TW200921277A - Radiation-sensitive resin composition - Google Patents
Radiation-sensitive resin composition Download PDFInfo
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- TW200921277A TW200921277A TW097130626A TW97130626A TW200921277A TW 200921277 A TW200921277 A TW 200921277A TW 097130626 A TW097130626 A TW 097130626A TW 97130626 A TW97130626 A TW 97130626A TW 200921277 A TW200921277 A TW 200921277A
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- 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
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
- C07D215/54—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3
- C07D215/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen attached in position 3 with oxygen atoms in position 4
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
- C07D237/04—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having less than three double bonds between ring members or between ring members and non-ring members
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/08—Bridged systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
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- 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
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- 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
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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- 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
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- 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
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- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
200921277 九、發明說明: 【發明所屬之技術領域】 本發明係有關感放射線性樹脂(rad i at i on-sen si ΐ ive resin)組成物。 【先前技術】200921277 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a composition of a radiation sensitive resin (rad i at i on- sen ive ive resin). [Prior Art]
在TFT-LCD液晶顯示裝置中多數利用之方式係TNMost of the methods used in TFT-LCD liquid crystal display devices are TN
(Twisted Nematic,扭轉向列)型 LCD。然而,TN 型 LCD 係有視角狹窄之大問題。為了解決如此之問題,而正在開 發 Multi-Domain Vertical Alignment 多域垂直定向,以 下簡寫為MVA)型LCD(垂直定向型液晶顯示器)。 已知此MVA型LCD中係於像素電極及共通電極上形成 切除圖案或突起,藉此使液晶分子之傾斜方向分散成複數 個,而可製造視角、對比度等優良,且也可不進行用以使 液晶定向之摩擦處理等而在製造過程之方面亦優良之 LCD。 s 此突起之形成一般係使用為硬化樹脂圖案之可見光穿 透率高之樹脂的感放射線性樹脂組成物,而組成物中所含 之感光劑提案如:下_化合物之—部之盼性絲經醒二 疊氮基磺酸所酯化之化合物的組成物(例如:參照專利文獻 1)。(Twisted Nematic, twisted nematic) type LCD. However, the TN type LCD has a problem of narrow viewing angle. In order to solve such a problem, a Multi-Domain Vertical Alignment multi-domain vertical orientation, which is abbreviated as an MVA type LCD (vertical directional liquid crystal display), is being developed. It is known that in the MVA type LCD, a cut-off pattern or a protrusion is formed on the pixel electrode and the common electrode, whereby the oblique direction of the liquid crystal molecules is dispersed into a plurality of pieces, and the viewing angle, the contrast, and the like can be manufactured excellently, and may not be used to make An LCD which is excellent in the manufacturing process, such as a rubbing treatment of liquid crystal orientation, and the like. s The formation of the protrusions is generally a radiation-sensitive resin composition using a resin having a high visible light transmittance of the cured resin pattern, and the sensitizer contained in the composition is proposed as follows: A composition of a compound esterified with a acenaphthylsulfonic acid (for example, refer to Patent Document 1).
320525 6 200921277 S-方面,在LCD中,為了將2片對向基板之間隔維 持於-定,-般係使用由使用同樣之感放射線性樹脂組成 物所形成之光阻式間隔件(ph〇t〇Spacer),來取代以往所使 用之小珠間隔件(bead spacei*)。 [專利文獻1]日本特開2004—333963號公報實施m 至4 【發明内容】 為了進一步提高在形成前述垂直定向型液晶顯示元件 用之突起或光阻式間隔件等之硬化樹脂圖案時之生產效 率’而對於所使用之感放射線性樹脂組成物,尋求進一步 之南感度化。 此外’為了進—步提高在形成前述垂直定向型液晶顯 不兀件用之突起或光阻式間隔件等之硬化樹脂圖案時之生 產终而尋求能顯示高膜殘留率(曝光、顯影後之未曝光 膜Ϊ減少量少)且較為高感度者,做為所使用之感放 射線性柄' 爿曰組成物。 本^明之目的在於提供:可賦予在可見光區具有高穿 透化樹脂圖案,且感度高的 w 本發明之目的在於提供:顯示高膜殘留率,且 感度尚之感放射線性樹脂組成物。 本發明人等為了找出可' S出1 %決上述問 脂組成物,經反覆研究後 I⑽射綠㈣ 南],即現’使用某種構造之感光 片J即可形成對於放射線之感声古日叮曰,. 硬化樹脂圖案。此外,見光之穿透率高的 糟由與和前述感光劑不同之另一種 320525 7 200921277 感ί劑組ί使用,即可形成對於放射線之感度高、可見光 牙透率同、且做為永久膜為優良之硬化樹脂圖案。 換言之’本發明係提供下述[丨]至[9 ]者。 [1 ] 一種感放射線性樹脂組成物,係含有:包.含衍生自不 餘和致酸之構成單元(al)及衍生自4有環狀醚基與碳 =炭不飽和鍵之化合物(惟,與不飽和羧酸不同)之構成 單^ (a2)之共聚物(a)、與醌二疊氮基續酸酯化合物(b) 的感放射線性樹脂組成物,其中,醌二疊氮基石黃酸醋 化合物(B)係在式(1)所示之酚化合物中,其一部分或 全部之酚性羥基經醌二疊氮基磺酸所酯化之化合物7 :320525 6 200921277 S-side, in the LCD, in order to maintain the interval between the two opposing substrates, a photoresist spacer formed by using the same radiation-sensitive resin composition is used. t〇Spacer), replacing the bead spacei* used in the past. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2004-333963. The present invention is directed to the production of a hardened resin pattern such as a projection for a vertical alignment type liquid crystal display device or a photoresist spacer. Efficiency' while seeking further south sensitivity for the radiation sensitive resin composition used. In addition, in order to further improve the production of the hardened resin pattern such as the protrusions for the vertical alignment type liquid crystal display or the photoresist spacer, it is sought to exhibit a high film residual ratio (exposure and development). If the amount of unexposed film defects is small, and the sensitivity is high, it is used as the radiation-sensitive handle 爿曰 composition. The purpose of the present invention is to provide a high-permeability resin pattern in the visible light region and to have a high sensitivity. The object of the present invention is to provide a radiation-sensitive resin composition which exhibits a high film residual ratio and is sensitive. In order to find out that the above-mentioned lipid composition can be determined by the inventors, I(10) shoots green (four) south after repeated research, that is, the photosensitive sheet J of a certain structure can be used to form a sense of radiation for the radiation. Sundial,. Hardened resin pattern. In addition, the high transmittance of light is used in combination with another 320525 7 200921277 sensitizer group which is different from the aforementioned sensitizer, so that the sensitivity to radiation is high, the visible tooth transmittance is the same, and it is permanent. The film is an excellent hardened resin pattern. In other words, the present invention provides the following [丨] to [9]. [1] A radiation sensitive resin composition comprising: a package comprising a derivatized and acid-forming constituent unit (al) and a compound derived from 4 having a cyclic ether group and a carbon = carbon unsaturated bond (only a radiation-sensitive resin composition of the copolymer (a) and the quinonediazide acrylate compound (b), which is different from the unsaturated carboxylic acid, wherein the quinonediazide-based stone The oleic acid vinegar compound (B) is a compound of the formula (1) in which a part or all of the phenolic hydroxyl group is esterified with quinonediazidesulfonic acid;
[式(1)中,R1至R12分別獨立地表示氫原子、齒素原子、 羥基、碳數1至1G之烷基、碳數3至1〇之環烷基、 石反數2至4之烯基、碳數1至10之院氧基或苯基(可 經奴數1至4之烷基、齒素原子/碳數丨至彳之烷氧 基取代),或表示在R1至R5及!^至中之兩個取代基 間可形成環之構造;惟,1^至卞8至Rlz之中,至 少一個表示經基]。 [] 種感放射線性樹脂組成物,係含有:包含衍生自不 飽。和羧酸之構成單元(al)及衍生自具有環狀醚基與碳 反不飽和鍵之化合物(惟,與不餘和叛酸不同)之構成 320525 8 200921277 單兀(a 2 )之共聚物(A )、與酚化合物之醌二疊氮基磺酸 酯化合物(B)的感放射線性樹脂組成物,其中,該酚化 合物係含有式⑴所示之齡化合物與式(2)所示^化 ,物’且為該酚化合物之一部分或全部之羥基經醌二 登氮基磺酸所酯化之化合物:[In the formula (1), R1 to R12 each independently represent a hydrogen atom, a dentate atom, a hydroxyl group, an alkyl group having 1 to 1 G carbon atoms, a cycloalkyl group having 3 to 1 carbon number, and an inverse number of 2 to 4; An alkenyl group, an alkoxy group having from 1 to 10 carbon atoms or a phenyl group (which may be substituted by an alkyl group of 1 to 4, a dentate atom/carbon number to an alkoxy group), or represented by R1 to R5 and ! The structure of the ring can be formed between the two substituents in the middle; however, at least one of 1^ to 卞8 to Rlz represents a meridine. [] A radiation-sensitive linear resin composition containing: derived from insufficient. And the constituent unit of the carboxylic acid (al) and the compound derived from the compound having a cyclic ether group and a carbon counter-unsaturated bond (except that it is different from the tickic acid) 320525 8 200921277 Copolymer of the monoterpene (a 2 ) (A), a radiation-sensitive resin composition of the quinone diazide sulfonate compound (B) of the phenol compound, wherein the phenol compound contains the compound of the formula represented by the formula (1) and the formula (2) And a compound which is a part or all of a hydroxyl group of the phenolic compound esterified with adenyl disulfonic acid:
R9 R1 R1 (1) U⑴中別獨立地表示氫原子 ㈣、碳數之規基、碳數3至1〇=^、 石反數2至4之烯基、.碳數2至4之俨&甘 衣、元土 碳數1至4之炫基、齒素原子、石炭=土或苯基(可經 取代)1,在苯環之碳原子上所分士 4之院氧基R9 R1 R1 (1) U(1) independently represents a hydrogen atom (4), a carbon number group, a carbon number of 3 to 1 〇 = ^, a stone inverse number of 2 to 4 alkenyl groups, and a carbon number of 2 to 4 Å &; Ganyi, the metacluster of the carbon number of 1 to 4, dentate atom, charcoal = soil or phenyl (may be substituted) 1, on the carbon atom of the benzene ring
R8至R12之間可形成碳數3至10之夕” m5、 至R12之中,至少一個表示經基] 且R至R、RBetween R8 and R12, a carbon number of 3 to 10 may be formed. "M5, to R12, at least one represents a trans group" and R to R, R
[式(2)中,Z1至Z9分別獨立地 基、氫原子或經基;惟,Z1 $ 79 二&素取代之烧 之中,至少兩個表示 320525 9 200921277 經基; R至R分別獨立地表示氳原子、鹵素原子、碳數1 至10之烧基、碳數3至1.0之環烧基、碳數2至4之 烯基、碳數3至6之烷氧基或苯基,或在兩個取代基 間可形成碳數3至10之環;前述苯基可經碳數丨至4 之院基、i素原子、碳數1至4之烧氧基取代]。 [3 ]如.[2 ]之感放射線性樹脂組成物,其中,式(1)所示之· 酚化合物之醌二疊氮基磺酸酯化合物(B1)與式(2)所 不之酚化合物之醌二疊氮基磺酸酯化合物(B2)之質量 比係在(bi)/(B2) = 1/1至3/1之範圍。 [4] 如[1]或[2]之感放射線性樹脂組成物,其中,在式(1) 中,R2、R8、R9及Rlfl係羥基。 [5] 如[1]至[4]中任一項之感放射線性樹脂組成物,其 中,具有環狀醚基與碳_碳不飽和鍵之化合物係如式(?) 所示之化合物: Q1 \ y ~Y—A—E (7) [式(7)中,Q1表示氫原子或甲基,· Y表示,氧基或亞,基氧基(methylene0Xy); 2不早鍵、或碳原子可經氧原子 之伸烷基; 主 £表示式⑻至⑽之任—者料之魏縣: 320525 10 200921277[In the formula (2), Z1 to Z9 are each independently a base, a hydrogen atom or a meridine; however, among Z1 $79 di- & prime, at least two represent 320525 9 200921277 per unit; R to R are independent Is a halogen atom, a halogen atom, a carbon number of 1 to 10, a cycloalkyl group having a carbon number of 3 to 1.0, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 3 to 6 carbon atoms or a phenyl group, or A ring having a carbon number of 3 to 10 may be formed between the two substituents; the phenyl group may be substituted with a carbon number of 院 to 4, an atom of an atom, and an alkoxy group having 1 to 4 carbon atoms]. [3] The radiation-sensitive linear resin composition of [2], wherein the quinone diazide sulfonate compound (B1) of the phenol compound represented by the formula (1) and the phenol of the formula (2) The mass ratio of the compound quinonediazide sulfonate compound (B2) is in the range of (bi) / (B2) = 1/1 to 3/1. [4] The radiation sensitive resin composition according to [1] or [2], wherein, in the formula (1), R2, R8, R9 and Rlf1 are a hydroxyl group. [5] The radiation sensitive resin composition according to any one of [1] to [4] wherein the compound having a cyclic ether group and a carbon-carbon unsaturated bond is a compound represented by the formula (?): Q1 \ y ~Y-A-E (7) [In the formula (7), Q1 represents a hydrogen atom or a methyl group, Y represents an oxy group or a benzyl group (methylene0Xy); 2 does not bond early, or carbon The atom can be extended to the alkyl group through the oxygen atom; the main £ represents the formula (8) to (10) - the material of Wei County: 320525 10 200921277
式⑻至(1G)中’ Q至分別獨立地表示氫原子或碳 數1至6之烴基;n分別獨立地表示0至4之整 數;惟,^及η之任—者不為〇 ;此外,QID至Q14中, 兩個基可鍵結而形成碳數3至1〇之環]。 [6 ]如[1 ]至[5 ]中任一項之感放射線性樹脂組成物,其 中,共聚物(A)之含量係相對於感放射線性樹脂組成物 之固形份,以質量分率計為60至g 5質量%。 [7 ]如[1 ]至[6 ]中任一項之感放射線性樹脂組成物,其 中,紛化合物之醌二豐氮基;5黃酸醋化合物(B)之含量係 相對於感放射線性樹脂組成物之固形份,以質量分率 計為5至40質量% 。 [8 ]如[1 ]至[7 ]中任一項之感放射線性樹脂組成物,其係 用以同時形成垂直定向型液晶顯示元件用之突起及光 阻式間隔件。 [9 ] 一種硬化樹脂圖案之製造方法,係於基板上塗布[工] 至[8 ]中任一項之感放射線性樹脂組成物,並隔著光罩 照射放射線後,顯影而形成預定圖案,接著再進行加 11 320525 200921277 熱。 根據本發明,可提供 樹脂圖案,且感 成了見先穿透率向之硬化 ^I^ 斤又鬲的感放射線性樹脂組成物。 且所开射線性樹脂組成物係由於感光度高,而 圖案在可見光區之穿透率高,並且解 侍之硬化樹脂圖案之形狀也良好,故適人用 於用以形成垂亩中a利+ 现週口用 元件用之、用^同吟形成垂直定向型液晶顯示 :之一且式間隔件,因此,本發明在工業上極 此外’根據本發明, 妓^ 度高之感放射線性樹脂組成物:、.…膜殘留率,且感 曝光本歧輯性樹额絲係由於感度高,而且 化樹腊圖案之形狀亦良好,故適合=二 型液晶顧+ -从 川趴用以开ν成垂直疋向 於用以同=:ΐ起或光蝴 式間隔件,因此i^向型液晶顯示元件用之突起及光阻 【實㈣^此,本發明似業上極為有用。 型液放射線性樹脂組成物係用以形成垂直定向 組成物,且為"1厂用之突起及/或間隔件的感放射線性樹脂 及衍生自有:包含衍生自不飽和羧酸之構成單元㈤) 不飽狀喊與碳—碳不餘和鍵之化合物(惟,與 文不同)之構成單元⑽之共聚物⑴、與酿二疊 320525 12 200921277 氮基磺酸酯化合物(B)的感放射線性樹脂組成物,其中,醒 二疊氮基磺酸酯化合物(B)係在式(1)所示之盼化合物中, 其一部分或全部之#性羥基經醌二疊氮基磺酸所§|化之化 合物。 此外,用以形成垂直定向型液晶顯示元件用之突起及 /或間隔件的本發明之感放射線性樹脂組成物,係含有: 包含衍生自不飽和羧酸之構成單元(al)及衍生自具有環狀 醚基與碳-碳不飽和鍵之化合物(惟,與不飽和缓酸不同) 之構成單元(a2)之共聚物(A)、與酚化合物之醌二疊氮基石碁 酸酯化合物(B)的感放射線性樹脂組成物,其中,該齡化合 物係含有式(1)所示之紛化合物與式(2 )所示之紛化合物, 且為該酚化合物之一部分或全部之羥基經醌二疊氮基磺酸 所酯化之化合物。In the formulae (8) to (1G), 'Q to independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms; n each independently represents an integer of 0 to 4; however, any of ^ and η is not 〇; In QID to Q14, two groups may be bonded to form a ring having a carbon number of 3 to 1 Å]. [6] The radiation sensitive resin composition according to any one of [1] to [5] wherein the content of the copolymer (A) is relative to the solid content of the radiation sensitive resin composition, by mass fraction It is 60 to g 5 mass%. [7] The radiation-sensitive resin composition according to any one of [1] to [6], wherein the compound is a ruthenium-nitrogen group; and the content of the yellow vinegar compound (B) is relative to the radiation-induced linearity. The solid content of the resin composition is 5 to 40% by mass in terms of mass fraction. [8] The radiation sensitive resin composition according to any one of [1] to [7], which is for simultaneously forming a protrusion for a vertical alignment type liquid crystal display element and a resistive spacer. [9] A method for producing a cured resin pattern, comprising applying a radiation-sensitive resin composition of any one of [A] to [8] on a substrate, irradiating radiation through a photomask, and developing to form a predetermined pattern. Then add 11 320525 200921277 heat. According to the present invention, a resin pattern can be provided, and a radiation-sensitive resin composition in which the penetration rate is hardened first is obtained. Moreover, since the radiant resin composition is high in sensitivity, the transmittance of the pattern in the visible light region is high, and the shape of the hardened resin pattern which is released is also good, so that it is suitable for forming a sage in the stalk + now A vertical alignment type liquid crystal display is formed by using a component for a peripheral port, and a spacer is used. Therefore, the present invention is industrially extremely different. According to the present invention, the radiation-sensitive resin composition having a high degree of susceptibility is high. :,.... Membrane residual rate, and the exposure of the fascinating tree frontal silk is high in sensitivity, and the shape of the tree wax pattern is also good, so it is suitable for = 2 type LCD Gu + - from Chuanxiong to open ν The vertical direction is used for the same =: pick-up or light-blind spacer, so that the protrusion and the photoresist for the i-type liquid crystal display element are practically useful. The liquid radiation linear resin composition is used to form a vertically oriented composition, and is a radiation sensitive resin of the protrusions and/or spacers used in the factory, and is derived from: a constituent unit derived from an unsaturated carboxylic acid. (5) The sensation of the copolymer (1) of the constituent unit (10) of the compound (10) which is not saturated with the carbon-carbon and the bond (only different from the text), and the feeling of the nitrogen-based sulfonate compound (B) a radiation-linear resin composition, wherein the awake diazido sulfonate compound (B) is in the desired compound represented by the formula (1), and a part or all of the hydroxy group of the quinone diazide sulfonic acid §|Chemical compounds. Further, the radiation sensitive resin composition of the present invention for forming protrusions and/or spacers for a vertical alignment type liquid crystal display element comprises: a constituent unit (al) derived from an unsaturated carboxylic acid and derived from a copolymer (A) of a constituent unit (a2) having a cyclic ether group and a carbon-carbon unsaturated bond (unless, different from an unsaturated buffer acid), and a quinone diazide phthalocyanate compound of a phenol compound ( The radiation-sensitive resin composition of B), wherein the compound of the formula contains a compound represented by the formula (1) and a compound represented by the formula (2), and is a part or all of a hydroxyl group of the phenol compound. A compound esterified with a diazide sulfonic acid.
基、碳數1至10之烷基、碳數3至1〇之環烷基、碳數2 至4之烯基、碳數2至4之烷氧基或苯基(可經碳數1至4 之烷基、鹵素原子、碳數1至4之烷氧基取代);惟,在苯 環之碳原子上所分別結合之R1至R5、V至f2之間可形成 碳數3至10之環,且R1至R5、!^至R12之中,至少一個表 示經基] 320525 13 200921277a group, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 1 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkoxy group having 2 to 4 carbon atoms or a phenyl group (having a carbon number of 1 to 4 alkyl, halogen atom, alkoxy group having 1 to 4 carbon atoms); however, a carbon number of 3 to 10 may be formed between R1 to R5 and V to f2 respectively bonded to the carbon atom of the benzene ring. Ring, and R1 to R5,! ^ to R12, at least one of which represents the basis of the base] 320525 13 200921277
S 3 4 R1R1 [式(2)中,Z1至Z9分別獨立地表示可經齒素取代之烷基、 氫3原子或羥基;惟,f至Z9之中,至少兩個表示羥基^ R至R18分別獨立地表示氫原子、鹵素原子、碳數1至 之烧基、碳數3至10之環烧基、碳數2至4之稀基、碳數 3至6之烷氧基或苯基,或在兩個取代基間可形成碳數3 至10之環;前述苯基可經碳數1至4之烷基、齒素原子、 碳數1至4之烷氧基取代]。 本發明中之共聚物(Α)係包含衍生自不飽和羧酸之構 成單元(al)及衍生自具有環狀醚基與碳-碳不飽和鍵之不 飽和化合物(惟’與不飽和羧酸不同)之構成單元U2)的高 分子化合物。 衍生出構成單元(al)之不飽和羧酸可舉例如:如不飽 和單羧酸、不飽和二羧酸等在分子中具有丨個或2個以上 之羧基之不飽和羧酸等,具體而言可舉例如:丙烯酸、甲 基丙烯酸、巴豆酸、伊康酸(丨tac〇nic acid)、馬來酸、富 馬酸、檸康酸(citraconic acid)、中康酸(mesaconic acid)、乙烯基苯甲酸等。 具有環狀醚基與碳-碳不飽和鍵之不飽和化合物(惟, 14 320525 200921277 除了不飽和幾酸以外)可S 3 4 R1R1 [In the formula (2), Z1 to Z9 each independently represent an alkyl group which may be substituted by dentate, a hydrogen atom of 3 or a hydroxyl group; however, at least two of f to Z9 represent a hydroxy group R to R18 Each independently represents a hydrogen atom, a halogen atom, a carbon number of 1 to an alkyl group, a cycloalkyl group having 3 to 10 carbon atoms, a dilute group having 2 to 4 carbon atoms, an alkoxy group having 3 to 6 carbon atoms, or a phenyl group. Or a ring having a carbon number of 3 to 10 may be formed between the two substituents; the aforementioned phenyl group may be substituted by an alkyl group having 1 to 4 carbon atoms, a dentin atom, and an alkoxy group having 1 to 4 carbon atoms]. The copolymer (Α) in the present invention comprises a constituent unit (al) derived from an unsaturated carboxylic acid and an unsaturated compound derived from a cyclic ether group and a carbon-carbon unsaturated bond (only 'with an unsaturated carboxylic acid The polymer compound of the constituent unit U2). The unsaturated carboxylic acid in which the structural unit (al) is derived may, for example, be an unsaturated carboxylic acid having one or two or more carboxyl groups in the molecule, such as an unsaturated monocarboxylic acid or an unsaturated dicarboxylic acid. For example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid (丨tac〇nic acid), maleic acid, fumaric acid, citraconic acid, mesaconic acid, ethylene Benzoic acid and the like. An unsaturated compound having a cyclic ether group and a carbon-carbon unsaturated bond (only, 14 320525 200921277, in addition to an unsaturated acid)
—y—a—e 舉例如式(7)所示之單體 [式(7)中,Q表示氫原子或甲矣. Y表示羰氧基或亞甲基氧基; A表不單鍵、或碳原子可經氧 之碳數1至12之伸烷基;、代且也可包含羰基碳 E表 不 式(8)至(1〇)之任—y—a—e is exemplified by a monomer represented by the formula (7). In the formula (7), Q represents a hydrogen atom or a formazan. Y represents a carbonyloxy group or a methyleneoxy group; A represents a single bond, or The carbon atom may be an alkyl group having a carbon number of 1 to 12 by oxygen; and may also contain a carbonyl carbon E, and represents any of the formulae (8) to (1).
