201120247 六、發明說明： 【發明所屬之技術領域】 本發明係關於含銅材料用蝕刻劑組成物及含鋼材 料之蝕刻方法，詳細而言，係關於一種能夠無形狀不良 地形成微細電路圖案（電路導線)之含銅材料用餘刻劑二 成物及含銅材料之钱刻方法。 【先前技術】 表面形成有電路導線之印刷電路板（或薄骐)被廣泛 地用於組裝電子零件或半導體元件等。然後，伴隨著近 年來電子機器之小型化及高功能化的要求，針對印刷電 路板（或薄膜）的電路導線亦被期望要能夠高密度化及薄 型化。. 形成高密度電路導線的方法已知有被稱為減成 (subtractive)法或半加成（semi_additive)法之方法。一般 來說，由於減成法係利用濕蝕刻之電路形成方法，故雖 步琢y、且成本低但被認為不適於微細電路圖案的形 成。 為了形成祕細電路導線，理想為蚀刻部分無殘膜、 從上方觀之導線的侧面為直線(直線性）、電路導線的剖 .面為矩形以及具有高餘刻係數(etcWng fact〇r)(電路導線 上部寬度^導線下部寬度的差較小），但實際上會發生 殘膜、直線性〜圭、纖刻、底切(under cut)以及導線 上部Μ㈣不良。因此，濕㈣中便被期望在 201120247 維持生產性之情況下，同時能夠抑制該等形狀不良。 針對上述電路導線的形狀不良已有各種藉由改善 钮刻劑組成物的成分來改良之技術被提出。 '例如，專利文獻1中揭示了一種由酸及水溶液所構 成並可抑制側蝕刻、電路導線的上部變細之銅或鋼合金 的蝕刻液，其中該酸係選自銅的氧化劑、鹽酸及有機酸 鹽所'組成之群，而該水溶液係含有至少1種選自聚稀烴 乙二醇及聚胺與聚烯烴乙二醇之共聚物所組成之群的 心·合物。此處，銅的氧化劑係揭示了二價銅離子及三價 鐵離子，用來產生二價鋼離子之化合物係揭示了氣.化銅 (Π)、>臭化鋼(π)及氫氧化銅(π)，用來產生三價鐵離子之 化合物係揭示了氣化鐵(III)、溴化鐵(111)、碘化鐵(111)、 碌酸鐵(III)、硝酸鐵(III)及醋酸鐵(Ιΐιρ又，聚烯烴乙 二醇係揭示了聚乙二醇、聚丙二醇、環氧乙烷·環氧丙 塚共聚物，聚胺與聚烯烴乙二醇之共聚物係揭示了乙二 骇、二伸乙三胺、三伸乙四胺、四伸乙五胺、五伸乙六 胺、N-乙基乙二胺之聚乙二醇、聚丙二醇、環氧乙烷· 環氧丙烷共聚物。 又’專利文獻2中揭示了一種由氧化性金屬.離子 源、選自無機酸或有機酸之酸、含有至少其中一種選自 唆(azole)、乙二醇及二醇醚之水溶液所構成並能抑制底 切的蝕刻劑’其中該唑係只具有作為環内的異原子之氮 原子。此處，氧化性金屬離子源係揭示了二價銅離子或 價鐵離子，酸係揭示了鹽酸。又，可添加在钱刻劑之 201120247 界面活性劑係揭示有脂肪酸鹽、烷基硫酸酯鹽及烷基磷 酸酯鹽等陰離子界面活性劑；聚氧乙烯烷醚、聚氧丙烯 烧喊及聚氧乙烯與聚氡丙烯之塊狀聚合物等非離子界 面活性劑；月桂基二甲基胺基乙酸甜菜鹼及月桂基羥基 磺基甜菜鹼等甜菜鹼、胺基羧酸等兩性界面活性劑。 專利文獻1 :日本特開2004-256901號公報 專利文獻2:曰本特開2005-330572號公報 然而，專利文獻1及2所揭示之蝕刻劑組成物會有 無法狻得能夠充分地對應於微細電路圖案的蝕刻性能 之門>€特別疋，在形成被去除之銅的姓刻間隙（線的 間隙，gap)狹窄之圖案(例如1〇μπι〜6〇μπι)時，會有電路 圖案形狀不良的情況發生。 【發明内容】 丘一伞^明係為解決上述問題所發明者，其目的在於提 仏種此夠無形狀不良地形成微細電路圖案含 料用飯刻齡成物及含銅材料之_方法。心㈣ 後的ΓΓ者等為了解決上述問題，經過多次詳細檢討 刻劑組成物的組成與微細電路圖案的 物而藉由具有敎組成_刻劑喊 並利用該蝕刻劑組成物來進行蝕 題’進而達成本發明。 jW上述問 亦即，本發明為一 特徵在於係由包含有以 種含鋼材料用钱刻 下成分之水溶液所 劑組成物，其 構成： 201120247 (A) 選自二價銅離子及三價鐵離子之至少1種氧化 劑成分0.1〜15質量％ ; (B) 氣化氮〇.1〜2〇質量％ ;及 (C) .以下述式⑴來表示且算術平均分子量為 500〜1，5GG之非離子性界面活性劑q g()i〜$質量％，[Technical Field] The present invention relates to an etchant composition for a copper-containing material and an etching method for a steel-containing material, and more particularly to a fine circuit pattern capable of forming a shape without defects ( The copper-containing material of the circuit lead) is a method of engraving the second component of the residual agent and the copper-containing material. [Prior Art] A printed circuit board (or a thin film) on which a circuit lead is formed is widely used for assembling electronic parts or semiconductor elements and the like. Then, with the demand for miniaturization and high functionality of electronic devices in recent years, circuit leads for printed circuit boards (or films) have been expected to be denser and thinner. A method of forming a high-density circuit wire is known as a method of a subtractive method or a semi-additive method. In general, since the subtractive method utilizes a circuit forming method of wet etching, it is considered to be unsuitable for the formation of a fine circuit pattern although it is low in cost and low in cost. In order to form a fine circuit wire, it is desirable that the etched portion has no residual film, the side of the wire viewed from above is straight (linear), the cross section of the circuit wire is rectangular, and has a high residual coefficient (etcWng fact〇r) ( The difference between the upper width of the circuit wire and the width of the lower portion of the wire is small, but in fact, residual film, linearity, smear, undercut, and upper 导线 (4) defects occur. Therefore, it is expected that wet (four) will maintain the productivity in 201120247, and at the same time, it is possible to suppress such shape defects. Various techniques for improving the shape of the above-mentioned circuit leads have been proposed by improving the composition of the button engraving composition. For example, Patent Document 1 discloses an etching solution of copper or a steel alloy which is composed of an acid and an aqueous solution and which can suppress side etching and thinning of an upper portion of a circuit lead, wherein the acid is selected from copper oxidizing agent, hydrochloric acid, and organic. The acid salt is a group of constituents, and the aqueous solution contains at least one core compound selected from the group consisting of polydiethylene glycol and a copolymer of a polyamine and a polyolefin glycol. Here, the oxidizing agent of copper reveals divalent copper ions and ferric ions, and the compound used to produce divalent steel ions reveals copper, bismuth, > odorized steel (π) and hydroxide. Copper (π), a compound used to produce ferric ions, reveals iron (III), iron (111), iron iodide (111), iron (III), iron (III) And iron acetate (Ιΐιρ, polyolefin ethylene glycol reveals polyethylene glycol, polypropylene glycol, ethylene oxide·epoxypropene copolymer, copolymer of polyamine and polyolefin glycol reveals B Diethylene, diethylenetriamine, triamethylenetetramine, tetraethyleneamine, pentaethyleneamine, N-ethylethylenediamine polyethylene glycol, polypropylene glycol, ethylene oxide·epoxy Propane copolymer. Further, Patent Document 2 discloses an oxidizing metal ion source, an acid selected from an inorganic acid or an organic acid, and at least one selected from the group consisting of azole, ethylene glycol, and glycol ether. An etchant composed of an aqueous solution and capable of suppressing undercuts, wherein the azole system has only a nitrogen atom as a hetero atom in the ring. Here, the oxidizing metal ion source is exposed. The divalent copper ion or valence iron ion, the acid system reveals hydrochloric acid. Moreover, the 201120247 surfactant agent which can be added to the money engraving agent reveals anionic interfacial activity such as fatty acid salt, alkyl sulfate salt and alkyl phosphate salt. Non-ionic surfactants such as polyoxyethylene alkyl ether, polyoxypropylene squeaking, and bulk polymers of polyoxyethylene and polyacrylonitrile; lauryl dimethylaminoacetic acid betaine and lauryl hydroxy sulfobeet An amphoteric surfactant such as a betaine or an amino carboxylic acid such as a base. Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-256901. The etchant composition may have a pattern that is incapable of sufficiently etching the etching performance corresponding to the fine circuit pattern. In particular, a pattern in which the gap of the removed copper (gap of the line) is narrowed (for example, When 1〇μπι~6〇μπι), there is a case where the shape of the circuit pattern is defective. [Summary of the Invention] Qiuyi Umbrella is the inventor of the above problem, and its purpose is to improve the shape of the object. In order to solve the above problems, the fine circuit pattern contains a meal of a meal and a copper-containing material. In order to solve the above problems, the composition of the composition of the composition and the fine circuit pattern are reviewed in detail. The present invention is achieved by having a composition of 敎 刻 并 并 并 并 并 并 ' ' ' j j j j j j j j j j j j j j j j j j j j j j j j j j j j j j j j j j j j j The composition of the aqueous solution of the component, the composition of which is: 201120247 (A) 0.1 to 15% by mass of at least one oxidizing agent component selected from the group consisting of divalent copper ions and ferric ions; (B) gasified nitrogen hydrazine. 1 to 2 〇 (%) and (C). The nonionic surfactant qg()i to $% by mass represented by the following formula (1) and having an arithmetic mean molecular weight of 500 to 1, 5GG,
式(1) : R-0-X-H (式⑴中，尺表示碳數8〜18的院基，X表示環氧乙 烧基單元及環氧㈣基單元隨機絲合錢狀之聚環 氧烷基）。 .又’本發明為—種含崎料之關方法，其特徵在 於：於厚度10〜4〇_、蝕刻間隙(etching space)l〇〜60μπι 之含銅材料的圖案化中，係使用上述侧劑組成物。 依據本赉明，則可提供一種能夠無形狀不良地形成 微細電路圖案之含崎料__組成物及含銅材料 之餘刻方法。 【實施方式】 本如明之含鋼材料用蝕刻劑組成物（以下稱為蝕刻 劑組成物)係由包含有以下成分之水溶液所構成：（Α)選 自二價鋼離子及三_離子之至少丨種氧化劑成分(以 下稱為(Α)成分）；（Β)氣化氫（以下稱為(Β)成分）；（C)特 定的非離子性界面活性劑（以下稱為(c)成分）。 (Α)成分為—種具有能將含銅材料氧化來進行蝕刻 的功旎之成分，可使用二價銅離子、三價鐵離子，或二 201120247 價銅離子與三價鐵離子的混合物。該等通常可將銅或銅 (II)化合物及/或鐵(III)化合物作為供給源來使用。銅(11) 化合物舉例有氣化二價銅、溴化二價銅、硫酸二價銅、 氫氧化二價銅及醋酸二價銅，鐵(111)化合物舉例有氯化 三價鐵、溴化三價鐵、碘化三價鐵、硫酸三價鐵、硝酸 三價鐵及醋酸三價鐵等。該等可單獨使用，亦或混人2 種類以上來使用。該等當中，從費用、钱刻劑組成物口的 穩定性、侧速度的控制性之觀點來看，較佳為銅、氮 =-價銅、硫酸二價銅及氯化三價鐵，更佳為氯化三價 •鐵0 或三====:，二價銅離子及/ 晋。/。〜質量％，較佳為H0質 0备（Α)成分的含量較01質量〇/〇要少時 :會f長、光阻會劣化或生產性會降低。又，在減；法 銅的殘膜去除性會變差。另一方面H果會降低，故 較15質量夕主 田（A)成分的含量 會惡化。4，則無法控魏刻速度或_係數 .又，若同時使用三價鐵離子盥二價 =控制敍刻劑紐成物的氧化還原電話，則 此情況下二價:離=，劑組成物的餘刻能力^ 質量。/❶，較佳A 置以銅離子來換算為0,5, °.5質㈣少時，則會有無法“-:望銅= 201120247 情況。另n當二價崎子的含量較丨β。 多時，則會有錄刻劑組成物中產生游逢之情、兄重/〇要 (Β)成分具有能夠去除㈣後之含鋼材;;表 氧化膜或銅氯化物之功能、穩定氧化劑之功能，r的鋼 高相對於含銅材料的平坦性之功能，為—‘夠提 刻之成分。 疋進麵 姓刻劑組成物中之⑻成分的含量為〇1〜2 %，較佳為〇_5〜10質量％。當(Β)成分的含量較〇 = %要少時，則無法獲得充分的使用效果。另一方面負里 ⑻成分的含量較20質量％要多時，則_ 得^ 剩，而變得無法控舰刻速度，或發生電路導線的开^ 不良。 (C)成77為-種具有能夠提高㈣劑組成物對電路 圖案的滲透性，並藉由降低電路圖案周圍之侧劑組成 物的滯留來賦予良好電路形狀的效果之成分。又，由於 (Ρ)成分相騎含崎料*具有崎化合物化或配位等 過度的親和性，故不會導致侧的速度降低等生産性惡 化。 心、 (C)成分係以下述式（1)來表示。Formula (1) : R-0-XH (In the formula (1), the ruler represents a carbon number of 8 to 18, and the X represents an epoxy group and an epoxy (tetra) group unit. base). Further, the present invention is a method for controlling the inclusion of a raw material, which is characterized in that the above-mentioned side is used in the patterning of a copper-containing material having a thickness of 10 to 4 Å and an etching space of 100 Å to 60 μm. Agent composition. According to the present invention, it is possible to provide a residual method of forming a fine material pattern and a copper-containing material without forming a fine circuit pattern. [Embodiment] The etchant composition for a steel-containing material (hereinafter referred to as an etchant composition) is composed of an aqueous solution containing the following components: (Α) selected from at least a divalent steel ion and a tri-ion. An oxidizing agent component (hereinafter referred to as (Α) component); (Β) vaporized hydrogen (hereinafter referred to as (Β) component); (C) a specific nonionic surfactant (hereinafter referred to as component (c)) . The (Α) component is a component having a function of oxidizing a copper-containing material for etching, and a divalent copper ion, a ferric ion, or a mixture of a valence copper ion and a ferric ion of 201120247 may be used. These can usually be used as a supply source of copper or a copper (II) compound and/or an iron (III) compound. Examples of the copper (11) compound include vaporized cupric copper, cupric brominated copper, cupric sulfate, cupric oxyhydroxide, and cupric acid acetate. Iron (111) compounds are exemplified by ferric chloride and bromination. Ferric iron, trivalent iron iodide, ferric iron sulfate, trivalent iron nitrate, and ferric acetate. These may be used alone or in combination of two or more types. Among these, from the viewpoints of the cost, the stability of the composition of the money engraving agent, and the controllability of the side velocity, copper, nitrogen=-valent copper, divalent copper sulfate, and trivalent iron chloride are preferable. Good for trivalent chlorination • iron 0 or three ====:, divalent copper ions and / Jin. /. ~% by mass, preferably H0. When the content of the component (Α) component is less than 01 mass 〇 / : : The length of the material is f, the photoresist resistance is deteriorated, or the productivity is lowered. Further, in the subtraction, the residual film removal property of the copper is deteriorated. On the other hand, the H fruit will decrease, so the content of the component (A) in the main mass of the 15th grade will deteriorate. 