201009038 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種黏著薄膜。更詳言之，係關於一種 黏著薄膜、使用該黏著薄膜之積層體、及合成樹脂製之成 形體之保護方法。 【先前技術】 屬於合成樹脂製之成形體之一實例的被稱爲「電扶梯（ escalator)」或「自動步道（moving walkway)」之乘客輸送 φ 機，係因其之目的而被設置於百貨公司或車站、機場等之公 共設施或各種大樓以供眾人利用。因此，對於用作爲其之移 動扶手的輸送機扶手（conveyer handrail )，則關於廣告宣傳 或指引等之標示方法方面而已有各種不同的方法之提案。 此等方法之一實例，則已有提案揭述一種在輸送機扶手 貼著經印刷資訊內容的樹脂製黏著薄膜之方法。此等黏著薄 膜係也具有可防止沾污例如輸送機扶手的合成樹脂製之成形 體之保護薄膜的功能，使得以擦拭即可輕易地去除污垢，且 〇 適當地更換保護薄膜時，則可長期保持合成樹脂製之成形體 之美觀。 由於輸送機扶手係與輸送機同時旋轉，對於貼著於輸送 機扶手之薄膜，則要求可追隨輸送機扶手之移動的可撓性。 因此，在專利文獻1中，則揭述一種附著文字、圖案之輸送 機扶手，其特徵爲：在輸送機扶手之裝飾橡膠層上，將藉由 酮系有機溶劑或鹵化烴有機溶劑加以表面處理所獲得之聚胺 基甲酸酯薄膜緊貼接著成使得其之表面處理面側會抵接。 此外，在專利文獻2中，則揭述一種輸送機扶手用黏著 201009038 片，其特徵爲：使用屬於經積層熱塑性聚胺基甲酸酯樹脂薄 膜與黏著劑層所獲得之黏著片，且該熱塑性聚胺基甲酸醋樹 脂薄膜在5%伸長時之「在應力爲零時之應變」爲0.4%以下爲 其特徵之輸送機扶手用黏著片。 〔先前技術文獻〕 (專利文獻） 專利文獻1:特開平第10-305487號公報 專利文獻2:特開第2006-347648號公報 φ 然而，發明專利文獻1之薄膜及發明專利文獻2之黏著 片，當貼著於由含有胺系抗老化劑的材料所構成之合成樹脂 製之成形體時，則卻有會造成黏著片變色之問題。 【發明内容】 (所欲解決之技術問題） 因此，本發明之目的係提供一種即使貼著於合成樹脂製 之成形體並重複使用也不易發生皺紋或剝離等、且也不易發 生基材變色之黏著薄膜。 ® (解決問題之技術方法） 爲解決如上所述之技術問題，本發明係首先提供一種黏 著薄膜，其係包括：基材層與黏著層，且 用於形成該基材層之樹脂組成物係苯乙烯含量爲30至 76莫耳％之芳香族乙烯基彈性體樹脂。本發明之黏著薄膜， 由於基材層係使用特定的芳香族乙烯基彈性體樹脂，因此即 使貼著於由含有胺系抗老化劑的材料所構成之成形體，也不 易發生黏著薄膜之變色。 本發明之黏著薄膜之基材層係只要其爲由苯乙烯含量爲 201009038 30至76%之芳香族乙烯基彈性體樹脂所形成時，則芳香族乙 烯基彈性體樹脂之種類係並無特殊的限制，但是較佳爲苯乙 烯-丁二烯無規共聚物及/或苯乙烯·丁二烯無規共聚物之氫化 物。 本發明之黏著薄膜係較佳爲其之2%伸長強度爲1至10 N/1 0 mm 〇 此外，本發明之黏著薄膜係較佳爲其之2%模數爲0.5至 8 MPa。 φ 並且，本發明之黏著薄膜係較佳爲在23°C、50% RH測 定條件下，以Lab色彩系統（color system)所測定之色相與 其之20天後的色相，經以下列數學式（1)所計算得之色差 △ E*ab爲10以下。此外，在數學式（1)中之L*、a*、b*係 各自代表在Lab色彩系統中L*、a*、b*軸之値。此外，AL* 、△ a*、△ b*係各自代表剛製成試樣後與20天後所測定之L* 、a* ' b* 之差。 (數學式1) ® AE*ab = { (Δ L*)2+ (Aa*)2+ (Δ b*)2}1/2 _ · · (1) 本發明之黏著薄膜係較佳爲在如前所述基材層積層光透 射性之保護薄膜。藉由積層如此之保護薄膜，則可抑制基材 層沾污或磨損。 本發明之黏著薄膜係較佳爲其之如前所述黏著層爲包含 丙烯酸系黏著劑者。 在本發明之黏著薄膜之基材層係較佳爲使其含有100質 量份之樹脂組成物、與0.08至3質量份之體積平均粒徑爲4 201009038 至25//m之粒子。因此，藉由調製成使其含有粒子，則可在 黏著薄膜之表面賦予適度的凹凸。 在此情形下，較佳爲設定樹脂組成物與在該樹脂組成物 中所含有的粒子之折射率之差爲0.04以下。其理由係欲保持 黏著薄膜之透明性的緣故。 其次，本發明係提供一種積層體，其係包括：黏著薄膜 、與積層於該黏著薄膜的合成樹脂製之成形體，且 在用於構成該成形體之合成樹脂中含有胺系抗老化劑。 φ 使用於本發明之積層體之該胺系抗老化劑之種類係並無 特殊的限制，其之較佳的一實例係使用伸苯基二胺系抗老化 劑。 本發明係更進一步地提供一種成形體之保護方法，其係 用於藉由在合成樹脂製之成形體貼著黏著薄膜以保護該成形 體，其中 用於形成該成形體之合成樹脂係含有苯乙烯-丁二烯橡 膠與胺系抗老化劑，且 ® 該黏著薄膜係使用本發明之黏著薄膜。 使用於以本發明之保護方法加以保護的成形體之該胺系 抗老化劑之種類係並無特殊的限制，其之較佳的一實例係使 用伸苯基二胺系抗老化劑。 在此，將關於本發明之術語加以說明。在本發明中，所 謂的「2%模數（2% modulus)」係意謂從以應力及應變爲座 標軸之遲滯曲線中，在拉伸時之曲線讀取伸度爲2%時之拉伸 強度，並除以黏著薄膜之總截面積所獲得之値。 此外，在本發明中，所謂的「苯乙烯含量」係代表在用 201009038 於構成樹脂芳香族乙烯基彈性體樹脂的全部單體中之苯乙烯 及/或苯乙烯取代物之含量° (發明之功效） 若根據本發明，則可提供一種即使貼著於合成樹脂製之 成形體並重複使用亦不易發生皴紋或剝離等且也不易發生基 材變色之黏著薄膜。 【實施方式】 (本發明之最佳實施方式） © 在下文中，則就用以實施本發明之較佳方式加以說明。 再者，以下所說明之實施方式係僅用於例示本發明之一代表 性實施方式，本發明之範圍理應不受限於此等實施方式。 (黏著薄膜） 本發明之黏著薄膜係包括：基材層與黏著層，且該基材 層係由苯乙烯含量爲30至76莫耳％之芳香族乙烯基彈性體樹 脂所形成者。本發明之黏著薄膜之特徵爲：以貼著於合成樹 脂製之成形體來使用時，則不易發生皴紋或剝離、不易發生 ® 基材變色。在下文中，則詳細地說明其之構成。 本發明之黏著薄膜之基材層係由苯乙烯含量爲30至76 莫耳％之芳香族乙烯基彈性體樹脂所形成者。 所謂的「芳香族乙烯基彈性體樹脂」係包含：芳香族乙 烯基烴之聚合物嵌段、與彈性體性之聚合物嵌段的嵌段共聚 物，且其之芳香族乙烯基烴之聚合物嵌段係構成硬質鏈段， 而彈性體性之聚合物嵌段則構成軟質鏈段。 一般而言，芳香族乙烯基彈性體樹脂係具有以芳香族乙 烯基烴聚合物嵌段-彈性體性聚合物嵌段、或芳香族乙烯基烴 201009038 聚合物嵌段-彈性體性聚合物嵌段-芳香族乙烯基烴聚合物嵌 段所代表之共聚合結構。 可用作爲本發明之黏著薄膜之基材層的芳香族乙烯基彈 性體樹脂之「芳香族乙烯基烴之聚合物嵌段」係包括：例如 ，苯乙烯、α-甲基苯乙烯、鄰-甲基苯乙烯、間·甲基苯乙烯 、對-甲基苯乙烯、1，3·二甲基苯乙烯、乙烯基萘、乙烯基蒽 等。其中，在構成芳香族乙烯基彈性體樹脂的全部單體中係 含有25至85莫耳％之苯乙烯及/或苯乙烯取代物。在苯乙烯 φ 及苯乙烯取代物之中係適合使用苯乙烯、α-甲基苯乙烯。此 等之聚合物嵌段係可單獨使用、或兩種以上倂用》 可用作爲本發明之黏著薄膜之基材層的芳香族乙烯基彈 性體樹脂之芳香族乙烯基烴之聚合物嵌段係只要其爲能顯現 彈性體性時，則並無特殊的限制，可使用共軛二烯系聚合物 嵌段、或其以外之聚合物嵌段，但是較佳爲使用共軛二烯系 聚合物嵌段。此時之具體實例係包括：例如，丁二烯、異戊 二烯、1，3-戊二烯、2,3-二甲基-1，3-丁二烯等。其中，特佳爲 〇 使用1，3-丁二烯、異戊二烯。 藉由適當地組合如前所述之芳香族乙烯基烴之聚合物嵌 段、與彈性體性聚合物嵌段，則可獲得「芳香族乙烯基彈性 體樹脂」。具體實例係包括：例如，苯乙烯·乙烯•丁烯共聚 物·苯乙烯（SEBS )、苯乙烯-乙烯•丙烯共聚物-苯乙烯（SEPS )、苯乙烯-丁二烯-苯乙烯（SBS)、苯乙烯-異戊二烯-苯乙 烯（SIS)等之「Α-Β-Α型」嵌段共聚物、無規共聚物、錐型 共聚物、星型嵌段共聚物、多嵌段共聚物及此等之氫化物。 此外’也包括··例如苯乙烯-丁二烯共聚物、苯乙烯·異戊 201009038 二烯共聚物之「A-B型」嵌段共聚物、無規共聚物、錐型共 聚物、星型嵌段共聚物、多嵌段共聚物及此等之氫化物。 此等之中，從耐磨損性、對於合成樹脂製之成形體之順 應性（conformability )、透明性的觀點來考慮，則較佳爲苯 乙烯-丁二烯無規共聚物及/或苯乙烯-丁二烯無規共聚物之氫 化物，特佳爲苯乙烯-丁二烯無規共聚物之完全氫化物。 在構成芳香族乙烯基彈性體樹脂的全部單體中之苯乙烯 含量爲30至76莫耳％，較佳爲50至76莫耳％。若構成芳香 φ 族乙烯基彈性體樹脂的全部單體中之苯乙烯含量爲少於30莫 耳％時，則有可能導致耐磨損性差，貼著於成形體來使用時， 則會造成刮傷而損及外觀之情況。此外，若苯乙烯含量爲超 過76莫耳％時，則有可能導致對於合成樹脂製之成形體之順 應性差，以致例如成形體在例如輸送機扶手等會與輸送機等 一起旋轉的形態之情況下，則將發生皺紋、浮起而損及外觀 之情況。 在本發明之芳香族彈性體樹脂物中之苯乙烯含量係以如 ® 下所述之方法測定： 裝置名： 超傳導核磁共振（NMR )裝置（日本電子股份有 限公司（JEOL Ltd.)製造、商品名「α -5 00」） 〇 試驗法： 以使用核磁共振來調査分子結構或運動狀態等之 性質的分析方法，使用氘化氯仿溶劑、或氘化 1，1，2,2-四氯乙烷溶劑且以TMS爲基準，而比較源 於苯基之質子波峰（6.5至7.5 ppm)與源於烷基 之質子波峰（〇·8至3 ppm)的強度。 -10- 201009038 本發明之黏著薄膜之基材層係只要其爲含有芳香族乙烯 基彈性體樹脂時，其他之調配則並無特殊的限制，可自由調 配其他之樹脂。 用於調配本發明之黏著薄膜之基材層的其他樹脂之具體 實例係包括：例如，烯烴系熱塑性彈性體（TPO)、聚胺基甲 酸酯系熱塑性彈性體（TPU )、聚酯系熱塑性彈性體、聚醯胺 系熱塑性彈性體、芳香族系樹脂等。其中，特別適合調配烯 烴系熱塑性彈性體（TPO)。 Φ 「烯烴系熱塑性彈性體」係包括：例如乙烯-丙烯共聚物 、或經將乙烯-丙烯共聚物分散於聚丙烯中所獲得者。 所謂的「聚胺基甲酸酯系熱塑性彈性體」係以聚醚或聚 酯與異氰酸酯（MDI、TDI、HDI )作爲原料所製造，且可根 據其之組合方式而分類爲聚醚系、聚酯系、MDI系、TDI系 、HDI系之聚胺基甲酸酯系熱塑性彈性體。 所謂的「聚酯系熱塑性彈性體」係以聚醚或聚酯與對苯 二甲酸伸烷基酯或萘二甲酸伸烷基酯爲原料所製造，且可根 © 據其之組合方式而分類爲聚醚系、聚酯系之聚酯系熱塑性彈 性體。 所謂的「聚醯胺系熱塑性彈性體」係以聚醚或聚酯與聚 醯胺作爲原料所製造，且可根據其之組合方式而分類爲聚醚 系、聚酯系之聚醯胺系熱塑性彈性體。 所謂的「芳香族系樹脂」係意謂在分子內具有一個以上 芳香環之樹脂，其係包括：例如，芳香族聚碳酸酯系樹脂、 芳香族聚酯系樹脂、聚苯醚系樹脂、芳香族乙烯基系樹脂、 聚苯硫醚系樹脂、N-芳香族取代順丁烯二醯亞胺系樹脂、聚 .201009038 醯亞胺系樹脂、芳香族環氧樹脂等，且此等之樹脂係可單獨 使用、或兩種以上混合使用。在該芳香族系樹脂之中，特佳 爲使用苯乙烯系樹脂》 用於調配本發明之黏著薄膜之基材層的樹脂組成物之調 配量係並無特殊的限制，但是相對於100質量份之該芳香族 乙烯基彈性體樹脂，則較佳爲5至20質量份之苯乙烯系樹脂 。藉由調配5質量份至20質量份之該芳香族系樹脂，則所獲 得之薄膜的剛性將變強而具有優越的貼著於合成樹脂製之成 φ 形體時之作業性，因此爲較佳。 本發明之黏著薄膜之2%伸長強度係較佳爲1至10 N/10 mm，更佳爲2至7 N/10 mm。其係因爲若在此範圍時，則黏 著薄膜之耐磨損性、或對於合成樹脂製之成形體之順應性不 易降低的緣故。 「2%伸長強度（2% stretching strength)」之測定方法 係以如下所述之方法測定： 裝置名： TENSILON拉伸試驗機（ORIENTEC Co.，LTD製 φ 造、商品名「UCT-500」）。 測定法： 以300毫米/分鐘之速度朝縱方向拉伸橫方向長度 爲20毫米、縱方向之夾持間隔爲100毫米之黏著 薄膜試料時，則將伸度爲2%時的拉伸強度換算成 1〇毫米寬度所獲得之値定義爲「2%伸長強度」。 此外，本發明之黏著薄膜之2%模數係較佳爲0.5至8 MPa ，更佳爲0.8至5 MPa，特佳爲0.8至3 MPa。藉由設定2% 模數爲0.5至8 MPa，由於黏著薄膜則將追隨合成樹脂製之成 形體之伸縮而伸縮，故在貼著於成形體時之耐磨損性、順應 -12- 201009038 性良好，不易發生剝離或扭歪等，因此爲較佳。此外，2%模 數之測定方法係在如後所述之實施例中加以揭示。 本發明之黏著薄膜之2%模數及2%伸長強度係藉由適當 地設定用於調配在黏著薄膜的樹脂之種類及含量等，則可加 以控制。 本發明之黏著薄膜之以Lab色彩系統所測定之色相與其 之20天後的色相，藉由如前所述數學式（1)所計算得之色 差AE + ab係較佳爲加以調整成在23°C、50% RH測定條件下 ❹ 爲10以下。其理由係欲防止黏著片變色的緣故。再者，色差 △ *ab之計算方法係在如後所述之實施例中加以揭示。 本發明之黏著薄膜係可在基材層表面設置光透射性之保 護層。保護層係用於保護基材層表面，以提高基材層之耐候 性。該保護層之具體實例係包括：例如，烯烴系熱塑性彈性 體、聚胺基甲酸酯系熱塑性彈性體、聚酯系熱塑性彈性體、 聚醯胺系熱塑性彈性體、偏二氟乙烯系樹脂與甲基丙烯酸酯 系樹脂之樹脂組成物、組成不同的該樹脂組成物之積層薄膜 等。在此等之中，特別是在本發明中，則較佳爲不易沾污附 著由於輸送機扶手等之合成樹脂製之成形體之連續運轉所發 生的污垢之偏二氟乙烯系樹脂。 偏二氟乙烯樹脂係只要其爲具有偏二氟乙烯單體單元之 乙烯基聚合物時，則並無特殊的限制，例如，可爲偏二氟乙 烯之均聚物、或偏二氟乙烯與其他之乙烯基化合物單體之共 聚物。可與偏二氟乙烯倂用的乙烯基化合物單體係包括：例 如，氟化乙烯、四氟化乙烯、三氟化氯乙烯、六氟化丙烯等 之加以氟化之乙烯基化合物；或苯乙烯、乙烯、丁二烯、丙 -13- 201009038 烯等之乙烯基單體。 偏二氟乙烯系樹脂視需要可添加交聯丙烯酸系樹脂、交 聯聚苯乙烯樹脂、交聯苯乙烯·丙烯酸系共聚物樹脂、抗菌劑 等。在基材層與保護層之間也可形成黏著層。 保護層之厚度係並無特殊的限制，可爲1至1，〇〇〇# m， 較佳爲10至500/zm，特佳爲30至300/zm。 本發明之黏著薄膜之基材層係較佳爲含有特定量的特定 大小之粒子。藉由使其含有粒子，則可在黏著薄膜之表面賦 φ 予凹凸，以提高黏著薄膜表面之防沾污性（stain resistance )° 用於形成粒子之材料係並無特殊的限制，例如，除了由 甲基丙烯酸甲酯聚合物、甲基丙烯酸甲酯-丙烯酸甲酯共聚物 、甲基丙烯酸甲酯-苯乙烯共聚物、苯乙烯聚合物等之熱塑性 樹脂所構成之交聯粒子以外，也可使用滑石、玻璃珠粒、聚 矽氧粒子等。 粒子之大小係以體積平均粒徑計爲在4至25 β m，較佳 ❹ 爲在6至20gm，更佳爲在8至12/zm之範圍者。若粒子之 體積平均粒徑爲小於4//m時，則有因不能對於黏著薄膜之表 面賦予足夠的凹凸而導致黏著薄膜之防沾污性降低之情況。 在另一方面，若超過30#m時’則有可能導致黏著薄膜之透 明性受損之情況，使得輸送機扶手等之合成樹脂製之成形體 的新式樣性變得模糊不清之情況。 本發明之黏著薄膜之基材層係可含有100質量份之樹脂 組成物與〇.〇8至3質量份之粒子，且較佳爲在〇·5至2.5質 量份，更佳爲在1.0至2質量份之範圍。若粒子之含量爲少於 -14- 201009038 0.08質量份時，則有因不能對於黏著薄膜之表面賦予足夠的 凹凸而導致不能獲得黏著薄膜之防沾污性之情況。在另一方 面，若超過3質量份時，則有可能導致黏著薄膜之透明性受 損之情況，使得輸送機扶手等之合成樹脂製之成形體的新式 樣性變得模糊不清之情況。 粒子之折射率係較佳爲與樹脂組成物之折射率之差（AR )爲0.04以下。若△ R爲超過0.04時，則有可能導致黏著薄 膜之透明性受損之情況，使得輸送機扶手等之合成樹脂製之 φ 成形體的新式樣性變得模糊不清之情況。再者，粒子之折射 率係視所使用的材料而定。因此，最好是配合所採用的樹脂 組成物之折射率來適當地選擇粒子之材料。 更進一步，本發明之黏著薄膜之基材層係可在不至於損 及其之物性範圍內含有各種添加劑。該添加劑之具體實例係 包括：例如，抗菌劑、著色劑、抗氧化劑、塡充劑、抗黏連 劑、抗靜電劑、難燃劑、紫外線吸收劑、潤滑劑、光穩定劑 等。 〇 在本發明之黏著薄膜之基材層可添加的「抗菌劑」之具 體實例係包括：例如，抗菌劑係銀、鋅、鋁、其他之金屬或 合金或金靥氧化物之粒子及陶瓷粒子之混合複合粒子等。 在本發明之黏著薄膜之基材層可添加的「著色劑」之具 體實例係包括：無機顏料、有機顏料、染料等。 在本發明之黏著薄膜之基材層可添加的「抗氧化劑」之 具體實例係包括：例如，位阻型酚系化合物、亞磷酸酯系化 合物、硫醚系化合物等之抗氧化劑。 在本發明之黏著薄膜之基材層可添加的「紫外線吸收劑 -15- 201009038 」之具體實例係包括：例如，二苯甲酮系紫外線吸收劑、苯 并三唑系紫外線吸收劑。 在本發明之黏著薄膜之基材層可添加「潤滑劑」之具體 實例係包括：例如，脂肪酸醯胺、石蠟、烴系樹脂及脂肪酸 0 在本發明之黏著薄膜之基材層可添加的「光穩定劑」之 具體實例係包括：例如，可降低由於與烯鍵性不飽和羧酸進 行酸鹼反應的產物之發生，及加以抑制之低鹸性、或中性高 〇 分子量型。 本發明之黏著薄膜之基材層的製造方法係並無特殊的限 制，可使用習知的方法。例如，可使用熔融捏合等或各種混 合裝置（單軸或雙軸擠壓機、輥、班布瑞密閉式混合機（ Banbury mixer)、各種捏合機等）來混合各成份，並以吹塑 薄膜法、T-模法、壓延加工法等將該混合物成型於薄膜上。 以捲筒狀儲存基材層時，則較佳爲設置剝離膜層（separator layer)以防止薄膜彼此之間的黏連（blocking)。 ® 本發明之黏著薄膜之基材層的厚度係並無特殊的限制， 但是較佳爲20至300#m，特佳爲30至200 /zm»經將基材 層之厚度設定爲20//m以上，藉此則可獲得足夠的耐磨損性 、耐變色性。此外，經將基材層之厚度設定爲3 00 /zm以下， 藉此則可製得具有優越的對於成形體之施工作業性之薄膜。 本發明之黏著薄膜之基材層係可爲單層或與其他樹脂層 積層之多層薄膜》可積層之樹脂層之具體實例係包括：例如 聚乙烯系樹脂、聚丙烯系樹脂等之聚烯烴系樹脂；例如苯乙 烯系熱塑性彈性體、烯烴系熱塑性彈性體、聚酯系熱塑性彈 -16- 201009038 性體'聚胺基甲酸酯系熱塑性彈性體、聚醯胺系熱塑性彈性 體等之熱塑性彈性體、偏二氟乙烯系樹脂等。 本發明之黏著薄膜之基材層係可設置廣告宣傳或指引等 之標記。經設置此等標記而可貼著於成形體上作爲廣告宣傳 媒體'資訊提供媒體。例如，由於在該基材層設置該標記， 則可在該基材層之至少單面上施加印刷。 在基材層之單面上施加印刷時之印刷方法係並無特殊的 限制’可使用凹版印刷、平版印刷、網版印刷、膠版印刷等 φ 之印刷方法；或噴墨方式、靜電調色劑方式、熱轉印方法等 之影像形成方法》此外，可使用之印墨也並無特殊的限制。 此時，在黏著薄膜之基材層上，可添加例如白色顔料。 「白色顏料」之具體實例係包括：例如氧化鈦等之鈦系白色 顏料；氧化鋅、硫化鋅等之鋅系白色顏料；鋅鋇白（lithopone )等之複合白色顏料；矽酸鎂、氧化鎂、碳酸鈣、硫酸鋇等 之塡充顏料等。此等之白色顔料係可單獨使用、或其兩種以 上混合使用。 G 在此等之白色顏料之中，較佳爲氧化鈦。氧化鈦之結晶 型係並無特殊的限制，但是更佳爲折射率大且具有優越的遮 蔽性之金紅石型。 本發明之黏著薄膜之黏著層係爲使黏著薄膜貼緊於合成 樹脂製之成形體上所形成者。該黏著層之材質係只要其爲能 使得本發明之黏著薄膜貼緊於成形體者時，則並無特殊的限 制，但是可爲例如含有橡膠系黏著劑、丙烯酸系黏著劑、丁 基系黏著劑等者。其中，丙烯酸系黏著劑係因可容易地進行 黏著性與再剝離性之設計而爲較佳。此外，丁基系黏著劑係 -17- 201009038 貼著於由含有胺系抗老化劑的材料所構成之成形體上時，則 可更進一步地抑制基材層之變色。此外，視需要可調配增黏 劑、抗老化劑、硬化劑等之各種添加劑。 「丙烯酸系黏著劑」之具體實例係包括：（甲基）丙烯 酸酯之均聚物、或與共聚合性單體之共聚物。「（甲基）丙 烯酸酯」之具體實例係包括：甲酯、乙酯、丁酯、2-乙基己 酯、辛酯等之「（甲基）丙烯酸烷基酯」；甲基丙烯酸二甲 基胺基乙酯、甲基丙烯酸三級-丁基胺基乙酯等之「（甲基） φ 芮烯酸烷基胺基烷基酯」；（甲基）丙烯酸縮水甘油酯、（ 甲基）丙烯酸、伊康酸、順丁烯二酸酐、（甲基）丙烯酸醯 胺、（甲基）丙烯酸N-羥基醯胺等。共聚合性單體之具體實 例係包括：醋酸乙烯酯、苯乙烯、丙烯腈等。 在此等之中，主單體係包括：其之均聚物之玻璃轉移溫 度爲-50°C以下者、例如，丙烯酸烷基酯等。 「增黏劑」係可考慮軟化點、與各成份之相溶性等來加 以選擇’例如，萜樹脂、松香樹脂、氫化松香樹脂、薰草酮 ® •節樹脂、苯乙烯系樹脂、脂肪族系石油樹脂、脂環族系石 油樹脂、萜-苯酚樹脂、二甲苯系樹脂、其他脂肪族烴樹脂或 芳香族烴樹脂等。增黏劑之軟化點係較佳爲65至13(TC，而 特佳爲軟化點爲65至130°C之石油樹脂之脂環族飽和烴樹脂 、軟化點爲80至130°C之聚萜樹脂、軟化點爲80至13(TC之 氫化松香之甘油酯等。 使用於丙烯酸系黏著劑之「硬化劑」係包括：例如，異 氰酸醋系硬化劑、環氧系硬化劑、胺系硬化劑等。此等係可 單獨使用、或其兩種以上混合使用。 -18 - 201009038 「異氰酸酯系硬化劑」之具體實例係包括：2,4-伸甲苯基 二異氰酸酯、2,6-伸甲苯基二異氰酸酯、1，3-伸茬基二異氣酸 酯' 1，4-二甲苯二異氰酸酯、4,4’-二苯基甲烷二異氰酸酯、 2,4’-二苯基甲烷二異氰酸酯、3-甲基二苯基甲烷二異氰酸酯 、六亞甲基二異氰酸酯、異佛酮二異氰酸酯、4,4’-二環己基 甲烷二異氰酸酯、2,4’·二環己基甲烷二異氰酸酯、離胺酸異 氰酸酯等之多元異氰酸酯化合物。 關於本發明之黏著薄膜，用於在基材層上形成黏著層之 φ 方法係並無特殊的限制，例如，可使用將由黏著劑、增黏劑 及抗老化劑等所構成之黏著劑溶液塗佈於基材層之單面並加 以乾燥之方法，或預先將黏著劑溶液塗佈於容後說明的剝離 膜（separator)之單面並將其乾燥，然後與基材層相貼合之 方法等。 本發明之黏著薄膜的黏著層之厚度，雖然可在不至於損 及黏著性或使用性之範圍內適當地選擇，但是可爲5至50// m，較佳爲10至30#ιη» Ο 在本發明之黏著薄膜之黏著層表面較佳爲設置剝離膜層 。經在黏著層表面設置剝離膜層，藉此則可防止基材層之收 縮、可防止在塗佈時之皺紋或剝離。此外，可將對於成形體 施工黏著薄膜時的使用性變得容易而提高施工性。 (積層體） 本發明之「積層體」係包括：如前所述本發明之黏著薄 膜、與積層於該黏著薄膜之合成樹脂製之成形體。 成形體係只要其爲可貼著於黏著薄膜之形狀時，則並無 特殊的限制，可爲棒狀、板狀、外罩等。具體言之，其係包 -19- 201009038 括走廊之扶手（handrail of corridor )、輸送機扶手、家庭電 器設備、汽車等。 