者戶斤 示之環狀醚基:The cyclic ether group of the household:
(8) 式⑻至(10)中, 至 及 ~娜正地表示0至4之整數;惟, 成碳—者不為G ;此外,Ql4+,兩個基可鍵結— 成石厌數3至1〇之環]。 正:數1至6之烴基可舉例如:甲基、乙基、正丙基、 J :¾.、jf A、甘 美 — 土 正己基專直鏈狀烴基;異丙基、二級丁 土、三級丁基等分枝狀烴基等。 式(8)所不之取代基可舉例如:環氧乙烷基 15 320525 200921277 、甲基環氧乙烧基、二μ環氧乙烧基、三甲 基環氧乙烧基等,較佳可舉例如:環氧 乙坑基、1-甲基裱氧乙烷基。 式(9)所示之取代基可舉例如··氧雜環丁烷美 基氧雜環丁烧基、乙基氧雜環丁:基、丙 二乳雜,丁絲、環己基氧雜環丁垸基、苯基氧雜環丁& 土、二齓甲基虱雜環丁烷基、五氟乙基氧 較佳可舉例如:氧雜環 ^絲專’ 氧雜環丁炫基。 絲 '乙基 環氧=所ΓΓ代基可舉例如:1,2-環氧環戍基、u-颂%戊基、3,4-環氧環戊基、1>2— , 氧環己基、3, 4-環氧環己基、i,:基2’ 3, 環庚基、3,4-環氧减基、2’3—環氧 辛基、2, 3-環氧環辛\ % 4 ^,庚基、環氧環 基、1 2-環氧環八其土9 %軋%辛基、4,5-環氧環辛 A _ J "六基、2, 3_環氧環癸基、3 4-環負产八I 4,5-環氧環癸基、5 6_ ,4%虱%癸基、 基、”…環甲nr,4—環氧環戍 ^環氧基-树2,2,⑽、 雙環[2,2,1]庚基、3,4— 「甲基-3,4一裱氧基- 二甲基-以-環氧基-雙環心土 ^以⑼庚基心-[2,2,2]辛基、^環氧基-參環[^基^^氧基-雙環 舉例如·· 3, 4-環氧環戊基 ,,]六基等,較佳可 參·,2,U]癸基 ,4,氣環己基、氧基- 式⑺所示之單體可舉例如:料基環氧丙基_叫 320525 16 200921277 glyCidylethe〇、2-曱基稀丙基環氧丙基峻等不飽和環氧 丙基醚;丙烯酸環氧丙酯、甲基丙烯酸環氧丙酯、伊康酸 環氧丙醋等不飽和環氧丙酉旨;(甲基)丙晞酸環氧丙氧基乙 酉旨、(甲基)丙稀酸環氧丙氧基丁酉旨等環氧兩基驗(甲基)丙 烯酸酷·,丙稀酸3,4-環氧環己基甲廊、甲基丙稀酸土3,4_ 環氧環己基曱_等環狀脂肪族環氧基(甲基)丙婦酸K甲 基)丙烯酸氧雜環丁以旨、(甲基)丙稀酸3_氧雜環丁燒基 甲醋、(甲基)丙稀酸(3-甲基I氧雜環丁烷基)甲醋 基)丙稀酸(3-乙基-3-氧雜環丁烧基)甲醋等(曱基)丙稀酸 氧雜環丁烧基酯。 環狀 具有環狀驗基及碳-碳不飽和鍵之單體可舉例如具有 _基及稀烴雙鍵之單體,亦可混合使用2種以上之單 具有環狀醚基及烯烴雙鍵之單 、 〜〜〜卞肢,你1示仔受足性之 以式(9)所不之單體為佳、以具有氧雜環丁烷基及 :至又鍵之單體較佳。具有氧雜環丁烷基之不飽和化合 =,除?,羧酸以外)可舉例如:3 —(甲基)丙稀酿 :土氧雜%< 丁烧、3~甲基一3~(▼基)丙烯醯氧基甲基氧 院、3~乙基_3-(甲基)丙_氧基甲基氧雜環丁炫、〗 二:其(7基)丙烯醯氧基甲基氧雜環丁烷、2-三氟甲; ▲㈣絲基甲基氧雜環丁院、2_五氟乙基_3—(έ ;:乙:之㈣氧雜環丁燒、基-3-(⑶丙婦· 料丁^^環n乙基甲基)丙_氧基乙基孝 ”"凡—本基~3—(τ基)丙烯醯氧基乙基氧雜環丁烷、 320525 17 200921277 2 -二氟曱基-3-(甲基)丙烯驢氧基乙基氧雜環丁烧、2 一五氟 乙基-3-(甲基)丙烯醯氧基乙基氧雜環丁烷等。 在本發明中之共聚物(A)中,可再含有選自由衍生自具 有烯經雙鍵之羧酸酯之構成單元(a31 )、衍生自芳香族乙埽 化合物之構成單元(a32)、衍生自氰化乙烯化合物之構成單 元(a33)、衍生自N-取代馬來醯亞胺化合物之構成單元 (a34)所成群組中之至少一種構成單元(a3〇)。 在此,具有烯烴雙鍵之缓酸酯可舉例如:丙稀酸曱酯、 曱基丙烯酸甲醋、丙烯酸乙醋、甲基丙烯酸乙§旨、丙烯酸 丁醋、甲基丙烯酸丁酯、丙烯酸2_經乙酯、曱基丙婦酸2_ 羥乙酯、丙烯酸苯甲醋、甲基丙烯酸苯曱§旨、丙烯酸環己 酯、甲基丙烯酸環己酯、丙烯酸異冰片(is〇b〇rnyl)酯、甲 基丙烯酸異冰Μ、丙烯酸二環戊@旨、?基丙烯酸二環戊 酯、丙烯酸丙酷、甲基丙烯酸丙酯、丙烯酸戊酯、曱基丙 烯酸戊酯、丙烯酸2-羥丁酯、甲基丙烯酸2_羥丁酯、丙婦 酸苯酯、曱基丙烯酸苯酯、馬來酸二乙酯、富馬酸二乙酯、 伊.康酸二乙g旨等不飽和緩酸g旨.;丙烯酸胺乙醋等不飽和胺 基烷f酯;乙酸乙烯酯、丙酸乙烯酯等羧酸乙烯酯等。 芳香族乙烯化合物可舉例如:苯乙烯、α _甲基苯乙 烯、乙烯基甲笨等。 土 氰化乙烯化合物可舉例如:丙稀腈、甲基丙稀腈1 氯丙烯腈等。 Ν-取代馬來酸亞胺化合物可舉例如:Ν_甲基馬來醯 胺、Ν-乙基馬來酸亞胺、卜正丁基馬來醯亞胺、^環己 320525 18 200921277 馬來醯亞胺、N-苯甲基馬來酿亞胺、N-苯基馬來醯亞胺、 N-(4-乙酿基苯基)馬來酿亞胺、N-(2, 6-二乙基苯基)馬來 酿亞胺、N-(4-二甲基胺基-3, 5-二硝基苯基)馬來醒亞胺、 N-琥珀醯亞胺基-3-馬來醯亞胺苯曱酸酯、.號珀酸亞胺基 -3-馬來醯亞胺丙酸酯、N_琥珀醯亞胺基—4_馬來醯亞胺丁 酉文酉θ、N-琥珀酸亞胺基—6 —馬來酸亞胺己酸醋、(1 _苯胺 基萘基-4)-馬來醯亞胺、N-[4 —(2-苯并噚唑基)苯基]馬來 酸亞胺、N-(9-吖啶基(acridinyi))馬來醯亞胺等。 構成單(a30)以甲基丙烯酸二環戊酯、丙烯酸二環戊 酯、甲基丙烯酸環己酯、丙烯酸環己酯、N_環己基馬來醯 亞胺、η-苯基馬來醯亞胺為特佳。 #衍生自具有烯烴雙鍵之綾酸酯之構成單元U31)、衍生 自芳香族乙烯化合物之構成單元(a32)、衍生自氰化乙烯化 合物之構成單元(a33)、省生自N —取代馬⑽亞胺化合物 之構成單元(a34)係分別可單獨使用或組合2種以上使用。 在本發明中之包含衍生自不飽和叛酸之構成單元⑷) 及衍生自具有環狀縣與碳—碳残和鍵之化合物(惟,除 了不飽和㈣以外)之構成單元⑽的共聚物⑷中,⑽ 相對於構成單元全體,以5至5 莫耳%較佳,U2)相對於構成I#。為以15至4〇 ,^ 對於構成早兀全體,以5至95莫耳% 為么、以15至85莫耳%較佳。 前=之絲物(A)中,因若(al)及⑽之構成比例在 顯二核對於顯影液具有適當之溶解速度且同時 …貝不同硬化性之傾向,故佳。 了 320525 19 200921277 當共聚物(A)包含構成單元(a3〇)時,該構成單元(心〇) 之含里以0. 1至90莫耳%為佳、以〇·〗至7〇莫耳%較佳。 〃本發明中之共聚物⑴可舉例如:3_乙基—3_甲基丙烯 氧基甲基氧雜環丁烧/甲基丙晞酸苯甲§|//甲基丙稀酸 共聚物、3-乙基-31基丙烯酸氧基甲基氧雜環丁 v甲基 丙烯酸苯甲酯/甲基丙烯酸/苯乙稀共聚物、3—乙基I 甲基丙烯酸氧基甲基氧雜環丁烧/甲基丙稀酸/苯乙土婦共 聚物、3-乙基I甲基丙烯酿氧基甲基氧雜環丁烧/τ基丙 稀酸/甲基丙烯酸環己醋共聚物、3_乙基_3_甲基㈣_ 基甲基氧雜環丁焼/甲基丙婦酸/甲基丙稀酸甲醋/苯乙 烯共H3-乙基-3-甲基丙烯酿氧基甲基氧雜環丁烧/甲 基丙稀酸/甲基丙稀酸三級丁醋共聚物、3_乙基一 3—甲基丙 稀酿氧基甲基氧雜環丁院/甲基丙稀酸/甲基丙稀酸I冰 片醋共聚物、3-乙基|甲基丙烯醯氧基甲基氧雜環丁烷/ 甲基丙烯酸/丙烯酸苯甲醋共聚物、3_乙基_3—甲基丙稀醯 氧基甲基氧雜環丁院"基丙婦酸/丙晞酸環己醋共聚 物、3—乙基―3'甲基丙_氧基甲基氧雜環丁院/曱基丙稀 酸/丙稀酸異冰片醋共聚物、3一乙基+甲基丙烯酸氧基甲 基氧雜環丁院々基丙稀酸/丙烯酸三 =—3:曱基丙婦嶋甲基氧雜環丁烧…二酸〉 馬來^亞胺共聚物、3—乙基-3-甲基丙埽轉基曱基氧 雜環丁烧/甲基丙婦酸/環己基馬來酿亞胺共聚物、Ϊ其 丙烯酸環氧丙甲基丙烯酸苯甲酯/甲基丙烯酸Μ 物、甲基丙缔酸環氧丙酯/甲基丙烯酸苯?醋,甲基丙烯 320525 20 200921277 酸/苯乙烯共聚物、甲基丙烯 # , p< #取此 铈酉夂%乳丙酯/甲基丙烯酸/ 二: 基丙烯酸環氧丙醋…丙烯酸/甲基 丙烯酸%己酯共聚物、甲基 ψ^ T暴兩烯酸裱氧丙酯/甲基丙烯酸 /甲基丙烯酸甲酯/苯乙烯丘繫 / » ^ ^ ^ / 碲/、彔物、甲基丙烯酸環氧丙酯 /甲土丙;^酉夂/甲基丙埽酸三級 瑷童兩萨/田甘 —、,及丁酉日共承物、甲基丙烯酸 = 婦酸,甲基丙烯酸異冰片酿共聚物、甲 氧㈣/甲基丙烯酸/⑽酸笨甲酷共聚物、 甲基丙稀酸環氧丙酯/甲其 审 甲基丙烯酸/丙烯酸環己酯共聚 ::基丙㈣氧丙醋"基丙婦"丙稀酸異冰片醋 4物、…烯酸環氧丙醋/甲基丙稀酸/丙稀酸:級 丁酯共聚物、甲基丙烯酴援$工& 丞内烯酉夂%乳丙酯"基丙烯酸/苯基馬 二其聚物、甲基丙婦酸環氧丙酯/甲基丙烯酸,環 己基馬來酿亞胺共聚物等,較佳可舉例如:3_乙基— 丙稀酸氧基甲基氧雜環丁燒/甲基丙烯酸苯甲〜基; 烯酉夂共聚物、3-乙基-3-甲基丙烯醯氧基f基氧雜環丁烧/ 甲基丙婦酸苯甲醋/甲基丙烯酸/苯乙烯共聚物、3—乙基 -.3-甲基丙_氧基甲基氧雜環丁烧/甲基丙稀酸/苯$ 烯共=物、3-乙基-3-甲基㈣醒氧基甲基氧雜環丁燒/甲 基丙缔酸/甲基丙稀酸環己酯共聚物、3-乙基-3-甲基丙烯 ,氧基甲基氧雜環丁烧/甲基丙烯酸,甲基丙稀酸甲醋/ 苯烯物3乙基-3-甲基丙烯酸氧基甲基氧雜環丁烧 /甲基丙烯酸/曱基丙稀酸三'級丁醋共聚物、乙H 甲,丙婦醯氧基甲基氧雜環丁烧/甲基丙烯酸/甲基土丙烯 I兴冰片酯共聚物、3_乙基_3—甲基丙烯醯氧基甲基氧雜環 320525 21 200921277 丁烷/甲基丙稀酸/丙烯酸苯甲酯共聚物、3-乙基-3_甲基 2烯醯氧基甲基氧雜環丁烷/甲基丙烯酸/丙烯酸環己酯 共聚物、3-乙基—3_γ基丙烯醯氧基f基氧雜環丁烷/甲基 丙烯酸(丙烯酸異冰片醋共聚物、3—乙基-3-甲基丙烯醯: 基f基氧雜環丁烷/甲基丙烯酸/丙烯酸三級丁酯共聚 =、3-乙基-3~ f基丙烯醯氧基甲基氧雜環丁烷/甲基丙烯 本土馬來醯亞版共聚物、3-乙基-3-甲基丙稀醯氧基甲 基氧雜環丁 k/▼基丙稀酸/環己基馬來酿亞胺共聚物, 更Ϊ土可舉例如· 3_乙基_3_甲基丙烯酿氧基甲基氧雜環丁燒 /甲基丙稀酸苯甲醋/甲基丙烯酸共聚物、乙基—3_甲基 丙烯I氧基甲基氧雜環丁烷/曱基丙烯酸/苯乙烯共聚 物、3-乙基-3—甲基丙烯醯氧基甲基氧雜環丁烷/曱基:烯 酸基丙烯酸環己酯共聚物、3_乙基〜基丙烯醯氧基 甲基氧雜環丁烧’甲基丙烯酸/甲基丙埽酸甲酉旨,苯乙烯 共聚物、3-乙基—3_甲基丙稀醯氧基甲基氧雜環丁烧/甲臭 丙烯酸/丙_環己s|、3_乙基+甲基丙制氧基甲基氧 雜壤丁烧/甲基丙蝉酸/甲基丙稀酸三級丁酯共聚物、3_ 土基-3-甲基丙烯醯氧基甲基氧雜環丁烷,甲基丙烯酸/ 本基馬來酿亞胺丘费物、q 一.7 | Q w甘 U 3乙基-3-甲基丙烯醯氧基甲基氧 雜壞丁烧/甲基丙烯酸//環己基馬㈣亞胺共聚物。 本發明中之共聚物⑴以聚苯乙婦做為標準物質依凝 膠滲透層析法所測得之重量平均分子量係以2_至 1〇〇_為佳、以2000至50_較佳、以3〇〇〇至3〇_尤 佳。由於若重量平均分子量在前述範圍内,則有維持㈣ 320525 22 200921277 時之膜殘留率且同時可得到高顯影速度之傾向,故佳。 在本發明之感放射線性樹脂組成物中,包含(a 1)及(a2) 之共聚物(A)之含量,相對於感放射線性樹脂組成物之「固 形份」質量分率以50至98%為佳、以60至95%較佳。在 此,本說明書中所謂固形份’係指除了感放射線性樹脂組 成物中之溶劑以外之成分之合計量。 本發明之感放射線性樹脂組成物係含有式(1 )所-之 酚化合物之醌二疊氮基磺酸酯(B1)。 此外,本發明之感放射線性樹脂組成物係含有式 所示之酚化合物之醌二疊氮基磺酸酯(B1)、與式(幻所示之 紛化合物之職二疊氮基績酸醋⑽。式⑴所^之齡化^ 之酉昆二疊氮基續酸s旨(B1)、與式⑵所示之紛化合物之酉曰二 疊氮基磺酸酯(B2)之莫耳比係以1 : 2 5* 比一 ,' 主4 .1為佳、以1 : 1至4 : 1較佳、以1 : 1至3 : 1更(8) In the formulas (8) to (10), the sum to the positive value of 0 to 4; only, the carbon is not G; in addition, Ql4+, the two bases can be bonded - the stone is disgusting 3 To the ring of 1〇]. Positive: The hydrocarbon group of 1 to 6 may, for example, be a methyl group, an ethyl group, a n-propyl group, a J:3⁄4., a jf A, a gansyl-n-hexyl-specific straight chain hydrocarbon group; an isopropyl group, a secondary butyl group, A tertiary butyl aliquot of a branched hydrocarbon group or the like. The substituent which is not represented by the formula (8) may, for example, be an ethylene oxide group 15 320525 200921277, a methyl epoxy group, a di-oxirane group, a trimethyloxirane group or the like. For example, an epoxy group and a 1-methyloxiranyl group are mentioned. The substituent represented by the formula (9) may, for example, be an oxetane mesotyloxycyclobutanyl group, an ethyloxetane group, a propylene diacetate, a butane or a cyclohexyloxyheterocycle. The butyl group, the phenyl oxetane & earth, the diterpene methyl azetidinyl group, and the pentafluoroethyl oxygen are preferably exemplified by an oxocyclohexane. The silk 'ethyl epoxide=the oxime group may, for example, be 1,2-epoxycyclodecyl, u-颂% pentyl, 3,4-epoxycyclopentyl, 1>2-, oxycyclohexyl , 3, 4-epoxycyclohexyl, i, group 2' 3, cycloheptyl, 3,4-epoxy minus, 2'3-epoxyoctyl, 2,3-epoxycyclooctene\% 4 ^, heptyl, epoxy ring group, 1 2-epoxy ring octahedral 9 % rolled % octyl, 4,5-epoxycyclooctane A _ J "hexa-based, 2, 3_ epoxy ring Sulfhydryl, 3 4-ring negatively produced octa I 4,5-epoxycyclodecyl, 5 6 _ , 4% 虱% fluorenyl, yl, "...cyclomethyl nr, 4-epoxy oxime ^ epoxy- Tree 2,2,(10),bicyclo[2,2,1]heptyl, 3,4-"methyl-3,4-monooxy-dimethyl-p-epoxy-bicyclic heart-to-heart (9) Heptyl heart-[2,2,2]octyl, ^epoxy-cyclohexa[^-yloxy-bicyclic ring, for example, 3, 4-epoxycyclopentyl,] hexyl, etc. More preferably, 2, U] fluorenyl, 4, gas cyclohexyl, oxy - the monomer represented by the formula (7) may, for example, be a base epoxy group _ called 320525 16 200921277 glyCidylethe〇, 2-曱Base propyl epoxide propyl sulphate unsaturated unsaturated propyl propyl ether; glycidyl acrylate, methacrylic acid ring Unsaturated propylene acrylates such as oxypropyl acrylate and itaconic acid propylene vinegar; (methyl) propyl phthalate epoxy propyl ethoxylate, (meth) acrylic acid epoxy propoxy fluorene Epoxy two-test (meth)acrylic acid, 3,4-epoxycyclohexyl gallic acid, methyl acrylate acid, 3,4_epoxycyclohexyl hydrazine, etc. (Methyl)-propylglycolate K-methyl)acrylic acid oxetane, (meth)acrylic acid 3 oxetanyl acetonate, (meth) acrylic acid (3-methyl I Oxetane)acetate)acrylic acid (3-ethyl-3-oxetanyl) methyl acetonate or the like (fluorenyl) acesulfonic acid oxetane ester. The monomer having a cyclic test group and a carbon-carbon unsaturated bond may, for example, be a monomer having a _ group and a dilute hydrocarbon double bond, or a mixture of two or more kinds having a single cyclic ether group and an olefin double bond. ~ ~ ~ 卞 limb, you 1 is a good one for the monomer (9) is not preferred, with oxetanyl and: to the bond of the monomer is preferred. Unsaturation of butyryl groups =, in addition to carboxylic acids, for example: 3-(methyl) Dilute: soil oxygen % < butyl, 3 ~ methyl - 3 ~ (▼ base) propylene methoxy methyl oxy, 3 ~ ethyl _ 3- (methyl) propyl oxymethyl oxygen Heterocyclic Ding Hyun, 〗 2: (7-based) propylene oxiranoxymethyl oxetane, 2-trifluoromethyl; ▲ (four) silk-based methyl oxetane, 2_ pentafluoroethyl _ 3-(έ;: B: (4) oxetane, keto-3-((3) 乙妇·丁丁^^环nethylmethyl)propyl-oxyethyl 孝""凡—本基~3—(τ-)propenyloxyethyloxetane, 320525 17 200921277 2 -difluorodecyl-3-(methyl)propenyloxyethyloxeane, 2-15 Fluoroethyl-3-(methyl)propenyloxyethyloxetane and the like. The copolymer (A) in the present invention may further contain a constituent unit (a32) derived from a constituent unit (a31) derived from a carboxylate having an olefinic double bond and derived from an aromatic acetamidine compound. At least one constituent unit (a3〇) of the group consisting of the constituent unit (a33) of the vinyl cyanide compound and the constituent unit (a34) derived from the N-substituted maleimide compound. Here, the retardation acid ester having an olefinic double bond may, for example, be decyl acrylate, methyl methacrylate, ethyl acrylate, methacrylic acid, butyl acrylate, butyl methacrylate, acrylic acid 2 _ Ethyl ester, 2-hydroxyethyl phthalate, benzyl acrylate, benzophenone methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate (is〇b〇rnyl) Ester, isoamyl methacrylate, dicyclopentyl acrylate @,? Dicyclopentyl acrylate, propyl acrylate, propyl methacrylate, amyl acrylate, amyl decyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, phenyl propyl acrylate, hydrazine Phenyl acrylate, diethyl maleate, diethyl fumarate, diethyl ketone, iso-glycolic acid, etc.; unsaturated aminoalkyl f-ester such as acetamide, acetic acid; acetic acid Vinyl carboxylate such as vinyl ester or vinyl propionate. The aromatic vinyl compound may, for example, be styrene, α-methylstyrene or vinyl. Examples of the vinyl cyanide compound include acrylonitrile, methyl acrylonitrile, and chloroacrylonitrile. The hydrazine-substituted maleimide compound may, for example, be Ν-methyl maleamide, Ν-ethyl maleimide, bu-butyl maleimide, ^cyclohexane 320525 18 200921277 Malayan Amine, N-benzylmaleimine, N-phenylmaleimide, N-(4-ethylphenylphenyl)maleimide, N-(2,6-diethyl Phenyl) maleimine, N-(4-dimethylamino-3, 5-dinitrophenyl)maleimide, N-succinimide-3-malaya Aminobenzoate, benzoic acid imido-3-maleimide propionate, N_amber quinone imine-4-maleimide, 酉 酉 酉, N-succinic acid Amino-6-maleic acid imide caproic acid vinegar, (1-anilinonaphthyl-4)-maleimide, N-[4-(2-benzoxazolyl)phenyl]male Acid imine, N-(9-acridinyi) maleimide, and the like. The composition sheet (a30) is dicyclopentanyl methacrylate, dicyclopentanyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, N-cyclohexylmaleimide, η-phenyl malayan Amines are especially good. #constituted from the constituent unit U31 of the phthalic acid ester having an olefinic double bond, the constituent unit derived from the aromatic vinyl compound (a32), the constituent unit derived from the vinyl cyanide compound (a33), and the province from the N-substituted horse (10) The constituent unit (a34) of the imine compound may be used alone or in combination of two or more. In the present invention, a copolymer (4) derived from an unsaturated tauic constituent unit (4)) and a constituent unit (10) derived from a compound having a cyclical state and a carbon-carbon residue and a bond (except for the unsaturated (tetra)) (4) In the above, (10) is preferably 5 to 5 mol% with respect to the entire constituent unit, and U2) is relative to the composition I#. For 15 to 4 〇, ^ is preferably 5 to 95 mol% and 15 to 85 mol% for the whole composition. In the yarn material (A) of the former =, it is preferable that the composition ratio of (al) and (10) is such that the second core has a suitable dissolution rate for the developer and at the same time tends to have different hardenability. 320525 19 200921277 When the copolymer (A) comprises a constituent unit (a3〇), the constituent unit (heart) is preferably 0.1 to 90% by mole, and 〇·〗 to 7〇. % is better. The copolymer (1) in the present invention may, for example, be 3-ethyl-3-methylpropenyloxymethyloxetane/methylpropionic acid benzoquinone §|//methacrylic acid copolymer , 3-ethyl-31-hydroxy oxymethyloxetane v benzyl methacrylate / methacrylic acid / styrene copolymer, 3-ethyl I methoxy oxymethyl oxocycle Butadiene/Methylacrylic acid/Benzene copolymer, 3-ethyl I methacryloxymethyloxyxetane/τ-acrylic acid/cyclohexyl methacrylate copolymer, 3_Ethyl_3_methyl(tetra)_ylmethyloxetane/methylpropanoic acid/methyl propyl methacrylate/styrene total H3-ethyl-3-methyl propylene ethoxylate Oxycyclobutane/Methylacrylic acid/Methylacrylic acid tertiary butyl acetate copolymer, 3-ethyl-3-methylpropanoloxymethyloxetane/methylpropyl Dilute acid/methyl acrylate I borneol vinegar copolymer, 3-ethyl | methacryloxymethyl oxetane / methacrylic acid / acrylic acid benzyl acetate copolymer, 3_ethyl _3 —Methyl acrylonitrile methyl oxetane" propyl propyl acrylate/propylene hexanoic acid copolymer, 3-B -3'Methylpropoxy-oxymethyloxetane/mercaptopropionic acid/acrylic acid isobornic vinegar copolymer, 3-ethylethyl methacrylate oxymethyl oxetane Mercapto-acrylic acid/acrylic acid three=—3: mercapto-propyl sulfonium methyl oxetane...diacids>Malay^imine copolymer, 3-ethyl-3-methylpropionate Oxycyclobutane/methylpropionic acid/cyclohexylmaleimine copolymer, acetonyl acrylate propyl methacrylate/methacrylic acid oxime, methyl propyl acrylate Ester / methacrylic acid benzene? Vinegar, methacrylic acid 320525 20 200921277 acid/styrene copolymer, methacrylic #, p<#取此铈酉夂% propyl acrylate / methacrylic acid / two: based acrylic propylene vinegar... acrylic / methyl Acrylic acid hexyl acrylate copolymer, methyl hydrazine T 暴 两 两 两 » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » » Glycidyl propyl ester / methic acid; ^ 酉夂 / methacrylic acid tertiary 瑷 两 两 / 田 田 田 田 田 田 田 田 田 田 田 田 田 田 田 田 田 田 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Copolymer, methoxy (tetra) / methacrylic acid / (10) acid benzoate copolymer, methyl propyl acrylate / methyl methacrylate / cyclohexyl acrylate copolymer:: propyl (tetra) oxypropylene vinegar "基丙妇"Acetic acid isobornic vinegar 4,...enoic acid propylene vinegar/methyl acrylic acid/acrylic acid: butyl acrylate copolymer, methacrylic hydrazine aid & 丞Alkene 乳 propyl acrylate " acrylic acid / phenyl horse dimer, methyl propyl acrylate methacrylate / methacrylic acid, cyclohexyl maleimide copolymer, etc., preferably For example: 3_ethyl-acrylic acid oxymethyloxeane/benzyl methacrylate-yl; olefin copolymer, 3-ethyl-3-methylpropenyloxy-oxyl Heterocyclic butyl ketone / methyl propyl benzoic acid / methacrylic acid / styrene copolymer, 3-ethyl-. 3-methylpropoxy-oxymethyl oxetane / methyl acrylate / Benzene / alkene = 3-ethyl-3-methyl (tetra) oxime methyl oxetane / methyl propionate / methyl methacrylate cyclohexyl ester copolymer, 3-ethyl 3-methylpropene, oxymethyloxetane/methacrylic acid, methyl acetonate methyl vinegar / phenylene 3 ethyl-3-methyl acrylate oxymethyl oxetane /methacrylic acid/mercaptopropionic acid tri-tert-butyl vinegar copolymer, ethyl H-methyl, propyl methoxymethyl oxetane/methacrylic acid/methyl propylene propylene I borneol ester copolymer, 3_Ethyl_3-methylpropenyloxymethyloxane 320525 21 200921277 Butane/Methylacrylic acid/Benzyl acrylate copolymer, 3-ethyl-3_methyl 2 olefinic oxygen Methyl oxetane / methacrylic acid / cyclohexyl acrylate copolymer, 3-ethyl - 3 - γ-based propylene oxy-oxyl oxygen Cyclobutane/methacrylic acid (isobornyl acrylate copolymer, 3-ethyl-3-methylpropene oxime: ke group oxetane / methacrylic acid / tertiary butyl acrylate copolymer =, 3- Ethyl-3~f-propenyloxymethyloxetane/methacrylic native malayan copolymer, 3-ethyl-3-methylpropenyloxymethyloxane Butan k / ▼ base acrylic acid / cyclohexyl maleimide copolymer, more alumina, for example, · 3_ethyl_3_methacryloxymethyloxyxetane / methyl propyl Dilute acid benzyl acetate/methacrylic acid copolymer, ethyl-3-methacrylic acid Ioxymethyloxetane/mercaptoacrylic acid/styrene copolymer, 3-ethyl-3-methylpropene Methoxyoxymethyloxetane/indenyl: cyclohexyl acrylate copolymer, 3-ethyl-propyl propylene methoxymethyl oxetane 'methacrylic acid/methyl propyl hydrazine Acid methyl hydrazine, styrene copolymer, 3-ethyl-3-methyl propyl methoxymethyl oxetane / odorous acrylic acid / propylene - cyclohexene s |, 3 - ethyl + methyl Propyloxymethyloxygenated butylate/methylpropionic acid/methyl propyl tertiary butyl ester Polymer, 3_ benzyl-3-methylpropenyloxymethyloxetane, methacrylic acid/benma-Malayimine, valence, q-.7 | Q w-G U 3 ethyl -3-Methyl propylene methoxymethyl oxazapine / methacrylic acid / / cyclohexyl horse (tetra) imine copolymer. The copolymer (1) of the present invention has a weight average molecular weight measured by gel permeation chromatography using polystyrene as a standard substance, preferably 2 to 1 Å, and preferably 2,000 to 50 Å. Take 3〇〇〇 to 3〇_尤佳. When the weight average molecular weight is within the above range, there is a tendency that the film residual ratio at (400) 320525 22 200921277 is maintained and a high development speed is obtained at the same time, which is preferable. In the radiation sensitive resin composition of the present invention, the content of the copolymer (A) comprising (a1) and (a2) is 50 to 98 with respect to the "solid content" mass fraction of the radiation sensitive resin composition. % is preferably, preferably 60 to 95%. Here, the term "solid portion" as used herein means a total amount of components other than the solvent in the radiation sensitive resin composition. The radiation sensitive resin composition of the present invention contains the quinonediazidesulfonate (B1) of the phenol compound of the formula (1). Further, the radiation sensitive resin composition of the present invention contains a quinonediazidesulfonate (B1) of a phenol compound represented by the formula, and a formula (a compound of the compound of the diazide-based acid vinegar) (10) The molar ratio of the quinone diazide sulfonate (B2) of the formula (1) and the compound of the formula (2) It is 1: 2 5* to one, 'main 4. 1 is better, 1:1 to 4: 1 is better, and 1:1 to 3: 1 is more
[式(1)中,R1至R12分別獨立地表示 ; 基、碳數1至10之烧基、碳數3 〇、、鹵素原子、 至4之龜、碳们至H)之絲環絲、碳畫 數1至4之烧基、鹵素原子、碳數 基(該苯基可經 惟,在笨環之碳原子上所分別結合4之垸氧基取代 間可形成碳數3至1 〇之環; 至R、R8至R12 320525 23 200921277 惟 至R5、R8至R12之中,至少一個表示羥基][In the formula (1), R1 to R12 are each independently represented; a ring, a carbon number of 1 to 10, a carbon number of 3 〇, a halogen atom, a turtle of 4, a carbon to H), a carbon number of 1 to 4, a halogen atom, a carbon number group (the phenyl group can be formed by a combination of 4 decyl groups on a carbon atom of a stupid ring to form a carbon number of 3 to 1 Å. Ring; to R, R8 to R12 320525 23 200921277 Only to R5, R8 to R12, at least one represents a hydroxyl group]
