200902669 九、發明說明： 【發明所屬之技術領域】 本發明係關於光罩保護用黏著膠帶，更詳言之，係 關於保護在印刷基板形成步驟中所使用之光罩的光罩保 護用黏著膠帶，其係即使密接於具有黏著性之光阻而重 複使用，亦可使剝離性不降低而使用之光罩保護用黏著 膠帶。 【先前技術】 於製作印刷配線板時，係使用液狀軟焊光阻等之光 阻。爲了保護密接於該光阻而使用之曝光用光罩的表面 污損及損傷等之目的，迄今係使用由聚酯基材而成之光 罩保護用黏著膠帶。然而，由於爲了顯現液狀軟焊光阻 之機能性大多使用具有黏著性之類型，因此光阻附著於 光罩保護用黏著膠帶表面，曝光後難以從光阻將光罩剝 離，而有機械停止之問題點。 爲了解決此等問題點’已硏究在光罩保護用黏著膠 帶的表面塗布脫膜層者。例如，在採用使用鉑系觸媒之 S i - C H = C Η 2與S i - Η之加成反應的剝離劑、或使用錫觸媒 系統之S i - Ο Η彼此的縮合反應之剝離劑的情況下，雖然 初期剝離性係爲優異，但是若重複密接曝光時’由於液 狀軟焊光阻中所含有之溶劑或添加劑的滲透’密接性降 低而發生脫膜劑之脫落。因此’專利文獻丨揭示：使用 在剝離層添加特定剝離劑與密接提升劑之硬化物’並且 設置底塗層。但是，對於期望在該情況下增加重複使用 200902669 次數之顧客需求，仍無法充分地對應。 另外，附脫膜劑層之光罩保護用黏著膠帶係由於脫 膜層之密接力不足，而當以醇類等之溶劑洗淨附著表面 之污染物時，脫膜層會脫落而亦有無法持續脫膜效果之 問題。 [專利文獻1]特開2003-96409號公報 【發明内容】 發明所欲解決夕課顕 本發明之目的係有鑑於先前技術之問題點，提供一 種在密接曝光之重複步驟中，對光阻而言將剝離性予以 持續之光罩保護用黏著膠帶。進一步地，係提供一種在 光罩保護用黏著膠帶之表面層有來自光阻之污染附著物 的情況下，即使以醇類等溶劑洗淨，表面層不會脫落之 光罩保護用黏著膠帶。 用以解決課穎之手段 本發明人等爲了達成上述目的，反覆鑽硏探討之結 果，發現一種光罩保護用黏著膠帶，其特徵係含有透明 基材薄膜或片材（A)、形成在其單面上之黏著劑層（B)、 與形成在與黏著劑層（B)面相反的側邊之面上的表面層 (C)之光罩保護用黏著膠帶，在表面層（C)使用由特定組成 物所形成之層，即使與具有黏著性之光阻密接重複使 用，亦可使剝離性不降低而使用。對該等發現，進一步 反覆檢討，而達成完成本發明。 亦即，根據本發明之第1發明，可以提供一種光罩 200902669 保護用黏著膠帶，其特徵爲：其係包括透明基材薄膜或 片材（A)、形成在其單面上之黏著劑層（B) '以及形成在 與黏著劑層（B )面相反的側邊之面上的表面層（c )之光罩 保護用黏著膠帶， 表面層（C)係由含有下述（X)及（y)的混合物之硬化物 所構成， (X):異氰酸酯矽烷 (y):在末端具有羥基之矽氧烷。 又，根據本發明之第2發明，提供如第1發明之光 罩保護用黏著膠帶，其中在基材薄膜或片材（A)與表面層 (C )之間設有中間層（D )時，中間層（D )係由從含有下述（z 1) 及/或（z2)的混合物所得到之硬化物所構成， (zl):三聚氰胺系化合物 (z2):胍胺系化合物。 又，根據本發明之第3發明，提供如第1發明之光 罩保護用黏著膠帶，其中在基材薄膜或片材（A)與表面層 (C)之間未設有中間層（D)時，表面層（C)係由從含有前述 (X)及（y)、再加上下述（zl)及/或（z2)的混合物所得到之硬 化物所構成， (zl):三聚氰胺系化合物 (z2):胍胺系化合物。 又，根據本發明之第4發明，提供如第1 ~ 3發明中 之任一項之光罩保護用黏著膠帶，其中異氰酸酯矽烷（X) 係3及/或4官能異氰酸酯矽烷。 200902669 又，根據本發明之第5發明，提供如第4發明之光 罩保護用黏著膠帶，其中前述3及/或4官能異氰酸酯矽 烷係甲基三異氰酸酯矽烷及/或四異氰酸酯矽烷。 又，根據本發明之第6發明，提供第1〜3發明中任 一項之光罩保護用黏著膠帶，其中在末端具有羥基之矽 氧烷（y)係在末端具有2個羥基之二醇。 又，根據本發明之第7發明，提供如第2或3發明 之光罩保護用黏著膠帶，其中三聚氰胺系化合物（zl)係羥 甲基三聚氰胺及/或其衍生物。 又，根據本發明之第8發明，提供如第7發明之光 罩保護用黏著膠帶，其中前述羥甲基三聚氰胺係六羥甲 基三聚氰胺。 又，根據本發明之第9發明，提供如第2或3發明 之光罩保護用黏著膠帶，其中胍胺系化合物U2)係苯胍胺 (benzo guanamine)及/或其衍生物。 發明效果 根據本發明之光罩保護用黏著膠帶，在第1發明中 之光罩保護用黏著膠帶，藉由使用（C)之表面層，在密接 曝光之重複步驟中對於光阻能夠有持續剝離性之效果。 又，第2發明中之光罩保護用黏著膠帶，藉由組合 (A)(C)(D)之特定層，提升表面層之密接性，而有在密接 曝光之重複步驟中對於光阻能夠持續剝離性，並且在光 罩保護用黏著膠帶之表面層有來自光阻之污染附著物 時，即使以醇類等溶劑洗淨，表面層亦不脫落之效果， ~8~ 200902669 能夠藉由效率上·經濟上優異之方法，來得到印刷配線 板。 又，第3發明中之光罩保護用黏著膠帶，藉由表面 層（C)係由含有（X)、（ y)及、（Z 1)及/或（z 2)之特定混合物所 形成，而爲具有同時兼備脫膜性及耐溶劑性之表面層的 光罩保護用黏著膠帶，除了在密接曝光之重複步驟中對 於光阻持續輕剝離性且再剝離性優異以外，即使以醇類 等溶劑洗淨，亦無發生脫膜層之脫落，因此脫膜效果不 會降低，而有重複曝光·使用時之耐久性亦良好之效果， 能夠藉由效率上·經濟上優異之方法，來得到印刷配線 板。 又，第4發明之光罩保護用黏著膠帶，由於異氰酸 酯矽烷（X)係特定爲3及/或4官能異氰酸酯矽烷，因此有 交聯在末端具有羥基之矽氧烷之性能優異之效果。 又，第5發明之光罩保護用黏著膠帶，由於前述3 或4官能異氰酸酯矽烷係特定爲甲基三異氰酸酯矽烷及/ 或四異氰酸酯矽烷，故有交聯在末端具有羥基之矽氧烷 之性能更爲優異之效果。 又，第6發明之光罩保護用黏著膠帶，由於在末端 具有羥基之矽氧烷（y)係特定爲在末端具有2個羥基之二 醇’因此有與異氰酸酯之交聯反應性優異之效果。 又，第7發明之光罩保護用黏著膠帶，由於三聚氰 胺系化合物（z 1 )係特定爲羥甲基三聚氰胺及/或其衍生 物’因此有表面層（C)或中間層（D)與作爲基材薄膜或片 200902669 材（A)使用之PET的密接性優異之效果。 又，第8發明之光罩保護用黏著膠帶，由於前述淫 甲基三聚氰胺係特定爲六羥甲基三聚氰胺，因此有表面 層（C)或中間層（D)之原料的硬化性混合物之反應性優異 之效果。 又’第9發明之光罩保護用黏著膠帶，由於胍胺系 化合物（z2)係特定爲苯胍胺及/或其衍生物，因此有表面 層（C)或中間層（D)與作爲基材薄膜或片材（A)使用之pET 的密接性優異之效果。 【實施方式】 實施發明之需住形態 以下’針對本發明之光罩保護用黏著膠帶加以詳細 地説明。 本發明之光罩保護用黏著膠帶特徵係包括透明基材 薄膜或片材（A)、形成在其單面上之黏著劑層（B)、與形 成在與黏著劑層（B)面相反的側邊之面上的表面層（C)之 G 光罩保護用黏著膠帶， 表面層（C)係由含有下述（X)及（y)的混合物之硬化物 所構成： (X):異氰酸酯矽烷 (y):在末端具有羥基之矽氧烷。 1.基材薄膜或片材（A) 作爲上述基材薄膜或片材（A)，宜爲使用於曝光之際 的紫外線透過率高者，例如，聚對苯二甲酸乙二酯 (PET)、聚萘酸乙二酯、聚丙烯、聚乙烯、聚氯乙烯、聚 -10- 200902669 苯乙烯、聚碳酸酯、三乙酸纖維素（T AC)、聚醯亞胺、丙 烯酸等之樹脂所構成之透明性優異的高分子薄膜係適合 使用。尤其是經雙軸拉伸之PET薄膜因機械強度、尺寸 安定性優異，因此適合使用。 上述基材薄膜或片材（A)之厚度較佳爲考慮光透過 性、處理性等加以適當決定，具體而言較佳爲 2〜100μ m、更佳爲m。若小於m，則膠帶的強 度不足而使處理變得困難，在貼付時會有產生縐折的情 形’若超過1 00 ^ m ,則有變得無法得到充分光透過性之 情況。 又’在本發明中，爲了提升透明基材薄膜或片材 (A)、與表面層（〇或中間層（D)及/或與黏著劑層（B)之密 接性’可進行表面處理。 例如’電暈處理、電漿處理等之放電處理，在對薄 的基材實施均句處理，爲了防止發生基材破損、孔穴等 之缺陷’期望處理能量低、弱的放電。另外，作爲其他 方法’已知藉由鹼之皂化處理。 2 .表面層（C) 表面層（C)係設置在透明基材薄膜或片材之上、 或在中間層（D)之上者，藉由使該表面層（c)貼著於光阻 表面，能夠有防止光阻被轉印於光罩保護用黏著膠帶的 污損產生之脫膜層的功用。 (1)硬化性混合物 (X):異氰酸酯矽烷 用於本發明之表面層（c)有交聯劑之異氰酸酯矽烷（χ) -11- 200902669 係 Si(NCO)4RnSi(NCO)4.n、（110)„51(1^(：0)4.11等。在此，R 係烴基、η爲1、2或3之數字。 此等化合物之中，由反應性之觀點而言，尤佳爲甲 基三異氰酸酯矽烷、四異氰酸酯矽烷等之3或4官能之 異氰酸酯矽烷。異氰酸酯矽烷係可單獨使用、亦可以2 種類以上之混合物來使用。 (y):在末端具有羥基之矽氧烷 作爲具有末端經基之砂氧院（y)，有經砂院醇變性、 經甲醇變性之二甲基聚矽氧烷。從與異氰酸酯之交聯反 應之觀點而言，較佳爲具有2個羥基之二醇。 (zl):三聚氰胺系化合物 在本發明中，在基材薄膜或片材（A)與表面層（C)之 間未設有中間層（D)時，表面層（C)較佳係由從含有前述（X) 及（y)、再加上下述（zl)及/或（z2)的混合物所得到之硬化 物所構成。 作爲在本發明所使用之三聚氰胺系化合物（z 1 )，係使 三聚氰胺與甲醛反應而得之羥甲基化三聚氰胺，可列舉 例如，來自單羥甲基三聚氰胺之六羥甲基三聚氰胺、或 其衍生物之烷基醚化體。該等之中，從OH基多、與PET 之密接性的觀點而言，期望爲六羥甲基三聚氰胺。 三聚氰胺系化合物係可單獨使用、亦可倂用2種類 以上。 藉由三聚氰胺系化合物之摻合，特徵爲即使不使用 用來提高與透明基材薄膜（A)之密接性的底塗層等，在以 醇類等溶劑洗淨之際，表面層（C)亦不容易脫落。 -12- 200902669 (z2):胍胺系化合物 作爲在本發明所使用之胍胺系化合物’可列舉苯胍 胺、乙胍胺（acetoguanamine)、環己院碳胍肢（cyclohexane carboguanamine)、環己嫌碳胍胺、降莰嫌碳胍胺、及其 衍生物之羥甲基化胍胺或烷基醚化體。 在含有胍胺系化合物之硬化物中’尤其是使用苯胍 胺及其衍生物之硬化物，係因與作爲薄膜或片材（A)而使 用之PET、及與表面層（C)之密接性良好，因而較佳。 三聚氰胺系化合物係可單獨使用’亦可倂用2種類 以上。 藉由胍胺系化合物之摻合，其特徵爲即使不採用用 以提升與透明基材薄膜（A)之密接的底塗層等’當以醇類 等之溶劑洗淨之際，表面層（C)係不容易脫落。 (2)摻合比 異氰酸酯矽烷U)與矽氧烷（y)之摻合比係相對於異 氰酸酯矽烷100重量份而言，矽氧烷5〜200重量份、較 佳爲10〜100重量份、更佳爲10~50重量份。若爲5重量 份以下，則脫膜性的顯現變差’在200重量份以上則有 與基材薄膜或片材（A)之密接性降低的情形。 又，在表面層（C)混合三聚氰胺系化合物（zl)及/或胍 胺系化合物（z2)時之摻合比’相對於異氰酸酯矽烷（X)與 矽氧烷（y)之混合量1〇〇重量份而言爲5重量份〜60重量 份，較佳爲1 0 ~ 5 0重量份。在5重量份以下則以醇類等 溶劑洗淨之耐溶劑性降低，且在60重量份以上則剝離性 降低。 -13- 200902669 (3)表面層（C)之製造 本發明之表面層（C)係形成在透明基材薄膜或片材 (A)或中間層（D)的一面上，係藉由將含有異氰酸酯矽烷（x) 及在末端具有羥基之矽氧烷（y)之混合物、或者是將含有 異氰酸酯矽烷（X )及在末端具有羥基之矽氧烷（y )再加上 三聚氰胺系化合物（zl)及/或胍胺系化合物（z2)之混合 物，以有機溶劑稀釋且塗布後加熱乾燥而得之硬化物所 形成。此時，各成分之摻合順序並無特別限定；又，作 爲塗布方法，可採用例如，旋轉塗布法、噴塗法、凹版 印刷等之輥塗法、模塗法等。 表面層（C)之厚度，從塗布均勻性、硬化性、密接性 等之理由而言，較佳爲0.01~2μ m、更佳爲0.02〜0·5μ m。 若小於0.01 μ m，變得難以均勻地塗布且對脫膜性有發生 偏差的可能，若超過2 /X m，則有硬化不佳或容易脫落的 可能。 異氰酸酯矽烷係作爲在末端具有羥基之矽氧烷的交 聯劑。在末端具有羥基之矽氧烷與爲其交聯劑之異氰酸 酯矽烷之交聯反應機構係認爲如下： (i) 經塗布在透明基材薄膜或片材（A)之異氰酸酯矽烷係 在乾燥段階與空氣中的水分反應、加水分解而形成矽烷 醇基；200902669 IX. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to an adhesive tape for reticle protection, and more particularly to a visor protective adhesive tape for protecting a reticle used in a printed circuit board forming step. It is an adhesive tape for reticle protection which can be used even if it is used in close contact with an adhesive photoresist. [Prior Art] When manufacturing a printed wiring board, a photoresist such as a liquid solder resist is used. In order to protect the surface of the exposure mask which is used in contact with the photoresist, such as surface contamination and damage, an adhesive tape for reticle protection made of a polyester substrate has hitherto been used. However, since the adhesiveness is mostly used to exhibit the function of the liquid solder resist, the photoresist adheres to the surface of the adhesive tape for the reticle protection, and it is difficult to peel off the reticle from the photoresist after the exposure, and there is a mechanical stop. The problem point. In order to solve such problems, the person who has applied the release layer to the surface of the adhesive tape for reticle protection has been studied. For example, a stripper which uses an addition reaction of S i - CH = C Η 2 and S i - 使用 using a platinum-based catalyst, or a stripping agent which uses a condensation reaction of S i - Η 锡 of a tin catalyst system In the case of the initial peeling property, the release property of the solvent or the additive contained in the liquid solder resist is reduced when the adhesion is repeated, and the release agent is peeled off. Therefore, the 'Patent Document 丨 discloses that a cured product of a specific release agent and an adhesion promoter is added to the release layer' and an undercoat layer is provided. However, for the customer demand that it is expected to increase the number of reuses of 200902669 in this case, it still cannot fully correspond. In addition, the adhesive tape for the reticle protective layer with the release agent layer is insufficient in the adhesion of the release layer, and when the contaminant on the adhesion surface is washed with a solvent such as an alcohol, the release layer may fall off or may not be able to be removed. The problem of continuous release of the film. [Patent Document 1] JP-A-2003-96409 SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art, and provides a photoresist in a repeating step of adhesion exposure. Adhesive tape for reticle protection that will continue to be peelable. Further, in the case where the surface layer of the reticle protective pressure-sensitive adhesive tape has a contaminated deposit from the photoresist, the visor protective adhesive tape which does not fall off even if it is washed with a solvent such as an alcohol. In order to achieve the above object, the present inventors have found a visor protective adhesive tape which is characterized in that it contains a transparent base film or sheet (A) and is formed thereon. Adhesive tape for mask protection on one side (B) and surface layer (C) formed on the side opposite to the side of the