TW418344B - Photomask raw glass with surface film protective layer and its production and protective layer forming liquid - Google Patents
Photomask raw glass with surface film protective layer and its production and protective layer forming liquid Download PDFInfo
- Publication number
- TW418344B TW418344B TW088118727A TW88118727A TW418344B TW 418344 B TW418344 B TW 418344B TW 088118727 A TW088118727 A TW 088118727A TW 88118727 A TW88118727 A TW 88118727A TW 418344 B TW418344 B TW 418344B
- Authority
- TW
- Taiwan
- Prior art keywords
- protective layer
- emulsion
- film surface
- acetate
- mixed
- Prior art date
Links
Landscapes
- Preparing Plates And Mask In Photomechanical Process (AREA)
- Paints Or Removers (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
418344418344
五、發明說明（i) 技術镅迠 I C用導線架或彩色電視用陰影遮罩、高密度印刷線路 板、小型齒輪、薄型顯示器（L C D、P D p )之電極或 間隔壁等之製造或形成時所必要的微細精密加工方法已有 所謂光學製造加工法（Photo-FabricatiorO廣為普及使 用。本發明係關於在該種光學製造加工法所使用的具有膜 面保護層之光罩原版及其製造方法以及保護層形成液之 術。V. Description of the Invention (i) Technology: When manufacturing or forming lead frames for ICs or shadow masks for color TVs, high-density printed circuit boards, small gears, electrodes or partition walls of thin displays (LCD, PD p), etc. The necessary micro-precision processing method has been widely used by the so-called optical manufacturing method (Photo-FabricatiorO). The present invention relates to a photomask original plate with a film surface protective layer used in this optical manufacturing processing method and a manufacturing method thereof And the formation of protective layer of fluid.
於該光學製造加工，有以耐蝕性覆膜包覆加工面，除去 一部份，使除去的面被溶解除去之光蝕刻加工法（ph〇t〇 -Etching)，以及以電鑄方式使金屬成長的光電成形法 (Photo-E 1 ectro-f.orming) f：。 無論在哪個場合，都是屬於把不加工的部份以具有耐蝕 陡的覆膜包覆的方法，係經過遮罩（Masking)工程而進行 的加工方法。此遮罩加工，係以對紫外線具有感光性的感 光性材料所製作的光罩上，重疊精密製作的相片原稿，經 過曝光、顯影、乾燥而進行的攝影法為一般習闬方法。使 用此攝影法的光罩原版，幾乎全部都是在基板上使明膠等In this optical manufacturing process, there are a photoetching process (ph0-Etching) in which a processed surface is covered with a corrosion-resistant film, a part of which is removed, and the removed surface is dissolved and removed, and the metal is electroformed. Photoelectric forming method (Photo-E 1 ectro-f.orming) f :. In any case, it is a method of covering the unprocessed part with a film with a corrosion-resistant steepness, which is a processing method performed through a masking process. This mask processing is a conventional method in which a photo manuscript made by superimposing a precision-made photo manuscript on a photomask made of a photosensitive material that is sensitive to ultraviolet rays is exposed, developed, and dried. Almost all of the original masks using this photography method are gelatin, etc. on the substrate.
為主成份的乳液感光乳劑層附著成為膜面狀態而形成者 (乳液光罩）。 本發明，係關於此光罩板板的光罩，特別是關於層積形 成供保護乳液光罩之用的膜面保護層的技術。 背景技術 從前的光罩原版，以目的之圖面或資料為基礎藉由An emulsion photosensitive emulsion layer containing a main component is formed by forming a film surface state (emulsion mask). The present invention relates to a photomask of the photomask plate, and more particularly to a technique of laminating a film surface protective layer for protecting an emulsion photomask. 2. Description of the Related Art Previous photomask originals were based on the purpose of drawing or data
Λ 18344 五、發明說明（2) 系統等作成曝光裝置（光學繪圖機等）用的資料，藉由此 資料於乳液乾板上描繪記錄圖形，使該被描繪的乾板，經 過顯影、固定、水洗、乾燥、修正、檢查之工程而完成光 翠原版。但是，如此製作的光罩原版的乳液光罩（乳液感 光乳劑層的膜面）’因為是以明膠為主成份的緣故，所以 相當柔軟’有膜面容易受傷的缺點。此外，還有在該光罩 的膜面附著到指紋等髒污時，除去相當困難的缺點。Λ 18344 V. Description of the invention (2) The system and other materials are used to create data for the exposure device (optical plotter, etc.). Based on this data, the recorded graphics are drawn on the dry emulsion board, and the drawn dry board is developed, fixed, washed, Drying, correction and inspection work to complete the original version of Guangcui. However, the emulsion mask (the film surface of the emulsion-sensitive emulsion layer) of the original photomask produced in this manner is relatively soft because gelatin is the main component, and has the disadvantage that the film surface is easily damaged. In addition, when the film surface of the photomask is attached to dirt such as fingerprints, it is disadvantageously difficult to remove.
作為解消該缺點的對策之一，首先有在該光罩膜面上層 疊8#〜12μ程度的薄膜作為保護膜的方法。但是此層疊 保護膜法’由於中介著保護膜，使得紫外線透過率降低 50%程度的緣故，有著感度變差的困難處。 一第2對策是將該光罩變更為乳液感光乳劑層的膜面（乳液 光罩）’在玻璃基板上以含有鉻的金屬膜（Cr9〇〇A)成形圖 案（鉻遮罩）的方法，但是鉻遮罩非常昂貴（價袼是乳液光 單的4〜5倍）’有著欠缺實用性的缺點。 本發明的目的，係藉由在以從前製法所製作的乳液光罩 ^形，第2層之保護層，而提供克服容易損傷、或膜面容 的缺點’同時防止如層積板保護膜那般降低紫外線 透過率’而價廉且具有耐久性的光罩。As one of the countermeasures for eliminating this disadvantage, there is first a method of laminating a thin film of about 8 to 12 µ on the photomask film surface as a protective film. However, this laminated protective film method has a difficulty that the sensitivity is deteriorated because a protective film is interposed, and the ultraviolet transmittance is reduced by about 50%. A second measure is a method of changing the photomask to the film surface (emulsion photomask) of the emulsion photosensitive emulsion layer, and forming a pattern (chrome mask) on a glass substrate with a metal film (Cr900) containing chromium. However, the chromium mask is very expensive (the price is 4 to 5 times that of the emulsion light sheet). It has the disadvantage of lacking practicality. The object of the present invention is to provide a protective layer of the second layer in the shape of an emulsion mask made by the previous method, to provide the advantages of overcoming shortcomings such as damage to the surface of the film or the surface of the film. A low-cost and durable photomask that reduces UV transmittance.
