TW201234115A - Photosensitive phenol resin composition for alkaline development, cured relief pattern, method for producing semiconductor, and biphenyl-diyl-trihydroxybenzene resin - Google Patents

Photosensitive phenol resin composition for alkaline development, cured relief pattern, method for producing semiconductor, and biphenyl-diyl-trihydroxybenzene resin Download PDF

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TW201234115A
TW201234115A TW100148770A TW100148770A TW201234115A TW 201234115 A TW201234115 A TW 201234115A TW 100148770 A TW100148770 A TW 100148770A TW 100148770 A TW100148770 A TW 100148770A TW 201234115 A TW201234115 A TW 201234115A
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resin composition
photosensitive
resin
compound
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TWI486712B (en
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Takahiro Sasaki
Taisuke Yamada
Jun Li
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Asahi Kasei E Materials Corp
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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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
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    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
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    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3424—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms non-conjugated, e.g. paracyclophanes or xylenes
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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Abstract

Provided are: an alkali-soluble phenol resin characterized by having a structure represented by general formula (1), -A-B1-A-B2-A-B3-A-BiA-Bn-A- (1) (in the formula: A each independently is a divalent organic group having 6-25 carbon atoms and having a phenolic hydroxyl group, the bonds of A existing in an aromatic ring having a phenolic hydroxyl group, and there optionally being a substituent group aside from the hydroxyl group in said aromatic ring; Bi is a divalent organic group having 1-15 carbon atoms and not having a phenolic hydroxyl group; i is an integer between 1 and n inclusive; and n is an integer between 2 and 1,000 inclusive), the average value (Sdi/n) of the shortest distance (di) between oxygen atoms in the phenolic hydroxyl group in two As that face each other sandwiching a Bi obtained by calculating the shortest distance (di) by means of molecular mechanics being at least 9 angstroms (AA), and the softening point being at least 100 DEG C; a photosensitizer; and a solvent-containing photosensitive phenol resin composition for alkaline development.

Description

201234115 六、發明說明： 【發明所屬之技術領域】 本發明之第一態樣係關於一種對用_成Μ體襄置中 之表面保護膜或層間絕緣膜等有用之鹼性 顒像用感光性酚 樹脂組合物、使用該組合物之高耐熱性 又1匕凸起圖案之製 造方法及具有該硬化凸起圖案之半導體 苯二基三羥笨樹脂、其 本發明之第二態樣係關於一種聯 製法及該樹脂之使用。 【先前技術】 先前以來’對於半導體裝置之表面保護膜及層間絕緣 膜’廣泛使用兼具優異之耐熱性、電氣特性、機械特性等 之聚酿亞胺樹脂或聚苯并噚唾樹脂。該等樹脂由於在各種 溶劑中之溶解性較低，故通常被用作以前驅物之形式溶解 於溶劑中之組合物。因此，於使用時需要使前驅物閉環之 步驟。該閉環步驟通常係藉由加熱至30(rc以上之熱硬化 而進行。 ,、、、、而，近年來，開發出了耐熱性較先前品差之半導體裝 置，對表面保護膜或層間絕緣膜之形成材料亦要求熱硬^ 溫度下降，尤其要求25(rc以下之熱硬化性之情形亦逐漸 變多。 對於該要求，作為無需閉環之樹脂，提出有使用成本及 感光性能優異之酚醛清漆等酚樹脂，並向其中添加交聯劑 或其他種類之聚合物，藉此提高耐熱性等之材料（專利文 獻1及2)。然而’即便將該等材料作為表面保護膜或層間 161182.doc 201234115 絕緣膜應用於半導體裝置中，軟化點亦較低，故於硬化時 無法獲得如設計般之凸起圖案，而且所得之硬化膜之伸長 率較低，故半導體裝置之可靠性較低，作為聚醯亞胺樹脂 及聚苯并噚唑樹脂之代替材料較為困難。 又，於以下之專利文獻3中，提出有於骨架中具有聯苯 化合物與酚類之縮合物之酚樹脂，亦提出有使用該縮合物 作為環氧樹脂之硬化劑之耐熱性環氧樹脂硬化物。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開2003-215789號公報 [專利文獻2]曰本專利特開2009-237125號公報 [專利文獻3]曰本專利特開平8-143648號公報 【發明内容】 [發明所欲解決之技術問題] 繁於上述現狀，於本發明之第一態樣中，本發明所欲解 決之課題在於可製作一種於應用於半導體裝置時可靠性較 高之半導體裝置，並提供一種鹼性顯像用感光性酚樹脂組 合物、使用該組合物之硬化凸起圖案之製造方法及具有該 硬化凸起圖案而形成之半導體裝置。 又’專利文獻1中所記載之樹脂由於軟化點較低，故耐 熱性較低’圖案形狀會發生變形，因此不適合用作基質樹 脂。又，專利文獻3中所記載之材料由於樹脂缺乏鹼溶解 性，故不具有充分之微影性（鹼可溶性）^ 馨於上述現狀’於本發明之第二態樣中，本發明所欲解 161182.doc 201234115 決之課題在於提供一種於應用於半導體裝置中之情形時具 有充分之微影性（驗可溶性）且耐熱性優異之樹脂、其製 法、使用該樹脂之組合物、以及使用該組合物之半導體裝 置之製法及半導體裝置。 [解決問題之技術手段] 本發明者發現，為了於應用於半導體裝置中時作為可形 成可靠性較高之硬化膜之材料，鹼可溶性酚樹脂中之軟化 點及酚性羥基彼此之配置較為重要，從而完成了本發明之 第一態樣。本發明之第一態樣係如下所述。 π] —種驗性顯像用感光性酚樹脂組合物，其包括： 鹼可溶性酚樹脂，其特徵在於：其具有下述通式（1): -A-B1-A-B2-A-B3-A-...Bi... A-Bn-A- ⑴ {式中’ A分別獨立為具有酚性羥基之碳數6〜25之2價有 機基’該A之結合鍵存在於具有盼性經基之芳香環上，且 於該芳香環上亦可存在除羥基以外之取代基；匕為不具有 酚性羥基之碳數1〜15之2價有機基；i為1以上且下之整 數；而且η為2以上且1，000以下之整數}所示之結構，且藉 由利用分子力學法計算隔著該Bi相對之2個Α内之酚性經基 中之氧原子間的最短距離山所獲得之該山之平均值（5：di/n) 為9埃（A)以上，且軟化點為1〇〇。〇以上； 感光劑；及 溶劑。 [2]如[1]之鹼性顯像用感光性酚樹脂組合物，其中藉由 對上述鹼性顯像用感光性酚樹脂組合物進行硬化所獲得之 161182.doc 201234115 硬化膜之伸長率為1 5%以上。 [3] 如[1]或[2]之鹼性顯像用感光性酚樹脂組合物，其中 上述山之平均值（Sdi/n)為10埃（A)以上。 [4] 如[1]至[3]中任一項之鹼性顯像用感光性酚樹脂組合 物’其中上述Bi為由下述通式（2): -X-L-Y-M-Z- (2) {式中，L及Μ為不具有酚性羥基且可具有除酚性羥基以 外之取代基的碳數6〜10之2價芳香族基，而且X、γ及ζ為 選自由單鍵、碳數1〜2之脂肪族鏈、醯胺基、羰基、醋 基、脲基、胺基曱酸酯基、醚基及硫醚基所組成之群中之 2價基}所示。 [5] 如[1 ]至[4] t任一項之驗性顯像用感光性酚樹脂組合 物’其中上述A具有2〜3個酚性羥基。 [6] 如[1]至[5]中任一項之鹼性顯像用感光性酚樹脂組合 物’其進而含有交聯劑。 [7] —種硬化凸起圖案之製造方法，其包括：將如π]至 [6]中任一項之驗性顯像用感光性紛樹脂組合物塗佈於基板 上之步驟；對該鹼性顯像用感光性酚樹脂組合物進行曝光 之步驟；對經曝光之鹼性顯像用感光性酚樹脂組合物進行 顯像而形成凸起圖案之步驟；及對該凸起圖案進行加熱而 形成硬化凸起圖案之步驟。 [8] —種半導體裝置，其係具有藉由如[7]之製造方法所 獲得之硬化凸起圖案而形成。 又，本發明者等人為解決上述本發明之第二態樣之課題 161I82.doc 201234115 而進行了潛心研究’反覆進行了實驗，結果發現，藉由使 用具有聯苯一基結構及三羥笨結構兩者之樹脂，可解決上 述課題，從而完成了本發明之第二態樣。 即，本發明之第二態樣係如下所述者： Π]種聯苯二基三羥苯樹脂，其係由下述通式（丨）： [化1]201234115 VI. Description of the Invention: [Technical Field] The first aspect of the present invention relates to a photosensitive image for use in a basic image for use in a surface protective film or an interlayer insulating film in a ruthenium-based body. a phenol resin composition, a method for producing a high heat resistance and a embossed pattern using the composition, and a semiconductor phenyldiyltrihydroxy phenyl resin having the hardened embossed pattern, and a second aspect thereof according to the present invention The co-production method and the use of the resin. [Prior Art] Polyurethane resin or polybenzopyrene resin which has excellent heat resistance, electrical properties, mechanical properties and the like has been widely used for the surface protective film and interlayer insulating film of a semiconductor device. These resins are generally used as a composition in the form of a precursor to be dissolved in a solvent because of their low solubility in various solvents. Therefore, the step of closing the precursor is required at the time of use. This closed-loop step is usually carried out by heating to 30 (thermal hardening of rc or more. In recent years, a semiconductor device having a heat resistance lower than that of the prior art has been developed, and a surface protective film or an interlayer insulating film has been developed. The material to be formed also requires a hot-melt temperature drop, and in particular, 25 (the thermal hardening property of rc or less is also gradually increased. For this requirement, as a resin which does not require a closed loop, a novolac having excellent use cost and excellent photosensitivity is proposed. A phenol resin, a crosslinking agent or another type of polymer is added thereto, thereby improving the heat resistance and the like (Patent Documents 1 and 2). However, even if these materials are used as a surface protective film or interlayer 161182.doc 201234115 The insulating film is applied to a semiconductor device, and the softening point is also low, so that a raised pattern such as a design cannot be obtained at the time of hardening, and the obtained cured film has a low elongation, so that the reliability of the semiconductor device is low, as a poly It is difficult to substitute a quinone imine resin and a polybenzoxazole resin. Further, in Patent Document 3 below, it is proposed to have a biphenyl compound in the skeleton. A phenol resin which is a condensate of a phenol, and a heat-resistant epoxy resin cured product using the condensate as a hardener of an epoxy resin is also proposed. [Prior Art Document] [Patent Document] [Patent Document 1] [Patent Document 2] JP-A-2009-237125 [Patent Document 3] Japanese Patent Laid-Open No. Hei 8-143648 (Invention) [Technical Problem to be Solved by the Invention] In the first aspect of the present invention, the object of the present invention is to provide a semiconductor device having high reliability when applied to a semiconductor device, and to provide a photosensitive phenol for alkaline development. A resin composition, a method for producing a cured bump pattern using the composition, and a semiconductor device comprising the cured bump pattern. Further, the resin described in Patent Document 1 has a low softening point, so that heat resistance is low. 'The shape of the pattern is deformed, so it is not suitable for use as a matrix resin. Moreover, the material described in Patent Document 3 does not have sufficient lithography due to the lack of alkali solubility of the resin (alkali Solubility) is in the second aspect of the present invention. In the second aspect of the present invention, the present invention is directed to 161182.doc 201234115. The problem is to provide a sufficient lithography when applied to a semiconductor device. A resin which is soluble and excellent in heat resistance, a method for producing the same, a composition using the resin, and a method and a semiconductor device for a semiconductor device using the composition. [Technical means for solving the problem] The inventors have found that, in order to apply to a semiconductor In the apparatus, as a material capable of forming a cured film having high reliability, the softening point and the phenolic hydroxyl group in the alkali-soluble phenol resin are important to each other, thereby completing the first aspect of the present invention. The spectroscopy is as follows. π] - a photosensitive phenol resin composition for assay development, comprising: an alkali-soluble phenol resin having the following general formula (1): -A-B1- A-B2-A-B3-A-...Bi... A-Bn-A- (1) where A is independently a divalent organic group having a phenolic hydroxyl group of 6 to 25 carbon atoms. The bond is present on the aromatic ring having a desired thiol group. a substituent other than a hydroxyl group may be present on the aromatic ring; 匕 is a divalent organic group having 1 to 15 carbon atoms which does not have a phenolic hydroxyl group; i is an integer of 1 or more and lower; and η is 2 or more and 1 a structure shown by an integer below 000, and the average of the mountains obtained by calculating the shortest distance between the oxygen atoms in the phenolic radicals of the two opposite iridium by the molecular mechanics method The value (5: di/n) is 9 angstroms (A) or more, and the softening point is 1 Å. 〇 Above; sensitizer; and solvent. [2] The photosensitive phenol resin composition for alkaline imaging according to [1], wherein the elongation of the cured film obtained by curing the photosensitive phenol resin composition for alkaline development is 161182.doc 201234115 It is more than 15%. [3] The photosensitive phenol resin composition for alkaline development according to [1] or [2], wherein the mountain average value (Sdi/n) is 10 angstroms (A) or more. [4] The photosensitive phenol resin composition for alkaline development according to any one of [1] to [3] wherein the above Bi is represented by the following formula (2): -XLYMZ- (2) { , L and oxime are a divalent aromatic group having 6 to 10 carbon atoms which does not have a phenolic hydroxyl group and may have a substituent other than a phenolic hydroxyl group, and X, γ and oxime are selected from a single bond, a carbon number of 1 to 2 is a divalent group in the group consisting of an aliphatic chain, a decylamino group, a carbonyl group, a acetoxy group, a ureido group, an amino phthalate group, an ether group, and a thioether group. [5] The photosensitive phenol resin composition for inspective imaging of any one of [1] to [4], wherein the above A has 2 to 3 phenolic hydroxyl groups. [6] The photosensitive phenol resin composition for alkaline development according to any one of [1] to [5] which further contains a crosslinking agent. [7] A method for producing a hardened convex pattern, comprising: a step of applying a photosensitive resin composition for an authentication for development according to any one of π] to [6] on a substrate; a step of exposing the photosensitive phenol resin composition for alkaline development; developing a photosensitive phenol resin composition for exposure to develop a convex pattern; and heating the convex pattern The step of forming a hardened convex pattern. [8] A semiconductor device comprising the hardened bump pattern obtained by the manufacturing method of [7]. Further, the inventors of the present invention conducted an experiment to solve the problem of the second aspect of the present invention, 161I82.doc 201234115, and found that by using a biphenyl-based structure and a trihydroxy-hydroxy structure. The resin of both can solve the above problems, thereby completing the second aspect of the present invention. That is, the second aspect of the present invention is as follows: Π] a biphenyldiyltrihydroxybenzene resin which is represented by the following formula (丨): [Chemical Formula 1]

⑴ {式中，R1為下述通式（2): [化2](1) In the formula, R1 is the following general formula (2): [Chemical 2]

(2) (R3)q 基或乙* ’而且，p與q分別獨立為〇〜4之整 )所不之聯本二基’ R2為選自氫、曱基及乙基中之基， 而且η為2〜150之整數}所示。 [2]如上述[1]之聯苯二基 .L 性本樹月曰’其中上述通式（1) 為由下述通式（3): [化3](2) (R3)q group or B*' and, p and q are each independently 〇~4, and the conjugated diyl group R2 is a group selected from the group consisting of hydrogen, fluorenyl and ethyl, and η is an integer of 2 to 150}. [2] The biphenyldiyl group of the above [1], wherein the above formula (1) is represented by the following formula (3): [Chemical 3]

161182.doc 201234115161182.doc 201234115

{式中， (4)： [化4J{式中, (4): [化4J

Rl及η與上述通式（1)中定義者相 同}或下述通式R1 and η are the same as those defined in the above formula (1)} or the following formula

(4) 義者相同}所示。 二羥苯樹脂’其中上述通 {式中，R1及η與上述通式（1)中定 [3]如上述[1]或[2]之聯苯二基 式（2)為由下述式（5): [化5] 中(4) The same as the righteousness}. In the above formula, R1 and η are the same as those in the above formula (1) [3], and the biphenyldiyl group (2) in the above [1] or [2] is represented by the following formula: (5): In [Chemical 5]

CH2— (5) ⑷如上述Π]至m中任一項之聯苯二基 上述式（5)為由下述式: [化6] 二窥苯樹脂，其 ~H2C~~h〇m〇>- CH2 — ( 6 ) 所示。 [5]—種如上述[1]至[4]中任一 之製造方法，其包括以下步驟： 項之聯苯二基三羥苯樹脂 161182.doc (7) (7)201234115 將下述通式（7): [化7]CH2—(5) (4) A biphenyldiyl group as defined in any one of the above Π] to m. The above formula (5) is represented by the following formula: [Chemical 6] bisporous benzene resin, which is ~H2C~~h〇m〇 >- CH2 — ( 6 ) is shown. [5] The production method according to any one of the above [1] to [4], which comprises the following steps: the biphenyldiyltrihydroxybenzene resin 161182.doc (7) (7)201234115 Equation (7): [Chem. 7]

{式中，R2為選自氫、甲基及乙基中之基}所示之化合物、 與下述通式（8): [化8]In the formula, R2 is a compound represented by a group selected from the group consisting of hydrogen, a methyl group and an ethyl group, and a compound of the following formula (8):

