TWI315030B - Photoresist stripper composition, and exfoliation method of a photoresist using it - Google Patents

Photoresist stripper composition, and exfoliation method of a photoresist using it Download PDF

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Publication number
TWI315030B
TWI315030B TW093118730A TW93118730A TWI315030B TW I315030 B TWI315030 B TW I315030B TW 093118730 A TW093118730 A TW 093118730A TW 93118730 A TW93118730 A TW 93118730A TW I315030 B TWI315030 B TW I315030B
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Taiwan
Prior art keywords
compound
composition
photosensitive
photosensitive adhesive
amine
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Application number
TW093118730A
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Chinese (zh)
Inventor
Hyuk-Jin Lee
Byoung-Mook Kim
Sun-Young Song
Hun-Pyo Hong
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Dongwoo Fine Chem Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
    • G03F7/343—Lamination or delamination methods or apparatus for photolitographic photosensitive material
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Description

1315030 九、發明說明： 【發明所屬之技術領域】 明侧於使用了感光糊離雜成物以及使用該組成物 之感光膠_離方法。說得更詳細-點，係有_在半導體元件 j液晶顯不it件等之製程中，於濕式腐似乾式腐#過程後， 將其所前的感光膠膜予以剝離時，所使用之娜液組成物以及 使用該組成物之感光膠的剝離方法。 【先前技術】 、半導體元件或液晶顯示元件之製造通常都是以如下製程順序 進^之。在料體基板或絲基板上設置金屬或金屬氧化物層之 金屬配線軸製程、設置感絲層之製程、在感光膠上轉錄光罩 模式之曝光製程、健模式細雜之雜製程、以及去除感光 膠之剝離製程。 附件的圖面乃順序說明如上述之曝光製程、腐蝕製程以及剝 離製程所進行之金屬模式形成製程的圖面。 第一圖表示在半導體基板或玻璃基板1〇、金屬或氧化膜層 2 0所順序層積之基板表面上設置感光膠層3 〇者。 “第二圖表示透過由既定模式而形成的光罩，在應形成前述感 光，，表面的模式部位上照射紫外線、電子束，或如χ射線般具 有兩能量之活性射線’形成了前述模式的潛影之後，以顯像液顯 像’形成感光膠模式者。 第三圖之中，將模式之形成部位以濕式腐蝕以及乾式腐蝕來 形成模式之後，如第四圖所示，以剝離液組成物去除模式形成後 所殘留之感光膠。 最近，半導體元件以及液晶顯示元件的高度積層化造成了一 種模式超微細化的傾向，因此金屬或氧化膜之腐蝕條件變得嚴 格’腐蚀製程所造成之變質與感光膠硬化的產生頻率變高。具體 的腐餘製程可分類為，使用了電子化學反應之濕式腐蝕、以及使 用了被等離子化之腐蝕氣體的自由基反應的乾式腐蝕。在這種腐 1315030 蝕製程之後發生的變質或硬化的感光膠，即使使用以往之一般感 光膠剝離液也很難去除。這種變質或硬化之感光膠若不完全去 除，會因為感光膠殘留物而在後續製程中成為斷線以及短路的原 因，會造成半導體元件或液晶顯示元件等在生產上之良率降低的 原因。 把被模式化之感光膠層予以剝離之溶液，亦即剝離劑方面， 一般可以舉出無機酸、無機鹼、或有機溶媒，例如，卣化有機溶 媒、烷基苯績酸、芳香族碳氫化合物溶媒與烷基苯續酸之混合物 等。然而，剝離劑之有效成分上若使用無機酸或無機鹼時，因為 會腐蝕下方金屬膜，或伴隨著對人體有害之缺點等作業上的困難 性，所以一般是使用有機溶媒，而最近，多使用包含了極性溶媒 以及胺的胺系列剝離劑。、 胺系列剝離劑中’大家知道胺成分是以烘烤（b a k i η g )、等離子腐蝕、離子注入（implantati〇n)，或 其他之^SI裝置的製程來有效除去交聯結合之感光膜時所必 須。但是，胺系列感光膠剝離劑時常引起如腐蝕般之嚴重問題， 特別是使用鋁基板時更是如此。 這種腐蝕，一般認為是在剝離階段後，殘留剝離液組成物殘 存於基板表面或基板的載體上，在使用水後一剝離清洗階段中， =留胺而被離子化的水使得雜進行。換言之，_組成物之 ’其本身雖然不會腐錄板，但可能扮演著激發的功能， μΙΛ起腐舰象。像這樣的腐侧題之外，還有因獅劑與水 異物溶解度的差異，而在剝離過程之後，立即以水清洗時， >谷解於殘_?液組成物中之物f被析出的情況。 hi 了解決這糊題’於剝離階段與使用水之後—娜清洗階 又B引進了使用了有機溶媒之中間清洗階段。 ^ ’眾所週知異丙醇或二曱亞财在這種目的上是有用 潘細士 i，在其他物質方面’還提出了添加防腐钱劑之胺系剝離 ’ ’匕可以緩和剝離後階段中殘存胺所引起的腐蝕問題。 1315030 ^出以上解決方案的文獻範例如下。 ，國專利公報第4, 6 i 7, 2 5 !號，公 口物〔例如，2 - (2-氨乙氧基）乙醇、2—/9包—35疋气化 乙醇’或其混合物〕以膽雜性雜（細^ /—ϋ氨）1315030 IX. Description of the invention: [Technical field to which the invention pertains] The bright side uses a photosensitive paste-offomer and a photosensitive gel-off method using the composition. To put it more in detail, it is used in the process of semiconductor element j liquid crystal display, etc., after the process of wet rot-like dry rot #, the front photosensitive film is peeled off, A liquid composition and a method of peeling off the photosensitive paste using the composition. [Prior Art] The manufacture of semiconductor elements or liquid crystal display elements is generally carried out in the following process sequence. A metal wiring shaft process for providing a metal or metal oxide layer on a material substrate or a silk substrate, a process for setting a photosensitive layer, an exposure process for a transcription mask mode on a photosensitive adhesive, a complicated pattern of a fine pattern, and removal The peeling process of the photoresist. The drawing of the attachment is a sequence diagram illustrating the metal pattern forming process performed by the exposure process, the etching process, and the stripping process described above. The first figure shows that a photosensitive adhesive layer 3 is provided on the surface of the substrate on which the semiconductor substrate or the glass substrate 1 〇, the metal or the oxide film layer 20 are sequentially laminated. "The second figure shows that through the reticle formed by the predetermined mode, the above-mentioned sensitization should be formed, and the mode portion of the surface is irradiated with ultraviolet rays, electron beams, or active rays having two energies like x-rays to form the aforementioned mode. After the latent image, the developing liquid image is formed by the developing liquid. In the third figure, after the pattern forming portion is formed by wet etching and dry etching, as shown in the fourth figure, the stripping liquid is used. The photoresist which remains after the formation of the composition removal mode. Recently, the high layering of the semiconductor element and the liquid crystal display element has caused a tendency for the pattern to be ultra-fine, so that the corrosion condition of the metal or the oxide film becomes strict, which is caused by the etching process. The deterioration and the frequency of curing of the photosensitive adhesive become higher. The specific corrosion process can be classified into wet etching using an electronic chemical reaction and dry etching using a radical reaction of a plasma-etched etching gas. Deterioration or hardening of the photoresist after the 1315030 etching process, even if the conventional photoresist stripping solution is used It is difficult to remove. If this kind of deteriorated or hardened photoresist is not completely removed, it will cause wire breakage and short circuit in the subsequent process due to the residue of the photoresist, which will result in good production of semiconductor components or liquid crystal display components. The reason for the decrease in the rate. The solution for stripping the patterned photosensitive layer, that is, the release agent, generally includes an inorganic acid, an inorganic base, or an organic solvent, for example, a deuterated organic solvent or an alkylbenzene acid. , a mixture of an aromatic hydrocarbon solvent and an alkyl benzoic acid, etc. However, when an inorganic acid or an inorganic base is used as an active ingredient of the release agent, it may corrode the underlying metal film or may be harmful to the human body. Although it is difficult to work, it is generally used as an organic solvent. Recently, an amine series stripper containing a polar solvent and an amine has been used. In the amine series stripper, it is known that the amine component is baked (baki η g ). Plasma etching, ion implantation, or other processes of the SI device are necessary to effectively remove the crosslinked photosensitive film. However, the amine series of photoresist strippers often cause serious problems such as corrosion, especially when using an aluminum substrate. This corrosion is generally considered to be after the stripping stage, the residual stripping solution remains on the substrate surface or substrate. On the carrier, in the stripping and cleaning stage after using water, the water which is ionized by leaving the amine makes the impurities. In other words, the composition of the _ itself does not rot the board, but may play an exciting function. ΙΛ ΙΛ 腐 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 In the case where the substance f is precipitated. hi solved this paste problem after the stripping stage and the use of water - Na cleaning step B introduced an intermediate cleaning stage using an organic solvent. ^ 'Isopropyl alcohol or diterpene is well known. Yacai is useful for this purpose. In other substances, 'there is also an amine-based stripping method that adds anti-corrosion agent'. It can alleviate the corrosion caused by residual amine in the post-stripping stage. question. 1315030 ^ The literature examples of the above solutions are as follows. , National Patent Bulletin No. 4, 6 i 7, 2 5 !, a public mouth (for example, 2-(2-aminoethoxy)ethanol, 2 -/9 bags - 35 疋 gasified ethanol' or a mixture thereof] With biliary impurities (fine ^ / - ϋ ammonia)

