201248327 六、發明說明： 【發明所屬之技術領域】 本發明關於適合吐出噴嘴式塗佈法的正型光阻組成物 以及使用該正型光阻組成物之光阻圖型形成方法。 本案係以2011年2月25日在日本申請的特願2011-040 168號爲基礎，主張優先權，在此援用其內容。 【先前技術】 以往’在使用小型玻璃基板的液晶顯示元件製造領域 中’作爲光阻塗佈方法，使用中央滴下後旋塗方法（下述 非專利文獻1 ) » 於中央滴下後自旋塗佈法中，雖然得到良好的塗佈均 勻性’但是例如當爲1 m見方等級的大型基板時，旋轉時 (自旋時）甩開的廢棄光阻量係相當多，而且發生高速旋 轉所致的基板之破裂、生產節拍時間（tact time )的確保 之問題。再者，中央滴下後旋塗方法的塗佈性能，由於依 賴於自旋時的旋轉速度與光阻的塗佈量，若採用於大型化 的第 5 世代基板（1000mmxl200mm 〜1280mmxl400mm 左 右）等’則沒有可得到必要的加速度之通用馬達，若特別 訂作如此的馬達，則有零件成本增大之問題。 又，即使基板尺寸或裝置尺寸大型化，例如塗佈均勻 性±3%、生產節拍時間60〜70秒/片等，由於塗佈步驟的 要求性能也幾乎沒有改變，故於中央滴下後旋塗方法中， 難以對應於塗佈均句性以外之要求。 -5- 201248327 如此地，基板係往大型化進展，在最近亦開始第10 世代基板（288 0mmx3 130mm )的製造中，作爲可適用於 第4世代基板（680mmx 880mm)以後，尤其第5世代基 板以後的大型基板之新的光阻塗佈方法，有提案藉由吐出 噴嘴式的光阻塗佈法。 吐出噴嘴式的光阻塗佈法，係藉由使吐出噴嘴與基板 相對地移動而在基板的塗佈面全面上塗佈正型光阻組成物 之方法，例如有提案使用具有複數的噴嘴孔以列狀排列的 吐出口或縫狀的吐出口，可將光阻組成物以帶狀吐出之吐 出噴嘴的方法。又，亦有提案在以吐出噴嘴式於基板的塗 佈面全面上塗佈光阻組成物後，使該基板自旋而調整膜厚 之方法。 作爲以對大型基板的塗佈爲目的之光阻組成物，有揭 示含有鹼可溶性酚醛清漆樹脂、含萘醌二疊氮基的化合物 、含丙二醇單甲基醚乙酸酯的有機溶劑及界面活性劑的正 型光阻組成物（專利文獻1 ):或，含有鹼可溶酚醛清漆 樹脂、萘醌二疊氮感光性化合物及含苯甲醇或苯甲醇衍生 物所成之有機溶劑的光阻組成物（專利文獻2 )。 〔先前技術文獻〕 〔專利文獻〕 〔專利文獻1〕特開2 0 0 5 - 1 0 7 1 3 0號公報 〔專利文獻2〕特表2007-531897號公報 〔非專利文獻〕 〔非專利文獻1〕電子雜誌（Electronic Journal) -6- 201248327 2002年8月號、121〜123頁。 【發明內容】 〔發明所欲解決的問題〕 關於吐出噴嘴式塗佈法，最近已開發、發表合適的塗 佈裝置，該塗佈法所用的光阻組成物之較佳化係成爲今後 重要的課題。 又，於大型基板中，在該塗佈後的乾燥，多使用減壓 乾燥裝置。使用減壓乾燥裝置時，基板之光阻組成物塗佈 面的相反面，係在以複數的針支持多點的狀態下進行減壓 乾燥。於該情況下，由於針的接點與其以外的部分之導熱 性的差異等’在乾燥後的塗膜會有針痕殘留的問題。此針 痕的問題係在光阻組成物的烘烤時亦會發生。 再者，於如上述的大型基板中，由於塗佈性能的要求 亦與小型基板相同，要求在塗佈後沒有霧斑或筋狀痕，而 可形成均勻的塗膜之光阻組成物。 本發明係鑒於前述情事而完成者，課題在於提供可適 用於吐出噴嘴式塗佈法的正型光阻組成物及使用該正型光 阻組成物之光阻圖型形成方法。 〔解決問題的手段〕 爲了解決上述問題’本發明採用以下的構成。 即，本發明的第一態樣係一種正型光阻組成物，其係 用於吐出噴嘴式塗佈法，該塗佈法具有藉由使吐出噴嘴與 201248327 基板相對地移動而在基板的塗佈面全體上塗佈光阻組成物 之步驟，該正型光阻組成物係將鹼可溶性酚醛清漆樹脂（ A)及含萘醌二#氮基的化合物（C)溶解在含有碳數6以 上的二醇（S1)之有機溶劑（S)中而成。 本發明的第二態樣係一種光阻圖型形成方法，其包含 :使吐出噴嘴與支持體相對地移動而在支持體的塗佈面全 面上塗佈前述第一態樣的正型光阻組成物之步驟、於前述 支持體上形成光阻膜之步驟、將前述光阻膜曝光之步驟及 將前述光阻膜鹼顯像以形成光阻圖型之步驟。 於本說明書及本申請專利範圍中，所謂的「烷基」， 只要沒有特別預先指明，則包含直鏈狀、支鏈狀及環狀的 1價飽和烴基。 所謂的「伸烷基」，只要沒有特別預先指明，則包含 直鏈狀、支鏈狀及環狀的2價飽和烴基。烷氧基中的烷基 亦同樣。 「曝光」係包含輻射線的照射總體之槪念。 〔發明的效果〕 若依照本發明，可提供適用於吐出噴嘴式塗佈法的正 型光阻組成物以及使用該正型光阻組成物的光阻圖型形成 方法。 【實施方式】 〔實施發明的形態〕 -8 - 201248327 《正型光阻組成物》 本發明的第一態樣之IE型光阻組成物係將鹼可溶性酚 醒清漆樹脂（A)(以下稱爲「（A)成分」）及含萘醌 二疊氮基的化合物（C)(以下稱爲「（c)成分」）溶解 在含有碳數6以上的二醇（Sl)之有機溶劑（s)(以下 稱爲「（S)成分」）中而成。 < (A )成分> 本發明中的（A)成分係鹼可溶性酚醛清漆樹脂，可 單獨1種或組合2種以上來使用通常作爲化學增幅型光阻 用的基材成分所用的鹼可溶性酚醛清漆樹脂。 此處，所謂的「基材成分」，就是具有膜形成能力的 有機化合物，較佳使用分子量爲500以上的有機化合物。 由於該有機化合物的分子量爲500以上’而提高膜形成能 力，而且容易形成奈米等級的光阻圖型。 作爲（A )成分的具體例’可舉出使酚類與醛類在酸 性觸媒下反應而得之酚醛清漆樹脂° 作爲前述酚類’例如可舉出苯酚；間甲酌、對甲酚、 鄰甲酚等的甲酚類；2,3-二甲苯酚、2,5·二甲苯酚、3，5_二 甲苯酚、3,4-二甲苯酚等的二甲苯酚類；間乙基苯酚、對 乙基苯酚、鄰乙基苯酹、2,3,5-三甲基苯酚、2,3,5-三乙基 苯酚、4-第三丁基苯酚、3-第三丁基苯酚、2_第三丁基苯 酚、2-第三丁基-4-甲基苯酚、2-第三丁基-5-甲基苯酚等 -9 - 201248327 的烷基酚類；對甲氧基苯酚、間甲氧基苯酚、對乙氧基苯 酚、間乙氧基苯酚、對丙氧基苯酚、間丙氧基苯酚等的烷 氧基酚類；鄰異丙烯基苯酚、對異丙烯基苯酚、2-甲基-4-異丙烯基苯酚、2-乙基-4-異丙烯基苯酚等的異丙烯基酚類 ;苯基苯酚等的芳基酚類；4,4’-二羥基聯苯、雙酚A、間 苯二酚、氫醌、焦掊酚等的多羥基酚類等。於此等酚類之 中，特佳係間甲酚、對甲酚。 此等酚類係可單獨使用，而且也可組合2種以上使用 。其中，較佳爲組合2種以上使用，最佳爲組合間甲酚與 對甲酚使用。 作爲前述醛類，例如可舉出甲醛、_三聚甲醛、三Π弯烷 、乙醛、丙醛、丁醛、三甲基乙醛、丙烯醛、巴豆醛、環 己醛、糠醛、呋喃基丙烯醛、苯甲醛、對苯二甲醛、苯基 乙醛、α-苯基丙基醛、β-苯基丙基醛、鄰羥基苯甲醛、間 羥基苯甲醛、對羥基苯甲醛、鄰甲基苯甲醛、間甲基苯甲 醛、對甲基苯甲醛、鄰氯苯甲醛、間氯苯甲醛、對氯苯甲 醛、桂皮醛等。於此等醛類之中，從取得的容易性來看， 較佳爲甲醛。 此等醛類係可單獨使用，而且也可組合2種以上使用 〇 作爲前述酸性觸媒，例如可舉出鹽酸、硫酸、甲酸、 草酸、對甲苯磺酸等，較佳爲草酸。 (Α)成分係可由1種的酚醛清漆樹脂所組成，也可 由2種以上的酚醛清漆樹脂所組成。特別地，藉由混合2 -10- 201248327 種以上的酚醛清漆樹脂，可適宜調整光阻組成物的感度。 本發明中’作爲（A )成分，較佳爲含有以下例示的 (A’）成分之酚醛清漆樹脂者。 〔（A’）成分〕 本發明中，（A’）成分係質量平均分子量（Mw)( 凝膠滲透層析術所測定的聚苯乙烯換算基準）爲1000〜 1 5 000的酚醛清漆樹脂，前述酚醛清漆樹脂係對於間甲酚 與對甲酚的投入比例（莫耳比）爲間甲酚/對甲酚=20/80〜 8 0/2 0之混合酚類，使用甲醛當作縮合劑所合成之酚醛清 漆樹脂。（A)成分中若含有（A’）成分，則適合高感度 的光阻組成物之調製，提高未曝光部的殘膜性而較佳。 (A’）成分中，間甲酚與對甲酚之投入比例（莫耳比 )特佳爲間甲酚/對甲酚=20/80〜50/50。 本發明中，（A )成分係可混合使用間甲酚與對甲酚 之投入比例或Mw不同的複數之（A’）成分，而且亦可含 有（A’）成分以外的酚醛清漆樹脂。惟，（A)成分中的 (A ’）成分之合計的含有比例較佳爲5 0質量％以上，更佳 爲90質量％以上，亦可爲100質量％。最佳爲100質量％ 又，作爲本發明的（A)成分，較佳係使用鹼溶解性 較佳爲25〜400nm /秒，更佳爲超過25nm /秒但400nm /秒 以下，尤佳爲50〜40〇nm/秒的範圍之酚醛清漆樹脂所成 之鹼可溶性酚醛清漆樹脂。鹼溶解性若爲前述範圍，則可 -11 - 201248327 調製作爲吐出噴嘴式塗佈法用的更合適之正型光阻組成物 0 特別地，鹼溶解性若在50〜400nm/秒的範圍內’則 由於得到高感度’在曝光部的殘澄少’對比優異’更且在 低NA條件下的高解析與光阻輪廓的垂直性優異，而較佳 〇 再者，於本說明書中，所謂的「鹼溶解性」，係指在 支持體上以指定的膜厚（〇·5〜2.〇l^m左右）設置由鹼可溶 性酚醛清漆樹脂所成的光阻層’將該光阻層浸漬在2.38 質童％氫氧化四甲銨（以下稱爲TMAH)水溶液（約23°C )中，求得該光阻層的膜厚成爲Ομηι爲止所需要的時間， 藉由下式〔.鹼溶解性=光阻層的膜厚/該膜厚成爲〇爲止所 需要的時間〕來算出之値（nm/秒）。由鹼可溶性酚醛清 漆樹脂所成的光阻層，例如係藉由將酚醛清漆樹脂溶解在 丙二醇單甲基醚乙酸酯（PGMEA )中而成爲20質量％濃 度的溶液，在3吋矽晶圓上旋塗，於設定在1 1 〇 °C的熱板 上進行90秒的加熱處理而形成。 前述「鹼溶解性」係可藉由調整構成（A)成分的構 成單位之種類或其比例、（A )成分的Mw等來控制。 (A )成分全體的Mw較佳爲1 000以上，更佳爲 2000〜15000，尤佳爲3000〜10000。該Mw若爲1000以 上，則在使光阻膜的膜厚成爲均勻上係較佳，光阻組成物 的微影特性係升高。 當（A )成分係由2種以上的酚醛清漆樹脂所組成時 -12- 201248327 ，各自的酚醛清漆樹脂之Mw係沒有特別的限定，較佳係 以作爲（A)成分全體的Mw成爲1 000以上之方式來調製 < (C )成分> 本發明中，（C)成分係含萘醌二疊氮基的化合物， 爲感光性成分。（C)成分係可使用以往作爲吐出噴嘴式 塗佈法用正型光阻組成物之感光性成分所用者。 作爲（C )成分的具體例，例如可舉出下述化學式（ II)所示之含酚性羥基的化合物與1,2-萘醌二疊氮磺酸化 合物之酯化反應生成物（cl)(以下稱爲（cl)成分）當 作合適者。 【化1】201248327 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a positive-type photoresist composition suitable for a discharge nozzle coating method and a photoresist pattern forming method using the positive-type photoresist composition. This case is based on the Japanese Patent Application No. 2011-040 168, which was filed on February 25, 2011, and claims priority. The content is hereby incorporated. [Prior Art] In the field of manufacturing liquid crystal display devices using small glass substrates, 'the method of photoresist coating is used as a photoresist coating method, and the central drip-coating method is used (Non-Patent Document 1 below) » Spin coating after centrifugation at the center In the method, although good coating uniformity is obtained, for example, when it is a large substrate of 1 m square, the amount of waste photoresist which is opened during rotation (at the time of spin) is quite large, and high-speed rotation occurs. The problem of the rupture of the substrate and the tact time of the production. In addition, the coating performance of the spin coating method in the center drip is dependent on the spin speed at the time of spin and the amount of photoresist applied, and is applied to a fifth-generation substrate (1000 mm x 120 mm to 1280 mm x 400 mm) that is enlarged. There is no general-purpose motor that can obtain the necessary acceleration. If such a motor is specifically ordered, there is a problem that the cost of parts increases. Further, even if the substrate size or the device size is increased, for example, the coating uniformity is ±3%, the production tact time is 60 to 70 seconds/piece, and the like, since the performance of the coating step is hardly changed, the spin coating is performed after the center is dripped. In the method, it is difficult to correspond to the requirements other than the coating uniformity. -5- 201248327 As a result, the substrate has been increasing in size, and in the recent manufacture of the 10th generation substrate (288 0mmx3 130mm), it is applicable to the 4th generation substrate (680mmx 880mm), especially the 5th generation substrate. A new photoresist coating method for a large substrate has been proposed by a nozzle-type photoresist coating method. The nozzle-type photoresist coating method is a method in which a positive-type photoresist composition is applied to a coated surface of a substrate by moving a discharge nozzle and a substrate, and for example, it is proposed to use a plurality of nozzle holes. A method of discharging a