有鑒於完全固化後的聚氨酯熱熔膠具有優異的抗候性，本發明之目的係提出一種利用聚氨酯熱熔膠加工織物的簡易方法，其無需使用有機溶劑，以達到環保目的，且藉由該方法所製得之織物能具有良好透濕性，並同時具有良好柔韌性、手感及耐水洗等性質。 本發明之另一目的係提供一種濕氣硬化反應型聚氨酯熱熔膠，其可具有良好的穩定性、加工性及附著性，並可用於鞋材成品及箱包之製造，亦可用作織物塗層或內部塗層，以取代現有技術的複合面料或用作人造皮革之泡沫聚氨酯塗層織物。 本發明之又一目的係提供一種濕氣硬化反應型聚氨酯熱熔膠之簡易製造方法。新穎濕氣硬化反應型聚氨酯熱熔膠
本發明提供一種濕氣硬化反應型聚氨酯熱熔膠，其包含由至少一種異氰酸酯與至少一種多元醇反應所得之胺基甲酸酯預聚物、及至少一種潛伏型固化劑，其中該至少一種多元醇包含至少一種聚酯多元醇或至少一種聚醚多元醇或其組合。 根據本發明之濕氣硬化反應型聚氨酯熱熔膠，其中該胺基甲酸酯預聚物因含有異氰酸酯基（-NCO）反應性官能基，故可與環境中水氣反應進行分子間架橋之固化反應，亦與含有活性氫的基材（如織物、皮革、紙張、木材、塑料等異材質材料）之間具有良好的表面親合性，進而發生架橋反應，故可展現優異的黏著性能。 為獲得濕氣硬化反應型聚氨酯，上述異氰酸酯之NCO基團對該多元醇之OH基團之莫耳比（NCO/OH）係大於1。在較佳具體實施例中，其大於或等於1.01、1.05、1.1、1.15、1.2、1.25、1.3、1.35、1.4、1.45、1.5、1.55、1.6、1.65、1.7、1.75、1.8、1.85、1.9、2、2.5、3或以上。於本發明一具體實施例中，該NCO/OH係1.5或1.6。 此外，當本發明熱熔膠將其熔融佈膠後與濕氣接觸時，其中潛伏型固化劑（或稱潛伏型架橋劑）始可與該胺基甲酸酯預聚物中之反應官能基反應，以調節固化速度並消除塗層起泡及針孔問題。適用於本發明之潛伏型固化劑可包含為此目的之任何已知化合物或混合物，例如，在水存在的情況下可水解成胺和羥基之潛伏型固化劑。文獻中指出若欲以潛伏型固化劑改性聚醚多元醇預聚體，在高NCO%之情況下，潛伏型固化劑於改善氣泡的效果上則有限。於本發明之一較佳實施例中，選用聚醚及聚酯多元醇為熱熔膠之混合原料可改善上述限制。 適合之潛伏型固化劑包括但不限於噁唑烷(1,3-oxazolidine)(例如選自Angus公司之Zoldine MS-Plus，Incorez公司之Incozol 2、Incozol 3)、氨酯二噁唑烷潛固化劑(Ureathane bisoxazolidine)、改性噁唑烷潛固化劑及氨酯改性噁唑烷潛固化劑(例如選自Bayer 公司之Harderner OZ，Incorez公司之Incorez 4、Incorez K、Incorez HP、Incorez NC、Incorez EH，另有其他廠家之ALT-101、ALT-301、ALT-401、ALT-402、ALT-403、SL-101、SL-401)。於本發明一具體實施例中，該潛伏型固化劑為氨酯二噁唑烷類化合物。 根據本發明之熱熔膠於80°C具有50ps至300ps之黏度。於本發明一較佳實施例中，該黏度係介於150ps和280ps。在最佳具體實施例中，該黏度係介於165ps和250ps之間。 用於合成本發明中之胺基甲酸酯預聚物之適當異氰酸酯，較佳包含兩個或三個NCO基之異氰酸酯，其包括習知之脂肪族、脂環族或芳香族單體二異氰酸酯。分子量較佳為從160克/莫耳至500克/莫耳。異氰酸酯包括但不限於，芳香族聚異氰酸酯，例如4,4'-二苯甲烷二異氰酸酯(MDI)、2,2'-二苯甲烷二異氰酸酯、二苯甲烷2,4'-二異氰酸酯、1,3-伸苯基二異氰酸酯、1,4-伸苯基二異氰酸酯、萘-1,5-二異氰酸酯(NDI)、甲苯二異氰酸酯(Toluene diisocyanate，TDI)、四甲基二甲苯二異氰酸酯、甲苯二異氰酸酯、萘、二和四烷基二苯甲烷二異氰酸酯、4,4'-二苄基二異氰酸酯，及其組合。 亦可使用脂族異氰酸酯，例如十二烷二異氰酸酯、二聚脂肪酸二異氰酸酯、4,4'-二苄基二異氰酸酯、1,6-二異氰酸基-2,4,4-三甲基己烷、1,4-二異氰丁酯、1,6-二異氰己酯(1,6-hexamethylene diisocyanate，HDI)、1,4-二異氰四甲氧丁酯、二環己甲烷二異氰酸酯、1,12-二異氰酸基十二烷，環狀二異氰酸酯例如4,4-二環己甲烷二異氰酸酯、1,3-環己烷或1,4-環己烷二異氰酸酯、1-甲基-2,4-二異氰酸基環己烷、1-異氰基甲基-3-異氰基-1,5,5-三甲基環己烷(異佛爾酮二異氰酸酯，Isophorone diisocyanate，IPDI)、氫化或部分氫化MDI([H]12MDI(氫化)或[H]6MDI(部分氫化))、二甲苯二異氰酸酯(XDI)、四甲基二甲苯二異氰酸酯(TMXDI)、二-和四亞烷基二苯甲烷二異氰酸酯。 具有兩個不同反應性之NCO基之較佳二異氰酸酯，係選自芳香族、脂肪族或脂環族二異氰酸酯之群組。亦可能包括至少部分寡聚二異氰酸酯例如脲基甲酸酯(allophanate)、羰二醯亞胺，來自二異氰酸酯之二縮脲縮合物，例如來自HDI、MDI、IPDI或其他異氰酸酯。可使用脂肪族或芳香族異氰酸酯之混合物。更佳為使用芳香族二異氰酸酯。 於本發明之較佳實施例中，該異氰酸酯係選自甲苯二異氰酸酯、二苯甲烷二異氰酸酯、1,6-二異氰己酯、或異佛爾酮二異氰酸酯或其混合物；或甲苯二異氰酸酯和二苯基甲烷二異氰酸酯之混合物。 根據本發明，前述至少一種多元醇係選自至少一種聚酯多元醇或至少一種聚醚多元醇或其組合。 聚酯多元醇係藉由多元羧酸和多元醇之反應而獲得者，且其已為技術人員所熟知。該聚酯多元醇包括結晶、半結晶及非結晶聚酯多元醇。可藉由共聚單體之類型調整聚酯多元醇之性質。結晶、半結晶和非結晶聚酯多元醇之製備方法已為技術人員所習知。該聚酯多元醇必需包含至少兩個羥基。可藉由不同組分設計聚酯之性質。例如，單直鏈脂族二元醇和直鏈脂族二元酸易產生半結晶聚合物。藉由增加二元酸之碳鏈長度或藉由利用對稱芳香族二元酸可增加其熔點。藉由增加共聚單體之數目或併入分支型脂族共聚單體，可獲得更多非晶型物質。該聚酯多元醇可包含其他官能基如NH或COOH，其亦可與一或多個異氰酸酯反應。 通過縮合一或多個具有較佳從2至30個碳原子之聚醇與一或多個具有較佳從2至14個碳原子之多元羧酸形成適當之聚酯多元醇。適當之聚醇包括亞烷基二醇，特別指具有2至30個碳原子之直鏈醇，其可含有四個OH基，較佳為兩個OH基；乙二醇醚；以及脂環族聚醇。適當聚醇之實例包括乙二醇、丙二醇如1,2-丙二醇和1,3-丙二醇、甘油醇、季戊四醇、三甲醇丙烷、丁二醇、戊二醇、己二醇、十二烷二醇、辛二醇、氯代戊二醇、甘油單烯丙基醚、甘油單乙基醚、二乙二醇、2-乙基己二醇、1,4-環己二醇、1,2,6-己三醇、1,3,5-己三醇、1,3-雙-(2-羥乙氧基)丙烷等。該聚醇可分開或混合使用。 多元羧酸之實例包括鄰苯二甲酸、間苯二甲酸、對苯二甲酸、四氯酞酸、順丁烯二酸、十二烷基順丁烯二酸、十八烯基順丁烯二酸、富馬酸、烏頭酸(aconitic acid)、偏苯三甲酸、1,2,3-丙三甲酸、3,3'-硫代二丙酸、琥珀酸、己二酸、辛二酸、壬二酸、丙二酸、戊二酸、庚二酸、癸二酸、環己-1,2-二羧酸、1,4-環己二烯-1,2-二羧酸、3-甲基-3,5-環己二烯-1,2-二羧酸以及其對應酸酐、氯化酸和酸性酯例如酞酸酐、鄰苯二甲醯氯和鄰苯二甲酸之二甲酯。亦可使用脂肪酸二聚體(dimer fatty acids)，其為單或多不飽合酸及/或其酯之二聚化產物。較佳之脂肪酸二聚體為C10至C30，更佳為C14至C22之碳酸之二聚體。適當之脂肪酸二聚體包括油酸、亞麻油酸、亞麻仁油酸、棕櫚油酸和反油酸(elaidic acid)之二聚化產物。亦可使用天然脂肪和油類，例如葵花油、大豆油、橄欖油、菜籽油、棉籽油和妥爾油(tall oil)，之水解中所獲得不飽合脂肪酸混合物之二聚化產物。除脂肪酸二聚體之外，二聚化反應通常導致不同數量之寡聚脂肪酸以及單聚脂肪酸殘基。基於脂肪酸二聚體起始材料之總重量，適當之脂肪酸二聚體具有大於75重量%之二聚酸含量。 其他適合聚酯多元醇為聚碳酸酯多元醇。聚碳酸酯多元醇可獲得自例如藉由二元醇如丙二醇、1,4-丁二醇或1,6-己二醇、二甘醇、三甘醇或二或多種其與碳酸二芳酯之混合物之反應。亦適合使用以ε-己內酯為基礎之聚酯。亦適合使用其聚合物鏈內含有一或多個胺基甲酸酯基之聚酯多元醇。 其他有用之聚酯多元醇包括，例如衍自油脂化學品之多元醇，以及含至少部分烯烴不飽合脂肪酸之脂肪混合物和含從1個碳原子至12個碳原子之至少一醇類之完全開環之環氧化三酸甘油脂，接著藉由三酸甘油脂衍生物之部分轉酯化而形成烷基鏈內具有1至12個碳原子之烷基酯多元醇。 本發明亦可使用市售聚酯多元醇，包括結晶或非結晶聚酯多元醇。術語「聚酯多元醇」係指其結構中包括聚酯之聚合物鏈及末端之羧基或醇基，較佳之聚酯多元醇為聚酯二元醇。 較佳多元羧酸為包含不超過14個碳原子之脂族和脂環族二羧酸以及含有不超過14個碳原子之芳香族二羧酸。在更佳具體實施例中，該至少一個聚酯多元醇包含一個鄰苯二甲酸酯(ortho-phthalate)。應瞭解本文中「包含鄰苯二甲酸酯」中之名詞「鄰苯二甲酸酯」被解讀為亦包括其衍生物，亦即，藉由反應混合物包括至少一鄰苯二甲酸酯、酞酸酐，或其衍生物或其組合所獲得之聚酯多元醇。在本發明中之一具體實施例中，該鄰苯二甲酸酯被包含在聚酯多元醇內。 於本發明中之一較佳實施例中，該聚酯多元醇係選自聚酯多元醇或芳香族聚酯多元醇。於本發明中之另一較佳實施例中，該聚酯多元醇為聚酯二元醇、聚ε-己內酯二元醇與聚碳酸脂二元醇或其混合物，且具有重量平均分子量為800至4000，較佳為1000至3000，更佳為1000至2000。 於本發明中之一更佳實施例中，該聚酯二元醇可為脂肪族型聚酯二元醇，如由為二元酸與二元醇所製者，例如聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、或聚己二酸己二醇酯二醇等；或芳香族型聚酯二元醇，如由芳香族二元酸、己二酸與二元醇所製者，例如聚鄰苯二甲酸二乙二醇酯二醇、聚鄰苯二甲酸新戊二醇酯二醇、聚鄰苯二甲酸己二醇酯二醇等。 本發明透過大量的實驗頃發現，隨著聚酯多元醇相對分子量的增加，本發明之熱熔膠的斷裂強度及斷裂伸長率皆有顯著提升。