鋼、四氫糖醇、異佛義、二甲亞讽、己二酸I 戊二酸二甲基、環丁碼、r-丁内醋、N，N—二H =¾合物）之正型感光膠剝離液組成物，此外美國專利^第 H7 °，7 1 3號，公佈了包含特定氨基化合物（例如，N #暖二1基乙醜胺）以及特定胺化合物（例如乙醇胺）之正型感 先膠剝離液組成物，此外，美國專利公報第4, 8 2 4 7 fi 2躲 ^佈了包含三胺（例如，二乙三胺）以及非極性溶媒[例如，N —甲基一2—吡咯烷酮、二曱基曱酰胺、丁内酯等）之正型感光 膠剝離液組成物，此外，美國專利公報第5, 2 7 9 , 7 g i號公 佈了包含氫氧胺（例如，氮氧基胺）、烧醇胺、以及任意的極性溶 媒之剝離液組成物。 ,美國專利公報第4, 7 8 6, 5 7 8號提案了用於感光膠剝離 後之清洗溶液，而前述清洗溶液包含了非離子界面活性劑（例如， 乙氧基化烧基酴酸）以及有機驗（例如，單，雙，或三_乙醇胺）。 美國專利公報第4, 8 2 4，7 6 2號公佈了包含乙二醇趟 (例如’二乙二醇單甲基醚、二丙二醇單曱基醚、三丙二醇單甲 基醚）以及脂肪族胺（例如，乙醇胺或三異丙醇胺）之感光膠剝 離後一清洗溶液，而前述之後一清洗溶液為非水性。 美國專利公報第4, 9 0 4, 5 7 1號公佈了包含溶媒（例 如，水、乙醇、醚、酮等），溶解於前述溶媒之鹼性化合物（例如， 1級胺、2級胺、3級胺、4級胺、環胺、多胺、4級銨胺、鎏 氫氧基、以及鹼氫氧基等），以及溶解於前述溶媒之氫化硼化合物 (例如，氫化硼鈉、二甲基胺硼、吡啶硼等）之印刷電路板的感 光膠剝離劑。 曰本特開平7 — 0 2 8 2 5 4號公佈了糖乙醇、乙醇胺、水 1315030 以及任意之4級錢水氧化物所構成之非腐蝕性感光膠剝離液組成 物。 國際公開專利WO第8 8 — 0 5 8 1 3號提案了，包含丁内 醋或己内酯、4級銨氫氧基化合物以及任意的非離子界面活性劑 之正型或負型感光膠剝離劑。 美國專利公報第5, 4 7 8, 4 4 3號以及美國專利公報第5 3 2 0，7 0 9號提案了，使用特定有機防腐蝕劑（乙二醇以及二’ 甲亞砜）以及含氟化合物（銨氟化物、氫氟酸、全氟酸等）來解 決金屬腐蝕問題。但是，這些組成物之中，需要大量的有機溶媒， 因此有必須去除大量廢棄物的缺點。 、 美國專利公報第5, 6 1 2, 3 0 4號，因為不易去除腐姓後 之殘留物，故提案了特定條件之極性溶媒、特定之烧醇胺、有氫 氧基的氨基酸，再者，提案了具有特定氧化還原電位之氧化還原 劑之剝離液組成物。關於上述文獻，其係說明具有氫氧基之氨基 酸莓作防腐餘劑使用，有機或無機酸使得含胺汽提塔溶液之驗性 降低，劣化剝離力者。 美國專利公報第2002-006824 4號提案了包含亞 烷基碳酸酯、有機過氧化物、以及N —置換嗎啡之中至少一種物 質之剝離劑。 —韓國公開專利公報第2 〇 qi-〇()1837 7號提案了包 含胺化合物、乙二醇系列溶劑、全氟烷基乙烯氧化物之感光膠剝 離劑。 韓國公，專利公報第2G0G-0G16878號提案了由 燒氧基N-氫氧基絲舰氨化物以及偶極子力矩在3以上之極 性物質、止損細以及鱗胺所組紅獅液組成物。 韓國公開專利公開第2001-0040496號提案了使 用喷咬化合物而翻於翻祕_/減減合物系列的 正型感光膠之剝離液組成物。 美國專利公報第5, 4 8 0, 5 8 5號以及日本特開平5 - 2 1315030 8 1 ^ 5 3號提案了包含化學式H3_nN ((CH2) m〇H) n (m 為2或3 ’/為丄、2或3)之烷醇胺、磺化合物或亞碼化合物 以5學式C6H6-n (〇H)n(n為卜2或3)之氫氧基化合 物的感光膠用有機剝離劑。 ^本特開平4- 1 2 4 6 6 8號提案了由有機胺20〜90 重量/6、碟酸酯界面活性劑〇 · 1〜2 〇重量％、2 _丁炔_ 1， 4一一醇〇·1〜2〇重量％、以及剩下部分的乙二醇單烷基醚 以及/或非原胺月柬性極性溶劑所組成之感光膠用剝離液組成 物。 ，述組成物中，在乙二醇單烷基醚上，使用了乙二醇單乙基 醚、一乙二醇單乙基醚、二乙二醇單甲鰱乙酸等，在非原胺月柬 性極性溶劑上，使用了二曱亞砜、Ν，Ν —二甲基乙酰胺等，2 —丁炔一1，4—二醇以及磷酸酯界面活性劑在不降低剝離特性 的限度内，為了防止因吸附於感光膠之有機胺而使得鋁以及銅等 金屬層腐钱而添加。 曰本特開昭6 4 — 4 2 6 5 3號提案了包含二曱亞砜5 〇重 量％以上，最好是7〇重量％以上，包含從二乙二醇單烷基醚、二 乙二醇二烷基醚、r_丁内酯、以及丄，3_二甲基_2—咪口 坐所選擇之至少一種溶劑1〜5 〇重量％，以及乙醇胺等之含氮 有機氫氧基化合物〇·1〜5重量％的感光膠用剝離液組成物。 此處記載著，二曱亞砜未滿5 〇重量％時，剝離性明顯低下， 含氮有機氫氧基化合物溶劑超過5重量％時，鋁等金屬層被腐蝕。 韓國公開專利公報第1999 — 0062480號提案了一 種剝離液’其特徵為由有機胺化合物、原胺月柬性乙二醇趟化合 物、非原胺月東性多極性化合物以及烧基η比咯烧酮化合物所組成。 韓國公開專利公報第2 0 00 —000810 3號提案了包 含5〜15重量％之烷醇胺、3 5〜5 5重量％之亞碼或磺化合 物、3 5〜5 5重量％之乙二醇醚以及界面活性劑之感光膠用剝 離液組成物。此處記載著，烷醇胺超過15重量％時，或^亞碼 1315030 或磺化合物未滿3 5重量％時，與L CD全膜質之吸故性變, 接觸角變大，氣動所產生之剝離性能低下。 Λ 但是’在這種先進技術中所提案的有機溶劑剝離劑對於感光 膠以及殘留物之剝離能力不足，對於形成感光膠之高分子物質的 溶解力不夠，所以被剝離之感光膠殘留物再度附著於半導體美板 或玻璃基板等’不只產生附加的溶劑副產物’因為製程條件^言 溫，所以在環境面以及處理費用上是不利的，在清洗殘留物^ 其限制，於後續的漂洗製程中，會有必須使用異丙醇、二 般之有機溶劑的問題。此外，在胺系列剝離液組成物或^ 中，當作添加劑使用的四曱基錢氫氧基（ΤΜΑΗ)等銨=人 物會腐餘銘、銅等金屬層，或促進腐餘。 〇 特別是，因最近半導體元件以及液晶顯示元件之大 大量生產化，較之既有剝離劑使用方式之浸潰（D £ 法，喷霧（S p r a y)法或一張一張處理的單片（s g ) 二wa f e r Sy s t em)方式、使用氣動方式之 發適合於喷霧法以及單片方式與氣動方 式的剝離劑組成物開發出來。 八兴轧動万 ^發明之感光膠剝離液組成物，係對濕式腐 ，中產生的變質或硬化的感光膠，以浸漬法、喷霧^ 或軋動方式，能以低溫，短時間内輕易剝離， ^片方式 J丙醇、二甲亞砜般之有機溶劑，可 =不:使 本發明之功效。 卬休，先，進而達成 【發明内容】 因此’本發明所欲解決之技術課題，# 化的 3d料乾式雜製程離 短時間内易於剝離’露出於_液組成物 1315030 氧=膜質上不產生損壞，於後續的漂洗製程中，不必 ί ϊ般ί i機溶#丨，只用水即可縣之感光膠娜液組成t 法，其使絲供—種制離方 【實施方式】 ' 為了達成上述技術課題，本發明中，對於組成物之換| 供一種剝離液組成物，其包含5〜5 0重量％ 風’， ίΓΓ^η 1 〇^5 0 口物、0〜3 0重量％的水溶性有機溶媒、〇 . i ) 之防腐蝕劑以及少量的純水。 重量％ 〔式1〕Steel, tetrahydro sugar, isophora, dimethyl succinyl, adipic acid I glutaric acid dimethyl, cyclobutyl, r-butane vinegar, N, N-di H = 3⁄4 compound) The type of photosensitive adhesive stripping liquid composition, in addition to U.S. Patent No. H7 °, No. 713, discloses the inclusion of a specific amino compound (for example, N #暖二基基乙胺) and a specific amine compound (such as ethanolamine). The first adhesive stripping liquid composition, in addition, U.S. Patent No. 4, 8 2 4 7 fi 2 contains a triamine (for example, diethylenetriamine) and a non-polar solvent [for example, N-methyl one). a positive type photosensitive adhesive stripping liquid composition of 2-pyrrolidone, dimethyl hydrazide, butyrolactone, etc., and a hydroxyamine (for example, nitrogen) is disclosed in U.S. Patent No. 5,269,7 gi. A stripping liquid composition of oxyamine), an alkoxylated amine, and any polar solvent. U.S. Patent No. 4,78,6,5,7,8, the disclosure of which is incorporated herein by reference in its entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire content And organic tests (for example, single, double, or tri-ethanolamine). U.S. Patent Publication No. 4, 8 2 4, 7 6 2 discloses the inclusion of ethylene glycol oxime (e.g., 'diethylene glycol monomethyl ether, dipropylene glycol monodecyl ether, tripropylene glycol monomethyl ether) and aliphatic The photoresist of the amine (for example, ethanolamine or triisopropanolamine) is stripped of a cleaning solution, and the latter cleaning solution is non-aqueous. U.S. Patent No. 4,904,576 discloses a basic compound (e.g., a primary amine, a secondary amine, a solvent) (e.g., water, ethanol, ether, ketone, etc.) dissolved in the solvent. a tertiary amine, a 4-grade amine, a cyclic amine, a polyamine, a 4- toluamine, a hydrazine hydroxyl group, a base hydroxy group, etc.), and a boron hydride compound dissolved in the aforementioned solvent (for example, sodium borohydride, dimethyl Photosensitive adhesive stripper for printed circuit boards of boronamine, pyridine boron, etc.).曰本特开平 7 — 0 2 8 2 5 No. 4 announced the composition of non-corrosive photosensitive gel stripping liquid composed of sugar ethanol, ethanolamine, water 1315030 and any 4 grade water oxide. International Patent No. WO 8 8 - 0 8 8 1 3 proposes the stripping of positive or negative photosensitive adhesive containing butyl vinegar or caprolactone, a 4-grade ammonium hydroxide compound and any nonionic surfactant. Agent. U.S. Patent No. 5, 4, 8, 8, 4, 4, and U.S. Patent No. 5,320,075, the disclosure of which is incorporated herein by reference to the entire entire entire entire entire entire entire entire content Compounds (ammonium fluoride, hydrofluoric acid, perfluoric acid, etc.) to solve metal corrosion problems. However, among these compositions, a large amount of organic solvent is required, and therefore there is a disadvantage that a large amount of waste must be removed. , U.S. Patent Publication No. 5, 6 1 2, No. 3 4, because it is difficult to remove the residue after the rot, so a specific condition of the polar solvent, a specific alkalamine, a hydroxyl-containing amino acid, and A