圖1中表示本發明之一實施形態之拉鏈之鏈布之積層結構。鏈布10具備底布11與貼附於底布11之至少一面之樹脂製膜12。樹脂製膜12具備：表皮層13，其係由含有金屬粉之聚胺基甲酸酯之膜所形成；及接著層14，其與表皮層13鄰接，且由交聯型聚胺基甲酸酯接著劑之硬化物所形成。即，鏈布10於表皮層13之底布11側具備接著層14，接著層14於底布11與表皮層13之間將各者接著。如此，如圖1所示，鏈布10具有於剖視圖中自紙面上側依序積層有表皮層13、接著層14、底布11之積層結構。 (1.底布) 作為底布11之材質，可設為通常用於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。可藉由將該等合成纖維梭織或針織而製作底布11。典型而言，可利用聚酯纖維進行梭織或針織。 (2.接著層) 接著層14係由交聯型聚胺基甲酸酯接著劑之硬化物所形成。交聯型聚胺基甲酸酯接著劑中，就提高環境性能之觀點而言，較佳為水性聚胺基甲酸酯接著劑。其中，就耐熱性及耐溶劑性等觀點而言，可適宜地使用二液硬化型水性聚胺基甲酸酯接著劑。此處，所謂「水性」意指使用水作為分散介質。交聯型聚胺基甲酸酯接著劑含有聚胺基甲酸酯、作為交聯劑(硬化劑)之異氰酸酯化合物、分散劑、及作為增黏劑之聚胺基甲酸酯樹脂等。 用作主劑之聚胺基甲酸酯典型而言為微粒子狀，例如可以聚胺基甲酸酯乳膠或聚胺基甲酸酯分散液之形態提供。聚胺基甲酸酯可使用業者已知之任意者，較佳為聚醚系聚胺基甲酸酯、聚酯系聚胺基甲酸酯、聚碳酸酯系聚胺基甲酸酯或聚己內酯系聚胺基甲酸酯並且具有親水性基者。其中，更佳為基於耐水解性、耐熱性、耐油性及耐磨耗性之理由而具有親水性基之聚碳酸酯系聚胺基甲酸酯。作為親水性基，有陽離子性、陰離子性或非離子性之親水性基，可單獨使用，亦可組合使用。作為陽離子性基，例如可列舉胺基。作為陰離子性之親水性基，例如可列舉羧基、膦酸基、磺酸基。作為非離子性之親水性基，例如可列舉聚環氧烷基(例如聚環氧乙烷基)、羥基。親水性基中，基於降低環境負荷之理由，較佳為羧基。就提高聚胺基甲酸酯之親水性之觀點而言，羧基等陰離子性之親水性基較理想為預先利用三乙胺、氨、2-胺基-2甲基丙醇等鹼進行中和。 用作交聯劑(硬化劑)之異氰酸酯化合物可含有脂肪族異氰酸酯、脂環族異氰酸酯、芳香族異氰酸酯或該等之組合。異氰酸酯例如可從二聚物、三聚物、異氰酸酯衍生物、異氰酸酯預聚物、封端異氰酸酯中加以選擇。芳香族異氰酸酯由於有黃變之傾向，故而脂肪族異氰酸酯、脂環族異氰酸酯或將該等組合而成者於耐變色性方面優異，使用期限(亦稱為使用壽命，於將硬化劑或觸媒等混合於接著劑中之後，至黏度或狀態不再耐受使用為止之時間)較長，因此較佳為該等。作為脂肪族異氰酸酯，例如可列舉：乙二異氰酸酯、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、十二亞甲基二異氰酸酯、2,2,4-三甲基己烷二異氰酸酯、離胺酸二異氰酸酯、2,6-二異氰酸基己酸甲酯、異佛酮二異氰酸酯、1,4-環己烷二異氰酸酯、4,4'-二環己基甲烷二異氰酸酯、雙(異氰酸基甲基)環己烷、環己二異氰酸酯、甲基環己二異氰酸酯。 作為適合於交聯型聚胺基甲酸酯接著劑之異氰酸酯化合物之形態並無特別限制，可適宜地使用溶解於準水系溶劑中而成者。所謂準水系溶劑係指可溶於水中之有機溶劑。準水系溶劑例如有二醇醚系(二乙二醇二甲醚、丙二醇單甲醚、甲氧基甲基丁醇等)、醇系(乙醇、異丙醇等)、萜烯系(d-檸檬烯)、吡咯啶酮系(N-甲基-2-吡咯啶酮)，該等中，就均勻分散之觀點而言，較佳為二醇醚系。 作為分散劑，為了降低環境負荷，較佳為使用水。即便於使用有機溶劑之情形時，為了降低環境負荷，亦較佳為不使用DMF(N,N-二甲基甲醯胺)，更佳為使用上述準水系溶劑。 增黏劑係為了調整黏度而添加之成分，較佳為以如下之程度含有，即，於下述表皮層(聚胺基甲酸酯分散液中之聚胺基甲酸酯)硬化之前、較佳為硬化反應之反應率為50%以下時，能夠於其上積層並塗佈交聯型聚胺基甲酸酯接著劑。「硬化之前」意指硬化反應完全結束而硬化反應不再進行之前。因此，於硬化反應部分地進行之情形時，亦視為「硬化之前」(以下亦相同)。又，硬化反應之反應率為50%以下係指交聯劑中所包含之異氰酸酯之殘存率為50%以上。異氰酸酯之殘存率可藉由IR(Infrared Radiation，紅外線輻射)測定而進行(以下亦相同)。 接著劑中之增黏劑之含量較佳為0～5質量%之範圍，更佳為0.5～4質量%之範圍。若超過5質量%，則會產生加工時之成膜性等之故障。作為增黏劑，可使用公知之任意增黏劑，就降低環境負荷之觀點而言，可適宜地使用水溶性增黏劑。作為水溶性增黏劑，例如可列舉：多糖類或明膠等天然高分子、聚氧乙烯或交聯聚(甲基)丙烯酸等合成高分子、蒙脫石或二氧化矽等無機礦物。又，增黏劑亦較佳為含有聚胺基甲酸酯樹脂。 交聯型聚胺基甲酸酯接著劑於交聯(硬化)時會產生溶劑之氣化及主劑與硬化劑之反應，最終獲得之接著層14主要係由在主劑與硬化劑之硬化反應中生成之交聯型聚胺基甲酸酯及增黏劑之固形物成分所構成。於接著層14中，若相對於主劑之硬化劑過少，則接著強度變得不足，硬化劑相對於主劑之質量比(固形物成分換算)較佳為設為10以上，更佳為設為12以上。但是，硬化劑過多會變硬而導致貼附後之鏈布之質感變差，因此硬化劑相對於主劑之質量比(固形物成分換算)較佳為設為25以下，更佳為設為23以下。 基於接著性之理由，接著層14之厚度較佳為設為110 μm以上，更佳為設為140 μm以上。另一方面，關於接著層14之厚度，若過厚，則於拉鏈之開合時滑件會滑動接觸而有損滑動性，因此較佳為設為180 μm以下，更佳為設為170 μm以下。 (3.表皮層) 表皮層13可以含有金屬粉之聚胺基甲酸酯之膜之形式形成。聚胺基甲酸酯可為水性聚胺基甲酸酯及有機溶劑系聚胺基甲酸酯之任一者。金屬粉可分散地存在於膜中。含有金屬粉之水性聚胺基甲酸酯之膜可藉由使於水中分散有聚胺基甲酸酯、典型而言微粒子狀之聚胺基甲酸酯及金屬粉而成之溶液乾燥並硬化而獲得。有機溶劑系聚胺基甲酸酯之膜係藉由使於有機溶劑中溶解有聚胺基甲酸酯、典型而言微粒子狀之聚胺基甲酸酯及金屬粉而成之溶液乾燥並硬化而獲得。又，針對水性聚胺基甲酸酯及有機溶劑系聚胺基甲酸酯之任一者，均可向於水中分散有聚胺基甲酸酯或於有機溶劑中溶解有聚胺基甲酸酯而成之溶液中添加交聯劑(硬化劑)而進行硬化反應。藉由添加硬化劑，可提高膜之強度。交聯型聚胺基甲酸酯中，就與接著劑之親和性、耐熱性及耐溶劑性等觀點而言，可適宜地使用二液硬化型聚胺基甲酸酯之膜。又，針對水性聚胺基甲酸酯及有機溶劑系聚胺基甲酸酯之任一者，均較理想為以於硬化前、較佳為硬化反應之反應率為50%以下時能夠於其上塗佈並積層接著劑之方式含有增黏劑，以提高黏性從而製成糊狀之形態。 上述聚胺基甲酸酯可使用業者已知之任意者，例如有聚醚系聚胺基甲酸酯、聚酯系聚胺基甲酸酯、聚碳酸酯系聚胺基甲酸酯、聚己內酯系聚胺基甲酸酯。該等中，基於膜本身之強度之理由，較佳為聚碳酸酯系聚胺基甲酸酯。 作為金屬粉，並無限定，可列舉鋁粉、鋅粉、金粉、銀粉、銅粉、鎳粉、鐵粉、鎂粉或包含該等金屬之合金粉末。該等中，基於耐久性、製品外觀之理由，較佳為鋁粉。金屬粉可使用一種，亦可將兩種以上組合而使用。就賦予金屬調之設計之觀點而言，形成表皮層(13)之聚胺基甲酸酯膜中之金屬粉之含量於表皮層中較佳為2.5質量%以上，更佳為3質量%以上，進而更佳為4質量%以上。另一方面，若形成表皮層之聚胺基甲酸酯膜中之金屬粉之含量變多，則與接著層之接著強度容易降低而耐磨性變差，進而，會產生於樹脂製膜之長邊方向側緣觀察到波紋形狀等不良情況。因此，就確保與接著層之接著強度之觀點、確保耐磨性之觀點、進而確保外觀品質之觀點而言，於表皮層中較佳為20質量%以下，更佳為15質量%以下，進而更佳為10質量%以下。 若以相對於樹脂製膜之表皮層(13)與接著層(14)之合計質量之含量表示，則金屬粉較佳為含有0.6～4.0質量%，更佳為含有1.0～3.0質量%。 基於製品外觀(亮度)之理由，金屬粉之平均粒徑較佳為5 μm以上，更佳為10 μm以上，進而更佳為15 μm以上。又，基於提高耐久磨耗性之理由或於樹脂製膜之長邊方向側緣防止波紋形狀之理由，金屬粉之平均粒徑30 μm以下，更佳為27 μm以下，進而更佳為25 μm以下。於本發明中，金屬粉之平均粒徑係指藉由雷射繞射・散射法求出粒徑之累積分佈時之體積基準之中值粒徑(D50)。 作為交聯劑(硬化劑)，可適宜地使用與接著層之說明中所述者相同之異氰酸酯化合物。 作為有機溶劑系聚胺基甲酸酯所使用之有機溶劑，並無特別限制，為了降低環境負荷，較佳為不使用DMF(N,N-二甲基甲醯胺)，可適宜地使用如上所述之準水系溶劑。就環境負荷之觀點而言，較理想為使用水，若將經由接著劑貼附於物品之布料時之接著強度或針對滑件之滑動之耐久性亦包含在內而綜合性地考慮，則最佳為使用準水系溶劑。 為了防止因與滑件之滑動而導致表皮層損傷，表皮層13較佳為含有聚矽氧化合物。為了有效地發揮針對滑動之耐久性，聚矽氧化合物於表皮層13中(固形物成分換算)較佳為占2質量%以上，更佳為占4質量%以上。但是，若聚矽氧化合物之含量過多，則有時表皮層反而變脆弱，因此聚矽氧化合物於表皮層13中較佳為占25質量%以下，更佳為占15質量%以下。就提高耐磨性(拉鏈往返開合耐久性)之方面而言，較理想為聚矽氧化合物之至少一部分係以與構成表皮層之聚胺基甲酸酯共聚合之形態存在。 基於提高耐磨耗性之理由，表皮層13之厚度較佳為設為20 μm以上，更佳為設為30 μm以上。另一方面，關於表皮層13之厚度，若過厚，則於拉鏈之開合時滑件會滑動接觸而有損滑動性，因此較佳為設為50 μm以下，更佳為設為40 μm以下。 基於獲得良好外觀之理由，表皮層13之外表面之算術平均高度Sa較佳為10 μm以下，更佳為6 μm以下，進而更佳為5 μm以下。基於獲得消光之外觀之理由，表皮層13之外表面之算術平均高度Sa較佳為2 μm以上，更佳為2.5 μm以上，進而更佳為4 μm以上。於本發明中，算術平均高度Sa係指利用非接觸式之三維表面性狀測量機並依據ISO 25178所測得之值。 基於獲得良好之外觀之理由，表皮層13之外表面之均方根高度Sq較佳為13 μm以下，更佳為7 μm以下，進而更佳為6 μm以下。基於獲得消光之外觀之理由，表皮層13之外表面之均方根高度Sq較佳為3 μm以上，更佳為4 μm以上，進而更佳為5 μm以上。於本發明中，均方根高度Sq係指利用非接觸式之三維表面性狀測量機並依據ISO 25178所測得之值。 (4.樹脂製膜之貼附) 對樹脂製膜12向底布11之貼附順序之一例進行說明。將含有成為樹脂製膜12之表皮層13之原料之金屬粉之聚胺基甲酸酯分散液塗佈於脫模膜之上。較理想為以金屬粉於表皮層中均勻地分散之方式將金屬粉與聚胺基甲酸酯分散液充分地混合後加以塗佈。表皮層13之外表面之表面性狀反映出脫模膜之表面性狀。藉由準備具有所需表面性狀之脫模膜，可控制表皮層之外表面之表面性狀。較佳為於該聚胺基甲酸酯分散液中之聚胺基甲酸酯硬化之前、較佳為硬化反應之反應率為50%以下時，於其上將交聯型聚胺基甲酸酯接著劑以積層之方式塗佈。塗佈交聯型聚胺基甲酸酯接著劑之時序亦可為聚胺基甲酸酯分散液中之聚胺基甲酸酯硬化之後，但藉由設為聚胺基甲酸酯分散液中之聚胺基甲酸酯硬化之前，可明顯提高含有金屬粉之表皮層與接著劑之間之接著強度。 繼而，於上述交聯型聚胺基甲酸酯接著劑硬化之前(較佳為硬化反應之反應率為50%以下時)，較理想為於上述聚胺基甲酸酯分散液中之聚胺基甲酸酯及上述交聯型聚胺基甲酸酯接著劑硬化之前(較佳為上述聚胺基甲酸酯分散液中之聚胺基甲酸酯及上述交聯型聚胺基甲酸酯接著劑兩者之硬化反應之反應率為50%以下時)，於其上貼附底布11。貼附時，較佳為一面進行加熱加壓，一面進行貼附。維持貼附有底布11之狀態而使聚胺基甲酸酯分散液及交聯型聚胺基甲酸酯接著劑硬化，藉此使聚胺基甲酸酯分散液變為構成表皮層13之聚胺基甲酸酯膜，接著劑成為硬化物。藉此，獲得將樹脂製膜12貼附於底布11之鏈布10。關於硬化，例如藉由在硬化溫度40～60℃且48小時以上之條件下進行硬化促進反應而使交聯接著劑硬化(使接著劑硬化之步驟)，藉此將底布11與樹脂製膜12牢固地接著。 根據本發明之拉鏈之一實施形態，接著層14與表皮層13之間之接著強度高於接著層14與底布11之間之接著強度。藉此，可消除因將金屬粉添加至表皮層中而引起之表皮層剝離之問題。 (5.拉鏈之實施形態) 於圖2～4中表示具備本發明之鏈布之防水拉鏈20之一例。圖2係防水拉鏈20整體之俯視圖，圖3係表示鏈齒排21於滑件22內嚙合之狀態之剖視圖，圖4係防水拉鏈20之一部分之立體剖視圖。於各鏈布10之底布11之一面上，沿著其側緣，利用縫紉機之雙重鏈縫之縫線24將內部插通有芯繩23之線狀型之線圈狀拉鏈鏈齒排21分別縫合。線圈狀拉鏈鏈齒排21可由聚醯胺、聚酯等合成樹脂之單絲所形成。一對鏈布10之樹脂製膜12可經由接著劑而接著於物品之布料。作為其他方法，可藉由高頻將樹脂製膜12與布料熔接，亦可進行縫合。使滑件插通左右之鏈齒排之間，變得能夠藉由使滑件滑動而控制拉鏈之開合狀態。亦可對縫線24實施撥水加工。 樹脂製膜12藉由相對於底布11之側緣向鏈齒排之嚙合中心線A側伸出，使左右之樹脂製膜12彼此變得容易密接，而防水性提高。若使樹脂製膜12之側緣以略微超過鏈齒排之嚙合中心線A之方式伸出，則於左右之鏈齒排嚙合時，左右之樹脂製膜12彼此密接，因此獲得更高之防水性。 於使用本實施形態之拉鏈20時，較佳為將貼附有樹脂製膜12之側設為外表面，將拉鏈鏈齒排21側設為內表面而安裝於被接著物。滑件22之拉片25可安裝於外表面側。又，可如圖2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5及圖6中表示本發明之另一實施形態之防水拉鏈之局部模式圖。具體而言，圖5表示構成本實施形態之防水拉鏈之拉鏈鏈帶27之一部分，圖6係假想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5及圖6所示，拉鏈鏈齒28係以將形成於鏈布30之端緣之芯部31之整體夾於正面背面間之方式射出成形。