adhesive layer (B), used in the surface layer (C) The layer formed of the specific composition can be used without being reduced in peelability even if it is used in close contact with the photoresist having adhesiveness. The findings were further reviewed and the present invention was completed. That is, according to the first invention of the present invention, it is possible to provide a protective cover tape for a mask 200902669, which is characterized in that it comprises a transparent base film or sheet (A) and an adhesive layer formed on one surface thereof. (B) 'and a cover layer (c) formed on the side opposite to the surface of the adhesive layer (B), the surface layer (C) containing the following (X) and (y): a hardened mixture of (y): isocyanate decane (y): a decane having a hydroxyl group at the terminal. According to a second aspect of the present invention, there is provided an adhesive tape for protecting a reticle according to the first aspect of the invention, wherein when the intermediate layer (D) is provided between the base film or the sheet (A) and the surface layer (C) The intermediate layer (D) is composed of a cured product obtained from a mixture containing the following (z 1) and/or (z2), (zl): a melamine-based compound (z2): a guanamine-based compound. According to a third aspect of the present invention, there is provided an adhesive tape for protecting a reticle according to the first aspect of the present invention, wherein the intermediate layer (D) is not provided between the base film or the sheet (A) and the surface layer (C). The surface layer (C) is composed of a cured product obtained by mixing the above (X) and (y), plus the following (zl) and/or (z2), (zl): a melamine compound (z2): a guanamine compound. According to a fourth aspect of the invention, the adhesive tape for reticle protection according to any one of the first to third aspects of the present invention, wherein the isocyanate decane (X) is a 3 and/or a tetrafunctional isocyanate decane. According to a fifth aspect of the invention, there is provided a viscous protective tape for a reticle according to the fourth aspect of the invention, wherein the 3 and/or 4 functional isocyanate decane-based methyl triisocyanate decane and/or tetraisocyanate decane. According to a sixth aspect of the invention, there is provided a viscous tape for protecting a reticle according to any one of the first to third aspects, wherein a oxime (y) having a hydroxyl group at a terminal is a diol having two hydroxyl groups at a terminal. . According to a seventh aspect of the invention, there is provided a viscous protective tape for a reticle according to the second or third aspect, wherein the melamine-based compound (zl) is hydroxymethyl melamine and/or a derivative thereof. According to a ninth aspect of the invention, there is provided a viscous tape for protecting a reticle according to the seventh aspect of the invention, wherein the methylol melamine-based hexamethylol melamine. According to a ninth aspect of the present invention, there is provided a viscous protective tape for a reticle according to the second or third aspect, wherein the guanamine compound U2) is benzoguanamine and/or a derivative thereof. According to the adhesive tape for reticle protection of the present invention, in the adhesive tape for reticle protection according to the first aspect of the invention, by using the surface layer of (C), the photoresist can be continuously peeled off in the step of repeating the adhesion exposure. The effect of sex. Further, in the adhesive tape for reticle protection according to the second aspect of the invention, by combining the specific layers of (A), (C) and (D), the adhesion of the surface layer is improved, and the photoresist can be formed in the repeating step of the adhesion exposure. When the surface of the reticle protective adhesive tape has a contaminant deposit from the photoresist, even if it is washed with a solvent such as an alcohol, the surface layer does not fall off. ~8~ 200902669 can be used for efficiency A method that is economically superior to obtain a printed wiring board. Further, in the adhesive tape for reticle protection according to the third aspect of the invention, the surface layer (C) is formed of a specific mixture containing (X), (y) and (Z1) and/or (z 2). In addition, in the adhesive tape for reticle protection having the surface layer which has both the release property and the solvent resistance, in addition to the light-resistance and the re-peelability of the photoresist in the repeating process of the adhesion exposure, even an alcohol or the like is used. When the solvent is washed and the release layer is not peeled off, the effect of releasing the film is not lowered, and the effect of repeating exposure and durability at the time of use is good, and it can be obtained by an efficient and economically excellent method. Printed wiring board. Further, in the adhesive tape for reticle protection of the fourth aspect of the invention, since the isocyanate decane (X) is specifically classified into 3 and/or a tetrafunctional isocyanate decane, it is excellent in the performance of crosslinking the oxime having a hydroxyl group at the terminal. Further, in the adhesive tape for reticle protection according to the fifth aspect of the invention, since the tris or tetrafunctional isocyanate decane is specifically methyltriisocyanate decane and/or tetraisocyanate decane, there is a property of crosslinking a oxane having a hydroxyl group at the terminal. More excellent results. Further, in the adhesive tape for reticle protection according to the sixth aspect of the invention, since the oxime (y) having a hydroxyl group at the terminal is specifically a diol having two hydroxyl groups at the terminal, the cross-linking reactivity with the isocyanate is excellent. . Further, in the adhesive tape for reticle protection according to the seventh aspect of the invention, the melamine-based compound (z 1 ) is specifically methylol melamine and/or a derivative thereof, and thus has a surface layer (C) or an intermediate layer (D) and The film of the base material or sheet 200902669 is excellent in the adhesion of PET used in the material (A). Further, in the adhesive tape for reticle protection according to the eighth aspect of the invention, since the oxomethyl melamine-based hexamethylol melamine is specifically used, the reactivity of the curable mixture of the raw material of the surface layer (C) or the intermediate layer (D) is obtained. Excellent results. In the adhesive tape for reticle protection according to the ninth aspect of the invention, since the guanamine compound (z2) is specifically benzoguanamine and/or a derivative thereof, the surface layer (C) or the intermediate layer (D) and the base layer are provided. The effect of the pET of the material film or sheet (A) is excellent. [Embodiment] The present invention is described in detail below. The adhesive tape for reticle protection of the present invention will be described in detail. The adhesive tape for reticle protection of the present invention is characterized by comprising a transparent substrate film or sheet (A), an adhesive layer (B) formed on one surface thereof, and a surface opposite to the surface of the adhesive layer (B). The surface layer (C) of the side surface (C) is a G-mask protective adhesive tape, and the surface layer (C) is composed of a cured product containing a mixture of the following (X) and (y): (X): Isocyanate Decane (y): a decane having a hydroxyl group at the terminal. 1. Substrate film or sheet (A) As the above-mentioned base film or sheet (A), it is preferable to use a high ultraviolet transmittance for exposure, for example, polyethylene terephthalate (PET). , polyethylene naphthalate, polypropylene, polyethylene, polyvinyl chloride, poly-10-200902669 styrene, polycarbonate, cellulose triacetate (T AC), polyimine, acrylic, etc. A polymer film excellent in transparency is suitable for use. In particular, the biaxially stretched PET film is suitable for use because of its excellent mechanical strength and dimensional stability. The thickness of the base film or the sheet (A) is preferably determined in consideration of light transmittance, handleability, and the like, and is specifically preferably 2 to 100 μm, more preferably m. If it is less than m, the strength of the tape is insufficient and the handling becomes difficult, and if it is more than 100 μm when it is attached, if it is more than 100 μm, sufficient light transmittance cannot be obtained. Further, in the present invention, surface treatment may be performed in order to enhance the transparent base film or sheet (A) and the surface layer (the adhesion between the surface layer (D) or the intermediate layer (D) and/or the adhesive layer (B). For example, a discharge treatment such as a corona treatment or a plasma treatment is performed on a thin substrate, and in order to prevent defects such as damage to the substrate or voids, it is desired to have a low processing energy and a weak discharge. The method 'is known to be saponified by alkali. 