stripping liquid composition of a redox agent having a specific oxidation-reduction potential is proposed. Regarding the above documents, it is explained that an amino acid raspberry having a hydroxyl group is used as an antiseptic agent, and an organic or inorganic acid lowers the testability of the amine stripper-containing solution and deteriorates the peeling force. A release agent comprising at least one of an alkylene carbonate, an organic peroxide, and an N-substituted morphine is proposed in U.S. Patent Publication No. 2002-006824. —Korea Public Patent Gazette No. 2 qi-〇() 1837 No. 7 proposes a photoresist stripping agent containing an amine compound, a glycol series solvent, and a perfluoroalkyl ethylene oxide. Korean Patent No. 2G0G-0G16878 proposes a composition consisting of an alkoxy N-hydroxyl sulphate amide and a polar material having a dipole moment of 3 or more, a stop loss fineness, and a squamous amine group. Korean Laid-Open Patent Publication No. 2001-0040496 proposes a peeling liquid composition of a positive type photosensitive adhesive which is turned over by a squeezing compound. U.S. Patent Publication Nos. 5, 4 80, 5 8 5 and Japanese Patent Laid-Open No. 5 - 2 1315030 8 1 ^ 5 3 propose the inclusion of the chemical formula H3_nN ((CH2) m〇H) n (m is 2 or 3 '/ An organic stripper for a photographic adhesive of a hydrazine, a sulfonate compound or a subcode compound of the formula C6H6-n (〇H)n (n is 2 or 3) . ^Bent Kaiping 4- 1 2 4 6 6 8 Proposal from organic amine 20~90 wt/6, dish ester surfactant 〇·1~2 〇% by weight, 2 _butyne _ 1, 4 one A stripping liquid composition for a photosensitive paste comprising 1% to 2% by weight of the alcohol and a remaining portion of the ethylene glycol monoalkyl ether and/or the non-original amine polar solvent. In the composition, ethylene glycol monoethyl ether, monoethylene glycol monoethyl ether, diethylene glycol monomethyl hydrazine acetic acid, etc. are used on the ethylene glycol monoalkyl ether, in the non-origin amine On the polar solvent, disulfoxide, hydrazine, hydrazine-dimethylacetamide, etc., 2-butyne-1,4-diol and phosphate ester surfactant are used within the limits of not reducing the peeling property. In order to prevent the metal layer such as aluminum and copper from being rotted by the organic amine adsorbed on the photosensitive paste, it is added.曰本特开昭6 4 — 4 2 6 5 3 proposes to contain bis sulfoxide 5 〇 by weight or more, preferably 7% by weight or more, including diethylene glycol monoalkyl ether, diethylene glycol Alcohol dialkyl ether, r-butyrolactone, and hydrazine, 3 dimethyl -2- hydrazine, at least one solvent selected from 1 to 5 〇 by weight, and nitrogen-containing organic hydroxy compound such as ethanolamine 〇·1 to 5 wt% of a peeling liquid composition for a photosensitive paste. Here, it is described that when the disulfoxide is less than 5% by weight, the peeling property is remarkably lowered, and when the nitrogen-containing organic hydroxy compound solvent is more than 5% by weight, a metal layer such as aluminum is corroded. Korean Laid-Open Patent Publication No. 1999- 0062480 proposes a stripping liquid which is characterized by an organic amine compound, a pro-amine ethylene glycol ruthenium compound, a non-pro-amine amine polypolar compound, and a calcination base. Composed of a ketone compound. Korean Laid-Open Patent Publication No. 2000-000810 proposes that 5 to 15% by weight of an alkanolamine, 3 5 to 55% by weight of a subcode or a sulfonic compound, and 3 to 5 to 55% by weight of ethylene glycol are proposed. A stripping liquid composition for a photosensitive paste of an ether and a surfactant. Here, when the alkanolamine is more than 15% by weight, or when the subcode 1315030 or the sulfonic compound is less than 35 % by weight, the pickling property with the L CD total film quality is changed, the contact angle is increased, and the pneumatic force is generated. Peeling performance is low. Λ However, the organic solvent release agent proposed in this advanced technology has insufficient peeling ability for the photosensitive adhesive and the residue, and the solubility of the polymer material forming the photosensitive adhesive is insufficient, so that the peeled photosensitive adhesive residue is reattached. 'In addition to the production of additional solvent by-products, such as semiconductor sheet or glass substrate, because of the process conditions, it is unfavorable in terms of environmental surface and processing cost. In the cleaning of residues, it is limited in the subsequent rinsing process. There is a problem that it is necessary to use isopropyl alcohol and a common organic solvent. In addition, in the amine series stripping liquid composition or the alloy, tetraammonium hydroxide such as tetrakisole, which is used as an additive, may be a metal layer such as ruthenium or copper, or promote the corrosion. In particular, due to the recent large-scale production of semiconductor components and liquid crystal display elements, it has been compared to the use of a stripping agent (D £ method, spray method or one-piece processing). (sg) Two wa fer Sy st em) methods, using a pneumatic method suitable for spray method and a one-piece and pneumatic stripper composition developed. The composition of the photosensitive adhesive stripping solution of Baxing Rolling Million ^ is a kind of metamorphic or hardened photosensitive glue produced by wet rot, which can be immersed, sprayed or rolled, can be low temperature, short time Easily peeled off, ^ film type J propanol, dimethyl sulfoxide-like organic solvent, can = not: make the effect of the present invention.卬 , , 先 先 先 先 先 先 先 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出 露出Damage, in the subsequent rinsing process, it is not necessary to use 丨 ί i 机 机 机 机 机 机 机 机 机 机 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县 县In the above technical problem, in the present invention, for the composition of the composition, a stripping liquid composition containing 5 to 50% by weight of air', ίΓΓ^η 1 〇^5 0 mouth, 0 to 30% by weight Water-soluble organic solvent, anti-corrosive agent of 〇. i) and a small amount of pure water. Weight% [Formula 1]