發明之掘禾 置取ΐ專利的第1發明’係一種具有膜面保護層之光 '乳液本’罢^特徵為：在基板上形成乳液感光乳劑層的膜面 、 而成的光罩原版的乳液感光乳劑層的膜面上， 、佈以在氟化樹脂與壓克力樹脂為主體的混合樹脂溶液與The first invention of the patent of the invention is a light "emulsion" with a film surface protective layer. It is characterized by forming a film surface of an emulsion photosensitive emulsion layer on a substrate, and a photomask original plate. The film surface of the emulsion photosensitive emulsion layer is composed of a mixed resin solution mainly composed of a fluorinated resin and an acrylic resin, and
418344 五、發明說明（3) 以聚異氰酸預聚體為主體的混合溶液被調和混合而成的保 護層形成液，使修邊層積形成2液架橋型的膜面保護層之' 具有膜面保護層之光罩原版。 <1 第1發明’特徵在於在基板上形成乳液感光乳劑層的膜 面（乳液光罩）而成的先罩原版上，層積形成作為第2層的2 液架橋型膜面保護層這一點。該2液架橋型的膜面保護 層’係以氟化樹脂與壓克力樹脂之混合樹脂溶液與以聚異 氰酸預聚體為主體的混合溶液在被調和混合修邊時可以^ 由化學變化硬化的2液架橋型合成樹脂製的膜面保護層。 該膜面保護層’密著性優異，對於壓克力樹脂、聚氯乙稀 樹脂、聚尿烷樹脂、玻璃等由軟質到硬質寬廣種類的基材 形成耐久性優異的覆膜，具有為無色透明液體、不易由於 折曲、延伸而引起白化，不會降低紫外線透過率等特性。 由於這樣的特性非常適合用於保護光罩原版。 所欲取得專利的第2發明，係一種具有膜面保護層之光 罩原版’其特徵為：在基板上形成乳液感光乳劑層的膜面 (乳液光罩）而成的光罩原版的乳液感光乳劑層的膜面上， 塗佈以在氟化樹脂與壓克力樹脂的混合樹脂内混合正乙酸 丁酯與曱基乙基甲酮（MEK)與甲基異丁基甲酮（MIBK)之溶 劑調和而成的2液架橋型防污性表面塗層劑為主劑，對此 調和混合聚異氰酸預聚體與乙酸乙酯而成的架橋硬化劑， 及正乙酸丁酯與曱基乙基甲酮（MEK)與乙酸甘醇單***酯 (ethylene glycol monoethy 1 ether acetate)所構成的 稀釋劑混合而成的保護層形成液，使修邊層積形成膜面保418344 V. Description of the invention (3) A protective layer forming solution prepared by mixing a mixed solution mainly composed of a polyisocyanate prepolymer, so that the trimming layer is formed into a two-liquid bridge type film surface protective layer. The original mask of the film surface protective layer. < 1 The first invention 'is characterized in that a pre-mask original plate formed by forming a film surface (emulsion mask) of an emulsion photosensitive emulsion layer on a substrate is laminated to form a 2 liquid bridge type film surface protective layer as a second layer. a little. The two-liquid bridge type film surface protective layer is a mixed resin solution consisting of a fluorinated resin and an acrylic resin and a mixed solution mainly composed of a polyisocyanate prepolymer, which can be blended and trimmed. Varying hardened 2 liquid bridge type synthetic resin film surface protective layer. This film surface protective layer is excellent in adhesion and forms a durable film for a wide range of substrates from soft to hard, such as acrylic resin, polyvinyl chloride resin, polyurethane resin, and glass, and is colorless Transparent liquid, easy to cause whitening due to bending and elongation, and does not reduce UV transmittance and other characteristics. Because of this feature, it is very suitable for protecting the original mask. The second invention to be patented is a photomask original plate having a film surface protective layer, which is characterized in that the emulsion photosensitivity of the photomask original plate is formed by forming a film surface (emulsion photomask) of an emulsion photoemulsion layer on a substrate. The film surface of the emulsion layer is coated with a solvent blend of butyl acetate, fluorenyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK) in a mixed resin of a fluorinated resin and an acrylic resin. The two-liquid bridging type antifouling surface coating agent is used as the main agent, and a bridging hardener made by mixing a polyisocyanate prepolymer and ethyl acetate, and n-butyl acetate and fluorenylethyl A protective layer forming solution composed of a ketone (MEK) and a diluent composed of ethylene glycol monoethy 1 ether acetate, so that the trimming layer is formed to form a film surface protection.
88118727.ptd 第7頁 418344 五、發明說明（4) 護層之具有膜面保護層之光罩原版。88118727.ptd Page 7 418344 V. Description of the invention (4) The original version of the photomask with a protective layer on the surface.