2. Surface layer (C) The surface layer (C) is disposed on the transparent substrate film or sheet, or on the intermediate layer (D), by The surface layer (c) is adhered to the surface of the photoresist, and has a function of preventing the photoresist from being transferred to the release layer of the reticle protective adhesive tape. (1) Curable mixture (X): isocyanate The decane used in the surface layer of the present invention (c) isocyanate decane having a crosslinking agent (χ) -11- 200902669 is Si(NCO)4RnSi(NCO)4.n, (110) „51(1^(:0) 4.11, etc. Here, the R-based hydrocarbon group and η are numbers of 1, 2 or 3. Among these compounds, from the viewpoint of reactivity, it is particularly preferred A 3- or 4-functional isocyanate decane such as a triisocyanate decane or a tetraisocyanate decane. The isocyanate decane may be used singly or in combination of two or more kinds. (y): a decane having a hydroxyl group at the terminal as a terminal In the case of the sand-oxygen institute (y), there is a dimethyl polyoxyalkylene which has been denatured by the alcohol and denatured by methanol. From the viewpoint of cross-linking reaction with isocyanate, it is preferred to have two hydroxyl groups. (zl): melamine-based compound In the present invention, when the intermediate layer (D) is not provided between the substrate film or sheet (A) and the surface layer (C), the surface layer (C) is preferably It is composed of a cured product obtained from the mixture containing the above (X) and (y), plus the following (zl) and/or (z2). As the melamine-based compound (z 1 ) used in the present invention, The methylolated melamine obtained by reacting melamine with formaldehyde, for example, an alkyl etherified compound derived from hexamethylol melamine of monomethylol melamine or a derivative thereof. Among these, from OH Quito, from the point of view of the adhesion to PET It is desirable to use hexamethylol melamine. The melamine-based compound may be used singly or in combination of two or more kinds. The blending of the melamine-based compound is characterized by the use of a film for improving the transparent substrate (A). The surface layer (C) is not easily peeled off when it is washed with a solvent such as an alcohol, etc. -12- 200902669 (z2): a guanamine compound is used as the present invention. The amine compound 'is exemplified by benzoguanamine, acetoguanamine, cyclohexane carboguanamine, cyclohexanol, guanidinium, and its derivatives. A decylamine or alkyl etherified body. In the hardened material containing a guanamine compound, the cured product of benzoguanamine and its derivatives is used in combination with PET used as a film or sheet (A) and surface layer (C). Good sex, so it is better. The melamine-based compound may be used singly or in combination of two or more types. By the blending of the amide-based compound, it is characterized in that the surface layer (when the solvent is washed with a solvent such as an alcohol or the like without using an undercoat layer for improving the adhesion to the transparent base film (A), the surface layer ( C) is not easy to fall off. (2) The blending ratio of the isocyanate decane U) to the decane (y) is 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the isocyanate decane. More preferably, it is 10 to 50 parts by weight. When the amount is 5 parts by weight or less, the release property is deteriorated. When the amount is 200 parts by weight or more, the adhesion to the base film or the sheet (A) may be lowered. Further, the blending ratio of the melamine-based compound (zl) and/or the amide-based compound (z2) in the surface layer (C) is relative to the amount of the mixture of the isocyanate decane (X) and the decane (y). The 〇 part by weight is 5 parts by weight to 60 parts by weight, preferably 10 to 50 parts by weight. When the amount is 5 parts by weight or less, the solvent resistance is lowered by washing with a solvent such as an alcohol, and when it is 60 parts by weight or more, the peeling property is lowered. -13- 200902669 (3) Production of surface layer (C) The surface layer (C) of the present invention is formed on one side of a transparent substrate film or sheet (A) or intermediate layer (D) by containing a mixture of isocyanate decane (x) and a oxane (y) having a hydroxyl group at the terminal, or a decyl oxide (y) containing an isocyanate decane (X) and a hydroxyl group at the terminal plus a melamine-based compound (zl) And/or a mixture of the guanamine compound (z2), which is formed by diluting with an organic solvent and heating and drying after coating. In this case, the order of blending the respective components is not particularly limited. Further, as the coating method, for example, a roll coating method such as a spin coating method, a spray coating method, or a gravure printing method, a die coating method, or the like can be used. The thickness of the surface layer (C) is preferably 0.01 to 2 μm, more preferably 0.02 to 0.5 μm, for reasons of coating uniformity, hardenability, adhesion, and the like. If it is less than 0.01 μm, it becomes difficult to apply uniformly and there is a possibility that the release property is deviated. If it exceeds 2 /X m, there is a possibility that the hardening is poor or it is easy to fall off. The isocyanate decane is a crosslinking agent of a decane having a hydroxyl group at the terminal. The cross-linking reaction mechanism of a decane having a hydroxyl group at the terminal and an isocyanate decane having a crosslinking agent thereof is considered as follows: (i) an isocyanate decane coated on a transparent substrate film or sheet (A) in a drying step Reacts with moisture in the air and hydrolyzes to form a stanol group;
Si-NCO + H2〇-> Si-OH + HNCO (ii) 藉由所形成之矽烷醇與矽氧烷之羥基的脫水縮合反 應而交聯；Si-NCO + H2〇-> Si-OH + HNCO (ii) is crosslinked by dehydration condensation reaction of the formed stanol with the hydroxyl group of the siloxane;
Si-OH + Si-OH — Si-〇-Si + H2〇 -14- 200902669 (ui)同時與在末端具有羥基之矽氧烷反應Si-OH + Si-OH — Si-〇-Si + H2〇 -14- 200902669 (ui) simultaneously reacts with a oxane having a hydroxyl group at the terminal
Si-0H + H0-Si(CH3)2-0 〜—Si-0-Si(CH3)2-〇〜+ H2〇 (iv)在（ii)及（iii)所生成之水分被供給至異氰酸酯矽烷而 進行交聯反應。 認爲是由於交聯反應導致HNCO變爲與水反應而產 生二氧化碳及氨，異氰酸酯基係被排出至反應系統外。 HNCO + H2〇-^ NH3 + CO2 又，藉由三聚氰胺系化合物（z 1)或胍胺系化合物（z 2) 之反應基的-NH2與-OH係與異氰酸酯矽烷或矽烷醇基同 時反應而得之本發明之表面層（C)，由於具有脫膜性及耐 溶劑性，即使以醇類等之溶劑洗淨亦不脫落，脫膜效果 不會降低，重複曝光曝光·使用時之耐久性亦爲良好。 因此，適合用來作爲在印刷基板形成步驟中，用以 保護密接於具有黏著性光阻而使用之曝光用光罩表面的 光罩保護用黏著膠帶之表面層（C)。 3.中間層（D) 在本發明中，當在基材薄膜或片材（A)與表面層（C) 之間設有中間層（D)時，中間層（D)係無特別限定，惟較 佳爲從含有下述三聚氰胺系化合物U1)及/或胍胺系化合 物（z2)的混合物所得到之硬化物所構成者。 (1) (z 1):三聚氰胺系化合物 在中間層使用三聚氰胺系化合物的情況’主要理由 爲提升與作爲基材薄膜或片材（A)所使用之PET及/或與 表面層（C)之密接性。 藉由使在中間層100重量份中，含有之三聚氰胺系 -15- 200902669 化合物爲5重量％以上、更佳爲1 5重量％>以上，能夠提 升與作爲基材薄膜或片材（A)所使用之PET及/或與表面 層（C)之密接性。若爲5重量％以下則無法得到充分的密 接性。 作爲三聚氰胺系化合物，從基材薄膜或片材（A)與表 面層（C)之密接力的觀點而言，期望爲在反應性佳之末端 有OH基的羥甲基系三聚氰胺。作爲羥甲基系三聚氰胺 係從單羥甲基三聚氰胺到六羥甲基三聚氰胺。羥甲基三 聚氰胺之中，從反應性之觀點而言，較佳爲六羥甲基三 聚氰胺。 三聚氰胺系化合物係可單獨使用，亦可倂用2種類 以上。 於中間層（D)，在不妨害三聚氰胺系化合物的黏著提 升作用之範圍內，除了三聚氰胺系化合物以外亦可含有 其他黏結劑樹脂等。 作爲黏結劑樹脂，可因應基材種類加以選擇與基材 之黏著性優良者。較佳爲，宜採用可與三聚氰胺系化合 物硬化之樹脂。藉由含有此種可與三聚氰胺系化合物硬 化之樹脂，能夠顯現中間層（D)之耐溶劑性、及中間層（D) 與基材（A)及/或與表面層（C)之密接性。在此，作爲與三 聚氰胺系化合物硬化之樹脂，有丙烯酸系樹脂、醇酸系 樹脂、聚酯系樹脂、聚矽氧系樹脂等。 作爲中間層（D)，形成含有三聚氰胺化合物之硬化物 層之方法’可在透明基材薄膜或片材（A)的單面上，將混 合物以有機溶劑稀釋且塗布後加熱乾燥而得。作爲塗布 -16- 200902669 方法，可使用旋轉塗布法、噴塗法、凹版印刷等之輥塗 法、模塗法等方法。 (2)(z2):胍胺系化合物 在中間層（D)使用胍胺系化合物的情況’主要理由爲 提升與作爲基材薄膜或片材（A)所使用之PET及/或與表 面層（C)之密接性。 藉由使在中間層1 00重量份中，所含有之胍胺系化 合物爲5重量％以上、更佳爲1 5重量％以上含有’能夠 提升與作爲基材薄膜或片材（A)所使用之PET及/或與表 面層（C)之密接性。若小於5重量％則無法得到充分之密 接性。 胍胺系化合物係可單獨使用，亦可倂用2種類以上。 作爲用於本發明之胍胺系化合物，可列舉苯胍胺、 乙胍胺、環己烷碳胍胺、環己烯碳胍胺、降莰烯碳胍胺 及其衍生物之羥甲基化胍胺或烷基醚化體。 含有胍胺系化合物的硬化物之中，尤其以使用苯胍 胺及其衍生物之硬化物係因與作爲薄膜或片材（A)而使 用之PET及/或與表面層（C)之密接性良好，因而較佳。 於中間層（D)，與使用三聚氰胺系化合物的情況同樣 地，在不妨害胍胺系化合物之黏著提升作用的範圍內， 可含有其他黏結劑樹脂等。 作爲黏結劑樹脂，可因應基材種類加以選擇與基材 之黏著性優良者。較佳爲，宜採用可與胍胺系化合物硬 化之樹脂。藉由含有此種可與胍胺系化合物硬化之樹 脂，能夠顯現中間層（C)之耐溶劑性、及中間層（D)與基 -17- 200902669 材（A)及/或與表面層（C)之密接性。 