(2) K⑵中’ Z丨至29分別獨立地表示可㈣素取代之烧基、 虱原子或羥基;惟,2丨 ηΐ3δ ρ18 ν 隈Ζ至Ζ之中,至少兩個表示羥基; 之、广其/刀山別獨立地表示氯原子、函素原子、礙數1至10 q 5元二厌數3至1Q之環烧基、碳數2至4之稀基、碳數 至10之7减或苯基,或在兩個取代基間可形成碳數3 石:前述苯基可經碳數1至4之烧基、齒素原子、 厌數至4之烷氧基取代]。 .. 芙炉2 ’藏二疊氮基續酸®旨可舉例如:丨,2-苯藏二疊氮 基酉夂酉旨、1 9 —笑两甘一晶片甘 美5石廿舱 示 虱基—4一磺酸酉旨、l2-萘醌二疊氮 基-5-¾酸酯、丨’卜萘醌二 焯 疊氮基〜酯、2]-萘=氮二 醌二疊氮基—6-磺酸酯等。且从知、2’卜萘 :數…。之烧基可舉例如:甲基、乙基、正丙基、 :庚I I"!基、二級丁基、三級丁基、正戊基、正己基、 基、:基。正壬基、正癸基等’較佳可舉例如:甲 碳數2至4之浠基可舉例如:乙烯基、丙烯基、 320525 .24 200921277 烯基、2-丁烯基等,較佳可舉 石炭數3至10之re Λ 1如·乙每基、丙烯基。 W f之展烷基可舉例如:㈣、環丁基、€ 戍基、%<己基、環庚基、環辛基、環 車: 佳可舉例如:環戊基、環己基。 、基等較 ,美碳氧基可舉例如1氧基、乙氧基、丙 ^ 虱土戊乳基等,較佳可舉例如氧基、乙氧 苯基(該苯基可經齒素原子、碳數i至4之院基、碳數 至4之烷氧基取代)可舉例如:苯基、(鄰 曱苯基、(2,3-、2,4-、2 5 ' 9 R , , 〇 苯基、(2,3,4-、2,3,5〜2’3^2 二;’)二甲基 一 ,0 43,6-、2,4,5-、2,4,6-、3,4,5-) 二甲基本基:(2’ 3’ 4’ 5-、2, 3, 4, 6_、2, 3, 5, 6 —)四甲基苯 ^、五甲基苯基、2~甲基~3一乙基苯基、2-甲基-4-乙基苯 土、2-曱基-5-乙基苯基、2一甲基_6_乙基苯基、3—甲基 乙基苯基、3_甲基—4—乙基苯基、3-甲基-5-乙基苯基、3一 甲基I乙基苯基、4~甲基-2-乙基苯基、4-甲基-3-乙基苯 基、2, 3-二甲基-4—乙基苯基、2, 3一二甲基_5—乙基苯基、 2,3 —二甲基I乙基苯基、2, 4-二甲基-3-乙基苯基、2,4一 —甲基-5-乙基苯基、2,4二甲基+乙基苯基、2,5一二甲 基~3—乙基苯基、2, 5'二甲基+乙基苯基、2, 5-二甲基一6_ =基苯基、2, 6—二甲基I乙基苯基、2, 6-二甲基+乙基 本基、2’6 —二甲基―5—乙基苯基、2, 3-二曱基-4, 5_二乙基 苯基、2, 3-二甲基-5, 6一二乙基苯基、2, 3_二甲基乂 6_二 乙基苯基、2,4-二甲基__3,5—二乙基苯基、2,4_二甲基-3,6 — 320525 25 200921277 二乙基苯基、2, 4-二曱基-5, 6-二乙基苯基、2, 5-二曱基 -3, 4-二乙基笨基、2, 5-二甲基-3, 6-二乙基苯基、2, 5-二 甲基-4, 6-二乙基苯基、2, 6-二甲基-3, 4-二乙基苯基、2, 6-二曱基-4, 5-二乙基苯基、2, 6_二曱基-3, 5_二乙基苯基、 2-甲基-3-丙基苯基、2-甲基-4-丙基苯基、2-甲基-5-丙基 苯基、2-曱基-6-丙基苯基、3-曱基-2-丙基苯基、3-曱基 -4-丙基苯基、3~甲基-5-丙基苯基、3-甲基-6-丙基苯基、 4-甲基-2-丙基笨基、4-甲基-3-丙基苯基、2, 3-二曱基-4-丙基苯基、2, 3-二甲基-5-丙基苯基、2, 3-二甲基-6-丙基 苯基、2, 4-二甲基—3-丙基苯基、2, 4-二甲基-5-丙基苯基.、 2, 4-二曱基―6-两基苯基、2, 5-二曱基-3-丙基苯基、2, 5-二甲基-4-丙基苯基、2, 5-二曱基_6-丙基苯基、2, 6-二曱 基-3-丙基苯基、2, 6-二甲基-4-丙基苯基、2, 6-二曱基-5-丙基苯基、2, 3-二甲基_4, 5二二丙基苯基、2, 3-二甲基-5, 6-二丙基苯基、2, 3-二甲基—4, 6-二丙基苯基、2, 4-二曱基 -3, 5-二丙基苯基、2, 4-二甲基-3, 6-二丙基苯基、2, 4-二 甲基-5, 6-二丙基苯基、2, 5一二曱基_3, 4_二丙基苯基、2, 5_ 二曱基-3, 6-二丙基苯基、2, 5_二甲基__4,6_二丙基苯基、 2, 6-二曱基-3, 4-二丙基苯基、2, 6-二甲基-4, 5-二丙基苯 基、2, 6-二甲基-3, 5_二丙基苯基、2_甲基—3_異丙基苯基、 2-甲基-4-異丙基苯基、2_曱基一5-異丙基苯基、2-曱基_6_ 異丙基笨基、3-甲基-2-異丙基苯基、3-甲基—4-異丙基苯 基、3-曱基-5-異丙基苯基、3-甲基-6-異丙基苯基、4-甲 基-2-異丙基苯基、4 -曱基-3-異丙基笨基、(2, 3-、2,4-、 320525 26 200921277 2 ’ 5-、2, 6-、3, 4_、3, 5-)二異丙基苯基、(鄰_、間_、對 -)正丁基苯基、(鄰-、間—、對―)三級丁基苯基、(鄰_、間 -、對-)正己基苯基、(鄰-、間—、對—)正辛基苯基、(鄰_、 間-、對-)環己基苯基、(鄰-、間_、對_)氯苯基、(2, 3-、 2, 4-、2, 5-、2, 6-、3, 4-、3, 5-)二氯苯基、(2, 3, 4-、2, 3, 5-、 2’ 3’ 6-、2’ 4’ 5-、2, 4, 6-、3, 4, 5-)三氯苯基、2-氯-3-甲 基苯基、2-氯-4-曱基苯基、2-氯-5-甲基苯基、2-氯-6-曱基苯基、3-氯-2-曱基苯基、3-氯-4-甲基苯基、3-氯-5-甲基苯基、3-氯-6-甲基苯基、4-氯-2-甲基苯基、4-氯-3-甲基本基、(鄰一、間_、對_)溴苯基、(2,3_、2, 4-、2, 5-、 2, 6-、3, 4-、3, 5-)二溴苯基、2, 3-二氯-4-甲基苯基、2, 3~ 二氯-5-甲基苯基、2, 3-二氯-6-甲基苯基、2,4-二氯-3~ 甲基苯基、2, 4-二氯-5_甲基苯基' 2, 4-二氯-6-曱基苯基、 2, 5-二氯-3-甲基苯基、2, 5-二氣-4-甲基苯基、2, 5-二氯 -6-甲基苯基、2, 6-二氯-3-甲基苯基、2, 6-二氯-4-曱基苯 基、2, 6-二氯-5-甲基苯基、(鄰_、間_、對_)甲氧基苯基、 (鄰-、間-、對-)乙氧基苯基、2_甲氧基_3_甲基苯基、2_ 甲氧基-4-甲基苯基、2-甲氧基_5_甲基苯基、2一甲氧基_6_ 曱基苯基、3-甲氧基-2-甲基苯基、3-甲氧基-4-曱基苯基、 3-甲氧基-5-甲基苯基、3-甲氧基曱基苯基、4_曱氧基 -2-甲基苯基、4-曱氧基-3—曱基苯基、2_氯_3_甲氧基一4_ 曱基苯基、2-氯_3-曱氧基-5_甲基苯基、2一氯_3_曱氧基 曱基苯基、2-氯-4-曱氧基甲基苯基、2_氯_4_曱氧基一5_ 甲基苯基、2-氯-4-甲氧基—6_甲基苯基、2一氯_5_甲氧基一3一 320525 27 200921277 甲基苯基、2-氯-5一甲氧基_4一甲基苯基、2__氯—5_甲氧基一 f基f基、2-氯-6_甲氧基一3—甲基苯基、2_氯_6_甲氧基一 甲基苯基、2~氯一6—甲氧基-5-f基苯基、3~氯-2-甲氧基一4—(2) In K(2), 'Z丨 to 29, respectively, independently represent a sulphur group, a ruthenium atom or a hydroxy group which may be substituted by (tetra); however, 2丨ηΐ3δ ρ18 ν 隈Ζ to Ζ, at least two represent a hydroxyl group; The /Knifeshan does not independently represent a chlorine atom, a hydroxyl atom, a ring-burning group of 3 to 1Q, a number of 3 to 1Q, a carbon number of 2 to 4, and a carbon number of 10 to 7 Or a phenyl group, or a carbon number 3 may be formed between the two substituents: the aforementioned phenyl group may be substituted with a carbon number of 1 to 4, a dentate atom, and an anodoxy group having an anisotropy of 4. .. Furnace 2 'Tibezide Azide Continued Acid® can be exemplified by: 丨, 2-Benzene diazide, 1 1, 9 两 甘 晶片 晶片 晶片 晶片 晶片 晶片 晶片 5 5 5 5 -4-sulfonic acid hydrazine, l2-naphthoquinonediazide-5-3⁄4 acid ester, 丨'b-naphthoquinone diazide azide-ester, 2]-naphthalene = nitrogen diazide diazide- 6 - sulfonate and the like. And from the knowledge, 2' naphthalene: number... Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, a heptyl group, a secondary butyl group, a tertiary butyl group, a n-pentyl group, a n-hexyl group, a group, and a group. For example, a fluorenyl group having a methyl group number of 2 to 4 may be, for example, a vinyl group, a propylene group, a 320525.24 200921277 alkenyl group, a 2-butenyl group or the like. It can be mentioned that the number of charcoal is 3 to 10, re Λ 1 such as B, and propylene. The alkyl group of W f may, for example, be: (iv), cyclobutyl, fluorenyl, % < hexyl, cycloheptyl, cyclooctyl, or cyclin: preferably, for example, a cyclopentyl group or a cyclohexyl group. The base of the carbosiloxane may, for example, be an oxy group, an ethoxy group, a propyl sulfoxide group or the like, and preferably an oxy group or an ethoxyphenyl group (the phenyl group may be a dentate atom). , the carbon number i to 4, the carbon number to 4 alkoxy substitution) may be, for example, phenyl, (o-phenylene, (2,3-, 2,4-, 2 5 ' 9 R, , phenyl, (2,3,4-, 2,3,5~2'3^2 bis; ') dimethyl one, 0 43,6-, 2,4,5-, 2,4, 6-, 3,4,5-) Dimethyl basic group: (2' 3' 4' 5-, 2, 3, 4, 6_, 2, 3, 5, 6 -) tetramethylbenzene ^, five Phenyl, 2~methyl~3-ethylphenyl, 2-methyl-4-ethylbenzene, 2-mercapto-5-ethylphenyl, 2-methyl-6-ethylbenzene , 3-methylethylphenyl, 3-methyl-4-ethylphenyl, 3-methyl-5-ethylphenyl, 3-methylethylethyl, 4-methyl- 2-ethylphenyl, 4-methyl-3-ethylphenyl, 2,3-dimethyl-4-ethylphenyl, 2,3-dimethyl-3-5-ethylphenyl, 2 ,3-dimethyl Iethylphenyl, 2,4-dimethyl-3-ethylphenyl, 2,4-monomethyl-5-ethylphenyl, 2,4 dimethyl + B Phenylphenyl, 2,5-dimethyl- 3-ethylphenyl, 2, 5 'Dimethyl+ethylphenyl, 2,5-dimethyl-6-=ylphenyl, 2,6-dimethylIethylphenyl, 2,6-dimethyl+ethyl-based, 2 '6-Dimethyl-5-ethylphenyl, 2,3-dimercapto-4,5-diethylphenyl, 2,3-dimethyl-5,6-diethylphenyl, 2, 3_Dimethylhydrazine 6_diethylphenyl, 2,4-dimethyl__3,5-diethylphenyl, 2,4-dimethyl-3,6 — 320525 25 200921277 II Ethylphenyl, 2,4-dimercapto-5,6-diethylphenyl, 2,5-dimercapto-3,4-diethylphenyl, 2,5-dimethyl-3 , 6-diethylphenyl, 2,5-dimethyl-4,6-diethylphenyl, 2,6-dimethyl-3,4-diethylphenyl, 2,6-di Mercapto-4, 5-diethylphenyl, 2,6-diindolyl-3,5-diethylphenyl, 2-methyl-3-propylphenyl, 2-methyl-4- Propyl phenyl, 2-methyl-5-propylphenyl, 2-mercapto-6-propylphenyl, 3-mercapto-2-propylphenyl, 3-mercapto-4-propyl Phenyl, 3-methyl-5-propylphenyl, 3-methyl-6-propylphenyl, 4-methyl-2-propylphenyl, 4-methyl-3-propylphenyl , 2, 3-dimercapto-4-propylphenyl, 2,3-dimethyl-5-propylphenyl, 2,3-dimethyl-6-propyl , 2, 4-dimethyl-3-propylphenyl, 2,4-dimethyl-5-propylphenyl, 2,4-dimercapto-6-diylphenyl, 2, 5-dimercapto-3-propylphenyl, 2,5-dimethyl-4-propylphenyl, 2,5-diindenyl-6-propylphenyl, 2,6-didecyl 3-propylphenyl, 2,6-dimethyl-4-propylphenyl, 2,6-dimercapto-5-propylphenyl, 2,3-dimethyl-4, 5 Dipropylphenyl, 2,3-dimethyl-5,6-dipropylphenyl, 2,3-dimethyl-4,6-dipropylphenyl, 2,4-didecyl- 3, 5-dipropylphenyl, 2,4-dimethyl-3,6-dipropylphenyl, 2,4-dimethyl-5,6-dipropylphenyl, 2, 5 Dimercapto-3-3,4-dipropylphenyl, 2,5-dimercapto-3,6-dipropylphenyl, 2,5-dimethyl__4,6-dipropylphenyl, 2 , 6-dimercapto-3, 4-dipropylphenyl, 2,6-dimethyl-4, 5-dipropylphenyl, 2,6-dimethyl-3, 5-dipropyl Phenyl, 2-methyl-3-isopropylphenyl, 2-methyl-4-isopropylphenyl, 2-mercapto-5-isopropylphenyl, 2-indenyl-6-isopropyl Base, 3-methyl-2-isopropylphenyl, 3-methyl-4-isopropylphenyl, 3-mercapto-5-isopropylphenyl, 3-methyl-6- Isopropyl Phenyl, 4-methyl-2-isopropylphenyl, 4-mercapto-3-isopropylphenyl, (2, 3-, 2, 4-, 320525 26 200921277 2 ' 5-, 2, 6-, 3, 4_, 3, 5-) diisopropylphenyl, (o-, m-, p-)-n-butylphenyl, (o-, m-, p-)-tert-butylbenzene Base, (o-, m-, p-)-n-hexylphenyl, (o-, m-, p-)-n-octylphenyl, (o-, m-, p-)cyclohexylphenyl, (o) -, _, _ _ chlorophenyl, (2, 3-, 2, 4-, 2, 5-, 2, 6-, 3, 4-, 3, 5-) dichlorophenyl, (2 , 3, 4-, 2, 3, 5-, 2' 3' 6-, 2' 4' 5-, 2, 4, 6-, 3, 4, 5-) trichlorophenyl, 2-chloro- 3-methylphenyl, 2-chloro-4-indolylphenyl, 2-chloro-5-methylphenyl, 2-chloro-6-nonylphenyl, 3-chloro-2-indenylphenyl , 3-chloro-4-methylphenyl, 3-chloro-5-methylphenyl, 3-chloro-6-methylphenyl, 4-chloro-2-methylphenyl, 4-chloro-3 -methyl group, (o-, m-, p-) bromophenyl, (2,3_, 2, 4-, 2, 5-, 2, 6-, 3, 4-, 3, 5-) Bromophenyl, 2, 3-dichloro-4-methylphenyl, 2,3~dichloro-5-methylphenyl, 2,3-dichloro-6-methylphenyl, 2,4- two Chloro-3~methylphenyl, 2,4-dichloro-5-methylphenyl' 2,4-dichloro-6-nonylphenyl, 2, 5-dichloro-3-methylphenyl , 2, 5-dioxa-4-methylphenyl, 2, 5-dichloro-6-methylphenyl, 2,6-dichloro-3-methylphenyl, 2,6-dichloro- 4-nonylphenyl, 2,6-dichloro-5-methylphenyl, (o-, m-, p-)methoxyphenyl, (o-, m-, p-)ethoxy Phenyl, 2-methoxy-3-methylphenyl, 2-methoxy-4-methylphenyl, 2-methoxy-5-methylphenyl, 2-methoxy_6_ fluorenyl Phenyl, 3-methoxy-2-methylphenyl, 3-methoxy-4-mercaptophenyl, 3-methoxy-5-methylphenyl, 3-methoxynonylbenzene , 4-methoxy-2-methylphenyl, 4-decyloxy-3-nonylphenyl, 2-chloro-3-ylmethoxy-4-ylnonylphenyl, 2-chloro-3-曱oxy-5-methylphenyl, 2-chloro-3-yloxycarbonylphenyl, 2-chloro-4-methoxymethylphenyl, 2-chloro-4-indolyl-5_ Methylphenyl, 2-chloro-4-methoxy-6-methylphenyl, 2-chloro-5-methoxy-3,320525 27 200921277 methylphenyl, 2-chloro-5-methoxy 4-tetramethylphenyl, 2-methyl-5-methoxy-f-f-yl, 2-chloro-6-methoxy 3-methylphenyl, 2-chloro-6-methoxy-methylphenyl, 2-chloro-6-methoxy-5-fphenyl, 3-chloro-2-methoxy-4 -
T基苯基、3 —氣I甲氧基I甲基苯基、3备2_甲氧基I 甲=,氯—4―甲财甲基苯基、3'氯+甲氧基+ =、'氯+甲氧基.甲基苯基、3'氯+甲氧基+ 7基本基、3-氯-5-f氧基_4_甲基苯基 f基苯基、4-氯-2-甲負A q田故++甘、 τ羊l巷b …… 氧基―3—甲基苯基、4~氯Μ氧基-5: f基本基、4-氯-2—甲氧基_6—甲基苯基、4'氯_3_甲氧基—卜 尹基苯基、4-氯-3—甲氧基_5一二土 ⑽等,較佳可舉例如.甲氧基+ ^(2,3--2;4-,2,5_, 2 6 3 4 (2 3 4- > 2 3 ^ 〇 〇 ’ ,4、3, 5~)二 f 基苯基、 甲基本基、(鄰…間-、對〇氯苯 )一 氧基苯基。 (鄰~、間-、·對―)曱T-phenyl, 3-methoxy I methoxy I methylphenyl, 3 bis 2 methoxy I methyl, chloro-4-methyl methyl phenyl, 3' chloro + methoxy + =, 'Chloro + methoxy. Methylphenyl, 3' chloro + methoxy + 7 basic, 3-chloro-5-foxy_4-methylphenyl f-phenyl, 4-chloro-2 - A negative A q field ++ Gan, τ sheep l Lane b ...... oxy-3-methylphenyl, 4~chloromethoxy-5: f basic, 4-chloro-2-methoxy _6-methylphenyl, 4'-chloro-3-yloxy-buyinylphenyl, 4-chloro-3-methoxy-5-dioxalate (10), etc., preferably methoxy-^ (2,3--2;4-,2,5_, 2 6 3 4 (2 3 4- > 2 3 ^ 〇〇' , 4, 3, 5~) bis-f-phenyl, methyl-based, (o...inter-, p-chlorobenzene)-oxyphenyl. (o-~, m-, ·---)曱
Re及R7分別獨立地可舉例如 山 之燒基、碳數2至4之縣,數1至10 基、乙基,更佳可舉例如:氨原;=如如^ 式⑴所示之紛化合物,具“言^ 所示之化合物等: 牛例如下述構造式 320525 28 200921277Re and R7 each independently may, for example, be a mountain base, a carbon number of 2 to 4, a number of 1 to 10 groups, an ethyl group, more preferably, for example, ammonia; and a compound such as the formula (1) , with the compound shown by the words ^, etc.: cattle such as the following structural formula 320525 28 200921277
29 320525 20092127729 320525 200921277
在此等之中,以下述構造之化合物為佳。Among these, a compound of the following structure is preferred.
醌二疊氮基磺酸酯可舉例如:1,2-苯醌二疊氮基磺酸 酯、1,2-萘醌二疊氮基-4-磺酸酯、1,2-萘醌二疊氮基-5-石黃酸I旨、1,2 -萘1昆二疊氮基-6 -續酸酯、2,1 -萘艇二疊氮基 -4-磺酸酯、2,卜萘醌二疊氮基-5-磺酸酯、2,卜萘醌二疊 氮基-6-續酸酯等。 式(1)所示之酚化合物之醌二疊氮基磺酸酯(B1)以酚 化合物每1莫耳,有1. 5莫耳以上之羥基經酯化為佳。 30 320525 200921277 本發明之感放射線性樹脂組成物係含有式 酚化合物之醌二疊氮基磺酸酯(B2)。 z7The quinonediazide sulfonate may, for example, be a 1,2-benzoquinonediazide sulfonate, 1,2-naphthoquinonediazide-4-sulfonate or 1,2-naphthoquinone Azido-5-hemeic acid I, 1,2-naphthalene 1 Kundidiazide-6-propanoate, 2,1-naphthalene diazide-4-sulfonate, 2, Bu Naphthoquinonediazide-5-sulfonate, 2, naphthoquinonediazide-6-thanoate, and the like. The quinonediazide sulfonate (B1) of the phenol compound represented by the formula (1) is preferably a phenol compound per 1 mol of a hydroxyl group having 1.5 mol or more. 30 320525 200921277 The radiation sensitive resin composition of the present invention contains a quinonediazidesulfonate (B2) of a phenolic compound. Z7
R至R18分別獨立地表示氳原 之絲、钱3至1()之魏基、碳數2至4之縣、碳數 之说乳基或苯基(可經碳數1至4之絲、卣素原 :數二烧氧基取代),或在兩個取代基間可形成 石反數3至1 〇之環]。 碳數1至10之院基可舉例如:甲基、乙基、正丙基、 異丙基、正丁基、二級丁基、三級丁基、正戊基、正己基、 正庚基、正辛基、正壬其、不&甘& ^ 土 正六基等,較佳可舉例如:甲 基、乙基、正丙基、異丙基。 碳數3至10之環烧基可舉例如:環丙基、環丁基、環 戊基U基、環庚基、環辛基、環壬基、環癸基等,較 佳可舉例如:環戊基、環己基。 碟數1至10之烧氧基可舉例b :甲氧基、乙氧基、丙 320525 31 200921277 氧基、丁氧基、戊氧基等,較佳可舉例如:甲氧基、乙氧 基。 苯基(該苯基可經鹵素原子、碳數1至4之縣、碳數 1至4之烧氧基取代)可舉例如:苯基、(鄰_、間_、對一) 甲苯基、(2’3_、2,4-、2, 5-、2, 6-、3, 4'、3, 5 —)二甲基 苯基、(2, 3, 4一、2, 3, 5~、2, 3, 6-、2, 4, 5-、2, 4, 6-、3, 4, 5-) 三曱基苯基、(2,3,4,5-、2,3,4,6_、2,3,5,6_)四曱基苯 基、五甲基苯基、2-甲基乙基苯基、2_甲基_4_乙基苯 基、2-曱基-5-乙基苯基、2—甲基—6_乙基苯基 、3-曱基-2- 乙基苯基、3-甲基-4-乙基苯基、3_甲基—5_乙基苯基、3_ 甲基-6-乙基苯基、4-甲基_2 一乙基苯基、4_甲基_3_乙基苯 基、2, 3-二甲基-4-乙基苯基、2,3_二甲基_5_乙基苯基、 2’3-二甲基-6-乙基苯基、2,4_二甲基_3—乙基苯基、2,4— 二曱基-5-乙基苯基、2,4-二甲基_6_乙基苯基、2,5_二曱 基-3-乙基苯基、2, 5-二甲基—4_乙基苯基、2, 5_二曱基一6 — 乙基苯基、2, 6-二甲基-3—乙基苯基、2, 6_二甲基_4_乙基 苯基、2, 6-二甲基-5-乙基苯基、2, 3„二甲基—4, 5_二乙基 苯基、2,3-二曱基-5,6-二乙基苯基、2,3_二甲基_4,6_二 乙基苯基、2, 4-二曱基-3, 5-二乙基苯基、2, 4一二甲基_3, 6— 一乙基苯基、2’ 4-二甲基—5, 6_二乙基苯基、2, 5_二甲基 -3,4-二乙基苯基、2,5-二甲基_3,6_二乙基苯基、2,5_二 甲基-4, 6-二乙基苯基、2, 6-二甲基-3, 4-二乙基苯基、2, 6-二甲基-4, 5-二乙基苯基、2, 6_二曱基_3,5_二乙基苯基、 2-甲基-3-丙基苯基、2-曱基_4_丙基苯基、2一曱基_5_丙基 320525 32 200921277 苯基、2 -甲基-6-丙基苯基、3 -曱基-2-丙基苯基、3 -甲基 -4-丙基苯基、3-曱基-5-丙基苯基、3-甲基-6-丙基苯基、 4 -曱基-2-丙基苯基、4 -曱基- 3_丙基苯基、2, 3-二曱基- 4-丙基苯基、2,3-二甲基-5-丙基苯基、2,3-二曱基-6-丙基 苯基、2, 4-二甲基-3 -丙基苯基、2, 二曱基-5-丙基苯基、 2,4-二甲基-6-丙基苯基、2, 5-二曱基-3-丙基苯基、2,5-二甲基-4-丙基苯基、2, 5-二曱基-6-丙基苯基、2, 6-二甲 基-3-丙基苯基、2, 6-二曱基-4-丙基苯基、2, 6-二曱基-5-丙基苯基、2, 3-二甲基-4, 5-二丙基苯基、2, 3-二甲基-5, 6- 二丙基苯基、2,3 -二曱基-4,6 -二丙基苯基、2,4 -二甲基 -3,5 -二丙基苯基、2,4-二甲基-3,6-二丙基苯基、2, 4-甲基-5, 6-二丙基苯基、2, 5-二曱基-3, 4-二丙基苯基、2, 5-二曱基-3, 6-二丙基苯基、2, 5-二甲基-4,6-二丙基笨基、 2,6-二甲基-3,4-二丙基苯基、2,6-二曱基- 4,5-二丙基苯· 基、2,6 -二甲基-3,5 -二丙基苯基、2 -曱基-3-異丙基苯基、 s 2-甲基-4-異丙基苯基、2-甲基-5-異丙基苯基、2-曱基— 異丙基苯基、3-曱基-2-異丙基苯基、3-曱基-4-異丙基笨 基、3-甲基-5-異丙基苯基、3-曱基-6-異丙基苯基、4-甲 基-2-異丙基苯基、4-曱基-3-異丙基苯基、(2, 3-、2, 4-、 r 2’5-、2,6-、3,4-、3,5-)二異丙基苯基、(鄰-、間-、對 )正丁基笨基、(鄰-、間-、對-)三級丁基苯基.、(鄰~、間 -、對-)正己基苯基、(鄰-、間-、對-)正辛基苯基、(鄰、 間—、對-)環己基苯基、(鄰-、間-、對-)氯苯基、(2, 3-、 2, 4-、2, 5-、2, 6-、3, 4-、3, 5-)二氯苯基、(2, 3, 4-、2, 3, 5-、 33 320525 200921277 2,3,6-、2,4,5-、2,4,6-、3,4,5-)三氯苯基、2_氯-3_曱 基笨基、2-氯-4-甲基苯基、2-氯-5-甲基笨基、2一氯—6一 曱基苯基、3-氯-2-曱基苯基、3-氯-4_曱基笨基、3-氯_5_ 曱基苯基、3-氯-6-甲基苯基、4-氯-2-曱基笨基、4_氯_3_ 甲基苯基、(鄰-、間—、對一)溴苯基、(2, 3一、2, 、2 5_、 2, 6-、3, 4-、3, 5-)二溴苯基、2, 3-二氯-4-甲基苯基、2,3_ 二氣-5-甲基苯基、2, 3-二氯-6-甲基苯基、2, 4-二氯-3— 曱基本基、2, 4-一虱-5-甲基苯基、2,4-二氯甲基苯其、 2, 5-二氯-3-曱基苯基、2, 5-二氣-4-甲基苯基、2 5-二氯 -6-甲基苯基、2, 6-二氯-3-甲基苯基、2, 6-二氯—4—甲基苯 基、2, 6-二氯-5-甲基苯基、(鄰_、間_、對甲氧基苯基、 (鄰-、間-、對-)乙氧基苯基、2-曱氧基-3-甲基苯基、2一 甲氧基-4-甲基苯基、2-甲氧基-5-甲基苯基、2-甲氧基—6 — 甲基苯基、3-甲氧基-2-甲基苯基、3-甲氧基-4-甲基苯基、 3-曱氧基-5-甲基苯基、3-甲氧基-6-甲基苯基、4-甲氧基 -2-曱基苯基、4-曱氧基一3_曱基苯基、2-氯-3-甲氧基-4一 甲基苯基、2-氯-3-甲氧基-5-甲基苯基、2-氯-3-甲氧基—6 — 曱基本基、2 -氣-4 -曱氣基—3-曱基苯基、2 -氯-4-甲氧基一5~ 甲基苯基、2-氯-4-曱氧基-6-甲基苯基、2-氯-5-甲氧基_3_ 曱基苯基、2-氯-5-曱氧基-4-甲基苯基、2-氯-5-甲氧基-6_ 曱基苯基、2-氯-6-曱氧基-3-曱基苯基、2-氯一6_曱氧基_4_ 甲基苯基、2-氯-6-曱氧基-5-曱基苯基、3_氯_2_曱氧基-4_ 曱基苯基、3-氯-2-曱氧基-5-甲基苯基、3-氯-2_甲氧基一6一 曱基苯基、3_氯-4-曱氧基-2-曱基苯基、3-氯-4-曱氧基—5一 320525 34 200921277 甲基苯基、3~氯+甲氧基+甲基苯基、 甲基苯基、3~翕r田与* 甲乳基、2. 虱一 甲氧基—4-甲基苯基、3-氯-5—甲氧 子基苯基、4-氣-η氧基_基苯基、4务2_=^ 甲基本基、4备2_甲氧基.甲基苯基、 二5、 甲基苯基、…-甲氧…基苯基、4妨甲甲, 甲基苯基等’較佳可舉例如:笨基、(鄰_、間二氧基* 基、(2, 3~、? l 9 c 。 )甲苯 r? , A 〇 、,5—、2,6—、3,4_、3,5_)二甲基笨義、 ,’ '、2’3, 5-'2, 3, 6-、2, 4, 5-、2, 4, 6-、3 4 5 ;、 甲基苯基、(鄰…間-、對侧基、(鄰_、間:,、對 氧基苯基。 #、)甲 刖述之酚化合物之醌二疊氮基磺酸酯中,醌二 化口物可舉例如!,2—苯醌二疊氮基磺酸酯 :基 氮基侧等,以上述之盼化合物W莫耳,有;=4 以上之羥基經酯化為佳。 '、耳 構造式所R to R18 independently represent the silk of the original, the Wei Ke of the money 3 to 1 (), the county with a carbon number of 2 to 4, the base of the carbon number or the phenyl group (the filaments of the carbon number 1 to 4, Alizarinogen: a few calcined oxy groups), or a ring of 3 to 1 Å between the two substituents. The base of the carbon number of 1 to 10 may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, dibutyl, tert-butyl, n-pentyl, n-hexyl or n-heptyl. And n-octyl, ruthenium, not & gan & ^ Orthohexyl, etc., preferably, for example, methyl, ethyl, n-propyl, isopropyl. The cycloalkyl group having 3 to 10 carbon atoms may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclopentyl U group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group or a cyclodecyl group, and preferably, for example, Cyclopentyl, cyclohexyl. The alkoxy group having a number of 1 to 10 may be exemplified by b: methoxy, ethoxy, propyl 320525 31 200921277 oxy, butoxy, pentyloxy, etc., preferably methoxy, ethoxy, for example . Phenyl group (the phenyl group may be substituted by a halogen atom, a carbon number of 1 to 4, or a carbon number of 1 to 4), for example, a phenyl group, an o-, an m-, a p-tolyl group, (2'3_, 2,4-, 2, 5-, 2, 6-, 3, 4', 3, 5 -) dimethylphenyl, (2, 3, 4, 2, 3, 5~ , 2, 3, 6-, 2, 4, 5-, 2, 4, 6-, 3, 4, 5-) tridecylphenyl, (2,3,4,5-, 2,3,4 , 6_, 2, 3, 5, 6_) tetradecylphenyl, pentamethylphenyl, 2-methylethylphenyl, 2-methyl-4-ylethyl, 2-mercapto-5 -ethylphenyl, 2-methyl-6-ethylphenyl, 3-mercapto-2-ethylphenyl, 3-methyl-4-ethylphenyl, 3-methyl-5-B Phenylphenyl, 3-methyl-6-ethylphenyl, 4-methyl-2-ethylphenyl, 4-methyl-3-ethylphenyl, 2,3-dimethyl-4-ethyl Phenylphenyl, 2,3-dimethyl-7-ethylphenyl, 2'3-dimethyl-6-ethylphenyl, 2,4-dimethyl-3-ylethyl, 2 , 4-dimercapto-5-ethylphenyl, 2,4-dimethyl-6-ethylphenyl, 2,5-didecyl-3-ethylphenyl, 2, 5-dimethyl 4- 4-ethylphenyl, 2,5-didecyl-6-ethylphenyl, 2,6-dimethyl-3-ethylphenyl, 2,6-dimethyl 4-4-ethylphenyl, 2,6-dimethyl-5-ethylphenyl, 2,3-dimethyl- 4,5-diethylphenyl, 2,3-didecyl- 5,6-Diethylphenyl, 2,3-dimethyl- 4,6-diethylphenyl, 2,4-dimercapto-3, 5-diethylphenyl, 2, 4 Dimethyl_3,6-ethylphenyl, 2'4-dimethyl-5,6-diethylphenyl, 2,5-dimethyl-3,4-diethylphenyl, 2,5-Dimethyl_3,6-diethylphenyl, 2,5-dimethyl-4,6-diethylphenyl, 2,6-dimethyl-3, 4-diethyl Phenyl, 2,6-dimethyl-4, 5-diethylphenyl, 2,6-didecyl-3,5-diethylphenyl, 2-methyl-3-propylbenzene Base, 2-indenyl-4-ylpropylphenyl, 2-indenyl_5-propyl 320525 32 200921277 Phenyl, 2-methyl-6-propylphenyl, 3-mercapto-2-propyl Phenyl, 3-methyl-4-propylphenyl, 3-mercapto-5-propylphenyl, 3-methyl-6-propylphenyl, 4-mercapto-2-propylphenyl , 4-mercapto-3-propylphenyl, 2,3-dimercapto-4-propylphenyl, 2,3-dimethyl-5-propylphenyl, 2,3-didecyl -6-propylphenyl, 2,4-dimethyl-3-propylphenyl, 2,didecyl-5-propylphenyl, 2,4-dimethyl-6-propylphenyl 2, 5-Dimercapto-3-propylphenyl, 2,5-dimethyl-4-propylphenyl, 2,5-didecyl-6-propylphenyl, 2,6-di Methyl-3-propylphenyl, 2,6-dimercapto-4-propylphenyl, 2,6-diamidino-5-propylphenyl, 2,3-dimethyl-4, 5-dipropylphenyl, 2,3-dimethyl-5,6-dipropylphenyl, 2,3-dimercapto-4,6-dipropylphenyl, 2,4-dimethyl 3-,5-dipropylphenyl, 2,4-dimethyl-3,6-dipropylphenyl, 2,4-methyl-5,6-dipropylphenyl, 2, 5 -dimercapto-3,4-dipropylphenyl, 2,5-dimercapto-3,6-dipropylphenyl, 2,5-dimethyl-4,6-dipropyl stupyl , 2,6-Dimethyl-3,4-dipropylphenyl, 2,6-dimercapto-4,5-dipropylbenzyl, 2,6-dimethyl-3,5- Dipropyl phenyl, 2-mercapto-3-isopropylphenyl, s 2-methyl-4-isopropylphenyl, 2-methyl-5-isopropylphenyl, 2-fluorenyl —isopropyl phenyl, 3-mercapto-2-isopropylphenyl, 3-mercapto-4-isopropylphenyl, 3-methyl-5-isopropylphenyl, 3-fluorenyl -6-isopropylphenyl, 4-methyl-2-isopropylphenyl, 4-mercapto-3-isopropylphenyl, (2, 3-, 2, 4-, r 2'5 -, 2, 6- , 3,4-, 3,5-)diisopropylphenyl, (o-, m-, p-)-n-butyl, (o-, m-, p-)-tert-butylphenyl. , (o-, m-, p-)-n-hexylphenyl, (o-, m-, p-)-n-octylphenyl, (o, m-, p-)cyclohexylphenyl, (o-), M-, p--chlorophenyl, (2, 3-, 2, 4-, 2, 5-, 2, 6-, 3, 4-, 3, 5-) dichlorophenyl, (2, 3 , 4-, 2, 3, 5-, 33 320525 200921277 2,3,6-, 2,4,5-, 2,4,6-, 3,4,5-)trichlorophenyl, 2-chloro -3_曱基笨基, 2-chloro-4-methylphenyl, 2-chloro-5-methylphenyl, 2-chloro-6-nonylphenyl, 3-chloro-2-indenylbenzene , 3-chloro-4-hydrazino, 3-chloro-5-nonylphenyl, 3-chloro-6-methylphenyl, 4-chloro-2-indolyl, 4-chloro-3-3 Methylphenyl, (o-, m-, p-) bromophenyl, (2, 3, 2, 2, 5, 2, 6-, 3, 4-, 3, 5-) dibromophenyl , 2, 3-dichloro-4-methylphenyl, 2,3-di-2-methylphenyl, 2,3-dichloro-6-methylphenyl, 2,4-dichloro-3 — 曱 basic group, 2, 4-indol-5-methylphenyl, 2,4-dichloromethylbenzene, 2, 5-dichloro-3-indolylphenyl, 2, 5-diox -4- Methylphenyl, 2 5-dichloro-6-methylphenyl, 2,6-dichloro-3-methylphenyl, 2,6-dichloro-4-methylphenyl, 2,6- Dichloro-5-methylphenyl, (o-, m-, p-methoxyphenyl, (o-, m-, p-)ethoxyphenyl, 2-decyloxy-3-methyl Phenyl, 2-methoxy-4-methylphenyl, 2-methoxy-5-methylphenyl, 2-methoxy-6-methylphenyl, 3-methoxy-2- Methylphenyl, 3-methoxy-4-methylphenyl, 3-decyloxy-5-methylphenyl, 3-methoxy-6-methylphenyl, 4-methoxy- 2-nonylphenyl, 4-decyloxy-3-indolylphenyl, 2-chloro-3-methoxy-4-methylphenyl, 2-chloro-3-methoxy-5-methyl Phenyl, 2-chloro-3-methoxy-6-fluorenyl, 2-air-4-fluorenyl-3-mercaptophenyl, 2-chloro-4-methoxy-5~ Phenyl, 2-chloro-4-indolyl-6-methylphenyl, 2-chloro-5-methoxy-3-ylnonylphenyl, 2-chloro-5-decyloxy-4-methyl Phenylphenyl, 2-chloro-5-methoxy-6-nonylphenyl, 2-chloro-6-decyloxy-3-indolylphenyl, 2-chloro-6-methoxy-_4_methyl Phenyl, 2-chloro-6-nonyloxy-5-mercaptophenyl, 3-chloro-2-indolyl-4-nonylphenyl, 3-chloro- 2-decyloxy-5-methylphenyl, 3-chloro-2-methoxy-hexamethylenephenyl, 3-chloro-4-indolyl-2-mercaptophenyl, 3-chloro -4-methoxy-5-320525 34 200921277 Methylphenyl, 3-Chloro+methoxy+methylphenyl, methylphenyl, 3~翕r field and *methylmercapto, 2. Methoxy- 4-methylphenyl, 3-chloro-5-methoxyphenyl, 4-vapor-n-oxyphenyl, 4-hydroxy-2_=^ methyl-based, 4-prepared 2- Oxy.methylphenyl, di-5, methylphenyl, ...-methoxyphenyl, 4-methyl, methylphenyl, etc., preferably, for example, stupid, (o), Dioxy* group, (2, 3~,? l 9 c . Toluene r?, A 〇,, 5-, 2,6-, 3,4_, 3,5_) dimethyl sin, , ' ', 2' 3, 5-'2, 3, 6-, 2 , 4, 5-, 2, 4, 6-, 3 4 5 ;, methylphenyl, (o-...--, p-side group, (o-, m-, p-oxyphenyl). In the quinonediazide sulfonate of the phenolic compound described in the above, the oxime oxime may be, for example, a 2-benzoquinonediazide sulfonate: a azo group side, etc., in the above-mentioned desired compound. W Moer, there; = 4 or more hydroxyl groups are preferably esterified. ', ear structure
