TW201217905A - in which the Haze of the support film is 0.01-2.0%, and the total particles with diameter greater than 5 μm and agglutinate with diameter greater than 5 μm in the support film are less than 5 per mm<SP>2</SP> - Google Patents
in which the Haze of the support film is 0.01-2.0%, and the total particles with diameter greater than 5 μm and agglutinate with diameter greater than 5 μm in the support film are less than 5 per mm<SP>2</SP> Download PDFInfo
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201217905 六、發明說明: 【發明所屬之技術領域】 本發明係有關感光性元件、使用其之光阻圖型之形成 方法及印刷電路板之製造方法及印刷電路板。 【先前技術】 以往,在印刷電路板之製造領域及金屬之精密加工領 域中,用於蝕刻、電鍍等之光阻材料係廣泛地用於由感光 性樹脂組成物層(以下稱爲「感光層」)、支持薄膜及保 護薄膜所構成的感光性元件’(參照特開平0 1 -22 1 735號公 報、特開平02-230 1 49號公報、特公昭56-040824號公報、 特開昭5 5-5 0 1 072號公報、特開昭47-000469號公報、特開 昭59-097 1 3 8號公報、特開昭59-216141號公報、特開昭63-1 97942號公報)。 印刷電路板係如下述所製造。首先,將感光性元件之 保護薄膜由感光層剝離後,將感光層層合於電路形成用基 板的導電膜上。其次,對感光層施加圖型曝光後’感光層 之未曝光部分以顯像液除去’形成光阻圖型。然後’依據 此光阻圖型,將導電膜進行圖型化形成印刷電路板。 近年,隨著印刷電路板之高密度化,使得電路形成用 基板與光阻材料之感光層的接觸面積變小。因此’形成感 光層的感光性樹脂組成物在蝕刻或電鍍步驟中,被要求優 異的機械強度、耐藥品性、柔軟性。同時需要與電路形成 用基板之優異的密著性及圖型形成時之優異的解像度。例 -5- 201217905 如揭示以電鍍耐性優異爲目的,含有具有特定構造之黏結 劑聚合物的感光性樹脂組成物(參照特開2006-234995號 公報、特開2008-03 9978號公報)。 通常使用感光性元件形成光阻時,將感光層層合於基 板上後,介於支持薄膜,對感光層進行曝光。因此爲了得 到圖型形成時之高解像度,不僅是感光性樹脂組成物,也 要考慮使用之支持薄膜的性質。 爲了得到高的解像度,例如提案在支持薄膜之一方的 最表面含有平均粒徑〇.〇1〜5μηι程度之無機或有機微粒子, 以降低支持薄膜之霧度,即使介於支持薄膜對感光層進行 曝光也可高解像度化的方法(例如參照特許第401 4872號 、國際公開第08/093 643號、特開平07-3 3 3 8 53號公報、國 際公開第00/079344號)。 【發明內容】 但是以往的手法可抑制因支持薄膜影響造成感光層之 解像度降低及某程度抑制硬化後之光阻形狀缺損(光阻缺 損),但是爲了滿足近年之感光性元件所要求的特性時, 需要進一步改善。 僅將以往感光性樹脂組成物與專利第40 1 48 72號、國 際公開第08/093 643號、特開平〇7_3 3 3 8 5 3號公報、國際公 開第〇〇/〇79344號所記載的支持薄膜組合時’欲達成近年 要求之顯像性及解像度時’有其限度’仍有進一步改善的 餘地。 -6 - 201217905 本發明有鑑於上述事項而完成者,本發明之目的係提 供可充分降低光阻缺損,且具有圖型形成時之優異的顯像 性及解像度的感光性元件。 本發明係提供一種感光性元件,其係具備支持薄膜與 形成於前述支持薄膜上之感光性樹脂組成物層的感光性元 件,前述支持薄膜之霧度爲0.01〜2.0%,且前述支持薄膜 所含之直徑5μηι以上之粒子及直徑5μηι以上之凝集物的總 數爲5個/mm2以下, 前述感光性樹脂組成物層含有:黏結劑聚合物、具有 乙烯性不飽和鍵之光聚合性化合物及光聚合起始劑, 前述黏結劑聚合物係酸價X爲60〜130mgKOH/g,重量 平均分子量Mw滿足以下述式(I)表示之關係。 10000 ^ Mw<4000e° 02x (I) [式(I )中,x係表示黏結劑聚合物之酸價,Mw係表 示黏結劑聚合物之重量平均分子量]。 本發明之感光性元件係因具備具有上述構成之支持薄 膜,可充分降低光阻缺損。又,本發明之感光性元件係因 具備具有上述構成之感光性樹脂組成物層,因此可充分降 低光阻缺損,具有圖型形成時之優異的顯像性及解像度。 上述具有乙烯性不飽和鍵之光聚合性化合物可含有以 下述一般式(II)表示之化合物。201217905 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to a photosensitive element, a method of forming a photoresist pattern using the same, a method of manufacturing a printed circuit board, and a printed circuit board. [Prior Art] Conventionally, in the field of manufacturing of printed circuit boards and the field of precision metal processing, photoresist materials for etching, plating, etc. are widely used for a layer composed of a photosensitive resin (hereinafter referred to as "photosensitive layer". </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. The printed circuit board is manufactured as follows. First, after the protective film of the photosensitive element is peeled off from the photosensitive layer, the photosensitive layer is laminated on the conductive film of the substrate for circuit formation. Next, after the pattern exposure is applied to the photosensitive layer, the unexposed portion of the photosensitive layer is removed by the developing liquid to form a photoresist pattern. Then, according to the photoresist pattern, the conductive film is patterned to form a printed circuit board. In recent years, with the increase in density of printed circuit boards, the contact area between the circuit-forming substrate and the photosensitive layer of the photoresist material has become small. Therefore, the photosensitive resin composition forming the photosensitive layer is required to have excellent mechanical strength, chemical resistance, and flexibility in the etching or plating step. At the same time, excellent adhesion to the substrate for forming a circuit and excellent resolution at the time of pattern formation are required. Example -5 - 201217905 A photosensitive resin composition containing a binder polymer having a specific structure for the purpose of excellent plating resistance is disclosed (see JP-A-2006-234995, JP-A-2008-03 9978). When a photosensitive element is usually used to form a photoresist, the photosensitive layer is laminated on a substrate, and then placed on a support film to expose the photosensitive layer. Therefore, in order to obtain a high resolution in the formation of a pattern, not only a photosensitive resin composition but also the properties of the supporting film to be used are considered. In order to obtain a high resolution, for example, it is proposed to contain inorganic or organic fine particles having an average particle diameter of about 〜1 to 5 μηι on the outermost surface of one of the supporting films to reduce the haze of the supporting film even if the supporting film is used for the photosensitive layer. The exposure can also be a method of high resolution (for example, refer to Japanese Patent No. 401 4872, International Publication No. 08/093643, Japanese Patent Publication No. Hei 07-3 3 3 8 53, and International Publication No. 00/079344). SUMMARY OF THE INVENTION However, in the conventional method, it is possible to suppress a decrease in the resolution of the photosensitive layer due to the influence of the supporting film and to suppress the photoresist shape defect (photoresist defect) after the curing is suppressed to some extent, but in order to satisfy the characteristics required for the photosensitive element in recent years. , need further improvement. Only the conventional photosensitive resin composition is described in Japanese Patent Publication No. 40 1 48 72, International Publication No. 08/093643, Japanese Patent Application Laid-Open No. Hei No. Hei. When supporting film combination, there is still room for further improvement when there is a limit to the 'requirement for resolution and resolution required in recent years. -6 - 201217905 The present invention has been made in view of the above, and an object of the present invention is to provide a photosensitive element which can sufficiently reduce a photoresist defect and which has excellent developability and resolution at the time of pattern formation. The present invention provides a photosensitive element comprising a photosensitive member having a support film and a photosensitive resin composition layer formed on the support film, wherein the support film has a haze of 0.01 to 2.0%, and the support film is provided The total number of particles having a diameter of 5 μm or more and agglomerates having a diameter of 5 μm or more is 5 pieces/mm 2 or less, and the photosensitive resin composition layer contains a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and light. In the polymerization initiator, the binder polymer has an acid value X of 60 to 130 mgKOH/g, and the weight average molecular weight Mw satisfies the relationship represented by the following formula (I). 10000 ^ Mw < 4000e ° 02x (I) [In the formula (I), x represents the acid value of the binder polymer, and Mw represents the weight average molecular weight of the binder polymer]. The photosensitive element of the present invention is provided with a support film having the above configuration, and the photoresist defect can be sufficiently reduced. Further, since the photosensitive element of the present invention has the photosensitive resin composition layer having the above-described configuration, the photoresist defect can be sufficiently reduced, and the image forming property and the resolution at the time of pattern formation are excellent. The photopolymerizable compound having an ethylenically unsaturated bond may contain a compound represented by the following general formula (II).
(H)(H)
201217905 一般式(Π)中’ R1及R係各自獨立表 基,Y係表示碳數2~6之伸烷基,η1及η2係各 整數,rikn2係4〜40,複數存在之Υ彼此可相 因含有上述一般式(Π)表示之化合物 、解像性及耐藥品性之平衡變佳,可形成極 型。 又,本發明之感光性元件係因黏結劑聚 一般式(ΠΙ) 、( IV )及(V )表示之2價 著性、解像性及剝離性之平衡變佳,可形成 圖型。 <πι> 示氫原子或甲 自獨立表示正 同或不同。 ’因此密著性 細線之光阻圖 合物具有下述 基團,因此密 極細線之光阻201217905 In the general formula (Π), 'R1 and R are independent of each other, Y is an alkylene group having 2 to 6 carbon atoms, η1 and η2 are integers, and rikn2 is 4 to 40. The polar type can be formed because the compound represented by the above general formula (Π) has a good balance of resolution and chemical resistance. Further, the photosensitive element of the present invention has a good balance between the valence, resolution and releasability represented by the general formula (ΠΙ), (IV) and (V) of the binder, and can form a pattern. <πι> indicates that a hydrogen atom or a radical is represented by the same or different. Therefore, the photoresist pattern of the adhesive fine line has the following groups, and thus the photoresist of the dense fine line
(IV) "CH2#e*C*—(IV) "CH2#e*C*—
<V) OR7 一般式(III ) (IV)及(V)中,R3 、R4及R6係各 201217905 自獨立表示氫原子或甲基,R5係表示碳數1〜4之烷基、碳 數1〜3之烷氧基、羥基或鹵素原子,R7係表示碳數卜10之 烷基’ P係表示0〜5之整數,p爲2以上時,複數存在之R5彼 此可相同或不同。 本發明之感光性元件係因黏結劑聚合物更具有下述一 般式(VI )表示之2價基團,因此密著性、解像性及剝離 性之平衡變得更佳。 R15 I 一 CH2-C— (VI)<V) OR7 In the general formula (III) (IV) and (V), R3, R4 and R6 each of 201217905 independently represent a hydrogen atom or a methyl group, and R5 represents an alkyl group having a carbon number of 1 to 4 and a carbon number. 1 to 3 of the alkoxy group, a hydroxyl group or a halogen atom, and R7 means an alkyl group having a carbon number of 10'. The P group represents an integer of 0 to 5, and when p is 2 or more, the plural R5 may be the same or different. In the photosensitive element of the present invention, since the binder polymer further has a divalent group represented by the following general formula (VI), the balance of adhesion, resolution and releasability is further improved. R15 I - CH2-C— (VI)
0入。 —般式(VI)中,R15係表示氫原子或甲基,Ri6係表 示碳數1〜4之烷基、碳數1〜3之烷氧基、羥基或鹵素原子, q係表示0〜5之整數’ q爲2以上時,複數存在之R16彼此可 相同或不同。 又’本發明之感光性元件中,光聚合起始劑可含有 2,4,5-三芳基咪唑二聚物。藉此可維持光感度,因此密著 性及解像性更優異,可形成極細線之光阻圖型。 又’本發明係提供一種光阻圖型之形成方法,其係含 有:將上述感光性元件依上述感光性樹脂組成物層、上述 -9 - 201217905 支持薄膜之順序層合於電路形成用基板上的層合步驟; 將活性光線通過前述支持薄膜,照射於前述感光性樹 脂組成物層之所定部分,在前述感光性樹脂組成物層上形 成光硬化部的曝光步驟: 除去前述光硬化部以外之前述感光性樹脂組成物層的 顯像步驟。依據本發明之光阻圖型之形成方法時,因使用 上述本發明之感光性元件,故可有效率得到極細線的光阻 圖型。 本發明係提供一種印刷電路板之製造方法,其係具有 對於形成有光阻圖型之電路形成用基板,施行蝕刻或鍍敷 的步驟的印刷電路板之製造方法及藉由上述製造方法所製 造的印刷電路板。依據本發明之印刷電路板之製造方法時 ,因採用使用上述本發明之感光性元件的光阻圖型之形成 方法,因此可得到具有極細線之配線圖型之高密度的印刷 電路板。 依據本發明之感光性元件時,可充分降低光阻缺損, 且可提供具有圖型形成時之優異的顯像性及解像度的感光 性元件。 較佳之實施例之說明 以下,必要時可參照圖面詳細說明本發明之較佳實施 形態。圖面中,上下左右等之位置關係,在無特別聲明時 ,係依據圖面所示之位置關係。此外,圖面之尺寸比率不 限於圖示之比率。又,本說明書中之「(甲基)丙烯酸酯 -10- 201217905 」係指「丙烯酸酯」及與其對應之「甲基丙烯酸酯」,「 (甲基)丙烯醯基」係指「丙烯醯基」及與其對應之「甲 基丙烯醯基」。 圖1係表示本發明之感光性元件之較佳實施形態的模 式剖面圖。圖1所示之感光性元件1係以支持薄膜10與感光 層(感光性樹脂組成物層)20所構成。感光層20係設置於 支持薄膜10之第1主面12上。又,支持薄膜10係在與第1主 面1 2相反側具有第2主面1 4。 (支持薄膜) 支持薄膜10係霧度爲0.01〜2.0 %,且支持薄膜10所含 之直徑5μηι以上之粒子及直徑5μπι以上的凝集物(以下僅 稱爲「粒子等」)之總數爲5個/mm2以下者。在此,支持 薄膜10所含之直徑5μιη以上之粒子等包括由支持薄膜1〇之 第1主面12及第2主面14突出者及存在於薄膜10之內部者之 兩者。又,直徑5μιη以上之粒子等包括直徑5μιη以上之一 次粒子及未達直徑5μπι之一次粒子的凝集物。 直徑5μιη以上之粒子等的總數,從減少曝光及顯像後 之光阻之一部份缺損的觀點,較佳爲5個/mm2以下,更佳 爲3個/mm2以下,更佳爲1個/mm2以下。此粒子等之總數超 過5個/mm2的感光性元件使用於印刷電路板之製造時,造 成蝕刻時產生烘烤不良或電鍍時產生短路不良的原因’而 有印刷電路板之製造良率降低的傾向。 即使支持薄膜10含有多數直徑未達之粒子等’對 -11 - 201217905 於光散射的影響不大》其主要原因係在後述曝光步驟中, 光照射於感光層20時,感光層20之光硬化反應不僅在光照 射部,雖爲一部分,但是也會對光未直接被照射之橫方向 (相對於光照射方向爲垂直方向)進行反應。因此,粒子 徑較小時,粒子正下部之光硬化反應充分進行,但是隨著 粒子徑變大,粒子正下部之光硬化反應未充分進行,可能 因此產生光阻之缺損(光阻缺損)。 支持薄膜10所含之直徑5μιη以上之粒子等係構成支持 薄膜10的成分,例如有聚合物之凝膠狀物、原料的單體、 製造時所使用的觸媒、必要時含有之無機或有機微粒子在 薄膜作製時,凝集形成的凝集物、於薄膜上塗佈含有滑劑 層時所產生之滑劑與接著劑所造成之膨脹,因薄膜中所含 有之直徑5μηι以上之粒子等所產生者。欲將直徑5μιη以上 之粒子等設定爲5個/mm2以下時,可在此等粒子等中,選 擇使用粒徑較小者或分散性優異者。 上述直徑5 μιη以上之粒子等的總數,可使用偏光顯微 鏡測定。直徑5 μιη以上之一次粒子與未達直徑5 μπι之一次 粒子凝集所形成的凝集物係當作1個計算。圖2係觀察具有 直徑5μιη以上之粒子等之支持薄膜表面的偏光顯微鏡相片 。圖2中,以圓圍繞的部分係表示相當於直徑5 μιη以上之粒 子等之部分的一例。圖3係使用在具有多數直徑5μιη以上之 粒子等之支持薄膜上,具備感光層之感光性元件所形成之 光阻圖型的掃描型顯微鏡相片。以框圍繞的部分係表示光 阻缺損處。如此,在支持薄膜之表面有多數直徑5 μιη以上 -12- 201217905 之粒子等時,會產生光阻缺損。 支持薄膜10的材料只要是直徑5 μιη以上之粒子等的總 數爲5個/mm2以下者時,無特別限制。支持薄膜10例如有 含有選自聚對苯二甲酸乙二酯(以下稱爲「PET」)等之 聚酯及聚丙烯及聚乙烯等之聚烯烴所成群之1種以上之樹 脂材料的薄膜。 支持薄膜10可爲單層或多層。例如使用由2層所構成 之2層支持薄膜時,在二軸配向聚酯薄膜之一面層合含有 微粒子之樹脂層所成之2層薄膜作爲支持薄膜使用,在與 形成含有上述微粒子之樹脂層之面相反側的面形成感光層 20較佳。支持薄膜10也可使用由3層所構成之多層支持薄 膜(例如A層/B層/A層)。多層支持薄膜之構成無特別限 制,但是從薄膜之滑性等的觀點,最外層(上述3層所構 成時爲A層)均爲含有微粒子之樹脂層較佳。 以往2層支持薄膜係將具有微粒子之樹脂層塗佈於二 軸配向聚酯薄膜上而製造,因此感光層之層合時,含有微 粒子的樹脂層容易剝離,剝離後的上述樹脂層附著於感光 層,可能造成不良的原因。因此,本實施形態中,較佳爲 使用由含有微粒子之樹脂層與二軸配向聚酯薄膜所構成之 3層所構成的多層支持薄膜。 本實施形態中,特佳爲支持薄膜1〇所含之直徑5μΐη以 上之粒子等的總數調整爲5個/mm2以下,同時具備含有這 種微粒子之樹脂層的多層支持薄膜。因此,薄膜之滑性變 佳,同時,抑制曝光時之光散射的平衡佳,可達到更高水 -13- 201217905 準。微粒子之平均粒子徑,較佳爲含有微粒子之樹脂層之 層厚之0」〜10倍,更佳爲〇.2~5倍。平均粒子徑未達0.1倍 時,滑性有變差的傾向,超過10倍時,感光層特別是有易 產生凹凸的傾向。 上述微粒子係在含有微粒子之樹脂層中,以樹脂的質 量爲基準,較佳爲含有0.01 ~50質量%。上述微粒子可使用 例如以各種核劑在聚合時生成的微粒子、凝集體、二氧化 矽微粒子(凝集氧化矽等))碳酸鈣微粒子、氧化鋁微粒 子、氧化鈦微粒子及硫酸鋇微粒子等之無機微粒子、交聯 聚苯乙烯微粒子、丙烯酸樹脂微粒子及醯亞胺樹脂微粒子 等之有機微粒子、及此等混合體。 3層以上之多層支持薄膜中,被含有微粒子之最外層 所挾之1以上的中間層可爲含有上述微粒子者或不含上述 微粒子者,從解像性的觀點,不含有上述微粒子者較佳。 中間層含有上述微粒子時,中間層之含量較佳爲最外層之 含量的1/3以下,更佳爲1/5以下。 又,從解像度的觀點,含有上述微粒子之樹脂層的層 厚較佳爲〇.〇1〜5μιη,更佳爲〇.〇5~3μηι,特佳爲0.1〜2μιη。 未與最外層之中間層對向的面,較佳爲具有1.2以下的靜 摩擦係數。靜摩擦係數超過1.2時,在薄膜製造時及感光 性元件製造時,容易產生皴紋,且容易產生靜電,而有容 易附著垃圾的傾向。本實施形態中,靜摩擦係數可依據 ASTMD 1 894進行測定。 欲將支持薄膜10中所含之直徑5 μηι以上之粒子等的總 -14- 201217905 數設定爲5個/mm2以下時,含有微粒子之樹脂層所含的微 粒子之粒徑,較佳爲未達5 μιη。爲了進一步降低曝光時之 光散射,配合微粒子之粒徑’適當調整含有微粒子之樹脂 層的層厚較佳。 支持薄膜10在不影響感光層20之感光性的範圍內’必 要時,可含有防靜電劑等。 支持薄膜10之霧度,從光感度及解像性優異的觀點, 較佳爲2.0%以下,更佳爲1.5%以下,更佳爲1.0%以下,特 佳爲0.5 %以下。在此「霧度」係指濁度。本實施形態中之 支持薄膜10之霧度係依據JIS Κ 71 05所規定之方法,使用 市售濁度計量測所得的値。上述霧度可使用例如NDH-1 00 1DP(日本電色工業公司製、商品名)之市售濁度計等 來量測。上述霧度之下限値,從光感度及解像性優異的觀 點,接近零較佳,從支持薄膜10之製作時之卷繞性等的觀 點,上述霧度設定爲0.01以上較佳。上述霧度未達0.01時 ,支持薄膜因不含微粒子等,造成支持薄膜之製造時之卷 繞有問題,有產生皴紋等的傾向。 支持薄膜10之厚度較佳爲5〜40μιη,更佳爲8〜35μιη, 更佳爲10〜30μιη,特佳爲12〜25μιη。厚度未達5μιη時,由感 光性元件上剝離支持薄膜時,支持薄膜有容易破裂的傾向 。又’厚度超過40μηι時,解像度有降低的傾向,同時,有 廉價性較差的傾向。 支持薄膜10可由市售一般工業用薄膜中,取得可作爲 感光性元件1之支持薄膜1 0使用者,也可經適當加工後使 -15- 201217905 用。可作爲支持薄膜10使用之市售之一般工業用薄膜,例 如有最外層含有微粒子之3層構造的PET薄膜「QS-48」( 東麗公司製、商品名)》 (感光層) 感光層20係由感光性樹脂組成物所構成的層。構成感 光層20之感光性樹脂組成物係含有(a)黏結劑聚合物( 以下稱爲「(A)成分」)、(B)具有乙烯性不飽和鍵之 光聚合性化合物及(C )光聚合起始劑(以下稱爲「( C ) 成分」)。以下詳細說明各成分。 (黏結劑聚合物) (A)成分之黏結劑聚合物只要是酸價x爲60〜 13 0mgKOH/g,重量平均分子量Mw滿足下述式(I)表示 之關係者時,無特別限定均可使用。 10000^Mw<4000e°°2x (I) 黏結劑聚合物之酸價X與重量平均分子量Mw之關係滿 足上述式之關係,可提供硬化後之諸特性(顯像性、密著 性、解像性、光阻側面之形狀及光阻缺損)優異的感光性 樹脂組成物。 黏結劑聚合物之酸價X係60〜130mgKOH/g,但是平衡 且滿足上述諸特性的觀點,較佳爲65〜130mgKOH/g,更佳 爲 90~130mgKOH/g,更佳爲 110 〜130mgKOH/g。 與酸價(中和試料lg所需之氫氧化鉀(KOH)之mg數 -16- 201217905 )同樣的指標,例如有酸當量(具有1當量之羧酸之聚合 物之g數),此等可互相換算。 黏結劑聚合物之重量平均分子量係滿足上述式(I) 表示之關係者。黏結劑聚合物之Mw之下限値係10000以上 ,從感光層之韌性優異的觀點,較佳爲1 50 00以上,更佳 爲20000以上,更佳爲25000以上。又,黏結劑聚合物之 Mw之上限値係WOOe^x以下,從平衡且滿足硬化後之諸 特性的觀點,較佳爲WOOjMx之90°/。