201037125 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種由聚胺甲酸酯積層體而成之皮革樣 片及其製造方法。 【先前技術】 習知，由聚胺甲酸酯積層體而成之皮革樣片已被泛用於 作爲鞋、衣服、皮包、家具等之表面素材。 如此皮革樣片之代表性構造，可列舉如下之構造：將於 不織布、織布、編布等之纖維質基材中含浸聚胺甲酸酯等 之複合纖維基材作爲基布，在如此之基布表面積層由聚胺 甲酸酯積層體而成之中間層後，在所形成的中間層表面， 進一步形成由聚胺甲酸酯或丙烯酸樹脂等所形成的粒面 層。該中間層係利用下列之方法所形成：將溶劑型聚胺甲 酸酯或水系聚胺甲酸酯塗布於基布表面上之後，進行乾燥 的方法；或藉由接著劑而在基布表面接著預先於脫模紙表 面所成膜的聚胺甲酸酯膜之方法。 然而’近年來爲了使環境負荷減低，於聚胺甲酸酯製品 之生產領域中，正尋求不大量使用有機溶劑之水性聚胺甲 酸酯或使用無溶劑型聚胺甲酸酯之製程。於皮革樣片之製 造中，使用水系聚胺甲酸酯之製程的一部分也已實用化。 然而’基於耐水性或耐久性等變差的觀點或基於乾燥效率 爲低的觀點等，水系聚胺甲酸酯尙未充分取代溶劑型聚胺 甲酸酯。 -4- 201037125 例如’於下列專利文獻1中’揭示一種可減低有機溶劑 之用量的皮革樣片之製造方法，其係使用熱熔融型濕氣硬 化聚胺基甲酸酯的方法。具體而言，於專利文獻1之〔第 3圖〕中’揭示在基板上，利用由熱熔融型濕氣硬化聚胺 基甲酸酯而成之接著劑’接著由熱熔融型濕氣硬化聚胺基 甲酸酯而成之皮膜層的方法。以下，詳細說明此方法。 於第1圖’顯示引用專利文獻1中所揭示的〔第3圖〕 之圖示。第1圖中’ 30係剝離紙（脫模紙）301之導出捲 Ο 軸；36係基材37之導出捲軸；38係製品的皮革樣片之捲 取捲軸；31、32、33a、33b、34、35 係輥；303 及 305 係 爲了分別塗布熱熔融型濕氣硬化聚胺基甲酸酯312、313之 刮刀塗布器；304係水蒸氣噴霧器。 於第1圖中，將被導出捲軸30所捲取的剝離紙301置 於輥3 1、3 2上而進行搬送。然後，利用刮刀塗布器3 〇 3， 藉由在剝離紙3 0 1表面塗布熔融狀態之熱熔融型濕氣硬化 〇 聚胺基甲酸酯312而形成皮膜層。接著，在由熱熔融型濕 氣硬化聚胺基甲酸酯312而成之皮膜層，利用水蒸氣噴霧 器304而噴吹水蒸氣。然後，置於輕33a、33b上而送入輥 34’利用刮刀塗布器305，在由熱熔融型濕氣硬化聚胺基 甲酸酯312而成之皮膜層上，進一步塗布作爲接著劑之熔 融狀態的熱熔融型濕氣硬化聚胺基甲酸酯313。然後，由 導出捲軸36供給基材37,利用輥35，將基材37貼合於熱 熔融型濕氣硬化聚胺基甲酸酯之接著層而製造皮革樣片。 201037125 專利文獻1 :特開2000-54272號公報 使用如專利文獻1所揭示的無溶劑型之熱熔融型 化聚胺基甲酸酯而形成皮膜層或接著劑層之情形下 能夠實現無溶劑化。然而，藉由利用如上述之方法 上連續生產皮革樣片之情形，具有如下之問題： 熱熔融型濕氣硬化聚胺基甲酸酯係藉由進行加 而被塗布於基材上，藉由塗布後予以冷卻至既定溫 固化。藉由具有如此之熱熔融性，發揮優異的塗布作 〇 如第1圖所示之製程中，在脫模紙301表面上’ 狀態下所塗布的熱熔融型濕氣硬化聚胺基甲酸酯3] 之皮膜層係於利用水蒸氣噴霧器304噴吹水蒸氣之 於輥33a、33b上而被導入輥34。於如此之步驟中 噴吹水蒸氣而加速硬化反應。還有，於噴吹水蒸氣之 由於硬化反應並未充分進行，在此表面仍殘存 (tack)。然後，藉由所噴射的水蒸氣等，隨著硬化反 r， 而予以高分子量化，黏著性將被抑制。而且’認爲 硬化反應加速而抑制黏著性，欲確保順利之搬送性 短時間內，硬化反應未完全進行，將殘存某種程度 性。因此，由熱熔融型濕氣硬化聚胺基甲酸酯312 的成膜層與輥33a、33b接觸之情形，由於殘存於熱 濕氣硬化聚胺基甲酸酯312之黏著性，熱熔融型濕 聚胺基甲酸酯312之皮膜層將附著於輥33a、33b之 捲繞於3 3 b之表面，發生妨礙順利搬送之問題。另 濕氣硬 ，確實 ，工業 熱熔融 度而再 f業性。 由熔融 1 2而成 後，置 ，藉由 :隨後， 黏著性 應進行 藉由使 。由於 之黏著 所形成 熔融型 氣硬化 表面而 外，藉 201037125 由使線之輸送速度成爲低速，並使由熱熔融型濕氣硬化聚 胺基甲酸酯3 1 2所形成的皮膜層予以更充分交聯硬化之情 形下，黏著性將某種程度變少，搬送性將有一定程度被改 善。然而此情形下，與由所積層的熱熔融型濕氣硬化聚胺 基甲酸酯313而成之層的接著性將無法充分變高。此係被 認爲由某種程度硬化反應已進行的熱熔融型濕氣硬化聚胺 基甲酸酯而成之表皮層上，欲進一步積層由熱熔融型濕氣 硬化聚胺基甲酸酯而成之中間層的情形下，藉由在表皮層 與中間層之間形成明確之界面，因而界面中之剝離強度將 變低。 如此方式，具有下列問題··使用熱熔融型濕氣硬化型聚 胺基甲酸酯而於工業之製程中連續生產皮革樣片之情形， 藉由輥等所進行的順利搬送將受到阻礙，另外無法使積層 體之接著性變得充分高。 【發明內容】 本發明之目的在於提供一種製造由聚胺甲酸酯積層體 而成之皮革樣片之方法，其係於製造在基布上具有由熱熔 融型濕氣硬化聚胺基甲酸酯而成之表皮層與中間層之皮革 樣片的情形下，步驟通過性良好，且積層部分之剝離強度 高。 本發明之一形態係一種皮革樣片之製造方法，其特徵係 具備：將已加熱熔融之第1熱熔融型濕氣硬化聚胺基甲酸 酯塗布於第1薄片表面的第1塗布步驟；於所塗布的該第 201037125 1熱熔融型濕氣硬化型聚胺基甲酸酯呈熔融或軟化中之狀 態下，將已加熱熔融之第2熱熔融型濕氣硬化型聚胺基甲 酸酯塗布於其表面的第2塗布步驟；及於所塗布的該第2 熱熔融型濕氣硬化型聚胺基甲酸酯呈熔融或軟化中之狀態 下，使第2薄片貼合於其表面的貼合步驟。 另外，本發明之另一形態係一種皮革樣片，其係藉由上 述之製造方法所得到。 本發明之目的、特徵、形態及優點係藉由以下之詳細說 明與附上圖示而變得更明白。 【實施方式】 發明之實施形態 本發明之皮革樣片之製造方法係包含一種聚胺甲酸酯 積層體之製造方法，其係具備：將已加熱熔融之第1熱熔 融型濕氣硬化聚胺基甲酸酯塗布於第1薄片表面的第1塗 布步驟；於所塗布的該第1熱熔融型濕氣硬化型聚胺基甲 酸酯呈熔融或軟化中之狀態下，將已加熱熔融之第2熱熔 融型濕氣硬化型聚胺基甲酸酯塗布於其表面的第2塗布步 驟；及於所塗布的該第2熱熔融型濕氣硬化型聚胺基甲酸 酯呈熔融或軟化中之狀態下，使第2薄片貼合於其表面的 貼合步驟。還有，該第1薄片及第2薄片係將皮革樣片之 製造中所用之基布（基材）或已形成聚胺甲酸酯層之基布 (基材）等使用於任一側之片。另外，也可以將脫模紙或 附脫模紙之聚胺甲酸酯膜等使用於另一側之片。 201037125 以下，一面參照第2圖’一面說明本發明之一實施形態。 第2圖係說明本實施形態之聚胺甲酸酯積層體之製造方 法的示意步驟圖。第2圖中，1係脫模紙、2係第1熱熔融 型濕氣硬化聚胺基甲酸酯、3係第2熱熔融型濕氣硬化型 聚胺基甲酸酯、4係基布。另外，1 1係脫模紙i之導出捲 軸、12係基布4之導出捲軸、13係皮革樣片1〇之捲取捲 軸。另外，2a係刮刀塗布器、3a係輥塗布器、2b與3b係 具備圖示中省略之加熱器的樹脂進料器。刮刀塗布器2a及 輥塗布器3a係在旋轉於第2圖中箭號方向的主輥R的周 圍，順著旋轉方向所配設。另外，已配設用以使由導出捲 軸12所導出的基布4貼合於熱熔融型濕氣硬化聚胺基甲酸 酯2之表面的壓延輥CR。 於第2圖之步驟中，首先從導出捲軸11連續地導出脫 模紙1，藉由旋轉於箭號方向之主輥R而予以搬送之後， 藉由捲取捲軸13予以捲取而形成線。 而且，朝向線上之脫模紙1，被收納於樹脂進料器2b中， 且被加熱熔融的第1熱熔融型濕氣硬化聚胺基甲酸酯2係 一面維持熔融狀態，一面予以流下，藉由刮刀塗布器2a而 在脫模紙1表面塗布成均一之厚度（第1塗布步驟）。 作爲本實施形態所使用的脫模紙1，除了可以使用表面 平滑之脫模紙之外，基於賦予表面圖案設計性之目的’也 可以使用如具有壓紋模樣之脫模紙。 於此，針對本實施形態所使用的熱熔融型濕氣硬化聚胺 201037125 基甲酸酯加以說明。 熱熔融型濕氣硬化聚胺基甲酸酯係以使聚醇與聚異氰 酸酯反應而得到的胺甲酸酯預聚物作爲主要成分所含有的 具備熱熔融性與濕氣硬化性之聚胺甲酸酯形成成分。 熱熔融型濕氣硬化聚胺甲酸酯所具有的熱熔融性係於 常溫下爲固體或是具有塗布爲困難程度之黏稠性的性質， 藉由加熱熔融而成爲可塗布的黏度，並藉由冷卻予以再固 化而發現接著性。如此方式，熱熔融型濕氣硬化聚胺基甲 ^ 酸酯係藉由進行加熱熔融而塗布於基布或脫模紙等，於塗 布後，藉由予以冷卻而再固化。 另一方面，熱熔融型濕氣硬化聚胺基甲酸酯所具有的濕 分（濕氣）硬化性係藉由胺基甲酸酯預聚物中之異氰酸酯 基末端與濕氣（水）進行反應而形成胺基甲酸酯鍵或脲鍵 的硬化反應所得到。另外，熱熔融型濕氣硬化型聚胺基甲 酸酯所具有的硬化性也進一步藉由所形成的胺基甲酸酯鍵 Q 或脲鍵與存在於反應系內反應所進行的交聯反應而得到。 而且，藉由經歷如此之硬化反應與交聯反應，使胺基甲酸 酯預聚物高分子量化而形成具優異的機械特性及耐水性等 之聚胺甲酸酯硬化物。 與短時間所產生的冷卻固化作一對照’熱熔融型濕氣硬 化聚胺基甲酸酯所具有的濕氣硬化反應係較長的時間’具 體而言，例如耗費約2 0〜5 0小時而進行完全硬化。因而’ 進行加熱熔融而塗布之後，冷卻固化之隨後’黏著性仍殘 -10- 201037125 存於表面。然後’藉由於既定之溫度及濕度條件下進行約 20〜50小時之熟成，交聯反應將進行而予以高分子量化。 於是，黏著性將消失。 如上述之熱熔融型濕氣硬化聚胺基甲酸酯中所含之胺 基甲酸酯預聚物能夠使用使聚醇與聚異氰酸酯反應所得到 的胺基甲酸酯預聚物。 例如，該聚醇能夠使用聚酯聚醇、聚醚聚醇、聚碳酸酯 聚醇等，其中，將本發明所得到的皮革樣片使用於鞋用途 之情形下，較佳使用聚醚聚醇、尤以使用聚四伸丁二醇特 別理想。另外，將該皮革樣片使用於汽車座位或家具構件 等之情形下，爲了尋求高耐久性（耐熱性或耐水解性等）， 較佳使用聚碳酸酯聚醇。相對於所使用的聚醇之總量而 言，該聚四伸丁二醇等之聚醚聚醇或聚碳酸酯聚醇較佳使 用40質量％以上。 另外，與該聚醇進行反應的聚異氰酸酯，例如，能夠使 用苯二異氰酸酯、甲苯二異氰酸酯、4，4’-二苯基甲烷二異 氰酸酯、2，4’-二苯基甲烷二異氰酸酯、萘二異氰酸酯、二 甲苯二異氰酸酯等之芳香族二異氰酸酯；伸己基二異氰酸 酯、離胺酸二異氰酸酯、環己烷二異氰酸酯、異佛酮二異 氰酸酯、二環己基甲烷二異氰酸酯、四甲基二甲苯二異氰 酸酯等之脂肪族二異氰酸酯或脂環族二異氰酸酯、4,4’-二 苯基甲烷二異氰酸酯之二聚體及三聚體等之聚二苯基甲烷 二異氰酸酯等。其中，基於防止因光所造成的變黃色之觀 -11- 201037125 點，爲了形成皮革樣片之表皮的熱熔融型濕氣硬化聚胺基 甲酸酯較佳使用具優異耐光性之不變黃色聚胺基甲酸酯的 萘二異氰酸酯、二甲苯二異氰酸酯等之芳香族二異氰酸 酯；伸己基二異氰酸酯、離胺酸二異氰酸酯、環己烷二異 氰酸酯、異佛酮二異氰酸酯、二環己基甲烷二異氰酸酯、 四甲基二甲苯二異氰酸酯。 該胺甲酸酯預聚物之製造，通常能夠於無溶劑下進行， 也可以於有機溶劑中進行製造。於有機溶劑中進行製造之 情形下，能夠使用不阻礙該聚醇與聚胺甲酸酯之反應的醋 酸乙酯、醋酸正丁酯、甲基乙基酮、甲苯等之有機溶劑， 於反應中途或反應結束後，藉由減壓加熱等之方法而去除 有機溶劑爲必要的。 該聚醇與該聚異氰酸酯之反應比例係該聚異氰酸酯中 之異氰酸酯基、與該聚醇中之羥基的當量比〔NCO/OH〕， 較佳爲1.1〜5.0之範圍內，更佳爲1.2〜3.0之範圍內。該 Q 當量比爲1.1以上之情形下，熱熔融型濕氣硬化聚胺基甲 酸酯之濕氣硬化性將變得良好。 熱熔融型濕氣硬化聚胺基甲酸酯中之胺基甲酸酯預聚 物的數量平均分子量較佳爲500〜30000，進一步更佳爲 1 000〜1 000 0之範圍。尤其，第1熱熔融型濕氣硬化聚胺 基甲酸酯中所含之胺基甲酸酯預聚物較佳爲具有5 00〜 5 000範圍之數量平均分子量。基於可容易調整起因於作業 性的熔融黏度之觀點，第2熱熔融型濕氣硬化聚胺基甲酸 -12- 201037125 酯中所含之胺基甲酸酯預聚物較佳爲具有600〜30000範 圍之數量平均分子量。若胺基甲酸酯聚合物之數量平均分 子量爲如此之範圍的話，能夠形成具有優異的柔軟性、機 械強度、耐摩耗性、耐水解性之聚胺甲酸酯層。 熱溶融型濕氣硬化聚胺基甲酸酯之熔融黏度係使用錐 板式黏度計而測出1 2 5 °C下的熔融黏度，第1熱熔融型濕 氣硬化聚胺基甲酸酯及第2熱熔融型濕氣硬化聚胺基甲酸 酯較佳爲皆100〜15000mpa.s之範圍內，進—步更佳爲皆 1000m〜10000 mPa*s之範圍內，由於薄膜方式進行塗布爲 可能而較佳。 通常’本實施形態中之熱熔融型濕氣硬化聚胺基甲酸酯 係使用以胺基甲酸酯預聚物爲主要成分的樹脂成分之外， 也可以使用作爲摻合胺基甲酸酯化觸媒、顏料等之著色 劑、增黏劑、交聯劑、交聯促進劑、抗氧化劑等之添加劑 的樹脂組成物。另外，欲將由熱熔融型濕氣硬化聚胺基甲 酸酯所形成的聚胺甲酸酯層作爲發泡聚胺基甲酸酯層而形 成之情形下，可摻合發泡劑。如此之樹脂組成物能夠於加 熱熔融狀態下而均一混合以胺基甲酸酯預聚物爲主要成分 之樹脂成分與其他之成分而得到。 使熱熔融型濕氣硬化聚胺基甲酸酯加熱熔融而塗布於 脫模紙1表面之塗布機構的具體例，可以使用除了如顯示 於第2圖之刮刀塗布器或輥塗布器之外，例如，可以使用 逆輥塗布器、逆向塗布器、接觸輥塗布器、噴霧塗布器、 -13- 201037125 T -模頭塗布器或刀塗布器（comma coater)等。還有，基 於可控制熱熔融型濕氣硬化聚胺基甲酸酯的熔融黏度之觀 點，於此等之塗布機構中，較佳爲具備加熱手段之塗布機 構。 基於塗裝作業性優異之觀點，塗布時之第1熱熔融型濕 氣硬化聚胺基甲酸酯的熔融黏度較佳爲1000〜15000mPa· s，進一步更佳爲2000〜10000mPa*s之範圍》 由第1熱熔融型濕氣硬化聚胺基甲酸酯所形成的聚胺基 甲酸酯層之厚度，基於可以具優異之柔軟性與機械強度的 皮革樣片之觀點，硬化後之厚度較佳爲5〜800μπι，進一步 更佳爲10〜500μιη之範圍。 接著，在脫模紙1表面所塗布的第1熱熔融型濕氣硬化 聚胺基甲酸酯呈熔融或軟化中之狀態下，將已加熱熔融之 第2熱熔融型濕氣硬化型聚胺基甲酸酯塗布於其表面（第 2塗布步驟）。 已塗布第1熱熔融型濕氣硬化聚胺基甲酸酯2之脫模紙 1係藉由旋轉於箭號方向之主輥R而被搬送至用以塗布第2 熱熔融型濕氣硬化型聚胺基甲酸酯3之輥塗布器3a方向。 然後，在樹脂進料器3 b中所收納的第2熱熔融型濕氣硬化 聚胺基甲酸酯3係藉由刮刀塗布器3a而呈熔融狀態下塗布 成均一之厚度。此時，在脫模紙1表面所塗布的第1熱熔 融型濕氣硬化聚胺基甲酸酯2係被維持於熔融或軟化狀 態。還有，第2熱熔融型濕氣硬化型聚胺基甲酸酯3可以 -14- 201037125 使用相同於上述之第1熱熔融型濕氣硬化聚胺基甲酸酯2 所用之物。 於此，所謂熱熔融型濕氣硬化聚胺基甲酸酯呈熔融或軟 化中之狀態下係意指所加熱熔融的熱熔融型濕氣硬化聚胺 基甲酸酯爲未固化之狀態，具體而言，該熱熔融型濕氣硬 化聚胺基甲酸酯本身保持著流動性之狀態、或該熱熔融型 濕氣硬化聚胺基甲酸酯係藉由外力而保持流動性之狀態， 或是此等熱熔融型濕氣硬化聚胺基甲酸酯至少部分保持著 流動性之狀態。更具體而言，維持著流動性之狀態較佳爲 熔融黏度維持如15〇〇〇mPa*s以下之狀態，進一步更佳爲 維持如l〇〇〇〇mPa*s以下之狀態。 還有，於第2塗布步驟中，第1熱熔融型濕氣硬化聚胺 基甲酸酯之熔融黏度較佳爲較該第2熱熔融型濕氣硬化型 聚胺基甲酸酯之熔融黏度爲高。另外，尤其使第1熱熔融 型濕氣硬化型聚胺基甲酸酯之熔融黏度成爲第2熱熔融型 濕氣硬化型聚胺基甲酸酯之熔融黏度的1.5〜2倍之範圍。 第2熱熔融型濕氣硬化型聚胺基甲酸酯係塗布於由呈熔融 或軟化中之狀態的第1熱熔融型濕氣硬化聚胺基甲酸酯而 成之塗布層。於此情形下，塗布第2熱熔融型濕氣硬化型 聚胺基甲酸酯之際的第1熱熔融型濕氣硬化聚胺基甲酸酯 的熔融黏度過低之情形下，第1熱熔融型濕氣硬化聚胺基 甲酸酯與第2熱熔融型濕氣硬化型聚胺基甲酸酯將摻混， 具有變得無法充分維持2層構造之傾向。基於如此之觀 -15- 201037125 點’於第2塗布步驟中，第1熱熔融型濕氣硬化型聚胺基 甲酸酯之熔融黏度更佳爲第2熱熔融型濕氣硬化型聚胺基 甲酸酯之熔融黏度的1.5〜2倍之範圍。 如此之熔融黏度的調整，例如，能夠進行如下之方式而 進行。 於第2圖中，第1熱熔融型濕氣硬化聚胺基甲酸酯2係 藉由刮刀塗布器2a所塗布，第2熱熔融型濕氣硬化型聚胺 基甲酸酯3係藉由輥塗布器3a所塗布。於此情形下，藉由 省略圖示之加熱器而分別控制刮刀塗布器2a或輥塗布器 3a，能夠控制於第2塗布步驟中之第1熱熔融型濕氣硬化 聚胺基甲酸酯2或第2熱溶融型濕氣硬化型聚胺基甲酸酯 3之熔融黏度。 另外，其他之形態係如第3圖所示，使用具備樹脂供應 部22b及刮刀塗布器22a、樹脂供應部23b及刮刀塗布器 23a所一體化的塗布機構25，相對於主輥R之旋轉方向而 言，將第1濕氣硬化聚胺基甲酸酯2收納於上流側之樹脂 供應部2 2b中；相對於主輥R之旋轉方向而言，將第2濕 氣硬化聚胺基甲酸酯3收納於下流側之樹脂供應部23b 中。此時，第1濕氣硬化聚胺基甲酸酯2係使用熔融黏度 相對較高的濕氣硬化胺甲酸酯；第2濕氣硬化聚胺基甲酸 酯3係使用熔融黏度相對較低的熱熔融型濕氣硬化胺甲酸 酯。如此方式，也可以藉由預先組合熔融黏度不同的熱熔 融型濕氣硬化聚胺基甲酸酯後使用而調整第2塗布步驟中 -16- 201037125 之第1熱熔融型濕氣硬化聚胺基甲酸酯2或第2熱熔融型 濕氣硬化型聚胺基甲酸酯3之熔融黏度。 基於塗布作業性優異之觀點，塗布第2熱熔融型濕氣硬 化型聚胺基甲酸酯之際的熔融黏度較佳爲1〇〇〇〜 1 0000mPa，s之範圍，進一步更佳爲2000〜7000mPa.s之 範圍。 另外’於第2塗布步驟中，第1熱熔融型濕氣硬化聚胺 基甲酸醋之溶融黏度較佳爲1500〜15000mPa.s，進一步更 佳爲 3500〜14000mPa*s。 另外，基於可以得到具優越之柔軟性與機械強度的皮革 樣片之觀點，由第2熱熔融型濕氣硬化型聚胺基甲酸酯所 形成的聚胺甲酸酯層之厚度，硬化後之厚度較佳爲5〜 8 00μιη之範圍’進一步更佳爲10〜 5 00 μιη2範圍。 接著’針對所塗布的第2熱熔融型濕氣硬化型聚胺基甲 酸酯3呈熔融或軟化中之狀態下，使第2薄片之基布4貼 合於其表面的貼合步驟加以說明。 