气(2)所示之朌化合物較佳可舉例如下述 之化合物等:The hydrazine compound represented by the gas (2) is preferably, for example, the following compounds:
紛化合物之酸 射線性樹脂組成物 以15至40%較佳 二疊氮基磺酸酯(B)之含量,相對於感放 之固形份,質量分率以2至5〇%為隹、 。因若醌二疊氮基磺酸酯之含量在前述 320525 35 200921277 範圍内,則未曝光部與曝光部之溶解速度差增加,而有可 維持向度之顯影膜殘留率之傾向,故佳。 本發明之感放射線性樹脂組成物通常係在經與溶 混合而稀釋之狀態下使用。 月 ' 溶劑CH)可舉例如:乙二醇單甲醚、乙二醇單***、 二醇單丙醚、乙二醇單丁醚等乙二醇單烷基醚類;二乙^ 醇二甲醚、二乙二醇二***、二乙二醇二丙醚、二乙二醇 一丁醚等二乙二醇二烷基醚類;甲基赛路蘇乙酸酉旨 (methylcellosolve acetate)、乙基赛路蘇乙酸酯等乙二 醇烷基醚乙酸酯類;丙二醇單曱醚乙酸 — 一知早乙鍵 =¾¾、丙二醇單丙醚乙酸醋等丙二醇烷基醚乙酸酯類; 本、曱苯、二甲苯、三甲苯(mesitylene)等芳香族烴類. 甲基乙基綱、丙酮、甲基戊基酮、甲基異丁基酉同己嗣 等酮類;乙醇、丙醇、丁醇、己醇、環已醇、.乙二醇、·° 油等醇類;2-經基異丁酸甲酉旨、乳酸乙酉旨、乳酸丁酉旨3甘 乙氧基丙酸乙醋、3-甲氧基丙酸甲醋等醋類;厂丁^ 環狀酯類等。較佳之溶劑可舉例如:2_絲異丁酸甲酉旨曰、、 乳酸乙酉旨、丙二醇單甲_乙酸酉旨、3—乙氧基丙酸乙, 其中尤以2-羥基異丁酸甲酯為佳。 曰、’ 、.溶劑⑻可單獨使用或組合2種以上使用,其使 對於感放射線性樹脂組成物之合計量,質量分率通a、、、、 至95質量% ’且以50至95質量%為佳。… :' 用以形成垂直定向型液晶顯示元件用之突起及 阻式間隔件的本發明之感放射線性樹脂組成物係顯示高膜 320525 36 200921277 歹4留率’且為高威声,廿α 率之硬化樹腊圖宰Γ而且:提供在可見光區具有高穿透 適合做為垂直定向型液曰顯由於^更化樹脂圖案係可形成 式間隔件用之形狀者,故做::用用或做為光阻 :二之f起或做為用以形成光阻式間隔件皆 間隔件,而在製造垂吉Λ 突起與光阻式 驟 、疋向型液晶顯示元件時可減少步 現,本d’、;!以同時形成之感放射線性樹脂組成物時發 ::月之感放射線性樹脂組成物因在該兩者之形成方 2用’所以特別適於用以同時形成垂直定向型液 曰曰顯示元件之突起與光阻式間隔件。 在本發月之感放射線性樹脂組成物中,除了共聚物 ^ )、酚化合物之醌二疊氮基磺酸酯⑻、溶劑⑻以外,依 需要,也可含有陽離子聚合起始劑((:)、敏化劑(D)、多元 酚化合物(E)、交聯劑(F)、聚合性單體(G)。 陽離子聚合起始劑(c)可舉例如鏘鹽(〇niumsalt)。鏽 鹽係由鑌鹽陽離子、與源自路易士酸(Lewis acid)之陰離 子所構成。 前述之鑌鹽陽離子之具體例可舉例如:二苯基鍈、雙 (對甲苯基)鎭、雙(對三級丁基苯基)鎖、雙(對辛基苯基) 錤、雙(對十八烷基苯基)錤、雙(對辛氧基苯基)錤、雙(對 十八烷氧基苯基)鎭、苯基(對十八烷氧基苯基)錤、(對甲 苯基)(對異丙基苯基)錤、甲基萘基錤、乙基萘基錤、三苯 基毓、(對甲苯基)二苯基毓、參(對曱苯基)锍、參(對異丙 320525 37 200921277 基苯基)毓、參(2, 6-二甲基苯基)毓、參(對三級丁基苯基) 毓、參(對氰苯基)毓、參(對氯苯基)鏡、二曱基萘基毓、 一乙基奈基銃、二曱基(4-羥基苯基)锍、二甲基(曱氧基苯 基)銃、二甲基(乙氧基苯基)毓、二甲基(丙氧基苯基)銃、 一甲基(丁氧基苯基)毓、二甲基(辛氧基苯基)毓、二甲基 八烷氧基苯基)毓、二甲基(異丙氧基苯基)毓、二曱基 (三級丁氧基苯基)毓、二甲基(環戊氧基苯基)锍、二甲基 (環己氧基苯基)毓、二甲基(氟甲氧基苯基)毓、二甲基(2_ 氯乙氧基苯基)毓、二曱基(3 —溴丙氧基苯基).鏡、二曱基(4一 乳丁氧基苯基)鏑、二甲基(8一硝基辛氧基笨基)锍、二曱基 (18-二氣甲基十八烷氧基苯基)毓、二甲基(2_羥基異丙氧 基苯基)鏡、二甲基(參(三氯甲基)甲基)毓、二苯基(4_經 苯基)鏑、甲基苯基(4-羥苯基)銃、二苯甲基苯基毓、二苯 甲基(4-經苯基)鏡、苯甲基曱基(4_.甲苯基)鏡、苯甲基甲 基(4-搜苯基)鏡、苯甲基曱基(4_乙酿氧基苯基)蔬、苯甲 基甲基(4-甲氧羰基氧基苯基)毓、甲基(4_羥苯基)(2 一甲基 苯甲基)銃、甲基(4-乙醯氧基苯基)(2_甲基苯甲基)蔬、環 己基甲基(2,基環己基)蔬等。較佳之錯鹽陽離子可舉例 如:二苯基鎭、雙(對甲苯基)鐄、(對甲苯基)(對異丙基苯 基)鎮、雙(對三級丁基苯基)鎖、三苯基鏡、(對甲苯基) 二苯基蔬、參(對三級丁基苯基)鏡、二苯基(4_經苯基)鏡、 甲基苯基(4-羥苯基)鏡、二苯甲基苯基鏡、二苯甲基* 經苯基)銃、苯甲基甲基(4—甲苯基)銃、苯甲基甲基(4-經 苯基)鏑、苯甲基甲基(4_乙醯氧基笨基)鏡、甲基(4_乙酿 320525 38 200921277 氧基苯基)(2—f基苯?基)毓、甲基(4-經苯基)(2-甲基苯 f基)銃、環己基甲基(2一酮基環己基)毓。 ^前述之源自路易士酸之陰離子之具體例可舉例如··六 氟鱗酸根料、六氟砰酸根離子、六㈣酸根離子、肆(五 亂苯基)顺根離子、甲磺酸根離子、乙石黃酸根離子、丁錯 酸根離子、戊賴根離子、己賴根離子、庚磺酸根離子、、 辛石只酉夂根離子、壬石黃酸根離子、癸石黃酸根離子、三氣甲續 酉夂,離子、全氟乙確酸根離子、全氟丙續酸根離子、全氣 丁續酸根離子、全氣戊石黃酸根離子、全氟己磺酸根離子、 全氟庚磺酸根離子、全氟辛賴根料、全氟壬續酸根離 子、全氟癸磺酸根離子、雙(三氟甲磺醯)亞胺根離子、雙(全 氟乙,醯)亞胺根離子、雙(全氟丙磺醯)亞胺根離子、雙(全 ,丁 =醯)亞胺根離子、雙(全氟戊磺醯)亞胺根離子、雙(全 ,己=醯)亞胺根離子、雙(全氟庚磺醯)亞胺根離子、雙(全 齓辛^醯)亞胺根離子、雙(全氟壬磺醯)亞胺根離子、雙(全 ^癸石黃酿)亞胺根離子|三1甲獅全氟丁相亞胺根離 、參(二氟甲磺醯)曱基負離子、參(全氟乙碏醯 離子、參(全氣丙石黃酿)甲基負離子、參(全氣;石黃醢 負離子等,較佳可舉例如:六氟磷酸根離子、六 離子、六a銻酸根離子或肆(五氟苯基)硼酸根離子、甲2 魏離子、三氟甲石黃酸根離子、全敦丁石黃酸根離子、全氟 =尹、I义根離子、雙(三氟甲磺醯)亞胺根離子、雙(全氟丁碏 酸)亞胺根離子。 * 月1J述之錯鹽陽離子及源自路易士酸之陰離子可任意組 320525 39 200921277 合。 陽離子聚合起始劑之具體例可舉例如:六氟磷酸二苯 基錤、六氟磷酸雙(對甲苯基)鐵、六氟磷酸雙(對三級丁基 苯基)鎭、六氟磷酸雙(對辛基苯基)錤、六氟磷酸雙(對十 八烷基苯基)鎖、六氟磷酸雙(對辛氧基苯基)錤、六氟磷酸 雙(對十八烷氧基苯基)錤、六氟磷酸苯基(對十八烷氧基苯 基)錤、六氟填酸(對曱苯基)(對異丙基苯基)鐵、六氟填酸 甲基萘基錤、六氟磷酸乙基萘基錤等六氟磷酸錤鹽。 此外,可舉例如:六農磷酸三苯基毓、六氟磷酸(對甲 苯基)二苯基毓、六氟磷酸參(對甲苯基)毓、六氟磷酸參(對 異丙基苯基)毓、六氟磷酸參(2, 6-二甲基苯基)毓、六氟磷 酸參(對三級丁基苯基)毓、六氟磷酸參(對氰苯基)锍、六 氟磷酸參(對氯苯基)毓、六氟磷酸二曱基萘基毓、六氟磷 酸二乙基萘基毓、六氟磷酸二甲基(甲氧基苯基)毓、六氟 磷酸二甲基(乙氧基苯基)毓、六氟磷酸二曱基(丙氧基苯基) 毓、六氟磷酸二甲基(丁氧基苯基)毓、六氟磷酸二曱基(辛 氧基苯基)鏑、六氟磷酸二甲基(十八烷氧基苯基)毓、六氟 磷酸二曱基(異丙氧基苯基)锍、六氟磷酸二曱基(三級丁氧 基苯基)毓、六氟磷酸二甲基(環戊氧基苯基)毓、六氟磷酸 二曱基(環己氧基苯基)锍、六氟磷酸二曱基(氟曱氧基苯基) 锍、六氟磷酸二甲基(2-氯乙氧基苯基)蔬、六氟磷酸二甲 基(3·~漠丙氧基苯基)蔬、六敗填酸二甲基(4 -氰丁氧基苯基) 鏡、六敗鱗酸二甲基(8 -頌基辛氧基苯基)蔬、六敦磷:酸二 甲基(18-三氟曱基十八烷氧基苯基)毓、六氟磷酸二曱基 40 320525 200921277 (2 -經基異丙氧基苯基)鏡、六氟鱗酸二甲基(參(三氯甲基) 甲基)毓、六氟磷酸二苯基(4-羥苯基)銃、六氟磷酸甲基苯 基(4-羥苯基)锍、六氟磷酸二苯甲基苯基毓、六氟磷酸二 苯甲基(4-羥苯基)毓、六氟磷酸苯甲基甲基(4-曱苯基) 毓、六氟磷酸苯曱基甲基(4-羥苯基)毓、六氟磷酸苯甲基 甲基(4-乙醯氧基苯基)锍、六氟磷酸苯甲基甲基(4-甲氧羰 基氧基苯基)锍、六氟磷酸甲基(4-羥苯基)(2-甲基苯甲基) 毓、六氟磷酸甲基(4-乙醯氧基苯基)(2-甲基苯甲基)毓、 六氟磷酸環己基曱基(2-酮基環己基)锍等六敦磷酸锍鹽。 此外,可舉例如:六It珅酸二苯基鎖、六氟神酸雙(對 甲苯基)錤、六氟砷酸雙(對三級丁基苯基)錤、六氟砷酸雙 (對辛基苯基)鐵、六氟神酸雙(對十八烧基苯基)錤、六氟 砷酸雙(對辛氧基苯基)錤、六氟砷酸雙(對十八烷氧基苯基) 錤、六氟砷酸苯基(對十八烷氧基苯基)錤、六氟砷酸(對曱 苯基)(對異丙基苯基)錤、六氟砷酸曱基萘基錤、六氟砷酸 乙基萘基鎭;六氟砷酸三苯基毓、六氟砷酸(對曱苯基)二 苯基毓、六氟砷酸參(對甲苯基)毓、六氟砷酸參(對異丙基 苯基)毓、六氟砷酸參(2, 6-二曱基苯基)毓、六氟砷酸參(對 三級丁基苯基)毓、六氟砷酸參(對氰苯基)毓、六氟砷酸參 (對氯苯基)毓、六氟砷酸二甲基萘基毓、六氟砷酸二乙基 萘基毓、六氟砷酸二曱基(曱氧基苯基)锍、六氟砷酸二甲 基(乙氧基苯基)毓、六氟砷酸二曱基(丙氧基苯基)锍、六 氟砷酸二甲基(丁氧基苯基)毓、六氟砷酸二曱基(辛氧基苯 基)毓、六氟砷酸二曱基(十八烷氧基苯基)毓、六氟砷酸二 41 320525 200921277 甲基(異丙氧基苯基)毓、六氟砷酸二甲基(三級丁氧基苯基) 蔬/、氟石申酸二甲基(環戊氧基苯基)銃、六氟坤酸二甲基 (環己氧基苯基)毓、六氟砷酸二甲基(氟曱氧基苯基)毓、 鼠申I —甲基(2-乳乙氧基苯基)鏡、六氟石申酸二甲基(3_ 溴丙氧基苯基)蔬、六氟砷酸二甲基(4_氰丁氧基苯基)毓、 八氟砷酸二甲基(8-硝基辛氧基苯基)毓、六氟砷酸二甲基 (18 —三氟甲基十八烷氧基苯基)毓、六氟砷酸二甲基(2-羥 基異丙氧基苯基)銃、六氟砷酸二甲基(參(三氣甲基)甲基) 毓、/、氟砷酸二苯基(4-羥苯基)毓、六氟砷酸甲基苯基(4— 羥苯基)毓、六氟砷酸二苯甲基苯基毓、六氟砷酸二苯曱基 (4-羥苯基)毓、六氟砷酸苯甲基甲基(4-曱苯基)毓、六氟 申酉文苯甲基甲基(4-羥苯基)毓、六氟砷酸苯甲基甲基(4一 ^酿氧基苯基)鏡、六氟坤酸苯甲基甲基(4_甲氧幾基氧基 苯基)毓、六氟砷酸甲基(4_羥苯基)(2_甲基苯甲基)毓、六 氟:酸甲基(4-乙醯氧基苯基>(2—甲基苯曱基)蔬、六氣^ 酉欠%、已基甲基(2-酮基環己基)毓等六氟砷酸毓鹽。 此外,可舉例如··六氟銻酸二苯基鐄、六氟銻酸雙(對 甲苯基)鐵、六氟錦酸雙(對三級丁基苯基)鎖、六_酸雙 (對辛基苯基)鎖、六氟錄酸雙(對十八烧基苯基)鎭、六氟 錦酸雙(對辛氧基苯基)錤、六氟録酸雙(對十八院氧基苯基) ^六㈣酸苯基(對十八烧氧基苯基)鐵、六氟銻酸(對甲 本基)(對異丙基苯基)錤、六氟㈣甲基萘絲、六氣錄酸 二基萘絲等六氟錄酸錤鹽;六氟銻酸三苯、六氣録 文對甲本基)二苯基毓、六氟銻酸參(對甲苯基)鏡、六氟 320525 42 200921277 銻S文參(對異丙基苯基)鏡、六氟銻酸參(2, 二甲基苯基) 毓、六氟銻酸參(對三級丁基苯基)毓、六氟銻酸參(對氛苯 基)毓、六氟銻酸參(對氯苯基)鏑、六氟銻酸二甲基萘基 毓、六氟銻酸二乙基萘基毓、六氟銻酸二曱基(曱氧基苯基) 毓、六氟銻酸二甲基(乙氧基苯基)毓、六氟銻酸二曱基(丙 氧基苯基)毓、六氟銻酸二曱基(丁氧基苯基)毓、六氟銻酸 二曱基(辛氧基苯基)毓、六氟銻酸二甲基(十八烷氧基苯基) 毓八氟銻酉文一甲基(異丙氧基苯基)毓、六氟録酸二甲基 (二級丁氧基苯基)毓、六氟銻酸二甲基(環戊氧基苯基) 毓、六氟銻酸二甲基(環己氧基笨基)毓、六氟銻酸二甲基 (氟甲氧基苯基)毓、六氟銻酸二甲基(2-氯乙氧基苯基) 毓、六氟銻酸二甲基(3-溴丙氧基苯基)毓、六氟銻酸二甲 基(4-氰丁氧基苯基)毓、六氟銻酸二甲基硝基辛氧基苯 基)鏑、六氟録酸二甲基(18—三氟甲基十八烷氧基苯"基) 毓、六氟銻酸二甲基(2—經基異丙氧基苯基)毓、六氟録酸 一甲基(參(二氯f基)曱基)毓、六氟銻酸二苯基(4_羥苯基) 毓、六氟銻酸甲基苯基(4—羥苯基)銃、六氟銻酸二^甲ς 苯基毓、六氟銻酸二苯甲基(4-羥苯基)毓、六氟銻酸苯〇 基曱基(4-甲苯基)鏑、六氟銻酸苯甲基曱基(4一羥苯基) ^、六氟銻酸苯甲基甲基(4-乙醯氧基苯基)毓、六氟銻酸 本曱基甲基(4-甲氧幾基氧基苯基)鏡、六氟銻酸甲基(4一 羥苯基)(2-甲基苯甲基)毓、六氟銻酸甲基(4_乙醯氧"基苯 基)(2-甲基苯曱基)毓、六氟銻酸環己基甲基(2-酮基環己 基)毓等六氟銻酸毓鹽。 衣 320525 43 200921277 此外,可舉例如:肆(五氟苯基)硼酸二苯基錤、肆(五 氟苯基)硼酸雙(對甲苯基)鎭、肆(五氟苯基)硼酸雙(對三 級丁基苯基)鎭、肆(五氟苯基)硼酸雙(對辛基苯基)錤、肆 (五氟苯基)硼酸雙(對十八烷基苯基)銷、肆(五氟苯基)硼 酸雙(對辛氧基苯基)鎭、肆(五氟苯基)硼酸雙(對十八烷氧 基苯基)鎭、肆(五氟苯基)硼酸苯基(對十八烷氧基苯基) 鏘、肆(五氟苯基)删酸(對甲苯基)(對異丙基苯基)銷、肆 (五氟苯基)硼酸甲基萘基錤、肆(五氟苯基)硼酸乙基萘基 鎭等肆(五氟苯基)硼酸鐄鹽;肆(五氟苯基)硼酸三苯基 毓、肆(五氟苯基)賴(對甲苯基)二苯基蔬、肆(五氣苯基) 魏參(對甲苯基)毓、肆(五說苯基)硼酸參(對異丙基苯基) 鏑、肆(五^苯基)猶參(2,6_二甲基苯基)蔬、肆(五氣苯 基)领I茶(對三級丁基苯基)疏、肆(五氟苯基)獨酸參(對 ^氰苯基).毓、肆(五氟苯基)硼酸參(對氯苯基)鏑、肆(五氟 本基)職二甲基萘基銃、肆(五氟苯基)棚酸二乙基蔡基 毓、肆(五氟苯基)蝴酸二甲基(甲氧基苯基)銃、肆(五氟苯 基)蝴酉文―甲基(乙氧基苯基)毓、肆(五氟苯基)删酸二甲芙 ^丙氧基苯基)毓、肆(五氟苯基)蝴酸二甲基(丁氧基苯基 ,、肆氟苯基)賢二甲基(辛氧基苯基)鏑、肆(五氟苯 :獨酸一甲基(十八院氧基苯基)蔬、肆(五氟苯基)蝴酸二 发土 (#異丙氧基苯基)銃、肆(五氟苯基)硼酸二甲基(三級丁 =基苯基)毓、肆(五氟苯基)硼酸二罗基(環戊氧基苯基) =肆(五氟苯基)蝴酸二甲基(環己氧基苯基)鏡、肆(五氟 本土硕H基(氟甲氧基苯基)鏡、肆(五氟苯基)观酸二 320525 44 200921277 甲基(2~氣乙氧基本基)鏡、肆(五氟苯基)蝴酸二甲基(3一 溴丙氧基笨基)毓、肆(五氟苯基)棚酸二p基(4_氰丁氧基 苯基)毓、肆(五氟苯基)蝴酸二甲基(8_硝基辛氧基苯基) 毓、肆(五氟苯基)硼酸二甲基(18—三氟甲基十八烷氧基苯 基)毓、肆(五氟苯基)硼酸二甲基(2_羥基異丙氧基苯基) 銃、肆(五氟苯基)硼酸二甲基(參(三氯甲基)甲基)毓、肆 (五氣苯基)删酸二苯基(4_經苯基邊、肆(五氣苯基)鄉酸 甲基苯基(4-羥苯基)毓、肆(五氟苯基)硼酸二苯曱基苯基 毓、肆(五氟苯基)硼酸二苯甲基(4 —羥苯基)毓、肆(五氟苯 基)賴苯甲基甲基(4 一甲苯基)蔬、肆(五氟苯基)賴苯甲 基曱基(4-經苯基)蔬、肆(五氟苯基)硼酸笨甲基甲基一 乙醯氧基苯基)毓、肆(五氟苯基)硼酸苯甲基甲基甲氧 幾基=基苯基)鏡、肆(五氟苯基)聽甲基(4_絲基)(2_ 甲基苯Τ基)銃、肆(五亂苯基)聲酸甲基一乙酿氧基苯 基)(2-甲基苯甲基)毓、肆(五氟苯基)删酸環己基甲基(2 一 酮基%己基)毓等肆(五氟苯基)硼酸毓鹽。 此外,可舉例如:甲磺酸二苯基鐄 '曱旙酸雙(對曱苯 基)錤、甲石黃酸雙(對三級丁基苯基)錤、甲續酸雙(對辛其 ^基)鐵、甲石黃酸雙(對十八燒基苯基)鎭、甲石黃酸雙(料 ^基苯基)鐄、甲石黃酸雙(對十八燒氧基苯基)鎖、甲石黃酸苯 十八f氧基苯基)鎮、甲續酸(對曱苯基)(對異丙基苯 =甲%^?基奈基鎭、甲石黃酸乙基萘基鮮甲石黃酸錤 此外,可舉例如:曱石黃酸三苯基鏡、曱石黃酸(對甲苯基) 320525 45 200921277 二苯絲、甲賴參(對甲苯基遍、甲雜參(對異丙基苯 基)鏑、甲續酸參(2, 6-二?基苯基)毓、甲續酸參(對三級 丁基苯基)鏡、甲續酸參(對氰苯基)鏑、甲項酸參(對氯苯 基)毓、曱石黃酸二甲基蔡基銃、曱石黃酸二曱基(曱氧基苯基) ^甲石貝酉夂一甲基(乙氧基苯基)鏡、甲石黃酸二甲基(丙氧基 ,基)鏑甲一甲基(丁氧基苯基)鏡、甲石黃酸二曱基(辛 氧基苯基)毓、甲績酸二甲基(十八烧氧基苯基)疏、甲石黃酸 一甲基(異丙氧基苯基)毓、甲磺酸二甲基(三級丁氧基苯基) 鏡、甲石黃酸二曱基(環戊氧基苯基)鏡、甲石黃酸二甲基(環己 氧基苯基)蔬、曱續酸二甲基(氟曱氧基苯基)鏡、曱磺酸二 甲基(2-氯乙氧基苯基)蔬、甲磺酸二甲基(3_演丙氧基苯基) 鏡甲只酉欠一甲基(4-氰丁氧基苯基)蔬、甲續酸二甲基(8_ 确基辛氧基苯基)毓、曱磺酸二甲基(1δ_三氟曱基十八院氧 f苯基)毓、甲續酸二甲基(2-絲異丙氧基苯基)毓、甲磺 酸二曱基(參(三氯曱基)曱基)蔬、曱石黃酸二苯基(4 —經苯基) 蔬甲石?、馱甲基苯基(4-羥苯基)毓、曱磺酸二苯曱基苯基 銃甲碩駄一苯曱基(4-羥苯基)毓、甲磺酸苯曱基甲基(4_ 甲苯基)毓、甲磺酸苯甲基甲基(4_羥苯基)毓、曱磺酸苯甲 基曱基(4-乙醯氧基苯基)毓、甲磺酸苯曱基曱基(4_曱氧羰 基氧基苯基)毓、曱磺酸甲基(4-羥苯基)(2-甲基苯甲基) =、曱磺酸曱基(4-乙醯氧基苯基)(2_甲基苯曱基)毓、曱 石κ 己基甲基(2 —酮基環己基)锍等甲磺酸毓鹽。 此外,可舉例如:三氟曱磺酸二苯基錤、三氟甲磺酸 雙(對甲苯基)錤、三氟曱磺酸雙(對三級丁基苯基)鎭、三 46 320525 200921277 氟曱磺酸雙(對辛基苯基)錤、三氟甲磺酸雙(對十八烷基苯 基)錤、三氟曱磺酸雙(對辛氧基苯基)錤、三氟曱磺酸雙(對 十八烷氧基苯基)鏔、三氟曱磺酸苯基(對十八烷氧基苯基) 錤、三氟甲磺酸(對甲苯基)(對異丙基苯基)鐄、三氟甲磺 酸甲基萘基鏘、三氟甲磺酸乙基萘基錤等三氟甲磺酸錤鹽。 此外,可舉例如:三氟甲磺酸三苯基毓、三氪甲磺酸(對 曱苯基)二苯基锍、三氟曱磺酸參(對曱苯基)毓、三氟曱磺 酸參(對異丙基苯基)毓、三氟甲磺酸參(2, 6-二甲基苯基) 鏑、三氟甲磺酸參(對三級丁基苯基)毓、三氟甲磺酸參(對 氰苯基)毓、三氟甲磺酸參(對氣苯基)毓、三氟曱磺酸二甲 基萘基鏡、三氟甲石黃酸二乙基萘基鏡、三氟甲石黃酸二甲基 (甲氧基苯基)锍、三氟曱磺酸二甲基(乙氧基苯基)毓、三 氟甲磺酸二曱基(丙氧基苯基)毓、三氟曱磺酸二甲基(丁氧 基苯基)毓、三氟曱磺酸二·甲基(辛氧基苯基)毓、三氟甲磺 酸二曱基(十八烷氧基苯基)毓、三氟曱磺酸二曱基(異丙氧 基苯基)鏡、三It曱續酸二甲基(三級丁氧基苯基)鏡、三氣 •V.. ' . 曱磺酸二曱基(環戊氧基苯基)毓、三氟曱磺酸二曱基(環己 氧基苯基)锍、三氟曱磺酸二甲基(氟甲氧基苯基)毓、三氟 甲石黃酸二甲基(2 -氯乙氧基苯基)鏡、三氟1甲石黃酸二曱基(3-溴丙氧基苯基)毓、三氟曱磺酸二甲基(4-氰丁氧基苯基) 毓、三氟甲磺酸二甲基(8-硝基辛氧基苯基)毓、三氟甲磺 酸二甲基(18-三氟曱基十八烷氧基苯基)毓、三氟曱磺酸二 曱基(2 -經基異丙氧基苯基)鏡、三說曱石黃酸二曱基(參(三 氯曱基)甲基)鏡、三氟曱石黃酸二苯基(4-經苯基)鏡、三氟 47 320525 200921277 曱磺酸甲基苯基(4-羥苯基)毓、三氟甲磺酸二苯曱基苯基 毓、三氟甲磺酸二苯甲基(4-羥苯基)毓、三氟甲磺酸苯甲 基甲基(4-甲苯基)毓、三氟甲磺酸苯甲基曱基(4-羥苯基) 鏡、三氣甲石黃酸苯甲基甲基(4 -乙酿氧基苯基)鏡、三氟甲 磺酸苯曱基曱基(4-曱氧羰基氧基苯基)毓、三氟曱磺酸曱 基(4-羥苯基)(2-甲基苯甲基)毓、三氟甲磺酸甲基(4-乙醯 氧基苯基)(2 -甲基苯甲基)鏡、三氟甲石黃酸環己基甲基(2_ 酮基環己基)鏑等三氟甲磺酸毓鹽。 此外,可舉例如:二苯基錤雙(三氟甲磺醯)亞胺、雙(對 曱苯基)錤雙(三氟曱磺醯)亞胺、雙(對三級丁基苯基)錤雙 (三氟曱磺醯)亞胺、雙(對辛基苯基)錤雙(三氟甲磺醯)亞 胺、雙(對十八烷基苯基)錤雙(三氟曱磺醯)亞胺、雙(對辛 氧基苯基)鎭雙(三氟甲磺醯)亞胺、雙(對十八烷氧基苯基) 鏘雙(三氟曱磺醯)亞胺、苯基(對十八烷氧基苯基)錤雙(三 氟曱磺醯)亞胺、(對甲苯基)(對異丙基苯基)錤雙(三氟曱 磺醯)亞胺、甲基萘基錤雙(三氟甲磺醯)亞胺、乙基萘基錤 雙(三氟甲磺醯)亞胺等錤雙(三氟甲磺醯)亞胺。 此外,可舉例如:三苯基毓雙(三氟曱磺醯)亞胺、(對 曱苯基)二苯基毓雙(三氟甲磺醯)亞胺、參(對甲苯基)鏡雙 (三氟甲石黃酿)亞胺、爹(對異丙基苯基)鏡雙(三氟曱石黃酸) 亞胺、參(2, 6-二甲基苯基)毓雙(三氟曱磺醯)亞胺、參(對 三級丁基苯基)毓雙(三氟曱磺醯)亞胺、參(對氰苯基)毓雙 (三氟曱磺醯)亞胺、參(對氯苯基)毓雙(三氟曱磺醯)亞 胺、二曱基萘基毓雙(三氟甲磺醯)亞胺、二乙基萘基毓雙 48 320525 200921277 (三氟甲磺醯)亞胺、二曱基(甲氧基苯基)毓雙(三氟曱磺醯) 亞胺、二甲基(乙氧基苯基)毓雙(三氟甲磺醯)亞胺、二曱 基(丙氧基苯基)毓雙(三氟曱磺醯)亞胺、二曱基(丁氧基苯 基)毓雙(三氟甲磺醯)亞胺、二甲基(辛氧基苯基)毓雙(三 氟甲磺醯)亞胺、二曱基(十八烷氧基苯基)毓雙(三氟曱磺 醯)亞胺、二曱基(異丙氧基苯基)毓雙(三氟曱磺醯)亞胺、 二甲基(三級丁氧基苯基)毓雙(三氟甲磺醯)亞胺、二甲基 (環戊氧基苯基)毓雙(三氟曱磺醯)亞胺、二曱基(環己氧基 苯基)毓雙(三氟甲磺醯)亞胺、二甲基(氟曱氧基苯基)毓雙 (三氟i甲石黃酿)亞胺、二甲基(2 -氯乙氧基苯基)疏雙(三氣曱 磺醯)亞胺、二甲基(3-溴丙氧基苯基)毓雙(三氟甲磺醯) 亞胺、二甲基(4-氰丁氧基苯基)毓雙(三氟甲磺醯)亞胺、 二甲基(8-硝基辛氧基苯基)毓雙(三氟甲磺醯)亞胺、二曱 基(18-三氟甲基十八烷氧基苯基)锍雙(三氟甲磺醯)亞 胺、二曱基(2-羥基異丙氧基苯基)毓雙(三氟甲磺醯)亞 胺、二曱基(參(三氯甲基)甲基)毓雙(三氟甲磺醯)亞胺、 二苯基(4-羥苯基)毓雙(三氟甲磺醯)亞胺、甲基苯基(4-羥苯基)毓雙(三氟甲磺醯)亞胺、二苯甲基苯基毓雙(三氟 甲磺醯)亞胺、二苯曱基(4-羥苯基)毓雙(三氟曱磺醯)亞 胺、苯甲基甲基(4-甲苯基)毓雙(三氟曱磺醯)亞胺、苯甲 基甲基(4-羥苯基)毓雙(三氟甲磺醯)亞胺、苯甲基甲基(4-乙醯氧基苯基)毓雙(三氟曱磺醯)亞胺、苯甲基甲基(4-曱 氧羰基氧基苯基)毓雙(三氟甲磺醯)亞胺、甲基(4-羥苯 基)(2-曱基苯曱基)锍雙(三氟曱磺醯)亞胺、曱基(4-乙醯 49 320525 200921277 氧基苯基)(2-甲基苯甲基)毓雙(三氟甲磺醯)亞胺、環己基 甲基(2-酮基環己基)毓雙(三氟甲磺醯)亞胺等毓雙(三氟 甲石黃醯)亞胺。 較佳可舉例如:六氟磷酸雙(對甲苯基)鎭、六氟磷酸 (對甲苯基)(對異丙基苯基)鎭、六氟磷酸雙(對三級-丁基苯 基)鎖、六1磷酸三苯基毓、六氟磷酸(對甲苯基)二苯基 銃、六氟磷酸參(對三級丁基苯基)毓、六氟磷酸二苯基 羥苯基)鏡、六氟磷酸甲基苯基(4_羥苯基)毓、六氟磷酸苯 甲基甲基(4-甲苯基)銃、六氟石粦酸苯甲基甲基(4_經苯基) 毓、六氣鱗酸苯甲基甲基(4—乙醯氧基苯基)鏡、六說^酸 甲基(4:乙酸氧基苯基)(2_甲基苯曱基)鏡、六氣峨酸甲基 (4經^苯基)(2-甲基苯甲基)毓、六氟磷酸環己基甲基(2-断基環己基)鏡、六氟鱗酸卜(2_酮基苯基乙基)鏡雜環 戊烷;1氟砂酸雙(對甲苯基)錤、六氟砷酸(對甲苯基)(對 =丙基苯基)錤、六氟砷酸雙(對三級丁基苯基)錤、六氟砷 酸三苯基銃、六氟碎酸(對甲苯基)二苯基銃、六氟珅酸參 .⑽二級丁基苯基)毓、六氟坤酸二苯基(4-羥苯基)銃、六 氟坤酸甲基苯基(4 —經苯基)鏑、六氟碎酸苯甲基甲基(4_ Γ苯基)銃、六氟坤酸苯甲基甲基⑷經苯基)毓、六氟石申酸 本:基甲基(4-乙酿氧基苯基)鏡、六氟石中酸甲基(4—乙醯氧 基苯基)(2-甲基苯甲基)銃、六氟砂酸甲基(4 —經苯基)(2 — I基^基)毓、六氟坤酸環己基甲基(2-酮基環己基)鏡、 雔 土本基乙基)銃雜環戊烷;六氟銻酸 又 基)鎭、六氟録酸(對T苯基)(對異丙基苯基) 320525 50 200921277 鎭、六氟銻酸雙(對三級丁基苯基)鎖、六氟銻酸三苯基銃、 六氟録酸(對f苯基)二苯基毓、六氟銻酸參(對三級丁基苯 基)銃、/、氟録酸二苯基(4-經苯基)鏡、六氟録酸甲基苯基 (4-羥苯基)毓' 六氟銻酸苯曱基甲基甲苯基)鏑、六氟 銻酸苯T基甲基(4-羥苯基)毓、六氟銻酸苯甲基甲基 乙醯氧基苯基)銃、六氟銻酸T基(4_乙醯氧基苯基)(2_甲 基苯甲基)鏑、六氟銻酸甲基(4-羥苯基)(2_甲基苯甲基) 毓、六氟銻酸環己基甲基(2_酮基環己基)毓、六氟銻酸 1-(2-酮基-2-苯基乙基)毓雜環戊烷;肆(五氟苯基)硼酸雙 (對甲苯基)鎭、肆(五氟苯基)硼酸(對甲苯基)(對異丙基苯 基)鍈、肆(五氟苯基)硼酸雙(對三級丁基苯基)鎖、肆(五 氟苯基)棚酸三苯基毓、肆(五氟苯基)蝴酸(對甲苯基)二苯 基鏑、肆(五氟苯基)硼酸參(對三級丁基苯基)毓、肆(五氟 苯基)蝴酸二苯基(4-羥苯基)毓、肆(五氟苯基)硼酸甲基苯 基(4-羥笨基)蔬、肆(五氟苯基)硼酸苯甲基曱基(4—甲苯基) 毓、肆(五氟苯基)硼酸苯曱基曱基(4_羥笨基)毓、肆(五^ 苯基)硼酸苯甲基甲基(4-乙醯氧基苯基)毓、肆(五氟苯基) 酸甲基(4-乙酿氧基苯基)(2_甲基苯甲基)毓、肆(五氣苯 基)硼酸甲基(4-羥苯基)(2-甲基苯甲基)蔬、肆(五氟苯基) 餐環己基甲基(2,基環己基)毓、肆(五氟苯基)蝴土酸 1-(2-酮基-2 —苯基乙基)毓雜環戊烷;三氟甲磺酸雙(對曱 苯基)鎭、三氟甲磺酸(對甲苯基)(對異丙基苯基)鎮、三氟 :磺酸雙(對三級丁基苯基)鎖、三氟甲磺酸三苯基毓了二 氟甲石男酸(對甲苯基)二苯基銃、三氟甲磺酸參(對三級丁基 320525 51 200921277 苯基)毓、三氟甲磺酸二苯基(4-羥苯基)鏑、三氟甲磺酸甲 基苯基(4-羥苯基)毓、三氟甲磺酸苯甲基甲基(4-甲苯基) 毓、三氟甲磺酸苯曱基甲基(4-羥苯基)毓、三氟甲磺酸苯 曱基曱基(4-乙醯氧基苯基)毓、三氟曱磺酸甲基(4-乙醯氧 基苯基)(2-曱基苯甲基)毓、三氟曱磺酸曱基(4-羥苯 基)(2-曱基苯曱基)毓、三氟曱磺酸環己基曱基(2-酮基環 己基)銳、三氟曱石黃酸1-(2 -酮基-2-苯基乙基)鏡雜環戊 烷;雙(對曱苯基)錤雙(三氟曱磺醯)亞胺、(對曱苯基)(對 異丙基苯基)錤雙(三氟曱磺醯)亞胺、雙(對三級丁基苯基) 錤雙(三氟曱磺醯)亞胺、三苯基毓雙(三氟曱磺醯)亞胺、 (對甲苯基)二苯基毓雙(三氟曱磺醯)亞胺、參(對三級丁基 苯基)鏡雙(三氟曱續醯)亞胺' 二苯基(4 -經苯基)蔬雙(三 氟曱磺醯)亞胺、曱基苯基(4-羥苯基)毓雙(三氟曱磺醯) 亞胺、苯曱基曱基(4-曱苯基)毓雙(三氟曱磺醯)亞胺、苯 曱基甲基(4-羥苯基)毓雙(三氟曱磺醯)亞胺、苯曱基曱基 (4-乙醯氧基苯基)鏑雙(三氟曱磺醯)亞胺、甲基(4-乙醯氧 基苯基)(2-甲基苯曱基)锍雙(三氟曱磺醯)亞胺、曱基(4-羥苯基)(2-甲基苯曱基)锍雙(三氟甲磺醯)亞胺、環己基曱 基(2-酮基環己基)锍雙(三氟曱磺醯)亞胺、1-(2-酮基-2-苯基乙基)鏑雜環戊烷雙(三氟曱磺醯)亞胺等。 更佳可舉例如:六氟銻酸雙(對甲苯基)錤、六氟銻酸 (對曱苯基)(對異丙基苯基)鐄、六氟銻酸雙(對三級丁基苯 基)錤、六氟銻酸三苯基毓、六氟銻酸參(對三級丁基苯基) 毓;肆(五氟苯基)硼酸雙(對甲苯基)錤、肆(五氟苯基)硼 52 320525 200921277 酸(對甲苯基)(對異丙基苯基)錤、肆(五氟苯基)硼酸雙(對 三級丁基苯基)錤、肆(五氟苯基)硼酸三苯基毓、肆(五氟 苯基)硼酸參(對三級丁基苯基)锍;三氟曱磺酸雙(對甲苯 基)錤、三氟甲磺酸(對甲苯基)(對異丙基苯基)錤、三氟甲 磺酸雙(對三級丁基苯基)錤、三氟甲磺酸三苯基毓、三氟 曱磺酸(對甲苯基)二苯基毓、三氟甲磺酸曱基苯基(4-羥苯 基)銃、三氟甲磺酸苯甲基曱基(4-甲苯基)鏑、三氟曱磺酸 苯甲基曱基(4-羥苯基)鏑、三氟曱磺酸苯甲基甲基(4-乙醯 氧基苯基)毓、三氟曱磺酸甲基(4-乙醯氧基苯基)(2-甲基 苯甲基)毓、三氟甲磺酸甲基(4-羥苯基)(2-甲基苯甲基) 毓、三氟甲磺酸環己基曱基(2-酮基環己基)毓、三氟甲磺 酸1-(2-酮基-2-苯基乙基)毓雜環戊烷;雙(對甲苯基)錤 雙(三氟曱磺醯)亞胺、(對甲苯基)(對異丙基苯基)錤雙(三 氟甲磺醯)亞胺、雙(對三級丁基苯基)鐄雙(三氟曱磺醯) 亞胺、三苯基毓雙(三氟曱磺醯)亞胺、(對曱苯基)二苯基 锍雙(三氟甲磺醯)亞胺、曱基苯基(4-羥苯基)毓雙(三氟甲 磺醯)亞胺、苯甲基曱基(4-甲苯基)毓雙(三氟甲磺醯)亞 胺、苯曱基甲基(4-羥苯基)毓雙(三氟甲磺醯)亞胺、苯甲 基甲基(4-乙醯氧基苯基)鏑雙(三氟曱磺醯)亞胺、曱基(4-'乙醯氧基苯基)(2-甲基苯曱基)毓雙(三氟甲磺醯)亞胺、甲 基(4-羥苯基)(2-甲基苯曱基)毓雙(三氟甲磺醯)亞胺、環 己基甲基(2-酮基環己基)毓雙(三氟甲磺醯)亞胺、1-(2-酮基-2-苯基乙基)毓雜環戊烷雙(三氟曱磺醯)亞胺等。 當使用陽離子聚合起始劑(C)時,其含量相對於感放射 53 320525 200921277 成物之固形份,質量分率以〇·〇ι至⑽為佳、 .=/°1佳°因若陽離子聚合起始劑(C)之含量在前 ㈣内:則有藉由提高熱硬化時之硬化速度,而抑制熱 硬化日之解析度降低現象,並且提高硬化膜 傾向,故佳。 ^ r 7 敏化劑⑻可舉例如小萘紛、2-萘m㈣萃、 ^3—二羥基萘、U-二羥基萘、1>5—二羥基萘、U—二羥 基萘、1,7-二經基萘、U二經基萘、23_;經基萘、2 6_ 一红基奈、2’7-二經基萘、4—甲氧基蔡齡等蔡紛類。特 別疋:以1-萘酚、2-萘酚、4—曱氧基+萘酚為佳。 田使用敏化劑⑻時,其含量相#於感放射線性樹脂组 成物之固形份,質量分率以G.Q1%以上1Q%以下為佳、以 〇.1%以上5%以下較佳。因若敏化劑(D)之含量在前述範 圍内’則由使用含有該敏化劑之感放射線性樹脂組成物所 形成之硬化膜之透明性會有不易降低之傾向,故佳。 多儿酚化合物(E)係在分子中具有2個以上之酚性羥 基之化合物’可舉例如:以絲苯乙烯做為原料單體而成 之聚合物、紛酸樹腊等。. 在分子中具有.2個以上之酚性羥基之化合物可舉例 如.二羥基二苯甲酮類、四羥基二苯甲酮類、五羥基二苯 甲酮類、六羥基二苯曱酮類、(聚羥基苯基)烷類等。 就至少以羥基苯乙烯做為原料單體而成之聚合物可舉 例如:聚羥基苯乙烯'羥基笨乙烯/曱基丙烯酸曱酯共聚 物、羥基苯乙烯/甲基丙烯酸環己酯共聚物、羥基苯乙烯 320525 54 200921277 /苯乙烯共聚物、减苯乙以絲基苯乙烯共聚物等夢 由將輕苯乙稀聚合而成之樹脂等。 齡賴脂可藉將選自㈣、及兒茶㈣成群組 中之至少-種化合物與選自藤類及酮所成群级中之一種以 上之化合物進行縮聚而得到。 當使用多元酚化合物⑻時,其含量相對於感放射線性 樹脂組成物之固形份,質量分率以〇1%以上.4〇%以下為 佳、以U以上25%以下較佳。因若含有多元齡化合物了 則有解析度會提高之傾向,故佳。若多元紛化合物⑻之含 量超過40% ’則有可見光穿透率會降低之傾向。 交聯劑(F)可舉例如:羥甲基化合物等。 匕經:基化合物可舉例如:烧氧基,基化三聚氰胺樹 脂、烧氧基甲基化尿素樹脂等烧氧基甲基化胺基樹脂等。 在此,烷氧基甲基化三聚氰胺樹脂.可舉例如··甲氧基甲基 化三聚氰胺樹脂、乙氧基甲基化三聚氰胺樹脂、正丙氧基 曱基化三聚氰胺樹脂、正丁氧基甲基三聚氰胺樹脂等,·烷 乳基甲基化尿讀脂可舉例如:甲氧基甲基化尿素樹脂、 ^氧基甲基化尿素樹脂、正丙氧基甲基化尿素樹腊、正丁 乳基甲基化尿素樹料。交聯劑⑺可單獨錢或組合2 種以上使用。 在本發明之感放射線性樹脂組成物卜當使用交聯劑 =)時,其含量相對於歧㈣性樹频成物之固形份,質 f分率以1%以上15%以下為佳。因若交聯劑之含量在 爾述範圍内,則有硬化膜之透明性會不易降低之傾向,故 320525 55 200921277 佳。 入聚合性單體⑻可舉例如:可經由加熱而進行The acid ray resin composition of the compound is preferably 15 to 40% by weight of the diazide sulfonate (B), and the mass fraction is 2 to 5 % by mass relative to the solid content of the sensitizing. Since the content of the quinone diazide sulfonate is in the range of 320525 35 200921277, the difference in the dissolution rate between the unexposed portion and the exposed portion is increased, and the development film retention ratio of the dimensionality is maintained, which is preferable. The radiation sensitive resin composition of the present invention is usually used in a state of being diluted with a solution. The month 'solvent CH) may, for example, be an ethylene glycol monomethyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycol monopropyl ether or ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol monobutyl ether; methylcellosolve acetate, ethyl Ethylene glycol alkyl ether acetate such as cyproacetate; propylene glycol monoterpene ether acetate - propylene glycol alkyl ether acetate such as dimethyl ether monopropyl ether acetate; propylene glycol monopropyl ether acetate vinegar; , xylene, mesylene and other aromatic hydrocarbons. Ketones such as methyl ethyl, acetone, methyl amyl ketone, methyl isobutyl hydrazine and hexanyl; ethanol, propanol, butanol, hexanol, cyclohexanol, Alcohols such as ethylene glycol and ·° oil; 2-acetate, acetate, lactic acid, glycerol, 3-methoxypropionic acid, vinegar, etc. Class; factory butyl ^ cyclic esters and so on. Preferred solvents include, for example, 2-methylisobutyric acid, lactic acid, propylene glycol monomethyl-acetate, and 3-ethoxypropionic acid, of which 2-hydroxyisobutyric acid Esters are preferred.曰,’,. The solvent (8) may be used singly or in combination of two or more kinds, and the mass fraction may be from a, to, to 95% by mass, and preferably from 50 to 95% by mass, based on the total amount of the radiation-sensitive resin composition. ... : ' The radiation sensitive resin composition of the present invention for forming a projection for a vertical alignment type liquid crystal display element and a resistive spacer exhibits a high film 320525 36 200921277 歹 4 retention rate 'and is a high power sound, 廿α rate The hardened tree wax is also used to provide a high-penetration in the visible light region and is suitable for vertical orientation. For the photoresist: the second f or as a spacer for forming the photoresist spacer, and in the manufacture of the Λ Λ protrusion and the photoresist type, the directional liquid crystal display element can reduce the step by step, this d ',;! When a radiation-sensitive linear resin composition is formed at the same time: the monthly radiation-sensitive linear resin composition is used in the formation of the two sides, so it is particularly suitable for simultaneously forming a vertically oriented liquid helium.