200932862 九、發明說明 【發明所屬之技術領域】 本發明係有關黏著劑組成物及使用該黏著劑組成物之 熱熔融黏著性構件。更詳細者係具有良好的黏著性、耐溫 水性及耐藥性等’適用於聚烯烴樹脂薄膜等之聚烯烴樹脂 成形體與其他構件之黏著之黏著劑組成物，及藉由此黏著 劑組成物使銘鉑等之金屬箔與熱熔融黏著性樹脂薄膜之接 〇 合所成之熱熔融黏著性構件。 【先前技術】 先行技術中被揭示有爲使缺乏黏著性之聚烯烴樹脂所 成之成形體接合於其他構件之各種黏著劑組成物。公知者 如：使氯化聚嫌烴與末端具有異氰酸酯官能基之特定樹脂 、與至少含有1個游離異氰酸酯基之聚胺基甲酸乙酯樹脂 藉由鏈延長劑反應取得之樹脂組成物爲主成份之黏著劑用 Ο 等之黏著劑（如：專利文獻1 )。又，公知者有於所定量 之聚乙嫌、乙烯·（甲基）丙烯酸酯共聚物等之基礎聚合 物、黏著賦予劑及聚烯烴中含有使苯乙烯系單體經接枝共 聚所成之改性聚烯烴之熱熔融黏著劑（如：專利文獻2 ) 〇 公知者更有由具有異氰酸酯基之聚酯系胺基甲酸乙酯 、氯戊一稀橡膠、聚異氰酸酯、鹵化劑及2 —乙基己酸酯 類所成之黏著劑組成物（如：專利文獻3 )。另外，公知 者有如：有機溶媒中溶解或分散含羥基之熱塑性彈性體、 -5- 200932862 聚烯烴聚醇及賦予黏著劑之液狀組 酸酯所成之黏著劑組成物（如：專 [專利文獻1] 特開平8-225629號公報 [專利文獻2] ' 特開平6-228529號公報 [專利文獻3] 0 特開平5 - 1 40 5 29號公報 [專利文獻4] WO 2004/041954號公報 專利文獻1所載之黏著劑用等 不易塗佈等之聚烯烴系樹脂，如於 耐石油性、耐氣候性及耐濕性等。 烴，故對於環境之考量觀點下，用 〇 利文獻2所載之熱熔融黏著劑中， 雖可用於聚烯烴系樹脂，惟其爲熱 足。更因具有適當黏著性，故記載 ，惟’相較於溶劑型，其於薄膜表 無法進行塗佈，導致工業上生產性 存在。 又，專利文獻3所載之黏著劑 聚醋系胺基甲酸乙酯，故未施予電 ，對於聚稀烴系材料可堅固黏著。 成物、以及多官能異氰 利文獻4 )。 之黏合劑中，說明即使 形成塗膜時，仍可提昇 惟，因其含有氯化聚烯 途等有所受限。又，專 依基礎聚合物之種類， 熔融型故耐熱性稍嫌不 爲可維持良好之作業性 面等較薄，且於高速下 及量產性均不良之問題 組成物中，說明因利用 暈放電處理等之前處理 惟，聚酯系胺基甲酸乙 -6- 200932862 酯容易水解，耐久性、耐藥性均不良，吸水率亦高，因此 耐水性（透濕性）亦差。更於專利文獻4所載之黏著劑組 成物中，說明聚烯烴系樹脂之黏著中，具有高度初期黏著 強度及最終黏著強度，黏著耐久性亦良好。惟，此黏著劑 ' 組成物中，由其組成視之，其無結晶性、或結晶性極低， ' 因此容易被溶劑侵蝕，與溶劑接觸時，黏著劑層易膨潤， 其結果導致降低黏著強度之問題產生。 ❹ 【發明內容】 本發明鑑於上述先行技術之問題，而以提供一種使原 本黏著性差之聚烯烴原料用於黏著時，可以充足的強度進 行黏著，且耐溫水性、耐藥性等均良好，適用於聚烯烴原 料用之黏著劑之黏著劑組成物，及藉由此黏著劑組成物使 鋁箔等之金屬箔與聚烯烴樹脂薄膜等之熱熔融黏著性樹脂 薄膜接合所成之熱熔融黏著性構件者爲其目的。 © 本發明係如下所述。 1. 具有有機溶媒’與溶解或分散於該有機溶媒之具 有羧基之聚烯烴樹脂’以及含於該有機溶媒之多官能異氰 酸酯化合物者爲其特徵之聚烯烴用黏著劑組成物。 2. 具有該羧基之聚烯烴樹脂依Jis K 7121爲基準所 測定之熔解能爲40mJ/mg以下之該κ所載之聚烯烴用黏著 劑組成物。 3. 含於具有該羧基之聚烯烴樹脂中之該羧基含量爲 每lg具有該羧基之聚烯烴樹脂之〇.1〇〜0.70毫莫耳之該1. 200932862 或2.所載之聚烯烴用黏著劑組成物。 4. 該多官能異氰酸酯化合物所具有之異氰酸酯基（ NCO)與構成該羧基之羥基（OH)之當量比（NCO/OH) 爲1.0〜10.0之該1.至3.中任一項之聚烯烴用黏著劑組成物 〇 5. 具備使該1.至4.中任一項之聚烯烴用黏著劑組成 物進行硬化所成之黏著劑層、與接合於該黏著劑層之單面 〇 之金屬箔、以及接合於該黏著劑層之另一面之熱熔融黏著 性樹脂薄膜層者爲其特徵之熱熔融黏著性構件。 本發明黏著劑組成物係適於聚烯烴樹脂薄膜等之聚烯 烴樹脂成形體與其他構件之黏著，如：適於聚烯烴樹脂以 外之樹脂所成之薄膜與聚烯烴樹脂薄膜之黏著，硬化後之 黏著劑層具有良好的耐溫水性、耐藥性等。此黏著劑組成 物適用於如：用於建築物之建材及外裝品，特別是海濱地 區等之建築物之建材等之耐鹽水性，用於輸液等之醫療用 ❹ 液之容器時之耐電解質性，用於進行播撒熔雪劑行走道路 之車輛構件等時之良好耐腐蝕性等，建築、醫療、汽車等 各種產業領域》 又，具有羧基之聚烯烴樹脂依JIS K 7 121爲基準所測 定之熔解能爲40mJ/mg以下時，易溶於有機溶媒，可輕易 作成極薄之黏著劑層，如：可以充足的黏著強度接合金屬 箔與熱熔融黏著性樹脂薄膜。 更且具有羧基之聚烯烴樹脂中之羧基含量爲每lg該聚 烯烴樹脂之0.10〜0.70毫莫耳時，其親水性被抑制，使黏 -8- 200932862 著劑組成物用於使用聚烯烴樹脂薄膜等之密封容器等之黏 著時，可抑制濕份之侵入。 另外，構成具有多官能異氰酸酯化合物之異氰酸酯基 (NCO)與殘基之羥基（OH)相互之當量比（NCO/OH) 爲1.0〜10.0時，可進一步提昇黏著性。 ' 藉由本發明熱熔融黏著性構件，使用此熱熔融黏著性 構件作爲收容食品、藥品等之密封容器時，可抑制濕份侵 〇 入，防止內容物之變質等。 【實施方式】 [發明實施之最佳形態] 以下進行本發明之詳細說明。 [1 ]黏著劑組成物 本發明之黏著劑組成物係具有有機溶媒、與溶媒或分 〇 散於有機溶媒之具有羧基之聚烯烴樹脂、與含於有機溶媒 之多官能異氰酸酯化合物，用於聚烯烴原料之黏著。 (1)具有羧基之聚烯烴樹脂 作爲該「具有羧基之聚烯烴樹脂」（以下，稱「聚烯 烴樹脂」）者，如：於聚烯烴中，使乙烯性不飽和羧酸或 其無水物進行接枝聚合之改性聚烯烴樹脂、及稀烴單體與 乙烯性不飽和羧酸之共聚樹脂例。作爲聚烯烴者，可使用 乙烯、丙烯、丁烯等之烯烴單體之單獨聚合物或共聚物， -9- 200932862 以及此等烯烴單體、與二環戊二烯、4 —甲基戊烯一 1、乙 酸乙烯酯等之共聚物等。作爲乙烯性不飽和羧酸者，如： 丙烯酸、甲基丙烯酸、馬來酸、延胡索酸、巴豆酸、衣康 酸、檸康酸、5_原菠烯一2,3—二羧酸等例，由其黏著劑 組成物之硬化後之特性及成本面觀之，又以馬來酸爲較佳 。此等乙烯性不飽和羧酸可單獨使用1種，亦可合倂2種使 用之。作爲聚烯烴樹脂者，如：丙嫌之單獨聚合物或與乙 〇 烯之共聚物經改性之樹脂，特別使丙烯單獨聚合物經改性 之樹脂爲較佳者。 聚烯烴樹脂並未特別限定，一般依JIS K 7121爲基準 所測定之熔解能爲40mJ/mg以下之樹脂者宜。又，熔解能 爲2〜40mJ/mg者較佳，3〜20mJ/mg，特別是5〜15mJ/mg 更佳。爲熔解能爲40nU/mg以下，則對於有機溶媒之溶解 性能’且具有充分之耐溫水性、耐藥性等之黏著耐久性之 黏著劑組成物之理想狀態。又，該聚烯烴樹脂具有該熔解 Ο 能’且熔解溫度爲8 0 °c以下，特別爲6 0〜8 0。(：者爲更理想 。只要爲該聚烯烴樹脂，則可作成低溫黏著性佳，硬化後 之黏著劑層具足夠之耐溫水性、耐藥性等之黏著耐久性之 黏著劑組成物。 聚烯烴樹脂中羧基之含量更未特別受限，一般以每lg 聚烯烴樹脂爲0.10〜0.70mmol者宜。此含量特別以0.15〜 0.24mmol爲更佳。只要羧基含量爲〇.10〜0.7〇mmol者，則 與濕份之親和性不會太高，將黏著劑組成物作爲用於收納 食品、藥品等之密封容器等之形成之熱熔融黏著性構件之 -10- 200932862 黏著劑層之使用時，可有效抑制濕份之滲透。 另外，羧基之含量係使由紅外線光譜之檢量線所算出 之聚烯烴樹脂中之酸含量以羧基之式量（45)除之，可求 出每1 g樹脂之値。 (2)有機溶媒 該「有機溶媒」只要可使聚烯烴樹脂溶解或分散即可 〇 ，並未特別限定，若可溶解更多聚烯烴樹脂之溶媒者爲更 佳。又，該有機溶媒以易於由黏著劑組成物藉由加熱等進 行揮發，去除之有機溶媒者宜。作爲該有機溶媒例者可使 用如：甲苯、二甲苯等之芳香族系有機溶媒、η-己烷等之 脂肪族系有機溶媒、環己烷、甲基環己烷等之脂環族系有 機溶媒、及丁酮等之酮系有機溶媒等。此等有機溶媒可單 獨使用1種，亦可倂用2種以上。 有機溶媒與聚烯烴樹脂之質量比例並未特別限定，一 〇 般以有機溶媒中可溶解更多之聚烯烴樹脂者宜，可溶解聚 烯烴樹脂全部之量者爲更佳。該質量比例可藉由有機溶媒 及聚烯烴樹脂各別之種類設定之，有機溶媒與聚烯烴樹脂 之合計爲100質量％時，其聚烯烴樹脂爲5〜25質量％者宜 ，特別以1 0〜20質量％爲最佳。只要爲該質量比例者，即 可輕易溶解更多之聚烯烴樹脂。 另外’使聚烯烴樹脂之全部之量溶解者係以棒塗層將 黏著劑組成物（樹脂濃度20質量％ )塗佈於聚對苯二甲酸 乙二醇酯等之薄膜上，形成厚度150〜200/zm之塗膜（塗 -11 - 200932862 膜乾燥後之被膜厚度爲30〜40ym)，該塗膜之表面粗度 可藉由5 0 # m以下進行判定之。塗膜之表面粗度可依 JIS B0651所規定之觸針式表面粗度計進行測定。 (3 )多官能異氰酸酯化合物 該「多官能異氰酸酯化合物」係與聚烯烴樹脂反應後 ，具有使黏著劑組成物硬化之作用。該多官能異氰酸酯化 © 合物並無特別限定，一般可使用甲苯二異氰酸酯、二苯基 甲烷二異氰酸酯、六甲撐二異氰酸酯、異佛爾酮二異氰酸 ΐ等之化合物，及使此等化合物進行三聚異氰酸酯改性、 縮二脲改性、以三羥甲基丙烷等之多價醇進行加成改性之 改性物等。此等多官能異氰酸酯化合物可單獨使用1種， 亦可合倂2種以上使用之。一般作爲此多官能異氰酸酯化 合物者，亦可使用溶於該（2)所載之有機溶媒中之多官 能異氰酸酯化合物。 G 作爲理想之多官能異氰酸酯化合物者，如：1分子中 具有3個以上之異氰酸酯基之改性異氰酸酯化合物，作爲 三聚異氰酸酯改性之市售品者之日本聚胺基甲酸乙酯工業 公司製之商品名「Colonet ΗΧ」、旭化成化學公司製之商 品名「Dulanet TPA-100」、三井武田化學公司製之商品 名「Takenet D-170N」等例。又，作爲縮二脲改性之市售 品之三井武田化學公司製之商品名「Takenet D-165NN」 等、及三羥甲基丙烷加成改性之市售品之日本聚胺基甲酸 乙酯工業公司製之商品名「Colonet L」、三井武田化學 -12- 200932862 公司製之商品名「TakenetD-102」、「TakenetD- 等例。更以阻斷劑覆蓋異氰酸酯作成穩定化之阻斷 酸酯者亦可，作爲該阻斷型異氰酸酯之市售品者如 聚胺基甲酸乙酯工業製之商品名「Colonet 25 07 Colonet 2513」等例。 聚烯烴樹脂與多官能異氰酸酯化合物之質量比 特別限定，一般構成多官能異氰酸酯化合物所具有 〇 酸酯基（NCO )與聚烯烴樹脂所具有之羧基之羥· )當量比（NCO/OH)爲1.0〜10.0之質量比例者宜 量比又以I·5〜10.0爲較佳，特別以1.8〜9.0更佳 9.0最爲理想。只要當量比爲1.0〜10.0者，則特別 具初期黏著性良好之黏著劑組成物，同時可形成具 的交聯密度，且柔軟性等良好之黏著劑層。 (4 )其他成份 G 黏著劑組成物中，除聚烯烴樹脂、多官能異氰 合物之外，亦配合反應促進劑，更可含有賦予黏著 未被酸改性之熱塑性彈性體，未被酸改性之熱塑性 可塑劑等。 (a )反應促進劑 配合爲促進聚烯烴樹脂與多官能異氰酸酯化合 應的反應促進劑。作爲該反應促進劑者，如：各種 化合物及第3級胺之例。反應促進劑可單獨使用1種 140N」 型異氰 :曰本 例並未 之異氰 i ( OH 。該當 ，3.5 〜 可作成 有充分 酸酯化 樹脂， 樹脂， 物之反 有機錫 ，亦可 -13- 200932862 倂用2種以上’亦可倂用有機錫化合物與第3級胺 (b )賦予黏著劑 作爲賦予黏著劑例者如：聚萜烯系樹脂、松脂系樹脂 月曰肪族系石油樹|曰、脂環族系石油樹脂、共聚系石油樹 脂及氫化石油樹脂等例。作爲聚萜烯系樹脂之例者如： α-蒎烯聚合物、/3-蒎烯聚合物、及此等與苯酚或雙酚a 〇 等之共聚物例，可使用如：YASUHARA化學公司製之商品 名「YS樹脂PX」、「丫8樹脂八」、「YS P〇lyStar τ」等 之市售品。作爲松脂系樹脂例者如：天然松脂、聚合松脂 及此等之酯衍生物等例，可使用如：荒川化學工業公司製 之商品名「Pencell D」、「Super ester A」等之市售品。 脂肪族系石油樹脂亦稱C5系樹脂，通常由石油之c5餾份所 合成之樹脂’可使用tonex公司製之商品名「escoretu」、 日本Z e ο η公司製之商品名「q u i nt ο η」、good year公司製 O 之商品名「Wingtac」等之市售品。