1377451 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種顯影液組成物，尤指—種光阻劑之 顯影液組成物，其可配製為高濃度之顯影液組成物，特別 5 適用於彩色濾光片用光阻劑之顯影用途上。 【先前技術】 | 一般在積體電路、印刷電路板和液晶顯示器等製程 中，為獲致精細圖像，常利用光阻劑等放射線敏感組成物 10以塗佈方式在基材上形成薄膜，經過放射線照射後，以驗 性顯影液顯像，來除去不要之塗膜部分，以獲致良好的圖 像。 常用的顯影方法有浸潰顯影、搖動顯影、嗔漢顯影和 靜置顯影等技術。由於一般光阻劑係由驗可溶性樹脂，例 15如.酚醛樹脂（Novolac)、壓克力樹脂、聚對_羥基苯乙烯等， 货搭配不同之放射線敏感物質，以形成正型或負型光阻劑。 光阻劑經過放射線照射後，改變其原來的溶解度而可以 t於鹼性顯影液中。驗性顯影液中所使㈣驗性化合物一 奴分，無機鹼及有機鹼兩大類，一般無機鹼可為氫氧化 20納、氫氧化卸、碳酸鈉、以及碳酸氣鋼等，一般有機驗可 為氫氧化四甲錢或烧醇胺等驗性化合物，其皆被廣泛使用 於顯影液中。 然根據習知顯影液之技術，光阻劑在塗膜並預烤、曝 光後，以鹼性顯影液來溶解除去未曝光而不要的塗膜部 4 1377451 二扣之現象產生係、因為該光阻劑中含有酸官能基。 开4^有機聚合物基^之酸基於驗溶液中财和，而 穑7 >谷性有機聚合物鹽。當所溶解之光阻劑於溶液 5 =殘=槽中開始形成不溶性有機物質，最後形成水不 或殘留物。此等再沉積之殘留物在顯影時卻容易 難以开粒子或未溶解物之殘存，因此顯影後比較 而开>成精痛的光阻劑圖像。尤其，近年來，隨著家 二化，為了提高色彩對比性和飽和度，液晶 10片光阻劑添加了更多的顏料微粒子，使 顯衫時顯影槽中被溶解的顏料微粒子或其他的成分等水: 塗膜上，、生士〜么办 一<系槓再儿積回基板或光阻 、咖色濾光片上殘留有殘逢、表面污染等瑕疵。 15 驗性上述之缺失’目前光阻劑之鹼性顯影液除了 勿外，還含有用於增強其清潔力之界面活性劑， 渣(_)之傾向。如美國專細7， 20 揭路添加非離子性界面活性劑有降低殘逢之效果。另外， 添加界面活性劑有增加顯影速率，提高生產效率的優點。 目前業界較常使用且具有卓越清潔力的非離子界面活 士。為％ =基類界面活性劑。為了達到最大的清潔力， 二氧烷基類界面活性劑，還會使用複數種類的 錢烧基類界面活性劑之混合物，其中包括不同莫耳數之 複數種類環氧炫基，如環氧乙貌或環氧丙貌等。 然而，此類驗性顯影液因添加有非離子界面活性劑， 所以會繼承代表界面活性劑性質之一的濁點（當驗性顯影 5 1377451 液之溫度升高或濃度提升時，導致該顯影液變成白濁之溫 度）。尤其是無機驗類顯影液偶爾會出現以下問題 影液可能在儲存或運送過程中受熱而變白濁及分層，進而 5 10 15 20 $出’嚴重的是，在賤中因為分層導致計量的濃度不正 ’上下層的濃度及成分比例都不相同，更嚴重的是，在 輸送的管路中因為溫度變化而分層析出，在管路的死角中 堆積，進而堵塞管路。 一般的驗性顯影液在低濃度時不易發現非離子界面活 性劑析出分層的規鱼 蚀. 吾…… 旦需配製高濃度的鹼性顯 〜之，’由㈣離子界面活性劑的疏水基團與水的疏水作1377451 VI. Description of the Invention: [Technical Field] The present invention relates to a developer composition, and more particularly to a developer composition of a photoresist, which can be formulated into a high concentration developer solution, in particular 5 It is suitable for the development of photoresists for color filters. [Prior Art] | Generally, in a process such as an integrated circuit, a printed circuit board, and a liquid crystal display, in order to obtain a fine image, a radiation sensitive composition such as a photoresist is often used to form a film on a substrate by a coating method. After the radiation exposure, the developer solution is developed to remove the unnecessary portion of the coating film to obtain a good image. Commonly used development methods include dipping development, shaking development, enamel development, and static development. Since the general photoresist is made of a soluble resin, such as phenolic resin (Novolac), acrylic resin, poly-p-hydroxystyrene, etc., the goods are matched with different radiation-sensitive substances to form positive or negative light. Resistor. After the photoresist is irradiated with radiation, its original solubility can be changed to be in an alkaline developer. In the test developer, (4) the test compound is a slave, inorganic base and organic base. The general inorganic base can be 20 nanometers of hydroxide, hydrogen peroxide, sodium carbonate, carbonic acid gas, etc. It is an organic compound such as tetramethyl oxyhydroxide or an alkaloid, which is widely used in a developing solution. However, according to the technique of the conventional developer, after the photoresist is pre-baked and exposed, the alkaline developer is used to dissolve and remove the unexposed film portion 4 1377451, because the light is generated. The resist contains an acid functional group. The 4^ organic polymer based