TW200928586A - Positive type radiation sensitive resin compound - Google Patents

Positive type radiation sensitive resin compound Download PDF

Info

Publication number
TW200928586A
TW200928586A TW097137031A TW97137031A TW200928586A TW 200928586 A TW200928586 A TW 200928586A TW 097137031 A TW097137031 A TW 097137031A TW 97137031 A TW97137031 A TW 97137031A TW 200928586 A TW200928586 A TW 200928586A
Authority
TW
Taiwan
Prior art keywords
compound
positive
weight
resin composition
parts
Prior art date
Application number
TW097137031A
Other languages
Chinese (zh)
Inventor
Kousuke Mori
Satoshi Ishikawa
Original Assignee
Jsr Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jsr Corp filed Critical Jsr Corp
Publication of TW200928586A publication Critical patent/TW200928586A/en

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/72—Benzo[c]thiophenes; Hydrogenated benzo[c]thiophenes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention discloses a positive type radiation sensitive resin compound with a better photo-resistance by using a slot way to carry out coating on a large size substrate above 100 mm x 100 mm. The invention relates to compound containing (A) 100 polymer by a weight factor having phenolic hydroxyl, (B) 10 to 50 polymer by a weight factor having quinodiazo, (C) 100 to 9900 solvent by a weight factor relative to total 100 by a weight factor of the aforementioned polymer having phenolic hydroxyl (A) and aforementioned polymer having quinodiazo (B), and (D) positive type radiation sensitive resin compound having 0.01 to 5 by a weight factor of the surface active agent, as the aforementioned compound (B) having quinodiazo and as the aforementioned surface active agent (D) having polyether modified poly siloxane, featuring a slot-way coating used in positive type radiation sensitive resin.

Description

200928586 九、發明說明 【發明所屬之技術領域】 本發明係關於使用於精密微細加工之光微影技術，於 所謂的光加工（Photofabrication )使用所適用的組成物及 ' 該組成物的圖型形成方法。更詳細爲’本發明係關於作爲 ' 使用於半導體、電子部品或顯像面板 '控觸板等配線形成 、電極形成等光加工領域所使用的乾蝕刻加工用的光罩劑 n 而言，使用較佳正型敏輻射線性樹脂組成物及該正型敏輻 射線性樹脂組成物所得之圖型形成方法。 【先前技術】 近年來，顯像面板之大型化，低成本化之急速進行。 其中，在大型基板上以簡便步驟下可穩定進行配線形成之 技術成爲必要。藉由光微影技術製圖光阻膜後，藉由乾蝕 刻法之配線形成的技術使用於過去半導體之領域中，普及 〇 於作爲比較容易提高生產性之製程，出現將該技術應用於 顯像面板等分野中的情況。 欲在大型基板上進行安定的乾蝕刻加工，經基板之表 面全體必須使光阻圖型爲同一形狀下形成。因此，塗膜之 * 膜厚爲均勻下，曝光邊限、顯像邊限等之製圖步驟的邊限 較廣變爲重要。 且，所謂曝光邊限爲，一定顯像時間（推薦顯像時間 )內，於規格CD値之±10%以内可達到光阻圖型的曝光量 幅度。所謂顯像邊限爲，一定曝光量（推薦曝光量）中， -4- 200928586 於規格CD値之± 1 0%以内可達到光阻圖型之顯像時間的幅 度。 在大型基板上塗佈光阻時，如轉動塗佈之迴轉型塗佈 裝置中，有著因基板的重量而於迴轉中拋出基板等安全上 的問題，故期待求得狹縫式塗佈下可均一塗佈之光阻。然 ’而，以狹縫式塗佈進行塗佈時，光阻由塗佈後基板端往中 央引縮，成爲所謂的“縮痕”之現象嚴重問題。其中特開 〇 2003-233174號公報中揭示特定配合比下酚醛清漆樹脂及 特定2種醌二疊氮酯化合物中以提高感度爲目的而添加特 定酚化合物的正型光阻組成物。使用該組成物，於 5 00 X 600mm2以上的大型玻璃基板上以轉動塗佈法進行塗 佈時的加熱不均或顯像不均可被改善。 然而，使用 lOOcmxlOOcm以上之大型基板時，或適 用於如前述的轉動塗佈法之正型光阻組成物中，因有著塗 佈性或面内均一性等諸特性並不充分等其他安全上問題等 〇 ，故一邊防止“縮痕”，一邊於大型基板表面上均一地塗佈 正型敏輻射線性樹脂組成物係爲困難。 〔專利文獻1〕特開2003 -23 3 1 74號公報 【發明內容】 欲解決上述問題，本發明係以提供一種塗佈後自基板 端往中央不會引起引縮現象，可成爲適用於lOOcmxlOOcm 以上的大型基板上以狹縫式塗佈進行塗佈的光阻之正型敏 輻射線性樹脂組成物爲目的。 -5- 200928586 本發明者有鑑於如此狀況進行詳細硏究結果，發現具 有特定組成之正型敏輻射線性樹脂組成物即使於狹縫式塗 佈亦可形成均一塗佈膜，不會引起“縮痕”，於 lOOcmxlOOcm以上的大型基板上亦持有可得到安定圖型形 ' 狀而充分廣的製圖步驟之邊限，成爲於大型基板以狹縫式 '塗佈進行塗佈爲佳的光阻，而完成本發明。 即，本發明的主旨如下所示。 φ 〔1〕一種正型敏輻射線性樹脂組成物，其爲含有 (A)具有酚性羥基之聚合物100重量份、（B)含有 醌二疊氮基之化合物1〇〜50重量份、（C)對於前述具有 酚性羥基之聚合物（A)及前述含有醌二疊氮基之化合物 (B)的合計100重量份而言爲100〜9900重量份之溶劑 、與（D)界面活性劑0.0 1〜5重量份者， 作爲前述含有醌二疊氮基之化合物（B)含有下述一 般式（I )所示化合物a，作爲前述界面活性劑（D )含有 φ 聚醚變性聚矽氧烷化合物，使用於狹縫式塗佈者。 〔化1〕200928586 IX. INSTRUCTIONS OF THE INVENTION [Technical Field to Be Invented by the Invention] The present invention relates to a photolithography technique used for precision microfabrication, a composition for use in so-called photofabrication, and a pattern of the composition. method. More specifically, the present invention relates to a photomask agent n for dry etching used in the field of optical processing such as wiring formation and electrode formation, such as a semiconductor, an electronic component, or a developing panel. A pattern forming method of a positive positive-sensitive radiation linear resin composition and a positive-type radiation-sensitive linear resin composition. [Prior Art] In recent years, the size of the development panel has increased, and the cost has been rapidly reduced. Among them, a technique for stably forming wiring on a large substrate in a simple step is necessary. After the photoresist film is patterned by photolithography, the technology formed by the wiring of the dry etching method is used in the field of semiconductors in the past, and is popularized as a process which is easy to improve productivity, and the technique is applied to imaging. The panel is divided into the wilderness. In order to perform a stable dry etching process on a large substrate, the entire surface of the substrate must be formed in the same shape as the photoresist pattern. Therefore, it is important that the film thickness of the coating film is uniform, and the margins of the drawing step such as the exposure margin and the development margin are wider. Moreover, the exposure margin is such that within a certain imaging time (recommended development time), the exposure amount of the photoresist pattern can be achieved within ±10% of the specification CD値. The so-called development margin is, in a certain exposure amount (recommended exposure amount), -4- 200928586 can reach the amplitude of the development time of the photoresist pattern within ±10% of the specification CD値. When a photoresist is applied to a large substrate, a rotary coating apparatus such as a rotary coating has a problem of safety in throwing a substrate during rotation due to the weight of the substrate, and thus it is desired to obtain a slit coating method. Uniform coated photoresist. However, when coating by slit coating, the photoresist is condensed from the substrate end after coating to the center, which is a serious problem of so-called "sink marks". A positive resist composition in which a specific phenol compound is added for the purpose of improving sensitivity in a specific mixture ratio of a novolac resin and a specific two kinds of quinonediazide compounds is disclosed in Japanese Laid-Open Patent Publication No. 2003-233174. With this composition, uneven heating or development at the time of coating by a spin coating method on a large glass substrate of 500 rpm to 600 mm 2 or more can be improved. However, when a large substrate of 100 cm×100 cm or more is used, or a positive resist composition suitable for the spin coating method as described above, other safety problems such as coating property or in-plane uniformity are insufficient. It is difficult to uniformly apply the positive-sensitive radiation linear resin composition on the surface of the large substrate while preventing the "shrink marks". [Patent Document 1] Japanese Laid-Open Patent Publication No. 2003-23-23 No. 1 74. SUMMARY OF THE INVENTION In order to solve the above problems, the present invention provides a coating which does not cause a shrinkage phenomenon from the substrate end to the center after coating, and can be applied to 100 cm x 100 cm. The above-mentioned large-sized substrate is intended to be a positive-sensitive radiation linear resin composition of a photoresist coated by slit coating. -5- 200928586 The present inventors have conducted detailed investigations in view of such a situation, and found that a positive-type radiation-sensitive linear resin composition having a specific composition can form a uniform coating film even in a slit coating, and does not cause "shrinkage". "Score", on the large substrate of lOOcmxlOOcm or more, also has a margin of a sufficiently wide drawing step to obtain a stable pattern shape, and is a good photoresist for coating on a large substrate by slit coating. The present invention has been completed. That is, the gist of the present invention is as follows. Φ [1] A positive-type radiation-sensitive linear resin composition comprising (A) 100 parts by weight of a polymer having a phenolic hydroxyl group; (B) 1 to 50 parts by weight of a compound containing a quinonediazide group, ( C) a solvent of 100 to 9900 parts by weight and (D) a surfactant for 100 parts by weight of the total of the phenolic hydroxyl group-containing polymer (A) and the quinonediazide group-containing compound (B) 0.01 to 5 parts by weight, the compound (B) containing the above quinonediazide group contains the compound a of the following general formula (I), and the above surfactant (D) contains φ polyether denatured polyoxyl An alkane compound used in slot coaters. 〔1

(上述一般式（I)中，R1、R2、R3各獨立爲氫原子或下 述式（III)所示基，R1、R2、R3不會全爲氫）。 200928586 〔化2〕(In the above general formula (I), R1, R2 and R3 each independently represent a hydrogen atom or a group represented by the following formula (III), and R1, R2 and R3 are not all hydrogen. 200928586 〔化2〕

〔2〕如上述〔1〕所記載之正型敏輻射線性樹脂組成 物，其特徵爲作爲前述含有醌二疊氮基之化合物（B)， 進一步含有下述一般式（II)所示化合物b。 〔化3〕 OR8 OR6[2] The positive-type radiation-sensitive linear resin composition according to the above [1], which is characterized in that the compound (B) containing the quinonediazide group further contains the compound b of the following general formula (II) . [Chemical 3] OR8 OR6

OR7 (Π)OR7 (Π)

