[發明所欲解決之問題] WO2014/010019所記載之技術於考慮到環境負荷，而使用水作為接著劑之分散介質之方面值得評價。然而，存在接著劑之乾燥需要較長時間之問題。另一方面，於日本專利第5213523號公報中，使用熱熔接著劑。熱熔接著劑係無溶劑型之接著劑，可消除乾燥時間之問題。然而，由於熱熔接著劑係使用熱塑性樹脂，故而耐熱性存在問題。 對此，已知有對熱熔接著劑賦予反應性之反應性熱熔接著劑。反應性熱熔接著劑係無溶劑型，又，耐熱性亦得以改善，因此可謂前景良好之接著劑。然而，就耐熱性、耐水解性及往復開合耐久性等之對防水性拉鏈鏈布所要求之特性、或環境負荷及生產性之綜合平衡性之觀點而言，仍有改善之餘地。 本發明係鑒於上述情況而完成者，其課題之一在於提供一種耐熱性、耐水解性及往復開合耐久性等之對防水性拉鏈鏈布所要求之特性、以及環境負荷及生產性之綜合平衡性得以改善之防水性拉鏈鏈布。又，本發明之另一課題之一在於提供一種上述防水性拉鏈鏈布之製造方法。 [解決問題之技術手段] 本發明者為了解決上述問題而努力進行研究，發現使用以特定之異氰酸酯基封端之胺基甲酸酯預聚物作為主成分之反應性熱熔接著劑製造防水性拉鏈鏈布而有效。本發明係基於該見解而完成者。 本發明之一態樣係一種拉鏈鏈布，其係具備底布、及貼附於底布之至少一面之止水膜者，且止水膜具有由聚胺基甲酸酯脲之膜形成之單層構造，該聚胺基甲酸酯脲係選自由聚碳酸酯系聚胺基甲酸酯脲、聚碳酸酯-聚醚系聚胺基甲酸酯脲、聚碳酸酯-聚酯系聚胺基甲酸酯脲、及聚碳酸酯-聚醚-聚酯系聚胺基甲酸酯脲所組成之群中之一種以上者，且具有胺基甲酸酯基及脲基，將胺基甲酸酯基及脲基之合計莫耳分率設為1時之脲基之莫耳分率為0.1～0.5。 於本發明之拉鏈鏈布之一實施形態中，構成上述止水膜之聚胺基甲酸酯脲為聚碳酸酯-聚醚-聚酯系聚胺基甲酸酯脲。 本發明之另一態樣係一種拉鏈鏈布，其係具備底布、及貼附於底布之至少一面之止水膜者，且止水膜具有具備包含聚胺基甲酸酯脲之膜之表層與鄰接於表層之聚胺基甲酸酯脲之接著層的積層構造，構成接著層之聚胺基甲酸酯脲係選自由聚碳酸酯系聚胺基甲酸酯脲、聚碳酸酯-聚醚系聚胺基甲酸酯脲、聚碳酸酯-聚酯系聚胺基甲酸酯脲、及聚碳酸酯-聚醚-聚酯系聚胺基甲酸酯脲所組成之群中之一種以上者，且具有胺基甲酸酯基及脲基，將胺基甲酸酯基及脲基之合計莫耳分率設為1時之脲基之莫耳分率為0.1～0.5。 於本發明之拉鏈鏈布之一實施形態中，構成表層之聚胺基甲酸酯脲含有聚碳酸酯系聚胺基甲酸酯脲。 於本發明之拉鏈鏈布之一實施形態中，構成接著層之聚胺基甲酸酯脲為聚碳酸酯-聚醚-聚酯系聚胺基甲酸酯脲。 本發明之進而另一態樣係一種拉鏈，其具備本發明之拉鏈鏈布。 本發明之進而另一態樣係一種拉鏈鏈布之製造方法，其包括如下步驟： 將反應性熱熔接著劑塗敷於底布上；及 使上述反應性熱熔接著劑進行濕氣硬化；且 反應性熱熔接著劑含有如下預聚物作為主成分，該預聚物係選自由聚碳酸酯系之異氰酸酯基封端之胺基甲酸酯預聚物、聚碳酸酯-聚醚系之異氰酸酯基封端之胺基甲酸酯預聚物、聚碳酸酯-聚酯系之異氰酸酯基封端之胺基甲酸酯預聚物、及聚碳酸酯-聚醚-聚酯系之異氰酸酯基封端之胺基甲酸酯預聚物所組成之群中之一種以上者，且以異氰酸酯基相對於胺基甲酸酯基之莫耳比成為0.5～1.5之方式具有胺基甲酸酯基及異氰酸酯基。 本發明之進而另一態樣係一種拉鏈鏈布之製造方法，其包括如下步驟： 經由反應性熱熔接著劑，將包含聚胺基甲酸酯脲之膜之表層與底布貼合；及 使反應性熱熔接著劑進行濕氣硬化；且 反應性熱熔接著劑含有如下預聚物作為主成分，該預聚物係選自由聚碳酸酯系之異氰酸酯基封端之胺基甲酸酯預聚物、聚碳酸酯-聚醚系之異氰酸酯基封端之胺基甲酸酯預聚物、聚碳酸酯-聚酯系之異氰酸酯基封端之胺基甲酸酯預聚物、及聚碳酸酯-聚醚-聚酯系之異氰酸酯基封端之胺基甲酸酯預聚物所組成之群中之一種以上者，且以異氰酸酯基相對於胺基甲酸酯基之莫耳比成為0.5～1.5之方式具有胺基甲酸酯基及異氰酸酯基。 本發明之進而另一態樣係一種拉鏈鏈布之製造方法，其包括如下步驟： 以於底布上依序積層接著層用之反應性熱熔接著劑及表層用之反應性熱熔接著劑之方式進行依序積層塗敷或同時積層塗敷；及 使接著層用之反應性熱熔接著劑及表層用之反應性熱熔接著劑均進行濕氣硬化；且 接著層用之反應性熱熔接著劑及表層用之反應性熱熔接著劑均含有如下預聚物作為主成分，該預聚物係選自由聚碳酸酯系之異氰酸酯基封端之胺基甲酸酯預聚物、聚碳酸酯-聚醚系之異氰酸酯基封端之胺基甲酸酯預聚物、聚碳酸酯-聚酯系之異氰酸酯基封端之胺基甲酸酯預聚物、及聚碳酸酯-聚醚-聚酯系之異氰酸酯基封端之胺基甲酸酯預聚物所組成之群中之一種以上者，且以異氰酸酯基相對於胺基甲酸酯基之莫耳比成為0.5～1.5之方式具有胺基甲酸酯基及異氰酸酯基。 [發明之效果] 本發明中所使用之反應性熱熔接著劑係無溶劑型且環境負荷較小，又，反應性及操作作業性優異，因此有助於提高防水性拉鏈鏈布之生產性。又，本發明中所使用之反應性熱熔接著劑能夠形成耐水解性、耐熱性、往復開合耐久性優異之硬化體。藉此，本發明之防水性拉鏈鏈布可改善耐熱性、耐水解性及往復開合耐久性等之對防水性拉鏈鏈布所要求之特性、以及環境負荷及生產性之綜合平衡性。[Problems to be Solved by the Invention] The technique described in WO2014/010019 is worthy of evaluation in terms of using an aqueous medium as a dispersion medium in consideration of an environmental load. However, there is a problem that drying of the adhesive takes a long time. On the other hand, in Japanese Patent No. 5213523, a hot melt adhesive is used. The hot melt adhesive is a solventless adhesive that eliminates the problem of drying time. However, since the hot-melt adhesive uses a thermoplastic resin, there is a problem in heat resistance. For this, a reactive hot melt adhesive which imparts reactivity to a hot melt adhesive is known. The reactive hot melt adhesive is solvent-free and has improved heat resistance, so it is a promising adhesive. However, there is still room for improvement in terms of the properties required for the waterproof zipper chain cloth, the overall balance of environmental load and productivity, such as heat resistance, hydrolysis resistance, and reciprocating opening durability. The present invention has been made in view of the above circumstances, and one of the problems is to provide a combination of characteristics required for waterproof zipper chain cloth, such as heat resistance, hydrolysis resistance, and reciprocating opening durability, as well as environmental load and productivity. Waterproof zipper chain fabric with improved balance. Further, another object of the present invention is to provide a method for producing the above-described waterproof zipper chain cloth. [Means for Solving the Problem] In order to solve the above problems, the inventors of the present invention have made an effort to produce water repellency using a reactive hot-melt adhesive having a specific isocyanate-terminated urethane prepolymer as a main component. The zipper chain is effective. The present invention has been completed based on this finding. One aspect of the present invention is a zipper chain cloth comprising a base fabric and a water-stop film attached to at least one side of the base fabric, and the water-stopping film has a film formed of a polyurethane film. In a monolayer structure, the polyurethaneurea is selected from the group consisting of polycarbonate-based polyurethane ureas, polycarbonate-polyether polyurethanes, and polycarbonate-polyesters. One or more of a group consisting of urethane urea and polycarbonate-polyether-polyester polyurethane urea, and having a urethane group and a urea group, and an amine group When the molar fraction of the formate group and the urea group is set to 1, the molar fraction of the urea group is from 0.1 to 0.5. In one embodiment of the fastener stringer of the present invention, the polyurethane urethane constituting the water stop film is a polycarbonate-polyether-polyester polyurethane. Another aspect of the present invention is a zipper chain cloth comprising a base fabric and a water retaining film attached to at least one side of the base fabric, and the water stop film has a film comprising polyurethane containing urea The laminated structure of the surface layer and the adhesive layer of the polyurethane urethane adjacent to the surface layer, and the polyurethane urethane which constitutes the adhesive layer is selected from the group consisting of polycarbonate-based polyurethane urea and polycarbonate. a group of polyether-based polyurethane ureas, polycarbonate-polyester polyurethanes, and polycarbonate-polyether-polyester polyurethanes One or more of them have a urethane group and a ureido group, and the molar fraction of the urea group when the total mole fraction of the urethane group and the ureido group is 1 is 0.1 to 0.5. In an embodiment of the fastener chain cloth of the present invention, the polyurethane urethane constituting the surface layer contains a polycarbonate-based polyurethane urea. In one