滑件29係以基於一點鏈線之假想線表示。鏈布30係藉由將樹脂製膜33貼附於底布32之外表面而形成。然後，如圖6所示，於嚙合時，將一側之拉鏈鏈齒28之前端(與另一側之鏈布對向之端部)密接於另一側之鏈布30，藉此發揮防水性。 [實施例] 為了進一步良好地理解本發明及其優勢，以下揭示實施例，但本發明並不限定於該等實施例。 ＜I.鋁粉末之含量所產生之影響之驗證＞ (1.樹脂製膜之製作) 於各例中使用之各材料如下所述。 (A)表皮層 聚碳酸酯系聚胺基甲酸酯：大日精化工業公司製造之商品名RESAMINE NES系列 (將聚碳酸酯系聚胺基甲酸酯溶解於有機溶劑中而成者；藉由向該溶液中添加交聯劑，而形成具有三維結構之表皮層) 鋁粉：大日精化工業公司製造之商品名Seika Seven(平均粒徑：30 μm) 交聯劑(異氰酸酯化合物)：大日精化工業公司製造之商品名RESAMINE X系列(二醇醚系之溶劑中之脂肪族異氰酸酯) (B)接著層 二液硬化型接著劑：大日精化工業公司製造之商品名RESAMINE UD系列 (將聚碳酸酯系聚胺基甲酸酯溶解於甲苯、甲基乙基酮及乙酸乙酯之混合溶劑中而成者；藉由向該溶液中添加交聯劑，而形成具有三維結構之接著性優異之接著劑) 交聯劑：大日精化工業公司製造之商品名RESAMINE D系列(二醇醚系之溶劑中之脂肪族異氰酸酯) 增黏劑：大日精化工業公司製造之商品名RESAMINE D系列(交聯聚(甲基)丙烯酸之合成高分子) 使用上述材料並根據以下之順序製作各鏈布。 將表皮層之材料以聚胺基甲酸酯：交聯劑＝100：3之質量比充分地混合而製備表皮層形成用漿料後，將該漿料塗佈於脫模膜(Lintec公司製造步驟紙)之上。此時，根據試驗編號而改變表皮層形成用漿料中之鋁粉末之含量，藉此改變表皮層中之鋁粉末之含量。 繼而，於硬化前(硬化反應之反應率為50%以下)之表皮層上塗佈將接著層之材料以二液硬化型接著劑：交聯劑：增黏劑＝100：10：1之質量比充分地混合而製作之接著層形成用漿料。於表皮層及接著層硬化之前(表皮層及接著層之硬化反應之反應率均為50%以下)，利用輥將由聚酯製之線織造而成之底布之鏈布進行加熱加壓而將其貼附於接著層上。其後，於硬化溫度40～60℃下進行48小時以上之硬化反應。如此，製作貼附有樹脂製膜之鏈布。 (2.鋁粉末之含量) 針對藉由上述順序而獲得之鏈布，利用島津製作所製造之ICP-OES(電感耦合電漿發射光譜儀分析裝置)並使用內部標準法測定表皮層及樹脂製膜中之鋁粉末之含量。測定試樣係向鏈布中添加酸並利用微波進行分解而製作。表皮層中之鋁量係根據表皮層及接著層之厚度而求出。具體而言，於樹脂製膜中之鋁粉末之含量為X質量%且表皮層及接著層之厚度分別為A μm及B μm之情形時，根據XA/(A＋B)之計算式計算表皮層中之鋁粉末之含量。將結果示於表1。再者，於本實施例中，表皮層與接著層之樹脂成分之密度實質上相同，兩者之被覆面積亦實質上相同，因此設為上述計算式，但於密度及被覆區域不同之情形時，需將該等考慮在內而計算表皮層中之鋁量。 (3.剝離試驗) 於將藉由上述順序而獲得之鏈布之樹脂製膜側經由熱熔接著劑貼附於聚酯製之織物布料後，使用Instron拉伸試驗機將鏈布自布料剝離。剝離試驗設為於拉伸速度50 mm/min之條件下進行180°剝離(JIS-K-6854-3)。除接著強度以外，亦確認剝離界面為接著層與底布之間或接著層與表皮層之間之何者。 於接著強度超過15 N/cm之情形時評價為○，於15 N/cm以下之情形時評價為×。 於剝離界面為接著層與底布之間之情形時評價為○，於剝離界面為接著層與表皮層之間之情形時評價為×。 將結果示於表1。 (4.往返開合耐久試驗) 使用藉由上述順序而獲得之鏈布組裝如圖2所示之防水性拉鏈，將滑件之滑動設為1000次進行往返開合耐久試驗，目視確認表皮層之外觀是否存在異常(表皮層之破損)。滑件滑動1次之滑件之移動距離設為50 mm。關於耐磨性之評價，於試驗後藉由目視明確地可見異常之情形時設為×，於幾乎不存在異常但部分可見能夠評價為異常之部位之情形時設為△，於完全未見到異常之情形時設為○，其試驗結果如表1所示。 (5.表面外觀) 根據藉由上述順序而獲得之樹脂製膜之長邊方向側緣之形狀對「外觀(形狀)」進行評價，針對鏈布之表皮層，根據色差之值對「外觀(顏色)」進行評價，根據光澤測定器之觸發值對「亮度」進行評價。 「外觀(形狀)」係藉由目視並基於以下之基準進行評價。 ○：於樹脂製膜之長邊方向側緣幾乎未見到波紋形狀。 △：於樹脂製膜之長邊方向側緣局部可見波紋形狀。 ×：於樹脂製膜之長邊方向側緣可見大量波紋形狀。 「外觀(顏色)」之評價基準如下所述。可使用一般之分光測色計，但此處使用柯尼卡美能達製造之CM-3700d。 ○：ΔE(CMC)＝5.0以內之情形 △：ΔE(CMC)＝超過5.0且為6.0以內之情形 ×：ΔE(CMC)＝超過6.0之情形 「亮度」之評價基準如下所述。可使用一般之光澤測定器，但此處使用柯尼卡美能達製造之CM-M6。 ○：觸發值＝9.0以上 △：觸發值＝7.0以上且未達9.0 ×：觸發值＝未達7.0 將結果示於表1。 [表1]
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> 表面外觀 </td><td> 剝離試驗 </td><td> 往返開合耐久試驗 </td><td> </td></tr><tr><td> 試驗編號 </td><td> 表皮層中之鋁粉含量 (質量%) </td><td> 樹脂製膜中之鋁粉含量 (質量%) </td><td> 外觀 (形狀) </td><td> 外觀 (顏色) </td><td> 亮度 </td><td> 接著強度 </td><td> 剝離界面 </td><td> 耐磨性 </td><td> 備註 </td></tr><tr><td> 1 </td><td> 0.0% </td><td> 0.0% </td><td> ○ </td><td> × </td><td> × </td><td> ○ </td><td> ○ </td><td> ○ </td><td> 比較例 </td></tr><tr><td> 2 </td><td> 2.0% </td><td> 0.4% </td><td> ○ </td><td> △ </td><td> △ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> 比較例 </td></tr><tr><td> 3 </td><td> 2.9% </td><td> 0.6% </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> </td></tr><tr><td> 4 </td><td> 4.9% </td><td> 1.0% </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> </td></tr><tr><td> 5 </td><td> 9.8% </td><td> 2.0% </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> </td></tr><tr><td> 6 </td><td> 14.7% </td><td> 3.0% </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> </td></tr><tr><td> 7 </td><td> 19.6% </td><td> 4.0% </td><td> × </td><td> ○ </td><td> ○ </td><td> ○ </td><td> × </td><td> ○ </td><td> </td></tr><tr><td> 8 </td><td> 21.6% </td><td> 4.4% </td><td> × </td><td> ○ </td><td> ○ </td><td> × </td><td> × </td><td> △ </td><td> 比較例 </td></tr></TBODY></TABLE>＜II.鋁粉末之平均粒徑所產生之影響之驗證＞ 將表皮層中之鋁粉末之平均粒徑改為表2所記載之條件，此外，藉由與試驗編號4相同之順序製作拉鏈。針對所獲得之拉鏈，進行與上述相同之剝離試驗及往返開合耐久試驗。又，藉由與上述相同之方式進行表面外觀之評價。將結果示於表2。 [表2]
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> 剝離試驗 </td><td> 往返開合耐久試驗 </td><td> 表面外觀 </td></tr><tr><td> 試驗編號 </td><td> 鋁粉平均粒徑 (μm) </td><td> 接著強度 </td><td> 剝離界面 </td><td> 耐磨性 </td><td> 外觀 (形狀) </td><td> 外觀 (顏色) </td><td> 亮度 </td></tr><tr><td> 4 </td><td> 15 </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td></tr><tr><td> 9 </td><td> 1 </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> × </td><td> × </td></tr><tr><td> 10 </td><td> 2 </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> △ </td><td> △ </td></tr><tr><td> 11 </td><td> 5 </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td></tr><tr><td> 12 </td><td> 30 </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td></tr><tr><td> 13 </td><td> 50 </td><td> ○ </td><td> ○ </td><td> △ </td><td> ○ </td><td> ○ </td><td> ○ </td></tr><tr><td> 14 </td><td> 80 </td><td> △ </td><td> △ </td><td> △ </td><td> △ </td><td> △ </td><td> △ </td></tr></TBODY></TABLE>＜III.表皮層之表面性狀所產生之影響之驗證＞ 使脫模膜之表面性狀之凹凸花紋、深度進行各種變化，藉此將表皮層之外表面之表面性狀改為表3及表4所記載之條件，此外，藉由與試驗編號4相同之順序製作拉鏈。針對所獲得之拉鏈，使用Canon公司製造之非接觸式之三維表面性狀測量機並依據ISO 25178測定表皮層之外表面之算術平均高度Sa或均方根高度Sq。又，藉由與上述相同之方式進行表面外觀之評價。將結果示於表3及表4。 [表3]
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> 表面性狀 </td><td> 表面外觀 </td></tr><tr><td> 試驗編號 </td><td> Sa(μm) </td><td> 外觀 (顏色) </td><td> 亮度 </td></tr><tr><td> 4 </td><td> 4.2 </td><td> ○ </td><td> ○ </td></tr><tr><td> 15 </td><td> 2 </td><td> ○ </td><td> △ </td></tr><tr><td> 16 </td><td> 2.5 </td><td> ○ </td><td> ○ </td></tr><tr><td> 17 </td><td> 5 </td><td> ○ </td><td> ○ </td></tr><tr><td> 18 </td><td> 10 </td><td> △ </td><td> ○ </td></tr></TBODY></TABLE>[表4]
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> 表面性狀 </td><td> 表面外觀 </td></tr><tr><td> 試驗編號 </td><td> Sq(μm) </td><td> 外觀 (顏色) </td><td> 亮度 </td></tr><tr><td> 4 </td><td> 5.3 </td><td> ○ </td><td> ○ </td></tr><tr><td> 19 </td><td> 3 </td><td> ○ </td><td> △ </td></tr><tr><td> 20 </td><td> 5 </td><td> ○ </td><td> ○ </td></tr><tr><td> 21 </td><td> 7 </td><td> ○ </td><td> ○ </td></tr><tr><td> 22 </td><td> 13 </td><td> △ </td><td> ○ </td></tr></TBODY></TABLE>＜IV.接著劑之種類所產生之影響之驗證＞ 作為接著劑，改為市售之熱熔型之接著劑後製作接著層形成用漿料，此外，藉由與試驗編號4相同之順序製作拉鏈。針對所獲得之拉鏈，進行與上述相同之剝離試驗及往返開合耐久試驗。又，實施120℃×30秒之熱壓下之耐熱試驗。關於評價，於樹脂製膜未自與鏈布之貼附位置偏移時設為○，於樹脂製膜自與鏈布之貼附位置偏移時設為×。將結果示於表5。 [表5]
