TWI289728B

TWI289728B - Method for forming resist pattern

Info

Publication number: TWI289728B
Application number: TW093115121A
Authority: TW
Inventors: Masaki Kurihara; Toshihiro Yamaguchi; Satoshi Niikura
Original assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2003-06-19
Filing date: 2004-05-27
Publication date: 2007-11-11
Also published as: JP2005010486A; KR100649921B1; KR20040111103A; TW200510933A

Abstract

A method for forming a resist pattern which is suitable for manufacturing a LCD can reduce variation in resist pattern size. The method includes (1) a step for forming an antireflection film on a substrate, (2) a step for coating a positive photoresist composition on the antireflection film to form a coating, (3) a step for prebaking the substrate with the film formed thereon, to form a resist coating film on the substrate, (4) a step for subjecting the resist coating film to selective exposure by using a mask, and (5) a step for subjecting the exposed resist coating film to develop by alkali solvent to form both a resist pattern for an integrated circuit with a pattern size of no more than 2.0 mum and a resist pattern for a liquid crystal display with a pattern size of more than 2.0 mum on the substrate.

Description

1289728 ⑴ 玖、發明說明【發明所屬之技術領域】本發明爲關於使用於一個基板上形成集顯示部分之基板製造的光阻圖型之形成方法【先前技術】〔發明所欲解決之課題〕迄今於使用玻璃基板之液晶顯示元件之光阻材料爲適於g射線、h射線、及i射線廉價，且靈敏度、解像性良好、可形成形狀型，故多利用使用酚醛淸漆樹脂做爲鹼可溶含有醌疊氮基之化合物做爲感光性成分的正，並且已報導（下述，參照專利文獻1〜4 ) 現在，第二代之LCD已廣泛進行於1 ’將驅動器、DAC (數模轉換器）、圖像處制器、RAM (隨機存取存儲器）等之集成電示部分同時形成，所謂「LCD系統」之高機術開發（下述，參照非專利文獻丨）。以下，於本說明書中，將如此於一個基電路和液晶顯示部分的基板，於便利上稱爲 L C D系統例如顯示部分之圖型尺寸爲 ’相對地集成電路部分爲以微細至〇.5〜2.0 寸形成。因此，於LC D系統製造用之光阻了要求可同時以良好形狀形成微細圖型和粗成電路和液晶製造領域中的曝光，由於較優良的光阻圖性樹脂、使用型光阻組成物〇枚玻璃基板上理器、視頻控路部分爲與顯 ^能L C D的技板上形成集成 LCD系統。 2〜1 0 // m左右 # m左右之尺組成物中，除糙圖型之能力 1289728 (2) (真實性）以外，且嚴格要求微細圖型之DOF (焦點深度寬；Depth of focus )特性爲良好。但，於液晶元件的製造領域中，因爲光阻材料中之靈敏度降低乃造成重大的生產量降低，故爲不佳，期望不會導致靈敏度之降低且可提高上述特性。迄今，並無關於LCD系統用之光阻材料的報告例，且於液晶顯示元件的製造領域中，強烈期望實現適於LCD 系統製造的光阻材料。特別於LCD之製造領域中，與製造半導體所用之矽晶圓等相比較，因爲使用遠大面積的玻璃基板，故基板的彎曲往往爲大，加上具有光阻被膜之下層的表面平滑性亦差的特有問題。因此，光阻被膜的膜厚易變成不均勻，整體效果的影響變大（下述，參照專利文獻5 )。其結果，經由光阻被膜的膜厚差而產生光阻圖型之尺寸變化率大的部分，且具有基板面內之光阻圖型尺寸的偏差變大之問題〇特別，於LCD系統，塞板面積有變爲更大之傾向，光阻圖型爲更加微細化，故此類問題爲顯著產生。〔專利文獻1〕特開2000·131835號公報〔專利文獻2〕特開200 1-75272號公報〔專利文獻3〕特開2000-181055號公報 -6 - 1289728 (3) 〔專利文獻4〕特開2000-112120號公報〔專利文獻5〕特開6-2 1 185號公報〔非專利文獻1〕1289728 (1) Field of the Invention The present invention relates to a method for forming a resist pattern for manufacturing a substrate on which a display portion is formed on one substrate. [Prior Art] [Problems to be Solved by the Invention] The photoresist material for a liquid crystal display element using a glass substrate is inexpensive for g-ray, h-ray, and i-ray, and has good sensitivity and resolution, and can be formed into a shape. Therefore, a phenolic enamel resin is often used as a base. A compound containing a hydrazine group is positive as a photosensitive component and has been reported (hereinafter, refer to Patent Documents 1 to 4). Now, the second generation LCD has been widely used in 1 'driver, DAC (number The integrated display portion such as an analog-to-analog converter, an image controller, and a RAM (random access memory) is simultaneously formed, and the so-called "LCD system" is highly developed (see the non-patent document hereinafter). Hereinafter, in the present specification, the substrate such as a base circuit and a liquid crystal display portion is conveniently referred to as an LCD system, for example, the display portion has a pattern size of 'relatively the integrated circuit portion is fine to 〇.5 to 2.0. Inch formation. Therefore, the photoresist used in the manufacture of the LC D system is required to simultaneously form fine patterns in the fine shape and the exposure in the field of the rough circuit and the liquid crystal manufacturing, because of the excellent photoresist pattern, the use of the photoresist composition. The illuminating glass substrate upper device and the video control portion form an integrated LCD system on the technical board of the display LCD. 2~1 0 // m around # m around the ruler composition, in addition to the ability of the rough pattern 1289728 (2) (authenticity), and strictly requires the DOF of the fine pattern (Depth of focus) The characteristics are good. However, in the field of manufacturing liquid crystal elements, since the decrease in sensitivity in the photoresist material causes a significant decrease in throughput, it is not preferable, and it is desired that the sensitivity is not lowered and the above characteristics can be improved. Heretofore, there has been no report on the photoresist material for LCD systems, and in the field of manufacturing liquid crystal display elements, it is strongly desired to realize a photoresist material suitable for the manufacture of an LCD system. Particularly in the field of manufacturing of LCDs, compared with silicon wafers used in the manufacture of semiconductors, the use of a large-area glass substrate tends to be large, and the surface smoothness of the layer below the photoresist film is also poor. Unique problem. Therefore, the film thickness of the photoresist film tends to become uneven, and the influence of the overall effect is increased (refer to Patent Document 5 below). As a result, a portion having a large dimensional change rate of the photoresist pattern is generated by the difference in film thickness of the photoresist film, and the variation in the size of the photoresist pattern in the substrate surface is large. The plate area has a tendency to become larger, and the photoresist pattern is more refined, so such problems are remarkably generated. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. 2000-75272 (Patent Document 3) JP-A-2000-181055 (Patent Document 3) JP-A-2000-112120 (Patent Document 5) JP-A-6-2 1185 (Non-Patent Document 1)

Semiconductor FPD World 200 1.9, pp.50-67 本發明爲鑑於前述情事，以提供適合使用於製造LCD 系統、且可抑制光阻圖型尺寸偏差之光阻圖型的形成方法爲其課題。【發明內容】〔解決課題之手段〕本發明爲根據以下手段解決前述課題。本發明之光阻圖型之形成方法爲包含（1)於支撐體上形成防止反射膜之步驟、（2 )於上述防止反射膜上塗佈正型光阻組成物，且形成塗膜之步騾、（3 )將形成上述塗膜之基板予以加熱處理（預烘烤），並於基板上形成光阻被膜之步驟、（4)對於上述光阻被膜，使甩描繪2.〇 /2 m以下之光阻圖型形成用光罩圖型、和超過2.0/im之光阻圖型形成用光罩圖型兩者之光罩，進行選擇性曝光之步驟、及（5 )對於上述選擇曝光後之光阻被膜，使用鹼水溶液實施顯像處理，且於上述基板上，同時形成圖型尺寸2.0//m以下之集成電路用之光阻圖型、和超過2.0// m 之液晶顯示部分用之光阻圖型之步驟爲其特徵之光阻圖型 1289728 (4) 的形成方法。〔發明之實施形態〕〔形成防止反射膜用組成物〕本發明所用之形成防止反射膜用組成物若有防止反射機能之膜者即可，並無特別限定。由含有吸光劑（染料）之樹脂溶液所構成，已有機系之物質、無機系之物質。以下，爲提案射膜之文獻的例示。特開 2002- 1 4879 1號< 200 1 -3 4 3 7 5 2 號公報、特開 200 1 -5 1 424 號公 1 1 - 2 9 5 8 8 8號公報、特開平9-456 1 4號公報、 1 2 940號公報、特開平7-86 1 27號公報、特開號公報等。又，亦提案使用光阻材料做爲有機射膜（特開200 1 -2 1 7 1 84號公報）。本發明中些形成防止反射膜用組成物。特別，至少被曝光之部分爲以光阻圖型之所用之鹼水溶液中可溶的形成防止反射膜用組像處理步驟後，未進行令除去光阻層露出部分膜予以乾式蝕刻步驟即可完成而言爲佳。例如，若使用特開平6- 3 1 3 96 8號公報所防止反射膜用組成物，則在曝光部分或未曝光成於鹼水溶液中可溶的防止反射膜。又，若使用含有（A )樹脂成分、（C ); 照射發生酸成分之化合物、（E )吸光劑、和: 爲可形成具一般而言，有各種報導有關防止反 ☆報、特開報、特開平特開平8-平 6-313968 系的防止反，可使用此顯像處理中成物，於顯之防止反射記載之形成部分均可形經由放射線有機溶劑， -8- 1289728 (5) 丨由前述（C)成分所發生爲難溶性之性質，變成對防止反射膜用組成物（增則可形成被曝光部分於鹼鹼水溶液爲難溶性的防止光部爲可溶性且未曝光部不需要用以除去防止反射型下層部分之防止反射膜經由在防止反射膜上產生得於防止反射膜與光阻層 (C)成分、反（E)成分特別限定，具體而言以滿者爲佳。 )鹼可溶性樹脂和（B ) a2 )反應產物。 ί ( a 1 )鹼可溶性樹脂、成物爲含有（B)下述一 ch2 …（I) 若加熱則形成交聯構造，其次經之酸成分的作用由對於鹼水溶液於鹼水溶液爲可溶性性質的形成強化學性型正型光阻組成物），水溶液中可溶，且未曝光部對於反射膜。如此，若對於鹼水溶液，曝爲難溶性，則於顯像處理步驟後膜的步驟，加上可抑制於光阻圖上發生副鈾刻，故爲更佳。又，交聯構造而變成堅固膜，故亦取之界面難發生混合現象之優點。此類含有前述（A )成分、之形成防止反射膜用組成物並無足下述（i)、（ii)之一者或兩 (i)含有（A)成分爲（al 下述一般式（I )所示化合物的（ (Π)前述（A)成分爲含ί 更且、前述形成防止反射膜用組般式（I )所示之化合物。 H2C = CH - 0 - R1- 0 - CH = 〔式中，R]爲表示亦可具有取代基之碳數】〜]0個的 1289728 (6) ί申或下述一般式（II)所示之基之任一者Semiconductor FPD World 200 1.9, pp. 50-67 In view of the foregoing, the present invention provides a method for forming a photoresist pattern suitable for use in the manufacture of an LCD system and capable of suppressing dimensional deviation of a photoresist pattern. [Disclosure of the Invention] [Means for Solving the Problems] The present invention solves the above problems by the following means. The method for forming the photoresist pattern of the present invention comprises the steps of: (1) forming a reflection preventing film on the support, (2) applying a positive photoresist composition on the antireflection film, and forming a coating film.骡, (3) a step of heat-treating (pre-baking) the substrate on which the coating film is formed, and forming a photoresist film on the substrate, and (4) drawing the ruthenium on the resist film by 2.甩/2 m The following photomask pattern forming mask pattern, and a mask of more than 2.0/im photoresist pattern forming mask pattern, a step of performing selective exposure, and (5) selecting exposure for the above The photoresist film is subjected to development processing using an aqueous alkali solution, and a photoresist pattern for an integrated circuit having a pattern size of 2.0//m or less and a liquid crystal display portion exceeding 2.0//m are simultaneously formed on the substrate. The step of using the photoresist pattern is a method of forming the photoresist pattern 1289728 (4). [Embodiment of the Invention] [The composition for forming an antireflection film] The film for forming an antireflection film used in the present invention is not particularly limited as long as it has a film for preventing reflection. It is composed of a resin solution containing a light absorbing agent (dye), and is an organic substance or an inorganic substance. The following is an illustration of the literature on the proposed film. JP-A-2002- 1 4879 No. 1 < 200 1 - 3 4 3 7 5 2, JP-A-200 1 - 5 1 424, 1 1 - 2 9 5 8 8 8 , and JP-A 9-456 1 Japanese Patent Publication No. 4, 940, pp. Further, it is also proposed to use a photoresist material as an organic film (JP-A-200 1 - 2 1 7 1 84). In the present invention, a composition for forming an antireflection film is formed. In particular, after at least the portion to be exposed is a group image processing step for forming an anti-reflection film which is soluble in an aqueous alkali solution for use in a photoresist pattern, the step of removing the photoresist layer is performed without performing a dry etching step. It is better. For example, when the composition for an antireflection film of JP-A-61-313396 is used, an antireflection film which is soluble in an exposed portion or which is not exposed to an aqueous alkali solution is used. Further, when a compound containing (A) a resin component, (C), a compound which irradiates an acid component, (E) a light absorbing agent, and a general formula, there are various reports relating to the prevention of anti-☆ reports and special reports. , special open Kaiping 8-Ping 6-313968 system to prevent the reverse, can use this development to process the medium, in the formation of the anti-reflection record can be formed through the radiation of organic solvents, -8-1289728 (5) In the case where the component (C) is inferior in solubility, it becomes a composition for an antireflection film (increasing the light-preventing portion which is formed by exposing the exposed portion to an alkali-alkali aqueous solution to be soluble, and the unexposed portion is not required to be used. The anti-reflection film from which the anti-reflection type lower layer portion is removed is particularly limited in terms of the anti-reflection film, the photoresist layer (C) component, and the anti-(E) component, and is particularly preferably full. Soluble resin and (B) a2) reaction product. ί ( a 1 ) alkali-soluble resin, a product containing (B) a ch2 (I) if heated to form a crosslinked structure, and secondly, the action of the acid component is soluble in an aqueous alkali solution in an aqueous alkali solution A strong chemical type positive resist composition is formed, which is soluble in an aqueous solution, and the unexposed portion is opposite to the reflective film. As described above, when the alkali aqueous solution is exposed to poor solubility, it is more preferable to carry out the step of the film after the development treatment step and to suppress the occurrence of secondary uranium engraving on the photoresist pattern. Further, since the crosslinked structure is a strong film, it is also advantageous in that the interface is difficult to be mixed. The component for forming an antireflection film containing the component (A) does not have one of the following (i) and (ii) or two (i) contains the component (A) (al is the following general formula (I) (() The compound of the above formula (A) is a compound represented by the formula (I) which is a group containing the anti-reflection film described above. H2C = CH - 0 - R1- 0 - CH = [ In the formula, R] is any one of 1289728 (6) or a group represented by the following general formula (II), which may have a carbon number of a substituent.

(式中，R4爲表示亦可具有取代基之碳數1〜10個的伸烷基’m爲表示〇或〇〕 • ( ）成分前述（a 1 )成分並無特別限制可使用光阻組成物中所用的鹼可溶性樹脂。具有酚性羥基者，就與（B )成分之反應性方面而言爲佳。 (a 1 )成分的適當例可列舉芳香族羥基化合物與醛類或酮類縮合反應所得的酚醛淸漆樹脂、聚羥基苯乙烯及其衍生物等。該芳香族羥基化合物可列舉例如苯酚；間-甲苯酚、對·甲苯酚、鄰-甲苯酚等之甲苯酚類；2,3-二甲苯酚、 2,5·二甲苯酚、3,5-二甲苯酚、3,4-二甲苯酚等之二甲苯酚類；間-乙基苯酚、對-乙基苯酚、鄰-乙基苯酚、2,3 55-三甲基苯酚、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-甲基苯酚等之烷基苯酚類；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-丙氧基苯酚等之烷氧基苯酚類；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 -異丙烯基苯酚等之異丙烯基苯酚類；苯基苯酚 ‘10- 1289728 (7) 等之芳基苯酚類；4,4，-二羥基聯苯、雙酚A、間苯二酚、羥醌、焦掊酚等之聚羥基苯酚類等。彼等可單獨使用，且亦可組合使用二種以上。該醛類可列舉例如甲醛、對甲醛、三卩f烷、乙醛、丙醛、丁醛、三甲基乙醛、丙烯醛、丁烯醛、環己烷醛、呋糠醛、呋喃基丙烯醛、苯甲醛、對酞醛、苯基乙醛、α-苯基丙醛、/3 ·苯基丙醛、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-氯基苯甲醛、間-氯基苯甲醛、鄰-氯基苯甲醛、肉桂酸醛等。彼等可單獨使用，且亦可組合使用二種以上。此些醛類中，由取得之容易度而言以醛爲佳，特別爲了提高耐熱性，乃以組合使用羥基苯甲醛類與甲醛爲佳。該酮類可列舉例如丙酮、甲基乙基酮、二乙基酮、二苯基酮等。彼等可單獨使用，且亦可組合使用二種以上。更且，亦可適當組合使用。該芳香族羥基化合物與醛類或酮類之縮合反應產物可於酸性觸媒存在下以公知方法製造。此時之酸性觸媒可使用鹽酸、硫酸、甲酸、草酸、對甲苯磺酸等。使用酚醛淸漆樹脂做爲（a 1 )成分時，其Μη (質量平均分子量）以1000〜50000左右、較佳爲]000〜20000左右，就靈敏度特性之觀點而言爲佳。更佳之Mw範圔爲 2 00 0〜1 5 000。此範圍對於耐熱性、圖型垂直性、圖型形狀 (尺寸）依賴性、解像力、高靈敏度化之方面爲適當。 -11 - 1289728 (8) 還有，於使用酚醛淸漆樹脂做爲（a 1 )成分之情形中 ’由組成物之長期保存安定性之觀點而言，期望倂用後述之（D)成分和保存安定劑。(wherein R4 is an alkylene group which has a carbon number of 1 to 10 which may have a substituent, and 'm is a hydrazine or a hydrazine.] ( ) component (a 1 ) is not particularly limited, and a photoresist may be used. The alkali-soluble resin used in the product has a phenolic hydroxyl group, and is preferably reactive with the component (B). Suitable examples of the component (a 1 ) include condensation of an aromatic hydroxy compound with an aldehyde or a ketone. The obtained phenolic enamel resin, polyhydroxy styrene, and derivatives thereof, etc. The aromatic hydroxy compound may, for example, be phenol; m-cresol such as m-cresol, p-cresol or o-cresol; a xylenol such as 3-xylenol, 2,5-xylenol, 3,5-xylenol or 3,4-xylenol; m-ethylphenol, p-ethylphenol, ortho- Ethylphenol, 2,3 55-trimethylphenol, 2,3,5·triethylphenol, 4·t-butylphenol, 3·t-butylphenol, 2·t-butylphenol, 2 - alkylphenols such as t-butyl-4-methylphenol, 2-t-butyl-5-methylphenol; p-methoxyphenol, m-methoxyphenol, p-ethoxy phenol Alkoxyphenols such as ethoxyphenol, p-propoxyphenol, m-propoxyphenol, etc.; o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-iso Isopropenylphenols such as propenylphenol and 2-ethyl-4-isopropenylphenol; arylphenols such as phenylphenol '10-1282928 (7); 4,4,-dihydroxybiphenyl, A polyhydroxyphenol such as bisphenol A, resorcin, oxindole or pyrogallol, etc., which may be used alone or in combination of two or more. Examples of the aldehyde include formaldehyde, paraformaldehyde, and trisole.卩f alkane, acetaldehyde, propionaldehyde, butyraldehyde, trimethyl acetaldehyde, acrolein, crotonaldehyde, cyclohexane aldehyde, furfural, furan acrolein, benzaldehyde, p-nonaldehyde, phenyl acetaldehyde , α-phenylpropanal, /3 · phenylpropanal, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p- Methyl benzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, o-chlorobenzaldehyde, cinnamic acid aldehyde, etc. They may be used singly or in combination of two or more. In the class, aldehyde is preferred from the viewpoint of ease of use, and in particular, in order to improve heat resistance, it is preferred to use hydroxybenzaldehyde and formaldehyde in combination. Examples of the ketone include acetone, methyl ethyl ketone, and diethyl ketone. The ketone, the diphenyl ketone, etc. may be used singly or in combination of two or more. The condensation reaction product of the aromatic hydroxy compound with an aldehyde or a ketone may be used. In the presence of an acidic catalyst, it is produced by a known method. At this time, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, p-toluenesulfonic acid, etc. can be used as the acidic catalyst. When phenolic enamel resin is used as the component (a 1 ), its Μ (quality) The average molecular weight is preferably from about 1,000 to 50,000, preferably from about 10,000 to about 20,000, and is preferably from the viewpoint of sensitivity characteristics. The better Mw Fan is 2 00 0~1 5 000. This range is suitable for heat resistance, pattern perpendicularity, pattern shape (size) dependency, resolution, and sensitivity. -11 - 1289728 (8) In the case of using phenolic enamel resin as the component (a 1 ), it is desirable to use the component (D) described later from the viewpoint of long-term storage stability of the composition. Save the stabilizer.