第2發明，把2液架橋型防污性表面塗層劑（主劑）與架橋 硬化劑溶於指定溶劑使其溶液化，同時將這2液適度稀釋 塗饰為薄膜狀’以容易控制化學變化的進度的稀釋劑創製 新的光罩保護層形成液，藉由將此塗佈、使修邊而層積形 成有實用性的膜面保護層之具有膜面保護層之光罩原版。 亦即’藉由在從前的光罩原版的乳液感光乳劑層之上塗佈 保護層形成液而層積形成不損及光罩的功能性強化耐久性 的臈面保護層作為第2層這一點為其特徵。該膜面保護膜 的主劑之2液架橋型防污性表面塗層劑’係把氟化樹脂與 壓克力樹脂的混合樹脂以溶劑溶解成為樹脂溶液狀之密著 性優異的2液架橋型的表面塗層劑，對於壓克力樹脂、聚 氯乙稀樹脂、聚尿烷樹脂、玻璃等由軟質到硬質寬廣 的基材形成耐久性優異的覆膜，具有為無色透=:種二 易由於折曲、延伸而引起白化，不會降低紫外線透過率等 特性。 此外’架橋硬化劑，係將聚異氰酸預聚體（構造式為： 六曱撐二異氰酸之三羥甲基丙烷加成化合物）以溶劑溶解 而成的混合溶液，這也藉由與透明度高的主劑混合而反應 形成架橋（侧鏈）同時硬化’形成透明度高的覆膜。 該保護層形成液，係以把該混合樹脂以溶劑溶解形成樹 脂溶液狀的2液架橋型的表面塗層劑作為主劑，於此混合 架橋硬化劑與稀釋液者。使用的溶劑或稀 工程結束的話不會殘存，所以形成的2液架橋劑型的膜為:保]In the second invention, a two-liquid bridging type antifouling surface coating agent (main agent) and a bridging hardener are dissolved in a designated solvent to make it a solution, and the two liquids are moderately diluted and coated into a thin film shape to facilitate chemical control. A diluent with a changing schedule creates a new mask protective layer forming liquid, and by applying this, trimming and laminating to form a practical mask original layer with a film protective layer. That is, 'the protective layer forming liquid is coated on the former emulsion photosensitive emulsion layer of the original mask original layer to form a second surface protective layer which does not impair the functionality of the photomask and enhances durability as the second layer. For its characteristics. The two-liquid bridging type antifouling surface coating agent of the main agent of this film surface protective film is a two-liquid bridging bridge which dissolves a mixed resin of a fluorinated resin and an acrylic resin in a solvent to form a resin solution with excellent adhesion. Type surface coating agent. It has excellent durability for a wide range of soft to hard substrates, such as acrylic resin, polyvinyl chloride resin, polyurethane resin, and glass. It is easy to cause whitening due to bending and elongation, and does not reduce the characteristics such as ultraviolet transmittance. In addition, the “cross-linking hardener” is a mixed solution obtained by dissolving a polyisocyanate prepolymer (structure formula: hexamethylene diisocyanate trimethylolpropane addition compound) in a solvent. It is mixed with a highly transparent main agent to react to form a bridge (side chain) and harden at the same time to form a highly transparent coating. The protective layer forming liquid is a two-liquid bridge type surface coating agent in which the mixed resin is dissolved in a solvent to form a resin solution as a main agent, and a bridge hardener and a diluent are mixed here. The solvent used or the dilute process will not remain after the project is completed.
88118727.ptd 第8頁 41834488118727.ptd Page 8 418344
護層，維持其主劑或架橋硬化劑的原來特性，因此本發明 j’、有膜面保護層之光罩原版，成為不易損傷、不易髒 /亏不會降低表外線透過率，而價廉且具有耐久性的光 所欲取得專利的第3發明，係一種具有膜面保護層之光 罩f版’其特徵為：在玻璃基板上形成乳劑層的膜面（乳 液光罩）而成的光罩原版的乳液感光乳劑層的膜面上，塗 佈以在氣化樹脂與壓克力樹脂的混合樹脂内混合正乙酸丁 酯與甲基乙基甲醐（MEK)與曱基異丁基甲酮（MIBK)之溶劑 調和而成的2架橋型防污性表面塗層劑為主劑佔25〜509ί， Λ 對此調和混合聚異氰酸預聚體與乙酸乙酯而成的架橋硬化'、 劑佔1〜6% ’及正乙酸丁酯與曱基乙基甲酮（ΜΕΚ)與乙酸甘 醇單***酯（ethylene glycol monoethyl ether acetate)所構成的稀釋劑佔46〜75混合而成的保護層形成 液’使其產生化學變化而層積形成膜面保護層之具有膜面 保護層之光罩原版。 第3發明’係藉由特定構成保護層形成液的主劑與架橋 硬化劑與稀釋劑之構成成份與各材料的混合比例，而供具 體化更佳的具有膜面保護層之光罩原版之發明。 .、 所欲取得專利的第4發明，係如第2發明或第3發明之具 ' ' 有膜面保護層之光罩原版，而以構成保護層形成液的主劑 之2液架橋型防污性表面塗層劑，係於氟化樹脂5〜20 %與 壓克力樹脂1 〇〜3 0 %的混合樹脂内，混合正乙酸丁酯2 0〜 3 0%與甲基乙基甲酮（MEK)30〜40%與甲基異丁基甲酮The protective layer maintains the original characteristics of its main agent or bridging hardener. Therefore, the j ', the original mask with a film surface protective layer according to the present invention, is not easy to be damaged, and is not easy to be soiled / defective. The third invention which is patented for durable light is a photomask f version with a film surface protective layer, which is characterized by forming a film surface (emulsion photomask) of an emulsion layer on a glass substrate. The film surface of the original emulsion emulsion emulsion layer of the photomask is coated to mix n-butyl acetate, methyl ethyl formamidine (MEK), and fluorenyl isobutyl ketone in a mixed resin of vaporized resin and acrylic resin. (MIBK) solvent