用於構成成形體之合成樹脂係可使用SBR橡膠、胺基甲 酸酯橡膠、氯磺化橡膠、乙烯-丙烯-二烯橡膠與苯乙烯-丁二 烯橡膠之摻合橡膠、乙烯-丙烯-二烯橡膠與氯磺化聚乙烯橡膠 之摻合橡膠等之任一者，但是特別是較佳爲含有胺系抗老化 劑作爲抗老化劑之樹脂。其係因爲本發明之黏著薄膜係貼著 於含有胺系抗老化劑的成形體上時，則特別不易變色的緣故 使用於本發明之積層體的成形體之「胺系抗老化劑」之 種類係並無特殊的限制，可自由地選擇使用習知的胺系抗老 化劑。例如，可選擇2,2,4-三甲基-1，2-二氫喹啉聚合物、6- 乙氧基-1,2-二氫-2,2,4-三甲基喹啉、二苯基胺與丙酮之反應 物等之「胺-酮系抗老化劑」；苯基-1-萘基胺、烷基化二苯基 胺、辛基化二苯基胺、4,4’-雙（二甲基苯甲基）二苯基 胺、對-(對-甲苯磺醯基醯胺基）二苯基胺、Ν，Ν’·二-2-萘基 • -對伸苯基二胺、Ν，Ν’-二苯基-對伸苯基二胺、Ν-苯基-Ν’-異 丙基-對伸苯基二胺、Ν- ( 1，3-二甲基丁基）-Ν’-苯基-對伸苯 基二胺、Ν-苯基-Ν’-(3-甲基丙烯醯氧基-2-羥基丙基）-對伸 苯基二胺等之「芳香族第二級胺系抗老化劑」；2,6-二-三級- 丁基-4-甲基苯酚、2,6-二·三級-丁基-4-乙基苯酚、一（或二 或三）（α-甲基苯甲基）苯酚等之「一元酚系抗老化劑」等 〇 在此等之中，特別是在本發明中，則較佳爲伸苯基二胺 系抗老化劑。其係因爲本發明之黏著薄膜係貼著於含有伸苯 -20- 201009038 基二胺系抗老化劑的成形體上時，則特別不易變色的緣故。 在本發明使用之黏著薄膜係在伸苯基二胺系抗老化劑之中特 別對於對伸苯基二胺系抗老化劑具有優越的耐變色性者。在 對伸苯基二胺系抗老化劑之中，則對於6C、6DP、81 ONA具 有優越的耐變色性，特別是對於6C具有優越的耐變色性。 將本發明之黏著薄膜貼著於成形體之方法係並無特殊的 限制，例如，可使用一種一面剝離設置於黏著層表面之剝離 膜層、一面以橡膠輥、刮漿板等加壓貼附於輸送機扶手之簡 〇 易貼附工具等，藉此則可加以貼著。 (成形體之保護方法） 本發明之保護方法係一種藉由在合成樹脂製之成形體貼 著如前所述本發明之黏著薄膜以保護該成形體之方法。 可以本發明之保護方法加以保護之成形體，係只要其爲 由如前所述之合成樹脂所形成者時，則並無特殊的限制，但 是本發明之保護方法，特別可有效地保護由含有苯乙烯·丁二 烯橡膠與胺系抗老化劑之合成樹脂所形成者。 ® 在此情形下，所使用的胺系抗老化劑之種類，雖然可自 由地選擇使用如前所述習知的胺系抗老化劑，但是本發明之 保護方法係特別適用於保護胺系抗老化劑係使用伸苯基二胺 系抗老化劑所獲得之成形體。 (實施例） 在下文中，則以實施例詳細地說明本發明，但是本發明 並沒有受限於此等實施例。 1. 關於包含在基材層之樹脂的檢討 (實施例1:黏著薄膜之製造） -21- 201009038 將100質量份之作爲芳香族乙烯基彈性體樹脂的苯乙烯-丁二烯嵌段共聚物之完全氫化物（旭化成工業股份有限公司 (Asahi Kasei Chemicals Corporation)製造、Tuftec Η1041 :苯乙烯含量爲30莫耳％、共軛二烯單體爲70莫耳％、氫化 率爲100%)，與5質量份之白色母體混合物（大日本油墨化 學工業股份有限公司（Dainippon Ink and Chemicals, Inc.)製 造、PEONY WHITE F-1 1060 )以乾式摻合後，使用配備螺桿 直徑爲100毫米的積層設備之單軸T-模擠壓機，貼合雙面PET ❹ 剝離膜（TORAY ADVANCED FILM Co.，Ltd.製造、Cerapeel “WD” 110/zin)與厚度爲80/im之透明的芳香族乙烯基彈性 體樹脂薄膜，以獲得積層薄膜》在該積層薄膜之芳香族乙烯 基彈性體樹脂側，貼合預先塗佈丙烯酸系水系黏著劑及環氧 系交聯劑並加以乾燥使得乾燥後之厚度爲20 所獲得之 110;zm剝離紙（paper separator)(住化加工紙股份有限公 司(Sumika-Kakoushi Co., Ltd.)製造、SL-80KCD7 )，以獲 得具有第一層爲110从m之雙面PET剝離膜、第二層爲80/zm φ 之芳香族乙烯基彈性體樹脂薄膜黏著薄膜、第三層爲20/zm 之丙烯酸系水系黏著劑、第四層爲U〇#m之剝離紙的複合薄 膜。經剝離該複合薄膜之剝離膜的第一層、第四層後的黏著 薄膜之2%模數爲0.8 MPa。然後，使用該黏著薄膜實施耐變 色性、順應性、耐磨損性之評估。 (2%模數之測定） 2%模數係使用TENSILON拉伸試驗機（ORIENTEC Co.， LTD製造、UCT-5 00 )，而以3 00毫米/分鐘之速度朝縱方向 拉伸橫方向長度爲25毫米、縱方向之夾持間隔爲100毫米之 -22- 201009038 黏著薄膜試料時，則將伸度爲2%時的拉伸強度除以試料截面 積所獲得之値定義爲「2%模數」。 (耐變色性之評估） 製造將胺系抗老化劑1(大內新興化學工業股份有限公司 (Ouchi Shinko Chemical Industrial Co.，Ltd.)製造、NOCRAC 6C)、胺系抗老化劑2(大內新興化學工業股份有限公司製 造、NOCRAC 6DP)、胺系抗老化劑3(大內新興化學工業股 份有限公司製造、NOCRAC 810NA )、胺系抗老化劑4 (大內 φ 新興化學工業股份有限公司製造、NOCRAC PA )，分別使其 之25質量份溶解於100質量份之丙酮，並將其塗佈8/ζιη厚 度所獲得之80 v m厚度LDPE薄膜。在該LDPE薄膜貼附經 剝離如上所述複合薄膜之剝離膜的第一層、第四層之黏著薄 膜試料，然後在23±2°C、50±5% RH之評估試驗室內，在一天 照射1 0小時之螢光燈下放置20天，然後使用分光測色計（ Konica-Minolta公司製造、CM-2500D)測定放置前後的色之 變化。色差△ E*ab係由經以Lab色彩系統所測定之L* (明度 ® ) 、a* (色度）、b* (色度）根據數學式（1)所計算得。 並且，以下列之表1之基準評估其之優劣。 表1 優良 色差△Ehb爲小於10者 良 色差△Ebb爲10以上且小於15者 不良 色差ΔΕ*Λ爲15以上者 (順應性之評估） 將經剝離如上所述複合薄膜之剝離膜的第一層、第四層 之黏著薄膜試料上更進一步地積層光透射性之保護層所獲得 之積層黏著薄膜，貼附於作爲合成樹脂製成形體之一實例的 -23- 201009038 SBR製之輸送機扶手上，並以目視觀察運轉30天後之表面狀 態，且以下列之表2之基準評估優劣。 ^此外，光透射性之保護層係經積層基材薄膜（substrate film)與黏著薄膜所獲得之透明的黏著薄膜，且藉由使用下列 之步驟所製造者。 (1) 基材薄膜之製造 將作爲使用於基材層之芳香族乙烯基彈性體樹脂的苯乙 烯-丁二烯無規共聚物之完全氫化物（旭化成工業股份有限公 φ 司製造、S.O.E. SS9000:苯乙烯含量爲70莫耳％、共鈮二烯 單體爲30莫耳％、氫化率爲100%)，以T-模法製造厚度爲 50/zm之透明的基材薄膜。以T-模法製造薄膜時，則以防止 黏連爲目的，而在聚對苯二甲酸乙二醇酯製之剝離膜（TORAY ADVANCED FILM Co.，Ltd.製造、Cerapeel “WD” m)之 單面加以積層吾所欲之基材薄膜。 (2) 黏著薄膜之製造 採用丙烯酸系水系黏著劑及環氧系交聯劑作爲黏著劑調 φ 配物，並以如前所述所製造之基材薄膜與使用剝離紙（住化 加工紙股份有限公司製造、SL-8 0KCD7 11〇m m)之轉印塗佈 法，製造黏著劑層之厚度爲20/zm之黏著薄膜。實際用作爲 保護層時，則將該黏著薄膜貼附於作爲合成樹脂製成形體之 一實例的SBR製之輸送機扶手後，剝除在第（1)項所提及之 聚對苯二甲酸乙二醇酯製之剝離膜來使用。 表2 優良 在β觀察不到皺紐浮起者 良 観察到浮起者 不良 ίείβ明顯地觀察到浮起者 -24- 201009038 (耐磨損性） 將經剝離如上所述複合薄膜之剝離膜的第一層、第四層 之黏著薄膜試料上更進一步地積層光透射性之保護層所獲得 之積層黏著薄膜，貼附於作爲合成樹脂製成形體之一實例的 SBR製之輸送機扶手上，並以目視觀察運轉3〇天後之表面狀 態，且以下列之表3之基準評估優劣。 表3 優良 觀察不到破裂者 良 觀察到破裂者 不良 觀察到破裂者 (實施例2) 除了使用苯乙烯-丁二烯無規共聚物之完全氫化物（旭化 成工業股份有限公司製造、S.O.E. SS9000:苯乙烯含量爲70 莫耳％、共軛二烯單體爲30莫耳％、氫化率爲100%)作爲芳 香族乙烯基彈性體樹脂以外，其餘則以與實施例1相同的方 式獲得黏著薄膜。其之2%模數爲0.8 MPa。 將所獲得之黏著薄膜以與實施例1相同的方式實施耐變 ❹ 色性、順應性、耐磨損性之評估。 (實施例3) 在容積爲1.3 m3之反應容器添加500公斤之含有150 ppm 四氫呋喃之環己烷、與8公斤之苯乙烯單體。其次’添加1520 毫升之含有10%正-丁基鋰之環己烷溶液。然後’―面保持容 器內部爲80°C、一面將52.0公斤之苯乙烯單體及1〇.〇公斤 之丁二烯分別以84公斤/小時、20公斤/小時之一定的飼入速 度添加。並且，將54.0公斤之苯乙烯單體及38.0公斤之丁二 烯分別以60.5公斤/小時、40.3公斤/小時之一定的飼入速度 -25- 201009038 添加。添加結束後，設定容器內部爲75 °C，並進一步匯總添 加63.6公斤之苯乙烯單體，一面冷卻一面繼續反應30分鐘。 反應結束後、設定容器內部爲70°C，並將高分子液移至其他 之容器。對其添加110克水以使陰離子聚合之活性末端去活 化，以獲得含有嵌段共聚物之高分子液。 在所獲得之高分子液，對於每100質量份之嵌段共聚物 ，將住友化學工業股份有限公司（Sumitomo Chemical Co.，Ltd. )製造之Sumilizer GS及千葉特用化學品公司（Ciba Specialty φ Chemicals Corp.)製造之IRGANOX 1076作爲穩定劑而分別 溶解0.40質量份、0.20質量份。將其加以預濃縮，並且以配 備減壓排氣之雙軸擠壓式加以脫氣擠出，以獲得苯乙烯含量 爲76莫耳％之苯乙烯-丁二烯無規共聚物。除了使用該樹脂以 外，其餘則以與實施例1相同的方式獲得2%模數爲5 MPa之 黏著薄膜。 將所獲得之黏著薄膜以與實施例1相同的方式實施耐變 色性、順應性、耐磨損性之評估。 〇 (比較例1) 除了使用苯乙烯-丁二烯共聚物（電氣化學工業公司（ Denki Kagaku Kogyo Kabushiki Kaisha)製造、12RN ：苯乙嫌 含量爲88莫耳％、共軛二烯單體爲12莫耳％)作爲芳香族乙 烯基彈性體樹脂以外，其餘則以與實施例1相同的方式獲得 黏著薄膜。其之2%模數爲12 MPa。 將所獲得之黏著薄膜以與實施例1相同的方式實施耐變 色性、順應性、耐磨損性之評估。 (比較例2) -26- 201009038 除了使用苯乙烯-丁二烯嵌段共聚物之完全氫化物（旭化 成工業股份有限公司製造之Tuftec H1221:苯乙烯含量爲12 莫耳°/❶、共軛二烯單體爲88莫耳％、氫化率爲1 〇〇% )作爲芳 香族乙烯基彈性體樹脂以外，其餘則以與實施例1相同的方 式獲得黏著薄膜。其之2%模數爲0.3 MPa。 將所獲得之黏著薄膜以與實施例1相同的方式實施耐變 色性、順應性、耐磨損性之評估。 (比較例3) φ 在作爲基材層的80/zm白色聚胺基甲酸酯薄膜（日本瑪 泰股份有限公司（Nihon Matai Co.，Ltd.)製造、Esmer URS )之單面，塗佈丙烯酸系水系黏著劑及環氧系交聯劑並加以 乾燥使得乾燥後之厚度爲20# m，以獲得2%模數爲0.8 MPa 之黏著薄膜。 將所獲得之黏著薄膜以與實施例1相同的方式實施耐變 色性、順應性、耐磨損性之評估。 (比較例4) φ 除了使用烯烴系熱塑性彈性體（Prime Polymer Co.，Ltd. 製造、R-11 0E)作爲基材層以外，其餘則以與實施例1相同 的方式獲得黏著薄膜。其之2%模數爲1.0 MPa。 將所獲得之黏著薄膜以與實施例1相同的方式實施耐變 色性、順應性、耐磨損性之評估。 (比較例5) 除了使用氯乙烯膠帶（電氣化學工業公司製造、白色電 線束膠帶（harness tape white))作爲基材層以外，其餘則 以與實施例1相同的方式獲得黏著薄膜。其之2%模數爲1.0 -27- 201009038 MPa 〇 將所獲得之黏著薄膜以與實施例1相同的方式實施耐變 色性、順應性、耐磨損性之評估》 各實施例及比較例之結果係如表4所示。 表4 實施例 比較例 1 2 3 1 2 3 4 5 紐之麵 SEBS SEBS SBS SBS SEBS 胺基 甲酸酯 TPO PVC 苯乙嫌含量（莫耳％) 30 70 76 88 12 - - 2%^¾ (MPa) 0.8 0.8 5 12 0.3 0.8 0.9 1 _色性 胺系抗老化劑1 5 4 4 4 5 16 14 16 胺系抗老化劑2 6 5 5 5 6 15 12 15 胺系抗老化劑3 8 7 7 7 8 15 13 15 胺系抗老化劑4 9 8 8 8 13 21 18 22 優良 優良 優良 優良 優良 不良 良 不良 順應性 優良 優良 優良 不良 優良 優良 優良 良 耐磨損性 優良 優良 優良 優良 良 優良 不良 優良 由表4即得知本發明之黏著薄膜係具有優越的貼著於成 形體時之順應性及耐磨損性’且即使貼著於由含有胺系抗老 化劑的材料所構成之成形體，也不易發生基材變色。 ❿ 與此相對，在使用苯乙稀含量爲超過76莫耳％之芳香族 乙烯基彈性體樹脂之比較例1，則順應性差。 相反地，在使用苯乙烯含量爲少於30莫耳％之芳香族乙 嫌基彈性體樹脂之比較例2，則如表4所示，耐磨損性稍微差 〇 此外’在使用聚胺基甲酸醋薄膜、燃烴系熱塑性彈性體 、氯乙烯膠帶之比較例3至5 ’則如表4所示，分別耐變色性 、耐磨損性、順應性爲差。 由以上之結果得知’在本發明之黏著薄膜，以使用苯乙 -28- 201009038 烯含量爲30至76莫耳％之芳香族乙烯基彈性體樹脂來形成則 有效。 2. 關於包含在基材層之粒子的檢討 檢討關於包含在黏著薄膜之基材層的粒子。 (實施例4) (1) 基材薄膜之製造 將100質量份之與實施例2相同的作爲使用於基材層之 芳香族乙烯基彈性體樹脂的苯乙烯-丁二烯無規共聚物之完 φ 全氫化物（旭化成工業股份有限公司製造、S.O.E. SS9000: 苯乙烯含量爲70莫耳％、共軛二烯單體爲30莫耳％、氫化率 爲100%、折射率爲1.555 )、與1質量份之折射率爲1.545 且與軟質樹脂之折射率差AR爲0.01且體積平均粒徑爲5/zm 之粒子（積水化成品工業股份有限公司（SekisuiPlasticsCo., Ltd.)製造、Techpolymer MBX-S系列）加以熔融捏合，並以 T-模法製造厚度爲50 jam之透明的基材薄膜。以T-模法製造 薄膜時，則以防止黏連爲目的，而在基材薄膜之單面加以積 〇 層聚對苯二甲酸乙二醇酯製之剝離膜（TORAY ADVANCED FILM Co.，Ltd.製造、Cerapeel “WD” 38# m)。 (2) 黏著薄膜之製造 採用丙烯酸系水系黏著劑及環氧系交聯劑作爲黏著劑調 配物，並以如前所述所製造之基材薄膜與使用剝離紙（住化 加工紙股份有限公司製造、SL-80KCD7 1 10 // m)之轉印塗佈 法，製造黏著劑層之厚度爲20 之黏著薄膜。 所獲得之黏著薄膜之2%伸長強度爲3.2 N/10 mm。使用 該黏著薄膜，以如下所述方法實施防沾污性、透明性之評估 -29- 201009038 、及十點平均粗糙度之測定。 (防沾污性） 將所獲得之黏著薄膜與印刷用黏著薄膜加以積層，並以 如下所述方式檢討貼著於成形體時之防沾污性。此外’印刷 用黏著薄膜係藉由使用下列之步驟所製造者。 將100質量份之作爲芳香族乙烯基彈性體樹脂的苯乙烯-丁二烯嵌段共聚物之完全氫化物（旭化成工業股份有限公司 製造、S.O.E. SS9000:苯乙烯含量爲70莫耳％、共軛二烯單 φ 體爲30莫耳％、氫化率爲100%)、與1質量份之白色母體混 合物（大日本油墨化學工業股份有限公司製造、PEONY WHITE F-1 1 060 )加以熔融捏合。其後，使用雙面PET剝離膜（TORAY ADVANCED FILM Co.，Ltd.製造、Cerapeel “WD”），在以 T-模成型所獲得之厚度爲80 之透明的芳香族乙烯基彈性體 樹脂薄膜之單面，貼合預先塗佈丙烯酸系水系黏著劑及環氧 系交聯劑並加以乾燥使得乾燥後之厚度爲20 y m所獲得之 110/z m剝離紙（住化加工紙股份有限公司製造、SL-80KCD7 〇 )，以獲得印刷用黏著薄膜。 將所獲得之黏著薄膜與印刷用黏著薄膜加以積層，然後 ，將其貼附於曰立製作所股份有限公司（Hitachi，Ltd.)製造 之電扶梯之輸送機扶手，然後，對於白色部使用分光測色計 (Konica-Minolta公司製造、CM-2500d)來測定3週後之色 差（A E*ab)，並以下列之表5所示之基準評估其之優劣。 表5 〇 色差△ESb爲小於10者 △ 色差AE^ab爲10以上且小於15者 X 色差爲15以上者 -30- 201009038 (透明性） 「透明性」係使用霧度計（日本電色工業股份有限公司 (Nippon Denshoku Industries Co., Ltd.)製造、NDH2000 ) 來測定所獲得之黏著薄膜之霧度，並以下列之表6所示基準 評估其之優劣。 表6 〇 霧度爲小於5者 Δ 霧度爲5以上且小於20者 X 霧度爲20以上者 0 (十點平均粗糙度） 「十點平均粗糙度」係使用小坂硏究所股份有限公司（ Kosaka Laboratory Ltd.)製造之 Surfcorder(表面形狀粗糖度 測定機），並根據JIS B0601之準則來測定所獲得之黏著薄膜 〇 (實施例5) 除了使用體積平均粒徑爲之積水化成品工業股份 有限公司製造之Techpolymer MBX-S系列作爲使用於基材層 〇 的粒子以外，其餘則以與實施例4相同的方式製造黏著薄膜 。使用所獲得之黏著薄膜，以與實施例4相同的方式，實施 防沾污性、透明性之評估、及十點平均粗糙度之測定。 (實施例6) 除了使用體積平均粒徑爲20/im之積水化成品工業股份 有限公司製造之Techpolymei· MBX-S系列作爲使用於基材層 的粒子以外，其餘則以與實施例4相同的方式製造黏著薄膜 。使用所獲得之黏著薄膜，以與實施例4相同的方式，實施 防沾污性、透明性之評估、及十點平均粗糙度之測定。 -31- 201009038 (實施例7) 除了變更使用於基材層的粒子之添加量爲0.1質量份以 外，其餘則以與實施例4相同的方式製造黏著薄膜。使用所 獲得之黏著薄膜，以與實施例4相同的方式，實施防沾污性 、透明性之評估、及十點平均粗糙度之測定。 (實施例8) 除了變更使用於基材層的粒子之添加量爲2.5質量份以 外，其餘則以與實施例4相同的方式製造黏著薄膜。使用所 〇 獲得之黏著薄膜，以與實施例4相同的方式，實施防沾污性 、透明性之評估、及十點平均粗糙度之測定。 (實施例9) 除了使用折射率爲1.525且與軟質樹脂之折射率差AR 爲0.03者作爲使用於基材層的粒子以外，其餘則以與實施例 4相同的方式製造黏著薄膜。使用所獲得之黏著薄膜，以與實 施例4相同的方式，實施防沾污性、透明性之評估、及十點 平均粗糙度之測定。 參 (實施例10) 除了使用體積平均粒徑爲2/zm之積水化成品工業股份 有限公司製造之Techpolymer MBX-S系列作爲使用於基材層 的粒子以外，其餘則以與實施例4相同的方式製造黏著薄膜 。使用所獲得之黏著薄膜，以與實施例4相同的方式，實施 防沾污性、透明性之評估、及十點平均粗糙度之測定。 (實施例11) 除了使用體積平均粒徑爲30//m之積水化成品工業股份 有限公司製造之Techpolymer MBX-S系列作爲使用於基材層 -32- 201009038 的粒子以外，其餘則以與實施例4相同的方式製造黏著薄膜 。使用所獲得之黏著薄膜，以與實施例4相同的方式，實施 防沾污性、透明性之評估、及十點平均粗糙度之測定》 (實施例12) 除了變更使用於基材層的粒子之添加量爲0.05質量份以 外，其餘則以與實施例4相同的方式製造黏著薄膜。使用所 獲得之黏著薄膜，以與實施例4相同的方式，實施防沾污性 、透明性之評估、及十點平均粗糙度之測定。 φ (實施例13) 除了變更使用於基材層的粒子之添加量爲4質量份以外 ，其餘則以與實施例4相同的方式製造黏著薄膜。使用所獲 得之黏著薄膜，以與實施例4相同的方式，實施防沾污性、 透明性之評估、及十點平均粗糙度之測定。 (實施例14) 除了使用折射率爲1.525且與軟質樹脂之折射率差AR 爲〇.〇5者作爲使用於基材層的粒子以外，其餘則以與實施例 β 4相同的方式製造黏著薄膜。使用所獲得之黏著薄膜，以與實 施例4相同的方式，實施防沾污性、透明性之評估、及十點 平均粗糙度之測定。 各實施例之結果係如表7所示。 -33- 201009038 表7 實施例 4 5 6 7 8 9 10 11 12 13 14 交聯離添加1：(質量份） 1 1 1 0.1 2.5 1 1 1 0.05 4 1 交聯撇粒徑Um) 5 12 20 12 12 12 2 30 12 12 12 十點平離接度Rz ( "m) 2.79 4.77 6.25 1.21 5.23 4.77 0.71 11.23 0.65 6.32 4.77 折射率差ΔΙΙ 0.01 0.01 0.01 0.01 0.01 0.03 0.01 0.01 0.01 0.01 0.05 2%f申長強度（N/10mm) 5 5 5 5 5 5 5 5 5 5 5 防沾污性 △ E*ab 7 7 7 7 7 7 12 5 17 5 7 fpfe 〇 〇 〇 〇 〇 〇 Δ 〇 X 〇 〇 透明性 HAZE 4 4 4 4 4 4 3 20 3 20 17 fNS 〇 〇 〇 〇 〇 〇 〇 X 〇 X Δ ❹201009038 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to an adhesive film. More specifically, it relates to a method of protecting an adhesive film, a laminate using the adhesive film, and a synthetic resin. [Prior Art] A passenger conveyor φ machine called "elevator" or "moving walkway", which is an example of a molded body made of a synthetic resin, is installed in a department store for its purpose. Public facilities or buildings of companies or stations, airports, etc. are available for everyone to use. Therefore, for the conveyor handrail used as the moving handrail for it, there have been proposals for various methods regarding the marking method of advertising or guidance. As an example of such methods, there has been proposed a method of attaching a resin-made adhesive film to a handrail of a conveyor with a printed information content. These adhesive film systems also have a function of preventing the staining of a protective film of a synthetic resin molded body such as a conveyor handrail, so that the dirt can be easily removed by wiping, and when the protective film is appropriately replaced, the adhesive film can be used for a long period of time. The appearance of the molded body made of synthetic resin is maintained. Since the conveyor armrest rotates at the same time as the conveyor, the flexibility of the movement of the handrail of the conveyor is required for the film attached to the handrail of the conveyor. Therefore, Patent Document 1 discloses a conveyor handrail with attached characters and patterns, characterized in that surface treatment is performed on a decorative rubber layer of a conveyor handrail by a ketone organic solvent or a halogenated hydrocarbon organic solvent. The obtained polyurethane film is adhered so that the surface-treated side thereof abuts. Further, in Patent Document 2, a sheet of adhesive for handrail 201009038 is disclosed, which is characterized in that an adhesive sheet obtained by laminating a thermoplastic urethane resin film and an adhesive layer is used, and the thermoplastic The film of the polyurethane vinegar resin has a strain of "when the stress is zero" at 5% elongation. 4% or less is an adhesive sheet for a conveyor handrail characterized by the following. [Patent Document] Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2006-347648. However, the film of the invention patent document 1 and the adhesive sheet of the invention patent document 2 When a molded article made of a synthetic resin composed of a material containing an amine-based anti-aging agent is attached, there is a problem that the adhesive sheet is discolored. DISCLOSURE OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION Therefore, an object of the present invention is to provide a molded article which is bonded to a synthetic resin and which is less likely to be wrinkled or peeled off, and which is less likely to cause discoloration of the substrate. Adhesive film. ® (Technical Solution to Problem) In order to solve the technical problems as described above, the present invention first provides an adhesive film comprising: a substrate layer and an adhesive layer, and a resin composition system for forming the substrate layer An aromatic vinyl elastomer resin having a styrene content of 30 to 76 mol%. In the adhesive film of the present invention, since the base layer is made of a specific aromatic vinyl elastomer resin, even if it is adhered to a molded body composed of a material containing an amine-based anti-aging agent, discoloration of the adhesive film is less likely to occur. The base material layer of the adhesive film of the present invention is not particularly limited as long as it is formed of an aromatic vinyl elastomer resin having a styrene content of 201009038 30 to 76%. It is preferably, but preferably, a hydride of a styrene-butadiene random copolymer and/or a styrene-butadiene random copolymer. The adhesive film of the present invention preferably has a 2% elongation strength of 1 to 10 N/100 mm. Further, the adhesive film of the present invention preferably has a 2% modulus of 0. 5 to 8 MPa. φ Moreover, the adhesive film of the present invention is preferably a hue measured by a Lab color system under the measurement conditions of 23 ° C and 50% RH, and a hue of 20 days later, by the following mathematical formula ( 1) The calculated color difference Δ E*ab is 10 or less. Further, the L*, a*, and b* systems in the mathematical formula (1) each represent the L of the L*, a*, and b* axes in the Lab color system. Further, each of AL*, Δ a*, and Δ b* represents the difference between L* and a* 'b* measured after 20 days from the preparation of the sample. (Formula 1) ® AE*ab = {(Δ L*) 2+ (Aa*) 2+ (Δ b*) 2} 1/2 _ · · (1) The adhesive film of the present invention is preferably The protective film of the substrate layered light transmissive layer as described above. By laminating such a protective film, it is possible to suppress contamination or abrasion of the substrate layer. The adhesive film of the present invention is preferably one in which the adhesive layer is an acrylic adhesive as described above. The substrate layer of the adhesive film of the present invention is preferably made to contain 100 parts by mass of the resin composition, and 0. 08 to 3 parts by mass of the particles having a volume average particle diameter of 4 201009038 to 25 / / m. Therefore, by modulating it so as to contain particles, it is possible to impart appropriate unevenness on the surface of the adhesive film. In this case, it is preferred to set the difference between the refractive index of the resin composition and the particles contained in the resin composition to be 0. 04 or less. The reason is to maintain the transparency of the adhesive film. Next, the present invention provides a laminate comprising an adhesive film and a molded body made of a synthetic resin laminated on the adhesive film, and an amine-based anti-aging agent contained in the synthetic resin for constituting the molded body. φ The type of the amine-based anti-aging agent used in the laminate of the present invention is not particularly limited, and a preferred example thereof is a phenylenediamine-based anti-aging agent. The present invention still further provides a method of protecting a molded body for protecting the formed body by adhering an adhesive film to a molded body made of a synthetic resin, wherein the synthetic resin for forming the formed body contains styrene. A butadiene rubber and an amine-based anti-aging agent, and the adhesive film is an adhesive film of the present invention. The type of the amine-based anti-aging agent to be used for the molded body protected by the protective method of the present invention is not particularly limited, and a preferred example thereof is a phenylenediamine-based anti-aging agent. Here, terms related to the present invention will be explained. In the present invention, the so-called "2% modulus" means stretching from a hysteresis curve in which the stress and strain are plotted on the axis of the curve, and the elongation at the time of stretching is 2%. Strength, and divided by the total cross-sectional area of the adhesive film. Further, in the present invention, the so-called "styrene content" means the content of the styrene and/or styrene substitute in the entire monomer constituting the resin aromatic vinyl elastomer resin of 201009038. According to the present invention, it is possible to provide an adhesive film which is less likely to cause crepe or peeling or the like, and which is less likely to cause discoloration of the substrate even when it is applied to a molded body made of a synthetic resin and reused. [Embodiment] (Best Mode for Carrying Out the Invention) © Hereinafter, a preferred mode for carrying out the invention will be described. Further, the embodiments described below are merely illustrative of one representative embodiment of the present invention, and the scope of the present invention is not limited to the embodiments. (Adhesive film) The adhesive film of the present invention comprises a base material layer and an adhesive layer, and the base material layer is formed of an aromatic vinyl elastomer resin having a styrene content of 30 to 76 mol%. The adhesive film of the present invention is characterized in that when it is applied to a molded body made of a synthetic resin, crepe or peeling is less likely to occur, and discoloration of the substrate is less likely to occur. Hereinafter, the constitution thereof will be described in detail. The base material layer of the adhesive film of the present invention is formed of an aromatic vinyl elastomer resin having a styrene content of 30 to 76 mol%. The "aromatic vinyl elastomer resin" includes a polymer block of an aromatic vinyl hydrocarbon, a block copolymer with an elastomeric polymer block, and polymerization of an aromatic vinyl hydrocarbon thereof. The block forms a hard segment and the elastomeric polymer block constitutes a soft segment. In general, the aromatic vinyl elastomer resin has an aromatic vinyl hydrocarbon polymer block-elastomer polymer block, or an aromatic vinyl hydrocarbon 201009038 polymer block-elastomer polymer A copolymerized structure represented by a segment-aromatic vinyl hydrocarbon polymer block. The "polymer block of an aromatic vinyl hydrocarbon" which can be used as the aromatic vinyl elastomer resin of the base material layer of the adhesive film of the present invention includes, for example, styrene, α-methylstyrene, ortho-A Styrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinyl anthracene, and the like. Among them, 25 to 85 mol% of a styrene and/or styrene substitute is contained in all the monomers constituting the aromatic vinyl elastomer resin. Among the styrene φ and styrene substitutes, styrene and α-methylstyrene are suitably used. These polymer blocks may be used singly or in combination of two or more. The polymer block system of the aromatic vinyl hydrocarbon which can be used as the aromatic vinyl elastomer resin of the base material layer of the adhesive film of the present invention. There is no particular limitation as long as it exhibits elastomericity, and a conjugated diene polymer block or a polymer block other than the polymer block can be used, but a conjugated diene polymer is preferably used. Block. Specific examples at this time include, for example, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like. Among them, it is particularly preferable to use 1,3-butadiene or isoprene. The "aromatic vinyl elastomer resin" can be obtained by appropriately combining the polymer block of the aromatic vinyl hydrocarbon