該聚羥基苯乙烯及其衍生物可列舉例如乙烯基苯酚之單聚物、乙烯基苯酚與可共聚之共聚單體的共聚物等。此共聚單體可列舉例如甲基丙烯腈、苯乙烯、α -甲基苯乙烯、對·甲基苯乙烯、鄰·甲基苯乙烯、對-甲氧基苯乙烯、對·氯基苯乙嫌等之苯乙嫌衍生物。使用羥基苯乙烯系樹脂做爲（a 1 )成分之情形中，其 Mw 以 1〇〇〇〜4 0000、較佳爲 1000〜8000、特別以 2000〜6000，就耐熱性、高靈敏度化、與交聯劑之反應性的安定性觀點爲佳。 (a 1 )成分可使用一種或二種以上。 • B成分Examples of the polyhydroxystyrene and derivatives thereof include a monomer of a vinyl phenol, a copolymer of a vinyl phenol and a copolymerizable comonomer, and the like. Examples of the comonomer include methacrylonitrile, styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene, p-chlorophenylbenzene. Suspected benzene and susceptibility derivatives. When a hydroxystyrene resin is used as the component (a1), the Mw is from 1 to 4,000,000, preferably from 1,000 to 8,000, particularly from 2,000 to 6,000, and heat resistance and sensitivity are improved. The stability of the reactivity of the crosslinking agent is preferred. The (a 1 ) component may be used alone or in combination of two or more. • Component B

(B)成分爲以前述一般式（I)所示之化合物，可作用爲交聯劑。於前述一般式（I)中，R1爲亦可具有取代基之碳數 1〜10個之分支鏈狀、直鏈狀之伸焼基、或前述一般式（I】 )所示者。還有，前述伸烷基亦可於主鏈含有氧鍵（醚鍵 )° 一般式（π )中，R4爲亦可具有取代基之碳數i〜；! 0 個之分支鏈狀、直鏈狀之伸院基，前述伸烷基亦可於主鏈含有氧鏈（醚鍵）以-c4h8-、 -c2h40C2H4-、. C2H4OC2H4OC2H4-'及一般式（Π)所示者等爲佳，其中 -12 - 1289728 (9) 亦以一般式（II )所示者爲佳，特別以R4之碳數爲1、m 爲1者爲佳。 (B )成分可使用一種或混合二種以上。 • ( a2)成分於前述（i )中，（a2 )成分爲（al )成分與（B )成分反應所得之反應產物，對於鹼性水溶液爲難溶性且具有經由酸成分之作用而變成可溶性的特性。The component (B) is a compound represented by the above general formula (I), and can be used as a crosslinking agent. In the above general formula (I), R1 is a branched or linear straight chain group having 1 to 10 carbon atoms which may have a substituent, or the above general formula (I). Further, the alkylene group may have an oxygen bond (ether bond) in the main chain. In the general formula (π), R4 is a carbon number which may have a substituent i~;! 0 branch chain, linear The above-mentioned alkyl group may also have an oxygen chain (ether bond) in the main chain, preferably -c4h8-, -c2h40C2H4-, .C2H4OC2H4OC2H4-', and general formula (Π), wherein - 12 - 1289728 (9) It is also preferred to use the general formula (II), especially if the carbon number of R4 is 1, and m is 1. The component (B) may be used alone or in combination of two or more. (a2) In the above (i), the component (a2) is a reaction product obtained by reacting the (al) component with the component (B), and is insoluble in the alkaline aqueous solution and has a property of being soluble by the action of the acid component. .

若令（a 1 )成分與（B )成分反應，則通常取得（B )成分之單一終端的乙烯基爲（a 1 )成分之例如具備結合至側鏈之酚性羥基之構成單位的反應產物。此類構成單位之具體例可列舉下述一般式（1 A )所示之構成單位或下述一般式（2 A )所示之構成單位。When the component (a 1 ) is reacted with the component (B), the vinyl group of the single terminal of the component (B) is usually obtained as a reaction product of the component (a1) having a phenolic hydroxyl group bonded to the side chain. . Specific examples of such a constituent unit include a constituent unit represented by the following general formula (1A) or a constituent unit represented by the following general formula (2A).

又，若令（al)成分與（B)成分反應，則取得（B )成分之兩終端之乙烯基爲（a 1 )成分中之例如於側鏈的二個酚性羥基分別存在結合部分的反應產物。此類構成單位之具體例可列舉下述一般式（〗B )所示之分子間交聯部分、或下述一般式（2B )所示之分子間交聯部分。還有，通常爲取得僅結合（B )成分之單一終端的構成單位（例如（1 A ) ( 2 A ))、和存在結合兩者部分（例如，（1 B ) ( 2B ))的反應產物（a2 )。 -13- 1289728 (10)Further, when the (al) component is reacted with the component (B), the vinyl group at the two terminals of the component (B) is obtained as a binding component of the two phenolic hydroxyl groups in the side chain, for example, in the (a1) component. reaction product. Specific examples of such a constituent unit include an intermolecular crosslinking portion represented by the following general formula (?B) or an intermolecular crosslinking portion represented by the following general formula (2B). Further, it is usually a constituent unit (for example, (1 A ) ( 2 A )) which obtains a single terminal which only binds the component (B), and a reaction product in which a combination of both (for example, (1 B ) ( 2B )) exists. (a2). -13- 1289728 (10)

-14 - 1289728 (11)-14 - 1289728 (11)

• · · (IB)• · · (IB)

——C—CH (12) 1289728 R1爲同前述，R2、R3爲分別獨立爲氫原子或直鏈或分支鏈狀之碳數1〜3個的烷基或芳基，R2爲氫原子或甲基爲佳’ R3爲氫原子、丙基、經苯基等爲佳。η爲1〜3之整數。前述（Β )成分爲經由與（a I )鹼可溶性樹脂之側鏈的經基預先結合，抑制形成防止反射膜材料的經時變化，且成爲靈敏度經時變化少的材料。其後，若將前述材料於支撐體（基板）上塗佈、加熱，則（a2 )成分之側鏈的未反應酚性羥基爲與前述構成單位（1 A )或（2 A )之終端乙烯基反應，並且形成交聯構造。藉此，光阻被膜爲對於光阻圖型形成時所用之鹼顯像液等之鹼性水溶液爲呈難溶性。於選擇性曝光步驟中，來自（C )成分所發生之酸若作用，則前述交聯構造裂解，且對於鹼性水溶液的溶解性增大。還有，選擇酚醛淸漆樹脂做爲（al)成分時，於（al )成分與（B )成分之反應中，即使未反應酸觸媒亦進行反應，故並不需要使用酸觸媒，當然若於反應系中存在酸成分，則就調製組成物後之保存安定性方面而言爲不佳。又’選擇經基苯乙燒系樹脂做爲（al)成分時，令（al) 成分與（B )成分反應時，必須嚴格控制酸成分濃度，若於（a 1 )成分中含有酸成分雜質則爲不佳。因此，與（B )成分反應前，嚴格進行除去（a 1 )成分所含之酸成分的操作爲佳。還有，酸成分爲例如酚醛淸漆樹脂之合成時所 -16- (13) 1289728 用的酸觸媒、反應溶劑中存在的游離酸等，爲草酸、丙酸、甲酸、醋酸等之有機酸。其可根據氣相層析等予以分析〇酸成分之除去方法可列舉公知之方法，例如可應用離子交換樹脂之使用、純水淸洗、以鹼予以中和等之方法。其次，與（B)成分反應前之（al)成分中的酸成分濃度爲〇 · 1 p p m以下、特別以0 · 0 1 p p m以下爲特佳。 (a 1 )與（B )成分反應所得之（a2 )成分的質量平均分子量，在選擇酚醛淸漆樹脂做爲（a 1 )成分時，爲 1 0000〜70000、特別爲 20000〜50000，在選擇羥基苯乙烯系樹脂做爲（al )成分時，爲 3 0000〜1 50000、特別爲 40000〜100000，就耐熱性等方面而言爲佳。 (B )成分在選擇酚醛淸漆樹脂做爲（a 1 )成分時，相對於（al)成分以1〜15質量％、較佳爲使用4〜8質量％之比例。未滿1質量％，則未曝光部之膜減少變大，恐對防止反射膜造成副蝕刻，若超過1 5質量％，則對於顯像液（鹼水溶液）之溶解性有顯著變差之傾向’恐發生靈敏度差，無法將圖型解像等之問題。還有，選擇羥基苯乙烯系樹脂做爲（a 1 )成分時’相對於（a 1 )成分以1〜1 5質量％、較佳爲使用5〜]0質量％之比例。前述（Π)與前述（i)大爲不同點爲在於（al)成分與（B )成分爲以未反應之狀態被包含於（A )成分此點〇 (B )成分在選擇酚醛淸漆樹脂做爲（a 1 )成分時， -17 - 1289728 (14) 相對於（a 1 )成分以1〜5 0質量。/〇、較佳爲使用5〜3 5質量 %之比例。未滿1質量％，則未曝光部之膜減少變大，恐令防止反射膜等被副蝕刻，若超過5 0質量％，則對於顯像液（鹼水溶液）之溶解性有顯著變差之傾向，恐發生靈敏度差，無法將圖型解像等等問題。還有，選擇羥基苯乙烯系樹脂做爲（al )成分時，相對於（al )成分以^50 質量％、較佳爲使用5〜40質量％之比例。含有（al)成分與（B)成分之形成防止反射膜用組成物若被加熱，則（B)成分之乙烯基爲與（al)成分的羥基，例如側鏈之酚性羥基反應形成交聯構造，因此對於鹼水溶液變成難溶性。其次，於選擇性曝光步驟中，若由（C )成分所發生之酸作用，則前述交聯構造裂解，且對於鹼水溶液變成可溶。 • ( C )成分 (C)成分若爲具有令曝光部經由曝光而發生酸，且經由形成交聯構造令對於鹼水溶性變成難溶性之膜的交聯構造分解，並且該膜變化成鹼可溶性的機能即可。具有此類機能之所謂經由放射線之照射而發生酸的化合物，爲增強化學性光阻所用之所謂的產酸劑，迄今已提案許多，由其中任意選擇即可。具體而言，可使用已知做爲增強化學性型正型光阻組成物之材料的光產酸劑，例如磺醯重氮甲烷系產酸劑、氧鏠鹽系產酸劑、肟磺酸酯系產酸劑等。 -18- 1289728 於形成防止反射膜用組成物中所配合之（c )成分，以選擇於光阻圖型形成中之選擇曝光步驟所用之波長中發生酸成分者爲佳。即，以形成光阻被膜所用之正型光阻組成物所感光之波長、和形成防止反射膜用組成物所感光之波長大約相等般爲其構成爲佳。特別，於LCD之製造中，因爲使用g射線、h射線、 i射線共存的紫外線，故（C )成分以接受此類紫外線照射時之產酸效率高的化合物爲佳。又，爲了提高光阻被膜中的解像度，以波長短之i射線爲較佳利用，特別，以對於i射線曝光之產酸效率高的化合物爲佳。 (C )成分例如以如下之化合物’因其對於i射線曝光之產酸效率高，故較佳使用。例如，以一般式（Cl )、 ( C2 )- C-CH (12) 1289728 R1 is the same as the above, R2, R3 are each independently a hydrogen atom or a linear or branched chain of 1 to 3 carbon atoms or aryl groups, R2 is a hydrogen atom or a The base is preferably 'R3 is a hydrogen atom, a propyl group, a phenyl group or the like. η is an integer of 1 to 3. The (Β) component is a material which is inhibited by a time-dependent change in the formation of the antireflection film material via a group of a side chain of the side chain of the (a I) alkali-soluble resin, and which has a small change in sensitivity with time. Thereafter, when the material is applied onto a support (substrate) and heated, the unreacted phenolic hydroxyl group of the side chain of the component (a2) is a terminal ethylene with the above-mentioned constituent unit (1 A ) or (2 A ). The base reacts and forms a crosslinked structure. Thereby, the photoresist film is insoluble in an alkaline aqueous solution such as an alkali developing solution used for forming a photoresist pattern. In the selective exposure step, if the acid generated from the component (C) acts, the crosslinked structure is cleaved and the solubility in the aqueous alkaline solution is increased. Further, when the phenolic enamel resin is selected as the (al) component, the reaction of the (al) component and the component (B) does not require the use of an acid catalyst even if the reaction is carried out without reacting the acid catalyst. If an acid component is present in the reaction system, it is not preferable in terms of storage stability after the composition is prepared. In addition, when the (al) component is selected as the (al) component, the acid component concentration must be strictly controlled when the (al) component is reacted with the component (B), and the acid component impurity is contained in the (a1) component. It is not good. Therefore, it is preferred to carry out the operation of removing the acid component contained in the component (a1) strictly before the reaction with the component (B). Further, the acid component is, for example, an acid catalyst for the synthesis of a phenolic enamel resin, an acid catalyst for use in a reaction solvent, and the like, and an organic acid such as oxalic acid, propionic acid, formic acid or acetic acid. . This can be analyzed by gas chromatography or the like. A method for removing the phthalic acid component can be exemplified by a known method, for example, a method of using an ion exchange resin, washing with pure water, neutralization with a base, or the like. Next, the concentration of the acid component in the (al) component before the reaction with the component (B) is 〇 · 1 p p m or less, particularly preferably 0 · 0 1 p p m or less. (a 1 ) The mass average molecular weight of the component (a2) obtained by the reaction with the component (B) is selected from the group consisting of the phenolic enamel resin as the component (a1), from 1,000,000 to 70,000, particularly from 20,000 to 50,000. When the hydroxystyrene resin is used as the (al) component, it is preferably from 30,000 to 150,000, particularly from 40,000 to 100,000, and is preferably in terms of heat resistance and the like. When the component (B) is selected as the component (a1), the component (B) is used in an amount of from 1 to 15% by mass, preferably from 4 to 8% by mass, based on the (al) component. When the amount is less than 1% by mass, the film thickness of the unexposed portion is increased, and the sub-etching of the reflective film is prevented. If the content is more than 15% by mass, the solubility of the developing solution (aqueous alkali solution) tends to be significantly deteriorated. 'There is a problem that the sensitivity is poor and the pattern cannot be solved. Further, when the hydroxystyrene resin is selected as the component (a1), it is used in an amount of from 1 to 15% by mass, preferably from 5 to 0% by mass, based on the component (a1). The above (Π) differs greatly from the above (i) in that the (al) component and the (B) component are contained in the unreacted state in the (A) component. The point (B) component is selected in the phenolic enamel resin. When it is (a 1 ) component, -17 - 1289728 (14) is 1 to 50 mass with respect to (a 1 ) component. /〇, preferably using a ratio of 5 to 35% by mass. When the amount is less than 1% by mass, the film thickness of the unexposed portion is increased, and the reflection film or the like is prevented from being sub-etched. When the amount is more than 50% by mass, the solubility of the developing solution (aqueous alkali solution) is remarkably deteriorated. The tendency is that the sensitivity is poor and the pattern cannot be solved. Further, when the hydroxystyrene-based resin is selected as the (al) component, it is preferably used in an amount of from 50 to 40% by mass, preferably from 5 to 40% by mass, based on the (al) component. When the composition for forming an anti-reflection film containing (a) component and (B) is heated, the vinyl group of the component (B) reacts with a hydroxyl group of the (al) component, for example, a phenolic hydroxyl group of a side chain to form a crosslink. The structure is thus insoluble in alkali aqueous solution. Next, in the selective exposure step, when the acid generated by the component (C) acts, the crosslinked structure is cleaved and becomes soluble in the aqueous alkali solution. (C) Component (C) is a crosslinked structure having a film which causes an exposure portion to generate an acid by exposure, and which forms a film which is poorly soluble in alkali water solubility by forming a crosslinked structure, and the film is changed to alkali solubility. The function can be. The so-called acid generator for the purpose of enhancing the chemical resistance of the chemical which is caused by the irradiation of radiation, which has such a function, has been proposed so far. Specifically, a photoacid generator known as a material for reinforcing a chemical type positive resist composition, for example, a sulfonium diazomethane acid generator, an oxonium salt acid generator, an oxime sulfonic acid can be used. An ester acid generator or the like. -18- 1289728 It is preferable to form the component (c) to be formed in the composition for preventing reflection film, and to select an acid component in the wavelength selected for the selective exposure step in the formation of the photoresist pattern. That is, it is preferable that the wavelength at which the positive resist composition for forming the resist film is formed and the wavelength at which the composition for preventing the antireflection film are formed are approximately equal. In particular, in the manufacture of an LCD, since ultraviolet rays in which g-rays, h-rays, and i-rays coexist are used, the component (C) is preferably a compound having high acid-producing efficiency when subjected to such ultraviolet irradiation. Further, in order to improve the resolution in the resist film, it is preferable to use i-rays having a short wavelength, and in particular, a compound having high acid-producing efficiency for i-ray exposure is preferred. The component (C) is preferably used, for example, because of its high acid-producing efficiency for i-ray exposure. For example, in the general formula (Cl ), ( C2 )

(式中 m，爲〇或1 ; X爲1或2 ; R,爲亦可經一個 -19- 1289728 (16) 或以上之 c ! - C ! 2烷基所取代的苯基、雜芳基等，或，於 m5爲0時再爲C2-C6烷氧羰基、苯氧羰基、CN等；R3爲 CrCw烷基等；R3’爲X=1時與R3同義，X = 2時爲C2-C12 伸烷基、伸苯基等；R4、R5獨立爲氫原子、鹵素、Crh 烷基等；A爲S、0、NR6等；R6爲氫原子、苯基等）所示之化合物（USP 6004724 )。具體而言，可列舉例如下述式（C3 )所示之含硫醇烷之肟磺酸酯等。(wherein m is 〇 or 1; X is 1 or 2; R is a phenyl or heteroaryl group which may also be substituted by a c-C 2 alkyl group of -19- 1289728 (16) or more) Or, when m5 is 0, it is further C2-C6 alkoxycarbonyl, phenoxycarbonyl, CN, etc.; R3 is CrCw alkyl; etc.; R3' is synonymous with R3 when X=1, and C2- when X=2 C12 alkyl, phenyl, etc.; R4, R5 are independently a hydrogen atom, a halogen, a Crh alkyl group, etc.; A is S, 0, NR6, etc.; R6 is a hydrogen atom, a phenyl group, etc.) (USP 6004724) ). Specifically, for example, an oxime sulfonate containing a thiol alkane represented by the following formula (C3) can be mentioned.