R^N L"^r1互相獨立，表現成氫原子、直鍵或分支鍵ch 氧基絲、直鍵*分支鍵C2—1D麟基錢氧基鏈4 土二或C：5 — 8環烷基或氫氧基環烷基，三個R1之中的— ▲ 氫氧基烷基、氫氧基鏈烯基或氫氧基環烷基。） Μ *、、、 〔式2〕 R2'〇- [(CHR3) m- (CH2) η] t-OH (式中，R2表示直鏈或分支鏈Cl —1〇烧基、例如，曱基、乙其、 丙基、異丙基、丁基、異丁基、戊基、己基、庚基、辛1，R1表 ^原子、或直鏈或分支鍵C㈠絲，m以及4自為的 整數’但是m+ η為2或3，t為1到5的整數。） 此外、’本發明之其他技術課題係由使用了剝離液組成物之剝 離方法來達成，此剝離液組成物係對組成物之總量包含了 5〜5 0重量/6之上述化學式1的有機胺化合物、1 〇〜5 〇重量％之 =上化學式2的乙二醇醚化合物、〇〜3 〇重量％之水溶性有機 溶媒、0 · 1〜1〇重量％之防腐蝕劑以及少量純水。 根據達成上述之其他技術課題的感光膠剝離方法，提供了感 光膠以及聚合物剝離方法，其特徵為使設有感光膠膜之基板與剝 11 1315030 離液組成物接觸。 活性 物 或三一 刺、ίίί或在其前^離液組成物令之添加刺可以包含界面 具體範例上之:口二物中_所1用之化學式1的有機胺化合 1-丙醇胺、單，二^展^^一乙醇胺 '單，二，或三 基二乙醇胺、N—n触、丁醇坡' 丁基乙醇胺、乙 f日月中’作為有機胺化合物上較佳 二乙醇胺、N-甲基氨基乙醇、異丙醇二—乙_、 乙醇t Ν:甲基氨基乙醇、異丙醇胺或其混合物。 * 二醇_生物係在分子内，共有_基與氫氧基， 二良ί的混。狀態，是"'種極佳的溶劑而被廣泛使用。添加 适種乙二，峨’乃是作為—種界面活性絲使用，降低溶液表 面張力，提升滲透力’在較低溫下強化剝離液組成物的剝離能力。 本^明中所使用之化學式2的乙二醇醚化合物一般是亞烷基 乙二醇單醚。3化學式2之化合物的較佳範例上，記號R2表示甲 基、丁基，R3表示氫原子，m+n為2或3，t為1、2或3的 化合物，具體範例上可舉出以下化合物等。 CH3CH2CH2CH2-0CH2CH2-0H ； CH3CH2CH2CH2-OCH2CH2-OCH2CH2-OH ; CH3CH2CH2CH2-OCH2CH2-OCH2CH2-OCH2CH2-OH ; CH3CH2CH2CH2-OCH2CH2-OCH2CH2-OCH2CH2-OCH2CH2-OH ; CH3-OCH2CH2-OH ; CH3-OCH2CH2-OCH2CH2-0H ; CH3-OCH2CH2-OCH2CH2-OCH2CH2-OH ; CH3-OCH2CH2-OCH2CH2-OCH2CH2-OCH2CH2-OH ; CH3-OCH2CH2CH2-OH ; CH3-OCH2CH2CH2-OCH2CH2CH2-OH ; CH3-OCH2CH2CH2-OCH2CH2CH2-OCH2CH2CH2-OH ; 12 1315030 CH3-0CH2CH2CH2-0CH2CH2CH2-0CH2CH2CH2-0CH2M^ . 的化學式2的化合物係乙二醇單甲趟乙酸、二乙二醇》 ▼謎乙酸、二甘醇單㈣6酸或其齡物。 醇早 ，發明之剝離液組成物中，水溶性有機 :，如痛甲醇、乙醇、η —丙基乙醇、異丙醇、η — f二二二醇、三甘醇、2 -甲基-1，3 -丙烷:醇 ，3 ''丁烷二醇、糠基乙醇、四氫糖醇等；醜胺A :!如，-甲基甲酰胺、N，N —二甲基甲跌胺、 例 ^醜胺、N-甲基-2-姆_等；内酿、例如，γ : Hi酯，例如，乳酸f基、乳酸乙基等；_、例如，_、〇 基乙基網、乙酰基丙酮等；環丁碼、例如，環丁碼等； 〒 如，二甲亞砜等；以及其他有機溶媒。 特佳的水溶性有機溶媒方面，可舉出丙二醇、三甘醇、 二三’ 3—丙烧二醇、3 —甲基—工，3_丁。二醇、 ^:二甘醇、Ν —曱基_ 2 —吨略燒酮、以及二甲亞讽或其現 、十、古組成物的純水，在獅溶液組成物巾，扮演了將前 速有機胺化合物活性化’強化絲糊離能力的角色，以及扮演 了把直接水漂洗製程中產生的氫氧基所引予 以緩和的角色。 興佴阀挪丁 片本發明之剝離液組成物的防腐姓劑方面，可使用將胺所產生 之氫氧基抑巾和的化合物，例如’糖乙賴、有機氧化合物或 芳香族氫氧基化合物等。 糖乙醇類方面，在直鏈多元醇上，可舉山梨糖醇、甘靈撼醇、 蘇糖、木糖醇等，其中特別是山梨糖醇、甘露糖醇、木糖醇或其 混合物。 ,前述山梨糖醇、甘露糖醇、木糖醇或其混合物，扮演的角色 為’有機胺與水的氫離子反應而產生的氫氧離子，可有效滲透到 感光膠層與基板之間的接觸面，形成與聚合物中所含的金屬物質 13 1315030 之螫合反應，提升剝離能力，還扮演 Ϊ應，防止自剝離液組成物所產生的氣“腐 〔式冗氧化合物-般町化料3之錢氧化合物。 r4c〇2h 氣)氧基、碳氧基，她=二= 作為本發明之防腐蝕劑使用的化學人 可控制造成金屬雜原因的氫氧基產只 中之金屬物質的螫合反應而去除，防止其J吸附:因㈡ 加適量的化學式3的化合物，不只可以保護金屬層= 可以有效去除殘留物中之金屬離子污染物質等。 還 在上述化學式3之化合物巾，記賊表稍原子 ίίΐί支鏈^其』烷基、直鏈或分支鏈。-10鏈縣t 烷基或Cm烯基，以上可用從鹵素、氫氧基、碳 酸基所組成之群帽擇之置換絲置換。化學式3之^ ΤΓ ?η Η®' 'T3' 'CH2CHzCH3 ' ' -(CH〇£HCH2- ^ -CH2-CO2H ' -CH2CH2-CO2H > -CH2CH2CH2-C〇2H > -cow -cis-CH2=CH-C〇2H 、 -trans-CH2=CH-C〇2H 、 -CH2C(OH)(C〇2H)CH2-C〇2H ^ -C6H4-2-CO2H > -CH2-OH ^ -CHrOHVH . -CH(0H)CH(0H)-〇)2H、-CH(0H)CH(0H)CH(0H)CH⑽)CH2〇H 3、 -C6H4_2-0H，以上對應於甲酸、醋酸、丙酸、丁酸、辛酸、壬酸、 癸酸、戊酸、異戊酸、丙二酸、丁二酸、戊二酸、乙二酸、順^ 烯二酸、反式丁烯二酸、擰檬酸、苯二酸、乙二醇酸、乳酸、酒 石酸、葡萄酸、以及水楊酸。本發明中，特佳之化學式3的化合 物係本一酸、乳酸、葡萄酸、辛酸、壬酸、癸酸、沒食子酸或其 1315030 混合物。 m^s- 8 - 3、4_四氫—8—報3—喧_、1、2、 U、焦W。盼等鱗_ ’對苯二盼、兒茶紛、間 丨ίΓ之剝離液組成物為了提升剝離之平均性，可把 3加 =用。添加劑的量不限制，但最好以全組 二在G.GQ1到1◦重频，更佳者是在〇.R^N L"^r1 is independent of each other and represents a hydrogen atom, a direct bond or a branched bond, a ch-oxyl wire, a straight bond, a *branched bond, a C2—1D, a benzyloxy chain, or a C:5-8 cycloalkane. a hydroxy or a cycloalkyl group, a ▲ hydroxyalkyl group, a hydroxyalkyl group or a hydroxycycloalkyl group among the three R1 groups. Μ *, , , [Formula 2] R2'〇- [(CHR3) m- (CH2) η] t-OH (wherein R2 represents a straight or branched chain Cl-1 group, for example, a fluorenyl group , B, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl 1, R1, atom, or linear or branched bond C (a) silk, m and 4 self-integer 'But m+ η is 2 or 3, and t is an integer of 1 to 5. Further, 'other technical problems of the present invention are achieved by a peeling method using a peeling liquid composition, and the peeling liquid composition is a composition. The total amount includes 5 to 50% by weight of the organic amine compound of the above Chemical Formula 1, 1 〇 to 5 〇% by weight = the glycol ether compound of the above Chemical Formula 2, and 水溶性~3 〇% by weight of the water-soluble organic compound Solvent, 0 · 1~1〇% by weight of anticorrosive agent and a small amount of pure water. According to the photosensitive adhesive peeling method which achieves the above-mentioned other technical problems, a photosensitive adhesive and a polymer peeling method are provided, which are characterized in that a substrate provided with a photosensitive film is brought into contact with a peeling composition of the strip 11 1315030. The active substance or the triad, ίίί or the chelating agent may be included in the specific example of the interface: the organic amine compound 1-propanolamine of the chemical formula 1 used in the mouth 2 Mono-, di-extension ^^-ethanolamine 'mono-, di- or tri-diethanolamine, N-n-touch, butanol s-butylethanolamine, B f in the middle of the month' as an organic amine compound on the preferred diethanolamine, N - methylaminoethanol, isopropanol di-b-, ethanol t Ν: methylaminoethanol, isopropanolamine or a mixture thereof. * The diol-biosystem is in the molecule and has a mixture of _ group and hydroxyl group, and liang. The state is "' an excellent solvent and is widely used. The addition of the appropriate species of ethylene, 峨' is used as an interfacial activator to reduce the surface tension of the solution