TWI323251B

TWI323251B - New compound, acid genelator, chemically amplified photoresist composition, resist laminate, and process for forming resist pattern

Info

Publication number: TWI323251B
Application number: TW95138227A
Authority: TW
Inventors: Koji Saito; Hideo Hada; Yasushi Washio
Original assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2005-10-19
Filing date: 2006-10-17
Publication date: 2010-04-11
Also published as: WO2007046442A1; TW200728264A

Description

1323251 (1) 九、發明說明【發明所屬之技術領域】本發明係關於一種新穎化合物、酸產生劑、型（Chemically amplified)光阻組成物、光阻層 _ 光阻圖型之形成方法。本案係依據2005年10月19日於曰本所申 2005-303926號及2005年10月19日於日本所願2005-304123號，主張優先權，於此處引用容。【先前技術】 • 目前，成爲精密微細加工技術之主流的光加 . 阻等之感光性樹脂組成物塗布於加工物表面以形藉光微顯蝕刻技術而塗膜圖型化，以此作爲掩罩學蝕刻、電解蝕刻及/或以電鍍作爲主體之電鑄 _ 半導體封裝體等之各種精密零件的技術總稱。近年，隨著電子機器之小型化，半導體封裝度封裝技術進展，謀求封裝體之多插腳薄瞑封裝體尺寸之小型化、依覆晶方式之2次元封裝技術次元封裝技術的封裝密度之提升。在如此之高密術中，就連接端子而言，例如，突出於封裝體上的突起電極（封裝端子）、或從晶圓上之週邊端再配線與封裝端子連接之金屬柱等被高精度地配上。增強化學層合體及請之特願申請之特其等之內工係將光成塗膜，而進行化，而製造體之高密化、封裝、依據3 度封裝技之凸塊等子延伸的置於基板 -6 - (2) 1323251 連接端子之形成係例如於支撐體上形成由光阻所構成之光阻層，介由特定之掩罩圖型而進行曝光，顯像，形成選擇性地除去（剝離）欲形成連接端子之部分的光阻圖型後，於此所除去之部分（非光阻部）藉電鍍而埋入銅等之 '導體，可藉由除去其周圍之光阻圖型來進行。現在，在連接端子之形成中，光阻圖型之形成主要係使用例如專利文獻1〜3所記載的光聚合性之感光性樹脂組成物作爲光阻，於曝光使用3 65nm以上之長波長區域的光例如 g 線（436nm) 、h 線（405nm) 、i 線（365nm) 等的紫外線區域之光而實施。另外，可使微細尺寸之光阻圖型再現的高解析性之光阻材料之一，已知有增強化學型光阻組成物，其係含有藉 . 酸之作用鹼溶解性進行變化之基材樹脂、及藉輻射線照射 (曝光）產生酸之化合物（酸產生劑）。增強化學型光阻之特徵係酸產生劑吸收所照射之輻射 €9 線而產生酸，從酸產生劑所產生之酸對於光阻中之基材樹脂等引起酸觸媒反應，使其鹼溶解性變化》於增強化學型光阻中係有：藉輻射線照射，鹼不溶性者進行鹼可溶化之正型、與鹼可溶者進行鹼不溶化之負型。於增強化學型光阻所使用之酸產生劑，係已有：硫鑰鹽系酸產生劑、碘鏺鹽系酸產生劑等之鎗鹽系酸產生劑或、肟磺酸酯系酸產生劑'醯亞胺磺酸酯系酸產生劑等各種提案。此等之中，鎰鹽系酸產生劑係因在使用波長短於 i線區域之輻射線、例如KrF準分子雷射（248nm )或 (3) 13232511323251 (1) Description of the Invention [Technical Field] The present invention relates to a novel compound, an acid generator, a chemically amplified photoresist composition, and a photoresist layer _ photoresist pattern formation method. The case is based on the Japanese Patent Application No. 2005-303926, issued on October 19, 2005, and the Japanese Patent Application No. 2005-304123, filed on Oct. 19, 2005. [Prior Art] At present, the photosensitive resin composition, which is the mainstream of precision microfabrication technology, is coated on the surface of the workpiece to form a pattern by photo-exposed etching technology. A general term for the technology of various precision parts such as etch etching, electrolytic etching, and/or electroforming, such as electroplating. In recent years, with the miniaturization of electronic devices, semiconductor package packaging technology has progressed, and the size of the package has been reduced by the size of the multi-pin thin package, and the package density of the sub-package technology of the flip chip technology has been improved. In such a high-density technique, for example, a bump electrode (package terminal) protruding from the package or a metal post connected to the package terminal from the peripheral end of the wafer is highly accurately matched. on. The reinforced chemical laminates and the special internals of the company are required to apply the film to the film, and the high density, package, and the extension of the bumps according to the 3 degree package technology. Forming the substrate -6 - (2) 1323251 The connection terminal is formed, for example, by forming a photoresist layer composed of a photoresist on the support, exposing it through a specific mask pattern, and developing the image to form a selective removal. (Peeling) After forming a photoresist pattern of a portion of the connection terminal, the portion (non-resistance portion) removed therefrom is buried by electroplating and the conductor of copper or the like can be removed by removing the photoresist pattern around it. Come on. In the formation of the connection terminal, the formation of the photoresist pattern is mainly performed by using, for example, a photopolymerizable photosensitive resin composition described in Patent Documents 1 to 3 as a photoresist, and a long wavelength region of 3 65 nm or more for exposure. The light is applied, for example, to light in an ultraviolet region such as g line (436 nm), h line (405 nm), or i line (365 nm). Further, one of the high-resolution photoresist materials which can reproduce a fine-grained photoresist pattern is known as a reinforced chemical-type photoresist composition which contains a substrate which changes in alkali solubility by an acid action. A resin, and an acid generating agent (acid generator) which is irradiated (exposed) by radiation. The characteristic of the enhanced chemical type resist is that the acid generator absorbs the irradiated radiation of the line 9 to generate an acid, and the acid generated from the acid generator causes an acid catalyst reaction to the substrate resin in the photoresist to cause the alkali to dissolve. In the enhanced chemical type photoresist, there are: a negative type in which an alkali-insoluble type is subjected to alkali solubilization and an alkali-insoluble type is insolubilized by alkali irradiation. The acid generator used for enhancing the chemical resist is a gun salt acid generator or an sulfonate acid generator which is a sulfuryl salt acid generator or an iodonium salt generator. Various proposals such as 'an imiline sulfonate acid generator. Among these, the strontium salt acid generator is due to the use of radiation having a wavelength shorter than the i-line region, such as KrF excimer laser (248 nm) or (3) 1323251.

ArF準分子雷射（193 nm )等之光微顯蝕刻而感度優，故目前一般最常使用。 [專利文獻1]特開平1 0-20705 7號公報 [專利文獻2]特開2000-39709號公報 [專利文獻3]特開2000-663 86號公報【發明內容】ArF excimer laser (193 nm) and other light micro-etching are excellent in sensitivity, so they are generally used most often. [Patent Document 1] JP-A-2000-39709 [Patent Document 3] JP-A-2000-663

(發明之揭示） (發明欲解決之問題）但，鑰鹽系酸產生劑係在3 65nm以上之長波長區域幾乎不吸收。因此，在3 65nm以上之長波長區域中之光加工中，使用鑰鹽系酸產生劑之增強化學型光阻係感度低，目前實質上無法利用。又，鑰鹽系酸產生劑之陽離子一般係可使用三苯基硫鑰等之疏水性高的陽離子，但具有如此之陽離子之鑰鹽系酸產生劑，對於用以溶解光阻之各種成分所使用的有機溶劑（光阻溶劑）之溶解性低之問題仍存在。對如此之光阻溶劑的溶解性低，係使光阻之隨時間安定性降低，伴隨其而產生光阻圖型形狀之惡化等。因此，在365 nm以上之長波長區域中之光加工中，實質上以鑰鹽系酸產生劑作爲酸產生劑之增強化學型光阻係目前仍無法利用》本發明係有鑑於上述事情而構成者，目的在於提供一種在 3 65nm以上之長波長區域中顯示高的吸收，在 -8 - (4) 1323251 3 6 5nm以上之長波長區域中之感度高’對有機溶劑之溶解性亦優之化合物、由該化合物所構成之酸產生劑、含有該酸產生劑之增強化學型光阻組成物、使用該增強化學型光阻組成物之光阻層層合體及光阻圖型形成方法。 '又，本發明之另一目的在於提供一種含有硫鎗鹽系酸產生劑作爲酸產生劑，且在3 65 nm以上之長波長區域中之感度高的增強化學型光阻組成物、使用該增強化學型光 φφ 阻組成物之光阻層層合體及光阻圖型形成方法。 (用以解決問題之手段）本發明人等專心硏究之結果，發現藉由具有特定之構 • 造的化合物可解決上述課題，終完成本發明。 . 亦即，本發明之第一態樣（a first aspect)係以下述通式（B1)所示之化合物。(Disclosure of the Invention) (The problem to be solved by the invention) However, the key salt acid generator is hardly absorbed in a long wavelength region of 3 65 nm or more. Therefore, in the optical processing in the long wavelength region of 3 65 nm or more, the enhanced chemical type resist using the key salt acid generator has a low sensitivity and is currently substantially unusable. Further, the cation of the key salt-based acid generator is generally a cation having a high hydrophobicity such as a triphenylsulfide, but a cation-based key acid generator having such a cation is used for various components for dissolving the photoresist. The problem of low solubility of the organic solvent (photoresist solvent) used still exists. The solubility in such a photoresist is low, and the stability of the photoresist with time is lowered, which causes deterioration of the shape of the photoresist pattern. Therefore, in the optical processing in the long wavelength region of 365 nm or more, the reinforced chemical resist system which substantially uses the key salt acid generator as the acid generator is still not available at present. The purpose is to provide a high absorption in a long wavelength region of 3 65 nm or more, and a high sensitivity in a long wavelength region of -8 - (4) 1323251 3 6 5 nm or more - excellent solubility in an organic solvent. A compound, an acid generator comprising the compound, a reinforced chemical resist composition containing the acid generator, a photoresist layer laminate using the reinforced chemical resist composition, and a photoresist pattern forming method. Further, another object of the present invention is to provide a reinforced chemical type resist composition containing a sulphur gun salt acid generator as an acid generator and having a high sensitivity in a long wavelength region of 3 65 nm or more, and using the same A photoresist layer laminate and a photoresist pattern forming method for enhancing a chemical type light φφ resistive composition. (Means for Solving the Problems) As a result of intensive studies by the present inventors, it has been found that the above problems can be solved by a compound having a specific structure, and the present invention has been completed. That is, the first aspect of the present invention is a compound represented by the following formula (B1).

[化1] R2—S+[Chemical 1] R2—S+

X (B1) [式（B1)中，R1、R2、R3係分別獨立地以下述通式 (B la)所示之基、烷基、或從芳香環除去一個氫原子之基’該芳香環亦可具有取代基，且R1、R2、R3之中至少一個係以下述通式（B la)所示之基，X-爲陰離子] -9- (5)1323251 [化2] Ο •一γ—c—Z (813)X (B1) [In the formula (B1), R1, R2, and R3 are each independently a group represented by the following formula (B la), an alkyl group, or a group in which one hydrogen atom is removed from the aromatic ring. Further, it may have a substituent, and at least one of R1, R2, and R3 is a group represented by the following formula (B la), and X- is an anion] -9-(5)1323251 [Chemical 2] Ο • γ —c—Z (813)

[式（B1 a)中，Y係從芳香環除去二個氫原子之基，該芳香環係亦可具有取代基；Z係從芳香環除去一個氫原子之基，該芳香環係亦可具有取代基；Y及z之中至少一者的芳香環爲至少具有一個烷氧基] 本發明之第二態樣（a second aspect)係由第一態樣之化合物所構成的酸產生劑。本發明之第三態樣（a third aspect )係一種增強化學型光阻組成物，其係含有U)藉酸使鹼溶解性變化之樹脂、及（b)藉輻射線照射產生酸之化合物，其特徵在於：該（b)藉輻射線照射產生酸之化合物含有第二態樣之酸產生劑。[In the formula (B1 a), Y is a group which removes two hydrogen atoms from an aromatic ring, and the aromatic ring system may have a substituent; Z is a group which removes one hydrogen atom from the aromatic ring, and the aromatic ring system may have a substituent; at least one of Y and z has at least one alkoxy group] The second aspect of the invention is an acid generator composed of the first aspect of the compound. The third aspect of the present invention is a reinforced chemical type resist composition comprising U) a resin which changes the solubility of an alkali by an acid, and (b) a compound which generates an acid by irradiation with a radiation. It is characterized in that: (b) the compound which generates an acid by irradiation with radiation contains a second aspect of the acid generator.

本發明之第四態樣（a fourth aspect)係一種光阻層層合體，其特徵在於：於支撐體上層合由第三態樣之增強化學型光阻組成物所構成之光阻層。本發明之第五態樣（a fifth aspect)係一種光阻圖型之形成方法，其特徵在於含有：於支撐體上層合由增強化學型光阻組成物所構成之光阻層而得到第四態樣之光阻層層合體之層合步驟、與對光阻層層合體選擇性地照射輻射線之曝光步驟、及於該曝光步驟後進行顯像而得到光阻圖型之顯像步驟。 -10- (6) 1323251 本發明之第六態樣（a sixth aspect)係一種增強化學型光阻組成物，其係含有（a)藉酸使鹼溶解性變化之樹脂、及（b)藉輻射線照射產生酸之化合物、及（c)以下述通式（C1)所示之化合物，該（b)藉輻射線照射產生酸之化合物含有硫鎗鹽系酸產生劑（b - 1)，A fourth aspect of the present invention is a photoresist layer laminate characterized in that a photoresist layer composed of a third-type reinforced chemical resist composition is laminated on a support. A fifth aspect of the present invention is a method for forming a photoresist pattern, characterized in that the photo-resist layer composed of a reinforced chemical resist composition is laminated on a support to obtain a fourth The step of laminating the photoresist layer of the aspect, the step of exposing the radiation to the photoresist layer selectively, and the developing step after the exposing step to obtain a resist pattern of the photoresist pattern. -10- (6) 1323251 The sixth aspect of the present invention (a sixth aspect) is a reinforced chemical type photoresist composition comprising (a) a resin which changes the solubility of an alkali by an acid, and (b) Radiation illuminating the compound which produces an acid, and (c) a compound represented by the following formula (C1), wherein (b) the compound which generates an acid by irradiation with a radiation contains a sulphur gun-based acid generator (b-1),

[式中，R1及R2係碳數1〜4之烷基，且rLr2]。[wherein, R1 and R2 are an alkyl group having 1 to 4 carbon atoms, and rLr2].