R7〇 CC13 (式中，R6、R7爲分別表示碳數1〜3個之烷基）所示之雙（三氯甲基）三畊化合物、或、前述化合物（C4 ) 與下述式（C5 ) -20- 1289728 (17) CC13 ζΛ=^Ν ...(⑸ CC13 (式中，z爲表示心烷氧苯基等）所示之雙（三氯甲基）三哄化合物之組合者（特開平6-28 96 1 4號公報、特開平7· 1 3 44 1 2號公報）。三哄化合物（C4)具體而言可列舉例如2-〔 2- ( 3,4-二甲氧苯基）乙烯基〕-4,6-雙（三氯甲基）-1，3,5-三畊、 2-〔 2-(3-甲氧基-4-乙氧苯基）乙烯基〕-4,6-雙（三氯甲基）-1，3,5-三畊、2-〔2-(3-甲氧基-4-丙氧苯基）乙烯基〕-4,6-雙（三氯甲基）-1,3,5-三畊、2-〔2- (3-乙氧基-4-甲氧苯基）乙烯基〕-4,6-雙（三氯甲基）-1，3,5-三哄、2-〔2-(3,4-二乙氧苯基）乙烯基〕-4,6-雙（三氯甲基）-1，3,5-二哄、2-〔 2- ( 3 -乙氧基-4-丙氧苯基）乙條基〕· 4,6-雙（三氯甲基）-1,3,5-三哄、2-〔2- (3-丙氧基甲氧苯基）乙烯基〕-4,6-雙（三氯甲基）-1，3，5-三哄、2-〔 2- (3-丙氧基-4-乙氧苯基）乙烯基〕-4,6-雙（三氯甲基 )-1，3 5 5 -三畊、2-〔2-(3,4-二丙氧苯基-4-乙氧苯基）乙烯基〕-4,6-雙（三氯甲基）-1，3,5-三畊等。此些三畊化合物可單獨使用，且亦可組合使用二種以上。另一方面，與上述三畊化合物（C4 )視所欲組合使用的上述三畊化合物（C5 )，可列舉例如2- ( 4-甲氧苯基 )-4,6-雙（三氯甲基）-1,3,5-三哄、2-(4-乙氧苯基）- -21 - (18) 1289728 4.6- 雙（三氯甲基）-1，3,5-三哄、2-(4-丙氧苯基）-4,6-雙（三氯甲基）-1，3,5-三畊、2-(4-丁氧苯基）-456-雙（三氯甲基）-1，3,5-三畊、2-(4-甲氧萘基）-4,6-雙（三氯甲基）-1,3,5-三畊、2- (4-乙氧萘基）-4,6-雙（三氯甲基 )-1，3,5-三畊、2-(4-丙氧萘基）-4,6-雙（三氯甲基）-1，3,5-三畊、2-(4-丁氧萘基）-4,6-雙（三氯甲基）- 1.3.5- 三畊、2- (4-甲氧基-6-羧萘基）-4,6-雙（三氯甲基 )-1，3,5-三畊、2-(4-甲氧基-6-羥萘基）-4,6-雙（三氯甲基）-153,5-三畊、2-〔2-(2-呋喃基）乙烯基〕-456-雙（三氯甲基）-1，3,5-三哄、2-〔 2-(5-甲基-2-呋喃基）乙烯基〕-4,6-雙（三氯甲基）·1，3,5-三畊、2-〔 2-(5-丙基- 2-呋喃基）乙烯基〕-4,6-雙（三氯甲基）-1，3,5-三畊、2-〔 2- (3,5-二甲氧苯基）乙烯基〕-4,6-雙（三氯甲基）- 1.3.5- 三哄、2-〔2- (3 -甲氧基-5-乙氧苯基）乙烯基〕- 4.6- 雙（三氯甲基）-1,3,5-三畊、2-〔2-(3-甲氧基-5-丙氧苯基）乙烯基〕-4,6-雙（三氯甲基）三畊、2-〔 2- (3-乙氧基-5·甲氧苯基）乙烯基〕·4,6·雙（三氯甲基 )-15355·三畊、2-〔2·(3,5-二乙氧苯基）乙烯基〕-4,6-雙（三氯甲基）-]，3,5-三畊、2-〔2-(3-乙氧基-5-丙氧苯基）乙烯基〕-4,6-雙（三氯甲基）-1,3,5-三畊、2·〔2-( 3- 丙氧基-5-甲氧苯基）乙烯基〕-4 ;6-雙（三氯甲基）-1，3,5 -三卩并、2·〔2-(3 -丙氧基·5 -乙氧苯基）乙烯基〕-456 -雙（三氯甲基）-15355-三畊、2-〔2-(3,5-二丙氧苯基）乙烯基〕-4,6-雙（三氯甲基）-];3,5-三D并、2- ( 3;5- -22- 1289728 9) 基苯氧二甲基甲氯三 Γ\ 雙 6 2 \_/ I 2 % 畊三 I 5 3 基烯乙基苯氧二甲 I 4 3 基甲氯三 ,--- 雙 * 6 5 3 用使合組可亦且 11311 種 1 用使可物合化哄三些此 Ο 等哄三種上以物合化之示所 6 C /IV 式述下舉列可又R7〇CC13 (wherein R6 and R7 are each an alkyl group having 1 to 3 carbon atoms), or a compound (C4) and a formula (C5) -20- 1289728 (17) CC13 ζΛ=^Ν ((5) CC13 (wherein, z is a naphthyloxyphenyl group, etc.) is a combination of bis(trichloromethyl)triazine compounds ( Japanese Laid-Open Patent Publication No. Hei 6-28 No. Hei. No. Hei. No. Hei. Vinyl]-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-[2-(3-methoxy-4-ethoxyphenyl)vinyl]- 4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-[2-(3-methoxy-4-propoxyphenyl)vinyl]-4,6-bis ( Trichloromethyl)-1,3,5-three tillage, 2-[2-(3-ethoxy-4-methoxyphenyl)vinyl]-4,6-bis(trichloromethyl)- 1,3,5-triazine, 2-[2-(3,4-diethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-diindole, 2-[2-(3-Ethoxy-4-propoxyphenyl)ethyl]] 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2- (3- Oxymethoxymethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3-propoxy-4-ethoxyphenyl) ) vinyl]-4,6-bis(trichloromethyl)-1,3 5 5 -three tillage, 2-[2-(3,4-dipropoxyphenyl-4-ethoxyphenyl)ethylene 4-]6-bis(trichloromethyl)-1,3,5-three tillage, etc. These three tillage compounds may be used singly or in combination of two or more. The above-mentioned three-till compound (C5) to be used in combination with the cultivating compound (C4) may, for example, be 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5. - triterpenoid, 2-(4-ethoxyphenyl)- -21 - (18) 1289728 4.6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-propoxyphenyl) )-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-(4-butoxyphenyl)-456-bis(trichloromethyl)-1,3,5- Three tillage, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-(4-ethoxynaphthyl)-4,6- Bis(trichloromethyl)-1,3,5-three tillage, 2-(4-propoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2 -(4-butoxynaphthyl)-4,6-bis(trichloromethyl)- 1.3.5- Three tillage, 2-(4-methoxy-6-carboxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-(4-methoxy-6 -hydroxynaphthyl)-4,6-bis(trichloromethyl)-153,5-three tillage, 2-[2-(2-furyl)vinyl]-456-bis(trichloromethyl)- 1,3,5-triazine, 2-[2-(5-methyl-2-furyl)vinyl]-4,6-bis(trichloromethyl)·1,3,5-three tillage, 2-[2-(5-propyl-2-furyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2-[2-(3,5 -dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)- 1.3.5- tris(2-(2-methoxy-3-ethoxyphenyl)ethene) 】- 4.6-bis(trichloromethyl)-1,3,5-three tillage, 2-[2-(3-methoxy-5-propoxyphenyl)vinyl]-4,6-double (trichloromethyl) three tillage, 2-[2-(3-ethoxy-5-methoxyphenyl)vinyl]·4,6·bis(trichloromethyl)-15355·three tillage, 2 -[2·(3,5-diethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-],3,5-three tillage, 2-[2-(3-ethoxy 5--5-propoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-three tillage, 2·[2-(3-propoxy-5-methoxy) Phenyl) 4-]6-bis(trichloromethyl)-1,3,5-triindole, 2·[2-(3-propoxy-5-ethoxyphenyl)vinyl]-456 - Bis(trichloromethyl)-15355-three tillage, 2-[2-(3,5-dipropoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-]; 3,5 -3D,2-( 3;5- -22- 1289728 9) phenoxy dimethyl chloroformate 双 double 6 2 \_/ I 2 % cultivating tris I 5 3 olefin ethyl phenoxy A I 4 3 -methyl chloroformate, --- double * 6 5 3 can be used in combination with 11311 species 1 to make it possible to combine the enthalpy of hydrazine, etc. C / IV

厂 A CNlcfFactory A CNlcf

N Π -----—/ R \ ο nn S Μπ ο / ο C6) (式中’ Ar爲經取代或未取代之苯基、萘基；R爲 C】-C9之烷基；η’爲表示2或3之整數）。此些化合物可單獨使用，且亦可組合使用二種以上。以上例示之化合物中，亦特別以式（C3 )所示之化合物及下述式（C7 )所示之化合物，因其對於i射線之產酸效率優良，故爲較佳使用。 n CN CN ^ % 〇 | I 0 ⑽今〇、〆丫丫c、/〇、^C4H9…(⑺ Ιί ^ I! 〇 0 (C )成分之配合量爲相對於（A )成分1 00質量份，以1〜30質量份、特別以]〜20質量份爲佳。於形成防止反射膜用組成物中，爲了提高拉置經時安定性（光阻層之圖型型式曝光所形成之潛在影像的後曝光安定性），配合鹼性化合物（較佳爲胺類）做爲（D )成 -23- 1289728 (20) 分爲佳。該化合物，若對於形成防止反射膜用組成物具有相溶性者即可，並無特別限制，可列舉例如特開平9-600 1號公報中記載的化合物。N Π ------/ R \ ο nn S Μπ ο / ο C6) (wherein Ar is substituted or unsubstituted phenyl, naphthyl; R is C)-C9 alkyl; η' To represent an integer of 2 or 3.) These compounds may be used singly or in combination of two or more. Among the compounds exemplified above, the compound represented by the formula (C3) and the compound represented by the following formula (C7) are preferably used because they have excellent acid-producing efficiency for i-rays. n CN CN ^ % 〇| I 0 (10) 〇, 〆丫丫c, /〇, ^C4H9...((7) Ιί ^ I! 〇0 (C) The compounding amount is 100 parts by mass relative to (A) It is preferably 1 to 30 parts by mass, particularly preferably 2 to 20 parts by mass. In the composition for forming an antireflection film, in order to improve the stability over time (the potential image formed by the pattern type exposure of the photoresist layer) The post-exposure stability) is preferably in combination with a basic compound (preferably an amine) as (D) into -23-1282928 (20). The compound is compatible with the composition for forming an antireflection film. For example, the compound described in JP-A-9-600 No. 1 is exemplified.

特別，經由配合下述一般式（111 )所示之較膨鬆的特定鹼性化合物（d 1 )，則不僅具有提高上述拉置安定性的效果，且抑制組成物中之酸的經時性生成，並且亦具有提高前述組成物之保存安定性的效果，故爲適當。In particular, by blending the relatively bulky specific basic compound (d 1 ) represented by the following general formula (111), it has an effect of improving the above-described tensile stability and suppressing the acidity of the acid in the composition. It is produced and has an effect of improving the storage stability of the above composition, and is therefore appropriate.

XX

I N ——Y ---(111)I N ——Y ---(111)

Z 於一般式（III )中，X、Y、Z中之一個以上（較佳爲.2個以上、最佳爲三個）爲選自（1 )〜（4 )之基：（1 )碳數4個以上之烷基、（2 )碳數三個以上之環烷基、Z is in the general formula (III), and one or more of X, Y, and Z (preferably .2 or more, and most preferably three) are selected from the group consisting of (1) to (4): (1) carbon a number of four or more alkyl groups, (2) a cycloalkyl group having three or more carbon atoms,

(3 )苯基、（4 )芳烷基。前述X、Y、Z中，非前述（1)〜（4)者爲（1，）碳數3個以下的烷基、（2’）氫原子中選出之基或原子。 X、Y、Z可彼此相同或相異，X、Y、Z中，二個以上爲由前述（I )——（4 )所選出之基時，此些基彼此相同者就效果安定性方面而言爲佳。 • ·(])碳數4個以上之烷基前述（1 )之情況，碳數未滿4個，則難提高經時安定性。碳數爲5個以上爲更佳。上限値雖無特別限定，但 -24- (21) 1289728 由察見經時安定性之效果，於商業上取得之方面而言，以 20個以下，特別以1 5個以下爲佳。烷基可爲直鏈狀、分支鏈狀之任一者。具體而言，例如以正癸基、正辛基、正戊基等爲佳。 • · (2)碳數3個以上之環烷基(3) Phenyl, (4) aralkyl. Among the above X, Y and Z, those other than the above (1) to (4) are (1,) an alkyl group having 3 or less carbon atoms, and a group or atom selected from (2') hydrogen atoms. X, Y, and Z may be the same or different from each other. When two or more of X, Y, and Z are selected from the above (I) to (4), the bases are identical to each other in terms of effect stability. It is better. • · ()) Alkali with 4 or more carbon atoms In the case of (1) above, if the number of carbon atoms is less than four, it is difficult to improve the stability over time. It is more preferable that the carbon number is 5 or more. The upper limit is not particularly limited, but -24- (21) 1289728 is effective in terms of stability over time, and in terms of commercial acquisition, it is preferably 20 or less, particularly preferably 15 or less. The alkyl group may be either a linear chain or a branched chain. Specifically, for example, a n-decyl group, an n-octyl group, a n-pentyl group or the like is preferred. • · (2) A cycloalkyl group with more than 3 carbon atoms

於前述環烷基中，特別以碳數4〜8個之環烷基爲商業上可取得，且提高經時安定性之效果優良，故爲佳。特別以碳數6個之環己基爲佳。 • · ( 4 )芳烷基芳烷基爲以一般式-R’-P ( R’爲伸烷基，P爲芳香族烴基）表示。 P可列舉苯基、萘基等，但以苯基爲佳。 R’之碳數可爲1個以上，較佳爲1〜3個。芳烷基例如以苄基、苯乙基等爲佳。Among the cycloalkyl groups, a cycloalkyl group having 4 to 8 carbon atoms is commercially available, and the effect of improving the stability over time is excellent. In particular, it is preferred to use a cyclohexene group having 6 carbon atoms. • The (4)aralkylaralkyl group is represented by the general formula -R'-P (R' is an alkylene group and P is an aromatic hydrocarbon group). P may, for example, be a phenyl group or a naphthyl group, but a phenyl group is preferred. The carbon number of R' may be one or more, preferably 1 to 3. The aralkyl group is preferably, for example, a benzyl group, a phenethyl group or the like.

還有，X、Y、Z中，非前述（1)〜（4)者爲由前述 (Γ)、（2’）中選出之基或原子。 (1，）可爲直鏈或分支鏈之任一者。特別以甲基、乙基爲佳。 (d 1 )成分以構成三級胺者爲佳，於X、Y、Z中’ 非前述（1)〜（4)者爲由（1’）中選出爲佳。此類（d 1 )成分具體而言可列舉例如三·正癸胺、甲基-二-正辛胺、三-正戊胺、Ν，Ν·二環己基甲胺、三苄胺等。其中，以三-正癸胺、甲基-二-正辛胺、三-正戊胺中 -25- 1289728 (22) 選出一種以上爲佳，特別以三.正癸胺爲佳。 (D)成分可使用一種或混合二種以上。 (D )成分爲相對於樹脂固形成分1 〇〇質量份，配合 0.0 1〜5 · 0質量°/〇、特別以0 · 1〜1 · 〇質量份之範圍，就效果方面而言爲佳。 • ( E )吸光劑 (E )成分若爲對於光阻被膜之感光特性波長區域具有高吸收能力、且可防止因基板反射所發生之駐波和基板表面之段差所引起的亂反射者即可，並無特別限制。例如，水楊酸酯系化合物、二苯酮系化合物、苯並三唑系化合物、氰基丙烯酸酯系化合物、偶氮系化合物、聚烯系化合物' 蔥醌系化合物、碾系化合物（較佳爲聯苯硕系化合物）、亞硕系化合物（聯苯亞硕系化合物）、葱系化合物等均可使用。其中，若以具有至少一個取代基選自羥基、羥院基、丈兀氧纟兀基、及殘基之Μ系化合物、雙苯基硕系化合物聯苯亞碾系化合物及二苯酮系化合物中選出至少一種，則i 射線及KrF激之激光的吸收能力高，於曝光源使用丨射線或KrF的光微影術中爲佳。還有，（E)成分可使用一種或二種以上。該一本酮系化合物可列舉例如2，4 ·二經基二苯嗣 2,3,4 -三羥基二苯酮、2,2’，4,4、四羥基二苯酮、2,2,.5.6，· 四羥基二苯酮、2;2、二羥基|甲氧基二苯酮、2,6•二經基-4-甲氧基二苯酮、2，2、二羥基_4;4、二甲氧基二苯酮、 - 26- 1289728 (23) 4- 二甲胺基- 2’，4^二羥基二苯酮、4-二甲胺基- 3’，4、二羥基二苯酮等。Further, among X, Y and Z, none of the above (1) to (4) is a group or an atom selected from the above (Γ) and (2'). (1,) can be either a straight chain or a branched chain. In particular, methyl or ethyl groups are preferred. The component (d 1 ) is preferably one which constitutes a tertiary amine, and is preferably selected from (1') in the cases of X, Y and Z. Specific examples of such a component (d 1 ) include tri-n-decylamine, methyl-di-n-octylamine, tri-n-pentylamine, hydrazine, hydrazine dicyclohexylmethylamine, and tribenzylamine. Among them, one or more selected from the group consisting of tri-n-decylamine, methyl-di-n-octylamine and tri-n-pentylamine -25- 1289728 (22), particularly preferably tri-n-decylamine. The component (D) may be used alone or in combination of two or more. The component (D) is in an amount of 1 part by mass based on the solid content of the resin, and is preferably in the range of 0.0 1 to 5 · 0 mass ° / 〇, particularly in the range of 0 · 1 to 1 · 〇 by mass. • (E) The light absorbing agent (E) component can be a high-absorption capacity for the photosensitive characteristic wavelength region of the photoresist film, and can prevent the disordered reflection caused by the difference between the standing wave generated by the substrate reflection and the surface of the substrate. There are no special restrictions. For example, a salicylate-based compound, a benzophenone-based compound, a benzotriazole-based compound, a cyanoacrylate-based compound, an azo-based compound, a polyene-based compound, an onion-based compound, and a milled compound (preferably It can be used as a biphenyl compound (a biphenyl compound), an aspirite compound (biphenyl sub-system), an onion compound, or the like. Wherein, the fluorene compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyl group, a hydrazine group, and a residue, a bisphenyl macro compound, a biphenyl sulphide compound, and a benzophenone compound If at least one of the selected ones is selected, the absorption power of the i-ray and KrF-excited laser is high, and it is preferable that the exposure source uses x-ray or KrF photolithography. Further, the component (E) may be used alone or in combination of two or more. The ketone-based compound may, for example, be 2,4·di-dibenzoquinone 2,3,4-trihydroxybenzophenone, 2,2′,4,4, tetrahydroxybenzophenone, 2, 2, .5.6, · tetrahydroxybenzophenone, 2; 2, dihydroxy | methoxy benzophenone, 2, 6 • di-based 4-methoxybenzophenone, 2, 2, dihydroxy 4; 4. Dimethoxybenzophenone, - 26- 1289728 (23) 4-dimethylamino-2',4^dihydroxybenzophenone, 4-dimethylamino-3',4,dihydroxydi Benzophenone and the like.