embodiment of the fastener stringer of the present invention, the polyurethane urethane constituting the adhesive layer is a polycarbonate-polyether-polyester polyurethane. Still another aspect of the present invention is a zipper comprising the zipper chain cloth of the present invention. Still another aspect of the present invention is a method of manufacturing a fastener chain cloth, comprising the steps of: applying a reactive hot melt adhesive to a base fabric; and subjecting the reactive hot melt adhesive to moisture hardening; Further, the reactive hot melt adhesive contains a prepolymer as a main component selected from a polycarbonate-based isocyanate-terminated urethane prepolymer and a polycarbonate-polyether system. Isocyanate-terminated urethane prepolymer, polycarbonate-polyester isocyanate-terminated urethane prepolymer, and polycarbonate-polyether-polyester isocyanate One or more of the group of the blocked urethane prepolymers, and having a urethane group in such a manner that the molar ratio of the isocyanate group to the urethane group is from 0.5 to 1.5 And isocyanate groups. According to still another aspect of the present invention, in a method of manufacturing a fastener tape, the method includes the steps of: bonding a surface layer of a film comprising a polyurethane film to a base fabric via a reactive hot melt adhesive; The reactive hot melt adhesive is subjected to moisture hardening; and the reactive hot melt adhesive contains a prepolymer as a main component selected from the group consisting of polycarbonate-based isocyanate-terminated urethanes. Prepolymer, polycarbonate-polyether isocyanate-terminated urethane prepolymer, polycarbonate-polyester isocyanate-terminated urethane prepolymer, and poly One or more of a group consisting of a carbonate-polyether-polyester isocyanate group-terminated urethane prepolymer, and the molar ratio of the isocyanate group to the urethane group becomes The form of 0.5 to 1.5 has a urethane group and an isocyanate group. According to still another aspect of the present invention, a method for manufacturing a fastener chain fabric, comprising the steps of: sequentially laminating a reactive hot-melt adhesive for a subsequent layer on a base fabric and a reactive hot-melt adhesive for a surface layer; The method comprises sequential lamination or simultaneous lamination; and the reactive hot-melt adhesive for the adhesive layer and the reactive hot-melt adhesive for the surface layer are both moisture-cured; and the reactive heat of the layer is subsequently used. The flux and the reactive hot melt adhesive for the surface layer each contain a prepolymer as a main component selected from the group consisting of polycarbonate-based isocyanate-terminated urethane prepolymers, and polycondensation. Carbonate-polyether isocyanate-terminated urethane prepolymer, polycarbonate-polyester isocyanate-terminated urethane prepolymer, and polycarbonate-polyether - one or more of the group consisting of polyester-based isocyanate-terminated urethane prepolymers, and having a molar ratio of isocyanate groups to urethane groups of 0.5 to 1.5 It has a urethane group and an isocyanate group. [Effects of the Invention] The reactive hot-melt adhesive used in the present invention is a solvent-free type and has a small environmental load, and is excellent in reactivity and handling workability, thereby contributing to improvement in productivity of water-repellent zipper chain cloth. . Moreover, the reactive hot-melt adhesive used in the present invention can form a cured body excellent in hydrolysis resistance, heat resistance, and reciprocating opening durability. As a result, the water-repellent zipper chain cloth of the present invention can improve the properties required for the waterproof zipper chain cloth, such as heat resistance, hydrolysis resistance, and reciprocating opening durability, as well as the overall balance of environmental load and productivity.
以下，一面參照圖式，一面對本發明之實施形態進行詳細敍述。 圖1表示本發明之第一實施形態之拉鏈之拉鏈鏈布之積層構造。拉鏈鏈布10a具備底布11、及貼附於底布11之至少一面之複層止水膜12a。複層止水膜12a具備包含聚胺基甲酸酯脲製之膜之表層13、及鄰接於表層13之聚胺基甲酸酯脲製之接著層14。接著層14係反應性熱熔接著劑之硬化體。即，拉鏈鏈布10a於表層13之底布11側具備接著層14，接著層14係於底布11與表層13之間將各者接著者。如此，拉鏈鏈布10a具有自圖1之紙面上側起依序積層表層13、接著層14、及底布11之積層構造。 圖2表示本發明之第二實施形態之拉鏈之拉鏈鏈布之積層構造。拉鏈鏈布10b具備底布11、及貼附於底布11之至少一面之聚胺基甲酸酯脲製之單層止水膜12b。單層止水膜12b係反應性熱熔接著劑之硬化體，與底布11直接接觸。即，拉鏈鏈布10b中之單層止水膜12b同時承擔第一實施形態中之表層13及接著層14之作用。如此，拉鏈鏈布10b具有自圖2之紙面上側起依序積層單層止水膜12b及底布11之積層構造。 (1.底布) 作為底布11之材質，可設為通常用於拉鏈鏈布之天然纖維或合成纖維，並無特別限制，例如可列舉聚醯胺纖維、聚酯纖維、丙烯酸系纖維等。藉由將該等合成纖維梭織而成或針織而成而可製作底布11。典型而言，可利用聚酯纖維梭織而成或針織而成。 (2.接著層及單層止水膜) 構成第一實施形態之接著層14及第二實施形態之單層止水膜12b之聚胺基甲酸酯脲係選自由聚碳酸酯系聚胺基甲酸酯脲、聚碳酸酯-聚醚系聚胺基甲酸酯脲、聚碳酸酯-聚酯系聚胺基甲酸酯脲、及聚碳酸酯-聚醚-聚酯系聚胺基甲酸酯脲所組成之群中之一種以上之聚胺基甲酸酯脲。就提高耐水解性、耐熱性及往復開合耐久性，且提高柔軟性之觀點而言，該聚胺基甲酸酯脲較佳為選自由聚碳酸酯-聚醚系聚胺基甲酸酯脲及聚碳酸酯-聚醚-聚酯系聚胺基甲酸酯脲所組成之群中之一種以上之聚胺基甲酸酯脲，就提高耐水解性、耐熱性、往復開合耐久性及柔軟性之綜合平衡性之觀點而言，該聚胺基甲酸酯脲更佳為聚碳酸酯-聚醚-聚酯系聚胺基甲酸酯脲。 構成第一實施形態之接著層14及第二實施形態之單層止水膜12b之聚胺基甲酸酯脲於聚合物單元彼此之鍵結部位具有胺基甲酸酯基(-NHCOO-)及脲基(-NHCONH-)。詳細條件於下文敍述，藉由使聚胺基甲酸酯脲以特定之比率具有胺基甲酸酯基與脲基，有助於獲得對拉鏈鏈布而言較佳之防水性、強度、耐候性、耐磨耗性、美觀及柔軟性之平衡。 所謂聚碳酸酯系聚胺基甲酸酯脲係指具有聚碳酸酯彼此藉由脲基而鍵結之部分及聚碳酸酯彼此藉由胺基甲酸酯基而鍵結之部分的聚合物。所謂聚碳酸酯-聚醚系聚胺基甲酸酯脲係指聚碳酸酯胺基甲酸酯與聚醚胺基甲酸酯之共聚物，典型而言為嵌段共聚物，且具有聚合物單元彼此藉由脲基而鍵結之部分及聚合物單元彼此藉由胺基甲酸酯基而鍵結之部分。所謂聚碳酸酯-聚酯系聚胺基甲酸酯脲係指聚碳酸酯胺基甲酸酯與聚酯胺基甲酸酯之共聚物，典型而言為嵌段共聚物，且具有聚合物單元彼此藉由脲基而鍵結之部分及聚合物單元彼此藉由胺基甲酸酯基而鍵結之部分。所謂聚碳酸酯-聚醚-聚酯系聚胺基甲酸酯脲係指聚碳酸酯胺基甲酸酯、聚醚胺基甲酸酯及聚酯胺基甲酸酯之共聚物，典型而言為嵌段共聚物，且具有聚合物單元彼此藉由脲基而鍵結之部分及聚合物單元彼此藉由胺基甲酸酯基而鍵結之部分。 如上所述，構成第一實施形態之接著層14及第二實施形態之單層止水膜12b之聚胺基甲酸酯脲具有胺基甲酸酯基(-NHCOO-)及脲基(-NHCONH-)時，聚胺基甲酸酯脲中之兩者之莫耳比會對接著層14及單層止水膜12b之特性或接著層14及單層止水膜12b硬化前之操作作業性、及反應性產生影響。若聚胺基甲酸酯脲中之脲基相對於胺基甲酸酯基之莫耳比變得過低，換言之，若硬化前之反應性熱熔接著劑中之異氰酸酯基(NCO基)相對於胺基甲酸酯基(-NHCOO-)之莫耳比變得過低，則黏度隨預聚物之分子量增大，操作作業性劣化。具體而言，材料補充需要較長時間，或變得難以塗佈。反之，若聚胺基甲酸酯脲中之脲基相對於胺基甲酸酯基之莫耳比變高，換言之，若硬化前之反應性熱熔接著劑中之異氰酸酯基(-NCO)相對於胺基甲酸酯基(-NHCOO-)之莫耳比變高，則可促進硬化反應，提高作為聚脲之特徵之耐水性、耐蝕性、耐磨耗性等功能。因此，將聚胺基甲酸酯脲中之胺基甲酸酯基及脲基之合計莫耳分率設為1時之脲基之莫耳分率較佳為0.1以上，更佳為0.2以上。 但是，若聚胺基甲酸酯脲中之脲基相對於胺基甲酸酯基之莫耳比變得過高，換言之，若硬化前之反應性熱熔接著劑中之異氰酸酯基(-NCO)相對於胺基甲酸酯基(-NHCOO-)之莫耳比變得過高，則容易於硬化時發泡量變多而有損美觀，或有損所獲得之聚胺基甲酸酯脲之柔軟性。因此，將聚胺基甲酸酯脲中之胺基甲酸酯基及脲基之合計莫耳分率設為1時之脲基之莫耳分率較佳為0.5以下，更佳為0.4以下。 聚胺基甲酸酯脲中之脲基之莫耳分率可藉由使用NMR測定裝置獲得