4, it is impossible to control the speed of the Wei or the _ coefficient. Also, if the trivalent iron ion 盥 two price = control of the redox phone of the control agent, then in this case, the price of the product: The ability of the moment ^ quality. /❶, preferably A is set to copper, which is converted to 0,5, °.5. When the quality is small (four), there will be no "-: hope copper = 201120247. Another n when the price of bismuth is higher than 丨β For a long time, there will be a feeling of engraving in the composition of the recording agent, the weight of the brother/healing (Β) has the steel material which can be removed after (4); the function of the oxide film or copper chloride, and the function of stabilizing the oxidizing agent. The function of the steel height of r relative to the flatness of the copper-containing material is - a sufficient ingredient to be engraved. The content of the component (8) in the composition of the surname is 〇1 to 2%, preferably 〇 _5 to 10% by mass. When the content of the (Β) component is less than 〇 = %, sufficient use effect cannot be obtained. On the other hand, when the content of the negative (8) component is more than 20% by mass, then _ ^ Remaining, and becomes unable to control the speed of the ship, or the opening of the circuit wire is poor. (C) 77 is a type that has the ability to improve the permeability of the (four) agent composition to the circuit pattern, and by reducing the circuit pattern around The component of the side agent is retained to give a good circuit shape effect. Compound or the like over an affinity ligand, it will not result in reduced production rate and other side of evil. Heart, (C) component based the following formula (1) below.
式(1) : R-0-X-H 上式G)中，R為碳數8〜18的烷基，可為直鏈或具 有分支鏈。又，Χ為環氧乙烷基單元(-CH2_CH2-0-)及環 氧丙烷基單元(_CRijj_CR2H 〇_(Ri與R2的其中一者為 氫原子，另一者為甲基))隨機或聚合成塊狀之聚環氧烷 201120247 基。此處，聚環氧烷基中，環氧丙烷基單元相對於環氧 乙烷基單元的數量比較佳為0.1〜1。該數量比較1要大 時，則會有無法獲得充分的直線性及蝕刻係數之情況。 另一方面，該數量比較0.1要小時，則會有無法獲得充 分的蝕刻係數之情況。該數量比的較佳範圍為 0.25〜0.5，只要是在此範圍内，則抑制導線的上部寬度 過細之效果會較顯著，且能夠獲得導線上部寬度與導線 下部寬度的差較小之蝕刻。 (C)成分的非離子性界面活性劑通常可以天然或合 成醇、環氧乙烷基及環氧丙烷基為原料來製造。上式（1) 中的R為自天然或合成醇所導入之官能基。該醇舉例有 辛醇、2-乙基己醇、2級辛醇、異辛醇、第三辛醇、壬 醇、異壬醇、2級壬醇、癸醇、2級癸醇、十一醇、2 .級十一醇、十二醇、2級十二醇、三癸醇、異三癸醇、 2級三癸醇、四癸醇、2級四癸醇、六癸醇、2級六癸 醇、十八醇及異十八醇等。上述R可單獨或混合2種以 上來使用。 (C)成分之非離子性界面活性劑的製造方法在該技 術領域中為公知技術，可依據公知的方法來製造，抑或 使用市面上販賣的非離子性界面活性劑。 (C)成分的算數平均分子量為500〜1,500。當算術平 均分子量較500要少時，則無法獲得充分的直線性及蝕 刻係數。另一方面，當算術平均分子量較1,500要多時， 則無法獲得充分的钮刻係數。算術平均分子量的較佳範 201120247 :〇Γ，_ ’只要是在此範圍内，則抑制導線的上 σ又匕細之效果會較顯著，且能夠獲得導線上 與導線下部寬度的差較小之钱刻。 又 么當劑組成物中的（c)成分含量多時，會因蝕刻 係數的提鬲或直線性的提高等而有電路形狀變佳之傾 向，但另一方面會有蝕刻的速度降低而造成生產性降低 之傾向。因此，蝕刻劑組成物中的成分含量為 0-=1〜5質量％，較佳為0.01〜2質量％，更佳為0.054 質量％。當(C)成分的含量較5質量％要多時，則無法大 幅地提高電路形狀之改善，且生產性降低的缺點會變 大。另一方面’當（c)成分的含量較0.001質量％要少時， 則無法獲得充分的使用效果。 本發明之蝕刻劑組成物在不阻礙本發明效果的範 圍内，除了以上所說明之必要成分(A)〜(C)以外，可添 加使用於該用途之公知的任意成分。該任意成分舉例有 (B)成分以外的無機酸、有機酸、二醇越類化合物；（〇 成分以外的界面活性劑、胺基酸類化合物、唑類·化合 物、嘧啶類化合物、硫脲類化合物、胺類化合物、烷基 咻咯酮類化合物、有機螯合劑化合物、聚丙烯醯胺類化 合物、過氧化氫、過酸鹽、無機鹽、一價銅離子及二價 鐵離子。使用該等任意成分時，濃度一般來說係介於 0.001質量％〜10質量％的範圍。 (B)成分以外的無機酸舉例有硫酸、硝酸、磷酸、 聚石粦酸荨。該等可單獨或混合2種以上來使用。 201120247 有機酸舉例有甲酸、乙酸、丙酸、丁酸、戊酸、葵 酸、丙烯酸、巴豆酸、異巴豆酸、修酸、丙二酸、琥珀 酸、戊二酸、已二酸、庚二酸、順丁烯二酸、反丁烯二 酸、草酸、蘋果酸、酒石酸'檸檬酸、甘醇酸、乳酸、 磺胺酸、菸鹼酸、抗壞血酸、羥基新戊酸、果糖酸及冷 -氯丙酸等之羧酸類、曱磺酸、乙磺酸、2-羥乙磺酸、丙 磺酸、苯磺酸及曱苯磺酸等之有機磺酸類。該等可單獨 或混合2種以上來使用。 ' 二醇醚類化合物舉例有乙二醇單曱基醚、乙二醇單 乙基醚、乙二醇單丁基醚、二乙二醇單甲基醚、二乙二 醇單乙基醚、二乙二醇單丁基醚、三乙二醇單曱基醚、 三乙二醇單乙基醚、三乙二醇單丁基醚、丙二醇單曱基 醚、丙二醇單乙基醚、丙二醇單丁基醚、二丙二醇單曱 基醚、二丙二醇單乙基醚、二丙二醇單丁基醚、三丙二 醇單曱基醚、三丙二醇單乙基醚及3-甲基-3-曱氧基-3-曱氧基丁醇等低分子二醇醚化合物；聚乙二醇單曱基 醚、聚乙二醇單乙基醚及聚乙二醇單丁基醚等高分子二 .醇醚化合物。該等可單獨或混合2種以上來使用。 (C)成分以外的界面活性劑舉例有陰離子性界面活 性劑、上述式（1)所表示之非離子性界面活性劑以外的非 離子性界面活性劑、陽離子性界面活性劑及兩性界面活 性劑等。 陰離子性界面活性劑舉例有高級脂肪酸鹽、高級醇 硫酸酯鹽、硫化烯烴鹽、高級烷基磺酸鹽、α-烯烴磺 11 201120247 峰鹽、硫酸化脂肪酸鹽、續化脂肪酸鹽、磷酸酯鹽、脂 肪酸酯之硫酸酯鹽、甘油酯硫酸酯鹽、脂肪酸酯之磺酸 鹽、磺基脂肪酸甲基酯鹽、聚氧伸烷基烷醚硫酸酯 鹽'聚氧伸烷基烷基苯醚硫酸酯鹽、聚氧伸烷基烷醚碳 酸鹽、醯化胜肽、脂肪酸烷基醯胺或其環氧烷附加物的 硫酸酯鹽、磺基琥珀酸酯、烷基苯磺酸鹽、烷基萘磺酸 鹽、烷基笨并咪唑磺酸鹽'聚氧伸烷基磺基琥珀酸鹽、 Ν-醯基-Ν-甲基牛續酸的鹽、Ν_醯基麵胺酸或其鹽、醯 氧基乙磺酸鹽、烷氧基乙磺酸鹽、Ν•醯基_石_丙胺酸或 其鹽、Ν-醯基-Ν-羧乙基牛磺酸或其鹽、Ν_醯基_Ν羧曱 基甘胺酸或其鹽、醯基乳酸鹽、Ν_醯基肌胺酸鹽及烧基 或烯基胺基羧甲基硫酸鹽等。 非離子性界面活性轉例有聚氧狀基㈣、·聚氧 伸烧基稀、聚氧乙烯聚氧丙稀烧醚(環氧乙烧盘環氧 =烷的附加形態可為雜亂狀、塊狀任一者）、聚/乙二醇 環氧丙烧附加物、聚丙二醇環氧乙燒附加物、伸烧基二 胺的環氧乙院與環氧城之雜㈣域塊狀附加物 、甘油 脂肪酸醋或其環氧乙_加物、山梨醇脂肪❹旨、聚氧 乙稀山梨義肪_、妓科萄料、麟酸單乙醇 ^或其環氧乙細加物、脂肪料·甲基單乙醇胺或其 環氧乙㈣加物、脂㈣二乙醇胺或其環氧乙烧附加 物、嚴糖脂肪酸醋、烧基（聚)甘油鱗、聚甘油脂肪酸醋、 聚乙二醇脂肪酸g旨、脂肪酸甲醋乙氧基化物及N長鍵 環氧烷基二曱基胺等。 12 201120247 陽離子性界面活性劑舉例有烷基（烯基）三曱基銨 鹽、二烷基(烯基)二甲基銨鹽、烷基(烯基）四級銨鹽、 •含有醚基、酯基或胺基之單烷基或二烷基(烯基）四級銨 鹽、烷基(烯基)吼啶鹽、烷基(烯基)二甲基苄基銨鹽、 烷基(烯基)異喹啉鹽、二烷基(烯基)嗎啉鹽、聚氧乙烯 烷基(烯基)胺、烷基(烯基)胺鹽、聚胺脂肪酸衍生物、 戊醇脂肪酸衍生物、氯化笨二曱烴銨及氣化笨銨松寧 兩性界面活性劑舉例有羧基甜菜鹼、磺基甜菜鹼、 填酸基甜菜驗、醯胺胺基酸及咪唑甜菜驗系界面活性劑 等。 上述界面活性劑可單獨或混合2種以上來使用。 胺基酸類化合物舉例有甘胺酸、丙胺酸、纈氨酸、 白胺酸、絲胺酸、***酸、色胺酸、麩胺酸、天冬胺 酸、離胺酸、筋胺酸及組胺酸等之胺基酸及該等鹼金屬 鹽及銨鹽等。該等可單獨或混合2種以上來使用。 唑類化合物舉例有咪唑、2_曱基咪唑、2十一基_4_ 曱基咪嗤、2·苯基❹、2·ψ基苯并μ等之烧基味嗤 類’苯并料、2·曱基笨并咪4、2_十—基笨并味唾、 2-笨基苯并❹、2·硫醇笨并㈣等之笨并哺唾類； 1,2,3-***、1，2,4-***、5-笨基***、5_胺基―丨又屯 •二唑、1，2,3_苯并***、丨_胺基苯并***、4_胺基苯并三 唑、1-雙胺基甲基苯并***、卜曱基-苯并三〇坐、甲基苯 并二氮唑、1-羥苯并***、5_曱基_1H笨并***、5_氯 13 201120247 苯弁三°坐等之三0^類；1 Η-四α坐、5 -胺基-1 Η-四α坐、5甲 基·1Η-四唑、5-苯基-1Η-四唑、5-硫醇基-1Η-四唑、1-苯基-5-硫醇基-1Η-四唑、1-環己基-5-硫醇基-1Η-四唑、 5,y-雙-1Η-四唑等之四唑類；苯并噻唑、2-硫醇苯并噻 唑、2-苯基噻唑、2-胺基苯并噻唑、2-胺基-6-亞苯并噻 唑、2-胺基-6-甲氧基苯并噻唑、2-胺基-6-氣苯并噻唑等 之噻唑類。該等可單獨或混合2種以上來使用。 嘧啶類化合物舉例有二胺基嘧啶、三胺基嘧啶、四 胺基嘧啶及硫醇嘧啶等。該等可單獨或混合2種以上來 使用。 硫脲類化合物舉例有硫脲、伸乙基硫脲、硫二甘醇 及硫醇等。該等可單獨或混合2種以上來使用。 胺類化合物舉例有二戊基胺、二丁基胺、三乙基 胺、三戊基胺、單乙醇胺、二乙醇胺、三乙醇胺、單異 丙醇胺、二異丙醇胺、三異丙醇胺、乙醇異丙醇胺、二 乙醇異丙醇胺、乙醇二異丙醇胺、聚烯丙基胺、聚乙烯 砒啶及該等氣酸鹽等。該等可單獨或混合2種以上來使 用。 · 烷基吡咯酮類化合物舉例有N-甲基-2-吡咯酮、N-4基-2-。比咯酮、N-丙基-2-吡咯酮、N-丁基-2-π比咯酮、 Ν-戊基-2-吡咯酮、Ν-己基-2-吡咯酮、Ν-庚基-2-吡咯酮 及Ν-正辛基-2-吡咯酮等。該等可單獨或混合2種以上 來使用。 有機螯合劑化合物舉例有乙二胺四醋酸、二伸乙三 14 201120247 胺五醋酸、三伸乙四胺六醋酸、四伸乙五胺七醋酸、五 伸乙六胺八醋酸、三甘胺酸及該等之鹼金屬鹽及銨鹽 等。該等可單獨或混合2種以上來使用。 聚丙烯醯胺類化合物舉例有聚丙烯醯胺及t-丁基 丙烯醯胺磺酸等。該等可單獨或混合2種以上來使用。 過酸鹽舉例有過硫酸錢、過硫酸鈉、過疏酸鉀，過 .氯酸銨，過氯酸鈉，及過氯酸鉀等。該等可單獨或混合 2種以上來使用。 無機鹽舉例有氯化鈉、氣化钾、氯化敍、碳酸氫錢、 碳酸氫鈉、碳酸氫鉀、碳酸銨、碳酸鈉、碳酸鉀、硫酸 銨、硫酸鋼、硫酸钟、墙酸納、硝酸卸、琐酸敍、氣酸 銨、氣酸鈉及氯酸鉀等。該等可單獨或混合2種以上來 使用。 供給一價銅離子之化合物舉例有氯化銅（I)、漠化銅 (I)、硫酸銅⑴及氫氧化銅(I)。又，供給二價鐵離子之化 合物舉例有氯化鐵(II)、溴化鐵(II)、碘化鐵(II)、硫酸 ’鐵(II)、硝酸鐵(II)及醋酸鐵(II)等。該等可單獨或混合2 種以上來使用。 本發明之姓刻劑組成物可藉由將上述成分與水加 以混合來調製。混合方法並未特別限定，使用公知的混 合裝置來混合即可。 依上述方式所獲得之本發明的蝕刻劑組成物的比 重較佳為1.050〜1.200。當比重較1.050要小時，則會有 無法獲得充分的蝕刻速度之情況。另一方面，當比重較 15 201120247 L200要大時’則會有直線性會降低之情況。 本發明之餘刻劑組成物雖可在含銅材料形成微細 圖案’但從形狀不良抑制效果及蝕刻速度的觀點來看， 則#寺別適於厚度5〜4〇 # m、蝕刻間隙4〜60 // m之含銅 材料的目案化’亦最適用於厚度1G〜4G/zm、#刻間隙 10〜60μ m之含鋼材料的圖案化。 