以下,更佳'爲80%以 下,更佳爲70%以下。上述重量平均分子量係使用藉由凝 膠滲透色譜(以下稱爲「GPC」)量測,換算成標準聚苯 乙烯的値,測定條件係與後述實施例所記載的條件相同。 黏結劑聚合物例如有丙烯酸樹脂、苯乙烯樹脂、環氧 樹脂、醯胺樹脂、醯胺環氧樹脂、醇酸樹脂及酚樹脂。此 等中,從鹼顯像性的觀點,較佳爲丙烯酸樹脂。此等可單 獨或組合2種以上使用。 黏結劑聚合物可藉由例如使聚合性單體進行自由基聚 合而製造。聚合性單體例如有苯乙烯、乙烯基甲苯、p -甲 基苯乙烯、P-氯苯乙烯、α-甲基苯乙烯及α-甲基苯乙烯衍 生物等可聚合的苯乙烯衍生物、丙烯醯胺、丙烯腈及乙烯 基-η-丁基酯等之乙烯醇的酯類、(甲基)丙烯酸烷酯、( 甲基)丙烯酸苄酯、(甲基)丙烯酸四氫糠酯、(甲基) 丙烯酸二甲基胺基乙酯、(甲基)丙烯酸二乙基胺基乙酯 、(甲基)丙烯酸縮水甘油酯、2,2,2-三氟乙基(甲基) 丙烯酸酯及2,2,3,3-四氟丙基(甲基)丙烯酸酯等之(甲 -17- 201217905 基)丙烯酸酯、(甲基)丙烯酸、α-溴(甲基)丙烯酸、 α-氯(甲基)丙烯酸、β-呋喃基(甲基)丙烯酸及β-苯乙 烯基(甲基)丙烯酸等之(甲基)丙烯酸衍生物、馬來酸 、馬來酸酐、馬來酸單甲酯、馬來酸單乙酯及馬來酸單異 丙酯等之馬來酸衍生物、富馬酸、肉桂酸、α-氰基肉桂酸 、衣康酸、巴豆酸及丙炔酸等。此等可單獨或組合2種以 上使用。0 into. In the general formula (VI), R15 represents a hydrogen atom or a methyl group, and Ri6 represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group or a halogen atom, and q represents 0 to 5 When the integer 'q is 2 or more, the plural R16s may be the same or different from each other. Further, in the photosensitive element of the present invention, the photopolymerization initiator may contain a 2,4,5-triarylimidazole dimer. Thereby, the light sensitivity can be maintained, so that the adhesion and the resolution are more excellent, and a photoresist pattern of an extremely thin line can be formed. Further, the present invention provides a method for forming a photoresist pattern, comprising: laminating the photosensitive element on a circuit-forming substrate in the order of the photosensitive resin composition layer and the -9 - 201217905 support film; a laminating step of exposing the active light to the predetermined portion of the photosensitive resin composition layer through the support film, and forming a photocured portion on the photosensitive resin composition layer: removing the photocuring portion a developing step of the photosensitive resin composition layer. According to the method for forming a photoresist pattern of the present invention, since the photosensitive element of the present invention described above is used, a photoresist pattern of an extremely fine line can be obtained efficiently. The present invention provides a method of manufacturing a printed circuit board, which is a method of manufacturing a printed circuit board having a step of performing etching or plating on a circuit for forming a circuit pattern having a photoresist pattern, and a method of manufacturing the same by the above-described manufacturing method Printed circuit board. According to the method for producing a printed wiring board of the present invention, a pattern of forming a photoresist pattern using the photosensitive element of the present invention is used, whereby a high-density printed circuit board having a wiring pattern of an extremely thin line can be obtained. According to the photosensitive element of the present invention, the photoresist defect can be sufficiently reduced, and a photosensitive element having excellent developability and resolution at the time of pattern formation can be provided. DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawing, the positional relationship of up, down, left, and right, etc., is based on the positional relationship shown in the drawing when there is no special statement. Further, the dimensional ratio of the drawings is not limited to the ratio shown. In addition, in this specification, "(meth)acrylate-10-201217905" means "acrylate" and the corresponding "methacrylate", and "(meth)acryloyl group" means "acryloyl group" And the corresponding "methacryl oxime". BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive member of the present invention. The photosensitive element 1 shown in Fig. 1 is composed of a support film 10 and a photosensitive layer (photosensitive resin composition layer) 20. The photosensitive layer 20 is provided on the first main surface 12 of the support film 10. Further, the support film 10 has a second main surface 14 on the side opposite to the first main surface 12. (Support film) The film 10 has a haze of 0.01 to 2.0%, and the total number of particles having a diameter of 5 μm or more and agglomerates having a diameter of 5 μm or more (hereinafter simply referred to as "particles" or the like) contained in the film 10 is 5 pieces. /mm2 or less. Here, the particles having a diameter of 5 μm or more contained in the support film 10 include both the first main surface 12 and the second main surface 14 of the support film 1 and those existing inside the film 10. Further, particles having a diameter of 5 μm or more include agglomerates of primary particles having a diameter of 5 μm or more and primary particles having a diameter of 5 μm or less. The total number of particles having a diameter of 5 μm or more is preferably 5 pieces/mm 2 or less, more preferably 3 pieces/mm 2 or less, and more preferably 1 part, from the viewpoint of reducing partial defects of light resistance after exposure and development. /mm2 or less. When a photosensitive element having a total number of particles or the like of more than 5/mm 2 is used in the production of a printed circuit board, it causes a baking failure during etching or a short-circuit defect during plating, and the manufacturing yield of the printed circuit board is lowered. tendency. Even if the support film 10 contains a large number of particles which are not in diameter, etc., the effect of 'preferential -11 - 201217905 on light scattering is small" is mainly due to the light hardening of the photosensitive layer 20 when light is irradiated onto the photosensitive layer 20 in the exposure step described later. The reaction is not only a part of the light-irradiating portion, but also reacts in the lateral direction (the vertical direction with respect to the light irradiation direction) in which the light is not directly irradiated. Therefore, when the particle diameter is small, the photohardening reaction in the lower portion of the particle proceeds sufficiently. However, as the particle diameter increases, the photohardening reaction in the lower portion of the particle does not sufficiently proceed, and a photoresist defect (photoresist defect) may occur. Particles having a diameter of 5 μm or more contained in the support film 10 constitute a component of the support film 10, and examples thereof include a gel of a polymer, a monomer of a raw material, a catalyst used in the production, and an inorganic or organic material if necessary. When the microparticles are formed in a film, agglomerates formed by agglutination, swelling caused by a slip agent and an adhesive generated when a lubricant layer is applied to the film, and particles having a diameter of 5 μm or more contained in the film are generated. . When the particles having a diameter of 5 μm or more are set to 5 pieces/mm 2 or less, those having a small particle diameter or excellent dispersibility can be selected among these particles and the like. The total number of particles having a diameter of 5 μm or more can be measured using a polarizing microscope. The aggregate formed by the primary particles having a diameter of 5 μm or more and the primary particles having a diameter of less than 5 μm is regarded as one calculation. Fig. 2 is a photograph of a polarizing microscope for observing the surface of a supporting film having particles having a diameter of 5 μm or more. In Fig. 2, a portion surrounded by a circle is an example of a portion corresponding to a particle having a diameter of 5 μm or more. Fig. 3 is a scanning-type micrograph of a resist pattern formed by a photosensitive member having a photosensitive layer on a support film having a plurality of particles having a diameter of 5 μm or more. The portion surrounded by the frame indicates the photoresist defect. Thus, when a large number of particles having a diameter of 5 μm or more and -12 to 201217905 are formed on the surface of the support film, a photoresist defect occurs. The material of the support film 10 is not particularly limited as long as the total number of particles having a diameter of 5 μm or more is 5 pieces/mm 2 or less. The support film 10 is, for example, a film containing one or more kinds of resin materials selected from the group consisting of polyesters such as polyethylene terephthalate (hereinafter referred to as "PET") and polyolefins such as polypropylene and polyethylene. . The support film 10 may be a single layer or a plurality of layers. For example, when a two-layer support film composed of two layers is used, a two-layer film formed by laminating a resin layer containing fine particles on one surface of a biaxially oriented polyester film is used as a support film, and a resin layer containing the above-mentioned fine particles is formed. It is preferable that the photosensitive layer 20 is formed on the surface on the opposite side. The support film 10 can also use a multilayer support film composed of three layers (e.g., layer A/layer B/layer A). The configuration of the multilayer support film is not particularly limited. However, from the viewpoint of the smoothness of the film and the like, the outermost layer (the layer A when the three layers are formed) is preferably a resin layer containing fine particles. In the conventional two-layer support film, a resin layer having fine particles is applied to a biaxially oriented polyester film, and thus, when the photosensitive layer is laminated, the resin layer containing fine particles is easily peeled off, and the resin layer after peeling adheres to the photosensitive layer. Layers may cause undesirable causes. Therefore, in the present embodiment, it is preferred to use a multilayer support film composed of three layers of a resin layer containing fine particles and a biaxially oriented polyester film. In the present embodiment, it is particularly preferable to adjust the total number of particles or the like of the support film 1 5 to 5 μm or less, and to provide a multilayer support film containing the resin layer of such fine particles. Therefore, the smoothness of the film is improved, and at the same time, the balance of light scattering at the time of exposure is suppressed, and a higher water level can be achieved -13 - 201217905. The average particle diameter of the fine particles is preferably from 0" to 10 times, more preferably from 2 to 5 times, the layer thickness of the resin layer containing the fine particles. When the average particle diameter is less than 0.1, the slip property tends to be deteriorated. When the average particle diameter is less than 10 times, the photosensitive layer tends to have irregularities. The fine particles are preferably contained in the resin layer containing fine particles in an amount of 0.01 to 50% by mass based on the mass of the resin. For the fine particles, for example, fine particles such as fine particles, aggregates, cerium oxide fine particles (such as aggregated cerium oxide) generated by various nucleating agents, calcium carbonate fine particles, alumina fine particles, titanium oxide fine particles, and barium sulfate fine particles can be used. Organic fine particles such as crosslinked polystyrene fine particles, acrylic resin fine particles, and yttrium imide fine particles, and the like. In the multilayer support film of three or more layers, the intermediate layer containing one or more of the outermost layers containing the fine particles may be one containing or not containing the fine particles, and it is preferable that the fine particles are not contained from the viewpoint of resolution. . When the intermediate layer contains the above fine particles, the content of the intermediate layer is preferably 1/3 or less, more preferably 1/5 or less, of the content of the outermost layer. Further, from the viewpoint of the resolution, the thickness of the resin layer containing the fine particles is preferably from 〇1 to 5 μm, more preferably from 〇5 to 3 μη, particularly preferably from 0.1 to 2 μηη. The surface which is not opposed to the intermediate layer of the outermost layer preferably has a static friction coefficient of 1.2 or less. When the static friction coefficient exceeds 1.2, ruthenium tends to occur during film production and photosensitive element production, and static electricity tends to occur, and there is a tendency for easy adhesion of garbage. In the present embodiment, the static friction coefficient can be measured in accordance with ASTM D 1894. When the total number of-14-201217905 such as particles having a diameter of 5 μη or more contained in the support film 10 is set to 5/mm 2 or less, the particle diameter of the fine particles contained in the resin layer containing fine particles is preferably not reached. 