13C-NMR圖譜，並對其進行解析而測定。具體而言，準備將止水膜或接著層切下50～100 mg(亦有其以下之情況)者作為試樣，設置於NMR測定裝置進行測定。測定條件設為如下。 測定核：13 C 共振頻率：500 MHz 累計次數：252次 測定溫度：25℃ 測定法：DDMAS法 ＊上述累計次數：可判斷波峰之最小值 (3.表層) 於第一實施形態中，構成表層13之聚胺基甲酸酯脲可採用能夠構成上述接著層14之聚胺基甲酸酯脲，亦可採用其他聚胺基甲酸酯脲。因此，構成表層13之聚胺基甲酸酯脲可與接著層14同樣地設為選自由聚碳酸酯-聚醚系聚胺基甲酸酯脲、聚碳酸酯-聚酯系聚胺基甲酸酯脲、及聚碳酸酯-聚醚-聚酯系聚胺基甲酸酯脲所組成之群中之一種以上之聚胺基甲酸酯脲。又，構成表層13之聚胺基甲酸酯脲可具有與構成接著層14之聚胺基甲酸酯脲相同之組成，亦可具有不同之組成。然而，關於表層13，亦可尤其重視機械強度及耐水解性而採用聚碳酸酯系聚胺基甲酸酯脲。所謂聚碳酸酯系聚胺基甲酸酯脲係指具有聚碳酸酯之末端彼此藉由脲基而鍵結之部分及聚碳酸酯之末端彼此藉由胺基甲酸酯基而鍵結之部分的聚合物。 (4.止水膜之厚度) 止水膜12a、12b之厚度若過薄則有損質地，因此較佳設為0.07 mm以上，更佳設為0.10 mm以上。另一方面，止水膜12a、12b之厚度若過厚，則拉鏈開合時滑件滑動接觸而有損滑動性，因此較佳設為0.25 mm以下，更佳設為0.20 mm以下。 (5.拉鏈鏈布之製造方法) 例示性地闡述本發明之拉鏈鏈布之若干種製造方法。 於本發明之拉鏈鏈布之製造方法之一實施形態中，包括如下步驟：經由反應性熱熔接著劑，將包含聚胺基甲酸酯脲之膜之表層與底布貼合；及使反應性熱熔接著劑進行濕氣硬化。該方法係以接著層與表層之複層構成止水膜之情形時之製造方法。 於本發明之拉鏈鏈布之製造方法之另一實施形態中，包括如下步驟：以於底布上依序積層接著層用之反應性熱熔接著劑及表層用之反應性熱熔接著劑之方式進行依序積層塗敷或同時積層塗敷；及使接著層用之反應性熱熔接著劑及表層用之反應性熱熔接著劑均進行濕氣硬化。該方法係以接著層與表層之複層構成止水膜之情形時之製造方法。 於本發明之拉鏈鏈布之製造方法之進而另一實施形態中，包括如下步驟：將反應性熱熔接著劑塗敷於底布上；及使上述反應性熱熔接著劑進行濕氣硬化。 反應性熱熔接著劑可藉由輥式塗佈機、模嘴塗佈機、液滴塗佈、及噴霧等先前公知之塗敷方法而塗敷於底布。反應性熱熔接著劑一般係於加溫狀態下塗敷至底布，為了亦可對耐熱性較低之底布使用，又，為了防止接著劑之穩定性降低，較佳為加溫至130℃以下而進行塗敷，更佳為加溫至120℃以下而進行塗敷。又，就提高接著劑之流動性及作業性之觀點而言，較佳為加溫至100℃以上而進行塗敷，進而更佳為加溫至110℃以上而進行塗敷。 又，就使上述溫度下之塗敷容易化之觀點而言，反應性熱熔接著劑之熔融黏度較佳為5 Pa・s/120℃～50 Pa・s/120℃，進而更佳為7 Pa・s/120℃～30 Pa・s/120℃。反應性熱熔接著劑之熔融黏度可於以下之條件下進行測定。 裝置：錐板黏度計(ICI製造) 20P CONE 溫度條件：120℃ 又，反應性熱熔接著劑之熔解溫度較佳為40℃～100℃，更佳為50～90℃。反應性熱熔接著劑之熔解溫度係指藉由依據JIS K7121：2012之DSC(Differential Scanning Calorimeter，示差掃描熱量計)測定而測得之值。 於上述任一實施形態中，反應性熱熔接著劑均較佳為含有如下預聚物作為主成分，該預聚物係選自由聚碳酸酯系之異氰酸酯基封端之胺基甲酸酯預聚物、聚碳酸酯-聚醚系之異氰酸酯基封端之胺基甲酸酯預聚物、聚碳酸酯-聚酯系之異氰酸酯基封端之胺基甲酸酯預聚物、及聚碳酸酯-聚醚-聚酯系之異氰酸酯基封端之胺基甲酸酯預聚物所組成之群中之一種以上者，且以異氰酸酯基相對於胺基甲酸酯基之莫耳比成為0.5～1.5之方式具有胺基甲酸酯基及異氰酸酯基。 此係基於以下之原因。考慮如下情況：使A mol之羥基與B mol之異氰酸酯基進行反應而獲得異氰酸酯基封端之胺基甲酸酯預聚物，使之濕氣硬化而獲得聚胺基甲酸酯脲。若B＞A，則藉由羥基與異氰酸酯基之反應而生成A mol之胺基甲酸酯基，殘留(B－A) mol之異氰酸酯基。異氰酸酯基與空氣中之水分進行反應而生成胺基甲酸，該胺基甲酸釋出二氧化碳而成為胺，該胺與其他異氰酸酯基進行反應而生成脲基。即，藉由以下之反應，由兩個異氰酸酯基生成一個脲基，因此生成之脲基成為(B－A)/2 mol。 R-NCO＋H
2O→R-NHCOOH→R-NH
2＋CO
2(R為有機基) R-NH
2＋R-NCO→RNHCONHR 因此，若生成胺基甲酸酯預聚物之前之異氰酸酯基相對於羥基之莫耳比不足夠高，則脲基之生成量亦不會變多。若異氰酸酯基相對於羥基之莫耳比未達1.5(換言之，異氰酸酯基封端之胺基甲酸酯預聚物中之異氰酸酯基相對於胺基甲酸酯基之莫耳比未達0.5)，則胺基甲酸酯預聚物之分子量(黏度)變得非常大，並且不會生成充分之脲基。於此情形時，操作作業性劣化，又，由於異氰酸酯基較少，故而有損反應性(濕氣硬化)。因此，生成胺基甲酸酯預聚物之前之異氰酸酯基相對於羥基之莫耳比較佳為1.5以上，更佳為1.7以上。換言之，異氰酸酯基封端之胺基甲酸酯預聚物中之異氰酸酯基相對於胺基甲酸酯基之莫耳比較佳為0.5以上，更佳為0.7以上。另一方面，若生成胺基甲酸酯預聚物之前之異氰酸酯基相對於羥基之莫耳比超過2.5(換言之，異氰酸酯基封端之胺基甲酸酯預聚物中之異氰酸酯基相對於胺基甲酸酯基之莫耳比超過1.5)，則硬化時發泡變多而有損美觀，或硬化體變得過硬而有損柔軟性。因此，生成胺基甲酸酯預聚物之前之異氰酸酯基相對於羥基之莫耳比較佳為2.5以下，更佳為2.3以下。換言之，異氰酸酯基封端之胺基甲酸酯預聚物中之異氰酸酯基相對於胺基甲酸酯基之莫耳比較佳為1.5以下，更佳為1.3以下。 反應性熱熔接著劑之濕氣硬化係於室溫下進行。因此，可減少加熱能量。若濕氣硬化經時性(例如24小時左右)地進展，則生成脲鍵，進而亦生成縮二脲鍵、脲基甲酸酯鍵等，三維交聯結構發達(熟化)。藉此，可獲得於底布上貼附有或形成有止水膜而具備防水性能之拉鏈鏈布。但是，難以定量地分析三維交聯，又，由於為微量，故而於本發明中不作為討論對象。 (6.拉鏈之實施形態) 圖3～5表示具備本發明之拉鏈鏈布之防水性拉鏈20之一例。圖3係防水性拉鏈20整體之俯視圖，圖4係表示鏈齒排21於滑件22內嚙合之狀態之剖視圖，圖5係防水性拉鏈20之一部分之立體剖視圖。於各拉鏈鏈布10之底布11之一面上，沿其側緣，藉由縫紉機(machine)之雙重鏈縫之縫線24而分別縫合有於內部插通有芯繩23之線狀型之環扣狀拉鏈鏈齒排21。環扣狀拉鏈鏈齒排21可由聚醯胺、聚酯等合成樹脂之單絲形成。一對拉鏈鏈布10之止水膜12可經由接著劑而接著於物品之布料。作為其他方法，可藉由高頻將止水膜12與布料熔接，亦可進行縫合。於左右之鏈齒排之間插通滑件，藉由使滑件滑動，而可控制拉鏈之開合狀態。亦可對縫線24實施撥水加工。 藉由使止水膜12相對於底布11之側緣而向鏈齒排之嚙合中心線A側伸出，左右之止水膜12彼此容易密接，防水性提高。若使止水膜12之側緣以略微超過鏈齒排之嚙合中心線A之方式伸出，則左右之鏈齒排嚙合時，左右之止水膜12彼此密接，因此可獲得更高之防水性。 使用本實施形態之拉鏈20時，較佳為將貼附有止水膜12之側作為外表面，將拉鏈鏈齒排21側作為內表面而安裝於被安裝物。滑件22之拉片25可安裝於外表面側。又，可如圖3所示般設置上止擋26，雖未圖示，但亦可安裝下止擋、可分離式嵌插件等。 又，圖6及圖7表示本發明之另一實施形態之防水性拉鏈之局部模式圖。具體而言，圖6表示構成本實施形態之防水性拉鏈之拉鏈鏈帶27之一部分，圖7係假想性地表示於本實施形態之拉鏈中，左右之拉鏈鏈齒28於滑件29內部嚙合之狀態之剖視圖。 於本實施形態中，如圖6及圖7所示，拉鏈鏈齒28係以自正面及背面夾持形成於拉鏈鏈布30之端緣之芯部31之整體之方式射出成形。滑件29係以單點鏈線之假想線表示。拉鏈鏈布30係藉由於底布32之外表面貼附止水膜33而形成。而且，如圖7所示，於嚙合時，一側之拉鏈鏈齒28之前端(與另一側之拉鏈鏈布對向之端部)密接於另一側之拉鏈鏈布30，藉此發揮防水性。 實施例 (1.反應性熱熔接著劑之準備) (實施例1) 準備以聚碳酸酯-聚醚-聚酯系之異氰酸酯基封端之胺基甲酸酯預聚物作為主成分之下述規格之反應性熱熔接著劑。 DIC股份有限公司製造，產品編號：Tyforce NH-470 熔融黏度：15 Pa・s/120℃ (實施例2) 準備以聚碳酸酯系之異氰酸酯基封端之胺基甲酸酯預聚物作為主成分之下述規格之反應性熱熔接著劑。 DIC股份有限公司製造，產品編號：Tyforce NH-460 熔融黏度：20 Pa・s/120℃ (實施例3) 準備以聚碳酸酯-聚醚系之異氰酸酯基封端之胺基甲酸酯預聚物作為主成分之下述規格之反應性熱熔接著劑。 DIC股份有限公司製造，產品編號：Tyforce NH-480 熔融黏度：10 Pa・s/120℃ (實施例4) 準備以聚碳酸酯-聚酯系之異氰酸酯基封端之胺基甲酸酯預聚物作為主成分之下述規格之反應性熱熔接著劑。 DIC股份有限公司製造，產品編號：Tyforce NH-490 熔融黏度：15 Pa・s/120℃ (比較例1) 準備以聚醚-聚酯系之異氰酸酯基封端之胺基甲酸酯預聚物作為主成分之下述規格之反應性熱熔接著劑。 DIC股份有限公司製造，產品編號：Tyforce NH-410 熔融黏度：15 Pa・s/120℃ (比較例2) 準備以聚碳酸酯-聚醚-聚酯系之異氰酸酯基封端之胺基甲酸酯預聚物作為主成分之下述規格之反應性熱熔接著劑。 DIC股份有限公司製造，產品編號：Tyforce NH-430 熔融黏度：5 Pa・s/120℃ (比較例3) 準備以聚碳酸酯-聚醚-聚酯系之異氰酸酯基封端之胺基甲酸酯預聚物作為主成分之下述規格之反應性熱熔接著劑。 DIC股份有限公司製造，產品編號：Tyforce NH-450 熔融黏度：20 Pa・s/120℃ 反應性熱熔接著劑之熔融黏度係依照上述測定條件，使用錐板黏度計(ICI製造)20P CONE進行測定。 (2.防水性拉鏈之製造) 將上述所準備之各反應性熱熔接著劑進行加熱熔融，於10 m/min、150 μm厚度之條件下，使用塗敷裝置以塗敷寬度180 mm於長條脫模紙上連續地進行同時積層塗敷。繼而，將所獲得之脫模紙-接著劑層之積層體貼附於環扣拉鏈之由聚酯製絲而織造之拉鏈鏈布面，於溫度80℃下加熱60秒，其後於常溫下使其濕氣硬化24小時以上後，剝離脫模紙，製作具有包含由聚胺基甲酸酯脲之膜形成之單層構造之止水膜的防水性拉鏈鏈布之各樣品。藉由於防水性拉鏈鏈布之各樣品安裝鏈齒及滑件，而製造圖3～5所示之構造之防水性拉鏈。 (3.脲基之莫耳分率) 對於各止水膜，使用NMR測定裝置(日本電子股份有限公司製造之型號JNX-ECX500)，藉由上述測定條件獲得
13C-NMR圖譜，並對其進行解析，由此求出將胺基甲酸酯基及脲基之合計莫耳分率設為1時之脲基之莫耳分率。試樣之採取係藉由利用剪刀剪下而進行。於
13C-NMR圖譜中，150～154 ppm之範圍之波峰對應於脲基，155～160 ppm之範圍之波峰對應於胺基甲酸酯基，由面積比求出莫耳分率。將結果示於表1。 (4.耐水解性試驗) 將各防水性拉鏈放入70℃相對濕度95%之恆溫恆濕槽內，進行固定時間之暴露試驗。對於暴露試驗後之防水性拉鏈，依據JIS S 3015(2007)，以M級進行伴隨100次開合之往復開合耐久試驗，以目視調查止水膜之剝離狀態。根據以下基準進行評價。將結果示於表1。 ◎＝9週後，膜剝離未達1 mm
2○＝5週後，膜剝離未達1 mm
2×＝5週後，膜剝離為1 mm
2以上 (5.開合耐久性試驗) 對於防水性拉鏈，依據JIS S 3015(2007)，以M級進行伴隨500次開合之往復開合耐久試驗，以目視調查止水膜之剝離狀態。根據以下基準進行評價。將結果示於表1。 ○＝膜剝離未達1 mm
2×＝膜剝離為1 mm
2以上 (6.外觀(耐發泡性)) 藉由目視觀察止水膜之外觀，以目視調查發泡情況，根據以下基準進行評價。將結果示於表1。 ○＝無由發泡產生之外觀變化 ×＝有由發泡產生之外觀變化 (7.耐熱性試驗) 以目視調查將防水性拉鏈於120℃下加熱6小時後之止水膜之白濁情況，根據以下基準進行評價。將結果示於表1。 ○＝完全無白濁 △＝局部有白濁 ×＝整體有白濁 (8.柔軟性試驗) 基於100%模數評價方法對各止水膜之柔軟性進行評價。具體而言，使各試驗例之反應性熱熔接著劑於120℃下加熱熔融，使用加熱至120℃之刮刀塗佈機，於脫模紙上成形為厚度100 μm之膜，將該膜於23℃50%RH之條件下固化72小時後，依據JIS K-7311-1995測定100%模數，根據以下基準進行評價。將結果示於表1。 ○＝皮膜之100%模數未達4 MPa △＝皮膜之100%模數為4 MPa以上且未達6 MPa ×＝皮膜之100%模數為6 MPa以上 [表1]