{式中，R3為甲基或乙基，13與£1分別獨立為〇〜4之整數，而 且R為選自由鹵素原子、羥基及碳數丨〜1〇之可具有不飽和 鍵之烷氧基所組成之群中之基}所示之化合物以5 :丨〜丨：5 之莫耳比混合，進而添加觸媒之步驟；及 於60°C以上加熱1分鐘〜48小時之步驟。 [6] —種感光性樹脂組合物，其特徵在於含有如上述 至[4]中任一項之聯苯二基三羥苯樹脂或藉由如上述[5]之 聯苯二基三經苯製造方法所獲得之樹脂及感光劑。 [7] 如上述[6]之感光性樹脂組合物，其中上述感光劑為 光酸產生劑。 [8] 如上述[6]之正型感光性樹脂組合物，其中上述减光 劑為萘醌二疊氮化合物。 161182.doc 201234115 [9] 一種半導體裝置之製造方法，其包括以下步驟： 於半導體基板上形成包含如上述[6]至中任一項之感 光性樹脂組合物之感光性樹脂層之步驟； 利用活性光線對該感光性樹脂層進行曝光之步驟； 對該經曝光之感光性樹脂層進行顯像而獲得凸起圖案之 步驟；及 對所得之凸起圖案進行加熱之步驟。 [10] —種半導體裝置，其係藉由如上述[9]之製造方法而 製造。 [發明之效果] 根據本發明之第一態樣，可將用以形成半導體裝置之表 面保護膜或層間絕緣膜之熱硬化溫度設定為相對較低之溫 度（例如25〇r以下）。又’根據本發明’可提高藉由對鹼性 顯像用感光性酚樹脂組合物進行硬化所獲得之硬化膜之伸 長率進而，根據本發明之第一態樣，不僅減少於對半導 體裝置施加由熱所引起之應力時之表面保護膜或層間絕緣 膜之裂痕，提高其可#性，而且亦可提高具有其而形成之 半導體裝置之可靠性。 根據本發明之第二態樣，可獲得—種同時滿足先前之紛 樹脂無法實現之微影性與樹㈣熱性、且兼具可應用於半 導體裝置之性他的聯笨二基三經苯樹脂，其製法，使用該 之”且。#進而使用該組合物之半導體裝置之製法及 半導體裝置。 【實施方式】 161182.doc 201234115 以下，首先對本發明之第一態樣之含有特定之鹼可溶性 酚樹脂、感光劑及溶劑之鹼性顯像用感光性酚樹脂組合物 (以下簡稱為「第一組合物」）進行說明。 <第一組合物中所使用之鹼可溶性酚樹脂> 本發明之第一態樣之組合物中所使用之鹼可溶性酚樹脂 係含有其重複單元中具有酚性羥基之化合物的高分子化合 物0 驗可溶性酚樹脂之特徵在於：具有下述通式（1): -A-B1-A-B2-A-B3-A-...Bi... A-Bn-A- ⑴ {式中’ A分別獨立為具有酚性羥基之碳數6〜25之2價有機 基，該A之結合鍵存在於具有酚性經基之芳香環上，且於 該芳香環上亦可存在除羥基以外之取代基；Bi為不具有酚 性羥基之碳數1〜15之2價有機基；丨為！以上且下之整 數，而且η為2以上且1，〇〇〇以下之整數}所示之結構，且軟 化點為ioo°c以上。又，於上述通式（1)中，11為2以上且 1，000以下之整數，較佳為5以上且8〇〇以下之整數。 本發明之第一態樣中所使用之鹼可溶性酚樹脂重要的是 具有如下結構：於隔著&相對之2個A中，一個A之酚性羥 基之氧原子與另一個A之酚性羥基之氧原子間的最近之距 離（以下亦稱為羥基間距離或最短距離d;)與通常之鹼可溶 性酚樹脂之羥基間距離相比更長。因此，本發明之第一態 樣中所使用之鹼可溶性酚樹脂之特徵在於：藉由利用分子 力學法計算隔著Bi相對之2個a内之酚性羥基中之氧原子間 的最短距離di所獲得之該山之平均值（Σ^η)為9埃（A)以 161182.doc 201234115 上。更詳細而言，於隔著Bi相對之2個A於分別具有單個或 複數個酚性羥基之情形時，一個A之酚性羥基之氧原子與 另一個A之酚性羥基之氧原子間的最短距離山係藉由分子 力學法而算出，而且最短距離山之平均值（2di/n)為9 A以 上0 於使用含有具有羥基間距離較長之結構之鹼可溶性齡樹 脂、感光劑及溶劑之鹼性顯像用感光性酚樹脂組合物將膜 成型’並對其進行加熱硬化時’可獲得具有優異之伸長率 之硬化膜。其理由尚不明確’但本發明者認為，於形成硬 化膜時於分子間所形成之氫鍵之配置之疏密對伸長率造成 較大影響。為了使樹脂硬化膜發揮較高之伸長率，必須於 對硬化膜施加外力時分子發生變形或分子鏈發生偏移而吸 收外力之能量，此時，若分子間之氫鍵密集地存在，則施 加外力時分子之變形量及分子鏈之偏移量變小，可吸收之 能量之大小亦變小。因此，由於吸收不完全之能量而引起 分子鏈之斷裂等，從而導致硬化膜產生裂痕等。相對於 此’若制具有㈣間_較大之結構之樹脂作為驗可溶 性酚樹脂，則分子間之氩鍵不會過於密集，硬化膜可具有 較高之伸長率’結果於用作表面保護膜、層間絕緣膜時， 可獲得可靠性較高之半導體裝置。 驗可溶性㈣脂中之隸間距離係藉由利用㈣ Laboratories公司製造之SymApps(註冊商標）利用分子力學 計算（分子力學法）之MM2法計算三維結構式而求出。驗可 溶性_於利用上述方法進行計算時，經基間距離必須 161182.doc 12 201234115 2埃以上，較佳為丨〇埃以上，更佳為1丨埃以上。就伸長 率與鹼溶解性之觀點而言，該距離之上限較佳為20埃以 下。因此，上述最短距離山之平均值（2：di/n)為9埃（A)以 上，較佳為10埃以上，更佳為11埃以上，又，上述最短距 離山之平均值（sdi/n)之上限值亦較佳為2〇埃以下。於a及& 刀别為種2價有機基之情形時，A-Br A中之最短距離山與 最-距離山之平均值（2di/n)本身相等。再者，於驗可溶性 紛樹脂為使用複數種2價有機基作為a，&/或使用複數種2 價有機基作為Bi之共聚物之情形時，以與上述同樣之方式 求出相對於可能存在之鍵之距_，並I據其實際之存在比 例利用加權平均算出。例如考慮使用兩種化合物（分別設 為1’、Bi")作為Bi之鹼可溶性酚樹脂之情形。此時，若設 為於A B, -A中經基間距離為5埃，而且於中經基間 S^m ^ l〇m > m^^JfflNMR(Nuclear Magnetic Resonance* 核磁共振）等對生成之鹼可溶性酚樹脂進行分析，樹脂中 所含之Βι’與ΒΓ之比為8/2之情形時，該鹼可溶性酚樹脂之 羥基間距離為6埃。於混合兩種以上之鹼可溶性酚樹脂之 情形時’可根據該等樹脂之混合比率同樣地求出鹼可溶性 酚樹脂中之羥基間距離。 本發明之第一態樣之鹼可溶性酚樹脂必須進一步軟化點 為100C以上。於將第一組合物成型為膜狀並形成凸起圖 案後製成硬化膜時，若鹼可溶性酚樹脂之軟化點未違 100 C，則所形成之凸起圖案之形狀變形。軟化點可利用 JIS K5601-2-2之環球法進行測定。軟化點較佳為12〇1以 161182.doc -13· 201234115 ’但就於溶劑或 其上限較佳為 上更佳為140°C以上。軟化點越高越佳 驗性顯像液中之溶解性之方面而言， 300〇C。 以下說明滿足上述條件之鹼可溶性酚樹脂之具體例。 驗可溶性紛樹脂可使形成上述通式⑴中之A部之化合物 例如具有酚性羥基之化合物與形成上述通式（1)中之&部之 化合物例如不具有酚性羥基的醛化合物、羥甲基化合物、 烷氧基曱基化合物或二烯化合物進行聚合而獲得。 又，亦可將具有酚性羥基之醛化合物、羥甲基化合物、 炫氧基曱基化合物或―烯化合物用於聚合。於此情形時， 該等化合物之中，將該化合物之與和具有酚性羥基之芳香 環鄰接之A部連結的部分設為^部，其他部分設為a部。 作為其具體例，可列舉：2,6_雙（羥基甲基）_對甲酚、 4’6-雙（羥基曱基）_鄰甲酚、2,4_雙（羥基曱基）·間甲酚、2,6_ 雙（甲氧基甲基）-對甲酚、2,6-雙（對羥基甲基苄基對曱酚 等，例如於使用2,6-雙（羥基甲基）_對甲酚時，將對曱酚結 構部視作A部，2個亞曱基結構部視作1部，於使用2,6-雙 (對羥基曱基苄基）-對甲酚時，將對曱酚結構部分視作A 部、2個對二曱苯結構部視作^部。 作為用作形成上述通式（1)中之A部之化合物的具有酚性 經基之化合物之例，可列舉：苯酚、甲酚、乙基苯酚、丙 基笨酚、丁基苯酚、戊基苯酚、苄基苯酚、金剛烷酚、苄 氧基本酌·、二甲本齡、兒茶盼、間苯二酴、乙基間苯二 酚、己基間笨二酚、對笨二酚、2,3_二羥基苯甲酸、2,4· 161182.doc •14· 201234115 二羥基苯曱酸、咖啡酸、3,4-二羥基苯曱酸、3,5-二羥基 苯甲酸、2,3-二羥基笨曱酸甲酯、2,4-二羥基苯甲酸甲 酯、2,6-二羥基笨曱酸曱酯、3,4-二羥基苯甲酸甲酯、3,5-二羥基苯甲酸甲酯、3,4-二羥基苯甲酸乙酯、 2,3-二羥基苯甲醯胺、2,4-二羥基苯甲醯胺、2,6-二羥基 苯曱醯胺、3,4-二羥基苯甲醯胺、3,5-二羥基苯甲醯胺、4-硝基兒茶酚、4-氟兒茶酚、4-氯兒茶酚、4-溴兒茶酚、4-硝基間苯二酚、4-氟間苯二酚、4-氯間苯二酚、4-溴間苯 二酚、2,3-二羥基苯曱醛、2,4-二羥基苯甲醛、2,6-二羥基 苯曱醛、3,4-二羥基苯曱醛、3,5·二羥基苯曱醛、2'，3，-二 羥基苯乙酮、2·，4·-二羥基苯乙酮、2，，6，-二羥基苯乙酮、 3·，4·-二羥基苯乙酮、3’，5，-二羥基苯乙酮、2,3-二羥基苯曱 腈、2,4-二羥基笨曱腈、2,6_二羥基苯曱腈、3,4_二羥基苯 甲腈、3,5-一經基笨甲腈、鄰苯三盼、間笨三紛、1,2,心三 羥苯、 >又食子酸、沒食子酸甲酯、沒食子酸乙酯、沒食子酸丙 酯、2’，3’，4’-三羥基笨乙酮、2，，4，，5，_三羥基苯乙酮、 2’，4，，6’-三羥基苯乙酮、3ι，4·，5，_三羥基苯乙酮、2,3,4-三羥 基二苯曱酮、2,4,5·三羥基二苯甲酮、2,4,6_三羥基二苯曱 酮、3,4,5-三羥基二苯甲酮、2,3,4_三羥基苯甲醛、2,4,5_ 三經基苯曱酿、2,4,6·三經基苯曱搭、3,4,5_三經基苯甲 酸、2,3’4·三經基笨甲酸、Μ，5·三經基笨曱酸、2,4,6•三 羥基苯甲酸3,4,5-二羥基苯甲酸、玫紅酸、聯苯酚、雙 酴Α、雙盼AF、雙紛β、雙盼F、雙齡s、二經基二苯基甲 161182.doc •15· 201234115 烷、1，1-雙（4-羥基苯基）環己烷、14雙（3羥基苯氧基 笨）、2,2-雙（4-羥基_3_曱基苯基）丙烷、α,α,-雙（4羥基苯 基）-1’4-二異丙基苯、9,9·雙（4羥基_3_曱基苯基）第' 2,2_ 雙（3-環己基-4·經基苯基）丙烷、2,2_雙（2·羥基_5_聯苯基） 丙烷等。 又，作為形成上述通式（1)中之A部之化合物，於上述化 β物中’較佳為具有2〜3個紛性經基之化合物。 於上述化合物中，為了使本發明之第一態樣獲得更佳之 效果’作為較佳之化合物’可列舉：兒茶酚、間苯二酚、 對苯二酚、2,3_二羥基苯曱酸、2,3_二羥基苯曱酸曱酯、 2’4-一羥基苯甲酸曱酯、2,6_二羥基苯曱酸甲酯、3,4_二羥 基苯曱酸曱酯、3,5-二羥基苯甲酸曱酯、3,4_二羥基苯曱 酸乙自旨、2,3-二經基苯甲酿胺、2,4二經基苯甲醯胺、2,6_ 一羥基苯甲醯胺、3,4-二羥基苯甲醯胺、3，5_二羥基苯甲 酿胺、2,3-一經基笨曱腈、2,4_二羥基苯曱腈、2,6_二羥基 苯曱腈、3,4-二羥基苯甲腈、3,5二羥基笨甲冑、鄰苯三 酚間苯二酚、1，2,4-三羥苯、沒食子酸曱酯、沒食子酸 乙酯及沒食子酸丙酯。 其次，記載形成上述通式U)中之Κ部之化合物之具體 例。 作為酿化合物，可列舉：甲搭、乙搭、丙链、新戍酸、 丁醛 '戊醛、己醛、三号烷、乙二醛、環己基醛、二苯基 乙路、乙基THM、桂該、二苯基㈣、反丁稀 二醛酸曱酯、3·甲基_2_ 丁烯醛、乙醛酸、5_降葙烯_2_甲 16M82.doc 201234115 醛、丙二醛、丁二醛、戊二醛、萘曱醛、對苯二曱醛等。 作為羥甲基化合物，可列舉：匕弘雙（羥基曱基）脲、核 糖醇、阿拉伯糖醇、阿洛醇、2,2-雙（羥基曱基）丁酸、i，3_ 丙一酵、2_苄氧基-1，3-丙二醇、2,2-二曱基-1,3-丙二醇、 2,2-二乙基_ι，3·丙二醇、單乙酸甘油酯、2_曱基_2_硝 基-1，3-丙二醇、5_降葙烯_2,2二甲醇、5_降葙烯_2,3·二甲 醇、季戊四醇、2-苯基-1，3-丙二醇、三羥曱基乙烧、三羥 甲基丙烷、3,6-雙（羥基甲基）均四甲苯、2_硝基-對苯二甲 醇、1，10-二羥基癸烷、丨，12_二羥基十二烷、丨，4_雙（羥基 甲基）環己烷、1，4-雙（羥基曱基）環己烯、丨，6_雙（羥基曱基） 金剛烷、1，4-笨二甲醇、i，3_笨二曱醇、2,6_雙（羥基曱基）_ 1，4-二曱氧基苯、2,3_雙（羥基曱基）萘、2,6-雙（羥基甲基） 萘、1’8-雙（羥基甲基）蒽、2,2，_雙（羥基甲基）二苯基醚、 4,4'-雙（羥基甲基）二苯基醚、4,4,_雙（羥基曱基）二苯基硫 醚、4,4’-雙（經基甲基）二苯甲酮、4經基甲基苯曱酸·4,_羥 基曱基苯醋、4-羥基曱基笨曱酸_4，_羥基曱基醯替苯胺、 4,4’_雙（經基甲基）苯基脲、4 4，_雙（羥基甲基）苯基胺基曱 酸醋、1，8-雙（羥基甲基）蒽、4,41_雙（羥基曱基）聯苯、2,2,_ 二甲基_4,4··雙（羥基曱基）聯苯、2,2-雙（4-羥基甲基苯基） 丙烷等。 作為烷氧基甲基化合物，可列舉：3 -二甲氧基丙烷、 13- 雙（曱氧基甲基）腺、2,2-雙（甲氧基甲基）丁酸、2,2-雙 (甲氧基甲基）-5-降葙烯、2,3-雙（曱氧基曱基）-5-降宿烯、 14- 雙（曱氧基甲基）環己烷、L4-雙（甲氧基曱基）環己烯、 161182.doc -17- 201234115 i，6-雙（甲氧基甲基）金剛烷、1，4-雙（甲氧基甲基）苯、丨，3_ 雙（甲氧基甲基）苯、2,6-雙（甲氧基甲基）-對甲酚、2,6-雙 (曱氧基曱基）-1，4·二甲氧基苯、2,3-雙（甲氧基甲基）萘、 2’6_雙（曱氧基甲基）萘、匕卜雙（甲氧基甲基）蒽、2,21_雙（甲 氧基甲基）二苯基醚、4,4，_雙（甲氧基甲基）二苯基醚、4,4，_ 雙（甲氧基甲基）二苯基硫醚、4,4，-雙（甲氧基甲基）二苯甲 酮、4-甲氧基甲基苯甲酸·4’_甲氧基甲基苯酯、4_甲氧基子 基苯曱酸-4·-甲氧基甲基醯替苯胺、4,4，-雙（甲氧基曱基）苯 基服、4,4’-雙（甲氧基甲基）苯基胺基甲酸酯、1，8-雙（甲氧 基曱基）蒽、4,4’-雙（甲氧基甲基）聯苯、2,2，-二曱基-4,4'-雙 (甲氧基甲基）聯笨、2,2_雙（4-甲氧基甲基苯基）丙烷等。 作為二烯化合物，可列舉：丁二烯、戊二烯、己二烯、 庚二烯、辛二烯、癸二烯、3-甲基-1,3-丁二烯、l，3-丁二 醇-二甲基丙烯酸酯、2,4_己二烯_丨_醇、甲基環己二烯、 環戊二烯、環己二烯、環己二烯、環辛二烯、二環戊二 烯、1-羥基二環戊二烯、丨_曱基環戊二烯、甲基二環戊二 烯、二烯丙基醚、二烯丙基硫醚、己二酸二烯丙酯、2,5· 降葙二烯、四氫節、5·亞乙基·2_降葙烯、5_乙烯基_2_降袼 烯、乙二酸二烯丙酯、戊二酸二烯丙酯、己二酸二烯丙 酯、氰尿酸三烯丙酯、氰尿酸二稀丙酯、氰尿酸二烯丙基 丙酗、異氰尿酸二烯丙酯、異氰尿酸二烯丙酯、異氰尿酸 一*稀丙基丙醋等。 上述Bi部較佳為下述通式（2): -X-L-Y-M-Z- 161182.doc (2) •18· 201234115 {式中’ L及Μ分別獨立為不具有酚性羥基且可具有除酚性 羥基以外之取代基的碳數6〜1〇之2價芳香族基，而且χ、γ 及Ζ分別獨立為選自由單鍵、碳數卜2之脂肪族基、醯胺 基、羰基、酯基、脲基、胺基曱酸酯基、醚基及硫醚基所 組成之群中的2價基}所示之結構。 對於本發明之第一態樣之鹼可溶性酚樹脂而言，可對上 述具有紛性經基之化合物藉由將羥甲基化合物、烧氧基曱 基化合物或二烯化合物一面分別脫水、脫醇或使不飽和鍵 斷裂一面進行聚合而樹脂化，於該聚合時，亦可使用酸性 或驗性之觸媒。作為酸性觸媒，可列舉：鹽酸、硫酸、石肖 酸、碟酸、亞磷酸、甲磺酸、對曱苯磺酸、二甲基硫酸、 二乙基硫酸、乙酸、乙二酸、丨_羥基亞乙基“，丨，·二膦酸、 乙酸鋅、三氟化硼、三氟化硼-酚錯合物、三氟化硼·醚錯 合物等。另一方面，作為鹼性觸媒，可列舉：氫氧化鋰、 氫氧化鈉、氫氧化鉀、氫氧化鈣、氫氧化鋇、碳酸鈉、三 乙胺、吡啶、4-N，N-二曱基胺基吡啶、哌啶、哌畊、1>4_ 二氮雜雙環[2.2.2]辛烷、1,8-二氮雜雙環[5.4.0]_7_十一 烤、1，5 -—氣雜雙環[4.3·0]-5 -壬烯、氨、六亞曱基四胺 等。 本發明之第一態樣之鹼可溶性酚樹脂之重量平均分子量 較佳為1，500以上，更佳為3,〇〇〇以上，最佳為4,〇〇〇以上。 重量平均分子量之測定係藉由膠滲層析法（GPC，Gel-Permeation Chromatography)而進行’藉由使用標準聚苯乙 烤製作之校正曲線而算出。 161182.doc •19· 201234115 <第一組合物中所使用之感光劑> 於第一組合物中含有感光劑作為必需成分。藉由選擇感 光劑之種類，可將第一組合物製成正型，亦可製成負裂。 於將驗性顯像用感光性驗樹脂組合物製成正型之情形時， 需要選擇光酸產生劑作為感光劑。於製成負型之情形時， 使用光酸產生劑或光驗產生劑，且需要下述交聯劑。作為 光酸產生劑’可使用萘醌二疊氮（NqD，Naphth〇quinone Diazide)化合物、鏽鹽、含有鹵素之化合物等就溶劑溶 解性及保存穩定性之觀點而言，較佳為下述nqd化合物。 作為上述鏽鹽，可列舉：錤鹽、錡鹽、鱗鹽、銨鹽、重 氮鏽鹽等’較佳為選自由二芳基鎖鹽、三芳紐鹽及三烧 基銃鹽所組成之群中之鏽鹽。 作為上述含有齒素之化合物，可列舉含有函烷基之烴化 合物等，較佳為三氣甲基三畊。 作為上述萘醌二疊氮化合物，可列舉丨，2_苯醌二疊氮結 構或具疊氮結構之化合物，該㈣於例如美 國專利第2,772,972號說明書、美國專利第2,797,213號說明 書及美國專利第3,669,658號說明書等中有記載。該蔡酿二 疊氮結構為選自由下文將詳述之具有特定結構之多經基化Wherein R3 is a methyl group or an ethyl group, and 13 and £1 are each independently an integer of 〇~4, and R is an alkoxy group which may be selected from a halogen atom, a hydroxyl group, and a carbon number of 〇~1〇 which may have an unsaturated bond. The compound represented by the group of the group is mixed with a molar ratio of 5: 丨 丨 丨: 5, and further a catalyst is added; and a step of heating at 60 ° C or higher for 1 minute to 48 hours. [6] A photosensitive resin composition characterized by containing the biphenyldiyltrihydroxybenzene resin according to any one of [4] above or by using a biphenyldiyltriazine as described in [5] above. The resin and sensitizer obtained by the manufacturing method. [7] The photosensitive resin composition according to [6] above, wherein the sensitizer is a photoacid generator. [8] The positive photosensitive resin composition according to the above [6], wherein the light-reducing agent is a naphthoquinonediazide compound. 161182.doc 201234115 [9] A method of manufacturing a semiconductor device, comprising the steps of: forming a photosensitive resin layer containing the photosensitive resin composition according to any one of [6] to [6] on a semiconductor substrate; a step of exposing the photosensitive resin layer by active light; a step of developing the exposed photosensitive resin layer to obtain a raised pattern; and a step of heating the obtained raised pattern. [10] A semiconductor device manufactured by the method of [9] above. [Effects of the Invention] According to the first aspect of the invention, the heat hardening temperature of the surface protective film or the interlayer insulating film for forming the semiconductor device can be set to a relatively low temperature (e.g., 25 〇r or less). Further, according to the present invention, the elongation of the cured film obtained by curing the photosensitive phenol resin composition for alkaline development can be increased. Further, according to the first aspect of the present invention, it is not only reduced to application to a semiconductor device. The crack of the surface protective film or the interlayer insulating film at the time of stress caused by heat improves the usability and improves the reliability of the semiconductor device formed therewith. According to the second aspect of the present invention, it is possible to obtain a bismuth-terminated benzene resin which simultaneously satisfies the lithography and tree (4) heat which cannot be achieved by the prior resin, and which has both properties applicable to a semiconductor device. The method for producing the semiconductor device using the composition and the semiconductor device are also used in the method of the invention. [Embodiment] 161182.doc 201234115 Hereinafter, the first aspect of the present invention contains a specific alkali-soluble phenol. A photosensitive phenol resin composition for alkaline development of a resin, a sensitizer, and a solvent (hereinafter simply referred to as "first composition") will be described. <Alkali-soluble phenol resin used in the first composition> The alkali-soluble phenol resin used in the composition of the first aspect of the invention contains a polymer compound having a compound having a phenolic hydroxyl group in the repeating unit 0 The soluble phenol resin is characterized by having the following general formula (1): -A-B1-A-B2-A-B3-A-...Bi... A-Bn-A- (1) { 'A is independently a divalent organic group having a phenolic hydroxyl group having 6 to 25 carbon atoms, and the bonding bond of the A is present on an aromatic ring having a phenolic radical, and a hydroxyl group may be present on the aromatic ring. a substituent; Bi is a divalent organic group having 1 to 15 carbon atoms which does not have a phenolic hydroxyl group; The above and below integers, and η is a structure represented by 2 or more and 1 and 〇〇〇 below the integer}, and the softening point is ioo °c or more. Further, in the above formula (1), 11 is an integer of 2 or more and 1,000 or less, preferably an integer of 5 or more and 8 Å or less. The alkali-soluble phenol resin used in the first aspect of the present invention is important in that it has a structure in which an oxygen atom of a phenolic hydroxyl group of A and a phenolic property of another A are present in two opposite A groups. The closest distance between the oxygen atoms of the hydroxyl group (hereinafter also referred to as the inter-hydroxyl distance or the shortest distance d;) is longer than the distance between the hydroxyl groups of the usual alkali-soluble phenol resin. Therefore, the alkali-soluble phenol resin used in the first aspect of the present invention is characterized in that the shortest distance between the oxygen atoms in the phenolic hydroxyl groups in the two opposite a of Bi is calculated by molecular mechanics. The average value of the mountain obtained (Σ^η) was 9 angstroms (A) to 161182.doc 201234115. More specifically, in the case where two A and two phenolic hydroxyl groups are respectively separated by Bi, the oxygen atom of the phenolic hydroxyl group of one A and the oxygen atom of the phenolic hydroxyl group of the other A The shortest distance mountain is calculated by the molecular mechanics method, and the average value of the shortest distance mountain (2di/n) is 9 A or more. 0 Use of an alkali-soluble resin, a sensitizer, and a solvent containing a structure having a long distance between hydroxyl groups. In the case of the photosensitive phenol resin composition for alkaline development, when the film is molded and cured by heating, a cured film having excellent elongation can be obtained. The reason for this is not clear. However, the inventors of the present invention considered that the density of the hydrogen bond formed between the molecules at the time of forming the hard film has a large influence on the elongation. In order for the resin cured film to exhibit a high elongation, it is necessary to absorb the external force when the external force is applied to the cured film, and the molecular chain is shifted to absorb the external force. In this case, if the hydrogen bonds between the molecules are densely present, the application is performed. When the external force is applied, the amount of deformation of the molecule and the offset of the molecular chain become smaller, and the amount of energy that can be absorbed also becomes smaller. Therefore, the molecular chain is broken or the like due to absorption of incomplete energy, thereby causing cracks or the like in the cured film. In contrast, if a resin having a structure of (four)-larger is used as the soluble phenol resin, the intermolecular argon bond is not too dense, and the cured film can have a high elongation, and the result is used as a surface protective film. In the case of an interlayer insulating film, a highly reliable semiconductor device can be obtained. The inter-sub-compartment distance in the soluble (tetra) lipid was determined by calculating the three-dimensional structural formula by the MM2 method of molecular mechanics calculation (molecular mechanics method) using SymApps (registered trademark) manufactured by Laboratories. The solubility is determined by the above method, and the distance between the bases must be 161182.doc 12 201234115 2 Å or more, preferably 丨〇 or more, more preferably 1 丨 or more. The upper limit of the distance is preferably 20 Å or less from the viewpoint of elongation and alkali solubility. Therefore, the average value (2: di/n) of the shortest distance mountain is 9 angstroms (A) or more, preferably 10 angstroms or more, more preferably 11 angstroms or more, and the average value of the shortest distance mountain (sdi/ n) The upper limit is also preferably 2 angstroms or less. In the case where a and & knife are a divalent organic group, the shortest distance mountain in A-Br A is equal to the average value of the most distant mountain (2di/n). Further, in the case where a plurality of divalent organic groups are used as a, &/or a plurality of divalent organic groups are used as the copolymer of Bi, the relative solubility is determined in the same manner as described above. The distance _ of the existing key is calculated by the weighted average according to its actual existence ratio. For example, it is considered to use two kinds of compounds (1', Bi" respectively) as the alkali-soluble phenol resin of Bi. In this case, if it is set to AB, -A has a base-to-base distance of 5 angstroms, and is generated by a pair of intermediate and intermediate S^m^l〇m > m^^Jffl NMR (Nuclear Magnetic Resonance* NMR). The alkali-soluble phenol resin was analyzed, and when the ratio of Βι' to yttrium contained in the resin was 8/2, the distance between the hydroxyl groups of the alkali-soluble phenol resin was 6 angstrom. In the case of mixing two or more kinds of alkali-soluble phenol resins, the distance between the hydroxyl groups in the alkali-soluble phenol resin can be similarly determined from the mixing ratio of the resins. The alkali-soluble phenol resin of the first aspect of the present invention must have a further softening point of 100 C or more. When the first composition is formed into a film shape and a convex pattern is formed to form a cured film, if the softening point of the alkali-soluble phenol resin does not violate 100 C, the shape of the formed convex pattern is deformed. The softening point can be measured by the ring method of JIS K5601-2-2. The softening point is preferably 12 〇 1 to 161182.doc -13· 201234115 ' but it is preferably 140 ° C or more in terms of the solvent or the upper limit thereof. The higher the softening point, the better the solubility in the test solution, 300 〇C. Specific examples of the alkali-soluble phenol resin satisfying the above conditions will be described below. The soluble resin can be used to form a compound of the above formula (1), for example, a compound having a phenolic hydroxyl group and a compound forming the & moiety in the above formula (1), for example, an aldehyde compound having no phenolic hydroxyl group, or a hydroxy group. A methyl compound, an alkoxyfluorenyl compound or a diene compound is obtained by polymerization. Further, an aldehyde compound having a phenolic hydroxyl group, a methylol compound, a decyloxy thiol compound or an olefin compound may be used for the polymerization. In this case, among these compounds, a portion of the compound which is bonded to the A portion adjacent to the aromatic ring having a phenolic hydroxyl group is referred to as a portion, and the other portion is a portion. Specific examples thereof include 2,6-bis(hydroxymethyl)_p-cresol, 4'6-bis(hydroxyindenyl)-o-cresol, and 2,4-bis(hydroxyindenyl). Cresol, 2,6-bis(methoxymethyl)-p-cresol, 2,6-bis (p-hydroxymethylbenzyl p-nonylphenol, etc., for example, using 2,6-bis(hydroxymethyl)_ In the case of p-cresol, the indophenol structure is regarded as part A, and the two indenylene structure parts are regarded as one part, and when 2,6-bis(p-hydroxydecylbenzyl)-p-cresol is used, The indophenol structure portion is regarded as the A portion and the two p-diphenylbenzene structure portions. As an example of a compound having a phenolic group as a compound for forming the A portion in the above formula (1), For example, phenol, cresol, ethyl phenol, propyl phenol, butyl phenol, amyl phenol, benzyl phenol, adamantol, benzyloxy, dimethyl ether, catechin, and meta-benzene Diterpenoid, ethyl resorcinol, hexyl streptophenol, p-diphenol, 2,3-dihydroxybenzoic acid, 2,4·161182.doc •14· 201234115 dihydroxybenzoic acid, caffeic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,3-dihydroxy Methyl bromide, methyl 2,4-dihydroxybenzoate, decyl 2,6-dihydroxyindole, methyl 3,4-dihydroxybenzoate, methyl 3,5-dihydroxybenzoate , 3,4-dihydroxybenzoic acid ethyl ester, 2,3-dihydroxybenzamide, 2,4-dihydroxybenzamide, 2,6-dihydroxybenzoguanamine, 3,4-di Hydroxybenzamide, 3,5-dihydroxybenzamide, 4-nitrocatechol, 4-fluorocatechol, 4-chlorocatechol, 4-bromocatechol, 4-nitro Resorcinol, 4-fluororesorcinol, 4-chlororesorcinol, 4-bromoresorcinol, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2, 6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2',3,-dihydroxyacetophenone, 2·,4·-dihydroxybenzene Ketone, 2,6,-dihydroxyacetophenone, 3·,4·-dihydroxyacetophenone, 3',5,-dihydroxyacetophenone, 2,3-dihydroxybenzonitrile, 2, 4-dihydroxyindole nitrile, 2,6-dihydroxybenzonitrile, 3,4-dihydroxybenzonitrile, 3,5-mono-p-carbonitrile, o-benzotrizene, stupid, 1, 2, heart trihydroxybenzene, > acetoin, methyl gallate, ethyl gallate, Propionate propylate, 2',3',4'-trihydroxy acetophenone, 2,4,5,3-trihydroxyacetophenone, 2',4,6'-trihydroxyacetophenone , 3ι, 4·, 5, _ trihydroxyacetophenone, 2,3,4-trihydroxybenzophenone, 2,4,5·trihydroxybenzophenone, 2,4,6-trihydroxy Phenyl ketone, 3,4,5-trihydroxybenzophenone, 2,3,4-trihydroxybenzaldehyde, 2,4,5-trisylbenzoquinone, 2,4,6·trisylbenzene曱, 3,4,5_ tri-perylene benzoic acid, 2,3'4·tri-perylene, hydrazine, 5·three-mersic acid, 2,4,6•trihydroxybenzoic acid 3, 4,5-dihydroxybenzoic acid, rosacenic acid, biphenol, biguanide, double-presence AF, double-diffused β, double-dose F, double-aged s, di-based diphenyl-based 161182.doc •15· 201234115 Alkane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 14 bis(3hydroxyphenoxy), 2,2-bis(4-hydroxy-3-indolylphenyl)propane, α, α,-bis(4-hydroxyphenyl)-1'4-diisopropylbenzene, 9,9·bis(4hydroxy-3-indolylphenyl)- 2,2_bis(3-cyclohexyl-4 • phenylphenyl)propane, 2,2-bis(2·hydroxy-5-biphenyl)propane, and the like. Further, as the compound forming the A moiety in the above formula (1), the compound in the above-mentioned β is preferably a compound having 2 to 3 divalent groups. Among the above compounds, in order to obtain a better effect of the first aspect of the present invention, 'preferable compounds' include catechol, resorcinol, hydroquinone, and 2,3-dihydroxybenzoic acid. , 2,3-dihydroxybenzoic acid decyl ester, 2'4-hydroxybenzoic acid decyl ester, 2,6-dihydroxybenzoic acid methyl ester, 3,4-dihydroxybenzoic acid decyl ester, 3, Ethyl 5-dihydroxybenzoate, 3,4-dihydroxybenzoic acid, self-property, 2,3-di-based benzoylamine, 2,4-dibenzylbenzamide, 2,6-monohydroxy Benzamide, 3,4-dihydroxybenzamide, 3,5-dihydroxybenzamide, 2,3-monopyridyl nitrile, 2,4-dihydroxybenzonitrile, 2,6 _Dihydroxybenzonitrile, 3,4-dihydroxybenzonitrile, 3,5 dihydroxy carbamoxime, pyrogallol resorcinol, 1,2,4-trihydroxybenzene, decyl gallate , gallic acid ethyl ester and propyl gallate. Next, a specific example of the compound forming the crotch portion in the above formula U) will be described. As the brewing compound, there may be mentioned, for example, methyl, ethylene, propylene, neodecanoic acid, butyraldehyde, 'pentanal, hexanal, hexane, glyoxal, cyclohexyl aldehyde, diphenyl ethane, ethyl THM. , Gui, diphenyl (tetra), anti-butadienyl phthalate, 3 · methyl 2 - crotonaldehyde, glyoxylic acid, 5 - norbornene 2 - methyl 16M82.doc 201234115 aldehyde, malondialdehyde , succinaldehyde, glutaraldehyde, naphthaldehyde, terephthalaldehyde, and the like. Examples of the methylol compound include ruthenium bis(hydroxyindenyl)urea, ribitol, arabitol, aldol, 2,2-bis(hydroxyindenyl)butyric acid, i,3-propanyl yeast, 2_benzyloxy-1,3-propanediol, 2,2-dimercapto-1,3-propanediol, 2,2-diethyl-I,3,propanediol, monoacetin, 2_mercapto 2_nitro-1,3-propanediol, 5_northene-2,2 dimethanol, 5_northene-2,3·dimethanol, pentaerythritol, 2-phenyl-1,3-propanediol, three Hydroxyl mercapto, trimethylolpropane, 3,6-bis(hydroxymethyl)tetramethylene, 2-nitro-p-diphenylmethanol, 1,10-dihydroxydecane, anthracene, 12_two Hydroxydodecane, anthracene, 4_bis(hydroxymethyl)cyclohexane, 1,4-bis(hydroxyindenyl)cyclohexene, anthracene, 6-bis(hydroxyindenyl)adamantane, 1,4- Stupid dimethanol, i, 3_ stupidyl alcohol, 2,6-bis(hydroxyindenyl)-1,4-dimethoxybenzene, 2,3-bis(hydroxyindenyl)naphthalene, 2,6- Bis(hydroxymethyl)naphthalene, 1'8-bis(hydroxymethyl)anthracene, 2,2,-bis(hydroxymethyl)diphenyl ether, 4,4'-bis(hydroxymethyl)diphenyl Ether, 4, 4, _ double (hydroxyl Mercapto) diphenyl sulfide, 4,4'-bis(ylmethyl)benzophenone, 4-methylbenzoic acid 4,-hydroxydecyl benzene vinegar, 4-hydroxy fluorenyl stupid曱4,_hydroxymercaptobenzidine, 4,4'-bis(methylidenemethyl)phenylurea, 4 4,_bis(hydroxymethyl)phenylamino citrate, 1,8 - bis(hydroxymethyl)anthracene, 4,41-bis(hydroxyindenyl)biphenyl, 2,2,_dimethyl- 4,4·bis(hydroxyindenyl)biphenyl, 2,2-double (4-hydroxymethylphenyl) propane and the like. Examples of the alkoxymethyl compound include 3-dimethoxypropane, 13-bis(decyloxymethyl) gland, 2,2-bis(methoxymethyl)butyric acid, and 2,2- Bis(methoxymethyl)-5-norbornene, 2,3-bis(decyloxy)-5-neneene, 14-bis(decyloxymethyl)cyclohexane, L4- Bis(methoxyindenyl)cyclohexene, 161182.doc -17- 201234115 i,6-bis(methoxymethyl)adamantane, 1,4-bis(methoxymethyl)benzene, anthracene, 3_bis(methoxymethyl)benzene, 2,6-bis(methoxymethyl)-p-cresol, 2,6-bis(decyloxyindenyl)-1,4-dimethoxybenzene , 2,3-bis(methoxymethyl)naphthalene, 2'6-bis(decyloxymethyl)naphthalene, anthracene bis(methoxymethyl)anthracene, 2,21-bis(methoxy Methyl)diphenyl ether, 4,4,_bis(methoxymethyl)diphenyl ether, 4,4,_bis(methoxymethyl)diphenyl sulfide, 4,4,- Bis(methoxymethyl)benzophenone, 4-methoxymethylbenzoic acid 4'-methoxymethylphenyl ester, 4-methoxyphenylbenzoic acid-4·-methoxy Methyl anilide, 4,4,-bis(methoxyindenyl)phenyl 4,4'-bis(methoxymethyl)phenylcarbamate, 1,8-bis(methoxyindenyl)anthracene, 4,4'-bis(methoxymethyl)biphenyl 2,2,-Dimercapto-4,4'-bis(methoxymethyl)biphenyl, 2,2-bis(4-methoxymethylphenyl)propane, and the like. Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, decadiene, 3-methyl-1,3-butadiene, and 1,3-butene. Glycol-dimethacrylate, 2,4-hexadiene-anol, methylcyclohexadiene, cyclopentadiene, cyclohexadiene, cyclohexadiene, cyclooctadiene, bicyclo Pentadiene, 1-hydroxydicyclopentadiene, indole-cyclopentadiene, methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl adipate , 2,5· norbornadiene, tetrahydrogen, 5·ethylene·2_norbornene, 5_vinyl_2_norbornene, diallyl oxalate, diene glutarate Propyl ester, diallyl adipate, triallyl cyanurate, dilute propyl cyanurate, diallyl cyanurate, diallyl isocyanurate, diallyl isocyanurate, Isocyanuric acid - * propyl propyl vinegar and the like. The Bi portion is preferably of the following formula (2): -XLYMZ-161182.doc (2) •18·201234115 {wherein L and oxime are independently phenolic hydroxyl groups and may have a phenolic hydroxyl group. The substituent has a carbon number of 6 to 1 fluorene of a divalent aromatic group, and χ, γ and Ζ are each independently selected from the group consisting of a single bond, an aliphatic group of a carbon number 2, a mercapto group, a carbonyl group, an ester group, and a urea. A structure represented by a divalent group in the group consisting of an amino group, an amino phthalate group, an ether group, and a thioether group. For the alkali-soluble phenol resin according to the first aspect of the present invention, the above-mentioned compound having a heterocyclic group can be dehydrated and dealcoholated by one side of a methylol compound, an alkoxypurine compound or a diene compound, respectively. Alternatively, the unsaturated bond may be polymerized and polymerized while being cleaved, and an acid or an organic catalyst may be used in the polymerization. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, tartaric acid, dish acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethylsulfuric acid, diethylsulfuric acid, acetic acid, oxalic acid, and hydrazine. Hydroxyethylene ", hydrazine, diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride-phenol complex, boron trifluoride ether ether complex, etc. On the other hand, as a basic touch The medium may, for example, be lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N,N-didecylaminopyridine or piperidine. Piper, 1>4_diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]_7_ eleven roasted, 1,5--heterobicyclo[4.3.0] -5 - terpene, ammonia, hexamethylenetetramine, etc. The weight average molecular weight of the alkali-soluble phenol resin of the first aspect of the invention is preferably 1,500 or more, more preferably 3 or more, Preferably, it is 4 or more. The measurement of the weight average molecular weight is carried out by gel permeation chromatography (GPC, Gel-Permeation Chromatography), which is calculated by using a calibration curve prepared by standard polystyrene baking. 1182.doc • 19·201234115 <Photosensitive agent used in the first composition> A photosensitive agent is contained as an essential component in the first composition. The first composition can be made by selecting the kind of the photosensitive agent. The positive type can also be made into a negative crack. When the photosensitive resin composition is made into a positive type, it is necessary to select a photoacid generator as a sensitizer. A photoacid generator or a photoinitiator is used, and a cross-linking agent is required. As the photo-acid generator, a naphthoquinone diazide (NqD, Naphth〇quinone Diazide) compound, a rust salt, a halogen-containing compound, or the like can be used. From the viewpoint of solvent solubility and storage stability, the following nqd compound is preferred. Examples of the rust salt include a phosphonium salt, a phosphonium salt, a scale salt, an ammonium salt, a diazogen salt, and the like. The rust salt in the group consisting of a diaryl sulfonium salt, a triaryl sulfonium salt, and a trisyl sulfonium salt is selected. The dentate-containing compound may, for example, be a hydrocarbon compound containing a functional group, preferably three gases. Methyl tillage. As the above naphthoquinone diazide compound The hydrazine, a 2 benzoquinone diazide structure or a compound having an azide structure may be mentioned, and the (4) is described in, for example, the specification of U.S. Patent No. 2,772,972, the specification of U.S. Patent No. 2,797,213, and the specification of U.S. Patent No. 3,669,658. The Cairo diazide structure is selected from a polybasic structure having a specific structure as will be described in detail below.