5 μιη. In order to further reduce the light scattering at the time of exposure, it is preferable to appropriately adjust the layer thickness of the resin layer containing the fine particles in accordance with the particle diameter of the fine particles. The support film 10 may contain an antistatic agent or the like when necessary in a range that does not affect the photosensitivity of the photosensitive layer 20. The haze of the support film 10 is preferably 2.0% or less, more preferably 1.5% or less, still more preferably 1.0% or less, and particularly preferably 0.5% or less from the viewpoint of excellent light sensitivity and resolution. Here, "haze" means turbidity. The haze of the support film 10 in the present embodiment is measured by a commercially available turbidity measurement in accordance with the method specified in JIS Κ 71 05. The haze can be measured using, for example, a commercially available turbidity meter such as NDH-1 00 1DP (manufactured by Nippon Denshoku Industries Co., Ltd.). The lower limit of the haze is preferably close to zero from the viewpoint of excellent light sensitivity and resolution, and the haze is preferably 0.01 or more from the viewpoint of the winding property at the time of production of the support film 10. When the haze is less than 0.01, the support film does not contain fine particles or the like, which causes problems in the winding of the support film, and tends to cause creases and the like. The thickness of the support film 10 is preferably 5 to 40 μm, more preferably 8 to 35 μm, still more preferably 10 to 30 μm, and particularly preferably 12 to 25 μm. When the thickness is less than 5 μm, the support film tends to be easily broken when the support film is peeled off from the photosensitive element. Further, when the thickness exceeds 40 μm, the resolution tends to decrease, and at the same time, the price tends to be inferior. The support film 10 can be obtained from a commercially available general industrial film as a support film 10 for the photosensitive element 1, or can be suitably processed to be used for -15-201217905. A commercially available general-purpose film which can be used as the support film 10, for example, a PET film "QS-48" (manufactured by Toray Industries, Inc.) having a three-layer structure containing fine particles in the outermost layer (photosensitive layer) photosensitive layer 20 A layer composed of a photosensitive resin composition. The photosensitive resin composition constituting the photosensitive layer 20 contains (a) a binder polymer (hereinafter referred to as "(A) component"), (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) light. A polymerization initiator (hereinafter referred to as "(C) component"). Each component will be described in detail below. (Binder Polymer) The binder polymer of the component (A) is not particularly limited as long as it has an acid value x of 60 to 130 mg KOH/g and a weight average molecular weight Mw satisfying the relationship represented by the following formula (I). use. 10000^Mw<4000e°°2x (I) The relationship between the acid value X of the binder polymer and the weight average molecular weight Mw satisfies the relationship of the above formula, and provides properties after hardening (developability, adhesion, resolution) Excellent photosensitive resin composition for the shape of the photoresist, the shape of the photoresist side, and the photoresist defect. The acid value X of the binder polymer is 60 to 130 mgKOH/g, but is preferably 65 to 130 mgKOH/g, more preferably 90 to 130 mgKOH/g, still more preferably 110 to 130 mgKOH/g, from the viewpoint of balance and satisfying the above characteristics. g. The same index as the acid value (mg of potassium hydroxide (KOH) required for neutralizing the sample lg-16 - 201217905), for example, an acid equivalent (g number of a polymer having 1 equivalent of a carboxylic acid), etc. Can be converted to each other. The weight average molecular weight of the binder polymer satisfies the relationship expressed by the above formula (I). The lower limit of the Mw of the binder polymer is 10,000 or more, and from the viewpoint of excellent toughness of the photosensitive layer, it is preferably 150,000 or more, more preferably 20,000 or more, still more preferably 25,000 or more. Further, the upper limit of the Mw of the binder polymer is less than or equal to WOOe^x, and from the viewpoint of balance and satisfying the properties after hardening, it is preferably 90 °/ of WOOjMx. Hereinafter, the better one is 80% or less, and more preferably 70% or less. The weight average molecular weight is measured by gel permeation chromatography (hereinafter referred to as "GPC") and converted to standard polystyrene. The measurement conditions are the same as those described in the examples below. The binder polymer is, for example, an acrylic resin, a styrene resin, an epoxy resin, a guanamine resin, a guanamine epoxy resin, an alkyd resin, and a phenol resin. Among these, an acrylic resin is preferred from the viewpoint of alkali developability. These may be used alone or in combination of two or more. The binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer. The polymerizable monomer is, for example, a polymerizable styrene derivative such as styrene, vinyl toluene, p-methylstyrene, P-chlorostyrene, α-methylstyrene or α-methylstyrene derivative, Ethyl alcohol esters such as acrylamide, acrylonitrile and vinyl-η-butyl ester, alkyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, Methyl) dimethylaminoethyl acrylate, diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate And (2,2,3,3-tetrafluoropropyl (meth) acrylate (A-17-201217905) acrylate, (meth)acrylic acid, α-bromo (meth)acrylic acid, α-chloride (Meth)acrylic acid, β-furyl (meth)acrylic acid, and (meth)acrylic acid derivatives such as β-styryl (meth)acrylic acid, maleic acid, maleic anhydride, monomethyl maleate Maleic acid derivatives such as maleic acid monoethyl ester and maleic acid monoisopropyl ester, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and bar Acid, propiolic acid and the like. These may be used alone or in combination of two or more.
黏結劑聚合物從對顯像液之耐性(顯像+液耐性)與剝 離性之平衡的觀點,較佳爲含有下述—般式(111 ) 、(IV ).及(V)表示之構造單位。又’因提高了顯像液耐性, 因此,有密著性及解像性提高的傾向。 <ΙΠ)The binder polymer preferably has a structure represented by the following general formulas (111), (IV), and (V) from the viewpoint of the balance between the resistance (development + liquid resistance) and the peelability of the developing solution. unit. Further, since the development liquid resistance is improved, there is a tendency that the adhesion and the resolution are improved. <ΙΠ)
〇 OH〇 OH
一般式(III) 、( IV)及(V)中 ’ R3、R4及 R6係各 -18- 201217905 自獨立表示氫原子或甲基,R5係表示碳數1〜4之烷基 '碳 數1~3之烷氧基、羥基或鹵素原子,R7係表示碳數之烷 基,P係表示0〜5之整數,p爲2以上時,複數存在之R5彼此 可相同或不同。 上述一般式(III)表示之構造單位係基於(甲基)丙 烯酸的構造單位,較佳爲基於甲基丙烯酸的構造單位( R3 =甲基)。 (A)黏結劑聚合物含有上述一般式(III)表示之構 造單位時,其含有比例係以共聚合物之(A )黏結劑聚合 物之固形分全量爲基準,從顯像性及剝離性又的觀點,較 佳爲10質量%以上,更佳爲15質量%以上,更佳爲20質量% 以上。又,從密著性及解像性優異的觀點,較佳爲5 0質量 %以下,更佳爲4〇質量%以下,更佳爲35質量%以下。 上述一般式(IV)表示之構造單位係基於苯乙烯( R4=氫原子、ρ = 〇)、苯乙烯衍生物、α -甲基苯乙烯 甲基、ρ = 0)及α -甲基苯乙烯衍生物的構造單位。本實施 形態中,「苯乙烯衍生物」及「α -甲基苯乙烯衍生物」係 指苯乙烯及α-甲基苯乙烯之苯環的氫原子被取代基R5 (碳 數1〜4之烷基、碳數1〜3之烷貞基 '羥基、鹵素原子)取代 者。上述苯乙烯衍生物例如有甲基苯乙烯、乙基苯乙稀、 tert-丁基苯乙烯、甲氧基苯乙烯、乙氧基苯乙烯、羥基苯 乙烯及氯苯乙烯,較佳爲P-位有R5取代的構造單位。α-申 基苯乙烯衍生物例如有在上述苯乙烯衍生物中,乙烯基之 α-位之氫原子被甲基取代者。 -19- 201217905 (A)黏結劑聚合物含有上述一般式(IV)表示之構 造單位時’其含有比例係以共聚物之(A )黏結劑聚合物 之固形分全量爲基準,從密著性及解像性優異的觀點,較 佳爲3質量%以上,更佳爲丨〇質量%以上,更佳爲1 5質量% 以上’特佳爲20質量%以上。又從剝離性及硬化後之光阻 的柔軟性的觀點,較佳爲60質量%以下,更佳爲55質量% 以下,更佳爲50質量%以下,更佳爲45質量%以下。 上述一般式(V)表示之構造單位係基於(甲基)丙 烯酸烷酯的構造單位。上述(甲基)丙烯酸烷酯例如有一 般式(V)中,R7爲碳數1〜12之烷基者。碳數1〜12之烷基 可爲直鏈狀或支鏈狀,可具有羥基、乙氧基、鹵素原子等 的取代基。(甲基)丙烯酸烷酯例如有(甲基)丙烯酸甲 酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基 )丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸 tert-丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、 (甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙 烯酸2-乙基己酯及這些之構造異構物。從提高解像度及縮 短剝離時間的觀點,其中R7較佳爲碳數1〜6的烷基’更佳 爲不具有取代基之碳數1~6的烷基,更佳爲甲基。 (A)黏結劑聚合物含有上述一般式(V)表示之構 造單位時,其含有比例係以共聚物之(A )黏結劑聚合物 的固形分全量爲基準’從剝離性優異的觀點,較佳爲1質 量%以上,更佳爲5質量%以上,更佳爲1〇質量%以上,特 佳爲1 5質量%以上。又從解像性優異的觀點’較佳爲5 5質 -20- 201217905 量%以下’更佳爲50質量%以下’更佳爲45質量%以下’更 佳爲40質量%以下。 又,(A )黏結劑聚合物係從密著性及解像性與剝離 性之平衡的觀點,更佳爲含有下述—般式(VI)表示之構 造單位。 —ch9-cIn the general formulae (III), (IV) and (V), 'R3, R4 and R6 are each -18-201217905 from independently representing a hydrogen atom or a methyl group, and R5 is an alkyl group having a carbon number of 1 to 4' carbon number 1. An alkoxy group of ~3, a hydroxyl group or a halogen atom, R7 represents an alkyl group having a carbon number, P represents an integer of 0 to 5, and when p is 2 or more, R5 which is present in plural plural may be the same or different. The structural unit represented by the above general formula (III) is based on the structural unit of (meth)acrylic acid, and is preferably a structural unit based on methacrylic acid (R3 = methyl group). (A) When the binder polymer contains the structural unit represented by the above general formula (III), the content ratio is based on the total solid content of the (A) binder polymer of the copolymer, and the development and releasability are based on Further, the viewpoint is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. In addition, from the viewpoint of excellent adhesion and resolution, it is preferably 50% by mass or less, more preferably 4% by mass or less, and still more preferably 35% by mass or less. The structural unit represented by the above general formula (IV) is based on styrene (R4 = hydrogen atom, ρ = 〇), styrene derivative, α-methylstyrene methyl group, ρ = 0) and α-methyl styrene. The structural unit of the derivative. In the present embodiment, the "styrene derivative" and the "α-methylstyrene derivative" mean that the hydrogen atom of the benzene ring of styrene and α-methylstyrene is substituted with a substituent R5 (carbon number 1 to 4). The alkyl group, the alkylene group having a carbon number of 1 to 3, a hydroxyl group, and a halogen atom are substituted. The above styrene derivatives are, for example, methyl styrene, ethyl styrene, tert-butyl styrene, methoxy styrene, ethoxy styrene, hydroxystyrene and chlorostyrene, preferably P-. A structural unit with a substitution of R5. The α-styrene styrene derivative is, for example, one in which the hydrogen atom at the α-position of the vinyl group is substituted with a methyl group in the above styrene derivative. -19- 201217905 (A) When the binder polymer contains the structural unit represented by the above general formula (IV), the ratio is based on the total solid content of the (A) binder polymer of the copolymer, and the adhesion is based on the adhesion. The viewpoint of excellent resolution is preferably 3% by mass or more, more preferably 丨〇% by mass or more, still more preferably 15% by mass or more, and particularly preferably 20% by mass or more. Further, from the viewpoint of the flexibility of the peeling property and the photoresist after curing, it is preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less, and still more preferably 45% by mass or less. The structural unit represented by the above general formula (V) is based on the structural unit of the alkyl (meth) acrylate. The above alkyl (meth)acrylate is, for example, a compound of the formula (V) wherein R7 is an alkyl group having 1 to 12 carbon atoms. The alkyl group having 1 to 12 carbon atoms may be linear or branched, and may have a substituent such as a hydroxyl group, an ethoxy group or a halogen atom. The alkyl (meth)acrylate may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate or butyl (meth)acrylate. Tert-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethyl (meth)acrylate Hexyl hexyl ester and structural isomers thereof. From the viewpoint of improving the resolution and shortening the peeling time, R7 is preferably an alkyl group having 1 to 6 carbon atoms. More preferably, it is an alkyl group having 1 to 6 carbon atoms which does not have a substituent, and more preferably a methyl group. (A) When the binder polymer contains the structural unit represented by the above general formula (V), the content ratio is based on the total solid content of the (A) binder polymer of the copolymer, and is superior from the viewpoint of excellent releasability. It is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 1% by mass or more, and particularly preferably 15% by mass or more. Further, from the viewpoint of excellent resolution, it is preferably from 5 to 20, and from 2012 to 175%, more preferably 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less. Further, the (A) binder polymer is preferably a structural unit represented by the following general formula (VI) from the viewpoint of balance between adhesion, resolution and releasability. —ch9-c
(VI)(VI)
—般式(VI)中,R15係表示氫原子或甲基,R16係表 示碳數1〜4之烷基、碳數1〜3之烷氧基、羥基或鹵原子。q 係表示〇〜5之整數,q爲2以上時,複數存在之R16彼此可相 同或不同。 上述一般式(VI)表示之構造單位係基於苄基(甲基 )丙烯酸酯及苄基(甲基)丙烯酸酯衍生物的構造單位。 上述苄基(甲基)丙烯酸酯衍生物例如有4-甲基苄基(甲 基)丙烯酸酯、4-乙基苄基(甲基)丙烯酸酯、4_tert_ 丁 基苄基(甲基)丙烯酸酯、4_甲氧基苄基(甲基)丙烯酸 酯、4_乙氧基苄基(甲基)丙烯酸酯、4-羥基苄基(甲基 )丙烯酸酯、4_氯苄基(甲基)丙烯酸酯。上述一般式( -21 - 201217905 VI)表示之構造單位係從顯像性、蝕刻耐性、電鍍耐性及 保持硬化膜之可撓性的觀點,其中較佳爲基於苄基(甲基 )丙烯酸酯(q = 〇時)的構造單位。 (A)黏結劑聚合物含有上述一·般式(VI)表示之構 造單位之含有比例係以共聚物之(A)黏結劑聚合物的固 形分全量爲基準,從密著性優異的觀點,較佳爲5質量%以 上,更佳爲10質量%以上,更佳爲20質量%以上。又從剝 離性及硬化後之光阻的柔軟性的觀點,較佳爲6 0質量%以 下,更佳爲5 5質量%以下,更佳爲5 0質量%以下,更佳爲 45質量%以下。 此等之黏結劑聚合物可1種或組合2種以上使用。組合 2種以上使用時之黏結劑聚合物之組合,例如有由不同共 聚合成分所構成之(含有不同重複單位作爲構成成分)2 種類以上之黏結劑聚合物、不同之重量平均分子量之2種 類以上的黏結劑聚合物、具有不同之分散度之2種類以上 的黏結劑聚合物等。又,也可使用特開平11-327137號公 報所記載之具有多種形態分子量分布的聚合物作爲黏結劑 聚合物。 後述顯像步驟爲在有機溶劑中進行顯像時,較丨圭爲少· 量調製具有竣機的聚合性單體。必要時》黏結齊彳聚合物可 具有感光性的官能基。 (A)成分之黏結劑聚合物之調配量係以(a)成分 及後述之(B )成分之總量1 0 0質量份爲基準,較佳爲 40〜70質量份’更佳爲45~65.質量份,更佳爲5〇〜60質量份 -22- 201217905 。此調配量未達40質量份時’藉由曝光硬化後的感光層有 變脆的傾向,超過7 0質量份時,有解像度及光感度不足的 傾向。 (具有乙烯性不飽和鍵之光聚合性化合物) (B)成分之具有乙烯性不飽和鍵之光聚合性化合物 係含有下述一般式(II)表示之化合物》In the general formula (VI), R15 represents a hydrogen atom or a methyl group, and R16 represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group or a halogen atom. The q system represents an integer of 〇~5, and when q is 2 or more, the R16 in which the plural number exists may be the same or different from each other. The structural unit represented by the above general formula (VI) is a structural unit based on a benzyl (meth) acrylate and a benzyl (meth) acrylate derivative. The above benzyl (meth) acrylate derivative is, for example, 4-methylbenzyl (meth) acrylate, 4-ethylbenzyl (meth) acrylate, 4 tert-butyl benzyl (meth) acrylate , 4-methoxybenzyl (meth) acrylate, 4-ethoxybenzyl (meth) acrylate, 4-hydroxybenzyl (meth) acrylate, 4-chlorobenzyl (methyl) Acrylate. The structural unit represented by the above general formula (-21 - 201217905 VI) is based on developmental properties, etching resistance, plating resistance, and flexibility of maintaining a cured film, and preferably based on benzyl (meth) acrylate ( The structural unit of q = 〇). (A) The binder polymer contains the content ratio of the structural unit represented by the above formula (VI) based on the total solid content of the (A) binder polymer of the copolymer, and is excellent in adhesion. It is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 20% by mass or more. Further, from the viewpoint of the flexibility of the peeling property and the photoresist after curing, it is preferably 60% by mass or less, more preferably 55% by mass or less, still more preferably 50% by mass or less, and still more preferably 45% by mass or less. . These binder polymers may be used alone or in combination of two or more. When a combination of two or more kinds of binder polymers is used, for example, there are two types of binder polymers composed of different copolymerization components (including different repeating units as constituent components), and two different weight average molecular weights. The above binder polymer, two or more types of binder polymers having different degrees of dispersion, and the like. Further, as the binder polymer, a polymer having various morphological molecular weight distributions described in JP-A-H11-327137 may be used. In the development step described later, when the image is developed in an organic solvent, the polymerizable monomer having a shutdown is prepared in a smaller amount. If necessary, the bonded polymer can have a photosensitive functional group. The amount of the binder polymer of the component (A) is preferably from 40 to 70 parts by mass, based on the total amount of the component (a) and the component (B) described later, preferably from 40 to 70 parts by mass. 65. Parts by mass, more preferably 5〇~60质量份-22- 201217905. When the amount is less than 40 parts by mass, the photosensitive layer after exposure curing tends to become brittle, and when it exceeds 70 parts by mass, the resolution and the light sensitivity tend to be insufficient. (Photopolymerizable compound having an ethylenically unsaturated bond) The photopolymerizable compound having an ethylenically unsaturated bond of the component (B) contains a compound represented by the following general formula (II)
