome black matrix is measured to obtain the corrosion degree value of the glass substrate. 〇: The chrome black matrix and the glass substrate are almost rotted with silver. △: The black matrix and the glass substrate were partially rotted. X: The chrome black matrix and the glass substrate are subject to considerable corrosion. 15 <Evaporation rate evaluation> 100 g of aqueous stripping solution was added to a glass beaker to keep it in
之百分比。 測試所得的結果列於下列表3。 【表3】 測試 樣本 剝離性The percentage. The results of the test are listed in Table 3 below. [Table 3] Test sample Peelability
18 1311585 實施例5 ----- 實施例6 ◎ 〇 10 竇施例7 ◎ 〇 11 會施例8 ◎ 〇 10 實施例9 ◎ 〇 9 實施例10 ◎ 〇 11 實施例11 ◎ 〇 11 實施例12 實施例13 ◎ 〇 10 ' ◎ 〇 9 " 竇施例14 ~ —◎ 〇 10 實施例15 ~' ◎ 〇 10 實施例16 ◎ 〇 9 會施例1 ^--- B ◎ 〇 10 竇施例2 ~~~ ◎ 〇 11 實施例3 ◎ 〇 10 實施例4 ◎ 〇 11 實施例5 ◎ 〇 10 實施例6 ~~ ◎ 〇 10 實施例7 ◎ 〇 11 實施例8_ ◎ 〇 10 實施例9 ◎ 〇 9 _ 實施例10 ◎ 〇 11 實施例11 i 〇 11 實施例12 ◎ 〇 10 實施例13 ◎ 〇 9 實施例14 ◎ 〇 10 — 實施例15 __ ◎ Δ 10 實施例16 ◎ 〇 9 — _ 比較例1 A ----- B ◎ 〇 10 比較例2 X Δ 11 比敍例3 X X 12 比較例1 __X X 11 比較例2 X Δ 11 比教例3 X X 12 J X X 11 請參考表3，i t (實施例〗至16)可·:、:二本發明之水性咖 陣樹脂、彩色&片去除各種光阻劑，如黑色 埶佯⑽隹 外線保護膜、感光間隔材光阻 ’同時亦顯示出其腐純非常低。 :時’表3也顯示了根據比較例⑴所得 組成物之剝離性不良且其會腐韻下層基板。 _ 易且5單2本么明之水性光阻剝離液組成物可用於; 林移除一不同的光阻，其經由製造TFT_LCD製程c 1918 1311585 Example 5 ----- Example 6 ◎ 〇 10 Sinus Example 7 ◎ 〇 11 Example 8 ◎ 〇 10 Example 9 ◎ 〇 9 Example 10 ◎ 〇 11 Example 11 ◎ 〇 11 Example 12 Example 13 ◎ 〇 10 ' ◎ 〇 9 " sinus application 14 ~ - ◎ 〇 10 Example 15 ~ ' ◎ 〇 10 Example 16 ◎ 〇 9 will apply example 1 ^--- B ◎ 〇 10 Dou Shi Example 2 ~~~ ◎ 〇 11 Example 3 ◎ 〇 10 Example 4 ◎ 〇 11 Example 5 ◎ 〇 10 Example 6 ～ ◎ 〇 10 Example 7 ◎ 〇 11 Example 8 ◎ 〇 10 Example 9 ◎ 〇9 _ Example 10 ◎ 〇 11 Example 11 i 〇 11 Example 12 ◎ 〇 10 Example 13 ◎ 〇 9 Example 14 ◎ 〇 10 - Example 15 __ ◎ Δ 10 Example 16 ◎ 〇 9 — _ Comparison Example 1 A ----- B ◎ 〇 10 Comparative Example 2 X Δ 11 Comparative Example 3 XX 12 Comparative Example 1 __X X 11 Comparative Example 2 X Δ 11 Comparative Example 3 XX 12 JXX 11 Please refer to Table 3, it (Examples to 16) can be::,: two aqueous ink crystal resins, color & tablets of the invention to remove various photoresists, such as black enamel (10) 隹 external line Protective film, the photosensitive resist spacers' but also shows its pure rot very low. The following Table 3 also shows that the composition obtained according to Comparative Example (1) has poor peelability and which would rot the underlying substrate. _ Easy and 5 single 2 of the water-based photoresist stripping liquid composition can be used; Lin removes a different photoresist, which is manufactured by manufacturing TFT_LCD process c 19