利用本發明之蝕刻劑組成物來進行含銅材料的蝕 刻可使用公知一般的方法來進行。被蝕刻材料之含銅材 料舉例有銀鋼合金'鋁銅合金等之銅合金及銅，又以銅 為特佳〔又，蝕刻方法亦未特別限定，可使用浸潰法或 噴塗法等’而關於蝕刻條件’只要配合所使用之蝕刻劑 組成物或蝕刻方法來適當地調整即可。再者，亦可使用 ^匕人式(batch type)、流動式(fl〇w type)、利用#刻劑的 氧化還原電位或比重、酸濃度而進行之自動控制式等公 知的各種方式。 利用喷塗法並使用本發明之蝕刻劑組成物時，較佳 地處理溫度為30〜5(Tc，處理壓力為〇 〇5〜〇 2MPa，處 理時間為20〜300秒。 又，利用本發明的蝕刻劑組成物所進行之蝕刻方法 中’為了回復因重複地進行财〗所導致溶液的劣化，亦 可添加補統。特別是上述自動控制式之㈣方法中， 補充液係被預先安裝在制裝置，#溶液劣化時則會被 添加至磁彳賴絲。該補歧為例如(A)齡、⑻成 分及水，（A)成分及(B)成分的濃度核刻劑組成·物的 16 201120247 1〜20倍左右。又，該補充液中，亦可依需要來添加本 發明蝕刻劑組成物的（C)成分或任意成分。 由於本發明之蝕刻劑組成物能夠無形狀不良地形成 微細圖案，故除了印刷電路板以外，亦可適用於要求微 細間距之封裝用基板、COF、TAB用途之減成法。 [實施例] X下雖係利用實施例及比較例來詳細說明本發 月但本發明並未限定於該等實施例及比較例。 、將下述實_錢㈣帽使用的非 離子性界面 活性劑顯示於表1及表2。Formula (1): R-0-X-H In the above formula G), R is an alkyl group having 8 to 18 carbon atoms, which may be a straight chain or have a branched chain. Further, hydrazine is an oxiranyl unit (-CH2_CH2-0-) and a propylene oxide group unit (_CRijj_CR2H 〇_ (one of Ri and R2 is a hydrogen atom, and the other is a methyl group)) random or polymerized A block of polyalkylene oxide 201120247. Here, in the polyalkylene oxide group, the amount of the propylene oxide group unit relative to the ethylene oxide group unit is preferably from 0.1 to 1. When the number is larger than 1, there is a case where sufficient linearity and etching coefficient cannot be obtained. On the other hand, if the amount is less than 0.1, there is a case where a sufficient etching coefficient cannot be obtained. The preferred range of the number ratio is 0.25 to 0.5. As long as it is within this range, the effect of suppressing the excessive width of the upper portion of the wire is remarkable, and etching with a small difference between the width of the upper portion of the wire and the width of the lower portion of the wire can be obtained. The nonionic surfactant of the component (C) can be usually produced by using a natural or synthetic alcohol, an ethylene oxide group or an propylene oxide group as a raw material. R in the above formula (1) is a functional group introduced from a natural or synthetic alcohol. Examples of the alcohol include octanol, 2-ethylhexanol, 2-octyl alcohol, isooctanol, third octanol, decyl alcohol, isodecyl alcohol, 2-grade sterol, decyl alcohol, 2-grade sterol, and eleven Alcohol, 2, undecyl alcohol, dodecyl alcohol, 2, dodecyl alcohol, tridecyl alcohol, isotridecyl alcohol, 2, 3,3,3,3,3,3 Hexacohol, stearyl alcohol and isostearyl alcohol. The above R may be used singly or in combination of two or more. The method for producing a nonionic surfactant of the component (C) is a well-known technique in the art, and can be produced according to a known method, or a commercially available nonionic surfactant can be used. The (A) component has an arithmetic mean molecular weight of 500 to 1,500. When the arithmetic mean molecular weight is less than 500, sufficient linearity and etching coefficient cannot be obtained. On the other hand, when the arithmetic mean molecular weight is more than 1,500, a sufficient button coefficient cannot be obtained. The preferred formula of the arithmetic mean molecular weight 201120247 : 〇Γ, _ ' As long as it is within this range, the effect of suppressing the upper σ of the wire is fine, and the difference between the width of the wire and the width of the lower part of the wire can be obtained. engraved. Further, when the content of the component (c) in the composition of the composition is large, the circuit shape tends to be improved due to improvement in the etching coefficient or improvement in linearity, but on the other hand, the etching speed is lowered to cause production. The tendency to reduce sexuality. Therefore, the content of the component in the etchant composition is 0 - 1 to 5 mass%, preferably 0.01 to 2 mass%, more preferably 0.054 mass%. When the content of the component (C) is more than 5% by mass, the improvement in the shape of the circuit cannot be greatly improved, and the disadvantage of the decrease in productivity is increased. On the other hand, when the content of the component (c) is less than 0.001% by mass, a sufficient use effect cannot be obtained. In the etchant composition of the present invention, in addition to the essential components (A) to (C) described above, any known components used for the purpose can be added without departing from the effects of the present invention. Examples of the optional component include a mineral acid other than the component (B), an organic acid, and a diol compound; (a surfactant other than the quinone component, an amino acid compound, an azole compound, a pyrimidine compound, or a thiourea compound) An amine compound, an alkylpyrrolidone compound, an organic chelating agent compound, a polypropylene guanamine compound, hydrogen peroxide, a persalt salt, an inorganic salt, a monovalent copper ion, and a divalent iron ion. In the case of the component, the concentration is generally in the range of 0.001% by mass to 10% by mass. The inorganic acid other than the component (B) is exemplified by sulfuric acid, nitric acid, phosphoric acid, or lanthanum lanthanum citrate. These may be used alone or in combination. The above examples are used. 201120247 Examples of organic acids are formic acid, acetic acid, propionic acid, butyric acid, valeric acid, sunflower acid, acrylic acid, crotonic acid, isocrotonic acid, acid, malonic acid, succinic acid, glutaric acid, and already Acid, pimelic acid, maleic acid, fumaric acid, oxalic acid, malic acid, tartaric acid 'citric acid, glycolic acid, lactic acid, sulfamic acid, nicotinic acid, ascorbic acid, hydroxypivalic acid, fructose And cold-chlorine An organic sulfonic acid such as carboxylic acid such as propionic acid, sulfonic acid, ethanesulfonic acid, 2-hydroxyethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid or benzenesulfonic acid. These may be used alone or in combination of two or more. Use. 