作爲與胍胺系化合物硬化之樹脂，有丙烯酸系樹 脂、醇酸系樹脂、聚酯系樹脂、聚矽氧系樹脂等。例如， 與經羥甲基化之胍胺系化合物之反應，可爲藉由加熱具 有矽烷醇基之聚矽氧系樹脂，進行縮合反應而使其硬化。 作爲中間層（D)，形成含有胍胺系化合物的硬化物層 之方法，可在透明基材薄膜或片材（A)的單面上將混合物 以有機溶劑稀釋並塗布後加熱乾燥而得。作爲塗布方 法’可採用旋轉塗布法、噴塗法、凹版印刷等之輥塗法' 模塗法等方法。 4 .黏著劑層（B ) 在本發明所使用之黏著劑層（B)係貼附在光罩之曝 光用原稿的表面之物，並無特別限制，惟若考慮透明性 時，較佳爲丙烯酸系黏著劑。作爲丙烯酸系黏著劑，較 佳爲以（甲基）丙烯酸酯單體與含有官能基之單體之共 聚物所構成之丙烯酸系聚合物爲主成分者，關於聚合方 法並無特別限制。 作爲（甲基）丙烯酸酯，可列舉（甲基）丙烯酸丁 酯、（甲基）丙烯酸-2-乙基己酯、（甲基）丙烯酸辛酯等， 可單獨使用、亦可倂用二種以上。其中，在低的黏彈 性之點而a ’較佳爲丙烯酸丁酯、丙烯酸乙基己酯。 作爲含有官能基之單體’可列舉例如，丙烯酸、甲 基丙烯酸等。 作爲上述丙烯酸系黏著劑，較佳爲在丙烯酸系聚合 物内部具有部分父聯構造者。藉由具有交聯構造可提高 -18- 200902669 黏著劑之凝集力，因此在膠帶剝離時變得不容易有膠殘 留。此種交聯構造係可藉由使用能夠與前述含有官能基 之單體反應的交聯劑而形成，作爲交聯劑’適合使用例 如，環氧基交聯劑、脂肪族或芳香族異氰酸酯系交聯劑 等。 作爲形成黏著劑層（B)之方法，可採用：使用凹版印 刷等之輥塗機、逗點塗布機（comma coater)、模塗機等， 在分隔壁（separator)的單面上直接塗布黏著劑並乾燥之 方法、或暫時在脫膜紙上以相同方法設置黏著劑層後， 轉印至分隔壁的單面之方法等。 上述黏著劑層（B)之厚度較佳爲依照黏著力等加以 適當決定，具體而言較佳爲卜50// m、更佳爲2〜25μ m。 若小於1 μ m，則對光罩的黏著強度不足、對於光罩 的凹凸在黏著時有捲入氣泡的情形，另一方面，若超過 5 0 μ m，則無法得到充分之光透過性、使用散射光之光源 時由於光散射而成爲圖案解析度降低的原因。 在本發明中，爲使黏著力提升，亦可摻合使用所謂 增黏樹脂（tackifier)成分。所謂增黏成分、亦可爲增黏 劑，係摻合在彈性體以提升黏著性機能之物質，通常爲 分子量從數百到數千之無定型低聚物、在常溫爲液狀或 固態之熱可塑性樹脂。 增黏成分（tackifier)的種類並無特別限定，可例示以 松香系樹脂、萜烯系樹脂爲代表之天然樹脂系、或脂肪 族系、芳香族系、共聚合系之石油樹脂、酚系樹脂、二 甲苯樹脂等之合成樹脂系。該等係可單獨使用、亦可倂 -19- 200902669 用2種類以上。 增黏成分由於通吊阻礙光的透過，爲了不使霧度値 增大且達成適合的黏著性能，較佳爲倂用松香系樹脂、 萜烯酚系樹脂來使用。 增黏成分之摻合量相對於黏著劑成分100重量份而 言’較佳爲5~80重量份、更佳爲8~50重量份。若增黏 成分之摻合量過少’則無法得到必要之黏著力，相反地， 若過多’於再剝離時在表面上無法一起剝離基材與黏著 層，亦即容易發生殘膠的問題，變得難以實際使用。 5 .其他層 (1)抗靜電層 在上述基材設有黏著劑層（B)之面的相反側面上，只 要不影響光透過性，可設置抗靜電層等。上述抗靜電層 具有防止膠帶帶有靜電而吸附空氣中的灰塵等之作用。 作爲上述抗靜電層，在不損及表面層（C)之密接性的 範圍內可自由地選擇。 作爲抗靜電劑，可單獨或組合使用例如，第4級錶 鹽 '第1 ~3級胺基等陽離子性抗靜電劑、磺酸鹽基、硝 酸酯鹽基、磷酸酯鹽基等陰離子性抗靜電劑、胺基酸系 之兩性抗靜電劑、甘油系或聚乙二醇系之非離子性抗靜 電劑等。 此外，可列舉將導電性微粒子分散在丙烯酸等之樹 脂中而成之物等。作爲上述導電性微粒子並無特別限 定，例如，氧化銻錫微粒子等係因不容易對光透過性產 生影響，因而較佳。 -20- 200902669 藉由將上述抗靜電劑塗布在塑膠製品的表面使混入 内部，可得抗靜電層。 (2)保護薄膜層 又’在黏著劑層（B)側的最外面爲了保護黏著劑層並 容易處理，較佳爲層積保護層。作爲上述保護層並無特 別限定’可列舉例如，形成有聚矽氧系脫膜層之聚對苯 二甲酸乙二酯薄膜等。該保護層係在將本發明之光罩保 護用黏著膠帶貼附於光罩之前，從黏著膠帶予以剝離。 保護薄膜的厚度並無特別限定，通常係使用12〜75m m之 範圍者。 6.光罩保護用黏著膠帶 本發明之光罩保護用黏著膠帶，其特徵係包括透明 基材薄膜或片材（A)、形成在其單面上之黏著劑層（B)、 以及形成在與黏著劑層（B)面相反的側邊之面上的表面 層（C)之光罩保護用黏著膠帶，表面層（C)係由含有異氰酸 酯矽烷（X)及在末端具有羥基之矽氧烷（y)的混合物之硬 化物所構成。 又，再者，亦可設置中間層（D)、及作爲其他層之抗 靜電層、保護層等。 因此，本發明之光罩保護用黏著膠帶係在密接曝光 的重複步驟中，可對光阻持續地具有剝離性。此外，有 來自光罩保護用黏著膠帶表面層之光阻的污染附著物 時，即使以醇類等之溶劑洗淨，表面層亦不脫落之光罩 保護用黏著膠帶之效果’其特徴爲能夠以效率上·經濟上 優異之方法製造印刷配線板。 -21- 200902669 實施例 以下藉由本發明之實施例及比較例進一步詳細地說 明本發明，惟本發明係不受此等實施例所限定。 1.評價方法 對於在實施例及比較例所得之光罩保護用黏著膠 帶，用以下方法進行評價。 (1) 乙醇磨耗試驗： 將用吸收了 1 g乙醇而弄濕之脫脂綿包住之200g砝 碼，負載於光罩保護用黏著膠帶的表面層，來回移動50 次及1 0 0次。在該試驗面以2 k g的滾筒押壓貼合丙烯酸 系黏著膠帶（日東電工公司製「#31B」），而製作評價用 試料。將該評價用試料在常溫放置3 0分鐘後，以剝離速 度3 00mm/分進行光罩保護用黏著膠帶之180度剝離試 驗，來測定剝離強度。與初期値相比，剝離強度增加量 少者爲佳。 (2) 密接曝光試驗： 首先’將光罩保護用黏著膠帶貼附於沒有圖案之素 面經顯影光罩（富士照相軟片公司製「I P L 1 7 5 S H G」）。 接著，在0.8mm厚的玻璃環氧基板上部，用經施加 銅箔厚3 5 μ m之測試圖案的測試基板、以網版印刷機塗 布顯影型軟焊光阻印墨光阻（太陽印墨公司製 PSR-4000 AUS308/CA-40AUS308 = 70/30)，以在 80°C 乾燥 30 分鐘後 之膜厚成爲大致3 0 μ m的方式來製作測試基板。用該基 板’以ORC製作所公司製HMW-20D，在紫外線照度 400mJ/cm2、真空抽弓| 750mmHg的條件下實施密接曝光試 -22- 200902669 驗。 實施密接曝光試驗1 ο 〇次及5 0 0次後，針對光罩保 護用黏著膠帶實施下述評價。 •外觀目視觀察 觀察白化之表面變化。 •光學特性 對經實施密接曝光試驗之附有光罩保護用黏著膠帶 的光罩’根據ns Κ 7105，用分球式濁度計（日本電色工 業公司製、NDH-20) ’測定霧度値（％)。沒附有光罩保護 用黏著膠帶之光罩的霧度爲5，附有光罩保護用黏著膠 帶的光罩爲6。密接曝光試驗後之霧度値變化爲少者係 爲良好。超過9者爲不佳。 •剝離強度 實施與乙醇摩耗試驗同樣的膠帶剝離試驗。與初期 値相比，剝離強度增加量少者爲良好。若超過 1.0N/25mm，則因裝置問題的可能性變高，因而不佳。 (3)綜合評價： 可使用之物（良品）記爲「〇」、特優之物記爲「◎」、 使用上有問題之物（不佳）記爲「X」。 2 .實施例及比較例 [實施例1] 在PET基材之單面經形成聚矽氧脫膜劑層之厚度 2 5从m的分隔壁（LINTEC公司製）上，以甲苯將異氰酸酯 交聯型之丙烯酸系黏著劑（綜硏化學公司製「SK DYNE 1425」）稀釋爲10重量％之固體成分濃度並塗布後，在120 -23- 200902669 °C乾燥30秒鐘，設置乾燥後之厚度5"m的黏著劑層。 接著，將上述黏著劑層與厚度6μιη之經雙軸延伸之透明 PET基材薄膜（東麗公司製「F53#6C」）積層，而製作成黏 著膠帶。 然後，將上述黏著膠帶之透明PET基材表面，以和 光純藥工業公司製「濕潤張力試驗用混合液N〇48.0」之 不沾的方式實施電暈處理後，在其上面以乙酸乙酯將三 異氰酸甲酯（松本製藥公司製「SI-310」）80重量份與二醇 矽氧烷（信越化學公司製「KF-9701」）20重量份之混合物 稀釋爲2重量％的固體成分濃度並塗布後，在ll〇°c乾燥 120秒鐘，而製作成設有乾燥後之厚度〇.iMm的表面層 之光罩保護用黏著膠帶。評價結果示於表1。 [實施例2 ] 在與實施例1同樣地施行電暈處理而作成之黏著膠 帶的上面，以MEK將作爲聚矽氧樹脂之聚矽氧樹脂（東 麗·道康寧公司製「SR2410」）60重量份、與作爲三聚氰 胺樹脂之羥甲基型甲基化三聚氰胺樹脂（三井CYTEC公 司製「Cymel 370」）40重量份之混合物稀釋爲5重量％ 之固體成分濃度並塗布後，在130 °C乾燥120秒鐘，而得 乾燥後之厚度Ο.ΐμ m之聚矽氧系樹脂與三聚氰胺樹脂所 構成之中間層。 在上述中間層的上面以乙酸乙酯將三異氰酸甲酯 (松本製藥公司製「SI-310」）80重量份與二醇矽氧烷（信 越化學公司製「KF-970 1」）20重量份的混合物稀釋成2 重量％之固體成分濃度並塗布後，在1 1 〇 °C乾燥1 2 0秒 -24- 200902669 鐘，而製作成設有乾燥後之厚度O.l^m的表面層（脫膜 層）之光罩保護用黏著膠帶。評價結果示於表1。 [實施例3 ] 將中間層以MEK、丁醇將聚矽氧系樹脂（東麗.道康 寧公司製「SR2410」）60重量份與作爲胍胺化合物之甲基 及η-丁基混合醚化苯胍胺（三和化學品公司製「NIKALAC ΒΧ-4000」）40重量份的混合物稀釋成5重量％之固體成 分濃度並塗布後，在130 °C乾燥120秒鐘，而製作成乾燥 後之厚度O.lwm之光罩保護用黏著膠帶以外，與實施例 2同樣地進行。評價結果示於表1 [實施例4] 除了將表面層（脫膜層）以乙酸乙酯將甲基三異氰酸 酯矽烷（松本製藥公司製「SI-310」）70重量份、四異氰酸 酯矽烷（松本製藥公司製「SI-400」）10重量份、與二醇矽 氧烷（信越化學公司製「KF-9701」）20重量份之混合物稀 釋成2重量％之固體成分濃度且塗布後，在1 l〇t乾燥120 秒鐘，製作成設有乾燥後之厚度0.1/zm的表面層（脫膜 層）之光罩保護用黏著膠帶以外，與實施例3同樣地進 行。評價結果示於表1。 [實施例5] 在與實施例1同樣地施行電暈處理而製成之黏著膠 帶上面，以MEK將甲基三異氰酸酯（松本製藥公司製 「SI-3 10」）80重量份、二醇矽氧烷（信越化學公司製 「KF-970 1」）20重量份、與作爲三聚氰胺系化合物之羥 甲基型甲基化三聚氰胺樹脂（三井CYTEC公司製「Cymel -25- 200902669 3 70」）40重量份的混合物稀釋成5重量％之固體成分濃度 且塗布後’在130°C乾燥120秒鐘，製作成設有乾燥後之 厚度O.l^m之表面塗布層的光罩保護用黏著膠帶。評價 結果不於表1。 [實施例6] 在與實施例1同樣地施行電暈處理而製成之黏著膠 帶上面’以MEK及丁醇將甲基三異氰酸酯（松本製藥公 司製「SI-310」）80重量份、二醇矽氧烷（信越化學公司製 「KF-970 1」）20重量份、與作爲胍胺系化合物之甲基及 η-丁基混合醚化苯胍胺（三和化學品公司製「NIKALAC ΒΧ-4000」）30重量份之混合物稀釋成5重量％之固體成 分濃度並塗布後，在1 30°C乾燥1 20秒鐘，製作成設有乾 燥後之厚度O.lMm之表面塗布層的光罩保護用黏著膠 帶。評價結果示於表1。 [比較例1 ] 將上述製作之實施例1的表面層以甲苯將加成反應 型聚矽氧（東麗·道康寧公司製「LTC750A」）100重量份與 鉬觸媒（東麗·道康寧公司製SRS212)1重量份及矽烷偶合 劑（7 -環氧丙氧基丙基三甲氧基敬院（Momentive Material Japan公司製「-TSL8350」））1重量份的混合物稀 釋成5重量％之固體成分濃度並塗布後’在11〇 °C乾燥120 秒鐘，製作成乾燥後之厚度變更爲m之光罩保護用 黏著膠帶。評價結果示於表1。 [比較例2] 除了在上述製作之實施例2的中間層上面，以甲苯 -26- 200902669 將加成反應型聚矽氧（東麗·道康寧公司製 「LTC7 5 0A」）1〇0重量份與鉑觸媒（東麗·道康寧公司製 SRS212)1重量份及矽烷偶合劑（r -環氧丙氧基丙基三甲 氧基砂院（Momentive Material Japan 公司製「TSL8350」））1 重量份之混合物稀釋成5重量％之固體成分濃度並塗布 後，在1 10°C乾燥120秒鐘，製作成設有乾燥後之厚度 0.3μιη之表面層（脫膜層）的光罩保護用黏著膠帶以外， 同樣地進行。評價結果示於表1。 [比較例3] 除了在上述製作之實施例3的中間層上面，製作比 較例2之設有表面脫膜層（表面層）的光罩保護用黏著膠 帶以外，與實施例3同樣地進行。評價結果示於表1。 [比較例4 ] 在與實施例5同樣地施行電暈處理製作之黏著膠帶 的上面，以ΜΕΚ將加成反應型聚矽氧（東麗·道康寧公司 製「LTC750A」）100重量份、鉑觸媒（東麗.道康寧公司製 「SRS212」）1重量份、與作爲三聚氰胺系化合物之羥甲 基型甲基化三聚氰胺樹脂（三井CYTEC公司製「Cymel 370」）40重量份的混合物稀釋成5重量％之固體成分濃度 並塗布後，在130°C乾燥120秒鐘，製作成設有乾燥後之 厚度0.3^m之表面塗布層的光罩保護用黏著膠帶。評價 結果示於表1。 [比較例5 ] 在與實施例5同樣地施行電暈處理所製作之黏著膠 帶的上面，以甲苯及MEK混合溶液將加成反應型聚矽氧 -27- 200902669 (東麗·道康寧公司製「LTC75 0A」）100重量份、鉑觸媒（東 麗·道康寧公司製「SRS212」）1重量份、與作爲胍胺系化 合物之甲基及η-丁基混合醚化苯胍胺（三和化學品公司 製「NIKALAC ΒΧ-4000」）30重量份的混合物稀釋成5重 量％之固體成分濃度並塗布後.，在130 °C乾燥120秒鐘， 製作成設有乾燥後之厚度0.3 w m的表面塗布層之光罩保 護用黏著膠帶。評價結果示於表i。 -28- 200902669 綜合評價 4髒塗 m 霧度(％) M El πυ ϋ 乙醇磨耗 實驗 N/25mm 雜> )¾¾ Μ 500次後 100次後 初期 500次後 100次後 初期 500次後 100次後 來回100次後 來回50次後 初期 構成 〇 〇〇 σ\ Ο 幾乎無 變化 無變化 透明 § p P δ δ 單層 實施例 1 ◎ ON 〇\ 幾乎無 變化 無變化 透明 δ Ο L〇 δ s δ to _ 實施例 2— ◎ ON ON !幾乎無 化 無變化 透明 δ s δ ο Lo δ I>〇 實施例 3 ◎ as 幾乎無 變化 無變化 透明 p s δ δ δ to _ 實施例 4 ◎ σ\ 幾乎無 變化 無變化 透明 δ δ δ δ δ 單層 實施例 5 ◎ CTn 〇\ 幾乎無 變化 無變化 透明 s δ δ δ δ 單層 實施例 6 X 1 !Ιλ On 1 nl· 透明 1 to to g δ 單層 比較例 1 X 1 〇〇 ON 1 Ol· 透明 1 •Κ) ο δ δ tsJ _ 比較例 2 X 1 CO 〇\ 1 El· 透明 1 to ρ δ δ _ 比較例 3 X 1 I—* On 1 透明 1 to to § δ 單層 比較例 4 X 1 5； Ο 1 nl· 透明 1 g δ 單層 CT ^ Μ 200902669 3 .評價結果 由表1之評價結果，與未滿足發明特定事項之比較例 做比較。 實施例1係不具有中間層（D)之構成，即使乙醇磨耗試 驗來回50次也幾乎沒有膠帶剝離力之變化，即使是重複密 接曝光試驗1 00次後，外觀變化及膠帶剝離性也幾乎沒有 變化。在乙醇磨耗試驗來回100次及重複曝光密接曝光試 驗1 00次後，外觀雖無變化但是膠帶剝離性有稍微上昇傾 向，爲能夠充分使用之良品的範圍。 比較例1係不具有中間層（D)、並非本發明之表面層的 構成，在乙醇磨耗試驗50次而膠帶剝離力的變化爲大，重 複曝光密接曝光試驗1 00次後的外觀發生白化、光阻成分 附著、對光阻之剝離性顯著降低。由於霧度的變化亦爲顯 著，膠帶之剝離力亦變爲初期的1 〇倍以上，因而不佳。 實施例2係具有中間層（D)之構成者，即使是乙醇磨耗 試驗來回1 00次及500次，亦幾乎沒有膠帶剝離力之變化， 進一步提高了實施例1之品質。此外，重複曝光密接曝光 試驗1 0 0次及5 0 0次後的外觀變化及膠帶剝離性亦幾乎沒 有變化，爲非常優異之良品。 比較例2係具有中間層（D)、並非本發明之表面層的構 成，在乙醇磨耗試驗50次及1 00次之膠帶剝離力的變化爲 小且良好。但是重複曝光密接曝光試驗1 〇〇次後的外觀發 生白化、光阻成分附著、且對光阻之剝離性顯著降低。由 於霧度的變化亦爲顯著，膠帶之剝離力也變爲初期的1 0倍 -30- 200902669 以上，因而不佳。 實施例3係將中間層（D)由實施例2的三聚氰胺系樹脂 變更爲含有胍胺系樹脂之物的構成’與實施例2同樣地進 行乙醇磨耗試驗來回100次及500次、與重複曝光密接曝 光試驗1 0 0次及5 0 0次後的外觀變化及膠帶剝離性幾乎沒 有變化，爲非常優異之良品。 實施例4係將實施例3的異氰酸酯矽烷再加上三異氰 酸甲酯矽烷摻合四異氰酸酯矽烷而成者，重複曝光密接曝 光試驗5 0 0次後之膠帶剝離性係稍微變化小之物’爲非常 優異之良品。 比較例3係將中間層（D)從比較例2的三聚氰胺系樹脂 變更爲含有胍胺系樹脂之物的構成。與比較例2同樣地進 行乙醇磨耗試驗50次及1 00次之膠帶剝離力的變化小係爲 良好。但是，重複曝光密接曝光試驗100次後的外觀發生 白化、光阻成分附著、且對光阻之剝離性顯著降低。由於 霧度的變化亦爲顯著，膠帶之剝離力也變爲初期的1〇倍以 上，因而不佳。 實施例5係不具有中間層（D)之構成者，即使乙醇磨耗 試驗來回100次及500次，亦幾乎沒有膠帶剝離力之變化。 此外，重複曝光密接曝光試驗1〇〇次及500次後之外觀變 化及膠帶剝離性亦幾乎無變化’具有與實施例2同等之品 質，爲非常優異之良品。 比較例4係將實施例5之表面層變更爲不是本發明之 表面層的構成，進行乙醇磨耗試驗50次，膠帶剝離力的變 -31 - 200902669 化大，重複曝光密接曝光試驗1 00次後的外觀發生白化、 光阻成分附著、對光阻之剝離性顯著降低。由於霧度的變 化亦爲顯著，膠帶之剝離力也變爲初期的1 0倍以上’因而 不佳。 實施例6係不具有中間層（D)之構成，且將實施例5的 三聚氰胺系樹脂變更爲胍胺系樹脂之物。即使進行乙醇磨 耗試驗來回1 0 0次及5 0 0次，幾乎沒有膠帶剝離力之變化。 此外，重複曝光密接曝光試驗1 〇 〇次及5 0 0次後的外觀變 化及膠帶剝離性亦幾乎無變化，具有與實施例3同等之品 質，爲非常優異之良品。 比較例5係將實施例6之表面層變更爲非本發明之表 面層之構成，進行乙醇磨耗試驗50次，膠帶剝離力的變化 大，重複曝光密接曝光試驗1 00次後的外觀發生白化、光 阻成分附著、對光阻之剝離性顯著降低。由於霧度的變化 亦爲顯著，膠帶之剝離力也變爲初期的1 0倍以上，因而不 佳。 因此，由表1之評價結果，可明白實施例所得之光罩 保護用黏著膠帶與比較例所得之光罩保護用黏著膠帶相 比，耐溶劑性優異、脫膜性優異，因此爲優良的光罩保護 用黏著膠帶。 產業上之可利用件 由以上可知，本發明之光罩保護用黏著膠帶係在密接 曝光的重複步驟中，可對光阻持續地具有剝離性。此外， 當有來自光罩保護用黏著膠帶表面層之光阻的污染附著物 -32- 200902669 時，即使以醇類等之溶劑洗淨，表面層亦不脫落’而有光 罩保護用黏著膠帶之效果，具有能夠以效率上·經濟上優異 之方法製造印刷配線板之特徴。因此，尤其適合作爲光罩 保護用黏著膠帶。 【圖式簡單說明】 第1圖爲顯示本發明之光罩保護用黏著膠帶的一個例 子之構成的模式剖面圖。（實施例1 '實施例5、實施例6) 第2圖爲顯示本發明之光罩保護用黏著膠帶的一個例 子之構成的模式剖面圖。