脂環族系石油樹脂亦 稱C9系樹脂，通常由石油之C9餾份所合成之樹脂，可使用 九善石油化學公司製之商品名「marucaretu」等之市售品 。共聚石油樹脂亦稱C5/C9*聚樹脂。可使用東邦化學工 業公司製之商品名「TOHO hight resin」等之市售品。氫 化烴基樹脂通常藉由上述各種石油樹脂之氫化所製造者， 可使用荒川化學工業製之商品名「ester gum Η」、「 Arcon」、YASUHARA化學公司製之商品名「Clearon」、 tonex公司製之商品名「escoretu」等。此等賦予黏著劑可 -14- 200932862 單獨使用1種，亦可倂用2種以上。 (c )其他 作爲未被酸改性之熱塑性彈性體者如：SEBS、SEPS 等爲理想例者。又，作爲未被酸改性之熱塑性樹脂者如： 乙烯·乙酸乙烯酯共聚樹脂、乙烯-乙基丙烯酸酯共聚樹脂 、蠟等爲理想例。作爲可塑劑者更以聚異戊二烯、聚丁烯 〇 等之液狀橡膠，操作油劑等爲理想例。 該（a)〜（c)之其他成份之含量對於使聚烯烴樹脂 、多官能異氰酸酯化合物及其他成份之合計爲100質量％ 時，其爲70質量％以下，特別是60〜10質量％，更以50〜 2 0質量％爲最佳者。當其他成份之含量爲70質量％以下時 ，則可作成具有充分黏著性、耐溫水性、耐藥性等之黏著 劑組成物。 本發明之黏著劑組成物可適用於爲收納食品、藥品等 ❹ 之樹脂薄膜製密封容器等之黏著劑層。如：可適用於使金 屬箔與熱熔融黏著性樹脂進行接合之黏著劑層。具有此金 屬箔與黏著劑層及熱熔融黏著性樹脂薄膜層之熱熔融黏著 性構件中，其滲透熱熔融黏著性樹脂薄膜之濕份進一步滲 透黏著劑層，到達金屬箔時，則出現降低於此界面之剝離 強度，出現剝離現象。爲抑制此強度下降及剝離現象，使 黏著劑層降低透濕性者宜。因此，黏著劑組成物依 JIS Z 0208爲基準所測定之透濕度爲100g/m2_24h以下，特 別是50g/m2*24h以下（一般10g/m2_24h以上）者最佳。只 -15- 200932862 要透濕度爲100g/in2*24h以下者，即可充分抑制濕份之滲 透’可有效抑制黏著劑層與金屬箔之界面中產生降低剝離 強度及剝離現象。 [2]熱熔融黏著性構件 本發明之熱熔融黏著性構件係如圖1，具備有：使本 發明之黏著劑組成物硬化所成之黏著劑層與接合於黏著劑 〇 層單面之金屬箔與於黏著劑層另一面所接合之熱熔融黏著 性樹脂薄膜層。 該「黏著劑層12」係將該[1]之黏著劑組成物塗佈於 金屬箔13及熱熔融黏著性樹脂薄膜層11所成之樹脂薄膜之 至少一方的表面，之後去除有機溶媒，接著，使金屬箔13 與樹脂薄膜向往塗佈黏著劑組成物之面進行層合，可藉由 加熱、壓延後形成，與此同時形成熱熔融黏著性構件1。 黏著劑層12之厚度亦依其材質等而異，並未特別限定，一 © 般爲1〜20/zm，特別爲2〜10/z m者最佳。只要黏著劑層 12之厚度爲1〜20/zm者，則易於進行熱熔融黏著性構件 之彎曲等加工。另外，一般黏著劑組成物多半塗佈於金屬 箔1 3之表面，並未特別限定。黏著劑組成物可藉由常法進 行塗佈，可使用如：棒塗層、影寫版塗層等進行塗佈。加 熱、壓延之條件並未特別限定，可藉由金屬箔13及熱溶融 黏著性樹脂薄膜層11所成之樹脂薄膜之各種材質等，以及 黏著劑組成物之組成等進行設定者宜。 該「金屬箔13」之材質並未特別限定，爲使具有良好 -16- 200932862 的加工性，一般使用鋁箔。金屬箔13之厚度亦依材質等而 異，並未特別限定，若爲鋁箔時，以20〜100//m，特別 是20〜80；/ m，更爲30〜60 最佳。鋁箔之厚度只要爲 20〜100 // m者，將不易受損，可輕易形成熱熔融黏著性 構件1。又，與形成金屬箔13之黏著劑層12之面之相反面 爲保護金屬箔13，且爲提昇密封容器等之外觀，亦可設置 樹脂層14。此樹脂層14之材質並未特別限定，一般可作成 © 由聚醯胺樹脂、聚酯樹脂等所成之樹脂層14。樹脂層14之 厚度亦未特別限定，一般爲30〜60 v m，特別是30〜50 "m者最佳。 該「熱熔融黏著性樹脂薄膜層1 1」可利用聚烯烴樹脂 薄膜、聚醯胺樹脂薄膜、聚酯樹脂薄膜等之各種樹脂薄膜 形成之。此等樹脂薄膜中又以聚烯烴樹脂薄膜爲較佳。聚 烯烴樹脂薄膜中，更又以聚丙烯薄膜，特別是熱熔融黏著 時之尺寸變化（收縮）少之無延伸聚丙烯薄膜爲更理想。 © 只要由聚烯烴樹脂薄膜所成之熱熔融黏著性樹脂薄膜層11 者，即可輕易熱熔融黏著，使熱熔融黏著性構件1之所定 個處輕易，且以充足之強度進行熱熔融黏著。熱熔融黏著 性樹脂薄膜層11之厚度亦依材質等而異，並未特別受限， —般如：無延伸聚丙烯薄膜時，爲10〜200 #m，特別是 20〜100"m，更以60〜100// m最理想。無延伸聚丙烯薄 膜之厚度只要爲10〜200"m者’則不易受損，可作成高 度耐久性之密封容器等。 -17- 200932862 [實施例] 以下藉由實施例進行本發明具體之說明。 [1]黏著劑組成物之製造 (實驗例1 ) 附設冷凝器及攪拌器之容量500ml燒瓶中，投入l70g 有機溶媒（質量比計爲甲基環己烷：丁酮=8: 2之混合溶 〇 劑），之後，置入30g之聚烯烴樹脂（馬來酸改性聚丙烯 ，日本製紙化學公司製，商品名「S-5212」（熔解能： 5mJ/mg，熔解溫度：77°C，酸價：l〇KOHmg/g，羧基含 量：0.33mmol/g，酸含量：1.5質量％)。接著，將燒瓶 內溫度作爲5 0 °C，進行3小時加熱攪拌，使樹脂溶解。之 後，冷卻至室溫，使作爲反應促進劑之二丁錫二月桂酸酯 對於樹脂而言，添加lOOppm，取得溶液黏度爲30mPa*s ( 25〇C )、樹脂濃度爲15質量％之淡黃色液狀黏著劑。 © 接著，以該液狀黏著劑爲主劑，於該主劑配合當量比 (NCO/OH)爲1.8之多官能異氰酸酯化合物（旭化成化學 公司製，商品名「Dulanet TPA-100」）’混合後’取得 黏著劑組成物。該黏著劑組成物配合多官能異氰酸酯化合 物後，於1小時內供應後述試驗片之製作。表1顯示配合組 成等。 (實驗例2 ) 如表1使多官能異氰酸酯化合物增量後’作成當量比 -18- 200932862 爲5.0之外，與實驗例1同法取得黏著劑組成物。 (實驗例3 ) 置入160g之有機溶媒，26.7g之聚烯烴樹脂之日本製 紙化學公司製’商品名「S-5 1 83」（馬來酸改性聚丙烯， 熔解能：10mJ/mg’熔解溫度：67t：，酸價：13KOHmg/g ，竣基含量：0.44mmol/g，酸含量：2.0質量％ )，及 © 13.2g之賦予黏著劑之荒川化學公司製，商品名「Arcon P- 100」（完全氫化C9樹脂，軟化點：100 °C)，如表1使多 官能異氰酸酯化合物增量後，當量比爲2.5之外，與實驗 例1同法取得黏著劑組成物。 (實驗例4 ) 如表1使多官能異氰酸酯化合物增量，作成當量比爲 9.0之外，與實驗例1同法取得黏著劑組成物。 -19- 200932862 ο© tlfi 寸 1 1 170 寸 Ο Os T*-H T—H ΙΤϊ ON 35.0 m 1 26.7 13.2 160 寸 Ό (N CN 1-H 00 Ο 寸 45.0 m n (N 1 1 170 寸 <N 〇 VO os Ο 37.0 1-H 1 1 170 ON C5 00 I lo.i νο 36.5 S-5212 (熔解能5mg/mg) /—N ω) Β "Sb S ο HD m <nc 00趾 1-H JfPP C/D w 賦予黏著樹脂Arcon P100 甲基環己烷/ 丁酮混合溶媒 多官能異氰酸酯化合物Duranet TPA-100 當量比(NCO/OH) 黏度（25°C) 1常態(初期） 溫水浸漬後 透濕度(g/m2*24小時） 酸改性聚丙烯 姻 缌a 槲s 龌3 -20- 200932862 (實驗例5 ) 如表2，未配合多官能異氰酸酯化合物之外，與實驗 例1同法取得黏著劑組成物。 (實驗例6 ) 以聚烯烴樹脂作爲三洋化成工業公司製，商品名「U-mix 101 0」（馬來酸改性聚丙烯，熔解能：52mJ/mg，熔 〇 解溫度：137 °c ，酸價：52KOHmg/g，羧基含量： 2.22mmol/g，酸含量：10質量，且，增量後，如表2 使多官能異氰酸酯化合物作成當量比2.0之配合量之外， 與實驗例1同法取得黏著劑組成物。 (實驗例7 ) 使用酸改性SEBS (旭化成化學公司製，商品名Γ Taphtee M-1913」（非晶性）取代馬來酸改性聚丙烯，如 〇 表2將多官能異氰酸酯化合物作成當量比爲2.5之配合量之 外，與貫驗例1同法取得黏著劑組成物。 200932862 o❿ 【(Ns 實驗例 卜 1 1 Ο 1 160 CN 550 卜 (N 143.0 1 Ο 寸 I 160 1 卜 〇 C4 未溶解 1 1 I I 1 170 1 1 1 Os CN Ο Γνϊ 30.0 όΰ a ---s s HD (N <EC 5魃 x/i O U-mix 1010 (熔解能52mg/mg) 酸改性 SEBS taphtec Μ-1913(非晶性） 甲基環己烷/丁酮混合溶媒 甲苯/丁酮混合溶媒 多官能異氰酸酯化合物Duranet TPA-100 當量比（NC0/0H) 黏度（25°C ) 常態（初期） 溫水浸漬後 透濕度（g/m、24小時） 酸改性聚丙烯 剝離黏著強度 (N./25mm) -22- 200932862 [2]性能評定 (1 )黏度 利用B型旋轉黏度計於2 5 °C下測定之。 (2 )透濕度 使黏者劑組成物爲乾燥後厚度50/zm，利用棒塗層進 行塗佈於剝離紙之剝離劑面，之後，室溫下揮散有機溶劑 〇 。接著，設定溫度40 °c之熱風循環式烤箱中，以老化5日 者作爲試驗片，依JIS Z 0208爲基準進行測定之。 (3 )剝離黏著強度 (A)試驗片之製作 將黏著劑組成物以棒塗層塗佈於厚度40/z m之鋁箔上 ，之後，收納於調溫爲100 °C之熱風循環式烤箱中，乾燥 6 0秒，去除含於黏著劑組成物之有機溶媒，形成膜厚6〜8 Ο μ m之黏著劑層。再將熱熔融黏著性樹脂薄膜厚度80 V m 之無延伸聚丙烯薄膜（以下簡稱CPP )貼合於黏著劑層， 利用熱傾斜試驗機進行黏著。此時之黏著條件爲溫度80°c ，壓力0.3 MPa，壓延時間3秒，由鋁面進行加壓壓延之。 黏著面積爲10x25 mm。接著將此試驗片收納於調溫成40°C 之熱風循環式烤箱，進行5天老化。 (B) T剝離黏著強度 (a )常態（初期） -23- 200932862 結束老化後，將試驗片裁成15mm，測定鉑箔與CPP間 之T剝離黏著強度（N/15mm)。 (b )溫水浸漬後 ' 將上述（a)裁成15mm寬之試驗片浸漬於85 °C之溫水 中7天後，以23 °C之水進行洗淨，洗淨後立刻測定鋁箔與 CPP間之T剝離黏著強度（N/15mm)。 0 另外，T剝離黏著強度其（a ) 、（ b )均使用張力試 驗機（東洋精製公司製），於溫度23 °C、張力速度 100mm/分鐘之條件下進行測定。 結果合倂記述於表1、2。 由表1結果證明，酸改性聚丙烯之熔解能及當量比（ NCO/OH )均爲理想範圍之實驗例1〜4中，其初期及溫水 浸漬後之剝離黏著強度均極強大，兼倂良好的黏著性與耐 溫水性。特別是，當量比更大之實驗例2中溫水浸漬後之 〇 剝離黏著強度大，更具良好的耐溫水性。又，當量比更大 之實驗例4中其初期及溫水浸漬後之剝離黏著強度均更強 ，特別更具良好的低溫黏著性及耐溫水性。 又，由表2結果證明，未含有多官能異氰酸酯化合物 之實驗例5中，其溫水浸漬後之剝離黏著強度小，耐溫水 性差。更有酸改性聚丙烯之熔解能太大之實驗例6中，其 酸改性聚丙烯因不溶於有機溶媒，因此無法測定其剝離黏 著之強度。又，使用非晶性之酸改性SEBS之實驗例7中， 其初期及溫水浸漬後之剝離黏著強度均小，黏著性、耐溫 -24- 200932862 水性均不良。 另外，實驗例1〜7之各個黏著劑組成物之透濕度値， 只要該透濕度爲50g/m2.24h以下者，則其黏著劑組成物之 剝離黏著強度並無影響。又，相同的黏著劑組成物之黏度 亦未特別影響剝離黏著強度。 【圖式簡單說明】 〇 [圖1]由斜方向所見熱熔融黏著性構件之圖，爲合倂 .說明截面之模式斜視圖。 