又，雙苯基碾系化合物及雙苯基亞硕系化合物以雙（羥苯基）硕、雙（羥苯基）亞碾、雙（聚羥苯基）硕、雙 (聚羥苯基）亞硕爲佳，此類化合物可列舉例如雙（4-羥苯基）碾、雙（3,5·二甲基-4-羥苯基）硕、雙（4-羥苯基 )亞硕、雙（3,5-二甲基-4-羥苯基）亞硕、雙（2,3-二羥苯基）硕、雙（5-氯基-2,3-二羥苯基）硕、雙（2,4-二羥苯基）硕、雙（2,4-二羥基-6 -甲基苯基）硕、雙（5-氯基- 2,4-二羥苯基）碾、雙（2,5-二羥苯基）碾、雙（3,4-二羥苯基）硕、雙（3,5-二羥苯基）硕、雙（2,3,4-三羥苯基）硕、雙（2,3,4-三羥基-6-甲基苯基）硕、雙（5-氯基-2,3,4·三羥苯基）硕、雙（2,4,6-三羥苯基）硕、雙（Further, the bisphenyl triazine compound and the bisphenyl subclass compound are bis(hydroxyphenyl), bis(hydroxyphenyl) submill, bis(polyhydroxyphenyl), and bis(polyhydroxyphenyl). It is preferable that such a compound may, for example, be bis(4-hydroxyphenyl) milled, bis(3,5·dimethyl-4-hydroxyphenyl), or bis(4-hydroxyphenyl) Bis(3,5-dimethyl-4-hydroxyphenyl)arsine, bis(2,3-dihydroxyphenyl), bis(5-chloro-2,3-dihydroxyphenyl) Bis(2,4-dihydroxyphenyl), bis(2,4-dihydroxy-6-methylphenyl), bis(5-chloro-2,4-dihydroxyphenyl) mill, double (2,5-dihydroxyphenyl) milled, bis(3,4-dihydroxyphenyl), bis(3,5-dihydroxyphenyl), bis (2,3,4-trihydroxyphenyl) Master, bis(2,3,4-trihydroxy-6-methylphenyl), bis (5-chloro-2,3,4·trihydroxyphenyl), double (2,4,6) - Trihydroxyphenyl) Master, Double (

5- 氯基-2,4,6-三羥苯基）碾、雙（2,3-二羥苯基）亞硕、雙（5-氯基·2,3·二羥苯基）亞碾、雙（2,4-二羥苯基）亞硕、雙（2,4-二羥基-6-甲基苯基）亞碾、雙（5-氯基二羥苯基）亞硕、雙（2,5-二羥苯基）亞硕、雙（3,4_二羥苯基）亞硕、雙（3,5-二羥苯基）亞硕、雙（253,4-三羥苯基）亞硕、雙（2,3，4-三羥基-6-甲基苯基）亞碾、雙 (5-氯基-2,3,4-三羥基苯基）亞硕、雙（2;4,6-三羥苯基 )亞碾、雙（5-氯基- 2,4,6-三羥苯基）亞硕等。更且，蒽系化合物可列舉例如下述式（Ε 1 )所示之化合物。 -27- 1289728 (24)5-Chloro-2,4,6-trihydroxyphenyl) milled, bis(2,3-dihydroxyphenyl)arsine, bis(5-chloro-2,3·dihydroxyphenyl) submill , bis(2,4-dihydroxyphenyl)arsine, bis(2,4-dihydroxy-6-methylphenyl) sub-milling, bis(5-chlorodihydroxyphenyl) sub-s, double ( 2,5-dihydroxyphenyl)arsine, bis(3,4-dihydroxyphenyl)arsine, bis(3,5-dihydroxyphenyl)arsine, bis(253,4-trihydroxyphenyl) Azul, bis(2,3,4-trihydroxy-6-methylphenyl) sub-milling, bis(5-chloro-2,3,4-trihydroxyphenyl) sub-, bis (2; 4,6-trihydroxyphenyl) sub-milling, bis(5-chloro-2,4,6-trihydroxyphenyl) sub- and the like. Furthermore, the oxime-based compound may, for example, be a compound represented by the following formula (Ε 1 ). -27- 1289728 (24)

(式中，z爲1〜10之整數，m爲〇〜8之整數，j爲 0〜6之整數，k爲0〜6之整數，但，k和m不同時爲0) 上述式（E 1 )所示之化合物具體而言可列舉卜羥蒽、卜羥蒽、1,2-二羥蒽、1，5-二羥蒽、9,10·二羥蒽、1，2,3- 三羥蒽、卜羥甲基蒽、9-羥甲基蒽、9-羥乙基蒽、9-羥3 基蒽、9-羥辛基蒽、9,10-二羥甲基蒽等，更以9-蒽羧酸、9，1 0 -蒽二羧酸、縮水甘油基化蒽羧酸、縮水甘油基化蒽基甲醇、蒽基甲醇與多元羧酸（例如，草酸、丙二酸、甲基丙二酸、乙基丙二酸、琥珀酸、甲基琥珀酸、2,2-二甲基琥珀酸、戊二酸、己二酸、庚二酸等）之縮合產物等均適於使用。其中，由反應性高、且滿足難發生混合現象等之條件、加上吸光性高之觀點而言，以蒽系化合物、特別以9-蒽甲醇、9,10-二蒽甲醇、9-蒽羧酸及9,10-蒽二羧酸爲佳〇 (E )成分於全固形成分中，配合〇·1〜50質量％爲佳，特別以10〜30質量％爲佳。於下限値以上則可提高效果，且於上限値以下則可令成膜性良好。 •有機溶劑形成防止反射膜用組成物的有機溶劑若爲增強化學性 •28- 1289728 (25) 型之正型光阻組成物中所用者即可，並無特別限定均可使用。可列舉例如丙二醇單烷醚醋酸酯（例如丙二醇單甲醚醋酸酯（PGMEA )等）、乳酸酯（例如乳酸乙酯等）等之酯系溶劑、和丙酮、甲基乙基酮、環己酮、甲基異戊基酮、2 -庚酮等之酮類；乙二醇、丙二醇、二甘醇、或彼等之單甲醚、單***、單丙醚、單丁醚或單苯醚等之多元醇類及其衍生物；二哼烷般之環式醚類；等之非酯系溶劑。還有，酯系溶劑由於係爲有機羧酸與醇的反應產物，故含有有機羧酸游離酸。因此，未配合前述（dl)成分的組成物、或未配合後述保存安定劑的組成物中，選擇不含有此類游離酸的非酯系溶劑爲佳，且特別以酮類（酮系之溶劑）爲佳。其中亦以2-庚酮由塗膜性、（C )成分之溶解性方面而言亦爲適當。還有，酯系溶劑和非酯系溶劑亦均經時性地分解生成酸，但於前述（dl)成分之存在下、或後述之保存安定劑的存在下，則可抑制前述分解反應。特別於酯系溶劑中此效果顯著，於前述（d 1 )成分、保存安定劑之存在下，當然以酯系溶劑爲佳，特別以PGMEA爲適當。還有，經由上述分解所副生成的酸成分例如於2 -庚酮時，可確認產生甲酸、醋酸、丙酸等。有機溶劑可使用一種或混合二種以上。雖無特別限定，但有機溶劑若使用固形成分之濃度爲 20〜50質量％、較佳爲25〜45質量％之配合量，則就塗佈 -29- 1289728 (26) 性之觀點而言爲佳。於形成防止反射膜用組成物中，視需要配合如下之保存安定劑爲佳。前述保存安定劑若具有抑溶劑分解反應之作用者即可，並無特別限定，可列舉例如特開昭58- 1 94834號公報中所記載的抗氧化劑。抗氧化劑已知有苯酚系化合物和胺系化合物，特別以苯酚系化合物爲佳，其中亦以2 5 6 ·二（第三丁基）-對·甲苯酚及其衍生物對於酯系溶劑、酮系溶劑之惡化爲有效，且可於商業上取得、廉價、且保存安定效果優良方面爲佳。特別對於丙二醇單烷醚醋酸酯、2-庚酮之防止惡化效果極爲優良。保存安定劑之配合量爲相對於樹脂固形成分1 00質量份，以0 · 〇 1〜3質量份、特別以〇 · 1〜1 · 〇質量份之範圍爲佳 •其他成分又，於形成防止反射膜用組成物中，在不損害本發明目的之範圍下，視需要，可含有具有相容性之添加物，例如改良防止反射膜性能等之加成性樹脂、可塑劑、安定劑、界面活性劑、令顯像之圖像更加可見的著色料、更加提高增感效果的增感劑和防眩用染料、密合性改善劑等之慣用的添加物。〔正型光阻組成物〕正型光阻組成物可無特別限定地使用先前所用者。可 -30- (27) 1289728 爲非增強化學性型、或增強化學性型。以下，列舉LCD系統製造中合適的正型光阻組成物的第一〜第四實施形態。第一〜第三之實施形態爲增強化學性型，第四之實施形態爲非增強化學性型的酚醛淸漆-萘醌系光阻組成物。(wherein z is an integer of 1 to 10, m is an integer of 〇8, j is an integer of 0 to 6, and k is an integer of 0 to 6, but k and m are not 0 at the same time) Specific examples of the compound shown in 1) include oxindole, oxindole, 1,2-dihydroxyindole, 1,5-dihydroxyindole, 9,10-dihydroxyindole, 1,2,3-tri Hydroxyl hydrazine, hydroxymethyl hydrazine, 9-hydroxymethyl hydrazine, 9-hydroxyethyl hydrazine, 9-hydroxy 3 hydrazine, 9-hydroxyoctyl hydrazine, 9,10-dimethylol hydrazine, etc. 9-indole carboxylic acid, 9,10-decanedicarboxylic acid, glycidylated hydrazine carboxylic acid, glycidylated hydrazino methanol, mercapto methanol and polycarboxylic acid (for example, oxalic acid, malonic acid, methyl The condensation products of malonic acid, ethylmalonic acid, succinic acid, methyl succinic acid, 2,2-dimethylsuccinic acid, glutaric acid, adipic acid, pimelic acid, and the like are suitable for use. Among them, from the viewpoint of high reactivity, satisfying conditions such as difficulty in mixing, and high absorbance, lanthanoid compounds, particularly 9-oxime methanol, 9,10-dioxanethanol, and 9-fluorene are used. The carboxylic acid and the 9,10-fluorene dicarboxylic acid are preferably the component (E) in the total solid content, and preferably 1 to 50% by mass, particularly preferably 10 to 30% by mass. When the lower limit is 値 or more, the effect can be improved, and when the upper limit is 値 or less, the film formability can be improved. • Organic solvent The organic solvent that forms the composition for the antireflection film is used for the chemical resistance of the positive resistive composition of the type 28-2828928 (25), and is not particularly limited. For example, an ester solvent such as propylene glycol monoalkyl ether acetate (for example, propylene glycol monomethyl ether acetate (PGMEA)) or a lactate (for example, ethyl lactate), and acetone, methyl ethyl ketone, and cyclohexane may be mentioned. Ketones such as ketone, methyl isoamyl ketone, 2-heptanone, etc.; ethylene glycol, propylene glycol, diethylene glycol, or their monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether Polyols and their derivatives; dioxane-like cyclic ethers; and other non-ester solvents. Further, since the ester solvent is a reaction product of an organic carboxylic acid and an alcohol, it contains an organic carboxylic acid free acid. Therefore, it is preferable to select a composition which does not contain the component of the above (dl) or a composition which does not contain a stabilizer which will be described later, and a non-ester solvent which does not contain such a free acid, and particularly a ketone (solvent) ) is better. Among them, 2-heptanone is also suitable in terms of coating property and solubility of the component (C). Further, both the ester solvent and the non-ester solvent are decomposed to form an acid over time, but the decomposition reaction can be suppressed in the presence of the component (dl) or in the presence of a storage stabilizer described later. Particularly, in the ester solvent, the effect is remarkable. In the presence of the component (d 1 ) and the storage stabilizer, the ester solvent is preferred, and PGMEA is particularly suitable. Further, when the acid component produced by the above decomposition is, for example, 2-heptanone, it is confirmed that formic acid, acetic acid, propionic acid or the like is produced. The organic solvent may be used alone or in combination of two or more. Although the organic solvent is used in an amount of 20 to 50% by mass, preferably 25 to 45% by mass, based on the concentration of the solid component, it is applied from the viewpoint of coating -29-1289728 (26). good. In the composition for forming an antireflection film, it is preferred to incorporate the following stabilizer as needed. The above-mentioned storage stabilizer is not particularly limited as long as it has a function of a solvolysis reaction, and an antioxidant described in JP-A-58-149834, for example. As the antioxidant, a phenol compound and an amine compound are known, and a phenol compound is particularly preferable, and among them, 2 5 6 · bis(t-butyl)-p-cresol and a derivative thereof are used for an ester solvent and a ketone. The deterioration of the solvent is effective, and it is preferably commercially available, inexpensive, and excellent in preservation stability. In particular, the propylene glycol monoalkyl ether acetate and 2-heptanone are extremely excellent in preventing deterioration. The amount of the stabilizer to be stabilized is 100 parts by mass relative to the solid content of the resin, and is preferably in the range of 0 · 〇 1 to 3 parts by mass, particularly in the range of 〇·1 to 1 · 〇 by mass. The composition for a reflective film may contain a compatible additive such as an additive resin for improving the performance of the antireflection film, a plasticizer, a stabilizer, and an interface, as long as the object of the present invention is not impaired. An active additive, a coloring material that makes the image of the image more visible, a sensitizer that further enhances the sensitizing effect, a conventional dye such as an anti-glare dye, and an adhesion improving agent. [Positive-type photoresist composition] The positive-type photoresist composition can be used without any particular limitation. -30- (27) 1289728 is a non-reinforced chemical type or a chemically enhanced type. Hereinafter, the first to fourth embodiments of a suitable positive resist composition in the manufacture of an LCD system will be described. The first to third embodiments are chemically enhanced, and the fourth embodiment is a non-reinforced chemical type phenolic enamel-naphthene-based photoresist composition.