nozzle in which a photoresist composition is discharged in a strip shape by a discharge port or a slit-shaped discharge port arranged in a row. Further, there has been proposed a method in which a photoresist composition is applied to a coating surface of a substrate by a discharge nozzle type, and then the substrate is spinned to adjust the film thickness. As a photoresist composition for the purpose of coating a large substrate, an organic solvent containing a base-soluble novolac resin, a naphthoquinonediazide-containing compound, a propylene glycol monomethyl ether acetate-containing organic solvent, and interfacial activity are disclosed. Positive-type photoresist composition of the agent (Patent Document 1): or a photoresist composition containing an alkali-soluble novolac resin, a naphthoquinonediazide photosensitive compound, and an organic solvent containing a benzyl alcohol or a benzyl alcohol derivative (Patent Document 2). [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] JP-A-2006-531897 (Non-Patent Document) [Non-Patent Document] [Non-Patent Document] 1] Electronic Journal -6- 201248327 August 2002 issue, 121-123 pages. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] With regard to the discharge nozzle coating method, a suitable coating device has recently been developed and published, and the improvement of the photoresist composition used in the coating method is important in the future. Question. Further, in the large substrate, a vacuum drying apparatus is often used for drying after the application. When the vacuum drying apparatus is used, the opposite surface of the coating surface of the resist composition of the substrate is dried under reduced pressure while supporting a plurality of needles. In this case, there is a problem that the coating film after drying has a needle mark remaining due to the difference in thermal conductivity between the contact portion of the needle and the other portion. This problem of stitching also occurs when the photoresist composition is baked. Further, in the large substrate as described above, since the coating performance is also the same as that of the small substrate, it is required to form a uniform photoresist film composition without fogging or rib-like marks after coating. The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a positive resist composition which can be applied to a discharge nozzle coating method and a photoresist pattern forming method using the positive resist composition. [Means for Solving the Problems] In order to solve the above problems, the present invention adopts the following configuration. That is, the first aspect of the present invention is a positive-type photoresist composition for use in a discharge nozzle coating method having a coating on a substrate by moving a discharge nozzle relative to a 201248327 substrate. a step of applying a photoresist composition on the entire surface of the cloth, the positive-type photoresist composition dissolving the alkali-soluble novolac resin (A) and the naphthoquinone-containing nitrogen compound (C) in a carbon number of 6 or more The diol (S1) is formed in an organic solvent (S). A second aspect of the present invention is a method for forming a photoresist pattern, comprising: moving a discharge nozzle relative to a support to apply a positive photoresist of the first aspect on a coated surface of the support; a step of forming a photoresist film on the support, a step of exposing the photoresist film, and a step of alkali imaging the photoresist film to form a photoresist pattern. In the present specification and the scope of the present application, the "alkyl group" includes a linear, branched, and cyclic monovalent saturated hydrocarbon group unless otherwise specified. The "alkylene group" includes a linear, branched, and cyclic divalent saturated hydrocarbon group unless otherwise specified. The same applies to the alkyl group in the alkoxy group. "Exposure" is a commemoration of the overall illumination of the radiation. [Effects of the Invention] According to the present invention, it is possible to provide a positive resist composition suitable for the discharge nozzle coating method and a resist pattern forming method using the positive resist composition. [Embodiment] EMBODIMENT OF THE INVENTION -8 - 201248327 <<Positive photoresist composition>> The IE type photoresist composition of the first aspect of the present invention is an alkali-soluble phenol awake resin (A) (hereinafter referred to as The "(A) component") and the naphthoquinonediazide-containing compound (C) (hereinafter referred to as "(c) component") are dissolved in an organic solvent (s) containing a carbon number of 6 or more (S1). ) (hereinafter referred to as "(S) component"). < (A) Component> The component (A) in the present invention is an alkali-soluble novolac resin, and may be used alone or in combination of two or more kinds thereof to use an alkali-soluble which is generally used as a substrate component for a chemically amplified photoresist. Novolak resin. Here, the "substrate component" is an organic compound having a film forming ability, and an organic compound having a molecular weight of 500 or more is preferably used. Since the molecular weight of the organic compound is 500 or more, the film forming ability is improved, and a nanometer-scale photoresist pattern is easily formed. Specific examples of the component (A) include a novolak resin obtained by reacting a phenol with an aldehyde under an acidic catalyst. The phenol is, for example, phenol, a phenol, a p-cresol, or a p-cresol. a cresol such as o-cresol; a xylenol such as 2,3-xylenol, 2,5-xylenol, 3,5-xylenol or 3,4-xylenol; Phenol, p-ethylphenol, o-ethylphenylhydrazine, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol , 2_t-butylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-5-methylphenol, etc.-9 - 201248327 alkylphenols; p-methoxyphenol , alkoxyphenols such as m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, m-propoxyphenol, etc.; o-isopropenylphenol, p-isopropenylphenol, Isopropenylphenols such as 2-methyl-4-isopropenylphenol and 2-ethyl-4-isopropenylphenol; arylphenols such as phenylphenol; 4,4'-dihydroxybiphenyl Polyphenols such as bisphenol A, resorcinol, hydroquinone, and pyrogallol. Among these phenols, particularly excellent inter-system cresol and p-cresol. These phenols may be used singly or in combination of two or more. Among them, it is preferred to use two or more kinds in combination, and it is most preferable to use a combination of m-cresol and p-cresol. Examples of the aldehydes include formaldehyde, _trimaldehyde, triterpene, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanal, furfural, and furyl. Acrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropyl aldehyde, β-phenylpropyl aldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methyl Benzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, and the like. Among these aldehydes, formaldehyde is preferred from the viewpoint of ease of availability. These aldehydes may