and enhance the penetration force to enhance the peeling ability of the composition of the stripping solution at a lower temperature. The glycol ether compound of Chemical Formula 2 used in the present invention is generally an alkylene glycol monoether. In a preferred embodiment of the compound of the formula 2, the symbol R2 represents a methyl group, a butyl group, R3 represents a hydrogen atom, m+n is 2 or 3, and t is 1, 2 or 3, and specific examples thereof include the following Compounds, etc. CH.sub.3CH. CH3-OCH2CH2-OCH2CH2-OCH2CH2-OH; CH3-OCH2CH2-OCH2CH2-OCH2CH2-OCH2CH2-OH; CH3-OCH2CH2CH2-OH; CH3-OCH2CH2CH2-OCH2CH2CH2-OH; CH3-OCH2CH2CH2-OCH2CH2CH2-OCH2CH2CH2-OH; 12 1315030 CH3- 0CH2CH2CH2-0CH2CH2CH2-0CH2CH2CH2-0CH2M^. The compound of Chemical Formula 2 is ethylene glycol monomethyl hydrazide acetic acid, diethylene glycol, "mystery acetic acid, diethylene glycol mono (tetra) 6 acid or its age. Alcohol early, in the stripping solution composition of the invention, water-soluble organic: such as pain methanol, ethanol, η-propyl alcohol, isopropanol, η-f didiol, triethylene glycol, 2-methyl-1 , 3-propane: alcohol, 3'' butanediol, mercaptoethanol, tetrahydro sugar, etc.; ugly amine A: !, such as - methylformamide, N, N-dimethylmethamine, examples ^ ugly amine, N-methyl-2-m_, etc.; internal brewing, for example, γ: Hi ester, for example, lactic acid f group, lactated ethyl group, etc.; _, for example, _, mercaptoethyl net, acetyl group Acetone or the like; a cyclobutyl code, for example, a cyclobutyl code or the like; for example, dimethyl sulfoxide or the like; and other organic solvents. Examples of the particularly preferred water-soluble organic solvent include propylene glycol, triethylene glycol, di-tri- 3-propane diol, 3-methyl-form, and 3-butene. Glycol, ^: diethylene glycol, fluorene-fluorenyl _ 2 - ton sulphonone, and dimethyl sulphate or its present, ten, ancient composition of pure water, played in the lion solution composition towel, played before The role of the fast-acting organic amine compound in activating the ability to reinforce the silk paste and the role of mitigating the hydroxyl groups produced in the direct water rinse process. In the aspect of the anti-corrosion agent of the stripping liquid composition of the present invention, a compound in which a hydroxyl group generated by an amine is used, such as 'sugar, an organic oxygen compound or an aromatic hydroxyl group, may be used. Compounds, etc. In the case of sugar alcohols, sorbitol, glycyrrhizol, threose, xylitol and the like may be mentioned on the linear polyol, and among them, sorbitol, mannitol, xylitol or a mixture thereof is particularly preferable. The aforementioned sorbitol, mannitol, xylitol or a mixture thereof plays the role of 'hydrogen and oxygen ions generated by the reaction of organic amines with hydrogen ions of water, and can effectively penetrate the contact between the photosensitive layer and the substrate. The surface is formed into a kneading reaction with the metal substance 13 1315030 contained in the polymer to enhance the peeling ability, and also acts as a gas to prevent the gas generated from the composition of the stripping liquid from being rotted. 3 oxygen compound. r4c〇2h gas)oxy group, carbonoxy group, she=2 = chemist used as the anticorrosive agent of the present invention can control the oxime of the metal substance which causes the metal hydride to cause the metal nucleus It is removed by the reaction to prevent its J adsorption: (2) Adding an appropriate amount of the compound of Chemical Formula 3, not only can protect the metal layer = can effectively remove metal ion contaminants in the residue, etc. Also in the compound towel of the above Chemical Formula 3, the thief A slightly atomic ίίΐί 链 ^ 其 其 其 其 』 』 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 烷基 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 -10 Replacement 3 η η Η® ' 'T3' 'CH2CHzCH3 ' ' -(CH〇£HCH2- ^ -CH2-CO2H ' -CH2CH2-CO2H > -CH2CH2CH2-C〇2H > -cow -cis-CH2 =CH-C〇2H, -trans-CH2=CH-C〇2H, -CH2C(OH)(C〇2H)CH2-C〇2H ^ -C6H4-2-CO2H > -CH2-OH ^ -CHrOHVH . -CH(0H)CH(0H)-〇)2H, -CH(0H)CH(0H)CH(0H)CH(10))CH2〇H 3, -C6H4_2-0H, the above corresponds to formic acid, acetic acid, propionic acid, butyl Acid, caprylic acid, citric acid, citric acid, valeric acid, isovaleric acid, malonic acid, succinic acid, glutaric acid, oxalic acid, cis-enedioic acid, trans-butenedioic acid, citric acid, Phthalic acid, glycolic acid, lactic acid, tartaric acid, gluconic acid, and salicylic acid. In the present invention, the compound of the chemical formula 3 is preferably an acid, a lactic acid, a gluconic acid, a caprylic acid, a citric acid, a citric acid, or not. a mixture of gallic acid or its 1315030. m^s- 8 - 3, 4_tetrahydro- 8 - reported 3 - 喧 _, 1, 2, U, Jiao W. Hope scales _ 'Phenyl benzene, catechu In order to improve the average of peeling, the amount of the additive may be 3 plus =. The amount of the additive is not limited, but it is better to repeat the frequency in the whole group 2 at G.GQ1 to 1◦, The best is in the hustle and bustle.