於本發明中之一較佳實施例中，使用具有分子量為800至4000之聚酯多元醇，可使熱熔膠具有最佳之接著強度。 適用於本發明之聚醚多元醇係屬通常知識者所習知者，其例示性化合物可參David Randall和Steve Lee合編，「聚胺基甲酸酯手冊」之第6章（John Wiley and Sons 2002出版）。使用由聚醚多元醇所製成之胺基甲酸酯預聚物，可使本發明之熱熔膠具有良好的耐水性、抗衝擊性和耐低溫性。 於本發明中之一較佳實施例中，該聚醚多元醇係選自聚氧化丙烯二醇(Polypropylene glycol)、聚乙二醇(Polyethylene glycol)，聚四氫呋喃醚二醇(Polytetramethylene glycol)或四氫呋喃-氧化丙烯共聚二醇(Tetrahydrofuranoxide propylene copolymer glycol)或其混合物，並具重量平均分子量為400至3000，較佳為1000至2000。 根據本發明之濕氣硬化反應型聚氨酯熱熔膠，其實質上不包含溶劑。「實質上無溶劑」術語係指除了可能在製造中所產生之雜質外，其不包含溶劑，且未向各組份添加溶劑。因此，溶劑含量以該熱熔膠之總重量計係小於1重量%，較佳小於0.8、0.5或0.1重量%，更佳小於0.01重量%。 術語「溶劑」通常為本發明所屬技術領域中所熟知者，其一般指能以一物理方式溶解其他固體材料之有機或無機液體。可用作溶劑之前提條件係其可將材料予以溶解但不會與之產生化學反應。因此，可藉由物理分離方法(例如，蒸餾、結晶、昇華、蒸發及/或吸附)回收被溶解組份。 根據本發明之濕氣硬化反應型聚氨酯熱熔膠基本上不包含有機溶劑，較佳不包含揮發性有機溶劑。更特定言之，該熱熔膠基本上不包含醚或二醇醚(例如，二乙醚、二丁醚、苯甲醚、二氧陸圜、單體四氫呋喃)、酮(例如，丙酮、丁酮、環己酮)、酯(例如乙酸乙酯)、氮化合物(例如二甲基甲醯胺、吡啶、N－甲基吡咯烷酮、乙腈)、硫化合物(例如硫化碳、二甲亞碸、環丁碸)、硝基化合物(例如硝基苯)、(氫)鹵烴(例如二氯甲烷、氯仿、四氯甲烷、三氯乙烯、四氯乙烯、1,2－二氯乙烷、氯氟碳化合物)、碳氫化合物，較佳者係具有大於60℃之沸點者(例如辛烷、甲基環己烷、萘烷、苯、甲苯、二甲苯)。 根據本發明之濕氣硬化反應型聚氨酯熱熔膠可視需要選用現有技術中已知之一或多種添加物。「添加物」術語係指鏈延長劑、催化劑、穩定劑、附著力促進劑、染料、填料(例如矽酸鹽、滑石粉、碳酸鈣、黏土或碳黑)、觸變劑(例如膨潤土、焦化矽酸、尿素衍生物、原纖化或漿粕短纖維)、色糊及/或色素、不同於根據本發明之聚氨酯熱熔膠之其他熱塑性聚合物、增塑劑、流變助劑、蠟油以及其任何組合。 術語「鏈延長劑」通常為本發明所屬技術領域中所熟知者。於本發明之一較佳實施例中，該鏈延長劑係選自乙二醇(Ethylene glycol)、丙二醇(Propylene glycol)、1,4-丁二醇(1,4-Butanediol)、1,6-己二醇(1,6-Hexylene glycol) 、新戊二醇(Neopentyl glycol)或三羥甲基丙烷(Trimethylolpropane)或其混合物。於本發明之一更佳實施例中，該鏈延長劑為1,4-丁二醇和三羥甲基丙烷(Trimethylolpropane)的混合物。 術語「催化劑」通常為本發明所屬技術領域中所熟知者，其可調節了本發明之熱熔膠或胺基甲酸酯預聚物之反應速度和固化速度。於本發明之一較佳實施例中，該催化劑係選自二月桂酸二丁基錫(Dibutyl tin dilaurate, DBTDL)、辛酸亞錫(Stannous octoate)、三乙烯二胺(Triethylene diamine)、三乙醇胺(Triethanolamine)或雙嗎啉基二乙基醚(Dimorpholinodiethyl ether，DMDEE)或其混合物。於本發明之一更佳實施例中，該催化劑為雙嗎啉基二乙基醚。 術語「穩定劑」通常為本發明所屬技術領域中所熟知者，其可阻止聚氨酯熱氧化，阻止由氧誘發的聚合物斷鏈反應。於本發明使用穩定劑可提高產品耐熱氧化和光老化性能。穩定劑包括但不限於抗氧化劑、紫外線穩定劑、水解穩定劑。這些成分之實例為高分子量之立體受阻酚、含硫和含磷酚或胺。此包括立體受阻酚類、多官能基酚類、硫醚、經取代苯并三唑、受阻二苯甲酮及/或立體受阻胺。水解穩定劑之實例包括寡聚及/或聚合脂族或芳香族碳二亞胺。此類成分可市面購得以及為通常知識者所習知，例如選自CHINOX 1010、CHIN0X1076、CHIN0X1098、CHIN0X1790或CHIN0X5726之抗氧劑；CHIS0RB234、CHIS0RB320、CHIS0RB5411、CHIS0RB5571、CHIS0RB335或CHISORB1268之光穩定劑。 術語「附著力促進劑」通常為本發明所屬技術領域中所熟知者，其可視需要以改善該熱熔膠與不同基質之相容性。舉例而言，附著力促進劑可為衍生自松脂酸、松脂酸酯、其他松香酯之樹脂、聚萜烯樹脂、萜烯/酚醛樹脂、苯乙烯化萜烯、聚-α-甲基苯乙烯、α-甲基苯乙烯-酚醛或脂環族、芳香族或芳香/脂環族碳氫樹脂或苯並呋喃茚樹脂，或衍自低分子量聚醯胺之樹脂。 根據本發明之聚氨酯熱熔膠可包含不同於聚氨酯之其他熱塑性聚合物，其包括但不侷限於EVA、橡膠型聚合物、苯乙烯共聚物、聚酯共聚物、聚碳酸酯、聚醯胺、聚丙烯酸樹脂以及熱塑性聚胺基甲酸酯。 術語「增塑劑」通常為本發明所屬技術領域中所熟知者，其條件為這些增塑劑不會干擾該黏膠之熱熔性能，其包括但不限於鄰苯二甲酸酯、苯甲酸酯、蔗糖酯、磺醯胺、酞酸二環己酯、環已烷二甲醇二苯甲酸酯、醋酸異丁酸蔗糖酯、鄰-/對-甲苯磺醯胺或N-乙基-鄰-甲苯磺醯胺。 於本發明之濕氣硬化反應型聚氨酯熱熔膠中，以重量份計，該熱熔膠包含10至200重量份聚酯多元醇或聚醚多元醇或其組合、5至50重量份異氰酸酯、0至10重量份鏈延長劑、0至0.005重量份穩定劑、0至0.1重量份催化劑及0至2重量份潛伏型固化劑。 於本發明一較佳實施例中，該熱熔膠包含15至40重量份聚酯多元醇、15至40重量份聚醚多元醇、1至5重量份鏈延長劑、0.01至0.05重量份穩定劑、15至40重量份異氰酸酯、0.05至0.1重量份催化劑及0.5至1重量份潛伏型固化劑。濕氣硬化反應型聚氨酯熱熔膠之製備方法
本發明提供一種製備濕氣硬化反應型聚氨酯熱熔膠之方法，其包含以下步驟： i) 將至少一種多元醇及視需要選用的鏈延長劑、穩定劑、附著力促進劑或其組合予以混合； ii) 將所得之混合物於減壓環境下加熱攪拌，使得該混合物混合均勻並脫水； iii) 降溫該混合物； iv) 使該混合物在氮氣下與至少一種異氰酸酯及視需要選用的催化劑反應，以製得胺基甲酸酯預聚物；且 v) 將潛伏型固化劑添加至該胺基甲酸酯預聚物，以製得該熱熔膠。 根據本發明之濕氣硬化反應型聚氨酯熱熔膠之製備方法，其包括以下步驟：取10至200重量份聚酯多元醇或聚醚多元醇或其組合、0至10重量份鏈延長劑、0至0.005重量份穩定劑在100至150°C下攪拌且真空脫水1至2小時，將該混合物降溫至60至80℃後，於氮氣中加入5至50重量份異氰酸酯至該混合物中，待適當反應後再添加0.5至1重量份潛伏型固化劑及0至0.1重量份催化劑並攪勻，隨後出料密封包裝，即製得反應型聚氨酯熱熔膠。 於本發明之一較佳實施例中，該製備方法包括：取15至40份聚酯多元醇、15至40份聚醚多元醇、1至5份鏈延長劑、0.01至0.05份穩定劑混合，在110至130°C下攪拌且真空脫水1至2小時，將該混合物降溫至65至75℃後，於氮氣中加入15至40份異氰酸酯至該混合物中，待反應30至90分鐘後再添加0.5至1重量份潛伏型固化劑及0.05至0.1份催化劑並攪勻，隨後出料密封包裝，即製得反應型聚氨酯熱熔膠。濕氣硬化反應型聚氨酯熱熔膠之使用方法與用途
本發明提供一種將上述熱熔膠施用至一基質層之方法，其包含以下步驟： i) 將該熱熔膠加熱，使其成熔融態；且 ii) 使該熔融態熱熔膠與該基質層接觸。 術語「基質層」可為任何能夠與本發明之聚氨酯熱熔膠形成一附著黏結之層，例如織物基質層、絮片基質層、纖維基質層、箔基質層、皮革層（較佳為剖層皮）或紡織層。織物基質層可由一層或多層相同或不同的彼此緊密互連之子層構成，例如由小孔狀或大孔機織物、針織物、編帶、網格(網眼布)構成。絮片基質層係由經隨機放置之纖維構成之片樣結構(實例係毛氈及纖維網)，其較佳可藉由一黏合劑黏結在一起。絮片基質層通常係經非水溶性浸漬劑加強之纖維素絮片或紡織絮片。纖維基質層係由用作一黏合劑之塑膠加強的鬆散隨機放置的纖維構成之製造物件，其係藉由(例如)將皮革纖維(較佳可自皮革廢料例如自經植物鞣製的皮革獲得)與黏合劑黏附在一起獲得。箔基質層包含由金屬或塑膠(例如，橡膠、PVC、聚醯胺、互聚物及諸如此類)構成之箔(較佳為勻質)的製造物件。一箔基質層較佳不納入纖維。紡織層可由以下材料所製造：棉花、亞麻布、聚酯、聚醯胺及/或聚胺基甲酸酯。 於本發明一較佳實施例中，該基質層係選自例如彈性布、針織布、平織布及撥水處理布料等織物、鞋材基質層或箱包基質層。 於本發明一較佳實施例中，熔融態熱熔膠可藉由離型轉貼或直接塗佈方式接觸該基質層。離型轉貼方式係指在前述接觸步驟前，該熔融態熱熔膠係先塗佈於剝離層上，隨後即與該基質接觸。可用的剝離層包括但不限於由金屬、塑膠、皮革及/或紡織材料構成之層，例如箔或離型紙。直接塗佈方式係指該熔融態熱熔膠係直接塗佈於前述基質層上。於本發明一實施例中，該塗佈步驟可藉由刀塗或輥塗完成。 於本發明一較佳實施例中，該熱熔膠之於基質層上之施用量為1至200g/m2
、較佳為5至150g/m2
，更佳為10g/m2
至50g/m2