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> 剝離試驗 </td><td> 往返開合耐久試驗 </td><td> 耐熱試驗 </td></tr><tr><td> 試驗編號 </td><td> 接著劑 </td><td> 接著強度 </td><td> 剝離界面 </td><td> 耐磨性 </td><td> 耐熱性 </td></tr><tr><td> 4 </td><td> 二液硬化型 </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td></tr><tr><td> 23 </td><td> 熱熔型 </td><td> ○ </td><td> ○ </td><td> × </td><td> × </td></tr></TBODY></TABLE>Fig. 1 shows a laminated structure of a chain zipper of an embodiment of the present invention. The chain fabric 10 includes a base fabric 11 and a resin film 12 attached to at least one surface of the base fabric 11. The resin film 12 includes a skin layer 13 formed of a film of a metal powder-containing polyurethane, and a subsequent layer 14 adjacent to the skin layer 13 and composed of a crosslinked polyurethane. A cured product of an ester binder is formed. That is, the chain fabric 10 is provided with the adhesive layer 14 on the side of the base fabric 11 of the skin layer 13, and the layer 14 is followed by each of the base fabric 11 and the skin layer 13. Thus, as shown in FIG. 1, the chain fabric 10 has a laminated structure in which the skin layer 13, the subsequent layer 14, and the base fabric 11 are sequentially laminated from the paper surface side in a cross-sectional view. (1. Base fabric) The material of the base fabric 11 is not particularly limited as long as it is a natural fiber or a synthetic fiber which is usually used for a chain cloth, and examples thereof include polyamide fibers, polyester fibers, and acrylic fibers. The base fabric 11 can be produced by weaving or knitting the synthetic fibers. Typically, polyester fibers can be used for weaving or knitting. (2. Adhesive layer) Next, the layer 14 is formed of a cured product of a crosslinked polyurethane sealant. Among the crosslinked type polyurethane adhesives, an aqueous polyurethane adhesive is preferred from the viewpoint of improving environmental performance. Among them, a two-liquid-curing aqueous polyurethane adhesive can be suitably used from the viewpoints of heat resistance and solvent resistance. Here, "aqueous" means using water as a dispersion medium. The cross-linking type polyurethane adhesive contains a polyurethane, an isocyanate compound as a crosslinking agent (hardener), a dispersing agent, and a polyurethane resin as a tackifier. The polyurethane used as the main agent is typically in the form of microparticles, for example in the form of a polyurethane latex or a polyurethane dispersion. The polyurethane may be any one known to the manufacturer, preferably a polyether polyurethane, a polyester polyurethane, a polycarbonate polyurethane or a polyhexyl. The lactone is a polyurethane and has a hydrophilic base. Among them, a polycarbonate-based polyurethane having a hydrophilic group based on hydrolysis resistance, heat resistance, oil resistance, and abrasion resistance is more preferable. The hydrophilic group may be a cationic, anionic or nonionic hydrophilic group, and may be used singly or in combination. As a cationic group, an amine group is mentioned, for example. Examples of the anionic hydrophilic group include a carboxyl group, a phosphonic acid group, and a sulfonic acid group. Examples of the nonionic hydrophilic group include a polyalkylene oxide group (for example, a polyethylene oxide group) and a hydroxyl group. Among the hydrophilic groups, a carboxyl group is preferred because of the environmental load reduction. From the viewpoint of improving the hydrophilicity of the polyurethane, an anionic hydrophilic group such as a carboxyl group is preferably neutralized with a base such as triethylamine, ammonia or 2-amino-2-methylpropanol in advance. . The isocyanate compound used as a crosslinking agent (hardener) may contain an aliphatic isocyanate, an alicyclic isocyanate, an aromatic isocyanate or a combination thereof. The isocyanate can be selected, for example, from a dimer, a trimer, an isocyanate derivative, an isocyanate prepolymer, and a blocked isocyanate. Since the aromatic isocyanate tends to be yellowish, the aliphatic isocyanate or the alicyclic isocyanate or the combination thereof is excellent in discoloration resistance, and the service life (also referred to as the service life) is to use a hardener or a catalyst. It is preferred that the time until the viscosity or state is no longer tolerated after use in the adhesive is longer. Examples of the aliphatic isocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, and 2,2,4-trimethylhexane diisocyanate. Amino acid diisocyanate, methyl 2,6-diisocyanatohexanoate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, double (iso) Cyanate methyl)cyclohexane, cyclohexamethylene diisocyanate, methylcyclohexane diisocyanate. The form of the isocyanate compound which is suitable for the cross-linking type polyurethane adhesive is not particularly limited, and can be suitably used by dissolving in a quasi-aqueous solvent. The quasi-aqueous solvent refers to an organic solvent which is soluble in water. Examples of the quasi-aqueous solvent include glycol ethers (diethylene glycol dimethyl ether, propylene glycol monomethyl ether, methoxymethylbutanol, etc.), alcohols (ethanol, isopropanol, etc.), and terpene systems (d- Limonene) and pyrrolidone (N-methyl-2-pyrrolidone) are preferred in terms of uniform dispersion from the viewpoint of uniform dispersion. As the dispersing agent, water is preferably used in order to reduce the environmental load. In the case where the organic solvent is easily used, in order to reduce the environmental load, it is preferred to use no DMF (N,N-dimethylformamide), and it is more preferred to use the above quasi-aqueous solvent. The tackifier is a component added for adjusting the viscosity, and is preferably contained to the extent that it is hardened before the skin layer (polyurethane in the polyurethane dispersion) is hardened. When the reaction rate of the hardening reaction is preferably 50% or less, a crosslinked type polyurethane adhesive can be laminated thereon and coated. "Before