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> 編號 </td><td> 脲基之莫耳分率 </td><td> 耐水解性 </td><td> 開合耐久性 </td><td> 外觀 (耐發泡性) </td><td> 耐熱性 </td><td> 柔軟性 </td></tr><tr><td> 實施例1 </td><td> 0.15 </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td></tr><tr><td> 實施例2 </td><td> 0.15 </td><td> ◎ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> △ </td></tr><tr><td> 實施例3 </td><td> 0.15 </td><td> ○ </td><td> ○ </td><td> ○ </td><td> △ </td><td> ○ </td></tr><tr><td> 實施例4 </td><td> 0.15 </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> △ </td></tr><tr><td> 比較例1 </td><td> 0.11 </td><td> × </td><td> ○ </td><td> ○ </td><td> × </td><td> 不進行評價 </td></tr><tr><td> 比較例2 </td><td> 0.55 </td><td> ○ </td><td> ○ </td><td> × </td><td> ○ </td><td> 不進行評價 </td></tr><tr><td> 比較例3 </td><td> 0.09 </td><td> ○ </td><td> × </td><td> ○ </td><td> ○ </td><td> 不進行評價 </td></tr></TBODY></TABLE>關於實施例1～4之止水膜為單層構造之防水性拉鏈，耐水解性、開合耐久性、外觀、耐熱性、柔軟性均無×之評價。尤其是將聚碳酸酯-聚醚-聚酯系之聚胺基甲酸酯脲用於止水膜之實施例1可平衡性良好地發揮各種特性。又，將聚碳酸酯系之聚胺基甲酸酯脲用於止水膜之實施例2之耐水解性尤其優異。由該結果可理解，於將止水膜設為積層構造之情形時，若採用聚碳酸酯系之聚胺基甲酸酯脲作為表層，採用聚碳酸酯-聚醚-聚酯系之聚胺基甲酸酯脲作為接著層，則可獲得各種特性優異之止水膜。 另一方面，比較例1由於不含聚碳酸酯成分，故而耐水解性及耐熱性不充分。比較例2雖然將聚碳酸酯-聚醚-聚酯系之聚胺基甲酸酯脲用於止水膜，但脲基之莫耳分率過大，因此發泡量變得過量，有損外觀。比較例3雖然將聚碳酸酯-聚醚-聚酯系之聚胺基甲酸酯脲用於止水膜，但脲基之莫耳分率過小，因此容易磨耗，開合耐久性不充分。
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Fig. 1 shows a laminated structure of a fastener stringer of a slide fastener according to a first embodiment of the present invention. The fastener chain cloth 10a includes a base fabric 11 and a multi-layer water-stopping film 12a attached to at least one surface of the base fabric 11. The multi-layer water-stopping film 12a is provided with the surface layer 13 which consists of the film of polyurethane urea, and the adhesive layer 14 of the polyurethane urea which is adjacent to the surface layer 13. Layer 14 is then a cured body of a reactive hot melt adhesive. In other words, the fastener chain fabric 10a is provided with the adhesive layer 14 on the side of the base fabric 11 of the surface layer 13, and the layer 14 is attached between the base fabric 11 and the surface layer 13, and each of them is attached. As described above, the fastener chain fabric 10a has a laminated structure in which the surface layer 13, the subsequent layer 14, and the base fabric 11 are sequentially laminated from the paper surface side of FIG. Fig. 2 is a view showing a laminated structure of a fastener stringer of a slide fastener according to a second embodiment of the present invention. The fastener chain fabric 10b is provided with the base fabric 11 and the single-layer water-stop film 12b of the polyurethane urea adhered on at least one surface of the base fabric 11. The single-layer water-stopping film 12b is a hardened body of a reactive hot-melt adhesive, and is in direct contact with the base fabric 11. That is, the single-layer water-stopping film 12b in the fastener chain fabric 10b simultaneously functions as the surface layer 13 and the adhesive layer 14 in the first embodiment. As described above, the fastener chain fabric 10b has a laminated structure in which the single-layer water-stopping film 12b and the base fabric 11 are sequentially laminated from the paper surface side of FIG. (1. Base fabric) The material of the base fabric 11 may be a natural fiber or a synthetic fiber which is generally used for a fastener chain cloth, and is not particularly limited, and examples thereof include polyamide fibers, polyester fibers, and acrylic fibers. . The base fabric 11 can be produced by woven or knitted the synthetic fibers. Typically, polyester fibers can be woven or knitted. (2. Adhesive layer and single-layer water-stopping film) The polyurethane urethane which comprises the adhesive layer 14 of the 1st Embodiment and the single-layer water-stop film 12b of 2nd Embodiment is selected from polycarbonate-type polyamine. Urethane urea, polycarbonate-polyether polyurethane urea, polycarbonate-polyester polyurethane, and polycarbonate-polyether-polyester polyamine More than one of the polyurethanes of the group consisting of formate urea. The polyurethane urethane is preferably selected from the group consisting of polycarbonate-polyether urethanes from the viewpoint of improving hydrolysis resistance, heat resistance, and durability of reciprocating opening and closing, and improving flexibility. One or more polyurethane ureas of a group consisting of urea and polycarbonate-polyether-polyester polyurethane urea improve hydrolysis resistance, heat resistance, and reciprocating durability From the viewpoint of the overall balance of softness, the polyurethane urea is more preferably a polycarbonate-polyether-polyester polyurethane. The polyurethane urethane constituting the adhesive layer 14b of the first embodiment and the single-layer water-stopping film 12b of the second embodiment has a urethane group (-NHCOO-) at a bonding site between the polymer units. And ureido (-NHCONH-). The detailed conditions are as follows. By having the urethane group and the urea group in a specific ratio, it is helpful to obtain water repellency, strength, and weather resistance for the zipper chain cloth. The balance of wear resistance, aesthetics and softness. The polycarbonate-based polyurethane urea refers to a polymer having a portion in which a polycarbonate is bonded to each other by a urea group and a portion in which a polycarbonate is bonded to each other by a urethane group. The term "polycarbonate-polyether-based polyurethane" refers to a copolymer of a polycarbonate urethane and a polyether urethane, typically a block copolymer, and having a polymer. A moiety in which the units are bonded to each other by a ureido group and a portion in which the polymer units are bonded to each other by a urethane group. The term "polycarbonate-polyester polyurethane" refers to a copolymer of a polycarbonate urethane and a polyester urethane, typically a block copolymer, and having a polymer. A moiety in which the units are bonded to each other by a ureido group and a portion in which the polymer units are bonded to each other by a urethane group. The term "polycarbonate-polyether-polyester polyurethane" refers to a copolymer of a polycarbonate urethane, a polyether urethane and a polyester urethane, typically It is a block copolymer and has a portion in which polymer units are bonded to each other by a urea group and a portion in which polymer units are bonded to each other by a urethane group. As described above, the polyurethane urethane constituting the adhesive layer 14 of the first embodiment and the single-layer water retaining film 12b of the second