'Glycol ether compounds are exemplified by ethylene glycol monodecyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monobutyl ether, triethylene glycol monodecyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol monodecyl ether, propylene glycol monoethyl ether, Propylene glycol monobutyl ether, dipropylene glycol monodecyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monodecyl ether, tripropylene glycol monoethyl ether and 3-methyl-3-oxime Low molecular weight glycol ether compounds such as benzyloxybutanol; polyethylene glycol monodecyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monobutyl ether, etc. These compounds may be used alone or in combination of two or more. The surfactant other than the component (C) is exemplified by an anionic surfactant and a nonionic boundary represented by the above formula (1). Nonionic surfactants, cationic surfactants, amphoteric surfactants, etc. other than the active agent. Examples of the anionic surfactants include higher fatty acid salts, higher alcohol sulfate salts, sulfurized olefin salts, and higher alkyl sulfonates. Α-olefin sulfonate 11 201120247 Peak salt, sulfated fatty acid salt, nucleating fatty acid salt, phosphate ester salt, fatty acid ester sulfate salt, glyceride sulfate salt, fatty acid ester sulfonate, sulfo fatty acid A Base ester salt, polyoxyalkylene alkyl ether ether sulfate salt, polyoxyalkylene alkyl phenyl ether sulfate salt, polyoxyalkylene alkyl ether carbonate, sulfonated peptide, fatty acid alkyl decylamine or a sulfate salt, a sulfosuccinate, an alkylbenzenesulfonate, an alkylnaphthalenesulfonate, an alkyl benzoxazole sulfonate, a polyoxyalkylene sulfosuccinate, a salt of Ν-mercapto-hydrazine-methyl oxen acid, Ν 醯 面 lysine or a salt thereof, decyloxyethane sulfonate, alkoxyethane sulfonate, hydrazine hydrazine _ stone propylamine Acid or its salt, Ν-mercapto-oxime-carboxyethyl taurine or its salt, Ν_醯-yl-carboxyl-glycolic acid or its salt Acyl lactate, Ν_ acyl alanine salts and burn muscle group or alkenyl group carboxymethyl sulfate. Examples of nonionic interfacial activity include polyoxylated groups (IV), polyoxyalkylene extended dilute bases, and polyoxyethylene polyoxypropylene dilute ethers (epoxy ether bromide epoxy = alkane in the form of clutter, block Any one of them), poly/ethylene glycol epoxidized admixture, polypropylene glycol epoxiconate addition, exfoliating diamine, epoxy epoxide and epoxy city (4) domain block addition, Glycerol fatty acid vinegar or its epoxy B-additive, sorbitol fat ❹, polyoxyethylene sorbent yummy _, 妓 萄 、 、, linic acid monoethanol ^ or its epoxy Ethyl adduct, fat material · A Monoethanolamine or its epoxy Ethylene (tetra), lipid (tetra) diethanolamine or its epoxy Ethylene addendum, Yan sugar fatty acid vinegar, alkyl (poly) glycerin scale, polyglycerin fatty acid vinegar, polyethylene glycol fatty acid g , fatty acid methyl acetate ethoxylate and N long bond epoxy alkyl decyl amine. 12 201120247 The cationic surfactant is exemplified by an alkyl (alkenyl) tridecyl ammonium salt, a dialkyl (alkenyl) dimethyl ammonium salt, an alkyl (alkenyl) quaternary ammonium salt, an ether group, Monoalkyl or dialkyl (alkenyl) quaternary ammonium salt of an ester group or an amine group, alkyl (alkenyl) acridine salt, alkyl (alkenyl) dimethyl benzyl ammonium salt, alkyl (alkenyl) Isoquinoline salt, dialkyl (alkenyl) morpholine salt, polyoxyethylene alkyl (alkenyl) amine, alkyl (alkenyl) amine salt, polyamine fatty acid derivative, pentanol fatty acid derivative, The chlorinated barium dihydrocarbylammonium chloride and the gasified stupid ammonium salt and amphoteric surfactant are exemplified by carboxybetaine, sulfobetaine, acid-filled beet test, guanamine amino acid and imidazole beet test surfactant. These surfactants can be used singly or in combination of two or more. Examples of the amino acid compound include glycine, alanine, valine, leucine, serine, phenylalanine, tryptophan, glutamic acid, aspartic acid, lysine, glutamic acid, and groups. An amino acid such as an amine acid or the like, and an alkali metal salt or an ammonium salt. These may be used alone or in combination of two or more. The azole compound is exemplified by imidazole, 2_mercaptoimidazole, 2-11-yl-4-methylidene, 2·phenylfluorene, 2·mercaptobenzopyrene, etc. · 曱 笨 并 并 咪 咪 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 1,2,4-triazole, 5-phenyltriazole, 5-amino-quinone-oxadiazole, 1,2,3-benzotriazole, hydrazine-aminobenzotriazole, 4_ Aminobenzotriazole, 1-diaminomethylbenzotriazole, dimercapto-benzotriazine, methylbenzodiazolyl, 1-hydroxybenzotriazole, 5_mercapto-1H And triazole, 5_chloro 13 201120247 benzoquinone three ° sitting three 0 ^ class; 1 Η-four α sitting, 5-amino-1 Η-four α sitting, 5 methyl · 1 Η - tetrazolium, 5- Phenyl-1 Η-tetrazole, 5-thiol-1 Η-tetrazole, 1-phenyl-5-thiol-1 Η-tetrazole, 1-cyclohexyl-5-thiol-1 Η-tetrazole , 4,y-bis-1Η-tetrazole, etc.; tetrazoles; benzothiazole, 2-thiol benzothiazole, 2-phenylthiazole, 2-aminobenzothiazole, 2-amino-6- Thiazoles such as benzothiazole, 2-amino-6-methoxybenzothiazole, 2-amino-6-gasbenzothiazole . These may be used alone or in combination of two or more. Examples of the pyrimidine compound include diaminopyrimidine, triaminopyrimidine, tetraaminopyrimidine, and thiol pyrimidine. These may be used alone or in combination of two or more. Examples of the thiourea compound include thiourea, ethyl thiourea, thiodiglycol, and mercaptan. These may be used alone or in combination of two or more. Examples of the amine compound are dipentylamine, dibutylamine, triethylamine, tripentylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanol. Amine, ethanol