合物之！，2萘酿二疊氮_4·續酸酷及該多經基化合物之H 萘酿二疊氮酸醋所組成之群中之至少_種化合物… 下亦稱為「NQD化合物」）。 用氣續酸或亞硫酿氣 ’使所得之萘醌二疊 該NQD化合物可藉由依照常法利 將萘醌二疊氮磺酸化合物製成磺醯氣 161182.doc 201234115 氮磺醢氣與多羥基化合物進行縮合反應而獲得。例如於二 呤烷、丙酮、四氫呋喃等溶劑中，於三乙胺等鹼性觸媒之 存在下使多羥基化合物與特定量之1，2-萘醌二疊氮-5-磺醯 氣或1,2-蔡醒二疊氣-4-續醯氣進行反應而醋化，對所得之 產物進行水洗、乾燥，藉此可獲得NQD化合物。 作為較佳之NQD化合物之例，例如可列舉下述者。 [化9]Compound! , 2 naphthalene diazide _4 · continued acid and at least one of the group consisting of the H-naphthalene dihalide vinegar of the poly-based compound (also referred to as "NQD compound"). The NQD compound obtained by the use of a gas-renewed acid or a sulfite gas can be made into a sulfonium gas by a naphthoquinonediazidesulfonic acid compound according to a conventional method. 161182.doc 201234115 Nitrogen sulfonium gas and The polyhydroxy compound is obtained by a condensation reaction. For example, in a solvent such as dioxane, acetone or tetrahydrofuran, a polyhydroxy compound is added to a specific amount of 1,2-naphthoquinonediazide-5-sulfonate or 1 in the presence of a basic catalyst such as triethylamine. 2- Cai Xing Er Die Qi-4-Continuous helium gas is reacted and vinegared, and the obtained product is washed with water and dried, whereby an NQD compound can be obtained. As an example of a preferable NQD compound, the following are mentioned, for example. [Chemistry 9]

{式中^ Q為氣原子或下述： [化 10] 〇 〇In the formula, Q is a gas atom or the following: [Chemical 10] 〇 〇

之萘醌二疊氮磺酸酯基，所有的Q不同時為氫原子}。 161182.doc -21 - 201234115 又’可使用在同一分*中併用4-萘酿二疊氮績酿基及5- 萘醌一疊氮磺醯基之萘醌二疊氮磺醯酯化合物，亦可將4_ 萘醌二疊氮磺醯酯化合物與5_萘醌二疊氮磺醯酯化合物混 合使用。 於本發明之第一態樣中，相對於鹼可溶性酚樹脂丨〇〇質 量份之感光劑之調配量較佳為卜“質量份，更佳為5〜3〇質 量份。於感光劑之上述調配量為丨質量份以上之情形時， 樹脂之形成圖案性良好，於為5Qf量份以下之情形時硬 化後之膜之拉伸延㈣H且曝光部之顯錢到泮珠） 較少。 作為光驗性產生劑，可列舉：聘型、胺基〒酸醋化合 物、四級銨鹽、胺醯亞胺化合物等，較佳為胺基甲酸醋化 合物。 <第一組合物中所使用之溶劑> 作為第一組合物中所使用之溶劑，可列舉：酿胺類、亞 颯類、脲類、酮類、醋類、内醋類、醚類、函化烴類、烴 類等’例如可使用：Ν-甲基_2·…酮、ν，ν_:甲基乙 醯胺、Ν，Ν-二甲基甲醯胺、二甲某 τ丞亞碾、四甲基脲、丙 酮、甲基乙基酮、甲基異丁基酮、 味戍鲖、環己酮、乙酸 甲酯、乙酸乙酯、乙酸丁酯、乙二 & 一乙酯、乳酸乙酯、 乳酸甲酯、乳酸丁酯、丁内 ^ Θθ丙二醇單曱基醚乙酸 酯、丙二醇單甲基醚、苯甲醇、_ 醇本醚、四氫糠基 醇、乙二醇二甲基醚、二乙二 -一甲基峻、四氫0夫喃、咮 啉、二氯f烷、1，2-二氣乙院、14 _ 1，4-一氣丁烷、氣苯、鄰 16ll82.doc •22· 201234115 一氣苯、苯甲醚、己烷、庚烷、苯、甲苯、二甲苯、均三 甲本等。該等之中，就樹脂之溶解性、樹脂組合物之穩定 性、對基板之接著性之觀點而言，較佳為N_甲基_2•吡咯 啶酮、一甲基亞砜、四甲基脲、乙酸丁酯、乳酸乙酯、丫_ 丁内自曰、丙一醇單甲基崎乙酸酯、丙二醇單甲基峻、笨甲 醇、乙二醇苯醚、四氫糠基醇。 於本發明之驗性顯像用感光性紛樹脂組合物中，相對於 鹼可溶性酚樹脂100質量份，溶劑之添加量為1〇〇〜1〇〇〇質 量伤，較佳為120〜700質量份，進而較佳為15〇〜5〇〇質量份 之範圍。 <第一組合物中所使用之交聯劑> 較佳為於本發明之第一態樣之鹼性顯像用感光性酚樹脂 組合物中進而含有交聯劑。 作為本發明之第一態樣中所使用之交聯劑，可列舉下述 1)〜10)所示之交聯劑： 1)環氧化合物’例如1，1，2,2-四（對羥基苯基）乙烷四縮水 甘基_、甘油三縮水甘基醚、鄰第二丁基苯基縮水甘基 醚、1，6-雙（2,3-環氧丙氧基）萘、二甘油聚縮水甘基醚、聚 乙二醇縮水甘基醚、異氰尿酸三縮水甘油酯，Epici〇nNaphthoquinonediazidesulfonate group, all Qs are not hydrogen atoms at the same time. 161182.doc -21 - 201234115 Also, 'naphthalene quinone diazide sulfonate compound can be used in the same sub-* and mixed with 4-naphthyl diazide and 5-naphthoquinone- azidesulfonyl group. A 4-naphthoquinonediazide sulfonate compound can be used in combination with a 5-naphthoquinonediazide sulfonate compound. In the first aspect of the present invention, the amount of the sensitizing agent relative to the alkali-soluble phenol resin is preferably "part by mass, more preferably 5 to 3 parts by mass. When the blending amount is 5% by mass or more, the patterning property of the resin is good, and when it is 5 parts by weight or less, the stretched film of the film after hardening is (4)H and the exposed portion is less expensive to the bead). The photoinitiator may be exemplified by a tying type, an amino phthalic acid vinegar compound, a quaternary ammonium salt, an amine quinone imine compound, etc., preferably an amino carboxylic acid vinegar compound. <Used in the first composition Solvent> Examples of the solvent used in the first composition include a brewed amine, an anthraquinone, a urea, a ketone, a vinegar, an internal vinegar, an ether, a functional hydrocarbon, a hydrocarbon, and the like. For example, Ν-methyl-2·... ketone, ν, ν_: methyl acetamide, hydrazine, hydrazine-dimethylformamide, dimethyl hydrazine, tetramethylurea, acetone, Methyl ethyl ketone, methyl isobutyl ketone, miso, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, ethylene bis & Ethyl ethyl ester, ethyl lactate, methyl lactate, butyl lactate, butane Θ θ propylene glycol monodecyl ether acetate, propylene glycol monomethyl ether, benzyl alcohol, _ alcohol ether, tetrahydrofurfuryl alcohol, B Glycol dimethyl ether, diethylene di-methyl sulphate, tetrahydro oxafuran, porphyrin, dichlorof alkane, 1,2-digas, 1,4-1,4-butane, gas Benzene, o. 16ll82.doc •22· 201234115 monogas benzene, anisole, hexane, heptane, benzene, toluene, xylene, mesity, etc. Among these, the solubility of the resin, the resin composition From the viewpoint of stability and adhesion to the substrate, N-methyl-2-pyrrolidone, monomethyl sulfoxide, tetramethyl urea, butyl acetate, ethyl lactate, and ruthenium are preferred. Self-carrying, propanol monomethyl sulphate acetate, propylene glycol monomethyl sulphate, stupid methanol, ethylene glycol phenyl ether, tetrahydrofurfuryl alcohol. Photosensitive resin composition for qualitative imaging of the present invention In the case of 100 parts by mass of the alkali-soluble phenol resin, the solvent is added in an amount of 1 〇〇 to 1 〇〇〇 mass damage, preferably 120 to 700 parts by mass, and more preferably 15 Å to 5 Å. In the photosensitive phenol resin composition for alkaline development of the first aspect of the present invention, it is preferred to further contain a crosslinking agent. The crosslinking agent used in the first aspect of the present invention may, for example, be a crosslinking agent represented by the following 1) to 10): 1) an epoxy compound such as 1,1,2,2-tetra (pair) Hydroxyphenyl)ethane tetraglycidyl, glyceryl triglycidyl ether, o-butyl phenyl glycidyl ether, 1,6-bis(2,3-epoxypropoxy)naphthalene, two Glycerol polyglycidyl ether, polyethylene glycol glycidyl ether, triglycidyl isocyanurate, Epici〇n