as described above and the elastomeric polymer block. Specific examples include, for example, styrene·ethylene·butene copolymer·styrene (SEBS), styrene-ethylene/propylene copolymer-styrene (SEPS), styrene-butadiene-styrene (SBS). , Α-Β-Α type block copolymer, random copolymer, tapered copolymer, star block copolymer, multi-block copolymerization of styrene-isoprene-styrene (SIS) And the hydrides of these. In addition, 'including styrene-butadiene copolymer, styrene·isoprene 201009038 diene copolymer "AB type" block copolymer, random copolymer, tapered copolymer, star block Copolymers, multi-block copolymers and such hydrides. Among these, styrene-butadiene random copolymer and/or benzene are preferred from the viewpoints of abrasion resistance, conformability to a molded body made of a synthetic resin, and transparency. A hydride of an ethylene-butadiene random copolymer, particularly preferably a complete hydride of a styrene-butadiene random copolymer. The styrene content in all the monomers constituting the aromatic vinyl elastomer resin is from 30 to 76 mol%, preferably from 50 to 76 mol%. When the styrene content in all the monomers constituting the aromatic φ group vinyl elastomer resin is less than 30 mol%, the abrasion resistance may be poor, and when it is used in close contact with a molded body, scraping may occur. Injury and damage to the appearance. In addition, when the styrene content is more than 76 mol%, the conformability to the molded body made of synthetic resin may be poor, so that, for example, the molded body may be rotated together with a conveyor or the like, for example, a conveyor handrail or the like. Underneath, wrinkles and floating will occur and the appearance will be damaged. The styrene content in the aromatic elastomer resin of the present invention is determined by the method described in the following: Device Name: Superconducting nuclear magnetic resonance (NMR) device (JEOL Ltd.) ) Manufacturing, trade name "α -5 00") 〇 test method: Analytical method for investigating the nature of molecular structure or motion state using nuclear magnetic resonance, using deuterated chloroform solvent, or deuterated 1,1,2,2 - tetrachloroethane solvent and based on TMS, compared to proton peaks derived from phenyl (6. 5 to 7. 5 ppm) and the intensity of proton peaks (〇·8 to 3 ppm) derived from alkyl groups. -10-201009038 The base layer of the adhesive film of the present invention is not particularly limited as long as it contains an aromatic vinyl-based elastomer resin, and other resins can be freely formulated. Specific examples of other resins for arranging the substrate layer of the adhesive film of the present invention include, for example, an olefin-based thermoplastic elastomer (TPO), a polyurethane-based thermoplastic elastomer (TPU), and a polyester-based thermoplastic. An elastomer, a polyamide-based thermoplastic elastomer, an aromatic resin, or the like. Among them, an olefinic thermoplastic elastomer (TPO) is particularly suitable. Φ "Olefin-based thermoplastic elastomer" includes, for example, an ethylene-propylene copolymer or a dispersion obtained by dispersing an ethylene-propylene copolymer in polypropylene. The "polyurethane-based thermoplastic elastomer" is produced by using a polyether or a polyester and an isocyanate (MDI, TDI, HDI) as a raw material, and can be classified into a polyether system or a poly group according to the combination thereof. An ester-based, MDI-based, TDI-based, or HDI-based polyurethane-based thermoplastic elastomer. The so-called "polyester thermoplastic elastomer" is made of polyether or polyester and alkylene terephthalate or alkylene naphthalate as raw materials, and can be classified according to the combination thereof. It is a polyester-based thermoplastic elastomer of a polyether type or a polyester type. The "polyamine-based thermoplastic elastomer" is produced by using a polyether or a polyester and a polyamide as a raw material, and can be classified into a polyether-based or polyester-based polyamine-based thermoplastic according to a combination thereof. Elastomer. The "aromatic resin" means a resin having one or more aromatic rings in the molecule, and includes, for example, an aromatic polycarbonate resin, an aromatic polyester resin, a polyphenylene ether resin, and a fragrance. Group vinyl resin, polyphenylene sulfide resin, N-aromatic substituted maleimide resin, poly. 201009038 A quinone imine resin or an aromatic epoxy resin, and these resins may be used singly or in combination of two or more. In the aromatic resin, the amount of the resin composition for arranging the base material layer of the adhesive film of the present invention is particularly limited, but is not particularly limited, but is relative to 100 parts by mass. The aromatic vinyl elastomer resin is preferably 5 to 20 parts by mass of a styrene resin. When 5 parts by mass to 20 parts by mass of the aromatic resin is blended, the obtained film has a high rigidity and is excellent in workability when it is bonded to a φ-shaped body made of a synthetic resin, so that it is preferable. . The 2% elongation strength of the adhesive film of the present invention is preferably from 1 to 10 N/10 mm, more preferably from 2 to 7 N/10 mm. If it is within this range, the abrasion resistance of the adhesive film or the compliance with the molded body made of a synthetic resin is not easily lowered. The measurement method of "2% stretching strength" was measured by the following method: Device name: TENSILON tensile tester (ORIENTEC Co.) , LTD made φ, the product name "UCT-500"). Measurement method: When the adhesive film having a length of 20 mm in the transverse direction and a holding interval of 100 mm in the longitudinal direction is stretched in the longitudinal direction at a speed of 300 mm/min, the tensile strength at the elongation of 2% is converted. The enthalpy obtained by the width of 1 mm is defined as "2% elongation strength". In addition, the 2% modulus of the adhesive film of the present invention is preferably 0. 5 to 8 MPa, more preferably 0. 8 to 5 MPa, especially preferably 0. 8 to 3 MPa. By setting the 2% modulus to 0. 5 to 8 MPa, since the adhesive film stretches and contracts in accordance with the expansion and contraction of the synthetic resin, the abrasion resistance and the conformability of the molded body are good, and the peeling or twisting is less likely to occur. Etc. Therefore, it is better. Further, the measurement method of the 2% modulus is disclosed in the examples as will be described later. The 2% modulus and 2% elongation strength of the adhesive film of the present invention can be controlled by appropriately setting the type and content of the resin to be applied to the adhesive film. The hue of the adhesive film of the present invention measured by the Lab color system and the hue of the film after 20 days are preferably adjusted to 23 by the color difference AE + ab calculated by the above formula (1). Under the conditions of °C and 50% RH, ❹ is 10 or less. The reason is to prevent discoloration of the adhesive sheet. Further, the calculation method of the color difference Δ *ab is disclosed in the embodiment as will be described later. The adhesive film of the present invention is provided with a light transmissive protective layer on the surface of the substrate layer. The protective layer is used to protect the surface of the substrate layer to improve the weather resistance of the substrate layer. Specific examples of the protective layer include, for example, an olefin-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, a vinylidene fluoride-based resin, and A resin composition of a methacrylate resin, a laminated film of the resin composition having a different composition, or the like. In particular, in the present invention, it is preferable that the vinylidene fluoride-based resin which is less likely to contaminate the dirt generated by the continuous operation of the molded body made of a synthetic resin such as a handrail of a conveyor. The vinylidene fluoride resin is not particularly limited as long as it is a vinyl polymer having a vinylidene fluoride monomer unit, and may be, for example, a homopolymer of vinylidene fluoride or vinylidene fluoride. A copolymer of other vinyl compound monomers. The vinyl compound single system which can be used with vinylidene fluoride includes, for example, a vinyl compound which is fluorinated such as fluorinated ethylene, tetrafluoroethylene, vinyl chloride, hexafluoropropylene or the like; or benzene A vinyl monomer such as ethylene, ethylene, butadiene, or C-13-201009038. The vinylidene fluoride-based resin may optionally be a crosslinked acrylic resin, a crosslinked polystyrene resin, a crosslinked styrene-acrylic copolymer resin, an antibacterial agent or the like. An adhesive layer may also be formed between the substrate layer and the protective layer. The thickness of the protective layer is not particularly limited and may be 1 to 1, 〇〇〇# m, preferably 10 to 500/zm, and particularly preferably 30 to 300/zm. The substrate layer of the adhesive film of the present invention preferably contains a specific amount of particles of a specific size. By containing particles, it is possible to impart φ to the surface of the adhesive film to improve the stain resistance of the surface of the adhesive film. There is no particular limitation on the material system for forming the particles, for example, In addition to the crosslinked particles composed of a thermoplastic resin such as a methyl methacrylate polymer, a methyl methacrylate-methyl acrylate copolymer, a methyl methacrylate-styrene copolymer, or a styrene polymer, Use talc, glass beads, polysiloxane particles, and the like. The size of the particles is in the range of 4 to 25 β m in terms of volume average particle diameter, preferably ❹ in the range of 6 to 20 gm, more preferably in the range of 8 to 12/zm. When the volume average particle diameter of the particles is less than 4/m, the anti-staining property of the adhesive film may be lowered due to the inability to impart sufficient irregularities to the surface of the adhesive film. On the other hand, when it exceeds 30 #m, the transparency of the adhesive film may be impaired, and the new form of the synthetic resin molded body such as the handrail of the conveyor may become unclear. The substrate layer of the adhesive film of the present invention may contain 100 parts by mass of the resin composition and ruthenium. 