制之剝離液組成物在L s1元件、液晶面板等之半導體 製造，中’對於組成半導體之氧化膜以及銘、H二， tln Qxide)金屬膜般之物質其具 有極低的腐蝕性，特別適合於紹膜材質。 為了獲得本發明之剝離液組成物，上述化合物可以用既定量 混合，齡方式不制限定，各種通㈣方式都可以 本發明之其他技術課題方面’關於本發明之剝離方法方面， 更佳者、將濕式舰以及乾式腐⑽程中產生之變質或硬化的感 光膠去除時可使用。The composition of the stripping liquid is extremely low in corrosiveness in the manufacture of semiconductors such as L s1 elements and liquid crystal panels, and is particularly suitable for a metal film like the oxide film constituting the semiconductor and the T, Qxide metal film. Yu Shao film material. In order to obtain the composition of the stripping liquid of the present invention, the above compound may be mixed in a quantitative manner, and the age is not limited. Various methods of the fourth aspect can be used in the aspect of the present invention. It can be used when the wet ship and the deteriorated or hardened photoresist produced in the dry rot (10) process are removed.

剝離方法上’可以該業界所一般週知的剝離方法來進行，若 為制離液組成物可與設有感光膠膜以及聚合物之基板接觸的方 法，則能獲得良好的結果。 ^發明的剝離方法上，使用了浸潰法、喷霧法、單片方式’ 以及氣動方式的方法等較為適用。 以浸潰法、噴霧法、單片方式，以及氣動方式來剝離時，在 制離條件上’溫度約在1 0到1 〇 〇 t：，2 0到8 0 °C較佳，浸潰 以及喷霧時間約5秒到3 0分鐘，較佳為10秒到10分鐘，但 本發明並不這麼嚴謹，可視業者喜好而定。 本發明之剝離液組成物，在去除濕式腐蝕以及乾式腐蝕製程 15 1315030 之中產生的變質或硬化的感光膠此性能上很優越，對於組成半導 體元件以及液晶顯示元件之金屬膜、氧化膜般之物質而言其腐蝕 性極低，結果，在清洗L S I元件、液晶面板等之半導體元件的 過程中可使用。 施例 以下，參照以下實施例詳述本發明，但本發明並不限於此實 在表2所示之處理條件下，將基板浸潰於從表i所示之化合 組成物中’以純水漂洗後’崎插電子顯微鏡 (SEM)(HITACH、S-47Q0)來觀測了&果。表2 磁纖下層咖雜能力。 〔剝離能力〕 X :不良 〔防腐蝕能力〕 ◎:良好 △:普通The peeling method can be carried out by a peeling method generally known in the art, and a good result can be obtained if the composition of the separating liquid can be brought into contact with a substrate provided with a photosensitive film and a polymer. In the peeling method of the invention, a dipping method, a spray method, a one-piece method, and a pneumatic method are preferably used. When peeling, spraying, monolithic, and pneumatic means, the temperature is about 10 to 1 〇〇t: 20 to 80 °C, and the impregnation is better in the separation conditions. The spraying time is from about 5 seconds to 30 minutes, preferably from 10 seconds to 10 minutes, but the invention is not so rigorous, depending on the preference of the practitioner. The stripping liquid composition of the present invention is superior in the performance of removing the deteriorated or hardened photosensitive paste generated in the wet etching and dry etching process 15 1315030, and is similar to the metal film and the oxide film constituting the semiconductor element and the liquid crystal display element. The substance is extremely low in corrosivity, and as a result, it can be used in the process of cleaning semiconductor elements such as an LSI element or a liquid crystal panel. EXAMPLES Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the present invention is not limited to the fact that the substrate is impregnated in the chemical composition shown in Table i from the chemical composition shown in Table 2 After the 'Sakisui electron microscope (SEM) (HITACH, S-47Q0) to observe & Table 2 The ability of the lower layer of magnetic fiber. [Peeling ability] X : Poor [Corrosion resistance] ◎: Good △: Normal