0RS OR4 (上述一般式（Π)中，R4、R5' R6、R7、R8各獨立爲氫 原子或下述式（III )所示基，R4、R5、R6、R7、R8不會 全爲氫）。 (III) 2009285860RS OR4 (In the above general formula (Π), R4, R5' R6, R7, and R8 are each independently a hydrogen atom or a group represented by the following formula (III), and R4, R5, R6, R7, and R8 are not all hydrogen. ). (III) 200928586

〔3〕如上述〔2〕所記載之正型敏輻射線性樹脂組成 ® 物，其特徵爲前述化合物a與前述化合物b之重量比（化 合物a/化合物b )爲3/1〜1/3。 〔4〕如上述〔2〕或〔3〕所記載的正型敏輻射線性 樹脂組成物，其特徵爲對於前述含有醌二疊氮基之化合物 (B ) 100重量份而言，含有合計30〜100重量份之前述 化合物a與前述化合物b。 〔5〕一種光阻圖型形成方法，其特徵爲含有 (i)將上述〔1〕〜〔4〕中任一所記載的正型敏輻 ® 射線性樹脂組成物於基板表面藉由狹縫式塗佈進行塗佈之 步驟、 . (ii)將塗佈於該基板表面之正型敏輻射線性樹脂組 成物藉由以UV光的曝光及/或電子線之描繪進行圖型曝光 的步驟、與 (iii)藉由將經由該圖型曝光步驟之正型敏輻射線性 樹脂組成物進行顯像，形成光阻圖型之步驟。 本發明爲提供一種成爲於lOOcmxlOOcm以上的大型 基板上以狹縫式塗佈進行塗佈爲佳的光阻的正型敏輻射線 -8 - 200928586 性樹脂組成物及使用該正型敏輻射線性樹脂組成物之光阻 圖型形成方法。 實施發明的最佳形態 以下，對本發明做具體說明。 〔正型敏輻射線性樹脂組成物〕 ❹ 有關本發明之正型敏輻射線性樹脂組成物爲，含有特 定比率的（A)具有酚性羥基之聚合物、（B)含有醌二疊 氮基之化合物、（C)溶劑、與（D)界面活性劑之正型敏 輻射線性樹脂組成物，作爲前述含有醌二疊氮基之化合物 (B)含有特定化合物（化合物a)，作爲前述界面活性 劑（D)含有聚醚變性聚矽氧烷化合物爲特徵者。以下， 對構成本發明之正型敏輻射線性樹脂組成物的各成分做說 明。 〇 <(A)具有酚性羥基之聚合物> 具有酚性羥基之聚合物（A)爲，藉由與含有醌二疊 氮基之化合物（B)所成的感光劑之組合使用’作爲於g 線、i線之波長區域具有感度之正型光阻而發揮其功能。 作爲具有酚性羥基之聚合物（A) ’可舉出以下所示酚醛 清漆樹脂，聚羥基苯乙烯及其衍生物。這些可單獨下使用 、或亦可混合使用。 200928586 (酚醛清漆樹脂） 本發明中所使用的酚醛清漆樹脂爲可溶解於鹼者，其 爲將m-甲酚及其他1種以上的酚類（以下，組合彼等亦 可僅稱爲酚類）與醛化合物進行縮合所得之樹脂’ 甲酚 之比率爲全酚類中40〜90質量％的酚醛清漆樹脂。 ‘ 作爲使用於酚醛清漆樹脂之原料的前述其他酚類，具 體可舉出例如〇-甲酚、P-甲酚、2,3-二甲苯酚、2,4-二甲 φ 苯酚、2，5 -二甲苯酚、3,4-二甲苯酚、3,5 -二甲苯酚及 2,3,5-三甲基酚等。彼等可單獨或組合2種以上使用。 這些中以P-二甲苯酚、2,3-二甲苯酚、2,4-二甲苯酚 、3,4-二甲苯酚及2,3,5-三甲基酚爲佳。 又，作爲m-甲酚與其他1種以上的酚類之較佳組合 ，可舉出m-甲酚/2,3-二甲苯酚、m-甲酚/p-甲酚、m-甲酚 /2,4-二甲苯酚、m-甲酚/2,3-二甲苯酚/3，4-二甲苯酚、m-甲酚/2,3,5-三甲基酚及m-甲酚/2,3-二甲苯酚/2,3,5-三甲基 ❿ 酣等。 又，作爲經縮合之醛化合物，例如可舉出甲醛、仲甲 醛、乙醛、苯甲醛、〇-羥基苯甲醛、· m-羥基苯甲醛、P-羥 基苯甲醛、乙二醛、戊二醛、對苯二甲醛、間苯二甲醛等 。彼等中特別使用甲醛、〇-羥基苯甲醛爲佳。 這些醛類亦可單獨或組合2種以上使用。如此醛化合 物的使用量以對於前述其他酚類1莫耳而言，較佳爲0.4 〜2莫耳，更佳爲0.6〜1.5莫耳。 酚類與醛化合物之縮合反應中一般可使用酸性觸媒。 -10- 200928586 作爲該酸性觸媒，例如可舉出鹽酸、硝酸、硫酸、甲酸、 草酸、乙酸、甲烷磺酸' P -甲苯磺酸等。如此酸性觸媒的 使用量一般對於酚類1莫耳而言爲lxl〇-5〜5χ10·ι莫耳。 縮合反應中’一般使用水作爲反應媒質，但自反應初 期爲不均系統時’作爲反應媒質例如可使用甲醇、乙醇、 丙醇、丁醇、丙二醇單甲基醚等醇類；四氫呋喃、二噁烷 等環狀醚類；乙基甲基酮、甲基異丁基酮、2-庚酮等酮類 Ο 。這些反應媒質一般爲每反應原料100重量份中，使用20 〜1，000重量份之量。 縮合反應之溫度配合原料之反應性，可適宜地調整， —般爲 10°C 〜200°c。 作爲反應方法’可適宜地採用將酹類、醛化合物、酸 性觸媒等一倂裝入的方法、及於酸性觸媒之存在下將酚類 、醛化合物等於反應進行的同時加入的方法等。 作爲縮合反應終了後的酚醛清漆樹脂之回收方法，存 ® 在於系統内的未反應原料，欲除去酸性觸媒及反應媒質等 時’將反應溫度上升至130 °C〜230 °C，減壓下除去揮發成 分，回收酚醛清漆樹脂之方法、或將所得之酚醛清漆樹脂 溶解於乙二醇單甲基醚乙酸酯、3 -甲氧基丙酸甲酯、乳酸 乙酯、甲基異丁基酮、2-庚酮、二噁烷、甲醇、乙酸乙酯 等良溶劑後，混合水、η-己烷、η-庚烷等弱溶劑，其次， 分離析出之樹脂溶液層，回收高分子量之酚醛清漆樹脂的 方法。 又，前述酚醛清漆樹脂之聚苯乙烯換算的重量平均分 -11 - 200928586 子量（以下’亦稱爲「Mw」）係由將正型敏輻射線性樹 脂組成物進行製膜時的作業性，作爲光阻使用時的顯像性 ’感度及耐熱性之觀點來看，以2,000〜20,000時爲佳， 3,000〜15,000時爲特佳。 <(B)含有醌二疊氮基之化合物> 本發明的正型敏輻射線性樹脂組成物爲含有特定比率 的含有醌二疊氮基之化合物（Β)，作爲該含有醌二叠氮 基之化合物（Β)含有下述一般式（I)所示化合物a爲特 徵。 〔化5〕[3] The positive-type radiation-sensitive linear resin composition of the above [2], wherein the weight ratio of the compound a to the compound b (compound a/compound b) is from 3/1 to 1/3. [4] The positive-type radiation-sensitive linear resin composition according to the above [2] or [3], which is characterized in that the total amount of the compound (B) containing the quinonediazide group is 100% by weight. 100 parts by weight of the aforementioned compound a and the aforementioned compound b. [5] A method for forming a resist pattern, comprising: (i) the positive-sensitive radiation-radiating resin composition according to any one of the above [1] to [4], which is formed on a substrate surface by a slit a step of coating the coating, (ii) a step of patternwise exposing the positive-type radiation-sensitive linear resin composition coated on the surface of the substrate by exposure to UV light and/or electron line drawing, And (iii) forming a photoresist pattern by developing a positive-sensitive radiation linear resin composition through the pattern exposure step. The present invention provides a positive-sensitive radiation -8 - 200928586 resin composition which is coated on a large substrate of 100 cm x 1000 cm or more and which is preferably coated with a slit coating, and a positive-sensitive radiation linear resin. A method of forming a photoresist pattern of a composition. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described. [Positive-type radiation-radiating linear resin composition] ❹ The positive-type radiation-sensitive linear resin composition of the present invention contains (A) a polymer having a phenolic hydroxyl group and (B) a quinonediazide group having a specific ratio. a compound, (C) solvent, and a positive-type radiation-sensitive linear resin composition of (D) a surfactant, wherein the compound (B) containing the quinonediazide group contains a specific compound (compound a) as the surfactant (D) Characterized by a polyether-denatured polyoxyalkylene compound. Hereinafter, the components constituting the positive-sensitive radiation linear resin composition of the present invention will be described. 〇<(A) Polymer having a phenolic hydroxyl group> The polymer (A) having a phenolic hydroxyl group is used in combination with a sensitizer formed by the compound (B) containing a quinonediazide group. It functions as a positive resist of sensitivity in the wavelength region of the g line or the i line. The polymer (A) having a phenolic hydroxyl group is exemplified by the following novolak resins, polyhydroxystyrene and derivatives thereof. These can be used alone or in combination. 200928586 (Phenolic varnish resin) The novolak resin used in the present invention is soluble in alkali, and is m-cresol and one or more other phenols (hereinafter, they may be referred to simply as phenols) The ratio of the resin 'cresol obtained by condensation with the aldehyde compound is 40 to 90% by mass of the novolac resin in the total phenol. The other phenols used as the raw material of the novolak resin may, for example, be cresol-cresol, P-cresol, 2,3-xylenol, 2,4-dimethylφphenol, 2,5. - xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, and the like. These may be used alone or in combination of two or more. Among these, P-xylenol, 2,3-xylenol, 2,4-xylenol, 3,4-xylenol and 2,3,5-trimethylphenol are preferred. Further, as a preferable combination of m-cresol and one or more other phenols, m-cresol/2,3-xylenol, m-cresol/p-cresol, m-cresol may be mentioned. /2,4-xylenol, m-cresol/2,3-xylenol/3,4-xylenol, m-cresol/2,3,5-trimethylphenol and m-cresol /2,3-xylenol/2,3,5-trimethylhydrazine hydrazine, and the like. Further, examples of the condensed aldehyde compound include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, hydrazine-hydroxybenzaldehyde, m-hydroxybenzaldehyde, P-hydroxybenzaldehyde, glyoxal, and glutaraldehyde. , terephthalaldehyde, isophthalaldehyde, and the like. Among them, formaldehyde and hydrazine-hydroxybenzaldehyde are particularly preferred. These aldehydes can also be used individually or in combination of 2 or more types. The amount of the aldehyde compound used is preferably from 0.4 to 2 moles, more preferably from 0.6 to 1.5 moles, per mole of the other phenols. An acidic catalyst can generally be used in the condensation reaction of a phenol with an aldehyde compound. -10- 200928586 Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, and methanesulfonic acid 'P-toluenesulfonic acid. The amount of the acid catalyst used is generally lxl 〇 -5 to 5 χ 10 · ι·m for the phenolic 1 Mo. In the condensation reaction, 'water is generally used as the reaction medium, but when the initial stage of the reaction is a heterogeneous system', as the reaction medium, for example, an alcohol such as methanol, ethanol, propanol, butanol or propylene glycol monomethyl ether; tetrahydrofuran or dioxane can be used. a cyclic ether such as an alkane; a ketone such as ethyl methyl ketone, methyl isobutyl ketone or 2-heptanone. These reaction media are generally used in an amount of from 20 to 1,000 parts by weight per 100 parts by weight of the reaction raw material. The temperature of the condensation reaction may be suitably adjusted in accordance with the reactivity of the raw material, and is usually from 10 ° C to 200 ° C. As the reaction method, a method of charging a hydrazine, an aldehyde compound, an acid catalyst or the like, and a method of adding a phenol or an aldehyde compound to the reaction in the presence of an acidic catalyst can be suitably employed. As a method for recovering the novolak resin after the end of the condensation reaction, the unreacted raw material in the system is used, and when the acid catalyst and the reaction medium are removed, the reaction temperature is raised to 130 ° C to 230 ° C under reduced pressure. A method of removing a volatile component, recovering a novolak resin, or dissolving the obtained novolak resin in ethylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl lactate, methyl isobutyl After a good solvent such as a ketone, 2-heptanone, dioxane, methanol or ethyl acetate, a weak solvent such as water, η-hexane or η-heptane is mixed, and then the precipitated resin solution layer is separated to recover a high molecular weight. A method of novolak resin. In addition, the polystyrene-equivalent weight average of -11 - 200928586 (hereinafter referred to as "Mw") of the novolak resin is an operation property when a positive-type radiation-sensitive linear resin composition is formed into a film. From the viewpoint of the visibility 'sensitivity and heat resistance at the time of use of the photoresist, it is preferably from 2,000 to 20,000, and particularly preferably from 3,000 to 15,000. <(B) Compound containing quinonediazide group> The positive-type radiation-sensitive linear resin composition of the present invention is a compound containing quinonediazide group (Β) containing a specific ratio as the quinonediazide The compound (Β) of the group contains the compound a represented by the following general formula (I). 〔化5〕