be used singly or in combination of two or more kinds. As the acidic catalyst, for example, hydrochloric acid, sulfuric acid, formic acid, oxalic acid or p-toluenesulfonic acid may be mentioned, and oxalic acid is preferred. The (Α) component may be composed of one type of novolak resin, or may be composed of two or more types of novolak resins. In particular, the sensitivity of the photoresist composition can be suitably adjusted by mixing 2 -10-201248327 or more novolak resins. In the present invention, the component (A) is preferably a novolac resin containing the component (A') exemplified below. [(A') component] In the present invention, the (A') component is a novolak resin having a mass average molecular weight (Mw) (based on polystyrene conversion measured by gel permeation chromatography) of 1000 to 15,000. The above-mentioned novolac resin is a mixed phenol with a ratio of m-cresol to p-cresol (mol ratio) of m-cresol/p-cresol=20/80 to 8 0/2 0, and formaldehyde is used as a condensing agent. The novolak resin synthesized. When the component (A') contains the component (A'), it is preferable to prepare a photoresist composition having a high sensitivity and to improve the residual film property of the unexposed portion. In the component (A'), the ratio of m-cresol to p-cresol (mol ratio) is particularly preferably m-cresol/p-cresol = 20/80 to 50/50. In the present invention, the component (A) may be a mixture of (A') components having a different ratio of m-cresol to p-cresol or a difference in Mw, and may contain a novolak resin other than the component (A'). The total content of the component (A') in the component (A) is preferably 50% by mass or more, more preferably 90% by mass or more, and may be 100% by mass. It is preferably 100% by mass. Further, as the component (A) of the present invention, it is preferred to use an alkali solubility of preferably 25 to 400 nm / sec, more preferably more than 25 nm / sec but 400 nm / sec or less, and particularly preferably 50. An alkali-soluble novolak resin made of a novolak resin in the range of ~40 〇nm/sec. When the alkali solubility is in the above range, -11 - 201248327 can be prepared as a more suitable positive resist composition for the discharge nozzle coating method. Specifically, the alkali solubility is in the range of 50 to 400 nm/second. 'The result is that the high sensitivity is less in the exposed portion, the contrast is excellent, and the high resolution under low NA conditions and the perpendicularity of the photoresist profile are excellent, and more preferably, in this specification, The "alkali solubility" means that a photoresist layer made of an alkali-soluble novolak resin is provided on the support at a predetermined film thickness (about 5 to 2. 〇l^m). Immersed in a 2.38 aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) (about 23 ° C), and determined the time required for the thickness of the photoresist layer to be Ομηι, by the following formula [. The solubility (nm/sec) was calculated as the solubility = the film thickness of the photoresist layer and the time required for the film thickness to become 〇. The photoresist layer formed of the alkali-soluble novolak resin is, for example, a solution of 20% by mass in a solution of a novolac resin dissolved in propylene glycol monomethyl ether acetate (PGMEA). The spin coating was carried out by heat treatment for 90 seconds on a hot plate set at 1 1 〇 ° C. The above "alkali solubility" can be controlled by adjusting the type or ratio of the constituent unit constituting the component (A), Mw of the component (A), and the like. The Mw of the entire component (A) is preferably 1,000 or more, more preferably 2,000 to 15,000, and still more preferably 3,000 to 10,000. When the Mw is 1000 or more, it is preferable to make the film thickness of the photoresist film uniform, and the lithographic characteristics of the photoresist composition are increased. When the component (A) is composed of two or more kinds of novolak resins, -12 to 201248327, the Mw of the novolak resin is not particularly limited, and it is preferable that the Mw of the entire component (A) is 1,000. In the above aspect, the component (C) is a compound containing a naphthoquinonediazide group and is a photosensitive component. As the component (C), those conventionally used as the photosensitive component of the positive resist composition for the discharge nozzle type coating method can be used. Specific examples of the component (C) include, for example, an esterification reaction product (cl) of a phenolic hydroxyl group-containing compound represented by the following chemical formula (II) and a 1,2-naphthoquinonediazidesulfonic acid compound. (hereinafter referred to as (cl) component) is considered appropriate. 【化1】
作爲前述1,2-萘醌二疊氮磺酸化合物，可舉出1，2-萘 醌二疊氮-5-磺醯基化合物、1,2-萘醌二疊氮-4-磺醯基化合 物等，較佳爲I，2-萘醌二疊氮-5-磺醯基化合物》 前述（cl)成分的平均酯化率較佳爲50〜70%，更佳 爲55〜65%。該平均酯化率若爲50%以上，從抑制鹼顯像 後的膜減少、殘膜率變高之點來看係較佳。該平均酯化率 若爲70%以下，則保存安定性升高。 前述（cl)成分在非常便宜而且可調製高感度的正型 -13- 201248327 光阻組成物之點係特佳。 又，作爲（C)成分，除了前述（cl)成分以外，還 可使用其它的醌二疊氮酯化物（c2)(以下稱爲（C2)成 分）。 作爲（c2 )成分，例如可舉出後述通式（in )所示之 含酚性羥基的化合物與1,2-萘醌二疊氮基磺酸化合物（較 佳1,2-萘醌二疊氮基-5-磺醯基化合物或1，2-萘醌二®氮 基-4-磺醯基化合物）之酯化反應生成物。 (C)成分中的（c2)成分之含有比例較佳爲50質量 %以下，特佳爲25質量％以下。 本發明的正型光阻組成物中之（C )成分的含有比例 ，相對於（A)成分與視需要配合的（B)成分（後述）之 合計量100質量份而言，較佳爲15〜40質量份的範圍內 ，更佳爲18〜35質量份的範圍內，尤佳爲18〜30質量份 的範圍內。（C )成分的含有比例若爲1 5質量份以上，則 轉印性升高，容易形成所欲形狀的光阻圖型。另一方面， (C )成分的含有比例若爲40質量份以下，則感度或解析 性升高，而且能抑制鹼顯像處理後的殘渣物之發生。 < (S )成分> 本發明的光阻組成物係藉由溶解在含有碳數6以上的 二醇（S1)(以下稱爲「（S1)成分」的）之（S)成分 中而製造。 (S)成分係除了（S1)成分，還可含有不相當於（ -14- 201248327 S1)成分的有機溶劑（S2)(以下稱爲「（μ)成 ((Si)成分） 本發明中，（s 1 )成分係碳數6以上的二醇。 作爲碳數6以上的二醇’較佳爲碳數6〜9的 具體地例如可舉出己二醇（2-甲基_2,4_戊二醇）、 1，5-戊二醇、2-乙基-1,3-己二醇 ' 1>2_ 己二醇、ι，6_ 、1,2-庚二醇、1，7-庚二醇、1，2-辛二醇、丨，8-辛 2,6-二甲基-3,5-庚二醇等。 其中，作爲本發明中的（S 1)成分，較佳爲碳 7的二醇，更佳爲己二醇、1，2-己二醇或丨，7-庚二醇 (S1)成分係可單獨使用1種，也可倂用2種J (S)成分中的（S1)成分之比例，相對於（S 的總質量而言，可爲1 〇〇質量％，較佳爲0.1〜40質 更佳爲0.5〜20質量％，尤佳爲1〜10質量％。藉由 範圍內，而減低減壓乾燥或烘烤時的針痕殘存，亦 膜的霧斑或筋狀痕。 ((S2)成分） (S2 )成分係沒有特別的限定，可適宜選擇1 種以上的以往吐出噴嘴式塗佈法所用的正型光阻組 有機溶劑而使用。 其中，作爲本發明中的（S 2 )成分，從塗佈性 二醇， 3_甲基_ 己二醇 二醇、 數 6〜 〇 以上。 )成分 1量％， 在上述 減低塗 種或2 成物之 優異， -15- 201248327 即使在大型玻璃基板上也光阻被膜的膜厚均勻性優異來看 ，較佳爲含有丙二醇單甲基醚乙酸酯（PGMEA )。 於（S2)成分中’最佳爲將PGMEA以單獨溶劑使用 ，但亦可倂用PGMEA以外的溶劑，例如可舉出乳酸乙酯 、γ -丁內酯 '丙二醇單丁基醚等。 使用乳酸乙酯時，相對於PGMEA而言，以質量比計 宜爲0.1〜1 0倍量，較佳以1〜5倍量的範圍來配合。 又，使用γ-丁內酯’相對於PGMEA而言，以質量比 計宜爲0.01〜1倍量’較佳以0.05〜0.5倍量的範圍來配 合。 (S)成分中的（S2)成分之比例’相對於（S)成分 的總質量而言’較佳爲60〜99.9質量％’更佳爲80〜99·5 質量％，尤佳爲9 0〜9 9.0質量％。 本發明中，使用（S)成分，正型光阻組成物中的上 述（A)成分及（C)成分與後述的（B)成分之合計比例 較佳爲3 0質量％以下’更佳爲2 5質量％以下’尤佳爲2 0 質量％以下°又’該比例較佳爲5質量％以上’更佳爲1 0 質量％以上》 即，使用（S )成分’正型光阻組成物中的上述（A ) 成分及（c)成分與後述的（B)成分之合計比例較佳爲5 質量％以上、3 0質量％以下’更佳爲5質量％以上、2 5質 量％以下，尤佳爲1 〇質量％以上、25質量％以下’特佳爲 1 〇質量％以上、20質量％以下。 該含有比例若爲前述範圍’則在光阻圖型形成中’於 -16- 201248327 自吐出噴嘴將正型光阻組成物吐出成帶狀而塗佈在支持體 上時，得到良好的塗佈性。又，於該塗佈後，即使自旋時 ，由於也得到良好的流動性，在良率佳地形成膜厚的均勻 性爲良好的光阻膜方面係較佳。 <任意成分.（B)成分> 本發明的正型光阻組成物，以感度提高等爲目的，較 佳爲更含有分子量1000以下之含酚性羥基的化合物（B) (以下稱爲「（B)成分」）。 (B)成分的分子量爲1000以下，較佳爲200〜1000 〇 (B)成分的分子量若爲1000以下，則容易得到感度 提高的效果。 特別地，於液晶元件製造等之使用吐出噴嘴式塗佈法 的領域中，通過料量的提高係非常大的問題，而且光阻消 耗量常常變多。因此，於正型光阻組成物的情況，較佳爲 高感度而且便宜，若使用該（B)成分，則可達成比較便 宜且高感度化。