〇 8 to 3 parts by mass of particles, and preferably at 〇·5 to 2. 5 mass parts, more preferably in 1. A range of 0 to 2 parts by mass. If the content of particles is less than -14- 201009038 0. When the amount is 08 parts by mass, the anti-staining property of the adhesive film cannot be obtained because sufficient unevenness cannot be imparted to the surface of the adhesive film. On the other hand, when it exceeds 3 parts by mass, the transparency of the adhesive film may be impaired, and the new form of the molded body made of a synthetic handrail such as a conveyor hand may be blurred. The refractive index of the particles is preferably a difference (AR) from the refractive index of the resin composition of 0. 04 or less. If Δ R is more than 0. At 04 o'clock, the transparency of the adhesive film may be impaired, and the new form of the φ formed body made of a synthetic resin such as a conveyor handrail may be blurred. Furthermore, the refractive index of the particles depends on the materials used. Therefore, it is preferable to appropriately select the material of the particles in accordance with the refractive index of the resin composition to be used. Furthermore, the substrate layer of the adhesive film of the present invention can contain various additives within a range of properties which are not impaired and its properties. Specific examples of the additive include, for example, an antibacterial agent, a colorant, an antioxidant, a chelating agent, an anti-blocking agent, an antistatic agent, a flame retardant, an ultraviolet absorber, a lubricant, a light stabilizer, and the like. Specific examples of the "antibacterial agent" which may be added to the base material layer of the adhesive film of the present invention include, for example, antibacterial agents such as silver, zinc, aluminum, other metals or alloys or particles of cerium oxide and ceramic particles. Mixed composite particles and the like. Specific examples of the "colorant" which can be added to the base material layer of the adhesive film of the present invention include inorganic pigments, organic pigments, dyes and the like. Specific examples of the "antioxidant" which can be added to the base material layer of the adhesive film of the present invention include, for example, an antioxidant such as a sterically hindered phenol compound, a phosphite compound, or a thioether compound. Specific examples of the "ultraviolet absorber -15 - 201009038" which can be added to the base material layer of the adhesive film of the present invention include, for example, a benzophenone-based ultraviolet absorber and a benzotriazole-based ultraviolet absorber. Specific examples of the "lubricant" to be added to the base material layer of the adhesive film of the present invention include, for example, fatty acid decylamine, paraffin wax, hydrocarbon resin, and fatty acid 0 which can be added to the base material layer of the adhesive film of the present invention. Specific examples of the light stabilizer include, for example, a reduction in the occurrence of a product which undergoes an acid-base reaction with an ethylenically unsaturated carboxylic acid, and a low-inhibition or neutral sorghum molecular weight type which is suppressed. The method for producing the base material layer of the adhesive film of the present invention is not particularly limited, and a conventional method can be used. For example, melt kneading or the like or various mixing devices (uniaxial or biaxial extruder, roll, Banbury mixer, various kneaders, etc.) may be used to mix the components and blow the film. The mixture is formed on the film by a method, a T-die method, a calendering method, or the like. When the substrate layer is stored in a roll shape, it is preferred to provide a separator layer to prevent blocking of the films. The thickness of the substrate layer of the adhesive film of the present invention is not particularly limited, but is preferably 20 to 300 #m, particularly preferably 30 to 200 /zm» by setting the thickness of the substrate layer to 20//. M or more, whereby sufficient abrasion resistance and discoloration resistance can be obtained. Further, by setting the thickness of the base material layer to 300 Å/zm or less, it is possible to obtain a film having excellent workability for a molded body. The base material layer of the adhesive film of the present invention may be a single layer or a multilayer film laminated with another resin. Specific examples of the resin layer which can be laminated include, for example, a polyolefin resin such as a polyethylene resin or a polypropylene resin. Resin; for example, thermoplastic elastomer of styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, polyester-based thermoplastic elastomer-16-201009038 plastomer 'polyurethane-based thermoplastic elastomer, polyamine-based thermoplastic elastomer, etc. Body, vinylidene fluoride resin, etc. The substrate layer of the adhesive film of the present invention may be provided with a mark such as an advertisement or a guide. By providing such a mark, it can be attached to the formed body as an advertising medium "information providing media". For example, since the mark is provided on the base material layer, printing can be applied to at least one side of the base material layer. There is no particular limitation on the printing method when printing is applied to one side of the substrate layer. 'Printing method using φ such as gravure printing, lithography, screen printing, offset printing, etc.; or ink jet method, electrostatic toner The image forming method of the method, the thermal transfer method, etc. Further, there is no particular limitation on the ink that can be used. At this time, for example, a white pigment may be added to the base material layer of the adhesive film. Specific examples of the "white pigment" include, for example, a titanium-based white pigment such as titanium oxide; a zinc-based white pigment such as zinc oxide or zinc sulfide; a composite white pigment such as lithopone; magnesium citrate or magnesium oxide; , such as calcium carbonate, barium sulfate, etc. These white pigments may be used singly or in combination of two or more. G Among these white pigments, titanium oxide is preferred. The crystal form of titanium oxide is not particularly limited, but is preferably a rutile type having a large refractive index and excellent concealing properties. The adhesive layer of the adhesive film of the present invention is formed by adhering an adhesive film to a molded body made of a synthetic resin. The material of the adhesive layer is not particularly limited as long as it is such that the adhesive film of the present invention is adhered to the molded body, but may be, for example, a rubber-based adhesive, an acrylic adhesive, or a butyl adhesive. Agents, etc. Among them, the acrylic adhesive is preferred because it can be easily designed for adhesion and removability. Further, when the butyl-based adhesive system -17-201009038 is attached to a molded body composed of a material containing an amine-based anti-aging agent, discoloration of the base material layer can be further suppressed. Further, various additives such as a tackifier, an anti-aging agent, and a hardener may be added as needed. Specific examples of the "acrylic adhesive" include a homopolymer of (meth) acrylate or a copolymer with a copolymerizable monomer. Specific examples of "(meth) acrylate" include "alkyl (meth) acrylate" such as methyl ester, ethyl ester, butyl ester, 2-ethylhexyl ester, octyl ester, etc.; "(Methyl) φ decenoic acid alkylaminoalkyl ester such as arylaminoethyl methacrylate or dimethyl methacrylate methacrylate; glycidyl (meth) acrylate, (methyl) Acrylic acid, itaconic acid, maleic anhydride, decyl (meth) acrylate, N-hydroxy decyl (meth) acrylate, and the like. Specific examples of the copolymerizable monomer include vinyl acetate, styrene, acrylonitrile, and the like. Among these, the master single system includes those in which the glass transition temperature of the homopolymer is -50 ° C or lower, for example, an alkyl acrylate or the like. "Tackifiers" can be selected by considering the softening point and the compatibility with each component. For example, enamel resin, rosin resin, hydrogenated rosin resin, xanthonone®, resin, styrene resin, aliphatic Petroleum resin, alicyclic petroleum resin, fluorene-phenol resin, xylene resin, other aliphatic hydrocarbon resin or aromatic hydrocarbon resin. The softening point of the tackifier is preferably 65 to 13 (TC, and particularly preferably an alicyclic saturated hydrocarbon resin of a petroleum resin having a softening point of 65 to 130 ° C, and a polyfluorene having a softening point of 80 to 130 ° C. The resin and the softening point are 80 to 13 (the hydrogenated rosin glyceride of TC, etc.) The "hardener" used for the acrylic adhesive includes, for example, an isocyanate-based hardener, an epoxy-based hardener, and an amine-based compound. A curing agent, etc. These may be used singly or in combination of two or more. -18 - 201009038 Specific examples of "isocyanate-based hardener" include: 2,4-tolyl diisocyanate, 2,6-extension Tolyl diisocyanate, 1,3-destenyl diiso-acid ester '1,4-dimethylbenzene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate , 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'. dicyclohexylmethane diisocyanate, a polyisocyanate compound such as an amino acid