上述一般式（I)中，R1、R2、R3各獨立爲氫原子或 下述式（III)所示基，R1、R2、R3不會全爲氫。 〔化6〕In the above general formula (I), R1, R2 and R3 each independently represent a hydrogen atom or a group represented by the following formula (III), and R1, R2 and R3 are not all hydrogen. [6]

上述一般式（I)中，例如R1爲式（III)所示基，R2 及R3爲氫時，化合物a爲如以下之化合物。 -12- 200928586 〔化7〕In the above general formula (I), for example, R1 is a group represented by the formula (III), and when R2 and R3 are hydrogen, the compound a is a compound as follows. -12- 200928586 〔化7〕

0 ❹ 如此化合物，例如可藉由將下述式（IV)所示化合物 與萘醌-1,2-二疊氮基-5-磺醯基氯化物接觸後進行酯化反 應而得。 〔化8〕0 ❹ Such a compound can be obtained, for example, by subjecting a compound represented by the following formula (IV) to naphthoquinone-1,2-diazide-5-sulfonyl chloride to carry out an esterification reaction. 〔化8〕

含有醌二疊氮基之化合物（B)爲藉由含有化合物a ，將正型敏輻射線性樹脂組成物塗佈於基板上，使正型敏 輻射線性樹脂組成物進行曝光、顯像後所得之光阻圖型的 形狀可精密地被控制。 又，本發明的正型敏輻射線性樹脂組成物由提高解像 性之觀點來看，作爲前述含有醌二疊氮基之化合物（B) ，進一步含有下述一般式（Π)所示化合物b爲佳。 -13- 200928586 化9〕 ORe ORe Ο 7Ν^ OR7/ Τ (Π) OR4 OR5 上述一般式（II)中，R4、R5、R6、R7、R8各獨立爲 氫原子或下述式（III )所示基，R4、R5、R6、R7、R8不 會全爲氫。 〔化 1 〇〕 0❹ f^v^S^N2 (III)The compound (B) containing a quinonediazide group is obtained by coating a positive-type radiation-sensitive linear resin composition on a substrate by containing the compound a, and subjecting the positive-sensitive radiation-linear resin composition to exposure and development. The shape of the photoresist pattern can be precisely controlled. Further, the positive-type radiation-sensitive linear resin composition of the present invention further contains the compound (B) represented by the following general formula (Π) as the quinonediazide group-containing compound (B) from the viewpoint of improving the resolution. It is better. -13- 200928586 9] ORe ORe Ο 7Ν^ OR7/ Τ (Π) OR4 OR5 In the above general formula (II), R4, R5, R6, R7 and R8 are each independently a hydrogen atom or the following formula (III) The groups, R4, R5, R6, R7, and R8 are not all hydrogen. 〔化1 〇〕 0❹ f^v^S^N2 (III)

上述一般式（II)中，例如R4爲式（III )所示基， R5、R6、R7、R8爲氫時，化合物b爲如以下所示化合物。 -14- 200928586 〔化 1 1〕In the above general formula (II), for example, R4 is a group represented by the formula (III), and when R5, R6, R7 and R8 are hydrogen, the compound b is a compound shown below. -14- 200928586 〔化1 1〕

OHOH

OHOH

OHOH

OHOH

n2 如此化合物，例如可由將下述式（V )所示化合物與 萘醌-1，2-二疊氮基-5-磺醯基氯化物接觸後使其進行酯化 反應而得到。N2 such a compound can be obtained, for example, by subjecting a compound represented by the following formula (V) to naphthoquinone-1,2-diazido-5-sulfonyl chloride to carry out an esterification reaction.

〔化 1 2〕[Chemical 1 2]

OH OHOH OH

OH (V)OH (V)