830、850、1050、N-680、N-690、N-695、N-770、HP-7200 、 HP-820 、 EXA-4850-1000(商 品名， DIC公 司製造） ， Denacol EX-201、EX-313、EX-314、EX-321、EX-411、 EX-511、EX-512、EX-612、EX-614、EX-614B、EX-731 、 EX-810 、 EX-911 、 EM，150(商 品名， Nagase ChemteX 16H82.doc -23- 201234115 公司製造）； 2) 氧雜環丁烷化合物，例如苯二甲基雙氧雜環丁烷、3_ 乙基-3 {[(3-乙基氧雜環丁烷-基）曱氧基]曱基）氧雜環丁 烷； 3) ·»号唑啉化合物’例如2,2，-雙（2-1»号唑啉）、2,2'-亞異丙 基雙（4-苯基-2-哼唑啉）、1，3-雙（4,5-二氫-2-嘮唑基）苯、 1，4-雙（4,5-二氫-2->»号唑基）苯，£卩〇(^〇8〖-2010£、1<：-2020Ε、Κ-2030Ε、WS-500、WS-700、RPS-1005(商品名， 日本觸媒公司製造）； 4) 破二醯亞胺化合物，例如Carbodilite SV-02、V-01、 V-02、V-03、V-04、V-05、V-07、V-09、E-01、E-02、 LA-1 (商品名，Nisshinbo Chemical公司製造）； 5) 醛及醛改質物，例如醛、曱醛、三聚曱醛、戊二醛、 六亞甲基四胺、三嘮烷、乙二醛、丙二醛、丁二醛； 6) 異氰酸酯化合物，例如4,4'-二苯基甲烷二異氰酸酯、 甲苯二異氰酸酯、1，3_苯雙亞曱基二異氰酸酯、二環己基 曱烷-4,4·-二異氰酸酯、異佛爾酮二異氰酸酯、六亞甲基 二異氰酸醋，Takenate 500、600，Cosmonate NBDI、 ND(商品名，三井化學公司製造），Duranate 17B-60PX、 TPA-B80E、MF-B60X、MF-K60X、E402-B80T(商品名， 旭化成化學公司製造）； 7) 金屬螯合劑，例如乙醯丙酮鋁（ΠΙ)鹽 '乙醯丙酮鈦 (IV)鹽、乙醢丙酮鉻（III)鹽、乙酿丙酮鎂（II)鹽、乙醯丙酮 鎳（II)鹽、三氟乙醯丙酮鋁（III)鹽、三氟乙醯丙酮鈦（IV) 161l82.doc • 24· 201234115 鹽、三氟乙醯丙酮鉻（III)鹽、三氟乙醯丙酮鎂（II)鹽、三 氟乙醯丙酮鎳（II)鹽； 8) N-羥甲基化合物，1WNikalacMW-30MH、MW-100LH、BL-60、MX-270、MX-280、MX-290(商品名， Sanwa Chemical 公司製造），Cymel 300、303、1123， Micoat 102、105(商品名，日本Sytecs公司製造）； 9) C·羥甲基化合物，例如1，4-雙（甲氧基曱基）苯、4,4'-雙 (曱氧基曱基）聯苯； 10) 含有不飽和鍵之化合物，例如乙酸乙烯酯、三羥曱 基丙烷三曱基丙烯酸酯、1，3,5-苯三曱酸三烯丙酯、偏苯 三曱酸三烯丙酯、均苯四甲酸四烯丙酯、季戊四醇五丙烯 酸酯、二季戊四醇五丙烯酸酯、三羥甲基丙烷三丙烯酸 酯、二-三羥曱基丙烷四丙烯酸酯，NK Ester 1G、2G、 3G、4G、9G、14G、NPG、BPE-100、BPE-200、BPE-500 、 BPE-1400 、 A-200 、 A-400 、 A-600 、 TMPT 、 A-TMM_3(商品名，新中村化學工業公司製造），BANI-M、 BANI-X(商品名，丸善石油化學股份有限公司製造）。 於上述交聯劑中，就所得之熱硬化膜之伸長率及耐熱性 之觀點而言，較佳為£?丨。1〇11 830、850、1050、：^-680、：^-690、N-695、N-770、HP-7200、HP-820、EXA-4850-1000，Denacol EX-201 ' EX-313 ' EX-314 ' EX-321 ' EX-411 ' EX-511 ' EX-512 ' EX-612 ' EX-614 ' EX-614B ' EX-731、EX-810、EX-911、EM-150，苯二甲基雙氧雜環 丁烷、3-乙基-3 {[(3-乙基氧雜環丁烷-基）甲氧基]曱基}氧 161182.doc -25· 201234115 雜環丁烷、1,3-雙（4,5-二氫-2-哼唑基）苯，Nikalac MW_ 30MH、MW-100LH、BL-60、MX-270、MX-280、MX-290，Cymel 300、303、1123，Micoat 102、105，1，4-雙 (甲氧基甲基）苯、4,4，-雙（甲氧基甲基）聯苯、乙酸乙烯 基 '二羥甲基丙烷三甲基丙烯酸酯、苯三甲酸三烯 丙Sa、偏苯二甲酸三烯丙酯、均苯四甲酸四烯丙酯、季戊 四醇五丙烯酸酯、二季戊四醇五丙烯酸酯、三羥甲基丙烷 三丙烯酸酯、二-三羥甲基丙烷四丙烯酸酯、ΒΑΝί·Μ及 ΒΑΝΙ-Χ 〇 作為使用交聯劑之情形之交聯劑之調配量，相對於驗可 溶性酚樹脂100質量份，較佳為〇卜”質量份❶ <第一組合物中所使用之其他添加劑> 於本發明之第一組合物中，視需要可含有染料、界面活 性劑、用以提高與基板之密著性之接著助劑、溶解促進 劑、交聯促進劑等。 々作為上述染料，例如可列舉：甲基紫、結晶紫、孔雀綠 等作為染料之調配量，相對於驗可溶性_脂_質量 份，較佳為〇·1〜30質量份。 作為上述界面活性劑，例如除了聚丙二醇、聚氧乙稀月 等包含聚二醇類或其衍生物之非離子系界面活性劑以 ::列如可列舉：Fl_ad(註冊商標’商品名，住友歸 ^製造）、Megafae(註冊商標，商品名，DainippQn w - 早八-❿A司製造）、LUmifl〇n(註冊商標，商品名，旭硝 A司製造)等氟系界面活性劑，例如κρ34ΐ(商品名信 161182.doc • 26 - 201234115 越化學工業公司製造）、DBE(商品名，Chisso公司製造）、 Glanol(商品名，Kyoeisha Chemical公司製造）等有機矽氧 院界面活性劑。 作為使用界面活性劑之情形之界面活性劑之調配量，相 對於驗可溶性紛樹脂100質量份，較佳為〇 〇1〜1〇質量份。 作為上述接著助劑，例如可列舉：烧基咪唾琳、丁酸、 烧基酸、聚經基苯乙稀、聚乙稀基甲基驄、第三丁基驗搭 清漆、環氧矽烷、環氧聚合物等及各種烷氧基矽烷。 作為烷氧基矽烷之|交佳例，例如可列舉：四燒氧基矽 院、雙（三烷氧基矽烷基）曱烷、雙（三烷氧基矽烷基）乙 院、雙（三院氧基矽烷基）乙烯、雙（三烷氧基矽烷基）己 烧、雙（三烷氧基矽烷基）辛烷、雙（三烷氧基矽烷基）辛二 烯、雙[3-(三烷氧基矽烷基）丙基]二硫醚、N_苯基_3·胺基 丙基三烷氧基矽烷、3-毓基丙基三烷氧基矽烷、2_(三烷氧 基矽烷基乙基）吡啶、3-曱基丙烯醯氧基丙基三烷氧基石夕 烷、3 -甲基丙烯醯氧基丙基二烧氧基烷基矽烷、乙烯基三 烧氧基矽院、3-脲基丙基三烧氧基石夕烧、3-異氰酸酯丙基 三烧氧基石夕烧、3-(三院氧基矽烧基）丙基破珀酸酐、N-(3-三烷氧基矽烷基丙基）-4,5-二氫咪唑、2-(3,4-環氡環己基） 乙基三烧氧基石夕烧、3-縮水甘油氧基丙基三烧氧基石夕燒、 3-縮水甘油氧基丙基二烧氧基烧基石夕烧、3 -胺基丙基三院 氧基矽烷及3-胺基丙基二烷氧基烷基矽烷及酸酐或酸二酐 之反應物、將3-胺基丙基三烷氧基矽烷或3-胺基丙基二院 氧基烷基矽烷之胺基轉變為胺基甲酸酯基或脲基而成者 161182.doc •27· 201234115 可列舉：均苯四甲酸 等°再者’作為上述化合物中之院基’可列舉：甲基、乙 基、丙基、丁基等’作為酸軒，可列舉：順丁稀二酸針、 鄰苯二甲酸if、5-W2,3_二㈣酐等，作為酸二針， 3,3'，4,4’-二苯甲酮四甲酸二 酐 等，作為胺基甲酸酯基，可 作為脲基，可列舉苯基胺基 酐、4,4·-氧二鄰苯二甲酸二酐 列舉：第三丁氧羰基胺基等， 羰基胺基等。 作為使用接著助劑之情形之接著助劑之調配量，相對於 鹼可溶性酚樹脂100質量份，較佳為〇1〜3〇質量份。 作為上述溶解促進劑，較佳為具有羥基或羧基之化合 物。作為具有羥基之化合物之例，可列舉··上述萘醌二疊 氮化合物所使用之壓載劑，及對枯基苯酚，雙酚類，間苯 二酚類，及Mtris PC、Mtetra PC等直鏈狀酚化合物， TdsP_HAP、THsP-PHB A、TrisP_PA等非直鏈狀酚化合物 (均為本州化學工業公司製造），二苯基甲烷之2〜5個之酚 取代物，3,3-一苯基丙烧之1〜5個之紛取代物，2,2•雙_(3_ 胺基-4-羥基苯基）六氟丙烷與5_降蓓烯_2,3_二羧酸酐的1比 2之反應物，雙-(3-胺基-4-羥基笨基）硬與丨，2_環己基二甲 酸酐的1比2之反應物’ N-經基號抬酸酿亞胺，N_經基鄰苯 一甲酸酿亞胺’ N-經基-5-降宿稀-2,3 -二叛酸醯亞胺等。 作為具有羧基之化合物之例，可列舉：3·苯基乳酸、4_ 經基苯基乳酸、4 -經基爲桃酸、3，4 -二經基扁桃酸、4 -羥 基-3-甲氧基扁桃酸、2-甲氧基-2-(1-萘基）丙酸、扁桃酸、 苯乳酸、乙醯基扁桃酸（例如0-乙醯基扁桃酸等）、α_甲氧 161182.doc • 28 · 201234115 基苯基乙酸、苯甲酸、鄰甲苯曱酸、間曱苯曱酸、對曱苯 甲酸等。 作為使用溶解促進劑之情形之溶解促進劑之調配量，相 對於鹼可溶性酚樹脂100質量份，較佳為0.1〜30質量份。 作為上述交聯促進劑，較佳為藉由熱或光而產生酸、 鹼、自由基者。作為藉由熱或光產生酸者，可列舉：丁卩呂-105、1000、DTS-105、NDS-105、165(商品名，Midori Kagaku 公司製造），DPI-DMAS、TTBPS-TF、TPS-TF、 DTBPI-TF(商品名，東洋合成公司製造）等鏽鹽，甲磺酸甲 酯、曱磺酸乙酯、苯磺酸甲酯、對甲苯磺酸甲酯、對曱苯 磺酸曱氧基乙酯等磺酸酯，NAI-100、101、105、106、 PAI-101(商品名，Midori Kagaku 公司製造），Irgacure PAG-103、108、121、203、CGI-1380、725、NIT、 1907、PNBT(商品名，BASF Japan公司製造）等肟磺酸酯 等。作為藉由熱或光而產生鹼者，可列舉：U-CATSA-1、 102、5 06、603、810(商品名，San-Apro 公司製造），CGI-1237 、 1290 、 1293( 商 品名， BASF Japan 公司 製造） 等胺 鹽，將2,6-哌啶或丁胺、二乙胺、二丁胺、Ν,Ν’-二乙基 -1，6-二胺基己烷、六亞甲基二胺等之胺基轉變為胺基甲酸 酯基或脲基而成者等。作為胺基曱酸酯基，可列舉第三丁 氧羰基胺基等，作為脲基，可列舉苯基胺基羰基胺基等。 作為藉由熱或光而產生自由基者，可列舉：Irgacure 65 1、 184、2959、127、907、369、379(商品名，BASF Japan公 司製造）等烧基酸，Irgacure 819(商品名，BASF Japan公司 161182.doc -29- 201234115 製造）等醯基膦氧化物，Irgacure 784(商品名，BASF Japan 公司製造）等二茂鈦，lrgacure 〇XE〇1、〇2(商品名，BaSF Japan公司製造）等肟酯等。 <第一態樣之驗性顯像用感光性齡·樹脂組合物之硬化膜> 藉由按照下文將說明之方法對本發明之第一態樣之驗性 顯像用感光性酚樹脂組合物進行硬化所獲得之硬化膜之伸 長率較佳為15%以上，更佳為20%以上。作為其理由，可 列舉：於使本發明之鹼性顯像用感光性酚樹脂組合物硬 化，用作表面保護膜或層間絕緣膜時，即便受到由熱所引 起之應力’亦不易產生裂痕，不僅提高其可靠性，而且亦 可提高具有其而形成之半導體裝置之可靠性。伸長率之上 限值係數值越大越佳，例如100〇/〇。 伸長率之測定方法如下所述。 將鹼性顯像用感光性酚樹脂組合物旋轉塗佈至矽晶圓 上’於加熱板上於loot下對該矽晶圓及旋轉塗佈膜加熱3 分鐘，於氮氣環境下於25〇t對該旋轉塗佈膜硬化1小時而 獲得厚度10 μπι之硬化物。藉由晶圓切割機以3 mm寬度對 該硬化物進行切割，利用23質量％氫氟酸水溶液進行處 理，藉此剝離矽晶圓，進而於溫度231、濕度50%之環境 中靜置24小時以上，獲得20支樣品，利用拉伸試驗機（例 如Tensilon(註冊商標，〇rientec公司製造））測定各樣品之拉 伸伸長率’於20支樣品之結果中，獲得高分5分之樣品之 平均值》拉伸試驗機之測定條件係如下述般設定。830, 850, 1050, N-680, N-690, N-695, N-770, HP-7200, HP-820, EXA-4850-1000 (trade name, manufactured by DIC), Denacol EX-201, EX -313, EX-314, EX-321, EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-731, EX-810, EX-911, EM, 150 (trade name, manufactured by Nagase ChemteX 16H82.doc -23-201234115); 2) oxetane compounds such as benzodimethyloxetane, 3-ethyl-3 {[(3-ethyl) Oxetane-yl)nonyloxycarbonyl)oxetane; 3) ·»-oxazoline compound' such as 2,2,-bis(2-1»oxazoline), 2,2 '-Isopropyl bis(4-phenyl-2-oxazoline), 1,3-bis(4,5-dihydro-2-oxazolyl)benzene, 1,4-bis(4,5 -dihydro-2->-oxazolyl)benzene, 卩〇(^〇8 〖-2010£, 1<:-2020Ε, Κ-2030Ε, WS-500, WS-700, RPS-1005 (commodity Name, manufactured by Nippon Shokubai Co., Ltd.; 4) Broken diterpene imine compounds, such as Carbodilite SV-02, V-01, V-02, V-03, V-04, V-05, V-07, V- 09, E-01, E-02, LA-1 (trade name, manufactured by Nisshinbo Chemical Co., Ltd. 5) aldehydes and aldehydes, such as aldehydes, furfural, trimeric furfural, glutaraldehyde, hexamethylenetetramine, trioxane, glyoxal, malondialdehyde, succinaldehyde; 6) Isocyanate compounds such as 4,4'-diphenylmethane diisocyanate, toluene diisocyanate, 1,3-benzenebis-indenyl diisocyanate, dicyclohexyldecane-4,4·-diisocyanate, isophorone Diisocyanate, hexamethylene diisocyanate, Takenate 500, 600, Cosmonate NBDI, ND (trade name, manufactured by Mitsui Chemicals, Inc.), Duranate 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402 -B80T (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd.); 7) Metal chelating agents, such as acetoacetate aluminum (ΠΙ) salt 'acetyl acetonate titanium (IV) salt, acetonitrile acetone chromium (III) salt, ethyl acetonate (II) salt, acetonitrile acetone nickel (II) salt, trifluoroacetic acid acetone aluminum (III) salt, trifluoroacetone acetone titanium (IV) 161l82.doc • 24· 201234115 salt, trifluoroacetic acid acetone chromium ( III) salt, magnesium trifluoroacetate (II) salt, trifluoroacetic acid nickel (II) salt; 8) N-methylol compound, 1WNikalacMW-30MH, MW-100L H, BL-60, MX-270, MX-280, MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, 303, 1123, Micoat 102, 105 (trade name, manufactured by Sytecs, Japan); 9) a C-hydroxymethyl compound such as 1,4-bis(methoxyindenyl)benzene, 4,4'-bis(decyloxyindenyl)biphenyl; 10) a compound containing an unsaturated bond, such as vinyl acetate Ester, trihydroxymercaptopropane tridecyl acrylate, triallyl 1,3,5-benzenetridecanoate, triallyl trimellitic acid, tetraallyl pyromellitate, pentaerythritol pentaacrylate Ester, dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, di-trihydroxydecylpropane tetraacrylate, NK Ester 1G, 2G, 3G, 4G, 9G, 14G, NPG, BPE-100, BPE- 200, BPE-500, BPE-1400, A-200, A-400, A-600, TMPT, A-TMM_3 (trade name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), BANI-M, BANI-X (trade name, Made by Maruzen Petrochemical Co., Ltd.). Among the above crosslinking agents, from the viewpoint of the elongation and heat resistance of the obtained thermosetting film, it is preferably 丨?. 1〇11 830, 850, 1050, :^-680, :^-690, N-695, N-770, HP-7200, HP-820, EXA-4850-1000, Denacol EX-201 'EX-313' EX-314 ' EX-321 ' EX-411 ' EX-511 ' EX-512 ' EX-612 ' EX-614 ' EX-614B ' EX-731, EX-810, EX-911, EM-150, Benzene Methyl dioxetane, 3-ethyl-3 {[(3-ethyloxetane-yl)methoxy]indolyl}oxy 161182.doc -25· 201234115 heterocyclobutane, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene, Nikalac MW_ 30MH, MW-100LH, BL-60, MX-270, MX-280, MX-290, Cymel 300, 303, 1123, Micoat 102, 105, 1,4-bis(methoxymethyl)benzene, 4,4,-bis(methoxymethyl)biphenyl, vinyl acetate dimethylolpropane trimethacrylate Ester, triallystrione sa, allyl propionate, tetraallyl pyromellitate, pentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, di- Trimethylolpropane tetraacrylate, ΒΑΝί·Μ, and ΒΑΝΙ-Χ 〇 as a crosslinking agent in the case of using a crosslinking agent, relative to the solubility of the test 100 parts by mass of the resin, preferably a "mass portion by mass" <other additives used in the first composition> In the first composition of the present invention, a dye, a surfactant, or a dye may be used as needed. A bonding aid, a dissolution promoter, a crosslinking accelerator, and the like which improve adhesion to a substrate. 々 As the dye, for example, methyl violet, crystal violet, malachite green, or the like is used as a dye. The soluble_lipid-mass portion is preferably from 1 to 30 parts by mass. As the above surfactant, for example, non-ionic interfacial activity including a polyglycol or a derivative thereof other than polypropylene glycol or polyoxyethylene The agent can be listed as follows: Fl_ad (registered trademark 'product name, manufactured by Sumitomo Chemicals Co., Ltd.), Megafae (registered trademark, trade name, manufactured by DainippQn w - 早八-❿A Division), LUmifl〇n (registered trademark, commodity A fluorine-based surfactant such as κρ34ΐ (trade name 161182.doc • 26 - 201234115 manufactured by Vietnam Chemical Industry Co., Ltd.), DBE (trade name, manufactured by Chisso Co., Ltd.), Glanol (trade name, etc.) Kyoeisha Che Mical company manufactures) organic surfactants such as surfactants. The amount of the surfactant to be used in the case of using the surfactant is preferably 〇1 to 1 part by mass based on 100 parts by mass of the soluble resin. Examples of the above-mentioned auxiliary auxiliary agent include: pyridyl sulfonate, butyric acid, alkyl amide, polyphenylene methacrylate, polyethylene methyl hydrazine, third butyl varnish, epoxy decane, Epoxy polymers and the like and various alkoxydecanes. As a preferred example of the alkoxy decane, for example, a tetrasodium oxy fluorene, a bis(trialkoxyalkyl) decane, a bis(trialkoxyalkyl) phenyl group, and a double (three-yard) Oxonium alkyl) ethylene, bis(trialkoxyalkyl) hexane, bis(trialkoxyalkyl)octane, bis(trialkoxyalkyl)octadiene, bis[3-(three Alkoxyalkylalkyl)propyl]disulfide, N_phenyl-3,aminopropyltrialkoxydecane, 3-mercaptopropyltrialkoxydecane, 2-(trialkoxyalkylene) Ethyl)pyridine, 3-mercaptopropenyloxypropyltrialkoxyindan, 3-methylpropenyloxypropyldioxaoxyalkyldecane, vinyl trisoxylate, 3 - Ureapropyl propyl trioxide, Oxygen, 3-isocyanate propyl trioxide, Oxygen, 3-(three-in-one oxyalkyl) propyl chlorate, N-(3-trialkoxy矽alkylpropyl)-4,5-dihydroimidazole, 2-(3,4-cyclodecylcyclohexyl)ethyltrioxoyl oxysulfate, 3-glycidoxypropyl tris-oxygen oxide, 3-glycidoxypropyl dialkyloxy burnt base, 3-aminopropyl three a reaction of oxydecane and 3-aminopropyl dialkoxyalkyl decane with an acid anhydride or acid dianhydride, 3-aminopropyltrialkoxydecane or 3-aminopropyldioxide The amino group of alkane decane is converted into a urethane group or a ureido group. 161182.doc •27· 201234115 For example, pyromellitic acid or the like can be cited as 'the hospital base in the above compound'. "Methyl, ethyl, propyl, butyl, etc." as the acid oxime, may be exemplified by a cis-butyl diacid needle, a phthalic acid if, a 5-W 2 , a 3 - di (tetra) anhydride, etc. 3,3',4,4'-benzophenonetetracarboxylic dianhydride, etc., as a urethane group, can be used as a ureido group, and phenylamino anhydride, 4,4·-oxydi-benzene Examples of the dicarboxylic acid dianhydride include a third butoxycarbonylamino group and the like, a carbonylamino group and the like. The amount of the auxiliary agent to be used in the case of using the auxiliary agent is preferably from 1 to 3 parts by mass based on 100 parts by mass of the alkali-soluble phenol resin. As the dissolution promoter, a compound having a hydroxyl group or a carboxyl group is preferred. Examples of the compound having a hydroxyl group include a ballast agent used in the above naphthoquinonediazide compound, and p-cumylphenol, bisphenols, resorcinol, and Mtris PC, Mtetra PC, etc. A chain phenol compound, a non-linear phenolic compound such as TdsP_HAP, THsP-PHB A, and TrisP_PA (all manufactured by Honshu Chemical Industry Co., Ltd.), 2 to 5 phenolic substituents of diphenylmethane, 3,3-benzene 1 to 5 of the substitutions of propylene, 1 2, 2, bis(3_amino-4-hydroxyphenyl)hexafluoropropane and 5_northene-2,3_dicarboxylic anhydride The reactant of 2, bis-(3-amino-4-hydroxyphenyl) hard and hydrazine, 2 to cyclohexyl dicarboxylic anhydride 1 to 2 of the reactant 'N- via the base number, the acid imine, N _Phenyl-phthalic acid-bromoimine 'N-carbyl-5-norborn-2,3-di-resorcinimide and the like. Examples of the compound having a carboxyl group include: 3-phenylphenyl lactic acid, 4-phenylphenyl lactic acid, 4 -alkyl group as citric acid, 3,4-di-trans-mandelic acid, 4-hydroxy-3-methoxy Mandelic acid, 2-methoxy-2-(1-naphthyl)propionic acid, mandelic acid, phenyl lactic acid, acetylated mandelic acid (such as 0-acetamidyl mandelic acid, etc.), α_methoxy 161182. Doc • 28 · 201234115 Phenylphenylacetic acid, benzoic acid, o-toluic acid, m-benzoic acid, p-benzoic acid, etc. The amount of the dissolution promoter to be used in the case of using the dissolution promoter is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the alkali-soluble phenol resin. As the crosslinking accelerator, those which generate an acid, a base or a radical by heat or light are preferred. As the person who generates acid by heat or light, Ding Lu - 105, 1000, DTS-105, NDS-105, 165 (trade name, manufactured by Midori Kagaku Co., Ltd.), DPI-DMAS, TTBPS-TF, TPS- TF, DTBPI-TF (trade name, manufactured by Toyo Syner Co., Ltd.) and other rust salts, methyl methanesulfonate, ethyl sulfonate, methyl benzenesulfonate, methyl p-toluenesulfonate, p-toluenesulfonate Sulfonic acid esters such as ethyl ester, NAI-100, 101, 105, 106, PAI-101 (trade name, manufactured by Midori Kagaku Co., Ltd.), Irgacure PAG-103, 108, 121, 203, CGI-1380, 725, NIT, 1907, PN sulfonate such as PNBT (trade name, manufactured by BASF Japan Co., Ltd.). Examples of the base which generates alkali by heat or light include U-CATSA-1, 102, 5 06, 603, 810 (trade name, manufactured by San-Apro Co., Ltd.), CGI-1237, 1290, 1293 (trade name, BASF Japan company) Amine salt, 2,6-piperidine or butylamine, diethylamine, dibutylamine, hydrazine, Ν'-diethyl-1,6-diaminohexane, hexamethylene The amine group such as a diamine is converted into a urethane group or a urea group. Examples of the amino decanoate group include a third butoxycarbonylamino group and the like, and examples of the ureido group include a phenylaminocarbonylamino group and the like. Examples of the radicals generated by heat or light include an alkyl acid such as Irgacure 65 1 , 184, 2959, 127, 907, 369, 379 (trade name, manufactured by BASF Japan Co., Ltd.), Irgacure 819 (trade name, BASF Japan 161182.doc -29- 201234115 Manufactured by thiol phosphine oxide, Irgacure 784 (trade name, manufactured by BASF Japan), ferrocene, lrgacure 〇XE〇1, 〇2 (trade name, BaSF Japan Manufacture) Ester esters, etc. <The cured film of the photosensitive age-resin composition for the first aspect of the present invention> The photosensitive phenol resin for the first aspect of the present invention is combined with the photosensitive phenol resin according to the method described below. The elongation of the cured film obtained by hardening the object is preferably 15% or more, more preferably 20% or more. The reason for this is that when the photosensitive phenol resin composition for alkaline development of the present invention is cured and used as a surface protective film or an interlayer insulating film, cracks are less likely to occur even if subjected to stress caused by heat. Not only the reliability is improved, but also the reliability of the semiconductor device formed therewith. Above the elongation, the larger the value of the limit coefficient, the better, for example, 100 〇 / 〇. The method of measuring the elongation is as follows. The alkaline photographic photosensitive phenol resin composition was spin-coated on a ruthenium wafer. The ruthenium wafer and the spin coating film were heated on a hot plate at a loot for 3 minutes under a nitrogen atmosphere at 25 〇t. The spin coating film was cured for 1 hour to obtain a cured product having a thickness of 10 μm. The cured product was cut by a wafer cutter at a width of 3 mm, and treated with a 23% by mass aqueous solution of hydrofluoric acid, thereby peeling off the silicon wafer and allowing it to stand in an environment of temperature 231 and humidity of 50% for 24 hours. In the above, 20 samples were obtained, and the tensile elongation of each sample was measured by a tensile tester (for example, Tensilon (registered trademark, manufactured by 〇rientec)) in the results of 20 samples, and a sample having a high score of 5 was obtained. The measurement conditions of the average value tensile tester were set as follows.