突起 The protrusions of the display element and the photoresist spacer. In addition to the copolymer ( ), the quinone diazide sulfonate (8) of the phenol compound, and the solvent (8), the cationic polymerization initiator may be contained in the radiation sensitive linear composition of the present month. ), sensitizer (D), polyhydric phenol compound (E), crosslinking agent (F), and polymerizable monomer (G). The cationic polymerization initiator (c) may, for example, be a cerium salt. The salt is composed of a phosphonium salt cation and an anion derived from Lewis acid. Specific examples of the above-mentioned phosphonium salt cation include diphenyl hydrazine, bis(p-tolyl) fluorene, and bis (pair). Tert-butylphenyl), bis(p-octylphenyl)anthracene, bis(p-octadecylphenyl)fluorene, bis(p-octyloxyphenyl)fluorene, bis(p-octadecyloxy) Phenyl) fluorene, phenyl (p-octadecyloxyphenyl) fluorene, (p-tolyl) (p-isopropylphenyl) fluorene, methylnaphthyl anthracene, ethylnaphthyl anthracene, triphenylanthracene , (p-tolyl)diphenylphosphonium, ginseng (p-phenylene) fluorene, ginseng (p-isopropyl 320525 37 200921277 phenyl) hydrazine, ginseng (2,6-dimethylphenyl) fluorene, ginseng P-tert-butylphenyl) hydrazine, ginseng (p-cyanophenyl) fluorene, ginseng (p-chlorophenyl) mirror, dinonylnaphthyl anthracene, monoethyl fluorenyl fluorene, dimercapto (4-hydroxybenzene)锍, dimethyl (decyloxyphenyl) hydrazine, dimethyl (ethoxyphenyl) hydrazine, dimethyl (propoxyphenyl) fluorene, monomethyl (butoxyphenyl) Anthracene, dimethyl (octyloxyphenyl) fluorene, dimethyl octadecyloxy phenyl) hydrazine, dimethyl (isopropoxyphenyl) fluorene, dimercapto (tertiary butoxyphenyl) ) hydrazine, dimethyl (cyclopentyloxyphenyl) fluorene, dimethyl (cyclohexyloxyphenyl) fluorene, dimethyl (fluoromethoxyphenyl) fluorene, dimethyl (2 - chloroethoxy) Phenyl) fluorene, dihydrazino (3-bromopropyloxyphenyl). Mirror, dimercapto (4-butylbutoxyphenyl) hydrazine, dimethyl (8-nitrooctyloxy) fluorene, dimercapto (18-dimethylmethyloctadecyloxyphenyl)毓, dimethyl (2-hydroxyisopropoxyphenyl) mirror, dimethyl (paras(trichloromethyl)methyl) fluorene, diphenyl (4 phenyl) fluorene, methyl benzene (4-hydroxyphenyl) fluorene, diphenylmethyl phenyl hydrazine, diphenylmethyl (4-phenyl) mirror, benzyl fluorenyl (4_. Tolyl) mirror, benzylmethyl (4-phenyl) mirror, benzyl sulfhydryl (4-ethoxyphenyl) vegetable, benzylmethyl (4-methoxycarbonyloxybenzene) , 甲基, methyl (4-hydroxyphenyl) (2-methylbenzyl) hydrazine, methyl (4-acetoxyphenyl) (2-methylbenzyl) vegetable, cyclohexyl Base (2, cyclohexyl) vegetables and the like. Preferred examples of the wrong salt cation include diphenyl hydrazine, bis(p-tolyl) fluorene, (p-tolyl) (p-isopropylphenyl), bis(p-terphenyl), and three. Phenyl mirror, (p-tolyl) diphenyl vegetable, ginseng (p-terphenyl) mirror, diphenyl (4-phenyl) mirror, methylphenyl (4-hydroxyphenyl) mirror , Diphenylmethylphenyl mirror, Diphenylmethyl* phenyl) fluorene, benzylmethyl (4-tolyl) fluorene, benzylmethyl (4-phenyl) fluorene, benzyl Methyl (4-ethenyloxy) mirror, methyl (4_ethyl 320525 38 200921277 oxyphenyl) (2-fylphenyl) hydrazine, methyl (4-phenyl) 2-methylbenzene f-based) fluorene, cyclohexylmethyl (2-ketocyclohexyl) fluorene. ^ Specific examples of the anion derived from Lewis acid include, for example, a hexafluorobase, a hexafluoroantimonate ion, a hexa(tetra) acid ion, a ruthenium pentoxide ion, and a mesylate ion. , ethyl sulphate ion, butyric acid ion, valeric ion, hexylene root, heptanosulfonate ion, cerium sulphate ion, strontium sulphate ion, sulphate ion, three gas Continuation, ion, perfluoro acetylate ion, perfluoropropionate ion, total gas butyrate ion, total gas pentoxide ion, perfluorohexane sulfonate ion, perfluoroheptanoate ion, Perfluorooctyl ray root, perfluoro sulfonate ion, perfluoro sulfonate ion, bis(trifluoromethanesulfonate)imide ion, bis(perfluoroethylene, fluorene)imide ion, double (all Fluorine sulfonate) imine ion, bis(all, butyl = oxime) imine ion, bis(perfluoropentanesulfonate) imine ion, bis(all, hexanyl) anthracene ion, double (Perfluoropentanesulfonate) imine ion, double (all oxime) anthracene ion, bis (perfluorofluorene)醯)imine ion, double (all ^ 癸石黄酿) imine ion | three 1 lion lion perfluorobutyl phase imine root separation, ginseng (difluoromethanesulfonate) sulfhydryl anion, ginseng (perfluoro Ethyl ruthenium ion, ginseng (all-aluminum yellow wine) methyl anion, ginseng (all gas; scutellaria anion, etc., preferably hexafluorophosphate ion, hexaion ion, hexa-a citrate ion or肆(pentafluorophenyl)borate ion, A 2 Wei ion, trifluoromethane ion, all Duntunine ion, perfluoro=Yin, I-Ion, bis(trifluoromethanesulfonate) Iminoate ion, bis(perfluorobutyric acid) imine ion. * The wrong salt cation described in the month 1J and the anion derived from Lewis acid can be any combination 320525 39 200921277. Specific examples of the cationic polymerization initiator For example, diphenylphosphonium hexafluorophosphate, bis(p-tolyl) iron hexafluorophosphate, bis(p-terphenyl)phosphonium hexafluorophosphate, bis(p-octylphenyl)phosphonium hexafluorophosphate , bis(p-octadecylphenyl) hexafluorophosphate, bis(p-octyloxyphenyl)phosphonium hexafluorophosphate, bis(hexafluorophosphate) Octamethoxyphenyl)anthracene, phenylphosphoric acid phenyl(p-octadecyloxyphenyl)anthracene, hexafluoro-acid (p-phenylene) (p-isopropylphenyl) iron, hexafluoro-acid Further, a bismuth hexafluorophosphate salt such as methylnaphthyl anthracene or ethyl cyanophosphonium hexafluorophosphate. Further, for example, triphenylphosphonium hexahydrate, hexafluorophosphoric acid (p-tolyl) diphenyl fluorene, hexafluorophosphate Phosphate (p-tolyl) hydrazine, hexafluorophosphoric acid (p-isopropylphenyl) hydrazine, hexafluorophosphoric acid ginseng (2,6-dimethylphenyl) hydrazine, hexafluorophosphoric acid ginseng (p-tert-butyl butyl) Phenyl)anthracene, hexafluorophosphoric acid (p-cyanophenyl)anthracene, hexafluorophosphoric acid (p-chlorophenyl)anthracene, dinonylnaphthylphosphonium hexafluorophosphate, diethylnaphthylphosphonium hexafluorophosphate, six Dimethyl(methoxyphenyl)phosphonium fluorophosphate, dimethyl(ethoxyphenyl)phosphonium hexafluorophosphate, dinonyl (propoxyphenyl)phosphonium hexafluorophosphate, dimethyl hexafluorophosphate (butoxyphenyl)anthracene, dinonyl (octyloxyphenyl) fluorene hexafluorophosphate, dimethyl (octadecyloxyphenyl) sulfonium hexafluorophosphate, dinonyl hexafluorophosphate (isopropyl Oxyphenyl) hydrazine, Dimethyl fluorophosphate (tertiary butoxyphenyl) fluorene, dimethyl (cyclopentyloxyphenyl) fluorene hexafluorophosphate, dinonyl hexafluorophosphate (cyclohexyloxyphenyl) fluorene, hexafluoro Dimethyl fluorenyl (fluoromethoxyphenyl) hydrazine, dimethyl (2-chloroethoxyphenyl) hexafluorophosphate, dimethyl hexafluorophosphate (3·~ propyloxyphenyl) , hexahydro acid dimethyl (4-cyanobutoxyphenyl) mirror, hexa-sodium succinate (8-fluorenyl octyloxyphenyl) vegetable, hexon phosphorus: acid dimethyl (18 -trifluorodecyl octadecyloxyphenyl) fluorene, difluoromethyl hexafluorophosphate 40 320525 200921277 (2-isopropoxyphenyl) mirror, hexafluorophosphate dimethyl (parachloride Methyl)methyl)anthracene, diphenyl(4-hydroxyphenyl)phosphonium hexafluorophosphate, methylphenyl(4-hydroxyphenyl)phosphonium hexafluorophosphate, diphenylmethylphenylphosphonium hexafluorophosphate, Diphenylmethyl hexafluorophosphate (4-hydroxyphenyl) fluorene, benzylmethyl hexafluoromethyl (4-indolylphenyl) hydrazine, phenylhydrinyl hexafluoromethyl (4-hydroxyphenyl) hydrazine, Phenylmethyl hexafluoromethyl (4-acetoxyphenyl) fluorene, benzyl hexafluorophosphate 4-(4-methoxycarbonyloxyphenyl)anthracene, methyl hexafluorophosphate (4-hydroxyphenyl)(2-methylbenzyl)hydrazine, hexafluorophosphate methyl (4-acetoxybenzene) (6-methylbenzyl) hydrazine, hexafluorophosphonocyclohexyl fluorenyl (2-ketocyclohexyl) hydrazine and the like. Further, for example, hexamethylene diphenyl sulfonate, bis(p-tolyl) hexafluoroantimonate, bis(p-terphenyl) hexafluoroarsenate, and hexafluoroarsenate bis (pair) Octylphenyl)iron, hexafluoroantimonic acid bis(p-octadecylidenephenyl)anthracene, bis(p-octyloxyphenyl)phosphonium hexafluoroarsenate, bis(p-octadecyloxy) hexafluoroarsenate Phenyl) hydrazine, hexafluoroarsenic acid phenyl (p-octadecyloxyphenyl) fluorene, hexafluoroarsenic acid (p-phenylene) (p-isopropylphenyl) fluorene, hexafluoroarsenate decyl naphthalene Base group, ethylnaphthyl hexafluoroarsenate; triphenyl sulfonium hexafluoroarsenate; hexafluoroarsenic acid (p-phenylene) diphenyl fluorene, hexafluoroarsenate bis(p-tolyl) fluorene, six Fluorine arsenate (p-isopropylphenyl) hydrazine, hexafluoroarsenate bis(2,6-dimercaptophenyl) fluorene, hexafluoroarsenate bis(p-tert-butylphenyl) fluorene, hexafluoro Arsenic acid ginseng (p-cyanophenyl) hydrazine, hexafluoroarsenic acid ginseng (p-chlorophenyl) hydrazine, hexafluoroarsenic acid dimethylnaphthyl fluorene, hexafluoroarsenate diethyl naphthyl fluorene, hexafluoroarsenic acid Dimethyl (decyloxyphenyl) fluorene, hexafluoroarsenate dimethyl (ethoxyphenyl) fluorene, six Di-decyl (propoxyphenyl) ruthenium arsenate, dimethyl (butoxyphenyl) ruthenium hexafluoroarsenate, dinonyl (octyloxyphenyl) ruthenium hexafluoroarsenate, hexafluoroarsenic acid Dimercapto (octadecyloxyphenyl) fluorene, hexafluoroarsenic acid II 41 320525 200921277 methyl (isopropoxyphenyl) fluorene, hexafluoroarsenate dimethyl (tertiary butoxyphenyl) Vegetable/, fluorescein dimethyl (cyclopentyloxyphenyl) fluorene, hexafluorokunic acid dimethyl (cyclohexyloxyphenyl) fluorene, hexafluoroarsenate dimethyl (fluorononyloxybenzene)毓, 申 I I - methyl (2-lactoxyphenyl) mirror, hexafluorolithic acid dimethyl (3 bromopropyloxy phenyl) vegetable, hexafluoroarsenate dimethyl (4 _Cyanoxybutoxyphenyl) fluorene, octafluoroarsenic acid dimethyl (8-nitrooctyloxyphenyl) fluorene, hexafluoroarsenic acid dimethyl (18-trifluoromethyloctadecyloxybenzene) Dimethyl hydrazine, hexafluoroarsenate dimethyl (2-hydroxyisopropoxyphenyl) fluorene, hexafluoroarsenic acid dimethyl (paraxyl (trimethyl)methyl) hydrazine, /, fluoroarsenic acid Phenyl (4-hydroxyphenyl) fluorene, hexafluoroarsenic acid methylphenyl (4-hydroxyphenyl) fluorene, hexafluoroarsenic acid diphenyl Phenyl phenyl hydrazine, diphenyl fluorenyl (4-hydroxyphenyl) fluorene hexafluoroarsenate, benzylmethyl hexafluoroarsenate (4-indolyl phenyl) fluorene, hexafluoro phenyl benzyl methyl group (4 -hydroxyphenyl)anthracene, benzylmethyl hexafluoroarsenate (4-methoxyphenyl) mirror, hexafluoroquinic acid benzylmethyl (4-methoxyloxyphenyl) fluorene , hexafluoroarsenic acid methyl (4-hydroxyphenyl) (2-methylbenzyl) hydrazine, hexafluoro: acid methyl (4-acetoxyphenyl) (2-methylphenyl fluorenyl)蔬 六 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Acid bis(p-tolyl) iron, hexafluoroantimonic acid bis(p-tert-butylphenyl) lock, hexa-acid bis(p-octylphenyl) lock, hexafluoro acid double (p-octadecanthene benzene)鎭, hexafluoroantimonic acid bis(p-octyloxyphenyl) fluorene, hexafluoro acid bis (p-octadecyloxyphenyl) ^hexa(tetra) acid phenyl (p-octadecano-oxyphenyl) Iron, hexafluoroantimonic acid (p-carbyl) (p-isopropylphenyl) fluorene, hexafluoro(tetra)methylnaphthene, hexafluoroic acid di-naphthyl, etc. Acid strontium salt; hexafluoroantimonic acid triphenyl, hexahydrate recording on methyl group) diphenyl hydrazine, hexafluoroantimonate ginseng (p-tolyl) mirror, hexafluoro 320525 42 200921277 锑S ginseng (for isopropyl Phenyl) mirror, hexafluoroantimonate (2, dimethylphenyl) hydrazine, hexafluoroantimonate (p-tert-butylphenyl) hydrazine, hexafluoroantimonate (p-phenyl) hydrazine , hexafluoroantimonate (p-chlorophenyl) hydrazine, dimethylnaphthyl hexafluoroantimonate, diethyl naphthyl hexafluoroantimonate, dinonyl hexafluoroantimonate (decyloxyphenyl) Bismuth, dimethyl(ethoxyphenyl)phosphonium hexafluoroantimonate, dinonyl (propoxyphenyl)phosphonium hexafluoroantimonate, diindolyl (butoxyphenyl)phosphonium hexafluoroantimonate, Didecyl hexafluoroantimonate (octyloxyphenyl) hydrazine, hexafluoroantimonate dimethyl (octadecyloxyphenyl) octafluorofluorene monomethyl (isopropoxyphenyl) hydrazine , hexafluoroanthenic acid dimethyl (secondary butoxyphenyl) fluorene, hexafluoroantimonate dimethyl (cyclopentyloxyphenyl) fluorene, hexafluoroantimonate dimethyl (cyclohexyloxy) ) bismuth, hexafluoroantimonate dimethyl (fluoromethoxyphenyl) fluorene, hexafluoroantimonate dimethyl 2-Chloroethoxyphenyl) hydrazine, dimethyl(3-bromopropyloxyphenyl)phosphonium hexafluoroantimonate, dimethyl(4-cyanobutoxyphenyl)phosphonium hexafluoroantimonate, six Dimethyl nitrooctyloxyphenyl) fluoroantimonate, dimethyl hexafluoroantimonate (18-trifluoromethyloctadecyloxybenzene), dimethyl hexafluoroantimonate 2--isopropoxyphenyl)anthracene, hexafluoroanthenic acid monomethyl (parade(dichlorofyl)decyl)anthracene, hexafluoroantimonate diphenyl (4-hydroxyphenyl) oxime, six Methylphenyl fluorophenyl (4-hydroxyphenyl) hydrazine, hexafluoroantimonic acid dimethyl hydrazine phenyl hydrazine, hexafluoroantimonate diphenylmethyl (4-hydroxyphenyl) hydrazine, hexafluoroantimonic acid benzene Indolyl (4-methylphenyl) fluorene, benzyl sulfonium hexafluoroantimony (4-hydroxyphenyl) ^, benzylmethyl hexafluoroantimonate (4-acetoxyphenyl) fluorene Benzyl hexafluoroantimonate (4-methoxyloxyphenyl) mirror, hexafluoroantimonate methyl (4-hydroxyphenyl) (2-methylbenzyl) hydrazine, hexafluoro Hydrazine methyl (4_acetamethylene) <phenylphenyl)(2-methylphenylhydrazino)fluorene, hexafluoroantimonycyclohexylmethyl (2-ketocyclohexyl)pyrene, etc. Bismuth citrate salt.衣320525 43 200921277 Further, for example, diphenyl hydrazine (pentafluorophenyl)borate, bis(p-tolyl) fluorene (pentafluorophenyl) borate, bis(pentafluorophenyl)borate bis (pair) Tertiary butylphenyl) ruthenium, osmium (pentafluorophenyl)borate bis(p-octylphenyl) ruthenium, osmium (pentafluorophenyl)borate bis(p-octadecylphenyl) pin, ruthenium (five Fluorophenyl)boronic bis(p-octyloxyphenyl)anthracene, quinone (pentafluorophenyl)boronic acid bis(p-octadecyloxyphenyl)anthracene, quinone (pentafluorophenyl)boronic acid phenyl (to ten Octaoxyoxyphenyl) hydrazine, hydrazine (pentafluorophenyl)-decanoic acid (p-tolyl) (p-isopropylphenyl) pin, hydrazine (pentafluorophenyl)boronic acid methylnaphthyl hydrazine, hydrazine (five Fluorine phenyl) ethyl naphthyl fluorenyl bromide (pentafluorophenyl) borate bismuth salt; bismuth (pentafluorophenyl) borate triphenyl sulfonium, iridium (pentafluorophenyl) lysine (p-tolyl) diphenyl Base vegetables, bismuth (penta-phenyl) Weishen (p-tolyl) oxime, bismuth (five phenyl) borate (p-isopropylphenyl) 镝, 肆 (5 phenyl) ginseng (2, 6_dimethylphenyl) vegetable, 肆Five gas phenyl) leading tea I (p-tert.butyl phenyl) sparse, tetrakis (pentafluorophenyl) acid alone parameters (p ^ cyanophenyl). 毓, 肆(pentafluorophenyl)boronic acid ginseng (p-chlorophenyl) fluorene, fluorene (pentafluorophenyl) dimethyl dimethyl naphthyl fluorene, hydrazine (pentafluorophenyl) linonic acid diethyl ketone oxime, hydrazine Pentafluorophenyl)pyruvate dimethyl(methoxyphenyl)anthracene, fluorene (pentafluorophenyl) oxime-methyl(ethoxyphenyl)anthracene, fluorene (pentafluorophenyl)-decanoate Dimethyl propyl p-propoxy phenyl) hydrazine, hydrazine (pentafluorophenyl) carboxylic acid dimethyl (butoxyphenyl, fluorenyl phenyl) succinyl (octyloxyphenyl) fluorene, hydrazine (Pentafluorobenzene: monomethyl monochloride (18-yard oxyphenyl) vegetable, bismuth (pentafluorophenyl) ruthenium bromide (#isopropoxyphenyl) hydrazine, hydrazine (pentafluorophenyl) Dimethyl dimethyl (tertiary butyl = phenyl) ruthenium, ruthenium (pentafluorophenyl) borate diroyl (cyclopentyloxyphenyl) = quinone (pentafluorophenyl) carboxylic acid dimethyl (ring Hexyloxyphenyl) Mirror, Bismuth (Pentafluoro-Phase) H-based (Fluoromethoxyphenyl) Mirror, Epoxy (Pentafluorophenyl) Physic Acid II 320525 44 200921277 Methyl (2~Vethoxyethoxy) Mirror, quinone (pentafluorophenyl) carboxylic acid dimethyl (3 bromopropoxy phenyl)毓, 肆 (pentafluorophenyl) linonic acid di-p-(4-cyanobutoxyphenyl) fluorene, hydrazine (pentafluorophenyl) carboxylic acid dimethyl (8-nitrooctyloxyphenyl) hydrazine , 肆(pentafluorophenyl)borate dimethyl(18-trifluoromethyloctadecyloxyphenyl)anthracene, quinone (pentafluorophenyl)boronic acid dimethyl (2-hydroxyisopropoxyphenyl)铳, 肆 (pentafluorophenyl)boronic acid dimethyl (glycol (trichloromethyl) methyl) hydrazine, hydrazine (pentaphene phenyl) deuterated diphenyl (4_ by phenyl side, hydrazine (five) Gas phenyl) m-phenylphenyl (4-hydroxyphenyl) hydrazine, hydrazine (pentafluorophenyl) borate diphenyl phenyl hydrazine, hydrazine (pentafluorophenyl) borate diphenylmethyl (4 - Hydroxyphenyl) hydrazine, hydrazine (pentafluorophenyl) benzylidene methyl (4-methylphenyl) vegetable, hydrazine (pentafluorophenyl) lysylbenzyl sulfhydryl (4-phenyl) vegetable, hydrazine (pentafluorophenyl)boronic acid, methylmethyl-ethyloxy phenyl) fluorene, hydrazine (pentafluorophenyl)boronic acid benzylmethylmethoxymethyl=phenyl) mirror, bismuth (pentafluoro Phenyl)-methyl (4-silyl) (2-methylphenyl fluorenyl) fluorene, hydrazine (five phenyl) Ethyl quinone (pentafluorophenyl) lanthanum bromide (2-methylbenzyl) hydrazine, hydrazine (pentafluorophenyl)-decanoic acid cyclohexylmethyl (2-keto-propylhexyl) hydrazine salt. Further, for example, diphenyl sulfonium methanesulfonate bis(p-phenylphenyl) fluorene, bisphosphonate bis (p-tert-butylphenyl) fluorene, and carboxylic acid bis (pair octyl) ^基) iron, tartaric acid bis(p-octadecylidenephenyl) hydrazine, tartaric acid bis(ylphenyl) hydrazine, tartaric acid bis(p-octadecano oxyphenyl) Lock, benzoate, phenyl 18-f-oxyphenyl), m-acid (p-phenyl) (p-isopropylbenzene = methyl phthalocyanine, ethyl naphthyl) In addition, bismuth yellow phthalate may be mentioned, for example, triphenyl mirror of fluorite, fluorescein (p-tolyl) 320525 45 200921277 diphenyl wire, lysine (p-tolyl benzoate, acetophene ( P-isopropylphenyl) hydrazine, methyl sulphate (2,6-di-phenyl) fluorene, methyl sulphate (p-tert-butylphenyl) mirror, methyl citrate (p-cyanophenyl) ) 镝, A acid ginseng (p-chlorophenyl) hydrazine, phthalocyanine dimethyl zebyl hydrazine, fluorescein didecyl (decyloxy phenyl) ^ 甲石贝酉夂 monomethyl (ethoxy Phenyl) mirror, dimethylglycolate dimethyl (propoxy) (butoxyphenyl) mirror, diterpene (octyloxyphenyl) sulfonate, dimethyl dimethyl octadecyl sulfonate, monomethyl methadinate Isopropoxyphenyl)anthracene, dimethyl sulfonate (tertiary butoxyphenyl) mirror, diuphyl (cyclopentyloxyphenyl) mirror, dimethyl sulphate (cyclohexyloxyphenyl) vegetable, dimethyl hexafluoro(fluoromethoxyphenyl) mirror, dimethyl sulfonic acid dimethyl (2-chloroethoxyphenyl) vegetable, dimethyl sulfonic acid (3_Propoxyphenyl) Mirror A 酉 一 一 4- (4-cyanobutoxyphenyl) vegetable, dimethyl dimethyl (8 _ eqyl octyloxy phenyl) oxime, sulfonate Acid dimethyl (1δ_trifluorodecyl octadecyloxyl phenyl) hydrazine, methyl dimethyl (2-silisopropoxyphenyl) hydrazine, methanesulfonic acid dimercapto Chloromethyl) sulfhydryl) vegetable, bismuth diphenyl (4-phenyl) phytolith, 驮methylphenyl (4-hydroxyphenyl) hydrazine, hydrazine sulfonate铳 铳 駄 曱 曱 曱 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- 4- (4-hydroxyphenyl) fluorene, benzyl sulfonic acid benzyl sulfonyl (4-acetoxyphenyl) fluorene, phenyl fluorenyl sulfonate (4 曱 carbonyl oxy phenyl) hydrazine , sulfonic acid methyl (4-hydroxyphenyl) (2-methylbenzyl) =, sulfonium sulfonate (4-acetoxyphenyl) (2-methylphenyl fluorenyl) hydrazine, A sulfonium methanesulfonate such as yttrium hexyl hexylmethyl (2-ketocyclohexyl) hydrazine. Further, for example, diphenyl sulfonium trifluorosulfonate or bis(p-tolyl) fluorene trifluoromethanesulfonate , trifluorosulfonium sulfonic acid bis(p-terphenyl)phosphonium, tri-46 320525 200921277 bis(p-octylphenyl)fluorene sulfonate, bis(p-octadecylphenyl) trifluoromethanesulfonate錤, bis(p-octyloxyphenyl) fluorene trifluorosulfonate, bis(p-octadecyloxyphenyl) fluorene trifluorosulfonate, phenyl trifluorosulfonate (p-octadecyloxy) Phenyl, fluorene, trifluoromethanesulfonic acid (p-tolyl) (p-isopropylphenyl) fluorene, methylnaphthyltrifluoromethanesulfonate, trinaphthyltrifluoromethanesulfonate, etc. Barium mesylate salt. Further, for example, triphenylsulfonium trifluoromethanesulfonate, trimethylsulfonic acid (p-phenylene) diphenylsulfonium, trifluorosulfonium sulfonate (p-phenylene) fluorene, trifluorosulfonium sulfonate Acidic acid (p-isopropylphenyl) hydrazine, trifluoromethanesulfonic acid ginseng (2,6-dimethylphenyl) fluorene, trifluoromethanesulfonic acid ginseng (p-tert-butylphenyl) fluorene, trifluoro Methanesulfonic acid ginseng (p-cyanophenyl) fluorene, trifluoromethanesulfonic acid ginseng (p-phenylene) fluorene, trifluoromethanesulfonic acid dimethylnaphthyl mirror, trifluoromethylene phthalate diethyl naphthyl mirror , dimethyl (methoxyphenyl) fluorene trifluoromethane, dimethyl (ethoxyphenyl) fluorene trifluoromethanesulfonate, dinonyl trifluoromethanesulfonate (propoxy phenyl)毓, dimethyl (butoxyphenyl) sulfonium trifluorosulfonate, dimethyl (octyloxyphenyl) fluorene trifluoromethanesulfonate, didecyl trifluoromethanesulfonate (octadecane) Oxyphenyl) fluorene, trimethyl sulfonium sulfonate (isopropoxy phenyl) mirror, triple octal acid dimethyl (tertiary butoxyphenyl) mirror, three gas · V. . ' . Didecyl sulfonate (cyclopentyloxyphenyl) fluorene, didecyl trifluorosulfonate (cyclohexyloxyphenyl) fluorene, trifluorosulfonium sulfonate dimethyl (fluoromethoxyphenyl) Bismuth, trifluoromethylene phthalate dimethyl (2-chloroethoxyphenyl) mirror, trifluoromethane naphthyldithiol (3-bromopropoxyphenyl) fluorene, trifluorosulfonium sulfonic acid Dimethyl (4-cyanobutoxyphenyl) fluorene, dimethyl (8-nitrooctyloxyphenyl) fluorene trifluoromethanesulfonate, dimethyl trifluoromethanesulfonate (18-trifluoroanthracene) Aryl octadecyloxyphenyl) fluorene, trimethyl sulfonium sulfonate (2-isopropoxy phenyl) mirror, three bismuth phthalate (dichloro fluorenyl) Methyl) mirror, diphenyl phthalate diphenyl (4-phenyl) mirror, trifluoro 47 320525 200921277 sulfonic acid methylphenyl (4-hydroxyphenyl) fluorene, trifluoromethanesulfonic acid Benzoylphenyl hydrazine, diphenylmethyl (4-hydroxyphenyl) fluorene trifluoromethanesulfonate, benzylmethyl (4-methylphenyl) sulfonium trifluoromethanesulfonate, benzoic acid trifluoromethanesulfonate Base fluorenyl (4-hydroxyphenyl) mirror, benzotrifluoride benzylmethyl (4-ethoxylated phenyl) mirror, trifluoromethanesulfonic acid Indolyl (4-oxocarbonyloxyphenyl) fluorene, trimethylsulfonium sulfonate (4-hydroxyphenyl) (2-methylbenzyl) hydrazine, trifluoromethanesulfonate methyl ( 4-Ethyloxyphenyl)(2-methylbenzyl) mirror, trifluoromethanesulfonic acid cyclohexylmethyl (2-ketocyclohexyl) hydrazine and the like triflate. Further, for example, diphenylphosphonium bis(trifluoromethanesulfonate)imide, bis(p-phenylphenyl)fluorene bis(trifluorosulfonium)imide, bis(p-terphenyl) Bis(trifluorosulfonium)imide, bis(p-octylphenyl)phosphonium bis(trifluoromethanesulfonate)imide, bis(p-octadecylphenyl)phosphonium bis(trifluorosulfonium sulfonate) Imine, bis(p-octyloxyphenyl)indole bis(trifluoromethanesulfonate)imide, bis(p-octadecyloxyphenyl)phosphonium bis(trifluorosulfonium)imide, phenyl (p-octadecyloxyphenyl)indole bis(trifluorosulfonium sulfonate)imide, (p-tolyl)(p-isopropylphenyl)fluorene bis(trifluorosulfonium)imide, methylnaphthalene A bis(trifluoromethanesulfonyl)imine such as bis(trifluoromethanesulfonate)imide or ethylnaphthyl anthracene bis(trifluoromethanesulfonate)imide. Further, for example, triphenylsulfonium bis(trifluorosulfonium)imide, (p-phenylphenyl)diphenylphosphonium bis(trifluoromethanesulfonate)imide, ginseng (p-tolyl) mirror double (Trifluoromethine yellow) imine, hydrazine (p-isopropylphenyl) mirror bis(trifluorophthalic acid) imine, ginseng (2, 6-dimethylphenyl) bismuth (trifluoro Iridium sulfonate, imine, ginseng (p-tert-butylphenyl) bis(trifluorosulfonium sulfonate) imine, ginseng (p-cyanophenyl) bis(trifluorosulfonium sulfonate) imine, ginseng p-Chlorophenyl)indole bis(trifluorosulfonium sulfonate)imide, dinonylnaphthyl bis(trifluoromethanesulfonate)imide, diethylnaphthylhydrazine double 48 320525 200921277 (trifluoromethanesulfonate) Imine, dimethyl (methoxyphenyl) bis(trifluorosulfonium sulfonate) imine, dimethyl (ethoxyphenyl) bis(trifluoromethanesulfonate) imine, diterpenoid (propoxyphenyl) bis(trifluorosulfonium sulfonate) imide, dimercapto (butoxyphenyl) bis(trifluoromethanesulfonate) imine, dimethyl (octyloxybenzene) Bis(bis(trifluoromethanesulfonyl)imide, dimethyl (octadecyloxyphenyl) fluorene (Trifluorosulfonium sulfonate) imine, dimercapto (isopropoxyphenyl) bis(trifluorosulfonium sulfonate) imine, dimethyl (tertiary butoxyphenyl) fluorene (trifluoro Methanesulfonate)imine, dimethyl(cyclopentyloxyphenyl)fluorene bis(trifluorosulfonium sulfonate)imide, dimercapto (cyclohexyloxyphenyl)phosphonium bis(trifluoromethanesulfonate) Imine, dimethyl (fluorodecyloxyphenyl) fluorene bis(trifluoroimethionine) imine, dimethyl (2-chloroethoxyphenyl) spallyl (trioxane sulfonium) Imine, dimethyl(3-bromopropoxyphenyl)fluorene bis(trifluoromethanesulfonate) imine, dimethyl(4-cyanobutoxyphenyl)phosphonium bis(trifluoromethanesulfonate) Imine, dimethyl (8-nitrooctyloxyphenyl) bis(trifluoromethanesulfonyl)imide, dimercapto (18-trifluoromethyloctadecyloxyphenyl) fluorene ( Trifluoromethanesulfonate)imine, dimercapto (2-hydroxyisopropoxyphenyl)phosphonium bis(trifluoromethanesulfonate)imide, dimercapto (trimethylenemethyl)methyl) Bis(trifluoromethanesulfonate)imide, diphenyl(4-hydroxyphenyl)indole bis(trifluoromethanesulfonate)imide, methylphenyl (4 -hydroxyphenyl)indole bis(trifluoromethanesulfonate)imide, benzhydrylphenyl bis(trifluoromethanesulfonate)imide, diphenylfluorenyl (4-hydroxyphenyl)fluorene double (three Fluorosulphonium)imide, benzylmethyl(4-methylphenyl)phosphonium bis(trifluorosulfonium)imide, benzylmethyl(4-hydroxyphenyl)phosphonium bis(trifluoromethanesulfonate醯) imine, benzylmethyl (4-acetoxyphenyl) bis(trifluorosulfonium sulfonate) imine, benzylmethyl (4-anthoxycarbonyloxyphenyl) fluorene (Trifluoromethanesulfonate) imine, methyl (4-hydroxyphenyl) (2-mercaptophenyl) bis(trifluorosulfonium sulfonate) imine, fluorenyl (4-ethyl hydrazine 49 320525 200921277 Oxyphenyl)(2-methylbenzyl)indole bis(trifluoromethanesulfonate)imide, cyclohexylmethyl(2-ketocyclohexyl)phosphonium bis(trifluoromethanesulfonate)imide, etc. Bis(trifluoromethane xanthine) imine. Preferably, for example, bis(p-tolyl)phosphonium hexafluorophosphate, hexafluorophosphoric acid (p-tolyl) (p-isopropylphenyl)fluorene, hexafluorophosphate bis(p-tert-butylphenyl) lock , triphenylphosphonium hexaphosphate, hexafluorophosphoric acid (p-tolyl) diphenylphosphonium, hexafluorophosphoric acid (p-tert-butylphenyl) fluorene, diphenylhydroxyphenyl hexafluorophosphate), six Methylphenyl fluorophenyl (4-hydroxyphenyl) hydrazine, benzylmethyl (4-methylphenyl) hexafluorophosphate, benzylmethyl hexafluoroantimonate (4 phenyl) hydrazine, Hexahydrate benzylmethyl (4-ethyloxyphenyl) mirror, six-acidic methyl (4: acetate phenyl) (2-methylphenyl fluorenyl) mirror, six gas 峨Acid methyl (4 phenyl) (2-methylbenzyl) hydrazine, cyclohexylmethyl hexafluoromethyl (2-cyclohexyl) mirror, hexafluoro sulphate (2-ketophenyl) Ethyl) fluorocyclopentane; 1 bis(p-tolyl) fluorene fluorene, hexafluoroarsenic acid (p-tolyl) (p-propylphenyl) hydrazine, hexafluoroarsenic bis (paired to tertiary butyl) Phenyl phenyl), triphenyl sulfonium hexafluoroarsenate, hexafluoro succinic acid (p-tolyl) diphenyl hydrazine Hexafluoroantimonate (10) Dibutyl phenyl) hydrazine, diphenyl (4-hydroxyphenyl) hydrazine hexafluorobutyrate, methyl phenyl hexafluorobutyrate (4-phenyl) hydrazine, hexafluoropicolin benzyl Methyl (4 Γ phenyl) hydrazine, hexafluoroquinic acid benzyl methyl (4) by phenyl) hydrazine, hexafluoride acid: methyl (4-ethyl oxyphenyl) mirror, hexafluoro Oleic acid methyl (4-ethyloxyphenyl) (2-methylbenzyl) fluorene, hexafluorosodium methyl (4 - phenyl) (2 - I group) 毓, six Fluoric acid cyclohexylmethyl (2-ketocyclohexyl) mirror, bauxite ethyl) sulfolane; hexafluoroantimonate hydrazine, hexafluoro acid (for T phenyl) ( P-isopropylphenyl) 320525 50 200921277 鎭, bis(p-tert-butylphenyl) hexafluoroantimonate, triphenyl sulfonium hexafluoroantimonate, hexafluoro acid (p-phenyl) diphenyl Bismuth, hexafluoroantimonate (p-tert-butylphenyl) fluorene, /, diphenyl (4-phenyl) mirror, hexafluoro-methylphenyl (4-hydroxyphenyl)毓 'Phenylmethylmethyltoluene hexafluoroantimonate), phenyl T-methylmethyl (4-hydroxyphenyl) fluorene hexafluoroantimonate, hexafluoroantimonic acid benzoate Methylacetoxyphenyl)anthracene, hexafluoroantimonic acid T-based (4-ethyloxyphenyl)(2-methylbenzyl)anthracene, hexafluoroantimonic acid methyl (4-hydroxyphenyl) (2-methylbenzyl) hydrazine, cyclohexylmethyl hexafluoroantimonate (2-ketocyclohexyl) hydrazine, 1-(2-keto-2-phenylethyl) hydrazine hexafluoroantimonate Heterocyclic pentane; bis(p-tolyl) hydrazine, quinone (pentafluorophenyl)boronic acid (p-tolyl) (p-isopropylphenyl) fluorene, quinone (pentafluorophenyl) ) bis(p-tert-butylphenyl) borate, quinone (pentafluorophenyl) linolenic acid triphenyl sulfonium, quinone (pentafluorophenyl) ruthenic acid (p-tolyl) diphenyl hydrazine, hydrazine (five Fluorophenyl)boronic acid ginseng (p-tert-butylphenyl) fluorene, fluorene (pentafluorophenyl)pyruvate diphenyl(4-hydroxyphenyl)anthracene, quinone (pentafluorophenyl)boronic acid methylphenyl (4-hydroxyphenyl) vegetable, hydrazine (pentafluorophenyl) borate benzyl fluorenyl (4-tolyl) fluorene, hydrazine (pentafluorophenyl) borate benzoquinone fluorenyl (4 hydroxy phenyl)毓,肆(5^phenyl)boronic acid benzylmethyl(4-acetoxyphenyl)anthracene, fluorene (pentafluorophenyl) Methyl (4-ethyloxyphenyl) (2-methylbenzyl) hydrazine, hydrazine (pentaphenoxyphenyl) borate methyl (4-hydroxyphenyl) (2-methylbenzyl) vegetable , fluorene (pentafluorophenyl) meal, cyclohexylmethyl (2, cyclyl) hydrazine, hydrazine (pentafluorophenyl) phthalic acid 1-(2-keto-2-phenylethyl) fluorene heterocycle Pentane; bis(p-phenylphenyl)fluorene trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tolyl) (p-isopropylphenyl), trifluoro:sulfonic acid bis (p-tert-butylbenzene) Base, triphenylsulfonate triphenyl sulfonate male acid (p-tolyl) diphenyl sulfonium, trifluoromethanesulfonic acid ginseng (p-tert-butyl 320525 51 200921277 phenyl) hydrazine, Diphenyl(4-hydroxyphenyl)fluorene trifluoromethanesulfonate, methylphenyl (4-hydroxyphenyl)fluorene trifluoromethanesulfonate, benzylmethyl trifluoromethanesulfonate (4-methylphenyl)毓, phenylhydrazine methyl trifluoromethanesulfonate (4-hydroxyphenyl) fluorene, phenyl fluorenyltrifluoromethanesulfonate (4-acetoxyphenyl) fluorene, trifluorosulfonium sulfonate (4-Ethyloxyphenyl)(2-mercaptobenzyl)anthracene, fluorenyltrifluorosulfonate (4-hydroxyphenyl)(2-mercaptophenylhydrazine)毓, trifluorosulfonium sulfonate cyclohexyl fluorenyl (2-ketocyclohexyl) sharp, trifluorophthalic acid 1-(2-keto-2-phenylethyl) mirror heterocyclopentane; Bis(p-phenyl) bis(trifluorosulfonium sulfonate) imine, (p-phenylene) (p-isopropylphenyl) bis(trifluorosulfonium sulfonate) imine, double (for tertiary Butylphenyl) bis(trifluorosulfonium)imide, triphenylsulfonium bis(trifluorosulfonium)imide, (p-tolyl)diphenylphosphonium bis(trifluorosulfonium) Amine, ginseng (p-tert-butylphenyl) mirror bis(trifluoromethyl hydrazine) imine 'diphenyl (4-phenyl) bis (trifluorosulfonium sulfonate) imine, nonylphenyl (4-Hydroxyphenyl)indole bis(trifluorosulfonium sulfonate) imine, phenylhydrazinyl (4-fluorenylphenyl) bis(trifluorosulfonium sulfonate) imine, benzoylmethyl (4 -Hydroxyphenyl)indole bis(trifluorosulfonium sulfonate)imide, phenylhydrazinyl (4-acetoxyphenyl) bis(trifluorosulfonium sulfonate) imine, methyl (4-B醯oxyphenyl)(2-methylphenylhydrazinyl)phosphonium bis(trifluorosulfonium sulfonate)imide, fluorenyl (4-hydroxyphenyl)(2-methylphenylhydrazino)fluorene (Trifluoromethanesulfonate) imine, cyclohexyldecyl (2-ketocyclohexyl) bis(trifluorosulfonium)imide, 1-(2-keto-2-phenylethyl)anthracene Heterocyclic pentane bis(trifluorosulfonium sulfonate) imine and the like. More preferably, for example, bis(p-tolyl) hexafluoroantimonate, hexafluoroantimonic acid (p-phenylene) (p-isopropylphenyl) fluorene, hexafluoroantimonic acid bis (p-tert-butylbenzene) , hydrazine, triphenylsulfonium hexafluoroantimonate, hexafluoroantimonic acid (p-tert-butylphenyl) hydrazine; bis(p-tolyl) hydrazine (pentafluorophenyl)borate Boron 52 320525 200921277 acid (p-tolyl) (p-isopropylphenyl) ruthenium, osmium (pentafluorophenyl) borate bis (p-terphenyl) ruthenium, iridium (pentafluorophenyl) boric acid Triphenyl hydrazine, hydrazine (pentafluorophenyl) borate (p-tert-butylphenyl) hydrazine; bis(p-tolyl) fluorene trifluorosulfonate, trifluoromethanesulfonic acid (p-tolyl) (pair) Isopropyl phenyl) hydrazine, bis(p-tert-butylphenyl) fluorene trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium sulfonic acid (p-tolyl)diphenylphosphonium, Nonylphenyl (4-hydroxyphenyl) fluorene triflate, benzyl fluorenyl (4-methylphenyl) sulfonium trifluoromethanesulfonate, benzyl fluorenyltrifluorosulfonate (4-hydroxyl) Phenyl)anthracene, trifluorosulfonium sulfonate benzylmethyl (4-acetamidine) Oxyphenyl) fluorene, trifluorosulfonium sulfonate methyl (4-acetoxyphenyl) (2-methylbenzyl) hydrazine, trifluoromethanesulfonic acid methyl (4-hydroxyphenyl) ( 2-methylbenzyl) fluorene, cyclohexyl fluorenyl trifluoromethanesulfonate (2-ketocyclohexyl) fluorene, 1-(2-keto-2-phenylethyl) fluorene trifluoromethanesulfonate Heterocyclic pentane; bis(p-tolyl)indole bis(trifluorosulfonium sulfonate)imide, (p-tolyl)(p-isopropylphenyl)fluorene bis(trifluoromethanesulfonate)imide, double ( P-tert-butylphenyl) bis(trifluorosulfonium sulfonate) imine, triphenylsulfonium bis(trifluorosulfonium sulfonate) imide, (p-phenylene) diphenyl bismuth (trifluoromethyl) Sulfo] imine, nonylphenyl (4-hydroxyphenyl) bis(trifluoromethanesulfonate) imine, benzyl fluorenyl (4-methylphenyl) bis(trifluoromethanesulfonate) Amine, phenylhydrazinomethyl(4-hydroxyphenyl)indole bis(trifluoromethanesulfonate)imide, benzylmethyl(4-acetoxyphenyl)indole bis(trifluorosulfonium sulfonate) Imine, mercapto (4-'acetoxyphenyl) (2-methylphenylhydrazino) bis(trifluoromethanesulfonate) imine, methyl (4-hydroxyphenyl) 2-methylphenylhydrazinyl)bis(trifluoromethanesulfonate)imide, cyclohexylmethyl(2-ketocyclohexyl)phosphonium bis(trifluoromethanesulfonate)imide, 1-(2-ketone Alkyl-2-phenylethyl)fluorene heterocyclopentane bis(trifluorosulfonium sulfonate) imine or the like. When the cationic polymerization initiator (C) is used, the content thereof is relative to the solid content of the radiation of 53 320525 200921277, and the mass fraction is preferably 〇·〇ι to (10). = / °1 is better if the content of the cationic polymerization initiator (C) is in the former (four): there is a decrease in the resolution of the heat hardening day by increasing the hardening speed at the time of thermal hardening, and the cured film is improved. Tendency, so good. The r 7 sensitizer (8) may, for example, be a small naphthalene, 2-naphthalene m (tetra), ^3-dihydroxynaphthalene, U-dihydroxynaphthalene, 1>5-dihydroxynaphthalene, U-dihydroxynaphthalene, 1,7 - Dipyridyl naphthalene, U dipyridyl naphthalene, 23 _; via naphthalene, 2 6 - erythrophthalene, 2'7-dipyridyl naphthalene, 4-methoxy chlorinated and so on. Special 疋: 1-naphthol, 2-naphthol, 4-anthraceneoxy + naphthol is preferred. When the sensitizer (8) is used, the content of the phase is in the solid content of the radiation-sensitive resin composition, and the mass fraction is G. Q1% or more is less than 1Q%, and 〇. 1% or more and 5% or less are preferred. When the content of the sensitizer (D) is within the above range, the transparency of the cured film formed by using the radiation sensitive resin composition containing the sensitizer tends to be less likely to be lowered, which is preferable. The polyphenol compound (E) is a compound having two or more phenolic hydroxyl groups in the molecule, and examples thereof include a polymer obtained by using silk styrene as a raw material monomer, and a sulphate wax. . Has in the molecule. For example, a compound of two or more phenolic hydroxyl groups can be exemplified. Dihydroxybenzophenones, tetrahydroxybenzophenones, pentahydroxybenzophenones, hexahydroxydibenzophenones, (polyhydroxyphenyl)alkanes, and the like. The polymer obtained by using at least hydroxystyrene as a raw material monomer may, for example, be a polyhydroxystyrene 'hydroxy styrene ethylene/mercapto acrylate copolymer, a hydroxystyrene/cyclohexyl methacrylate copolymer, Hydroxystyrene 320525 54 200921277 / Styrene copolymer, styrene-based styrene-based copolymer, etc. Dreaming of the polymerization of light styrene and other resins. The lyophilized fat can be obtained by polycondensing at least one compound selected from the group consisting of (4) and catechu (4) and a compound selected from the group consisting of vines and ketones. When the polyhydric phenol compound (8) is used, its content is relative to the solid content of the radiation sensitive resin composition, and the mass fraction is 〇1% or more. It is preferably 4% or less, more preferably 25% or less. If a compound of a plurality of ages is contained, the resolution tends to increase, which is preferable. If the content of the multi-component compound (8) exceeds 40% ', the visible light transmittance tends to decrease. The crosslinking agent (F) may, for example, be a methylol compound or the like. The hydrazine: the base compound may, for example, be an alkoxy group-containing resin such as an alkoxy group, a melamine-based resin or an alkoxymethylated urea resin. Here, alkoxymethylated melamine resin. For example, methoxymethylated melamine resin, ethoxymethylated melamine resin, n-propoxylated melamine resin, n-butoxymethyl melamine resin, etc., alkyl lactyl methylation Examples of the urine reading grease include a methoxymethylated urea resin, an oxymethylated urea resin, a n-propoxymethylated urea tree wax, and a n-butyl milk methylated urea tree material. The crosslinking agent (7) can be used singly or in combination of two or more. In the radiation sensitive linear resin composition of the present invention, when the crosslinking agent =) is used, the content thereof is preferably 1% or more and 15% or less based on the solid content of the dissimilar (tetra) sex tree. If the content of the crosslinking agent is within the range described above, the transparency of the cured film tends to be less likely to be lowered, so 320525 55 200921277 is preferred. The polymerizable monomer (8) can be, for example, heated.