。In view of the excellent weather resistance of the fully cured polyurethane hot melt adhesive, the object of the present invention is to provide a simple method for processing a fabric using a polyurethane hot melt adhesive, which does not require the use of an organic solvent for environmental protection purposes, and The fabric obtained by the method can have good moisture permeability, and at the same time has good flexibility, hand feeling and water washing resistance. Another object of the present invention is to provide a moisture hardening reaction type polyurethane hot melt adhesive which can have good stability, workability and adhesion, can be used for the manufacture of finished shoe materials and bags, and can also be used as a fabric coating. A layer or inner coating to replace the prior art composite fabric or a foamed polyurethane coated fabric used as an artificial leather. Still another object of the present invention is to provide a simple manufacturing method of a moisture hardening type polyurethane hot melt adhesive. Novel moisture curing reactive polyurethane hot melt adhesive of the present invention provides a moisture curing reactive polyurethane hot melt adhesive, comprising at least one isocyanate with a urethane prepolymer obtained from the reaction of at least one polyol, and at least one A latent curing agent, wherein the at least one polyol comprises at least one polyester polyol or at least one polyether polyol or a combination thereof. The moisture hardening type polyurethane hot melt adhesive according to the present invention, wherein the urethane prepolymer contains an isocyanate group (-NCO) reactive functional group, so that it can react with water vapor in the environment to carry out intermolecular bridging. The curing reaction also has a good surface affinity with a substrate containing active hydrogen (such as fabric, leather, paper, wood, plastic, etc.), and a bridging reaction occurs, so that excellent adhesion properties can be exhibited. In order to obtain a moisture-hardening type polyurethane, the NCO group of the above isocyanate has a molar ratio (NCO/OH) of OH groups to the polyol of more than 1. In a preferred embodiment, it is greater than or equal to 1.01, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 2, 2.5, 3 or above. In a specific embodiment of the invention, the NCO/OH system is 1.5 or 1.6. In addition, when the hot melt adhesive of the present invention is melted and brought into contact with moisture, the latent curing agent (or latent bridging agent) can be reacted with the reactive functional group in the urethane prepolymer. The reaction is used to adjust the cure speed and eliminate coating blistering and pinhole problems. The latent curing agent suitable for use in the present invention may comprise any known compound or mixture for this purpose, for example, a latent curing agent which hydrolyzes to an amine and a hydroxyl group in the presence of water. It is pointed out in the literature that if a polyether polyol prepolymer is to be modified with a latent curing agent, the latent curing agent has a limited effect on improving the bubble at a high NCO%. In a preferred embodiment of the invention, the use of polyether and polyester polyols as a blend of hot melt adhesives can improve the above limitations. Suitable latent curing agents include, but are not limited to, 1,3-oxazolidine (for example, Zoldine MS-Plus from Angus, Incozol 2, Incozol 3 from Incorez), latent curing of urethane dioxazole Ureathane bisoxazolidine, modified oxazolidine latent curing agent and urethane modified oxazolidine latent curing agent (eg selected from Harderner OZ of Bayer Company, Incorez 4 of Incorez Company, Incorez K, Incorez HP, Incorez NC, Incorez EH, other manufacturers of ALT-101, ALT-301, ALT-401, ALT-402, ALT-403, SL-101, SL-401). In a specific embodiment of the invention, the latent curing agent is a urethane dioxazolidine compound. The hot melt adhesive according to the present invention has a viscosity of 50 ps to 300 ps at 80 °C. In a preferred embodiment of the invention, the viscosity is between 150 ps and 280 ps. In the most preferred embodiment, the viscosity is between 165 ps and 250 ps. Suitable isocyanates for the synthesis of the urethane prepolymers of the invention preferably comprise two or three NCO-based isocyanates, including the customary aliphatic, cycloaliphatic or aromatic monomeric diisocyanates. The molecular weight is preferably from 160 g/mol to 500 g/mole. Isocyanates include, but are not limited to, aromatic polyisocyanates such as 4,4'-diphenylmethane diisocyanate (MDI), 2,2'-diphenylmethane diisocyanate, diphenylmethane 2,4'-diisocyanate, 1, 3-phenylene diisocyanate, 1,4-phenylene diisocyanate, naphthalene-1,5-diisocyanate (NDI), toluene diisocyanate (TDI), tetramethylxylene diisocyanate, toluene Isocyanate, naphthalene, di- and tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, and combinations thereof. It is also possible to use aliphatic isocyanates such as dodecane diisocyanate, dimer fatty acid diisocyanate, 4,4'-dibenzyl diisocyanate, 1,6-diisocyanato-2,4,4-trimethyl. Hexane, 1,4-diisocyanobutyrate, 1,6-hexamethylene diisocyanate (HDI), 1,4-diisocyanate, dicyclohexylmethane Diisocyanate, 1,12-diisocyanatodecane, cyclic diisocyanate such as 4,4-dicyclohexanemethane diisocyanate, 1,3-cyclohexane or 1,4-cyclohexane diisocyanate, 1-methyl-2,4-diisocyanatocyclohexane, 1-isocyanomethyl-3-isocyano-1,5,5-trimethylcyclohexane (isophorone II Isocyanate, Isophorone diisocyanate, IPDI), hydrogenated or partially hydrogenated MDI ([H]12MDI (hydrogenated) or [H]6MDI (partially hydrogenated)), xylene diisocyanate (XDI), tetramethylxylene diisocyanate (TMXDI) , di- and tetraalkylenediphenylmethane diisocyanate. Preferred diisocyanates having two different reactive NCO groups are selected from the group of aromatic, aliphatic or alicyclic diisocyanates. It is also possible to include at least part of the oligomeric diisocyanates such as allophanate, carbodiimide, diuret condensates from diisocyanates, for example from HDI, MDI, IPDI or other isocyanates. Mixtures of aliphatic or aromatic isocyanates can be used. More preferably, an aromatic diisocyanate is used. In a preferred embodiment of the invention, the isocyanate is selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, 1,6-diisocyanohexyl ester, or isophorone diisocyanate or mixtures thereof; or toluene diisocyanate And a mixture of diphenylmethane diisocyanate. According to the invention, the aforementioned at least one polyol is selected from at least one polyester polyol or at least one polyether polyol or a combination thereof. Polyester polyols are obtained by the reaction of polycarboxylic acids and polyols and are well known to the skilled person. The polyester polyols include crystalline, semi-crystalline, and non-crystalline polyester polyols. The nature of the polyester polyol can be adjusted by the type of comonomer. Processes for the preparation of crystalline, semi-crystalline and non-crystalline polyester polyols are well known to the skilled person. The polyester polyol must contain at least two hydroxyl groups. The properties of the polyester can be designed by different components. For example, a single linear aliphatic diol and a linear aliphatic dibasic acid are susceptible to producing a semicrystalline polymer. The melting point can be increased by increasing the carbon chain length of the dibasic acid or by utilizing a symmetric aromatic dibasic acid. More amorphous materials can be obtained by increasing the number of comonomers or incorporating branched aliphatic comonomers. The polyester polyol may contain other functional groups such as NH or COOH, which may also be reacted with one or more isocyanates. A suitable polyester polyol is formed by condensing one or more polyalcohols having preferably from 2 to 30 carbon atoms with one or more polycarboxylic acids having preferably from 2 to 14 carbon atoms. Suitable polyalcohols include alkylene glycols, especially linear alcohols having from 2 to 30 carbon atoms, which may contain four OH groups, preferably two OH groups; glycol ethers; and alicyclic groups. Polyol. Examples of suitable polyalcohols include ethylene glycol, propylene glycol such as 1,2-propanediol and 1,3-propanediol, glycerol, pentaerythritol, trimethylolpropane, butanediol, pentanediol, hexanediol, dodecanediol , octanediol, chloropentanediol, glycerol monoallyl ether, glycerin monoethyl ether, diethylene glycol, 2-ethylhexanediol, 1,4-cyclohexanediol, 1,2, 6-hexanetriol, 1,3,5-hexanetriol, 1,3-bis-(2-hydroxyethoxy)propane, and the like. The polyol can be used separately or in combination. Examples of the polycarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, tetrachlorodecanoic acid, maleic acid, dodecyl maleic acid, octadecyl nonamylene Acid, fumaric acid, aconitic acid, trimellitic acid, 1,2,3-propanetricarboxylic acid, 3,3'-thiodipropionic