blended 2 bridge type antifouling surface coating agent as the main agent accounted for 25 ~ 509 ί, Λ for this blending mixed polyisocyanate prepolymer and ethyl acetate bridge hardening ', The agent accounts for 1 ~ 6% 'and the diluent composed of n-butyl acetate, methyl ethyl ketone (MEK) and ethylene glycol monoethyl ether acetate accounts for 46 ~ 75. Layer-forming liquid 'causes it to undergo chemical changes to form a film surface The covering mask precursor having a protective layer of the membrane surface. The third invention is a mixture of the main component of the protective layer forming liquid, the bridging hardener, and the diluent, and the proportion of each material, so that the original mask with a film surface protective layer can be better embodied. invention. . The 4th invention to be patented is the original version of the photomask with a protective layer on the film surface like the 2nd or 3rd invention, and the 2 liquid bridge type anti-blocking agent is the main agent of the protective layer forming liquid. Fouling surface coating agent, mixed with 5 ~ 20% of fluorinated resin and 10 ~ 30% of acrylic resin, mixed with n-butyl acetate 20 ~ 30% and methyl ethyl ketone (MEK) 30 ~ 40% with methyl isobutyl ketone
88118727.ptd 第9頁 _ 41B344_ 五、發明說明（6) (ME IBK) 5〜1 0%之溶劑調和的混合樹脂溶液；架橋硬化 劑，係混合聚異氰酸預聚體70〜80%與乙酸乙酯20〜30%而 成的混合溶液；稀釋劑，係混合正乙酸丁酯1 〇〜2 0 %與甲 基乙基甲酮（MEK)50〜60%與乙酸甘醇單***酯（ethylene glycol monoethyl ether acetate)25 〜40% 所構成混合溶 液為其特徵之具有膜面保護層之光罩原版。 第4發明，係作為第2發明或第3發明的從屬項，藉由更 具體地特定構成保護層形成液的主劑與架橋硬化劑與稀釋 劑之構成成份與各材料的混合比例，而具體化較佳的具有 膜面保護層之光罩原版之發明。 所欲取得專利的第5發明，係一種具有膜面保護層之光 罩原版的製造方法’其特徵為：準備在基板上形成乳液感 光乳劑層的膜面（乳液光罩）而成的乳液乾板，於此描繪後 進行顯影、固定、水洗、乾燥等顯影處理之後，經過檢 查、修正處理工程而製作的光罩原版的乳液感光乳劑層的 膜面上；以浸泡塗佈、旋轉塗佈、滚筒塗佈、喷霧塗佈等 方法’塗佈在氟化樹脂與壓克力樹脂的混合樹脂内，以混 合正乙酸丁酯與曱基乙基曱酮（MEK)與甲基異丁基曱酮 (ΜIBK)之溶劑調和而成的2液架橋型防污性表面塗層劑為 主劑’對此調和混合聚異氰酸預聚體與乙酸乙酯而成的架 橋硬化劑’及正乙酸丁酯與甲基乙基甲酮（)與乙酸甘 醇單乙 自旨（ethylene glycol monoethyl ether acetate)所構成的稀釋劑混合而成的保護層形成液之後， 藉由修邊處理，層積形成膜面保護層。88118727.ptd Page 9_ 41B344_ V. Description of the invention (6) (ME IBK) 5 ~ 10% solvent-blended mixed resin solution; bridging hardener, which is a mixed polyisocyanate prepolymer 70 ~ 80% and A mixed solution of 20 ~ 30% ethyl acetate; a diluent, which is a mixture of butyl n-acetate 10 ～ 20% and methyl ethyl ketone (MEK) 50 ～ 60% and ethylene glycol monoethyl ether ( Ethylene glycol monoethyl ether acetate) 25 ~ 40% The original solution of the photomask with a protective layer on the surface is a mixed solution. The fourth invention is a subordinate item of the second invention or the third invention, and specifically specifies the mixing ratio of the constituents of the main agent constituting the protective layer forming solution, the bridging hardener, and the diluent with each material, and more specifically, The invention of a better original mask with a film surface protective layer. The fifth invention to be patented is a method for manufacturing a photomask original plate having a film surface protective layer, which is characterized in that an emulsion dry plate prepared by forming a film surface (emulsion mask) of an emulsion photosensitive emulsion layer on a substrate is prepared. After the drawing, development, fixing, water washing, drying and other development processes are performed, and the film surface of the emulsion photosensitive emulsion layer of the photomask original plate produced after inspection and correction processing is performed; immersion coating, spin coating, and roller Coating, spray coating and other methods' coated in a mixed resin of fluorinated resin and acrylic resin to mix n-butyl acetate with fluorenyl ethyl fluorenone (MEK) and methyl isobutyl fluorenone (MIBK) solvent-based two-liquid cross-linking antifouling surface coating agent as the main agent 'a cross-linking hardener made by mixing a polyisocyanate prepolymer and ethyl acetate' and butyl n-acetate A protective layer forming solution composed of an ester, methyl ethyl ketone (), and a diluent composed of ethylene glycol monoethyl ether acetate is then laminated to form a film by trimming treatment. Face protection.