hardening" means that the hardening reaction is completely over and the hardening reaction is not carried out before. Therefore, when the hardening reaction is partially carried out, it is also considered as "before hardening" (the same applies hereinafter). Further, the reaction rate of the curing reaction is 50% or less, and the residual ratio of the isocyanate contained in the crosslinking agent is 50% or more. The residual ratio of the isocyanate can be measured by IR (Infrared Radiation) (the same applies hereinafter). The content of the tackifier in the subsequent agent is preferably in the range of 0 to 5% by mass, more preferably in the range of 0.5 to 4% by mass. When it exceeds 5% by mass, a failure such as film formation property during processing may occur. As the tackifier, any known tackifier can be used, and from the viewpoint of reducing the environmental load, a water-soluble tackifier can be suitably used. Examples of the water-soluble tackifier include natural polymers such as polysaccharides and gelatin, synthetic polymers such as polyoxyethylene or cross-linked poly(methyl)acrylic acid, and inorganic minerals such as montmorillonite or cerium oxide. Further, the tackifier preferably also contains a polyurethane resin. When the crosslinked polyurethane sealant is crosslinked (hardened), it will cause vaporization of the solvent and reaction of the main agent with the hardener, and finally the adhesive layer 14 is mainly obtained by hardening the main agent and the hardener. The cross-linked polyurethane formed in the reaction and the solid component of the tackifier. In the adhesive layer 14, when the amount of the curing agent relative to the main agent is too small, the strength is insufficient, and the mass ratio of the curing agent to the main agent (in terms of solid content) is preferably 10 or more, more preferably It is 12 or more. However, if the amount of the hardener is too hard, the texture of the chain cloth after the adhesion is deteriorated. Therefore, the mass ratio of the curing agent to the main agent (in terms of solid content) is preferably 25 or less, and more preferably set to 23 or less. The thickness of the adhesive layer 14 is preferably 110 μm or more, and more preferably 140 μm or more, for the reason of adhesion. On the other hand, when the thickness of the adhesive layer 14 is too thick, the slider is in sliding contact with the slide fastener when the slide fastener is opened and closed, and the sliding property is impaired. Therefore, it is preferably 180 μm or less, and more preferably 170 μm. the following. (3. Skin layer) The skin layer 13 may be formed in the form of a film of a metal powder-containing polyurethane. The polyurethane may be any of an aqueous polyurethane and an organic solvent-based polyurethane. The metal powder is dispersed in the film. A film of an aqueous polyurethane containing a metal powder can be dried and hardened by a solution obtained by dispersing a polyurethane in a water, typically a microscopic polyurethane and a metal powder. And get. The film of the organic solvent-based polyurethane is dried and hardened by a solution obtained by dissolving a polyurethane in a organic solvent, typically a micro-sized polyurethane and a metal powder. And get. Further, for any of the aqueous polyurethane and the organic solvent-based polyurethane, the polyurethane may be dispersed in water or the polyaminocarboxylic acid may be dissolved in an organic solvent. A hardening reaction is carried out by adding a crosslinking agent (hardener) to the ester solution. The strength of the film can be increased by adding a hardener. Among the crosslinked polyurethanes, a two-liquid-curable polyurethane film can be suitably used from the viewpoints of affinity with an adhesive, heat resistance, solvent resistance, and the like. Further, it is preferable that any of the aqueous polyurethane and the organic solvent-based polyurethane can be used in the case where the reaction rate before curing, preferably the curing reaction, is 50% or less. The adhesive is applied by coating and laminating the adhesive to improve the viscosity to form a paste. The above-mentioned polyurethane may be any one known to the manufacturer, and examples thereof include a polyether polyurethane, a polyester polyurethane, a polycarbonate polyurethane, and a polyhexyl ester. Lactone is a polyurethane. Among these, a polycarbonate-based polyurethane is preferred because of the strength of the film itself. The metal powder is not limited, and examples thereof include aluminum powder, zinc powder, gold powder, silver powder, copper powder, nickel powder, iron powder, magnesium powder, and alloy powder containing the metals. Among these, aluminum powder is preferred because of durability and appearance of the product. The metal powder may be used alone or in combination of two or more. The content of the metal powder in the polyurethane film forming the skin layer (13) is preferably 2.5% by mass or more, and more preferably 3% by mass or more in the skin layer, from the viewpoint of imparting a metal tone design. Further, it is more preferably 4% by mass or more. On the other hand, when the content of the metal powder in the polyurethane film forming the skin layer is increased, the adhesion strength to the adhesive layer is likely to be lowered, and the abrasion resistance is deteriorated, and further, the resin is formed into a film. A problem such as a corrugated shape was observed on the side edges of the long sides. Therefore, from the viewpoint of ensuring the adhesion strength to the adhesive layer, the viewpoint of ensuring abrasion resistance, and further ensuring the appearance quality, the skin layer is preferably 20% by mass or less, more preferably 15% by mass or less, and further More preferably, it is 10% by mass or less. The metal powder is preferably contained in an amount of from 0.6 to 4.0% by mass, more preferably from 1.0 to 