又本發明之第七態樣（ a seventh aspect )係一種光阻層層合體，其特徵在於：於支撐體上層合由第六態樣的增強化學型光阻組成物所構成之光阻層。本發明之第八態樣（a eighth aspect)係一種光阻圖型之形成方法，其特徵在於含有：於支撐體上層合由增強化學型光阻組成物所構成之光阻層而得到第七態樣之光阻層層合體之層合步驟、與對光阻層層合體選擇性地照射輻射線之曝光步驟、及於該曝光步驟後進行顯像而得到光阻圖型之顯像步驟。 (發明之效果） -11 - (7) 1323251 若依本發明，可提供一種在3 65nm以上之長波長區域中顯示高的吸收，在3 65nm以上之長波長區域中之感度高，對有機溶劑之溶解性亦優之化合物、由該化合物所構成之酸產生劑、含有該酸產生劑之增強化學型光阻組成 _ 物、使用該增強化學型光阻組成物之光阻層層合體及光阻圖型形成方法。又，若依本發明，可提供一種含有硫鑰鹽系酸產生劑作爲酸產生劑，且在3 6 5nm以上之長波長區域中之感度高的增強化學型光阻組成物、使用該增強化學型光阻組成物之光阻層層合體及光阻圖型形成方法。 ' (用以實施發明之最佳形態） - 以下詳細說明本發明。 <化合物>Further, a seventh aspect of the present invention is a photoresist layer laminate characterized in that a photoresist layer composed of a sixth-type enhanced chemical type photoresist composition is laminated on a support. The eighth aspect of the present invention is a method for forming a photoresist pattern, characterized by comprising: laminating a photoresist layer composed of a reinforced chemical resist composition on a support to obtain a seventh The step of laminating the photoresist layer of the aspect, the step of exposing the radiation to the photoresist layer selectively, and the developing step after the exposing step to obtain a resist pattern of the photoresist pattern. (Effects of the Invention) -11 - (7) 1323251 According to the present invention, it is possible to provide a high absorption in a long wavelength region of 3 65 nm or more, a high sensitivity in a long wavelength region of 3 65 nm or more, and an organic solvent. a compound having excellent solubility, an acid generator composed of the compound, a reinforced chemical resist composition containing the acid generator, a photoresist layer laminate using the reinforced chemical resist composition, and light Resistance pattern formation method. Further, according to the present invention, it is possible to provide a reinforced chemical type resist composition containing a sulphuric acid generator as an acid generator and having a high sensitivity in a long wavelength region of 365 nm or more, and using the enhanced chemistry A photoresist layer laminate of a photoresist composition and a photoresist pattern forming method. '(Best form for carrying out the invention) - The present invention will be described in detail below. <Compound>

本發明之第一態樣之化合物（以下有時稱爲化合物 (B1))係以上述通式（B1)所示。式（B1)中，R1、R2、R3係分別獨立地以下述通式（Bla) 所示之基、烷基、或從芳香環除去一個氫原子之基。「從芳香環除去一個氫原子之基」中，該芳香環亦可具有取代基。在本發明中R1、R2、R3之中至少一個係必須以下述通式（Bla)所示之基，X’爲陰離子]。藉由具有以式（Bla) 所示之基，化合物（B1 )在3 6 5nm以上之長波長區域 -12- (8) 1323251 中，使用來作爲酸產生劑顯示充分的吸收。式（B1)中，Y及Z中之芳香環並無特別限定，而可舉例如碳數爲6〜1 8之芳香環例如苯、萘等。在本發明中，在Y及Z之中至少一者的芳香環必須至少具有一個烷氧基作爲取代基。尤其，Y及Z中之芳香環的兩者宜具有烷氧基。烷氧基係以R-〇-[R爲直鏈狀、分枝狀或環狀之烷基] φφ 所示。R並無特別限定，但宜爲直鏈狀或分枝狀之烷基，更宜爲直鏈狀之烷基。烷基之碳數宜爲1〜12，更宜爲 1〜4。具體上，可舉例如甲氧基、乙氧基、丙氧基、丁氧基等。結合於芳香環之烷氧基的數目並無特別限定，爲本發 . 明之效果宜爲1〜3，尤宜爲1。 Υ及Ζ中之芳香環係亦可具有烷氧基以外之取代基。烷氧基以外之取代基可舉例如烷基、羥基等。該烷基，並 9Φ 無特別限定，可舉例如碳數1~12之直鏈狀、分枝狀或環狀之院基。 R^R3之「烷基J係無特別限定，可舉例如碳數卜12 之直鏈狀、分枝狀或環狀之烷基。具體上，可舉例如甲基、乙基、正丙基、異丙基、正丁基、異丁基、正戊基、環戊基、己基、環己基、壬基、癸基等。在R^R3之「從芳香環除去一個氫原子之基」中之芳香環，無特別限定，可舉例如碳數爲6〜1 8之芳香環、例如苯、萘、蔥等。R1〜R3中之芳香環係與上述X及Y中之 -13- (9) 1323251 芳香環同樣，亦可具有烷氧基、烷基、羥基等之取代基。在本發明中，「從芳香環除去一個氫原子之基」中之芳香環，爲從苯或萘除去一個氫原子之基、亦即，更宜爲苯基或萘基，最宜爲苯基。式（B1)中，X·爲陰離子。X·係無特別限定，亦可爲提出來作爲在習知增強化學型光阻組成物中所使用的公知之酸產生劑的陰離子之任意者。The compound of the first aspect of the present invention (hereinafter sometimes referred to as the compound (B1)) is represented by the above formula (B1). In the formula (B1), R1, R2 and R3 are each independently a group represented by the following formula (Bla), an alkyl group or a group in which one hydrogen atom is removed from the aromatic ring. In the "group of a hydrogen atom removed from the aromatic ring", the aromatic ring may have a substituent. In the present invention, at least one of R1, R2 and R3 must be a group represented by the following formula (Bla), and X' is an anion]. By having a group represented by the formula (Bla), the compound (B1) is used in the long-wavelength region -12-(8) 1323251 of 365 nm or more, and is used as an acid generator to exhibit sufficient absorption. In the formula (B1), the aromatic ring in Y and Z is not particularly limited, and examples thereof include an aromatic ring having a carbon number of 6 to 18, such as benzene or naphthalene. In the present invention, at least one of Y and Z must have at least one alkoxy group as a substituent. In particular, both of the aromatic rings in Y and Z preferably have an alkoxy group. The alkoxy group is represented by R-〇-[R is a linear, branched or cyclic alkyl group] φφ. R is not particularly limited, but is preferably a linear or branched alkyl group, more preferably a linear alkyl group. The carbon number of the alkyl group is preferably from 1 to 12, more preferably from 1 to 4. Specifically, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group or the like can be mentioned. The number of the alkoxy groups bonded to the aromatic ring is not particularly limited, and the effect of the present invention is preferably from 1 to 3, particularly preferably 1. The aromatic ring system in ruthenium and osmium may also have a substituent other than an alkoxy group. The substituent other than the alkoxy group may, for example, be an alkyl group or a hydroxyl group. The alkyl group and 9Φ are not particularly limited, and examples thereof include a linear, branched or cyclic group having a carbon number of 1 to 12. The alkyl group of R^R3 is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having a carbon number of 12, and specific examples thereof include a methyl group, an ethyl group, and a n-propyl group. , isopropyl, n-butyl, isobutyl, n-pentyl, cyclopentyl, hexyl, cyclohexyl, decyl, decyl, etc. In R^R3, "the base of a hydrogen atom is removed from the aromatic ring" The aromatic ring is not particularly limited, and examples thereof include an aromatic ring having a carbon number of 6 to 18, such as benzene, naphthalene or onion. The aromatic ring in R1 to R3 may have a substituent such as an alkoxy group, an alkyl group or a hydroxyl group, similarly to the -13-(9) 1323251 aromatic ring in the above X and Y. In the present invention, the aromatic ring in the "group of one hydrogen atom removed from the aromatic ring" is a group which removes one hydrogen atom from benzene or naphthalene, that is, preferably a phenyl group or a naphthyl group, and most preferably a phenyl group. . In the formula (B1), X· is an anion. The X· is not particularly limited, and may be any of the anions of the known acid generator used in the conventional enhanced chemical resist composition.

在本發明中，尤其，X·宜爲其烷基的氫原子之至少— 個被氟原子取代之氟化烷基磺酸離子，尤其，其烷基的氫原子之全部爲被氟原子取代之全氟烷基磺酸離子。氟化烷基磺酸離子之烷基的碳數，無特別限定，但就 • 所產生之酸的總體高與酸之擴散長而言，宜爲1〜12，更宜爲1~4。在本發明中，因本發明之效果優，故rLr3之中的一個爲以通式（Bla)所示之基，在R1〜R3之中的2個爲從 49 芳香環除去一個氫原子之基，尤宜爲苯基。化合物（B 1 )尤其宜以下述通式（B2 )所示之化合物，本發明之效果優，佳。 [化3]In the present invention, in particular, X is preferably a fluorinated alkylsulfonic acid ion of at least one of the hydrogen atoms of the alkyl group, and in particular, all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms. Perfluoroalkylsulfonate ion. The carbon number of the alkyl group of the fluorinated alkylsulfonic acid ion is not particularly limited, but it is preferably from 1 to 12, more preferably from 1 to 4, in terms of the total height of the acid produced and the long diffusion of the acid. In the present invention, since the effect of the present invention is excellent, one of rLr3 is a group represented by the general formula (Bla), and two of R1 to R3 are groups for removing one hydrogen atom from the 49 aromatic ring. Especially suitable for phenyl. The compound (B 1 ) is particularly preferably a compound represented by the following formula (B2), and the effects of the present invention are excellent. [Chemical 3]

X (B2) (10) 1323251 [式（B2 )中，R4、R5係分別獨主地爲烷基、苯基或萘基；R6、R7係分別獨主地爲烷氧基；X·爲陰離子] 式（B2 )中，R4、R5之烷基，係可舉例如與上述相同者作爲RLR3中之烷基。r4、r5之苯基或萘基亦可具有烷氧基、烷基、羥基等之取代基，亦可不具有。 R6及R7中之烷氧基，係可舉例如與舉出作爲Y及Z 中之芳香環的取代基之烷氧基同樣者。R6之烷氧基與R7 φφ 之烷氧基可分別爲相同亦可爲相異。 X‘係與上述相同。本發明之化合物（Β 1 )之較佳的一例，可舉例如以下述式（Β3)所示之化合物。 ' [化 4] h3coX (B2) (10) 1323251 [In the formula (B2), R4 and R5 are each independently alkyl, phenyl or naphthyl; R6 and R7 are each independently alkoxy; X is an anion In the formula (B2), the alkyl group of R4 and R5 may, for example, be the same as the above as the alkyl group in RLR3. The phenyl or naphthyl group of r4 or r5 may have a substituent such as an alkoxy group, an alkyl group or a hydroxyl group, and may or may not be. The alkoxy group in R6 and R7 is, for example, the same as the alkoxy group which is a substituent of the aromatic ring in Y and Z. The alkoxy group of R6 and the alkoxy group of R7 φφ may be the same or different. X' is the same as above. A preferred example of the compound (Β 1 ) of the present invention is a compound represented by the following formula (Β3). '[4] h3co

och3 上述本發明之化合物（Β1)係可適宜使用來作爲增強化學型光阻組成物、尤其365nm以上之波長的輻射線用之增強化學型光阻組成物用之酸產生劑。 (酸產生劑〉本態樣之第二態樣的酸產生劑（以下’有時稱爲酸產生劑（bl ))係由上述第一態樣的化合物（Β 1 )所構成 -15- (11) 1323251 者。酸產生劑（b〇係可由上述化合物（B 所構成，亦可由化合物（B1)之2種以』成。《增強化學型光阻組成物》本態樣之第三態樣的增強化學型光阻i φφ (a)藉酸使鹼溶解性變化之樹脂（以下，成分）、及（b)藉輻射線照射產生酸之化^ 時稱爲（b)成分），其特徵在於：該（b) 本發明之酸產生劑（bl)，可爲負型亦可：! ' 以下，說明負型之情形的例。 - (a)成分增強化學型光阻組成物爲負型時，（使鹼溶解性降低之樹脂，若爲一般可使用司 ·· 強化學型光阻的基材樹脂之樹脂即可，無年使用於曝光之光源，而可從以往公知者任用。例如，以酚醛清漆樹脂作爲主成分者g 故一般被廣泛地使用。特別佳之（a )成分係可例示（I )酣 (Π)—種以上之樹脂選自具有羥基苯乙持合物所構成者。故此係可很容易地控制塗度。 (I)酚醛清漆樹脂（以下，稱爲（I) 1 )之一種單獨 .的混合物所構成物係係含有有時稱爲（a ) 物（以下，有成分含有上述正型。 a )成分係藉酸 5作爲負型之增 Ϊ別限定，依照意地選擇而使自其特性良好，醛清漆樹脂、 &構成單元之聚布性、顯像速成分）係可藉 -16- (12) 1323251 由使例如具有酚性羥基之芳香族化合物（以下，僅稱爲「酚類」）與醛類在酸觸媒下加成縮合而得到。此時，所使用之酚類可舉例如酚、鄰甲酚、間甲酚、對甲酚、鄰乙基酚、間乙基酚、對乙基酚、鄰丁基酚、間丁基酚、對丁基酚、2,3-二甲基酚、2,4-二甲基酚'2,5· 二甲基酚、2，6-二甲基酚、3，4-二甲基酚、3,5-二甲基酚、2,3,5-三甲基酚、3,4,5-三甲基酚、對-苯基酚 '間苯 φφ 二酚、氫醌、氫醌單甲基醚' 苯三酚、氟胺基乙醇、羥基二苯基、雙酚A、沒食子酸、沒食子酸酯、α-萘酚、/5- 萘酚等》又，醛類可舉例如甲醛、糠醛、苯醛、硝基苯醛、乙醛等。加成縮合反應時之觸媒，無特別限定，但例如在酸觸媒中，可使用鹽酸、硝酸、硫酸、蟻酸、藻酸、醋酸等。Och3 The above-mentioned compound (Β1) of the present invention can be suitably used as an acid generator for a chemical-resistant resist composition for reinforcing a chemical-type photoresist composition, particularly a radiation having a wavelength of 365 nm or more. (Acid generator> The second aspect of the acid generator of the present aspect (hereinafter referred to as "acid generator (bl)) is composed of the first aspect of the compound (Β 1 ) -15- (11) 1323251. An acid generator (b〇 can be composed of the above compound (B or two of the compounds (B1).) Enhanced chemical resist composition. Enhancement of the third aspect of this aspect. The chemical type resist i φφ (a) is a resin (hereinafter, a component) which changes the solubility of an alkali by an acid, and (b) is a component (b) when it is irradiated with radiation to generate an acid, and is characterized by: (b) The acid generator (bl) of the present invention may be of a negative type: ! ' Hereinafter, an example of a negative type will be described. - (a) When the component-enhanced chemical-type photoresist composition is a negative type, (Resin which lowers alkali solubility can be used as a resin which can generally use a base resin of a strong chemical type resist, and can be used for a light source for exposure, and can be used by a conventionally known person. For example, The novolac resin is generally used as a main component. Particularly preferred (a) component can be exemplified (I)酣(Π)—The resin of the above kind is selected from those having a hydroxybenzene-ethyl conjugate. Therefore, the coating degree can be easily controlled. (I) Novolak resin (hereinafter, referred to as (I) 1 ) A system composed of a single mixture is sometimes referred to as (a) (hereinafter, some components contain the above positive form. a) The component is limited by the addition of acid 5 as a negative type, and is selected according to the intention. Since its characteristics are good, the aldehyde varnish resin, the poly-polymerization property of the constituent unit, and the imaging speed component can be derived from, for example, an aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as The "phenol" is obtained by addition and condensation with an aldehyde under an acid catalyst. In this case, examples of the phenol to be used include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, and Ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol '2,5·dimethylphenol , 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, P-phenylphenol 'm-benzene φ φ diphenol, Bismuth, hydroquinone monomethyl ether 'benzene phenol, fluoroaminoethanol, hydroxy diphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol,/5-naphthol, etc. Further, examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. The catalyst for the addition condensation reaction is not particularly limited, and for example, hydrochloric acid or nitric acid may be used in the acid catalyst. Sulfuric acid, formic acid, alginic acid, acetic acid, etc.