（實施例2、實施例3、實施例4) 【主要元件符號說明】 A 透明基材薄膜或片材 B 黏著劑層 C 表面層 D 中間層 -33-Si-0H + H0-Si(CH3)2-0~-Si-0-Si(CH3)2-〇~+ H2〇(iv) The water generated in (ii) and (iii) is supplied to the isocyanate decane The cross-linking reaction is carried out. It is considered that the HNCO reacts with water to cause carbon dioxide and ammonia due to the crosslinking reaction, and the isocyanate group is discharged to the outside of the reaction system. HNCO + H2〇-^ NH3 + CO2 Further, the -NH2 and -OH groups of the melamine-based compound (z 1) or the amide-based compound (z 2) are simultaneously reacted with an isocyanate decane or a stanol group. Since the surface layer (C) of the present invention has a release property and a solvent resistance, even if it is washed with a solvent such as an alcohol, it does not fall off, and the release effect is not lowered, and the durability during repeated exposure, exposure, and use is also For the good. Therefore, it is suitably used as a surface layer (C) for protecting the surface of the exposure mask for use in an exposure mask having an adhesive photoresist in the step of forming the printed substrate. 3. Intermediate Layer (D) In the present invention, when the intermediate layer (D) is provided between the base film or the sheet (A) and the surface layer (C), the intermediate layer (D) is not particularly limited. However, it is preferably composed of a cured product obtained from a mixture containing the following melamine-based compound U1) and/or a amide-based compound (z2). (1) (z 1): When a melamine-based compound is used as a melamine-based compound in the intermediate layer, the main reason is to enhance the PET and/or the surface layer (C) used as the base film or sheet (A). Adhesion. By making the melamine-based compound -15-200902669 compound 5% by weight or more, more preferably 15% by weight or more, based on 100 parts by weight of the intermediate layer, it can be improved as a base film or sheet (A) The PET used and/or the adhesion to the surface layer (C). If it is 5% by weight or less, sufficient adhesion cannot be obtained. From the viewpoint of the adhesion between the base film or the sheet (A) and the surface layer (C), the melamine-based compound is preferably a methylol-based melamine having an OH group at the end of the reactivity. As the methylol melamine, it is a monomethylol melamine to hexamethylol melamine. Among the methylol melamine, hexamethylol melamine is preferred from the viewpoint of reactivity. The melamine-based compound may be used singly or in combination of two or more. In the intermediate layer (D), other binder resins may be contained in addition to the melamine-based compound insofar as the adhesion of the melamine-based compound is not impaired. As the binder resin, the adhesion to the substrate can be selected depending on the type of the substrate. Preferably, a resin which is hardenable with a melamine-based compound is preferably used. By containing such a resin which can be cured with the melamine-based compound, the solvent resistance of the intermediate layer (D) and the adhesion between the intermediate layer (D) and the substrate (A) and/or the surface layer (C) can be exhibited. . Here, examples of the resin to be cured with the melamine-based compound include an acrylic resin, an alkyd resin, a polyester resin, and a polyoxymethylene resin. As the intermediate layer (D), a method of forming a cured layer containing a melamine compound can be obtained by diluting a mixture on one surface of a transparent base film or a sheet (A) with an organic solvent, coating, and then heating and drying. As a method of coating -16-200902669, a roll coating method such as a spin coating method, a spray coating method, or a gravure printing method, or a die coating method can be used. (2) (z2): When a guanamine-based compound is used as the base layer (D), the main reason is to enhance the PET and/or the surface layer used as the base film or sheet (A). (C) The adhesion. 5% by weight or more, more preferably 15% by weight or more of the content of the amide-based compound contained in 100 parts by weight of the intermediate layer can be improved and used as a base film or sheet (A) PET and/or adhesion to the surface layer (C). If it is less than 5% by weight, sufficient adhesion cannot be obtained. The guanamine compound may be used singly or in combination of two or more. Examples of the guanamine-based compound used in the present invention include hydroxymethylation of benzoguanamine, acetamide, cyclohexanecarbamine, cyclohexenecarbammine, norbornenecarboguanamine and derivatives thereof. Indoleamine or alkyl etherified body. Among the cured products containing a guanamine-based compound, in particular, a cured product using benzoguanamine or a derivative thereof is adhered to PET and/or surface layer (C) used as a film or sheet (A). Good sex, so it is better. In the intermediate layer (D), as in the case of using a melamine-based compound, other binder resin or the like may be contained in a range that does not impair the adhesion-promoting effect of the amide-based compound. As the binder resin, the adhesion to the substrate can be selected depending on the type of the substrate. Preferably, a resin which can be hardened with a guanamine compound is preferably used. By containing such a resin which can be cured with the amide-based compound, the solvent resistance of the intermediate layer (C), and the intermediate layer (D) and the base layer (A) and the surface layer (A) and/or the surface layer ( C) the adhesion. Examples of the resin which is cured with the guanamine-based compound include acrylic resin, alkyd resin, polyester resin, and polyoxyn resin. For example, the reaction with a methylolated guanamine compound can be carried out by heating a polyfluorene-based resin having a stanol group to carry out a condensation reaction. As the intermediate layer (D), a method of forming a cured layer containing a guanamine-based compound can be obtained by diluting and coating a mixture on one surface of a transparent base film or a sheet (A) with an organic solvent, followed by heating and drying. As the coating method, a method such as a roll coating method such as a spin coating method, a spray coating method or a gravure printing method, or a die coating method can be employed. 4. Adhesive layer (B) The adhesive layer (B) used in the present invention is attached to the surface of the exposure original of the photomask, and is not particularly limited, but when transparency is considered, it is preferably Acrylic adhesive. The acrylic polymer is preferably an acrylic polymer composed of a copolymer of a (meth) acrylate monomer and a functional group-containing monomer as a main component, and the polymerization method is not particularly limited. Examples of the (meth) acrylate include butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate. These may be used alone or in combination. the above. Among them, a ' is preferably butyl acrylate or ethyl hexyl acrylate at a point of low viscoelasticity. The monomer which contains a functional group ', for example, acrylic acid, methacrylic acid, etc. are mentioned. As the acrylic pressure-sensitive adhesive, it is preferred to have a part of the parent structure in the acrylic polymer. By having a crosslinked structure, the cohesive force of the adhesive of -18-200902669 can be improved, so that it is not easy to have glue residue when the tape is peeled off. Such a crosslinked structure can be formed by using a crosslinking agent capable of reacting with the above-mentioned functional group-containing monomer, and as the crosslinking agent, it is suitable to use, for example, an epoxy crosslinking agent, an aliphatic or aromatic isocyanate system. Crosslinking agent, etc. As a method of forming the adhesive layer (B), a roll coater such as gravure printing, a comma coater, a die coater, or the like may be used, and the adhesive layer may be directly coated on one side of a separator. The method of drying and drying the agent, or temporarily adding the adhesive layer to the release paper in the same manner, and then transferring it to one side of the partition wall. The thickness of the above-mentioned adhesive layer (B) is preferably determined in accordance with the adhesive force or the like, and is specifically preferably 50/m, more preferably 2 to 25 μm. When the thickness is less than 1 μm, the adhesive strength to the mask is insufficient, and when the unevenness of the mask is