具體而言，從導出捲軸12送出基布4，所塗布的第2熱 熔融型濕氣硬化型聚胺基甲酸酯3呈熔融或軟化中之狀態 下，藉由壓延輥CR而被貼合。 本實施形態所使用的基布4之具體例，例如，可列舉： 在不織布或織布、編布等之一般性皮革樣片所用之纖維基 材；上述纖維基材中含浸溶劑系、水系、乳液系或無溶劑 系的聚胺甲酸酯樹脂、丙烯酸樹脂及丁二烯系樹脂（SBR、 -17- 201037125 NBR、MBR)等之複合纖維基材等。此等纖維基材之中， 基於可以得到具有柔軟觸感與更優異的機械強度的皮革樣 片之觀點，特別適合使用於由極細纖維所形成的不織布中 含浸聚胺甲酸酯樹脂而成的複合纖維基材。不織布可以使 用藉由習知之短纖維織物、紡絲黏合法或溶融流動法等之 習知方法所得到的織物，並無特別限定而可以使用。另外 必要時，也可以於形成織物之後，重疊複數片之織物後， 依照針軋處理等而纏繞所得到的不織布。形成不織布之纖 D 維的具體例，例如，可列舉：聚胺甲酸酯纖維、聚對苯二 甲酸乙二酯（PET)纖維、各種聚醯胺系纖維、聚丙烯酸系 纖維、各種聚烯烴系纖維、聚乙烯醇系纖維等。形成不織 布之纖維係纖維徑較佳爲如0.1〜50μίη、進一步更佳爲如1 〜1 5 μιη之極細纖維。由於如此之極細纖維係剛性爲低的、 柔軟的，基於可以得到具有柔軟觸感的皮革樣片之觀點而 較佳。基於柔軟觸感之皮革樣片可以得到之觀點及步驟通 過性優異之觀點’不織布之基重較佳爲50〜2000g/m2之範 圍，進一步更佳爲100〜1000g/m2之範圍。 此情形下，爲了調整所塗布的第2熱熔融型濕氣硬化型 聚胺基甲酸酯3之熔融或軟化狀態，也可以將加熱型之壓 延輥作爲壓延輥CR使用。 然後，藉由依照壓延輥CR，使基布4貼合於呈熔融或軟 化狀態的第2熱熔融型濕氣硬化型聚胺基甲酸酯3之表面 而形成皮革樣片1 〇。然後，所得到的皮革樣片1 0係於被 -18- 201037125 脫模紙1所覆蓋的狀態下，藉由捲取捲軸13而予以捲取。 然後，藉由既定時間養護所捲取的皮革樣片1 0，第1熱 熔融型濕氣硬化聚胺基甲酸酯2及第2熱熔融型濕氣硬化 型聚胺基甲酸酯3之濕氣硬化反應將進行，熱熔融型濕氣 硬化聚胺基甲酸酯將被高分子量化。 所得到的皮革樣片10之熟成條件較佳以溫度20〜40 °C、相對濕度50〜80%之條件，進行約20〜50小時之熟 成。藉由以如此之熟成條件進行熟成，熱熔融型濕氣硬化 D 聚胺基甲酸酯將進行濕氣硬化及濕氣交聯。藉此，將可以 得到具優異之機械強度或耐水性的皮革樣片。還有，皮革 樣片係剝離表面所被覆的脫模紙之皮革樣片。 關於第1熱熔融型濕氣硬化聚胺基甲酸之塗布口與第2 熱熔融型濕氣硬化聚胺基甲酸之塗布口的位置（例如，顯 示於第3圖之2個刮刀塗布器22a與23a的距離），只要 能夠於所塗布的該第1熱熔融型濕氣硬化聚胺基甲酸酯呈 q 熔融或軟化中之狀態下，將已加熱熔融之第2熱熔融型濕 氣硬化型聚胺基甲酸酯塗布於其表面即可，並未予以特別 限定，基於能夠穩定維持該第1熱熔融型濕氣硬化聚胺基 甲酸酯呈熔融或軟化中之狀態的觀點，較佳爲lm以內，更 佳爲50cm以內。 以上’於如所說明的步驟中，第1熱熔融型濕氣硬化聚 胺基甲酸酯2被塗布於脫模紙1表面之後、進行再固化之 前’第2熱熔融型濕氣硬化型聚胺基甲酸酯3係呈加熱熔 -19- 201037125 融狀態下被塗布。因而’在由第1熱熔融型濕氣硬化聚胺 基甲酸酯2所形成的聚胺甲酸酯層與由第2熱熔融型濕氣 硬化聚胺基甲酸酯3所形成的聚胺甲酸酯層之界面相互進 行交聯’在界面上之剝離強度將變高。另外，熔融或軟化 之狀態的第1熱溶融型濕氣硬化聚胺基甲酸酯2並未充分 進行硬化反應。因此，在第1熱熔融型濕氣硬化聚胺基甲 酸酯2與第2熱熔融型濕氣硬化型聚胺基甲酸酯3在此等 之界面上’能夠形成充分之交聯構造，或是使此等之層界 面成爲不明確。 將經由如此之步驟所得到的皮革樣片1 〇之剖面示意圖 顯示於第4圖。 如第4圖所示，皮革樣片1 0係藉由剝離在表面所被覆 的脫模紙1而完成。於如此之皮革樣片10中，由於在由第 1熱熔融型濕氣硬化聚胺基甲酸酯2所形成的第1胺基甲 酸酯層與由第2熱熔融型濕氣硬化型聚胺基甲酸酯3所形 成的第2胺基甲酸酯層之界面上形成交聯構造，因此第1 胺基甲酸酯層與第2胺基甲酸酯層之接著力將充分提高。 還有，於本實施形態中，從導出捲軸1 1，將脫模紙1作 爲第1薄片而導出，從導出捲軸12，將基布4作爲第2薄 片而導出，也可以更換供應脫模紙1與供應基布4之順序， 從導出捲軸11，將基布4作爲第1薄片而導出，從導出捲 軸12，將脫模紙1作爲第2薄片而導出。但是，此情形係 具有變更所使用的熱熔融型濕氣硬化聚胺基甲酸酯之組合 -20- 201037125 的必要。 以上雖例示有關本發明之製造方法之一例 不受如上所述之製程所限制，於皮革樣片之 之製程並無特別之限定而能夠適用：於將熱 化聚胺基甲酸酯塗布於基布或脫模紙之後， 濕氣硬化聚胺基甲酸酯呈熔融或軟化中之狀 熱熔融狀態之第2熱熔融型濕氣硬化型聚胺 進行如此方式所得到的皮革樣片係由第1 v 硬化聚胺基甲酸酯2所形成的聚胺甲酸酯層 融型濕氣硬化聚胺基甲酸酯3所形成的第2 能夠維持高的緊貼性。因此，於所得到的皮 有皺褶細且均一性之外觀性或觸感將提高。 還有，對於所得到的皮革樣片，進一步藉 爲了賦予表面圖案設計性，也可以將溶劑系 系或無溶劑系之聚胺甲酸酯樹脂或丙烯酸 Q 部’或是適當進行拋光加工或壓紋加工等之 進行如此方式所得到的皮革樣片可適^ 鞋、衣服、皮包、家具等之表面素材的皮革 實施例 以下’藉由實施例更具體說明本發明，但 受實施例所任意限定。 首先’針對本實施例中之熔融黏度之測 明。 ，但本發明並 製造中，如下 熔融型濕氣硬 第1熱熔融型 態下，塗布加 基甲酸酯。 熱熔融型濕氣 與由第2熱熔 聚胺甲酸酯層 革樣片中，具 由習用方法， 、水系、乳液 樹脂塗布表層 後加工。 甲於作爲形成 樣片。 是本發明並不 定方法加以說 -21- 201037125 各熱熔融型濕氣硬化聚胺基甲酸酯的熔融黏度（mPa*s) 係使用錐板式黏度計（ICI公司製），將錐板之溫度設定成 既定之溫度而測定。還有，第2塗布步驟中之第2熱熔融 型濕氣硬化型聚胺基甲酸酯的熔融黏度係定義爲第2塗布 步驟的塗布溫度（刮刀塗布器溫度）中之第2熱熔融型濕 氣硬化型聚胺基甲酸酯的熔融黏度。再者，第2塗布步驟 中之第1熱熔融型濕氣硬化型聚胺基甲酸酯的熔融黏度係 設爲測定即將塗布第2熱熔融型濕氣硬化型聚胺基甲酸酯 〇 v 之前所塗布的第1熱熔融型濕氣硬化聚胺基甲酸酯之表面 溫度，此溫度中之熔融黏度。 另外，以下彙整本實施例所用之原材料而加以說明。 <基布> 由平均纖度〇.〇7Dtex之極細纖維而成之纏繞不織布中 含浸水溶性聚胺甲酸酯（DIC (股）公司製 HYDRAN WLS612)。得到厚度 1mm、基重 550g/m2、比重 0.55g/cm3 Q 之基布。 <熱熔融型濕氣硬化型聚胺基甲酸酯A> 於 120 °C，熔融混合 TYFORCE EXP-BH50(DIC (股） 製之熱熔融型濕氣硬化聚胺基甲酸酯）100質量份、顏料 (POLYTON PU-9382 BLACK、DIC (股）製、以下相同） 15質量份。藉此’得到120°C下的熔融黏度爲2780mPa.s 之熱熔融型濕氣硬化聚胺基甲酸酯A。 <熱熔融型濕氣硬化型聚胺基甲酸酯B> -22- 201037125 於 125°C，熔融混合 TYFORCE ΚΜΜ-100 ( DIC (股）製 之熱熔融型濕氣硬化聚胺基甲酸酯）100質量份、顏料15 質量份。藉此，得到120°C下的熔融黏度爲3 200mPa 之 熱熔融型濕氣硬化聚胺基甲酸酯Β。 <熱熔融型濕氣硬化型聚胺基甲酸酯C> 於 135°C，熔融混合 TYFORCEKMM-100(DIC (股）製 之熱熔融型濕氣硬化聚胺基甲酸酯）100質量份、顏料15 質量份、發泡劑2質量份。藉此，得到1 20 °C下的熔融黏 度爲3 200mPa 1之發泡型熱熔融型濕氣硬化聚胺基甲酸酯 C。還有，發泡劑係使用乙二醇（EG) /水/POLYCAT-8〔 Air ProductsJapan公司製、N，N-二甲基環己基胺（DMCHA)〕 =0.5/0.05/0.1 (質量份）之組成物。 <脫模紙> LINTEC (股）製之具皺褶的脫模紙R-8。 〔實施例1〕 使用如第2圖所示之製造程序而製造皮革樣片。 具體而言，第1薄片首先以lm/分鐘之速度而從導出捲 軸11連續導出脫模紙1，藉由於箭號方向旋轉的主輥R進 行搬送，藉由捲取捲軸13捲取而形成線。此時，主輥R之 表面溫度係成爲50°C之方式來控制。然後，朝向線上之脫 模紙’第1熱熔融型濕氣硬化聚胺基甲酸酯2係在ll〇°C 下、熔融樹脂進料器2b中所收納的熱熔融型濕氣硬化聚胺 基甲酸酯A的狀態下流下，藉由刮刀塗布器2a而以均一厚 -23- 201037125 度塗布於脫模紙1表面（第1塗布步驟）。還有’刮刀塗 布器2a之表面溫度係藉由省略圖示之加熱器而控制於110 。(：。已將此時之刮刀塗布器2a與脫模紙之間隔調整至 ' 5 0 μηι ° 接著，在脫模紙1表面所塗布的熱熔融型濕氣硬化聚胺 基甲酸酯Α呈熔融之狀態下，第2熱熔融型濕氣硬化型聚 胺基甲酸酯3係將在135。(：下予以熔融的熱熔融型濕氣硬 化聚胺基甲酸酯C塗布於其表面（第2塗布步驟）。此時’ 〇 輥塗布器3a之表面溫度係藉由省略圖示之加熱器而成爲 1 3 5 °C之方式來加以控制。此時之刮刀塗布器3 a與脫模紙 之間隔係成爲250μιη之方式來加以調整。於此第2塗布步 驟中，所塗布的熱熔融型濕氣硬化聚胺基甲酸酯Α之表面 溫度係約120°C，此時之熔融黏度約爲5000mPa.s。另外， 熱熔融型濕氣硬化聚胺基甲酸酯C之於135 °C下的熔融黏 度約爲2500mPa*s。因而，第2塗布步驟中之熱熔融型濕 Q 氣硬化聚胺基甲酸酯A的熔融黏度係熱熔融型濕氣硬化聚 胺基甲酸酯C的熔融黏度之約2倍。 接著，所塗布的熱熔融型濕氣硬化聚胺基甲酸醋C呈熔 融中之狀態下，將第2薄片之基布4貼合於其表面（貼合 步驟）。具體而言，從導出捲軸12導出基布4,熱熔融型 濕氣硬化聚胺基甲酸酯C呈熔融中之狀態下，藉由壓延輕 CR而貼合。還有’壓延輥CR之表面溫度係藉由省略圖示 之加熱器而被控制於5(TC。進行如此方式，形成具有如第 -24- 201037125 4圖所示之層構造的皮革樣片1 〇。然後，所得到的皮革樣 片係於被脫模紙所被覆的狀態下，藉由捲取捲軸13而被捲 取。 然後，於所捲取的狀態下，以溫度40°C、相對濕度6〇 %之條件，進行皮革樣片10之35小時熟成。熟成後，僅 既定之面積切斷所得到的皮革樣片10,剝離脫模紙，藉由 以下之方法而評估層間接著性。 π (層間接著性） 〇 在脫模紙被剝離的皮革樣片之第2聚胺基甲酸酯層的表 面，於130°C，進行5秒鐘之布熱熔融膠帶〔商標：Melco Tape、Sun化成（股）製〕的熱壓黏之後，以20 0mm/分鐘 之頭端速度，依據JISK6854-2，使用TENSIRON(島津製 作所製）而測定剝離強度。另外，確認此時之剝離部分的 位置。 其結果，所得到的皮革樣片的剝離強度係 Ο 1 1 .〇kg/25mm，在基布4層內進行內部剝離。 〔實施例2〕 除了使用塗布機構不同的如第3圖所示之製造程序，再 者，第1熱熔融型濕氣硬化聚胺基甲酸酯2係使用熱熔融 型濕氣硬化聚胺基甲酸酯B以外，進行相同於實施例1之 方式而製造皮革樣片。 具體而言，如第3圖所示，使用具備收納二個刮刀塗布 器22a、23a與熱熔融型濕氣硬化聚胺基甲酸酯的二個樹脂 -25- 201037125 供應部22b、23b之所一體化的塗布機構25。然後，在樹脂 進料器22b中，第1熱熔融型濕氣硬化聚胺基甲酸酯2係 收納熱熔融型濕氣硬化聚胺基甲酸酯B;在樹脂進料器2 3b 中，第2熱熔融型濕氣硬化聚胺基甲酸酯3係收納熱熔融 型濕氣硬化聚胺基甲酸酯C。 然後，從導出捲軸11，第1薄片係以lm/分鐘之速度連 續導出脫模紙1，藉由旋轉於箭號方向之主輥R而進行搬 送，藉由捲取捲軸13捲取而形成線。此時，主輥R之表面 〇 溫度係成爲50°c之方式來控制。然後，朝向線上之脫模紙 1，在熔融樹脂進料器2 2b中所收納的熱熔融型濕氣硬化聚 胺基甲酸酯B的狀態下流下，藉由刮刀塗布器22a而以均 一厚度塗布於脫模紙1表面（第1塗布步驟）。於其後， 隨即於熔融樹脂進料器2 3 b中所收納的熱熔融型濕氣硬化 聚胺基甲酸酯C的狀態下流下，藉由刮刀塗布器23a而以 均一厚度塗布（第2塗布步驟）。還有，刮刀塗布器22a Q 與脫模紙表面之間隔已調整至5 0 μπι，刮刀塗布器2 3 a與脫 模紙表面之間隔已調整至250μιη。刮刀塗布器22a及樹脂 供應部22b係被控制至1 l〇°c ;刮刀塗布器23a及樹脂供應 部2 3b係被控制至120 °C。於第2塗布步驟中，在第1塗布 步驟所塗布的熱熔融型濕氣硬化聚胺基甲酸酯B之表面溫 度約爲110°C，此時之熔融黏度約爲5000mPa.s。另外， 熱熔融型濕氣硬化聚胺基甲酸酯之12(TC下的熔融黏度約 爲3200 mPa.s。因而，第2塗布步驟中之熱熔融型濕氣硬 -26- 201037125 化聚胺基甲酸酯B的熔融黏度係熱熔融型濕氣硬化聚胺基 甲酸酯C的熔融黏度之約1.6倍。 以後之步驟係進行相同於實施例1之方式而製造皮革樣 片。其結果，所得到的皮革樣片的剝離強度係 10.2kg/25mm，在基布4層內已內部剝離。 〔實施例3〕 除了於第1塗布步驟中’在100°C熔融熱熔融型濕氣硬 化聚胺基甲酸酯A的狀態下流下，於第2塗布步驟中，在 140 °C熔融熱熔融型濕氣硬化聚胺基甲酸酯C的狀態下流 下以外，進行相同於實施例1之方式而製造皮革樣片。此 時，輥塗布器3a之表面溫度係藉由省略圖示之加熱器而被 控制成爲1 4 0 °C之方式來加以控制。此時，於第2塗布步 驟中，第1塗布步驟所塗布的熱熔融型濕氣硬化聚胺基甲 酸酯A之熔融黏度約成爲6500 mPa.s，熱熔融型濕氣硬化 聚胺基甲酸酯C之熔融黏度約爲i8〇〇mPa.s。因而，第2 塗布步驟中之熱熔融型濕氣硬化聚胺基甲酸酯A的熔融黏 度係熱熔融型濕氣硬化聚胺基甲酸酯C的熔融黏度之約 3 · 6倍。於所得到的皮革樣片之剝離強度測定中，主要在基 布4層內進行內部剝離，即使稍微在聚胺甲酸酯層彼此之 界面也觀察到剝離，剝離強度係高達1 0 · 1 kg/2 5 mm。 〔實施例4〕 除了於第1塗布步驟中，在120 °C熔融熱熔融型濕氣硬 化聚胺基甲酸酯A的狀態下流下，於第2塗布步驟中，在 -27- 201037125 1 1 5 °C熔融熱熔融型濕氣硬化聚胺基甲酸酯C的狀態下流 下以外，進行相同於實施例1之方式而製造皮革樣片。此 時’輥塗布器3a之表面溫度係藉由圖示中省略之加熱器而 被控制成爲115 °C之方式來加以控制。此時，於第2塗布 步驟中，第1塗布步驟所塗布的熱熔融型濕氣硬化聚胺基 甲酸酯A之熔融黏度約成爲2700 mPa.s，熱熔融型濕氣硬 化聚胺基甲酸酯C之熔融黏度約爲4000mPa.s。因而，第 2塗布步驟中之熱熔融型濕氣硬化聚胺基甲酸酯A的熔融 黏度係熱熔融型濕氣硬化聚胺基甲酸酯C的熔融黏度之約 0.7倍。所得到的皮革樣片的剝離強度係10.6kg/25 mm，在 基布4層內已內部剝離。還有，由熱熔融型濕氣硬化聚胺 基甲酸酯A所形成的聚胺甲酸酯層與由熱熔融型濕氣硬化 聚胺基甲酸酯C所形成的聚胺甲酸酯層係存在部分混合之 部分。 〔比較例1〕 使用如第1圖所示之製程而製造皮革樣片。 具體而言，如第1圖所示，從導出捲軸30而朝向捲取 捲軸3 8，以1 m/分鐘之速度導出而形成線。然後，將被導 出捲軸30所捲取的脫模紙1置於輥31、32上而搬送。然 後，第1熱熔融型濕氣硬化聚胺基甲酸酯312係藉由利用 刮刀塗布器303，將12CTC所加熱熔融的熱熔融型濕氣硬化 聚胺基甲酸酯A塗布於剝離紙表面而形成皮膜層。此時， 將塗布厚度成爲50μιη之方式來調整。接著，利用水蒸氣 -28- 201037125 噴霧器3 04’將水蒸氣噴吹於由熱熔融型濕氣硬化聚胺基 甲酸酯A而成之皮膜層表面。然後，置於輥33a、33b上而 送入輥34’第2熱熔融型濕氣硬化聚胺基甲酸酯313係利 用刮刀塗布器3 05’將塗布厚度成爲200 μηι之方式來加以 調整而塗布以1 20 °C所加熱熔融的熱熔融型濕氣硬化聚胺 基甲酸酯C。然後，從導出捲軸36供應基布37，利用輥 35，將基布貼合於熱熔融型濕氣硬化聚胺基甲酸酯C而製 造皮革樣片。 於上述步驟中，第1熱熔融型濕氣硬化聚胺基甲酸酯2 之黏著性部分殘留於表面。因此，對於顯示於第1圖之輥 33a、33b而捲繞積層中間體，步驟通過性將發生問題。 〔比較例2〕 除了藉由以0.5m/分鐘之速度導出脫模紙1以取代i.0m/ 分鐘之速度導出，使線速度降低以外，進行相同於比較例 1之方式而製造、評估皮革樣片，藉由使線速度降低，表 面黏著性某種程度被抑制，連生產性也被改善。 以溫度40 °C、相對濕度60%之條件，進行所得到的皮 革樣片之3 5小時熟成。於熟成後，僅既定面積切斷所得到 的皮革樣片’剝離脫模紙，藉由相同於實施例1之方法而 評估層間接著性。其結果，皮革樣片的剝離強度係 6.5kg/25mm，由熱熔融型濕氣硬化聚胺基甲酸酯a而成之 層與由熱熔融型濕氣硬化聚胺基甲酸酯B而成之層的界面 已界面剝離。 -29- 201037125 如以上之實施例結果所示，有關本發明申請案之實施例 1〜4所得到的皮革樣片，無論任一種剝離強度皆高。另外， 於實施例1〜2、4中，在聚胺甲酸酯層彼此之界面，完全 未觀察到剝離。認爲此係藉由以熔融狀態而積層2種熱熔 融型濕氣硬化聚胺基甲酸酯，界面變得不明確，另外，由 於在界面上充分形成交聯構造所致。還有，於實施例3中， 雖然在由熱熔融型濕氣硬化聚胺基甲酸酯A所形成的聚胺 甲酸酯層與由熱熔融型濕氣硬化聚胺基甲酸酯C所形成的 f) I 聚胺甲酸酯層的界面，觀察到部分些微之剝離，但是剝離 強度係充分的高。 另一方面，如比較例1所示，塗布熱熔融型濕氣硬化聚 胺基甲酸酯A而予以再固化之時，殘留黏著性之情形下， 步驟通過性不佳，連續生產係困難的。另外，如比較例2 所示，塗布熱熔融型濕氣硬化聚胺基甲酸酯A，利用使黏 著性消除之程度進行固化般之低速的線而生產之情形下， Q 剝離強度顯著降低。認爲此係由於2層之聚胺甲酸酯層中 之界面變得明確，另外，2層間未形成充分之交聯構造所 致。 如以上所說明’本發明之一形態係一種皮革樣片之製造 方法’其係具備：將已加熱熔融之第1熱熔融型濕氣硬化 聚胺基甲酸酯塗布於第1薄片表面的第1塗布步驟；於所 塗布的該第1熱熔融型濕氣硬化型聚胺基甲酸酯呈熔融或 軟化中之狀態下’將已加熱熔融之第2熱熔融型濕氣硬化 -30- 201037125 型聚胺基甲酸酯塗布於其表面的第2塗布步驟；及於所塗 布的該第2熱熔融型濕氣硬化型聚胺基甲酸酯呈熔融或軟 化中之狀態下，使第2薄片貼合於其表面的貼合步驟。 