上述酚醛清漆樹脂係質量平均分子量爲3000〜1 0000 ，宜爲6000〜9000，更宜爲7000〜8000之範圍內者。若質量平均分子量爲3〇〇〇以上，可充分抑制顯像後嗔減少 (變薄）之傾向，又，若質量平均分子量爲10000 可防止顯像後殘渣會殘留者，佳。具有（Π)經基苯乙嫌構成單元之聚合物（以 *稱 (II)成分），可舉例如對羥基苯乙烯等之羥基苯乙綿、 α -甲基羥基苯乙烯、乙基羥基苯乙烯等之α-焓^ 力基羥基苯乙烯等之羥基苯乙烯構成單元所構成的自由基灸或離子聚合物、或由前述羥基苯乙烯構成單元與宜公 ^外之 •17- (13) 1323251 構成單元所構成的共聚物。聚合物中之羥基苯乙烯構成單元的比率，宜爲1質量％以上，更宜爲1 0〜3 0質量％。此係若羥基苯乙烯構成單元的比率爲10質量％以上，故有顯像性、解析性優之傾向。又’前述（II)成分的質量平均分子量宜爲5 00 0以下’更宜爲2000以上4000以下。此係因若質量平均分子量爲5000以下，有解析性優之傾向。The above novolak resin has a mass average molecular weight of 3,000 to 10,000, preferably from 6,000 to 9000, more preferably from 7,000 to 8,000. When the mass average molecular weight is 3 Å or more, the tendency of enthalpy reduction (thinning) after development can be sufficiently suppressed, and if the mass average molecular weight is 10,000, it is preferable to prevent the residue from remaining after development. A polymer having a (Π)-based phenylethylene-constituting unit (referred to as a component (II)), and examples thereof include hydroxyacetophenone, α-methylhydroxystyrene, and ethylhydroxybenzene, such as p-hydroxystyrene. A free radical moxibustion or ionic polymer composed of a hydroxystyrene component such as α-焓^ hydroxy styrene such as ethylene, or a hydroxystyrene unit composed of the above-mentioned hydroxystyrene and 17-(13) 1323251 A copolymer composed of constituent units. The ratio of the hydroxystyrene constituent unit in the polymer is preferably 1% by mass or more, more preferably 10% to 30% by mass. When the ratio of the hydroxystyrene structural unit is 10% by mass or more, the development property and the analytical property tend to be excellent. Further, the mass average molecular weight of the component (II) is preferably 5,000 or less, and more preferably 2,000 or more and 4,000 or less. This is because if the mass average molecular weight is 5,000 or less, there is a tendency to be excellent in analyticity.

形成前述羥基苯乙烯構成單元以外之構成單元之單體較佳係以其他之基取代羥基苯乙烯構成單元的羥基之單體或具有α，/9-不飽和雙鍵之單體等。取代前述羥基苯乙烯構成單元的羥基之其他的基，係可使用不被酸解離之鹼溶解抑制基。不被酸解離之鹼溶解抑制基係可舉例如取代或未取代之苯磺醯氧基 '取代或未取代之萘磺醯氧基 '取代或未取代之苯羰基氧基、取代或未取代之萘羰基氧基等，取代或未取代之苯磺醯氧基之具體例宜爲苯磺醯氧基、氯苯磺醯氧基、甲基苯磺醯氧基、乙基苯磺醯氧基、丙基苯磺醯氧基、甲氧基苯磺醯氧基、乙氧基苯磺醯氧基、丙氧基苯磺醯氧基、乙醯胺基苯磺醯氧基等，又，取代或未取代之萘磺醯氧基之具體例宜爲萘磺醯氧基、氯萘磺醯氧基、甲基萘磺醯氧基 '乙基萘磺醯氧基、丙基萘磺醯氧基、甲氧基萘磺醯氧基、乙氧基萘磺醯氧基、丙氧基萘磺醯氧基、乙醯胺基萘磺醯氧基等。進一步，可舉例如取代或未取代之苯羰基氧基及取代或未取代之萘羰基氧基等可舉例如將前 -18· (14) 1323251 述取代或未取代之磺醯氧基取代成羰氧基者。其中，宜爲乙醯胺基苯磺醯氧基或乙醯胺基萘磺醯氧基等。又’具有α,θ-不飽和雙鏈之單體的具體例可舉例如苯乙烯、氯苯乙烯、氯甲基苯乙烯、乙烯基甲苯、α -甲 ‘基苯乙烯等的苯乙烯系單體、丙烯酸甲酯、甲基丙烯酸甲酯、甲基丙烯酸苯酯等之丙烯酸單體 '醋酸乙烯酯、安息香酸乙烯酯等之醋酸乙烯酯系單體等，但其中宜爲苯乙烯。由羥基苯乙烯與苯乙烯所得到之共聚物、例如聚（4-羥基苯乙烯-苯乙烯）共聚物、聚（4_羥基苯乙烯-甲基苯乙烯）共聚物等係顯示高解析性同時耐熱性亦高。進一步’於（a)成分中係就適度地控制物理性、化學特性之目的’可含有其他之樹脂成分。可舉例如 , (III )丙烯酸樹脂（以下，稱爲（III ) ) 、（ V )乙烯基樹脂（以下，稱爲（V)成分）。 (ΠΙ)成分；The monomer forming the constituent unit other than the hydroxystyrene structural unit is preferably a monomer which substitutes a hydroxyl group of a hydroxystyrene constituent unit or a monomer having an α,/9-unsaturated double bond, or the like. In place of the other group of the hydroxyl group of the hydroxystyrene structural unit, an alkali-dissolving inhibiting group which is not dissociated by an acid can be used. The base dissolution inhibiting group which is not dissociated by acid may, for example, be substituted or unsubstituted phenylsulfonyloxy 'substituted or unsubstituted naphthylsulfonyloxy' substituted or unsubstituted phenylcarbonyloxy group, substituted or unsubstituted Specific examples of the substituted or unsubstituted benzenesulfonyloxy group such as a naphthylcarbonyloxy group, etc. are preferably a benzenesulfonyloxy group, a chlorobenzenesulfonyloxy group, a methylbenzenesulfonyloxy group, an ethylbenzenesulfonyloxy group, Propyl phenylsulfonyloxy, methoxybenzenesulfonyloxy, ethoxybenzenesulfonyloxy, propoxyphenylsulfonyloxy, acetaminophensulfonyloxy, etc. Specific examples of the unsubstituted naphthylsulfonyloxy group are preferably naphthalenesulfonyloxy, chloronaphthalenesulfonyloxy, methylnaphthalenesulfonyloxyethylidenesulfonyloxy, propylnaphthalenesulfonyloxy, Methoxy naphthylsulfonyloxy, ethoxy naphthylsulfonyloxy, propoxy naphthylsulfonyloxy, ethenylnaphthalenesulfonyloxy and the like. Further, for example, a substituted or unsubstituted phenylcarbonyloxy group and a substituted or unsubstituted naphthalenecarbonyloxy group may, for example, be substituted with a substituted or unsubstituted sulfonyloxy group as a carbonyl group. Oxygen. Among them, it is preferably an acetaminophen benzenesulfonyloxy group or an ethenylnaphthalenesulfonyloxy group. Further, specific examples of the monomer having an α, θ-unsaturated double chain include styrene sheets such as styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, and α-methyl styrene. An acrylic monomer such as methyl acrylate, methyl methacrylate or phenyl methacrylate, or a vinyl acetate monomer such as vinyl acetate or benzoic acid, which is preferably styrene. A copolymer obtained from hydroxystyrene and styrene, such as a poly(4-hydroxystyrene-styrene) copolymer or a poly(4-hydroxystyrene-methylstyrene) copolymer, exhibits high resolution simultaneously The heat resistance is also high. Further, in the component (a), the purpose of appropriately controlling the physical properties and the chemical properties may be contained in other resin components. For example, (III) an acrylic resin (hereinafter referred to as (III)) and (V) a vinyl resin (hereinafter referred to as a (V) component). (ΠΙ) ingredients;

(ΠΙ)成分之丙烯酸樹脂係只要爲鹼可溶性之丙烯酸樹脂即可，無特別限定，但，尤宜含有從具醚鍵之聚合性化合物所衍生之構成單元（sructural unit)、及具有殘基之聚合性化合物所衍生物的構成單元。具醚鍵之聚合性化合物係可例示具有2-甲氧基乙基 (甲基）丙烯酸酯、甲氧基三乙二醇（甲基）丙烯酸酯、 3 -甲氧基丁基（甲基）丙烯酸酯、乙基卡必醇（甲基）丙烯酸酯、苯氧基聚乙二醇（甲基）丙烯酸酯、甲氧基聚丙二醇（甲基）丙烯酸酯、四氫糠醇（甲基）丙烯酸酯等之 -19- (15) 1323251 醚鍵及醋鍵之（甲基）丙烧酸衍生物等，較佳係2 -甲氧基乙基丙烯酸酯、甲氧基三乙二醇丙烯酸酯。此等之化合物係可單獨或組合2種以上而使用。具有羧基之聚合性化合物係可例示具有丙烯酸、甲基 _ 丙烯酸、巴豆酸等之單羧酸；馬來酸 '富馬酸、衣康酸等之二羧酸；2-甲基丙烯醯氧乙基琥珀酸、2_甲基丙烯醯氧乙基馬來酸、2 -甲基丙烯醯氧乙基酞酸、2 -甲基丙烯醯氧 φφ 乙基六氫酞酸等之羧基及酯鍵之化合物等，較佳係丙烯酸、甲基丙烯酸。此等之化合物係可單獨或組合2種以上而使用。 (V)成分 (V)成分之乙烯基樹脂係聚（乙烯基低級烷基醚）’由以下述通式（I)所示之乙烯基低級烷基醚的單獨或2種以上之混合物進行聚合所得到之（共）聚合物所構成。The acrylic resin of the (ΠΙ) component is not particularly limited as long as it is an alkali-soluble acrylic resin, but particularly preferably contains a sructural unit derived from a polymerizable compound having an ether bond, and has a residue. A constituent unit of a derivative of a polymerizable compound. The polymerizable compound having an ether bond can be exemplified by having 2-methoxyethyl (meth) acrylate, methoxy triethylene glycol (meth) acrylate, and 3-methoxy butyl (methyl). Acrylate, ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate Iso--19-(15) 1323251 (meth)propionic acid derivative or the like of an ether bond and an aceton bond, preferably 2-methoxyethyl acrylate or methoxy triethylene glycol acrylate. These compounds may be used alone or in combination of two or more. The polymerizable compound having a carboxyl group may, for example, be a monocarboxylic acid having acrylic acid, methyl-acrylic acid or crotonic acid; a dicarboxylic acid such as maleic acid 'fumaric acid or itaconic acid; 2-methylpropene-oxygen B Carboxylic acid and ester bond of succinic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxyethyl phthalic acid, 2-methyl propylene oxime φ φ ethyl hexahydro phthalic acid The compound or the like is preferably acrylic acid or methacrylic acid. These compounds can be used singly or in combination of two or more. The vinyl resin-based poly(vinyl lower alkyl ether) of the component (V) is polymerized by a single or a mixture of two or more kinds of vinyl lower alkyl ethers represented by the following formula (I). The resulting (co)polymer is composed of.

[化5] hc=ch2[化5] hc=ch2

II

0 (在上述通式（I)中，R6表示碳數1〜5的直鏈狀或分枝狀之烷基）在通式（I)中，碳數1〜5的直鏈狀或分枝狀之烷 -20- (16) 1323251 基，可舉例如甲基、乙基、正丙基、異丙基、正丁基、異丁基、正戊基、環戊基等。此等之烷基中，宜爲甲基、乙基、異丁基’尤宜爲甲基、乙基。在本發明中，尤佳之聚 (乙稀基低級院基醚）係聚（乙燃基甲基酸）、聚（乙嫌基乙基醚）。又，（a)成分爲由含有（I)成分與（Π)成分之混合樹脂所構成之情形’使（I)成分與（II)成分之總和 φφ 爲100質量份，而（I)成分爲50~98質量份，較佳係 55〜95質量份，（II)成分爲50〜2質量份，更宜爲45~5 質量份。 (b )成分在本發明中，（b)成分必須含有上述本發明之酸產生酸產生劑（bl)係可單獨使用，亦可組合2種以上而使用。0 (In the above formula (I), R6 represents a linear or branched alkyl group having 1 to 5 carbon atoms.) In the general formula (I), a linear or branched carbon number of 1 to 5 The alkylene-20-(16) 1323251 group may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a n-pentyl group or a cyclopentyl group. Among these alkyl groups, a methyl group, an ethyl group, and an isobutyl group are preferable, and a methyl group or an ethyl group is particularly preferable. In the present invention, a particularly preferred poly(ethylene-based lower-grade pendant ether) is poly(ethyl ketone methyl acid) or poly(ethyl ketone ethyl ether). Further, the component (a) is composed of a mixed resin containing the component (I) and the component ('), and the sum φφ of the component (I) and the component (II) is 100 parts by mass, and the component (I) is 50 to 98 parts by mass, preferably 55 to 95 parts by mass, and (II) component is 50 to 2 parts by mass, more preferably 45 to 5 parts by mass. (b) In the present invention, the component (b) must contain the above-mentioned acid-producing acid generator (bl), which may be used singly or in combination of two or more.