acid is based on the test solution in the middle of the acid, while the 穑7 > glutenic organic polymer salt. When the dissolved photoresist starts to form an insoluble organic substance in the solution 5 = residual = tank, water or residue is finally formed. These re-deposited residues are prone to hard-to-open particles or undissolved materials during development, so that after development, the image of the photoresist is made fine. In particular, in recent years, in order to improve color contrast and saturation, in order to improve color contrast and saturation, liquid crystal 10 photoresists are added with more pigment fine particles, so that the pigment particles or other components dissolved in the developing tank are displayed. Waiting for water: On the film, the student will do a thing. If you stick back to the substrate or the photoresist, the coffee color filter will have residual defects and surface contamination. 15 Inferiority of the above-mentioned defects The alkaline developer of the current photoresist does not have a tendency to enhance the cleaning power of the surfactant, slag (_). Such as the United States special fine 7, 20 Jie Road added non-ionic surfactant has the effect of reducing the residual. In addition, the addition of a surfactant has the advantage of increasing the development rate and increasing the production efficiency. A non-ionic interface that is currently used in the industry and has excellent cleaning power. For % = base class surfactants. In order to achieve maximum cleaning power, the dioxoalkyl surfactants also use a mixture of a plurality of types of money-based surfactants, including a plurality of types of epoxy groups, such as epoxy B. Look or epoxy appearance. However, such an animated developer, due to the addition of a nonionic surfactant, inherits a cloud point representing one of the properties of the surfactant (when the temperature of the developer 5 1377451 liquid increases or the concentration increases, the development is caused The liquid turns into a cloudy temperature). In particular, the inorganic test developer occasionally has the following problems: the liquid may be turbid and stratified by heat during storage or transportation, and then 5 10 15 20 $ out of severity, the measurement is caused by delamination in the sputum. The concentration is not the same as the concentration of the upper and lower layers and the composition ratio is different. More seriously, it is separated in the pipeline to be transported due to temperature changes, and accumulates in the dead angle of the pipeline, thereby blocking the pipeline. In general, the developer solution is not easy to find the non-ionic surfactant precipitation layered fish eclipse at low concentration. I... It is necessary to prepare a high concentration of alkali, which is the hydrophobic base of the (tetra) ionic surfactant. Hydrophobic work of the mass and water
用大於親水基團的親水作用’因而發生分層進而析出的問 題。 J -故此類驗性顯影液的濃度會受其濁點的限制，而無 二常常在此類型的顯影液中有相當部份是溶The problem of delamination and precipitation occurs with a hydrophilic action larger than that of the hydrophilic group. J - Therefore, the concentration of such an experimental developer is limited by its cloud point, and no two are often dissolved in this type of developer.