溫度：23°C 16ll82.doc 30· 201234115 濕度：50% 初期樣品長度·· 50 mm 试驗速度：40 mm/min. 定額荷重元：2 kgf &lt;第一態樣之硬化凸起圖案之形成方法&gt; 以下示出使用本發明之第一態樣之鹼性顯像用感光性酚 樹脂組合物於基板上形成硬化凸起圖案之方法之一例。 首先，將含有感光劑之組合物塗佈於適當之支持體或基 板上，例如矽晶圓、陶瓷、鋁基板等。此時，為了確保所 形成之圖案與支持體之耐水接著性，亦可預先於支持體或 基板上塗佈矽烷偶合劑等接著助劑。該組合物之塗佈方法 係藉由使用旋轉器之旋轉塗佈、使用喷塗器之喷霧塗佈、 ’文凊、印刷、滾塗等進行。其次，於8〇〜14〇(&gt;c下進行預烤 而乾燥塗膜後，對鹼性顯像用感光性酚樹脂組合物進行曝 光。作為進行曝光之光化射線，可使用χ射線、電子束、 、卜線了見光線荨，較佳為〜500 nm之波長之射線。 就圖案之解析度及操作性之方面而言，該光源波長較佳為 水銀燈之g射線、h射線或i射線’可單獨使用亦可進行混 合。作為曝光裝置，尤佳為接觸式料機、鏡面投影 機及步進機。 + 其-人進仃顯像’可自浸潰法、覆液法、旋轉喷射法等方 法中選擇而進b可藉由顯像自所塗佈之驗性顯像 性紛樹脂組合物中溶出去除曝光部或未曝光部，獲得^ 圖案。作為顯像液，可使用氫氧化鈉、碳酸鈉、矽酸鈉、 161182.doc 201234115 氨水等無機鹼類，乙胺、二乙胺、三乙胺、三乙醇胺等有 機胺類’氫氧化四甲基録、氫氧化四丁基錄等四級錄鹽類 等之水溶液，及視需要添加有適當量之曱醇、乙醇等水溶 性有機溶劑或界面活性劑的水溶液。該等之中，較佳為氣 氧化四曱基銨水溶液，其濃度較佳為〇.5〜1〇質量％，進而 較佳為1.0〜5.0質量％。 顯像後，藉由利用淋洗液進行洗淨並去除顯像液，可獲 得凸起圖案。作為淋洗液，可單獨使用蒸餾水、甲醇、乙 醇、異丙醇等或加以組合而使用。 最後，可藉由對如此獲得之凸起圖案進行加熱而獲得硬 化凸起圖案。加熱溫度較佳為l5〇〇c以上且28(Γ(：以下。 於使用通常所使用之聚醯亞胺或聚苯并噚唑前驅物組合 物之硬化凸起圖案之形成方法中’需要藉由加熱至3〇(rc 以上進行脫水環化反應，而轉變成聚醢亞胺或聚苯并η号哇 等，而於本發明之第一態樣之硬化凸起圖案之製造方法中 並無此必要性，故亦可合適地用於不耐熱之半導體裝置等 中。若列舉一例’則可合適地用於具有包含對製程溫度有 限制之雨介電質材料或強介電質材料例如欽、紐或銓等高 熔點金屬之氧化物之絕緣層的半導體裝置。 若為半導體裝置不具有此種耐熱性方面之限制之情形， 則當然於本發明之第一態樣之方法中亦可進行加熱至 300〜400°C之處理。此種加熱處理可藉由使用加熱板、洪 箱或可設定溫控程式之升溫式烘箱而進行。作為進行加熱 處理時之環境氣體，可使用空氣，亦可使用氮氣、氬氣等 161182.doc -32- 201234115 惰性氣體。又，於需要於更低之溫度下進行熱處理時，亦 可利用真空泵等在減壓下進行加熱。 &lt;第一態樣之半導體裝置&gt; 又，具有使用本發明之第一態樣之鹼性顯像用感光性酚 樹脂組合物製造之硬化凸起圖案而形成之半導體裝置亦為 本發明之一態樣。本發明之半導體裝置可藉由將上述硬化 凸起圖案作為表面保護膜、&amp;間絕緣膜、再配線用絕緣 膜、倒裝晶片裝置用保護膜或具有凸塊構造之裝置之保護 膜，並與已知之半導體裝置之製造方法組合而製造。 以下，詳細地說明本發明之第二態樣。 &lt;聯苯二基三羥苯樹脂之合成方法〉 主鏈上具有聯本—基結構之三窥笨樹脂（以下簡稱為 「聯笨二基三㈣樹脂」）為含有具有三㈣結構及聯苯 二基結構之重複單元之聚合物。本發明之聯苯二基三經苯 樹脂係由特定之三羥笨化合 0物興具有聯笨二基之化合物合 成。 如上所述 ⑴： [化 11] 本I月之聯笨二基三羥笨樹脂係由下述通式Temperature: 23°C 16ll82.doc 30· 201234115 Humidity: 50% Initial sample length·· 50 mm Test speed: 40 mm/min. Constant load element: 2 kgf &lt; Formation of hardened convex pattern of the first aspect Method&gt; An example of a method of forming a cured convex pattern on a substrate using the photosensitive phenol resin composition for alkaline development according to the first aspect of the present invention is shown below. First, the composition containing the sensitizer is applied to a suitable support or substrate, such as a germanium wafer, a ceramic, an aluminum substrate, or the like. In this case, in order to ensure the water-resistant adhesion between the formed pattern and the support, a bonding aid such as a decane coupling agent may be applied to the support or the substrate in advance. The coating method of the composition is carried out by spin coating using a spinner, spray coating using a sprayer, 'texture, printing, roll coating, and the like. Then, after pre-baking and drying the coating film at 8 〇 to 14 〇 (c), the photosensitive phenol resin composition for alkaline development is exposed. As the actinic ray for exposure, x-ray can be used. The electron beam, the ray, the light ray, preferably a wavelength of ~500 nm. In terms of resolution and operability of the pattern, the wavelength of the light source is preferably g-ray, h-ray or i of a mercury lamp. The ray 'can be used alone or in combination. As an exposure device, it is especially a contact type hopper, a mirror projector and a stepper. + Its - human 仃 仃 ' ' self-immersion method, liquid coating method, rotation By selecting a method such as a spray method, the exposed portion or the unexposed portion can be removed from the applied annographic resin composition by development to obtain a pattern. As the developing solution, hydrogen can be used. Sodium oxide, sodium carbonate, sodium citrate, 161182.doc 201234115 Aqueous water and other inorganic bases, ethylamine, diethylamine, triethylamine, triethanolamine and other organic amines 'tetramethyl hydroxide, tetrabutyl hydroxide Record the aqueous solution of the four grades, such as salt, and add it as needed. a water-soluble organic solvent such as decyl alcohol or ethanol or an aqueous solution of a surfactant. Among these, a gas oxidized tetradecyl ammonium aqueous solution is preferred, and the concentration thereof is preferably 〇.5 〜1 〇 mass%, and further Preferably, it is 1.0 to 5.0% by mass. After development, a convex pattern can be obtained by washing with an eluent and removing the developing liquid. As the eluent, distilled water, methanol, ethanol, or isopropanol can be used alone. Alternatively, it may be used in combination. Finally, the hardened convex pattern may be obtained by heating the convex pattern thus obtained. The heating temperature is preferably 15 〇〇 c or more and 28 (Γ (: below). In the method for forming a hardened convex pattern of a polyimide or polybenzoxazole precursor composition used, it is required to be converted into a polyimide or a ruthenium by heating to 3 Torr (the above is subjected to a dehydration cyclization reaction or The polybenzene n is not included in the method for producing the cured bump pattern of the first aspect of the present invention, and therefore can be suitably used in a heat-resistant semiconductor device or the like. 'There can be suitably used to have a pair A semiconductor device having a limited temperature of a rain dielectric material or a ferroelectric material such as an insulating layer of a high melting point metal such as a Chin, New Zealand or Nd. If the semiconductor device does not have such a limitation in heat resistance In this case, of course, in the method of the first aspect of the present invention, heating to 300 to 400 ° C may be performed. The heat treatment may be performed by using a heating plate, a flood box or a temperature-programmable temperature control program. It is carried out in an oven. As the ambient gas for the heat treatment, air may be used, or an inert gas such as nitrogen or argon may be used. Further, when heat treatment is required at a lower temperature, Heating by a vacuum pump or the like under reduced pressure. <Semiconductor device of the first aspect> Further, there is a hardened embossing produced by using the photosensitive phenol resin composition for alkaline development of the first aspect of the present invention. The semiconductor device formed by the pattern is also an aspect of the present invention. In the semiconductor device of the present invention, the hardened bump pattern can be used as a surface protective film, an insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a protective film having a device having a bump structure. It is manufactured in combination with a manufacturing method of a known semiconductor device. Hereinafter, the second aspect of the present invention will be described in detail. &lt;Synthesis method of biphenyldiyltrihydroxybenzene resin> The three-pigmented resin (hereinafter referred to as "joint bi-base three (four) resin) having a conjugate-based structure in the main chain) has a structure of three (four) and a polymer of repeating units of a benzenediyl structure. The biphenyldiyltriazine benzene resin of the present invention is synthesized from a compound having a specific trihydroxyl compound. As described above (1): [Chemical Formula 11] This I-month of the stupid dibasic trihydroxyl resin is derived from the following formula

{式中，Rl為下述通式（2): 161182.doc -33· (1 ) (2) 201234115 [化 12]{wherein, Rl is the following general formula (2): 161182.doc -33· (1) (2) 201234115 [Chem. 12]

(式中，R3為曱基或乙基’而且，P與q分別獨立為〇〜4之整 數）所不之聯苯二基，R2為選自氫、甲基及乙基中之基， ^且η為2〜150之整數}所示。三羥苯結構與聯笨二基結構 可以任意之順序鍵結。就鹼溶解性之觀點而言，較佳為三 羥笨結構與聯苯二基結構經由亞甲基鍵結。 其中，就更佳地發揮本發明之第二態樣之效果之觀點而 言，較佳為上述通式U)為下述通式（3): , [化 13](wherein, R3 is a fluorenyl group or an ethyl group, and P and q are each independently an integer of 〇~4), and a biphenyldiyl group is not included, and R2 is a group selected from the group consisting of hydrogen, a methyl group and an ethyl group, ^ And η is an integer of 2 to 150}. The trihydroxybenzene structure and the biphenyl structure can be bonded in any order. From the viewpoint of alkali solubility, it is preferred that the trihydroxyl structure and the biphenyldiyl structure are bonded via a methylene group. Among them, in view of exerting the effect of the second aspect of the present invention more preferably, the above formula U) is preferably the following formula (3): [Chemical 13]

定義者相同}或下述通式 (式中，R〗及η與上述通式（1)中 (4)： [化 14]The definition is the same} or the following formula (where R and η are in the above formula (1) (4): [Chem. 14]

U) {式中 R及η與上述通式（1)中 定義者相同}所示之聯苯二 161182.doc •34- 201234115 基三羥苯樹脂。 又’就更佳地發揮本發明之第二態樣之效果之觀點而 S，亦較佳為上述通式（2)為下述式（5): [化 15]U) {In the formula, R and η are the same as defined in the above formula (1)} Biphenyl 161182.doc • 34- 201234115-based trihydroxybenzene resin. Further, it is preferable that the above-described general formula (2) is the following formula (5):

所示之聯苯二基三羥苯樹脂。 進而，較佳為上述式（5)為下述式（6): [化 16] CH2— (6) 所示之聯苯二基三羥苯樹脂。 作為本發明之第二態樣之聯苯二基三羥笨樹脂之製造方 ^，例如可列舉具有聯笨二基結構之化合物（以下簡稱為 「聯笨二基化合物」）與三羥苯類化合物之縮合反應。具 體而言’可藉由包括以下步驟： 將下述通式（7): [化 17]The biphenyldiyltrihydroxybenzene resin shown. Further, the above formula (5) is preferably a formula (6): a biphenyldiyltrihydroxybenzene resin represented by CH2 to (6). The production method of the biphenyldiyltrihydroxybenzene resin according to the second aspect of the present invention includes, for example, a compound having a biphenyl structure (hereinafter referred to as "co-diphenyl compound") and a trihydroxybenzene. The condensation reaction of the compound. Specifically, the following steps can be included: The following general formula (7): [Chem. 17]

(式中，R2為選自氫 甲基及乙基中之基}所示之化合物、 161182.doc 35· (8) 201234115 與下述通式（8): [化 18] r4~h2c(wherein, R2 is a compound selected from the group consisting of a hydrogen methyl group and an ethyl group}, 161182.doc 35· (8) 201234115 and the following general formula (8): [Chemical 18] r4 to h2c