若根據如此之製造方法，藉由形成第1熱熔融型濕氣硬 化聚胺基甲酸酯與第2熱熔融型濕氣硬化型聚胺基甲酸酯 相互交聯的界面，界面上之剝離強度將變高。再者，因爲 難以形成由上述之習知製造方法所形成的明確界面而使界 面變得不明確，使界面上之剝離強度變得更高。另外，熔 融或軟化之狀態的第1熱熔融型濕氣硬化聚胺基甲酸酯係 由於在硬化反應充分進行之前，已塗布該第2熱熔融型濕 氣硬化型聚胺基甲酸酯，能夠於該第1熱熔融型濕氣硬化 聚胺基甲酸酯所形成的層與該第2熱熔融型濕氣硬化型聚 胺基甲酸酯所形成的層之間形成充分交聯之構造。再者， 於進行連續生產之際’由於由第1熱熔融型濕氣硬化聚胺 基甲酸酯而成之層與由該第2熱熔融型濕氣硬化型聚胺基 甲酸酯而成之層係表面分別被第1薄片及第2薄片所覆 蓋，起因於未硬化之熱熔融型濕氣硬化聚胺基甲酸酯的黏 著性並未出現。因此，也具優異之步驟通過性。 另外，於該第2塗布步驟中，該第1熱熔融型濕氣硬化 聚胺基甲酸酯的熔融黏度較該第2熱熔融型濕氣硬化型聚 胺基甲酸酯的熔融黏度爲高，再者，該第1熱熔融型濕氣 硬化聚胺基甲酸酯的熔融黏度較佳爲該第2熱熔融型濕氣 硬化型聚胺基甲酸酯的熔融黏度之1.5〜2倍。塗布第2熱 -31 - 201037125 熔融型濕氣硬化型聚胺基甲酸酯之際的第1熱熔融型濕氣 硬化聚胺基甲酸酯的熔融黏度過低之情形下，先前所塗布 的第1熱熔融型濕氣硬化聚胺基甲酸酯層與所新塗布的第 2熱熔融型濕氣硬化聚胺基甲酸酯將混合，具有無法充分 維持各層特性之傾向。 另外’該第1熱熔融型濕氣硬化聚胺基甲酸酯及/或該 第2熱熔融型濕氣硬化型聚胺基甲酸酯含有發泡劑之情形 下’能夠容易形成具有如作爲中間層所用之彈性的聚胺甲 酸酯層。 另外’藉由上述任一種製造方法所得到的皮革樣片係由 第1熱熔融型濕氣硬化聚胺基甲酸酯所形成的第1聚胺基 甲酸酯層與由第2熱熔融型濕氣硬化聚胺基甲酸酯所形成 的第2聚胺基甲酸酯層能夠維持高的緊貼性與一體感。因 此’所得到的皮革樣片係皺褶爲細的，具優異的均一性之 外觀性或觸感等。 [產業上利用之可能性] 若根據本發明，提供一種皮革樣片之製造方法，其能夠 充分提高由熱熔融型濕氣硬化聚胺基甲酸酯所形成的2層 聚胺甲酸酯積層部分的界面剝離強度。 【圖式簡單說明】 第1圖係引用專利文獻1所揭示的〔第3圖〕之圖示。 第2圖係說明第1實施形態皮革樣片之製造方法的示意 步驟圖。 -32- 201037125 第3圖係說明第1實施形態變形例之製造方法的示意步 驟圖。 第4圖係藉由第1實施形態之步驟所得到的皮革樣片的 剖面示意圖。 【主要元件符號說明】 1 2 2 a 2b 3 3 a 3b 4 10 11 12 13201037125 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a leather sample obtained from a polyurethane laminate and a method for producing the same. [Prior Art] It is known that a leather plaque made of a polyurethane laminate has been widely used as a surface material for shoes, clothes, purses, furniture, and the like. The representative structure of the leather swatches is a structure in which a composite fiber base material such as a polyurethane substrate such as a nonwoven fabric, a woven fabric, or a knitted fabric is impregnated with a polyurethane or the like as a base fabric. After the cloth surface area layer is formed of an intermediate layer of a polyurethane laminate, a grain surface layer formed of a polyurethane or an acrylic resin is further formed on the surface of the formed intermediate layer. The intermediate layer is formed by applying a solvent-type polyurethane or an aqueous polyurethane to the surface of the base fabric, followed by drying; or by adhering to the surface of the base fabric by an adhesive A method of forming a polyurethane film on the surface of a release paper in advance. However, in recent years, in order to reduce environmental load, in the field of production of polyurethane products, an aqueous polyurethane which does not use an organic solvent in a large amount or a process using a solventless polyurethane has been sought. In the manufacture of leather swatches, a part of the process using aqueous polyurethanes has also been put into practical use. However, based on the viewpoint of deterioration in water resistance, durability, etc., or based on the viewpoint that the drying efficiency is low, the aqueous polyurethane oxime does not sufficiently replace the solvent-type polyurethane. -4-201037125 For example, 'the following Patent Document 1' discloses a method for producing a leather plaque which can reduce the amount of the organic solvent, which is a method of using a hot-melt type moisture-hardening urethane. Specifically, in [Fig. 3] of Patent Document 1, 'disclosed is an adhesive using a hot-melt type moisture-cured polyurethane on a substrate, followed by a hot-melt type moisture-cured polymerization. A method of forming a film layer of a urethane. Hereinafter, this method will be described in detail. The illustration of [Fig. 3] disclosed in Patent Document 1 is shown in Fig. 1'. In Fig. 1, the derivation roll of the 30-series release paper (release paper) 301; the take-up reel of the 36-series substrate 37; the take-up reel of the leather sample of the 38-series product; 31, 32, 33a, 33b, 34 35 series rolls; 303 and 305 are blade applicators for applying hot-melt type moisture-cured polyurethanes 312 and 313, respectively; 304-type steam sprayers. In Fig. 1, the release paper 301 taken up by the take-up reel 30 is placed on the rolls 3 1 and 32 and transported. Then, a film layer is formed by applying a hot-melt type moisture-curing 〇 polyurethane 312 in a molten state to the surface of the release paper 301 by a doctor blade applicator 3 〇 3 . Next, the water vapor is sprayed by the steam atomizer 304 on the film layer formed by the hot-melt type moisture-curing polyurethane 312. Then, it is placed on the light 33a, 33b, and the feeding roller 34' is further coated with a melt as a binder on the film layer formed by the hot-melt type moisture-curable polyurethane 312 by the blade coater 305. The state of the hot-melt type moisture-cured polyurethane 313. Then, the base material 37 is supplied from the take-up reel 36, and the base material 37 is bonded to the adhesive layer of the hot-melt type moisture-cured polyurethane by the roll 35 to produce a leather sample. In the case of forming a film layer or an adhesive layer by using a solventless hot melt-type polyurethane as disclosed in Patent Document 1, it is possible to achieve solventlessness. . However, by continuously producing a leather swatch by the above method, there is a problem that the hot-melt type moisture-cured polyurethane is applied to a substrate by being applied by coating. It is then cooled to a predetermined temperature for curing. By having such a thermal meltability, an excellent coating is exerted, as in the process shown in Fig. 1, a hot-melt type moisture-cured polyurethane coated on the surface of the release paper 301 3] The film layer is introduced into the roll 34 by blowing water vapor onto the rolls 33a and 33b by the steam atomizer 304. In such a step, water vapor is sprayed to accelerate the hardening reaction. Further, since the hardening reaction does not sufficiently proceed in the spraying of the water vapor, the surface remains on the surface. Then, by the water vapor to be sprayed or the like, the polymer is quantified as the hardening reverse r, and the adhesion is suppressed. Further, it is considered that the hardening reaction is accelerated and the adhesion is suppressed, and in order to ensure smooth transportability, the hardening reaction does not proceed completely in a short period of time, and a certain degree remains. Therefore, when the film-forming layer of the hot-melt type moisture-cured polyurethane 312 is in contact with the rolls 33a and 33b, the heat-melt type is retained due to the adhesion of the heat-moisture-hardening polyurethane 312. The film layer of the wet polyurethane 312 adheres to the surface of the roller 33a, 33b wound around the 3 3 b, and the problem of hindering smooth conveyance occurs. Another moisture is hard, indeed, industrial thermal melting and then industry. After melting by 1 2, set, by: then, adhesion should be made by making. Since the adhesion forms a molten gas-hardened surface, by 201037125, the conveying speed of the wire is made low, and the film layer formed by the hot-melt moisture-curing polyurethane 3 1 2 is more fully utilized. In the case of cross-linking hardening, the adhesion is reduced to a certain extent, and the conveyability is improved to some extent. However, in this case, the adhesion to the layer formed by the heat-melting type moisture-curable polyurethane 313 which is laminated may not be sufficiently high. This is considered to be formed by a hot-melt type moisture-cured polyurethane which has been hardened by a certain degree of hardening reaction, and is further laminated with a hot-melt type moisture-cured polyurethane. In the case of the intermediate layer, by forming a clear interface between the skin layer and the intermediate layer, the peel strength in the interface will become low. In this way, there is a problem that the use of the hot-melt type moisture-curable polyurethane to continuously produce a leather sample in an industrial process, the smooth transfer by a roll or the like is hindered, and the The adhesion of the laminate is sufficiently high. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a leather plaque formed from a polyurethane laminate, which is manufactured by using a hot-melt type moisture-cured polyurethane on a base fabric. In the case of the leather sheet of the skin layer and the intermediate layer, the step passability is good, and the peel strength of the laminate portion is high. One aspect of the present invention provides a method for producing a leather sample, comprising: a first coating step of applying a first hot-melt type moisture-cured polyurethane which is heated and melted to a surface of a first sheet; The coated first hot melt type moisture-curable polyurethane is coated in the molten or softened state, and the second hot-melt type moisture-curable polyurethane coated and heated is coated. a second coating step on the surface thereof; and a paste in which the second sheet is bonded to the surface in a state in which the second hot-melt moisture-curable polyurethane is applied in a state of being melted or softened. Step by step. Further, another aspect of the present invention is a leather plaque obtained by the above-described production method. The objects, features, aspects and advantages of the present invention will become more apparent from [Embodiment] The method for producing a leather sample of the present invention includes a method for producing a polyurethane laminate, comprising: a first hot-melt type moisture-cured polyamine group which has been heated and melted a first coating step of applying a formate to the surface of the first sheet; and heating and melting the first hot-melt moisture-curable polyurethane to be applied in a state of being melted or softened 2 a second coating step of applying a hot-melt type moisture-curable polyurethane to the surface thereof; and melting or softening the second hot-melt type moisture-curable polyurethane coated In the state of bonding, the second sheet is bonded to the surface thereof. In addition, the first sheet and the second sheet are sheets used on either side of a base fabric (base material) used for the production of a leather sample sheet or a base fabric (base material) having a polyurethane layer formed thereon. . Further, a release paper or a polyurethane film to which release paper is attached may be used for the other side. 201037125 Hereinafter, an embodiment of the present invention will be described with reference to Fig. 2'. Fig. 2 is a schematic flow chart showing a method of producing the polyurethane laminate of the present embodiment. In Fig. 2, 1 type release paper, 2 types of first hot-melt type moisture-cured polyurethane, 3 types of 2nd hot-melt type moisture-curable polyurethane, and 4 type base fabric . Further, the 1 1 is a take-up reel of the release paper i, a take-up reel of the 12-series base fabric 4, and a take-up reel of the 13-series leather swatch. Further, the 2a-type blade coater, the 3a-type roll coater, and 2b and 3b are resin feeders having heaters omitted from the drawings. The blade coater 2a and the roll coater 3a are arranged around the main roll R in the direction of the arrow in Fig. 2, and are arranged in the direction of rotation. Further, a calender roll CR for bonding the base fabric 4 led out from the take-up reel 12 to the surface of the hot-melt type moisture-curable polyurethane 2 has been disposed. In the step of Fig. 2, first, the release paper 1 is continuously ejected from the take-up reel 11, and is conveyed by being rotated by the main roll R in the direction of the arrow, and then wound up by the take-up reel 13 to form a line. In addition, the release paper 1 facing the line is stored in the resin feeder 2b, and the first hot-melt type moisture-cured polyurethane 2 which is heated and melted flows while being maintained in a molten state. The surface of the release paper 1 is applied to a uniform thickness by the blade coater 2a (first coating step). As the release paper 1 used in the present embodiment, in addition to the release paper having a smooth surface, it is also possible to use a release paper such as an embossed pattern for the purpose of imparting design to the surface pattern. Here, the hot-melt type moisture-curing polyamine 201037125 carboxylic acid ester used in the present embodiment will be described. The hot-melt type moisture-cured polyurethane is a thermomelt and moisture-curable polyamine contained in a urethane prepolymer obtained by reacting a polyhydric alcohol with a polyisocyanate as a main component. The acid ester forms a component. The hot-melt moisture-curing polyurethane has a hot melt property which is solid at normal temperature or has a viscosity which is difficult to apply, and becomes a coatable viscosity by heating and melting. Cooling was re-cured to find adhesion. In this manner, the hot-melt moisture-curing polyaminomethane ester is applied to a base fabric, release paper, or the like by heat fusion, and after refining, it is re-solidified by cooling. On the other hand, the moisture (moisture) hardening property of the hot-melt type moisture-cured polyurethane is carried out by the isocyanate terminal and the moisture (water) in the urethane prepolymer. It is obtained by a hardening reaction which forms a urethane bond or a urea bond by reaction. Further, the hardenability of the hot-melt type moisture-curable polyurethane is further cross-linked by the reaction of the formed urethane bond Q or urea bond with the reaction system. And get it. Further, by undergoing such a hardening reaction and a crosslinking reaction, the urethane prepolymer is polymerized to form a cured polyurethane cured product having excellent mechanical properties and water resistance. In contrast to the cooling and solidification produced in a short period of time, the hot-melt moisture-curing polyurethane has a moisture-hardening reaction system for a long period of time. Specifically, for example, it takes about 20 to 50 hours. And it is completely hardened. Therefore, after heat-melting and coating, the subsequent solidification of the curing is still -10- 201037125 on the surface. Then, by performing the aging for about 20 to 50 hours under the predetermined temperature and humidity conditions, the crosslinking reaction proceeds and is highly polymerized. As a result, the adhesion will disappear. The urethane prepolymer contained in the hot-melt type moisture-cured polyurethane as described above can be a urethane prepolymer obtained by reacting a polyhydric alcohol with a polyisocyanate. For example, the polyester can be a polyester polyol, a polyether polyol, a polycarbonate polyol, or the like. Among them, in the case where the leather sheet obtained by the present invention is used for a shoe, a polyether polyol is preferably used. It is particularly desirable to use polytetramethylene glycol. Further, in the case where the leather piece is used for a car seat or a furniture member or the like, in order to seek high durability (heat resistance, hydrolysis resistance, etc.), polycarbonate polyol is preferably used. The polyether polyol or the polycarbonate polyol of the polytetramethylene glycol or the like is preferably used in an amount of 40% by mass or more based on the total amount of the polyalcohol to be used. Further, as the polyisocyanate to be reacted with the polyhydric alcohol, for example, phenyl diisocyanate, toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, naphthalene can be used. Aromatic diisocyanate such as isocyanate or xylene diisocyanate; exohexyl diisocyanate, octadecyl diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethyl xylene diisocyanate An aliphatic diisocyanate or an alicyclic diisocyanate, a dimer of 4,4'-diphenylmethane diisocyanate, a polydiphenylmethane diisocyanate such as a trimer, or the like. Among them, based on the prevention of yellowing caused