isocyanate. For the adhesive film of the present invention, The method of forming the adhesive layer on the substrate layer is not particularly limited. For example, an adhesive solution composed of an adhesive, a tackifier, an anti-aging agent, or the like may be applied to one side of the substrate layer. The method of drying, or previously applying the adhesive solution to one side of a separator which is described later, and drying it, and then adhering it to the substrate layer, etc. Adhesion of the adhesive film of the present invention. The thickness of the layer, although suitably selected within the range which does not impair adhesion or usability, may be 5 to 50 / / m, preferably 10 to 30 #ιη» Ο in the adhesive film of the present invention Preferably, the surface of the adhesive layer is provided with a release film layer, and a release film layer is provided on the surface of the adhesive layer, whereby shrinkage of the substrate layer can be prevented, wrinkles or peeling during coating can be prevented. In the construction of the adhesive film, the usability is improved, and the workability is improved. (Laminate) The "laminate" of the present invention includes the adhesive film of the present invention and the synthetic resin laminated on the adhesive film. Formed body. Forming The system is not particularly limited as long as it can be attached to the shape of the adhesive film, and may be a rod shape, a plate shape, a cover, etc. Specifically, the package -19-201009038 includes a handrail of a corridor (handrail of Corridor ), conveyor handrails, household electrical equipment, automobiles, etc. The synthetic resin used to form the shaped body can be SBR rubber, urethane rubber, chlorosulfonated rubber, ethylene-propylene-diene rubber and styrene. - any of blended rubber of butadiene rubber, blended rubber of ethylene-propylene-diene rubber and chlorosulfonated polyethylene rubber, but particularly preferably contains an amine-based anti-aging agent as an anti-aging agent When the adhesive film of the present invention is applied to a molded article containing an amine-based anti-aging agent, it is particularly difficult to discolor and is used in the molded article of the laminated body of the present invention. There are no special restrictions on the types, and it is free to choose a conventional amine-based anti-aging agent. For example, a 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, An amine-ketone anti-aging agent such as a reaction of diphenylamine with acetone; phenyl-1-naphthylamine, alkylated diphenylamine, octylated diphenylamine, 4,4' - bis(dimethylphenyl)diphenylamine, p-(p-toluenesulfonylguanidino)diphenylamine, hydrazine, Ν'·di-2-naphthyl•-p-phenylene Diamine, hydrazine, Ν'-diphenyl-p-phenylenediamine, fluorenyl-phenyl-hydrazide-isopropyl-p-phenylenediamine, hydrazine-(1,3-dimethylbutyl )-Ν'-phenyl-p-phenylenediamine, fluorenyl-phenyl-hydrazone--(3-methylpropenyloxy-2-hydroxypropyl)-p-phenylenediamine Group II amine anti-aging agent"; 2,6-di-tris-butyl-4-methylphenol, 2,6-di-tertiary-butyl-4-ethylphenol, one (or Among the two or three) (mono-phenolic anti-aging agents) such as (α-methylbenzyl) phenol, etc., particularly in the present invention, it is preferably a phenyldiamine-based antibody. Aging agent. This is because the adhesive film of the present invention is particularly resistant to discoloration when it is applied to a molded article containing a benzene-20-201009038-based diamine-based anti-aging agent. The adhesive film used in the present invention is particularly excellent in discoloration resistance to a phenylenediamine anti-aging agent among phenyldiamine-based anti-aging agents. Among the p-phenylenediamine anti-aging agents, it has excellent discoloration resistance to 6C, 6DP, and 81 ONA, and particularly has excellent discoloration resistance to 6C. The method of adhering the adhesive film of the present invention to the molded body is not particularly limited. For example, one side may be peeled off from the release film layer provided on the surface of the adhesive layer, and the pressure may be applied by a rubber roller or a squeegee. It can be attached to the handrail of the conveyor, so that it can be attached. (Protection method of the molded body) The protective method of the present invention is a method of protecting the molded body by adhering the above-described adhesive film of the present invention to a molded body made of a synthetic resin. The molded article which can be protected by the protective method of the present invention is not particularly limited as long as it is formed of the synthetic resin as described above, but the protective method of the present invention is particularly effective for protecting the contained A synthetic resin of styrene-butadiene rubber and an amine-based anti-aging agent. ® In this case, the type of the amine-based anti-aging agent to be used, although the amine-based anti-aging agent as described above can be freely selected, the protective method of the present invention is particularly suitable for protecting the amine-based anti-aging agent. The aging agent is a molded body obtained by using a phenyldiamine-based anti-aging agent. (Embodiment) Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited to the examples. 1. Review of Resin Contained in Substrate Layer (Example 1: Production of Adhesive Film) -21- 201009038 Completely 100 parts by mass of a styrene-butadiene block copolymer as an aromatic vinyl elastomer resin Hydride (manufactured by Asahi Kasei Chemicals Corporation, Tuftec® 1041: styrene content 30 mol%, conjugated diene monomer 70 mol%, hydrogenation rate 100%), and 5 mass White parent mixture (Dainippon Ink and Chemicals, Inc.) ), manufactured by PEONY WHITE F-1 1060), after dry blending, using a single-axis T-die extruder equipped with a laminating device with a screw diameter of 100 mm, and a double-sided PET 剥离 release film (TORAY ADVANCED FILM Co.) ,Ltd. Manufacture, Cerapeel "WD" 110/zin) and a transparent aromatic vinyl elastomer resin film having a thickness of 80/im to obtain a laminated film" on the side of the aromatic vinyl elastomer resin of the laminated film Applying an acrylic water-based adhesive and an epoxy-based crosslinking agent and drying them to a thickness of 20 after drying to obtain 110; zm paper separator (Sumika-Kakoushi Co., Ltd.) , Ltd. Manufactured, SL-80KCD7) to obtain a double-sided PET release film having a first layer of 110 m from m, an aromatic vinyl elastomer resin film adhesive film having a second layer of 80/zm φ, and a third layer of 20 The /zm acrylic water-based adhesive and the fourth layer are a composite film of U〇#m release paper. The 2% modulus of the adhesive film after peeling off the first layer and the fourth layer of the release film of the composite film is 0. 8 MPa. Then, the adhesive film was used to evaluate the resistance to color change, compliance, and abrasion resistance. (Measurement of 2% modulus) 2% modulus is used with TENSILON tensile tester (ORIENTEC Co.) , manufactured by LTD, UCT-5 00), and stretched in the longitudinal direction at a speed of 300 mm/min in a longitudinal direction of 25 mm and a longitudinal clamping interval of 100 mm. -22-201009038 Adhesive film sample, Then, the enthalpy obtained by dividing the tensile strength at the elongation of 2% by the cross-sectional area of the sample is defined as "2% modulus". (Evaluation of discoloration resistance) Manufacture of amine-based anti-aging agent 1 (Ouchi Shinko Chemical Industrial Co., Ltd.) ,Ltd. ) Manufacturing, NOCRAC 6C), amine-based anti-aging agent 2 (manufactured by Ouchi Shinko Chemical Co., Ltd., NOCRAC 6DP), amine-based anti-aging agent 3 (manufactured by Ouchi Shinko Chemical Co., Ltd., NOCRAC 810NA), amine An anti-aging agent 4 (manufactured by Daine φ Emerging Chemical Industry Co., Ltd., NOCRAC PA), which is prepared by dissolving 25 parts by mass of 100 parts by mass of acetone and applying it to a thickness of 8 ζηη. Thickness LDPE film. Adhesive film samples of the first layer and the fourth layer of the release film of the composite film peeled off as described above are attached to the LDPE film, and then irradiated in a test chamber at 23±2° C. and 50±5% RH in one day. After 10 hours under a fluorescent lamp for 10 hours, the color change before and after the placement was measured using a spectrophotometer (manufactured by Konica-Minolta Co., Ltd., CM-2500D). The color difference Δ E*ab is calculated from the L* (lightness ® ), a* (chromaticity), and b* (chromaticity) measured by the Lab color system according to the mathematical formula (1). Also, evaluate the merits and demerits on the basis of Table 1 below. Table 1 Excellent color difference ΔEhb is less than 10, and the color difference ΔEbb is 10 or more and less than 15 (the evaluation of compliance is poor). The first film of the composite film is peeled off as described above. A laminated adhesive film obtained by further laminating a light-transmitting protective layer on the adhesive film of the fourth layer and the fourth layer, attached to a conveyor handrail made of -23-201009038 SBR as an example of a shape made of synthetic resin The surface state after 30 days of operation was visually observed, and the merits were evaluated on the basis of Table 2 below. Further, the light-transmitting protective layer is a transparent adhesive film obtained by laminating a substrate film and an adhesive film, and is manufactured by using the following steps. (1) Production of a base film A complete hydride of a styrene-butadiene random copolymer as an aromatic vinyl elastomer resin used for a base material layer (manufactured by Asahi Kasei Industrial Co., Ltd., S. O. E. SS9000: a styrene content of 70 mol%, a conjugated diene monomer of 30 mol%, and a hydrogenation rate of 100%), and a transparent base film having a thickness of 50/zm was produced by a T-die method. When the film is produced by the T-die method, the