acid, succinic acid, adipic acid, suberic acid, Azelaic acid, malonic acid, glutaric acid, pimelic acid, sebacic acid, cyclohex-1,2-dicarboxylic acid, 1,4-cyclohexadiene-1,2-dicarboxylic acid, 3- Methyl-3,5-cyclohexadiene-1,2-dicarboxylic acid and its corresponding anhydride, chlorinated acid and acidic esters such as phthalic anhydride, phthalic acid chloride and dimethyl phthalate. Dimer fatty acids, which are dimerization products of mono- or polyunsaturated acids and/or their esters, can also be used. Preferred fatty acid dimers are C10 to C30, more preferably C14 to C22 carbonic acid dimers. Suitable fatty acid dimers include dimerization products of oleic acid, linoleic acid, linoleic acid, palmitoleic acid, and elaidic acid. It is also possible to use natural fats and oils such as sunflower oil, soybean oil, olive oil, rapeseed oil, cottonseed oil and tall oil to obtain a dimerization product of the unsaturated fatty acid mixture obtained in the hydrolysis. In addition to fatty acid dimers, dimerization reactions typically result in varying amounts of oligomeric fatty acids as well as mono-poly fatty acid residues. Suitable fatty acid dimers have a dimer acid content of greater than 75% by weight, based on the total weight of the fatty acid dimer starting material. Other suitable polyester polyols are polycarbonate polyols. The polycarbonate polyol can be obtained, for example, from a glycol such as propylene glycol, 1,4-butanediol or 1,6-hexanediol, diethylene glycol, triethylene glycol or two or more thereof with a diaryl carbonate. The reaction of the mixture. It is also suitable to use a polyester based on ε-caprolactone. It is also suitable to use a polyester polyol having one or more urethane groups in its polymer chain. Other useful polyester polyols include, for example, polyols derived from oleochemicals, and fat blends containing at least a portion of the olefinic unsaturated fatty acids and at least one alcohol containing from 1 carbon atom to 12 carbon atoms. The ring-opened epoxidized triglyceride is then partially esterified by a triglyceride derivative to form an alkyl ester polyol having from 1 to 12 carbon atoms in the alkyl chain. Commercially available polyester polyols, including crystalline or non-crystalline polyester polyols, can also be used in the present invention. The term "polyester polyol" means a polymer chain including a polyester and a carboxyl group or an alcohol group at the terminal, and preferably the polyester polyol is a polyester diol. Preferred polycarboxylic acids are aliphatic and alicyclic dicarboxylic acids containing no more than 14 carbon atoms and aromatic dicarboxylic acids containing no more than 14 carbon atoms. In a more preferred embodiment, the at least one polyester polyol comprises an ortho-phthalate. It should be understood that the term "phthalate" as used in "including phthalates" is to be interpreted as including also derivatives thereof, that is, by the reaction mixture comprising at least one phthalate, A polyester polyol obtained by phthalic anhydride, or a derivative thereof or a combination thereof. In one embodiment of the invention, the phthalate is included in the polyester polyol. In a preferred embodiment of the invention, the polyester polyol is selected from the group consisting of polyester polyols or aromatic polyester polyols. In another preferred embodiment of the present invention, the polyester polyol is a polyester diol, a poly-ε-caprolactone diol and a polycarbonate diol or a mixture thereof, and has a weight average molecular weight. It is from 800 to 4,000, preferably from 1,000 to 3,000, more preferably from 1,000 to 2,000. In a preferred embodiment of the present invention, the polyester diol may be an aliphatic polyester diol, such as those prepared from dibasic acids and glycols, such as polyethylene adipate. Alcohol ester diol, polybutylene adipate diol, or polyhexane adipate diol diol, etc.; or aromatic polyester diol, such as aromatic dibasic acid, adipic acid As the diol, for example, diethylene glycol phthalate diol, polypentylene glycol phthalate diol, polybutylene phthalate diol or the like. The present invention has found through a large number of experiments that as the relative molecular weight of the polyester polyol increases, the breaking strength and elongation at break of the hot