【主要元件符號說明】 I :熱熔融黏著性構件 II :熱熔融黏著性樹脂薄膜層 1 2 :黏著劑層 13 :金屬箔（鋁箔） ❹ 1 4 :樹脂層 -25-BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition and a heat-melt adhesive member using the same. More specifically, it is an adhesive composition which is excellent in adhesion, temperature resistance, and chemical resistance, and is suitable for adhesion of a polyolefin resin molded body such as a polyolefin resin film to other members, and is composed of the adhesive. A heat-melting adhesive member formed by bonding a metal foil such as platinum or the like to a heat-fusible adhesive resin film. [Prior Art] Various adhesive compositions for bonding a molded body of a polyolefin resin lacking in adhesion to other members have been disclosed in the prior art. It is known that a resin composition obtained by reacting a chlorinated polyene hydrocarbon with a specific resin having an isocyanate functional group at the terminal and a polyurethane resin having at least one free isocyanate group by a chain extender is used as a main component. The adhesive is an adhesive such as Ο (for example, Patent Document 1). Further, it is known that a base polymer, an adhesion-imparting agent, and a polyolefin of a predetermined amount of polyethylene, ethylene/(meth)acrylate copolymer, etc., are obtained by graft copolymerization of a styrene monomer. A hot-melt adhesive for a modified polyolefin (for example, Patent Document 2). It is also known that a polyester-based urethane having an isocyanate group, a chloropentyl rubber, a polyisocyanate, a halogenating agent, and a 2-B An adhesive composition formed of a hexanoic acid ester (for example, Patent Document 3). In addition, it is known that: an organic solvent dissolves or disperses a hydroxyl group-containing thermoplastic elastomer, -5-200932862 polyolefin polyol, and an adhesive composition of a liquid group acid ester imparting an adhesive (for example: [Patent Document 2] Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The polyolefin-based resin which is difficult to apply, such as an adhesive for use in the adhesive document, is a hydrocarbon-resistant, weather-resistant, moisture-resistant, etc. hydrocarbon. Therefore, from the viewpoint of environmental considerations, the use of the patent document 2 Among the hot-melt adhesives, although it can be used for polyolefin-based resins, it is a hot foot. It has a proper adhesiveness, so it is described that it cannot be coated on a film sheet compared to a solvent type. In addition, the adhesive of the patent document 3 contains the urethane-based urethane, so that it is not applied, and it can be firmly adhered to the poly-hydrocarbon-based material. The product and the polyfunctional isocyanide Literature 4). In the adhesive, it is shown that even when a coating film is formed, it is improved, and it is limited because of its chlorinated polyene. In addition, depending on the type of the base polymer and the molten type, the heat resistance is not so thin that the work surface can be maintained, and the composition is poor at high speed and mass productivity. Prior to the discharge treatment, the polyester urethane ethane-6-200932862 ester is easily hydrolyzed, has poor durability and chemical resistance, and has high water absorption, so that water resistance (water permeability) is also poor. Further, in the adhesive composition disclosed in Patent Document 4, it is described that the adhesion of the polyolefin-based resin has a high initial adhesive strength and a final adhesive strength, and the adhesive durability is also good. However, in the composition of the adhesive, it has no crystallinity or crystallinity, so it is easily eroded by a solvent. When it comes into contact with a solvent, the adhesive layer is easily swollen, and as a result, the adhesion is lowered. The problem of strength arises. ❹ 发明 发明 鉴于 鉴于 鉴于 鉴于 鉴于 鉴于 鉴于 鉴于 鉴于 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃 聚烯烃An adhesive composition suitable for an adhesive for a polyolefin material, and a heat-melt adhesive bond between a metal foil such as an aluminum foil and a heat-fusible resin film such as a polyolefin resin film by the adhesive composition The component is for its purpose. © The present invention is as follows. An adhesive composition for polyolefins characterized by having an organic solvent 'and a polyolefin resin having a carboxyl group dissolved or dispersed in the organic solvent and a polyfunctional isocyanate compound contained in the organic solvent. 2. A polyolefin resin composition having a carboxyl group-containing polyolefin resin having a melting energy of 40 mJ/mg or less as measured on a basis of Jis K 7121. 3. The content of the carboxyl group contained in the polyolefin resin having the carboxyl group is 0.1% to 0.70 millimoles per lg of the polyolefin resin having the carboxyl group. The polyolefin for use in the 200932862 or 2. Adhesive composition. The polyolefin of any one of the above-mentioned items 1. to 3. which has an equivalent ratio (NCO/OH) of the isocyanate group (NCO) of the polyfunctional isocyanate compound to the hydroxyl group (OH) constituting the carboxyl group of 1.0 to 10.0. The adhesive composition 〇5. The adhesive layer obtained by hardening the polyolefin adhesive composition according to any one of the above items 1. to 4, and the metal bonded to the single-sided enamel of the adhesive layer A foil and a heat-fusible adhesive film characterized by being bonded to the other side of the adhesive layer. The adhesive composition of the present invention is suitable for adhesion of a polyolefin resin molded body such as a polyolefin resin film to other members, such as adhesion of a film made of a resin other than a polyolefin resin to a polyolefin resin film, and after