OHOH

OH 如上述，本發明的正型敏輻射線性樹脂組成物作爲含 -15- 200928586 有醌二疊氮基之化合物（B)而含有化合物a，但由提高 解像性之觀點來看，化合物&爲4-(^( 4-羥基苯基）-1_ 甲基乙基〕-6· (1-甲基-1-苯基乙基）-1,3 -苯二醇1.〇莫 耳、與萘醌-1，2 -二疊氮基-5-磺醯基氯化物1.0莫耳之酯化 ' 反應生成物爲佳。 又，本發明的正型敏輻射線性樹脂組成物爲如前述含 有化合物b者爲佳，但由提高解像性之觀點來看’化合物 G b爲4,6-雙〔1-雙（3-甲基-4-羥基苯基）甲基〕-P-甲酚 1.0莫耳、與萘醌-1,2 -二疊氮基-5-磺醯基氯化物2.0莫耳 之酯化反應生成物時爲特佳。 前述化合物a與化合物b之重量比（化合物a/化合物 b )，由提高解像性之觀點來看，以3/1〜1/3爲佳，較佳 爲 1 /1。 又，對於前述含有醌二叠氮基之化合物（B) 100重 量份而言，化合物a與化合物b之含有量合計，由提高感 ® 度、解像性之觀點來看，以30〜100重量份爲佳，較佳爲 40〜90重量份。 本發明的正型敏輻射線性樹脂組成物，作爲含有醌二 疊氮基之化合物（B)，亦可單獨含有上述化合物a及化 合物b以外的其他含有醌二疊氮基之化合物、或含有2種 以上。 作爲其他前述含有醌二疊氮基之化合物，可舉出與聚 羥基二苯甲酮類，（聚）羥基苯基鏈烷類、雙〔（聚）羥 基苯基〕鏈烷類、參（羥基苯基）甲烷類或其甲基取代體 -16- 200928586 、雙（環己基羥基苯基）羥基苯基甲烷類或其甲基取代體 、或4,4’-〔l-〔4-〔 1-(4-羥基苯基）-1-甲基乙基〕苯基 〕亞乙基〕二酚或7-羥基-4-(4，-羥基苯基）-2-甲基-2-( 2'，4'-二羥基）苯基香豆素、4-〔 1- (4-羥基苯基）-1-甲基 乙基〕-6-( 1-甲基-1-苯基乙基）-u-苯二醇、4,6_雙〔1-'雙（3-甲基-4-羥基苯基）甲基〕-P-甲酚、4,6-雙〔1-(4-羥基苯基）-1-甲基乙基〕-丨_羥基_3_甲氧基苯、或酚醛清 ❹ 漆樹脂、焦掊酚-丙酮樹脂、p-羥基苯乙烯之均聚物或與此 共聚合所得之單體的共聚合物、或具有羥基或胺基之化合 物等；與 醌二疊氮基含有磺酸或萘醌-1，2-二疊氮基-5-磺醯基 氯化物等的完全酯化合物、部分酯化合物、醯胺化物或部 分醯胺化物等。 作爲具體之前述聚羥基二苯甲酮類’可舉出將 2,3,4-三羥基二苯甲酮'2,4,4、三羥基二苯甲酮、2,4,6-三 © 羥基二苯甲酮、2,3,6-三羥基二苯甲酮、2,3,4-三羥基-2·-甲基二苯甲酮、2,3,4,4，-四羥基二苯甲酮、2,2'，4,4'-四羥 基二苯甲酮、2,3，，4,4|，6-五羥基二苯甲酮、2,2'，3,4,4'-五 羥基二苯甲酮、2,2',3,4,5-五羥基二苯甲酮、 2，3 ', 4，4', 5 ', 6 -六羥基二苯甲酮、2，3，3 ’，4，4 ·，5 ’ -六羥基二苯 甲酮等，作爲前述雙〔（聚）羥基苯基〕鏈烷類’可舉出 雙（2,4·二羥基苯基）甲烷、雙（2,3,4·三羥基苯基）甲烷 、2- ( 4-羥基苯基）-2- ( 41-羥基苯基）丙烷、2· ( 2,4-二 羥基苯基）-2-(2，，4，-二羥基苯基）丙烷、2_(2,3,4·三羥 -17- 200928586 基苯基）-2- (2'，3’，4'-三羥基苯基）丙烷等，作爲前述參 (羥基苯基）甲烷類或其甲基取代體，可舉出參（4-羥基 苯基）甲烷、雙（4-羥基-3,5-二甲基苯基）-4-羥基苯基甲 烷、雙（4-羥基-2,5-二甲基苯基）-4-羥基苯基甲烷、雙（ ' 4-羥基-3,5-二甲基苯基）-2-羥基苯基甲烷、雙（4-羥基- 2,5-二甲基苯基）-2-羥基苯基甲烷、雙（4-羥基-2,5-二甲 基苯基）-3,4-二羥基苯基甲烷、雙（4-羥基-3,5-二甲基苯 〇 基）-3，4-二羥基苯基甲烷等，作爲前述雙（環己基羥基苯 基）羥基苯基甲烷類或其甲基取代體，可舉出雙（3-環己 基-4-羥基苯基）-3-羥基苯基甲烷、雙（3-環己基-4-羥基 苯基）-2-羥基苯基甲烷、雙（3-環己基-4-羥基苯基）-4-羥基苯基甲烷、雙（5-環己基-4-羥基-2-甲基苯基）-2-羥 基苯基甲烷、雙（5-環己基-4-羥基-2-甲基苯基）-3-羥基 苯基甲烷、雙（5-環己基-4-羥基-2_甲基苯基）-4-羥基苯 基甲烷、雙（3-環己基-2-羥基苯基）-3-羥基苯基甲烷、 © 雙（5-環己基-4-羥基-3-甲基苯基）-4-羥基苯基甲烷、雙 (5-環己基-4-羥基-3-甲基苯基）-3-羥基苯基甲烷、雙（ 5-環己基-4-羥基-3-甲基苯基）-2-羥基苯基甲烷、雙（3-環己基-2-羥基苯基）-4-羥基苯基甲烷、雙（3-環己基-2-羥基苯基）-2-羥基苯基甲烷、雙（5-環己基-2-羥基-4-甲 基苯基）-2-羥基苯基甲烷、雙（5-環己基-2-羥基-4-甲基 苯基）-4-羥基苯基甲烷等，作爲具有前述羥基或胺基之化 合物，可舉出酚、P-甲氧基酚、二甲基酚、氫醌、萘酚、 焦兒茶酚、焦掊酚、焦掊酚單甲基醚、焦掊酚-1,3-二甲基 -18- 200928586 醚、没食子酸、苯胺、p-胺基二苯胺、4,4'-二胺二苯甲酮 等，作爲醌二疊氮基含有磺酸，可舉出萘醌-1，2-二疊氮 基-5-磺酸、萘醌-1，2-二疊氮基-4-磺酸 '鄰蒽醌二疊氮磺 酸等。 本發明的正型敏輻射線性樹脂組成物中含有醌二疊氮 基之化合物（B)之含有量對於具有酚性羥基之聚合物（A )1〇〇重量份而言爲10〜50重量份，較佳爲15〜40重量 © 份，更佳爲20〜35重量份。 < (C )溶劑> 作爲溶劑（C)，具體可舉出乙二醇單甲基醚、乙二 醇單乙基醚、乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙 酸酯、二乙二醇單甲基醚，二乙二醇單乙基醚、丙二醇單 甲基醚乙酸酯、丙二醇單丙基醚乙酸酯’ 2_羥基丙酸乙酯 、2-羥基-2-甲基丙酸乙酯、乙氧基乙酸乙酯、羥基乙酸乙 ® 酯、2-羥基-3-甲基丁酸甲酯、3-甲氧基丙酸甲酯、3·乙氧 基丙酸乙酯、3-甲氧基丙酸乙酯、乙酸丁酯、丙酮酸甲酯 、丙酮酸乙酯等。 且，亦可使用N-甲基甲醯胺、N，N-二甲基甲醯胺、 N-甲基甲醯苯胺、N-甲基乙醯胺、N，N-二甲基乙醯胺、N-甲基吡咯烷酮、二甲基亞楓、苯甲基乙基醚、二己基醚、 丙酮基丙酮、異佛爾酮、己酸、辛酸、辛醇、1-壬醇、 苯甲醇、乙酸苯甲酯、安息香酸乙酯、草酸二乙酯、馬來 酸二乙酯、γ-丁內酯、碳酸乙烯酯、碳酸丙烯酯、乙二醇 -19- 200928586 單苯基醚乙酸酯等高沸點溶劑。 這些溶劑，可單獨或組合2種以上使用。彼等中以2-羥基丙酸乙酯爲佳。 這些溶劑爲，將所得之正型敏輻射線性樹脂組成物塗 佈於基板上，塗佈至5μιη以下之厚度時，正型敏輻射線性 樹脂組成物之固體成分濃度一般至1重量％〜5 0重量％， 較佳爲5重量％〜25重量％之範圍下使用。即，對於前述 ® 具有酚性羥基之聚合物（Α)及含有醌二疊氮基之化合物 (B)的合計100重量份而言，前述溶劑一般爲100〜 9900重量份，較佳爲300〜1900重量份之量下使用。 < (D)界面活性劑> 本發明的正型敏輻射線性樹脂組成物係以提高塗佈性 、消泡性、塗平性等，並抑制塗佈直後的塗膜之劣化爲目 的下含有界面活性劑（D )，特別以欲達到抑制塗佈直後 © 的塗膜劣化的目的，作爲界面活性劑（D)含有聚醚變性 聚矽氧烷化合物作爲特徵。 作爲界面活性劑（D)含有聚醚變性聚矽氧烷化合物 時，經正型敏輻射線性樹脂組成物之狹縫式塗佈的塗佈性 會顯著提高，以狹縫式塗佈一旦塗膜於基板被塗佈後，自 塗膜端部往中央部移動光阻，於lOOcmxlOOcm以上之大 型基板上亦可解消所謂之“縮痕”。 作爲前述聚醚變性聚矽氧烷化合物，例如可舉出{〇^ 245，KL-2 70 (共榮公司化學（股）製），下述一般式（ -20- 200928586 VI)所示聚合物 〔化 1 3〕ch3CH,—Si—0- CH3 ch3ISi—O CH3OH As described above, the positive-type radiation-sensitive linear resin composition of the present invention contains the compound a as the compound (B) having a quinone diazide group of -15-200928586, but from the viewpoint of improving the resolution, the compound &; 4-(^(4-hydroxyphenyl)-1_methylethyl]-6·(1-methyl-1-phenylethyl)-1,3-benzenediol 1. It is preferable to form a reaction product of 1.0 mol of naphthoquinone-1,2-diazido-5-sulfonyl chloride. Further, the positive-sensitive radiation linear resin composition of the present invention contains as described above. The compound b is preferred, but from the viewpoint of improving the resolution, the compound G b is 4,6-bis[1-bis(3-methyl-4-hydroxyphenyl)methyl]-P-cresol. 1.0 molar, particularly excellent in esterification reaction product with 2.0 mol of naphthoquinone-1,2-diazido-5-sulfonyl chloride. The weight ratio of the aforementioned compound a to compound b (compound a / Compound b) is preferably from 3/1 to 1/3, preferably from 1:1, from the viewpoint of improving the resolution. Further, the weight of the compound (B) containing the quinonediazide group is 100% by weight. In terms of parts, the total content of compound a and compound b is From the viewpoint of high sensitivity and resolution, it is preferably 30 to 100 parts by weight, preferably 40 to 90 parts by weight. The positive-sensitive radiation linear resin composition of the present invention contains quinonediazide group The compound (B) may contain the quinonediazide group-containing compound other than the above-mentioned compound a and the compound b, or may contain two or more types. The other compound containing the quinonediazide group may be mentioned as Polyhydroxybenzophenones, (poly)hydroxyphenylalkanes, bis[(poly)hydroxyphenyl]alkanes, cis (hydroxyphenyl)methanes or methyl substituents thereof-16-200928586, Bis(cyclohexylhydroxyphenyl)hydroxyphenylmethane or its methyl substituent, or 4,4'-[l-[4-[1-(4-hydroxyphenyl)-1-methylethyl] Phenyl]ethylidene diol or 7-hydroxy-4-(4,-hydroxyphenyl)-2-methyl-2-(2',4'-dihydroxy)phenylcoumarin, 4- [ 1- (4-Hydroxyphenyl)-1-methylethyl]-6-( 1-methyl-1-phenylethyl)-u-benzenediol, 4,6_bis[1-' Bis(3-methyl-4-hydroxyphenyl)methyl]-P-cresol, 4,6-bis[1-(4-hydroxybenzene) a homopolymer of a lacquer resin, a pyrogallol-acetone resin, p-hydroxystyrene or copolymerized therewith, or a homopolymer of p-hydroxystyrene a copolymer of the obtained monomer, or a compound having a hydroxyl group or an amine group; and a sulfonium diazide group containing a sulfonic acid or naphthoquinone-1,2-diazido-5-sulfonyl chloride a completely ester compound, a partial ester compound, a amide or a partial amide, etc. As the specific polyhydroxybenzophenone, 2,3,4-trihydroxybenzophenone '2, 4 , 4, trihydroxybenzophenone, 2,4,6-tri-hydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2·- Benzophenone, 2,3,4,4,-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,,4,4|,6 - pentahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, 2,2',3,4,5-pentahydroxybenzophenone, 2,3 ', 4,4', 5 ',6-hexahydroxybenzophenone, 2,3,3 ',4,4 ·,5 '-hexahydroxybenzophenone, etc., as the aforementioned bis[(poly)hydroxyphenyl group 〕Alkane' can be cited as double (2,4) Dihydroxyphenyl)methane, bis(2,3,4·trihydroxyphenyl)methane, 2-(4-hydroxyphenyl)-2-(41-hydroxyphenyl)propane, 2· (2,4 -dihydroxyphenyl)-2-(2,4,-dihydroxyphenyl)propane, 2_(2,3,4·trihydroxy-17- 200928586 phenyl)-2- (2',3' 4'-trihydroxyphenyl)propane, etc., as the above-mentioned quinone (hydroxyphenyl)methane or a methyl substituent thereof, exemplified by (4-hydroxyphenyl)methane and bis(4-hydroxy-3, 5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis('4-hydroxy-3,5 -Dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-di Methylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenylhydrazino)-3,4-dihydroxyphenylmethane, etc., as the aforementioned double (ring Examples of hexylhydroxyphenyl)hydroxyphenylmethane or a methyl substituent thereof include bis(3-cyclohexyl-4-hydroxyphenyl)-3-hydroxyphenylmethane and bis(3-cyclohexyl-4- Hydroxyphenyl)-2-hydroxyphenyl Alkane, bis(3-cyclohexyl-4-hydroxyphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, double (5-Cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane , bis(3-cyclohexyl-2-hydroxyphenyl)-3-hydroxyphenylmethane, © bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-4-hydroxyphenylmethane, double (5-Cyclohexyl-4-hydroxy-3-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane , bis(3-cyclohexyl-2-hydroxyphenyl)-4-hydroxyphenylmethane, bis(3-cyclohexyl-2-hydroxyphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl- 2-hydroxy-4-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-2-hydroxy-4-methylphenyl)-4-hydroxyphenylmethane, etc., as having the aforementioned hydroxyl group Or an amine group compound, and examples thereof include phenol, P-methoxyphenol, dimethylphenol, hydroquinone, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol- 1,3-dimethyl-18- 200928 586 ether, gallic acid, aniline, p-aminodiphenylamine, 4,4'-diamine benzophenone, etc., as the quinonediazide group contains sulfonic acid, which can be mentioned as naphthoquinone-1,2-double Nitro-5-sulfonic acid, naphthoquinone-1,2-diazido-4-sulfonic acid 'o-quinonediazidesulfonic acid, and the like. The content of the compound (B) containing a quinonediazide group in the positive-sensitive radiation linear resin composition of the present invention is 10 to 50 parts by weight based on 1 part by weight of the polymer (A) having a phenolic hydroxyl group. Preferably, it is 15 to 40 parts by weight, more preferably 20 to 35 parts by weight. <(C) Solvent> As the solvent (C), specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl Ethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate '2-hydroxypropionate ethyl ester, Ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, 3 Ethyl ethoxypropionate, ethyl 3-methoxypropionate, butyl acetate, methyl pyruvate, ethyl pyruvate, and the like. Further, N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethylacetamide can also be used. , N-methylpyrrolidone, dimethyl sulfite, benzylethyl ether, dihexyl ether, acetonyl acetone, isophorone, hexanoic acid, octanoic acid, octanol, 1-nonanol, benzyl alcohol, acetic acid Benzyl methyl ester, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol-19- 200928586 monophenyl ether acetate, etc. High boiling point solvent. These solvents may be used alone or in combination of two or more. Among them, ethyl 2-hydroxypropionate is preferred. These solvents are obtained by applying the obtained positive-type radiation-sensitive linear resin composition onto a substrate and coating it to a thickness of 5 μm or less, and the solid content of the positive-type radiation-sensitive linear resin composition is generally 1% by weight to 5 0. It is used in the range of % by weight, preferably 5% by weight to 25% by weight. That is, the solvent is generally 100 to 9900 parts by weight, preferably 300 to 100 parts by weight of the total of the polymer of the phenolic hydroxyl group (Α) and the quinonediazide group-containing compound (B). It is used in an amount of 1900 parts by weight. < (D) Surfactant> The positive-type radiation-sensitive linear resin composition of the present invention is intended to improve coatability, defoaming property, flatness, and the like, and to suppress deterioration of the coating film after application. The surfactant (D) is contained, and in particular, it is characterized in that the surfactant (D) contains a polyether-denatured polysiloxane compound for the purpose of suppressing deterioration of the coating film by coating. When the surfactant (D) contains a polyether-denatured polysiloxane compound, the coating property of the slit coating by the positive-sensitive radiation linear resin composition is remarkably improved, and the coating is applied by slit coating. After the substrate is coated, the photoresist is moved from the end portion of the coating film to the central portion, and the so-called "shrinkage" can be eliminated on a large substrate of 100 cm x 100 cm or more. The polyether-denatured polyoxane compound is, for example, a polymer represented by the following general formula (-20-200928586 VI), which is a product of the following general formula (manufactured by Kyoei Chemical Co., Ltd.). [Chemical 1 3] ch3CH, -Si—0- CH3 ch3ISi—O CH3