(b)成分中，酸產生劑（bl)之比率係爲本發明之效果，較佳係50質量％以上，更佳係80~1 00質量％，最佳係1 0 0質量％。在本發明中，增強化學型光阻組成物係除酸產生劑 (bl)以外，亦可含有在習知之增強化學型光阻組成物中所使用的公知之酸產生劑（以下，有時稱爲酸產生劑 (b2 ) ) 〇酸產生劑（b2 )係藉光直接或間接地產生酸之化合物’只要爲酸產生劑（b 1 )所含有者即可，無特別限定。 -21 - (17) 1323251 具體上，可舉例如 2,4-雙（三氯甲基）-6-[2- ( 2-呋喃基）-乙烯基]-5-三嗪、2,4-雙（三氯甲基）-6-[2-(5-甲基-2-呋喃基）乙烯基]-s-三嗪、2,4-雙（三氯甲基）-6-[2-^ (5-乙基-2-呋喃基）乙烯基]-s-三嗪' 2,4-雙（三氯甲基）-6·[2-(5-丙基-2-呋喃基）乙烯基]-s-三嗪、2,4-雙 (三氯甲基）-6-[2-(3,5-二甲氧基苯基）乙烯基]-s-三嗪、2,4-雙（三氯甲基）-6-[2-(3,5-二乙氧基苯基）乙烯 φφ 基]-s-三嗪、2,4-雙（三氯甲基）-6-[2-(3,5-二丙氧基苯基）乙烯基]-8-三嗪、2,4-雙（三氯甲基）-6-[2-(3,4-亞甲基二氧苯基）乙烯基]-s_三嗪、2，4·雙（三氯甲基）-6-(3，4·亞甲基二氧苯基）乙烯基）-s-三嗪、2，4-雙-三氯甲 - 基-6- (3-溴-4甲氧基）苯基-s-三嗪、2，4-雙-三氯甲基- 6-(2-溴-4甲氧基）苯基-3-三嗪、2,4-雙-三氯甲基-6-(2-溴-4甲氧基）苯乙烯基-s-三嗪、2,4_雙-三氯甲基- 6-( 3-溴-4甲氧基）苯乙烯基-s-三嗪、2-(4-甲氧基苯基）- 4.6- 雙（三氯甲基）-1,3,5-三嗪、2- (4 -甲氧基萘基）- 4.6- 雙（三氯甲基）-1,3,5-三嗪、2-[2-(2-呋喃基）乙烯基]-4,6-雙（三氯甲基）-1，3,5-三嗪'2-[2-(5-甲基-2-呋喃基）乙烯基]·4,6-雙（三氯甲基）-I,3,5-三嗪、2-[2- (3,5-二甲氧基苯基）乙烯基]-4,6-雙（三氯甲基）-1，3,5-三嗪、2-[2-(3,4·二甲氧基苯基）乙烯基]-4,6-雙 (三氯甲基）-1,3,5-三嗪、2- (3，4-亞甲基二氧苯基）- 4.6- 雙（三氯甲基）-1,3,5-三嗪、三（1,3-二溴丙基）-]，3,5-三嗪 '三（2,3-二溴丙基）-1,3,5-三嗪等之含鹵素 -22- (18) 1323251 三嗪化合物及三（2,3-二溴丙基）三聚異氰酸酯等的下述通式（i)所示之含有鹵素三嗪化合物； [化6]The ratio of the acid generator (b1) in the component (b) is the effect of the present invention, and is preferably 50% by mass or more, more preferably 80 to 10,000% by mass, and most preferably 100% by mass. In the present invention, the enhanced chemical type photoresist composition may contain, in addition to the acid generator (bl), a known acid generator used in a conventional enhanced chemical type photoresist composition (hereinafter, sometimes referred to as The acid generator (b2)) The citric acid generator (b2) is a compound which generates an acid by direct or indirect light, and is not particularly limited as long as it is contained in the acid generator (b1). -21 - (17) 1323251 Specifically, for example, 2,4-bis(trichloromethyl)-6-[2-(2-furyl)-vinyl]-5-triazine, 2,4- Bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2- ^(5-Ethyl-2-furyl)vinyl]-s-triazine' 2,4-bis(trichloromethyl)-6·[2-(5-propyl-2-furyl)ethene Base]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)vinyl]-s-triazine, 2,4- Bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)ethene φφ-yl]-s-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(3,5-dipropoxyphenyl)vinyl]-8-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxy) Phenyl)vinyl]-s_triazine, 2,4.bis(trichloromethyl)-6-(3,4·methylenedioxyphenyl)vinyl)-s-triazine, 2, 4-bis-trichloromethyl-yl-6-(3-bromo-4methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4) Oxy)phenyl-3-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4methoxy)styryl-s-triazine, 2,4_bis-three Chloromethyl-6-(3-bromo-4) Styryl-s-triazine, 2-(4-methoxyphenyl)-4.6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxy Naphthyl)- 4.6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-furyl)vinyl]-4,6-bis(trichloromethyl)- 1,3,5-triazine '2-[2-(5-methyl-2-furyl)vinyl]·4,6-bis(trichloromethyl)-I,3,5-triazine, 2-[2-(3,5-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3, 4. Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxyphenyl)- 4.6-bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl)-],3,5-triazine' tris(2,3-dibromopropyl a halogen-containing 22-(18) 1323251 triazine compound and tris(2,3-dibromopropyl)trimeric isocyanate such as -1,3,5-triazine, etc., represented by the following formula (i) Containing a halogen triazine compound; [Chem. 6]

R1 xr r3/ γν ο (式（i )中，R1〜R3係可分別表示同一亦可相異之鹵化烷基）。 ' α-(對-曱苯磺醯氧亞胺基）-苯基乙腈、α-(苯磺 - 醯氧亞胺基）2,4-二氯苯基乙腈、α-(苯磺醯氧亞胺基） 2,6-二氯苯基乙腈、££-(2-氯苯磺醯氧亞胺基）_4-甲氧基苯基乙腈、α-(乙基磺醯氧亞胺基）-1-環戊烯基乙膳、以下述通式（ii )所示之化合物； [化7] r4-^c=n-o—so2r5) CN Π (式（ii)中，R4表示一價〜三價之有機基、R5表示取代或未取代之飽和烴基、不飽和烴基或芳香族性化合物基，η表示1〜3之自然數。此處所謂芳香族性化合物基係R1 xr r3/ γν ο (In the formula (i), R1 to R3 may each represent the same or different halogenated alkyl group). 'α-(p-Indolylsulfonyloxyimino)-phenylacetonitrile, α-(phenylsulfonyl-noniminoimido) 2,4-dichlorophenylacetonitrile, α-(phenylsulfonate) Amino) 2,6-dichlorophenylacetonitrile, £-(2-chlorophenylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)- a 1-cyclopentenyl group, a compound represented by the following formula (ii); [Chemical 7] r4-^c=no-so2r5) CN Π (in the formula (ii), R4 represents a monovalent to a trivalent The organic group, R5 represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group, and η represents a natural number of 1 to 3. Here, the aromatic compound group is used.

〈S -23- (19) 1323251 指於芳香族化合物顯示特有之物理性/化學性性質之化合物的基’可舉例如苯基、萘基等之芳香族烴基、或呋喃基、噻吩基等之雜環基。此等係亦可於環上具有適當的取代基例如鹵原子、烷基、烷氧基、硝基等1個以上。又， R5尤宜爲碳數1〜4的烷基，可舉例如甲基、乙基、丙<S -23- (19) 1323251 The base of the compound which exhibits a characteristic physical/chemical property to the aromatic compound is, for example, an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, or a furyl group or a thienyl group. Heterocyclic group. These may also have one or more suitable substituents such as a halogen atom, an alkyl group, an alkoxy group, and a nitro group on the ring. Further, R5 is particularly preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a C group.

基、丁基。尤其R4爲芳香族性化合物基，R5爲低級烷基之化合物。以上述通式所示之酸產生劑係n=l時，R4爲苯基、甲基苯基、甲氧基苯基之任一者，R5爲甲基之化合物，具體上可舉例如α-(甲基磺醯基氧亞胺基）-1-苯基乙腈、〇：-(甲基磺醯基氧亞胺基）-1-(對-甲基苯基）乙腈、α-(甲基磺醯基氧亞胺基）-1-(對-甲氧基苯基）乙腈。n = 2時，以上述通式所示之酸產生劑具體上可舉例如以下述化學式（iii)所示之酸產生劑。） [化8] 含—Ο—-Cr=M-〇—S-^CH3Base, butyl. In particular, R4 is an aromatic compound group, and R5 is a compound of a lower alkyl group. When the acid generator represented by the above formula is n = 1, R4 is any one of a phenyl group, a methylphenyl group and a methoxyphenyl group, and R5 is a methyl group, and specifically, for example, α- (Methylsulfonyloxyimino)-1-phenylacetonitrile, hydrazine: -(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methyl Sulfhydryl oxyimino)-1-(p-methoxyphenyl)acetonitrile. When n = 2, the acid generator represented by the above formula is specifically exemplified by the acid generator represented by the following chemical formula (iii). ) [化8] Containing -Ο--Cr=M-〇-S-^CH3

C4H9—S—CH^=9—0—S-O4H9 °2 CN °2C4H9—S—CH^=9—0—S-O4H9 °2 CN °2

-24- (20) 1323251-24- (20) 1323251

雙（對-甲苯磺醯基）二偶氮甲烷、雙（1，1-二甲基乙基磺醯基）二偶氮甲烷、雙（環己基磺醯基）二偶氮甲烷、雙（2,4-二甲基苯基磺醯基）二偶氮甲烷等之二磺醯基二偶氮甲烷類；對·甲苯磺酸2-硝基苯甲基酯、對-甲苯磺酸2,6-二硝基苯甲基酯、硝基苯甲基甲苯磺酸酯、二硝基苯甲基甲苯磺酸酯、硝基苯甲基磺酸酯、硝基苯甲基碳酸酯、二硝基苯甲基碳酸酯等之硝基苯甲基衍生物；苯三酚均苯三甲酸酯、苯三酚甲苯磺酸酯、苯甲基甲苯磺酸酯、苯甲基磺酸酯、N-甲基磺醯基氧琥珀醯亞胺、N-三氯甲基磺醯基氧琥珀醯亞胺、N-苯基磺醯基氧馬來醯亞胺、 N-甲基磺醯氧酞醯亞胺等之磺酸酯；N-羥基酞醯亞胺、N-羥基萘醯亞胺等之三氟甲烷磺酸酯；二苯基碘鏺六氟磷酸酯、（4-甲氧基苯基）苯基碘鎗三氟甲烷磺酸酯、雙（對第三丁基苯基）碘鎗三氟甲烷磺酸酯、三苯基硫鑰六氟磷酸酯、（4_甲氧基苯基）二苯基硫鑰三氟甲烷磺酸酯、 (對第三丁基苯基）二苯基硫鐵三氟甲烷磺酸酯等之鎗鹽；苯偶因甲基磺酸酯、〇：-甲基苯偶因甲基磺酸酯等之 -25- (21) 1323251 苯偶因甲基磺酸酯類；其他之二苯基碘鎗鹽 '三苯基硫鑰鹽、苯基二偶氮鐺鹽、苯甲基碳酸酯等。酸產生劑（b2 )係可單獨使用此等之化合物，亦可組合2種以上而使用。 ‘在本發明之增強化學型光阻組成物中，（b)成分之含量相對於（a)成分100質量份宜爲0.1〜2 0質量份的範圍，更宜爲1〜10質量份，最宜爲1〜5質量份。若（b)成分之含量爲0.1質量份以上，可得到高的感度，可充分地進行像成形。又，若爲2 0質量份以下，顯像後之光阻層的殘膜率高，顯像性優。增強化學型光阻組成物爲負型時，除上述（a)成分 - 及（b)成分以外，進一步可含有交聯劑。本發明所使用之交聯劑，無特別限定，可從公知之任意增強化學型負型光阻組成物所使用之交聯劑適當選擇而使用。可使用例如三聚氰胺樹脂、尿素樹脂、鳥糞胺樹 99 脂、甘脲-甲醛樹脂、琥珀醯胺-甲醛樹脂、乙烯尿素-甲醛樹脂等，但尤其適宜使用烷氧基甲基化三聚氰胺樹脂或烷氧基甲基化尿素樹脂等之烷氧基甲基化胺基樹脂等。前述烷氧基甲基化胺基樹脂係例如使於沸騰水溶液中使三聚氰胺或尿素與福馬林反應而得之縮合物以甲醇、乙醇、丙醇、丁醇、異丙醇等之低級醇類醚化，然後，冷卻反應後而析出來製造。前述烷氧基甲基化胺基樹脂具體上可舉例如甲氧基甲基化三聚氰胺樹脂、乙氧基甲基化三聚氰胺樹脂、丙氧基 -26- (22) 1323251 甲基化三聚氰胺樹脂、丁氧基甲基化三聚氰胺樹脂 '甲氧基甲基化尿素樹脂、乙氧基甲基化尿素樹脂 '丙氧基甲基化尿素樹脂、丁氧基甲基化尿素樹脂等。前述烷氧基甲基化胺基樹脂係可單獨或組合2種以上而使用。尤其烷氧基甲基化三聚氰胺樹脂係可形成樹脂圖型對於輻射線之照射量變化的尺寸變化量很小且安定之光阻圖型而佳。其中，適宜爲甲氧基甲基化三聚氰胺樹脂、乙氧基甲基化三聚氰胺樹脂、丙氧基甲基化三聚氰胺樹脂及丁氧基甲基化三聚氰胺樹脂。前述交聯劑宜相對於（a)成分100質量份含有1~3 0 • 質量份的範圍。若交聯劑爲1質量份以上，所得到之膜的 . 耐電鍍性、耐藥品性、密接性高，所形成之光阻圖型形狀爲良好。又，若爲3〇質量份以下，顯像時很難引起顯像不良。Bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, double (2 , 4-dimethylphenylsulfonyl)diazomethane, etc.; di-sulfonyldisazomethane; p-toluenesulfonic acid 2-nitrobenzyl ester, p-toluenesulfonic acid 2,6 -dinitrobenzyl ester, nitrobenzyltoluenesulfonate, dinitrobenzyltoluenesulfonate, nitrobenzylsulfonate, nitrobenzyl carbonate, dinitro a nitrobenzyl derivative such as benzyl carbonate; benzenetriol trimellitate, benzenetriol tosylate, benzyl tosylate, benzylsulfonate, N-A Alkylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methylsulfonyloxyimine a sulfonate; a trifluoromethanesulfonate such as N-hydroxy quinone imine or N-hydroxynaphthyl imine; diphenyl iodonium hexafluorophosphate, (4-methoxyphenyl) benzene Base iodine gun trifluoromethanesulfonate, bis(p-butylphenyl) iodine gun trifluoromethyl Alkane sulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl)diphenylthiotrifluoromethanesulfonate, (p-tert-butylphenyl)diphenylsulfate a gun salt of a trifluoromethanesulfonate or the like; a benzoin methanesulfonate, a hydrazine: a methyl benzoin methanesulfonate or the like - 25-(21) 1323251 benzoin methanesulfonate Other; other diphenyl iodine salt 'triphenyl sulfide salt, phenyl diazo sulfonium salt, benzyl carbonate and the like. The acid generator (b2) may be used alone or in combination of two or more. In the reinforced chemical resist composition of the present invention, the content of the component (b) is preferably in the range of 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the component (a). It is preferably 1 to 5 parts by mass. When the content of the component (b) is 0.1 part by mass or more, high sensitivity can be obtained, and image formation can be sufficiently performed. Further, when it is 20 parts by mass or less, the residual photoresist ratio of the photoresist layer after development is high, and the development property is excellent. When the reinforced chemical resist composition is a negative type, a crosslinking agent may be further contained in addition to the above components (a) and (b). The crosslinking agent used in the present invention is not particularly limited, and can be appropriately selected from any known crosslinking agent used for enhancing the chemical type negative photoresist composition. For example, melamine resin, urea resin, guanamine amine 99 resin, glycoluril-formaldehyde resin, succinimide-formaldehyde resin, ethylene urea-formaldehyde resin, etc. may be used, but alkoxymethylated melamine resin or alkane is particularly suitable. An alkoxymethylated amine-based resin such as an oxymethylated urea resin. The alkoxymethylated amine-based resin is, for example, a condensate obtained by reacting melamine or urea with formalin in a boiling aqueous solution, and a lower alcohol ether such as methanol, ethanol, propanol, butanol or isopropanol. Then, after cooling the reaction, it is precipitated and produced. Specific examples of the alkoxymethylated amine-based resin include methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxy-26-(22) 1323251 methylated melamine resin, and butyl Oxymethylated melamine resin 'methoxymethylated urea resin, ethoxymethylated urea resin' propoxymethylated urea resin, butoxymethylated urea resin, and the like. The alkoxymethylated amine-based resin may be used singly or in combination of two or more. In particular, the alkoxymethylated melamine resin can form a resin pattern which is excellent in the amount of change in the amount of irradiation of the radiation and which is small in stability and stable in stability. Among them, a methoxymethylated melamine resin, an ethoxylated methylated melamine resin, a propoxymethylated melamine resin, and a butoxymethylated melamine resin are suitable. The crosslinking agent is preferably contained in an amount of from 1 to 30% by mass based on 100 parts by mass of the component (a). When the amount of the crosslinking agent is 1 part by mass or more, the obtained film has high electroplating resistance, chemical resistance, and adhesion, and the shape of the photoresist pattern formed is good. Further, when it is 3 parts by mass or less, it is difficult to cause development failure during development.