hardening The adhesive layer has good temperature resistance, chemical resistance and the like. The adhesive composition is suitable for, for example, a building material and an exterior product for a building, particularly a salt water resistance of a building material such as a beach area, and is resistant to a medical sputum container for infusion or the like. Electrolytic properties, good corrosion resistance for vehicle components such as snow melting agent travel roads, etc., various industrial fields such as construction, medical treatment, and automobiles. Further, polyolefin resin having carboxyl group is based on JIS K 7 121. When the melting energy of the measurement is 40 mJ/mg or less, it is easily dissolved in an organic solvent, and can be easily formed into an extremely thin adhesive layer, for example, a metal foil and a hot-melt adhesive resin film can be bonded with sufficient adhesive strength. Further, when the carboxyl group content of the polyolefin resin having a carboxyl group is 0.10 to 0.70 mmol per lg of the polyolefin resin, the hydrophilicity thereof is suppressed, and the binder composition is used for the use of the polyolefin resin. When the sealed container or the like of the film is adhered, the intrusion of moisture can be suppressed. Further, when the equivalent ratio (NCO/OH) of the isocyanate group (NCO) having a polyfunctional isocyanate compound to the hydroxyl group (OH) of the residue is 1.0 to 10.0, the adhesion can be further improved. When the hot-melt adhesive member is used as a sealed container for storing foods, medicines, etc., the hot-melt adhesive member of the present invention can suppress moisture intrusion and prevent deterioration of contents. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. [1] Adhesive Composition The adhesive composition of the present invention has an organic solvent, a polyolefin resin having a carboxyl group dispersed in an organic solvent and a polyfunctional isocyanate compound contained in an organic solvent, and is used for polymerization. Adhesion of olefin raw materials. (1) A polyolefin resin having a carboxyl group is used as the "polyolefin resin having a carboxyl group" (hereinafter referred to as "polyolefin resin"), for example, in an polyolefin, an ethylenically unsaturated carboxylic acid or an anhydride thereof is subjected to An example of a graft polymerized modified polyolefin resin and a copolymer resin of a poor hydrocarbon monomer and an ethylenically unsaturated carboxylic acid. As the polyolefin, a single polymer or copolymer of an olefin monomer such as ethylene, propylene or butylene can be used, -9-200932862 and these olefin monomers, and dicyclopentadiene, 4-methylpentene A copolymer of vinyl acetate or the like. As the ethylenically unsaturated carboxylic acid, such as: acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, 5_ raw spinene-2,3-dicarboxylic acid, and the like, Maleic acid is preferred from the characteristics and cost of the adhesive composition of the adhesive. These ethylenically unsaturated carboxylic acids may be used singly or in combination of two or more. As the polyolefin resin, for example, a resin which is a single polymer or a copolymer modified with ethylene, and a resin which is modified with a propylene polymer alone is preferable. The polyolefin resin is not particularly limited, and it is generally preferred that the melting energy measured according to JIS K 7121 is 40 mJ/mg or less. Further, the melting energy is preferably 2 to 40 mJ/mg, more preferably 3 to 20 mJ/mg, particularly preferably 5 to 15 mJ/mg. In order to have a melting energy of 40 nU/mg or less, it is an ideal state of an adhesive composition which has sufficient solubility in water resistance and resistance to organic solvents. Further, the polyolefin resin has the melting energy and the melting temperature is 80 ° C or less, particularly 60 to 80. (The one is more desirable. As long as it is a polyolefin resin, it can be made into a low-temperature adhesiveness, and the adhesive layer after hardening has the adhesive composition of the adhesive durability with sufficient temperature resistance, the resistance, and the like. The content of the carboxyl group in the olefin resin is not particularly limited, and is generally 0.10 to 0.70 mmol per lg of the polyolefin resin. The content is particularly preferably 0.15 to 0.24 mmol, as long as the carboxyl group content is 〇.10 to 0.7〇mmol. When the adhesive composition is used, the adhesive composition is used as a heat-melting adhesive member for storing a sealed container such as a food or a drug, and the use of the adhesive layer is -10-200932862. In addition, the content of the carboxyl group is such that the acid content in the polyolefin resin calculated from the calibration curve of the infrared spectrum is divided by the formula of the carboxyl group (45), and each 1 g can be determined. (2) Organic solvent The "organic solvent" is not particularly limited as long as it can dissolve or disperse the polyolefin resin, and it is more preferable to dissolve the solvent of the polyolefin resin. Organic solvent is easy The adhesive composition is preferably volatilized by heating or the like, and the organic solvent is removed. As the organic solvent, an aromatic organic solvent such as toluene or xylene or an aliphatic organic compound such as η-hexane can be used. An alicyclic organic solvent such as a