又，若使用（B)成分，則由於在光阻圖 型形成中表面難溶化層係強固地形成，在鹼顯像時未曝光 部分的光阻膜之膜減少量係少，可抑制由於顯像時間的差 所產生的顯像不均之發生而較佳。 作爲（B )成分，可適宜使用以往吐出噴嘴式塗佈法 用之正型光阻組成物中所用的分子量1 〇〇〇以下之含酚性 羥基的化合物。 -17- 201248327 作爲（B )成分的具體例，例如可舉出下述通式（III )所示之含酚性羥基的化合物當作合適者，因爲可有效地 提高感度。 【化2】The 1,2-naphthoquinonediazidesulfonic acid compound may, for example, be a 1,2-naphthoquinonediazide-5-sulfonyl compound or a 1,2-naphthoquinonediazide-4-sulfonyl group. The compound or the like is preferably an I,2-naphthoquinonediazide-5-sulfonyl compound. The average esterification ratio of the component (cl) is preferably from 50 to 70%, more preferably from 55 to 65%. When the average esterification ratio is 50% or more, it is preferable from the viewpoint of suppressing reduction of the film after alkali development and increasing the residual film ratio. When the average esterification ratio is 70% or less, the storage stability is increased. The above-mentioned (cl) component is particularly excellent in that it is very inexpensive and can modulate a high-sensitivity positive-type -13-201248327 photoresist composition. Further, as the component (C), in addition to the above (cl) component, other quinonediazide ester compound (c2) (hereinafter referred to as (C2) component) may be used. The (c2) component may, for example, be a phenolic hydroxyl group-containing compound represented by the following formula (in) and a 1,2-naphthoquinonediazidesulfonic acid compound (preferably 1,2-naphthoquinone quinone). An esterification reaction product of a nitrogen-5-sulfonyl compound or a 1,2-naphthoquinone® nitrogen-4-sulfonyl compound. The content ratio of the component (c2) in the component (C) is preferably 50% by mass or less, and particularly preferably 25% by mass or less. The content ratio of the component (C) in the positive resist composition of the present invention is preferably 15 parts by mass based on 100 parts by mass of the total of the component (B) and the component (B) to be blended as necessary (described later). The range of ~40 parts by mass is more preferably in the range of 18 to 35 parts by mass, and particularly preferably in the range of 18 to 30 parts by mass. When the content ratio of the component (C) is 15 parts by mass or more, the transfer property is increased, and a photoresist pattern having a desired shape is easily formed. On the other hand, when the content ratio of the component (C) is 40 parts by mass or less, the sensitivity or the resolution is improved, and the occurrence of the residue after the alkali development treatment can be suppressed. < (S) Component> The photoresist composition of the present invention is dissolved in the (S) component containing a diol (S1) having a carbon number of 6 or more (hereinafter referred to as "(S1) component"). Manufacturing. The (S) component may contain an organic solvent (S2) which is not equivalent to the component (-14-201248327 S1) except for the component (S1) (hereinafter referred to as "(μ)成((Si) component)) The (s 1 ) component is a diol having a carbon number of 6 or more. Specific examples of the diol of a carbon number of 6 or more, preferably 6 to 9 carbon atoms, are exemplified by hexanediol (2-methyl-2, 4). _Pentanediol), 1,5-pentanediol, 2-ethyl-1,3-hexanediol '1> _ hexanediol, ι, 6_, 1,2-heptanediol, 1,7- Heptanediol, 1,2-octanediol, anthracene, 8-octane 2,6-dimethyl-3,5-heptanediol, etc. Among them, as the component (S 1) in the present invention, it is preferably The diol of carbon 7 is more preferably hexanediol, 1,2-hexanediol or hydrazine, and the 7-heptanediol (S1) component may be used singly or in combination of two kinds of J (S) components. The ratio of the (S1) component in the middle may be 1 〇〇 mass%, preferably 0.1 to 40, more preferably 0.5 to 20 mass%, and particularly preferably 1 to 10 mass, based on the total mass of S. %. By reducing the amount of needle marks remaining under reduced pressure drying or baking, the film also has fog or streaks. ((S2) component) (S2) component is not special In the above, the positive-type resist group organic solvent used in the conventional discharge nozzle coating method can be appropriately selected and used. The (S 2 ) component in the present invention is a coating diol, 3_ Methyl _ hexanediol diol, number 6 to 〇 or more. ) Component 1 % by weight, excellent in the above-mentioned reduction coating or 2%, -15-201248327 Film thickness of the photoresist film even on a large glass substrate In terms of excellent uniformity, propylene glycol monomethyl ether acetate (PGMEA) is preferred. Among the components (S2), it is preferred to use PGMEA as a solvent alone, but it is also possible to use a solvent other than PGMEA, for example Ethyl lactate, γ-butyrolactone, propylene glycol monobutyl ether, etc., when using ethyl lactate, it is preferably 0.1 to 10 times by mass, preferably 1 to 1 part by mass of PGMEA. Further, the γ-butyrolactone is preferably used in a range of 0.01 to 1 times by mass in terms of mass ratio, preferably in a range of 0.05 to 0.5 times, relative to PGMEA. The ratio of the (S2) component in the component 'is preferably 60 to 9 with respect to the total mass of the (S) component. 9.9 mass%' is more preferably 80 to 99.5% by mass, and particularly preferably 90 to 99.0% by mass. In the present invention, the component (A) in the positive resist composition is used as the component (S) and The total ratio of the component (C) to the component (B) to be described later is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 2% by mass or less. Further, the ratio is preferably 5 mass%. % or more is more preferably 10% by mass or more. That is, the total ratio of the above (A) component and (c) component to the (B) component described later in the positive electrode resist composition of the (S) component is preferably used. 5% by mass or more and 30% by mass or less, more preferably 5% by mass or more, and 25% by mass or less, and particularly preferably 1% by mass or more and 25% by mass or less, particularly preferably 1% by mass or more, and 20%. Below mass%. When the content ratio is in the range of 'there is a pattern in the formation of the photoresist pattern', the coating is applied to the support from the discharge nozzle at the time of the formation of the photoresist pattern at -16-201248327, and good coating is obtained. Sex. Further, even after the application, even if spin is applied, good fluidity is obtained, and it is preferable to form a photoresist film having a good film thickness with good yield. <Optional component. (B) component> The positive-type resist composition of the present invention preferably contains a phenolic hydroxyl group-containing compound (B) having a molecular weight of 1,000 or less for the purpose of improving sensitivity and the like (hereinafter referred to as "(B) component"). When the molecular weight of the component (B) is 1000 or less, preferably 200 to 1000 Å, and the molecular weight of the component (B) is 1000 or less, the effect of improving the sensitivity is easily obtained. In particular, in the field of the use of the discharge nozzle type coating method for manufacturing