由操作性良好、且原料費用便宜之方面而言以非增強化學性型爲佳。特別於LCD之製造中，以i射線（3 65 rim )用之酚醛淸漆-萘醌系之光阻組成物爲佳。另一方面，增強化學性型爲未曝光部分與曝光部分之顯像對比度大，且解像性及DOF特性優良。〈第一實施形態〉It is preferable to use a non-reinforced chemical type from the viewpoint of good workability and low cost of raw materials. Particularly in the manufacture of LCDs, a phenolic enamel-naphthoquinone-based photoresist composition for i-ray (3 65 rim ) is preferred. On the other hand, the enhanced chemical type has a large developing contrast ratio between the unexposed portion and the exposed portion, and is excellent in resolution and DOF characteristics. <First Embodiment>

本實施形態之正型光阻組成物爲含有（A5 )樹脂成分、和（C ’）經由放射線照射而發生酸成分的化合物、和有機溶劑，且藉由前述（C5 )成分所發生之酸成分的作用，則具有增大對於鹼水溶液之溶解性的性質。 • ( A’）成分 (A )成分爲含有（a ’）全酚性羥基之一部分爲經酸解離性溶解抑制基所保護的鹼可溶性樹脂。構成（a ’）成分的驗可溶性樹脂成分並無特別限定，可由通常被使用做爲正型光阻組成物中之被膜形成物質者中任意選擇，且較佳爲芳香族羥基化合物與醛類或酮類縮合反應所得之酚醛淸漆樹脂、聚羥基苯乙烯及其衍生物等 -31 - 1289728 (28) 具體例可列舉與前述形成防止反射膜用組成物之（a 1 )成分同樣者。本實施形態中之（a ’）鹼可溶性樹脂之經酸解離性溶解抑制基所保護前之質量平均分子量（Mw )的較佳範圍爲1 000〜20000、較佳爲2000〜5 0000、更佳爲3 000〜3 0000 。（a5 )成分之M w若小於上述範圍，則恐解像性降低，若超過上述範圍則塗佈性變差。於本實施形態中，（a5 )成分中之全酚性羥基的至少一部分爲經由酸觸媒反應分解變化成鹼可溶性之基，所謂經酸解離性溶解抑制基所保護。此類酸解離性溶解抑制基若爲可由（C，）成分所發生之酸予以解離者即可，可列舉例如1-乙氧甲基、i -乙氧乙基、1-丙氧甲基、1-丙氧乙基、正丁氧甲基、^異丁氧甲基、1-第三丁氧甲基等之烷氧烷基；第三丁氧羰基、第二丁氧羰甲基、第三丁氧羰乙基等之烷氧羰烷基；四氫呋喃基；四氫卩比喃基；直鏈狀或分支鏈狀乙縮醛基；環狀乙縮醛基；二甲基甲矽烷基、三乙基甲砂垸基、三苯基甲矽院基等之二院基甲5夕院基。其中亦以下述化學式（IV-])所示之乙氧乙基及下述化學式C IV-2 )所示之第三丁氧羰基爲取得解像性優良之光阻組成物上爲佳，特別以乙氧乙基爲佳。 —CH-—〇—C2H5 ...(ivh) CH3 -32- 1289728 (29) -:-〇-C(CH3)3 …（IV-2) Ο • ( C ’）、（ D ’）、有機溶劑本實施形態中之（C ’）成分及有機溶劑可與上述形成防止反射膜用組成物中之（C )成分及有機溶劑分別相同之構成。又，於本實施形態中，爲了提高拉置安定性，以配合 (D ’）鹼性化合物爲佳。此類鹼性化合物爲與上述形成防止反射膜用組成物中之（D )成分相同。又，視需要配合與形成防止反射膜用組成物同樣之保存安定劑爲佳。又，於本實施形態之光阻組成物中，在不損害本發明目的之範圍下，視需要可含有具有相容性的添加物，例如用以改良光阻膜性能等之加成性樹脂、可塑劑、安定劑、界面活性劑、令顯像之像能進一步可見的著色料、更加提高增感效果的增感劑和防眩用染料、密黏改善劑等慣用的添加物。 <第二之實施形態> 正型光阻組成物之第二實施形態爲含有（A ’）樹脂成分、和（C 5 )經由放射線之照射發生酸成分的化合物、和有機溶劑，且經由前述（C ’）成分所發生之酸成分的作用，具有增大對於鹼水溶液之溶解性的性質。 -33- 1289728 (30) • ( A5 )成分 (A ’）成分爲含有（a 1 )鹼可溶性樹脂和（b 5 )上述一般式（I )所示化合物的（a2 )反應產物。 (A’）成分之（al)成分、（B，）成分、及（a2)成分可與前述形成防止反射膜用組成物中之（A)成分的（ al )成分、（B )成分、及（a2 )成分分別同樣之構成。 • (C5)、（D，）、有機溶劑本實施形態中之（C ’）成分及有機溶劑可與上述形成防止反射膜用組成物中之（C )成分及有機溶劑分別同樣之構成。又，於本實施形態中，爲了提高拉置安定性，亦以配合（D ’）鹼性化合物爲佳。此類鹼性化合物爲與上述形成防止反射膜用組成物中之（D )成分相同。又，視需要配合與形成防止反射膜用組成物同樣之保存安定劑爲佳。又，本實施形態之光阻組成物亦與上述第一實施形態同樣地，在不損害本發明目的之範圍下，視需要可含有具有相容性的添加物。 <第三之實施形態> 正型光阻組成物之第三實施形態爲含有（樹脂成分、和（C ’）經由放射線之照射發生酸成分的化合物、和有機溶劑，且若來自前述（C ’）成分所發生之酸成分作用 -34- 1289728 (31) ，則具有增大對於鹼水溶液之溶解性的性質。 • ( A’）成分、（B’）成分 (A5 )成分爲含有（al )鹼可溶性樹脂，且前述光阻組成物爲再含有（B ’）前述一般式（I )所示之化合物。 (A’）成分之（al)成分、及（B’）成分可與前述形成防止反射膜用組成物中之（a 1 )成分及（B )成分分別同樣之構成。 • (C’）、（D’）、有機溶劑本實施形態中之（C ’）成分及有機溶劑可與上述形成防止反射膜用組成物中之（C )成分及有機溶劑分別同樣之構成。又，於本實施形態中，爲了提高拉置安定性，亦以配合（D ’）鹼性化合物爲佳。此類鹼性化合物爲與上述形成防止反射膜用組成物中之（D )成分相同。又，視需要配合與形成防止反射膜用組成物同樣之保存安定劑爲佳。又，本實施形態之光阻組成物亦與前述第一實施形態同樣地，在不損害本發明目的之範圍下，視需要可含有具有相容性的添加物。 <第四之實施形態> 正型光阻組成物之第四實施形態爲含有（A”）鹼可溶性樹脂、（B5 )萘醌二疊氮基酯化物、（C”）分子量 1 〇〇〇以下之含有酚性羥基之化合物、及（D”）有機溶劑 -35- 1289728 (32) 本實施形態中之（A”）成分並無特別限定，可由通常使用做爲正型光阻組成物中之形成被膜物質中，任意選擇使用一種或二種以上。具體例可列舉與前述形成防止反射膜用組成物之（a 1 )成分同樣之物質。本實施形態中之（A”）成分之以凝膠滲透層析所得之換算成聚苯乙烯的質量平均分子量，爲根據其種類而異，但由靈敏感和形成圖型的觀點而言爲以2000〜100000、較佳爲 3000〜30000。 (B”）成分一般於正型光阻組成物中，若爲使用做爲感光性成分者即可，並無特別限制，可任意選擇使用一種或二種以上。其中特別以下述一般式（I”）The positive-type resist composition of the present embodiment is a compound containing (A5) a resin component and (C') an acid component generated by radiation irradiation, and an organic solvent, and an acid component generated by the above (C5) component The effect is to increase the solubility to the aqueous alkali solution. (A') Component (A) is an alkali-soluble resin containing a part of the (a ') all-phenolic hydroxyl group which is protected by an acid-dissociable dissolution inhibiting group. The component of the soluble resin component constituting the component (a ') is not particularly limited, and may be arbitrarily selected from those generally used as a film-forming material in a positive-type photoresist composition, and is preferably an aromatic hydroxy compound and an aldehyde or The phenolic enamel resin, the polyhydroxy styrene, and the derivative thereof obtained by the ketone condensation reaction, etc. - 31 - 1289728 (28) Specific examples thereof are the same as the component (a 1 ) which forms the composition for an antireflection film described above. The mass average molecular weight (Mw) before the acid dissociable dissolution inhibiting group of the (a ') alkali-soluble resin in the present embodiment is preferably from 1,000 to 20,000, preferably from 2,000 to 50,000, more preferably It is 3 000~3 0000. When the Mw of the component (a5) is less than the above range, the resolution is lowered, and if it exceeds the above range, the coatability is deteriorated. In the present embodiment, at least a part of the total phenolic hydroxyl group in the component (a5) is a group which is converted to an alkali solubility by an acid catalyst reaction, and is protected by an acid dissociable dissolution inhibiting group. The acid dissociable dissolution inhibiting group may be any one which can be dissociated by an acid generated by the component (C), and examples thereof include 1-ethoxymethyl, i-ethoxyethyl and 1-propoxymethyl. Alkoxyalkyl group such as 1-propoxyethyl, n-butoxymethyl, isobutoxymethyl, 1-tert-butoxymethyl; third butoxycarbonyl, second butoxycarbonylmethyl, An alkoxycarbonylalkyl group such as a tributyloxycarbonylethyl group; a tetrahydrofuranyl group; a tetrahydroindenyl group; a linear or branched acetal group; a cyclic acetal group; a dimethylformyl group; The base of the second hospital, such as triethylmethicone, triphenylmethyl sulfonate, etc. Among them, an ethoxyethyl group represented by the following chemical formula (IV-]) and a third butoxycarbonyl group represented by the following chemical formula C IV-2) are preferred for obtaining a photoresist composition excellent in resolution, particularly Ethoxyethyl is preferred. —CH——〇—C2H5 ...(ivh) CH3 -32- 1289728 (29) -:-〇-C(CH3)3 ...(IV-2) Ο • ( C '), ( D '), organic Solvent The component (C') and the organic solvent in the present embodiment are the same as those in the component (C) and the organic solvent in the composition for forming an antireflection film. Further, in the present embodiment, in order to improve the stability of the pull, it is preferred to blend (D ') a basic compound. Such a basic compound is the same as the component (D) in the above composition for forming an antireflection film. Further, it is preferable to mix and retain the stabilizer similar to the composition for forming an antireflection film as needed. Further, in the photoresist composition of the present embodiment, it is possible to contain a compatible additive, for example, an additive resin for improving the performance of the photoresist film, etc., without impairing the object of the present invention. A plasticizer, a stabilizer, a surfactant, a coloring material which can further visualize the image, a sensitizer which further enhances the sensitizing effect, a conventional dye such as an anti-glare dye, and a tackifier. <Second Embodiment> The second embodiment of the positive resist composition is a compound containing (A ') a resin component and (C 5 ) an acid component generated by radiation irradiation, and an organic solvent, and The action of the acid component generated by the above (C') component has the property of increasing the solubility in the aqueous alkali solution. -33- 1289728 (30) • The component (A ') of (A5) is a reaction product of (a2) containing (a1) an alkali-soluble resin and (b5) the compound of the above general formula (I). The (al) component, the (B) component, and the component (a2) of the component (A') may be the (al) component and the (B) component of the component (A) in the composition for forming an antireflection film, and The components (a2) are identically constructed. (C5), (D), and organic solvent The (C') component and the organic solvent in the present embodiment can be formed in the same manner as the component (C) and the organic solvent in the composition for forming an antireflection film. Further, in the present embodiment, in order to improve the stability of the pull, it is preferable to use a compound (D '). Such a basic compound is the same as the component (D) in the composition for forming an antireflection film described above. Further, it is preferable to mix and retain the stabilizer similar to the composition for forming an antireflection film as needed. Further, in the same manner as in the above-described first embodiment, the photoresist composition of the present embodiment may contain a compatible additive as needed, without departing from the object of the present invention. <Third Embodiment> The third embodiment of the positive-type photoresist composition is a compound containing a resin component and (C') by an irradiation of radiation, and an organic solvent, and from the above ( The acid component of the C ') component acts as -34-1282928 (31), which has the property of increasing the solubility in the aqueous alkali solution. • The (A') component and the (B') component (A5) component are contained ( Al) an alkali-soluble resin, wherein the photoresist composition further contains (B') a compound represented by the above formula (I). The (al) component and the (B') component of the (A') component may be as described above The components (a 1 ) and (B) in the composition for preventing reflection film are respectively formed in the same manner. • (C'), (D'), organic solvent (C ') component and organic solvent in the present embodiment. It can be configured similarly to the component (C) and the organic solvent in the composition for forming an antireflection film described above. Further, in the present embodiment, in order to improve the stability of the pull, the (D ') basic compound is also blended. Good. Such basic compounds are The component (D) in the composition for forming an antireflection film is the same. It is preferable to mix and hold a stabilizer similar to the composition for forming an antireflection film, if necessary. Further, the photoresist composition of the present embodiment is also the same as described above. In the same manner as in the first embodiment, a compatible additive may be contained as needed within the scope of the object of the present invention. <Fourth embodiment> The fourth embodiment of the positive resist composition is (A") alkali-soluble resin, (B5) naphthoquinonediazide esterate, (C") phenolic hydroxyl group-containing compound having a molecular weight of 1 〇〇〇 or less, and (D") organic solvent - 35-1268928 (32) The component (A") in the present embodiment is not particularly limited, and one or two or more kinds of the film-forming substances which are generally used as the positive-type resist composition can be used arbitrarily. The material of the (a1) component of the composition for preventing reflection film is the same. The mass average molecular weight of the component (A") in the present embodiment converted into polystyrene by gel permeation chromatography is the root. It varies depending on the type, but it is 2000 to 100000, preferably 3000 to 30000 from the viewpoint of sensitivity and pattern formation. The (B") component is generally used in a positive photoresist composition, if used for use. The photosensitive component is not particularly limited, and one or two or more of them may be used arbitrarily. Among them, the following general formula (I")

〔式中，R1 5〜R4' R5〜R8爲分別獨立表示氫原子、鹵原子、碳數1〜6個之院基、碳數1〜6個之垸氧基、或碳數 3〜6個之環烷基；R]()、R]]爲分別獨立表示氫原子或碳數 1〜6個之烷基；R9可爲氫原子或碳數1〜6個之烷基，此時，Q 1爲氫原子、碳數]〜6個之烷基或下述化學式（11”） - 36- 1289728 (33) 所示之殘基[wherein R1 5 to R4' R5 to R8 each independently represent a hydrogen atom, a halogen atom, a group having 1 to 6 carbon atoms, a decyloxy group having 1 to 6 carbon atoms, or a carbon number of 3 to 6 a cycloalkyl group; R] (), R]] are each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R9 may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, in this case, Q 1 is a hydrogen atom, an alkyl group having a carbon number of ~6 or a residue represented by the following chemical formula (11") - 36- 1289728 (33)