Is圓 影液的濃度，以減少溶劑體積進而減少 進而二广會有濁點下降至室溫以下’導致溶解度不佳， 進而刀層析出的問題。 點之：離鹼性顯影液濁點方式，就是使用具有高濁 活性劑’但加入高濁點之非離子界面活性 料#ι :赤^生其他的副作用，如在光阻膜上會殘存界面活 性劑，或是產生殘渣等。 另一種提高驗性顯影液濁點方式，就是添加一古 ::::加劑’例如TW2嶋026公開專利所提及的加二 -特别結構的單幾酸化合物，例如加入苯甲酸納， 6 οι 二的提高濁點’但還是會產生其他的副作用，如可 月匕導致廢水池中的微生物死亡。 【發明内容】 陰離提供—種顯影液組成物，其使用具有高濁點之 得太路⑷劑，因1^可提高顯影液组成物之濃度，使 發明之顯影液組成物言 + 服顯影液組成物可能在;運：：：有高濁點，可克 刀層進而析出的問題，同時 ^及 疲。 良好…，可有效減少殘渣、表面污染等瑕 據此’本發明提供一The concentration of the Is shadow liquid is reduced by reducing the volume of the solvent, and the cloud point is lowered to below the room temperature, resulting in poor solubility and further problem of knife chromatography. Point: from the alkaline developer liquid point mode, is to use a high turbidity active agent 'but the addition of high cloud point non-ionic interface active material #ι : 赤 ^ other side effects, such as the residual interface on the photoresist film The active agent or the residue is produced. Another way to improve the cloud point of the invisible developer is to add an ancient:::additive', for example, the bis-acid structure of the mono-acid compound mentioned in the TW2嶋026 public patent, for example, adding sodium benzoate, 6 Οι II raises the cloud point' but still produces other side effects, such as the death of microorganisms in the wastewater pond caused by the moon. SUMMARY OF THE INVENTION An anion-providing developer composition is used, which uses a high-cloud point of the Tailu (4) agent, because the concentration of the developer composition can be increased, so that the developer composition of the invention can be developed. The liquid composition may be in; transport::: there is a high cloud point, the problem of the knife layer and the precipitation, and ^ and fatigue. Good...can effectively reduce residue, surface contamination, etc. According to the present invention, a
^ ^ % ； (b)^ τ α)„ _ 1 I ^ ^ ^ II 水， 不之陰離子性界面活性劑；以及（c) -CH3 _ CH2-CH2-0^ ^ % ; (b)^ τ α)„ _ 1 I ^ ^ ^ II water, not an anionic surfactant; and (c) -CH3 _ CH2-CH2-0
ch2- ch2- 0 - S03 - X 其中’ X為氣、銘睡 λ ia l 叙鹽、鹼金屬或鹼土金屬之陽離子， R|為虱原子或C|4烧其.D = 至10之m .日 或C|-4烷基，、為0 ，m為4至20之整數。於式（I)中，％及 尺2較佳分別為氫原子或 西社及 —土’更佳為甲基’而η較佳為〇0 相較於一般習釦gs旦，, 衫液，由於習知係使用非離子界面 活性劑，因此，當裎古月s 丨®5 呵"肩衫液的濃度時，會有溶解度不 之析出問題，進而導_鼓甚5旦，、± — 顯衫速度下降與殘渣殘留；然而， 本發明所使用之陰離子枓R …、 拴界面活性劑本身具有高濁點，因 1377451 此可解決習知技術之濁點等問題，進而可提高顯影液組成 物的濃度。 於本發明之顯影液組成物中，（a)鹼性化合物可為一般 周知之鹼性化合物，較佳可為，鋰、鉀、鈉等鹼金屬之氫 5 氧化物、碳酸氫鹽、磷酸鹽、硼酸鹽或氨等無機鹼性化合 物；或是氫氧化四甲銨、氫氧化2-氫氧化乙基三甲銨、單 甲基胺、二曱基胺、三甲基胺、單乙基胺、二乙基胺、三 乙基胺、單異丙基胺、二異丙基胺、三異丙基胺、單乙醇 ►胺、二乙醇胺、三乙醇胺、或單乙醇二甲基胺等之有機鹼 10 性化合物，也可為上述化合物之混合物。 於本發明之顯影液組成物中，（b)陰離子性界面活性劑 具體實例包括：聚環氧乙烯烷基醚（polyoxyethylene alkyl ether)、聚環氧乙烯烷基芳基醚（polyoxyethylene alkylphenyl ether)、聚環氧乙烯脂肪酸酯（polyoxyethylene 15 fatty acid ester)、山梨醣醇酐脂肪酸醋（sorbitan fatty acid ester)、聚環氧乙烯山梨醣醇酐脂肪酸酯（polyoxyethylene • sorbitan fatty acid ester)、聚環氧乙稀苯乙烯化芳基醚 (polyoxyethylene styrenated phenyl ether)、聚環氧乙稀二 苯乙稀化芳基越（polyoxyethylene distyrenated phenyl 20 ether)、聚環氧乙稀三苯乙稀化芳基越（polyoxyethylene triistyrenated phenyl ether)、聚環氧乙稀氧化丙稀共聚物 (polyoxyethylene polyoxypropylene ether)等非離子界面活 性劑之陰離子化產物，也可為上述物質之混合物。