by light, -11-201037125 points, in order to form the hot-melt moisture-cured polyurethane of the skin of the leather sample, it is preferable to use a constant yellow polyg with excellent light resistance. An aromatic diisocyanate such as naphthalene diisocyanate or xylene diisocyanate of urethane; exohexyl diisocyanate, diazonic acid diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate , tetramethyl xylene diisocyanate. The production of the urethane prepolymer can be usually carried out without a solvent or in an organic solvent. In the case of production in an organic solvent, an organic solvent such as ethyl acetate, n-butyl acetate, methyl ethyl ketone or toluene which does not inhibit the reaction between the polyhydric alcohol and the polyurethane can be used in the middle of the reaction. After the completion of the reaction, it is necessary to remove the organic solvent by a method such as heating under reduced pressure. The reaction ratio of the polyhydric alcohol to the polyisocyanate is an equivalent ratio of the isocyanate group in the polyisocyanate to the hydroxyl group in the polyalcohol [NCO/OH], preferably in the range of 1.1 to 5.0, more preferably 1.2 to 1. Within the scope of 3.0. When the Q equivalent ratio is 1.1 or more, the moisture-curing property of the hot-melt type moisture-cured polyurethane is good. The number average molecular weight of the urethane prepolymer in the hot-melt type moisture-cured polyurethane is preferably from 500 to 30,000, more preferably from 1,000 to 1,000. In particular, the urethane prepolymer contained in the first hot-melt type moisture-cured polyurethane has a number average molecular weight in the range of 500 to 5,000. The urethane prepolymer contained in the second hot-melt type moisture-curable polyurethane 40-201037125 ester preferably has 600 to 30000, based on the viewpoint that the melt viscosity due to workability can be easily adjusted. The number average molecular weight of the range. When the number average molecular weight of the urethane polymer is in such a range, a polyurethane layer having excellent flexibility, mechanical strength, abrasion resistance, and hydrolysis resistance can be formed. The melt viscosity of the hot melt type moisture-cured polyurethane is measured by a cone-and-plate viscometer to measure the melt viscosity at 1 25 ° C, the first hot-melt type moisture-cured polyurethane and the first 2 The hot-melt type moisture-cured polyurethane is preferably in the range of 100 to 15000 mpa.s, and more preferably in the range of 1000 m to 10000 mPa*s, which is possible by coating by a thin film method. Better. In general, the hot-melt type moisture-cured polyurethane in the present embodiment may be used as a blended urethane in addition to a resin component containing a urethane prepolymer as a main component. A resin composition of an additive such as a catalyst, a pigment, or the like, an additive such as a tackifier, a crosslinking agent, a crosslinking accelerator, or an antioxidant. Further, in the case where a polyurethane layer formed of a hot-melt type moisture-cured polyurethane is to be formed as a foamed polyurethane layer, a foaming agent can be blended. Such a resin composition can be obtained by uniformly mixing a resin component containing a urethane prepolymer as a main component and other components in a heated molten state. A specific example of a coating mechanism for heat-melting a hot-melt type moisture-cured polyurethane to be applied to the surface of the release paper 1 can be used in addition to the blade coater or roll coater as shown in FIG. For example, a reverse roll coater, a reverse coater, a contact roll coater, a spray coater, a -13-201037125 T-die coater or a comma coater, or the like can be used. Further, based on the viewpoint of controlling the melt viscosity of the hot-melt type moisture-cured polyurethane, such a coating means is preferably a coating means provided with a heating means. The melt viscosity of the first hot-melt type moisture-cured polyurethane at the time of application is preferably from 1000 to 15,000 mPa·s, and more preferably from 2000 to 10000 mPa*s, from the viewpoint of excellent coating workability. The thickness of the polyurethane layer formed of the first hot-melt type moisture-cured polyurethane is preferably a thickness after hardening based on a leather plaque which can have excellent flexibility and mechanical strength. It is preferably 5 to 800 μm, and further preferably in the range of 10 to 500 μm. Next, the second hot-melt type moisture-curing polyamine which has been heated and melted in a state in which the first hot-melt type moisture-cured polyurethane coated on the surface of the release paper 1 is melted or softened The carbamic acid ester is applied to the surface (second coating step). The release paper 1 to which the first hot-melt type moisture-cured polyurethane 2 has been applied is conveyed to the second hot-melt type moisture-curing type by being rotated by the main roll R in the direction of the arrow. Roller applicator 3a direction of polyurethane 3. Then, the second hot-melt type moisture-cured polyurethane 3 accommodated in the resin feeder 3b is applied in a molten state to a uniform thickness by the blade coater 3a. At this time, the first hot-melt type moisture-cured polyurethane 2 applied on the surface of the release paper 1 is maintained in a molten or softened state. Further, the second hot-melt type moisture-curable polyurethane 3 can be used in the same manner as the above-mentioned first hot-melt type moisture-cured polyurethane 2 -14-201037125. Here, the state in which the hot-melt type moisture-cured polyurethane is melted or softened means that the hot-melt type moisture-cured polyurethane which is heated and melted is in an uncured state, specifically In other words, the hot-melt type moisture-cured polyurethane itself maintains a fluid state, or the hot-melt moisture-cured polyurethane maintains fluidity by an external force, or It is such a state in which the hot-melt type moisture-cured polyurethane retains at least partially fluidity. More specifically, the state in which the fluidity is maintained is preferably maintained in a state in which the melt viscosity is maintained at 15 μmPa*s or less, and more preferably maintained in a state of less than 10 μm*s. Further, in the second coating step, the melt viscosity of the first hot-melt type moisture-cured polyurethane is preferably the melt viscosity of the second hot-melt type moisture-curable polyurethane. High. In addition, the melt viscosity of the first hot-melt type moisture-curable polyurethane is in the range of 1.5 to 2 times the melt viscosity of the second hot-melt type moisture-curable polyurethane. The second hot-melt type moisture-curable polyurethane is applied to a coating layer formed of a first hot-melt type moisture-cured polyurethane which is in a molten or softened state. In this case, when the first hot-melt type moisture-cured polyurethane is coated with the second hot-melt type moisture-curable polyurethane, the first heat is too low, and the first heat is applied. The molten moisture-cured polyurethane and the second hot-melt moisture-curable polyurethane are blended, and the two-layer structure tends to be insufficiently maintained. In the second coating step, the melt viscosity of the first hot-melt type moisture-curable polyurethane is more preferably the second hot-melt type moisture-curable polyamine group. The range of the melt viscosity of the formate is 1.5 to 2 times. Such adjustment of the melt viscosity can be carried out, for example, in the following manner. In Fig. 2, the first hot-melt type moisture-cured polyurethane 2 is applied by the blade coater 2a, and the second hot-melt type moisture-curable polyurethane 3 is used. The roll coater 3a is coated. In this case, the blade coater 2a or the roll coater 