(式中，R12及R13爲分別獨立表示氫原子、鹵原子、碳數1〜6個之烷基、碳數1〜6個之烷氧基、或碳數3〜6 個之環烷基；c爲表示1〜3之整數）’或者，Q1可與R9 之終端結合，此時，Q]爲表示R9及Q1與R9之間的碳原子共同形成碳鏈3〜6個之環烷基；a、b爲表示1〜3之整數；d爲表示0〜3之整數；a、b或d爲3時，分別不爲 R3’、R6、R8; η爲表示〇〜3之整數〕所示之苯酚化合物、和萘醌二疊氮基磺酸化合物之酯化物爲適於使用i射線的光微影術，或於低N A條件下良好形成2.0 // m以下之微細光阻圖型形狀之情況中爲合適。即，高解像度方面爲佳，且於線性方面亦爲佳。還有，Q1與R9、及Q1與R9之間之碳原子共同形成碳鏈3〜6個之環烷基之情形中，Q1與R9爲結合，形成碳數2〜5個的伸烷基。相當於一般式（I”）的苯酚化合物可列舉三（4 -羥苯基）甲烷、雙（4·羥基-3-甲基苯基）-2-羥苯基甲烷、雙 (4-羥基-2,3;5-三甲基苯基）-2-羥苯基甲烷、雙（4_羥基-3;5-二甲基苯基）-4-羥苯基甲烷、雙（4-羥基-3:5-二甲基苯基）-3_羥苯基甲烷、雙（I羥基-3:5-二甲基苯基 -37- 1289728 (34) )-2-羥苯基甲烷、雙（4-羥基-2,5-二甲基苯基）Μ-羥苯基甲烷、雙（4-羥基-2,5·二甲基苯基）-3-羥苯基甲烷、雙（4-羥基-2,5-二甲基苯基）-2-羥苯基甲烷、雙（4-羥基-3,5-二甲基苯基）-3,4-二羥苯基甲烷、雙（4-羥基-2,5-二甲基苯基）-3,4-二羥苯基甲烷、雙（4·羥基-2,5-二甲基苯基）-2,4-二羥苯基甲烷、雙（4-羥苯基）-3-甲氧基-[羥苯基甲烷、雙（5-環己基-4-羥基-2-甲基苯基）-4-羥苯基甲烷、雙（5-環己基-4-羥基-2_甲基苯基）-3-羥苯基甲烷、雙（5-環己基-4-羥基-2-甲基苯基）-2-羥苯基甲烷、雙（5-環己基-4-羥基-2-甲基苯基）-3,4·二羥苯基甲烷等之三酚型化合物； 2,4-雙（3,5-二甲基-4-羥苄基）-5-羥基苯酚、2,6-雙 (2,5-二甲基-4-羥苄基）-4 -甲基苯酚等之線型三核體苯酚化合物；1,1-雙〔3- ( 2-羥基-5-甲基苄基）-4-羥基- 5-環己基苯基〕異丙烷、雙〔255-二甲基-3- (4-羥基-5-甲基苄基）-4-羥苯基〕甲烷、雙〔2,5-二甲基-3-(4-羥苄基）·4·羥苯基〕甲烷、雙〔3- ( 3,5-二甲基-4·羥苄基）· 4-羥基·5-甲基苯基〕甲烷、雙〔3-(3,5-二甲基-4-羥苄基 )-4-羥基-5-乙基苯基〕甲烷、雙〔3- ( 3，5-二乙基-4-羥苄基）-4-羥基-5-甲基苯基〕甲烷、雙〔3-(3,5-二乙基-4-羥苄基）-4·羥基-5-乙基苯基〕甲烷、雙〔2-羥基-3-( 3;5·二甲基羥苄基）-5-甲基苯基〕甲烷、雙〔2-羥基-3-(2·羥基-5-甲基苄基）-5-甲基苯基〕甲烷、雙〔4·羥基-3-(2-羥基-5-甲基苄基）-5 -甲基苯基〕甲烷、雙〔 - 38- 1289728 (35) 2,5 -二甲基-3- (2 -羥基-5 -甲基苄基）_4·羥苯基〕甲烷等之線型四核體苯酚化合物；2,4-雙〔2-羥基-3- ( 4-羥苄基 )-5 -甲基苄基〕-6 -環己基苯酚' 2,4·雙〔4 -羥基- 3-(4- 羥苄基）-5-甲基苄基〕-6-環己基苯酚、2,6-雙〔2,5-二甲基-3- (2 -羥基-5-甲基苄基）-[羥苄基〕-4 -甲基苯酚等之線型五核體苯酚化合物等之線型多酚化合物；雙（2,3,4-三羥苯基）甲烷、雙（2,4-二羥苯基）甲烷、2 5 3 5 4 -三羥苯基-4、羥苯基甲烷、2-(2,3,4-三羥苯基 )-2- ( 2，，3’，4、三羥苯基）丙烷、2- ( 2,4·二羥苯基-2-( 2’，4’-二羥苯基）丙烷、2-(4-羥苯基）-2-(4’·羥苯基）丙烷、2- ( 3-氟基-4-羥苯基）-2- ( 3^氟基-4’-羥苯基）丙烷、2- (2,4-二羥苯基）-2- (4，-羥苯基）丙烷、2·( 2,3;4-三羥苯基）-2-(4，-羥苯基）丙烷、2-(2,3,4-三羥苯基）-2- ( 45-羥基-3二甲基苯基）丙烷等之雙酚性化合物；1·〔 1- ( 4-羥苯基）異丙基〕-心〔1，1-雙（4-羥苯基）乙基〕苯、1-〔 1-(3-甲基-4-羥苯基）異丙基〕-4-〔〗，1_雙（3·甲基-4·羥苯基）乙基〕苯等之多核分支型化合物；；U卜雙（I羥苯基）環己烷等之縮合型苯酚化合物等。彼等可使用一種或組合使用二種以上。其中，以三苯酚型化合物做爲主成分者就高靈敏度化和解像性方面而言爲佳，特別以雙（5-環己基·4·羥基- 2-甲基苯基）-3;4-二羥苯基甲烷〔以下簡寫爲（Β15)〕、雙（4·羥基- 2,3 5 5 -三甲基苯基）-2-羥苯基甲烷〔以下簡寫 -39- 1289728 (36) 爲（B 3 ’）〕爲佳。又，於調製解像性、靈敏度、耐熱性、D OF特性、線性等光阻特性之全部平衡優良的光阻組成物之目的中，令線型多酚化合物、雙酚型化合物、多核分支型化合物、及縮合型苯酚化合物等與上述三苯酚型化合物倂用爲佳，特別若倂用雙酚型化合物中之雙（2,4·二羥苯基）甲烷〔以下簡稱爲（B25 )〕，則可調整全部平衡優良的光阻組成物。還有，以下，將前述（Bl，）、（B2，）、（B3，）之各個萘醌二疊氮基酯化物簡寫爲（B 1 )、（ B 2 )、（ B 3 )° 使用（Bl)、（B3)時，（B”）成分中之配合量分別爲1 〇質量％以上、更且以1 5質量％以上爲佳。又’全部使用（B 1 ) 、（ B 2 ) 、（ B 3 )時，由效果方面而言分別之配合量爲（B1)爲5 0〜9 0質量％、較佳爲 60〜80質量。/〇，（B2)之配合量爲5〜20質量％、較佳爲 10〜15質量°/。，（B3)之配合量爲5〜20質量％、較佳爲 1 0〜1 5質量°/。。令上述一般式（I ”）所示化合物之全部或一部分酚性羥基予以萘醌二疊氮基磺酸酯化之方法，可依常法進行。例如，萘醌二疊氮基磺醯氯與上述一般式（I”）所示之化合物縮合則可取得。具體而言，例如令上述一般式（1 ”）所示之化合物、與萘醌-1，2 -二疊氮基-4 (或5 )-磺醯氯，於二Df烷、正甲基吡咯烷酮、二甲基乙醯胺、四氫呋喃等之有機溶劑中以 -40- 1289728 (37) 指定量溶解，並於其中加入一種以上三乙胺、三乙醇胺、吡啶、碳酸鹼、碳酸氫鹼等之鹼性觸媒且反應’將所得之產物水洗、乾燥則可調製。本實施形態中之（B ”）成分爲如上述’除了此處例示之較佳的蔡醌二疊氮基酯化物以外，亦可使用其他的萘醌二疊氮基酯化物，例如亦可使用聚羥基二苯酮和没食子酸烷酯等之苯酚化合物與萘醌二疊氮基磺酸化合物的酯化反應產物等。此等其他之萘醌二疊氮基酯化物之使用量爲（B ”）感光性成分中，以8 0質量％以下、特別爲5 0質量％以下，就提高本發明效果之觀點爲佳。光阻組成物中之（B”）成分的配合量爲相對於（a” )成分和下述（C”）成分之合計量以20〜70質量％、較佳爲25〜60質量％。經由令（B ”）成分的配合量爲上述下限値以上，則可取得對圖型忠實的畫像，且提高轉印性。經由作成上述上限値以下，則可防止靈敏度的惡化，且提高所形成光阻膜的均質性，取得提高解像性的效果。 (C，，）成分經由使用（C”）成分，則提高靈敏度效果優良，且即使5、低N A f木件之i射線曝光步驟中，亦可取得高靈敏度、问解像度’適於製造LCD的材料，更佳爲取得線性優良之適於LCD系統的材料。 -41 ^ 1289728 (38) 、較佳爲7 0 0以下 ’就上述效果而言 (C”）成分之分子量爲ι000以下 ’實質上爲200以上、較佳爲300以上爲佳。 (C”）成分爲提高靈敏度之材料、或增感劑，爲一般光阻組成物中所使用之含有酚性羥基的化合物，較佳爲滿足上述分子量之條件即可，並無特別限制，可任意選擇使用一種或二種以上。其中，亦以下述一般式（In„ )(wherein 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; c is an integer representing 1-3) or Q1 may be bonded to the terminal of R9. In this case, Q] is a cycloalkyl group which represents a carbon atom between R9 and Q1 and R9 to form a carbon chain of 3 to 6; a and b are integers representing 1 to 3; d is an integer representing 0 to 3; when a, b or d is 3, they are not R3', R6, and R8, respectively; η is an integer representing 〇3 to 3) The phenol compound and the esterified product of the naphthoquinonediazidesulfonic acid compound are photolithography suitable for using i-rays, or form a fine photoresist pattern shape of 2.0 // m or less under low NA conditions. In the case it is appropriate. That is, high resolution is preferred, and linearity is also preferred. Further, in the case where Q1 and R9, and carbon atoms between Q1 and R9 together form a cycloalkyl group having 3 to 6 carbon chains, Q1 and R9 are bonded to form an alkylene group having 2 to 5 carbon atoms. Examples of the phenol compound corresponding to the general formula (I") include tris(4-hydroxyphenyl)methane, bis(4.hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, and bis(4-hydroxy-). 2,3;5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3;5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy- 3:5-dimethylphenyl)-3_hydroxyphenylmethane, bis(I hydroxy-3:5-dimethylphenyl-37-1268928 (34))-2-hydroxyphenylmethane, bis ( 4-hydroxy-2,5-dimethylphenyl)indole-hydroxyphenylmethane, bis(4-hydroxy-2,5·dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxyl -2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis (4- Hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4.hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, Bis(4-hydroxyphenyl)-3-methoxy-[hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis (5 -cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenyl a trisphenol type compound such as methane or bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4.dihydroxyphenylmethane; 2,4-bis(3,5-dimethyl a linear trinuclear phenol compound such as 4-hydroxybenzyl)-5-hydroxyphenol or 2,6-bis(2,5-dimethyl-4-hydroxybenzyl)-4-methylphenol; 1-bis[3-(2-hydroxy-5-methylbenzyl)-4-hydroxy-5-cyclohexylphenyl]isopropane, bis[255-dimethyl-3-(4-hydroxy-5-) Methylbenzyl)-4-hydroxyphenyl]methane, bis[2,5-dimethyl-3-(4-hydroxybenzyl)-4-hydroxyphenyl]methane, bis[3-(3,5 -Dimethyl-4·hydroxybenzyl)· 4-hydroxy·5-methylphenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5 -ethylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, bis[3-(3,5- Diethyl-4-hydroxybenzyl)-4.hydroxy-5-ethylphenyl]methane, bis[2-hydroxy-3-(3;5.dimethylbenzyl)-5-methylbenzene Methane, bis[2-hydroxy-3-(2.hydroxy-5-methylbenzyl)-5-methylphenyl]methane, bis[4.hydroxy-3-(2-hydroxy-5-methyl) Benzyl)-5-methylphenyl]methane, Linear tetranuclear phenol compound such as bis[ - 38- 1289728 (35) 2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane; 2,4 - bis[2-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol' 2,4·bis[4-hydroxy-3-(4-hydroxybenzyl) -5-methylbenzyl]-6-cyclohexylphenol, 2,6-bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-[hydroxybenzyl]- a linear polyphenol compound such as a linear penta-nuclear phenol compound such as 4-methylphenol; bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, 2 5 3 5 4 -trihydroxyphenyl-4, hydroxyphenylmethane, 2-(2,3,4-trihydroxyphenyl)-2-(2,3',4,trihydroxyphenyl)propane, 2 - ( 2,4·Dihydroxyphenyl-2-( 2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2 - (3-Fluoro-4-hydroxyphenyl)-2-(3^fluoro-4-'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(4,- Hydroxyphenyl)propane, 2·( 2,3;4-trihydroxyphenyl)-2-(4,-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2- Double (45-hydroxy-3dimethylphenyl)propane Phenolic compound; 1·[1-(4-hydroxyphenyl)isopropyl]-heart [1,1-bis(4-hydroxyphenyl)ethyl]benzene, 1-[1-(3-methyl) a polynuclear branched compound of -4-hydroxyphenyl)isopropyl]-4-[], 1_bis(3.methyl-4.hydroxyphenyl)ethyl]benzene; A condensed phenol compound such as phenyl)cyclohexane. These may be used alone or in combination of two or more. Among them, a trisphenol type compound as a main component is preferable in terms of high sensitivity and resolution, particularly bis(5-cyclohexyl·4·hydroxy-2-methylphenyl)-3; Dihydroxyphenylmethane [hereinafter abbreviated as (Β15)], bis(4.hydroxy-2,3 5 5 -trimethylphenyl)-2-hydroxyphenylmethane [hereinafter abbreviated as -39-1289728 (36) (B 3 ') is better. In addition, in the purpose of a photoresist composition having excellent balance of modulation properties such as modulation, sensitivity, heat resistance, D OF characteristics, and linearity, a linear polyphenol compound, a bisphenol compound, and a multinuclear branched compound are used. And a condensed phenol compound or the like is preferably used together with the above-mentioned trisphenol type compound, and particularly if bis(2,4-dihydroxyphenyl)methane (hereinafter abbreviated as (B25)) in the bisphenol type compound is used, All balanced photoresist compositions can be adjusted. Further, in the following, each of the naphthoquinonediazide esterates of (Bl,), (B2,) and (B3) is abbreviated as (B 1 ), (B 2 ), (B 3 )° ( In the case of (B3), the amount of the component (B3) is preferably 1% by mass or more, more preferably 15% by mass or more. Further, all of (B 1 ) and (B 2 ) are used. In the case of (B 3 ), the blending amount is (B1) of 50 to 90% by mass, preferably 60 to 80% by mass. /〇, (B2) is 5 to 20 by mass. %, preferably 10 to 15 mass%, and the compounding amount of (B3) is 5 to 20% by mass, preferably 10 to 15 mass%, of the compound represented by the above general formula (I"). The method of esterifying all or a part of the phenolic hydroxyl group with naphthoquinonediazidesulfonate can be carried out according to a usual method. For example, a naphthoquinonediazidesulfonyl chloride can be obtained by condensing with a compound represented by the above general formula (I"). Specifically, for example, a compound represented by the above general formula (1"), and naphthoquinone- 1,2-diazido-4 (or 5)-sulfonyl chloride, in the organic solvent of di Df, n-methylpyrrolidone, dimethylacetamide, tetrahydrofuran, etc. -40 - 1289728 (37) The specified amount is dissolved, and one or more alkaline catalysts such as triethylamine, triethanolamine, pyridine, carbonic acid base, and hydrogencarbonate base are added thereto, and the reaction is carried out by washing and drying the obtained product. The component (B") in the present embodiment may be other than the above-described preferred cockroach diazide ester compound as exemplified above, and other naphthoquinonediazide ester compounds may be used, and for example, it may be used. An esterification reaction product of a phenolic compound such as polyhydroxybenzophenone and an alkyl gallate with a naphthoquinonediazidesulfonic acid compound, etc. The other naphthoquinonediazide esters are used in an amount of (B). The photosensitive component is preferably 80% by mass or less, particularly preferably 50% by mass or less, from the viewpoint of improving the effects of the present invention. The amount of the component (B") in the resist composition is 20 to 70% by mass, preferably 25 to 60% by mass based on the total amount of the component (a") and the following (C") component. When the blending amount of the component (B ′) is at least the above lower limit ,, a faithful image can be obtained and the transfer property can be improved. By making the above upper limit 値 or less, it is possible to prevent the deterioration of the sensitivity, improve the homogeneity of the formed resist film, and obtain an effect of improving the resolution. The (C,) component is excellent in sensitivity improvement by using the component (C"), and high sensitivity and resolution can be obtained even in the i-ray exposure step of 5 or low NA f wood parts. The material is more preferably a material suitable for an LCD system which is excellent in linearity. -41 ^ 1289728 (38), preferably 700 or less. 'For the above effect, the molecular weight of the (C") component is ι000 or less. It is preferably 200 or more, preferably 300 or more. The (C") component is a material for improving sensitivity or a sensitizer, and the phenolic hydroxyl group-containing compound used in the general photoresist composition is preferably a condition satisfying the above molecular weight, and is not particularly limited. You can use one or more of them arbitrarily. Among them, the following general formula (In„ )

〔式中，r21〜r28爲分別獨立表示氫原子、鹵原子、碳數1〜6個之烷基、碳數1〜6個之烷氧基、或碳數3〜6個之環烷基；R3G、爲分別獨立表示氫原子或碳數1〜6個之烷基；R29可爲氫原子或碳數1〜6個之烷基，此時，Q2 爲表示氫原子、碳數1〜6個之烷基或下述化學式（IV”）所示之殘基 R32[wherein, r21 to r28 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; R3G is an alkyl group independently represented by a hydrogen atom or a carbon number of 1 to 6; R29 may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and in this case, Q2 represents a hydrogen atom and has a carbon number of 1 to 6 An alkyl group or a residue R32 represented by the following chemical formula (IV")

(式中，R32及R33爲分別獨立表示氫原子、鹵原子 -42 - 1289728 (39) 、碳數1〜6個之烷基、碳數1〜6個之烷氧基、或碳數3〜6 個之環烷基；g爲表示〇〜3之整數），或者，Q2可與R29 之終端結合，此時，Q2爲與R29及、Q2與R29間之碳原子共同表示碳鍵3〜6個之環烷基；e、f爲表示1〜3之整數 ;h爲表示0〜3之整數；e、f或h爲3時，分別不爲R23 、R26、R28 ; m爲表示0〜3之整數〕所示之化合物爲良好顯不上述之特性’故爲佳。(wherein R32 and R33 each independently represent a hydrogen atom, a halogen atom -42 - 1289728 (39), an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a carbon number of 3~ 6 cycloalkyl groups; g is an integer representing 〇~3), or Q2 may be bonded to the terminal of R29. In this case, Q2 is a carbon atom between R29 and Q2 and R29, which together represent carbon bonds 3~6. a cycloalkyl group; e, f is an integer representing 1 to 3; h is an integer representing 0 to 3; when e, f or h is 3, it is not R23, R26, R28, respectively; m is 0 to 3 It is preferable that the compound represented by the integer] is excellent in the above characteristics.

具體而言，例如上述（B ”）成分中所例示之苯酚化合物之萘醌二疊氮基酯化物中所用之苯酚化合物以外，以雙 (3-甲基-4-羥苯基）-4-異丙苯基甲烷、雙（3-甲基-4-羥苯基）-苯基甲烷、雙（2_甲基羥苯基）-苯基甲烷、雙 (3-甲基-2·羥苯基）-苯基甲烷、雙（3,5-二甲基-4-羥苯基）-苯基甲烷、雙（3-乙基-4_羥苯基）-苯基甲烷、雙（ 2-甲基-4-羥苯基苯基甲烷、雙（2-第三丁基-4,5-二羥苯基苯基甲烷等之三苯基型化合物爲適於使用。其中亦以雙（2 -甲基-4·羥苯基）-苯基甲烷、1-〔 1- ( 4-羥苯基）異丙基〕·4·〔 151-雙（4-羥苯基）乙基〕苯爲佳。 (c ”）成分的配合量由效果方面而言，相對於（A ” )成分以10〜70質量％、較佳爲20〜60質量％之範圍。 (D”）成分 (D”）成分若爲光阻組成物中所用之一般成分即可，並無特別限制，可選擇使用一種或二種以上，但以含有丙二醇單烷醚醋酸酯、和/或2 -庚酮者爲塗佈性優良，且 -43- 1289728 (40) 於大型玻璃基板上之光阻被膜的膜厚均勻性優良，故爲佳〇還有，亦可使用丙二醇烷醚醋酸酯和2-庚酮兩者，但多以分別單獨使用、或與其他有機溶劑混合使用，就利用旋塗法等之塗佈時的膜厚均勻性方面而言爲佳。丙二醇單烷醚醋酸酯爲於（D”）成分中，含有 50〜100質量％爲佳。丙二醇單烷醚醋酸酯爲例如具有碳數1〜3個的直鏈或分支鏈狀烷基，其中，以丙二醇單甲醚醋酸酯（以下，簡寫爲PGMEA)因爲於大型玻璃基板上之光阻被膜的膜厚均勻性非常優良，故爲特佳。另一方面，2-庚酮並無特別限定，爲如上述般之（B” )萘醌二疊氮基酯化物，與非二苯酮系之感光性成分組合時的適當溶劑。 2-庚酮若與PGMEA相比較，則耐熱性優良，且具有提供減低浮渣發生之光阻組成物的特性，爲非常良好的溶劑。 2 -庚酮於單獨、或與其他有機溶劑混合使用時，於（ D”）成分中，含有50〜100質量％爲佳。又，於此些較佳之溶劑中，亦可混合其他溶劑供使用。例如，若配合乳酸甲酯、乳酸乙酯等（較佳爲乳酸乙酯 )之乳酸烷酯，則光阻被膜之膜厚均勻性優良，且可形成形狀優良的光阻圖型，故爲佳。將丙二醇單烷醚醋酸酯與乳酸烷酯混合使用時，相對 -44- 1289728 (41) 於丙二醇單烷醚醋酸酯配合質量比〇 ·]〜]〇倍量、較佳爲 1〜5倍量之乳酸烷酯爲佳。又，亦可使用Τ-丁內酯和丙二醇單丁醚等之有機溶 .劑。於使用r - 丁內酯之情形中，相對於丙二醇單烷醚醋酸酯配合質量比0.01〜1倍量、較佳爲0.05〜0.5倍量之範圍爲佳。還有，其他可配合之有機溶劑具體而言可列舉例如下列溶劑。即，丙酮、甲基乙基酮、環己酮、甲基異戊基酮等之酮類；乙二醇、丙二醇、二甘醇、乙二醇單醋酸酯、丙二醇單醋酸酯、二甘醇單醋酸酯、或彼等之單甲醚、單*** 、單丙醚、單丁醚或單苯醚等之多元醇類及其衍生物；二口等烷等之環·式醚類；及醋酸甲酯、醋酸乙酯、醋酸丁酯、丙酮酸甲酯、丙酮酸乙酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯等之酯類等。使用此些溶劑時，於（D”）成分中，期望以50質量 %以下。於本實施形態之正型光阻組成物中’在不損害本發明目的之範圍內，視需要可含有具有相容性的添加物，例如用以改良光阻膜性能等的加成性樹脂、可塑劑、保存安定劑、界面活性劑、令經顯像之像更加可見的著色料、用以更加提高增感效果的增感劑和防眩用染料、密黏性改善劑等之慣用的添加物。 -45- 1289728 (42) 防眩用染料可使用紫外線吸收劑（例如2 5 2，，4,4，-四羥基二苯酮、4 -二甲胺基-二羥基二苯酮、5_胺基- 3-甲基-1-苯基·4-(4 -經苯基偶氮基）d比D坐、4-二甲胺基- 4，· 羥基偶氮基苯 '心二乙胺基-4’-乙氧基偶氮基苯、4_二乙胺基偶氮基苯、姜黃素等）等。界面活性劑可添加例如用以防止線紋等，例如可使用Specifically, for example, bis(3-methyl-4-hydroxyphenyl)-4-, other than the phenol compound used in the naphthoquinonediazide ester compound of the phenol compound exemplified in the above (B") component. Phenylphenylmethane, bis(3-methyl-4-hydroxyphenyl)-phenylmethane, bis(2-methylhydroxyphenyl)-phenylmethane, bis(3-methyl-2.hydroxybenzene) Phenylmethane, bis(3,5-dimethyl-4-hydroxyphenyl)-phenylmethane, bis(3-ethyl-4-hydroxyphenyl)-phenylmethane, bis(2- A triphenyl type compound such as methyl-4-hydroxyphenylphenylmethane or bis(2-tert-butyl-4,5-dihydroxyphenylphenylmethane is suitable for use. -Methyl-4.hydroxyphenyl)-phenylmethane, 1-[1-(4-hydroxyphenyl)isopropyl]·4·[ 151-bis(4-hydroxyphenyl)ethyl]benzene Preferably, the amount of the component (c") is from 10 to 70% by mass, preferably from 20 to 60% by mass based on the effect of the (A") component. (D") Component (D") The component is not particularly limited as long as it is a general component used in the photoresist composition, and one or more of them may be used, but Propylene glycol monoalkyl ether acetate and/or 2-heptanone are excellent in coatability, and -43-1228928 (40) is excellent in uniformity of film thickness of a photoresist film on a large glass substrate. Further, both propylene glycol alkyl ether acetate and 2-heptanone may be used, but they may be used alone or in combination with other organic solvents, and the film thickness uniformity in coating by spin coating or the like may be used. The propylene glycol monoalkyl ether acetate is preferably contained in the component (D") in an amount of 50 to 100% by mass. The propylene glycol monoalkyl ether acetate is, for example, a linear or branched chain having 1 to 3 carbon atoms. In the case of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA), it is particularly preferable because the film thickness uniformity of the photoresist film on a large glass substrate is extremely excellent. The ketone is not particularly limited, and is a suitable solvent when the (B") naphthoquinonediazide ester compound is combined with a non-benzophenone-based photosensitive component as described above. 2-heptanone is compared with PGMEA. The heat resistance is excellent, and the photoresist composition for reducing scum generation is provided. The characteristics are very good solvents. When 2-heptanone is used alone or in combination with other organic solvents, it is preferably 50 to 100% by mass in the component (D"). In addition, other solvents may be mixed and used. For example, when a lactate alkyl ester such as methyl lactate or ethyl lactate (preferably ethyl lactate) is blended, the film thickness of the photoresist film is excellent and the shape can be formed. Excellent light resistance pattern, so it is better. When propylene glycol monoalkyl ether acetate is mixed with alkyl lactate, the relative mass ratio of -44-1282928 (41) to propylene glycol monoalkyl ether acetate is 〇·]~]〇 A multiple amount, preferably 1 to 5 times the amount of the alkyl lactate is preferred. Further, an organic solvent such as bismuth-butyrolactone or propylene glycol monobutyl ether may also be used. In the case of using r-butyrolactone, it is preferably in the range of 0.01 to 1 times by mass, preferably 0.05 to 0.5 times the mass ratio of the propylene glycol monoalkyl ether acetate. Further, as the other organic solvent which can be blended, for example, the following solvents can be mentioned. Namely, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol Monoacetate, or a monohydric alcohol such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether; and a derivative thereof; a cyclic ether of a di-alkane or the like; and acetic acid Esters such as methyl ester, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate, and the like. When the solvent is used, it is desirably 50% by mass or less in the component (D"). In the positive resist composition of the present embodiment, it may contain a phase as needed within a range not impairing the object of the present invention. Capacitive additives, such as additive resins, plasticizers, storage stabilizers, surfactants, and coloring materials that make the image of the image more visible, to enhance the sensitization of the photoresist film. A sensitizer for effects, a conventional additive such as an anti-glare dye, a tackifier, etc. -45- 1289728 (42) An anti-glare dye can be used as an ultraviolet absorber (for example, 2 5 2, 4, 4, -tetrahydroxybenzophenone, 4-dimethylamino-dihydroxybenzophenone, 5-amino-3-methyl-1-phenyl-4-(4-phenylphenyl)d ratio D Sodium, 4-dimethylamino-4, hydroxyazobenzene 'cardodiethylamino-4'-ethoxyazobenzene, 4-diethylaminoazobenzene, curcumin, etc.) Etc. Surfactants can be added, for example, to prevent lines, etc., for example, can be used