合之自由基聚合性單體、可奸陽離子聚合之陽 ^ 性單體等,較佳可舉例如 子t S 合性單體。 W心料Μ之陽離子聚 自由基聚合性單體可幾^仓,丨丄θ > σ . ^ 舉例如具有聚合性碳 '碳不飽和 鍵之化合物,該具有聚合性碳+铯和 如·早吕成基之自由基聚合性單體、2官能基之自由基聚J 合性=體、或3官能基以上之自由基聚合性單體等。 單官能基之自由基聚合性單體可舉例如··正壬基美 卡必醇丙雜目旨(㈣。nylphenyWbitQl、、二 壬基苯基卡必醇甲基丙烯酸酷、丙稀酸2n3—苯氧基 正丙酯、甲基丙_ 2-經基—3—苯氧基正丙酯.、2_乙基: 己基卡必醇㈣㈣m正己基卡必醇甲基丙婦酸 酉旨、丙稀酸2-經乙酉旨、甲基丙婦酸2一經乙酉旨、N_乙稀基吨 咯啶酮等。 2官能基之自由基聚合性單體可舉例如:1,正己二 醇二丙烯酸酯、1>6-正己二醇二甲基丙烯酸酯、乙二醇二 丙烯酸醋、乙二醇二甲基丙烯酸酉旨、新戊二醇二丙烯酸酯、 新戊二醇二甲基丙烯酸酯、三乙二醇二丙烯酸酯、三乙二 醇二甲基丙烯酸g旨、雙紛A之雙(丙稀醯氧基乙基)祕、3_ 曱基正戊二醇二丙烯酸醋、3一甲基正戊二醇二甲基丙烯酸 酉旨等。 3官能基以上之自由基聚合性單體可舉例如:三羥甲 320525 56 200921277 基丙烧三丙烯酸酯、三經甲基丙烧三曱基丙稀酸醋、季戊 四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇四 丙烯酉夂酉曰、季戊四醇四甲基丙烯酸醋、季戊四醇五丙稀酸 醋、季戊四醇五甲基丙烯酸酯、二季戊四醇六丙烯酸酉旨、 一季戊四醇六甲基丙烯酸酯等。 在别述之自由基聚合性單體中,尤以使用2官能基或 3、官能基以上之自由基聚合性單體為佳。具體而言,以季 戊四醇四丙稀酸醋、二季戍四醇六丙稀酸醋等為佳,以二 四醇六丙烯酸醋較佳。此外,也可將2官能基或3官 'Hi之自由基聚合性單體、與單官能基之自由基聚合 性早體予以組合而使用。 :進行陽離子聚合之聚合性單體可舉例如:含有乙稀 丙縣縣、氧雜環丁㈣等陽料聚合性官能 基之陽離子聚合性單體。 f有乙埽基SI基之陽離子聚合性單體可舉例如:三乙 稀基醚、U-環己燒二甲醇二乙物、“丁 ^子十二燒基乙稀基趟等;含有丙稀㈣基之陽 戍^Y性單體可舉例如(卜丙烯氧基WH,3-二氧 〇n二 Τ'—(1卿州〇卿, 如:雔ί3_^Α雜環丁 f基之陽離子聚合性單體可舉例 =s乙基氧雜環丁烷基)甲基}醚、1,4-雙{3-(3 - 環丁乳基}本、U-雙(3-(3—乙基氧雜 燒其减} f基苯、U-雙<3-(3一乙基氧雜環丁 减}環己燒、U —雙叫3-乙基氧雜環丁規基) 320525 57 200921277 = 乙基氧雜環-…基㈣ 前述之聚合性單體((?)可 用。告存田取人 使用或组合2種以上借 用田使用聚合性單體⑻時,並含认禋以上使 脂組成物之ϋ形份3里相對於感放射線性樹 社 η 分率以〇.〇U以上20%以下盔 佳、以〇· 1%以上〗5%以下籽处 丄以下為 量在fr、f HI m 較佺。因若聚合性單體(G)之含 傾向,故佳。 、狀可見光穿透率會增大之 ★:本發明之感放射線性樹脂組成物中,依需要,也可 有ί他成分,例如:界面活性劑(聚錢系、氣系、 ^ …陽離子系、非離子系等)、抗氧化劑、溶解抑制 剩、紫外線吸收劑、接著性改良劑(例如石夕絲合劑)、電 子供體等各種添加物。 本發明之感放射線性樹脂組成物可依例如將由共聚物 (Α)’合於/合劑(η)中而成之溶液、由盼化合物之醌二疊氮基 石只酸酯(Β)溶於溶劑(Η)中而成之溶液予以混合之方法而製 造。此外,混合後,也可再加入溶劑(Η)。混合後,以過濾 去除固形物為佳,以使用例如孔徑在3 # m以下(較佳係在 0. 1 // m以上2 // m以下左右)之過濾器過濾為佳。對前述之 各成分使用之溶劑可皆相同,且只要為可相溶者則也可不 同0 在使用本發明之感放射線性樹脂組成物形成硬化樹脂 圖案時,只要例如將本發明之感放射線性樹脂組成物層(1) 形成於基板(2)之上,並隔著光罩(3)對該層(1)照射放射線 58 320525 200921277 (4)並進行曝光後,再進行顯影即可。 基板(2)可舉例如:除了透明玻璃板、矽晶圓等以外, 其餘可列舉如碳酸酯基板、聚酯基板、芳香族聚醯胺基板、 聚醯胺醯亞胺基板、聚醯亞胺基板等樹脂基板等。於前述 之基板上’也可預先形成:CCD(Charge_c〇upledDevice, 電荷耦合裝置)或TFT(Thin-Film Transistor,薄膜電晶 體)之電路、濾色器、透明電極等。 感放射線性樹脂組成物層(丨)可依一般方法,例如將本 务明之感放射線性樹脂組成物塗布於基板(2 )上之方法而 升y成塗布係依據例如旋轉塗布(spin coat ing)法、流鱗. 塗布法、輕塗布法、狹缝與旋轉塗布法、狹縫塗布法等使 用省液塗布器塗布之方法等周知塗布方法而進行。塗布 後,經由加熱乾燥(預烤(pre_bake))使溶劑揮發,而形成 感放射線性樹脂組成物層(丨),但使溶劑揮發後之感放射線 14树知組成物層(1)係由感放射線性樹脂組成物之固形份 s所組成,幾乎不含揮發成分。此外,感放射線性樹脂組成 物層之厚度係例如1至5 /z in左右。 接者,於感放射線性樹脂組成物層(1)上,隔著光罩(3) 照射放射線(4)。光罩(3)之圖案可依硬化樹脂圖案之目標 圖案而適當選擇。放射線可使用例如:g射線、丨射線等光 線。放射線係以對於感放射線性樹脂組成物層,使用例如 光罩對準曝光機(mask al igner)或步進機(stepper)(無圖 示)等照射為佳。 、 如此進行曝光後,再進行顯影。顯影可依據例如使曝 320525 59 200921277 光後之感放射線性樹脂組成物層(1)接觸顯影液之方法 進行。顯影液可使用驗性水溶液。驗性水溶液可使用 化合物之水溶液,*性化合物可為無機驗性化合物,也 為有機驗性化合物。 ^無機驗性化合物可舉例如:氫氧化 酸氫二鈉、磷酸二氫鈉、磷酸氫二銨、磷酸二氫銨、磷酸 一虱鉀、砍酸納、砍酸麵、端赌杨^ _ 山卜 f反i鈉、碳酸鉀、碳酸氫鈉、 碳酸氫鉀、獨酸鈉、酸卸、氨水等。 有機驗性化合物可舉例如:氫氧化四甲錢、 經乙基三甲基錄、單甲胺、二甲胺、三甲胺、單乙胺、二 乙胺、三乙胺、單異丙胺、二異丙胺、乙醇月安等。前述驗 :=ι=δ或組合2種以上使用。顯影液以顯影 液:⑽貝…有鹼性化合物0 01至1〇質量份為佳、 以含有〇. i至5質量份較佳^ 〃 :::液中也可含有界面活性劑。界面活性劑可舉例 系界面活性料。 離子轉面活㈣、陰離子 :離:士界面活性劑可舉例如:聚氧伸乙基炫基醚、 t乳伸乙基♦基喊、聚氧伸乙其^ # 軒m气m /甲乙基坑基方基_等聚氧伸乙基 何生物,乳伸乙基/氧伸丙基嵌段共聚物㈤妙 COPW)、山梨糖醇酐脂肪酸醋、聚氧伸 臟酸醋、聚氧伸乙基山梨糖醇脂肪酸醋、甘油:= 醋、聚乳伸乙基脂肪酸醋、聚氧伸乙基燒基胺等。欠 陽離子系界面活性劑可舉例如:硬脂基胺鹽酸鹽等胺 320525 60 200921277 氯化月桂基二甲基錢等四級銨鹽等。 陰離子界面活性劑可舉例如:月桂醇 硫酸醋納等高級醇硫酸醋鹽;月桂基硫酸納、二= 銨等烧基硫酸m基料酸鈉、十二㈣^ 水烷基芳基磺酸鹽等。此等界面 二二, 2種以上使用。 刀別早獨或組合 例如此:,顯影液也可含有有機溶劑。前述有機溶劑可舉 例如.甲醇、乙醇等水溶性有機溶劑等。一了舉 :感:射線性樹脂組成物層⑴接觸顯影 =例如.«(puddnng)法、浸潰法或琳浴法等。經= &而使感放射線性樹脂組成物層、 照射放射線之放鼾结日力如r丄 仕无則曝先時經 使未昭射;Ltr 域(12)會溶解於顯影液中,並 . '射線之放射線未照射區域U1)不會溶;& 中而殘s,因此而形成圖案⑸。 曰/奋於颂衫液 本發明之感放射線性_組成物由 物之㈣中之-部分或全部之經 =4) ’故即使令感放射線性樹脂組成物層 = 液接觸之眛門 θ、丨j只顯影 除。此外,由二:有=⑷咖射區域⑽溶解而去 納*t,D、 3有式(1)所示之酚化合物之醌二疊氮武庐 -夂酉曰(β),故即使令感放射線 金土尹、 接觸之時間延長,放射線未====顯影液 影液中而消失。 求禾',、、紅域(11)也不會因溶於顯 2影後m行水洗並錢。錢後,有時亦 ;仔之圖案(5)上照射放射—線。此時,放射線之照射通常 320525 61 200921277 ==光。但以對於整個圖案全面進行照射放射線為 可從基板背二Γ;?射線之基板時,放射線之照射也 外線為佳,而每單位2,照射之放射線以紫外線或深紫 射量多為佳 積之照射量係以較先前曝光時之照 秘也可將如此進行所形成之圖案(5)再經由加熱處理(後 、post-bake)),而提高硬化樹脂圖案之耐熱性、耐溶劑 加熱處理係依據將照射放射線後之基板以加熱板、 無塵洪箱一續加熱裝置進行加熱之方法而進 X加熱溫度通常係峨至靴,以i耽至職左 右為佳,加熱時間通常係5分鐘至12〇分鐘,以i 5分鐘至 〇刀&左右為佳.。經由加熱,圖案會再硬化,而形成更堅 固之硬化樹脂圖案。 如此進行所形成之硬化樹脂圖案係耐熱性、时溶劑性 優良1且可適合使用於做為形成選自由垂直定向型液晶顯 不兀件用之突起及光阻式間隔件所成群組中之至少一者的 硬化樹脂圖案。 (實施例) :以下’依照實施例更詳細說明本發明,但本發明當然 不叉此等實施例所限定。 (.實施例1). 共聚物(A-1):甲基丙稀酸/N—環己基馬來酸亞胺/3_乙基 I甲基丙_氧基f基氧雜環了燒共聚物(聚合時之莫耳 比:25/35/40)60 質量份; 320525 62 200921277 共聚物(A-2)·共聚物(a-ι)與和前述相同之單體種之共聚 物,莫耳比為不同之(聚合時之莫耳比:32/28/4〇)4〇質 量份; 酚化合物之醌二疊氮基磺酸酯(B1):在式(1)所示之化合物 t’R2、R5、R6mRl、M^,Rl、R1^, n、R9及R1。為經基,且該經基中,平均2.7莫耳係經 式(3-1)所不之醌二疊氮基化合物所酯化,剩餘1. 3莫耳為 殘留之經基的化合物。 " 式(3)所示之化合物中之^至p4中,平均其2 7莫耳為式 (3-1)所示之取代基’剩# "Μ耳為氫原子的酿二疊氮基 磺酸酯(30質量份); 陽離子聚合S始劑⑹:San_Aid SI-1隱(三新化學工業 (股)製)2質量份; 冷背彳(H).在23 C混合二乙二醇甲基乙基醚(35〇.質量份) 後通過孔徑1. 0 # m之聚四氟乙烯製濾筒(cartridge (fliter)亚加壓過濾’而得到感放射線性樹脂組成物丨之濾 液:The radical polymerizable monomer, the cation-polymerizable monomer, and the like are preferably, for example, a sub-T-synthesis monomer. The cationic polyradical polymerizable monomer of W 心 可 can be several 仓, 丨丄 θ > σ . ^ For example, a compound having a polymerizable carbon 'carbon unsaturated bond, the polymerizable carbon + 铯 and such as · The radical polymerizable monomer of the arsenyl group, the radical copolymerization of the bifunctional group, or the radically polymerizable monomer having a trifunctional or higher group. The monofunctional radical polymerizable monomer may, for example, be a fluorenyl carbaryl alcohol ((4). nylpheny WbitQl, dimethyl phenyl carbitol methacrylic acid, 2n3 acrylic acid) Phenoxyl n-propyl ester, methyl propyl 2-p-yl-3-phenoxy n-propyl ester, 2_ethyl: hexyl carbitol (4) (iv) m-n-hexyl carbitol methyl acetoacetate, C Dilute acid 2-, ethyl acetoacetate 2, acetaminophen, N-ethene trohydrofurfurone, etc. The 2-functional radical polymerizable monomer may, for example, be 1, n-hexanediol diacrylate Ester, 1>6-n-hexanediol dimethacrylate, ethylene glycol diacrylate vinegar, ethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, Triethylene glycol diacrylate, triethylene glycol dimethacrylate g, double a pair of bis (acryloxyethyl) secret, 3 fluorenyl n-pentanediol diacrylate vinegar, 3-methyl n-Pentyl diol dimethacrylate oxime, etc. The radically polymerizable monomer having 3 or more functional groups may, for example, be trishydroxycarbonyl 320525 56 200921277 propyl acrylate triacrylate, Trimethyl methacrylate tridecyl acrylate vinegar, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetrapropene hydrazine, pentaerythritol tetramethacrylate vinegar, pentaerythritol pentaacetic acid vinegar, pentaerythritol five a methacrylate, a dipentaerythritol hexaacrylate, a pentaerythritol hexamethacrylate, etc. Among the radically polymerizable monomers described above, a radical polymerization property of a bifunctional group or a functional group or more is used. Preferably, a monomer is preferred. Specifically, pentaerythritol tetraacrylic acid vinegar, diquaternic acid pentaerythritol hexaacetic acid vinegar, or the like is preferred, and ditetraol hexaacrylate vinegar is preferred. Further, a bifunctional group or 3 may be used. The radical polymerizable monomer of the official 'Hi is used in combination with a radically polymerizable precursor of a monofunctional group. The polymerizable monomer to be subjected to cationic polymerization may, for example, contain ethylene benzoate or an oxygen heterocycle. a cationically polymerizable monomer having a cationic polymerizable functional group such as butyl (tetra). The cationically polymerizable monomer having an acetyl group-based SI group may, for example, be triethyl ether or U-cyclohexane dimethanol diethyl ether. "Ding ^zi twelve Ethyl sulfonyl ruthenium or the like; an yttrium-containing y-type monomer containing propylene (tetra) group may, for example, be (dipropenyloxy-W, 3-dioxo-n-di-'- (1 qingzhou 〇qing, such as: 雔阳离子 _ Α 阳离子 阳离子 f 基 基 f cation of the cationically polymerizable monomer can be exemplified by = sethyl oxetanyl) methyl} ether, 1,4-double {3-(3 - cyclobutyl aryl) U-bis(3-(3-ethyloxy) decyl benzene, U-double <3-(3-ethyl oxirane minus) hexene burn, U - double-called 3-B Cyclohexyloxy) 320525 57 200921277 = Ethyloxyheterocyclic-yl group (IV) The above-mentioned polymerizable monomer ((?) is usable. It is used for the use of a combination of two or more borrowing fields. In the case of the body (8), the ratio of the ϋ3 of the lipid composition is higher than that of the sensitized linear tree, and the η.〇U or more is 20% or less, and the 盔·1% or more is 5%. The following seeds are below the amount of fr, f HI m. It is preferred because the polymerizable monomer (G) has a tendency to be contained. The visible light transmittance will increase. ★: In the radiation sensitive resin composition of the present invention, if necessary, it may also have other components, such as: surfactant (poly money system, gas system, ^ ... cation system) Various additives such as an anti-oxidant, a dissolution inhibitor, a UV absorber, an adhesion improver (for example, Shishi silk mixture), and an electron donor. The radiation sensitive resin composition of the present invention can be dissolved in a solvent, for example, by a solution obtained by combining a copolymer (Α) with a mixture (η), and a bismuth azide sulphate (Β) of a desired compound. The solution obtained in (Η) is prepared by mixing. Further, after mixing, a solvent (Η) may be further added. After mixing, it is preferred to remove the solid matter by filtration, and it is preferred to use, for example, a filter having a pore diameter of 3 # m or less (preferably, about 0.1 / m or more and 2 / / m or less). The solvent used for each of the above components may be the same, and may be different as long as it is compatible. When the cured resin pattern is formed using the radiation sensitive resin composition of the present invention, for example, the radiation of the present invention is linear. The resin composition layer (1) is formed on the substrate (2), and the layer (1) is irradiated with radiation 58 320525 200921277 (4) via a mask (3), and exposed, and then developed. The substrate (2) may be, for example, a transparent glass plate or a tantalum wafer, and examples thereof include a carbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyimide substrate, and a polyimide. A resin substrate such as a substrate. A circuit such as a CCD (Charge_c〇upled Device) or a TFT (Thin-Film Transistor), a color filter, a transparent electrode, or the like may be formed in advance on the substrate. The radiation-sensitive resin composition layer (丨) can be applied to the substrate (2) by a general method, for example, by applying a radiation-sensitive resin composition of the present invention to the substrate (2), for example, spin coating. The method and the flow scale are carried out by a known coating method such as a coating method, a light coating method, a slit coating method, a slit coating method, or the like using a liquid-saving applicator coating method. After coating, the solvent is volatilized by heat drying (pre-bake) to form a radiation-sensitive resin composition layer. However, the radiation 14 after volatilization of the solvent is known as the composition layer (1). It consists of the solid content s of the radiation-linear resin composition and contains almost no volatile components. Further, the thickness of the radiation sensitive resin composition layer is, for example, about 1 to 5 / z in. Then, on the radiation-sensitive resin composition layer (1), the radiation (4) is irradiated through the mask (3). The pattern of the mask (3) can be appropriately selected depending on the target pattern of the cured resin pattern. For the radiation, for example, a light such as a g-ray or a x-ray can be used. The radiation is preferably applied to the radiation sensitive resin composition layer using, for example, a mask al igner or a stepper (not shown). After the exposure is performed in this way, development is performed. The development can be carried out, for example, by a method in which the radiation-sensitive resin composition layer (1) after exposure to 320525 59 200921277 is exposed to the developer. An aqueous solution can be used as the developer. As the aqueous test solution, an aqueous solution of the compound can be used, and the * compound can be an inorganic test compound or an organic test compound. ^Inorganic compounds include, for example, disodium hydrogen hydride, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium monobasic phosphate, sodium citrate, diced acid, gambling yang _ mountain卜f anti-sodium, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium monochloride, acid unloading, ammonia water, and the like. The organic compound may, for example, be tetramethylammonium hydroxide, ethyltrimethylamine, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, or Isopropylamine, ethanol, etc. The above test: = i== or a combination of two or more types. The developing solution is a developing solution: (10) shells; preferably having a basic compound of 0 01 to 1 part by mass, containing 〇. i to 5 parts by mass, preferably 〃::: a liquid may also contain a surfactant. The surfactant can be exemplified by an interface active material. Ion-transformation (IV), anion: from: the surfactant can be exemplified by: polyoxyethyl ether ethyl ether, t-emulsion ethyl ♦ base shout, polyoxygen acetonitrile ^ # 轩 m gas m / methyl ethyl Pit base square_equal polyoxygen extension ethylhe bio, milk stretch ethyl/oxypropyl propyl block copolymer (five) COPW), sorbitan fatty acid vinegar, polyoxygenated vinegar, polyoxygen A sorbitol fatty acid vinegar, glycerin: = vinegar, polyemulsion ethyl vinegar, polyoxyalkylene amide, and the like. The under-cationic surfactant may, for example, be an amine such as stearylamine hydrochloride. 320525 60 200921277 A quaternary ammonium salt such as lauryl dimethyl chlorate or the like. The anionic surfactant may, for example, be a higher alcohol sulfate vinegar such as lauryl sulfate or the like; sodium lauryl sulfate, bis-ammonium, etc., sodium sulfonate m-base sodium, twelve (tetra) water alkyl aryl sulfonate Wait. These interfaces are two or two, and more than two are used. The knife may be used alone or in combination. For example, the developer may also contain an organic solvent. The organic solvent may, for example, be a water-soluble organic solvent such as methanol or ethanol. One thing: Sense: Radiation resin composition layer (1) contact development = for example, «(puddnng) method, dipping method or Lin bath method. After the = & and the radiation-sensitive resin composition layer, the radiation of the radiation, the daily force of the radiation, such as r丄shi, is exposed to the first time; the Ltr domain (12) is dissolved in the developer, and The 'radiation non-irradiated area U1 of the ray does not dissolve; and s is left in the &, and thus the pattern (5) is formed.曰/奋 颂 颂 液 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本 本丨j only develops. In addition, there are two: there is = (4) the area of the shot (10) dissolved and the *t, D, 3 have the phenolic compound of the formula (1), the quinone diazide 庐 庐 - 夂酉曰 (β), so even if The radiation of the golden earth Yin, the contact time is prolonged, and the radiation is not ==== the developer liquid solution disappears. Qihe ',,, red domain (11) will not be dissolved in the water after the 2 shadows. After the money, sometimes also; the pattern of the child (5) is irradiated with radiation-line. At this time, the radiation is usually 320525 61 200921277 == light. However, when the entire pattern is irradiated with radiation, it is possible to carry the radiation from the substrate; when the substrate is irradiated, the radiation is also excellent, and per unit 2, the radiation is mostly in the form of ultraviolet rays or deep purple. The irradiation amount is improved by heat treatment and solvent heat treatment of the cured resin pattern by patterning the pattern (5) thus formed by heat treatment (post-bake). According to the method of heating the substrate after the radiation is heated by a heating plate or a dust-free flooding box, the heating temperature is usually tied to the boot, and the heating time is usually 5 minutes. To 12 minutes, it is better to use i 5 minutes to the sickle & Upon heating, the pattern re-hardens to form a more rigid hardened resin pattern. The cured resin pattern formed in this manner is excellent in heat resistance and solvent property, and can be suitably used as a group formed by forming protrusions and photoresist spacers for vertical alignment type liquid crystal display members. At least one of the hardened resin patterns. (Embodiment): The present invention will be described in more detail in the following, but the invention is of course not limited by the examples. (Example 1). Copolymer (A-1): methyl acrylate / N-cyclohexylmaleic acid imine / 3 - ethyl I methyl propyl oxy oxy ke group (molar ratio at the time of polymerization: 25/35/40) 60 parts by mass; 320525 62 200921277 Copolymer (A-2)·copolymer (a-ι) and a copolymer of the same monomer species as described above, The ear ratio is different (moth ratio at the time of polymerization: 32/28/4 〇) 4 parts by mass; the quinone diazide sulfonate of the phenol compound (B1): the compound t represented by the formula (1) 'R2, R5, R6mRl, M^, Rl, R1^, n, R9 and R1. It is a mercapto group, and an average of 2.7 moles of the mercapto group is esterified with a quinone diazide compound of the formula (3-1), and the remaining 1. 3 moles is a residual radical compound. " Among the compounds represented by the formula (3), an average of 2 7 moles is a substituent represented by the formula (3-1) 'remaining # " Base sulfonate (30 parts by mass); cationic polymerization S-starting agent (6): San_Aid SI-1 hidden (manufactured by Sanshin Chemical Industry Co., Ltd.) 2 parts by mass; cold-backed 彳 (H). mixed with two-two at 23 C After the alcohol methyl ethyl ether (35 〇. parts by mass), the filtrate of the radiation sensitive linear resin composition was obtained through a filter cartridge of a polytetrafluoroethylene having a pore size of 1.00 m (cartridge (fliter). :