melt adhesive of the present invention are significantly improved. In a preferred embodiment of the invention, the use of a polyester polyol having a molecular weight of from 800 to 4000 provides the hot melt adhesive with optimum bond strength. Polyether polyols suitable for use in the present invention are known to those of ordinary skill in the art, and exemplary compounds thereof can be found in David Randall and Steve Lee, Chapter 6 of the "Polyurethane Handbook" (John Wiley and Sons 2002)). The use of a urethane prepolymer made of a polyether polyol allows the hot melt adhesive of the present invention to have good water resistance, impact resistance and low temperature resistance. In a preferred embodiment of the present invention, the polyether polyol is selected from the group consisting of polypropylene glycol, polyethylene glycol, polytetramethylene glycol or tetrahydrofuran. - Tetrahydrofuran oxide propylene copolymer glycol or a mixture thereof, and having a weight average molecular weight of from 400 to 3,000, preferably from 1,000 to 2,000. The moisture-hardening type polyurethane hot melt adhesive according to the present invention does not substantially contain a solvent. The term "substantially solvent-free" means that it does not contain a solvent other than impurities which may be produced in the production, and no solvent is added to each component. Accordingly, the solvent content is less than 1% by weight, preferably less than 0.8, 0.5 or 0.1% by weight, more preferably less than 0.01% by weight, based on the total weight of the hot melt adhesive. The term "solvent" is generally used in the art to which the invention pertains and generally refers to an organic or inorganic liquid that is capable of physically dissolving other solid materials. The conditions preceded by use as a solvent are such that it dissolves the material but does not chemically react therewith. Thus, the dissolved components can be recovered by physical separation methods (eg, distillation, crystallization, sublimation, evaporation, and/or adsorption). The moisture hardening type polyurethane hot melt adhesive according to the present invention contains substantially no organic solvent, and preferably does not contain a volatile organic solvent. More specifically, the hot melt adhesive contains substantially no ether or glycol ether (eg, diethyl ether, dibutyl ether, anisole, dioxane, monomeric tetrahydrofuran), ketone (eg, acetone, methyl ethyl ketone) , cyclohexanone), ester (such as ethyl acetate), nitrogen compounds (such as dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (such as carbon sulfide, dimethyl hydrazine, cycline)碸), nitro compounds (such as nitrobenzene), (hydrogen) halocarbons (such as dichloromethane, chloroform, tetrachloromethane, trichloroethylene, tetrachloroethylene, 1,2-dichloroethane, chlorofluorocarbon) The compound), a hydrocarbon, preferably has a boiling point of more than 60 ° C (for example, octane, methylcyclohexane, decalin, benzene, toluene, xylene). The moisture-curing reactive polyurethane hot melt adhesive according to the present invention may optionally be selected from one or more additives known in the art. "Additive" term refers to chain extenders, catalysts, stabilizers, adhesion promoters, dyes, fillers (eg, citrate, talc, calcium carbonate, clay or carbon black), thixotropic agents (eg bentonite, coking) Ceric acid, urea derivative, fibrillated or pulp short fiber), color paste and/or pigment, other thermoplastic polymer, plasticizer, rheological additive, wax different from polyurethane hot melt adhesive according to the invention Oil and any combination thereof. The term "chain extender" is generally as known in the art to which the invention pertains. In a preferred embodiment of the present invention, the chain extender is selected from the group consisting of ethylene glycol, propylene glycol, 1,4-butanediol, 1,6 Hexadiol (1,6-Hexylene glycol), neopentyl glycol or Trimethylolpropane or a mixture thereof. In a further preferred embodiment of the invention, the chain extender is a mixture of 1,4-butanediol and Trimethylolpropane. The term "catalyst" is generally known in the art to which the present invention modulates the rate of reaction and cure rate of the hot melt or urethane prepolymer of the present invention. In a preferred embodiment