adhered, bubbles are caught. On the other hand, if it exceeds 50 μm, sufficient light transmittance cannot be obtained. When a light source of scattered light is used, the resolution of the pattern is lowered due to light scattering. In the present invention, in order to improve the adhesion, a so-called tackifier component may be blended. The so-called tackifying component, which may also be a tackifier, is a substance which is blended in an elastomer to improve the adhesive function, and is usually an amorphous oligomer having a molecular weight of several hundred to several thousand, and is liquid or solid at normal temperature. Thermoplastic resin. The type of the tackifier is not particularly limited, and examples thereof include a natural resin represented by a rosin-based resin or a terpene-based resin, or an aliphatic, aromatic, or copolymeric petroleum resin or a phenolic resin. A synthetic resin such as xylene resin. These systems can be used alone or in two or more categories from -19 to 200902669. The tackifying component is preferably used in the rosin-based resin or the terpene phenol-based resin in order to prevent the light from passing through, and to achieve an appropriate adhesive property without increasing the haze. The blending amount of the tackifying component is preferably from 5 to 80 parts by weight, more preferably from 8 to 50 parts by weight, per 100 parts by weight of the adhesive component. If the blending amount of the tackifying component is too small, the necessary adhesive force cannot be obtained. On the contrary, if the excess is not peeled off on the surface and the adhesive layer on the surface at the time of re-peeling, the problem of residual adhesive is liable to occur. It is difficult to use in practice. 5. Other layer (1) Antistatic layer An antistatic layer or the like may be provided on the opposite side of the surface on which the adhesive layer (B) is provided on the substrate, as long as it does not affect the light transmittance. The antistatic layer has a function of preventing the tape from being electrostatically charged and adsorbing dust or the like in the air. The antistatic layer can be freely selected within a range that does not impair the adhesion of the surface layer (C). As the antistatic agent, for example, a cationic antistatic agent such as a 4th to 3th amino group, a sulfonate group, a nitrate ester group or a phosphate group may be used alone or in combination. An electrostatic agent, an amino acid-based amphoteric antistatic agent, a glycerin-based or polyethylene glycol-based nonionic antistatic agent. Further, a material obtained by dispersing conductive fine particles in a resin such as acrylic acid or the like can be mentioned. The conductive fine particles are not particularly limited. For example, tin antimony fine particles or the like are preferred because they do not easily affect light transmittance. -20- 200902669 An antistatic layer is obtained by applying the above antistatic agent to the surface of a plastic article to be mixed therein. (2) Protective film layer Further, in order to protect the adhesive layer on the outermost side of the adhesive layer (B) side, it is preferable to laminate the protective layer. The protective layer is not particularly limited, and examples thereof include a polyethylene terephthalate film formed with a polyfluorene-based release layer. This protective layer is peeled off from the adhesive tape before the adhesive tape for mask protection of the present invention is attached to the mask. The thickness of the protective film is not particularly limited, and a range of 12 to 75 m is usually used. 6. Adhesive tape for reticle protection The adhesive tape for reticle protection of the present invention is characterized by comprising a transparent substrate film or sheet (A), an adhesive layer (B) formed on one surface thereof, and The surface layer (C) of the surface layer (C) opposite to the surface of the adhesive layer (B) is protected by an adhesive tape, and the surface layer (C) is composed of an isocyanate-containing decane (X) and a hydroxyl group having a hydroxyl group at the terminal. A cured product of a mixture of alkane (y). Further, an intermediate layer (D) and an antistatic layer, a protective layer or the like as another layer may be provided. Therefore, the adhesive tape for reticle protection of the present invention can be continuously peeled off to the photoresist in the repeated step of the adhesion exposure. In addition, when there is a contaminant adhering material from the photoresist of the surface layer of the adhesive tape for the reticle protection, the effect of the viscous tape for protecting the visor that does not fall off even if the solvent is washed with a solvent such as an alcohol is characterized in that it is capable of A printed wiring board is manufactured by an efficient and economically excellent method. - 21 - 200902669 EXAMPLES The present invention will now be described in further detail by way of examples and comparative examples of the invention, but the invention is not limited by these examples. 1. Evaluation method The adhesive tape for reticle protection obtained in the examples and the comparative examples was evaluated by the following method. (1) Ethanol abrasion test: A 200 g weight code wrapped with a degreased cotton moistened with 1 g of ethanol was placed on the surface layer of the adhesive tape for mask protection, and moved back and forth 50 times and 100 times. An acrylic adhesive tape ("#31B" manufactured by Nitto Denko Corporation) was attached to the test surface by a 2 k g roller press to prepare a sample for evaluation. After the evaluation sample was allowed to stand at room temperature for 30 minutes, a 180-degree peeling test of the mask protective pressure-sensitive adhesive tape was performed at a peeling speed of 300 mm/min to measure the peel strength. It is better to increase the amount of peel strength compared to the initial flaw. (2) Adhesive exposure test: First, the adhesive tape for mask protection was attached to a non-patterned surface-developed mask ("I P L 1 7 5 S H G" manufactured by Fuji Photo Film Co., Ltd.). Next, on a 0.8 mm thick glass epoxy substrate, a developing type solder resist photoresist (sun ink) was applied by a screen printing machine using a test substrate having a test pattern of a copper foil thickness of 35 μm. The company's PSR-4000 AUS308/CA-40AUS308 = 70/30) was used to produce a test substrate by drying at 80 ° C for 30 minutes and having a film thickness of approximately 30 μm. Using this substrate, HMW-20D manufactured by ORC Co., Ltd. was subjected to a close exposure test -22-200902669 under the conditions of ultraviolet illuminance of 400 mJ/cm 2 and vacuum drawing of 750 mmHg. After performing the adhesion exposure test 1 ο 〇 and 500 times, the following evaluation was performed for the adhesive tape for mask protection. • Appearance visual observation Observe the surface changes of whitening. • Optical characteristics The photomask of the viscous-protective adhesive tape that has been subjected to the close-contact exposure test is measured according to ns Κ 7105, using a ball turbidity meter (Nippon Denshoku Industries Co., Ltd., NDH-20) value(%). There is no reticle protection. The haze of the adhesive tape is 5, and the visor with the visor protection adhesive tape is 6. It is good that the haze change after the adhesion test is small. More than 9 are not good. • Peel strength The same tape peeling test as the ethanol abrasion test was carried out. Compared with the initial enthalpy, the increase in peel strength is small. If it exceeds 1.0 N/25 mm, the possibility of a device problem becomes high, which is not preferable. (3) Comprehensive evaluation: The usable product (good product) is marked as "〇", the special object is marked as "◎", and the problematic object (poor) is recorded as "X". 