R1 H2C=C-C-^Y-〇 0 上述一般式(π)中,R1及R2係各自獨立表示氫原子 或甲基,較佳爲甲基。Y係表示碳數2〜6之伸烷基。η1及η2 係各自獨立表示正整數,t^+n2係4〜40之整數,較佳爲 6~34之整數,更佳爲8~30之整數,更佳爲8〜28之整數,特 佳爲8〜2 0之整數,極佳爲8~16之整數,最佳爲8〜12之整數 。nkri2之値未達4時,與黏結劑聚合物之相溶性降低,店 路形成用基板上層合感光性元件時,有容易剝離的傾向, η 1+n2之値超過40時,感光層之親水性增加,顯像時,光 阻容易剝離,耐電鍍性有降低的傾向》分子內複數存在之 Y可相同或相異。 上述碳數2〜6之伸烷基例如有伸乙基、伸丙基、伸異 丙基、伸丁基、伸戊基及伸己基。此等中,從提高解像度 及耐電鍍性的觀點,較佳爲伸乙基及伸異丙基,更佳爲伸 -23- 201217905 乙基。 上述一般式(II)中之芳香環可具有取代基。這些取 代基例如有鹵素原子、碳數1〜20之烷基、碳數3~1〇之環院 基、碳數6~ 18之芳基、苯醯甲基、胺基、碳數之烷基 胺基、碳數2~20之二烷基胺基、硝基、氰基、羰基、氫硫 基、碳數1~1〇之烷基氫硫基、烯丙基、羥基、碳數卜20之 羥烷基、羧基、烷基之碳數爲卜之羧烷基、烷基之碳數 爲1〜10之醯基、碳數1〜2 0之烷氧基、碳數1〜2 0之烷氧羰基 、碳數2~10之烷基羰基、碳數2~10之烯基、碳數2〜10之N-烷基胺基甲醯基及含有雜環的基團、及被此等之取代基取 代的芳基。上述取代基也可形成縮合環,或此等之取代基 中的氫原子可被鹵素原子等之上述取代基等取代。又,取 代基之數分別爲2以上時。2以上之取代基分別可相同或不 同。 上述一般式(Π)表示之化合物,例如有2,2-雙(4-((甲基)丙烯氧基聚乙氧基)苯基)丙烷、2,2-雙(4-((甲基)丙烯氧基聚丙氧基)苯基)丙烷、2,2-雙(4-((甲基)丙烯氧基聚丁氧基)苯基)丙烷及2,2-雙(4-((甲基)丙嫌氧基聚乙氧基聚丙氧基)苯基)丙院等之 雙酚A系(甲基)丙烯酸酯化合物。 上述一般式(II )表示之化合物之具體例,例如有Ri 及R2爲氫原子、Y爲伸乙基、i^+nLlO (平均値)之E〇改 性雙酚A二丙烯酸酯(日立化成工業股份公司製、商品名 :FA-32 1 Μ )。 -24- 201217905 (B)成分中之親水性成分與疎水性成分之調配平衡 ,會影響解像性、密著性、硬化後之剝離特性等。由此觀 點,爲了得到解像性、密著性、硬化後之剝離特性等優異 的感光性元件時,(B)成分較佳爲含有聚烷二醇二(甲 基)丙烯酸酯。聚烷二醇二(甲基)丙烯酸酯較佳爲例如 有下述一般式(VII) 、(VIII)或(IX)表示之化合物。 Ο 0 CH2=C—丛一〇—^EQ-^-^-PO-) ( EO^—I—e==CH2 ⑽ R8 Γ δ1 χ2 R9 一般式(VII )中’ R8及R9係各自獨立表示氫原子或 甲基,EO係表示氧乙烯基,P〇係表示氧丙烯基,s1係表示 1〜30之整數,r1及r2係分別表示0〜30之整數,J+r2 (平均 値)係1〜30之整數。 0II CHo^C一C* 2 I R10 •Ο— r3 fp〇-)~ s3 ΟII c- •C ΌΗ2 (VI)R1 H2C=C-C-^Y-〇 0 In the above general formula (π), R1 and R2 each independently represent a hydrogen atom or a methyl group, preferably a methyl group. The Y system represents an alkylene group having 2 to 6 carbon atoms. Η1 and η2 each independently represent a positive integer, and t^+n2 is an integer of 4 to 40, preferably an integer of 6 to 34, more preferably an integer of 8 to 30, more preferably an integer of 8 to 28, particularly preferably It is an integer of 8 to 20, and is preferably an integer of 8 to 16, and is preferably an integer of 8 to 12. When the nkri2 is less than 4, the compatibility with the binder polymer is lowered, and when the photosensitive element is laminated on the substrate for forming a shop, the film tends to be easily peeled off. When the η 1+n2 is more than 40, the hydrophilic layer is hydrophilic. When the image is increased, the photoresist is easily peeled off, and the plating resistance is lowered. The Y in the intramolecular plural may be the same or different. The above alkylene group having 2 to 6 carbon atoms is, for example, an exoethyl group, a propyl group, an exopropyl group, a butyl group, a pentyl group and a hexyl group. Among these, from the viewpoint of improving the resolution and the electroplating resistance, it is preferred to extend the ethyl group and extend the isopropyl group, and more preferably to extend the -23-201217905 ethyl group. The aromatic ring in the above general formula (II) may have a substituent. These substituents are, for example, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a ring-membered group having a carbon number of 3 to 1 fluorene, an aryl group having 6 to 18 carbon atoms, an phenylhydrazine methyl group, an amine group, and an alkyl group having a carbon number. Amino group, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, thiol group, alkyl thio group having 1 to 1 carbon number, allyl group, hydroxyl group, carbon number The hydroxyalkyl group, the carboxyl group, the alkyl group has a carbon number of carboxyalkyl group, the alkyl group has a carbon number of 1 to 10, an alkoxy group having a carbon number of 1 to 2, and a carbon number of 1 to 2 0. An alkoxycarbonyl group, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylaminocarbamyl group having 2 to 10 carbon atoms, a group having a hetero ring, and the like Substituent substituted aryl. The above substituent may also form a condensed ring, or the hydrogen atom in the substituent may be substituted with the above substituent or the like of a halogen atom or the like. Further, when the number of substitution bases is 2 or more, respectively. The substituents of 2 or more may be the same or different. The compound represented by the above general formula (Π) is, for example, 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis(4-((methyl) Propyleneoxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl)propane and 2,2-bis(4-((A) A bisphenol A-based (meth) acrylate compound such as a propylene-polyoxypolyethoxypolypropoxy)phenyl) propyl compound. Specific examples of the compound represented by the above general formula (II) include, for example, E〇-modified bisphenol A diacrylate wherein Ri and R2 are a hydrogen atom, Y is an ethylidene group, and i^+nL10 (average 値) (Hitachi Chemical Co., Ltd.) Industrial Co., Ltd., trade name: FA-32 1 Μ ). -24- 201217905 The balance of the hydrophilic component and the hydrophobic component in the component (B) affects the resolution, adhesion, and peeling properties after hardening. From this point of view, in order to obtain a photosensitive element excellent in resolution, adhesion, and peeling property after curing, the component (B) preferably contains a polyalkylene glycol bis(meth)acrylate. The polyalkylene glycol di(meth)acrylate is preferably, for example, a compound represented by the following general formula (VII), (VIII) or (IX). Ο 0 CH2=C—丛一〇—^EQ-^-^-PO-) ( EO^—I—e==CH2 (10) R8 Γ δ1 χ2 R9 In general (VII), the R8 and R9 systems are independently represented. A hydrogen atom or a methyl group, EO represents an oxyethylene group, P〇 represents an oxypropylene group, s1 represents an integer of 1 to 30, and r1 and r2 each represent an integer of 0 to 30, and J+r2 (average 値) An integer from 1 to 30. 0II CHo^C_C* 2 I R10 •Ο— r3 fp〇-)~ s3 ΟII c- •C ΌΗ2 (VI)
R 11 —般式(VIII)中’ RlQ及R11係分別表示氫原子或甲 基。EO係表示氧乙烯基’ PO係表示氧丙烯基,r3係表示 1〜30之整數,s2及s3係分別表示0〜30之整數,s2 + s3 (平均 値)係1〜30之整數。 -25- 201217905 ο II ch2=9—c 一〇 R12R 11 is a compound of the formula (VIII) wherein R 1 R and R 11 represent a hydrogen atom or a methyl group, respectively. The EO system represents an oxyethylene group. PO represents an oxypropylene group, r3 represents an integer of 1 to 30, s2 and s3 each represent an integer of 0 to 30, and s2 + s3 (average 値) is an integer of 1 to 30. -25- 201217905 ο II ch2=9-c 一〇 R12
\ II ^c-c=ch2 s R13 (E) —般式(IX)中,R12及R13係各自獨立表示氫原子或 甲基,較佳爲甲基。EO係表示氧乙烯基,PO係表示氧丙 烯基。r4係表示1〜30之整數,S4係表示1〜30之整數。 上述一般式(VII) 、(VIII)及(IX)中,氧乙烯基 之構造單位(EO、氧乙烯單位)及氧丙烯基之構造單位( PO、氧丙烯單位)複數存在時,複數之氧乙烯單位及氧丙 烯單位可分別連續嵌段方式存在或無規則存在。氧丙烯單 位爲氧異丙烯基之構造單位時,丙烯基之2級碳可與氧原 子結合,1級碳可與氧原子結合。 上述一般式(VII) 、(VIII)及(IX)中之氧乙烯單 位之總數(rUr2、r3及r4 )係各自獨立爲1~30之整數,較 佳爲4以上之整數,更佳爲5以上之整數。從掩蔽信賴性及 光阻形狀優異的觀點,較佳爲1 〇以下之整數,更佳爲9以 下之整數,更佳爲8以下之整數。 上述一般式(VII) 、(VIII)及(IX)中之氧丙烯單 位的總數(S1、s2 + s3及S4 )係各自獨立爲1〜30之整數,但 是從解像性及低淤渣的觀點,較佳爲5以上之整數,更佳 爲8以上之整數,更佳爲1〇以上之整數。從解像性及低淤 渣的觀點,較佳爲20以下之整數,更佳爲16以下之整數, 更佳爲14以下之整數。 上述一般式(VII )表示之化合物之具體例,例如有 -26- 201217905 R8及R9爲甲基、1^ + ^ = 6 (平均値)'skuC平均値)的 乙烯基化合物(日立化成工業股份公司製、商品名:FA_ 023M )。 上述一般式(VIII )表示之化合物之具體例,例如有 R1()及R11爲甲基、γ3 = 6 (平均値)、s2 + s3=12 (平均値) 之乙烯基化合物(日立化成工業股份公司製、商品名: FA-024M )。 上述一般式(IX )表示之化合物之具體例,例如有 R12及R13爲氫原子、r4=l (平均値)、s4 = 9 (平均値)之 乙烯基化合物(新中村化學工業股份公司製、商品名: NK ester HEMA-9P )。 這些可單獨1種或組合2種以上使用。 (B)成分從提高掩蔽性優異的觀點,較佳爲含有具 有胺基甲酸乙酯鍵的(甲基)丙烯酸酯化合物等之胺基甲 酸乙酯單體。 上述胺基甲酸乙酯單體例如有於β位具有羥基之(甲 基)丙烯酸單體與異佛爾酮二異氰酸酯、2,6-甲苯二異氰 酸酯、2,4-甲苯二異氰酸酯及1,6-六甲撐二異氰酸酯等之 二異氰酸酯化合物的加成反應物、三((甲基)丙烯氧基 四乙二醇異氰酸酯)六甲撐三聚異氰酸酯、ΕΟ改性胺基甲 酸乙酯二(甲基)丙烯酸酯、及ΕΟ,ΡΟ改性胺基甲酸乙酯 二(甲基)丙烯酸酯。經ΕΟ改性的化合物係具有環氧乙烷 基的嵌段結構。此外’經Ρ〇改性的化合物係具有環氧丙烷 基的嵌段結構° Ε0改性胺基甲酸乙酯二(甲基)丙烯酸酯 -27- 201217905 例如有新中村化學工業(股)製、製品名「UA-ll」等。此 外,ΕΟ,ΡΟ改性胺基甲酸乙酯二(甲基)丙烯酸酯例如有 新中村化學工業(股)製、製品名「UA-13」等。此等可單 獨1種或組合2種以上使用。 (Β)成分係在密著性、解像性及剝離性優異的觀點 ,較佳爲含有使多元醇與α,β -不飽和羧酸反應而得到的化 合物。此等化合物,例如有三羥甲基丙烷二(甲基)丙烯 酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、ΕΟ改性三羥甲 基丙烷三(甲基)丙烯酸酯、ΡΟ改性三羥甲基丙烷三(甲 基)丙烯酸酯、ΕΟ,ΡΟ改性三羥甲基丙烷三(甲基)丙烯 酸酯、二季戊四醇五(甲基)丙烯酸酯及二季戊四醇六( 甲基)丙烯酸酯。ΕΟ改性三羥甲基丙烷三(甲基)丙烯酸 酯,例如有Sartomer公司製、商品名「SR-454」。此等可 單獨1種或組合2種以上使用。 (B )成分係在密著性、解像性及剝離性優異的觀點 ,較佳爲含有具有1個乙烯性不飽和鍵之光聚合性化合物 。具有1個乙烯性不飽和鍵之光聚合性化合物,較佳爲含 有下述一般式(X)表示之化合物。\ II ^c-c=ch2 s R13 (E) In the general formula (IX), R12 and R13 each independently represent a hydrogen atom or a methyl group, preferably a methyl group. EO represents an oxyethylene group, and PO represents an oxypropylene group. R4 represents an integer from 1 to 30, and S4 represents an integer from 1 to 30. In the above general formulas (VII), (VIII) and (IX), when the structural unit (EO, oxyethylene unit) of the oxyethylene group and the structural unit (PO, oxypropylene unit) of the oxypropylene group are present in plural, the plural oxygen The ethylene unit and the oxypropylene unit may be present in a continuous block manner or irregularly, respectively. When the oxypropylene unit is a structural unit of oxyisopropenyl group, the propylene-based secondary carbon may be bonded to the oxygen atom, and the first-order carbon may be bonded to the oxygen atom. The total number of oxyethylene units (rUr2, r3 and r4) in the above general formulas (VII), (VIII) and (IX) are each independently an integer of from 1 to 30, preferably an integer of 4 or more, more preferably 5 The above integer. From the viewpoint of excellent masking reliability and photoresist shape, it is preferably an integer of 1 〇 or less, more preferably an integer of 9 or less, and still more preferably an integer of 8 or less. The total number of oxypropylene units (S1, s2 + s3 and S4) in the above general formulas (VII), (VIII) and (IX) are each independently an integer of from 1 to 30, but from the resolution and low sludge The viewpoint is preferably an integer of 5 or more, more preferably an integer of 8 or more, and more preferably an integer of 1 or more. From the viewpoint of resolution and low sludge, it is preferably an integer of 20 or less, more preferably an integer of 16 or less, and still more preferably an integer of 14 or less. Specific examples of the compound represented by the above general formula (VII), for example, a vinyl compound having -26 to 201217905 R8 and R9 being a methyl group, 1^ + ^ = 6 (average 値) 'skuC average () (Hitachi Chemical Industry Co., Ltd.) Company system, product name: FA_ 023M). Specific examples of the compound represented by the above general formula (VIII) include, for example, a vinyl compound in which R1 () and R11 are a methyl group, γ3 = 6 (average 値), and s2 + s3 = 12 (average 値) (Hitachi Chemical Industry Co., Ltd. Company system, trade name: FA-024M). Specific examples of the compound represented by the above formula (IX) include, for example, a vinyl compound in which R12 and R13 are a hydrogen atom, r4 = 1 (average 値), and s4 = 9 (average 値) (manufactured by Shin-Nakamura Chemical Co., Ltd., Product Name: NK ester HEMA-9P ). These may be used alone or in combination of two or more. The component (B) is preferably an amine urethane monomer containing a (meth) acrylate compound having a urethane bond, from the viewpoint of improving the masking property. The above-mentioned ethyl urethane monomer is, for example, a (meth)acrylic monomer having a hydroxyl group at the β-position, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, and 1,6. An addition reaction product of a diisocyanate compound such as hexamethylene diisocyanate, tris((meth)acryloxytetraethyleneethylene glycol isocyanate) hexamethylene terephthalate, or hydrazine-modified urethane di(methyl) Acrylate, and hydrazine, hydrazine-modified urethane di(meth) acrylate. The ruthenium-modified compound has a block structure of an oxirane group. In addition, the 'ruthenium-modified compound has a propylene oxide-based block structure. Ε0-modified urethane di(meth)acrylate-27-201217905, for example, is manufactured by Shin-Nakamura Chemical Industry Co., Ltd. Product name "UA-ll" and so on. Further, ytterbium, yttrium modified urethane di(meth) acrylate is, for example, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., product name "UA-13", and the like. These may be used alone or in combination of two or more. The (Β) component is preferably a compound obtained by reacting a polyol with an α,β-unsaturated carboxylic acid from the viewpoint of excellent adhesion, resolution and releasability. Such compounds are, for example, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, hydrazine-modified trimethylolpropane tri(meth)acrylate, hydrazine-modified Trimethylolpropane tri(meth)acrylate, hydrazine, hydrazine modified trimethylolpropane tri(meth) acrylate, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa(meth) acrylate . The hydrazine-modified trimethylolpropane tri(meth)acrylate is, for example, a product of the company Sartomer, trade name "SR-454". These may be used alone or in combination of two or more. The component (B) is excellent in adhesion, resolution and releasability, and preferably contains a photopolymerizable compound having one ethylenically unsaturated bond. The photopolymerizable compound having one ethylenically unsaturated bond preferably contains a compound represented by the following general formula (X).