3a is separately controlled by a heater (not shown), and the first hot-melt type moisture-cured polyurethane 2 in the second coating step can be controlled. Or the melt viscosity of the second hot melt type moisture-curable polyurethane 3. In addition, as shown in FIG. 3, the coating mechanism 25 including the resin supply unit 22b and the blade coater 22a, the resin supply unit 23b, and the blade coater 23a is integrated with the rotation direction of the main roll R. The first moisture-cured polyurethane 2 is housed in the resin supply portion 22b on the upstream side, and the second moisture-cured polyurethane is used in the direction of rotation of the main roll R. The ester 3 is housed in the resin supply portion 23b on the downstream side. In this case, the first moisture-cured polyurethane 2 uses a moisture-curing urethane having a relatively high melt viscosity; and the second moisture-cured polyurethane 3 has a relatively low melt viscosity. Hot melt type moisture hardening urethane. In this manner, the first hot-melt type moisture-cured polyamine group of the first coating step -16-201037125 in the second coating step can be adjusted by previously combining the hot-melt type moisture-curing polyurethane having different melt viscosities. The melt viscosity of the formate 2 or the second hot-melt moisture-curable polyurethane 3. The melt viscosity of the second hot-melt type moisture-curable polyurethane is preferably from 1 〇〇〇 to 1 0000 mPa, s, and more preferably from 2000 to 10,000 mPa, based on the excellent coating workability. The range of 7000mPa.s. Further, in the second coating step, the melt viscosity of the first hot-melt type moisture-cured polyurethane carboxylic acid hydrate is preferably 1,500 to 15,000 mPa·s, and more preferably 3,500 to 14,000 mPa*s. Further, the thickness of the polyurethane layer formed of the second hot-melt type moisture-curable polyurethane is hardened based on the viewpoint of obtaining a leather piece having excellent flexibility and mechanical strength. The thickness is preferably in the range of 5 to 800 μm, and further preferably in the range of 10 to 500 μm 2 . Next, a description will be given of a bonding step in which the base fabric 4 of the second sheet is bonded to the surface of the second heat-melt type moisture-curable polyurethane 3 to be applied while being melted or softened. . Specifically, the base fabric 4 is sent out from the take-up reel 12, and the applied second hot-melt type moisture-curable polyurethane 3 is melted or softened, and is bonded by the calender roll CR. . Specific examples of the base fabric 4 used in the present embodiment include, for example, a fibrous base material for a general leather sample such as a non-woven fabric, a woven fabric, or a knitted fabric; and the fibrous base material is impregnated with a solvent system, a water system, and an emulsion. A composite fiber substrate such as a polyurethane-free resin, an acrylic resin, and a butadiene-based resin (SBR, -17-201037125 NBR, MBR). Among these fiber base materials, based on the viewpoint of obtaining a leather plaque having a soft touch and more excellent mechanical strength, it is particularly suitable for use in a composite in which a polyurethane resin is impregnated with a nonwoven fabric formed of ultrafine fibers. Fiber substrate. The nonwoven fabric can be used without any particular limitation, and can be used by a conventional method such as a conventional short fiber fabric, a spinning adhesive method or a melt flow method. Further, if necessary, after the fabric is formed, the plurality of sheets of the fabric may be stacked, and the obtained nonwoven fabric may be wound in accordance with the needle rolling treatment or the like. Specific examples of the D-dimensional shape of the nonwoven fabric are exemplified by polyurethane fibers, polyethylene terephthalate (PET) fibers, various polyamide fibers, polyacryl fibers, and various polyolefins. A fiber, a polyvinyl alcohol fiber, or the like. The fiber diameter of the fiber-forming nonwoven fabric is preferably from 0.1 to 50 μηη, more preferably from 1, 1 to 1 5 μηη. Since such an ultrafine fiber system is low in rigidity and soft, it is preferable from the viewpoint of obtaining a leather plaque having a soft touch. The viewpoint of the softness-feeling leather swatch and the viewpoint of excellent passageability are as follows. The basis weight of the non-woven fabric is preferably in the range of 50 to 2000 g/m2, and more preferably in the range of 100 to 1000 g/m2. In this case, in order to adjust the molten or softened state of the applied second heat-melt type moisture-curable polyurethane 3, a heating type calender roll may be used as the calender roll CR. Then, the base fabric 4 is bonded to the surface of the second hot-melt type moisture-curable polyurethane 3 in a molten or softened state in accordance with the calender roll CR to form a leather piece 1 〇. Then, the obtained leather piece 10 is taken up by the take-up reel 13 in a state covered by the release paper 1 of -18-201037125. Then, the leather sample 10 taken by the predetermined time curing, the first hot-melt type moisture-cured polyurethane 2 and the second hot-melt type moisture-curable polyurethane 3 are wet. The gas hardening reaction will proceed, and the hot melt type moisture hardening polyurethane will be polymerized. The ripening condition of the obtained leather sample 10 is preferably carried out at a temperature of 20 to 40 ° C and a relative humidity of 50 to 80% for about 20 to 50 hours. By performing the ripening under such ripe conditions, the hot-melt type moisture-curing D-polyurethane will be subjected to moisture hardening and moisture crosslinking. Thereby, a leather piece having excellent mechanical strength or water resistance can be obtained. Further, the leather piece is a leather piece of the release paper coated on the peeling surface. The position of the coating port of the first hot-melt type moisture-curing polyurethane and the coating port of the second hot-melt type moisture-curing polyurethane (for example, the two blade coaters 22a shown in FIG. 3 and The second hot-melt type moisture-curing type which has been heated and melted in a state in which the first hot-melt type moisture-curing polyurethane applied is melted or softened in q. The polyurethane is not particularly limited as long as it is applied to the surface thereof, and is preferably based on the viewpoint of stably maintaining the state in which the first hot-melt moisture-curing polyurethane is melted or softened. Within lm, more preferably within 50 cm. In the above-described step, the first hot-melt type moisture-cured polyurethane 2 is applied to the surface of the release paper 1 and before re-solidification. The urethane 3 is coated by heating -19-201037125 in a molten state. Thus, 'the polyurethane layer formed by the first hot-melt type moisture-cured polyurethane 2 and the polyamine formed by the second hot-melt type moisture-cured polyurethane 3 The interface of the formate layer crosslinks with each other' peel strength at the interface will become high. Further, the first hot-melt type moisture-cured polyurethane 2 in a molten or softened state is not sufficiently hardened. Therefore, the first hot-melt type moisture-cured polyurethane 2 and the second hot-melt type moisture-curable polyurethane 3 can form a sufficient cross-linking structure at the interface. Or make the layer interface of these layers unclear. A schematic cross-sectional view of the leather piece 1 obtained by such a step is shown in Fig. 4. As shown in Fig. 4, the leather piece 10 is completed by peeling off the release paper 1 coated on the surface. In the leather sample sheet 10, the first urethane layer formed by the first hot-melt type moisture-curable polyurethane 2 and the second heat-melt type moisture-curable type polyamine