Furoride FC-430、FC431(商品名、住友 3Μ (股）製）、Efutop EF122A、EF122B、EF122C、EF126(商品名： Tokem Products (股）製）等之氟系界面活性劑、04 、Megafac R-08 (商品名、大日本油墨化學工業（股）製 )等。本賓施形態之正型光阻組成物較佳爲（A”）成分、（ B ”）成分、（C ”）成分及視需要之其他成分於（d ”）有機溶劑中溶解後，視需要進行過濾則可調製。還有，（D”）成分之使用量爲較佳將（A”）〜（C”）成分及視需要使用之其他成分溶解，且適當調整成可取得均勻的正型光阻組成物。較佳的固形成分濃度〔（A”）〜 (C”）成分及視需要使用之其他成分〕爲1〇〜50質量％、更佳爲使用20〜35質量％。本實施形態之正型光阻組成物爲令該光阻組成物所含之固形成分的Mw爲5 000〜3 0000範圍內般調製爲佳，更佳爲Mw爲60 00〜1 0000。經由令該光阻組成物之固形成分的Mw爲上述之範圍，則不會令靈敏度降低，可達成高耐熱性、高解像性，並且取得線性及DOF特性優良的正 -46 - (43) 1289728 型光阻組成物。前述光阻組成物之固形成分的Mw若小於上述範圍，則耐熱性、解像性、線性、及DOF特性不夠充分，若超過上述範圍，則靈敏度的降低顯著，恐損害光阻組成物的塗佈性。將Mw調製成如上述較佳範圍之方法爲例如，（1 ) 於混合前對於（A )成分進行分級操作，並將（A )成分之Mw於適當範圍中調整，令全部成分混合後之Mw爲如上述範圍般之方法、（2)準備數種Mw不同的（A)成分 ’將其適當配合並將前述固形成分之Mw調整至上述範圍之方法等。特別以根據上述（2 )之調製方法，就調整光阻分子里、及5周整靈敏度谷易方面而言爲更佳。此處’本發明中正型光阻組成物之質量平均質量（ Mw )値，爲使用下列之gpc系統所測定之値。裝置名：SYSTEM 11 (製品名、昭和電工公司製）Furoride FC-430, FC431 (trade name, Sumitomo 3Μ (share) system), Efutop EF122A, EF122B, EF122C, EF126 (trade name: Tokem Products), etc., fluorine-based surfactant, 04, Megafac R- 08 (trade name, Dainippon Ink Chemical Industry Co., Ltd.), etc. The positive resistive composition of the present embodiment is preferably a (A") component, a (B") component, a (C") component, and other components as needed, dissolved in the (d") organic solvent, as needed. It can be modulated by filtering. Further, the amount of the component (D") is preferably such that the components (A") to (C") and other components which are used as needed are dissolved, and are appropriately adjusted to obtain a uniform positive resist composition. The preferred solid content concentration [(A") to (C") component and other components as needed] is from 1 to 50% by mass, more preferably from 20 to 35% by mass. The positive photoresist of this embodiment The composition is preferably such that the Mw of the solid component contained in the photoresist composition is in the range of 5,000 to 30,000, more preferably Mw is 60 00 to 1 0000. The solid component is formed by the photoresist composition. When the Mw is in the above range, the sensitivity is lowered, high heat resistance and high resolution are achieved, and a positive-46 - (43) 1289728 type photoresist composition excellent in linearity and DOF characteristics is obtained. When the Mw of the solid content of the composition is less than the above range, heat resistance, resolution, linearity, and DOF characteristics are insufficient. When the content exceeds the above range, the sensitivity is lowered remarkably, and the coatability of the photoresist composition is impaired. A method of modulating Mw into a preferred range as described above is taken as an example. For example, (1) pre-mixing the component (A), and adjusting the Mw of the component (A) in an appropriate range, so that the Mw after mixing all the components is as in the above range, and (2) preparing Several kinds of (A) components having different Mw's are appropriately blended, and the Mw of the above-mentioned solid component is adjusted to the above range. In particular, the photoresist is adjusted according to the above-mentioned (2), and the photoresist is adjusted for 5 weeks. The overall sensitivity is better in terms of glutinous. Here, the mass average mass (Mw) 正 of the positive resist composition in the present invention is determined by using the following gpc system. Device name: SYSTEM 11 (product name) , Showa Denko Co., Ltd.)