第10頁 8811S727.ptd 418344 五、發明說明（7) _ 該第5發明，係罝古槪：， 之發明。係於製作的来置呆5蒦層之光罩原版的製造方法 液之後，以藉由:’塗佈指定的保護層形成 膜面保護層的方式形=藉由化學變化與乾燥而層積 塗佈、滾筒塗佈你ί伟方法雖有浸泡塗佈、旋轉 較佳者為採；噴霧= 成臈厚數微米的極薄膜， 臈面保護層I之光罩a版的制ί作者。才目關於本發明的具有 <1 層形成液，以及進行均勺的；：ί ’只要調製適當的保護 膜面的平面性良佈處理’自然就可以製作出 拖光研磨處理等作f工程：層，因為不需要 成：第6發明，係一種光罩原版用保護層形 、、’「特彳政為：在氟化樹脂與壓克力樹脂的混合樹脂 ’以混合正乙酸丁酯與甲基乙基甲酮（ΜΕΚ)與甲基異丁 基甲酮（ΜΙΒΚ)之溶劑調和而成的2液架橋型防污性表面塗 層劑為主劑’對此調和混合聚異氰酸預聚體與乙酸乙酯而 成的架橋硬化劑，及正乙酸丁酯與甲基乙基甲酮（ΜΕκ)) 與乙 8义甘醇單乙趙酯（ethyiene glycol monoethyl ether acetate)所構成的稀釋劑混合而成。 所欲取得專利的第7發明，係一種光罩原版用保護層形 成液’其特徵為：主劑之2液架橋型防污性表面塗層劑， 係於氟化樹脂5〜20%與壓克力樹脂10〜30%的混合樹脂 内，混合正乙酸丁酯20〜30%與甲基已基曱酮（MEK)30〜 40%與甲基異丁基甲酮（MIBK)5〜10%之溶劑調和的混合樹Page 10 8811S727.ptd 418344 V. Description of the invention (7) _ The fifth invention is an ancient invention. After the manufacturing method of the photomask original plate containing 5 layers, it is formed by: 'applying a specified protective layer to form a film surface protective layer = layered coating by chemical change and drying Although the method of coating cloth and roller is dip coating, it is better to rotate; spray = to make a thin film with a thickness of several micrometers, the author of the mask a version of the surface protection layer I. The purpose of the present invention is to provide a layer-forming solution of <1 layer, and to uniformly disperse it: ‚'As long as a proper flat cloth treatment with a suitable protective film surface is prepared', a polishing process such as polishing can be produced naturally. : Layer, because it does not need to be formed: The sixth invention is a protective layer for the original mask, "" Special government policy: a mixed resin of fluorinated resin and acrylic resin "to mix n-butyl acetate with A two-component bridge type antifouling surface coating agent based on the solvent blending of methyl ethyl ketone (MEK) and methyl isobutyl ketone (ΜΙΒΚ) as the main agent. In this blend, a polyisocyanate prepolymer is blended. Cross-linking hardener made with ethyl acetate, and diluent consisting of n-butyl acetate and methyl ethyl ketone (MEK)) and ethyiene glycol monoethyl ether acetate The seventh invention to be patented is a protective layer forming solution for a photomask original plate, which is characterized in that the main agent is a two-liquid bridge type antifouling surface coating agent, which is based on a fluorinated resin 5 to 20 % And acrylic resin mixed with 10 ~ 30% resin Mixed tree with 20 ~ 30% of butyl acid and 30 ~ 40% of methylhexylfluorenone (MEK) and 5 ~ 10% of methyl isobutyl ketone (MIBK)
88118727.ptd 第11頁 418344 五、發明說明（8) 脂溶液；架橋硬化劑，係混合聚異氰酸預聚體7 0〜8 〇 %與 乙酸乙酯2 0〜3 0 %而成的混合溶液；稀釋劑，係混合玉乙 酸丁酯10〜20%與f基乙基甲酮（MEK)50〜60%與乙酸甘醇 單***酯（ethylene glycol monoethyl ether acetate)25〜40%所構成混合溶液；而以前述主劑25〜 50%，前述架橋硬化劑1〜6%，稀釋劑46〜75%的比例調和 混合而成。88118727.ptd Page 11 418344 V. Description of the invention (8) Fat solution; bridging hardener, which is a mixture of polyisocyanate prepolymer 70 ~ 80% and ethyl acetate 20 ~ 30% Solution; thinner, mixed with 10 ~ 20% of butyl acetate and 50 ~ 60% of f-ethyl ethyl ketone (MEK) and 25 ~ 40% of ethylene glycol monoethyl ether acetate A solution; and a mixture of 25 to 50% of the aforementioned main agent, 1 to 6% of the aforementioned bridging hardener, and 46 to 75% of the diluent.
第7發明’係藉由更具體地特定構成光罩原版用保護層 形成液的主劑與架橋硬化劑與稀釋劑之構成成份與各材料 的混合比例’而可以具體化較佳的具有膜面保護層之光罩 原版之發明。 圖面之簡單說明 第1圖係顯示相關於本發明的具有膜面保護層之光罩原 版的製造工程之流程圖’與顯示伴隨著相關於本發明的具 有膜面保護層之光罩原版的製造工程的進行之構造變化的 說明圖》 供f施發明之最佳形態 以下根據圖示實施例詳細說明本發明。 0 第1圖係顯示具有膜面保護層之光罩原版的製造工程之 流程圖，與顯示伴隨著具有膜面保護層之光罩原版的製造 工程的進行之構造變化的說明圖。 第1工程’係根據由客戶所提供的圖面或者資料，藉由 CAD系統作成曝光裝置（光學繪圖機等）用的資料。 第2工程，係於玻璃基板上形成乳液感光乳劑層的膜面The seventh invention "specifies the mixing ratio of the constituents of the main component, the bridging hardener, and the diluent, and the respective materials of the protective layer forming solution for the photomask original plate more specifically", and it is possible to specify a preferable film surface. The invention of the original mask of the protective layer. Brief Description of the Drawings Fig. 1 is a flowchart showing a manufacturing process of a mask original with a film surface protective layer according to the present invention, and a display showing a process accompanying the mask original with a film surface protective layer according to the present invention. [Explanation diagram of structural changes in progress of manufacturing process] The best mode for applying the invention The invention will be described in detail below with reference to the illustrated embodiments. 0 Fig. 1 is a flowchart showing a manufacturing process of a mask original plate having a film surface protective layer, and an explanatory diagram showing a structural change accompanying the manufacturing process of a mask original plate having a film surface protective layer. The first process is to create data for an exposure device (optical plotter, etc.) using a CAD system based on drawings or data provided by the customer. The second process is to form a film surface of an emulsion photosensitive emulsion layer on a glass substrate
88118727.ptd 第12頁 41834488118727.ptd Page 12 418344
(:圖液形光罩)而成的乳液乾板上’根據前述資料以输圖機插 固定、水 第3工程係將描繪後的乳液乾版，進行顯影 洗、乾燥等顯影處理。 與藉由外觀檢 製法，係根據 第4工程係藉由測長機進行各部的測定， 査機進行缺陷檢查。 第5工程係修正白缺陷、黑缺陷。從前的 這些工程完成光罩原版。(: Liquid-shaped photomask) The emulsion dry plate ′ is inserted and fixed with a plotter according to the foregoing information, and the third engineering department develops the dried emulsion after drawing, and performs development processing such as washing and drying. According to the appearance inspection method, the measurement of each part is performed by the length measuring machine according to the fourth engineering department, and the inspection machine performs the defect inspection. The fifth engineering department corrected white defects and black defects. These previous projects completed the original mask.