於上述 陰離子化產物中，其陰離子基較佳為磺酸基，其配對的陽 8 5 離子a。:鹽、驗金屬或驗土金屬陽離子。 * * 至30重量柊迕y+ 至里马100重量份時，以〇·(Η 至他=圭至為;51至… 物之ΡΗ範圍較佳為;重量份，而所得顯像液組成 10 使用量，：:=員影液組成物中，㈨陰離子界面活性劑之 。·。二^r成物總重量為_重量份時，以 性劑使用量不滿。則：:；：::份。陰離子界面活 留膜產生;但若超過3〇=:時其，不充分，容易有殘 溶解度下降與起泡性嚴重等問題。“易發生驗性化合物 15 20 水中2發月之顯影液組成物中，為了增加驗性化合物於 劑士 Γ解度或調整顯影的效率，可選擇性地添加助溶 酿’溶性佳的有機溶劑。舉例包括：乙醇、異丙醇'丁 =醇、^己醇、辛醇、異壬醇、乙二醇、甘油等醇類 二或疋乙—醇單烷基醚類、二乙二醇單烷基醚類、 :乙二醇二貌基趟類、以及醋酸丙二醇單炫基賴等化合 。上述助溶劑的使用量，相對於顯影液組成物總重量為 〇〇重量份時，較佳為小於5重量份。 於本發明之顯影液組成物中，除上述成分外，其餘比 為Κ水為一 k使用之水，例如可以是純水、去離子水 或蒸餾水。 9 1377451 本發明之顯影液組成物可配製為高濃度之顯影液組成 物’一般在生產線上使用時，會以二十倍或二十倍重量以 上之純水稀釋。 本發明之顯影液組成物，可應用於含有著色劑之著色 5 感光性樹脂的顯影製程。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。惟在彩色感 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（binder resin)、感光性化合 > 物及溶劑等成份’上述之鹼可溶性之黏結樹脂可為：熱塑 10 性酿搭樹脂（Novolac resin)、丙稀酸系樹脂（acryiate resin)、順丁 缔二酐（Maleic anhydride)或其半酯（half ester) 之聚合物、或是聚經基苯乙稀（polyhydroxy styrene)等，其 中以丙烯酸系樹脂為佳。其可能的具體實例，例如（曱基） 丙稀酸甲醋/乙稀酴（hydroxyl phenol)/苯乙烯/(曱基）丙烯 15 酸共聚物、（甲基）丙烯酸苄醋（benzyl methacrylate )/(甲基） 丙烯酸/苯乙烯共聚物、（曱基）丙烯酸甲酯/(曱基）丙烯酸/ 齡 苯乙烯共聚物、（甲基）丙烯酸甲酯/(甲基）丙烯苄酸/(甲基） 丙烯酸共聚物。上述聚合物之平均分子量較佳為介於5〇〇〇 至200000之間’更佳為介於8000至60000之間。 20 【實施方式】 使用以下特定實施例進一步詳細描述本發明： 下述實施例對本發明實施的方法有較具體的說明，然 本發明所主張之權利範圍非僅限於下述實施例。本文中， 10 1377451 遭度未特別標記的部分係以重量為基準β 以下’列舉1組實施例及5組對照例，如表一所示。 《高濃度顯影液組成物的調配》 5 依照表一的重量比例，將（al)鹼性化合物1、（a2)鹼性 化合物2、（bl)界面活性劑丨、（b2)界面活性劑2，再加入超 純水進行混合’配製成重量為100克之水溶液。 > 《濁點的測定》 將依照表一調配後的「顯影液組成物」置於燒杯中， 然後慢慢加熱，並用溫度計量測其溫度，當溶液由澄清變 成渾濁時，讀取溫度計之溫度值，此讀取溫度值即 (Could P0int C.P.p 1點 15 表一 顯影液 組成物 (al) 鹼性化合 物1 (a2) 鹼性化 合物2 (bl) 界面活性 劑1 (b2)~ 界面活性 劑2 濁點 (°C) --- 備註 對照例1 1_55 克 Na2C03 0.6克 NaHC03 克 8-K 45 遭縮液 對照例2 3.1克 Na2C03 1·2克 NaHC03 7克 8-K — 34 20倍 濃縮液 濃縮液 對照例3 --- 3.1克 Na2C03 1.2克 NaHC03 3.5克 8-K 編----- 35 1377451 對照例4 1.55 克 Na2C03 0‘6克 NaHC03 3.5克 8-K 1克 DSP-208 38 10倍 濃縮液 對照例5 3.1克 Na2C03 1.2克 NaHC03 7克 8-K 2克 DSP-208 27 20倍 濃縮液 實施例1 4.65 克 Na2C03 1.8克 NaHC03 10.5 克 8K-Anion ic — >60 30倍 濃縮液 8-K非離子界面活性劑結構如下所示： ch3 CH2-CH2-〇 -Η DSP-208非離子界面活性劑結構如下所示：Ch2- ch2- 0 - S03 - X where 'X is gas, Ming sleep λ ia l salt, alkali metal or alkaline earth metal cation, R| is a cesium atom or C|4 burns it. D = to 10 m. Day or C|-4 alkyl, 0, m is an integer from 4 to 20. In the formula (I), % and the size 2 are preferably a hydrogen atom or a mixture of Xishe and Tu', preferably a methyl group, and η is preferably 〇0, compared to the general application of GS Dan, shirt liquid, Since the conventional use of non-ionic surfactants, when the concentration of the sputum s 丨 5 5 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩 肩The speed of the shirt is reduced and the residue remains; however, the anionic 枓R ... and 拴 surfactant used in the present invention have a high cloud point, which can solve the problem of the cloud point of the prior art by the 1377451, thereby improving the composition of the developer. The concentration of the substance. In the developer composition of the present invention, the (a) basic compound