solvent, cyclohexane or methylcyclohexane, or a ketone-based organic solvent such as methyl ethyl ketone. These organic solvents may be used singly or in combination of two or more. The mass ratio of the solvent to the polyolefin resin is not particularly limited, and it is preferred that the polyolefin resin is more soluble in the organic solvent, and the total amount of the polyolefin resin is preferably dissolved. The mass ratio can be obtained by When the total amount of the organic solvent and the polyolefin resin is 100% by mass, the polyolefin resin is preferably 5 to 25% by mass, particularly preferably 10 to 20% by mass. Preferably, as long as it is the mass ratio, more polyolefin resin can be easily dissolved. In addition, the entire amount of the polyolefin resin is dissolved by coating the adhesive composition (resin concentration: 20% by mass) with a bar coating. cloth On a film of polyethylene terephthalate or the like, a coating film having a thickness of 150 to 200/zm is formed (coating film of -11 - 200932862 film is dried to a thickness of 30 to 40 μm), and the surface roughness of the coating film is obtained. The thickness of the coating film can be measured according to the stylus surface roughness meter specified in JIS B0651. (3) Polyfunctional isocyanate compound The "polyfunctional isocyanate compound" is determined. The reaction with the polyolefin resin has the effect of hardening the adhesive composition. The polyfunctional isocyanate compound is not particularly limited, and generally, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, or the like can be used. a compound such as phorone diisocyanate or the like, and a modified product obtained by subjecting these compounds to trimerization, biuret modification, and addition modification with a polyvalent alcohol such as trimethylolpropane Wait. These polyfunctional isocyanate compounds may be used alone or in combination of two or more. As the polyfunctional isocyanate compound, a polyfunctional isocyanate compound dissolved in the organic solvent contained in the above (2) can also be used. G is an ideal polyisocyanate compound, such as a modified isocyanate compound having three or more isocyanate groups in one molecule, and is manufactured by Japan Polyurethane Industrial Co., Ltd., which is a commercially available product of trimer isocyanate modification. The trade name "Colonet ΗΧ", the product name "Dulanet TPA-100" manufactured by Asahi Kasei Chemicals Co., Ltd., and the trade name "Takenet D-170N" manufactured by Mitsui Takeda Chemical Co., Ltd., and the like. In addition, as a commercial product of the biuret modification, the product name "Takenet D-165NN" manufactured by Mitsui Takeda Chemical Co., Ltd., and the commercially available product of the trimethylolpropane addition modification are Japanese polyaminocarbamate B. Trade name "Colonet L" manufactured by Ester Industries Co., Ltd., Mitsui Takeda Chemicals-12-200932862 The company's trade names "Takenet D-102", "TakenetD-, etc.. Blocking agent is also used to block isocyanate to stabilize the blocking acid. The ester can also be used as a commercial product of the blocked isocyanate, for example, the product name "Colonet 25 07 Colonet 2513" manufactured by the polyurethane. The mass ratio of the polyolefin resin to the polyfunctional isocyanate compound is particularly limited, and the equivalent ratio (NCO/OH) of the carboxyl group (NCO) of the polyfunctional isocyanate compound to the carboxyl group of the polyolefin resin is generally 1.0. The mass ratio of ~10.0 is preferably 1 to 50.0, and particularly preferably 1.8 to 9.0. When the equivalent ratio is 1.0 to 10.0, an adhesive composition having excellent initial adhesion is formed, and an adhesive layer having a good crosslink density and excellent flexibility can be formed. (4) Other components G Adhesive compositions, in addition to polyolefin resins and polyfunctional isocyanates, may also be combined with a reaction accelerator, and may further contain a thermoplastic elastomer which imparts no acid modification to the adhesion, and is not acid. Modified thermoplastic plasticizer, etc. (a) Reaction accelerator A reaction accelerator which promotes the combination of a polyolefin resin and a polyfunctional isocyanate. As the reaction accelerator, there are examples of various compounds and tertiary amines. The reaction accelerator may be used alone as a type of 140N" isocyanide: 异 is not an isocyanide i (OH.., 3.5 ~ can be made into a fully acidified resin, resin, anti-organic tin, or - 13- 200932862 2Use two or more kinds of 'organic tin compounds and third-grade amines (b) to give adhesives as an adhesive-imparting agent such as polydecene-based resin and rosin-based resin Examples of the resin, the alicyclic petroleum resin, the copolymerized petroleum resin, and the hydrogenated petroleum resin, etc. Examples of the polydecene-based resin are: α-pinene polymer, /3-pinene polymer, and the like For example, a copolymer of phenol or bisphenol a ruthenium or the like can be used, for example, a product such as YS resin PX, 丫8 resin VIII, and YS P〇lyStar τ manufactured by YASUHARA Chemical Co., Ltd. As an example of the rosin-based resin, such as natural turpentine, polymeric turpentine, and ester derivatives thereof, for example, a product such as "Pencell D" and "Super ester A" manufactured by Arakawa Chemical Industries Co., Ltd. can be used. Aliphatic petroleum resin, also