of the invention, the catalyst is selected from the group consisting of Dibutyl tin dilaurate (DBTDL), Stannous octoate, Triethylene diamine, Triethanolamine. Or Dimorpholinodiethyl ether (DMDEE) or a mixture thereof. In a further preferred embodiment of the invention, the catalyst is bismorpholinyl diethyl ether. The term "stabilizer" is generally known in the art to which it is known to prevent thermal oxidation of the polyurethane and to prevent polymer chain scission reactions induced by oxygen. The use of a stabilizer in the present invention improves the thermal oxidation resistance and photoaging properties of the product. Stabilizers include, but are not limited to, antioxidants, UV stabilizers, hydrolysis stabilizers. Examples of such ingredients are high molecular weight sterically hindered phenols, sulfur containing and phosphorus containing phenols or amines. This includes sterically hindered phenols, polyfunctional phenols, thioethers, substituted benzotriazoles, hindered benzophenones, and/or sterically hindered amines. Examples of hydrolysis stabilizers include oligomeric and/or polymeric aliphatic or aromatic carbodiimides. Such components are commercially available and are known to those of ordinary skill, such as antioxidants selected from CHINOX 1010, CHIN0X1076, CHIN0X1098, CHIN0X1790 or CHIN0X5726; light stabilizers of CHIS0RB234, CHIS0RB320, CHIS0RB5411, CHIS0RB5571, CHIS0RB335 or CHISORB1268. The term "adhesion promoter" is generally known in the art to which the present invention pertains, as needed to improve the compatibility of the hot melt adhesive with different substrates. For example, the adhesion promoter may be a resin derived from rosin acid, rosinate, other rosin esters, a polyterpene resin, a terpene/phenolic resin, a styrenated terpene, a poly-α-methylstyrene. , α-methylstyrene-phenolic or alicyclic, aromatic or aromatic/alicyclic hydrocarbon resins or benzofuranium resins, or resins derived from low molecular weight polyamines. The polyurethane hot melt adhesive according to the present invention may comprise other thermoplastic polymers other than polyurethane, including but not limited to EVA, rubber type polymers, styrene copolymers, polyester copolymers, polycarbonates, polyamines, Polyacrylic resin and thermoplastic polyurethane. The term "plasticizer" is generally known in the art to which the present invention pertains, provided that the plasticizer does not interfere with the hot melt properties of the adhesive, including but not limited to phthalates, phthalic acid. Acid esters, sucrose esters, sulfonamides, dicyclohexyl phthalate, cyclohexane dimethanol dibenzoate, sucrose acetate isobutyrate, o-/p-toluenesulfonamide or N-ethyl- O-toluenesulfonamide. In the moisture hardening type polyurethane hot melt adhesive of the present invention, the hot melt adhesive comprises 10 to 200 parts by weight of a polyester polyol or a polyether polyol or a combination thereof, and 5 to 50 parts by weight of an isocyanate, by weight, 0 to 10 parts by weight of a chain extender, 0 to 0.005 parts by weight of a stabilizer, 0 to 0.1 part by weight of a catalyst, and 0 to 2 parts by weight of a latent curing agent. In a preferred embodiment of the present invention, the hot melt adhesive comprises 15 to 40 parts by weight of a polyester polyol, 15 to 40 parts by weight of a polyether polyol, 1 to 5 parts by weight of a chain extender, and 0.01 to 0.05 parts by weight of a stabilizer. The agent is 15 to 40 parts by weight of isocyanate, 0.05 to 0.1 part by weight of the catalyst, and 0.5 to 1 part by weight of the latent curing agent. Method for preparing moisture-hardening reactive polyurethane hot melt adhesive The present invention provides a method for preparing a moisture hardening reactive polyurethane hot melt adhesive, comprising the steps of: i) at least one polyol and optionally a chain extender, a stabilizer, an adhesion promoter or a combination thereof is mixed; ii) the resulting mixture is heated and stirred under reduced pressure to uniformly mix and dehydrate the mixture; iii) to cool the mixture; iv) to make the mixture under nitrogen At least one isocyanate and optionally a catalyst are reacted to produce a urethane prepolymer; and v) a latent curing agent is added to the urethane prepolymer to produce the hot melt adhesive . A method for