may be a generally known basic compound, preferably a hydrogen 5 oxide, a hydrogencarbonate or a phosphate of an alkali metal such as lithium, potassium or sodium. An inorganic basic compound such as borate or ammonia; or tetramethylammonium hydroxide, ethyl 2-trimethylammonium hydroxide, monomethylamine, didecylamine, trimethylamine, monoethylamine, Organic bases such as diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, monoethanol\amine, diethanolamine, triethanolamine, or monoethanol dimethylamine A compound of 10, which may also be a mixture of the above compounds. In the developer composition of the present invention, (b) specific examples of the anionic surfactant include: polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, Polyoxyethylene 15 fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polycyclic ring Polyoxyethylene styrenated phenyl ether, polyoxyethylene distyrenated phenyl 20 ether, polyethylene oxide triphenylethylene aryl (a polyoxyethylene triistyrenated phenyl ether), an anionized product of a nonionic surfactant such as a polyoxyethylene polyoxypropylene ether, or a mixture of the above. In the above anionized product, the anionic group is preferably a sulfonic acid group, and the paired cation 8 a is a. : salt, metal or soil metal cations. * * To 30 weights 柊迕y+ to 100 parts by weight of Rima, 〇·(Η到他=圭至为; 51至... The range of the product is preferably; parts by weight, and the resulting imaging liquid composition is 10 Amount, :: = member liquid composition, (9) anionic surfactant. · The total weight of the two components is _ parts by weight, the amount of the agent used is not full. Then::;::: parts. The anion interface is produced by the residence film; however, if it exceeds 3 〇 =: it is insufficient, and there is a problem that the residual solubility is lowered and the foaming property is severe. "The test compound 15 20 is in the water for 2 months. In order to increase the solubility of the test compound in the dosage of the agent or to adjust the efficiency of development, an organic solvent having good solubility can be selectively added. Examples include: ethanol, isopropanol, butyl alcohol, and hexanol Alcohols such as octanol, isodecyl alcohol, ethylene glycol, glycerol, or bis-ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, ethylene glycol dimorphic hydrazines, and acetic acid a combination of propylene glycol monoterpene and the like, and the amount of the above-mentioned co-solvent used is 〇〇 by weight relative to the total weight of the developer composition. It is less than 5 parts by weight. In the developer composition of the present invention, in addition to the above components, the water used for the hydrophobic water is one k, and may be, for example, pure water, deionized water or distilled water. The developer composition can be formulated as a high-concentration developer composition. When used in a production line, it is diluted with 20 times or 20 times