liquid crystal elements, the increase in the amount of the material is a very large problem, and the amount of photoresist loss often increases. Therefore, in the case of the positive-type resist composition, it is preferably high-sensitivity and inexpensive, and when the component (B) is used, it is possible to achieve comparatively high and high sensitivity. Further, when the component (B) is used, since the surface insoluble layer is strongly formed during the formation of the photoresist pattern, the amount of film reduction of the photoresist film in the unexposed portion at the time of alkali development is small, and it is possible to suppress the occurrence of the film. It is preferable that the unevenness of the image produced by the difference in time occurs. As the component (B), a phenolic hydroxyl group-containing compound having a molecular weight of 1 Å or less which is used in a positive resist composition for a conventional discharge nozzle coating method can be suitably used. -17-201248327 Specific examples of the component (B) include, for example, a phenolic hydroxyl group-containing compound represented by the following formula (III), because the sensitivity can be effectively improved. [Chemical 2]
(式中’R〜R各自獨立地表示氫原子、鹵素原子、碳數 1〜ό的烷基、碳數1〜6的烷氧基、或碳數3〜6的環烷基 ;R9〜R11各自獨立地表示氫原子或碳數1〜6的烷基；q 表示氣原子、碳數1〜6的烷基、與R9鍵結合形成的碳數 3〜6的環院基、或下述化學式（IV)所示的殘基：b 表示1〜3的整數：d表示〇〜3的整數：n表示〇〜3的整 數）。 【化3】 (式中，R12及R 碳數1〜6的烷基(wherein R to R each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 碳, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms; R9 to R11; Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; q represents a gas atom, an alkyl group having 1 to 6 carbon atoms, a ring group having a carbon number of 3 to 6 bonded to an R9 bond, or the following chemical formula Residues shown in (IV): b represents an integer of 1 to 3: d represents an integer of 〇3 to 3: n represents an integer of 〇3 to 3). [Formula 3] (wherein R12 and R are alkyl groups having 1 to 6 carbon atoms;
鹵 碳數1〜6的烷氧基、或碳雲 子、 6的 環烷基；c表示1〜3 此等可使用任1 的整數）。 種，也可倂用2種以上。 -18- 201248327 前述式（III)中，R1〜R*各自獨立表示氫原子、鹵 素原子、碳數1〜6的烷基、碳數1〜6的烷氧基、或碳數 3〜6的環烷基。 R1〜R8中’作爲鹵素原子’較佳爲氟原子 '氯原子、 溴原子、碘原子等，特佳爲氟原子。 作爲碳數1〜6的烷基，較佳爲甲基、乙基、丙基、 正丁基或第三丁基，最佳爲甲基。 作爲碳數1〜6的烷氧基，較佳爲甲氧基、乙氧基、 正丙氧基、異丙氧基、正丁氧基或第三丁氧基。 作爲碳數3〜6的環烷基，可舉出環丙基、環丁基、 環戊基、環己基。 其中，作爲R1〜R8，較佳爲氫原子或甲基。 R9〜R11各自獨立表示氫原子或碳數1〜6的烷基，較 佳爲氫原子或甲基。 a、b表示1〜3的整數’最佳爲卜 d表示〇〜3的整數’最佳爲 η表示〇〜3的整數’最佳爲0或 Q表示氫原子、碳數1〜6的烷基、與R9鍵結形成的 碳數3〜6的環烷基、或前述通式（IV)所示的殘基，最 佳爲前述通式（IV )所示的殘基。 前述式（iv)中，R12及R13各自獨立表示氫原子、 鹵素原子、碳數1〜6的烷基、碳數1〜6的烷氧基、或碳 數3〜6的環烷基，最佳爲氫原子。 作爲Ri2及R13，可舉出與R1〜r8同樣者。 -19 - 201248327 c表示1〜3的整數’最佳爲1。 於上述之中，特佳爲下述化學式（1)或（Γ)所示之 含酚性羥基的化合物，因爲感度、殘膜率特別優異。 【化4】The alkoxy group having 1 to 6 carbon atoms or the carbon cloud, 6 cycloalkyl group; c is 1 to 3, and any integer of 1 may be used. Two or more types can also be used. -18- 201248327 In the above formula (III), R1 to R* each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a carbon number of 3 to 6; Cycloalkyl. In R1 to R8, 'as a halogen atom' is preferably a fluorine atom 'chlorine atom, a bromine atom, an iodine atom or the like, and particularly preferably a fluorine atom. The alkyl group having 1 to 6 carbon atoms is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group, and most preferably a methyl group. The alkoxy group having 1 to 6 carbon atoms is preferably a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group or a third butoxy group. Examples of the cycloalkyl group having 3 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Among them, R1 to R8 are preferably a hydrogen atom or a methyl group. R9 to R11 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a methyl group. a, b represents an integer of 1 to 3, 'best is d, and d represents an integer of 〇~3'. Optimum η represents an integer of 〇3 to 3, preferably 0 or Q represents a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. The group having a carbon number of 3 to 6 bonded to R9 or a residue represented by the above formula (IV) is preferably a residue represented by the above formula (IV). In the above formula (iv), R12 and R13 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. Good is a hydrogen atom. Examples of Ri2 and R13 include the same as R1 to r8. -19 - 201248327 c indicates that the integer of 1 to 3 is optimally 1. Among the above, a phenolic hydroxyl group-containing compound represented by the following chemical formula (1) or (Γ) is particularly preferable because the sensitivity and the residual film ratio are particularly excellent. 【化4】
本發明中，（Β)成分係可單獨使用1種，也可倂用 2種以上。 當本發明的正型光阻組成物含有（Β)成分時，（Β) 成分的配合量，相對於（Α)成分的鹼可溶性酚醛清漆樹 脂1〇〇質量份而言，較佳爲1〜25質量份，更佳爲5〜20 質量份的範圍。光阻組成物中的（Β)成分的含量若過少 ，則無法充分得到高感度化、高殘膜率化的提高效果，若 過多則顯像後的基板表面上容易發生殘渣物，而且原料成 本亦變高而不宜。 <任意成分· （Ε)成分> -20- 201248327 本發明的正型光阻組成物》以抑制筋狀痕的發生爲目 的，較佳爲更含有界面活性劑（E)(以下稱爲「（E)成 分」）。（E)成分的含量，相對於正型光阻組成物全體 而言，在可有效地爲止筋狀痕的發生之點，較佳爲 900ppm以下的範圍內。 作爲（E )成分，並沒有特別的限制，例如可使用1 種或2種以上的以往作爲光阻用界面活性劑已知的化合物 〇 作爲（E)成分，氟-矽系界面活性係合適，其中，較 佳爲全氟烷基酯基、烷基矽氧烷基、乙烯氧基與丙烯氧基 所鍵結的非離子性氟-矽系界面活性劑（E-1 )。作爲該界 面活性劑（E-1)，例如可舉出Megafac R-08' R-60(製 品名，大日本油墨化學工業社製）等。 又’更佳係氟含量爲10〜25質量％且矽含量爲3〜1〇 質量％的界面活性劑成分（E-2 )，例如可舉出X-70-090 、X-70-09 1、X-70-092、X-70-093 (製品名，信越化學工 業社製）等’特別地X-70-093由於即使光阻滴下量爲少 量，也抑制筋狀痕或乾燥斑的發生之效果高故較佳。 再者，亦較佳爲具有特定的矽氧烷骨架之聚酯改性聚 二烷基矽氧烷系界面活性劑（E-3 )，例如可舉出8丫1(：-3 10、BYK-3 15、（製品，BYK化學公司製）等，特別地 ，BYK-3 10由於可良好地抑制霧斑或滴下痕及筋狀斑（筋 狀痕）之發生而更佳。 此等（E -1 )〜（E - 3 )的界面活性劑之合計量較佳爲 -21 - 201248327 佔（E )成分中的50質量％以上，其比例亦可爲丨00質量 %。 作爲上述（E-1 )〜（E-3 )以外的界面活性劑之具體 例，可舉出防止條紋用的界面活性劑，例如可舉出 Fluorad FC-430、FC431 (製品名，住友 3M 公司製）、 Eftop EF122A、EF122B、EF122C、EF126 (製品名， TOHKEM PRODUCTS公司製）等的氟系界面活性劑。 (E)成分只要滿足上述範圍的氟含量及矽含量，則 沒特別的限定，但作爲合適的具體例，可舉出商品名乂-70-090、X-70-091、X-70-092、X-70-093 (皆信越化學工 業公司製）之全氟烷基與烷基矽氧烷基和烯氧基所鍵結的 非離子性氟·聚矽氧系界面活性劑等。此處舉出具體例皆 氟含量2 1質量％、矽含量7質量％。 於此等之中，特別地X-7 0-09 3由於即使光阻滴下量 爲少fi，也抑制筋狀痕或乾燥斑的發生之效果高故較佳。 (E)成分的配合量，爲了有效果且高效率地防止吐 出噴嘴式塗佈法的筋狀痕之發生，相對於光阻組成物中的 有機溶劑（S)與（E)成分以外的固體成分而言，較佳爲 0.001〜1質量％，更佳爲0.01〜0.5質量％的範圍。 <其它成分> 於本發明的組成物中，在不損害本發明目的之範圍內 ，可更使用保存安定劑等的各種添加劑。 例如，可適宜含有暈光防止用的紫外線吸收劑。作爲 -22- 201248327 紫外線吸收劑，例如可舉出2,2’，4,4’-四羥基二苯基酮、4-二甲基胺基_2’，4’-二羥基二苯基酮、5-胺基-3-甲基-1-苯 基-4- ( 4-羥基苯基偶氮基）吡唑、4-二甲基胺基-4’-羥基 偶氮基苯、4-二乙基胺基-4’-乙氧基偶氮基苯、4-二乙基 胺基偶氮基苯、薑黃素等。 又，爲了提高由光阻組成物所成的層與其下層的密接 性，可適宜含有密接性改良劑（G ) ( ( G )成分）。作 爲密接性改良劑，較佳爲2- ( 2-羥乙基）吡啶，藉由在光 阻組成物適宜含有其，例如當在Cr膜等的金屬膜上形成 光阻圖型時，可有效地提高由光阻組成物所成的層與金屬 膜之密接性。 含有密接性改良劑時，其配合量若過多，則光阻組成 物的經時變化有變差的傾向，若過少則無法充分得到密捺 性改良效果。因此，密接性改良劑的配合量，相對於全部 固體成分而言，較佳爲0.1〜10質量％的範圍內。 如以上說明，本發明的正型光阻組成物係適合吐出噴 嘴方式的塗佈法，在自吐出噴嘴將光阻組成物吐出成帶狀 而塗佈在基板上時，可防止霧斑或筋狀痕的發生，而且在 將該塗膜乾燥或烘烤時，可減低針痕的發生。 得到上述效果的理由雖然未明，但判斷本發明的正型 光阻組成物因爲含有（S 1 )成分，而可降低正型光阻組成 物的（S )成分之揮發性’而且可使該塗膜的乾燥步驟或 供烤步驟中之（s )成分的揮發速度均一化。 於LCD製造領域中’與半導體元件製造領域所使用 -23- 201248327 的矽晶圓比較下，由於通常使用大型的基板（例如 360mmx460mm以上），故適用吐出噴嘴式塗佈法。又， 於LCD製造用的基板表面上，非常大的凹凸存在，而且 基板本身的畸變亦存在等，塗佈有光阻組成物的基板表面 之狀態，在LCD製造用與半導體元件製造用中係相異。 因此，LCD製造用的光阻組成物與半導體元件製造用的光 阻組成物係技術上相異》 藉由本發明的正型光阻組成物，而對支持體上的潤濕 性優異。形成光阻膜的支持體，即使爲LCD製造用的大 型玻璃角基板，或即使爲在基板的表面上形成有鉬層或鉬 合金層等之含有鉬當作主要成分的層（表面層）之支持體 ，也有效地得到該效果。 '因此’本發明的正型光阻組成物係可適用作爲使用吐 出噴嘴式塗佈法的液晶元件製造用者。 本發明的光阻組成物亦適合於藉由吐出噴嘴式塗佈法 在基板的塗佈面全面上，以最終要求的膜厚塗佈光阻組成 物而不進行自旋之方法（非自旋法），而且亦適合於基板 的塗佈面全面上塗佈光阻組成物後，使基板自旋而進行膜 厚的調整之方法。