ch3Si—O CH3ISi—CH3ch3Si—O CH3ISi—CH3

XX

Jy CH3 CH2—^C2H4-〇^-r13 (VI) ¥ 上述式中，R13爲氫原子或碳數1〜5的烷基，n爲1 〜20之整數，X、y各獨立爲2〜100之整數。 作爲上述一般式（VI)所示聚醚變性矽氧烷化合物可 舉出 SH-28PA ' SH8400、SH-190、同-193、SF-8428 ( Dow Corning Toray公司（股）製），這些可使用1種或 組合2種以上。 作爲其他界面活性劑，例如可舉出BM- 1 000，BM-1100(BM凱米公司製）、美格夫克F142D、同F172、同 F173、同F183(大曰本油墨化學工業（股）製）、夫羅 拉多 FC-135、同 FC-170C、同 FC-430、同 FC-431(住友 3M (股）製）、SurflonS-112、同 S-113、同 S-131、同 S-141、同 S-145(旭硝子（股）製）、sZ-6032 (Toray 聚 矽氧（股）製）、NBX-15 ( NeOS (股）製）等名稱所販 賣的氟系界面活性劑； SF-8418、SF-8427、SF-8428、SF-8416 ( Dow Corning Toray公司製）等名稱所販賣的矽系界面活性劑； 又’可舉出非離子S-6、非離子〇_4、Pronon201、 -21 - 200928586Jy CH3 CH2—^C2H4-〇^-r13 (VI) ¥ In the above formula, R13 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n is an integer of 1 to 20, and X and y are each independently 2 to 100. The integer. Examples of the polyether-modified siloxane compound represented by the above general formula (VI) include SH-28PA 'SH8400, SH-190, homo-193, and SF-8428 (manufactured by Dow Corning Toray Co., Ltd.), which can be used. One type or a combination of two or more types. Examples of other surfactants include BM-1 000, BM-1100 (manufactured by BM Kemi Co., Ltd.), Megkov F142D, F172, F173, and F183 (Otsuka Ink Chemical Industry Co., Ltd.). System), Flora FC-135, with FC-170C, with FC-430, with FC-431 (Sumitomo 3M (share) system), SurflonS-112, with S-113, with S-131, with S- 141. Fluorine-based surfactants sold under the names S-145 (Asahi Glass Co., Ltd.), sZ-6032 (Toray Polyoxane), and NBX-15 (NeOS); SF -8418, SF-8427, SF-8428, SF-8416 (made by Dow Corning Toray Co., Ltd.) and other brands of lanthanide surfactants; and 'non-ionic S-6, non-ionic 〇4, Pronon201 , -21 - 200928586

Pronon204 (日本油脂（股）製）、EmulgenA-60、同 A-90、同八-500(花王（股）製）、1^-600(共榮公司化學 (股）製）等名稱所販賣的非離子系界面活性劑等，這些 可使用1種或組合2種以上。 這些界面活性劑（D)對於前述具有酚性羥基之聚合 物（A) 100重量份而言，使用0.01〜5重量份爲佳，較佳 爲0.01〜2重量份之量。 ❹ < (E )其他成分> 本發明的正型敏輻射線性樹脂組成物，作爲其他成分 可含有以下者。 (多核酚化合物） 多核酚化合物雖非本發明之正型敏輻射線性樹脂組成 物中的必須成分，但因含於其中可提高正型敏輻射線性樹 〇 脂組成物之鹼溶解性，可更精密地控制光阻圖型之形狀。 其中作爲多核酚化合物，表示具有2個以上獨立存在之苯 環，且1分子中具有2個以上於該苯環之一部分結合羥基 之酚性羥基的化合物。具體可舉出，例如4,4’-〔 1-〔 4-〔 1-(4-羥基苯基）-1-甲基乙基〕苯基〕亞乙基〕二酚、 2,2-雙（1,5-二甲基-4-羥基苯基）丙酸甲基酯、4,6-雙〔 1-(4-羥基苯基）-1-甲基乙基〕-1，3-苯二醇、1,1-雙（ 2,5-二甲基-4-羥基苯基）丙酮等。 這些多核酚化合物含於本發明之正型敏輻射線性樹脂 -22- 200928586 組成物時，多核酚化合物對於具有酚性羥基之聚合物（A )100重量份而言，使用5〜40重量份，較佳爲使用1〇〜 3 〇重量份之量。以上述範圍含有時，特別可精密地控制光 阻圖型之形狀。 〔本發明的光阻圖型形成方法〕 本發明的光阻圖型形成方法係以含有以下步驟爲特徵 〇 (i)將本發明之正型敏輻射線性樹脂組成物藉由狹縫式 塗佈於基板表面進行塗佈之步驟 (Π)將塗佈於該基板表面之正型敏輻射線性樹脂組成物 藉由以UV光的曝光及/或以電子線的描繪進行圖型曝光的 步驟 (iii)藉由將經由該圖型曝光步驟的正型敏輻射線性樹脂 組成物進行顯像，形成光阻圖型之步驟。 欲於lOOcmxlOOcm以上之大型基板上形成光阻圖型 ’必須藉由狹縫式塗佈將正型敏輻射線性樹脂組成物塗佈 於基板表面。使轉動塗佈等基板進行轉動而塗佈之裝置上 ’因會有基板的重量所引起的轉動中基板拋出等安全上問 題’於大型基板表面上難以均勻地塗佈正型敏輻射線性樹 脂組成物。 然而本發明的正型敏輻射線性樹脂組成物如上述，含 有特定比率的具有酚性羥基之聚合物（A)，含有醌二疊 氮基之化合物（B )，溶劑（C )及界面活性劑（D )，作 -23- 200928586 爲界面活性劑（D)因含有聚醚變性聚矽氧烷化合物’於 100 cm xlOOcm以上的大型基板上亦可解除所謂的“縮痕”’ 因含有作爲含有醌二疊氮基之化合物（B)的特定化合物 ，可形成微細光阻圖型。 【實施方式】 〔實施例〕 〇 以下將本發明藉由實施例做具體說明，但本發明並未 限定於此。又，若無特別限定，份表示重量份，％表示重 量％。 〔調製例〕正型敏輻射線性樹脂組成物之調製 使用以下之（A)〜（E)成分，調製出正型敏輻射線 性樹脂組成物（（1 -1 )〜（1 -1 3 ))。 ® <(A)具有酚性羥基之聚合物（酹醛清漆樹脂）的合成> 合成例1 將m-甲酚、2,3-二甲苯酚、3,4-二甲苯酚以重量比60 :3 0 : 1 0的比率下進行混合，於此加入甲醛水，使用草酸 觸媒將丙二醇單甲基醚作爲反應溶劑，於100°C進行6小 時加熱後，將反應生成物溶解於乳酸乙酯並與水混合，回 收樹脂層後得到重量平均分子量8000之酚醛清漆樹脂。 該樹脂作爲酚醛清漆樹脂A-1。 -24- 200928586 合成例2 將m-甲酚與p-甲酚以重量比5 0 : 50的比率進行混合 ，於此加入甲醛水，使用草酸觸媒，與合成例1同樣下進 行縮合反應並得到重量平均分子量5000的酚醛清漆樹脂 。將該樹脂作爲酚醛清漆樹脂A-2。 <(B)含有醌二疊氮基之化合物> 〇 使用以下之化合物。 B-1 : 4-〔 1- (4-羥基苯基）-1-甲基乙基〕-6- ( 1-甲基-1-苯基乙基）-1，3-苯二醇（參照下述式）1.0莫耳、與萘醌_ 1，2-二疊氮基-5-磺醯基氯化物1.0莫耳之酯化反應生成物 ((股）三寶化學硏究所）， 〔化 1 4〕Pronon204 (made by Japan Oil & Fats Co., Ltd.), Emulgen A-60, A-90, Tongba-500 (King (share) system), 1^-600 (Kyoei Chemical Co., Ltd.) These may be used alone or in combination of two or more. The surfactant (D) is preferably used in an amount of 0.01 to 5 parts by weight, preferably 0.01 to 2 parts by weight, per 100 parts by weight of the polymer (A) having a phenolic hydroxyl group. ❹ < (E) Other components> The positive-type radiation-sensitive linear resin composition of the present invention may contain the following as other components. (Polynuclear Phenol Compound) Although the polynuclear phenol compound is not an essential component in the positive-sensitive radiation linear resin composition of the present invention, it can be used to increase the alkali solubility of the positive-sensitive radiation linear dendritic resin composition. Finely control the shape of the photoresist pattern. The polynuclear phenol compound is a compound having two or more benzene rings independently present and having two or more phenolic hydroxyl groups bonded to a hydroxyl group in one of the benzene rings. Specifically, for example, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]diphenol, 2,2-double (1,5-Dimethyl-4-hydroxyphenyl)propionic acid methyl ester, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-benzene A diol, 1,1-bis(2,5-dimethyl-4-hydroxyphenyl)acetone or the like. When the polynuclear phenol compound is contained in the composition of the positive-type radiation-sensitive linear resin-22-200928586 of the present invention, the polynuclear phenol compound is used in an amount of 5 to 40 parts by weight based on 100 parts by weight of the polymer (A) having a phenolic hydroxyl group. It is preferably used in an amount of from 1 to 3 parts by weight. When it is contained in the above range, the shape of the resist pattern can be precisely controlled. [Method for Forming Photoresist Pattern of the Present Invention] The photoresist pattern forming method of the present invention is characterized by the following steps: (i) the positive-type radiation-sensitive linear resin composition of the present invention is coated by slit coating a step of coating on the surface of the substrate (Π) a step of patternwise exposing the positive-type radiation-sensitive linear resin composition coated on the surface of the substrate by exposure to UV light and/or by drawing of electron lines The step of forming a photoresist pattern by developing a positive-type sensitive radiation linear resin composition through the pattern exposure step. It is desirable to form a photoresist pattern on a large substrate of 100 cm x 100 cm or more. The positive-sensitive radiation linear resin composition must be applied to the surface of the substrate by slit coating. It is difficult to uniformly apply a positive-sensitive radiation linear resin on the surface of a large substrate on a device that is rotated by coating a substrate such as a spin coating to have a safety problem such as throwing a substrate due to the weight of the substrate. Composition. However, the positive-sensitive radiation linear resin composition of the present invention has a specific ratio of the polymer (A) having a phenolic hydroxyl group, the compound (B) containing a quinonediazide group, a solvent (C) and a surfactant as described above. (D), -23- 200928586 is a surfactant (D) containing a polyether-denatured polyoxyalkylene compound on a large substrate of 100 cm x 100 cm or more, so that the so-called "sink marks" can be removed. A specific compound of the quinonediazide compound (B) can form a fine photoresist pattern. [Embodiment] [Embodiment] Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited thereto. Further, unless otherwise specified, parts represent parts by weight, and % means % by weight. [Preparation Example] Modification of positive-type radiation-sensitive linear resin composition Using the following components (A) to (E), a positive-type radiation-sensitive linear resin composition ((1 -1 ) to (1 -1 3 )) was prepared. . ® <(A) Synthesis of a polymer having a phenolic hydroxyl group (furfural varnish resin) > Synthesis Example 1 Weight ratio of m-cresol, 2,3-xylenol, 3,4-xylenol The mixture was mixed at a ratio of 60:3 0 :10, and formaldehyde water was added thereto, and propylene glycol monomethyl ether was used as a reaction solvent using oxalic acid catalyst, and the reaction product was dissolved in lactic acid after heating at 100 ° C for 6 hours. The ethyl ester was mixed with water, and the resin layer was recovered to obtain a novolak resin having a weight average molecular weight of 8,000. This resin was used as the novolak resin A-1. -24- 200928586 Synthesis Example 2 M-cresol and p-cresol were mixed at a weight ratio of 50:50, and formaldehyde water was added thereto, and a condensation reaction was carried out in the same manner as in Synthesis Example 1 using an oxalic acid catalyst. A novolak resin having a weight average molecular weight of 5,000 was obtained. This resin was used as the novolak resin A-2. <(B) Compound containing quinonediazide group> 〇 The following compounds were used. B-1 : 4-[1-(4-hydroxyphenyl)-1-methylethyl]-6-(1-methyl-1-phenylethyl)-1,3-benzenediol (Ref. The following formula) 1.0 molar, and naphthoquinone-1,2-diazido-5-sulfonyl chloride 1.0 molar synthesis product ((S) Sanbao Chemical Research Institute), 1 4]