preparing a moisture-hardening reactive polyurethane hot melt adhesive according to the present invention, comprising the steps of: taking 10 to 200 parts by weight of a polyester polyol or a polyether polyol or a combination thereof, 0 to 10 parts by weight of a chain extender, 0 to 0.005 parts by weight of the stabilizer is stirred at 100 to 150 ° C and vacuum-dehydrated for 1 to 2 hours, and after the mixture is cooled to 60 to 80 ° C, 5 to 50 parts by weight of isocyanate is added to the mixture under nitrogen, to be After the appropriate reaction, 0.5 to 1 part by weight of the latent curing agent and 0 to 0.1 part by weight of the catalyst are added and stirred, and then the sealed package is discharged to obtain a reactive polyurethane hot melt adhesive. In a preferred embodiment of the present invention, the preparation method comprises: taking 15 to 40 parts of polyester polyol, 15 to 40 parts of polyether polyol, 1 to 5 parts of chain extender, and 0.01 to 0.05 parts of stabilizer mixture. After stirring at 110 to 130 ° C and vacuum dehydration for 1 to 2 hours, after cooling the mixture to 65 to 75 ° C, 15 to 40 parts of isocyanate is added to the mixture under nitrogen, and the reaction is carried out for 30 to 90 minutes. A reactive polyurethane hot melt adhesive is prepared by adding 0.5 to 1 part by weight of a latent curing agent and 0.05 to 0.1 part of a catalyst and stirring it, followed by discharging the sealed package. Method and use of moisture hardening reactive polyurethane hot melt adhesive The present invention provides a method for applying the above hot melt adhesive to a substrate layer, comprising the steps of: i) heating the hot melt adhesive to a molten state And ii) contacting the molten hot melt adhesive with the substrate layer. The term "matrix layer" may be any layer capable of forming an adhesion bond with the polyurethane hot melt adhesive of the present invention, such as a fabric substrate layer, a flake substrate layer, a fibrous substrate layer, a foil substrate layer, a leather layer (preferably a split layer). Leather) or textile layer. The fabric substrate layer may be composed of one or more layers of the same or different sub-layers that are closely interconnected to each other, such as a small hole or large hole woven fabric, a knitted fabric, a braid, a mesh (mesh cloth). The flake substrate layer is a sheet-like structure (examples of felts and webs) composed of randomly placed fibers, which are preferably bonded together by an adhesive. The flake substrate layer is typically a cellulosic flake or textile flake reinforced with a water insoluble impregnant. A fibrous substrate layer is a manufactured article consisting of a plastic-reinforced loosely randomly placed fiber used as a binder by, for example, leather fibers (preferably available from leather waste such as tanned leather). Adhered to the adhesive to obtain. The foil substrate layer comprises a fabricated article of foil (preferably homogenous) of metal or plastic (e.g., rubber, PVC, polyamide, interpolymer, and the like). A foil substrate layer is preferably not incorporated into the fibers. The textile layer can be made from cotton, linen, polyester, polyamide and/or polyurethane. In a preferred embodiment of the invention, the substrate layer is selected from the group consisting of elastic fabrics, knitted fabrics, plain woven fabrics, and water repellent fabrics, shoe substrate layers, or luggage substrate layers. In a preferred embodiment of the invention, the molten hot melt adhesive can be contacted by the release layer or direct coating. The release transfer method means that the molten hot melt adhesive is first applied to the release layer and then to the substrate before the contacting step. Useful release layers include, but are not limited to, layers of metal, plastic, leather, and/or textile materials, such as foil or release paper. The direct coating method means that the molten hot melt adhesive is directly applied to the aforementioned substrate layer. In an embodiment of the invention, the coating step can be accomplished by knife coating or roll coating. In a preferred embodiment of the present invention, the hot melt adhesive is applied to the substrate layer in an amount of 1 to 200 g/m 2 , preferably 5 to 150 g/m 2 , more preferably 10 g/m 2 to 50 g / m 2 .