isopropanolamine, diethanol isopropanolamine, ethanol diisopropanolamine, polyallylamine, polyvinyl acridine, and the like. These may be used alone or in combination of two or more. · Alkylpyrrolidone compounds are exemplified by N-methyl-2-pyrrolidone and N-4yl-2-. Berolone, N-propyl-2-pyrrolidone, N-butyl-2-π pyrrolidone, Ν-pentyl-2-pyrrolidone, Ν-hexyl-2-pyrrolidone, Ν-heptyl- 2-pyrrolidone and fluorene-n-octyl-2-pyrrolidone. These may be used alone or in combination of two or more. The organic chelating agent compound is exemplified by ethylenediaminetetraacetic acid, diamethylene ethene 14, 201120247, amine pentaacetic acid, triamethylenetetraamine hexaacetic acid, tetraamethylene acetaminoacetic acid, pentaethylene hexamine acetic acid, triglycine. And such alkali metal salts and ammonium salts. These may be used alone or in combination of two or more. Examples of the polypropylene amide compound include polypropylene decylamine and t-butyl acrylamide sulfonate. These may be used alone or in combination of two or more. Examples of the peracid salt include persulfate, sodium persulfate, potassium perchlorate, ammonium perchlorate, sodium perchlorate, and potassium perchlorate. These may be used alone or in combination of two or more. Examples of the inorganic salt are sodium chloride, potassium carbonate, chlorinated water, hydrogen carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium carbonate, sodium carbonate, potassium carbonate, ammonium sulfate, sulfuric acid steel, sulfuric acid clock, wall acid sodium, Nitric acid unloading, tribasic acid, ammonium oxyacid, sodium carbonate and potassium chlorate. These may be used alone or in combination of two or more. Examples of the compound which supplies monovalent copper ions include copper (I) chloride, copper (I), copper (1) sulfate, and copper (I) hydroxide. Further, examples of the compound which supplies divalent iron ions include iron (II) chloride, iron (II) bromide, iron (II) iodide, iron (II) sulfate, iron (II) nitrate, and iron (II) acetate. Wait. These may be used alone or in combination of two or more. The surname composition of the present invention can be prepared by mixing the above components with water. The mixing method is not particularly limited, and it may be mixed using a known mixing device. The specific gravity of the etchant composition of the present invention obtained in the above manner is preferably from 1.050 to 1.200. When the specific gravity is smaller than 1.050, there is a case where a sufficient etching speed cannot be obtained. On the other hand, when the specific gravity is larger than 15 201120247 L200, there will be a case where the linearity will decrease. The remnant composition of the present invention can form a fine pattern in the copper-containing material, but from the viewpoint of the shape defect suppressing effect and the etching rate, the #寺 is suitable for a thickness of 5 to 4 〇 #m, and an etching gap 4~ The 60*m copper-containing material catalogue is also most suitable for the patterning of steel-containing materials with a thickness of 1G to 4G/zm and a thickness of 10 to 60 μm. The etching of the copper-containing material using the etchant composition of the present invention can be carried out by a known general method. The copper-containing material of the material to be etched is exemplified by a copper alloy such as a silver-steel alloy 'aluminum-copper alloy and copper, and copper is particularly preferable. Further, the etching method is not particularly limited, and a dipping method or a spray method may be used. The etching conditions may be appropriately adjusted in accordance with the etchant composition or etching method to be used. Further, various known methods such as a batch type, a flow type, and an automatic control type using an oxidation-reduction potential or a specific gravity of an agent and an acid concentration can be used. When the etchant composition of the present invention is used by the spray coating method, the treatment temperature is preferably 30 to 5 (Tc, the treatment pressure is 〇〇5 to 〇2 MPa, and the treatment time is 20 to 300 seconds. Further, the present invention is utilized. In the etching method performed by the etchant composition, in order to recover the deterioration of the solution caused by repeated refinement, a supplement may be added. In particular, in the above-mentioned automatic control method (4), the replenishing liquid system is pre-installed in When the solution is degraded, the solution is added to the magnetic ray. The difference is, for example, (A) age, (8) component and water, and the concentration of the component (A) and the component (B). 16 201120247 1 to 20 times. Further, in the replenishing liquid, the component (C) or the optional component of the etchant composition of the present invention may be added as needed. Since the etchant composition of the present invention can be formed without shape In addition to the printed circuit board, it can be applied to a substrate for packaging that requires fine pitch, and a subtractive method for COF and TAB applications. [Examples] Although X is described in detail by using examples and comparative examples, the present invention will be described in detail. Month but the invention is not Examples and Comparative Examples given in these embodiments., _ The following solid nonionic surfactant (iv) the cap money used is shown in Table 1 and Table 2.