B-2: 4,6-雙〔1-雙（3-甲基-4-羥基苯基）甲基〕-P-甲酚 (參照下述式）1.0莫耳、與萘醌-1，2-二疊氮基-5-擴醯基 氯化物2.0莫耳之酯化反應生成物（（股）三寶化學硏究 所）， -25- 200928586 〔化 1 5〕 σB-2: 4,6-bis[1-bis(3-methyl-4-hydroxyphenyl)methyl]-P-cresol (refer to the following formula) 1.0 mol, and naphthoquinone-1, 2 -Production of esterification reaction of dimercapto-5-anthracene chloride 2.0 mol ((S) Sanbao Chemical Research Institute), -25- 200928586 [Chem. 1 5] σ

Β-3: 4,6-雙〔1-雙（3-甲基-4-羥基苯基）甲基〕-ρ-甲酚 1.0莫耳、與萘醌-1,2-二疊氮基-5-磺醯基氯化物3.0莫耳 之酯化反應生成物（（股）三寶化學硏究所）， Β-4: 4,6-雙〔1-(4-羥基苯基）-1-甲基乙基〕-1-羥基-3-甲氧基苯（參照下述式）1.0莫耳與萘醌-1，2-二疊氮基-5-磺醯基氯化物2.0莫耳之酯化反應生成物（（股）三寶化 學硏究所），Β-3: 4,6-bis[1-bis(3-methyl-4-hydroxyphenyl)methyl]-ρ-cresol 1.0 mol, and naphthoquinone-1,2-diazide- 5-sulfonyl chloride 3.0 molar synthesis product ((S) Sanbao Chemical Research Institute), Β-4: 4,6-bis[1-(4-hydroxyphenyl)-1-methyl Ethyl ethyl]-1-hydroxy-3-methoxybenzene (refer to the following formula) 1.0 molar and naphthoquinone-1,2-diazide-5-sulfonyl chloride 2.0 molar esterification Reaction product ((S) Sanbao Chemical Research Institute),

B_5: 4,4'-〔 1-〔4-〔 1-(4-羥基苯基）-1-甲基乙基 〕苯基〕亞乙基〕二酚（參照下述式）1.0莫耳、與萘醌-1,2-二疊氮基-5_磺醯基氯化物1.0莫耳之酯化反應生成物 ((股）三寶化學硏究所）。 -26- 200928586 〔化 1 7〕B_5: 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]diphenol (refer to the following formula) 1.0 mol, Esterification reaction product with 1.0 mol of naphthoquinone-1,2-diazido-5-sulfonyl chloride ((S) Sanbao Chemical Research Institute). -26- 200928586 〔化1 7〕