CH2 - R4 {式中，R3為甲基或乙基，卩與召分別獨立為〇〜4之整數，而 且R4為選自由函素原子、經基及碳數之可具有不飽和 鍵之燒氧基所組成之群中之基}所示之化合物以5:卜】·· $ 之莫耳比進行混合，進而添加觸媒之步驟；及 於6(TC以上加熱！分鐘〜48小時之步驟； 之製造方法製造聯苯二基三羥苯樹脂。 化合物亦可於苯環上具有U、乙基作為除經 舉· 12=代基。作為三㈣類化合物之較佳例，可列 舉.1，2,3-三羥苯（鄰苯= 1，2,4·三經苯n ，三㈣(間苯三盼)、 、中 就顯像性之觀St 三經笨、⑶-:經策w ，較佳為m 用。 -红本。該4可單獨使用，亦可混合使 作為可與三經苯類化合物縮合 可列舉：4,4,_雙氯 ， 冑本—基化合物，例如 芰玑f基聯本、4,4，_聯芏- 氧㈣)聯笨等。除此以外，亦可：=、4,4，·雙(甲 等取代基者。作為聯苯二基化合物:=有甲基、乙基 結構’但例如亦可為具有2,2，-、23具體例，列舉了”’· 構之化合物。其中就封熱性之觀點而：/^等其他取代結 .而3，較佳為經4,4·-取 16M82.doc • 36 - 201234115 代之聯苯—基化合物。該等聯笨二基化合物可單獨使用— 種’或組合使用兩種以上。 — 聯苯二基化合物與三經苯類化合物之縮合反應係藉由將 三經苯類化合物與聯笨二基化合物以莫耳比為5: w. 卜較佳^:卜⑽：卜更佳為^:卜^之比進行 混合，添加觸媒並於6(rc以上、較佳為8〇它以上更佳為 100 C以上進行加熱而進行。作為酸性觸媒，可列舉：鹽 酸、硫酸、硝酸、磷酸、亞磷酸、曱磺酸、對曱笨磺酸、 一甲基硫酸、二乙基硫酸、乙酸、乙二酸、羥基亞乙基 -1，1’-二膦酸、乙酸鋅、三氟化硼、三氟化硼_酚錯合物、 三氟化硼-醚錯合物等。另一方面，作為鹼性觸媒，可列 舉.氫氧化鐘、氫氧化鈉、氫氧化鉀、氫氧化約、氫氧化 鋇、碳酸鈉、三乙胺、吡啶、4-N，N-二甲基胺基吡啶、哌 咬、派畊、1，4-二氮雜雙環[2.2.2]辛烷、1，8-二氮雜雙環 [5.4.0]-7-十一烯、1，5-二氮雜雙環[4·3.0]-5-壬烯、氨、六 亞甲基四胺等。 又，於上述縮合反應中，亦可使用二乙二醇二曱基醚 (DMDG，Diethylene Glycol Dimethyl Ether)、Ν-甲基-2-0比 洛咬綱（NMP，N-methyl-2-pyrrolidone)、二曱基乙酿胺 (DMAc » Dimethylacetamide) ' 二甲基曱醯胺（DMF， Dimethylformamide)、γ-丁 内酉旨（GBL，Gama Butyrolactone)、 二甲基亞硬（DMSO，Dimethyl Sulfoxide)等溶劑。 聯苯二基三羥苯樹脂之重量平均分子量較佳為 1，500〜200,000，更佳為1，500~100,00()，進而較佳為 161182.doc •37· 201234115 2,000〜50,000。 〈本發明之第二態樣之感光性樹脂組合物&gt; 含有聯苯二基三經苯樹脂之感光性樹脂組合物只要為感 應以紫外線、電子束、X射線為代表之放射線而可形成樹 脂圖案之組合物，則並無特別限定，可為負型、正型之任 一感光性組合物。 於感光性樹脂組合物被用作負型感光性組合物之情形 時’感光劑較佳為光酸產生劑β光酸產生劑受到放射線照 射而產生酸，所產生之酸可引起上述聯苯二基三羥苯樹脂 與下述交聯劑之交聯反應。作為此種化合物，例如可列 舉：三氣曱基-均三畊類、二芳基錤鹽類、三芳基銃鹽 類、重氮曱酮化合物、硬化合物、續酸化合物、績醯亞胺 化合物、肟酯化合物、重氮甲烷化合物。 其中’較佳為肪酯化合物’具體可列舉·· 2-[2·(4-甲基 苯基續醯氧基亞胺基）]-2,3-二氫嘆吩-3-亞基]-2-(2-曱基苯 基）乙腈（汽巴精化公司之商品名「lrgacure PAG 12 1」）、 [2-(丙基磺醯氧基亞胺基）·2,3-二氫噻吩_3-亞基]-2-(2-曱基 苯基）乙腈（汽巴精化公司之商品名r Irgacure PAgi〇3」）、 [2-(正辛績醯氧基亞胺基）_2,3-二氫噻吩_3·亞基]-2-(2·曱基 笨基）乙腈（汽巴精化公司之商品名「Irgacure PAG108」）、 α-(正辛磺酿氧基亞胺基）_4·曱氧基苯乙腈（汽巴精化公司之 商品名「CGI725」）等。 感光性樹脂組合物亦可用作正型感光性組合物。於此情 形時，作為感光劑’較佳為光酸產生劑，光酸產生劑較佳 16H82.doc -38- 201234115 為含有萘醌二疊氮衍生物 卜巧丄逆奈醌二疊氮衍生物， 可列舉U2-苯酿二疊氮結構或具有❻蔡酿二疊氮結構之 化合物’該等化合㈣藉由例如美國專利第2,772,972號說 明書、美國專利第2,797 213跋句杏 就說明書、美國專利第 3’669,658號說明書等而公知。該萘酿二疊氮衍生物為選自 由下文將詳述之具有特定結構之多經基化合物之^-蔡酿 二疊氮-4-磺酸酯及該多羥基化合物之丨，2_萘醌二疊氮_5-磺 酸酯所組成之群中的至少一種化合物（以下亦稱為「nqd 化合物」）。 就感度及伸長率等硬化膜物性之觀點而言，作為較佳之 NQD化合物之例，例如可列舉下述者： [化 19]CH2 - R4 {wherein, R3 is a methyl group or an ethyl group, and 卩 and 召 are each independently an integer of 〇~4, and R4 is an oxygen-burning gas which may be selected from a functional atom, a radical and a carbon number which may have an unsaturated bond. a compound represented by a group of base groups is mixed with a molar ratio of 5:b.··$, and a catalyst is added; and a step of heating at 6 (TC or more! minutes to 48 hours; The production method is to produce a biphenyldiyltrihydroxybenzene resin. The compound may have U and an ethyl group as a thiol group on the benzene ring. Preferred examples of the tris(4) compound include, for example, 2,3-trihydroxybenzene (o-benzene = 1,2,4·tri-benzene n, tri-(tetra) (meta-phenylene), and the concept of imaging in St. Sanjing, (3)-: Economic policy Preferably, it is used for m. - Red. The 4 may be used singly or in combination to condense with the tri-benzene compound: 4,4,_dichloro, sulfonate-based compound, such as hydrazine f 联联本, 4,4, _ 芏 芏 氧 氧 氧 氧 氧 氧 氧 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 There are methyl and ethyl structures' but for example It is also possible to have a specific example of 2, 2, -, and 23, and exemplify the compound of the structure of ''. Among them, in terms of heat sealing: /^ and other substitutions, and 3, preferably 4, 4·- Take 16M82.doc • 36 - 201234115 to a biphenyl-based compound. These bi-phenyl compounds can be used alone or in combination of two or more. - Condensation of biphenyldiyl compounds with tri-benzene compounds The reaction is carried out by mixing a tri-benzene compound and a biphenyl compound with a molar ratio of 5: w. 卜 preferably ^: 卜 (10): 卜更优选为^: It is carried out by heating at 6 (rc or more, preferably 8 Å or more, more preferably 100 C or more. Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, sulfonic acid, and hydrazine. Sulfonic acid, monomethylsulfate, diethylsulfate, acetic acid, oxalic acid, hydroxyethylidene-1,1'-diphosphonic acid, zinc acetate, boron trifluoride, boron trifluoride-phenol complex , a boron trifluoride-ether complex, etc. On the other hand, as an alkaline catalyst, a hydroxide, a sodium hydroxide, a potassium hydroxide, and a hydroxide are mentioned. , barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N,N-dimethylaminopyridine, piperidine, arable, 1,4-diazabicyclo[2.2.2]octane, 1 , 8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene, ammonia, hexamethylenetetramine, etc. In the above condensation reaction, diethylene glycol dimethyl ether (DMDG, Diethylene Glycol Dimethyl Ether), N-methyl-2-pyrrolidone, NMP, N-methyl-2-pyrrolidone, DMAc » Dimethylacetamide 'DMF, Dimethylformamide, γ-Binger (GBL, Gama Butyrolactone), Dimethyl Sulfoxide (DMSO, Dimethyl Sulfoxide) . The weight average molecular weight of the biphenyldiyltrihydroxybenzene resin is preferably 1,500 to 200,000, more preferably 1,500 to 100,00 (), still more preferably 161182.doc • 37·201234115 2,000 to 50,000. <Photosensitive Resin Composition of the Second Aspect of the Invention> The photosensitive resin composition containing a biphenyldiyltriphenylbenzene resin can form a resin by sensing radiation represented by ultraviolet rays, electron beams, and X-rays. The composition of the pattern is not particularly limited, and may be any of a negative or positive photosensitive composition. When the photosensitive resin composition is used as a negative photosensitive composition, the photosensitive agent is preferably a photoacid generator β photoacid generator which is irradiated with radiation to generate an acid, and the acid produced may cause the above biphenyl The crosslinking reaction of the hydroxybenzene resin with the crosslinking agent described below. Examples of such a compound include a trigassulfonyl group - a tri-negative group, a diarylsulfonium salt, a triarylsulfonium salt, a diazonium ketone compound, a hard compound, a reductive acid compound, and a bismuth imine compound. , oxime ester compounds, diazomethane compounds. Specifically, 'preferably a fatty ester compound' can be exemplified by 2-[2·(4-methylphenyl hydrazinyloxyimino)]-2,3-dihydro-septin-3-ylidene] -2-(2-mercaptophenyl)acetonitrile (trade name "lrgacure PAG 12 1" from Ciba Specialty Chemicals Co., Ltd.), [2-(propylsulfonyloxyimino)·2,3-dihydrogen Thiophene-3-(3-phenylidene)-2-(2-mercaptophenyl)acetonitrile (commercial name r Irgacure PAgi〇3) of Ciba Specialty Chemicals Co., Ltd.), [2-(正辛醯methoxyimino)_2, 3-dihydrothiophene-3 subunit]-2-(2·indolyl)acetonitrile (trade name "Irgacure PAG108" of Ciba Specialty Chemicals Co., Ltd.), α-(n-octanesulfonyloxyimino) )_4·曱-oxyphenylacetonitrile (trade name “CGI725” of Ciba Specialty Chemicals Co., Ltd.). The photosensitive resin composition can also be used as a positive photosensitive composition. In this case, as the sensitizer 'preferably a photoacid generator, the photoacid generator preferably 16H82.doc -38 - 201234115 is a naphthoquinone diazide derivative containing a ruthenium diazide derivative. A U2-benzene-stirred diazide structure or a compound having a ruthenium-clad-diazide structure is described. For example, the specification of U.S. Patent No. 2,772,972, U.S. Patent No. 2,797,213, the disclosure of which is incorporated herein by reference. '669, 658, etc. is known. The naphthoquinone diazide derivative is selected from the group consisting of poly-based compounds having a specific structure as described in detail below, and the polyhydroxy compound, 2 - naphthoquinone At least one compound of the group consisting of diazide-5-sulfonate (hereinafter also referred to as "nqd compound"). From the viewpoint of physical properties of the cured film such as sensitivity and elongation, examples of preferred NQD compounds include the following: [Chem. 19]

{式中，Q為氫原子或下述： 161182.doc •39- 201234115 [化 20]In the formula, Q is a hydrogen atom or the following: 161182.doc •39- 201234115 [Chem. 20]

所不之萘醌二疊氮磺酸酯基，所有的Q不同時為氫原子}。 又，可使用在同一分子中併用4_萘醌二疊氮磺醯基及5_ 萘酿一疊氮項醯基之萘酿二疊氮確醯醋化合物作為nqd化 a物亦可將4-备酿一疊氮續酿g旨化合物與5 -萘親二疊氮 磺醯酯化合物混合使用。 感光性樹脂組合物中之感光劑之添加量較佳為相對於聯 苯二基三羥苯樹脂100質量份而為〗〜5〇質量份。若該添加 量為1質量份以上，則藉由放射線照射而產生之酸之量變 充分，感度提高，若該添加量為5〇質量份以下，則硬化後 之機械物性變良好。 又，藉由在感光性樹脂組合物中添加交聯劑，亦可於對 塗膜進行加熱硬化時強化機械物性、耐熱性、耐化學品性 等膜性能。為了充分地強化膜性能，交聯劑較佳為具有選 自由環氧基、氧雜環丁烷基、_N_(CH2_〇R)*{式中，r為 氫或碳數卜4之烧基}及心灿魏⑷式中，尺為氣或碳 數1〜4之烷基}所組成之群中之至少2個基的化合物。具體 而言，可使用本發明之第-態樣t記述之交聯劑β八 添加乂聯劑之情形之添加量較佳為相對於聯笨二基三羥 161182.doc 201234115 笨樹月曰100質量份而為1〜60質量份，更佳為3〜5 0質量份。 又，3有聯苯二基三羥苯樹脂之感光性樹脂組合物係採 用將该等成分溶解於溶劑中之清漆狀之形態。作為此處所 使用之溶劑，可列舉：醢胺類、亞硬類、腺類、綱類、醋 類、内醋類、趟類、齒化烴類、烴類等，其中，就樹脂之 =解性、樹脂組合物之敎性、對基板之接著性之觀點而 Β ’較佳為Ν-曱基_2_吼0各唆嗣、三甲基乙酿胺、二甲基 曱醯胺、二曱基亞砜甲基脲'乙酸丁酯、乳酸乙酯、 γ-丁内酯、二乙二醇二甲基醚'丙二醇單甲基醚乙酸酯、 丙二醇單甲基醚、#甲醇、乙二醇苯醚、四氫呋喃、四氫 糠基醇’料可㈣錢，亦可混合錢。耗之使用量 係根據所得之膜厚而不同，相對於聯苯二基^苯樹脂 100質量份而於70〜1900質量份之範圍内使用。 含有本發明之第二態樣之聯苯二基三㈣樹脂之感光性 樹脂組合物可如下述般使用。首先，藉由使用旋轉塗佈機 之旋轉塗佈或輥式塗佈機將該組合物塗佈於適當之基板， 例如石夕晶圓、m板、紹基板等上。使用烘箱或加熱板 於50 14GC下對其乾燥1G秒〜i小時，經由光罩使用接觸式 對準機或步進機進行光化射線之照射（曝光步驟）。其次， 利用顯像液溶解去除照射部，繼而進行利用淋洗液之沖 洗，藉此獲得所需之凸起圖案（顯像步驟）。作為顯像方 法’可為喷射、覆液、浸潰、超音波等方式。淋洗液可使 用蒸顧水 '脫離子水等。可將所得之凸起圖案於16〇〜 赋下加熱處理10秒〜2小時，形成耐熱性覆膜(加熱步 161182.doc -41 - 201234115 驟）。 上述感光性樹脂組合物不僅於半導體用途中有用，作為 多層電路之層間絕緣或可撓性銅箔板之蓋層、阻焊膜或液 晶配向膜而亦有用。半導體用途之具體之較佳例為半導體 表面保護膜、層間絕緣膜、再配線用絕緣膜、倒裝晶片裝 置用保護膜、具有凸塊構造之裝置之保護膜等。 [實施例] 以下，藉由參考例、實施例及比較例具體說明本發明之 第一態樣，但本發明並不限定於此。 再者，實施例中之測定條件係如下所示。 &lt;重量平均分子量（Mw)&gt; 藉由膠滲層析法（GPC)，利用標準聚苯乙烯（昭和電工公 司製造之有機溶劑系標準試樣STANDARD SM-105)換算而 算出。所使用之GPC裝置及測定條件係如下所述。 泵：JASCO PU-980 檢測器：JASCO RI-930None of the naphthoquinonediazide sulfonate groups, all Qs are not hydrogen atoms at the same time. Further, a naphthalene-doped azide quinone vinegar compound which is used in the same molecule and which is a mixture of a 4-naphthoquinonediazidesulfonyl group and a 5-naphthene-based azide-based fluorenyl group may be used as the nqd-a substance. A mixture of a nitrogen-containing compound and a 5-naphtho-diazanesulfonate compound is used in combination. The amount of the sensitizer added to the photosensitive resin composition is preferably from 〜5 parts by mass based on 100 parts by mass of the biphenyldiphenyl hydroxybenzene resin. When the amount is more than 1 part by mass, the amount of the acid generated by the radiation irradiation is sufficient, and the sensitivity is improved. When the amount is 5 parts by mass or less, the mechanical properties after curing are improved. Further, by adding a crosslinking agent to the photosensitive resin composition, it is possible to enhance film properties such as mechanical properties, heat resistance, and chemical resistance when the coating film is heat-cured. In order to sufficiently enhance the film properties, the crosslinking agent preferably has a group selected from the group consisting of an epoxy group, an oxetane group, a _N_(CH2_〇R)*{, wherein r is hydrogen or a carbon number And a compound of at least two groups of a group consisting of a gas or an alkyl group having 1 to 4 carbon atoms in the formula (4). Specifically, the amount of the cross-linking agent β-addition of the crosslinking agent described in the first aspect of the present invention may be preferably added in an amount relative to the biphenyldihydroxyl 161182.doc 201234115 stupid tree 100 The mass fraction is 1 to 60 parts by mass, more preferably 3 to 50 parts by mass. Further, the photosensitive resin composition having 3 biphenyldiyltrihydroxybenzene resins is in the form of a varnish in which the components are dissolved in a solvent. Examples of the solvent to be used herein include guanamines, subhards, glands, classes, vinegars, internal vinegars, anthraquinones, toothed hydrocarbons, hydrocarbons, and the like.性, 树脂 曱 曱 _2 曱 曱 曱 曱 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱Mercaptosulfone methylurea butyl acetate, ethyl lactate, γ-butyrolactone, diethylene glycol dimethyl ether 'propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, # methanol, B Glycol phenyl ether, tetrahydrofuran, tetrahydrofurfuryl alcohol 'material can be (four) money, can also mix money. The amount of use varies depending on the film thickness obtained, and is used in the range of 70 to 1900 parts by mass based on 100 parts by mass of the biphenyldiphenylbenzene resin. The photosensitive resin composition containing the biphenyldiyltri(tetra) resin of the second aspect of the present invention can be used as follows. First, the composition is applied to a suitable substrate, such as a Shihwa wafer, an m-plate, a substrate, or the like, by a spin coating or a roll coater using a spin coater. It was dried using an oven or a hot plate at 50 14 GC for 1 G seconds to i hours, and irradiated with actinic rays (exposure step) using a contact aligner or a stepper via a photomask. Next, the illuminating portion is removed by dissolution using a developing solution, followed by washing with an eluent, whereby a desired convex pattern (developing step) is obtained. As the developing method, it may be a method such as spraying, liquid coating, dipping, or ultrasonic. The eluent can be used to divert water from the water. The resulting raised pattern can be heat treated for 16 seconds to 2 hours to form a heat resistant film (heating step 161182.doc -41 - 201234115). The photosensitive resin composition is useful not only for semiconductor applications, but also as a interlayer insulating layer of a multilayer circuit or a cap layer of a flexible copper foil plate, a solder resist film or a liquid crystal alignment film. Specific preferred examples of the semiconductor use are a semiconductor surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, a protective film for a device having a bump structure, and the like. [Examples] Hereinafter, the first aspect of the present invention will be specifically described by way of Reference Examples, Examples and Comparative Examples, but the present invention is not limited thereto. Further, the measurement conditions in the examples are as follows. &lt;Weight average molecular weight (Mw)&gt; was calculated by gel permeation chromatography (GPC) using standard polystyrene (standard organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko Co., Ltd.). The GPC apparatus and measurement conditions used are as follows. Pump: JASCO PU-980 Detector: JASCO RI-930

柱烘箱：JASCO CO-965，40°CColumn oven: JASCO CO-965, 40 ° C

柱：串聯2根 ShodexKD-806M 流動相：0.1 mol/1，EtBr/N-甲基π比°各〇定酮 流速：1 ml/min。 &lt;羥基間距離（最短距離di)&gt; 首先’利用Bio-Rad Laboratories公司製造之Chem Window(註冊商標）描晝驗可溶性盼樹脂之A-Bj-A之化學結 構式。 161182.doc -42- 201234115 此時即便於成為A(形成A部）之具有酚性羥基之化合物 與成為Bi(形成艮部）之化合物鍵結時之鍵結位置為複數個 之凊形時，亦設定為僅其中一個鍵結。該情形之鍵結位置 於隔著Bi相對之2個八分別具有1個酚性羥基之情形時，酚 挫羥基之2,6-位最優先，於此兩者經氫原子以外之取代基 所占之情形時，設定為與4·位鍵結。於2,6·位兩者均可鍵 結之情形時，以鄰接之3,5_位之取代基之體積較小者為優 先。例如於A為間甲酚之情形時，設定為與6_位鍵結。 又，於隔著匕相對之2個八分別具有2個酚性羥基之情形 時，若為兒茶酚類，則設定為3,6_位最優先，作為其次之 優先順序，設定為4,5-位鍵結，若為間苯二酚類，則設定 為2-位最優先，作為其次之優先順序，設定為七6-位鍵 結，若為對苯二酚類，則設定為2,6_位最優先，作為其次 之優先順序，設定為3,5_位鍵結，該情形亦以與酚性羥基 為1個之情形同樣地考慮鄰接之取代基之體積並且決定鍵 結位置。又，於隔著^相對之2個A分別具有3個酚性羥基 之情形時，若為鄰苯三酚類，則考慮鄰接之取代基之體積 並且自4’6-位中選擇，於其任一者上具有除氫原子以外之 取代基之情形時，設定為5_位鍵結，若為間苯三酚類，則 設定為2,4,6-位中無取代基之位置鍵結，若為i’K三羥苯 類，則設定為3-位鍵結，於3-位上具有取代基之情形時， 設定為5-位鍵結’若5·位上亦具有取代基，則設定為6—立 鍵結。關於以上之取代位置，於將酚性羥基之位置設定為 1-位且A内之酚性羥基為2個以上而考慮複數個取代位置之 161182.doc •43· 201234115 才曰疋法之情形時，係以所有酚性羥基之取代位置成為儘可 I小之數字之方式決定，其他則遵循IUpAC(lnternati〇naiColumn: 2 in series Shodex KD-806M Mobile phase: 0.1 mol/1, EtBr/N-methyl π ratio ° hydrazine ketone Flow rate: 1 ml/min. &lt;Inter-hydroxyl distance (shortest distance di)&gt; First, the chemical structure of A-Bj-A of the soluble expectant resin was examined by Chem Window (registered trademark) manufactured by Bio-Rad Laboratories. 161182.doc -42- 201234115 At this time, even when the bonding site of the compound having a phenolic hydroxyl group which is A (forming part A) and the compound which becomes Bi (forming a crotch portion) is plural, Also set to only one of the keys. In the case where the bonding position of the case has one phenolic hydroxyl group per two of the two opposite Bi, the 2,6-position of the phenolic hydroxyl group is most preferential, and the substituents of the two are substituted by a hydrogen atom. In the case of the situation, it is set to be bonded to the 4 digit. In the case where both of the 2,6-positions can be bonded, the smaller of the substituents of the adjacent 3,5-position is preferred. For example, when A is m-cresol, it is set to bond with the 6-position. In the case where there are two phenolic hydroxyl groups in each of the two bismuth compartments, the catechol is set to 3, 6 _ position is the highest priority, and the second priority is set to 4, 5-position bonding, if it is resorcinol, it is set to the 2-position first, and the second priority is set to the 7-position bond. If it is hydroquinone, it is set to 2. The 6_ bit is the highest priority, and the second priority is set to the 3,5_bit bond. In this case, the volume of the adjacent substituent is considered and the bonding position is determined in the same manner as in the case of the phenolic hydroxyl group. . Further, in the case where the two opposite A have three phenolic hydroxyl groups, if they are pyrogallols, the volume of the adjacent substituents is considered and selected from the 4'6-position. In the case where any substituent other than a hydrogen atom is present, it is set to a 5-position bond, and if it is a phloroglucin type, it is set to a position-bonded bond having no substituent in the 2, 4, 6-position. If it is i'K trihydroxybenzene, it is set to a 3-position bond, and when it has a substituent at the 3-position, it is set to a 5-position bond, and if it has a substituent at the 5 position, Then set to 6 - vertical key knot. Regarding the above-mentioned substitution position, the position of the phenolic hydroxyl group is set to 1-position and the phenolic hydroxyl group in A is two or more, and a plurality of substitution positions are considered. 161182.doc •43·201234115 , the position of all phenolic hydroxyl groups is determined to be as small as possible, and the others follow IUpAC (lnternati〇nai