>第6工程，本發明係於攝影原版之光罩原版塗佈保護層 形成液而以層積膜面保護層的方式形成。 該保護層形成液，其主劑之2液架橋型防污性表面塗層 劑’係於氟化樹脂5〜2 0 %與壓克力樹脂1 〇〜3 0 %的混合樹 脂内，混合正乙酸丁酯20〜30%與甲基乙基甲酮（MEK)30〜 40%與f基異丁基甲酮（MIBK)5〜10%之溶劑調和的混合樹 脂溶液；架橋硬化劑，係混合聚異氰酸預聚體70〜80%與 乙酸乙酯2 0〜3 0 %而成的混合溶液；稀釋劑，係混合正乙 酸丁酯10〜20%與甲基乙基甲酮（MEK)50〜60%與乙酸甘醇 單乙 醋（ethylene glycol monoethyl ether acetate) 25〜40%所構成混合溶液；而以前述主劑25〜 50%，前述架橋硬化劑1〜6%，稀釋劑46〜75%的比例調和 混合而成。 又，詳細說明保護層形成液的調和比率時’以如表1所 示者較佳。 表1> In the sixth process, the present invention is formed by applying a protective layer forming solution to a mask original plate of a photographic original plate and laminating a film surface protective layer. This protective layer forming liquid is composed of a two-liquid bridge type antifouling surface coating agent 'of the main agent, which is contained in a mixed resin of 5 to 20% of fluorinated resin and 1 to 30% of acrylic resin. Mixed resin solution of 20 ~ 30% of butyl acetate and 30 ~ 40% of methyl ethyl ketone (MEK) and 5 ~ 10% of f-based isobutyl ketone (MIBK); a bridging hardener, a mixed polyisocyanate A mixed solution of 70 to 80% of cyanic acid prepolymer and 20 to 30% of ethyl acetate; a diluent, which mixes 10 to 20% of n-butyl acetate with 50% of methyl ethyl ketone (MEK) 60% and ethylene glycol monoethyl ether acetate (25 ~ 40%) mixed solution; and the aforementioned main agent 25 ~ 50%, the aforementioned bridging hardener 1 ~ 6%, diluent 46 ~ 75% Blended in proportions. When the blending ratio of the protective layer-forming liquid is described in detail, it is preferable to use those shown in Table 1. Table 1
88118727.ptd 第13頁 418144 五、發明說明（ίο) 主劑 硬化劑 稀釋劑 樹脂 氟化樹脂 5 〜20% 壓克力樹脂 10 〜30% 聚異氰酸預聚體 70 〜80% 溶劑 正乙酸丁酯 20 〜30% MEK 30 〜40% MIBK 5 〜1 0 % 乙酸乙酯 20 〜30% 正乙酸丁酯 10 〜20% MEK 50 〜60% 乙酸甘醇單己醚酯 25 〜40% 固體成 份濃度 30 〜33% 調和比率 2 5〜5 0 % 1% 〜6% 46% 〜75% 本實施例之保護層形成液的調和例如下。 <第1例> 主劑 1 0 0 g (成份） 氟化樹脂 10〜20% 壓克力樹脂 10〜20% 甲基乙基曱酮（MEK) 30〜40% 曱基異丁基曱酮（MIBK) 5〜10 % 正乙酸丁酯 2 0〜3 0 % 架橋硬化劑 6 g (成份）聚異氰酸預聚體 70〜80%88118727.ptd Page 13 418144 V. Description of the invention (ίο) Main agent hardener diluent resin fluorinated resin 5 to 20% acrylic resin 10 to 30% polyisocyanate prepolymer 70 to 80% solvent n-acetic acid Butyl 20 ~ 30% MEK 30 ~ 40% MIBK 5 ~ 10% ethyl acetate 20 ~ 30% n-butyl acetate 10 ~ 20% MEK 50 ~ 60% glycol monohexyl acetate 25 ~ 40% solid content The concentration is 30 to 33%. The blending ratio is 25 to 50%. 1% to 6%. 46% to 75%. The blending of the protective layer forming liquid of this embodiment is as follows. < First example > Base agent 100 g (component) Fluorinated resin 10 ~ 20% Acrylic resin 10 ~ 20% Methyl ethyl fluorenone (MEK) 30 ~ 40% fluorenyl isobutyl fluorene Ketone (MIBK) 5 to 10% n-butyl acetate 2 0 to 30% bridging hardener 6 g (ingredient) polyisocyanate prepolymer 70 to 80%
88118727.ptd 第U頁 4 18344 五、發明說明（11) 乙酸乙酯 20 〜30% 稀釋劑3 0 0g (成份）甲基乙基曱酮（MEK) 5 0 〜6 0 % 正乙酸丁酯 10 〜20% 乙酸甘醇單***酯（ethylene glycol monoethyl ether acetate) 25 〜40% <苐2例> 主劑 100g C成份）說化樹脂 5 〜10% 壓克力樹脂 20 〜30% 甲基乙基甲酮（MEK) 3 0 ~ 4 0 % 甲基異丁基甲酮（MIBK) 5 〜1 0% 正乙酸丁酯 20 〜30% 架橋硬化劑 3g (成份）聚異氰酸預聚體 70 〜80% 乙酸乙酯 20 〜30% 稀釋劑 400g (成份）甲基乙基甲酮（MEK) 50 〜60% 正乙酸丁酯 10 〜20% 乙酸甘醇單乙酸酯（ethylene glycol monoethyl ether acetate) 2 5 ~ 4 0 % 此外’形成膜面保護層的方法， 如第2表所示可以採用 浸泡塗佈、旋轉塗佈、滾筒塗佈、 喷霧塗佈等方法。本實 施例採用喷霧塗佈。88118727.ptd Page U 4 18344 V. Description of the invention (11) Ethyl acetate 20 ~ 30% Diluent 3 0 0g (ingredient) methyl ethyl fluorenone (MEK) 5 0 ~ 60 0% n-butyl acetate 10 ～ 20% ethylene glycol monoethyl ether acetate 25 ～ 40% < 2 cases > base agent 100g C component) chemical resin 5 ～ 10% acrylic resin 20 ～ 30% methyl Ethyl ketone (MEK) 3 0 ~ 40% Methyl isobutyl ketone (MIBK) 5 ～ 10% n-butyl acetate 20 ～ 30% bridging hardener 3g (ingredient) polyisocyanate prepolymer 70 ～ 80% ethyl acetate 20 to 30% diluent 400g (composition) methyl ethyl ketone (MEK) 50 to 60% butyl acetate 10 to 20% ethylene glycol monoethyl ether acetate 2 5 ~ 40% In addition, the method of forming a film surface protective layer may be a method such as dip coating, spin coating, roll coating, or spray coating, as shown in Table 2. This embodiment uses spray coating.