2. Examples and Comparative Examples [Example 1] The isocyanate was crosslinked with toluene on a single side of a PET substrate by forming a thickness of a polyfluorene stripper layer of 2 from m partition walls (manufactured by LINTEC). A type of acrylic adhesive ("SK DYNE 1425" manufactured by Kokusai Chemical Co., Ltd.) was diluted to a solid concentration of 10% by weight and applied, and dried at 120 -23 - 200902669 °C for 30 seconds to set the thickness after drying. ;m adhesive layer. Then, the adhesive layer and a biaxially stretched transparent PET base film ("F53#6C" manufactured by Toray Industries, Inc.) having a thickness of 6 μm were laminated to form an adhesive tape. Then, the surface of the transparent PET substrate of the adhesive tape was subjected to corona treatment so as not to adhere to the "wet tension test mixture N〇48.0" manufactured by Wako Pure Chemical Industries, Ltd., and then ethyl acetate was placed thereon. A mixture of 80 parts by weight of methyl triisocylate ("SI-310" manufactured by Matsumoto Pharmaceutical Co., Ltd.) and 20 parts by weight of a diol oxirane ("KF-9701" manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted to 2% by weight of a solid component. After the concentration was applied, it was dried at ll 〇 °c for 120 seconds to prepare a visor protective adhesive tape having a surface layer of a thickness of 〇.iMm after drying. The evaluation results are shown in Table 1. [Example 2] The top surface of the adhesive tape which was prepared by the corona treatment in the same manner as in Example 1, and the weight of the polyoxyxylene resin ("SR2410" manufactured by Toray Dow Corning Co., Ltd.) as a polyoxyxylene resin by MEK was 60 weights. The mixture was diluted with a mixture of 40 parts by weight of a methylol type methylated melamine resin (Cymel 370 manufactured by Mitsui Chemicals Co., Ltd.) as a melamine resin to a solid concentration of 5% by weight, and then dried at 130 ° C. In seconds, an intermediate layer composed of a polysiloxane resin having a thickness of Ο.ΐm and a melamine resin is obtained. 80 parts by weight of methyl triisocylate ("SI-310" manufactured by Matsumoto Pharmaceutical Co., Ltd.) and diol oxirane ("KF-970 1" manufactured by Shin-Etsu Chemical Co., Ltd.) 20 were added to the upper surface of the intermediate layer by ethyl acetate. After the mixture of the parts by weight is diluted to a solid content concentration of 2% by weight and coated, it is dried at 1 1 〇 ° C for 1 to 20 seconds - 24 to 02,02669 minutes to prepare a surface layer having a thickness of 0.01 μm after drying ( Adhesive tape for reticle protection of the release layer). The evaluation results are shown in Table 1. [Example 3] 60 parts by weight of a polyfluorene-based resin ("SR2410" manufactured by Toray Dow Corning Co., Ltd.) and ME and η-butyl mixed etherified benzene as a guanamine compound in an intermediate layer of MEK and butanol 40 parts by weight of a mixture of decylamine ("NIKALAC ΒΧ-4000" manufactured by Chemicals Co., Ltd.) was diluted to a solid concentration of 5% by weight and coated, and then dried at 130 ° C for 120 seconds to prepare a dried thickness. The adhesive tape for reticle protection of O.lwm was carried out in the same manner as in Example 2. The evaluation results are shown in Table 1. [Example 4] 70 parts by weight of methyl triisocyanate decane ("SI-310" manufactured by Matsumoto Pharmaceutical Co., Ltd.) and tetraisocyanate decane ( Matsumoto) were added to the surface layer (release layer). 10 parts by weight of a "SI-400" manufactured by a pharmaceutical company, and a mixture of 20 parts by weight of a diol oxirane ("KF-9701" manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted to a solid content concentration of 2% by weight and coated, and then 1 This was carried out in the same manner as in Example 3 except that the surface layer (release layer) having a thickness of 0.1/zm after drying was formed to dry for 120 seconds. The evaluation results are shown in Table 1. [Example 5] 80 parts by weight of methyl triisocyanate ("SI-3 10" manufactured by Matsumoto Pharmaceutical Co., Ltd.) and diol oxime were subjected to corona treatment in the same manner as in Example 1. 20 parts by weight of oxyalkylene ("KF-970 1" manufactured by Shin-Etsu Chemical Co., Ltd.) and hydroxymethyl-type methylated melamine resin ("Cymel -25- 200902669 3 70" manufactured by Mitsui Chemicals Co., Ltd.) as a melamine-based compound 40 weight The mixture was diluted to a solid content concentration of 5% by weight, and after coating, it was dried at 130 ° C for 120 seconds to prepare a mask protective adhesive tape having a surface coating layer having a thickness of 0.01 μm after drying. The evaluation results are not shown in Table 1. [Example 6] 80 parts by weight of methyl triisocyanate ("SI-310" manufactured by Matsumoto Pharmaceutical Co., Ltd.), which was obtained by performing corona treatment in the same manner as in Example 1, and 80 parts by weight of MEK and butanol. 20 parts by weight of an alcohol oxime ("KF-970 1" manufactured by Shin-Etsu Chemical Co., Ltd.), and a mixture of a methylamine and a η-butyl group as a guanamine-based compound, an etherified benzoguanamine ("NIKALAC 制", manufactured by Sanwa Chemical Co., Ltd. -4000") 30 parts by weight of the mixture was diluted to a solid content concentration of 5% by weight and coated, and then dried at 1 30 ° C for 1 20 seconds to prepare a light having a surface coating layer having a thickness of 0.1 Mm after drying. Adhesive tape for cover protection. The evaluation results are shown in Table 1. [Comparative Example 1] 100 parts by weight of an addition reaction type polyfluorene ("LTC750A" manufactured by Toray Dow Corning Co., Ltd.) and molybdenum catalyst (manufactured by Toray Dow Corning Co., Ltd.) in the surface layer of Example 1 prepared above. SRS212) 1 part by weight and a decane coupling agent (7-glycidoxypropyltrimethoxy sulfonate ("TSL 8350", manufactured by Momentive Material Japan Co., Ltd.)) 1 part by weight of a mixture diluted to a solid concentration of 5% by weight After coating, it was dried at 11 ° C for 120 seconds to prepare an adhesive tape for mask protection which was changed to a thickness of m after drying. The evaluation results are shown in Table 1. [Comparative Example 2] In addition to the above-mentioned intermediate layer of Example 2, an addition reaction type polyoxo ("LTC7 5 0A" manufactured by Toray Dow Corning Co., Ltd.) was added in an amount of 1 to 0 parts by weight in toluene-26-200902669. 1 part by weight of a platinum catalyst (SRS212 manufactured by Toray Dow Corning Co., Ltd.) and a decane coupling agent (r-glycidoxypropyltrimethoxy sands ("TSL8350" manufactured by Momentive Material Japan Co., Ltd.)) 1 part by weight The mixture was diluted to a solid content concentration of 5% by weight and applied, and then dried at 10 ° C for 120 seconds to prepare a mask protective adhesive tape having a surface layer (release layer) having a thickness of 0.3 μm after drying. , the same goes on. The evaluation results are shown in Table 1. [Comparative Example 3] The same procedure as in Example 3 was carried out except that the adhesive layer for mask protection provided with the surface release layer (surface layer) of Comparative Example 2 was produced on the intermediate layer of Example 3 produced as described above. The evaluation results are shown in Table 1. [Comparative Example 4] In the same manner as in Example 5, 100 parts by weight of the addition reaction type polyfluorene ("LTC750A" manufactured by Toray Dow Corning Co., Ltd.) and platinum touch were applied to the upper surface of the adhesive tape produced by the corona treatment. 1 part by weight of a medium ("SRS212" manufactured by Toray Dow Corning Co., Ltd.) and a mixture of 40 parts by weight of a methylolated melamine resin (Cymel 370, manufactured by Mitsui Chemicals Co., Ltd.) as a melamine-based compound, diluted to 5 parts by weight After the solid content concentration of % was applied and dried, it was dried at 130 ° C for 120 seconds to prepare a mask protective adhesive tape having a surface coating layer having a thickness of 0.3 μm after drying. The evaluation results are shown in Table 1. [Comparative Example 5] The top surface of the adhesive tape prepared by corona treatment was applied in the same manner as in Example 5, and the addition reaction type polyoxyn oxynitride-27-200902669 (manufactured by Toray Dow Corning Co., Ltd.) was used as a mixed solution of toluene and MEK. LTC75 0A") 100 parts by weight, 1 part by weight of a platinum catalyst ("SRS212" manufactured by Toray Dow Corning Co., Ltd.), and a mixture of methyl and η-butyl groups as a guanamine compound (3 and chemistry) 30 parts by weight of a mixture of "NIKALAC ΒΧ-4000" manufactured by Seiko Co., Ltd. was diluted to a solid concentration of 5% by weight and coated, and dried at 130 ° C for 120 seconds to prepare a surface having a thickness of 0.3 wm after drying. Adhesive tape for reticle protection of the coating layer. The evaluation results are shown in Table i. -28- 200902669 Comprehensive evaluation 4 Dirty coating m Haze (%) M El πυ 乙醇 Ethanol abrasion test N/25mm Miscellaneous > 3⁄43⁄4 Μ After 500 times, 100 times after the initial 500 times, 100 times, after the initial 500 times, 100 times After 100 rounds, back and forth 50 times, the initial composition 〇〇〇σ\ Ο almost no change, no change, transparent § p P δ δ single layer example 1 ◎ ON 〇\ almost no change, no change, transparent δ Ο L〇δ s δ To _ Example 2 - ◎ ON ON ! Almost no change without change δ s δ ο Lo δ I> 〇 Example 3 ◎ as almost no change no change transparent ps δ δ δ to _ Example 4 ◎ σ\ almost none Change without change Transparent δ δ δ δ δ Single layer Example 5 ◎ CTn 〇\ Almost no change No change Transparent s δ δ δ δ Single layer Example 6 X 1 !