known as C5 resin, usually from petroleum The resin synthesized by the c5 fraction can be obtained from the trade name "escoretu" manufactured by Tonex Corporation, the trade name "qui nt ο η" manufactured by Zee Japan Co., Ltd., and the trade name "Wingtac" manufactured by Good Year Corporation. The alicyclic petroleum resin is also known as a C9-based resin, and a resin which is usually synthesized from a C9 fraction of petroleum, and a commercial product such as "Marucaretu" manufactured by Nine-Tsing Petrochemical Co., Ltd. can be used. Petroleum resin is also known as C5/C9* poly resin. Commercial products such as "TOHO hight resin" manufactured by Toho Chemical Co., Ltd. can be used. Hydrogenated hydrocarbon-based resins are usually produced by hydrogenation of various petroleum resins mentioned above. The brand name "ester gum Η", "Arcon" manufactured by Arakawa Chemical Industry Co., Ltd., the trade name "Clearon" manufactured by YASUHARA Chemical Co., Ltd., and the trade name "escoretu" manufactured by Toxex Co., Ltd., etc. These adhesives can be used alone -14-200932862 One type may be used, or two or more types may be used. (c) Other thermoplastic elastomers which are not acid-modified, such as SEBS and SEPS, are preferred. Further, as a thermoplastic resin not modified by an acid. For example, an ethylene-vinyl acetate copolymer resin, an ethylene-ethyl acrylate copolymer resin, a wax, etc. are ideal examples. As a plasticizer, a liquid rubber such as polyisoprene or polybutene is used as an oil agent. The content of the other components (a) to (c) is 70% by mass or less, particularly 60%, when the total of the polyolefin resin, the polyfunctional isocyanate compound, and other components is 100% by mass. 10% by mass, more preferably 50 to 20% by mass. When the content of the other components is 70% by mass or less, an adhesive composition having sufficient adhesion, temperature resistance, chemical resistance, and the like can be prepared. The adhesive composition of the present invention can be applied to an adhesive layer such as a sealed container made of a resin film for storing foods, pharmaceuticals, and the like. For example, it can be applied to an adhesive layer that bonds a metal foil to a hot-melt adhesive resin. In the hot-melt adhesive member having the metal foil and the adhesive layer and the heat-melt adhesive resin film layer, the moisture of the heat-fusible adhesive resin film penetrates further into the adhesive layer, and when it reaches the metal foil, it is lowered. The peel strength of this interface was peeled off. In order to suppress this strength drop and peeling phenomenon, it is preferable to reduce the moisture permeability of the adhesive layer. Therefore, the moisture permeability of the adhesive composition measured based on JIS Z 0208 is 100 g/m2_24h or less, and particularly preferably 50 g/m2*24h or less (generally 10 g/m2_24h or more). Only -15-200932862 To achieve a moisture permeability of 100g/in2*24h or less, the penetration of moisture can be sufficiently suppressed, and the peeling strength and peeling phenomenon at the interface between the adhesive layer and the metal foil can be effectively suppressed. [2] Hot-melt Adhesive Member The heat-fusible adhesive member of the present invention is characterized in that, as shown in Fig. 1, an adhesive layer formed by hardening the adhesive composition of the present invention and a metal bonded to one side of the adhesive layer The foil is a layer of a heat-fusible adhesive resin film bonded to the other side of the adhesive layer. In the "adhesive layer 12", the adhesive composition of [1] is applied onto at least one surface of a resin film formed of the metal foil 13 and the heat-fusible resin film layer 11, and then the organic solvent is removed, and then the organic solvent is removed. The metal foil 13 and the resin film are laminated on the surface on which the adhesive composition is applied, and can be formed by heating and rolling, and the heat-fusible adhesive member 1 is formed at the same time. The thickness of the adhesive layer 12 varies depending on the material and the like, and is not particularly limited. It is preferably 1 to 20/zm, particularly 2 to 10/z m. As long as the thickness of the adhesive layer 12 is 1 to 20/zm, it is easy to perform processing such as bending of the heat-melt adhesive member. Further, the general adhesive composition is usually applied to the surface of the metal foil 13 and is not particularly limited. The adhesive composition can be applied by a usual method, and can be applied by, for example, a bar coat, a photolithographic coating, or the like. The heating and rolling conditions are not particularly limited, and may be set by various materials such as the resin film formed of the metal foil 13 and the hot-melt adhesive resin film layer 11, and the composition of the adhesive composition. The material of the "metal foil 13" is not particularly limited, and aluminum foil is generally used in order to have good workability of -16 to 200932862. The thickness of the metal foil 13 varies depending on the material and the like, and is not particularly limited. When it is an aluminum foil, it is preferably 20 to 100 / / m, particularly 20 to 80; / m, more preferably 30 to 60. When the thickness of the aluminum foil is 20 to 100 // m, it is not easily damaged, and the heat-melting adhesive member 1 can be easily formed. Further, the