embodiment has a urethane group (-NHCOO-) and a urea group (- In the case of NHCONH-), the molar ratio of the two of the polyurethanes will operate on the properties of the adhesive layer 14 and the single-layer water-stopping film 12b or before the hardening of the layer 14 and the single-layer water-stopping film 12b. Sex, and reactivity have an impact. If the molar ratio of the urea group to the urethane group in the polyurethane urea is too low, in other words, if the isocyanate group (NCO group) in the reactive hot melt adhesive before curing is relatively When the molar ratio of the urethane group (-NHCOO-) is too low, the viscosity increases with the molecular weight of the prepolymer, and the workability deteriorates. In particular, material replenishment takes a long time or becomes difficult to coat. On the other hand, if the molar ratio of the urea group to the urethane group in the polyurethane urea becomes high, in other words, if the isocyanate group (-NCO) in the reactive hot melt adhesive before curing is relatively When the molar ratio of the urethane group (-NHCOO-) is increased, the hardening reaction can be promoted, and the functions such as water resistance, corrosion resistance, and abrasion resistance which are characteristics of the polyurea are improved. Therefore, the molar fraction of the urea group when the total molar fraction of the urethane group and the urea group in the polyurethaneurea is 1 is preferably 0.1 or more, more preferably 0.2 or more. . However, if the molar ratio of the urea group to the urethane group in the polyurethane urea becomes too high, in other words, if the isocyanate group (-NCO) in the reactive hot melt adhesive before curing When the molar ratio with respect to the urethane group (-NHCOO-) becomes too high, the amount of foaming tends to increase at the time of hardening, which is detrimental to the appearance, or detracts from the obtained polyurethane furreate. Softness. Therefore, the molar fraction of the urea group when the total mole fraction of the urethane group and the urea group in the polyurethaneurea is 1 is preferably 0.5 or less, more preferably 0.4 or less. . The molar fraction of the urea group in the polyurethane urea can be determined by obtaining a 13 C-NMR spectrum using an NMR measuring apparatus and analyzing it. Specifically, a sample in which a water-stop film or an adhesive layer is cut by 50 to 100 mg (including the following) is prepared as a sample, and is placed in an NMR measuring apparatus for measurement. The measurement conditions were set as follows. Measurement core: 13 C Resonance frequency: 500 MHz Cumulative number: 252 times Measurement temperature: 25 ° C Measurement method: DDMAS method * The above cumulative number: The minimum value of the peak can be judged (3. Surface layer) In the first embodiment, the surface layer is formed The polyurethane of 13 may be a polyurethane urethane which can constitute the above-mentioned adhesive layer 14, and other polyurethane urethanes may be used. Therefore, the polyurethane urethane constituting the surface layer 13 can be selected from the polycarbonate-polyether-based polyurethane urethane and the polycarbonate-polyester-based polyamine group similarly to the adhesive layer 14. One or more of the polyurethane ureas of the acid urea group and the polycarbonate-polyether-polyester polyurethane urea. Further, the polyurethane urethane constituting the surface layer 13 may have the same composition as that of the polyurethane urethane constituting the adhesive layer 14, and may have a different composition. However, regarding the surface layer 13, a polycarbonate-based polyurethane urea can also be used in particular in terms of mechanical strength and hydrolysis resistance. The term "polycarbonate-based polyurethane" refers to a portion having a terminal in which a terminal of a polycarbonate is bonded to each other by a urea group, and a portion in which a terminal of the polycarbonate is bonded to each other by a urethane group. Polymer. (4. Thickness of Water-Retaining Film) If the thickness of the water-stopping films 12a and 12b is too thin, the texture is impaired. Therefore, it is preferably 0.07 mm or more, and more preferably 0.10 mm or more. On the other hand, if the thickness of the water-stopping films 12a and 12b is too thick, the sliding member is in sliding contact with the zipper when the zipper is opened and closed, and the sliding property is impaired. Therefore, it is preferably 0.25 mm or less, and more preferably 0.20 mm or less. (5. Method of Manufacturing Zipper Chain Cloth) Several manufacturing methods of the fastener chain cloth of the present invention are exemplarily illustrated. In one embodiment of the method for producing a fastener chain cloth of the present invention, the method comprises the steps of: bonding a surface layer of a film comprising a polyurethane film to a base fabric via a reactive hot melt adhesive; and reacting the reaction; The hot melt adhesive is subjected to moisture hardening. This method is a manufacturing method in the case where a water-repellent film is formed of a composite layer of an adhesive layer and a surface layer. In another embodiment of the method for producing a fastener chain cloth of the present invention, the method comprises the steps of: sequentially laminating a reactive hot-melt adhesive for the subsequent layer on the base fabric and a reactive hot-melt adhesive for the surface layer. The method is carried out by sequentially laminating or simultaneously laminating; and the reactive hot-melt adhesive for the adhesive layer and the reactive hot-melt adhesive for the surface layer are both moisture-cured. This method is a manufacturing method in the case where a water-repellent film is formed of a composite layer of an adhesive layer and a surface layer. In still another embodiment of the method for producing a fastener tape according to the present invention, the method comprises the steps of: applying a reactive hot melt adhesive to the base fabric; and