一般式(X)中、R14係氫原子或甲基,較佳爲氫原子 。乙係與上述一般式(II)中之Y同義’較佳爲伸乙基* k -28- 201217905 係表示4〜2〇之整數,從顯像性的觀點,較佳爲5〜18之整數 ,更佳爲6〜12之整數,更佳爲6〜10之整數。又,上述—般 式(X)中之芳香環可具有取代基,彼等取代基例如有與 上述一般式(II)中之芳香環同樣的取代基。 上述一般式(X)表示之化合物,具體例有壬基苯氧 基聚氧乙烯(polyethylenoxy)(甲基)丙烯酸酯、壬基 苯氧基聚氧丙烯(甲基)丙烯酸酯、丁基苯氧基聚氧乙嫌 (甲基)丙烯酸酯、丁基苯氧基聚氧丙烯(甲基)丙烯酸 酯。 上述壬基苯氧基聚氧乙烯(甲基)丙烯酸酯例如有壬 基苯氧基四氧乙烯(甲基)丙烯酸酯、壬基苯氧基五氧乙 烯(甲基)丙烯酸酯、壬基苯氧基六氧乙烯(甲基)丙烯 酸酯、壬基苯氧基七氧乙烯(甲基)丙烯酸酯、壬基苯氧 基八氧乙烯(甲基)丙烯酸酯、壬基苯氧基九氧乙烯(甲 基)丙烯酸酯、壬基苯氧基十氧乙烯(甲基)丙烯酸酯、 壬基苯氧基十一氧乙烯(甲基)丙烯酸酯、壬基苯氧基十 二氧乙烯(甲基)丙烯酸酯。 上述丁基苯氧基聚氧乙烯(甲基)丙烯酸酯,例如有 丁基苯氧基四氧乙烯(甲基)丙烯酸酯、丁基苯氧基五氧 乙烯(甲基)丙烯酸酯、丁基苯氧基六氧乙烯(甲基)丙 烯酸酯、丁基苯氧基七氧乙烯(甲基)丙烯酸酯、丁基苯 氧基八氧乙烯(甲基)丙烯酸酯、丁基苯氧基九氧乙烯( 甲基)丙烯酸酯、丁基苯氧基十氧乙烯(甲基)丙烯酸酯 及丁基苯氧基十一氧乙烯(甲基)丙烯酸酯。此等可單獨 -29- 201217905 使用1種或組合兩種以上。 (B) 成分中可含有具有上述以外之乙烯性不飽和鍵 之光聚合性化合物。其他之(B )光聚合性化合物,例如 有使含縮水甘油基的化合物與α、β -不飽和羧酸反應而得 到的化合物、苯二甲酸系化合物及(甲基)丙烯酸烷酯。 上述苯二甲酸系化合物,例如有γ -氯- β-羥基丙基_β,_ (甲基)丙烯醯氧基乙基-〇-苯二甲酸酯及β-羥烷基- β’-( 甲基)丙烯醯氧基烷基-〇-苯二甲酸酯。此等可單獨1種或 組合2種以上使用。 (Β)成分之具有乙烯性不飽和鍵之光聚合性化合物 之調配量係以(A )成分及(Β )成分之總量1 00質量份爲 基準,較佳爲30〜60質量份,更佳爲35~55質量份,更佳爲 40〜50質量份。此調配量未達30質量份時,有解像度及光 感度不足的傾向,超過60質量份時,藉由曝光硬化後的感 光層有變脆的傾向。 (光聚合起始劑) (C) 成分之光聚合起始劑,從光感度及密著性優異 的觀點,較佳爲含有2,4,5-三芳基咪唑二聚物。2,4,5-三芳 基咪唑二聚物例如有2- ( 〇-氯苯基)-4,5-二苯基咪唑二聚 物、2-(〇 -溴苯基)-4,5 -二苯基咪唑二聚物、2-(〇 -氟苯 基)-4,5-二苯基咪唑二聚物、2-(〇-甲氧基苯基)_4,5-二 苯基咪唑二聚物、2- (p-甲氧基苯基)-4,5-二苯基咪唑二 聚物、2-(〇-氯苯基)-4,5-二(甲氧基苯基)咪唑二聚物 -30- 201217905 、2-(〇-氯苯基)-4,5-二(?-氟苯基)咪唑二聚物、2_(_ 2,6_二氯苯基)_4,5-二苯基咪唑二聚物、2_(0_氯苯基) 4,5-二(P-氟苯基)咪唑二聚物、2_ ( 〇_溴苯基)_4,5-一 (p-碘苯基)咪唑二聚物、2- ( 〇_氯苯基)_4,5_二(广 萘基)咪唑二聚物、2-(〇-氯苯基)_4,5-一(P_氯本棊 咪唑二聚物、2-(〇-溴苯基)_4,5-二(0_氯甲氧棊本 )咪唑二聚物、2-(〇-氯苯基)-4,5-二(〇,Ρ-一氣察基 . 咏 咪唑二聚物、2-(〇_氯苯基)-4,5-二(〇,Ρ-—溴苯棊 一( 备兹| )咪# 嗤二聚物、2-(0,m_:氯苯基)-4,5-—(Ρ-氛蔡基; 一 ΑΛΛ 、 2 - 聚物 2-( 甘、 (o,p-二氯苯基)_4,5_二(m-甲氧基苯基)咪哩二聚物、 ,—* 2,4-二(p-甲氧基苯基)-5-苯基咪唑二聚物、2- (2,心一 甲氧基苯基)_4,5_二苯基咪唑二聚物、2_(P-甲基藝硫基 苯基)-4,5-二苯基咪唑二聚物、2·(Ρ-溴苯基)_4,5-一 基咪唑二聚物、2_(〇_溴苯基)-4,5-二(〇,Ρ_二氯苯基) 咪唑二聚物、2-(m-溴苯基)-4,5-二苯基咪唑二聚物、2_ (m,p·二溴苯基)_4,5_二苯基咪唑二聚物、2,2’-雙漠 苯基)-4,4’,5,5,-四(p-氣-p -甲氧基苯基)咪哩一聚物 2-(〇-氯苯基)-4,5_二(〇,p-二氯苯基)咪唑二聚物、2_ (〇-氯苯基)-4,5-二(〇,P-二溴苯基)咪唑二聚物、2_ ( 〇-溴苯基)-4,5-二(〇,p-二氯苯基)咪唑二聚物及2,4,5_二 (o,p-二氯苯基)咪唑二聚物。此等中’從提高密著性及 光感度的觀點,較佳爲2- ( 〇-氯苯基)_4,5-二苯基咪挫一 聚物。 -31 - 201217905 2,4,5-三芳基咪唑二聚物中,2個2,4,5-三芳基咪唑之 芳基之取代基爲相同,可提供對稱的化合物,或可不相同 ,提供非對稱的化合物。 (C)成分含有2,4,5 -三芳基咪唑二聚物時’該含有比 例係以(C )成分之總量爲基準,較佳爲70〜1 00質量%, 更佳爲85〜100質量%,更佳爲90〜100質量%,特佳爲 93〜100質量%。以此比例含有2,4,5-三芳基咪唑二聚物, 本實施形態之感光性元件係具有更優異的密著性及光感度 者。 (C)成分之光聚合起始劑除了上述2,4,5-三芳基咪唑 二聚物外,可使用其他的光聚合起始劑。其他的光聚合起 始劑例如有芳香族酮類、P-胺基苯基酮類、蒽醌類、苯偶 因醚化合物、苯偶因化合物、苄基衍生物、吖啶衍生物、 香豆素系化合物、肟酯類、N-芳基-α-胺基酸化合物、脂 肪族多官能硫醇化合物、醯基氧化膦類、噻噸酮類、3級 胺化合物類,可組合此等化合物使用。 本實施形態之(C)光聚合起始劑,除了 2,4,5-三芳基 咪唑二聚物外,較佳爲含有上述芳香族酮類,其中較佳爲 含有Ν,Ν’-四乙基-4,4’-二胺基二苯甲酮(米蚩酮)。 (C )成分之光聚合起始劑的調配量係以(A )成分及 (B )成分之總量1〇〇質量份爲基準,較佳爲0.1 ~20質量份 ’更佳爲0.2~10質量份,特佳爲0.5〜5質量份。此調配量未 達〇」質量份時,光感度有不足的傾向,超過20質量份時 ’曝光時,感光性樹脂組成物表面之光吸收增加,內部之In the general formula (X), R14 is a hydrogen atom or a methyl group, preferably a hydrogen atom. B is synonymous with Y in the above general formula (II). Preferably, exoethyl*k-28-201217905 represents an integer of 4 to 2, and is preferably an integer of 5 to 18 from the viewpoint of development. More preferably, it is an integer of 6 to 12, and more preferably an integer of 6 to 10. Further, the aromatic ring in the above formula (X) may have a substituent, and the substituents thereof have, for example, the same substituents as the aromatic ring in the above general formula (II). The compound represented by the above general formula (X), specifically exemplified by polyethylenoxy (meth) acrylate, nonyl phenoxy polyoxypropylene (meth) acrylate, butyl phenoxy Polyoxyethylene (meth) acrylate, butyl phenoxy polyoxypropylene (meth) acrylate. The above nonylphenoxy polyoxyethylene (meth) acrylate is, for example, a nonyl phenoxy tetraoxyethylene (meth) acrylate, a nonyl phenoxy pentoxide (meth) acrylate, a nonyl benzene Oxyhexaoxyethylene (meth) acrylate, nonyl phenoxy hexaoxyethylene (meth) acrylate, nonyl phenoxy oxyethylene (meth) acrylate, nonyl phenoxy hexaoxyethylene (Meth) acrylate, nonylphenoxy oxyethylene (meth) acrylate, nonyl phenoxy undecoxy ethylene (meth) acrylate, nonyl phenoxy oxydooxyethylene (methyl) )Acrylate. The above butylphenoxypolyoxyethylene (meth) acrylate, for example, butyl phenoxytetraoxyethylene (meth) acrylate, butyl phenoxy pentoxide (meth) acrylate, butyl Phenoxyhexaoxyethylene (meth) acrylate, butyl phenoxy heptaoxyethylene (meth) acrylate, butyl phenoxy ethoxy oxy (meth) acrylate, butyl phenoxy hexaoxy Ethylene (meth) acrylate, butyl phenoxy oxyethylene (meth) acrylate, and butyl phenoxy unoxyethylene (meth) acrylate. These can be used alone or in combination of -29- 201217905. (B) The component may contain a photopolymerizable compound having an ethylenically unsaturated bond other than the above. The other (B) photopolymerizable compound is, for example, a compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, a phthalic acid compound, and an alkyl (meth)acrylate. The above phthalic acid-based compound is, for example, γ-chloro-β-hydroxypropyl_β, _(meth)acryloxyethyl-terpene-phthalate and β-hydroxyalkyl-β'- (Methyl) acryloxyalkyl-indole-phthalate. These may be used alone or in combination of two or more. The amount of the photopolymerizable compound having an ethylenically unsaturated bond of the (Β) component is preferably from 30 to 60 parts by mass based on 100 parts by mass of the total of the components (A) and (Β). Preferably, it is 35 to 55 parts by mass, more preferably 40 to 50 parts by mass. When the amount is less than 30 parts by mass, the resolution and the photosensitivity tend to be insufficient. When the amount is more than 60 parts by mass, the photosensitive layer after exposure curing tends to become brittle. (Photopolymerization initiator) The photopolymerization initiator of the component (C) preferably contains a 2,4,5-triarylimidazole dimer from the viewpoint of excellent photosensitivity and adhesion. The 2,4,5-triaryl imidazole dimer is, for example, 2-( 〇-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(〇-bromophenyl)-4,5 - Diphenylimidazole dimer, 2-(anthracene-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(anthracene-methoxyphenyl)-4,5-diphenylimidazolium Polymer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(〇-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole Dimer-30- 201217905, 2-(〇-chlorophenyl)-4,5-di(?-fluorophenyl)imidazole dimer, 2_(_ 2,6-dichlorophenyl)_4,5 -diphenylimidazole dimer, 2_(0-chlorophenyl) 4,5-di(P-fluorophenyl)imidazole dimer, 2_(〇_bromophenyl)_4,5-one (p- Iodophenyl)imidazole dimer, 2-( 〇-chlorophenyl)-4,5-bis(polynaphthyl)imidazole dimer, 2-(〇-chlorophenyl)_4,5-one (P_ Chloroquinone imidazole dimer, 2-(〇-bromophenyl)-4,5-bis(0-chloromethoxyindole) imidazole dimer, 2-(〇-chlorophenyl)-4,5-二(〇,Ρ-一气察基. 咏imidazole dimer, 2-(〇-chlorophenyl)-4,5-di(〇,Ρ--bromophenyl hydrazine one ( 备兹| )咪# 嗤二Polymer, 2-(0,m _: chlorophenyl)-4,5--(Ρ-氛蔡基; 一ΑΛΛ, 2-polymer 2-(甘, (o,p-dichlorophenyl)_4,5_二(m-甲Oxyphenyl)imidine dimer, —* 2,4-di(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2, cardiomethoxyphenyl )_4,5_diphenylimidazole dimer, 2_(P-methylyithiophenyl)-4,5-diphenylimidazolium dimer, 2·(Ρ-bromophenyl)_4,5 -monoimidazole dimer, 2_(〇-bromophenyl)-4,5-di(indole, fluorene-dichlorophenyl) imidazole dimer, 2-(m-bromophenyl)-4,5 -diphenylimidazole dimer, 2_(m,p.dibromophenyl)_4,5-diphenylimidazole dimer, 2,2'-bis-diphenyl)-4,4',5, 5,-tetrakis (p-gas-p-methoxyphenyl) oxime polymer 2-(anthracene-chlorophenyl)-4,5-di(anthracene, p-dichlorophenyl)imidazole dimerization , 2_(〇-chlorophenyl)-4,5-di(indole, P-dibromophenyl)imidazole dimer, 2_(〇-bromophenyl)-4,5-di(〇,p- Dichlorophenyl)imidazole dimer and 2,4,5-di(o,p-dichlorophenyl)imidazole dimer. Among these, 'from the viewpoint of improving adhesion and light sensitivity, it is preferred 2- ( 〇-chloride — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — To be identical, symmetric compounds may be provided, or may be different, providing asymmetric compounds. When the component (C) contains a 2,4,5-triaryl imidazole dimer, the ratio is based on the total amount of the component (C), preferably 70 to 10,000% by mass, more preferably 85 to 100%. The mass %, more preferably 90 to 100% by mass, particularly preferably 93 to 100% by mass. The 2,4,5-triarylimidazole dimer is contained in this ratio, and the photosensitive element of the present embodiment has more excellent adhesion and light sensitivity. Photopolymerization initiator of component (C) In addition to the above 2,4,5-triarylimidazole dimer, other photopolymerization initiators can be used. Other photopolymerization initiators include, for example, aromatic ketones, P-aminophenyl ketones, anthraquinones, benzoin ether compounds, benzoin compounds, benzyl derivatives, acridine derivatives, and peas a compound, an oxime ester, an N-aryl-α-amino acid compound, an aliphatic polyfunctional thiol compound, a fluorenyl phosphine oxide, a thioxanthone, a tertiary amine compound, and these compounds can be combined use. The photopolymerization initiator (C) of the present embodiment preferably contains the above aromatic ketones in addition to the 2,4,5-triarylimidazole dimer, and preferably contains ruthenium, Ν'-tetrazine. Base-4,4'-diaminobenzophenone (milaxone). The amount of the photopolymerization initiator of the component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10, based on 1 part by mass of the total of the components (A) and (B). The mass fraction is particularly preferably 0.5 to 5 parts by mass. When the amount is less than 5% by mass, the light sensitivity tends to be insufficient, and when it exceeds 20 parts by mass, the light absorption on the surface of the photosensitive resin composition increases during exposure.