本發明之增強化學型光阻組成物係爲使上述各成分溶解，可調配有機溶劑（光阻溶劑）。有機溶劑係只要可溶解所使用之各成分，形成均一的溶液即可，以往作爲增強化學型光阻之溶劑，可從公知者之中適宜選擇任意者1種或2種而使用。有機溶劑具體上可舉例如丙詷、甲乙酮、環己酮、甲基異戊酮、2-庚酮等之酮類；乙二醇 '乙二醇單乙酸酯、二乙二醇、二乙二醇單乙酸酯、丙二醇、丙二醇單乙酸酯、二丙二醇或二丙二醇單乙酸酯之單甲基醚、單乙基 -27- (23) (23)The reinforced chemical resist composition of the present invention is an organic solvent (photoresist solvent) which is prepared by dissolving the above components. The organic solvent is a solvent which can be used to form a uniform solution, and it can be used as a solvent for enhancing the chemical resistance, and any one or two of them can be appropriately selected from known ones. Specific examples of the organic solvent include ketones such as propylene glycol, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol 'ethylene glycol monoacetate, diethylene glycol, and diethyl ether. Monomethyl ether of diol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate, monoethyl-27- (23) (23)

1323251 醚、單丙基醚、單丁基醚或單苯基醚等之多元物；二噁烷之環式醚類；及乳酸甲酯、乳酸乙酯、醋酸乙酯、醋酸丁酯、丙酮酸甲酯、丙酮氧基丙酸甲酯、乙氧基丙酸乙酯等之酯類。此使用，亦可混合2種以上而使用。此等之中，從本發明之酸產生劑（bl) 言，宜爲多元醇類及其衍生物，更宜爲丙二醇有機溶劑一般係增強化學型光阻組成物中度以成爲1〜65質量％之範圍內的量使用。其中，使用增強化學型光阻組成物於連接等之情形，係使用旋塗法，例如爲得到5 μ m 的厚膜光阻層，宜增強化學型光阻組成物中之成爲30〜65質量％之範圍內的量。固形分濃度. 以上之情形，係容易得到適宜於連接端子之製若爲65質量％以下，組成物之流動性良好，且易以旋塗法得到均一之光阻膜。於本發明之增強化學型光阻組成物係在無性的範圍，可進一步依所希望添加含有具混合例如用以改良光阻膜性能之加成樹脂、可塑劑 '安定劑、着色劑、界面活性劑等所慣用者其次，表示正型之例。正型之情形，係不需要交聯劑。又，（b 機溶劑係與負型之情形相同，但，（a)成分溶解性變高之樹脂。此（a)成分若爲一般可醇及其衍生酯、醋酸甲酸乙酯 '甲等係可單獨的溶解性而單甲基醚。之固形分濃端子的製造以上之膜厚固形分濃度爲3 0質量％造的厚膜，易處理*尙損本質之特性之添加物劑、接着助 )成分及有係藉酸使鹼使用來作爲 -28- (24) 1323251 正型之增強化學型光阻的基材樹脂之樹脂即可，無特別限定，依照使用於曝光之光源，而可從以往公知者任意地選擇而使用。例如，以丙烯酸樹脂作爲主成分，其羥基之至少一部份會被以酸進行解離之鹼溶解抑制基所取代者，或以具有羥基苯乙烯構成單元之聚合物作爲主成分，宜爲其羥基之至少一部份會被以酸進行解離之鹼溶解抑制基所取代者。1323251 a mixture of ether, monopropyl ether, monobutyl ether or monophenyl ether; a cyclic ether of dioxane; and methyl lactate, ethyl lactate, ethyl acetate, butyl acetate, pyruvic acid An ester of methyl ester, methyl acetonate or ethyl ethoxy propionate. This can also be used by mixing two or more types. Among these, from the acid generator (bl) of the present invention, it is preferably a polyhydric alcohol and a derivative thereof, and more preferably a propylene glycol organic solvent is generally an enhanced chemical resist composition to be 1 to 65 mass. The amount within the range of % is used. Wherein, in the case of using a reinforced chemical type photoresist composition for connection or the like, a spin coating method is used, for example, to obtain a thick film photoresist layer of 5 μm, it is preferable to enhance the quality of the chemical type photoresist composition to 30 to 65 mass. The amount within the range of %. In the case of the above, it is easy to obtain a system suitable for the connection terminal, and if it is 65 mass% or less, the fluidity of the composition is good, and a uniform photoresist film can be easily obtained by spin coating. The reinforced chemical resist composition of the present invention is in a range of asexuality, and may further contain, as desired, an addition resin having a mixture, for example, for improving the properties of the photoresist film, a plasticizer, a stabilizer, a colorant, and an interface. The active agent or the like is followed by an example of a positive type. In the case of a positive type, no crosslinking agent is required. Further, (the solvent of the machine b is the same as that of the negative type, but the (a) component has a high solubility. The component (a) is a general alcohol and a derivative thereof, and an ethyl acetate ethyl ester. Separately soluble and monomethyl ether. The solid content of the thick terminal is manufactured. The above film thickness is 30% by mass. The thick film is made of a thick film, which is easy to handle. The component and the resin which is used as a base resin of the -28-(24) 1323251 positive type chemically enhanced photoresist by the acid, and are not particularly limited, and can be used according to the light source used for exposure. It has been arbitrarily selected and used by a person skilled in the art. For example, an acrylic resin is used as a main component, and at least a part of a hydroxyl group thereof is replaced by an alkali dissolution inhibiting group which is dissociated by an acid, or a polymer having a hydroxystyrene structural unit as a main component, preferably a hydroxyl group thereof. At least a portion of it will be replaced by an alkali dissolution inhibiting group which is dissociated with an acid.

尤佳之（a)成分係可例示：由一種以上選自由具有與上述之負型相同的（II)羥基苯乙烯構成單元之聚合物、（III )丙烯酸樹脂之樹脂所構成，且其羥基之至少一部份會被以酸進行解離之鹼溶解抑制基所取代者。此係因可容易地控制塗布性、顯像速度。藉酸之作用進行解離之鹼溶解抑制基係可舉例如宜至少_種選自第三丁氧基、第三戊氧基等之第三級烷氧基：四氫吡喃基氧、四氫呋喃基氧基等之環狀縮醛氧基；乙氧基乙基氧基、甲氧基丙基氧等之鏈狀縮醛氧基；環已基氧、環戊基氧等之環烷基氧基；1-甲基環己基氧基、1-乙基環烷基氧基等之1-烷基環烷基氧基；1-甲基金剛烷基氧基、1-乙基金剛烷基氧基等之1·烷基-聚環烷基氧等。又，進一步，於（a)成分中係就適度地控制物理性、化學特性之目的，可含有其他之樹脂成分。可舉例如與上述負型相同之（Ο酚醛樹脂、（Π)乙烯基樹脂。在上述負型之例中，除了交聯劑及（a)成分外可使用（b)成分及有機溶劑、其他之成分係相同者。 -29- (25) 1323251 本發明之增強化學型光阻組成物，係可使用於支撐體上形成光阻層者。尤其，本發明之增強化學型光阻組成物係對於3 65nni 以上之輻射線之感度高，及對於酸產生劑（bl)之有機溶劑（光阻溶劑）的溶解性高，可得到固形分濃度高之光阻溶液，故可容易地形成膜厚爲5μπι以上之膜厚光阻層，例如後述般，適宜使用於連接端子之製造等。More preferably, the component (a) is exemplified by one or more resins selected from the group consisting of a polymer having (II) a hydroxystyrene unit and a (III) acrylic resin having the same negative type as described above, and a hydroxyl group thereof. At least a portion will be replaced by an alkali dissolution inhibiting group which is dissociated with an acid. This is because the coatability and development speed can be easily controlled. The alkali dissolution inhibiting group which is dissociated by the action of an acid may, for example, be at least a third alkoxy group selected from the group consisting of a third butoxy group and a third pentyloxy group: tetrahydropyranyloxy group, tetrahydrofuranyl group a cyclic acetaloxy group such as an oxy group; a chain acetaloxy group such as an ethoxyethyloxy group or a methoxypropyloxy group; a cycloalkyloxy group such as a cyclohexyloxy group or a cyclopentyloxy group; 1-methylcyclohexyloxy, 1-ethylcycloalkyloxy, etc. 1-alkylcycloalkyloxy; 1-methyladamantyloxy, 1-ethyladamantyloxy Etc. 1 alkyl-polycycloalkyl oxygen and the like. Further, in the component (a), for the purpose of moderately controlling physical properties and chemical properties, other resin components may be contained. For example, the phenolic resin or the oxime vinyl resin may be used in the same manner as the above negative type. In the negative example, the component (b) and the organic solvent may be used in addition to the crosslinking agent and the component (a). The composition is the same. -29- (25) 1323251 The reinforced chemical resist composition of the present invention can be used for forming a photoresist layer on a support. In particular, the reinforced chemical resist composition of the present invention It has high sensitivity to radiation above 3 65nni and high solubility in organic solvent (resist solvent) of acid generator (bl), and a photoresist solution with high solid content concentration can be obtained, so that the film thickness can be easily formed into 5μπι The above-mentioned film thickness resist layer is suitably used for the manufacture of a connection terminal, etc., as mentioned later.

《第四態樣之光阻層層合體》本發明之光阻層層合體，係於支撐體上層合由前述增強化學型光阻組成物所構成之光阻層者。 * 支撐體係無特別限定，可使用以往公知者，例如可例示電子零件用之基板、或於此形成特定配線圖型者等。該基板可舉例如矽、氮化矽、鈦、鉬、鈀、鈦、鎢、銅、鉻 '鐵、鋁等之金屬製的基板或玻璃基板等。配線圖 99 型之材料可使用例如銅、錫、鉻、鋁、鎳、金等。尤其，支撐體爲於基板或配線圖型等支撐體之至少光阻層側的表面至少一部份可使用銅者之情形，以往係與銅接觸之部分的增強化學型光阻的作用受銅阻礙，在其部分產生所謂拖尾等顯像不良的基板依存性之問題，但較使用上述本發明之酸產生劑（bl)作爲（b)成分，更可減少基板依存性。因此，可形成形狀優之光阻圖型。本發明之增強化學型光阻組成物的調製，例如使上述之成分以一般之方法進行混合、攪拌，亦可依照需要，而 (S ) -30- (26) 1323251 使用溶解機、均質機、3根輥磨機（a triple roll mill)等之分散機，分散、混合。又，混合之後，亦可進一步使用篩網、過濾膜等而進行過濾。本發明之光阻層層合體係例如可如以下般進行製造。亦即’如上述般所調製之增強化學型光阻組成物之溶液塗布於基板上’以加熱除去溶劑而形成所希望之塗膜（光阻層）。<<Traditional Photoresist Layer Laminate>> The photoresist layer laminate of the present invention is obtained by laminating a photoresist layer composed of the above-mentioned enhanced chemical type photoresist composition on a support. * The support system is not particularly limited, and a conventionally known one can be used. For example, a substrate for an electronic component or a specific wiring pattern can be formed. The substrate may, for example, be a metal substrate such as tantalum, tantalum nitride, titanium, molybdenum, palladium, titanium, tungsten, copper, chromium, iron or aluminum, or a glass substrate. Wiring diagram Type 99 materials such as copper, tin, chromium, aluminum, nickel, gold, etc. can be used. In particular, the support is such that at least a portion of the surface of the support such as the substrate or the wiring pattern can be made of copper, and the effect of the enhanced chemical resist of the portion in contact with the copper is affected by copper. There is a problem that the substrate dependency of the development failure such as tailing is caused in some cases, but the substrate-dependent property is further reduced by using the acid generator (b1) of the present invention as the component (b). Therefore, a shape-improving photoresist pattern can be formed. In the preparation of the chemistive resist composition of the present invention, for example, the above components may be mixed and stirred in a usual manner, and (S) -30-(26) 1323251 may be used as a dissolving machine or a homogenizer, as needed. A disperser such as a triple roll mill is dispersed and mixed. Further, after mixing, it may be further filtered using a sieve, a filter membrane or the like. The photoresist layer lamination system of the present invention can be produced, for example, as follows. That is, the solution of the enhanced chemical type photoresist composition prepared as described above is coated on the substrate to remove the solvent by heating to form a desired coating film (photoresist layer).