3.0% by mass, based on the total mass of the skin layer (13) and the back layer (14) of the resin film. The average particle diameter of the metal powder is preferably 5 μm or more, more preferably 10 μm or more, and still more preferably 15 μm or more, for the reason of the appearance (brightness) of the product. Moreover, the reason why the metal powder has an average particle diameter of 30 μm or less, more preferably 27 μm or less, and even more preferably 25 μm or less, for the reason of improving the durability of the abrasion resistance or preventing the corrugated shape from the side edges in the longitudinal direction of the resin film. . In the present invention, the average particle diameter of the metal powder refers to a volume-based median diameter (D50) when a cumulative distribution of particle diameters is obtained by a laser diffraction/scattering method. As the crosslinking agent (hardener), the same isocyanate compound as described in the description of the subsequent layer can be suitably used. The organic solvent used in the organic solvent-based polyurethane is not particularly limited, and in order to reduce the environmental load, DMF (N,N-dimethylformamide) is preferably not used, and the above may be suitably used. The quasi-aqueous solvent. From the viewpoint of environmental load, it is preferable to use water, and if the adhesion strength to the cloth of the article via the adhesive or the durability against the sliding of the slider is also comprehensively considered, the most Good use of quasi-aqueous solvents. In order to prevent damage to the skin layer due to sliding with the slider, the skin layer 13 preferably contains a polysiloxane. In order to effectively exhibit the durability against sliding, the polyoxynitride is preferably contained in the skin layer 13 (in terms of solid content) in an amount of 2% by mass or more, more preferably 4% by mass or more. However, when the content of the polyoxyxene compound is too large, the skin layer may become weaker. Therefore, the polysiloxane compound preferably accounts for 25% by mass or less, and more preferably 15% by mass or less in the skin layer 13. In terms of improving wear resistance (zipper reciprocating durability), it is preferred that at least a part of the polyoxynitride is present in a form copolymerized with the polyurethane constituting the skin layer. The thickness of the skin layer 13 is preferably 20 μm or more, and more preferably 30 μm or more, for the reason of improving the abrasion resistance. On the other hand, when the thickness of the skin layer 13 is too thick, the slider is in sliding contact with the slider when the slide fastener is opened and closed, and the sliding property is impaired. Therefore, it is preferably 50 μm or less, and more preferably 40 μm. the following. The arithmetic mean height Sa of the outer surface of the skin layer 13 is preferably 10 μm or less, more preferably 6 μm or less, and still more preferably 5 μm or less, for the reason of obtaining a good appearance. The arithmetic mean height Sa of the outer surface of the skin layer 13 is preferably 2 μm or more, more preferably 2.5 μm or more, and still more preferably 4 μm or more, for the reason of obtaining the matte appearance. In the present invention, the arithmetic mean height Sa refers to a value measured by a non-contact three-dimensional surface property measuring machine in accordance with ISO 25178. The root mean square height Sq of the outer surface of the skin layer 13 is preferably 13 μm or less, more preferably 7 μm or less, and still more preferably 6 μm or less, for the reason of obtaining a good appearance. The root mean square height Sq of the outer surface of the skin layer 13 is preferably 3 μm or more, more preferably 4 μm or more, and still more preferably 5 μm or more, for the reason of obtaining the appearance of the matte layer. In the present invention, the root mean square height Sq refers to a value measured by a non-contact three-dimensional surface property measuring machine in accordance with ISO 25178. (4. Attachment of Resin Film Forming) An example of the order of attaching the resin film 12 to the base fabric 11 will be described. A polyurethane dispersion containing a metal powder which is a raw material of the skin layer 13 of the resin film 12 is applied onto the release film. It is preferable to sufficiently mix the metal powder and the polyurethane dispersion in such a manner that the metal powder is uniformly dispersed in the skin layer, and then apply it. The surface properties of the outer surface of the skin layer 13 reflect the surface properties of the release film. The surface properties of the outer surface of the skin layer can be controlled by preparing a release film having a desired surface property. Preferably, the crosslinked polyaminocarboxylic acid is used before the polyurethane in the polyurethane dispersion is cured, preferably after the reaction rate of the curing reaction is 50% or less. The ester adhesive is applied in a layered manner. The timing of applying the crosslinked polyurethane sealant may also be after the polyurethane in the polyurethane dispersion is cured, but by setting the polyurethane dispersion Before the polyurethane is hardened, the adhesion strength between the skin layer containing the metal powder and the adhesive can be remarkably improved. Then, before the crosslinking of the above-mentioned crosslinked polyurethane adhesive (preferably, the reaction rate of the curing reaction is 50% or less), it is preferable to use the polyamine in the above polyurethane dispersion. Before the urethane and the above-mentioned crosslinked polyurethane adhesive are hardened (preferably the polyurethane in the above polyurethane dispersion and the above-mentioned crosslinked polyaminocarboxylic acid) When the reaction rate of the hardening reaction of both of the ester adhesives is 50% or less, the base fabric 11 is attached