(¾ s£) PO表示環氧丙炫基單元，RQ矣一 量，η表示環氧乙烷基的妖:環氣乙烷基單元’ m表示環氧丙烧基單元的數 17 201120247 表2] 非離子性界面活性劑 構造 算數平均分子量 C-9 C 丨 3h27o(c2h4o)4h 330 C-10 c13h27o (C2H40)8H 550 C-11 c13h270 (C2H40),〇H 640 C-12 HO(C3H6O)30(C2H4O)25H 2,900 C-13 HO(C3H60)56(C2H4〇)i2H 3,800 C-14 ho(c3h6o)56(c2h4o)28〇h 15,500 (實施例1及比較例1) 將表1及表2所示之非離子性界面活性劑、氯化三 價鐵(三價鐵離子）、氯化氫、銅（二價銅離子)及水以表3 的組成來混合而獲得蝕刻劑組成物。又，表3之含量的 殘餘部分為水。 [表3] 名虫刻劑 組成物 No. 含量(質量％) 三價鐵離子 二價銅離子 氣化氫 非離子性界面活性劑 1 實施例1-1 1 2.6 2.9 2.6 C-l(0.6) !實施例1-2 2 2.6 2.9 2.6 C-2(0.6) 實施例1-3 3 2.6 2.9 2.6 C-3(0.6) !實施例1_4 4 2.6 2.9 2.6 C-4(0.6) !實施例1-5 5 2.6 2.9 2.6 C-5(0.3) 丨實施例1-6 6 2.6 2.9 2.6 C-5(0.6) i實施例1-7 7 2.6 2.9 2.6 C-6(0.6) ,實施例1-8 8 2.6 2.9 2.6 C-7(0.6) |實施例1-9 9 2.6 2.9 2.6 C-3(0.6) C-7(0.3) 1實施例1-10 10 2.6 2.9 2.6 C-5(0.6) C-7(0.6) 比較例Μ 11 2.6 2.9 2.6 - 201120247 比較例1-2 12 2.6 2.9 2.6 C-12(0.6) 比較例1-3 13 2.6 2.9 2.6 C-13(0.6) 比較例1~4 14 2.6 2.9 2.6 0-14(0.6) (實施例2及比較例2) 於具有厚度20# m銅箔之樹脂基體上形成有線，寬 100 # m、特定的線間隙（餘刻間隙）的圖案的乾膜光阻 (dry film resist)之試驗基板中，利用上述實施例及比較 例所獲得之钱刻劑組成物，並於特定的條件下進行喷霧 餘刻。之後，次潰在5質罝％的氫氧化鈉水溶液(5〇。匸） 内1分鐘來去除乾膜光阻。針對所獲得之銅電路的形狀 進行以下評估。 (1)導線上部寬度(頂部寬度） =用光學賴鏡之剖峨察(_3 seetkm)來測定。 單位為/z m。 π、％「邱見没（坻邵寬度） 利用光學顯微鏡之剖面觀Ϊ(刪s section)來測定。 早位為μ m。 (3) 底部寬度與頂部寬度的差 利用下式來求得。單位為 邻寬度與頂部寬度的差=底部寬度的測定值-頂 4見度的測定值 (4) 殘膜(3⁄4 s£) PO represents an epoxy thiophene unit, RQ is a quantity, η represents an oxirane group: the cyclohexane group unit 'm represents the number of propylene-based units. 2011 20247 Table 2 Non-ionic surfactant construction arithmetic average molecular weight C-9 C 丨3h27o(c2h4o)4h 330 C-10 c13h27o (C2H40)8H 550 C-11 c13h270 (C2H40), 〇H 640 C-12 HO(C3H6O)30 (C2H4O)25H 2,900 C-13 HO(C3H60)56(C2H4〇)i2H 3,800 C-14 ho(c3h6o)56(c2h4o)28〇h 15,500 (Example 1 and Comparative Example 1) Tables 1 and 2 The nonionic surfactant, ferrous chloride (ferric ion), hydrogen chloride, copper (divalent copper ion), and water were mixed in the composition of Table 3 to obtain an etchant composition. Further, the residual portion of the content of Table 3 was water. [Table 3] Nominal composition No. Content (% by mass) Ferric ion divalent copper ion vaporized hydrogen nonionic surfactant 1 Example 1-1 1 2.6 2.9 2.6 Cl (0.6) ! Example 1-2 2 2.6 2.9 2.6 C-2 (0.6) Example 1-3 3 2.6 2.9 2.6 C-3 (0.6) ! Example 1_4 4 2.6 2.9 2.6 C-4 (0.6) ! Example 1-5 5 2.6 2.9 2.6 C-5(0.3) 丨Example 1-6 6 2.6 2.9 2.6 C-5(0.6) i Example 1-7 7 2.6 2.9 2.6 C-6(0.6) , Example 1-8 8 2.6 2.9 2.6 C-7(0.6) |Example 1-9 9 2.6 2.9 2.6 C-3(0.6) C-7(0.3) 1Example 1-10 10 2.6 2.9 2.6 C-5(0.6) C-7(0.6 Comparative Example 11 2.6 2.9 2.6 - 201120247 Comparative Example 1-2 12 2.6 2.9 2.6 C-12 (0.6) Comparative Example 1-3 13 2.6 2.9 2.6 C-13 (0.6) Comparative Example 1~4 14 2.6 2.9 2.6 0 -14 (0.6) (Example 2 and Comparative Example 2) Dry film photoresist having a pattern of a line width of 100 # m and a specific line gap (remaining gap) was formed on a resin substrate having a thickness of 20 #m copper foil. In the test substrate of (dry film resist), the money engraving composition obtained in the above examples and comparative examples was used, and spray residue was carried out under specific conditions. Thereafter, the dry film resist was removed by sublimating in a 5 mass% aqueous sodium hydroxide solution (5 Torr. Torr) for 1 minute. The following evaluation was made for the shape of the obtained copper circuit. (1) Width of the upper part of the wire (top width) = measured by the optical ray mirror (_3 seetkm). The unit is /z m. π, % "Qiu Jianwei (坻 Width) is measured by the section of the optical microscope (deletion of s section). The early position is μ m. (3) The difference between the bottom width and the top width is obtained by the following formula. The unit is the difference between the adjacent width and the top width = the measured value of the bottom width - the measured value of the top 4 (4) residual film
= Γ^ΕΥΕΝ(：Ε公司製的雷射顯微鏡所進行之觀 則部分有殘餘者為「有」，未觀察到蚀 19 201120247 刻部分有殘餘者為「無」。 將上述評估的結果顯示於表4〜5。 [表4] 姓刻 劑組 成物 No. 蝕刻間隙 〇um) 評估項目 (1) (2) (3) 實施例2-1 1 20 72.56 84.10 11.54 無 實施例2-2 1 28 68.22 75.24 7.02 無 實施例2-3 2 20 66.44 76.32 9.88 無 實施例2-4 2 28 59.18 70.21 11.03 無 實施例2-5 3 20 77.86 87.46 9.6 無 實施例2-6 3 28 64.16 77.01 12.85 無 實施例2-7 4 20 80.49 80.84 0.35 無 實施例2-8 4 28 77.58 78.04 0.46 無 實施例2-9 5 20 79.92 83.29 3.37 無 實施例2-10 5 28 75.06 74.72 -0.34 無 實施例2-11 6 20 81.75 88.44 6.69 無 實施例2-12 6 28 76.55 78.50 1.95 無 實施例2-13 7 20 62.04 71.87 9.83 . 無 實施例2-14 7 28 53.30 64.96 11.66 無 實施例2-15 8 20 62.61 72.32 9.71 無 實施例2-16 8 28 54.84 64.95 10.11 無 實施例2-17 9 20 71.35 81.30 9.95 無 實施例2-18 9 28 61.53 70.27 8.74 無 實施例2-19 10 20 71.53 79.98 8.45 無 實施例2-20 10 28 60.84 71.81 10.97 無 (備註） 喷霧蝕刻係在處理時間240秒，處理壓力O.IMPa，處理溫度45°C下進行。 20 201120247 [表5] 触刻 劑組 成物 No. 處理壓 力 (MPa) 處理時 間 (秒） 蝕刻間隙 (um) 評估項目 (1) (3) (4) 比較例 2-1 11 0.1 120 20 71.87 87.98 16.11 無 比較例 2-2 11 0.1 120 28 66.96 79.53 12.57 無 比較例 2-3 11 0. 1 240 20 36.22 50.44 14.22 無 比較例 2-4 11 0.1 240 28 29.48 43.87 14.39 無 比較例 2-5 11 0.2 120 28 54.27 68.67 14.40 無 比較例 2-6 11 0.2 150 28 42.56 57.99 15.43 無 比較例 2-7 12 0.1 240 28 61.98 82.26 20.28 無 比較例 2-8 13 0.1 300 28 29.82 60.96 31.14 有、 比較例 2-9 14 0.1 160 28 52.67 70.21 17.54 無 (備註） 噴霧蝕刻的處理溫度為45°C。 如表4及5之結果所示，於利用含有特定的非離子 性界面活性劑之钮刻劑組成物No.1〜10來進行蚀刻之 •實施例2-1〜2〜20中，相較於利用不含特定的非離子性 界面活性劑之钱刻劑組成物No. 11〜14來進行截刻之比 較例2-1〜2-9，對維持頂部寬度較佳，且頂部寬度與底 部寬度的差較小。特別是，利用钱刻劑組成物No.4〜6 來進行蝕刻之實施例2-7〜2-12中，其效果最為顯著。 (實施例3及比較例3) 21 201120247 將表1及表2所示之非離子性界面活性劑、氯化三 價鐵、氯化氫、銅及水以表6的組成來混合而獲得蝕刻 劑組成物。又，表6之含量的殘餘部分為水。 [表6] 蚀刻劑組 含量(質量％) 成物No. 三價鐵離子 二價銅離子 氣化氫 非離子性界面活性劑 賁施例3_1 15 3.4 4.0 3.5 C-8(1.0) 貪施例3-2 16 2.6 2.9 2.6 C-8(0.7) 貪施例3-3 17 3.4 3.9 3.4 C-8(0.4) 實施例3-4 18 3.0 3.5 0.9 C-7(0.3) C-8(0.4) fcb較例3**1 19 3.4 4.0 3.5 C-9(1.0) tb較例3-2 20 3.4 4.0 3.5 C-lO(l.O) 比較例3_3 21 3.4 4.0 3.5 C-l 1(1.0) (實施例4及比較例4) 除了利用上述實施例3及比較例3所獲得的蝕刻劑 組成物來進行喷霧蝕刻以外，並針對相同於實施例2及 比較例2的方法而獲得之銅電路的形狀進行上述（1)〜(4) 的評估。將其結果顯示於表7。 22 201120247 [表7] 触刻 劑組 成物 No. 