by weight of pure water. The developer composition of the present invention can be applied to contain Coloring of the coloring agent 5 Development process of the photosensitive resin. The photosensitive resin is not particularly limited. It may be a positive or negative photosensitive resin composition. However, in the case of a color photosensitive resin composition, it usually contains There are: organic or inorganic pigments (colorants), soluble binder resins, photosensitive compounds, and solvents. The above-mentioned alkali-soluble binder resin can be: thermoplastic 10 (Novolac resin), acrylic acid resin, polymer of maleic anhydride or its half ester, or polyh-phenylene oxide (polyh) Ydroxy styrene), etc., among which acrylic resin is preferred. Possible examples thereof are, for example, (mercapto) methic acid/acetic acid phenol/styrene/(mercapto) propylene 15 acid copolymer. , benzyl methacrylate / (meth) acrylate / styrene copolymer, (mercapto) methyl acrylate / (mercapto) acrylic / aged styrene copolymer, (meth) acrylic Ester/(meth)acrylic acid/(meth)acrylic acid copolymer. The average molecular weight of the above polymer is preferably between 5 Å and 200,000', more preferably between 8,000 and 60,000. [Embodiment] The present invention will be described in more detail by the following specific examples. The following examples are intended to be illustrative of the embodiments of the present invention, and the scope of the invention is not limited to the following examples. Herein, 10 1377451 is not particularly marked with a portion based on the weight of β below. One set of examples and five sets of comparative examples are shown, as shown in Table 1. "Preparation of Composition of High Concentration Developer Solution" 5 According to the weight ratio of Table 1, (al) basic compound 1, (a2) basic compound 2, (bl) surfactant 丨, (b2) surfactant 2 Then, adding ultrapure water for mixing' is formulated into an aqueous solution having a weight of 100 g. > "Measurement of cloud point" Place the "developing solution composition" prepared according to Table 1 in a beaker, then slowly heat it, and measure the temperature by temperature. When the solution turns from clarification to turbidity, read the thermometer. Temperature value, this reading temperature value is (Could P0int CPp 1 point 15 Table 1 developer composition (al) basic compound 1 (a2) basic compound 2 (bl) surfactant 1 (b2) ~ surfactant 2 Cloud point (°C) --- Remarks Comparative Example 1 1_55 gram Na2C03 0.6 gram NaHC03 gram 8-K 45 condensed liquid Comparative Example 2 3.1 gram Na2C03 1/2 gram NaHC03 7 gram 8-K — 34 20 times concentrated solution Concentrate Comparative Example 3 --- 3.1 g Na2C03 1.2 g NaHC03 3.5 g 8-K----- 35 1377451 Comparative Example 4 1.55 g Na2C03 0'6 g NaHC03 3.5 g 8-K 1 g DSP-208 38 10 Concentrate concentrate Comparative Example 5 3.1 g Na2C03 1.2 g NaHC03 7 g 8-K 2 g DSP-208 27 20-fold concentrate Example 1 4.65 g Na2C03 1.8 g NaHC03 10.5 g 8K-Anion ic — > 60 30-fold concentrate The structure of 8-K nonionic surfactant is as follows: ch3 CH2-CH2-〇-Η DSP-208 nonionic surfactant structure Below:
SK-Anionic陰離子界面活性劑結構如下所示. -CH2-CH2-〇 一 s〇3NH4 12 10 1377451 由表一之對照例i及對照例2「濁點的測定」結果得 ’曲且成物的濃度提高—倍（1Q倍濃縮提高至2〇 =縮）’濁點由45t降至34°C ’由對照例4及對照例5 渴點的測定」結果得知，當顯影液組成物的濃度提高一 倍（10倍浪縮提高至20倍濃縮），濁點由38。〇降至27。〇。 由表-之實施例i「濁點的測^」結果得知，加人8KAnionic 陰離子界面活性劑’即使提高至3()倍濃縮，濁點還是大於 60C ’故本發明之顯影液組餘確實可有效提高顯影液組 成物之濁點。 ’ 《彩色光阻骐之顯影實驗》 於彩色光阻劑曝光後，使用本發明之顯影液組成物， 以形成圖像，彩色光阻劑之組成物成份及使用量如下表二 所示： 表二、彩色光阻劑之組成物成份 組成份 成份的具體例 (公克） 甲基丙烯酸/丙烯酸甲酯/甲基丙烯藏~ -—_ 黏結樹脂 苄酯共聚物（25 : 25 : 50，GPC量測 4.00 重量平均分子量30,000) 多官能基 Aronix Μ-400 ~~-—- 單體 (Toagosei Co., Ltd.商品） l.2〇 13 1377451The structure of the SK-Anionic anionic surfactant was as follows. -CH2-CH2-〇-s〇3NH4 12 10 1377451 From the comparison of the control example i of Table 1 and the control 2, the measurement of the cloud point was obtained. The concentration is increased - times (1Q times the concentration is increased to 2 〇 = shrink). The cloud point is lowered from 45t to 34 ° C. 'The measurement of the thirst point of Comparative Example 4 and Comparative Example 5' shows that the concentration of the developer composition is Doubled (10 times the wave size increased to 20 times the concentration), the cloud point is 38. 〇 fell to 27. Hey. From the results of Table - Example i "measurement of cloud point", it is known that the addition of 8KAnionic anionic surfactant 'even if it is increased to 3 () times concentrated, the cloud point is still greater than 60 C', so the developer solution of the present invention is indeed It can effectively increase the cloud point of the developer composition. 'Development Experiment of Color Resistance 》 After the exposure of the color photoresist, the developer composition of the present invention is used to form an image, and the composition and usage amount of the color photoresist are as shown in Table 2 below: 2. Specific examples of the composition of the components of the color resist (g) Methyl acrylate/methyl acrylate/methacryl condensate ~ -__ Benzene copolymer of binding resin (25: 25: 50, GPC amount) Measured 4.00 Weight average molecular weight 30,000) Polyfunctional Aronix Μ-400 ~~--- Monomer (Toagosei Co., Ltd.) l.2〇13 1377451
光起始劑 IRGACURE 369 (Ciba Specialty Chemicals 商品） 0.30 Chemcure-ITX (Chembridge International Corp 商品） 0.08 有機溶劑 丙二醇單甲基醚乙酸酯 (Propyleneglycol methyl etheracetate ; PGMEA) 9.54 顏料 C.I. Red Pigment 177 / C.I. Red Pigment 254 (Dai Nippon Ink 商品） 4.00 彩色光阻膜之形成 將前述各成份以攪拌器混合之溶液塗覆在已經形成 90微米X 230微米之圖案遮光層（黑色樹脂矩陣，Black 5 Matrix, BM)之無鹼玻璃基板上，再以340rpm的旋轉塗覆 20秒，可得一均勻光阻膜。 於90°C之潔淨烘箱内進行1〇分鐘預烘烤，形成膜厚 > 約2 // m厚度的光阻膜。 其次，將此基板冷卻至室溫後，使用高壓水銀燈產生 10 紫外線，透過線寬為90 " m的光罩，對光阻膜，以100 mJ/cm2之曝光量進行曝光。 顯影液組成物的調配 使用超純水，將上述表一之顯影液組成物濃縮液稀釋 15 成如表一備註攔位的幾倍重量的水溶液。如對照例1取1〇 14 1377451 克^液以超純水稀釋成1G倍重量的水溶液，也就是加入 克超純水，最後配成100克的顯影液組成物，1 =浸於2rc之上述顯影液組成物中12。秒鐘一面緩 =搖面浸潰而㈣。顯像後，以超純水錢將其洗 平’並且以氮氣吹乾之。 …此乾燥後的圖案，接著進行曝後硬烤，置於22〇 相’硬烤時間40分鐘。 