特別地，適合後者之方法，因爲可一邊 抑制光阻塗佈量’一邊防止自旋後的筋狀痕，而能有助於 光阻消耗量的削減、良率提高、成本減低》 《光阻圖型之形成方法》 本發明之第二態樣的光阻圖型之形成方法，具有使用 -24- 201248327 吐出噴嘴式塗佈法，將上述本發明的正型光阻組成物塗佈 在基板上之步驟。 此塗佈步驟係可藉由具備使吐出噴嘴與基板相對地移 動之手段的裝置來進行。吐出噴嘴只要是將自其吐出的正 型光阻組成物以帶狀塗佈在基板上之構成者即可，並沒有 特別的限定，但例如可使用具有複數的噴嘴孔以列狀排列 的吐出口之吐出噴嘴，或具有縫狀的吐出口之吐出噴嘴。 作爲具有該塗佈步驟的塗佈裝置，已知非自旋方式的 TR28000S 、 TR45000S 、 TR63000S 、 TR70000S 、 TR90000S 、TR1 1 7000S、TR 1 3 0000S (皆製品名；東京應化工業（ 股）製）等。 又，上述塗佈步驟係在藉由吐出噴嘴式塗佈法於基板 上塗佈正型光阻組成物後，亦可使用使基板自旋而將膜厚 調薄之手段。作爲具有該塗佈步驟的塗佈裝置，已知狹縫 &自旋方式的SK-1100G (製品名；大日本SCREEN製造 (股）製）、MMN (多微噴嘴）的掃描塗佈+自旋方式的 CL1200 (製品名；東京電子（股）製）、塗覆&自旋方式 的TR6 3 000F (製品名；東京應化工業（股）製）等。 如此地在基板的塗佈面全面上塗佈正型光阻組成物後 之形成光阻膜用的步驟，及形成光阻圖型用的步驟，係可 適宜使用周知的方法。 例如，將塗佈有光阻組成物的基板以100〜140°C左右 加熱乾燥（預烘烤）而形成光阻被膜。然後，對光阻被膜 ，通過所欲的光罩圖型，進行選擇的曝光。曝光時的波長 -25- 201248327 係可採用ghi線（g線、h線及i線）或i線，各自使用適 宜的光源。 此後，對選擇曝光後的光阻被膜，使用由鹼性水溶液 所成的顯像液，例如1〜10質量％氫氧化四甲銨（TM A Η )水溶液進行顯像處理。 作爲使光阻被膜接觸顯像液之方法，例如可使用從基 板的一端部至另一端部浸液之方法，或藉由自基板中心附 近之上部所設置的顯像液滴下噴嘴，使顯像液遍及基板表 面全體之方法。 然後，靜置50〜60秒左右而顯像後，藉由使用純水 等的沖洗液來洗掉光阻圖型表面上所殘留的顯像液之沖洗 步驟，而得到光阻圖型。 若依照如此的光阻圖型的形成方法，由於使用吐出噴 嘴式塗佈法，即使基板尺寸、裝置尺寸進行大型化，也不 使塗佈均勻性或生產節拍時間變差，而可在基板上形成光 阻被膜。 而且，所用的光阻組成物係對吐出噴嘴方式合適化者 ，防止光阻被膜的筋狀痕、霧斑的發生或針痕的發生。特 別地，於塗佈後進行自旋時，由於可邊抑制光阻塗佈fl邊 防止筋狀痕的發生，故有助於製造成本的減低。 〔實施例〕 其次，藉由實施例來更詳細說明本發明，惟本發明不 受此等例所限定。 -26- 201248327 〔實施例1〜7、比較例1〜5〕 將表1中所示的各成分混合及溶解’以調製正型的光 阻組成物。 【表1】 (A) 成分 (B) 成分 (O fk^ (E) 成分 (G) 成分 (s) 成分 實施例 1 (A)-1 [1〇〇] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] ^_t36] (S) — 2 [685] 實施例 2 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (s)〜11 ___t3] (S)—2 [718] 實施例 3 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (S)〜11 __iz] (S) — 2 [714] 實施例 4 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (S) »11 ⑻一2 [649] 實施例 5 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (s)〜n (S)-2 [577] 實施例 6 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (S)~12 [36] ⑻一2 [685] 實施例 7 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (S) — 13 [36] (S)-2 [685] 比較例 1 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (S)〜14 [36] (S)-2 [685] 比較例 2 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (S) — 15 [36] (S)-2 [685] 比較例 3 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (S)-16 [36] (S) — 2 [685] 比較例 4 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (S) —17 [361 (S)-2 [685] 比較例 5 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [13 (S)~18 [36] (S)-2 [685] 表1中的各略號具有以下的意義。又，〔〕內的數 値係配合量（質量份）。 (A) -1:以甲醛爲縮合劑，使用草酸觸媒，藉由常 用方法，將間甲酚/對甲酚=40/60 (投入莫耳比）的混合酚 類予以縮合反應，將所得之酚醛清漆樹脂，藉由水-甲醇 混合溶劑施予分級處理而得之Mw = 5 000的酚醛清漆樹脂 -27- 201248327 (B) -1:下述化合物（B) -1。 (C) -1:下述化合物（C) -1。 (E) -1 : BYK-3 10 (商品名，BYK化學公司製）。 (G ) -1 : 2- ( 2-羥乙基）吡啶。 (S ) -1 1 :己二醇。 (S ) -12 : 1，2-己二醇。 (S ) -13 : 1，7-庚二醇。 (S ) -14 :苯甲醇。 (S ) -15 : 1，4-丁 二醇。 (S ) -16 : 1,2-丁 二烯。 (S ) -17 : 1，5-戊二醇。 (S ) -1 8 :丙二醇。 (S ) -2 : PGMEA。 【化5】In the present invention, the (Β) component may be used singly or in combination of two or more. When the positive resist composition of the present invention contains a (ruthenium) component, the amount of the (ruthenium) component is preferably 1 to 1 part by mass based on 1 part by mass of the alkali-soluble novolak resin of the (Α) component. 25 parts by mass, more preferably in the range of 5 to 20 parts by mass. When the content of the (Β) component in the resist composition is too small, the effect of improving the high sensitivity and the high residual film ratio cannot be sufficiently obtained. If the amount is too large, the residue on the surface of the substrate after development is likely to occur, and the raw material cost It is also high and not suitable. <Optional Component·(Ε)Component> -20- 201248327 The positive-type photoresist composition of the present invention preferably contains a surfactant (E) for the purpose of suppressing the occurrence of rib-like marks (hereinafter referred to as "(E) component"). The content of the component (E) is preferably in the range of 900 ppm or less from the viewpoint of the occurrence of the tendon traces in the entire positive resist composition. The component (E) is not particularly limited. For example, one or two or more kinds of compounds known as conventional surfactants for photoresist can be used as the component (E), and the fluorine-ruthenium interfacial activity is suitable. Among them, a nonionic fluoro-antimony surfactant (E-1) to which a perfluoroalkyl ester group, an alkyl sulfoxyalkyl group, a vinyloxy group and a propyleneoxy group are bonded is preferable. As the surfactant (E-1), for example, Megafac R-08' R-60 (product name, manufactured by Dainippon Ink and Chemicals, Inc.) and the like can be mentioned. Further, a surfactant component (E-2) having a fluorine content of 10 to 25% by mass and a cerium content of 3 to 1% by mass is more preferably X-70-090 or X-70-09 1 , X-70-092, X-70-093 (product name, Shin-Etsu Chemical Co., Ltd.), etc. 'Specially X-70-093 suppresses the occurrence of ribs or dry spots even if the amount of photoresist drops is small. The effect is high, so it is better. Further, a polyester-modified polydialkylnonane-based surfactant (E-3) having a specific siloxane skeleton is also preferable, and for example, 8丫1 (:-3-10, BYK) is exemplified. -3 15, (product, manufactured by BYK Chemical Co., Ltd.), etc., in particular, BYK-3 10 is more preferable because it can suppress the occurrence of fogging spots or dripping marks and tendon spots (ribs). The total amount of the surfactant of -1) to (E - 3 ) is preferably from 21 to 201248327, and accounts for 50% by mass or more of the component (E), and the ratio thereof may be 丨 00% by mass. Specific examples of the surfactant other than the above-mentioned (E-3) include a surfactant for preventing streaks, and examples thereof include Fluorad FC-430, FC431 (product name, manufactured by Sumitomo 3M Co., Ltd.), and Eftop EF122A. A fluorine-based surfactant such as EF122B, EF122C, or EF126 (product name, manufactured by TOHKEM PRODUCTS). The component (E) is not particularly limited as long as it satisfies the fluorine content and the cerium content in the above range, but is a suitable specific example. For example, the perfluorocarbons of the trade names 乂-70-090, X-70-091, X-70-092, and X-70-093 (all manufactured by Shin-Etsu Chemical Co., Ltd.) can be cited. A nonionic fluorine-polyfluorene-based surfactant to which a group is bonded to an alkylphosphonium group and an alkenyloxy group, etc. Specific examples thereof include a fluorine content of 21% by mass and a cerium content of 7% by mass. Among them, in particular, X-7 0-09 3 is preferable because it suppresses the occurrence of rib-like marks or dry spots even if the amount of the photoresist drop is small, and the amount of the component (E) is preferably In order to prevent the occurrence of the rib-like marks in the discharge nozzle coating method, the solid content of the organic solvent (S) and the component (E) in the photoresist composition is preferably 0.001. ～1质量%, more preferably in the range of 0.01 to 0.5% by mass. <Other components> In the composition of the present invention, various additives such as a stabilizer can be further used without departing from the object of the present invention. For example, a UV absorber for preventing halation may be suitably contained. Examples of the ultraviolet absorber of -22-201248327 include 2,2',4,4'-tetrahydroxydiphenyl ketone and 4-dimethyl group. Amino 2',4'-dihydroxydiphenyl ketone, 5-amino-3-methyl-1-phenyl-4-(4-hydroxyphenyl azo Pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-diethylamino-4'-ethoxyazobenzene, 4-diethylaminoazo Benzene, curcumin, etc. Further, in order to improve the adhesion between the layer formed of the photoresist composition and the lower layer, the adhesion improving agent (G) ((G) component) may be suitably contained. 