release film made of polyethylene terephthalate (TORAY ADVANCED FILM Co.) is used for the purpose of preventing adhesion. ,Ltd. Manufacture, Cerapeel “WD” m) One side of the substrate film. (2) The adhesive film is manufactured by using an acrylic water-based adhesive and an epoxy-based crosslinking agent as an adhesive to adjust the φ compound, and the base film and the use of the release paper (the chemical processing paper stock) manufactured as described above. Co., Ltd. manufactured, SL-8 0KCD7 11〇mm) transfer coating method, the adhesive film layer thickness of 20 / zm adhesive film. When it is actually used as a protective layer, the adhesive film is attached to a handrail made of SBR made of an example of a synthetic resin, and the polyterephthalic acid mentioned in the item (1) is peeled off. A release film made of ethylene glycol ester is used. Table 2 Excellent in the observation of β wrinkles in the floater, the sputum is found to be poor. ίείβ Obviously observed the floater-24- 201009038 (Abrasion resistance) The release film of the composite film as described above will be peeled off. The laminated adhesive film obtained by further laminating the light-transmissive protective layer on the first and fourth adhesive film samples is attached to the armrest of the SBR conveyor as an example of the synthetic resin. The surface state after 3 days of operation was visually observed, and the pros and cons were evaluated on the basis of Table 3 below. Table 3 Excellent No crackers were observed Good fractures were observed Poorly observed Crackers (Example 2) In addition to the use of a complete hydride of a styrene-butadiene random copolymer (manufactured by Asahi Kasei Kogyo Co., Ltd., S. O. E. SS9000: a styrene content of 70 mol%, a conjugated diene monomer of 30 mol%, and a hydrogenation rate of 100%) were obtained in the same manner as in Example 1 except for the aromatic vinyl elastomer resin. Adhesive film. Its 2% modulus is 0. 8 MPa. The obtained adhesive film was evaluated for resistance to variability, compliance, and abrasion resistance in the same manner as in Example 1. (Example 3) The volume was 1. A 3 m3 reaction vessel was charged with 500 kg of cyclohexane containing 150 ppm of tetrahydrofuran and 8 kg of styrene monomer. Next, add 1520 ml of a cyclohexane solution containing 10% n-butyllithium. Then, the inside of the container is 80 ° C and the side is 52. 0 kg of styrene monomer and 1 〇. The butadiene of 〇 kg was added at a certain feeding speed of 84 kg/hr and 20 kg/hr, respectively. And, will be 54. 0 kg of styrene monomer and 38. 0 kg of diacetylene is 60. 5 kg / hour, 40. A certain feeding speed of 3 kg / h -25- 201009038 added. After the end of the addition, set the inside of the container to 75 °C, and further add 63. 6 kg of styrene monomer was allowed to react for 30 minutes while cooling. After the completion of the reaction, the inside of the container was set to 70 ° C, and the polymer liquid was transferred to another container. 110 g of water was added thereto to deactivate the active end of the anionic polymerization to obtain a polymer liquid containing the block copolymer. In the obtained polymer liquid, for every 100 parts by mass of the block copolymer, Sumitomo Chemical Co., Ltd. (Sumitomo Chemical Co.) ,Ltd. ) manufactured by Sumilizer GS and Chiba Specialty Chemicals Corp. (Ciba Specialty φ Chemicals Corp.) ) manufactured IRGANOX 1076 as a stabilizer and dissolved 0. 40 parts by mass, 0. 20 parts by mass. This was pre-concentrated and degassed and extruded by a biaxial extrusion equipped with a reduced pressure exhaust gas to obtain a styrene-butadiene random copolymer having a styrene content of 76 mol%. An adhesive film having a 2% modulus of 5 MPa was obtained in the same manner as in Example 1 except that the resin was used. The obtained adhesive film was evaluated for resistance to discoloration, compliance, and abrasion resistance in the same manner as in Example 1. 〇 (Comparative Example 1) A styrene-butadiene copolymer (manufactured by Denki Kagaku Kogyo Kabushiki Kaisha, 12 RN: styrene content of 88 mol%, and conjugated diene monomer of 12) was used. The adhesive film was obtained in the same manner as in Example 1 except that the aromatic vinyl elastomer resin was used. Its 2% modulus is 12 MPa. The obtained adhesive film was evaluated for resistance to discoloration, compliance, and abrasion resistance in the same manner as in Example 1. (Comparative Example 2) -26- 201009038 In addition to the use of a complete hydride of a styrene-butadiene block copolymer (Tuftec H1221 manufactured by Asahi Kasei Kogyo Co., Ltd.: styrene content of 12 mol/❶, conjugated The adhesive film was obtained in the same manner as in Example 1 except that the vinyl monomer was 88 mol% and the hydrogenation rate was 1% by weight. Its 2% modulus is 0. 3 MPa. The obtained adhesive film was evaluated for resistance to discoloration, compliance, and abrasion resistance in the same manner as in Example 1. (Comparative Example 3) φ 80/zm white polyurethane film as a substrate layer (Nihon Matai Co., Ltd.) ,Ltd. ), one side of the manufactured, Esmer URS), coated with an acrylic water-based adhesive and an epoxy-based crosslinking agent and dried to a thickness of 20 # m after drying to obtain a 2% modulus of 0. Adhesive film of 8 MPa. The obtained adhesive film was evaluated for resistance to discoloration, compliance, and abrasion resistance in the same manner as in Example 1. (Comparative Example 4) φ In addition to the use of an olefin-based thermoplastic elastomer (Prime Polymer Co.) ,Ltd. The adhesive film was obtained in the same manner as in Example 1 except that the substrate layer was produced, R-11 0E). Its 2% modulus is 1. 0 MPa. The obtained adhesive film was evaluated for resistance to discoloration, compliance, and abrasion resistance in the same manner as in Example 1. (Comparative Example 5) An adhesive film was obtained in the same manner as in Example 1 except that a vinyl chloride tape (manufactured by Denki Kagaku Kogyo Co., Ltd., white harness tape white) was used as the substrate layer. Its 2% modulus is 1. 0 -27-201009038 MPa 评估 The obtained adhesive film was evaluated for discoloration resistance, compliance, and abrasion resistance in the same manner as in Example 1. The results of the respective examples and comparative examples are shown in Table 4. . Table 4 Example Comparative Example 1 2 3 1 2 3 4 5 New Face SEBS SEBS SBS SBS SEBS Amino TPO PVC Benzene B Content (Mole%) 30 70 76 88 12 - - 2%^3⁄4 ( MPa) 0. 8 0. 8 5 12 0. 3 0. 8 0. 9 1 _chromogenic amine anti-aging agent 1 5 4 4 4 5 16 14 16 Amine anti-aging agent 2 6 5 5 5 6 15 12 15 Amine anti-aging agent 3 8 7 7 7 8 15 13 15 Amine anti-aging agent Aging agent 4 9 8 8 8 13 21 18 22 Excellent, excellent, excellent, excellent, excellent, poor, good, poor, good, good, excellent, excellent, good, bad, good, good, good, good, good, good, abrasion resistance, excellent, good, good, good, good, good, bad, excellent, and the present invention is known from Table 4. The adhesive film has excellent conformability and abrasion resistance when it is attached to a molded article, and even if it is adhered to a molded body composed of a material containing an amine-based anti-aging agent, discoloration of the substrate is less likely to occur. On the other hand, in Comparative Example 1 using an aromatic vinyl elastomer resin having a styrene content of more than 76 mol%, the compliance was poor. On the contrary, in Comparative Example 2 using an aromatic ethylenic elastomer resin having a styrene content of less than 30 mol%, as shown in Table 4, the abrasion resistance was slightly inferior, in addition to the use of polyamine groups. Comparative Examples 3 to 5' of the formic acid vinegar film, the hydrocarbon-fired thermoplastic elastomer, and the vinyl chloride tape were inferior in discoloration resistance, abrasion resistance, and compliance, respectively, as shown in Table 4. From the above results, it is known that the adhesive film of the present invention is formed by using an aromatic vinyl elastomer resin having a styrene content of 30 to 76 mol% of phenethyl -28-201009038. 2. Review of particles contained in the substrate layer Review the particles contained in the substrate layer of the adhesive film. (Example 4) (1) Production of base film A 100 parts by mass of the same styrene-butadiene random copolymer as the aromatic vinyl elastomer resin used for the substrate layer was obtained in the same manner as in Example 2. Complete φ total hydride (manufactured by Asahi Kasei Industrial Co., Ltd., S. O. E. SS9000: styrene content of 70 mol%, conjugated diene monomer of 30 mol%, hydrogenation rate of 100%, and refractive index of 1. 555), and the refractive index of 1 part by mass is 1. 545 and the refractive index difference AR with the soft resin is 0. 01 and particles with a volume average particle size of 5/zm (Sekisui Plastics Co., Ltd. (SekisuiPlasticsCo.) , Ltd. The manufacturing, Techpolymer MBX-S series) was melt-kneaded, and a transparent base film having a thickness of 50 mm was produced by a T-die method. When a film is produced by the T-die method, a release film of polyethylene terephthalate is deposited on one side of the base film for the purpose of preventing adhesion (TORAY ADVANCED FILM Co.) ,Ltd. Made, Cerapeel “WD” 38# m). (2) The adhesive film is manufactured by using an acrylic water-based adhesive and an epoxy-based crosslinking agent as an adhesive formulation, and the base film and the use of the release paper (Suihua Paper Co., Ltd.) manufactured as described above. A transfer coating method of manufacturing, SL-80KCD7 1 10 // m) was used to produce an adhesive film having an adhesive layer thickness of 20. The 2% elongation strength of the obtained adhesive film was 3. 