Precolumn : KF-G (製品名、Shodex 公司製）柱·· KF-805 ' Kb 8 03、KF- 8 02 (製品名、Shodex公司製）檢測器： UV4] ( Shodex 公司製）、以 28〇nm 測定。 $劑等··以流量1 ·〇毫升/分鐘流入四氫呋喃，並於 3 5 °C測定。 '測定試料調製方法：將欲測定之光阻組成物，調整爲固形成分濃度爲3 0質量％，並以四氫呋喃稀釋，作成固形成分濃度爲〇· 1質量。的測定試料。將前述測定試料2〇 -47- 1289728 (44) 微升打入上述裝置並且進行測定。〔光阻圖型之形成方法〕以下，說明本發明之光阻圖型形成方法。首先，將上述之形成防止反射膜用組成物’於支撐體上以旋塗器等予以塗佈，且視需要進行加熱處理形成防止反射膜。此處之支撐體包含各種基板、及該基板上形成各種之膜。基板以玻璃基板爲佳。玻璃基板於通常使用非晶質矽石之LCD系統領域中，以低溫聚矽氧烷等爲佳。此玻璃基板爲使用 500mm x600mm以上、特別爲 550mmx650mm 以上之大型基板。此步騾之加熱溫度並無特別限定，但於形成防止反射膜用組成物爲經由加熱形成交聯構造之組成物時，例如以 1 10〜2 0 0°c、較佳爲130〜180°c。加熱時間爲50〜180秒鐘、較佳爲60〜120秒鐘。防止反射膜之厚度由防止反射能力方面而言，例如以 0.1~3.5//171、較佳爲0.2~3/^11：1。其次，於前述防止反射膜上，將正型光阻組成物以旋塗器等在基板上塗佈形成塗膜。其次’將形成此塗膜之玻璃基板予以加熱熱處理（預烘烤）除去殘存溶劑’形成光阻被膜。預烘烤方法爲在熱板與基板之間進行具有間隙的鄰近供烤爲佳。 80〜130 此步驟的加熱溫度爲根據材料而異，但可爲 -48 · 1289728 (45) °C '較佳爲9 0〜1 1 0 °C。加熱時間爲5 0〜1 8 0秒鐘、較佳爲 6 0〜1 2 0秒鐘。正型光阻層之厚度爲〇·3〜8// ηι、較佳爲〇.5〜5//m。接著’對於上述光阻膜，使用描繪光罩圖型的光罩進行選擇性曝光。此光罩以使用形成2.0# m以下之光阻圖型用之光罩圖型、和形成超過2.0//m之光阻圖型用之光罩圖型兩者之光罩爲佳。又’光源以使用用以形成微細圖型之i射線（3 6 5 nm )爲佳。又，此曝光下所採用的曝光過程爲NA (開口數 ;numerical aperture)爲0.3以下、較佳爲〇·2以下、更佳爲0 · 1 5以下之低N A條件的曝光過程爲佳。其次，對於選擇性曝光後之光阻被膜，施行加熱處理 (後曝光烘烤：PEB )。使用增強化學性型者做爲正型光阻組成物時，於選擇性曝光步驟中由（C ’）產酸成分生成酸，且於p E B步驟中由（C5)成分所生成之酸爲作用爲觸媒，且（a，）樹脂成分變成鹼可溶性。因此，此時P E B步驟爲必須的。p E B 方法爲於熱板與基板之間進行具有間隙的鄰近烘烤爲佳。此步驟之加熱溫度、加熱時間由控制酸成分擴散方面而言，分別以1 00〜1 80°c、較佳爲1 1 0〜1 50°c，45〜]80秒鐘、較佳爲60〜]20秒鐘。另一方面，使用非增強化學性型者做爲正型光阻組成物時，PEB步驟雖非必須的，但因可取得改善形狀效果故以進行爲佳。 -49- 1289728 (46) 即’曝光步驟後，於曝光部之光阻被膜中，存在正型光阻組成物中所含之（B，）成分，例如來自含有醌二疊氮基之化合物的可溶化茚羧酸。經由設置PEB步驟，則可令此類茚羧酸於光阻被膜內均勻、且充分擴散至細部，其結果’推測達成改善光阻圖型形狀、高解像性化之效果。又’特別以前述第四實施形態之光阻組成物爲經由施以加熱’則可於光阻圖型之頂部（光阻被膜之未曝光部的上部）’於顯像液顯像後形成膜減薄難的表面不溶化層，故形成張角形狀且矩形性良好的光阻圖型。特別於形成防止反射膜時’光阻圖型有呈現拉邊形狀的傾向，故進行前述PEB步驟爲有效的。此時，PEG溫度較佳爲90〜150°C、更佳爲100〜140t 。經由令PEB溫度爲上述範圍內，則可輕易形成表面不溶化層。又’ PEG方法可使用於熱板與基板之間具有間隙（空隙）之鄰近烘烤、於熱板與基板之間不具有間隙的直接烘烤任一種，特別，以利用兩者爲佳。其中，以進行鄰近烘烤後，進行直接烘烤爲佳。更具體而言，進行以90〜150 °C、較佳爲1〇〇〜140 °C，5〜100秒鐘、較佳爲 10〜50秒鐘，間隙爲 0.05〜5mm、較佳爲 0 · 1〜]m m之鄰近烘烤後，進行以 9 0〜1 5 0 °C、較佳爲〗00〜140°C ，5〜200秒鐘、較佳爲30〜80秒鐘、間隙爲 0mm的直接烘烤爲佳。最初進行鄰近烘烤下，可抑制基板爲經由熱而彎曲反 - 50- 1289728 (47) 轉之現象。又，接著進行直接烘烤，則可對於光阻被膜的曝光部分，充分提供前述熱所造成之酸成分的擴散效果。還有，此類PEB步驟亦可對於增強化學性型之正型光阻組成物施行，且可同樣取得改善形狀效果。接著，對於上述PEB後之光阻被膜，若使用鹼性水溶液施以顯像處理，則曝光部分被溶解除去，且於基板上同時形成集成電路用之光阻圖型和液晶顯示部分用之光阻圖型。此顯像處理爲例如使用2.38質量％氫氧化四甲基銨水溶液，且以60秒鐘左右之時間進行。更且，將光阻圖型表面殘留的顯像液以純水等之洗滌液予以洗落，則可形成光阻圖型。其後，較佳爲對於所形成的光阻圖型施以加熱處理（後烘烤）。此後烘烤爲於注入步驟時減低來自光阻圖型之脫氣量的目的中進行，且於接近注入時所加熱溫度之溫度條件下加熱處理。具體而言以100〜200 °C左右之加熱溫度下進行，且加熱時間爲6 0〜2 4 0秒鐘左右。若根據本發明，於支撐體上設置防止反射膜，並於其上設置由光阻組成物所構成的光阻被膜，則可防止LCD 系統製造中的尺寸偏差。特別，上述第一〜第四實施形態之光阻組成物爲線性、靈敏度、DOF、解像性等之於LCD系統製造中所要求之特性優良，故可取得可忠實再現光罩圖型之微細圖型的 -51 - 1289728 (48) 光阻圖型。因此，於同時形成上述光阻圖型之步驟中，可於上述基板上，同時形成圖型尺寸2.0// m以下之集成電路用之光阻圖型、和超過2·0//ιώ之液晶顯示部分用之光阻圖型。又，若防止反射膜之至少曝光部分爲於鹼水溶液中可溶之構成，則於形成光阻圖型後，並不需要以乾式蝕刻等除去防止反射膜的步驟，令步驟簡略化。更且，若經由加熱交聯，且使用經由酸成分之作用而成爲鹼可溶性之組成物形成防止反射膜，則可防止光阻圖型下層部分之防止反射膜的副蝕刻，故爲佳。又，亦可防止於防止反射膜與光阻圖型之界面中的混合。【實施方式】〔實施例〕以下，示出實施例詳細說明本發明。於以下之實施例及比較例中，支撐體爲使用於形成 Ti膜之玻璃基板上，形成由形成防止反射膜用組成物所構成的防止反射膜者、及未形成者。 (1 )線性評價：將正型光阻組成物使用大型基板用光阻塗佈裝置（裝置名：TR3 6000東京應化工業（股）製），於形成防止反射膜之支撐體（5 5 0 m m X 6 5 0 m m )上塗佈後，令熱板溫度爲]〇〇 °C，且以約1mm間隔之鄰近烘烤進行90秒鐘之第 1回乾燥，其次令熱板之溫度爲9 0 °C，以〇 · 5 m m之間隔 -52· (49) 1289728 形成1 . 4 8 // m的光阻被膜。其次，透過同時描出令3.0 μ m線/空間（L&S )及 L&S之光阻圖型再現之光罩圖型的Testchart光罩 (Reticule )，使用i射線曝光裝置（裝置名：F X - 7 0 2 J、 Nikkon公司製；ΝΑ = 0·14 )，並以可忠實再現 1.5 // m L&S之曝光量（Εορ曝光量）進行選擇性曝光。其次，令熱板溫度爲120 °C，以0.5 mm之間隔，經由鄰近烘烤，施以3 0秒鐘的加熱處理，其次以相同溫度且無間隔的直接烘烤施以60秒鐘的加熱處理。其次，23°C、使用2.38質量％ TMAH水溶液（具有將氫氧化四甲基銨水溶液予以狹縫塗層管嘴之顯像裝置（裝置名：TD· 3 9 000型機、東京應化工業（股）製，且如圖1所示般由基板端部X經過Y至Z，歷1 0秒鐘令基板上溢液，保持5 5秒鐘後，水洗3 0秒鐘，旋轉乾燥。圖中符號1爲基板（支撐體）。其後，以SEM (掃描型電子顯微鏡）照片觀察所得光阻圖型的剖面形狀，且評價3 · 0 // m L & S的光阻圖型再現性。 3 · 0 /z m L& S之尺寸變化率爲± 1 〇 %以內者以A (良好 )表示，超過±10%者以C (差）表示。 (2 )靈敏度評價：以可忠實再現].5 /i m L & S光阻圖型之曝光量（Εορ )表示（m】）。 (3 ) DOF特性評價：於前述曝光量（Εορ )中，將焦點適當地上下移動， -53- (50) 1289728 ^ 1 · 5 β m L & S爲土 1 0 %尺寸變化率之範圍內所得之焦點 ^度範圍以// m單位求出。 (4 )解像性評價：求出前述Εορ曝光量中的界限解像度。 (5 )光阻尺寸偏差評價於圖1中’於支撐體之符號a〜i所分別表示的9點中 ’ δ十測所形成之光阻圖型的尺寸。9點中，光阻圖型之尺寸爲1 · 5 // m 土 1 0 〇/〇以下之點數爲8或9時以A (良好）表不，5〜7時以B (好）、4以下時以c (差）表示。 (實施例1 ) 將下述之各成分以下述之配合混合後，使用孔徑0.2 # m之膜濾器進行過濾，調製光阻組成物。所得之光阻組成物的分子量（Mw)爲8000。 (A”）鹼可溶性樹脂：使用間-甲苯酚/ 3,4_二甲苯酚=8 / 2 (莫耳比）之混合苯酚1莫耳、和甲醛〇. 8 1莫耳且依吊法所合成之Mw=l9000、Mw/Mn = 5.1的酌酸淸漆樹脂、]〇〇質量份 (B ”）蔡醌二疊氮基酯化物：（B丨/ B 2 / B 3 = 6 / 1 / 1 (質量比）之混合物）、3 9質量份 B1:雙（5 -環己基-4-羥基-2-甲基苯基）·3,4-二羥苯基甲烷（Bl’）1莫耳和ι;2-萘醌二疊氮基·5·磺醯氯〔以下，簡寫爲（5-NQD ) 〕2莫耳之酯化反應產物 Β2 ··雙（2;4-二羥苯基）甲烷（Β2: ) 1莫耳和5- -54- 1289728 (51) NQD 2莫耳之酯化反應產物 B3:雙（4-羥基-2,3,5-三甲基苯基）-2-羥苯基甲烷 (B3’）1莫耳和5-NQD2莫耳之酯化反應產物 (C”）含有酚性羥基之化合物：雙（2-甲基·4·羥苯基）-苯基甲烷、30質量份 (D”）有機溶劑：PGMEA、507質量份形成防止反射膜用組成物爲使用含有蜜胺系化合物做爲樹脂成分，含有2,2’，4 5 4 ’-四羥基二苯酮做爲吸光劑所構成的SWK Τ5 D60 (商品名；東京應化工業（股）），並且使用上述正型光阻組成物分別評估上述（1 )〜（5 ) 各項目。其結果示於下述表1。形成防止反射膜之步驟爲於基板上塗佈形成防止反射膜用組成物，乾燥後，於180°C進行90秒鐘之加熱處理，形成膜厚0.1 // m的防止反射膜。 (比較例1 ) 除了使用未形成防止反射膜之基板以外，同實施例1 處理且分別評價上述（1 )〜（5 )之各項目。其結果示於下述表1。 -55- 1289728 (52) 表1Precolumn: KF-G (product name, manufactured by Shodex) column · KF-805 'Kb 8 03, KF- 8 02 (product name, manufactured by Shodex) detector: UV4] (manufactured by Shodex), 28〇 Measured in nm. $ Agent, etc., was flowed into tetrahydrofuran at a flow rate of 1 〇ml/min and measured at 35 °C. 'Measurement sample preparation method: The photoresist composition to be measured was adjusted to have a solid component concentration of 30% by mass, and diluted with tetrahydrofuran to obtain a solid concentration of 〇·1. Determination of the sample. The above-mentioned measurement sample 2 〇 -47 - 1289728 (44) was microlitered into the above apparatus and measured. [Method of Forming Photoresist Pattern] Hereinafter, a method of forming a photoresist pattern of the present invention will be described. First, the above-mentioned composition for forming an antireflection film is applied onto a support by a spin coater or the like, and if necessary, heat treatment is performed to form an antireflection film. The support herein includes various substrates and various films formed on the substrate. The substrate is preferably a glass substrate. The glass substrate is preferably a low temperature polyoxane or the like in the field of an LCD system in which amorphous vermiculite is usually used. This glass substrate is a large substrate using 500 mm x 600 mm or more, particularly 550 mm x 650 mm or more. The heating temperature in this step is not particularly limited. However, when the composition for forming an antireflection film is a composition which forms a crosslinked structure by heating, for example, it is 1 10 to 2 0 ° C, preferably 130 to 180 °. c. The heating time is 50 to 180 seconds, preferably 60 to 120 seconds. The thickness of the antireflection film is, for example, 0.1 to 3.5//171, preferably 0.2 to 3/^11:1, in terms of antireflection ability. Next, on the antireflection film, a positive photoresist composition is applied onto a substrate by a spinner or the like to form a coating film. Next, the glass substrate on which the coating film is formed is subjected to heat treatment (prebaking) to remove the residual solvent to form a photoresist film. The prebaking method is preferably carried out with a gap between the hot plate and the substrate. 80~130 The heating temperature of this step varies depending on the material, but it can be -48 · 1289728 (45) °C 'preferably 9 0~1 1 0 °C. The heating time is from 50 to 180 seconds, preferably from 60 to 1,200 seconds. The thickness of the positive resist layer is 〇·3~8//ηι, preferably 〇.5~5//m. Next, for the above-mentioned photoresist film, selective exposure is performed using a photomask that depicts a reticle pattern. The reticle is preferably a reticle pattern for forming a photoresist pattern of 2.0 # m or less and a reticle pattern for forming a photoresist pattern of more than 2.0/m. Further, the light source is preferably an i-ray (3 6 5 nm) for forming a fine pattern. Further, the exposure process employed in this exposure is preferably an exposure process in which the NA (numerical aperture) is 0.3 or less, preferably 〇·2 or less, and more preferably 0·15 or less. Next, heat treatment (post exposure baking: PEB) was performed on the photoresist film after selective exposure. When a chemically enhanced type is used as the positive photoresist composition, an acid is generated from the (C ') acid generating component in the selective exposure step, and the acid formed by the (C5) component in the p EB step acts. It is a catalyst, and (a,) the resin component becomes alkali-soluble. Therefore, the P E B step is necessary at this time. The p E B method is preferably performed with a gap between the hot plate and the substrate. The heating temperature and the heating time in this step are, in terms of controlling the diffusion of the acid component, respectively, from 100 to 180 ° C, preferably from 1 10 to 150 ° C, from 45 to 80 seconds, preferably 60. ~] 20 seconds. On the other hand, when a non-reinforced chemical type is used as the positive resist composition, the PEB step is not essential, but it is preferable because the shape improving effect can be obtained. -49- 1289728 (46) That is, after the exposure step, the (B,) component contained in the positive resist composition is present in the photoresist film of the exposed portion, for example, from a compound containing a quinonediazide group. Soluble hydrazine carboxylic acid. By the step of providing the PEB, the ruthenium carboxylic acid can be uniformly dispersed in the resist film and sufficiently diffused to the fine portion. As a result, it is estimated that the effect of improving the shape of the resist pattern and high resolution can be achieved. Further, in particular, the photoresist composition of the fourth embodiment is formed by forming a film on the top of the photoresist pattern (the upper portion of the unexposed portion of the photoresist film) by applying heat to the developing solution. The surface insolubilization layer which is difficult to thin is thinned, so that a photoresist pattern having an angular shape and a good squareness is formed. In particular, when the antireflection film is formed, the photoresist pattern tends to have a drawn shape, so that the above PEB step is effective. At this time, the PEG temperature is preferably from 90 to 150 ° C, more preferably from 100 to 140 t. By setting the PEB temperature within the above range, the surface insolubilization layer can be easily formed. Further, the PEG method can be used for the direct baking which has a gap (space) between the hot plate and the substrate, and the direct baking which does not have a gap between the hot plate and the substrate, and in particular, it is preferable to use both. Among them, it is preferred to perform direct baking after performing adjacent baking. More specifically, it is carried out at 90 to 150 ° C, preferably 1 to 140 ° C, 5 to 100 seconds, preferably 10 to 50 seconds, and the gap is 0.05 to 5 mm, preferably 0. After baking in the vicinity of 1~]mm, it is carried out at a temperature of 90 to 150 ° C, preferably 00 to 140 ° C, 5 to 200 seconds, preferably 30 to 80 seconds, and a gap of 0 mm. Direct baking is preferred. Initially, adjacent baking can inhibit the substrate from bending through the heat - 50-1289728 (47). Further, by performing direct baking, the diffusion effect of the acid component by the heat can be sufficiently provided to the exposed portion of the resist film. Also, such a PEB step can be carried out for a chemical-type positive resist composition, and the shape improving effect can be similarly obtained. Then, when the development process of the photoresist film after the PEB is performed by using an alkaline aqueous solution, the exposed portion is dissolved and removed, and the photoresist pattern for the integrated circuit and the light for the liquid crystal display portion are simultaneously formed on the substrate. Resistance pattern. This development treatment is carried out, for example, using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, and is carried out for about 60 seconds. Further, the photoresist remaining on the surface of the resist pattern is washed with a washing liquid such as pure water to form a photoresist pattern. Thereafter, it is preferred to apply heat treatment (post-baking) to the formed photoresist pattern. Thereafter, the baking is carried out for the purpose of reducing the amount of degassing from the photoresist pattern at the time of the injection step, and is heat-treated at a temperature close to the heating temperature at the time of the injection. Specifically, it is carried out at a heating temperature of about 100 to 200 ° C, and the heating time is about 60 to 240 seconds. According to the present invention, by providing an antireflection film on a support and providing a photoresist film composed of a photoresist composition thereon, dimensional deviation in the manufacture of the LCD system can be prevented. In particular, the photoresist compositions of the first to fourth embodiments are excellent in characteristics required for the manufacture of an LCD system such as linearity, sensitivity, DOF, resolution, etc., so that a fine faithful reproduction of the mask pattern can be obtained. Figure-51 - 1289728 (48) Photoresist pattern. Therefore, in the step of simultaneously forming the photoresist pattern, a photoresist pattern for an integrated circuit having a pattern size of 2.0//m or less and a liquid crystal exceeding 2·0//m may be simultaneously formed on the substrate. Show the part of the photoresist pattern used. Further, if at least the exposed portion of the antireflection film is soluble in the aqueous alkali solution, the step of removing the antireflection film by dry etching or the like is not required after the formation of the photoresist pattern, and the steps are simplified. Further, when the antireflection film is formed by crosslinking by heating and using an alkali-soluble composition by the action of an acid component, it is preferable to prevent the sub-etching of the reflective film in the lower portion of the resist pattern. Further, it is also possible to prevent mixing between the reflective film and the resist pattern. [Embodiment] [Embodiment] Hereinafter, the present invention will be described in detail with reference to examples. In the following examples and comparative examples, the support was used on a glass substrate on which a Ti film was formed, and an antireflection film composed of a composition for forming an antireflection film was formed, and was not formed. (1) Linear evaluation: A photoresist coating apparatus for large-sized substrates (device name: TR3 6000, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used for the positive-type photoresist composition to form a support for the anti-reflection film (5 50) After the application of mm X 6 5 0 mm ), the hot plate temperature is 〇〇 ° C, and the first drying is performed for 90 seconds at a spacing of about 1 mm, and then the temperature of the hot plate is 9 0 °C, at a distance of 〇·5 mm -52· (49) 1289728 A photoresist film of 1. 4 8 // m is formed. Next, using an i-ray exposure apparatus (device name: FX) by simultaneously drawing a Retouchule of a reticle pattern that reproduces the photoresist pattern of 3.0 μm line/space (L&S) and L&S - 7 0 2 J, manufactured by Nikkon; ΝΑ = 0·14 ), and selectively exposed with an exposure amount (Εορ exposure) that faithfully reproduces 1.5 // m L&S. Secondly, the hot plate temperature is 120 ° C, at intervals of 0.5 mm, by adjacent baking, applying heat treatment for 30 seconds, and secondly, direct baking at the same temperature and without interval is applied for 60 seconds. deal with. Next, at 23 ° C, a 2.38 mass % TMAH aqueous solution (a developing device having a slit coating nozzle for an aqueous solution of tetramethylammonium hydroxide) (device name: TD·3 9 000 type machine, Tokyo Yinghua Industrial Co., Ltd.)股), and as shown in Figure 1, through the substrate end X through Y to Z, for 10 seconds to cause the substrate to overflow, hold for 5 5 seconds, then wash for 30 seconds, spin dry. Reference numeral 1 is a substrate (support). Thereafter, the cross-sectional shape of the obtained resist pattern was observed by SEM (scanning electron microscope) photograph, and the resist pattern reproducibility of 3·0 // m L & S was evaluated. 3 · 0 /zm L& S The dimensional change rate of S is within ± 1 〇%, and is expressed by A (good). If it exceeds ±10%, it is expressed by C (difference). (2) Sensitivity evaluation: faithfully reproduced] .5 /im L & S exposure pattern (Εορ ) indicates (m)) (3) Evaluation of DOF characteristics: In the aforementioned exposure amount (Εορ ), the focus is appropriately moved up and down, -53- (50) 1289728 ^ 1 · 5 β m L & S is the range of the range of dimensional change of 10% of the soil. The range of the focus is obtained in / m units. (4) Resolution Evaluation: The limit resolution in the above-mentioned Εορ exposure amount is obtained. (5) The photoresist size deviation is evaluated in Fig. 1 'in the 9 points indicated by the symbols a to i of the support body' The size of the pattern. In 9 points, the size of the photoresist pattern is 1 · 5 // m. The number of points below 1 0 〇 / 〇 is 8 or 9 when A (good) is not, 5 to 7 is B (good) and c or less when it is 4 or less. (Example 1) Each of the following components was mixed and mixed as described below, and then filtered using a membrane filter having a pore size of 0.2 m to prepare a photoresist composition. The obtained photoresist composition had a molecular weight (Mw) of 8,000. (A") Alkali-soluble resin: mixed phenol 1 mol using m-cresol / 3,4-dimethylphenol = 8 / 2 (mole ratio) And formaldehyde oxime. 8 1 molar and according to the hanging method synthesized Mw = l9000, Mw / Mn = 5.1 of the appropriate enamel paint resin,] 〇〇 mass parts (B ”) Cai Wei diazide ester: (B丨 / B 2 / B 3 = 6 / 1 / 1 (mass ratio) mixture), 39 parts by mass of B1: bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)·3, 4-dihydroxyphenylmethane (Bl') 1 Mo and ι; 2- Naphthoquinonediazide-5·sulfonyl chloride [hereinafter, abbreviated as (5-NQD)] 2 molar esterification reaction product Β2 ··bis(2;4-dihydroxyphenyl)methane (Β2: ) 1 Moter and 5-54- 1289728 (51) NQD 2 molar esterification product B3: bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane ( B3') 1 molar and 5-NQD2 molar esterification reaction product (C") a compound containing a phenolic hydroxyl group: bis(2-methyl-4-hydroxyphenyl)-phenylmethane, 30 parts by mass ( D") Organic solvent: PGMEA and 507 parts by mass of a composition for forming an antireflection film using a melamine-containing compound as a resin component and 2,2',4 5 4 '-tetrahydroxybenzophenone as a light absorbing agent The SWK Τ5 D60 (trade name; Tokyo Chemical Industry Co., Ltd.) was constructed, and the above items (1) to (5) were evaluated using the above-described positive-type photoresist composition. The results are shown in Table 1 below. The step of forming the antireflection film was to form a composition for preventing the reflection film on the substrate, and after drying, it was subjected to heat treatment at 180 ° C for 90 seconds to form an antireflection film having a film thickness of 0.1 / m. (Comparative Example 1) Each of the above items (1) to (5) was evaluated in the same manner as in Example 1 except that the substrate on which the antireflection film was not formed was used. The results are shown in Table 1 below. -55- 1289728 (52) Table 1

線性靈敏度 DOF 解像性光阻尺寸 (m J ) (μ m) (// IB ) 之偏差實施例1 A 60 28 0.5 A 比較例1 A 50 18 0.8 B 如此’於本發明之實施例中，抑制尺寸的偏差。又，靈敏度、解像性、線性特性、DOF特性亦優良。〔發明之效果〕如以上說明般若根據本發明之光阻圖型形成方法，則適合使用於製造L C D系統，且可抑制光阻圖型尺寸的偏差。【圖式簡單說明】〔圖1〕爲了評價線性，將正型光阻組成物塗佈至玻璃基板，且烘烤乾燥，令圖型曝光後，以具有狹縫塗餍器 β _像裝置將顯像液由基板端部X溢液至Z之說明圖。 [主要元件符號說明】 1 :基板（支撐體） -56-Deviation of linear sensitivity DOF resolution resist size (m J ) (μ m) (// IB ) Example 1 A 60 28 0.5 A Comparative Example 1 A 50 18 0.8 B Thus, in the embodiment of the present invention, Suppress the deviation of the dimensions. Moreover, sensitivity, resolution, linear characteristics, and DOF characteristics are also excellent. [Effects of the Invention] As described above, according to the photoresist pattern forming method of the present invention, it is suitable for use in the manufacture of an L C D system, and the variation in the size of the photoresist pattern can be suppressed. [Simplified description of the drawing] [Fig. 1] In order to evaluate the linearity, the positive photoresist composition is applied to a glass substrate, and baked and dried, and after the pattern is exposed, the device having a slit applicator will be used. An explanatory diagram of the developer liquid overflowing from the end portion X of the substrate to Z. [Main component symbol description] 1 : Substrate (support) -56-

Claims

1289728 (1) 拾、申請專利範圍 1·一種光阻圖型之形成方法，其特徵爲包含（])於支撐體上形成防止反射膜之步驟、（2 )於上述防止反射膜上塗佈正型光阻組成物，形成塗膜之步驟、（3 )將形成上述塗膜之支撐體予以加熱處理（預烘烤），且於支撐體上形成光阻被膜之步驟、（4 )對於上述光阻被膜，使用描繪了形成2.0//m以下之光阻圖型用光罩圖型、和形成超過2.0//m之光阻圖型用光罩圖型兩者之光罩進行選擇性曝光之步驟、及（5 )對於上述選擇曝光後之光阻被膜’使用鹼水溶液施行顯像處理，並於上述支撐體上，同時形成圖型尺寸2· O/im以下之集成電路用之光阻圖型、和超過2 · 0 // m之液晶顯示部分用之光阻圖型之步驟。 2 ·如申請專利範圍第1項之光阻圖型之形成方法，其爲於上述步驟（4 )與（5 )之間，對於上述選擇性曝光後之光阻被膜’進行施以加熱處理（後曝露烘烤）之步驟。 3 .如申請專利範圍第〗或2項之光阻圖型之形成方法 ’其爲於上述步驟（5 )之後，對於上述光阻圖型進行施以加熱處理（後烘烤）之步驟。 4 ·如申請專利範圍第1項之光阻圖型之形成方法，其爲使用i射線（3 6 5 nm )用之酚醛淸漆-萘醌系之光阻材料做爲該正型光阻組成物。 5 .如申請專利範圍第1項之光阻圖型之形成方法，其中上述（4 )選擇性曝光之步驟爲於光線使用i射線，且於NA爲0·3以下之低NA條件下進行曝光過程。 -57-1289728 (1) Pickup, Patent Application No. 1. A method for forming a photoresist pattern, comprising: () a step of forming an anti-reflection film on a support, and (2) coating the anti-reflection film a photoresist composition, a step of forming a coating film, (3) a step of heat-treating (pre-baking) the support forming the coating film, and forming a photoresist film on the support, and (4) for the light The resist film is selectively exposed using a mask which is formed by forming a mask pattern of a resist pattern of 2.0//m or less and a mask pattern of a resist pattern of more than 2.0//m. Steps and (5) performing a development process on the photoresist film selected after exposure, using an aqueous alkali solution, and forming a photoresist pattern for an integrated circuit having a pattern size of 2·O/im or less on the support. The steps of the type, and the photoresist pattern used for the liquid crystal display portion exceeding 2 · 0 // m. 2. The method for forming a photoresist pattern according to claim 1, wherein between the above steps (4) and (5), the photoresist film after the selective exposure is subjected to heat treatment ( After exposure to baking). 3. A method of forming a photoresist pattern according to the scope of claim 2 or 2, which is a step of subjecting the photoresist pattern to heat treatment (post-baking) after the above step (5). 4 · A method for forming a photoresist pattern according to claim 1 of the patent application, which is a phenolic enamel-naphthoquinone-based photoresist material using i-ray (3 6 5 nm) as the positive-type photoresist Things. 5. The method for forming a photoresist pattern according to claim 1, wherein the step (4) of selectively exposing is to use i-rays for light and to expose to light at a low NA condition of NA of 0.3 or less. process. -57-