-32- 201217905 光硬化有不足的傾向。 感光性樹脂組成物中必要_時可含有分子內具有至少1 個可陽離子聚合之環狀醚基的光聚合性化合物(氧環丁烷 化合物等)、陽離子聚合起始劑、孔雀石綠(Malachite green )等之染料、三溴苯基楓及無色結晶紫等之光發色 劑、熱發色防止劑、對甲苯磺醯胺等之可塑劑 '顏料、塡 充劑、消泡劑、難燃劑、4-t-丁基鄰苯二酚等的安定劑、 抑制劑、平坦劑、剝離促進劑、抗氧化劑、香料、顯像劑 (Imaging Agent )及熱交聯劑等的添加劑。此等可使用單 獨1種或組合兩種以上使用。此等添加劑在不影響本實施 形態之目的的範圍內,以(A)成分及(B)成分之總量 100質量份爲基準,各自可含有〇·〇〇〇1~2〇質量份。 感光性樹脂組成物必要時係溶解於甲醇、乙醇、丙酮 、甲基乙基酮、甲基溶纖素、乙基溶纖素、甲苯、Ν,Ν-二 甲基甲醯胺及丙二醇單甲醚等之溶劑或此等之混合溶劑中 ,成爲固形物爲30〜60質量%左右的溶液來調製。 本實施形態之感光性元件1中之感光層20係藉由將上 述感光性樹脂組成物塗佈於支持薄膜1〇上,除去溶劑後而 形成。其中塗佈方法可使用例如有輥塗佈、雙輥筒塗佈( comma coat )、凹版塗佈、氣刀刮塗、模塗佈(die coat. )及棒塗佈等之習知的方法。此外,可用例如以70〜1 5 0°C 的溫度處理5~30分鐘以去除溶劑。此外,感光層20中的殘 存有機溶劑量,從防止後續步驟之有機溶劑擴散的觀點, 較佳爲2質量%以下。 -33- 201217905 如此形成之感光層20的厚度係乾燥後的厚度’較佳爲 3〜25μιη,更佳爲5~25μηι,更佳爲7~20μπι,特佳爲 10〜15 μιη。此厚度未達3μιη時,將感光層層合於電路形成 用基板時,有容易產生不良,或掩蔽(tenting)性不足的 傾向,在顯像及蝕刻步驟中,光阻產生破損,可能造成出 口( OPEN )不良的原因之一,印刷電路板之製造良率有 降低的傾向。而厚度超過25 μιη時,有感光層20之解像度不 足,蝕刻液之液移動不足的傾向。此外,側蝕刻的影響可 能變大,製造高密度之印刷電路板有困難的傾向。 又,感光性元件1係在與感光層20之支持薄膜10接觸 之第一主面12之相反側的主面上,可具備保護薄膜(無圖 示)。保護薄膜較佳爲使用相較於感光層2 0與支持薄膜10 之間的接著力而言,感光層20與保護薄膜之間之接著力較 小的薄膜,可使用低魚眼(fish eye )的薄膜。具體而言 ,例如有聚乙烯及聚丙烯等之惰性的聚烯烴薄膜。從由感 光層20上之剝離性的觀點,較佳爲聚乙烯薄膜。保護薄膜 之厚度係依用途而異,較佳爲約1〜100 μιη。 感光性元件1除了支持薄膜10、感光層20及保護薄膜 外,可再具有緩衝層、接著層、光吸收層及阻氣層等之中 間層或保護層。 本實施形態之感光性元件1可以例如感光性元件狀態 ’或於感光層20上再層合保護薄膜者捲繞成滾筒狀之卷芯 的狀態下貯藏存。此時,支持薄膜10成爲最外層的狀態, 捲繞成滾筒狀較佳。捲繞成滾筒狀的感光性元件1之端面 -34- 201217905 ,從端面保護的觀點,較佳爲設置端面隔離片,從耐熔邊 的觀點’較佳爲設置防濕端面隔離片。梱包方法較佳爲包 於透濕性較低之黑色薄片進行包裝。 卷芯的材料例如有聚乙烯樹脂、聚丙烯樹脂、聚苯乙 烯樹脂、聚氯乙烯樹脂及ABS (丙烯腈-丁二烯-苯乙烯共 聚物)等的塑膠。 (光阻圖型之形成方法) 本實施形態之光阻圖型的形成方法係包括下述步驟的 方法: 將上述感光性元件1依前述感光層20、支持薄膜10之 順序層合於電路形成用基板上的層合步驟;將活性光線通 過上述支持薄膜10,照射於感光層20之所定部分,在感光 層20上形成光硬化部的曝光步驟;除去前述光硬化部以外 之感光層20之部分的顯像步驟。 層合步驟中,將感光層20層合於電路形成用基板上的 方法,例如感光層20上存在保護薄膜時’除去上述保護薄 膜後,將感光層20加熱至約7〇〜13 0°C ’同時以0.1〜1 MPa程 度的壓力壓黏於電路形成用基板,進行層合的方法等。此 層合步驟中,也可在減壓下層合。電路形成用基板之被層 合的表面通常爲金屬面,但是無特別限制。爲了進一步提 高層合性,可將電路形成用基板進行預熱處理。 其次,對於上述層合步驟層合完成的感光層20’將具 有負或正遮罩圖型的光罩對準位置於支持薄膜10之第2主 -35- 201217905 面14,使之密著。然後,在曝光步驟係對於感光層20,通 過上述光罩及支持薄膜1 0,使活性光線呈圖像狀照射,在 感光層2〇形成光硬化部。上述活性光線的光源係公知之光 源,例如有碳極電弧燈、水銀蒸氣電弧燈、高壓水銀燈及 氙燈等有效放射紫外線、可見光者。此外,可使用雷射直 接描繪法在感光層20形成光硬化部。 其次,上述曝光步驟後,將光罩由支持薄膜10上剝離 。接著,將支持薄膜10由感光層20上剝離除去。其次,顯 像步驟中,藉由鹼性水溶液、水系顯像液、有機溶劑等之 顯像液之濕式顯像、乾式顯像等除去感光層20之未曝光部 (光硬化部),進行顯像可製造光阻圖型。 鹼性水溶液例如有0.1〜5質量%碳酸鈉的稀薄溶液、 0.1〜5質量%碳酸鉀的稀薄溶液及〇.1~5質量%氫氧化鈉的稀 薄溶液。上述鹼性水溶液的pH較佳爲9~1 1的範圍,其溫度 可配合感光層20的顯像性來調節。此外,鹼性水溶液中可 混入界面活性劑、消泡劑、有機溶劑等。顯像的方式例如 有浸漬方式、噴霧方式、沖洗及洗滌。 此外,顯像步驟後的處理,必要時可藉由以60〜250°C 左右的加熱或〇.2~10J/cm2之曝光量進行曝光,使光阻圖型 再硬化。 (印刷電路板之製造方法) 本實施形態之印刷電路板之製造方法係藉由上述光阻 圖型之形成方法,對於形成有光阻圖型之電路形成用基板 -36 201217905 ,藉由蝕刻或電鍍來進行。本實施形態之感光性元件,特 別是適合於藉由含有電鍍步驟之方法製造印刷電路板,其 中適合使用於半加成製程(SAP; semiadditive process) 。本發明人等係如下述想到適合使用於SAP的理由。以 SAP生產之印刷電路板的線寬係相較於.以減去法生產的印 刷電路板,有非常細的傾向。又,SAP的情形,光阻形狀 爲直接被轉印成電鍍線形狀。具有以SAP生產之極細線圖 型的印刷電路板時,有產生微小之光阻缺損,或生產良率 降低的傾向。由此等之要求,本實施形態之感光性元件特 別是適合使用於SAP。 蝕刻用的蝕刻液例如有氯化銅溶液、氯化鐵溶液及鹼 蝕刻溶液。 電鍍例如有鍍銅、焊接鏟敷、鑛鎳及鍍金。 蝕刻或電鍍後,光阻圖型例如可使用比顯像所使用之 鹼性水溶液更強鹼性的水溶液進行剝離。此強鹼性的水溶 液例如可使用1〜1 〇質量%氫氧化鈉水溶液及1〜1 0質量%氫 氧化鉀水溶液。剝離方式例如有浸漬方式及噴霧方式。形 成有光阻圖型的印刷電路板可爲多層印刷電路板,或具有 小徑貫穿孔。 又,對於具備絕緣層與在絕緣層上形成之導體層的電 路形成用基板進行電鍍時,需要去除圖型以外的導體層。 此除去方法例如有將光阻圖型剝離後,稍微蝕刻的方法或 上述電鍍後,接著進行焊接鍍敷等,然後將光阻圖型剝離 ,而配線部分以焊接掩蔽,其次使用僅可蝕刻導體層的蝕 -37- 201217905 刻液進行處理的方法等》 如上述,本實施形態之感光性元件可使用於印刷電路 板。 / (半導體封裝基板的製造方法) 本實施形態之感光性元件1可用於具備有硬質基板與 形成於該硬質基板上之絕緣膜的封裝基板。此時,感光層 20之光硬化部作爲絕緣膜使用即可。感光層20之光硬化部 例如作爲半導體封裝用之阻焊劑使用時,上述光阻圖型之 形成方法中之顯像終了後,爲了提高對於焊接耐熱性、耐 藥品性等,較佳爲藉由高壓水銀燈之紫外線照射或進行加 熱。照射紫外線時,必要時可調整其照射量,例如可以 0_2~10J/cm2程度的照射量進行照射。對光阻圖型加熱時, 較佳爲在10 0~ 170 °c程度的範圍,進行約15 ~9 0分鐘。可同 時進行紫外線照射與加熱,或其中之一實施後,再實施另 一。同時進行紫外線之照射與加熱時,從有效賦予對於焊 接耐熱性、耐藥品性等的觀點,更佳爲加熱至604 50°c。 由本實施形態之感光性元件所形成之阻焊劑係兼具對 基板施予焊接後之配線的保護膜,且抗拉強度及延伸率等 之物理特性及耐熱衝撃性優異,因此可作爲半導體封裝用 的永久光罩使用。 如上述’具備光阻圖型的封裝基板,其後實施半導體 元件等之組裝(例如線接合、焊接連接),再安裝於電腦 等之電子機器。 -38 - 201217905 以上,依據其實施形態詳細說明本發明,但是本發明 不限於上述實施形態。本發明在不超脫本發明之實質的範 圍內,可爲各種的變形形態。 【實施方式】 〔實施例〕 以下依據其實施形態詳細說明本發明,但是本發明不 限於此等實施形態。 (實施例1~9及比較例1〜10) 合成具有下述表1或2所示之組成的(A)黏結劑聚合 物。 黏結劑聚合物之重量平均分子量係藉由凝膠滲透層析 法(GPC )測定,使用標準聚苯乙烯的校正曲線換算導出 。GPC之條件及酸價測定順序如下述,測定結果如表1或2 所示。 (GPC條件) 泵:日立 L-6000型((股)日立製作所製、商品名) 管柱:Gelpack GL-R420、Gelpack GL-R430、Gelpack GL-R440 (共計3支)(以上爲日立化成工業(股)製、商品 名)-32- 201217905 There is a tendency for light hardening to be insufficient. When necessary, the photosensitive resin composition may contain a photopolymerizable compound (oxycyclobutane compound or the like) having at least one cationically polymerizable cyclic ether group in the molecule, a cationic polymerization initiator, malachite green (Malachite) Green), such as dyes, tribromophenyl maple, colorless crystal violet, etc., photochromic agent, thermal hair color preventive agent, p-toluenesulfonamide and other plasticizers' pigments, enamels, defoamers, flame retardants Additives such as a stabilizer, an inhibitor, a flattening agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, and a thermal crosslinking agent such as 4-t-butyl catechol. These may be used alone or in combination of two or more. These additives may contain ~·〇〇〇1 to 2 parts by mass based on 100 parts by mass of the total of the components (A) and (B), within the range which does not affect the object of the present embodiment. The photosensitive resin composition is dissolved in methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, hydrazine, hydrazine-dimethylformamide, and propylene glycol alone. A solvent such as ether or a mixed solvent of these is prepared by preparing a solution having a solid content of about 30 to 60% by mass. The photosensitive layer 20 in the photosensitive element 1 of the present embodiment is formed by applying the above-mentioned photosensitive resin composition onto a support film 1 and removing the solvent. Among the coating methods, for example, a conventional method such as roll coating, comma coat, gravure coating, air knife coating, die coating, and bar coating can be used. Further, the solvent may be removed by, for example, treating at a temperature of 70 to 150 ° C for 5 to 30 minutes. Further, the amount of the residual organic solvent in the photosensitive layer 20 is preferably 2% by mass or less from the viewpoint of preventing the diffusion of the organic solvent in the subsequent step. The thickness of the photosensitive layer 20 thus formed is preferably from 3 to 25 μm, more preferably from 5 to 25 μm, even more preferably from 7 to 20 μm, particularly preferably from 10 to 15 μm. When the thickness is less than 3 μm, when the photosensitive layer is laminated on the substrate for circuit formation, defects may occur easily or the tenting property may be insufficient. In the development and etching steps, the photoresist may be damaged, which may cause an exit. (OPEN) One of the causes of defects is that the manufacturing yield of printed circuit boards tends to decrease. On the other hand, when the thickness exceeds 25 μm, the resolution of the photosensitive layer 20 is insufficient, and the liquid movement of the etching liquid tends to be insufficient. Further, the influence of the side etching may become large, and it is difficult to manufacture a high-density printed circuit board. Further, the photosensitive element 1 may be provided with a protective film (not shown) on the main surface opposite to the first main surface 12 which is in contact with the support film 10 of the photosensitive layer 20. The protective film preferably uses a film having a smaller adhesion between the photosensitive layer 20 and the protective film than the adhesion between the photosensitive layer 20 and the support film 10, and a fish eye can be used. Film. Specifically, for example, an inert polyolefin film such as polyethylene or polypropylene is used. From the viewpoint of the releasability from the photosensitive layer 20, a polyethylene film is preferred. The thickness of the protective film varies depending on the application, and is preferably about 1 to 100 μm. The photosensitive element 1 may further have an intermediate layer or a protective layer such as a buffer layer, an adhesive layer, a light absorbing layer, and a gas barrier layer in addition to the support film 10, the photosensitive layer 20, and the protective film. The photosensitive element 1 of the present embodiment can be stored in a state in which, for example, a photosensitive element state or a layer in which a protective film is laminated on a photosensitive layer 20 and wound into a roll-shaped winding core. At this time, the support film 10 is in the state of the outermost layer, and it is preferable to wind it into a roll shape. The end surface of the photosensitive element 1 wound in a roll shape is -34 to 201217905. From the viewpoint of end face protection, it is preferable to provide an end face spacer, and it is preferable to provide a moisture-proof end face spacer from the viewpoint of resistance to melting. The bag method is preferably packaged in a black sheet having a low moisture permeability. The core material is, for example, a plastic such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, or an ABS (acrylonitrile-butadiene-styrene copolymer). (Formation Method of Photoresist Pattern) The method for forming a photoresist pattern according to the present embodiment includes a method of laminating the photosensitive element 1 in the order of the photosensitive layer 20 and the support film 10 in the circuit formation. a step of laminating on the substrate; an active light is passed through the support film 10, irradiated to a predetermined portion of the photosensitive layer 20, and an exposure step of forming a photocured portion on the photosensitive layer 20; and removing the photosensitive layer 20 other than the photocured portion Part of the imaging steps. In the laminating step, a method of laminating the photosensitive layer 20 on a substrate for forming a circuit, for example, when a protective film is present on the photosensitive layer 20, 'after removing the protective film, the photosensitive layer 20 is heated to about 7 〇 to 13 ° C. 'At the same time, a method of laminating the substrate for circuit formation with a pressure of about 0.1 to 1 MPa, and laminating. In this lamination step, it is also possible to laminate under reduced pressure. The laminated surface of the circuit-forming substrate is usually a metal surface, but is not particularly limited. In order to further improve the high-level compatibility, the substrate for circuit formation can be pre-heat treated. Next, the photosensitive layer 20' laminated for the lamination step is aligned with the mask having the negative or positive mask pattern at the second main surface of the support film 10 to be adhered. Then, in the exposure step, the photosensitive layer 20 is irradiated with active light rays in the form of an image by the photomask and the support film 10, and a photocured portion is formed on the photosensitive layer 2. The light source of the above-mentioned active light is a known light source, and for example, a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, and a xenon lamp are effective for emitting ultraviolet rays or visible light. Further, a photohardening portion can be formed on the photosensitive layer 20 by laser direct drawing. Next, after the above exposure step, the photomask is peeled off from the support film 10. Next, the support film 10 is peeled off from the photosensitive layer 20. In the development step, the unexposed portion (photocured portion) of the photosensitive layer 20 is removed by wet development or dry development of a developing solution such as an aqueous alkaline solution, a water-based developing solution, or an organic solvent. Imaging can produce a resist pattern. The alkaline aqueous solution is, for example, a thin solution of 0.1 to 5% by mass of sodium carbonate, a dilute solution of 0.1 to 5% by mass of potassium carbonate, and a dilute solution of 5% to 5% by mass of sodium hydroxide. The pH of the above aqueous alkaline solution is preferably in the range of 9 to 1 1 and the temperature thereof can be adjusted in accordance with the developability of the photosensitive layer 20. Further, a surfactant, an antifoaming agent, an organic solvent or the like may be mixed in the alkaline aqueous solution. The methods of development include, for example, dipping, spraying, rinsing, and washing. Further, the treatment after the development step may be performed by, for example, heating at a temperature of about 60 to 250 ° C or an exposure of 2 2 to 10 J/cm 2 to re-harden the photoresist pattern. (Manufacturing Method of Printed Circuit Board) The method of manufacturing a printed