Union of pure and Applied Chemistry ’ 國際純粹與應用化 學聯合會）之命名法。 其次，將利用ChemWindow(註冊商標）作圖而成之鹼可 溶性酚樹脂之結構式複製至Bi〇_Rad Lab〇rat〇ries公司製造 之SymApps(註冊商標）中，計算三維結構式後，選擇八之 羥基中距離最近之組來表示氧原子間之距離，藉此求出羥 基間距離（最紐距離小）。又，於使用複數種2價有機基作為 A、及/或使用複數種2價有機基作為艮之共聚物之情形 時，求出該等之加權平均值。 於混合鹼可溶性酚樹脂之情形時，對各鹼可溶性酚樹脂 進行上述計异後，按照混合比求出其加權平均。 &lt;軟化點&gt; 依照JIS K5601-2-2，使用ASP-M2SP(明峰社製作所公司 製造）’使用作為熱介質之甘油，利用環球法進行測定。 將即便升溫至170。(：亦未軟化之樣品記載為&gt;17〇β(：。 &lt;本發明之第一態樣之參考例j &gt; 於容量0.5 L之附帶迪恩-斯達克裝置之可分離式燒瓶 中，將兒茶酚66.1 g(〇.6 m〇i)、4,4，_雙（甲氧基甲基）聯苯 72.7 g(0.3 mol)、二乙基硫酸21 g(〇 15 m〇1)、二乙二醇二 甲基醚27g於70°C下混合攪拌，使固形物溶解。 藉由油浴將混合溶液加熱至12〇t，由反應液確認到曱 醇之產生。直接於120°C下將反應液授拌2小時。 J61182.doc • 44 - 201234115 其次，於大氣中冷卻反應容器，向其中另添加四氫呋喃 100 g並攪拌。於高速攪拌下將上述反應稀釋液滴加至4 ^ 之水中而使樹脂分散析出，對其進行回收，適當進行水 洗、脫水後實施真空乾燥，以產率73%獲得酚樹脂（p-丨）。 P-1之藉由GPC算出之重量平均分子量以聚苯乙烯換算為 4，100。 關於P 1 ’將利用Bio-Rad Laboratories公司製造之 SymApps(註冊商標）進行之藉由分子力學計算（分子力學 法）之MM2法所得的三維結構式示於圖丨中。於圖丨中，斜 線球體部表示氫原子，砂地球體部表示氧原子，而且白色 球體部表示碳原子。 〈本發明之第一態樣之參考例2&gt; 使用鄰笨三酚56.7 g(0.45 mol)代替上述參考例1之兒茶 驗’並以與參考例1相同之方式進行合成，以產率77%獲 得酚樹脂（P-2)。P-2之藉由GPC算出之重量平均分子量以 聚苯乙烯換算為7,700。 &lt;本發明之第一態樣之參考例3&gt; 使用間苯三酚56.7 g(〇 45 m〇1)代替參考例i之兒茶酚， 使用2,6-雙（羥基甲基）萘56 5 g(〇 3 m〇1)代替44,_雙（曱氧基 甲基）聯笨72.7 g(〇.3 mol)，並以與參考例1相同之方式進 行合成’以產率65〇/。獲得酚樹脂（ρ·3)。p_3之藉由GPc算出 之重量平均分子量以聚苯乙烯換算為5,600。 &lt;本發明之第一態樣之參考例4&gt; 使用4,4，·雙（甲氧基甲基）聯苯36.3 g(0.15 mol)與1，4-雙 161182.doc -45- 201234115 (甲氧基曱基）苯24.9 g(〇.15 m〇1: 氧基甲基）聯苯72.7 g(〇.3 m〇1)， m〇l)代替參考例1之4,4·-雙（曱 〇1) ’並以與參考例1相同之方Union of pure and Applied Chemistry's nomenclature of the International Union of Pure and Applied Chemistry. Next, the structural formula of the alkali-soluble phenol resin formed by using ChemWindow (registered trademark) is copied to SymApps (registered trademark) manufactured by Bi〇_Rad Lab〇rat〇ries, and after calculating the three-dimensional structure, eight is selected. The group closest to the hydroxyl group represents the distance between the oxygen atoms, thereby obtaining the distance between the hydroxyl groups (the maximum distance is small). Further, when a plurality of divalent organic groups are used as A and/or a plurality of divalent organic groups are used as a copolymer of ruthenium, a weighted average of these is obtained. In the case of mixing an alkali-soluble phenol resin, the alkali-soluble phenol resin is subjected to the above-described measurement, and the weighted average thereof is obtained from the mixing ratio. &lt;Softening Point&gt; The glycerin as a heat medium was used in accordance with JIS K5601-2-2 using ASP-M2SP (manufactured by Mingfeng Seisakusho Co., Ltd.), and the measurement was carried out by a ring and ball method. Will heat up to 170. (: The sample which has not been softened is described as &gt; 17 〇 β (: &lt; Reference Example j &gt; of the first aspect of the present invention; separable flask with a Dean-Stark apparatus having a capacity of 0.5 L Among them, catechol 66.1 g (〇.6 m〇i), 4,4,_bis(methoxymethyl)biphenyl 72.7 g (0.3 mol), diethyl sulfate 21 g (〇15 m〇) 1), 27 g of diethylene glycol dimethyl ether was mixed and stirred at 70 ° C to dissolve the solid matter. The mixed solution was heated to 12 Torr by an oil bath, and the production of sterol was confirmed from the reaction liquid. The reaction solution was stirred for 2 hours at 120 ° C. J61182.doc • 44 - 201234115 Next, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was added thereto and stirred. The above reaction dilution was added to the mixture under high-speed stirring. The resin was dispersed and precipitated in 4 ^ of water, and it was recovered, washed with water, dehydrated, and then vacuum dried to obtain a phenol resin (p-丨) in a yield of 73%. The weight average of P-1 by GPC The molecular weight is 4,100 in terms of polystyrene. About P 1 ' will use SymApps (registered trademark) manufactured by Bio-Rad Laboratories The three-dimensional structural formula obtained by the MM2 method of molecular mechanics calculation (molecular mechanics method) is shown in Fig. 于. In the figure, the oblique sphere body represents a hydrogen atom, the sand earth body represents an oxygen atom, and the white sphere portion represents Carbon atom. Reference Example 2 of the first aspect of the present invention&gt; Using 56.7 g (0.45 mol) of o-p-trisphenol in place of the above-mentioned tea of the reference example 1 and synthesizing in the same manner as in Reference Example 1 The phenol resin (P-2) was obtained in a yield of 77%. The weight average molecular weight calculated by GPC of P-2 was 7,700 in terms of polystyrene. < Reference Example 3 of the first aspect of the present invention> Using benzene Trisphenol 56.7 g (〇45 m〇1) replaces the catechol of Reference Example i, using 2,6-bis(hydroxymethyl)naphthalene 56 5 g (〇3 m〇1) instead of 44,_double (oxygen) The base methyl group was 72.7 g (〇.3 mol), and was synthesized in the same manner as in Reference Example 1 to obtain a phenol resin (ρ·3) in a yield of 65 Å. The p_3 was calculated by GPc. The weight average molecular weight is 5,600 in terms of polystyrene. <Reference Example 4 of the first aspect of the present invention> 4,4,·bis(methoxymethyl) linkage is used. 36.3 g (0.15 mol) and 1,4-double 161182.doc -45- 201234115 (methoxy methoxy) benzene 24.9 g (〇.15 m〇1: oxymethyl)biphenyl 72.7 g (〇.3 M〇1), m〇l) instead of 4, 4·-double (曱〇1) ' of Reference Example 1 and in the same way as Reference Example 1

式進行合成，以產率70%獲得酚樹脂（ρ_4卜ρ_4之藉由GPCSynthesis was carried out to obtain a phenol resin in a yield of 70% (ρ_4 ρ_4 by GPC)

(鄰苯三盼-亞曱基-聯苯二基-亞甲基 鄰苯三酚）單元： 11.346 埃 (鄰笨三紛-苯二甲基-鄰笨三紛）單元：8 339埃 Ρ·4 : 11.346x0.43 + 8·339χ〇.57=9.632埃 &lt;鹼性顯像用感光性酚樹脂組合物之製備&gt; 將酚樹脂100質量份、交聯劑20質量份、感光劑12質量 份溶解於γ_丁内酯122質量份中製成均勻溶液後，利用孔 徑1 μπι之薄膜過濾器進行過濾，製備表丨所示之鹼性顯像 用感光性驗樹脂組合物溶液。 作為酚樹脂，使用上述參考例U中合成之ρ」〜3或下文 所示者。 EP4080G(曱酚酚醛清漆樹脂，商品名，旭有機材工業公 司製造） I6ll82.doc •46- 201234115 HF-4M(苯酚酚醛清漆樹脂，商品名，明和化成公司製 造） MEH-785 1-S(苯酚-聯苯二基樹脂，商品名，明和化成公 司製造） 作為交聯劑，使用以下者。 MX-270(Nikalac MX-270，商品名，Sanwa Chemical 公 司製造） 作為感光劑，使用以下者。 TPPA{以下： [化 21](o-phthalo-p-indenyl-biphenyldiyl-methylene pyrogallol) unit: 11.346 angstroms (o-stupid-tris-benzoyl-n-stupid) unit: 8 339 angstroms 4: 11.346x0.43 + 8·339χ〇.57=9.632 angstroms &lt;Preparation of photosensitive phenol resin composition for alkaline development&gt; 100 parts by mass of phenol resin, 20 parts by mass of crosslinking agent, sensitizer 12 The mass fraction was dissolved in 122 parts by mass of γ-butyrolactone to prepare a homogeneous solution, and then filtered through a membrane filter having a pore size of 1 μm to prepare a photosensitive resin composition solution for alkaline development shown in Table 。. As the phenol resin, ρ" to 3 synthesized in the above Reference Example U or the ones shown below were used. EP4080G (nonoxyphenol novolac resin, trade name, manufactured by Asahi Organic Materials Co., Ltd.) I6ll82.doc •46- 201234115 HF-4M (phenol novolak resin, trade name, manufactured by Minghe Chemical Co., Ltd.) MEH-785 1-S (phenol - Biphenyldiyl resin, trade name, manufactured by Mingwa Chemical Co., Ltd.) As a crosslinking agent, the following is used. MX-270 (Nikalac MX-270, trade name, manufactured by Sanwa Chemical Co., Ltd.) As a sensitizer, the following was used. TPPA {Here: [Chem. 21]

H3C--ch3H3C--ch3

(式中，Q中之83%為下述結構： [化 22](In the formula, 83% of Q is the following structure: [Chem. 22]

161182.doc -47- 201234115 其餘為氫原子）中表示結構}。 表1中之評價項目係如以下般進行試驗。 &lt;伸長率&gt; 依照上述測定方法’利用萬能試驗機Tensil〇n UTM-II-20(Orientec公司製造）進行測定。 &lt; 熱循環（TC，Thermal Cycle)試驗〉 藉由 Clean Track-Mark8(Tokyo Electron公司製造）將驗性 顯像用感光性紛樹脂組合物旋轉塗佈於6忖石夕晶圓上，利 用120°C之加熱板加熱3分鐘，獲得厚度1〇 μιη之膜。膜厚 係利用膜厚測定裝置Lambda ACE(大日本網屏（Dainippon Screen)製造公司製造）進行測定。通過附帶測試圖案之光 罩並使用具有1射線（365 nm)之曝光波長之步進機 NSR2005i8A(Nikon公司製造）使曝光量階段性地變化而對 該塗膜照射i射線，藉此進行曝光。其次，利用aean Track-MarkS於23°C下使用2.38%氫氧化四甲基銨水溶液 AZ-300MIF(AZ Electronic Materials公司製造）顯像 2〇〇秒， 利用純水沖洗後，利用立式固化爐VF200B(K〇y〇 Therm〇 Systems公司製造）於氮氣環境下於25(rc下進行}小時硬 化，獲得硬化凸起圖案。於在該階段中5〇 μιη四方之凸起 圖案之大小與顯像後之時刻相比較有1〇%以上不同之情形 時，於表1之TC试驗之欄中記載為_。對所得之凸起圖案使 用熱腔室TSE-ll(Espec公司製造），於_65°C〜135。(：内每30 分鐘為1循環而進行1000循環之試驗後，利用光學顯微鏡 觀察膜表面。將膜上無裂痕者視為A，有裂痕者視為B。 161182,doc -48- 201234115 [表i] &lt;本發明之第一態樣&gt; 聚合物 軟化點(°C) 羥基間距離(A) 伸長率 TC試驗 實施例1 P-1 105 11.346 36 A 實施例2 P-2 &gt;170 11.346 51 A 實施例3 P-l/P-2=l/l 155 11.346 45 A 實施例4 P-3 &gt;170 9.452 28 A 實施例5 P-4 &gt;170 9.632 36 A 比較例1 EP4080G 149 3.291 3 B 比較例2 HF-4M 102 5.414 4 B 比較例3 MEH-7851-S 75 11.346 42 画 根據表1之結果可知，軟化點為1 oo°c以上且羥基間距離 (最短距離山）超過9埃者可獲得如設計般之凸起圖案，於TC 試驗中不產生裂痕，可形成可靠性較高之硬化膜。 以下，藉由實施例具體說明本發明之第二態樣。 將以下之實施例中所使用之測定方法示於以下。 (1)凝膠滲透層析法（GPC)測定 管柱：昭和電工公司製造，商標名：Shodex KD-806M (串聯兩根） 溶析液：NMP(0.01 mol/L，LiBr)，40°C 流速：1.0 ml/分鐘 檢測器：JASCO RI-93 0 P^H-NMR 測定 161182.doc -49- 201234115 裝置：日本電子股份有限公司製造之ECS400 溶劑：ISOTEC，氘代二曱基亞砜（DMSO-d6) 測定溫度：25°C (3)紅外線吸收（IR)光譜測定 裝置：Thermo Scientific公司製造之AVATAR 360 FT-IR 測定方法：透過法（KBr片劑） [本發明之第二態樣之實施例U &lt;聯笨二基三羥笨樹脂（P_n)之合成&gt; 於容量0.5升之附帶迪恩-斯達克裝置之可分離式燒瓶中 將鄰苯三酚50.4 g(0.4 mol)、4,4'-雙（甲氧基甲基）聯苯72.7 g (0.3 mol)、二乙基硫酸 2.1 g(〇.i5 mol)、DMDG 27 g於 7 0 °C下混合槐拌，使固形物溶解。 藉由油浴將混合溶液加熱至12〇。〇，由反應液確認到甲 醇之產生。直接於120°C下將反應液攪拌2小時。 其次，於大氣中冷卻反應容器，向其中另添加四氫呋喃 100 g並進行攪拌。於咼速攪拌下將上述反應稀釋液滴加 至4 L之水中而使樹脂分散析出，對其進行回收適當進 行水洗、脫水後實施真空乾燥，以產率7〇%獲得具有以下 所示之結構·161182.doc -47- 201234115 The rest is a hydrogen atom) in the structure}. The evaluation items in Table 1 were tested as follows. &lt;Elongation&gt; The measurement was carried out by a universal testing machine Tensil〇n UTM-II-20 (manufactured by Orientec Co., Ltd.) according to the above-described measurement method. &lt; Thermal cycle (TC, Thermal Cycle) test> The photosensitive resin composition for the test development was spin-coated on a 6-inch wafer by a Clean Track-Mark 8 (manufactured by Tokyo Electron Co., Ltd.), and 120 was used. The hot plate of ° C was heated for 3 minutes to obtain a film having a thickness of 1 μm. The film thickness was measured by a film thickness measuring device Lambda ACE (manufactured by Dainippon Screen Manufacturing Co., Ltd.). The coating film was irradiated with i-rays by stepwise change of the exposure amount using a stepper of the test pattern and a stepper NSR2005i8A (manufactured by Nikon Co., Ltd.) having an exposure wavelength of 1 ray (365 nm), thereby performing exposure. Next, using aean Track-MarkS at 23 ° C, using 2.38% aqueous solution of tetramethylammonium hydroxide AZ-300 MIF (manufactured by AZ Electronic Materials) for 2 sec seconds, rinsed with pure water, and then used a vertical curing oven. VF200B (manufactured by K〇y〇 Therm〇 Systems Co., Ltd.) was hardened under a nitrogen atmosphere at 25 (rc) for 9 hours to obtain a hardened convex pattern. In this stage, the size and image of the convex pattern of 5 〇μηη square When the time after the difference is more than 1%, it is described as _ in the column of the TC test in Table 1. The heat pattern chamber TSE-ll (manufactured by Espec) is used for the obtained convex pattern, at _ 65 ° C to 135. (: After 1000 cycles of one cycle every 30 minutes, the surface of the film was observed by an optical microscope. Those without cracks on the film were regarded as A, and those with cracks were regarded as B. 161182, doc -48- 201234115 [Table i] &lt;First aspect of the invention&gt; Polymer softening point (°C) Inter-hydroxyl distance (A) Elongation TC test Example 1 P-1 105 11.346 36 A Example 2 P-2 &gt; 170 11.346 51 A Example 3 Pl/P-2=l/l 155 11.346 45 A Example 4 P-3 &gt; 170 9.45 2 28 A Example 5 P-4 &gt; 170 9.632 36 A Comparative Example 1 EP4080G 149 3.291 3 B Comparative Example 2 HF-4M 102 5.414 4 B Comparative Example 3 MEH-7851-S 75 11.346 42 Draw the results according to Table 1. It can be seen that a softening point of 1 oo °c or more and a distance between the hydroxyl groups (the shortest distance mountain) exceeding 9 angstroms can obtain a raised pattern as designed, and no crack is generated in the TC test, and a highly reliable cured film can be formed. Hereinafter, the second aspect of the present invention will be specifically described by way of examples. The measurement methods used in the following examples are shown below. (1) Gel permeation chromatography (GPC) measurement column: Showa Denko Made by the company, trade name: Shodex KD-806M (two in series) Eluent: NMP (0.01 mol/L, LiBr), 40 °C Flow rate: 1.0 ml/min Detector: JASCO RI-93 0 P^H- NMR measurement 161182.doc -49- 201234115 Device: ECS400 manufactured by JEOL Ltd. Solvent: ISOTEC, deuterated dimethyl sulfoxide (DMSO-d6) Determination temperature: 25 ° C (3) Infrared absorption (IR) spectroscopy Measuring device: AVATAR 360 FT-IR method by Thermo Scientific: Permeation method (KBr piece) [Preparation of the second aspect of the present invention U &lt;Synthesis of phenylidene-tribasic resin (P_n)&gt; in a separable flask equipped with a Dean-Stark apparatus having a capacity of 0.5 liter Pyrogallol 50.4 g (0.4 mol), 4,4'-bis(methoxymethyl)biphenyl 72.7 g (0.3 mol), diethyl sulfate 2.1 g (〇.i5 mol), DMDG 27 g Mix and mix at 70 °C to dissolve the solids. The mixed solution was heated to 12 Torr by an oil bath. 〇, the production of methanol was confirmed from the reaction solution. The reaction solution was stirred directly at 120 ° C for 2 hours. Next, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was further added thereto and stirred. The diluted reaction solution was added dropwise to 4 L of water under idling to disperse and precipitate the resin, and it was recovered, washed with water, dehydrated, and then vacuum dried to obtain a structure having the following structure at a yield of 7 % by weight. ·

-50- 161182.doc 201234115 之聯苯二基三羥苯樹脂（P-11)。 如此合成之樹脂（P-11)之藉由GPC所測定之重量平均分 子量以聚笨乙烯換算為11〇〇〇。圖2中示出樹脂（p_u)之 H_NMR之測定結果。圖2中，1H-NMR訊號波峰：3.8 ppm(m)、6.0〜6 5 ppm(m)、7.0〜7.2 ppm(br)、7.5 ppm (br) 8.2 ppm⑴、8 8卯瓜⑷。又’圖3中示出樹脂（ρ·】j) 之IR光譜。 [本發明之第二態樣之實施例2] &lt;聯苯二基三羥苯樹脂（P-12)之合成&gt; 使用間笨三酚50.4 g(〇.4 mol)代替實施例1之鄰苯三酚， 以與實施例1相同之方式進行合成，以產率7〇%獲得具有 以下所示之結構： [化 24]-50- 161182.doc 201234115 Biphenyldiyltrihydroxybenzene resin (P-11). The weight average molecular weight measured by GPC of the thus synthesized resin (P-11) was 11 Å in terms of polystyrene. Fig. 2 shows the results of measurement of H_NMR of the resin (p_u). In Fig. 2, 1H-NMR signal peaks: 3.8 ppm (m), 6.0 to 6 5 ppm (m), 7.0 to 7.2 ppm (br), 7.5 ppm (br) 8.2 ppm (1), 8 8 cucurbits (4). Further, the IR spectrum of the resin (ρ·j) is shown in Fig. 3 . [Example 2 of the second aspect of the present invention] &lt;Synthesis of biphenyldiyltrihydroxybenzene resin (P-12)&gt; The use of m-trisphenol 50.4 g (〇.4 mol) was used instead of Example 1. Pyrogallol was synthesized in the same manner as in Example 1, and a structure having the following structure was obtained in a yield of 7 % by weight: [Chem. 24]