thereto. At the time of attaching, it is preferable to apply heat and pressure while attaching. The polyurethane coating dispersion and the crosslinked polyurethane adhesive are cured by adhering the state in which the base fabric 11 is attached, whereby the polyurethane dispersion is formed into the skin layer 13 The polyurethane film, the adhesive becomes a cured product. Thereby, the chain fabric 10 which attached the resin film 12 to the base fabric 11 was obtained. In the case of hardening, for example, a curing agent is cured at a curing temperature of 40 to 60 ° C for 48 hours or more to harden the crosslinking agent (step of hardening the adhesive), thereby forming the base fabric 11 and the resin film. 12 firmly followed. According to one embodiment of the zipper of the present invention, the adhesion strength between the subsequent layer 14 and the skin layer 13 is higher than the adhesion strength between the subsequent layer 14 and the base fabric 11. Thereby, the problem of peeling of the skin layer due to the addition of the metal powder to the skin layer can be eliminated. (5. Embodiment of Zipper) An example of the waterproof slide fastener 20 provided with the chain fabric of the present invention is shown in Figs. 2 to 4 . 2 is a plan view showing the entire waterproof zipper 20, FIG. 3 is a cross-sectional view showing a state in which the element rows 21 are engaged in the slider 22, and FIG. 4 is a perspective cross-sectional view showing a portion of the waterproof zipper 20. On one side of the base fabric 11 of each of the chain fabrics 10, along the side edges thereof, the linear-shaped coil-shaped fastener element rows 21 through which the core cords 23 are inserted are respectively inserted by the double-seam stitches 24 of the sewing machine Stitching. The coil-shaped fastener element row 21 can be formed of a monofilament of synthetic resin such as polyamide or polyester. The resin film 12 of the pair of chain fabrics 10 can be attached to the cloth of the article via an adhesive. As another method, the resin film 12 can be welded to the cloth by high frequency, and the film can be sewn. When the slider is inserted between the left and right element rows, it becomes possible to control the opening and closing state of the zipper by sliding the slider. The suture 24 can also be subjected to water repellent processing. The resin film 12 is extended toward the meshing center line A side of the element row with respect to the side edge of the base fabric 11, and the resin film 12 of the left and right is easily adhered to each other, and the water repellency is improved. When the side edges of the resin 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 resin films 12 are in close contact with each other, thereby obtaining a higher waterproofing. Sex. When the zipper 20 of the present embodiment is used, it is preferable that the side on which the resin film 12 is attached is the outer surface, and the side of the fastener element row 21 is the inner surface, and it is attached to the object to be attached. The pull tab 25 of the slider 22 can be mounted on the outer surface side. Further, the upper stopper 26 may be provided as shown in Fig. 2. Although not shown, a lower stopper, a separable insert, or the like may be attached. Further, Fig. 5 and Fig. 6 are partial schematic views showing a waterproof slide fastener according to another embodiment of the present invention. Specifically, FIG. 5 shows a part of the fastener stringer 27 constituting the waterproof slide fastener of the present embodiment, and FIG. 6 is a view showing a state in which the left and right fastener elements 28 are engaged inside the slider 29 in the slide fastener of the embodiment. Cutaway view. In the present embodiment, as shown in FIGS. 5 and 6, the fastener element 28 is injection-molded so that the entire core portion 31 formed on the edge of the chain fabric 30 is sandwiched between the front and back surfaces. The slider 29 is represented by an imaginary line based on a point chain. The chain fabric 30 is formed by attaching the resin film 33 to the outer surface of the base fabric 32. Then, as shown in FIG. 6, at the time of meshing, the front end of the one side fastener element 28 (the end opposite to the chain cloth on the other side) is adhered to the chain cloth 30 on the other side, thereby waterproofing Sex. [Examples] In order to further understand the present invention and its advantages, the following examples are disclosed, but the present invention is not limited to the examples. <I. Verification of the influence of the content of the aluminum powder> (1. Production of resin film formation) Each material used in each example is as follows. (A) Skin layer polycarbonate-based polyurethane: RESAMINE NES series manufactured by Daisei Seiki Co., Ltd. (formed by dissolving polycarbonate-based polyurethane in organic solvent; A crosslinking agent is added to the solution to form a skin layer having a three-dimensional structure. Aluminum powder: Seika Seven (average particle diameter: 30 μm) manufactured by Daisei Seiki Co., Ltd. Crosslinking agent (isocyanate compound): large RESAMINE X series (aliphatic isocyanate in glycol ether solvent) manufactured by Nissei Seisakusho Co., Ltd. (B) Adhesive two-liquid hardening type adhesive: RESAMINE UD series manufactured by Daisei Seiki Co., Ltd. The polycarbonate-based polyurethane is dissolved in a mixed solvent of toluene, methyl ethyl ketone and ethyl acetate; by adding a crosslinking agent to the solution, a three-dimensional structure is formed. Excellent adhesive) Crosslinking agent: RESAMINE D series manufactured by Daisei Seiki Co., Ltd. (aliphatic isocyanate in glycol ether solvent) Adhesive: RESAMINE D series manufactured by Dairi Seiki Co., Ltd. ( Linked poly (meth) acrylate of synthetic polymer) material and is made by using the fabric of each strand of the following sequence. The material of the skin