88118727.ptd 第15頁 ^ 18344 五、發明說明（12) 又，構成前述保護層形成液的物質名稱的化學式或構造 式如下。 表2 物質名稱 化學式或構造式 氟化樹脂 — 壓克力樹脂 — 聚異氰酸預聚體 六甲撐二異氰酸之三羥曱基丙 烧加成化合物 甲基乙基甲酮（MEK) c4h8o 甲基異丁基曱酮（MIBK) c6h120 正乙酸丁酯 Hi2 〇2 乙酸乙酯 ch3cooc2h5 乙酸甘醇單***酯 ch3cooch2ch2oc2h5 表3 塗佈方法 (1 )對應尺寸（2 )塗佈厚度（3)平面性 喷霧塗佈 (1) 800 Xl350m/m 以下 (2) 1〜2弘m (3) 佳 旋轉塗佈 (1)500 X600m/m 以下 (2 ) 1〜2夂m (3 )最佳 ， 浸泡塗佈 ( 1 ) 5 00 X 600m /m ΐλ Τ (2) 3 〜8 /ζιπ (3) 佳88118727.ptd Page 15 ^ 18344 5. Description of the invention (12) In addition, the chemical formula or structural formula of the name of the substance constituting the protective layer forming liquid is as follows. Table 2 Substance name Chemical formula or structural formula Fluorinated resin — acrylic resin — polyisocyanate prepolymer hexamethylene diisocyanate trimethylol propane addition compound methyl ethyl ketone (MEK) c4h8o Methyl isobutyl fluorenone (MIBK) c6h120 n-butyl acetate Hi2 〇2 ethyl acetate ch3cooc2h5 ethylene glycol monoethyl ether ch3cooch2ch2oc2h5 Table 3 Coating method (1) Corresponding size (2) Coating thickness (3) Flatness Spray coating (1) 800 Xl350m / m or less (2) 1 to 2 m (3) Best spin coating (1) 500 X600m / m or less (2) 1 to 2 夂 m (3) Best, soak Coating (1) 5 00 X 600m / m ΐλ Τ (2) 3 ～ 8 / ζιπ (3)
88118727.ptd 第16頁 418344 五、發明說明（13) 滚筒塗佈 (1)6〇〇 x8〇〇m 以下 (2)5 〜 (3)可 第7工私’修邊同時以5〇〜120 t乾燥18〜72小時，完成 具有膜面保護層之光罩原版。 ，行測試比較如此製造之具有膜面保護層之光罩原版的 表4 乳液 層積 本發明 鉻遮罩 測試方法 鉛筆硬度 4〜3B 2〜B F〜Η 5Η JIS-5400 防污性 X △ ◎ ◎ 以乙醇擦拭 簽字筆跡 摩擦測試 10> 20> 100< 100< 以紙巾摩擦 密著性 ◎ Δ ◎ ◎ 透明膠帶剝 離 UV透過率 丨丨__ 84% 60% 84% 90% 36 5nm 覆膜膜厚 8 〜1 0 // 1 〜2 // (1)乳液：從前乳液乾板不施以加工者 (2 )層積··於乳液乾板上層積保護膜者 (3)鉻遮罩：於玻璃積板上以金屬膜（Cr9〇〇A)形成圖案者 特徵，與從前的光罩原版的特徵。其結果顯示於表3。88118727.ptd Page 16 418344 V. Description of the invention (13) Roller coating (1) 600x800m or less (2) 5 to (3) The 7th industrial and private work can be trimmed at the same time by 50 to 120 t Dry for 18 ~ 72 hours to complete the original mask with a film surface protective layer. Table 4 compares the original photomask with the film surface protective layer thus manufactured. Table 4 Emulsion lamination The chromium mask test method of the present invention Pencil hardness 4 ~ 3B 2 ~ BF ~ Η 5Η JIS-5400 Antifouling X △ ◎ ◎ Wipe signature hand rubbing test with ethanol 10 > 20 > 100 < 100 < Friction adhesion with paper towel ◎ Δ ◎ ◎ Transparent tape peeling UV transmittance 丨 丨 _ 84% 60% 84% 90% 36 5nm film thickness 8 ～ 1 0 // 1 ～ 2 // (1) Emulsion: The former emulsion dry board was not processed (2) Laminated ·· The protective film was laminated on the latex dry board (3) Chrome mask: On the glass laminate Features of patterning with a metal film (Cr900A), and features of the original mask original. The results are shown in Table 3.
利用可能性 本發明，係以在基板形成乳液感光乳劑層的膜面（乳 光罩）而成的光罩原版的乳液感光乳劑層的膜面上，法飞 以在氟化樹脂與壓克力樹脂的混合樹脂内， &佈 此合正乙酸丁Exploitability The present invention relates to a film surface of an emulsion photosensitive emulsion layer of a photomask original plate formed by forming a film surface (emulsion mask) of an emulsion photosensitive emulsion layer on a substrate. Resin Blend
4 18344 五、發明說明（14) 酿與甲基乙基曱酮（MEK)與曱基異丁基甲酮（MIBK)之溶劑 調和而成的2液架橋型防污性表面塗層劑為主劑，對此調 和混合聚異氰酸預聚體與乙酸乙酯而成的架橋硬化劑，及 乙酸丁酯與甲基乙基甲酮（MEK)與乙酸甘醇單***酯 (ethylene glycol monoethy 1 ether acetate)戶斤構成的 稀釋劑混合而成的保護層形成液，使修邊層積形成膜面保 護層為特徵之具有膜面保護層之光罩原版，及其製造方 法，暨光罩原版用保護層形成液。4 18344 V. Description of the invention (14) 2 liquid bridge type antifouling surface coating agent blended with solvents of methyl ethyl fluorenone (MEK) and methyl isobutyl ketone (MIBK) as the main agent, A bridging hardener made by mixing polyisocyanate prepolymer and ethyl acetate, and butyl acetate, methyl ethyl ketone (MEK), and ethylene glycol monoethy 1 ether acetate. ) A protective layer forming liquid composed of a diluent composed of household weights, a photomask original with a film surface protective layer, which is characterized in that trimming is laminated to form a film surface protective layer, and a method for manufacturing the same, and a photomask original plate for protection. Layer forming liquid.