處理壓 力 (MPa) 處理時 間 (秒） 蝕刻間隙 評估項目 ⑴ (2) (3) (4) 實施例 4-1 16 0.1 270 20 83.23 84.49 1.26 無 實施例 4-2 16 0.1 270 28 81.12 83.58 2.46 無 實施例 4-3 16 0.2 120 28 79.98 77.87 -2.11 無 實施例 4-4 16 0.2 150 28 69.47 67.30 -2.17 無 實施例 4-5 15 0.1 240 38 86.20 85.35 -0.85 無 實施例 4-6 17 0.1 200 20 88.44 91.35 2.91 無 實施例 4-7 Π 0.1 200 28 87.01 85.46 -1.55 無 實施例 4-8 17 0.1 200 38 85.47 82.66 -2.81 無 實施例 4-9 18 0.1 120 28 82.78 84.32 1.54 無 比較例 4-1 19 0.1 240 38 82.50 118.50 36.00 有 比較例 4-2 20 0.1 240 38 80.90 93.06 12.16 無 比較例 4-3 21 0.1 240 38 75.84 92.54 16.70 無 (備註） 喷霧蝕刻的處理溫度為45°C。 如表7之結果所示，利用含有特定的非離子性界面 活性劑之银刻劑組成物No. 15〜18來進行触刻之實施例 4-1〜4〜9中，相較於利用不含特定的非離子性界面活性 劑之蚀刻劑組成物No. 19〜21來進行银刻之比較例 23 201120247 4-1〜4-3，對維持頂部寬度較佳，且頂部寬度與底部寬 度的差較小。 由以上結果可知，依據本發明則可提供一種能夠無 形狀不良地形成微細電路圖案之含銅材料用蝕刻劑組 成物及含銅材料之蝕刻方法。 【圖式簡單說明】 無 【主要元件符號說明】 無 24= Γ^ΕΥΕΝ (: The remaining part of the laser microscope made by the company is "Yes", and no etch is observed. 19 201120247 Some of the remaining parts are "None". The results of the above evaluation are shown in Tables 4 to 5. [Table 4] Surname composition No. Etching gap 〇um) Evaluation item (1) (2) (3) Example 2-1 1 20 72.56 84.10 11.54 No example 2-2 1 28 68.22 75.24 7.02 None Example 2-3 2 20 66.44 76.32 9.88 No example 2-4 2 28 59.18 70.21 11.03 No example 2-5 3 20 77.86 87.46 9.6 No example 2-6 3 28 64.16 77.01 12.85 No example 2-7 4 20 80.49 80.84 0.35 None Example 2-8 4 28 77.58 78.04 0.46 None Example 2-9 5 20 79.92 83.29 3.37 None Example 2-10 5 28 75.06 74.72 -0.34 No Example 2-11 6 20 81.75 88.44 6.69 None Example 2-12 6 28 76.55 78.50 1.95 None Example 2-13 7 20 62.04 71.87 9.83 . No Example 2-14 7 28 53.30 64.96 11.66 None Example 2-15 8 20 62.61 72.32 9.71 No implementation Example 2-16 8 28 54.84 64.95 10.11 None Example 2-17 9 20 71.35 81.30 9.95 No Example 2-18 9 28 61.53 70.27 8.74 None Example 2-19 10 20 71.53 79.98 8.45 None Example 2-20 10 28 60.84 71.81 10.97 None (Remarks) Spray etching is carried out for 240 seconds, treatment pressure O.IMPa, treatment temperature 45° Under C. 20 201120247 [Table 5] Tactile composition No. Treatment pressure (MPa) Treatment time (seconds) Etching gap (um) Evaluation item (1) (3) (4) Comparative example 2-1 11 0.1 120 20 71.87 87.98 16.11 No comparative example 2-2 11 0.1 120 28 66.96 79.53 12.57 No comparative example 2-3 11 0. 1 240 20 36.22 50.44 14.22 No comparative example 2-4 11 0.1 240 28 29.48 43.87 14.39 No comparative example 2-5 11 0.2 120 28 54.27 68.67 14.40 No comparative example 2-6 11 0.2 150 28 42.56 57.99 15.43 No comparative example 2-7 12 0.1 240 28 61.98 82.26 20.28 No comparative example 2-8 13 0.1 300 28 29.82 60.96 31.14 Yes, Comparative Example 2 9 14 0.1 160 28 52.67 70.21 17.54 None (Remarks) The spray etch treatment temperature is 45 °C. As shown in the results of Tables 4 and 5, in the examples 2-1 to 2 to 20, the etching was carried out using the button engraving compositions No. 1 to 10 containing a specific nonionic surfactant. Comparative Examples 2-1 to 2-9 were carried out by using the money engraving composition No. 11 to 14 containing no specific nonionic surfactant, and the top width and the bottom were better for maintaining the top width. The difference in width is small. In particular, in Examples 2-7 to 2-12 which were etched using the money engraving composition Nos. 4 to 6, the effect was most remarkable. (Example 3 and Comparative Example 3) 21 201120247 The nonionic surfactants, ferric chloride, hydrogen chloride, copper, and water shown in Tables 1 and 2 were mixed in the composition of Table 6 to obtain an etchant composition. Things. Further, the residual portion of the content of Table 6 was water. [Table 6] Etchant group content (% by mass) Product No. Ferric ion divalent copper ion gasification hydrogen nonionic surfactant 贲 Example 3_1 15 3.4 4.0 3.5 C-8 (1.0) Greedy example 3-2 16 2.6 2.9 2.6 C-8(0.7) Greedy Example 3-3 17 3.4 3.9 3.4 C-8(0.4) Example 3-4 18 3.0 3.5 0.9 C-7(0.3) C-8(0.4) Fcb Comparative Example 3**1 19 3.4 4.0 3.5 C-9(1.0) tb Comparative Example 3-2 20 3.4 4.0 3.5 C-lO(lO) Comparative Example 3_3 21 3.4 4.0 3.5 Cl 1(1.0) (Example 4 and Comparative Example 4) Except that the etchant composition obtained in the above Example 3 and Comparative Example 3 was used for the spray etching, the shape of the copper circuit obtained in the same manner as in the methods of Example 2 and Comparative Example 2 was carried out. (1) ~(4) assessment. The results are shown in Table 7. 22 201120247 [Table 7] Tactile composition No. Processing pressure (MPa) Processing time (seconds) Etching gap evaluation item (1) (2) (3) (4) Example 4-1 16 0.1 270 20 83.23 84.49 1.26 None Example 4-2 16 0.1 270 28 81.12 83.58 2.46 No Example 4-3 16 0.2 120 28 79.98 77.87 -2.11 No Example 4-4 16 0.2 150 28 69.47 67.30 -2.17 No Example 4-5 15 0.1 240 38 86.20 85.35 -0.85 No example 4-6 17 0.1 200 20 88.44 91.35 2.91 No example 4-7 Π 0.1 200 28 87.01 85.46 -1.55 No example 4-8 17 0.1 200 38 85.47 82.66 -2.81 No example 4 9 18 0.1 120 28 82.78 84.32 1.54 No comparative example 4-1 19 0.1 240 38 82.50 118.50 36.00 There are comparative examples 4-2 20 0.1 240 38 80.90 93.06 12.16 No comparative example 4-3 21 0.1 240 38 75.84 92.54 16.70 None (Remarks) The spray etch treatment temperature was 45 °C. As shown in the results of Table 7, in Examples 4-1 to 4 to 9 in which the silver engraving agent compositions No. 15 to 18 containing a specific nonionic surfactant were used, compared with the use of Comparative Example 23 201120247 4-1~4-3 with etchant composition No. 19 to 21 containing a specific nonionic surfactant, preferably maintaining the top width, and the top width and the bottom width The difference is small. As apparent from the above results, according to the present invention, it is possible to provide an etching method for a copper-containing material etchant composition and a copper-containing material which can form a fine circuit pattern without a shape defect. [Simple description of the diagram] None [Key component symbol description] None 24