subjecting the reactive hot melt adhesive to moisture curing. The reactive hot melt adhesive can be applied to the base fabric by a conventionally known coating method such as a roll coater, a die coater, a droplet coating, and a spray. The reactive hot melt adhesive is generally applied to the base fabric under heating, and can also be used for a base fabric having a low heat resistance, and in order to prevent the stability of the adhesive from being lowered, it is preferably heated to 130 ° C. The coating is carried out in the following manner, and it is more preferred to apply the coating to a temperature of 120 ° C or lower. Moreover, from the viewpoint of improving the fluidity and workability of the adhesive, it is preferred to apply the film to a temperature of 100 ° C or higher, and more preferably to a temperature of 110 ° C or higher. Further, from the viewpoint of facilitating coating at the above temperature, the melt viscosity of the reactive hot-melt adhesive is preferably 5 Pa·s/120 ° C to 50 Pa·s/120 ° C, and more preferably 7 Pa・s/120°C to 30 Pa・s/120°C. The melt viscosity of the reactive hot melt adhesive can be measured under the following conditions. Apparatus: Cone-plate viscometer (manufactured by ICI) 20P CONE Temperature condition: 120 ° C Further, the melting temperature of the reactive hot-melt adhesive is preferably from 40 ° C to 100 ° C, more preferably from 50 to 90 ° C. The melting temperature of the reactive hot melt adhesive refers to a value measured by DSC (Differential Scanning Calorimeter) according to JIS K7121:2012. In any of the above embodiments, the reactive hot melt adhesive preferably comprises a prepolymer as a main component, and the prepolymer is selected from the group consisting of polycarbonate-based isocyanate-terminated urethane pre-preparations. Polymer, polycarbonate-polyether isocyanate-terminated urethane prepolymer, polycarbonate-polyester isocyanate-terminated urethane prepolymer, and polycarbonate One or more of the group consisting of an ester-polyether-polyester isocyanate-terminated urethane prepolymer, and the molar ratio of the isocyanate group to the urethane group is 0.5. The form of ~1.5 has a urethane group and an isocyanate group. This is for the following reasons. A case is considered in which an amino group of A mol is reacted with an isocyanate group of B mol to obtain an isocyanate group-terminated urethane prepolymer, which is moisture-hardened to obtain a polyurethane urethane. When B>A, an A mol urethane group is formed by reaction of a hydroxyl group with an isocyanate group, and (B-A) mol of an isocyanate group remains. The isocyanate group reacts with moisture in the air to form an aminocarboxylic acid which releases carbon dioxide to form an amine which reacts with other isocyanate groups to form a urea group. That is, one urea group is formed from two isocyanate groups by the following reaction, and thus the urea group formed becomes (B-A)/2 mol. R-NCO+H 2 O→R-NHCOOH→R-NH 2 +CO 2 (R is an organic group) R-NH 2 +R-NCO→RNHCONHR Therefore, the isocyanate group before the urethane prepolymer is formed relative to the hydroxyl group If the molar ratio is not high enough, the amount of urea groups formed will not increase. If the molar ratio of the isocyanate group to the hydroxyl group is less than 1.5 (in other words, the molar ratio of the isocyanate group to the urethane group in the isocyanate-terminated urethane prepolymer is less than 0.5), Then, the molecular weight (viscosity) of the urethane prepolymer becomes very large, and a sufficient urea group is not formed. In this case, the workability is deteriorated, and since the isocyanate group is small, the reactivity (moisture hardening) is impaired. Therefore, the isocyanate group before the formation of the urethane prepolymer is preferably 1.5 or more, more preferably 1.7 or more, based on the mole of the hydroxyl group. In other words, the isocyanate group in the isocyanate group-terminated urethane prepolymer is preferably 0.5 or more, more preferably 0.7 or more, based on the mole of the urethane group. On the other hand, if the molar ratio of the isocyanate group to the hydroxyl group before the formation of the urethane prepolymer exceeds 2.5 (in other words, the isocyanate group in the isocyanate-terminated urethane prepolymer is relative to the amine When the molar ratio of the urethane group exceeds 1.5), the foaming at the time of hardening increases and the appearance is impaired, or the hardened body becomes too hard to impair the flexibility. Therefore, the isocyanate group before the formation of the urethane prepolymer is preferably 2.5 or less, more preferably 2.3 or less, based on the mole of the hydroxyl group. In other words, the isocyanate group in the isocyanate group-terminated urethane prepolymer is preferably 1.5 or less, more preferably 1.3 or less, based on the mole of the urethane group. The moisture hardening of the reactive hot melt adhesive is carried out at room temperature. Therefore, the heating energy can be reduced. When the moisture hardening progresses over time (for example, about 24 hours), a urea bond is formed, and a biuret bond, an allophanate bond, etc. are formed, and a three-dimensional crosslinked structure is developed (cooked). Thereby, it is possible to obtain a fastener chain cloth having a water-repellent film attached to or formed with a water-repellent film on the base fabric. However, it is difficult to quantitatively analyze three-dimensional cross-linking, and since it is a trace amount, it is not considered as a subject in the present invention. (6. Embodiment of the zipper) Figs. 3 to 5 show an example of the waterproof slide fastener 20 including the fastener stringer of the present invention. 