弋(3)中p至p分別獨立地表示式(3 — ι)所示之取代基 或氫原子]。 將感放射線性樹脂組成物丨之濾液旋轉塗布於5㈣見 320525 63 200921277 方之透明玻璃基板[# 1737,CORNING公司製]後,使用烘 箱在10(TC加熱(預烤)3分鐘而形成感放射線性樹脂膜,並 使用觸針式膜厚計[DEKTAK3,ULVAC公司.製]測定膜厚後, 結果為3. 6 “ m 〇 之後,對此感放射線性樹脂組成物膜,隔著光罩(3 ),_ 且使光罩至塗膜之間隙隔開200 /Zm.而照射i射線[波長 365nm]。i射線之光源係使用超高壓水銀燈。光罩(3)係使 (用形成間隔件尺寸之線寬之線/空間(1 :丨)與突起 尺寸之線寬10 y m之線/空間(丨:1)圖案的光罩。 曝光後,浸潰於27t之氫氧化鉀水溶液(在1〇〇質量 份中含有氫氧缺(M質量份與了基萘磺酸㈣.2% )中同 時以手動搖晃9 〇秒而顯影後,以超純水洗淨並乾燥。由此 時之顯影所得之膜殘留率係88%。乾燥後,在無塵洪箱中 在220 加熱30分鐘’而形成硬化樹脂圖案(垂直定向型 液晶顯示元件用之突起)。若以在線與空間皆達ι〇〇“ 、之光罩曝光之曝級做為實際有效之感度,則實際有效之 感度係187mJ/W。此時,之3〇 ws圖案之膜之高度係 10WS圖案之膜之高度係u":。所形成之 硬化樹脂圖案之剖面並非异丑 __ 非長方形,而是上方凸出之曲線 狀’而為形狀良好。 〈可見光穿透率〉 1制/邊長5Cm見方之透明玻璃基板1737, CORNING公 司衣j上,除了不進行藉由 者 影處理步驟之後使用_^^貝%之曝先步驟’而在顯 用卿燈[_-50·,liSHIO(股)製]照 320525 64 200921277 射於全面(以波長313nm為基準之曝光量係3〇〇mJ/cm2)以 外,其餘依與上述相同之方法形成硬化樹脂膜。使用八光 計[0SP-2 0 0,OLYMPUS光學工業(股)製]測定所得之硬二樹 脂膜之可見光穿透率,此外,使用接解式膜厚計[dektak3, (股)ULVAC公司製]測定其膜厚。所得之硬化樹脂膜每」" =在波長400至750nm之可見光平均穿透率係99%,顯示 高透明性,且未觀察到著色。 (實施例2) <藉由高解析曝光機形成細微圖案之評估> 關於感放射線性樹脂組成物1,評估其做為使用高解 析曝光機形成半導體製造用之細微圖案用之光阻的性:。 將實施例1所得之感放射線性樹脂組成物丨旋轉塗布 於4英吋矽晶圓上後,使用加熱板在丨⑽它加熱(預烤μ 分鐘而·形成感放射線性樹脂組成物膜,"並使用光學式膜厚 計[LAMBDA ACE,大日本SCREEN製造(股)製]測定膜厚 結果為3. β // m。 之後’於此感放射線性樹脂膜上’使用i射線步進機 [NSR-1755i7A,Nikon(股)製,NA=0.5],隔著光罩⑶照 射放射線(4),並進行曝光。光罩(3)係使用用以形成線寬 3//m之線/空間(1 :丨)圖案的光罩。 曝光後,浸潰於23°C之氫氧化四曱銨水溶液(在1〇〇 質量份中含有氫氧化四曱銨〇.4質量份)中70秒而顯影 後,以超純水洗淨並乾燥。若以在顯影後之圖案中,在線 與空間皆達3.0 之光罩曝光之曝光量做為實際有效之 320525 65 200921277 感度,則貫際有效之感度係USnjj/cm2。乾燥後,在無塵 烘相中在220 C加熱30分鐘,而形成硬化樹脂圖案。所形 成之細微圖案之形狀係正錐形(f〇rward tapered汕叩幻 (圖案之剖面形狀為底部較上部大之台形形狀)而為良好。 (實施例3) 除了在齡化合物之醌二疊氮基續酸酯(B)之化合物之 式(3)中之p至p4中,變更為平均其3 5莫耳為式(3一丄) 所示之取代基且剩餘〇. 5莫耳為氫原子之醌二疊氮基橫酸 酯以外,其餘與實施例1同樣操作,而得到感放射線性樹 脂組成物2 〇 進行與貫施例2同樣之操作,而於基板上藉由高解析 曝光機形成細微圖案。將實際有效之感度為141mJ/cm2且 3 # m之線與空間圖案予以析像。所形成之細微圖案之形狀 係正錐形而為良好。與實施例丨同.樣操作而測得之光線穿 透率為99%而顯示高透明性,且未觀察到著色。 (比較例1) 除了將酚化合物之醌二疊氮基磺酸酯(B)變更為式(4) 所示之化合物(P5至P7皆為式(34 )所示之取代基的醌二疊 '氮基續酸醋化合物)的醌二疊氮基磺酸酯以外,其餘與實施 例1同樣操作,而得到感放射線性樹脂組成物4。 66 320525 200921277In the ruthenium (3), p to p each independently represent a substituent represented by the formula (3 - ι) or a hydrogen atom]. The filtrate of the radiation sensitive resin composition was spin-coated on 5 (four), see 320525 63 200921277, a transparent glass substrate [# 1737, manufactured by CORNING Co., Ltd.], and then irradiated at 10 (TC heating (pre-baked) for 3 minutes to form radiation. After measuring the film thickness using a stylus film thickness meter [DEKTAK3, manufactured by ULVAC Co., Ltd.], the result was 3.6" m 〇, after the radiation-sensitive resin composition film was passed through the mask ( 3), _ and the gap between the mask and the coating film is separated by 200 /Zm. and the i-ray [wavelength 365nm] is irradiated. The source of the i-ray is an ultra-high pressure mercury lamp. The mask (3) is used to form a spacer. Dimensional line width line/space (1: 丨) and protrusion size line width 10 ym line/space (丨: 1) pattern mask. After exposure, immerse in 27t potassium hydroxide aqueous solution (at 1 The mass parts of the crucible containing hydrogen and oxygen (M mass parts and naphthalenesulfonic acid (IV). 2%) were simultaneously shaken by hand for 9 sec seconds, then washed with ultrapure water and dried. The obtained film residual ratio was 88%. After drying, it was heated in 220 in a dust-free flood box for 30 minutes to form a hardening. The grease pattern (protrusion for the vertical alignment type liquid crystal display element). If the exposure level of the reticle exposure is measurable as the actual effective sensitivity, the actual effective sensitivity is 187 mJ/W. At this time, the height of the film of the 3〇ws pattern is the height of the film of the 10WS pattern u": The profile of the formed hardened resin pattern is not ugly __ non-rectangular, but curved above the curve' The shape is good. <Visible light transmittance> 1 system / side length 5Cm square transparent glass substrate 1737, CORNING company's clothing j, except for the use of _^^贝% exposure step after the shadow processing step In the case of the use of the Qing dynasty lamp [_-50·, liSHIO (share) system] 320525 64 200921277 shot in full (exposure amount based on wavelength 313nm is 3〇〇mJ/cm2), the rest is the same as above The method of forming a hardened resin film, and measuring the visible light transmittance of the obtained hardened resin film using an octameter [0SP-200, manufactured by OLYMPUS Optical Industries Co., Ltd.], and using a junction type film thickness meter [dektak3, (share) manufactured by ULVAC Co., Ltd.] The film thickness was measured. The average transmittance of the visible film of the resin film at a wavelength of 400 to 750 nm was 99%, showing high transparency, and no coloration was observed. (Example 2) <Formation of fine patterns by a high-resolution exposure machine Evaluation of the radiation-sensitive resin composition 1 was evaluated as a photoresist for forming a fine pattern for semiconductor fabrication using a high-resolution exposure machine: The radiation-sensitive resin composition obtained in Example 1 was obtained. After spin coating on a 4 inch wafer, use a hot plate to heat it in the crucible (10) (pre-bake for μ minutes to form a film of the radiation-sensitive resin composition, " and use an optical film thickness meter [LAMBDA ACE, large The film thickness of the SCREEN manufacturing system was 3. β // m. Then, on the radiation-sensitive resin film, an i-ray stepper [NSR-1755i7A, manufactured by Nikon Co., Ltd., NA = 0.5] was used, and the radiation (4) was irradiated through the mask (3), and exposure was performed. The photomask (3) is a photomask for forming a line/space (1: 丨) pattern having a line width of 3/m. After exposure, it was immersed in an aqueous tetra-ammonium hydroxide solution (containing 4 parts by mass of tetraammonium hydroxide in 4 parts by mass) at 23 ° C for 70 seconds, and then washed with ultrapure water. dry. If the exposure amount of the reticle exposed to 3.0 in the pattern after development is the actual effective 320525 65 200921277 sensitivity, the effective sensitivity is USnjj/cm2. After drying, it was heated at 220 C for 30 minutes in a dust-free baked phase to form a hardened resin pattern. The shape of the fine pattern formed is good in a forward taper shape (the cross-sectional shape of the pattern is a trapezoidal shape in which the bottom portion is larger than the upper portion). (Example 3) In addition to the age-old compound The p to p4 in the formula (3) of the compound of the nitrogen nitrate (B) is changed to an average of 3 5 moles of the substituent represented by the formula (3 丄) and the remaining 〇. 5 mol is The same procedure as in Example 1 was carried out except that the hydrogen atom was a quinone diazide-based cross-acid ester, and the radiation-sensitive resin composition 2 was obtained. The same operation as in Example 2 was carried out, and high-resolution exposure was performed on the substrate. The machine forms a fine pattern, and the actual effective sensitivity is 141 mJ/cm 2 and the line of 3 # m is resolved with the spatial pattern. The shape of the formed fine pattern is positively tapered and is good. The measured light transmittance was 99%, and high transparency was observed, and no coloration was observed. (Comparative Example 1) The phenolic compound of the quinonediazidesulfonate (B) was changed to the formula (4). The compound shown (P5 to P7 are all substituted by the formula (34)) Other than the compound) a quinone diazide sulfonic acid ester, remaining in the same manner as in Example 1, to give a sense of the radiation-sensitive resin composition 320,525,200,921,277 4.66
進行與實施例2同樣之操作,而於基板上藉由高解析 曝光機形成細微圖案。將實際有效之感度為286mJ/cm2且 3/z m之線與空間圖案予以析像。 (比較例2) 除了將酚化合物之醌二疊氮基磺酸酯(B)變更為式(5) 所示之化合物以外’其餘與實施例丨同樣操作,而得到感 放射線性樹脂組成物5。 OP8 CHa CH^ np”The same operation as in Example 2 was carried out, and a fine pattern was formed on the substrate by a high-resolution exposure machine. The actual effective sensitivity is 286 mJ/cm2 and the line of 3/z m is resolved with the spatial pattern. (Comparative Example 2) The same procedure as in Example , was carried out except that the quinonediazidesulfonate (B) of the phenol compound was changed to the compound represented by the formula (5), and the radiation sensitive resin composition 5 was obtained. . OP8 CHa CH^ np”
S〇2 (3-1) ⑸ [惟,P8至P11中,式(5)所示之化合物每i莫耳經2. 6莫耳 之式(3 -1) ♦示之取代基取代’剩餘1 · 4莫耳為氫原子]。 進行與實施例2同樣之操作,而藉由高解析曝光機形 成細微圖案後,結果實際有效之感度為437mJ/cm2之低感 度。所形成之細微圖案之形狀係正錐形而為良好。 (比較例3) 除了將酚化合物之醌二疊氮基磺酸酯(B)變更為式(β) 所示之化合物以外’其餘與實施例1同樣操作,而得到感 320525 67 200921277 放射線性樹脂組成物6。S〇2 (3-1) (5) [However, in the case of P8 to P11, the compound represented by the formula (5) is substituted by 2. 6 moles of the formula (3 -1) ♦ the substituent is substituted for 'remaining 1 · 4 moles are hydrogen atoms]. The same operation as in Example 2 was carried out, and after forming a fine pattern by a high-resolution exposure machine, the practically effective sensitivity was a low sensitivity of 437 mJ/cm2. The shape of the formed fine pattern is positively tapered and is good. (Comparative Example 3) The same procedure as in Example 1 was carried out except that the quinonediazidesulfonate (B) of the phenol compound was changed to the compound represented by the formula (β), and a radiation resin of 320525 67 200921277 was obtained. Composition 6.
[惟P12至P14中,式(6)所示之化合物每.1莫耳經2莫耳 之式(3-1)所示之取代基取代,剩餘丨莫耳為殘留之羥基]。 進行與貫施例2同樣之操作,而藉由高解析曝光機形 成細微圖案後,結果實際有效之感度為327mJ/cm2之低感 度。與實施例1同樣操作而測得之光線穿透率係99%。所 形成之細微圖案之形狀係正錐形而為良好。 (比較例4) 將比較例1所使用之感放射線性樹脂組成物4進行與 i實施例1同樣之操作,於基板上,使用形成間隔件尺寸之 線寬30//Π1之線/空間(1 : υ與突起尺寸之線寬心瓜之 線/空間(.1. 1)圖案的光罩而形成硬化樹脂圖案。由此時 之顯影所得之膜殘留率係98%。將丨0 β m之線與空間圖案 予以析像之實際有效之感度為294mJ/cm2之低感度。此日7 之3M mL/S圖案之膜之高度係3 3/zm,1〇#mL/s圖案 之膜之尚度係1.9" m。所形成之硬化樹脂圖案之形狀為良 好二與實施例1同樣操作而測得之光線穿透率係99%而ς 示高透明性,且未觀察到著色。 ‘、、、、 32〇525 68 200921277 (比較例5) 使用比較例2所使用之感放射線性樹脂組成物5進行 與貫施例1同樣之操作,而於基板上形成硬化樹脂圖案(垂 直定向晶顯示元件用之突起)。即使卩働mi/cm2之 放射線進行曝光,曝光部之膜也無法完全溶解,而未形成 突起圖案。由此時之顯影所得之膜殘留率係97%。與實施 例1同樣操作而測得之光線穿透率係95%,穿透率低。 (比較例6) 將比#乂抝3所使用之感放射線性樹脂組成物6進行與 實施例1同樣之操作,而於基板上形成硬化樹脂圖案/由 此時之顯影所得之膜殘留率係97%。將1Mm線與空間圖 案予以析像之實際有效之歧為311nJ,em2之低感度。此 時之30/z mL/S圖案之膜之高度係3 2/zm,1〇#mL/s圖 案之膜之尚度係1. 8 # m。所形成之硬化樹脂圖案之形狀為 良好。與實施例1同樣操作而測得之光線穿透率係99% 。 (實施例4) 共聚物(A-1):曱基丙烯酸/N—環己基馬來醯亞胺/3_乙基 -3-曱基丙烯醯氧基甲基氧雜環丁烷共聚物(聚合時之莫耳 比:25/35/40)15質量份(DAICEL化學工業(股)製); 共聚物(A-2):共聚物(a-ι)與和前述相同之單體種之共聚 物,莫耳比為不同之(聚合時之莫耳比:32/28/4〇)85質 量份(DAICEL化學工業(股)製); 酚化合物之醌二疊氮基磺酸酯(B1):在式(3)所示之化合物 中之P至P中,平均其2.7莫耳為式(3-1)所示之取代基, 320525 69 200921277 剩餘1· 3莫耳為氫原子的醌二疊氮基磺酸酯(3〇質量份); ’谷劑(H).在23C混合一乙一醇罗基乙基_(35〇質量份) 後’通過孔径1. 0以m之聚四氟乙烯製濾筒並加愿過濾,而 得到感放射線性樹脂組成物7之濾、液。[In the case of P12 to P14, the compound represented by the formula (6) is substituted per mole of 2 moles of the substituent represented by the formula (3-1), and the remaining oxime is the residual hydroxy group]. The same operation as in Example 2 was carried out, and after forming a fine pattern by a high-resolution exposure machine, the practically effective sensitivity was a low sensitivity of 327 mJ/cm2. The light transmittance measured in the same manner as in Example 1 was 99%. The shape of the fine pattern formed is good in a forward taper shape. (Comparative Example 4) The radiation-sensitive resin composition 4 used in Comparative Example 1 was subjected to the same operation as in the first embodiment, and a line/space which formed a line width of 30//Π1 of the spacer size was used on the substrate ( 1 : A film of the pattern of the line/space (.1.1) of the line of the protrusion and the size of the protrusion is formed to form a hardened resin pattern. The film residual ratio obtained by the development at this time is 98%. The actual effective sensitivity of the line and space pattern is 294mJ/cm2. The height of the film of 3M mL/S pattern of 7 is 3 3/zm, and the film of 1〇#mL/s pattern is still The degree of the hardened resin pattern formed was 1.9 " m. The shape of the cured resin pattern formed was good. The light transmittance measured in the same manner as in Example 1 was 99%, indicating high transparency, and no coloration was observed. 32, 525 68 200921277 (Comparative Example 5) The same procedure as in Example 1 was carried out using the radiation sensitive resin composition 5 used in Comparative Example 2, and a hardened resin pattern was formed on the substrate (vertical directional crystal display) The protrusion for the component). Even if the radiation of 卩働mi/cm2 is exposed, the film of the exposed portion cannot be finished. The film was completely dissolved without forming a protrusion pattern. The film residual ratio obtained by the development at this time was 97%. The light transmittance measured in the same manner as in Example 1 was 95%, and the transmittance was low. The radiation sensitive resin composition 6 used in the above-mentioned #乂拗3 was subjected to the same operation as in Example 1 to form a cured resin pattern on the substrate/the film residual ratio obtained by the development at that time was 97%. The actual effective difference between the 1Mm line and the spatial pattern is 311nJ, the low sensitivity of em2. At this time, the height of the film of 30/z mL/S pattern is 3 2/zm, and the film of 1〇#mL/s pattern The degree of the cured resin pattern formed was good. The light transmittance measured in the same manner as in Example 1 was 99%. (Example 4) Copolymer (A-1) ): mercaptoacrylic acid/N-cyclohexylmaleimide/3-ethyl-3-mercaptopropenyloxymethyloxetane copolymer (Mohr ratio during polymerization: 25/35/ 40) 15 parts by mass (manufactured by DAICEL Chemical Industry Co., Ltd.); copolymer (A-2): a copolymer of the copolymer (a-ι) and the same monomer species as described above, the molar ratio is different (polymerization) Time Moerby: 32/28/4 〇) 85 parts by mass (manufactured by DAICEL Chemical Industry Co., Ltd.); quinone diazide sulfonate (B1) of phenol compound: in the compound represented by formula (3) In P to P, an average of 2.7 moles is a substituent represented by the formula (3-1), 320525 69 200921277, and a remaining 1·3 mole of a quinonediazidesulfonate which is a hydrogen atom (3 parts by mass) ; 'Valent (H). After mixing the monoethylol rosylethyl _ (35 〇 parts by mass) in 23C, 'pass the PTFE filter cartridge with a pore size of 1.0 to add a filter, and get a sense Filtration and liquid of the linear resin composition 7.
[式(3)中,f至P4分別獨立地表示式(3 —丨)所示之取代基 或氫原子;| 〇 將感放射線性樹脂組成物丨之濾液旋轉塗布於5cm見 =之透明玻璃基板[# 1737,c〇RNING公司製]後,使用烘 Is在100 C加熱(預烤)3分鐘而形成感放射線性樹脂膜,並 使用觸針式膜料⑽遺即測定麟後,結果為3 =後,對此感放射線性樹脂組成物膜,隔著光罩(3), 且使光罩至塗膜之間隔隔開200仰而照射i射線[波長 365nm]。1射線之光源係使用超高壓水銀燈。光罩⑶係使 用形成間隔件尺寸之線寬3G//m之線/空間(1 :與突起 尺寸之^見10 # m之線/空間(1: 1)圖案的光罩。 曝光後,浸潰於2rc之氫氧化卸水溶液(在1〇〇質 份:含有ft氧化鉀U5 f量份與丁基萘#酸鋼G1% ')中 同1以手動搖晃8〇秒而顯影後,以超純水洗淨並乾燥 之膜殘留率係㈣。乾燥後,在無塵烘箱 甲在22〇C加妖30八於 τ· ,、、 U刀鐘,而形成硬化樹脂突起圖案。若以 320525 70 200921277 .在線與空間皆達10.0 Am之光罩曝光之爆光量做為實際有 效之感度,則實際有效之感度係2〇8mJ/cm2。此時之$3〇 Z/mL/S圖案之膜之高度係27/(Zm,1〇//inL/s圖案之膜 之南度係1.4^111。所形成之硬化樹脂突起圖案之形狀係錐 形而為良好_。 (比較例7) 除了將酚化合物之醌二疊氮基磺酸酯(B)變更為 所示之化合物(P5至P7皆為式(S—DK示之取代基的醌二疊 氮基磺酸酯化合物)的醌二疊氮基磺酸酯以外,其餘與實施 例4同樣操作,而得到感放射線性樹脂組成物8:、、 OP5[In the formula (3), f to P4 each independently represent a substituent represented by the formula (3 - 丨) or a hydrogen atom; | 〇 The filtrate of the radiation sensitive resin composition is spin-coated on a transparent glass of 5 cm see = After the substrate [# 1737, manufactured by c〇RNING Co., Ltd.], the radiation-sensitive resin was heated (pre-baked) at 100 C for 3 minutes to form a radiation-sensitive resin film, and the stylus film (10) was used to measure the lining. After 3 =, the radiation-sensitive resin composition film was irradiated with i-rays [wavelength 365 nm] through the mask (3) and the gap between the mask and the coating film was 200. The source of the 1 ray is an ultra high pressure mercury lamp. The photomask (3) is a mask having a line width of 3 G//m which forms a spacer size (1: a line/space (1:1) pattern with a protrusion size of 10 #m. After exposure, dip Crushed in 2rc of aqueous hydrazine solution (in 1 〇〇 part: containing ft potassium oxide U5 f parts and butyl naphthalene # acid steel G1% ') in the same 1 after manual shaking for 8 〇 seconds and developed, super The residual rate of the film washed and dried by pure water is (4). After drying, the dust-free oven is added at 22 〇C to the τ·, ,, U knife clock to form a hardened resin protrusion pattern. 200921277. The amount of exposure of the reticle exposure of 10.0 Am both online and space is the actual effective sensitivity, and the actual effective sensitivity is 2〇8mJ/cm2. At this time, the height of the film of $3〇Z/mL/S pattern is The ratio of the film of 27/(Zm, 1〇//inL/s pattern to the south is 1.4^111. The shape of the formed cured resin protrusion pattern is tapered and is good. (Comparative Example 7) In addition to the phenol compound The quinone diazide sulfonate (B) is changed to the quinonediazide group of the compound shown (P5 to P7 are all quinonediazide sulfonate compounds of the formula (S-DK) Sulfur Outside ester, remaining in the same manner as in Example 4, to give a sense of the radiation-sensitive resin composition 8: ,, OP5
⑷於2 ίί〇2 (3-1) 〇(4) on 2 ίί〇2 (3-1) 〇
將此感放射線性樹脂組成物8進行與實施例4同樣之 汽/乍而於基板上形成硬化樹脂突起圖案。由此時之顯影 :知之膜殘留率為99%之高膜殘留率,但將10 // m之線與 二間圖案予以析像之實際有效之感度為316mJ/cm2之低感 度此時之SOvmL/S圖案之膜之高度係3 2/zm , 1〇/ZmL /圖水之膜之向度係1. 8 # m。所形成之硬化樹脂突起圖 案之形狀係錐形而為良好。 (實施例5) 除了將酚化合物之醌二疊氮基磺酸酯(β)變更為實施 320525 71 200921277 例4所使用之醌二疊氮基磺酸酯22 5重量份與比較例7 所使用之醌一®氮基續酸酯7. 5重量份以外,其餘與實施 例4同樣操作’而得到感放射線性樹脂組成物9。 將此感放射線性樹脂組成物9進行與實施例4同樣之 操作,而於基板上形成硬化樹脂突起圖案。由此時之顯影 所得之膜殘留率係94% ,並將實際有效之感度為245mJ/ cm且1〇 # m之線與空間圖案予以析像。此時之 圖案之膜之咼度係2. 9 // m,10 # mL/S圖案之膜之高度係 1. 6 # m。所形成之硬化樹脂突起圖案之形狀係錐形而為良 好。 (實施例6) 除了將酚化合物之醌二疊氮基磺酸酯(β)變更為實施 例4所使用之醌二疊氮基磺酸酯15重量份與比較例7所使 用之醒二疊氮基石黃酸酯15重量份以外,其餘與實施例4 同樣操作’而得到感放射線性樹脂組成物10。 將此感放射線性樹脂組成物10進行舆實施例4同樣之 操作,而於基板上形成硬化樹脂突起圖案。由此時之顯影 所得之膜殘留率係96% ,並將實際有效之感度為272mJ/ cm2且1 〇私m之線與空間圖案予以析像。此時之3〇 # s 圖木之膜之向度係3.0/^πι’ 10# fflL/ S圖案之膜之高度係 • 6 // m所形成之硬化樹脂突起圖案之形狀係錐形而為良 好。 ° (產業上之利用可能性) 若依據使用本發明之感放射線性樹脂组成物所形成之 320525 72 200921277 硬化樹脂圖案,則TFT基板或遽色器基板之生產性皆優良。 【圖式簡單說明】 無。 【主要元件符號說明】 無。This radiation sensitive resin composition 8 was subjected to the same vapor/enthalpy as in Example 4 to form a cured resin projection pattern on the substrate. The development at this time: the film residual rate is 99% of the high film residual ratio, but the actual effective sensitivity of the line of 10 / m and the two patterns is 316 mJ / cm 2 low sensitivity at this time SOvmL The height of the film of the /S pattern is 3 2 / zm, the orientation of the film of 1 〇 / ZmL / water film is 1. 8 # m. The shape of the formed cured resin projection pattern was tapered and was good. (Example 5) In addition to changing the quinonediazidesulfonate (β) of the phenol compound to 22 5 parts by weight of the quinonediazidesulfonate used in Example 4 of 320525 71 200921277, and the use of Comparative Example 7 The radiation-sensitive resin composition 9 was obtained in the same manner as in Example 4 except that the hydrazine-based acid acrylate was used in an amount of 7.5 parts by weight. This radiation sensitive resin composition 9 was subjected to the same operation as in Example 4 to form a cured resin projection pattern on the substrate. The film residual ratio obtained by the development at this time was 94%, and the actually effective sensitivity was 245 mJ/cm and the line and space pattern of 1 〇 #m were resolved. At this time, the film of the pattern is 2. 9 // m, and the height of the film of the 10 # mL/S pattern is 1. 6 # m. The shape of the formed hardened resin protrusion pattern is tapered and is good. (Example 6) except that the quinonediazidesulfonate (β) of the phenol compound was changed to 15 parts by weight of the quinonediazidesulfonate used in Example 4 and the awake stack used in Comparative Example 7. The radiation-sensitive linear resin composition 10 was obtained in the same manner as in Example 4 except that 15 parts by weight of the carboralithic acid ester was used. This radiation sensitive resin composition 10 was subjected to the same operation as in Example 4 to form a cured resin protrusion pattern on the substrate. The film residual ratio obtained by the development at this time was 96%, and the actual effective sensitivity was 272 mJ/cm2 and the line and space pattern of 1 〇 private m were resolved. At this time, the angle of the film of the film of the 3 s# s wood is 3.0/^πι' 10# The height of the film of the fflL/S pattern is 6 * m The shape of the hardened resin protrusion pattern formed is tapered good. ° (Industrial Applicability) According to the 320525 72 200921277 hardened resin pattern formed by using the radiation sensitive resin composition of the present invention, the productivity of the TFT substrate or the color filter substrate is excellent. [Simple description of the diagram] None. [Main component symbol description] None.
73 32052573 320525
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