layer was sufficiently mixed in a mass ratio of polyurethane:crosslinker=100:3 to prepare a slurry for forming a skin layer, and then the slurry was applied to a release film (manufactured by Lintec Co., Ltd.). Step paper) above. At this time, the content of the aluminum powder in the slurry for forming a skin layer was changed according to the test number, thereby changing the content of the aluminum powder in the skin layer. Then, the material of the adhesive layer is applied to the skin layer before hardening (the reaction rate of the hardening reaction is 50% or less) as a two-liquid hardening type adhesive: crosslinking agent: tackifier=100:10:1. A slurry for forming an adhesive layer which is produced by sufficiently mixing. Before the skin layer and the adhesive layer are hardened (the reaction rate of the hardening reaction of the skin layer and the adhesive layer is 50% or less), the base fabric of the base fabric woven from the polyester thread is heated and pressurized by a roller. It is attached to the adhesive layer. Thereafter, the hardening reaction was carried out at a curing temperature of 40 to 60 ° C for 48 hours or more. In this manner, a chain cloth to which a resin film was attached was produced. (2. Content of aluminum powder) For the chain cloth obtained by the above procedure, the ICP-OES (Inductively Coupled Plasma Emission Spectrometer Analyzer) manufactured by Shimadzu Corporation was used and the internal standard method was used to measure the skin layer and the resin film. The content of aluminum powder. The measurement sample was prepared by adding an acid to the chain cloth and decomposing it by microwave. The amount of aluminum in the skin layer is determined from the thickness of the skin layer and the back layer. Specifically, when the content of the aluminum powder in the resin film is X% by mass and the thicknesses of the skin layer and the back layer are A μm and B μm, respectively, the skin layer is calculated according to the calculation formula of XA/(A+B). The content of aluminum powder. The results are shown in Table 1. Further, in the present embodiment, the density of the resin component of the skin layer and the adhesive layer is substantially the same, and the coverage areas of the two layers are substantially the same. Therefore, the calculation formula is used, but when the density and the coating area are different, The amount of aluminum in the skin layer needs to be taken into account. (3. Peeling test) After the resin film side of the chain fabric obtained by the above procedure was attached to the polyester fabric by a hot melt adhesive, the chain cloth was peeled off from the cloth using an Instron tensile tester. . The peeling test was carried out at 180° peeling (JIS-K-6854-3) under the conditions of a tensile speed of 50 mm/min. In addition to the strength, it was confirmed that the peeling interface was between the back layer and the base fabric or between the back layer and the skin layer. When the strength was more than 15 N/cm, the evaluation was ○, and when it was 15 N/cm or less, it was evaluated as ×. When the peeling interface was between the adhesive layer and the base fabric, it was evaluated as ○, and when the peeling interface was between the adhesive layer and the skin layer, it was evaluated as ×. The results are shown in Table 1. (4. Reciprocating test for the reciprocating opening and closing) The waterproof zipper shown in Fig. 2 was assembled using the chain cloth obtained by the above procedure, and the sliding of the sliding member was set to 1000 times for the reciprocating test, and the skin layer was visually confirmed. Whether there is an abnormality in appearance (damage of the skin layer). The moving distance of the slider in which the slider slides once is set to 50 mm. The evaluation of the abrasion resistance was set to × when the abnormality was clearly observed by visual observation after the test, and was set to Δ when there was almost no abnormality but a part where the abnormality was partially observed, and it was not seen at all. In the case of an abnormality, it is set to ○, and the test results are shown in Table 1. (5. Appearance) The "appearance (shape)" was evaluated based on the shape of the side edge in the longitudinal direction of the resin film obtained by the above procedure, and the appearance of the skin layer of the chain cloth was based on the value of the color difference ( The color was evaluated, and the "brightness" was evaluated based on the trigger value of the gloss meter. "Appearance (shape)" was evaluated by visual observation based on the following criteria. ○: A corrugated shape was hardly observed on the side edge in the longitudinal direction of the resin film. △: A corrugated shape was partially observed on the side edge in the longitudinal direction of the resin film. ×: A large number of corrugated shapes were observed on the side edges in the longitudinal direction of the resin film. The evaluation criteria for "appearance (color)" are as follows. A general spectrophotometer can be used, but the CM-3700d manufactured by Konica Minolta is used here. ○: ΔE (CMC) = 5.0 or less Δ: ΔE (CMC) = more than 5.0 and less than 6.0 ×: ΔE (CMC) = more than 6.0 The evaluation criteria of "brightness" are as follows. A general gloss tester can be used, but the CM-M6 manufactured by Konica Minolta is used here. ○: Trigger value = 9.0 or more △: Trigger value = 7.0 or more and less than 9.0 ×: Trigger value = less than 7.0 The results are shown in Table 1. [Table 1]