3 is a plan view showing the entire waterproof zipper 20, FIG. 4 is a cross-sectional view showing a state in which the element rows 21 are engaged in the slider 22, and FIG. 5 is a perspective cross-sectional view showing a part of the waterproof zipper 20. On one side of the base fabric 11 of each zipper chain cloth 10, along the side edges thereof, a thread-like type in which the core cord 23 is inserted is respectively sewn by a double-stitch stitch 24 of a sewing machine. A loop-shaped zipper element row 21. The loop-shaped fastener element row 21 can be formed of a monofilament of synthetic resin such as polyamide or polyester. The water retaining film 12 of the pair of zipper fabrics 10 can be attached to the fabric of the article via an adhesive. As another method, the water stop film 12 may be welded to the cloth by high frequency, or may be sewn. The sliding member is inserted between the left and right chain rows, and the opening and closing state of the zipper can be controlled by sliding the slider. The suture 24 can also be subjected to water repellent processing. By the water-repellent film 12 projecting toward the meshing center line A side of the element row with respect to the side edge of the base fabric 11, the left and right water-repellent films 12 are easily adhered to each other, and the water repellency is improved. If the side edges of the water-stopping film 12 are protruded slightly beyond the meshing center line A of the element rows, when the left and right element rows are engaged, the left and right water-stopping films 12 are in close contact with each other, thereby achieving higher waterproofing. Sex. When the zipper 20 of the present embodiment is used, it is preferable that the side on which the water-stopping film 12 is attached is an outer surface, and the side of the fastener element row 21 is attached as an inner surface to the object to be mounted. The pull tab 25 of the slider 22 can be mounted on the outer surface side. Further, as shown in FIG. 3, the upper stopper 26 may be provided. Although not shown, a lower stopper, a separable insert, or the like may be attached. 6 and 7 are partial schematic views showing a waterproof slide fastener according to another embodiment of the present invention. Specifically, Fig. 6 shows a part of the fastener stringer 27 constituting the waterproof slide fastener of the present embodiment, and Fig. 7 is imaginarily shown in the slide fastener of the embodiment, and the left and right fastener elements 28 are engaged inside the slider 29. A cross-sectional view of the state. In the present embodiment, as shown in FIGS. 6 and 7, the fastener element 28 is injection-molded so as to sandwich the entire core portion 31 formed on the edge of the fastener stringer 30 from the front and the back. The slider 29 is represented by an imaginary line of a single-dot chain line. The fastener chain fabric 30 is formed by attaching the water stopping film 33 to the outer surface of the base fabric 32. Further, as shown in Fig. 7, at the time of meshing, the front end of the fastener element 28 on one side (the end opposite to the fastener tape on the other side) is in close contact with the fastener tape 30 on the other side, thereby exerting Waterproof. EXAMPLES (1. Preparation of Reactive Hot Melt Adhesive) (Example 1) Preparation of a polycarbonate-polyether-polyester isocyanate group-terminated urethane prepolymer as a main component A reactive hot melt adhesive of the specification. Manufactured by DIC Co., Ltd., product number: Tyforce NH-470 Melt viscosity: 15 Pa・s/120 °C (Example 2) Prepared with a polycarbonate-based isocyanate-terminated urethane prepolymer as the main A reactive hot melt adhesive of the following specifications of the composition. Manufactured by DIC Co., Ltd., product number: Tyforce NH-460 Melt viscosity: 20 Pa·s/120 ° C (Example 3) Preparation of polycarbonate-polyether isocyanate-terminated urethane prepolymerization A reactive hot melt adhesive of the following specifications as a main component. Manufactured by DIC Co., Ltd., product number: Tyforce NH-480 Melt viscosity: 10 Pa・s/120 °C (Example 4) Preparation of polycarbonate-polyester isocyanate-terminated urethane prepolymerization A reactive hot melt adhesive of the following specifications as a main component. Manufactured by DIC Co., Ltd., product number: Tyforce NH-490 Melt viscosity: 15 Pa·s/120 ° C (Comparative Example 1) Preparation of polyether-polyester isocyanate-terminated urethane prepolymer A reactive hot melt adhesive having the following specifications as a main component. Manufactured by DIC Co., Ltd., product number: Tyforce NH-410 Melt viscosity: 15 Pa·s/120 ° C (Comparative Example 2) Preparation of amino acid terminated with polycarbonate-polyether-polyester isocyanate group The ester prepolymer is a reactive hot melt adhesive of the following specifications as a main component. Manufactured by DIC Co., Ltd., product number: Tyforce NH-430 Melt viscosity: 5 Pa·s/120 ° C (Comparative Example 3) Preparation of amino acid terminated with polycarbonate-polyether-polyester isocyanate group The ester prepolymer is a reactive hot melt adhesive of the following specifications as a main component. Manufactured by DIC Co., Ltd., product number: Tyforce NH-450 Melt viscosity: 20 Pa・s/120 °C The melt viscosity of the reactive hot melt adhesive is determined by the cone and plate viscometer (manufactured by ICI) 20P CONE according to the above measurement conditions. Determination. (2. Manufacture of water-repellent zipper) Each of the reactive hot-melt adhesives prepared above was heated and melted, and a coating apparatus was used to coat a width of 180 mm at a thickness of 10 m/min and 150 μm. Simultaneous lamination coating is continuously performed on the strip release paper. Then, the laminated body of the obtained release paper-adhesive layer was attached to the zipper chain surface of the loop zipper which was woven by the polyester yarn, and heated at a temperature of 80 ° C for 60 seconds, and then allowed to stand at room temperature. After the moisture was hardened for 24 hours or more, the release paper was peeled off, and each sample of the water-repellent zipper cloth having a water-stop film having a single-layer structure formed of a film of polyurethane urethane was