DMS O + NM P (60%)DMS O + NM P (60%)

MET -XL〇%) MEa li〇%) bdg ll〇%) 1315030 6 Μ I PA (1 0%) BDG (9 0%) — — — 7 Μ I PA (3 0%) BDG (30%) DMSO (40%) — — 8 Μ I P A (3 0%) BDG (30%) DMSO (39·9%) 木糖醇 (0·1%) — 9 Μ I PA (3 0%) BDG (30%) DMSO (20%) — 少量 10 ME A (1 0%) — DMSO (60%) 兒茶酚 (2%) 少量 11 Μ I P A (1%) BDG (1 5%) DMSO (6 0%) 蘇糖 (0·1%) 少量 12 Μ I P A (30%) — 木糖醇 (1%) 少量 13 ME A (6 0%) BDG (1 0%) — 木糖醇 (1%) 少量 14 ME A (30%) BDG (30%) — 兒茶酚 (1%) 少量 15 ME A (30%) BDG (30%) — BTA (1%) 少量 16 ME A (3 0%) BDG (30%) — 蘇糖 (1%) 少量 17 ME A (1 0%) BDG (5 0%) — 蘇糖 (0-1%) 少量 18 ME A (2 0%) BDG (1 0%) — 山梨糖醇 (1%) 少量 19 ME A (30%) EGB (20%) — 木糖醇 (2%) 少量 20 ME A (30%) TEGB (30%) — 甘露糖醇 (5%) 少量 2 1 Μ I P A (30%) BDG (30%) — 木糖醇 (1%) 少量 22 MI PA (30%) BDG (30%) — 8 —喹琳紛 (1%) 少量 2 3 Μ I P A (1 0%) BDG (1 0%) DMSO (1 0%) 蘇糖 (0·1%) 少量 24 MI PA (1 0%) BDG (1 0%) NMP (1 0%) 木糖醇 (0·1%) 少量 17 1315030 2 5 Μ I P A (1 0%) BDG (1 0%) THF A (1 0%) 木糖醇 (0·1%) 少量 2 6 ME A (2 0%) BDG (20%) DMSO (20%) 山梨糖醇 (1%) 少量 2 7 ME A (3 0%) EGB (30%) DMSO (30%) 木糖醇 (2%) 少量 28 ME A (3 0%) EGB (30%) DMSO (30%) 8 —喧琳紛 (2%) 少量 2 9 ME A (3 0%) TEGB (30%) DMSO (20%) 甘露糖醇 (5%) 少量 3 0 ME A (3 0%) TEGB (30%) DMSO (20%) 2 —唾琳紛 (5%) 少量 3 1 ME A (30%) BDG (30%) DMSO (20%) 木糖醇 (1%) 少量 註）ΤΜΑΗ :四曱基銨氳氧基MET -XL〇%) MEa li〇%) bdg ll〇%) 1315030 6 Μ I PA (1 0%) BDG (9 0%) — — — 7 Μ I PA (3 0%) BDG (30%) DMSO (40%) — — 8 Μ IPA (30%) BDG (30%) DMSO (39.9%) Xylitol (0.1%) — 9 Μ I PA (30%) BDG (30%) DMSO (20%) — small amount 10 ME A (1 0%) — DMSO (60%) catechol (2%) small amount 11 Μ IPA (1%) BDG (1 5%) DMSO (60%) sorbose (0·1%) Small amount 12 Μ IPA (30%) — Xylitol (1%) Small amount 13 ME A (60%) BDG (1 0%) — Xylitol (1%) Small amount 14 ME A ( 30%) BDG (30%) — catechol (1%) small amount 15 ME A (30%) BDG (30%) — BTA (1%) small amount 16 ME A (30%) BDG (30%) — Sucrose (1%) Small amount 17 ME A (1 0%) BDG (50%) — Sucrose (0-1%) Small amount 18 ME A (20%) BDG (1 0%) — Sorbitol ( 1%) Small amount 19 ME A (30%) EGB (20%) — Xylitol (2%) Small amount 20 ME A (30%) TEGB (30%) — Mannitol (5%) Small amount 2 1 Μ IPA (30%) BDG (30%) — xylitol (1%) small amount 22 MI PA (30%) BDG (30%) — 8 — quinoline (1%) small amount 2 3 Μ IPA (1 0%) BDG (1 0%) DMSO (1 0%) Sucrose (0.1%) 24 MI PA (1 0%) BDG (1 0%) NMP (1 0%) Xylitol (0·1%) Small amount 17 1315030 2 5 Μ IPA (1 0%) BDG (1 0%) THF A ( 1 0%) xylitol (0·1%) small amount 2 6 ME A (20%) BDG (20%) DMSO (20%) sorbitol (1%) small amount 2 7 ME A (30%) EGB (30%) DMSO (30%) xylitol (2%) small amount 28 ME A (30%) EGB (30%) DMSO (30%) 8 — 喧 纷 (2%) small amount 2 9 ME A (30%) TEGB (30%) DMSO (20%) mannitol (5%) a small amount of 3 0 ME A (30%) TEGB (30%) DMSO (20%) 2 - saliva (5% A small amount of 3 1 ME A (30%) BDG (30%) DMSO (20%) xylitol (1%) a small amount of injection) ΤΜΑΗ: tetradecyl ammonium oxime

MEA:乙醇胺 Μ I PA :異丙醇胺 NMP:N—曱基一2_吡咯烷酮 DMSO:二曱亞讽 THFA:四氫糖醇 BDG:二乙二醇單甲醚乙酸 E GB :乙二醇單甲醚乙酸 TEGB:三甘醇單甲醚乙酸 E G :乙二醇 P G :丙二醇 TEG:三甘醇 BTA:苯并三口坐 【表2】MEA: ethanolamine oxime I PA : isopropanolamine NMP: N-fluorenyl-2-pyrrolidone DMSO: diterpene THF: tetrahydro sugar BDG: diethylene glycol monomethyl ether acetate E GB : ethylene glycol single Methyl ether acetate TEGB: triethylene glycol monomethyl ether acetate EG: ethylene glycol PG: propylene glycol TEG: triethylene glycol BTA: benzotriene sit [Table 2]