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Surface appearance</td><td> Peel test</td ><td> Round-trip opening and endurance test</td><td> </td></tr><tr><td> Test number</td><td> Aluminum powder content in the skin layer (% by mass) </td><td> Aluminium powder content in resin film (% by mass) </td><td> Appearance (shape) </td><td> Appearance (color) </td><td> Brightness < /td><td> Next strength</td><td> Peeling interface</td><td> Wear resistance</td><td> Remarks</td></tr><tr><td> 1 </td><td> 0.0% </td><td> 0.0% </td><td> ○ </td><td> × </td><td> × </td><td> ○ </td><td> ○ </td><td> ○ </td><td> Comparative example</td></tr><tr><td> 2 </td><td> 2.0% < /td><td> 0.4% </td><td> ○ </td><td> △ </td><td> △ </td><td> ○ </td><td> ○ </ Td><td> ○ </td><td> Comparative Example</td></tr><tr><td> 3 </td><td> 2.9% </td><td> 0.6% </ Td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td> <td> </td></tr><tr><td> 4 </td><td> 4.9% </td><td> 1.0% </td><td> ○ </td><td > ○ </td><td> ○ </td>< Td> ○ </td><td> ○ </td><td> ○ </td><td> </td></tr><tr><td> 5 </td><td> 9.8% </td><td> 2.0% </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ < /td><td> ○ </td><td> </td></tr><tr><td> 6 </td><td> 14.7% </td><td> 3.0% </td ><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td>< Td> </td></tr><tr><td> 7 </td><td> 19.6% </td><td> 4.0% </td><td> × </td><td> ○ </td><td> ○ </td><td> ○ </td><td> × </td><td> ○ </td><td> </td></tr><tr ><td> 8 </td><td> 21.6% </td><td> 4.4% </td><td> × </td><td> ○ </td><td> ○ </td ><td> × </td><td> × </td><td> △ </td><td> Comparative Example </td></tr></TBODY></TABLE><II. Aluminum Verification of the influence of the average particle diameter of the powder> The average particle diameter of the aluminum powder in the skin layer was changed to the conditions described in Table 2, and a slide fastener was produced in the same manner as in Test No. 4. For the obtained zipper, the same peeling test and round-trip opening endurance test as described above were carried out. Further, the evaluation of the surface appearance was carried out in the same manner as described above. The results are shown in Table 2. [Table 2]
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Peel test</td><td> Round trip endurance test </td><td> Surface appearance</td></tr><tr><td> Test number</td><td> Average particle size of aluminum powder (μm) </td><td> Then intensity < /td><td> Stripping interface</td><td> Wear resistance</td><td> Appearance (shape) </td><td> Appearance (color) </td><td> Brightness </ Td></tr><tr><td> 4 </td><td> 15 </td><td> ○ </td><td> ○ </td><td> ○ </td>< Td> ○ </td><td> ○ </td><td> ○ </td></tr><tr><td> 9 </td><td> 1 </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> × </td><td> × </td></tr><tr ><td> 10 </td><td> 2 </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td>< Td> △ </td><td> △ </td></tr><tr><td> 11 </td><td> 5 </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td></tr><tr><td> 12 </td ><td> 30 </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td>< Td> ○ </td></tr><tr><td> 13 </td><td> 50 </td><td> ○ </td><td> ○ </td><td> △ </td><td> ○ </td><td> ○ </td><td> ○ </td></tr><tr><td> 14 </ Td><td> 80 </td><td> △ </td><td> △ </td><td> △ </td><td> △ </td><td> △ </td> <td> △ </td></tr></TBODY></TABLE><III. Verification of the influence of the surface properties of the skin layer> Various changes in the embossing and depth of the surface properties of the release film Thus, the surface properties of the outer surface of the skin layer were changed to the conditions described in Tables 3 and 4, and the slide fastener was produced in the same manner as in Test No. 4. For the obtained zipper, a non-contact three-dimensional surface property measuring machine manufactured by Canon Corporation was used and the arithmetic mean height Sa or the root mean square height Sq of the outer surface of the skin layer was measured in accordance with ISO 25178. Further, the evaluation of the surface appearance was carried out in the same manner as described above. The results are shown in Tables 3 and 4. [table 3]
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Surface Properties</td><td> Surface Appearance</td ></tr><tr><td> Test Number</td><td> Sa(μm) </td><td> Appearance (Color) </td><td> Brightness</td></tr ><tr><td> 4 </td><td> 4.2 </td><td> ○ </td><td> ○ </td></tr><tr><td> 15 </td ><td> 2 </td><td> ○ </td><td> △ </td></tr><tr><td> 16 </td><td> 2.5 </td><td > ○ </td><td> ○ </td></tr><tr><td> 17 </td><td> 5 </td><td> ○ </td><td> ○ < /td></tr><tr><td> 18 </td><td> 10 </td><td> △ </td><td> ○ </td></tr></TBODY> </TABLE>[Table 4]
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Surface Properties</td><td> Surface Appearance</td ></tr><tr><td> Test Number</td><td> Sq(μm) </td><td> Appearance (Color) </td><td> Brightness</td></tr ><tr><td> 4 </td><td> 5.3 </td><td> ○ </td><td> ○ </td></tr><tr><td> 19 </td ><td> 3 </td><td> ○ </td><td> △ </td></tr><tr><td> 20 </td><td> 5 </td><td > ○ </td><td> ○ </td></tr><tr><td> 21 </td><td> 7 </td><td> ○ </td><td> ○ < /td></tr><tr><td> 22 </td><td> 13 </td><td> △ </td><td> ○ </td></tr></TBODY> </TABLE><IV. Verification of the influence of the type of the adhesive agent> As an adhesive, a commercially available hot-melt type adhesive was used to prepare a slurry for forming an adhesive layer, and further, with Test No. 4 Make the zipper in the same order. For the obtained zipper, the same peeling test and round-trip opening endurance test as described above were carried out. Further, a heat resistance test under a hot press of 120 ° C × 30 seconds was carried out. In the evaluation, when the resin film was not offset from the attachment position of the chain cloth, it was set to ○, and when the resin film was displaced from the attachment position of the chain cloth, it was set to ×. The results are shown in Table 5. [table 5]
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> Peel test</td><td> Round trip endurance test </td><td> Heat resistance test</td></tr><tr><td> Test number</td><td> Next agent</td><td> Next strength</td><td> Peeling interface</td><td> Abrasion resistance</td><td> Heat resistance</td></tr><tr><td> 4 </td><td> Two-liquid hardening type </td ><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td></tr><tr><td> 23 </td><td > Hot Melt Type</td><td> ○ </td><td> ○ </td><td> × </td><td> × </td></tr></TBODY></ TABLE>