2-(2-hydroxyethyl)pyridine can be effectively improved by the photoresist composition by suitably containing it in the photoresist composition, for example, when a photoresist pattern is formed on a metal film of a Cr film or the like. The adhesion between the formed layer and the metal film. When the amount of the adhesion improving agent is too large, the change with time of the photoresist composition tends to be inferior, and if it is too small, the sealing property improving effect cannot be sufficiently obtained. Therefore, the blending amount of the adhesion improving agent is preferably in the range of 0.1 to 10% by mass based on the total solid content. As described above, the positive-type resist composition of the present invention is suitable for a coating method of a discharge nozzle method, and can prevent fogging or ribs when the photoresist composition is discharged into a strip shape from a discharge nozzle and applied to a substrate. The occurrence of scratches and the occurrence of needle marks can be reduced when the film is dried or baked. Although the reason for obtaining the above effects is not known, it is judged that the positive resist composition of the present invention can reduce the volatility of the (S) component of the positive resist composition by containing the (S 1 ) component and can be used for the coating. The rate of volatilization of the (s) component in the drying step of the film or in the bake step is uniform. In the field of LCD manufacturing, a large-sized substrate (for example, 360 mm x 460 mm or more) is generally used in comparison with a silicon wafer used in the field of semiconductor device manufacturing, -23-201248327. Therefore, a discharge nozzle coating method is applied. In addition, in the surface of the substrate for LCD manufacturing, very large irregularities are present, and the distortion of the substrate itself is also present, and the surface of the substrate on which the photoresist composition is applied is used in the manufacture of LCDs and semiconductor devices. Different. Therefore, the photoresist composition for LCD manufacturing is technically different from the photoresist composition for manufacturing a semiconductor device. The positive photoresist composition of the present invention is excellent in wettability on a support. The support for forming the photoresist film is a large-sized glass-corner substrate for LCD production, or a layer (surface layer) containing molybdenum as a main component, such as a molybdenum layer or a molybdenum alloy layer, on the surface of the substrate. The support body also effectively achieves this effect. Therefore, the positive resist composition of the present invention can be suitably used as a liquid crystal element manufacturer using a discharge nozzle coating method. The photoresist composition of the present invention is also suitable for coating a photoresist composition on a coated surface of a substrate by a discharge nozzle coating method at a final desired film thickness without spin (non-spin) The method is also suitable for the method of adjusting the film thickness by applying a photoresist composition to the coated surface of the substrate and then rotating the substrate. In particular, it is suitable for the latter method, because it can suppress the amount of photoresist coating while preventing the rib-like marks after the spin, which contributes to the reduction of the amount of photoresist consumed, the improvement of the yield, and the cost reduction. Method for Forming Patterns According to a second aspect of the present invention, a method for forming a resist pattern has a positive photoresist composition of the present invention coated on a substrate using a discharge nozzle coating method of -24 to 201248327. The steps above. This coating step can be carried out by means of a means for moving the discharge nozzle relative to the substrate. The discharge nozzle is not particularly limited as long as it is a member in which a positive resist composition which is discharged from the substrate is applied to the substrate in a strip shape. For example, a discharge having a plurality of nozzle holes arranged in a row may be used. A discharge nozzle for the outlet or a discharge nozzle having a slit-shaped discharge port. As a coating apparatus having such a coating step, TR28000S, TR45000S, TR63000S, TR70000S, TR90000S, TR1 1 7000S, and TR 1 3 0000S which are non-spin type are known (all products name; Tokyo Toka Chemical Co., Ltd.) Wait. Further, in the coating step, after the positive resist composition is applied onto the substrate by the discharge nozzle coating method, the substrate may be spinned to reduce the film thickness. As a coating apparatus having this coating step, a slit-and-spin SK-1100G (product name; manufactured by Dainippon SCREEN Co., Ltd.) and MMN (multi-micro nozzle) are known. CL1200 (product name; Tokyo Electronics Co., Ltd.), coating & spin type TR6 3 000F (product name; Tokyo Chemical Industry Co., Ltd.). The step of forming a photoresist film after applying a positive resist composition to the entire coated surface of the substrate and the step of forming a photoresist pattern can be suitably carried out by a known method. For example, the substrate coated with the photoresist composition is dried by heating (prebaking) at about 100 to 140 ° C to form a photoresist film. Then, the photoresist is selectively exposed to the photoresist pattern through the desired mask pattern. The wavelength at the time of exposure -25- 201248327 can be used with ghi lines (g line, h line and i line) or i line, each using an appropriate light source. Thereafter, the photoresist film after the selective exposure is subjected to development processing using a developing solution made of an alkaline aqueous solution, for example, an aqueous solution of 1 to 10% by mass of tetramethylammonium hydroxide (TM A Η ). As a method of bringing the photoresist film into contact with the developing solution, for example, a method of immersing liquid from one end portion to the other end portion of the substrate or a developing nozzle for liquid droplets provided from an upper portion near the center of the substrate may be used. A method in which the liquid spreads over the entire surface of the substrate. Then, after standing for about 50 to 60 seconds and developing, the rinsing step of the developing liquid remaining on the surface of the