produced. The waterproof zipper of the structure shown in FIGS. 3 to 5 was produced by attaching the sprocket and the slider to each sample of the waterproof zipper chain cloth. (3. Mohr fraction of urea group) For each water-stopping film, a 13 C-NMR spectrum was obtained by the above measurement conditions using an NMR measuring apparatus (model JNX-ECX500 manufactured by JEOL Ltd.). The analysis was carried out to determine the molar fraction of the urea group when the total molar fraction of the urethane group and the urea group was 1. The sample was taken by cutting with scissors. In the 13 C-NMR spectrum, the peak in the range of 150 to 154 ppm corresponds to the urea group, and the peak in the range of 155 to 160 ppm corresponds to the urethane group, and the molar fraction is determined from the area ratio. The results are shown in Table 1. (4. Hydrolysis resistance test) Each waterproof zipper was placed in a constant temperature and humidity chamber having a relative humidity of 95% at 70 ° C, and subjected to a fixed-time exposure test. For the waterproof zipper after the exposure test, according to JIS S 3015 (2007), the reciprocating opening and closing endurance test with 100 opening and closing was performed in the M class, and the peeling state of the water stopping film was visually investigated. Evaluation was performed based on the following criteria. The results are shown in Table 1. ◎=9 weeks later, the film peeling did not reach 1 mm 2 ○=5 weeks, after the film peeling did not reach 1 mm 2 ×=5 weeks, the film peeling was 1 mm 2 or more (5. Opening and closing durability test) The zipper was subjected to a reciprocating opening and closing endurance test with 500 opening and closing in accordance with JIS S 3015 (2007) to visually investigate the peeling state of the water retaining film. Evaluation was performed based on the following criteria. The results are shown in Table 1. ○ = film peeling was less than 1 mm 2 × = film peeling was 1 mm 2 or more (6. Appearance (foaming resistance)) The appearance of the water-stop film was visually observed, and the foaming was visually observed, and the following criteria were used. Evaluation. The results are shown in Table 1. ○=No change in appearance due to foaming ×=Change in appearance due to foaming (7. Heat resistance test) The turbidity of the water-stopping film after the water-repellent zipper was heated at 120 ° C for 6 hours was visually investigated. Evaluation was performed based on the following criteria. The results are shown in Table 1. ○ = no white turbidity △ = partial white turbidity × = overall turbidity (8. flexibility test) The softness of each water-stopping film was evaluated based on a 100% modulus evaluation method. Specifically, the reactive hot-melt adhesive of each test example was heated and melted at 120 ° C, and formed into a film having a thickness of 100 μm on a release paper using a knife coater heated to 120 ° C, and the film was applied to 23 After curing for 72 hours under the conditions of ° C 50% RH, 100% modulus was measured in accordance with JIS K-7311-1995, and evaluation was performed based on the following criteria. The results are shown in Table 1. ○=100% modulus of the film is less than 4 MPa △=100% modulus of the film is 4 MPa or more and less than 6 MPa ×=100% modulus of the film is 6 MPa or more [Table 1] <TABLE border="1"borderColor="#000000"width="85%"><TBODY><tr><td>number</td><td> molar fraction of urea base</td><td> hydrolysis resistance</td><td> Opening and closing durability</td><td> Appearance (foam resistance) </td><td> Heat resistance</td><td>Softness</td></tr><tr><td> Example 1 </td><td> 0.15 </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td></tr><tr><td> Example 2 </td><td> 0.15 </td><td> ◎ </td><td> ○ </ Td><td> ○ </td><td> ○ </td><td> △ </td></tr><tr><td> Example 3 </td><td> 0.15 </td ><td> ○ </td><td> ○ </td><td> ○ </td><td> △ </td><td> ○ </td></tr><tr><td > Example 4 </td><td> 0.15 </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td > △ </td></tr><tr><td> Comparative Example 1 </td><td> 0.11 </td><td> × </td><td> ○ </td><td> ○ </td><td> × </td><td> No evaluation</td></tr><tr><td> Comparative Example 2 </td><td> 0.55 </td><td > ○ </td><td> ○ </td><td> × </td><td> ○ </td><td> No evaluation</td></tr><tr><td> Comparative example 3 </td><td> 0.09 </td><td> ○ </td><td> × </td><td> ○ </td><td> ○ </td><td>Evaluation</td></tr></TBODY></TABLE> The water-repellent zippers of the single-layer structure of the water-stopping films of Examples 1 to 4 are resistant to hydrolysis, opening and closing durability, appearance, heat resistance, There was no evaluation of softness. In particular, in Example 1 in which a polycarbonate-polyether-polyester-based polyurethane urea was used for the water-stopping film, various characteristics were exhibited in a well-balanced manner. Further, the hydrolysis resistance of Example 2 in which a polycarbonate-based polyurethane urea was used for the water-stopping film was particularly excellent. From the results, it is understood that when a water-repellent film is used as a laminated structure, if a polycarbonate-based polyurethane urea is used as a surface layer, a polycarbonate-polyether-polyester polyamine is used. When the urethane urea is used as the adhesive layer, a water stop film excellent in various properties can be obtained. On the other hand, in Comparative Example 1, since the polycarbonate component was not contained, hydrolysis resistance and heat resistance were insufficient. In Comparative Example 2, a polycarbonate-polyether-polyester-based polyurethane urea was used for the water-stopping film, but the molar fraction of the urea group was too large, so that the amount of foaming was excessive and the appearance was impaired. In Comparative Example 3, the polycarbonate-polyether-polyester-based polyurethane urea was used for the water-stopping film, but the molar fraction of the urea group was too small, so that it was easily worn and the opening and closing durability was insufficient.