於被處理基板上之塗布方法係可採用旋塗法、輥塗法 '網版印刷法、薄層塗覆法等之方法。本發明之組成物的塗膜之預烘烤條件係依組成物中之各成分的種類、調配比率、塗布膜厚等而異，但一般係 70〜130°C，宜爲80~120°C，2〜60分鐘左右》光阻層之膜厚係無特別限定。特別地在本發明中，係光阻層若膜厚爲5/zm以上之膜厚光阻層，可適當地使用於連接端子的製造等。膜厚光阻層之膜厚係下限値宜爲 20//m以上，更宜爲30/zm以上，最宜爲55#m以上。又，上限値係無特別限定，但宜爲1 000 /z m以下，更宜爲500/zm以下，最宜爲150/zm以下，尤宜爲120/zm以下，更尤宜爲75//m以下。《第5態樣之光阻圖型形成方法〉本發明之光阻圖型之形成方法，其特徵在於含有：於支撐體上，層合由增強化學型光阻組成物所構成之光阻層，而得到本發明之光阻層層合體之層合步驟、與對光阻 -31 - (27) (27)The coating method on the substrate to be processed may be a method such as a spin coating method, a roll coating method, a screen printing method, or a thin layer coating method. The prebaking conditions of the coating film of the composition of the present invention vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, and the like, but are generally 70 to 130 ° C, preferably 80 to 120 ° C. 2 to 60 minutes or so. The film thickness of the photoresist layer is not particularly limited. In particular, in the present invention, the photoresist layer having a film thickness of 5/zm or more can be suitably used for the production of a connection terminal or the like. The film thickness of the film thickness resist layer is preferably 20/m or more, more preferably 30/zm or more, and most preferably 55#m or more. Further, the upper limit is not particularly limited, but is preferably 1 000 /zm or less, more preferably 500/zm or less, most preferably 150/zm or less, particularly preferably 120/zm or less, and more preferably 75//m. the following. <<Formation Method of Photoresist Pattern of Fifth Aspect> The method for forming a photoresist pattern of the present invention, comprising: laminating a photoresist layer composed of a reinforced chemical resist composition on a support And obtaining the lamination step of the photoresist layer laminate of the present invention, and the photoresist - 31 - (27) (27)

1323251 層層合體選擇性地照射輻射線之曝光步驟後進行顯像而得到光阻圖型之顯像步層合步驟係可與上述光阻層層合‘ 行。曝光步驟係例如使用負型之增強化得到之光阻層介由特定圖型之掩罩，可線、例如波長爲300〜500nm之紫外線輻射線之線源係可使用低壓水銀燈、高水銀燈、金屬鹵素燈、氬氣雷射等。此外線、可見光、遠紫外線、X光、電子其適宜爲以3 65nm以上之長被長區域曝光步驟。輻射線照射量係依組成物中之各成率、塗膜之膜厚等而異，但使用超ϋ (4 3 6 nm ) 、h 線（405nm) 、i 線（包情形，爲 100〜2000mJ/cm2。繼而，曝光後，使用公知之方法而酸之產生與擴散，而使此曝光部份之光化。繼而，進行顯像步驟。顯像步驟係鹼性水溶液作爲顯像液來進來，藉顯像需要的部份而得到特定之光阻圖型。顯像液係可使用例如氫氧化鈉、氫水溶液。又，亦可使用於前述鹼類之水驟、及於該曝光步驟。濃之製造同樣地進學型光阻時，於所選擇性地照射輻射或可見光。此等之壓水銀燈、超高壓處所謂輻射線係紫束等。本發明係尤的輻射線所進行的分的種類、調配比 ί壓水銀燈（g線含3 65nm )等）之進行加熱，俾促進阻層的鹼溶解性變例如可使用特定之液可溶解、除去不氧化鉀等之鹼類的溶液中添加甲醇' -32- (28) 1323251 乙醇等之水溶性有機溶劑或界面活性劑適當量的水溶液作爲顯像液。顯像時間係依組成物中之各成分的種類、調配比率、組成物之膜厚等而異，但一般爲1~3 0分鐘，又，顯像之方法亦可爲盛液法、浸漬法' 槳式法、噴塗顯像法等之任 —者。顯像後，係進行流水洗淨3 0〜90秒，使用空***或烘箱等而乾燥。1323251 The layered layer is selectively irradiated with an exposure step of the radiation to obtain a pattern of the photoresist pattern. The lamination step can be laminated with the photoresist layer. The exposure step is, for example, a mask of a specific pattern obtained by enhancement of a negative type, and a line source of ultraviolet radiation such as a wavelength of 300 to 500 nm can be used as a low-pressure mercury lamp, a high mercury lamp, or a metal. Halogen lamps, argon lasers, etc. The external line, the visible light, the far ultraviolet ray, the X-ray, and the electron are suitably exposed to a long area of 3 65 nm or more. The amount of radiation exposure varies depending on the respective yields in the composition, the film thickness of the coating film, etc., but uses ultra-ϋ (4 3 6 nm), h-line (405 nm), and i-line (in the case of a package, it is 100 to 2000 mJ). /cm2. Then, after exposure, the exposure and diffusion of the acid are carried out, and the exposed portion is photochemically. Then, the development step is carried out. The development step is carried out by using an aqueous alkaline solution as a developing solution. A specific photoresist pattern can be obtained by the portion required for image development. For example, sodium hydroxide or an aqueous hydrogen solution can be used for the image liquid, and it can also be used for the water of the above-mentioned alkali and in the exposure step. When the same type of photoresist is produced, the radiation or visible light is selectively irradiated. Such a mercury lamp, a so-called radiant purple beam, etc. at the ultrahigh pressure, etc. The type and the mixing ratio are heated by a mercury lamp (g line containing 3 65 nm), etc., and the alkali solubility of the barrier layer is promoted, for example, by adding a solution in which a specific liquid can dissolve or remove a base such as potassium peroxide. Methanol '-32- (28) 1323251 ethanol, etc. A suitable amount of aqueous solution of a water-soluble organic solvent or surfactant is used as the developing solution. The development time varies depending on the type of each component in the composition, the blending ratio, the film thickness of the composition, and the like, but is generally 1 to 30 minutes. Further, the method of developing may be a liquid-filling method or a dipping method. ' Paddle method, spray imaging, etc. -. After the image is developed, it is washed with running water for 30 to 90 seconds, and dried using an air gun or an oven.

接着，於如此做法所得到之光阻圖型的非光阻部（以鹼顯像液所除去之部分），藉例如電鍍等而埋入金屬等之導體，俾可形成金屬架或凸塊等之連接端子。又，電鍍處理方法係無特別限定，而可採用自以往公知之各種方法。電鍍液特別適宜使用焊錫電鍍、鍍銅液。殘留之光阻圖型最後係依常用方法而使用剝離液等除去。如上述般，本發明之化合物（B1 )係在365nm以上 φφ 之長波長區域發揮酸產生劑功能顯示充分之吸收，即使使用3 65ηπι以上之波長的輻射線之曝光，亦可於光阻圖型之形成產生足夠量的酸。又，對光阻所使用之有機溶劑的溶解性亦高。因此，由化合物（Β1)所構成之酸產生劑 (bl)係可適宜使用於增強化學型光阻組成物尤其365nm 以上之波長的輻射線用之增強化學型光阻組成物，含有酸產生劑（bl)之增強化學型光阻組成物係具有高的感度。又，本發明之增強化學型光阻組成物係基板依存性亦低，無關所使用之基板的種類，而可形成形狀或精度優之 -33- (29) 1323251 光阻圖型。亦即，以往使用例如於支撐體之至少一部分使用銅或鋁等的金屬之支撐體時，於與金屬接觸之部分的增強化學型光阻（負型之情形係不除去膜等，正型之情形係密接不良等）產生顯像不良之基板依存性的問題仍存在，但藉由使用本發明之化合物（B1)所構成的酸產生劑 (bl)作爲（b)成分，俾降低基板依存性。基板依存性之降低效果，推測係本發明之化合物（B 1 )易與銅等之金 φφ 屬反應的基，例如不具有-C Ν等。進一步，本發明之化合物（Β1)對有機溶劑的溶解性高，故本發明之增強化學型光阻組成物係可提高光阻之有機溶劑溶液的固形分濃度，故適於形成膜厚爲以上之厚膜光阻層。 - 又，本發明之化合物（B1)對有機溶劑的溶解性高，故本發明之增強化學型光阻組成物係期待瓶體隨時間安定性（strage stability as a resist solution in a bottle)亦優。又，推測隨其而亦可防止性能隨時間劣化造成的感度降低或光阻圖型形狀之惡化》《增強化學型光阻組成物> 本態樣之第六態樣的增強化學型光阻組成物係其特徵在於：含有U)藉酸使鹸溶解性變化之樹脂（以下，有時稱爲（a )成分）、（b)藉輻射線照射產生酸之化合物（以下’有時稱爲（b )成分）'及（c)以通式（C1)所示之化合物（以下，有時稱爲（c)成分），前述（b)成分含有硫鎰 -34- (30) 1323251 鹽系酸產生劑（b-1) ’可爲負型亦可爲正型。以下，說明負型之情形的例。又，在本態樣中’ （a )成份係與前述第一態樣的 (a)成分相同，故省略說明。 (b )成分在本發明中，（b )成份係必須含有硫鑰鹽系酸產生劑（b-Ι )(以下，有時稱爲酸產生劑（b-Ι ))。Then, in the non-resistance portion (the portion removed by the alkali developing solution) obtained by such a method, a conductor such as a metal is buried by, for example, plating, and a metal frame or a bump can be formed. Connection terminal. Further, the plating treatment method is not particularly limited, and various methods known from the prior art can be employed. The plating solution is particularly suitable for solder plating or copper plating. The residual photoresist pattern is finally removed by a stripping solution or the like according to a usual method. As described above, the compound (B1) of the present invention exhibits sufficient absorption of an acid generator function in a long wavelength region of 365 nm or more and φφ, and can be used in a photoresist pattern even when exposure is performed using a radiation having a wavelength of 3 65 η π or more. The formation produces a sufficient amount of acid. Further, the solubility in the organic solvent used for the photoresist is also high. Therefore, the acid generator (bl) composed of the compound (Β1) can be suitably used for a reinforced chemical resist composition for reinforcing a chemical type photoresist composition, particularly a wavelength of 365 nm or more, containing an acid generator. The enhanced chemical type photoresist composition of (bl) has a high sensitivity. Further, the substrate of the reinforced chemical resist composition of the present invention is also low in dependency, and the shape or precision can be formed to be excellent in shape or precision irrespective of the type of substrate to be used. -33- (29) 1323251. In other words, when a support of a metal such as copper or aluminum is used for at least a part of the support, for example, a chemically resistive film is formed in a portion in contact with the metal (in the case of a negative type, the film is not removed, and the positive type is used. In the case where the adhesion is poor, etc.), there is still a problem of substrate dependency which causes development failure. However, by using the acid generator (b1) composed of the compound (B1) of the present invention as the component (b), the substrate dependency is lowered. . The effect of reducing the substrate dependency is estimated to be a group in which the compound (B 1 ) of the present invention easily reacts with gold φφ such as copper, and does not have -C Ν or the like. Further, since the compound (Β1) of the present invention has high solubility in an organic solvent, the reinforced chemical resist composition of the present invention can increase the solid content concentration of the organic solvent solution of the photoresist, so that it is suitable for forming a film thickness or more. Thick film photoresist layer. Further, since the compound (B1) of the present invention has high solubility in an organic solvent, the reinforced chemical resist composition of the present invention is expected to have a stable stability as a resist solution in a bottle. . Further, it is presumed that it is also possible to prevent deterioration of sensitivity due to deterioration of performance with time or deterioration of shape of photoresist pattern. "Enhanced Chemical Type Photoresist Composition" The enhanced chemical type photoresist composition of the sixth aspect of the present aspect The system is characterized in that it contains U) a resin which changes the solubility of hydrazine by acid (hereinafter, sometimes referred to as component (a)), and (b) a compound which generates an acid by irradiation with radiation (hereinafter referred to as (sometimes referred to as ( b) components)' and (c) are compounds represented by the formula (C1) (hereinafter sometimes referred to as component (c)), and the component (b) contains sulfonium-34-(30) 1323251 salt acid The generating agent (b-1)' may be either negative or positive. Hereinafter, an example of a case of a negative type will be described. Further, in the present aspect, the '(a) component is the same as the component (a) of the first aspect, and thus the description thereof is omitted. (b) Component In the present invention, the component (b) must contain a sulfonate-based acid generator (b-Ι) (hereinafter, sometimes referred to as an acid generator (b-Ι)).

在本發明中，酸產生劑（b-Ι)係可從被提出作爲增強化學型光阻組成物用之硫鑰鹽系酸產生劑任意選擇而使用。又，在本發明中所謂「硫鑰鹽系酸產生劑」係以硫鑰離子作爲陽離子部，且具有藉輻射線之照射而產生酸之特性者。該硫鑰離子可舉例如以下述通式（IX )所示者。 [化3] R11 (IX) R12—S- R13 上述通式（IX)中，RM~R13係分別獨主地表示芳基或院基。 R11〜R 13之中，宜至少—個爲芳基，RU~R 13之中，更宜2個以上爲芳基，最宜R11〜R 13之全部爲芳基。 R1]~R13之芳基可舉例如以後述之通式（Bla)所示之 -35- (31) 1323251 基、或爲碳數6〜2 0之芳基，亦可不被烷基、鹵原子等所取代之芳基、萘基等。亦可被該芳基取代之烷基，無特別限定，可舉例如碳數1〜5之直鏈或分枝狀之烷基等。又，亦可被該芳基取代之鹵原子可舉例如氯原子、氟原子、碘原子、溴原子等。 R11〜R13之烷基可舉例如碳數1~1〇之直鏈狀、分枝狀或環狀之烷基等。In the present invention, the acid generator (b-oxime) can be arbitrarily selected from the sulfuryl salt-based acid generator which is proposed as a chemical-resistant resist composition. In the present invention, the "sulfonate-based acid generator" has a sulfur atom as a cation portion and has an acid property by irradiation with radiation. The sulfur atom can be, for example, represented by the following formula (IX). R11 (IX) R12-S-R13 In the above formula (IX), RM to R13 each independently represent an aryl group or a yard group. Among R11 to R13, at least one of them is an aryl group, and among RU to R13, more preferably two or more are aryl groups, and most preferably all of R11 to R13 are aryl groups. The aryl group of R1] to R13 may, for example, be a -35-(31) 1323251 group represented by the following formula (Bla), or an aryl group having a carbon number of 6 to 20, or may not be an alkyl group or a halogen atom. An aryl group, a naphthyl group or the like substituted. The alkyl group which may be substituted with the aryl group is not particularly limited, and examples thereof include a linear or branched alkyl group having 1 to 5 carbon atoms. Further, the halogen atom which may be substituted by the aryl group may, for example, be a chlorine atom, a fluorine atom, an iodine atom or a bromine atom. The alkyl group of R11 to R13 may, for example, be a linear, branched or cyclic alkyl group having 1 to 1 carbon atoms.