< (C )溶劑> 作爲溶劑（C )亦可使用以下者。 C-1 : 2-羥基丙酸乙酯。 <(D)界面活性劑> 可使用以下者。 D-l : SH8400 ( Dow Corning Tor ay 公司製）聚魅變性聚 矽氧烷， D-2 : KL-270 (共榮公司製）聚醚變性聚矽氧烷， D-3 : KL-24 5 (共榮公司製）聚醚變性聚矽氧烷， D-4: NBX-15 (Neos (股）製）雙甘油EO加成物全氟壬 烯醚。 < (E)其他成分> 可使用以下$ ° -27- 200928586 E-l: 1,1-雙（2,5-二甲基-4-羥基苯基）丙酮。 <正型敏輻射線性樹脂組成物（組成物（1 -1 )〜（1 -13 ) )之調製> (組成物（1-1)之調製） ' 添加78份的酚醛清漆樹脂A-1、6份的含有醌二疊氮 基之化合物B-1、3份的B-3、1 1份的B-4、0.0 1份的界 © 面活性劑D-2、22份的多核酚化合物E-1、260份的C_1 並混合溶解後，使用孔徑Ιμιη之膜濾器進行過濾’調製出 組成物（1 - 1 )。 (組成物（1-2)〜（1-13)之調製） 使用表1所示材料，並與組成物（1 -1 )同樣順序下 調製。 ❹ -28- 200928586 〔表1〕 組成物 (A)具有租性羥基 的聚合物 (B)含有醒二叠氮 基之化合物 (C)溶劑 (D)界面活性》 (Ε)其他成分 1-1 A-1/7B 部 B-1/6 部 B-3/3部 B-4/11 部 C-1/260部 D-2/0. P1 部 Ε-1/22 部 1-2 A-1/78 部 B-1/6部 B-2/3 部 B-4/11 部 C-1/260部 D-2/0. 01S6 Ε-1/22 部 1—3 A-1/78 部 B-1/6 部 B-2/3 部 B-3/3部 C-1/260部 D-2/0. 01 部 Ε-1/22 部 1-4 A-2/78 部 B-1/6部 B-2/3部 B-3/3部 B-4/11 部 C-1/260部 D-2/0. 01 部 Ε-1/22 部 1-5 A-1/7 8 部 B-1/6 部 B-2/3部 B-3/3部 B-4/11 部 C-1/260部 D-2/0. 01 部 Ε-1/22 部 1 一6 A-V78 部 B-1/6 部 B-2/3 部 日一3/3部 B-4/11 部 C-1/260部 D-2/0. 05部 Ε-1/22 部 1—7 A-1/7 8 部 B-1/6 部 日一2/3部 B-3/3 部 B-4/11 部 C-1/260部 D-2/0. 1 部 Ε-1/22 部 1-8 A-1/78 部 B-1/6 部 B-2/3部 B-3/3部 B-4/11 部 C-1/260部 D-3/0. 1 部 Ε-1/22 部 1 一9 A-1/78 部 B-1/6 部 B-2/3部 B-3/3 部 B-4/11 部 C-1/260部 D-1/0. 1 部 Ε-1/22 部 1-10 A-1/78 部 B-1/6 部 B-2/3部 B—3/3部 B-4/11 部 C-1/260部 D-4/0. 01 部 Ε-1/22 部 1-11 A-1/78 部 B-4/11 部 B-5/10 部 C-1/260部 D-2/0. 01 部 Ε-1/22 部 1-12 A-1/78 部 B-1/6 部 B-2/3部 B-3/3部 B-4/1.1 部 C-1/260部 無 E-V22 部 1-13 A-1/7B 部 無 C-1/260部 D-2/0. 01 部 Ε-1/22 部 〔實施例1〜9，比較例1〜4〕 <塗佈性評估1 > 將由調製例所得之正型敏輻射線性樹脂組成物以狹縫 式塗佈於i〇〇cmXl〇0cm玻璃基板進行塗佈’並以加熱板 進行乾燥後，觀察自基板端的塗膜之引縮’並以以下基準 -29- 200928586 進行評估，評估結果以◎、〇、△、X表示。結果如表2所 示。 塗佈性1 ◎:完全未觀察到自基板端的塗膜之引縮。 . 〇：自基板端的塗膜之引縮未達1mm。 △:自基板端的塗膜之引縮爲1mm以上而未達5mm ❿ x:自基板端的塗膜之引縮爲5mm以上。 <塗佈性評估2> 將調製例所得之正型敏輻射線性樹脂組成物以狹縫式 塗佈於 lOOcmxlOOcm玻璃基板進行塗佈，並以加熱板進 行乾燥後，觀察自基板端之5mm位置與中心部之膜厚差 ，並依據以下基準進行評估，評估結果以◎、〇、△、X表 ® 示。結果如表2所示。 塗佈性2 ◎:自基板端的5mm位置與中心部之膜厚差未達±2% 〇 〇：自基板端的5mm位置與中心部之膜厚差爲±2%以 上而未達± 5 %。 △:自基板端的5mm位置與中心部之膜厚差爲±5%以 上而未達±10%。 -30- 200928586 / χ:自基板端的5mm位置與中心部之膜厚差爲±ι〇 %以 上。 <製圖性評估> (光阻塗膜形成） - 將由調製例所得之正型敏輻射線性樹脂組成物於 5 cm X 5 cm之玻璃基上以狹縫式塗佈進行塗佈後，並以加熱 〇 板加熱至1 〇〇°C，經1分鐘烘焙後得到光阻膜。 (曝光、顯像） 以上述要領下所製造的製作的基板中，將塗佈性良好 的基板介著光罩進行曝光後，並以鹼性顯像，實施製圖評 估。評估條件如以下所示。 曝光機：Mask Aligner MA150 ’ ® ( SUSS MicroTec 公司製，Contact eyeliner ) ’ 曝光量：200mJ/cm2 ( 42Onm 附近）， 曝光樣式：硬式接觸曝光， 顯像：2.38質量％四甲基銨氫氧化物水溶液中藉由浸 漬方式進行。且，顯像時間爲進行6 0秒。 (製圖性評估） 對於經曝光、顯像之基板’以光學顯微鏡SEM ’觀察 L/S = 3um/3um圖型之光阻部分，並依據以下基準進行評估 -31 - 200928586 。結果如表2所示。此時的光阻圖型尺寸結果亦如表2所 7f\ ° 製圖性 ◎:完全未觀察到圖型的飛出’光罩尺寸之規格未達 ±10%下可形成圖型。 〇：雖完全未觀察到圖型的飛出，但光罩尺寸之規格 〇 爲±10%以上且±20%以下之尺寸下可形成圖型。 △:圖型的一部分自基板剝落。 X:所有的圖型自基板剝落。 <乾蝕刻耐性> 光阻經乾鈾刻後，將L/S = 3um/3um圖型由光學顯微鏡 進行觀察並依據以下基準進行評估。結果如表2所示。 乾蝕刻耐性 ◎:光阻的剝落完全未觀察到。 © X :觀察到光阻之剝落。 -32- 200928586 〔表2〕<(C) Solvent> The following may be used as the solvent (C). C-1 : ethyl 2-hydroxypropionate. <(D) Surfactant> The following can be used. Dl : SH8400 (made by Dow Corning Tor ay Co., Ltd.) Polyester-denatured polyoxyalkylene, D-2 : KL-270 (made by Kyoritsu Co., Ltd.) Polyether modified polyoxyalkylene, D-3 : KL-24 5 (Total Polyether modified polyoxyalkylene, D-4: NBX-15 (manufactured by Neos) diglycerin EO adduct perfluorodecene ether. <(E) Other ingredients> The following $ ° -27- 200928586 E-l: 1,1-bis(2,5-dimethyl-4-hydroxyphenyl)acetone can be used. <Preparation of positive-sensitive radiation linear resin composition (composition (1 -1 ) to (1 -13 ))> (Preparation of composition (1-1)) 'Addition of 78 parts of novolac resin A- 1, 6 parts of compound B-1 containing quinonediazide group, 3 parts of B-3, 11 parts of B-4, 0.01 part of boundary © surfactant D-2, 22 parts of polynuclear phenol Compound E-1 and 260 parts of C_1 were mixed and dissolved, and then filtered using a membrane filter having a pore size of Ιμηη to prepare a composition (1 - 1 ). (Preparation of Compositions (1-2) to (1-13)) The materials shown in Table 1 were used, and they were prepared in the same order as the composition (1-1). ❹ -28- 200928586 [Table 1] Composition (A) Polymer having a rentable hydroxyl group (B) Compound containing azide-diazide group (C) Solvent (D) interfacial activity (Ε) Other components 1-1 A-1/7B Part B-1/6 Part B-3/3 Part B-4/11 Part C-1/260 Part D-2/0. P1 Part Ε-1/22 Part 1-2 A-1 /78 Part B-1/6 Part B-2/3 Part B-4/11 Part C-1/260 Part D-2/0. 01S6 Ε-1/22 Part 1-3 A-1/78 Part B -1/6 Part B-2/3 Part B-3/3 Part C-1/260 Part D-2/0. 01 Part Ε-1/22 Part 1-4 A-2/78 Part B-1/ 6 parts B-2/3 part B-3/3 part B-4/11 part C-1/260 part D-2/0. 01 part Ε-1/22 part 1-5 A-1/7 8 parts B-1/6 Part B-2/3 Part B-3/3 Part B-4/11 Part C-1/260 Part D-2/0. 01 Part Ε-1/22 Part 1 A 6 A-V78 Part B-1/6 Part B-2/3 Part One Day 3/3 Part B-4/11 Part C-1/260 Part D-2/0. 05 Part Ε-1/22 Part 1-7 A- 1/7 8 Part B-1/6 Part One Day 2/3 Part B-3/3 Part B-4/11 Part C-1/260 Part D-2/0. 1 Part Ε-1/22 Part 1 -8 A-1/78 Part B-1/6 Part B-2/3 Part B-3/3 Part B-4/11 Part C-1/260 Part D-3/0. 1 Part Ε-1/ 22 Part 1-9 A-1/78 Part B-1/6 Part B-2/3 Part B-3/3 Part B-4/11 Part C-1/260 Part D-1/0. 1 Part Ε -1/22 Part 1-10 A-1/78 Part B-1/6 B-2/3 Part B—3/3 Part B-4/11 Part C-1/260 Part D-4/0. 01 Part Ε-1/22 Part 1-11 A-1/78 Part B-4 /11 Part B-5/10 Part C-1/260 Part D-2/0. 01 Part 1/2-1/22 Part 1-12 A-1/78 Part B-1/6 Part B-2/3 B-3/3 Part B-4/1.1 Part C-1/260 Part No E-V22 Part 1-13 A-1/7B Part No C-1/260 Part D-2/0. 01 Part Ε-1 /22 [Examples 1 to 9, Comparative Examples 1 to 4] <Coating property evaluation 1 > The positive-type radiation-sensitive linear resin composition obtained by the preparation example was applied to the slit layer by i〇〇cmXl〇 The coating of the 0 cm glass substrate was carried out and dried by a hot plate, and the shrinkage of the coating film from the substrate end was observed and evaluated by the following reference -29-200928586, and the evaluation results were expressed by ◎, 〇, Δ, and X. The results are shown in Table 2. Coating property 1 ◎: The shrinkage of the coating film from the substrate end was not observed at all. 〇: The shrinkage of the coating film from the substrate end is less than 1 mm. △: The shrinkage of the coating film from the substrate end was 1 mm or more and less than 5 mm. ❿ x: The shrinkage of the coating film from the substrate end was 5 mm or more. <Coating property evaluation 2> The positive-type radiation-sensitive linear resin composition obtained in the preparation example was applied by slit coating on a 100 cm x 100 cm glass substrate, and dried by a hot plate, and then observed at a position of 5 mm from the substrate end. The film thickness difference from the center is evaluated according to the following criteria, and the evaluation results are shown in ◎, 〇, △, and X. The results are shown in Table 2. Coating property 2 ◎: The film thickness difference from the 5 mm position of the substrate end to the center portion was less than ±2%. 〇 〇: The difference in film thickness between the 5 mm position and the center portion from the substrate end was ±2% or more and less than ±5 %. △: The film thickness difference from the 5 mm position of the substrate end to the center portion was ±5% or more and less than ±10%. -30- 200928586 / χ: The film thickness difference from the 5mm position of the substrate end to the center is ± 〇 〇 % or more. <Drawing property evaluation> (Photoresist film formation) - The positive-type radiation-sensitive linear resin composition obtained by the preparation example was applied by slit coating on a glass base of 5 cm X 5 cm, and The film was heated to 1 〇〇 ° C with a heated crucible, and baked for 1 minute to obtain a photoresist film. (Exposure, development) In the substrate produced by the above-described method, a substrate having good applicability was exposed through a photomask, and an image was evaluated by alkaline development. The evaluation conditions are as follows. Exposure machine: Mask Aligner MA150 ' ® (Contact eyeliner, manufactured by SUSS MicroTec) ' Exposure: 200mJ/cm2 (near 42Onm), Exposure style: Hard contact exposure, Development: 2.38 mass% tetramethylammonium hydroxide aqueous solution It is carried out by dipping. Moreover, the development time is 60 seconds. (Drawing evaluation) The resist portion of the L/S = 3 um / 3 um pattern was observed by an optical microscope SEM ' of the exposed and developed substrate, and evaluated according to the following criteria - 31 - 200928586 . The results are shown in Table 2. The results of the photoresist pattern size at this time are also shown in Table 2 for 7f\°. ◎: The flyout of the pattern is not observed at all. The size of the mask size is less than ±10%. 〇: Although the pattern is not observed at all, the size of the mask size 〇 is ±10% or more and ±20% or less. △: A part of the pattern peeled off from the substrate. X: All patterns are peeled off from the substrate. <Dry etching resistance> After the photoresist was engraved with dry uranium, the L/S = 3 um / 3 um pattern was observed by an optical microscope and evaluated according to the following criteria. The results are shown in Table 2. Dry etching resistance ◎: The peeling of the photoresist was not observed at all. © X: Observed peeling of the photoresist. -32- 200928586 [Table 2]