metal foil 13 is protected from the surface opposite to the surface on which the adhesive layer 12 of the metal foil 13 is formed, and the resin layer 14 may be provided to enhance the appearance of the sealed container or the like. The material of the resin layer 14 is not particularly limited, and generally, a resin layer 14 made of a polyamide resin, a polyester resin or the like can be used. The thickness of the resin layer 14 is also not particularly limited, and is generally 30 to 60 v m, particularly 30 to 50 " The "hot-melt adhesive resin film layer 1 1" can be formed by various resin films such as a polyolefin resin film, a polyamide resin film, and a polyester resin film. Among these resin films, a polyolefin resin film is preferred. Further, in the polyolefin resin film, a polypropylene film, in particular, a non-stretch polypropylene film having a small dimensional change (shrinkage) upon heat fusion bonding is more preferable. © As long as the hot-melt adhesive resin film layer 11 made of a polyolefin resin film is easily melted by heat, the heat-melting adhesive member 1 can be easily fixed and thermally fused at a sufficient strength. The thickness of the heat-fusible adhesive resin film layer 11 varies depending on the material and the like, and is not particularly limited. For example, when the polypropylene film is not stretched, it is 10 to 200 #m, particularly 20 to 100 "m, It is ideal for 60~100//m. The thickness of the non-stretched polypropylene film is not easily damaged as long as it is 10 to 200 "m, and it can be used as a sealed container of high durability. -17- 200932862 [Embodiment] Hereinafter, the present invention will be specifically described by way of examples. [1] Manufacture of adhesive composition (Experimental Example 1) In a 500 ml flask equipped with a condenser and a stirrer, 110 g of an organic solvent (mass ratio of methylcyclohexane: butanone = 8: 2) was added. Tanning agent), and then placed 30 g of a polyolefin resin (manic acid-modified polypropylene, manufactured by Nippon Paper Chemical Co., Ltd., trade name "S-5212" (melting energy: 5 mJ/mg, melting temperature: 77 ° C, Acid value: l〇KOHmg/g, carboxyl group content: 0.33 mmol/g, acid content: 1.5% by mass. Then, the temperature in the flask was heated at 50 ° C for 3 hours to dissolve the resin. Thereafter, cooling was carried out. To the room temperature, dibutyltin dilaurate as a reaction accelerator was added to 100 ppm of the resin to obtain a pale yellow liquid adhesive having a solution viscosity of 30 mPa*s (25 〇C) and a resin concentration of 15% by mass. Then, a polyfunctional isocyanate compound (product name "Dulanet TPA-100" manufactured by Asahi Kasei Chemicals Co., Ltd.) having a ratio of equivalent ratio (NCO/OH) of 1.8 to the main component is used as the main component of the liquid adhesive. After mixing, 'obtaining the adhesive composition. The adhesive composition is matched After the functional isocyanate compound, the test piece described later was supplied in one hour. Table 1 shows the compounding composition, etc. (Experimental Example 2) As shown in Table 1, the polyfunctional isocyanate compound was incremented and the equivalent ratio -18-200932862 was 5.0. In the same manner as in Experimental Example 1, the adhesive composition was obtained. (Experimental Example 3) 160 g of an organic solvent and 26.7 g of a polyolefin resin manufactured by Nippon Paper Chemical Co., Ltd., 'product name' S-5 1 83' (Ma) Acid-modified polypropylene, melting energy: 10mJ/mg 'melting temperature: 67t:, acid value: 13 KOHmg / g, sulfhydryl content: 0.44mmol / g, acid content: 2.0% by mass), and © 13.2g Adhesive Arakawa Chemical Co., Ltd., trade name "Arcon P-100" (fully hydrogenated C9 resin, softening point: 100 °C), as shown in Table 1, after increasing the polyfunctional isocyanate compound, the equivalent ratio is 2.5, and Experimental Example 1 An adhesive composition was obtained by the same method. (Experimental Example 4) An adhesive composition was obtained in the same manner as in Experimental Example 1 except that the polyfunctional isocyanate compound was incremented in Table 1 to give an equivalent ratio of 9.0. 200932862 ο© tlfi inch 1 1 170 inch Ο Os T*-HT-H ΙΤϊ ON 35.0 m 1 26.7 13.2 160 inch Ό (N CN 1-H 00 Ο inch 45.0 mn (N 1 1 170 inch <N 〇VO os Ο 37.0 1-H 1 1 170 ON C5 00 I lo.i νο 36.5 S-5212 (melting energy 5mg/mg) /—N ω) Β "Sb S ο HD m <nc 00 toe 1-H JfPP C/D w to give adhesive resin Arcon P100 methyl ring Hexane/butanone mixed solvent polyfunctional isocyanate compound Duranet TPA-100 Equivalent ratio (NCO/OH) Viscosity (25°C) 1 Normal state (initial) Moisture permeability after warm water immersion (g/m2*24 hours) Acid modification Polypropylene Infant a 槲s 龌 3 -20- 200932862 (Experimental Example 5) As shown in Table 2, an adhesive composition was obtained in the same manner as in Experimental Example 1 except that the polyfunctional isocyanate compound was not blended. (Experimental Example 6) A polyolefin resin was used as a product of Sanyo Chemical Industry Co., Ltd. under the trade name "U-mix 101 0" (maleic acid-modified polypropylene, melting energy: 52 mJ/mg, melting temperature: 137 °c, Acid value: 52 KOHmg/g, carboxyl group content: 2.22 mmol/g, acid content: 10 mass, and, after the increment, as shown in Table 2, the polyfunctional isocyanate compound was made into an equivalent ratio of 2.0, and the same as Experimental Example 1. The adhesive composition was obtained by the method. (Experimental Example 7) The maleic acid-modified polypropylene was replaced with an acid-modified SEBS (manufactured by Asahi Kasei Chemical Co., Ltd., trade name Γ Taphtee M-1913) (amorphous), as shown in Table 2 The polyfunctional isocyanate compound was prepared in an equivalent ratio of 2.5, and the adhesive composition was obtained in the same manner as in Test Example 1. 