Since the cross-linking structure is formed at the interface of the second urethane layer formed of the carboxylic acid ester 3, the adhesion between the first urethane layer and the second urethane layer is sufficiently improved. Further, in the present embodiment, the release paper 1 is taken out as the first sheet from the take-up reel 1 1, and the base fabric 4 is taken out as the second sheet from the take-up reel 12, and the release paper may be exchanged. In the order of supplying the base fabric 4, the base fabric 4 is taken out as the first sheet from the take-up reel 11, and the release sheet 12 is taken out as the second sheet from the take-up reel 12. However, this case is necessary to change the combination of the hot-melt type moisture-cured polyurethane used -20-201037125. Although the above description is directed to an example of the production method of the present invention which is not limited by the above-described process, the process of the leather sample is not particularly limited and can be applied: applying the heat-treated polyurethane to the base fabric After the release paper, the moisture-cured polyurethane is in a molten or softened state, and the second hot-melt type moisture-curable polyamine is obtained by the first method. The second formed of the polyurethane-formed moisture-cured polyurethane 3 formed of the cured polyurethane 2 can maintain high adhesion. Therefore, the appearance and the tactile sensation of the obtained skin which is wrinkled and uniform can be improved. Further, in order to impart a surface pattern design to the obtained leather sample, a solvent-based or solvent-free polyurethane resin or an acrylic Q portion may be used or may be appropriately polished or embossed. The leather sample obtained by the above-described method can be applied to the leather material of the surface material of shoes, clothes, bags, furniture, etc. Hereinafter, the present invention will be more specifically described by way of examples, but it is arbitrarily limited by the examples. First, the measurement of the melt viscosity in the present embodiment was made. However, in the production of the present invention, the molten type is wet-hardened in the first hot-melt type as follows. The hot-melt type moisture is applied to the second hot-melt polyurethane layer sample by a conventional method, a water-based method, or an emulsion resin. A is used as a sample. According to the present invention, the melt viscosity (mPa*s) of each of the hot-melt moisture-cured polyurethanes is a cone-plate viscometer (manufactured by ICI), and the temperature of the cone and plate is used. It is measured by setting it to a predetermined temperature. In addition, the melt viscosity of the second hot-melt moisture-curable polyurethane in the second coating step is defined as the second hot-melt type in the coating temperature (blade applicator temperature) of the second coating step. The melt viscosity of a moisture-curing polyurethane. In addition, the melt viscosity of the first hot-melt type moisture-curable polyurethane in the second coating step is measured by applying the second hot-melt type moisture-curable polyurethane 〇v. The surface temperature of the first hot-melt moisture-cured polyurethane previously applied, and the melt viscosity at this temperature. In addition, the raw materials used in the present embodiment will be described below. <Foundry cloth> A woven non-woven fabric made of an ultrafine fiber of an average fineness of 〇. 7Dtex impregnated with a water-soluble polyurethane (HYDRAN WLS612, manufactured by DIC Co., Ltd.). A base fabric having a thickness of 1 mm, a basis weight of 550 g/m 2 and a specific gravity of 0.55 g/cm 3 Q was obtained. <Hot-melt type moisture-curing type polyurethane urethane A> Melt and mix TYFORCE EXP-BH50 (thermal melting type moisture-curing polyurethane made by DIC) at 120 °C Parts, pigment (POLYTON PU-9382 BLACK, DIC (product), the same below) 15 parts by mass. Thus, a hot-melt type moisture-cured polyurethane A having a melt viscosity at 120 ° C of 2780 mPa·s was obtained. <Hot-melt type moisture-curing polyurethane|> -22- 201037125 Melt-mixing TYFORCE ΚΜΜ-100 at 125 ° C (thermal melting type moisture-cured polyurethane by DIC) Ester) 100 parts by mass, and 15 parts by mass of the pigment. Thereby, a hot-melt type moisture-cured polyurethane bismuth oxime having a melt viscosity of 3 200 mPa at 120 °C was obtained. <Hot-melt type moisture-curing polyurethane|> 100 parts by mass of TYFORCEK MM-100 (hot-melt type moisture-cured polyurethane manufactured by DIC) was melt-mixed at 135 °C 15 parts by mass of pigment and 2 parts by mass of foaming agent. Thereby, a foaming type hot-melt type moisture-curing polyurethane C having a melt viscosity of 3 200 mPa 1 at 1 20 °C was obtained. Further, as the foaming agent, ethylene glycol (EG) / water / POLYCAT-8 [manufactured by Air Products Japan Co., Ltd., N,N-dimethylcyclohexylamine (DMCHA)] = 0.5 / 0.05 / 0.1 (parts by mass) was used. Composition. <release paper> Ruffled release paper R-8 made by LINTEC. [Example 1] A leather piece was produced using the manufacturing procedure as shown in Fig. 2. Specifically, the first sheet firstly ejects the release paper 1 from the take-up reel 11 at a speed of lm/min, and is conveyed by the main roll R that rotates in the direction of the arrow, and is wound by the take-up reel 13 to form a line. . At this time, the surface temperature of the main roll R was controlled to be 50 °C. Then, the release paper toward the line, the first hot-melt type moisture-cured polyurethane 2, is a hot-melt type moisture-cured polyamine accommodated in the molten resin feeder 2b at ll ° ° C. The carboxylic acid ester A was applied to the surface of the release paper 1 by a knife coater 2a at a uniform thickness of -23 to 201037125 (the first coating step). Further, the surface temperature of the blade applicator 2a is controlled at 110 by a heater (not shown). (: The interval between the blade coater 2a and the release paper at this time has been adjusted to '50 μm, and then the hot-melt type moisture-cured polyurethane coated on the surface of the release paper 1 is In the molten state, the second hot-melt type moisture-curable polyurethane 3 is applied to the surface of the hot-melt type moisture-cured polyurethane C which is melted at 135 ((:: melted) The second coating step). At this time, the surface temperature of the roll coater 3a is controlled by a heater (not shown) to be 135 ° C. At this time, the blade coater 3 a and the mold release are controlled. The paper is adjusted in such a manner that the interval between the papers is 250 μm. In the second coating step, the surface temperature of the hot-melt moisture-cured polyurethane urethane applied is about 120 ° C, and the melt viscosity at this time. Further, the hot-melt type moisture-cured polyurethane C has a melt viscosity of about 2500 mPa*s at 135 ° C. Thus, the hot-melt type wet Q gas in the second coating step Melt viscosity of hardened polyurethane A melt viscosity of hot melt moisture cured polyurethane Then, the coated hot-melt moisture-curing polyurethane condensate C is melted, and the base fabric 4 of the second sheet is bonded to the surface (bonding step). The base fabric 4 is taken out from the take-up reel 12, and the hot-melt moisture-cured polyurethane C is melted, and is bonded by calendering light CR. Also, the surface temperature of the calender roll CR is borrowed. It is controlled by 5 (TC) by a heater (not shown). In this manner, a leather piece 1 having a layer structure as shown in Fig. 24-70, 137, 254 is formed. Then, the obtained leather piece is tied to the quilt. In the state in which the release paper is covered, the take-up reel 13 is taken up. Then, in the wound state, the leather sample 10 is subjected to a temperature of 40 ° C and a relative humidity of 6 〇 %. After the aging, the obtained leather swatch 10 was cut only in a predetermined area, and the release paper was peeled off, and the interlayer adhesion was evaluated by the following method: π (interlayer adhesion) 皮革 Leather peeled off from the release paper The surface of the second polyurethane layer of the sample was subjected to 5 seconds at 130 ° C After hot-pressing of the hot-melt tape (trademark: Melco Tape, Sun Chemicals Co., Ltd.), the peel strength was measured using TENSIRON (manufactured by Shimadzu Corporation) at a head end speed of 20 0 mm/min according to JIS K6854-2. Further, the position of the peeled portion at this time was confirmed. As a result, the peel strength of the obtained leather piece was Ο1 1 .