circuit board according to the present embodiment is formed by etching the pattern of the circuit-forming substrate-36 201217905 formed by the resist pattern. Electroplating is carried out. The photosensitive element of the present embodiment is particularly suitable for producing a printed circuit board by a method including a plating step, and is suitably used in a semi-additive process (SAP). The inventors of the present invention have reason to be suitable for use in SAP as described below. The line width of printed circuit boards produced by SAP has a very fine tendency compared to printed circuit boards produced by subtractive methods. Further, in the case of SAP, the photoresist shape is directly transferred into a plating line shape. When a printed circuit board having an extremely thin line pattern produced by SAP has a slight photoresist defect, the production yield tends to decrease. Therefore, the photosensitive element of the present embodiment is particularly suitable for use in SAP. The etching liquid for etching includes, for example, a copper chloride solution, a ferric chloride solution, and an alkali etching solution. Electroplating is, for example, copper plating, welding shovel, nickel ore and gold plating. After etching or electroplating, the photoresist pattern can be peeled off, for example, using an aqueous solution which is more alkaline than the alkaline aqueous solution used for development. As the strongly alkaline aqueous solution, for example, a 1 to 1% by mass aqueous sodium hydroxide solution and a 1 to 10% by mass aqueous potassium hydroxide solution can be used. The peeling method includes, for example, a dipping method and a spraying method. The printed circuit board forming the photoresist pattern may be a multilayer printed circuit board or have a small diameter through hole. Further, when plating a circuit board for forming a circuit layer having an insulating layer and a conductor layer formed on the insulating layer, it is necessary to remove the conductor layer other than the pattern. For the removal method, for example, after the photoresist pattern is peeled off, a method of etching is slightly performed or after the plating, followed by solder plating or the like, and then the photoresist pattern is peeled off, and the wiring portion is masked by soldering, and secondly, only the conductor can be etched. Layer etch - 37 - 201217905 Method for processing etchant, etc. As described above, the photosensitive element of the present embodiment can be used for a printed circuit board. (Manufacturing Method of Semiconductor Package Substrate) The photosensitive element 1 of the present embodiment can be used for a package substrate including a hard substrate and an insulating film formed on the hard substrate. At this time, the light-cured portion of the photosensitive layer 20 may be used as an insulating film. When the photocured portion of the photosensitive layer 20 is used as a solder resist for a semiconductor package, for example, after the development of the photoresist pattern is completed, it is preferable to improve solder heat resistance, chemical resistance, and the like. Ultraviolet irradiation or heating of a high pressure mercury lamp. When irradiating ultraviolet rays, the amount of irradiation can be adjusted as necessary, and for example, irradiation can be performed at an irradiation amount of about 0 to 10 J/cm2. When the photoresist pattern is heated, it is preferably in the range of about 10 to 170 ° C for about 15 to 90 minutes. UV irradiation and heating can be performed at the same time, or one of them can be carried out before another. At the same time, when ultraviolet light is irradiated and heated, it is more preferably heated to 604 50 ° C from the viewpoint of effectively imparting heat resistance to soldering, chemical resistance, and the like. The solder resist formed of the photosensitive element of the present embodiment has a protective film for wiring after soldering to the substrate, and is excellent in physical properties such as tensile strength and elongation, and heat-resistant punchability, and thus can be used as a semiconductor package. The permanent reticle is used. As described above, the package substrate having the resist pattern is used, and then assembly of semiconductor elements or the like (for example, wire bonding or soldering connection) is performed, and then mounted on an electronic device such as a computer. -38 - 201217905 The present invention will be described in detail based on the embodiments thereof, but the present invention is not limited to the above embodiments. The present invention can be variously modified without departing from the spirit of the invention. [Embodiment] [Embodiment] Hereinafter, the present invention will be described in detail based on the embodiments thereof, but the present invention is not limited to the embodiments. (Examples 1 to 9 and Comparative Examples 1 to 10) (A) A binder polymer having a composition shown in the following Table 1 or 2 was synthesized. The weight average molecular weight of the binder polymer is determined by gel permeation chromatography (GPC) and is derived using a calibration curve of standard polystyrene. The GPC conditions and the acid value measurement procedure are as follows, and the measurement results are shown in Table 1 or 2. (GPC condition) Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd., trade name) Pipe column: Gelpack GL-R420, Gelpack GL-R430, Gelpack GL-R440 (3 in total) (The above is Hitachi Chemical Industry (share) system, product name)
溶離液:四氫呋喃 測定溫度:40°C -39- 201217905 流量:2.05mL/分鐘 檢測器:日立L-3 3 00型RI ((股)日立製作所製、商品 名) (酸價測定方法) 三角燒瓶中秤取合成後之黏結劑聚合物約1 g,添加混 合溶剤(質量比:甲苯/甲醇=70/30 )溶解後,添加適量的 指示藥劑酚酞溶液,以〇. 1N之氫氧化鉀水溶液進行滴定, 藉由下述式(α )測定酸價。 χ= 1 〇χ Vfx56. l/(WpxI) ...(a) 式(a)中,x係表示酸價(mgKOH/g ) ,Vf係表示 0. IN之KOH水溶液的滴定量(mL ) ,Wp係表示測定後之 樹脂溶液的質量(g ) ,I係表示測定後之樹脂溶液中之不 揮發分的比例(質量%)。測定結果如表1及2所示。 [表1] 黏結劑聚合物 實施例 1 2 3 4 5 6 7 8 9 合成時之 投入量 (g) 甲基丙烯酸 100 100 100 100 85 75 70 60 50 甲基丙烯酸甲酯 150 150 150 150 165 175 180 190 200 苯乙烯 200 — 200 200 200 200 200 200 200 甲基丙烯酸苄酯 一 200 — 重量平均分子量 30000 30000 40000 50000 30000 25000 24000 18000 13000 酸價(mmgKOH) 130 130 130 130 110 100 90 80 65 -40- 201217905 [表2] 黏結劑 比較例 1 2 3 4 5 6 7 8 9 10 合成時之 投入量 (g) 甲基丙嫌酸 100 100 85 70 60 60 50 100 100 100 甲基丙烯酸甲酯 150 150 190 180 180 180 200 150 150 150 苯乙烯 200 200 200 200 200 200 200 200 200 - 甲基丙烯酸苄酯 一 一 200 重量平均分子量 60000 54000 60000 30000 25000 22000 16000 8000 30000 30000 酸價(酬gKOH) 130 130 110 90 80 80 65 130 130 130 調配下述表3所示之各成分,調製感光性樹脂組成物 [表3] 成分 調配量u) (A)成分 表1或2所示之 組成物 150(固形分-· 60) (B)成分 FA-321 M·1 20 FA-023M12 5 UA-1 1 13 10 SR-454·4 5 (C)成分 EAB15 0. 1 B-CIM16 3 其他成分 UCV17 0. 3 MKG18 0. 03 TBC19 0. 03 溶劑 甲醇 5 丙酮 9 甲苯 5 -41 - 1 1 :EO改性雙酚A二甲基丙烯酸酯(日立化成工業股份公司製、商品名) * 2: ΕΟ,ΡΟ改性二甲基丙烯酸酯(日立化成工業股份公司製、商品名) * 3: Ε0改性g基甲酸乙酯二甲基丙烯酸酯(新中村化學工業(股)製、商品名) » 4:E0改性二羥甲基丙焼三甲基丙稀酸酯(Sartomer公司製、商品名) * 5: Ν,Ν'-四甲基-4,-二胺基二苯甲酮 * 6: 2-(〇-氯苯基)-4,5-二苯基咪唑二聚物 *7:無色結晶紫 *8:孔雀石綠 * 9 : 4-t-丁基鄰苯二甲酚 201217905 (感光性元件之製作) 準備表4或表5所示之「PET」薄膜作爲感光性元件的 支持薄膜。測定各PET薄膜所含有之5μΐη以上之粒子等的 總數及霧度的結果如表4及表5所示。 上述粒子等之總數係使用偏光顯微鏡測定存在於於 1 mm2單位之5 μιη以上之粒子等之數的測定値。此時之η數 (測定數)爲5。又,支持薄膜的霧度係依據JIS Κ 7105測 定的値。此等支持薄膜的厚度均爲16μπι。 其次,將上述感光性樹脂組成物之溶液以均勻厚度塗 佈於各PET薄膜上。然後,以100 °C之熱風對流乾燥機乾燥 2分鐘,除去溶劑形成感光層。乾燥後,以聚乙烯製保護 薄膜(TAMAPOLY公司製、商品名「NF-15」、厚度20μιη )被覆感光層,得到感光性元件。乾燥後之感光層的厚度 均爲1 5 μιη。 (層合體之製作) 將兩面層合有銅箔(厚度:35 μιη)之玻璃環氧材之貼 銅層合板(日立化成工業公司製、商品名「MLC-E-679」 )的銅表面,使用MEC etch BOND CZ-8100(MEC公司製 )進行表面粗化,經酸洗及水洗後,以空氣流乾燥。將所 得之貼銅層合板加熱至80°C,將保護薄膜剝離,同時感光 層接觸銅表面的方式,層合感光性元件。如此得到依序層 合有貼銅層合板、感光層、支持薄膜的層合體。層合係使 -42- 201217905 用120°C之加熱輥,以〇.4MPa之壓黏壓力、1.5m/分鐘之輥 速度進行。此等層合體係作爲以下所示之試驗的試驗片使 用。 (最少顯像時間之測定) 將層合於125mmx 200mm四方之基板的感光層進行噴 霧顯像,測定完全除去未曝光部的時間,作爲最少顯像時 間。測定結果如表4及5所示。 (光感度之測定試驗) 試驗片之支持薄膜上載置作爲負像之Stauffer21段曝 光格數片(Step Tablets ),使用具有高壓水銀燈之曝光 機((股)OAK公司製、商品名「EXM-1201」),以 lOOmJ/cm2之照射能量,使感光層曝光。接著,將支持薄 膜剝離,將3 0°C之1質量%碳酸鈉水溶液以最少顯像時間之 2倍時間進行噴霧顯像,除去未曝光部分後進行顯像。藉 由測定形成於貼銅層合板上之光硬化膜之曝光格數片的段 數,評價感光性樹脂組成物之光感度。結果如表4及表5所 示。光感度係以曝光格數片的段數表示,此曝光格數片的 段數越高,表示光感度越高。 (解像度之測定試驗) 爲了硏究解像度,而將具有Stauffer2 1段曝光格數片 之圖像工具與作爲解像度評價用負像之具有線寬/空間寬 -43- 201217905 爲2/2〜3 0/3 0 (單位:μη〇之配線圖型之氣體色層型的圖 像工具密著於試驗片之支持薄膜上,使用具有高壓水銀燈 之曝光機((股)〇ΑΚ製作所製、商品名「ΕΧΜ-1201」), 以SUuffer21段曝光格數片之顯像後之殘存階梯段數成爲 5.0之照射能量進行曝光。其次,將支持薄膜剝離,使用 30°C之1質量%碳酸鈉水溶液以最少顯像時間之4倍時間進 行噴霧顯像,除去未曝光部分後進行顯像。其中解像度係 藉由顯像處理可完全除去未曝光部被之線寬間之空間寬之 最小値(單位:μηι )進行評價。解像度之評價係數値越小 表示越佳的値。結果如表4及表5所示。 (光阻線之側面形狀之評價) 以上述解像度之測定試驗評價的基板中,以掃描型電 子顯微鏡(股份公司日立高科技製、商品名SU- 1 5 00 )觀 察光阻線之側面形狀,並以下述評價》結果如表4及5所示 〇 A :滑順的形狀 B :稍微粗糙形狀 C :粗糙的形狀 (密著性之測定試驗) 爲了硏究密著性,而將具有Stauffer21段曝光格數片 之圖像工具與作爲密著性評價用負像之具有線寬/空間寬 爲2/1000-3 0/1 0 00 (單位:μιη)之配線圖型之氣體色層型 -44- 201217905 的圖像工具密著於試驗片之支持薄膜上’使用具有高壓水 銀燈之曝光機((股)〇ΑΚ製作所製、商品名「ΕΧΜ-12〇1」 ),以Stauffer21段曝光格數片之顯像後之殘存階梯段數 成爲8.0之照射能量進行曝光。其次’將支持薄膜剝離’ 使用3 0 °C之1質量%碳酸鈉水溶液’以最少顯像時間之4倍 時間進行噴霧顯像,除去未曝光部分後進行顯像。密著性 係藉由顯像處理可完全除去未曝光部之線寬爲最小寬度( 單位:μηι )評價密著性。密著性之評價係數値越小越佳的 値。結果如表4及表5所示。 (光阻缺損之發生數之測定試驗) 爲了硏究光阻缺損之發生數,而將具有StaUffer21段 曝光格數片之圖像工具與具有線寬/空間寬爲10/30 (單位 :μηι)之配線圖型之氣體色層型的圖像工具密著於試驗片 之支持薄膜上,使用具有高壓水銀燈之曝光機,以 StaUffer21段曝光格數片之顯像後之殘存階梯段數成爲5.0 之照射能量進行曝光。其次,將支持薄膜剝離,使用30°C 之1質量%碳酸鈉水溶液,以最少顯像時間之2倍時間進行 噴霧,除去未曝光部分。接著,使用顯微鏡計數光阻缺損 數。以線長度爲1 mm ’且線條數爲1 〇條作爲觀察單位’ η 數爲5時之平均値作爲光阻缺損之發生數。結果如表4及5 所示* -45- 201217905 [表4] 項目 實施例 1 2 3 4 5 6 7 8 9 支持 薄膜 商品名 QS-48*1 QS-48*' QS-48*' QS-48·1 QS-48*' QS-48*1 QS-48*' QS-48*1 QS-48*' 膜厚Wm) 16 16 16 16 16 16 16 16 16 粒子等之個數 1 1 1 1 1 1 1 1 霧度 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 最少顯像時間(秒) 12 12 13 16 13 18 13 14 14 光感度 5 5 5 5 5 5 5 5 5 密著性(//m) 5 4 4 4 4 5 5 5 6 解像度(//m) 6 6 7 7 6 5 5 5 5 光阻側面之形狀 A A A A A A A A A 光阻缺損之發生數 0 0 0 0 0 0 0 0 0 * 1:表裏具有含微粒子之層之3層構造的二軸配向PET薄膜、東麗股份公司製 [表5] 項目 比較例 1 2 3 4 5 6 7 8 9 10 支持 薄膜 商品名 QS-48., QS-48·, QS-48*' QS-48*' QS-48*' QS-48*' QS-48*, QS-48*1 HTF-01 *2 HTR-02 *3 膜厚(㈣) 16 16 16 16 16 16 16 16 16 16 粒子等之個數 1 1 1 1 1 1 1 1 28 318 霧度 0,4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.2 2 最少顯像時間(秒) >40 23 >40 >40 >40 20 18 7 12 12 光感度 — 5 — — - 5 5 5 5 5 密著性("m) — 4 — — — 5 5 12 5 5 解像度(Um) — 9 — — — 8 12 5 6 7 光阻側面之形狀 — A — — - A A C B C 光阻缺損之發生數 — 0 — — 一 0 0 42 13 213 * 1:表裏具有含微粒子之層之3層構造的二軸配向PET薄膜、東麗股份公司製 *2:微粒子之含有率在表裏不同之2層構造的二軸配向PET薄膜、帝人DuPon股份公司製 *3:表裏具有含微粒子之層之3層構造的二軸配向PET^膜、帝人DuPon股份公司製Isolation liquid: tetrahydrofuran measurement temperature: 40 ° C -39 - 201217905 Flow rate: 2.05 mL / min Detector: Hitachi L-3 3 00 type RI (manufactured by Hitachi, Ltd., trade name) (acid value measurement method) The medium scale takes about 1 g of the synthesized binder polymer, and after adding the mixed solution (mass ratio: toluene/methanol=70/30), the appropriate amount of the indicator phenolphthalein solution is added, and the 1N potassium hydroxide aqueous solution is used. For titration, the acid value was determined by the following formula (α). χ = 1 〇χ Vfx56. l/(WpxI) (a) In the formula (a), x represents the acid value (mgKOH/g), and Vf represents the titer of the KOH aqueous solution of 0. IN (mL) Wp is the mass (g) of the resin solution after the measurement, and I is the ratio (% by mass) of the nonvolatile content in the resin solution after the measurement. The measurement results are shown in Tables 1 and 2. [Table 1] Adhesive Polymer Example 1 2 3 4 5 6 7 8 9 Input amount during synthesis (g) Methacrylic acid 100 100 100 100 85 75 70 60 50 Methyl methacrylate 150 150 150 150 165 175 180 190 200 Styrene 200 — 200 200 200 200 200 200 200 Benzyl methacrylate-200 — Weight average molecular weight 30000 30000 40000 50000 30000 25000 24000 18000 13000 Acid value (mmgKOH) 130 130 130 130 110 100 90 80 65 -40 - 201217905 [Table 2] Adhesives Comparative Example 1 2 3 4 5 6 7 8 9 10 Input amount during synthesis (g) Methyl acrylic acid 100 100 85 70 60 60 50 100 100 100 Methyl methacrylate 150 150 190 180 180 180 200 150 150 150 Styrene 200 200 200 200 200 200 200 200 200 - Benzyl methacrylate - 200 Weight average molecular weight 60000 54000 60000 30000 25000 22000 16000 8000 30000 30000 Acid price (paid gKOH) 130 130 110 90 80 80 65 130 130 130 The components shown in Table 3 below were prepared to prepare a photosensitive resin composition [Table 3] Composition amount u) (A) Composition 150 shown in Table 1 or 2 (solid content) -· 60) (B) into FA-321 M·1 20 FA-023M12 5 UA-1 1 13 10 SR-454·4 5 (C) Component EAB15 0. 1 B-CIM16 3 Other components UCV17 0. 3 MKG18 0. 03 TBC19 0. 