實施例 組成物 塗佈性評估 製圖性 乾蝕刻耐性 塗佈性1 塗佈性2 圖型尺寸 實施例1 1 一1 ◎ ◎ 〇 ◎ 2. 5um 實施例2 1-2 ◎ ◎ 〇 ◎ 2. 6um 實施例3 1-3 ◎ ◎ ◎ ◎ 2. 9um 實施例4 1-4 ◎ ◎ ◎ ◎ 3. Oum 實施例5 1-5 ◎ ◎ ◎ ◎ 3. Oum 實施例6 1 一6 ◎ 〇 ◎ ◎ 3. lum 實施例7 1 一7 ◎ 〇 ◎ ◎ 3. Oum 實施例8 1-8 ◎ ◎ ◎ ◎ 2. 9um 實施例9 1-9 〇 〇 ◎ ◎ 2. 9um 比較例1 1-10 △ Δ ◎ ◎ 2. 8um 比較例2 1-11 ◎ ◎ X 一 未觀察到 比較例3 1 一 12 X X — 一 — 比較例4 1-13 ◎ ◎ X 一 未觀察到 -33-EXAMPLES Composition Coating Evaluation Evaluation Drawing Dry Etching Resistance Coating Property 1 Coating Property 2 Drawing Size Example 1 1 - 1 ◎ ◎ 〇 ◎ 2. 5 um Example 2 1-2 ◎ ◎ 〇 ◎ 2. 6 um Example 3 1-3 ◎ ◎ ◎ 2. 9 um Example 4 1-4 ◎ ◎ ◎ 3. Oum Example 5 1-5 ◎ ◎ ◎ ◎ 3. Oum Example 6 1 - 6 ◎ 〇 ◎ ◎ 3 Lum Example 7 1-7 ◎ 〇 ◎ 3. Oum Example 8 1-8 ◎ ◎ ◎ ◎ 2. 9 um Example 9 1-9 〇〇 ◎ ◎ 2. 9 um Comparative Example 1 1-10 Δ Δ ◎ ◎ 2. 8um Comparative Example 2 1-11 ◎ ◎ X I did not observe Comparative Example 3 1 - 12 XX - I - Comparative Example 4 1-13 ◎ ◎ X I did not observe -33-

Claims (1)

200928586 十、申請專利範圍 ~種正型敏輻射線性樹脂組成物，其爲含有 (A) 具有酚性羥基之聚合物100重量份、 (B) 含有醌二疊氮基之化合物1〇〜5〇重量份、 (C) 對於該具有酚性羥基之聚合物（a)及該含有醌 二疊氮基之化合物（B)之合計100重量份而言爲1〇〇〜 9 9 0 0重量份的溶劑、與 O (D)界面活性劑〇.〇1〜5重量份者，其特徵爲 作爲該含有醌二疊氮基之化合物（B)含有下述一般 式（I )所示化合物a， 作爲該界面活性劑（D )含有聚醚變性聚矽氧烷化合 物，並使用於 狹縫式塗佈者； 〔化1〕200928586 X. Patent Application Scope - A positive-type radiation-sensitive linear resin composition containing 100 parts by weight of (A) a polymer having a phenolic hydroxyl group, and (B) a compound containing quinonediazide group 1〇~5〇 The parts by weight, (C) is from 1 to 990 parts by weight based on 100 parts by weight of the total of the phenolic hydroxyl group-containing polymer (a) and the quinonediazide group-containing compound (B). The solvent and the O (D) surfactant 〇1 to 5 parts by weight are characterized in that the compound (B) containing the quinonediazide group contains the compound a of the following general formula (I) as The surfactant (D) contains a polyether-denatured polyoxyalkylene compound and is used in a slit coater; (上述一般式（I)中，R1、R2、R3各獨立爲氫原子或下 述式（III)所示基，R1、R2、R3不會全爲氫） -34- (III) 200928586 〔化2〕(In the above general formula (I), R1, R2 and R3 are each independently a hydrogen atom or a group represented by the following formula (III), and R1, R2 and R3 are not all hydrogen) -34- (III) 200928586 2〕 2 .如申請專利範圍第1項之正型敏輻射線性樹脂組 成物，其中作爲該含有醌二疊氮基之化合物（B)，進一 步含有下述一般式（II)所示化合物b;2. The positive-type radiation-sensitive linear resin composition of claim 1, wherein the quinonediazide-containing compound (B) further contains the compound b of the following general formula (II); OR8OR8 OR7 (Π)OR7 (Π) OR5 OR4 (上述一般式（II)中，R4、R5、R6、R7、R8各獨立爲氫 原子或下述式（ΠΙ )所示基，R4、R5、R6、R7、R8不會 全爲氫） -35- (III) 200928586OR5 OR4 (In the above general formula (II), R4, R5, R6, R7 and R8 are each independently a hydrogen atom or a group represented by the following formula (ΠΙ), and R4, R5, R6, R7 and R8 are not all hydrogen. ) -35- (III) 200928586 3 ·如申請專利範圍第2項之正型敏輻射線性樹脂組 ® 成物，其中該化合物a與該化合物b之重量比（化合物a/ 化合物b)爲3/1〜1/3。 4·如申請專利範圍第2項或第3項之正型敏輻射線 性樹脂組成物’其中對於該含有醌二疊氮基之化合物（B )100重量份而言，含有合計30〜1〇〇重量份之該化合物 a與該化合物b。 5. —種光阻圖型的形成方法，其特徵爲含有 (i)將如申請專利範圍第1項至第4項中任一項之 @ 正型敏輻射線性樹脂組成物於基板表面藉由狹縫式塗佈進 行塗佈之步驟、 (Π )將塗佈於該基板表面之正型敏輻射線性樹脂組 成物，藉由以UV光之曝光及/或以電子線之描繪進行圖型 曝光的步驟、與 (iii )藉由將經由該圖型曝光步驟之正型敏輻射線性 樹脂組成物進行顯像而形成光阻圖型之步驟。 -36- 200928586 無 明 說 單 ί簡 無乾 :键 為符 圖件 表元 代之 定圖 指表 :案代 圖本本 表' ' 代 定一二 指c C 七 e 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無 ❹ -3-3. The positive-type radiation-sensitive linear resin group of claim 2, wherein the weight ratio of the compound a to the compound b (compound a/compound b) is 3/1 to 1/3. 4. The positive-type radiation-sensitive linear resin composition of claim 2 or 3, wherein 100 parts by weight of the compound (B) containing the quinonediazide group is 30 to 1 合 in total The compound a and the compound b are parts by weight. 5. A method for forming a photoresist pattern, characterized by comprising (i) a positive-polarizing radiation linear resin composition of any one of items 1 to 4 of the patent application scope on a substrate surface a method of coating by slit coating, (Π) a positive-type radiation-sensitive linear resin composition coated on the surface of the substrate, and performing pattern exposure by exposure to UV light and/or by electron line drawing And the step of (iii) forming a photoresist pattern by developing a positive-sensitive radiation linear resin composition through the pattern exposure step. -36- 200928586 无明说单 简 无 无 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : Please reveal the chemical formula that best shows the characteristics of the invention: no ❹ -3-
TW097137031A 2007-11-29 2008-09-26 Positive type radiation sensitive resin compound TW200928586A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007308933 2007-11-29
JP2008155421A JP2009151266A (en) 2007-11-29 2008-06-13 Positive radiation-sensitive resin composition

Publications (1)

Publication Number Publication Date
TW200928586A true TW200928586A (en) 2009-07-01

Family

ID=40920432

Family Applications (1)

Application Number Title Priority Date Filing Date
TW097137031A TW200928586A (en) 2007-11-29 2008-09-26 Positive type radiation sensitive resin compound

Country Status (3)

Country Link
JP (1) JP2009151266A (en)
KR (1) KR20090056895A (en)
TW (1) TW200928586A (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5924760B2 (en) * 2011-12-06 2016-05-25 東京応化工業株式会社 Method for producing resist for spinless coating
JP6186766B2 (en) * 2012-03-30 2017-08-30 東レ株式会社 Photosensitive siloxane composition, cured film formed therefrom, and device having the cured film
TWI490653B (en) * 2013-09-10 2015-07-01 Chi Mei Corp Positive photosensitive resin composition and method for forming patterns by using the same

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3632420B2 (en) * 1997-12-26 2005-03-23 Ｊｓｒ株式会社 Positive resist composition
KR100973799B1 (en) * 2003-01-03 2010-08-03 삼성전자주식회사 Photoresist composition for multi-micro nozzle head coater
JP4152852B2 (en) * 2003-09-30 2008-09-17 東京応化工業株式会社 POSITIVE PHOTORESIST COMPOSITION FOR DISCHARGE NOZZLE TYPE COATING METHOD AND METHOD FOR FORMING RESIST PATTERN
JP4121925B2 (en) * 2003-09-30 2008-07-23 東京応化工業株式会社 Positive photoresist composition
JP4545553B2 (en) * 2004-03-12 2010-09-15 東京応化工業株式会社 Non-spin coating positive photoresist composition and resist pattern forming method
JP2005284114A (en) * 2004-03-30 2005-10-13 Nippon Zeon Co Ltd Radiation sensitive resin composition for spinless slit coat and use thereof
JP4655864B2 (en) * 2004-10-14 2011-03-23 住友化学株式会社 Radiation sensitive resin composition
KR101112545B1 (en) * 2004-12-16 2012-03-13 스미또모 가가꾸 가부시끼가이샤 Photosensitive resin and thin film panel comprising pattern made of the photosensitive resin and method for manufacturing the thin film panel
JP4553140B2 (en) * 2005-12-13 2010-09-29 信越化学工業株式会社 Positive photoresist composition

Also Published As

Publication number Publication date
KR20090056895A (en) 2009-06-03
JP2009151266A (en) 2009-07-09

Similar Documents

Publication Publication Date Title
US20040197704A1 (en) Photoresist compositions
JP2010039237A (en) Resin composition for photoresist
TWI518117B (en) Resin composition of photoresist
JP5407563B2 (en) Positive radiation sensitive resin composition
US6905809B2 (en) Photoresist compositions
TW200306324A (en) Novolak resin solution, positive photoresist composition, and method of producing same
JP2011063667A (en) Novolac phenol resin and resin composition for photoresist
TW200928586A (en) Positive type radiation sensitive resin compound
JP4209297B2 (en) POSITIVE PHOTORESIST COMPOSITION FOR DISCHARGE NOZZLE TYPE COATING METHOD AND METHOD FOR FORMING RESIST PATTERN
TW200307013A (en) Novolak resin mixtures and photosensitive compositions comprising the same
JP6140506B2 (en) Positive resist composition and resist pattern forming method
JP3324898B2 (en) Manufacturing method of positive resist pattern
JP5720157B2 (en) Resin composition for photoresist
JP2009075510A (en) Photoresist resin composition
TWI557158B (en) Photoresist resin composition
JP3844236B2 (en) Photosensitive resin composition containing photosensitive resin composition coatability improver
TWI546323B (en) Novolac type phenolic resin, photoresist composition and manufacturing method of liquid crystal device
JP4405293B2 (en) POSITIVE PHOTORESIST COMPOSITION FOR DISCHARGE NOZZLE TYPE COATING METHOD AND METHOD FOR FORMING RESIST PATTERN
JP5189909B2 (en) Positive resist composition for lift-off
JP3635598B2 (en) Positive photoresist composition
JP4661064B2 (en) Method for producing phenolic resin for photoresist and photoresist composition
JP2005097331A (en) Production method of phenol resin for photoresist, and photoresist composition
JP3452206B2 (en) Positive radiation-sensitive resin composition
JP4112416B2 (en) POSITIVE PHOTORESIST COMPOSITION FOR DISCHARGE NOZZLE TYPE COATING METHOD AND METHOD FOR FORMING RESIST PATTERN
JP2005284115A (en) Radiation sensitive resin composition for slit spin coat and its usage