該保護層形成液，形成密著性佳，耐久性優異的薄覆 臈，具有為無色透明液體、不易由於折曲、延伸而引起白 化’不會降低紫外線透過率等特性。因此，塗佈此保護層 形成液’使修邊層積形成膜面保護層的具有膜面保護層之 光罩原版，係不易損傷、不易髒污，不會降低紫外線透過 率者，其有用性被強化。This protective layer-forming liquid forms a thin coating with good adhesion and excellent durability, and is a colorless transparent liquid that is less prone to whitening due to bending and elongation 'and does not lower ultraviolet transmittance. Therefore, applying this protective layer forming liquid to laminate the trimming layer to form a film surface protective layer. The original mask with a film surface protective layer is not easy to be damaged, is not easily soiled, and does not reduce the ultraviolet transmittance. Its usefulness Be strengthened.
88ll8727.ptd 第18頁 ___〆88ll8727.ptd page 18 ___ 〆
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11743898A JPH11305420A (en) | 1998-04-27 | 1998-04-27 | Photomask raw glass with surface film protective layer and its production and protective layer forming liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW418344B true TW418344B (en) | 2001-01-11 |
Family
ID=14711661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW088118727A TW418344B (en) | 1998-04-27 | 1999-10-27 | Photomask raw glass with surface film protective layer and its production and protective layer forming liquid |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH11305420A (en) |
| TW (1) | TW418344B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100800010B1 (en) | 1999-10-20 | 2008-01-31 | 가부시키가이샤 신에이샤 | Photomask original form having layer for protecting film surface and method for preparing the same, and protective layer-forming liquid for photomask original form |
| JP2002214761A (en) * | 2001-01-16 | 2002-07-31 | Dainippon Printing Co Ltd | Photomask for photolithography and method for manufacturing the same |
| JP4688324B2 (en) * | 2001-03-19 | 2011-05-25 | 株式会社きもと | Method for manufacturing photomask with protective film |
| TWI286674B (en) | 2002-12-27 | 2007-09-11 | Asml Netherlands Bv | Container for a mask, method of transferring lithographic masks therein and method of scanning a mask in a container |
| JP4376610B2 (en) | 2003-12-18 | 2009-12-02 | 株式会社きもと | Surface protective film and surface protective film using the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH077207B2 (en) * | 1987-05-16 | 1995-01-30 | 出光石油化学株式会社 | Durable pattern forming member |
| JP2831737B2 (en) * | 1989-10-13 | 1998-12-02 | 株式会社東芝 | Pattern printing plate for shadow mask and method of manufacturing the same |
| JP2963029B2 (en) * | 1995-06-16 | 1999-10-12 | 株式会社日本触媒 | Composition for paint |
| JP3577145B2 (en) * | 1995-10-13 | 2004-10-13 | 株式会社きもと | Hard coat film |
-
1998
- 1998-04-27 JP JP11743898A patent/JPH11305420A/en active Pending
-
1999
- 1999-10-27 TW TW088118727A patent/TW418344B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11305420A (en) | 1999-11-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103869622B (en) | Photosensitive composition for the black matrix in liquid crystal display device, the black matrix with the composition and the method for forming black matrix using the composition | |
| JPS599639A (en) | Liquid crystal display element | |
| US6811931B1 (en) | Photomask original form having layer for protecting film surface and method for preparing the same, and protective layer-forming liquid for photomask original form | |
| TW418344B (en) | Photomask raw glass with surface film protective layer and its production and protective layer forming liquid | |
| JP2004053706A (en) | Image forming method | |
| US679501A (en) | Photographic process and product. | |
| JPS63128302A (en) | Color filter and its production | |
| CH284109A (en) | Process for the production of objects provided with graduations, grids, line drawings, area marks etc. | |
| JP2607732B2 (en) | Light-shielding thin film composition | |
| US2041853A (en) | Method of decorating large surfaces by photography | |
| JPH0115858B2 (en) | ||
| JPH04318955A (en) | Glass board for dummy wafer | |
| KR950033597A (en) | Manufacturing method of color filter and liquid crystal display | |
| JP2005292329A (en) | Light shielding film for display device, method for forming same, substrate for image formation, color filter, and transfer material | |
| JPS6088945A (en) | Aqueous processing solution for image copying material | |
| JP2002072452A (en) | Photomask with emulsion side protecting layer and method for, producing the same | |
| US1877310A (en) | Method for the manufacture of screens | |
| JPH0429239A (en) | Light shieldable masking film for panchromatic photographic paper | |
| US730454A (en) | Process of producing colored photographs. | |
| JP2956732B2 (en) | Method for manufacturing color filter of solid-state imaging device | |
| KR101157870B1 (en) | Photosensitive composition, photosensitive transfer material, light shielding layer for display device, color filter, liquid crystal display device, substrate with light shielding layer for display device and method of manufacturing the same | |
| JPS60114807A (en) | Production of fine color filter | |
| JPH10307405A (en) | Method and device for developing | |
| JPH06281925A (en) | Manufacture of liquid crystal display panel | |
| JP2005092066A (en) | Mask protecting liquid for exposure and mask for exposure having conductivity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GD4A | Issue of patent certificate for granted invention patent | ||
| MM4A | Annulment or lapse of patent due to non-payment of fees |