ίο 表三、 蠡 材上烤㈣光賴，叫顯微鏡分析未曝光區域基 材上所形成之殘留程度，得到如下表三結果：Photoinitiator IRGACURE 369 (Ciba Specialty Chemicals) 0.30 Chemcure-ITX (Chembridge International Corp) 0.08 Organic solvent Propyleneglycol methyl etheracetate (PGMEA) 9.54 Pigment CI Red Pigment 177 / CI Red Pigment 254 (Dai Nippon Ink product) 4.00 Formation of color photoresist film The solution of the above components mixed with a stirrer is applied to a patterned light-shielding layer (Black Resin Matrix, Black 5 Matrix, BM) which has formed 90 μm×230 μm. On the alkali-free glass substrate, coating was further applied at 340 rpm for 20 seconds to obtain a uniform photoresist film. The film was pre-baked in a clean oven at 90 ° C for 1 minute to form a film thickness of > 2 / m thickness. Next, after cooling the substrate to room temperature, a high-pressure mercury lamp was used to generate 10 ultraviolet rays, and a photoresist having a line width of 90 " m was used to expose the photoresist film at an exposure amount of 100 mJ/cm 2 . Preparation of Developer Composition Using the ultrapure water, the developer solution concentrate of Table 1 above was diluted 15 into an aqueous solution of several times the weight of the remarks in Table 1. For example, in Comparative Example 1, 1 〇 14 1377451 g of liquid was diluted with ultrapure water to a 1 G solution of aqueous solution, that is, gram of ultrapure water was added, and finally 100 g of the developer composition was prepared, 1 = immersed in 2 rc 12 in the developer composition. The second side is slow = the shake surface is soaked (4). After development, it was washed with ultrapure water and dried by nitrogen. ...the dried pattern, followed by hard baking after exposure, placed in a 22 〇 phase hard baking time of 40 minutes. Ίο Table 3, baking on the enamel (4) ray, called the microscope to analyze the residual level formed on the unexposed area of the substrate, the following table results are obtained:
由上結果得知’本發明之龜旦/ V 4 J- όί] Μ - ^ s ja 顯如液組成物確實可將基材 上的膜Θ降至最低，具有優異的顯影效果。 综上所陳，本發明無論就目 技術層面與研發設計上，均顯 功效’或就其 徵。惟應注意的是，上述諸夕其週異於習知技術之特 夕貫知例僅係為了便於說明故 15 15 1377451 舉例闡述之，而本發明所主張之權利範圍自應以申請專利 範圍所述為準，而非僅限於上述實施例。 【圖式簡單說明】 5 無。 【主要元件符號說明】From the above results, it was found that 'the turtle of the present invention/V 4 J- όί 】 Μ - ^ s ja is a liquid composition which can minimize the film enthalpy on the substrate and has an excellent developing effect. In summary, the present invention has the effect of either the technical level and the research and development design. It should be noted that the above-mentioned ceremonies of the above-mentioned Japanese ceremonies are merely exemplified for convenience of explanation, and the scope of claims claimed by the present invention is intended to be within the scope of patent application. The description is not intended to be limited to the above embodiments. [Simple description of the diagram] 5 None. [Main component symbol description]
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