03 Solvent Methanol 5 Acetone 9 Toluene 5 -41 - 1 1 : EO modified bisphenol A dimethacrylate (manufactured by Hitachi Chemical Co., Ltd.) * 2: ΕΟ, ΡΟ modified dimethacrylate (Hitachi Chemical Co., Ltd.) Industrial Co., Ltd., product name) * 3: Ε0 modified g-based ethyl ester dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name) » 4: E0 modified dimethylol propyl hydride Methyl acrylate (manufactured by Sartomer Co., Ltd.) * 5: Ν, Ν'-tetramethyl-4,-diaminobenzophenone* 6: 2-(anthracene-chlorophenyl)-4 ,5-diphenylimidazole dimer*7: colorless crystal violet*8: malachite green* 9 : 4-t-butyl phthalic phenol 201217905 (production of photosensitive element) Preparation of Table 4 or Table 5 The "PET" film shown is used as a support film for a photosensitive element. Table 4 and Table 5 show the total number of haze and the like of the particles of 5 μΐη or more contained in each PET film. The total number of the above-mentioned particles and the like is measured by a polarizing microscope to measure the number of particles or the like present in 5 μm or more of 1 mm 2 unit. The number of η (measurement number) at this time was 5. Further, the haze of the supporting film is 値 measured in accordance with JIS Κ 7105. The thickness of these support films is 16 μm. Next, a solution of the above photosensitive resin composition was applied to each PET film in a uniform thickness. Then, it was dried by a hot air convection dryer at 100 ° C for 2 minutes to remove the solvent to form a photosensitive layer. After drying, the photosensitive layer was coated with a polyethylene protective film (manufactured by TAMAPOLY Co., Ltd., trade name "NF-15", thickness 20 μm) to obtain a photosensitive element. The thickness of the photosensitive layer after drying was 15 μm. (Production of Laminated Fabric) The copper surface of a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name "MLC-E-679") of a glass epoxy material having a copper foil (thickness: 35 μm) was laminated on both sides. The surface was roughened using MEC etch BOND CZ-8100 (manufactured by MEC Co., Ltd.), and after pickling and washing with water, it was dried by air flow. The obtained copper clad laminate was heated to 80 ° C, and the protective film was peeled off while the photosensitive layer was in contact with the copper surface to laminate the photosensitive member. Thus, a laminate in which a copper clad laminate, a photosensitive layer, and a support film were laminated in this order was obtained. The laminating system was carried out by using a heating roller of 120 ° C at a pressure of 〇 4 MPa and a roller speed of 1.5 m / min. These laminate systems were used as test pieces of the test shown below. (Measurement of minimum development time) The photosensitive layer laminated on a substrate of 125 mm x 200 mm square was subjected to spray development, and the time for completely removing the unexposed portion was measured as the minimum development time. The measurement results are shown in Tables 4 and 5. (Measurement of Photosensitivity Test) The support film of the test piece was placed on a Stauffer 21-segment exposure tablet (Step Tablets) as a negative image, and an exposure machine having a high-pressure mercury lamp (manufactured by OAK Co., Ltd., trade name "EXM-1201" was used. ”), the photosensitive layer was exposed to light at an irradiation energy of 100 mJ/cm 2 . Next, the support film was peeled off, and a 1% by mass aqueous sodium carbonate solution at 30 ° C was spray-developed at twice the minimum development time to remove the unexposed portion, followed by development. The photosensitivity of the photosensitive resin composition was evaluated by measuring the number of stages of the exposed patches of the photocured film formed on the copper-clad laminate. The results are shown in Tables 4 and 5. The light sensitivity is expressed by the number of segments of the exposure grid, and the higher the number of segments of the exposure grid, the higher the light sensitivity. (Measurement test of resolution) In order to solve the resolution, the image tool having the Stauffer 2-segment exposure cell and the negative image for the resolution evaluation have a line width/space width of -23 - 201217905 of 2/2 to 3 0 /3 0 (The unit of the gas layer type image of the wiring pattern of μη〇 is attached to the support film of the test piece, and the exposure machine with a high-pressure mercury lamp (manufactured by the company) is used. ΕΧΜ-1201"), the exposure energy of the SUuffer 21-segment exposure image is exposed to an irradiation energy of 5.0. Secondly, the support film is peeled off, using a 1% by mass aqueous sodium carbonate solution at 30 ° C to minimize The development was carried out four times as long as the development time, and the unexposed portion was removed for development, wherein the resolution was completely removed by the development process to completely remove the space width between the line widths of the unexposed portions (unit: μηι The evaluation was performed. The smaller the evaluation coefficient 解 of the resolution, the better the enthalpy. The results are shown in Tables 4 and 5. (Evaluation of the side shape of the photoresist line) The substrate evaluated by the measurement test of the above resolution The side shape of the photoresist line was observed by a scanning electron microscope (manufactured by Hitachi High-Tech Co., Ltd., trade name SU- 1 500), and the results of the following evaluations are shown in Tables 4 and 5: A: smooth shape B: slightly rough shape C: rough shape (measurement test of adhesion) In order to investigate the adhesion, the image tool having the Stauffer 21-segment exposure grid and the negative image for the adhesion evaluation have a line The width/space width is 2/1000-3 0/1 0 00 (unit: μιη). The wiring pattern of the gas color layer type -44- 201217905 The image tool is attached to the test piece of the support film. The exposure lamp of the mercury lamp (manufactured by the company), the product name "ΕΧΜ-12〇1", is exposed by the irradiation energy of 8.0 after the image of the Stauffer 21-segment exposure image is displayed. The support film was peeled off using a 1% by mass aqueous sodium carbonate solution at 30 ° C for 4 times of the minimum development time, and the unexposed portion was removed for development. The adhesion was developed by imaging. Can completely remove the unexposed part of the line width is the most The small width (unit: μηι) was used to evaluate the adhesion. The evaluation coefficient of the adhesion was as small as possible, and the results were as shown in Tables 4 and 5. (Measurement test of the number of occurrences of photoresist defects) The number of occurrences of photoresist defects, and an image tool with a StaUffer 21-segment exposure grid image and a gas color layer type image tool having a wiring pattern with a line width/space width of 10/30 (unit: μηι) On the support film of the test piece, an exposure machine having a high-pressure mercury lamp was used, and exposure was performed with an irradiation energy of 5.0 after the development of the StaUffer 21-segment cell. Next, the support film was peeled off, and a 1% by mass aqueous sodium carbonate solution at 30 ° C was used for spraying at twice the minimum development time to remove the unexposed portion. Next, the number of photoresist defects was counted using a microscope. The average 値 of the line length is 1 mm ′ and the number of lines is 1 〇 as the observation unit η number is 5 as the number of occurrences of the photoresist defect. The results are shown in Tables 4 and 5 * -45- 201217905 [Table 4] Item Example 1 2 3 4 5 6 7 8 9 Support film trade name QS-48*1 QS-48*' QS-48*' QS- 48·1 QS-48*' QS-48*1 QS-48*' QS-48*1 QS-48*' Film thickness Wm) 16 16 16 16 16 16 16 16 16 Number of particles etc. 1 1 1 1 1 1 1 1 Haze 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Minimum development time (seconds) 12 12 13 16 13 18 13 14 14 Light sensitivity 5 5 5 5 5 5 5 5 5 Adhesion (//m) 5 4 4 4 4 5 5 5 6 Resolution (//m) 6 6 7 7 6 5 5 5 5 Shape of the photoresist side AAAAAAAAA Photorefractive defect occurrence 0 0 0 0 0 0 0 0 0 * 1: The table has Biaxial alignment PET film of three-layer structure containing microparticles, manufactured by Toray Co., Ltd. [Table 5] Item Comparative Example 1 2 3 4 5 6 7 8 9 10 Support film trade name QS-48., QS-48· , QS-48*' QS-48*' QS-48*' QS-48*' QS-48*, QS-48*1 HTF-01 *2 HTR-02 *3 Film thickness ((4)) 16 16 16 16 16 16 16 16 16 16 Number of particles etc. 1 1 1 1 1 1 1 1 28 318 Haze 0,4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.2 2 Minimum development time (seconds) >40 23 >40 > ;40 >40 20 18 7 12 12 Light sensitivity — 5 — — — 5 5 5 5 5 Adhesion ("m) — 4 — — — 5 5 12 5 5 Resolution (Um) — 9 — — — 8 12 5 6 7 Shape of the photoresist side— A — — — AACBC Photorefractive defect occurrence — 0 — — A 0 0 42 13 213 * 1: Two-axis alignment PET film with a three-layer structure with microparticle-containing layers in the table, Toray Co., Ltd.*2: Microparticles The two-axis alignment PET film of the two-layer structure, which is different in the table, and the three-axis alignment PET film of the three-layer structure with the microparticle-containing layer in the watch, made by Teijin DuPon Co., Ltd.
如表4及5所示得知,實施例1〜9及比較例9使用之PET -46 - 201217905 薄膜之霧度大致同等,但是實施例1〜9使用之PET薄膜之存 在於1mm2單位之5μιη以上之粒子等的總數爲1個,相較於 比較例9使用之PET薄膜(粒子等之總數爲28個)爲極少。 因此,在光阻缺損之發生數方面,實施例1〜9可得到光阻 缺損之發生數爲0,相較於比較例9爲極少的結果。又,使 用比較例1 〇之粒子等之總數爲3 1 8個的支持薄膜時,光阻 缺損之發生數增大爲2 1 3個。實施例1 ~9係顯像後之光阻側 面之形狀爲滑順,形成良好的光阻圖型。 如表4所示可知,實施例1〜9使用的(A)成分之酸價 與重量平均分子量係在適當的範圍內,因此最少顯像時間 極短,印刷電路板之生產性不會降低。由上述式(I )所 求得之適當的重量平均分子量的範圍係酸價130mgKOH/g 時爲1~5·39萬,酸價110mgKOH/g時爲1~3·6萬,酸價90 mgKOH/g時爲1〜2.4萬,酸價8 OmgKOH/g時爲1〜2.0萬。 【圖式簡單說明】 圖1係表示本發明之感光性元件之較佳實施形態的模 式剖面圖,圖2係觀察具有直徑5μιη以上之粒子等之支持薄 膜表面的偏光顯微鏡相片,圖3係使用在具有多數直徑5μιη 以上之粒子等的支持薄膜上,具備感光層的感光性元件所 形成之光阻圖型之掃描型顯微鏡相片。 【主要元件符號說明】 1 :感光性元件 -47- 201217905 ι〇 :支持薄膜 12 :第1主面 14 :第2主面 20 :感光層(感光性樹脂組成物層) -48-As shown in Tables 4 and 5, the haze of the PET-46 - 201217905 film used in Examples 1 to 9 and Comparative Example 9 was substantially the same, but the PET film used in Examples 1 to 9 was present in 5 μm of 1 mm 2 unit. The total number of the above particles and the like was one, and the PET film used in Comparative Example 9 (the total number of particles and the like was 28) was extremely small. Therefore, in the number of occurrences of the photoresist defect, the number of occurrences of the photoresist defect in Examples 1 to 9 was 0, which was extremely inferior to that of Comparative Example 9. Further, when a total of 318 support films of the particles of Comparative Example 1 and the like were used, the number of occurrences of photoresist defects increased to 213. The shape of the photoresist side after the development of the examples 1 to 9 was smooth, and a good photoresist pattern was formed. As shown in Table 4, the acid value and the weight average molecular weight of the component (A) used in Examples 1 to 9 were within an appropriate range, so that the minimum development time was extremely short, and the productivity of the printed circuit board was not lowered. The range of the weight average molecular weight determined by the above formula (I) is from 1 to 539,000 at an acid value of 130 mgKOH/g, from 1 to 30,000,000 at an acid value of 110 mgKOH/g, and an acid value of 90 mgKOH. When it is /g, it is 1 to 24,000, and when the acid value is 8 OmgKOH/g, it is 1 to 2,000,000. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a preferred embodiment of a photosensitive element of the present invention, and Fig. 2 is a view showing a polarizing microscope photograph of a surface of a supporting film having particles having a diameter of 5 μm or more, and Fig. 3 is used. A scanning-type micrograph of a resist pattern formed of a photosensitive element having a photosensitive layer on a support film having a plurality of particles having a diameter of 5 μm or more. [Main component symbol description] 1 : Photosensitive element -47- 201217905 ι〇 : Support film 12 : 1st main surface 14 : 2nd main surface 20 : Photosensitive layer (photosensitive resin composition layer) -48-
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JPWO2018100730A1 (en) * | 2016-12-02 | 2019-10-17 | 日立化成株式会社 | Photosensitive element, resist pattern forming method, and printed wiring board manufacturing method |
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