200932862 o❿ [(Ns Experimental Example 1 1 Ο 1 160 CN 550 卜 (N 143.0 1 Ο inch) I 160 1 Divination C4 Undissolved 1 1 II 1 170 1 1 1 Os CN Ο Γνϊ 30.0 όΰ a ---ss HD (N <EC 5魃x/i O U-mix 1010 (melting energy 52mg/mg) Acid modified SEBS taphtec Μ-1913 (amorphous) methylcyclohexane / butanone mixed solvent toluene / butanone mixed solution Polyfunctional isocyanate compound Duranet TPA-100 Equivalent ratio (NC0/0H) Viscosity (25°C) Normal (initial) Moisture permeability after warm water immersion (g/m, 24 hours) Acid-modified polypropylene peel adhesion strength (N. /25mm) -22- 200932862 [2]Performance evaluation (1) Viscosity is measured at 25 °C using a B-type rotary viscometer. (2) The moisture permeability is such that the composition of the adhesive is 50/zm after drying. The stripping agent was applied to the release agent surface of the release paper, and then the organic solvent enthalpy was evaporated at room temperature. Then, the hot air circulating oven was set at a temperature of 40 ° C, and the aging was performed for 5 days as a test piece according to JIS. Z 0208 was measured as a reference. (3) Peel adhesion strength (A) Preparation of test piece The adhesive composition was applied to a 40/zm thick aluminum foil with a bar coating, and then stored at a temperature of 100 °. In a hot air circulating oven of C, it is dried for 60 seconds, and the organic solvent contained in the adhesive composition is removed to form an adhesive layer having a film thickness of 6 to 8 μm. The thickness of the hot-melt adhesive resin film is 80 V m. The non-stretched polypropylene film (hereinafter referred to as CPP) is attached to the adhesive layer, Thermal inclined adhesion tester. At this time the condition of a temperature of adhesive 80 ° c, pressure 0.3 MPa, 3 seconds calendering, the calender is pressurized by the aluminum surface. The adhesive area is 10x25 mm. Then, the test piece was placed in a hot air circulating oven adjusted to 40 ° C, and aged for 5 days. (B) T-peel adhesion strength (a) Normal state (initial) -23- 200932862 After the aging was completed, the test piece was cut into 15 mm, and the T-peel adhesion strength (N/15 mm) between the platinum foil and the CPP was measured. (b) After immersion in warm water' The test piece cut into 15 mm width (a) was immersed in warm water of 85 °C for 7 days, and then washed with water at 23 °C. Immediately after washing, aluminum foil and CPP were measured. T peel adhesion strength (N/15mm). In addition, the T-peel adhesion strengths (a) and (b) were measured using a tensile tester (manufactured by Toyo Seisakusho Co., Ltd.) under the conditions of a temperature of 23 ° C and a tensile speed of 100 mm/min. The results are collectively described in Tables 1 and 2. From the results in Table 1, it was confirmed that in the experimental examples 1 to 4 in which the melting energy and the equivalent ratio (NCO/OH) of the acid-modified polypropylene were all in a desired range, the peeling adhesion strength at the initial stage and the warm water immersion was extremely strong. Good both good adhesion and temperature resistance. In particular, in the experimental example 2 in which the equivalent ratio is larger, the 剥离 peeling adhesive strength after the warm water immersion is large, and the temperature is more excellent. Further, in Experimental Example 4 in which the equivalent ratio was larger, the peeling adhesion strength at the initial stage and the warm water immersion was stronger, and particularly, the low-temperature adhesion and the temperature-resistant water resistance were better. Further, as a result of the results of Table 2, in Experimental Example 5 which did not contain a polyfunctional isocyanate compound, the peeling adhesive strength after warm water immersion was small, and the temperature resistance was poor. In the case of the acid-modified polypropylene, the acid-modified polypropylene was insoluble in the organic solvent, and thus the strength of the peeling adhesion could not be measured. Further, in Experimental Example 7 in which SEBS was modified with an amorphous acid, the peeling adhesive strength at the initial stage and the warm water immersion was small, and the adhesiveness and temperature resistance were both poor in the water content of -24-200932862. Further, in the moisture permeability of each of the adhesive compositions of Experimental Examples 1 to 7, as long as the moisture permeability was 50 g/m or less and 2.24 h or less, the peeling adhesive strength of the adhesive composition was not affected. Also, the viscosity of the same adhesive composition did not particularly affect the peel adhesion strength. [Simplified description of the drawings] 〇 [Fig. 1] A view of a hot-melt adhesive member seen from an oblique direction, which is a combined view. [Explanation of main component symbols] I : Thermal fusion adhesive member II : Thermally-melt adhesive resin film layer 1 2 : Adhesive layer 13 : Metal foil (aluminum foil) ❹ 1 4 : Resin layer -25-