resist pattern is washed by using a rinsing liquid such as pure water to obtain a photoresist pattern. According to the method for forming such a resist pattern, since the discharge nozzle type coating method is used, even if the substrate size and the device size are increased, the coating uniformity or the tact time is not deteriorated, and the substrate can be made on the substrate. A photoresist film is formed. Further, the photoresist composition to be used is suitable for the discharge nozzle method, and the occurrence of rib-like marks, fogging, or pin marks of the photoresist film is prevented. In particular, when spin is applied after coating, the occurrence of rib-like marks can be prevented while suppressing the photoresist coating fl, which contributes to a reduction in manufacturing cost. [Embodiment] Next, the present invention will be described in more detail by way of examples, but the invention is not limited by the examples. -26-201248327 [Examples 1 to 7 and Comparative Examples 1 to 5] The respective components shown in Table 1 were mixed and dissolved to prepare a positive resist composition. [Table 1] (A) Component (B) Component (O fk ^ (E) Component (G) Component (s) Component Example 1 (A)-1 [1〇〇] (B)-1 [14] ( 0-1 [22] (E)-1 [0.4] (G)-1 [1] ^_t36] (S) — 2 [685] Example 2 (A)-1 [100] (B)-1 [ 14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (s)~11 ___t3] (S)—2 [718] Example 3 (A)-1 [100] ] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (S)~11 __iz] (S) — 2 [714] Example 4 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (S) »11 (8)1-2 [649] Example 5 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (s)~n (S) -2 [577] Example 6 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (S) ~12 [36] (8) - 2 [685] Example 7 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (S) — 13 [36] (S)-2 [685] Comparative Example 1 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (S)~14 [36] (S)-2 [685] Comparative Example 2 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (S) — 15 [36] (S)-2 [685] Comparative Example 3 (A)-1 [100] (B)- 1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [1] (S)-16 [ 36] (S) — 2 [685] Comparative Example 4 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4] (G)-1 [ 1] (S) —17 [361 (S)-2 [685] Comparative Example 5 (A)-1 [100] (B)-1 [14] (0-1 [22] (E)-1 [0.4 ] (G)-1 [13 (S)~18 [36] (S)-2 [685] The respective symbols in Table 1 have the following meanings. Further, the number in the [] is the amount (parts by mass). (A) -1: Using formaldehyde as a condensing agent, using a oxalic acid catalyst, the mixed phenols of m-cresol/p-cresol=40/60 (into the molar ratio) are subjected to a condensation reaction by a usual method. The novolac resin was subjected to a classification treatment by a water-methanol mixed solvent to obtain a novolak resin of Mw = 5,000 - 27848327 (B) -1: the following compound (B)-1. (C) -1: The following compound (C)-1. (E) -1 : BYK-3 10 (trade name, manufactured by BYK Chemical Co., Ltd.). (G ) -1 : 2-(2-hydroxyethyl)pyridine. (S) -1 1 : hexanediol. (S) -12 : 1,2-hexanediol. (S) -13 : 1,7-heptanediol. (S) -14 : Benzyl alcohol. (S) -15 : 1,4-butanediol. (S) -16 : 1,2-butadiene. (S) -17 : 1,5-pentanediol. (S) -1 8 : Propylene glycol. (S ) -2 : PGMEA. 【化5】
-28- 201248327 使用孔徑〇·2μηι的薄膜過濾器，將上述所得之正型光 阻組成物過濾而成爲「試料」，使用該試料，藉由以下所 示的方法形成光阻膜，分別進行筋狀痕的評價、霧斑的評 價、減壓乾燥時的針痕之評價及烘烤時的針痕之評價。 <光阻膜之形成> 使用具備減壓乾燥裝置及加熱處理裝置等的非自旋塗 佈方式用塗佈裝置（東京應化工業公司製，製品名 TR45000S )，將實施例1〜7及比較例1〜5的正型光阻組 成物塗佈在形成有Cr膜的玻璃基板（ 680 x880mm)上後 ，於60Pa的減壓條件下減壓乾燥（減壓乾燥步驟）。接 著，使熱板的溫度成爲11〇 °C，藉由空出約2 mm的間隔之 近接烘烤，進行60秒的第1次乾燥，於第2次中直接在 熱板上施予80秒的乾燥，而形成膜厚1.5μπι的光阻膜（ 烘烤步驟）。 〔霧斑、筋狀痕之評價〕 於鈉燈下觀察所形成的光阻膜之表面’依照下述基準 分別進行霧斑或筋狀痕（縱筋）的評價。表2中顯示其結 果。 5 :沒有看到霧斑或筋狀痕。 4 :若仔細觀察則有霧斑或筋狀痕。 3 :有霧斑或筋狀痕。 2:霧斑或筋狀痕爲立刻察覺的程度° -29- 201248327 1 :霧斑或筋狀痕非常濃。 〔針痕之評價〕 於鈉燈下觀察減壓乾燥（VCD )步驟後或烘烤步驟_ 的光阻膜之表面，依照下述基準分別進行針痕之評價。表 2中顯示其結果。 5 :沒有看到針痕》 4 :若仔細觀察則有針痕。 3 :有針痕。 2 :針痕爲立刻察覺的程度。 1 :針痕非常濃。 【表2】 霧斑 筋狀痕 VCD 針痕 烘烤 針痕 實施例1 5 5 5 5 實施例2 5 5 5 5 實施例3 5 5 5 5 實施例4 5 5 5 5 實施例5 5 5 5 5 實施例6 5 5 5 5 實施例7 5 5 5 5 比較例1 3 3 3 3 比較例2 3 2 3 3 比較例3 2 2 2 3 比較例4 3 2 3 3 比較例5 2 2 2 3 -30- 201248327 由上述結果可確認，與比較例1〜5的光阻組成物相 比，本發明的實施例1〜7之光阻組成物係能減低霧斑、 筋狀痕及針痕之發生。 -31 --28-201248327 The positive-type photoresist composition obtained above was filtered using a membrane filter having a pore size of 2·2μηι to form a “sample”, and a photoresist film was formed by the method described below, and the ribs were respectively used. The evaluation of the marks, the evaluation of the fog spots, the evaluation of the needle marks at the time of drying under reduced pressure, and the evaluation of the needle marks at the time of baking. <Formation of Photoresist Film> Using a coating device for a non-spin coating method (product name TR45000S, manufactured by Tokyo Ohka Kogyo Co., Ltd.) equipped with a vacuum drying device, a heat treatment device, and the like, Examples 1 to 7 were used. The positive resist composition of Comparative Examples 1 to 5 was applied onto a glass substrate (680 x 880 mm) on which a Cr film was formed, and then dried under reduced pressure at 60 Pa under reduced pressure (a drying step under reduced pressure). Next, the temperature of the hot plate was set to 11 ° C, and the first drying was performed for 60 seconds by vacating the adjacent baking at intervals of about 2 mm, and the hot plate was directly applied to the hot plate for 80 seconds in the second time. The film was dried to form a photoresist film having a film thickness of 1.5 μm (baking step). [Evaluation of fogging spots and rib-like marks] The surface of the formed photoresist film was observed under a sodium lamp. The evaluation of the fogging spots or the rib-like marks (longitudinal ribs) was carried out according to the following criteria. The results are shown in Table 2. 5: No fog or ribs were seen. 4: If you look closely, there are fog spots or gluten marks. 3: There are fog spots or ribs. 2: The degree of fog or ribs is immediately noticeable. -29- 201248327 1 : The fog or tendons are very thick. [Evaluation of Needle Mark] The surface of the photoresist film after the vacuum drying (VCD) step or the baking step _ was observed under a sodium lamp, and the needle marks were evaluated according to the following criteria. The results are shown in Table 2. 5: No needle marks are seen. 4: If you look closely, there are needle marks. 3: There are needle marks. 2: The needle mark is the degree of immediate detection. 1: The needle marks are very thick. [Table 2] Fog ridge mark VCD needle mark baking needle mark Example 1 5 5 5 5 Example 2 5 5 5 5 Example 3 5 5 5 5 Example 4 5 5 5 5 Example 5 5 5 5 5 Example 6 5 5 5 5 Example 7 5 5 5 5 Comparative Example 1 3 3 3 3 Comparative Example 2 3 2 3 3 Comparative Example 3 2 2 2 3 Comparative Example 4 3 2 3 3 Comparative Example 5 2 2 2 3 -30-201248327 From the above results, it was confirmed that the photoresist compositions of Examples 1 to 7 of the present invention can reduce fog, ribs and needle marks as compared with the photoresist compositions of Comparative Examples 1 to 5. occur. -31 -