在本發明中，尤其宜酸產生劑（b-l)含有以前述通式（B 1 )所示之化合物（以下，有時化合物（B 1 ))。藉此，在 365 nm以上之長波長區域的感度會進一步提昇’又化合物（B 1 )係與前述第一態樣中之化合物 (B 1 )相同，省略說明。酸產生劑（b-l)係可單獨使用，亦可組合2種以上而使用。 (b) 成分中，酸產生劑（b-l)之比率，爲了本發明之效果，係宜爲50質量％以上，更宜爲80~1〇〇質量％，最宜爲1 0 0質量％。在本發明中，增強化學型光阻組成物係（b )成分，除酸產生劑（b-l)以外，亦可含有在以往增強化學型光阻組成物中所使用之公知酸產生劑（以下有時稱爲酸產生劑（b-2 ))。又，此處酸產生劑（b-2 )係與在前述第一態樣中之酸產生劑（b2 )相同者，故省略說明。 (c) 成分 (c)成份係以則述通式（C1)所示之化合物。藉由 C £ ) -36- (32) 1323251 含有如此之（c)成分，本發明之增強化學型光阻組成物係即使含有硫鍚鹽系酸產生劑（b-1 )作爲（b )成分，亦對365 nm以上之長波長區域的輻射線具有高的感度。式（C1 )中，R1及 R2係碳數1〜4之烷基，且 RkR2。在本發明中係尤其本發明之效果優，故R1及R2 宜爲乙基或正丁基，更宜爲R、R2 =正丁基。In the present invention, the acid generator (b-1) is particularly preferably a compound represented by the above formula (B 1 ) (hereinafter, sometimes a compound (B 1 )). Thereby, the sensitivity in the long wavelength region of 365 nm or more is further increased. The compound (B 1 ) is the same as the compound (B 1 ) in the first aspect, and the description thereof is omitted. The acid generator (b-1) may be used singly or in combination of two or more. In the component (b), the ratio of the acid generator (b-1) is preferably 50% by mass or more, more preferably 80% by mass to 1% by mass, and most preferably 100% by mass. In the present invention, the chemical-resistant photoresist composition (b) may be contained in addition to the acid generator (bl), and may contain a known acid generator used in a conventional enhanced chemical-type resist composition (hereinafter, It is called acid generator (b-2)). Further, since the acid generator (b-2) is the same as the acid generator (b2) in the first aspect, the description thereof is omitted. (c) Component (c) The component is a compound represented by the formula (C1). By containing such a component (c), C £ ) -36- (32) 1323251, the reinforced chemical resist composition of the present invention contains the sulfonium salt-based acid generator (b-1) as the component (b) It also has a high sensitivity to radiation in the long wavelength region above 365 nm. In the formula (C1), R1 and R2 are an alkyl group having 1 to 4 carbon atoms, and RkR2. In the present invention, especially the effect of the present invention is excellent, so R1 and R2 are preferably an ethyl group or an n-butyl group, and more preferably R, R2 = n-butyl group.

在本發明之增強化學型光阻組成物中，（c )成分對 (b)成分之比率宜爲5~30質量％之範圍，更宜爲10〜25 質量％，最宜爲15〜20質量％。若爲5質量％以上，可得到高的感度，可充分地進行像形成。又，若爲30質量％以下，不會對感度有不良影響。增強化學型光阻組成物爲負型之情形，除上述（a) 成分、（b)成分及（c)成分以外，進一步尙可含有交聯劑。又，有關交聯劑係與前述第一態樣中之交聯劑相同，故省略說明。又，同樣地，有關有機溶劑係與前述第一態樣中之交聯劑相同，故省略說明。進而，有關「正型之例」、「光阻層層合體」、「光阻圖型形成方法」亦與前述同樣，故省略說明。如上述般，含有硫鑰鹽系酸產生劑（b-1 )及（c )成分之本發明的增強化學型光阻組成物係具有高的感度。此係因（c)成分具有作爲硫鎗鹽系酸產生劑（b-Ι)之增感劑的功能。又，本發明之增強化學型光阻組成物係基板依存性亦 -37- (33) 1323251 低，無關所使用之基板的種類，而可形成形狀或精度優之光阻圖型。亦即，以往使用例如於支撐體之至少一部分使用銅等的金屬之支撐體時，於與金屬接觸之部分的增強化學型光阻（負型之情形係不除去膜等，正型之情形係密接不良等）產生顯像不良之基板依存性的問題仍存在，但藉由使用硫鑰鹽系酸產生劑（b-Ι)作爲（b)成分，俾降低基板依存性。基板依存性之降低效果，推測係硫鑰鹽系酸產生劑（b-1 )易與銅等之金屬反應的基，例如不具有-CN 等。又，在本發明中，尤其若使用上述化合物（B1)作爲硫鎗鹽系酸產生劑（b-1 )，則上述效果優。此係化合物 • ( B1 )在3 6 5nm以上之長波長區域發揮酸產生劑功能顯示充分之吸收，即使使用3 6 5nm以上之波長的輻射線之曝光，亦可於光阻圖型之形成產生足夠量的酸。又，化合物（B1)係對光阻所使用之有機溶劑的溶解性亦高。是 φφ 故，可提高光阻之有機溶劑溶液的固形分濃度，因此適於形成膜厚爲5/zm以上之厚膜光阻層。又，化合物（B1) 對有機溶劑的溶解性高，故增強化學型光阻組成物係期待瓶體隨時間安定性亦優。又，隨其而推測亦可防止性能隨時間劣化造成的感度降低或光阻圖型形狀之惡化。【實施方式】實施例以下，藉實施例及比較例具體地說明本發明，但本發 -38- (34) 1323251 明不限定於此等之例。 [樹脂合成例1]〈酚醛清漆樹脂之合成〉使間甲酚與對甲酚以質量比60: 40之比率混合，再加入福馬林’使用草酸觸媒以常用方法進行縮合而得到甲酌酌醒清漆樹脂。對此樹脂分別實施處理，截取低分子區域而得到質量平均分子量800〇之酚醛清漆樹脂。以此樹脂作爲（Α·1 )。 [實施例1 ]〈增強化學型光阻組成物之調製〉使樹脂合成例1得到之樹脂（A- 1 ) 90質量份、以上 ' 述式（Β 3 )所示之酸產生劑（Β -1 ) 3質量份、交聯劑 - (六甲氧基甲基化三聚氰胺（三和化學公司製、商品名：In the reinforced chemical resist composition of the present invention, the ratio of the component (c) to the component (b) is preferably in the range of 5 to 30% by mass, more preferably 10 to 25% by mass, most preferably 15 to 20% by mass. %. When it is 5% by mass or more, high sensitivity can be obtained, and image formation can be sufficiently performed. Moreover, if it is 30 mass% or less, it will not adversely affect a sensitivity. In the case where the enhanced chemical resist composition is a negative type, in addition to the above components (a), (b) and (c), a further crosslinking agent may be contained. Further, since the crosslinking agent is the same as the crosslinking agent in the first aspect, the description thereof is omitted. Further, in the same manner, the organic solvent is the same as the crosslinking agent in the first aspect, and thus the description thereof will be omitted. Further, the "positive example", the "photoresist layer laminate", and the "resist pattern forming method" are also the same as described above, and thus the description thereof is omitted. As described above, the reinforced chemical type resist composition of the present invention containing the sulphuric acid salt generator (b-1) and the component (c) has high sensitivity. This component (c) has a function as a sensitizer for a sulfur gun acid generator (b-oxime). Further, the substrate of the reinforced chemical resist composition of the present invention is also low in dependence of -37-(33) 1323251, and it is possible to form a photoresist pattern having excellent shape or precision regardless of the type of substrate to be used. In other words, in the case where a support of a metal such as copper is used for at least a part of the support, for example, a chemically resistive film is formed in a portion in contact with the metal (in the case of a negative type, the film is not removed, and the positive type is used. There is still a problem of substrate dependency that causes development failure due to poor adhesion, etc. However, by using a sulfonate-based acid generator (b-Ι) as the component (b), the substrate dependency is lowered. The effect of reducing the substrate dependency is estimated to be a group in which the sulfuryl salt-based acid generator (b-1) easily reacts with a metal such as copper, and does not have -CN or the like, for example. Further, in the present invention, in particular, when the above compound (B1) is used as the sulfur gun-based acid generator (b-1), the above effects are excellent. This compound (B1) exhibits sufficient absorption in the long-wavelength region of 3 6 5 nm or more, and exhibits sufficient absorption even in the form of radiation pattern using radiation of a wavelength of 365 nm or more. A sufficient amount of acid. Further, the compound (B1) is also highly soluble in the organic solvent used for the photoresist. It is φφ, which improves the solid content concentration of the organic solvent solution of the photoresist, and is therefore suitable for forming a thick film photoresist layer having a film thickness of 5/zm or more. Further, since the compound (B1) has high solubility in an organic solvent, it is expected that the chemically-resistant photoresist composition is excellent in stability over time. Further, it is presumed that it is possible to prevent deterioration of sensitivity due to deterioration of performance with time or deterioration of shape of a resist pattern. [Embodiment] Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples. However, the present invention is not limited to the examples. [Resin Synthetic Example 1] <Synthesis of Novolak Resin> Mix m-cresol with p-cresol at a mass ratio of 60:40, and then add formalin. The oxalate catalyst is condensed by a usual method to obtain a discretion. Wake up the varnish resin. The resin was separately treated, and a low molecular region was cut to obtain a novolak resin having a mass average molecular weight of 800 Å. Use this resin as (Α·1). [Example 1] <Preparation of Reinforced Chemical Photoresist Composition> 90 parts by mass of the resin (A-1) obtained in Resin Synthesis Example 1 and an acid generator represented by the above formula (Β3) (Β - 1) 3 parts by mass, cross-linking agent - (hexamethoxymethylated melamine (manufactured by Sanwa Chemical Co., Ltd., trade name:

NikalaCMw_l〇〇) ) 10質量份於丙二醇單甲基醚乙酸酯中進行混合而形成均一溶液後，通過孔徑1/zm之過濾膜而進行過濾’得到固形分濃度50質量％之增強化學型負型光阻組成物。 [比較例1 ] 除使用三苯基硫鎗三氟甲烷磺酸酯（酸產生劑（Β-2) ) 3質量份取代（酸產生劑（Β-1 ) ) 3質量份以外，其餘係與實施例1同樣做法而調製增強化學型負型光阻組成物。 -39- (35) 1323251 〈評估〉有關上述合成例1得到之酸產生劑（B -1 )及比較例 1所使用之酸產生劑（B-2 )，如以下般做法而評估其溶解性，其結果表示於表1中。〈溶解性〉 5質量％〜1質量％以1質量％刻度改變濃度，而調整各酸產生劑之丙二醇單甲基醚乙酸酯溶液。調整後，攪拌各溶液而測定各酸產生劑完全溶解之濃度。表1 酸產生劑（B -1 ) 酸產生劑（B-2 ) 溶解性（質量％) 3 1 有關於上述實施例及比較例得到之增強化學型負型光 βφ 阻組成物，進行以下之評估。首先，於5英吋之銅濺鍍晶圓上，使用旋塗器而塗布增強化學型負型光阻組成物成爲膜厚約30// m，以11 0°C 在加熱板上預烘烤6分鐘而進行光阻層層合體。然後，介由解析度測定用之圖型掩罩，使用步進器（Canon公司製、Canon PLA-501F、ghi 線 multi、hard contact )，在 100〜lOOOOmJ/cm2之範圍階段性進行紫外線曝光。曝光後，在130°C下進行4分鐘之PEB (曝光後加熱），再以顯像液（2.38質量％氫氧化四甲基銨水溶液）顯像7分 -40- (36) 1323251 鐘。此後，流水洗淨，吹入氮氣而得下做法評估其感度、圖型形狀、殘膜 2中。又，於本評估之露光中係使用g (405nm ) 、i 線(3 6 5 nm )混合光，對於i線（3 65nm)之感度高，即使：曝光亦可得到同樣之效果。到光阻圖型。以如以率。其結果表示於表線（436nm) 、h 線但本發明之組成物係 i線（ 365nm)單獨之NikalaCMw_l〇〇)) 10 parts by mass of propylene glycol monomethyl ether acetate was mixed to form a uniform solution, and then filtered through a filter membrane having a pore size of 1/zm to obtain an enhanced chemical type negative concentration of 50% by mass. Type resist composition. [Comparative Example 1] Except that 3 parts by mass of a triphenylsulfur gun trifluoromethanesulfonate (acid generator (?-2)) was used (acid generator (?-1)), 3 parts by mass, In the same manner as in Example 1, the enhanced chemical type negative resist composition was prepared. -39- (35) 1323251 <Evaluation> The acid generator (B-1) obtained in the above Synthesis Example 1 and the acid generator (B-2) used in Comparative Example 1 were evaluated for their solubility as follows. The results are shown in Table 1. <Solubility> 5 mass% to 1 mass% The concentration was changed by 1 mass%, and the propylene glycol monomethyl ether acetate solution of each acid generator was adjusted. After the adjustment, each solution was stirred to measure the concentration at which each of the acid generators was completely dissolved. Table 1 Acid generator (B-1) Acid generator (B-2) Solubility (% by mass) 3 1 For the reinforced chemical type negative light β φ resistance composition obtained in the above Examples and Comparative Examples, the following Evaluation. First, on a 5 inch copper sputter wafer, a reinforced chemical type negative photoresist composition was applied using a spin coater to a film thickness of about 30//m, pre-baked on a hot plate at 110 °C. The photoresist layer laminate was carried out for 6 minutes. Then, through the pattern mask for the measurement of the resolution, a stepper (manufactured by Canon, Canon PLA-501F, ghi line multi, hard contact) was used, and ultraviolet exposure was performed stepwise in the range of 100 to 100 mJ/cm2. After the exposure, PEB (heating after exposure) was performed at 130 ° C for 4 minutes, and then developed with a developing solution (2.38 mass% aqueous solution of tetramethylammonium hydroxide) for 7 minutes - 40 - (36) 1,323,251. Thereafter, the running water was washed, and nitrogen gas was blown in, and the sensitivity, pattern shape, and residual film 2 were evaluated. Further, in the exposure of the present evaluation, the light is mixed with g (405 nm) and i-line (3 6 5 nm), and the sensitivity to the i-line (3 65 nm) is high, and the same effect can be obtained even by exposure. To the photoresist pattern. Take the rate. The results are shown on the surface (436 nm), h line, but the composition of the present invention is i line (365 nm) alone.