2 N/10 mm. Using the adhesive film, the anti-staining property and the transparency were evaluated by the method described below -29-201009038, and the measurement of the ten-point average roughness. (Anti-staining property) The obtained adhesive film and the adhesive film for printing were laminated, and the anti-staining property at the time of sticking to the molded body was examined as follows. Further, the adhesive film for printing is manufactured by using the following steps. 100 parts by mass of a complete hydride of a styrene-butadiene block copolymer as an aromatic vinyl elastomer resin (manufactured by Asahi Kasei Kogyo Co., Ltd., S. O. E. SS9000: a styrene content of 70 mol%, a conjugated diene mono φ body of 30 mol%, a hydrogenation rate of 100%), and 1 part by mass of a white matrix mixture (manufactured by Dainippon Ink Chemical Co., Ltd., PEONY WHITE F-1 1 060 ) is melt-kneaded. Thereafter, a double-sided PET release film (TORAY ADVANCED FILM Co.) was used. ,Ltd. Manufactured, Cerapeel "WD"), one side of a transparent aromatic vinyl elastomer resin film having a thickness of 80 obtained by T-die molding, and a pre-coated acrylic water-based adhesive and epoxy-based adhesive The joint agent was dried and dried to obtain a 110/zm release paper (manufactured by Sugai Paper Co., Ltd., SL-80KCD7 〇) obtained by a thickness of 20 μm to obtain an adhesive film for printing. The obtained adhesive film and the adhesive film for printing were laminated, and then attached to Hitachi, Ltd. (Hitachi, Ltd.). ) The conveyor handrail of the escalator manufactured, and then the spectrophotometer (manufactured by Konica-Minolta Co., Ltd., CM-2500d) was used for the white portion to measure the color difference (AE*ab) after 3 weeks, and is shown in Table 5 below. The benchmarks shown assess their strengths and weaknesses. Table 5 〇 Color difference ΔESb is less than 10 △ Color difference AE^ab is 10 or more and less than 15 X color difference is 15 or more -30- 201009038 (Transparency) "Transparency" is a haze meter (Nippon Electric Industry) Nippon Denshoku Industries Co. , Ltd. ) Manufacture, NDH2000) to determine the haze of the obtained adhesive film, and evaluate its merits on the basis of Table 6 below. Table 6: Haze with a haze of less than 5 Δ Haze of 5 or more and less than 20 X Haze of 20 or more 0 (10-point average roughness) "10-point average roughness" is used by Kosei Research Institute Co., Ltd. (Kosaka Laboratory Ltd. ) manufactured Surfcorder (surface shape coarseness measuring machine), and measured the obtained adhesive film 根据 according to the guidelines of JIS B0601 (Example 5) except that the volume average particle diameter is used for the Techpolymer manufactured by Sekisui Kogyo Co., Ltd. The adhesive film was produced in the same manner as in Example 4 except that the MBX-S series was used as the particles used for the substrate layer. Using the obtained adhesive film, anti-staining property, transparency evaluation, and measurement of ten-point average roughness were carried out in the same manner as in Example 4. (Example 6) The same procedure as in Example 4 was carried out except that the Techpolymei·MBX-S series manufactured by Sekisui Kogyo Shoji Co., Ltd. having a volume average particle diameter of 20/im was used as the particles used for the substrate layer. The way to make an adhesive film. Using the obtained adhesive film, anti-staining property, transparency evaluation, and measurement of ten-point average roughness were carried out in the same manner as in Example 4. -31-201009038 (Example 7) The addition amount of the particles used for the substrate layer was changed to 0. An adhesive film was produced in the same manner as in Example 4 except for 1 part by mass. Using the obtained adhesive film, the anti-staining property, the evaluation of the transparency, and the measurement of the ten-point average roughness were carried out in the same manner as in Example 4. (Example 8) The addition amount of the particles used for the substrate layer was changed to 2. An adhesive film was produced in the same manner as in Example 4 except for 5 parts by mass. The anti-staining property, the evaluation of the transparency, and the measurement of the ten-point average roughness were carried out in the same manner as in Example 4 using the adhesive film obtained by the method. (Example 9) Except that a refractive index of 1. 525 and the refractive index difference AR with the soft resin is 0. The adhesive film was produced in the same manner as in Example 4 except that the particles were used for the substrate layer. Using the obtained adhesive film, anti-staining property, transparency evaluation, and measurement of ten-point average roughness were carried out in the same manner as in Example 4. (Example 10) The same procedure as in Example 4 was carried out except that the Techpolymer MBX-S series manufactured by Sekisui Seisakusho Co., Ltd. having a volume average particle diameter of 2/zm was used as the particles used for the substrate layer. The way to make an adhesive film. Using the obtained adhesive film, anti-staining property, transparency evaluation, and measurement of ten-point average roughness were carried out in the same manner as in Example 4. (Example 11) In addition to the use of the Techpolymer MBX-S series manufactured by Sekisui Kogyo Shoji Co., Ltd., which has a volume average particle diameter of 30/m, as the particles used for the substrate layer -32-201009038, The adhesive film was produced in the same manner as in Example 4. Using the obtained adhesive film, anti-staining property, transparency evaluation, and measurement of ten-point average roughness were carried out in the same manner as in Example 4 (Example 12) except that the particles used for the substrate layer were changed. The added amount is 0. An adhesive film was produced in the same manner as in Example 4 except for 05 parts by mass. Using the obtained adhesive film, the anti-staining property, the evaluation of the transparency, and the measurement of the ten-point average roughness were carried out in the same manner as in Example 4. φ (Example 13) An adhesive film was produced in the same manner as in Example 4 except that the amount of the particles used in the substrate layer was changed to 4 parts by mass. Using the obtained adhesive film, the anti-staining property, the evaluation of the transparency, and the measurement of the ten-point average roughness were carried out in the same manner as in Example 4. (Example 14) In addition to using a refractive index of 1. 525 and the refractive index difference AR of the soft resin is 〇. The adhesive film was produced in the same manner as in Example β 4 except that the particles were used as the particles of the substrate layer. Using the obtained adhesive film, anti-staining property, transparency evaluation, and measurement of ten-point average roughness were carried out in the same manner as in Example 4. The results of the examples are shown in Table 7. -33- 201009038 Table 7 Example 4 5 6 7 8 9 10 11 12 13 14 Crosslinking addition 1: (mass) 1 1 1 0. 1 2. 5 1 1 1 0. 05 4 1 Cross-linking particle size Um) 5 12 20 12 12 12 2 30 12 12 12 Ten-point flatness Rz ( "m) 2. 79 4. 77 6. 25 1. 21 5. 23 4. 77 0. 71 11. 23 0. 65 6. 32 4. 77 refractive index difference ΔΙΙ 0. 01 0. 01 0. 01 0. 01 0. 01 0. 03 0. 01 0. 01 0. 01 0. 01 0. 05 2%f strength (N/10mm) 5 5 5 5 5 5 5 5 5 5 5 Anti-staining △ E*ab 7 7 7 7 7 7 12 5 17 5 7 fpfe 〇〇〇〇〇〇Δ 〇X 〇〇Transparent HAZE 4 4 4 4 4 4 3 20 3 20 17 fNS 〇〇〇〇〇〇〇X 〇X Δ ❹
如表7所示，在涉及實施例4至9之經添加0.08至3質 量份之體積平均粒徑爲4至25/zm且與軟質樹脂之折射率之 差爲〇.〇4以下的粒子之黏著薄膜，則係透明性、防沾污性、 皮帶順應性全部皆爲良好。 與此相對，在涉及實施例1〇之所添加的珠粒之平均粒徑 爲小於4/zm之黏著薄膜，則卻造成防沾污性爲差之結果。 相反地，在渉及實施例11之所添加的珠粒之平均粒徑爲 超過25 之黏著薄膜，則卻造成透明性爲差之結果。 此外，在涉及實施例12之珠粒之添加量爲少於0.08質 量份之黏著薄膜，則卻造成防沾污性爲差之結果。 相反地，在涉及實施例13之珠粒之添加量爲超過3質量 份之黏著薄膜，則卻造成透明性爲差之結果。 並且，在涉及實施例14之所添加的珠粒之折射率與軟質 樹脂之折射率之差爲超過0.04之黏著薄膜，則卻造成透明性 爲差一些的結果。 由以上之結果得知，較佳爲所添加的粒子之體積平均粒 徑爲4至25/zm、添加量爲0.08至3質量份，並且，較佳爲 -34- 201009038 所添加的粒子之折射率與樹脂組成物之折射率之差爲0.04以 下。 (產業上之利用可能性） 本發明之黏著薄膜係經貼著於配備在走廊之扶手、輸送 機扶手、家庭電器設備、汽車等之合成樹脂製之成形體來使 用，藉此則可在不易發生皺紋或剝離、不易發生基材變色之 狀態下保護成形體。 【圖式簡單說明】 ❿ 無。 【主要元件符號說明】 Μ 。 -35-As shown in Table 7, in the case of the examples 4 to 9, 0.08 to 3 parts by mass of the particles having a volume average particle diameter of 4 to 25/zm and a difference in refractive index from the soft resin of 〇.〇4 or less were added. Adhesive film is all good in transparency, anti-staining property and belt compliance. On the other hand, in the case of the adhesive film in which the average particle diameter of the beads added in Example 1 was less than 4/zm, the anti-staining property was poor. On the contrary, in the case where the beads added in the same manner as in Example 11 had an average particle diameter of more than 25, the transparency was poor. Further, in the case where the amount of the beads involved in Example 12 added was less than 0.08 parts by mass, the anti-staining property was poor as a result. On the contrary, when the amount of the beads involved in Example 13 added was more than 3 parts by mass, the transparency was poor. Further, in the case of the adhesive film in which the difference between the refractive index of the beads added in Example 14 and the refractive index of the soft resin was more than 0.04, the transparency was inferior. From the above results, it is preferred that the particles to be added have a volume average particle diameter of 4 to 25/zm, an addition amount of 0.08 to 3 parts by mass, and preferably a refractive index of the added particles of -34 to 201009038. The difference between the ratio and the refractive index of the resin composition is 0.04 or less. (Industrial Applicability) The adhesive film of the present invention is used by being applied to a molded body made of a synthetic resin such as an armrest of a corridor, a conveyor handrail, a household electrical appliance, or an automobile. The molded article is protected in the state where wrinkles or peeling occur and the substrate is not easily discolored. [Simple description of the diagram] ❿ No. [Main component symbol description] Μ . -35-