區分 處理條件 剝離能力 防腐蝕能力 溫度（°C) 時間（分） 1 40 10 ◎ X 2 4 0 10 Δ X 3 40 10 Δ X 18 1315030 4 40 1 0 Δ X 5 40 1 0 Δ Δ 6 40 1 0 Δ X 7 40 1 0 Δ Δ 8 40 10 Δ Δ 9 40 1 0 Δ X 10 40 1 0 Δ Δ 11 40 1 0 Δ Δ 12 40 1 0 Δ △ 13 40 1 0 Δ X 14 40 - 0 Δ Δ 15 40 - 0 Δ Δ 16 40 1 0 ◎ ◎ 17 40 1 0 ◎ ◎ 18 40 1 0 ◎ ◎ 19 40 1 0 ◎ ◎ 2 0 40 1 0 ◎ ◎ 2 1 4 0 1 0 ◎ ◎ 2 2 40 1 0 ◎ ◎ 2 3 40 1 0 ◎ ◎ 24 40 10 ◎ ◎ 2 5 40 1 0 ◎ ◎ 2 6 40 1 0 ◎ ◎ 2 7 4 0 1 0 ◎ ◎ 2 8 40 1 0 ◎ ◎ 2 9 40 1 0 ◎ ◎ 3 0 40 1 0 ◎ ◎ 3 1 40 1 0 ◎ ◎ R . T . 1 0 ◎ ◎ 【圖式簡單說明】 第一圖：表示在半導體基板或玻璃基板、金屬或氧化膜層所順序 層積之基板表面上設置感光膠層者，而說明其曝光製程。 1315030 狱祕朗料，麵職前述感光 雜上騎f外線m絲狀 f =線’形成了前述模式的潛影之 ^以顯像液顯像，形成感光膠模式者，而說明其顧 製程。 第三圖:將模式之形成部位以濕式腐敍以及乾式腐餘來形成模式。 第四圖：關離敝錄絲模式形成频殘留之祕膠，說明 剝離製程之金屬模式形成製程之圖。 【主要元件符號說明】 1〇半導體基板或玻璃基板 20金屬或氧化膜層 30感光膠層Distinguishing treatment conditions Peeling ability Corrosion resistance temperature (°C) Time (minutes) 1 40 10 ◎ X 2 4 0 10 Δ X 3 40 10 Δ X 18 1315030 4 40 1 0 Δ X 5 40 1 0 Δ Δ 6 40 1 0 Δ X 7 40 1 0 Δ Δ 8 40 10 Δ Δ 9 40 1 0 Δ X 10 40 1 0 Δ Δ 11 40 1 0 Δ Δ 12 40 1 0 Δ Δ 13 40 1 0 Δ X 14 40 - 0 Δ Δ 15 40 - 0 Δ Δ 16 40 1 0 ◎ ◎ 17 40 1 0 ◎ ◎ 18 40 1 0 ◎ ◎ 19 40 1 0 ◎ ◎ 2 0 40 1 0 ◎ ◎ 2 1 4 0 1 0 ◎ ◎ 2 2 40 1 0 ◎ ◎ 2 3 40 1 0 ◎ ◎ 24 40 10 ◎ ◎ 2 5 40 1 0 ◎ ◎ 2 6 40 1 0 ◎ ◎ 2 7 4 0 1 0 ◎ ◎ 2 8 40 1 0 ◎ ◎ 2 9 40 1 0 ◎ ◎ 3 0 40 1 0 ◎ ◎ 3 1 40 1 0 ◎ ◎ R . T . 1 0 ◎ ◎ [Simplified description of the drawings] First figure: shows the sequential lamination of a semiconductor substrate, a glass substrate, a metal or an oxide film layer. The photosensitive layer is provided on the surface of the substrate, and the exposure process is explained. 1315030 Prison secret material, face the above-mentioned photosensitivity, riding on the outer line m wire f = line 'formed the latent image of the above model ^ to develop the imaging liquid to form the photosensitive glue mode, and explain its process. The third picture: the formation of the pattern is formed by wet rot and dry rot. The fourth picture: the secret glue that forms the frequency residue from the 敝 敝 silk pattern, which shows the metal pattern forming process of the stripping process. [Main component symbol description] 1〇Semiconductor substrate or glass substrate 20Metal or oxide film layer 30Acoustic layer

Claims (1)

1315030 十、申請專利範圍： 一種感光膠剝離液組成物，相對於組成物總量而言，含有 50重量％之烷醇胺化合物、i〇〜5〇重量％之烷基二醇 T燒基趟化合物、〇〜3 〇重量％之水溶性有機溶媒、〇 . 1〜 離1=4林_族氫氧化合物以及少量純水之感光膠剝 JUiJ.如ΐ請專利範圍第1項所述之一種感光膠剝離液組成物’ 二、巧為剷述之烧醇胺化合物係乙醇胺、二乙醇胺、三乙醇胺、 ^醇胺、二丙醇胺、三丙醇胺、異丙醇胺、二異丙醇胺、三異 °私丁醇胺、丁基乙醇胺、Ν—曱基乙醇胺、乙基二乙醇胺 或以上之混合物。 1胜睛ί利範圍第1項所述之—種感光膠剝離液組成物， ^醇胺輯職合物係乙醇胺、Ν—曱基乙醇胺、異 复特圍第1項所述之一種感光膠剝離液組成物， 卡必醇、三甘醇單乙鍵或其混合物。暖 利範圍第1項所述之—種感光膠剝離液組成物， =徵為^水溶性有機溶媒係四氫糖醇、Ν 2 烷_、二甲亞砜或其混合物。 乙比各 範圍第1項所述之 具特徵為則述芳香族氫氧基化合物 ^^物 〜氧化物、2-喧_、3—喧啉二彳紛勹啥啉f N 8—喹啉酚或其混合物。 4一四氫一 其特徵為二，膠剝離液組成物， 的變質或硬化_光_斜。誠切轉財所產生 211315030 X. Patent application scope: A photosensitive adhesive stripping liquid composition containing 50% by weight of an alkanolamine compound, i〇~5〇% by weight of an alkyl glycol T-based base relative to the total amount of the composition Compound, 〇~3 〇% by weight of water-soluble organic solvent, 〇. 1~ From 1=4 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Photosensitive adhesive stripping liquid composition' II. The alcoholic amine compound which is described as shovel is ethanolamine, diethanolamine, triethanolamine, alkanolamine, dipropanolamine, tripropanolamine, isopropanolamine, diisopropanol Amine, triisobutylbutanolamine, butylethanolamine, hydrazine-mercaptoethanolamine, ethyldiethanolamine or a mixture of the above. 1 wins the eye, the range of the photosensitive adhesive stripping solution described in the first item, the alcohol amine complex is ethanolamine, hydrazine-mercaptoethanolamine, and a kind of photosensitive adhesive according to item 1 of the special compound Stripping liquid composition, carbitol, triethylene glycol monoethyl bond or a mixture thereof. The composition of the photosensitive gel stripping solution described in the first paragraph of the warming range, = is a water-soluble organic solvent, tetrahydrosaccharitol, decane, dimethyl sulfoxide or a mixture thereof. The characteristics of the first aspect of the present invention are as described in the first item, the aromatic hydroxy compound, the oxide, the 2-oxo-, the 3-carboline, the quinone porphyrin f N 8 -quinolinol. Or a mixture thereof. 4 - tetrahydrogen - characterized by two, the composition of the gel stripping solution, deterioration or hardening _ light _ oblique. Sincerely turning the money to produce 21 _ 1315030 9.如申請專利範圍第1至7項中任一項所述之一種感光膠剝 離液組成物，其特徵為該感光膠剝離液組成物係被使用來剝離在 備製半導體元件或液晶顯示元件之製程中所殘留的感光膠膜。A photosensitive adhesive stripping liquid composition according to any one of claims 1 to 7, wherein the photosensitive adhesive stripping liquid composition is used to peel off a prepared semiconductor element or liquid crystal. The photosensitive film remaining in the process of the display element. 22twenty two
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US11639487B2 (en) 2013-12-06 2023-05-02 Fujifilm Electronic Materials U.S.A., Inc. Cleaning formulation for removing residues on surfaces
US11407966B2 (en) 2018-03-28 2022-08-09 Fujifilm Electronic Materials U.S.A., Inc. Cleaning compositions

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CN1261827C (en) 2006-06-28
JP3953476B2 (en) 2007-08-08
KR100647516B1 (en) 2006-11-23

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