〈感度〉顯像後，測定線寬40/zm之密曝光量。接光阻線圖型殘留之<Sensitivity> After development, a dense exposure amount of 40/zm in line width was measured. Residual photoresist pattern residual

〈圖型形狀〉使用光學顯微鏡或電子顯微鏡而型的形狀，以下述之評估基準判定。〇：所形成之光阻圖型的形狀爲 X :所形成之光阻圖型的形狀爲內之數字表示圖型與基板之接觸角）觀察所形成之光阻圖矩形倒梯形形狀（圓括弧〈殘膜率〉測定所形成之光阻圖型的膜厚，膜厚而膜殘留之比率作爲殘膜率。計算相對於顯像前之 -41 - 1323251 (37) 表2 實施例1 比較例1 感度（mJ/cm2) 400 2000 圖型形狀（接觸角）〇（90。） X (1 〇〇°) 殘膜率 90% 2 0% [樹脂合成例2]〈酚醛清漆樹脂之合成〉<Shape shape> A shape determined by an optical microscope or an electron microscope is determined by the following evaluation criteria. 〇: The shape of the formed photoresist pattern is X: the shape of the formed photoresist pattern is the number inside, indicating the contact angle between the pattern and the substrate. Observing the formed resist pattern, the rectangular inverted trapezoidal shape (circular bracket) <Residual film rate> The film thickness of the photoresist pattern formed was measured, and the ratio of the film thickness to the film remaining ratio was defined as the residual film ratio. The calculation was compared with -41 - 1323251 before the development (37). Table 2 Example 1 Comparative Example 1 Sensitivity (mJ/cm2) 400 2000 Pattern shape (contact angle) 〇(90.) X (1 〇〇°) Residual film rate 90% 2 0% [Resin Synthesis Example 2] <Synthesis of Novolak Resin>

使間甲酚與對甲酚以質量比60 : 40之比率混合，再加入福馬林，使用草酸觸媒以常用方法進行縮合而得到甲酚酚醛清漆樹脂。對此樹脂分別實施處理，截取低分子區域而得到質量平均分子量8000之酚醛清漆樹脂。以此樹脂作爲（A-1 1 )。 [實施例2 ]〈增強化學型光阻組成物之調製〉使樹脂合成例2得到之樹脂（A-1 1 ) 90質量份、以上述式（B 3 )所示之化合物（B -1 1 ) 3質量份、交聯劑 (六甲氧基甲基化三聚氰胺（三和化學公司製 '商品名：The m-cresol and p-cresol were mixed at a mass ratio of 60:40, and then added to formalin, and condensed by a usual method using an oxalic acid catalyst to obtain a cresol novolak resin. This resin was separately treated to cut a low molecular region to obtain a novolak resin having a mass average molecular weight of 8,000. Use this resin as (A-1 1 ). [Example 2] <Preparation of Reinforcing Chemical Photoresist Composition> 90 parts by mass of the resin (A-1 1 ) obtained in Resin Synthesis Example 2, the compound represented by the above formula (B 3 ) (B -1 1 3 parts by mass, cross-linking agent (hexamethoxymethylated melamine (made by Sanwa Chemical Co., Ltd.)

Nikalac Mw-100) ) 1〇質量份、9，〗0-二（正丁氧基）憲 0.15質量份於丙二醇單甲基醚乙酸酯中進行混合而形成均 —溶液後’通過孔徑1/zm之過濾膜而進行過濾’得到固形分濃度40質量％之增強化學型負型光阻組成物。 [實施例3]〈增強化學型光阻組成物之調製〉除使9，10-二（正丁氧基）蔥之調配量爲〇·3質量份 -42- (38) 1323251 以外，其餘係與實施例2同樣做法而得到增強化學型負型光阻組成物。 [實施例4]〈增強化學型光阻組成物之調製〉除使9,10 -二（正丁氧基）蔥之調配量爲0.5質量份以外，其餘係與實施例2同樣做法而得到增強化學型負型光阻組成物。Nikalac Mw-100) ) 1 part by mass, 9, 0-di(n-butoxy) 0.15 parts by mass in propylene glycol monomethyl ether acetate to form a homo-solution after 'passing aperture 1/ The filtration membrane of zm was filtered to obtain a reinforced chemical type negative photoresist composition having a solid content concentration of 40% by mass. [Example 3] <Preparation of enhanced chemical type photoresist composition> Except that the amount of 9,10-di(n-butoxy) onion was adjusted to 〇·3 parts by mass to 42-(38) 1323251 An enhanced chemical type negative photoresist composition was obtained in the same manner as in Example 2. [Example 4] <Preparation of enhanced chemical type photoresist composition> The addition was carried out in the same manner as in Example 2 except that the amount of the 9,10-di(n-butoxy) onion was 0.5 parts by mass. A chemical type negative photoresist composition.

[比較例2]〈增強化學型光阻組成物之調製〉除未調配9,10-二（正丁氧基）蔥以外，其餘係與實施例2同樣做法而得到增強化學型負型光阻組成物。〈評估〉[感度] 有關所得到之增強化學型負型光阻組成物，進行以下之評估。[Comparative Example 2] <Preparation of enhanced chemical type photoresist composition> A chemically-resistant negative type resist was obtained in the same manner as in Example 2 except that 9,10-di(n-butoxy) onion was not prepared. Composition. <Evaluation> [Sensitivity] For the obtained enhanced chemical type negative resist composition, the following evaluation was carried out.

首先，於5英吋之銅濺鍍晶圓上，使用旋塗器而塗布增強化學型負型光阻組成物成爲膜厚約30ym，以110 °C 在加熱板上預烘烤6分鐘而進行光阻層層合體。然後，介由解析度測定用之圖型掩罩，使用步進器（Canon公司製、Canon PLA-501F ' hard contact )，在 100~1 OOOOmJ/ cm2之範圍階段性進行紫外線曝光。曝光後，在130°C下進行4分鐘之PEB (曝光後加熱），再以顯像液（2.38質量％氫氧化四甲基銨水溶液）顯像7分鐘。此後，流水洗淨，吹入氮氣而得到光阻圖型。 -43- (39) 1323251 此時，求出形成 4〇 Am之密接線圖型之曝光量 (mJ/cm2 )作爲感度。其結果表示於表3中。又，於本評估之露光中係使用g線（ 436ηηι) 、11線 (405nm ) 、i線（365nm )混合光，但本發明之組成物係對於i線（365 nm)之感度高，即使i線（365 nm)單獨之曝光亦可得到同樣之效果。 [表3] 實施例2 實施例3 實施例4 比較例2 感度 (mJ/cm2) 300 250 200 350First, on a 5 inch copper sputter wafer, a reinforced chemical type negative photoresist composition was applied using a spin coater to a film thickness of about 30 μm, and prebaked on a hot plate at 110 ° C for 6 minutes. Photoresist layer laminate. Then, the pattern mask used for the measurement of the resolution was subjected to ultraviolet exposure in a range of 100 to 1 OOOOmJ/cm2 using a stepper (Canon Co., Ltd., Canon PLA-501F 'hard contact). After the exposure, PEB (heating after exposure) was carried out for 4 minutes at 130 ° C, and developed with a developing solution (2.38 mass% aqueous solution of tetramethylammonium hydroxide) for 7 minutes. Thereafter, the running water was washed, and nitrogen gas was blown in to obtain a photoresist pattern. -43- (39) 1323251 At this time, the exposure amount (mJ/cm2) which forms the dense wiring pattern of 4〇 Am is obtained as the sensitivity. The results are shown in Table 3. Further, in the exposure of the present evaluation, light is mixed using g-line (436 ηηι), 11-line (405 nm), and i-line (365 nm), but the composition of the present invention has high sensitivity to i-line (365 nm) even if i The same effect can be obtained by direct exposure of the line (365 nm). [Table 3] Example 2 Example 3 Example 4 Comparative Example 2 Sensitivity (mJ/cm2) 300 250 200 350

. [產業上之利用可能性] 本發明係可適用於一種在3 65nm以上之長波長區域中顯示高的吸收，在365 nm以上之長波長區域中之感度 €0 高，對有機溶劑之溶解性亦優之化合物、由該化合物所構成之酸產生劑、含有該酸產生劑之增強化學型光阻組成物、使用該增強化學型光阻組成物之光阻層層合體及光阻圖型形成方法。 -44-[Industrial Applicability] The present invention is applicable to a high absorption in a long wavelength region of 3 65 nm or more, a high sensitivity in a long wavelength region of 365 nm or more, and dissolution in an organic solvent. An excellent acid compound, an acid generator comprising the compound, a reinforced chemical resist composition containing the acid generator, a photoresist layer laminate using the enhanced chemical resist composition, and a photoresist pattern Forming method. -44-

Claims

1323251 _______ 公告本 |98· 9. 1 d _ ，年月日修正本十、申請專利範圍第95138227號專利申請案中文申請專利範圍修正本月15日修正民國98年9 1.—種以下述通式（B2)所示之化合物，1323251 _______ Announcement|98· 9. 1 d _ , Year, Month and Sunday Amendment 10, Patent Application No. 95138227 Patent Application Revision of Chinese Patent Application Range Amendment 15th of this month, Republic of China 98 years 9 a compound of the formula (B2),

[式（B2 )中，R4、R5係分別獨主地爲之烷基、苯基或萘基，該烷基、苯基或萘基 1至12之烷氧基、碳數1至12之烷基及羥少1種之取代基；R6、R7係分別獨主地爲碳烷氧基；X·爲碳數1至12之氟化烷基離子] 2.如申請專利範圍第1項之化合物 (B3)所示， [化3] 碳數〗至12 可具有由碳數基所選出之至數1至12之〇，其係以下述[In the formula (B2), R4 and R5 are each independently an alkyl group, a phenyl group or a naphthyl group, and the alkyl group, a phenyl group or a naphthyl group having 1 to 12 alkoxy groups and a carbon number of 1 to 12 are used. a substituent having one less than a hydroxyl group; R6 and R7 are each independently a carbamoyloxy group; X. is a fluorinated alkyl ion having a carbon number of 1 to 12] 2. A compound as in the first aspect of the patent application (B3), [Chemical 3] Carbon number to 12 may have a number selected from the carbon number group to the number 1 to 12, which is as follows

(B3) 1323251 3 - 一種酸產生劑，其係由如申請專利範圍第1或2 項的化合物所構成。 4· 一種增強化學型光阻組成物，其係含有（a)藉酸使鹼溶解性變化之樹脂、及（b)藉輻射線照射產生酸之化合物，其特徵在於：該（b)藉輻射線照射產生酸之化合物含有如申請專利範圍第3項之酸產生劑。 5 ·如申請專利範圍第4項之增強化學型光阻組成物，其係爲365nm以上之波長的幅射線用。 6·—種光阻層層合體，其特徵在於：於支撐體上層合由申請專利範圍第4項之增強化學型光阻組成物所構成之光阻層。 7. 申請專利範圍第6項之光阻層層合體，其中該支撐體爲於光阻層側之表面的至少一部分使用銅之支撐體。 8. —種光阻圖型之形成方法，其特徵在於含有：於支撐體上層合由增強化學型光阻組成物所構成之光阻層而得到申請專利範圍第6項之光阻層層合體之層合步驟、與對光阻層層合體選擇性地照射輻射線之曝光步驟、及於該曝光步驟後進行顯像而得到光阻圖型之顯像步驟。 9. 一種增強化學型光阻組成物，其係含有（a)藉酸使鹼溶解性變化之樹脂，及（b)藉輻射線照射產生酸之化合物，及（c)以下述通式（C1)所示之化合物，該（b)藉輻射線照射產生酸之化合物爲含有下述通式（B 2)所示之硫鑰鹽系酸產生劑（b - 1)， -2- 1323251 O-R1(B3) 1323251 3 - An acid generator comprising the compound of claim 1 or 2 of the patent application. 4. A reinforced chemical resist composition comprising (a) a resin which changes solubility of an alkali by an acid, and (b) a compound which generates an acid by irradiation with radiation, characterized in that: (b) by radiation The compound which generates an acid by line irradiation contains an acid generator as in the third item of the patent application. 5. The reinforced chemical resist composition of claim 4, which is a ray having a wavelength of 365 nm or more. A photoresist layer laminate characterized in that a photoresist layer composed of a reinforced chemical resist composition of the fourth application of the patent application is laminated on a support. 7. The photoresist layer laminate of claim 6, wherein the support body uses a support of copper on at least a portion of the surface of the photoresist layer side. 8. A method for forming a photoresist pattern, comprising: laminating a photoresist layer composed of a reinforced chemical resist composition on a support to obtain a photoresist layer laminate of claim 6 The laminating step, the exposing step of selectively irradiating the radiation to the photoresist layer, and the developing after the exposing step to obtain a resist pattern forming step. A reinforced chemical resist composition comprising (a) a resin which changes solubility in an alkali by an acid, and (b) a compound which generates an acid by irradiation with radiation, and (c) has the following formula (C1) The compound shown, (b) the compound which generates an acid by irradiation with radiation is a sulphuric acid generator (b-1) represented by the following formula (B2), -2-1323251 O- R1

(Cl) [式中，R1及R2係碳數1〜4之烷基’且RkR2](Cl) [wherein R1 and R2 are alkyl groups having 1 to 4 carbon atoms] and RkR2]

[式（B2 )中，R4、R5係分別獨主地爲碳數1至12 之烷基、苯基或萘基，該烷基、苯基或萘基可具有由碳數 1至12之烷氧基、碳數1至12之烷基及羥基所選出之至少1種之取代基；R6、R7係分別獨主地爲碳數1至1 2之烷氧基；X·爲碳數1至12之氟化烷基離子]。 1〇·如申請專利範圍第9項之增強化學型光阻組成物’其中該通式（B2)所示化合物，爲以下述通式（B3)所示之化合物 -3- 1323251[In the formula (B2), R4 and R5 are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group or a naphthyl group, and the alkyl group, phenyl group or naphthyl group may have an alkyl group having 1 to 12 carbon atoms. a substituent of at least one selected from the group consisting of an oxy group, an alkyl group having 1 to 12 carbon atoms, and a hydroxyl group; and R6 and R7 are each independently alkoxy groups having 1 to 12 carbon atoms; and X is a carbon number of 1 to 12 fluorinated alkyl ion]. 1. The reinforced chemical resist composition of claim 9 wherein the compound represented by the formula (B2) is a compound represented by the following formula (B3) -3- 1323251

(B3) 11. 如申請專利範圍第9項的增強化學型光阻組成物，其係爲365nm以上之波長的輻射線用。 12. —種光阻層層合體，其特徵在於：於支撐體上層合由申請專利範圍第9項的增強化學型光阻組成物所構成之光阻層。 13. 申請專利範圍第12項之光阻層層合體，其中該支撐體爲於光阻層側之表面的至少一部分使用銅之支撐體。 14. 一種光阻圖型之形成方法，其特徵在於含有：於支撐體上層合由增強化學型光阻組成物所構成之光阻層而得到申請專利範圍第1 2項之光阻層層合體之層合步驟、與對光阻層層合體選擇性地照射輻射線之曝光步驟、及於該曝光步驟後進行顯像而得到光阻圖型之顯像步驟。(B3) 11. The reinforced chemical resist composition according to claim 9 of the patent application, which is a radiation having a wavelength of 365 nm or more. A photoresist layer laminate characterized in that a photoresist layer composed of the reinforced chemical resist composition of claim 9 of the patent application is laminated on a support. 13. The photoresist layer laminate of claim 12, wherein the support body uses a copper support on at least a portion of the surface of the photoresist layer side. A method for forming a photoresist pattern, comprising: laminating a photoresist layer composed of a reinforced chemical resist composition on a support to obtain a photoresist layer laminate of claim 12; The laminating step, the exposing step of selectively irradiating the radiation to the photoresist layer, and the developing after the exposing step to obtain a resist pattern forming step.