η 之聯苯二基三羥苯樹脂（ρ_丨2)。 如此合成之樹脂（P-12)之藉由GPC所測定之重量平均分 子量以聚苯乙烯換算為32,000。 圖4中示出樹脂（p_12)之1H-NMR之測定結果。圖4中， 11以1^111訊號波峰：3.6〜4,0卩卩111(111)、5.8〜6.2卩？111(111)、7.3 卩口111((1-&lt;1)、8-1卩卩111(1)1')、8.9~9.2卩卩111(111)。又，圖5中示出 樹脂（P-12)之IR光譜。 161182.doc •51 · 201234115 [本發明之第二態樣之實施例3] &lt;感光性樹脂組合物之製備及其評價&gt; 將實施例1中獲得之樹脂（P-11) : 100質量份、具有下述 結構： [化 25]η Biphenyldiyltrihydroxybenzene resin (ρ_丨2). The weight average molecular weight measured by GPC of the thus synthesized resin (P-12) was 32,000 in terms of polystyrene. Fig. 4 shows the results of 1H-NMR measurement of the resin (p_12). In Figure 4, 11 is 1^111 signal peak: 3.6~4, 0卩卩111(111), 5.8~6.2卩? 111 (111), 7.3 mouth 111 ((1-&lt;1), 8-1卩卩111(1)1'), 8.9~9.2卩卩111(111). Further, Fig. 5 shows the IR spectrum of the resin (P-12). 161182.doc •51 · 201234115 [Example 3 of the second aspect of the invention] &lt;Preparation and evaluation of photosensitive resin composition&gt; Resin (P-11) obtained in Example 1 : 100 mass Parts, with the following structure: [Chem. 25]

之交聯劑MX-270(商品名 Nikalac MX-270，Sanwa Chemical 公司製造）：20質量份、具有下述結構： [化 26]Crosslinking agent MX-270 (trade name: Nikalac MX-270, manufactured by Sanwa Chemical Co., Ltd.): 20 parts by mass, having the following structure: [Chem. 26]

{式中，Q中83%為以下結構： [化 27]In the formula, 83% of Q is the following structure: [Chem. 27]

161182.doc -52- 201234115 、、為氫原子}的感光劑（C_1): 12質量份溶解於GBL· 114 質匕量份中’利用（Μ㈣之過濾ϋ進行過渡而製備感.光性樹 脂組合物，評價其微影性、对熱性。將評價結果示於以下 之表2中。 [本發明之第二態樣之實施例4] 於實施例3中，除了將樹脂！&gt;_u替換為實施例2中獲得之 樹脂OM2)以外，以與實施例3相同之方式製備感光性樹脂 組合物，評價其微影性、耐熱性。將評價結果示於以下之 表2中。 ’ [本發明之第二態樣之比較例1 ] 於實施例3中，除了將樹脂P-11替換為下述樹脂（P-13)以 外，以與實施例3相同之方式製備感光性樹脂組合物，評 價其微影性、耐熱性。將評價結果示於以下之表2中。 樹脂IM3 : ΜΕΗ·7851_4Η(聯苯二基盼樹脂，明和化成 公司製造） [化 28]161182.doc -52- 201234115, a sensitizer (C_1) which is a hydrogen atom: 12 parts by mass dissolved in GBL·114 匕 匕 ' 利用 利用 利用 利用 Μ Μ Μ Μ Μ 四 四 四 四 四 四 四 四 四 四 四 四 四 光 光 光 光 光 光 光 光 光The evaluation results are shown in Table 2 below. [Example 4 of the second aspect of the present invention] In Example 3, except that resin!&gt;_u was replaced with A photosensitive resin composition was prepared in the same manner as in Example 3 except for the resin OM2) obtained in Example 2, and the lithiation property and heat resistance were evaluated. The evaluation results are shown in Table 2 below. [Comparative Example 1 of the second aspect of the invention] In Example 3, a photosensitive resin was prepared in the same manner as in Example 3 except that the resin P-11 was replaced with the following resin (P-13). The composition was evaluated for its lithiation and heat resistance. The evaluation results are shown in Table 2 below. Resin IM3 : ΜΕΗ·7851_4Η (biphenyl bisbase resin, manufactured by Minghe Chemical Co., Ltd.) [Chem. 28]

樹脂!M3之藉由GPC所測定之重量平均分子量以聚苯乙 烯換算為11，000 » &lt;微影性評價&gt; 利用Tokyo Electron公司製造之旋轉塗佈機（cleantrack 161182.doc •53· 201234115 MK-8)將實施例3、實施例4及比較例1中獲得之感光性樹脂 組合物旋轉塗佈於6吋矽晶圓上，利用120t之加熱板進行 180秒預烘烤’形成9 μπι之塗膜。膜厚係利用Dainippon Screen製造公司製造之膜厚測定裝置（Lambda acE)測定。 通過附帶測試圖案之光罩使用具有i射線（365 nm)2曝光波 長之Nikon公司製造之步進機（NSR2〇〇5i8A)使曝光量階段 性地變化而對該塗膜進行曝光。使用Az ElectronicResin! M3 The weight average molecular weight measured by GPC is 11,000 in terms of polystyrene. &lt;Micro-shadow evaluation&gt; Using a spin coater manufactured by Tokyo Electron Co., Ltd. (cleantrack 161182.doc •53·201234115 MK-8) The photosensitive resin compositions obtained in Example 3, Example 4, and Comparative Example 1 were spin-coated on a 6-inch wafer, and pre-baked for 180 seconds using a 120-ton hot plate to form 9 μm Coating film. The film thickness was measured by a film thickness measuring device (Lambda acE) manufactured by Dainippon Screen Manufacturing Co., Ltd. The coating film was exposed by stepwise change of the exposure amount by a stepper (NSR2〇〇5i8A) manufactured by Nikon Co., Ltd. having an i-ray (365 nm) 2 exposure wavelength. Use Az Electronic

Materials公司製造之鹼性顯像液（AZ300MIF顯影液，2,38 重量。Z氫氧化四甲基銨水溶液），以顯像時間6〇秒進行顯 像，形成正型凸起圖案。 依照以下評價基準對所得之凸起圖案之微影性進行評 價： A :解析出經700 mJ/cm·2曝光之1〇微米寬之圖案。 B :未解析經700 mJ/cm·2曝光之1〇微米寬之圖案。 &lt;耐熱性評價（軟化點測定）&gt; 依照JIS K2207測定樹脂（p-ii)、樹脂（p_12)及樹脂（ρ·ΐ3) 之軟化點。所使用之裝置為Meitec公司製造之Asp_M2sp。 如以下之表2所示，可知藉由使用本發明之第二態樣之 感光性樹脂組合物，可以適當之顯像時間形成解析圖案， 及本發明之聯苯二基三羥苯樹脂（p_u)與（p_12)由於具有 較先前技術之樹脂（P-13)更高之軟化點，因此具有良好之 耐熱性。 161182.doc •54· 201234115 [表2] &lt;本發明之赛上態樣&gt;Alkaline developing solution (AZ300MIF developer, 2,38 wt. Z aqueous solution of tetramethylammonium hydroxide) manufactured by Materials, was developed at a development time of 6 sec to form a positive convex pattern. The lithography of the obtained convex pattern was evaluated in accordance with the following evaluation criteria: A: A pattern of 1 〇 micron width exposed at 700 mJ/cm·2 was analyzed. B: A pattern of 1 〇 micron width exposed at 700 mJ/cm·2 was not resolved. &lt;Heat resistance evaluation (softening point measurement)&gt; The softening points of the resin (p-ii), the resin (p_12), and the resin (ρ·ΐ3) were measured in accordance with JIS K2207. The device used was Asp_M2sp manufactured by Meitec. As shown in the following Table 2, it is understood that the use of the photosensitive resin composition of the second aspect of the present invention can form an analytical pattern at an appropriate development time, and the biphenyldiyltrihydroxybenzene resin of the present invention (p_u) ) and (p_12) have good heat resistance due to a higher softening point of the resin (P-13) than the prior art. 161182.doc •54· 201234115 [Table 2] &lt;The game aspect of the present invention&gt;

樹脂 微影性 耐熱性(軟化點） 實施例3 Ρ-11 A 170°C 實施例4 Ρ-12 A &gt;170°C 比較例1 Ρ-13 B 114°C 於實鈿例4中，可知於170。〇之前之軟化點測定中未觀測 到軟化點，軟化點為高s17(rc之溫度。 [產業上之可利用性] 本發明之第一態樣之鹼性顯像用感光性酚樹脂組合物可 合適地用作半導體裝置及發光裝置之表面保護膜、層間絕 緣膜、再配線用絕緣膜、倒裝晶片裝置用保護膜、具有凸 塊構造之裝置之保護膜、多層電路之層間絕緣膜、可撓性 銅箔板之蓋層、阻焊膜及液晶配向膜等。 本發月之第一態樣之聯苯二基三罗呈苯樹脂組合物可合適 地用作半導體裝置及發光裝置之表面保護膜、層間絕緣 膜、再配線用絕緣膜、倒裝晶片裝置用保護膜、具有凸塊 構造之裝置之保護臈、多層電路之層間絕緣膜、可撓性銅 羯板之蓋層 '阻焊膜及液晶配向膜等。 【圖式簡單說明】 圖1係表示於本發明之第一態樣中，參考例丨中之酚樹脂 (Ρ-1)之由分子力學法所得之三維結構式之圖，斜線球體部 表示氫原子，砂地球體部表示氧原子，而且白色球體部表 161182.doc •55· 201234115 示碳原子。 圖2係於本發明之第二態樣中，實施例1中合成之樹脂 (P-11)之1H-NMR之測定結果。 圖3係於本發明之第二態樣中，實施例1中合成之樹脂 (P-11)之IR光譜之測定結果。 圖4係於本發明之第二態樣中，實施例2中合成之樹脂 (P-12)之1H-NMR之測定結果。 圖5係於本發明之第二態樣中，實施例2中合成之樹脂 (P-12)之IR光譜之測定結果。 161182.doc -56-Resin lithographic heat resistance (softening point) Example 3 Ρ-11 A 170 ° C Example 4 Ρ-12 A &gt; 170 ° C Comparative Example 1 Ρ-13 B 114 ° C In Example 4, it is known At 170. The softening point was not observed in the softening point measurement before the enthalpy, and the softening point was high s17 (temperature of rc. [Industrial Applicability] The photosensitive phenol resin composition for alkaline imaging of the first aspect of the present invention It can be suitably used as a surface protective film of a semiconductor device and a light-emitting device, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, a protective film of a device having a bump structure, an interlayer insulating film of a multilayer circuit, a cap layer of a flexible copper foil sheet, a solder resist film, a liquid crystal alignment film, etc. The biphenyldiyltriazole-based benzene resin composition of the first aspect of the present month can be suitably used as a semiconductor device and a light-emitting device. Surface protective film, interlayer insulating film, insulating film for rewiring, protective film for flip chip device, protective device for device having bump structure, interlayer insulating film for multilayer circuit, and cap layer of flexible copper plate Solder film, liquid crystal alignment film, etc. [Schematic description of the drawings] Fig. 1 shows a three-dimensional structure obtained by molecular mechanics method of the phenol resin (Ρ-1) in the reference example in the first aspect of the present invention. Figure, slash sphere The hydrogen atom is shown, the body of the sand earth represents an oxygen atom, and the white sphere portion 161182.doc • 55· 201234115 shows a carbon atom. Fig. 2 is a resin synthesized in Example 1 in the second aspect of the invention (P) -11) Results of 1H-NMR measurement. Fig. 3 is a measurement result of IR spectrum of the resin (P-11) synthesized in Example 1 in the second aspect of the present invention. Fig. 4 is a view of the present invention. In the second aspect, the result of 1H-NMR measurement of the resin (P-12) synthesized in Example 2. Fig. 5 is a resin synthesized in Example 2 in the second aspect of the present invention (P-12) The measurement results of the IR spectrum. 161182.doc -56-

Claims (1)

201234115 七、申請專利範圍： 1* 一種驗性顯像用感光性酚樹脂組合物，其包括： 鹼可溶性酚樹脂，其特徵在於： 具有下述通式（1): (1) {式中’ A分別獨立為具有酴性羥基之碟數6〜2 5之2價有 機基’該A之結合鍵存在於具有酚性羥基之芳香環上， 且於該芳香環上亦可存在除羥基以外之取代基；Bi為不 具有紛性經基之碳數1〜丨5之2價有機基；i為1以上且η以 下之整數，而且η為2以上且1，〇〇〇以下之整數}所示之結 構，且藉由利用分子力學法計算該隔著Bi相對之2個Α内 之酚性羥基中之氧原子間的最短距離山而獲得之該山之 平均值（Σφ/η)為9埃（人）以上，且軟化點為1〇〇。〇以上； 感光劑；及 溶劑。 .如求項1之驗性顯像用感光性紛樹脂組合物，其中藉 由使上述驗性顯像用感光性齡樹脂組合物硬化所獲得之 硬化膜之伸長率為15%以上。 3. 如請求項1或2之鹼性顯像用感光性酚樹脂組合物，其中 上述Φ之平均值（Σί1ί/η)為1〇埃（人）以上。 4. 如請求項1至3中任一項之鹼性顯像用感光性酚樹脂組合 物’其中上述Bj係由下述通式: -X-L-Y-M-Z- ⑺ {式中，L及Μ為不具有酚性羥基且可具有除酚性羥基以 161182.doc 201234115 外之取代基的碳數6〜10之2價芳香族基，而且χ、γ及Z 為選自由單鍵、碳數之脂肪族鏈、醯胺基、羰基、 醋基、脲基、胺基曱酸酯基、醚基及硫醚基所組成之群 中之2價基}所示。 5. 如s青求項1至4中任一項之驗性顯像用感光性驗樹脂組合 物’其中上述A具有2〜3個驗性經基。 6. 如凊求項1至5中任一項之驗性顯像用感光性龄樹脂組合 物’其進而含有交聯劑。 7. —種硬化凸起圖案之製造方法，其包括： 將如請求項1至6中任一項之鹼性顯像用感光性酚樹脂 組合物塗佈於基板上之步驟；對該鹼性顯像用感光性酚 樹脂組合物進行曝光之步驟；對經曝光之鹼性顯像用感 光性酚樹脂組合物進行顯像而形成凸起圖案之步驟；及 對該凸起圖案進行加熱而形成硬化凸起圓案之步驟。 8. 一種半導體裝置，其係具有藉由如請求項7之製造方法 所獲得之硬化凸起圖案而形成。 9_ 一種聯苯二基三羥苯樹脂，其係由下述通式（丨）： [化1]201234115 VII. Patent application scope: 1* A photosensitive phenol resin composition for qualitative imaging, comprising: an alkali-soluble phenol resin having the following general formula (1): (1) {wherein' A is independently a divalent organic group having 6 to 2 5 of a disc having a hydrophobic hydroxyl group. The bonding bond of the A is present on an aromatic ring having a phenolic hydroxyl group, and a hydroxyl group may be present on the aromatic ring. a substituent; Bi is a divalent organic group having a carbon number of 1 to 5 without a hetero group; i is an integer of 1 or more and η or less, and η is 2 or more and 1 is an integer below }} The structure shown, and the average value (Σφ/η) of the mountain obtained by calculating the shortest distance between the oxygen atoms in the phenolic hydroxyl groups in the two bismuths relative to each other by the molecular mechanics method is 9 Above ang (man), and the softening point is 1 〇〇. 〇 Above; sensitizer; and solvent. The photosensitive resin composition for an inspective imaging of claim 1, wherein the cured film obtained by curing the photosensitive resin composition for use in the above-mentioned test development has an elongation of 15% or more. 3. The photosensitive phenol resin composition for alkaline development according to claim 1 or 2, wherein the average value of Φ (Σί1ί/η) is 1 Å or more. 4. The photosensitive phenol resin composition for alkaline development according to any one of claims 1 to 3, wherein the above Bj is represented by the following formula: -XLYMZ- (7) {wherein, L and oxime are not phenolic a hydroxyl group and may have a divalent aromatic group having a carbon number of 6 to 10 in addition to a phenolic hydroxyl group having a substituent other than 161182.doc 201234115, and χ, γ, and Z are selected from a single bond, a carbon number aliphatic chain, The divalent group in the group consisting of amidino group, a carbonyl group, a acetoxy group, a urea group, an amino phthalate group, an ether group, and a thioether group is shown. 5. The photosensitive resin composition for verification imaging according to any one of items 1 to 4, wherein the above A has 2 to 3 tester radicals. 6. The photosensitive age-sensitive resin composition for inspective imaging according to any one of claims 1 to 5, which further contains a crosslinking agent. 7. A method of producing a hardened convex pattern, comprising: a step of applying a photosensitive phenol resin composition for alkaline development according to any one of claims 1 to 6 to a substrate; a step of exposing the photosensitive phenol resin composition for development; developing a photosensitive phenol resin composition for exposure to develop a convex pattern; and forming the convex pattern by heating The step of hardening the convex round case. A semiconductor device comprising the hardened bump pattern obtained by the manufacturing method of claim 7. 9_ A biphenyldiyltrihydroxybenzene resin which is represented by the following formula (丨): [Chemical Formula 1] {式中，R1為下述通式（2): 161182.doc (2) 201234115 [化2]{wherein, R1 is the following general formula (2): 161182.doc (2) 201234115 [Chemical 2] (式中，R3為甲基或乙基，而且，p與q分別獨立為0〜4之 整數）所示之聯苯二基’ R2為選自氫、甲基及乙基中之 基，而且η為2〜150之整數}所示。 10-如請求項9之聯苯二基三羥苯樹脂，其中上述通式（1)為 下述通式（3): [化3](wherein, R3 is a methyl group or an ethyl group, and p and q are each independently an integer of 0 to 4), and the biphenyldiyl group 'R2 is a group selected from the group consisting of hydrogen, a methyl group and an ethyl group, and η is an integer of 2 to 150}. 10. The biphenyldiyltrihydroxybenzene resin according to claim 9, wherein the above formula (1) is the following formula (3): [Chemical 3] (3) {式中，R1及η與上述通式（1)中定義者相同}或下述通式 (4)： [化4](3) where R1 and η are the same as defined in the above formula (1)} or the following formula (4): [Chemical 4] (4) (式中汉及η與上述通式（1)中定義者相同丨所示。 請求項9或10之聯笨二基三羥 ⑺係由下述式（5): 这通式 161182.doc 201234115 [化5] —Η2〇(4) (wherein and η are the same as those defined in the above formula (1). The bismuth-trihydroxyl (7) of claim 9 or 10 is represented by the following formula (5): .doc 201234115 [化5] —Η2〇 CH2- (5) 所示。 12.如請求項9至丨1中任一項之聯苯二基三羥笨樹脂，其中 上述式（5)係由下述式（6): [化6] CH2— ( 6 ) 所示。 13. —種如請求項9至12中任一項之聯苯二基三羥苯樹脂之 製造方法，其包括以下步驟： 將下述通式（7): [化7]CH2- (5) is shown. The biphenyldiyltrihydroxybenzene resin according to any one of claims 9 to 1, wherein the above formula (5) is represented by the following formula (6): [Chem. 6] CH2 - (6). A method for producing a biphenyldiyltrihydroxybenzene resin according to any one of claims 9 to 12, which comprises the following steps: The following general formula (7): [Chemical 7] {式中，R2為選自氫、甲基及乙基中之基}所示之化合 物、與下述通式（8)= [化8]In the formula, R2 is a compound represented by a group selected from the group consisting of hydrogen, a methyl group and an ethyl group, and the following formula (8) = [Chemical 8] 161182.doc -4- 201234115 {式中，R3為甲基或乙基，{)與£1分別獨立為〇〜4之整數， 而且R4為選自由函素原子、羥基及碳數卜1〇之可具有不 飽和鍵之院氧基所組成之群中之基}所示之化合物以5 : 1〜1 : 5之莫耳比進行混合，進而添加觸媒之步驟 於60 C以上加熱1分鐘〜48小時之步驟。 及 14· 一種感光性樹脂組合物，其特徵在於含有如請求項9至 12中任一項之聯苯二基三羥苯樹脂或藉由如請求項Η之 製造方法所獲得之樹脂及感光劑。 15.如請求項14之感光性樹脂組合物，μ上述感光劑為光 酸產生劑。 16. 如請求項14之正型感光性樹脂組合物，其中上述感光劑 為蔡酿一疊氣化合物。 17. —種半導體裝置之製造方法，其包括以下步驟： 於半導體基板上形成包含如請求項14至16中任一項之 感光性樹脂組合物之感光性樹脂層之步驟； 利用活性光線對該感光性樹脂層進行曝光之步驟； 對該經曝光之感光性樹脂層進行顯像而獲得凸起圖案 之步驟；及 對所得之凸起圖案進行加熱之步驟。 18. —種半導體裝置，其係藉由如請求項口之方法而製造。 161182.doc161182.doc -4- 201234115 {wherein, R3 is a methyl group or an ethyl group, {) and £1 are each independently an integer of 〇~4, and R4 is selected from a functional atom, a hydroxyl group, and a carbon number. The compound represented by the group of the group having the unsaturated bond may be mixed at a molar ratio of 5:1 to 1:5, and further heated at 60 C or more for 1 minute by adding a catalyst. 48 hours step. And a photosensitive resin composition characterized by containing the biphenyldiyltrihydroxybenzene resin according to any one of claims 9 to 12 or a resin and a sensitizer obtained by the production method of the claim . The photosensitive resin composition of claim 14, wherein the photosensitive agent is a photoacid generator. 16. The positive-type photosensitive resin composition of claim 14, wherein the sensitizer is a co-duct gas compound. 17. A method of manufacturing a semiconductor device, comprising the steps of: forming a photosensitive resin layer comprising the photosensitive resin composition according to any one of claims 14 to 16 on a semiconductor substrate; a step of exposing the photosensitive resin layer; a step of developing the exposed photosensitive resin layer to obtain a raised pattern; and a step of heating the obtained raised pattern. 18. A semiconductor device manufactured by the method of claiming a port. 161182.doc
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