Ιλ On 1 nl· Transparent 1 to to g δ Single layer Comparative Example 1 X 1 〇〇 ON 1 Ol· Transparent 1 • Κ) ο δ δ tsJ _ Comparative Example 2 X 1 CO 〇 \ 1 El · Transparent 1 to ρ δ δ _ Comparative Example 3 X 1 I—* On 1 Transparent 1 to to § δ single layer comparison example 4 X 1 5; Ο 1 nl· transparent 1 g δ single Layer CT ^ Μ 200902669 3. Evaluation results The evaluation results in Table 1 are compared with the comparative examples that do not satisfy the specific matters of the invention. In the first embodiment, the intermediate layer (D) was not provided, and even if the ethanol abrasion test was repeated 50 times, there was almost no change in the tape peeling force. Even after repeating the close exposure test for 100 times, the appearance change and the tape peeling property were hardly observed. Variety. After 100 times of the ethanol abrasion test and 100 times of the repeated exposure exposure test, the appearance did not change, but the tape peelability slightly increased, which was a range in which the product could be fully used. Comparative Example 1 is a structure which does not have the intermediate layer (D) and is not the surface layer of the present invention, and the change in the peeling force of the tape is large in the ethanol abrasion test 50 times, and the appearance is whitened after repeated exposure exposure test for 100 times. The photoresist component adheres and the peeling property to the photoresist is remarkably lowered. Since the change in haze is also remarkable, the peeling force of the tape is also more than 1 初期 times earlier than the initial one, which is not preferable. In the second embodiment, the intermediate layer (D) was used. Even if the ethanol abrasion test was repeated 100 times and 500 times, there was almost no change in the tape peeling force, and the quality of the first embodiment was further improved. Further, the appearance change and the tape peeling property after repeated exposure and exposure test 10 times and 500 times were hardly changed, and it was a very good product. In Comparative Example 2, the intermediate layer (D) was not provided in the surface layer of the present invention, and the change in the tape peeling force in the ethanol abrasion test 50 times and 100 times was small and good. However, after repeated exposure and exposure test 1, the appearance was whitened, the photoresist component was adhered, and the peeling property against the photoresist was remarkably lowered. Since the change in haze is also remarkable, the peeling force of the tape is also changed to the initial 10 times -30-200902669 or more, which is not preferable. In the third embodiment, the intermediate layer (D) was changed from the melamine-based resin of Example 2 to the composition containing the guanamine-based resin. In the same manner as in Example 2, the ethanol abrasion test was performed 100 times and 500 times, and repeated exposure. The appearance change and the tape peeling property after the close exposure test of 100 times and 500 times were hardly changed, and it was a very excellent product. In Example 4, the isocyanate decane of Example 3 was added with tetraisocyanoate decane and tetraisocyanate decane. The tape peelability after repeated exposure exposure test was changed slightly. 'It is a very good product. In Comparative Example 3, the intermediate layer (D) was changed from the melamine resin of Comparative Example 2 to the composition containing the guanamine resin. In the same manner as in Comparative Example 2, the change in the tape peeling force of the ethanol abrasion test 50 times and 100 times was small. However, the appearance of the repeated exposure exposure test 100 times was whitened, the photoresist component adhered, and the peeling property against the photoresist was remarkably lowered. Since the change in haze is also remarkable, the peeling force of the tape is also more than 1 times of the initial stage, which is not preferable. Example 5 is a composition which does not have the intermediate layer (D), and even if the ethanol abrasion test is repeated 100 times and 500 times, there is almost no change in the tape peeling force. Further, the appearance change and the tape peeling property after repeated exposure and exposure test 1 time and 500 times were almost unchanged, and the quality was the same as that of Example 2, and it was a very excellent product. In Comparative Example 4, the surface layer of Example 5 was changed to a configuration other than the surface layer of the present invention, and the ethanol abrasion test was carried out 50 times, and the tape peeling force was changed to -31 - 200902669, and the exposure exposure test was repeated for 00 times. The appearance is whitened, the photoresist component is adhered, and the peeling property against the photoresist is remarkably lowered. Since the change in haze is also remarkable, the peeling force of the tape is also changed to 10 times or more in the initial state, which is not preferable. Example 6 is a structure which does not have the intermediate layer (D), and the melamine-based resin of Example 5 is changed to a guanamine-based resin. Even if the ethanol abrasion test was performed 100 times and 500 times, there was almost no change in the tape peeling force. Further, the appearance change and the tape peeling property after repeated exposure and exposure test 1 〇 及 and 500 times were almost unchanged, and the quality was the same as that of Example 3, and it was a very excellent product. In Comparative Example 5, the surface layer of Example 6 was changed to a surface layer other than the surface layer of the present invention, and the ethanol abrasion test was carried out 50 times, and the change in the tape peeling force was large, and the appearance of the repeated exposure and close-contact exposure test was whitened, and the appearance was whitened. The photoresist component adheres and the peeling property to the photoresist is remarkably lowered. Since the change in haze is also remarkable, the peeling force of the tape is also more than 10 times that of the initial stage, which is not preferable. Therefore, it is understood from the results of the evaluation of Table 1 that the adhesive tape for reticle protection obtained in the examples is excellent in solvent resistance and excellent in release property as compared with the adhesive tape for reticle protection obtained in the comparative example, and therefore is excellent in light. Adhesive tape for cover protection. INDUSTRIAL APPLICABILITY As described above, the adhesive tape for reticle protection of the present invention can be continuously peeled off from the photoresist in the repeated step of the adhesion exposure. In addition, when there is a contamination deposit from the photoresist of the surface layer of the reticle protective adhesive tape -32-200902669, the surface layer does not fall off even if it is washed with a solvent such as an alcohol, and there is a visor protective adhesive tape. The effect is that it is possible to manufacture a printed wiring board by an efficiency and economical method. Therefore, it is particularly suitable as an adhesive tape for mask protection. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing the configuration of an example of an adhesive tape for reticle protection of the present invention. (Embodiment 1) [Embodiment 5 and Embodiment 6] Fig. 2 is a schematic cross-sectional view showing a configuration of an example of an adhesive tape for reticle protection of the present invention. (Example 2, Example 3, Example 4) [Explanation of main component symbols] A Transparent substrate film or sheet B Adhesive layer C Surface layer D Intermediate layer -33-