〇kg/25 mm, and internal peeling was performed in the base fabric 4 layer. [Example 2] In addition, the first hot-melt type moisture-cured polyurethane 2 is made of a hot-melt type moisture-cured polyurethane B, and the manufacturing process is shown in FIG. A leather swatch was produced in the same manner as in Example 1. Specifically, as shown in Fig. 3, a supply portion 22b, 23b having two resins - 25 - 201037125 including two blade coaters 22a, 23a and a hot-melt type moisture-cured polyurethane is used. An integrated coating mechanism 25. Then, in the resin feeder 22b, the first hot-melt type moisture-cured polyurethane 2 accommodates the hot-melt type moisture-cured polyurethane B; in the resin feeder 23b, The second hot-melt type moisture-cured polyurethane 3 is a hot-melt type moisture-cured polyurethane C. Then, from the lead-out reel 11, the first sheet is continuously taken out at a speed of lm/min, and conveyed by the main roll R rotated in the direction of the arrow, and the take-up reel 13 is taken up to form a line. . At this time, the surface 〇 temperature of the main roll R was controlled to be 50 ° C. Then, the release paper 1 facing the line flows down in the state of the hot-melt type moisture-cured polyurethane B accommodated in the molten resin feeder 22b, and has a uniform thickness by the blade coater 22a. It is applied to the surface of the release paper 1 (first coating step). After that, it flows down in the state of the hot-melt type moisture-cured polyurethane C accommodated in the molten resin feeder 2 3 b, and is applied in a uniform thickness by the blade coater 23a (second Coating step). Further, the interval between the blade coater 22a Q and the surface of the release paper has been adjusted to 50 μm, and the interval between the blade coater 23 3 a and the surface of the release paper has been adjusted to 250 μm. The blade coater 22a and the resin supply portion 22b were controlled to 1 l ° ° C; the blade coater 23a and the resin supply portion 2 3b were controlled to 120 °C. In the second coating step, the surface temperature of the hot-melt type moisture-cured polyurethane B applied in the first coating step is about 110 ° C, and the melt viscosity at this time is about 5000 mPa·s. In addition, the hot-melt type moisture-cured polyurethane 12 (melt viscosity at TC is about 3200 mPa·s. Therefore, the hot-melt type wet -26-201037125 polyamine in the second coating step The melt viscosity of the carbazate B is about 1.6 times that of the hot-melt type moisture-cured polyurethane C. The subsequent steps were carried out in the same manner as in Example 1 to produce a leather plaque. The obtained leather piece had a peeling strength of 10.2 kg/25 mm and was internally peeled off in the four layers of the base fabric. [Example 3] In addition to the first coating step, 'melting hot-melt type moisture-curing polyamine at 100 ° C In the state of the urethane A, the second coating step is carried out in the same manner as in the first embodiment except that the hot-melt type moisture-cured polyurethane C is melted at 140 ° C. The leather sample piece was produced. At this time, the surface temperature of the roll coater 3a was controlled so as to be controlled to 140 ° C by a heater (not shown). At this time, in the second coating step, the first Hot-melt type moisture-cured polyurethane A coated by the coating step The melt viscosity is about 6500 mPa.s, and the hot-melt moisture-cured polyurethane C has a melt viscosity of about i8 〇〇 mPa.s. Therefore, the hot-melt type moisture-cured polyamine in the second coating step The melt viscosity of the carbamate A is about 3.6 times the melt viscosity of the hot-melt moisture-cured polyurethane C. In the peel strength measurement of the obtained leather sample, mainly on the base fabric 4 layers Internal peeling was carried out, and peeling was observed even at a slight interface between the polyurethane layers, and the peel strength was as high as 10 · 1 kg / 2 5 mm. [Example 4] In addition to the first coating step, 120 ° C molten hot-melt moisture-cured polyurethane A flow down, in the second coating step, at -27-201037125 1 15 °C molten hot-melt moisture-cured polyamine A A leather sample piece was produced in the same manner as in Example 1 except that the acid ester C was flowed down. At this time, the surface temperature of the roll coater 3a was controlled to 115 ° C by the heater omitted from the drawing. By way of control, at this time, in the second coating step, the first coating step is applied. The hot-melt moisture-cured polyurethane A has a melt viscosity of about 2700 mPa·s, and the hot-melt moisture-cured polyurethane C has a melt viscosity of about 4000 mPa·s. Thus, the second The melt viscosity of the hot-melt type moisture-cured polyurethane A in the coating step is about 0.7 times the melt viscosity of the hot-melt type moisture-cured polyurethane C. The peel strength of the obtained leather sample It is 10.6kg/25mm and has been internally peeled off in the 4th layer of the base fabric. Also, the polyurethane layer formed by the hot-melt type moisture-cured polyurethane A and the hot-melt type moisture The polyurethane layer formed by the cured polyurethane C has a partially mixed portion. [Comparative Example 1] A leather sample piece was produced by using the process shown in Fig. 1. Specifically, as shown in Fig. 1, a line is formed from the take-up reel 30 toward the take-up reel 3 8, at a speed of 1 m/min. Then, the release paper 1 taken up by the take-up reel 30 is placed on the rolls 31, 32 and conveyed. Then, the first hot-melt type moisture-cured polyurethane 312 is applied to the surface of the release paper by using the blade coater 303 to heat-melt the hot-melt type moisture-cured polyurethane A which is heated and melted by 12CTC. The film layer is formed. At this time, the coating thickness was adjusted so as to be 50 μm. Next, water vapor was sprayed onto the surface of the film layer formed by hot-melt type moisture-curing polyurethane A using a water vapor -28-201037125 sprayer 3 04'. Then, it is placed on the rolls 33a and 33b and fed to the roll 34'. The second hot-melt type moisture-cured polyurethane 313 is adjusted by using a blade coater 305' to apply a coating thickness of 200 μm. The hot-melt type moisture-cured polyurethane C which was heated and melted at 1 20 ° C was applied. Then, the base fabric 37 is supplied from the take-up reel 36, and the base fabric is bonded to the hot-melt type moisture-cured polyurethane C by the roll 35 to produce a leather sample. In the above step, the adhesive portion of the first hot-melt type moisture-cured polyurethane 2 remains on the surface. Therefore, when the laminated intermediate is wound around the rolls 33a and 33b shown in Fig. 1, the step passability causes a problem. [Comparative Example 2] Leather was produced and evaluated in the same manner as in Comparative Example 1, except that the release paper 1 was taken out at a speed of 0.5 m/min, and the speed was reduced in place of i.0 m/min. In the sample, by lowering the linear velocity, surface adhesion is suppressed to some extent, and even productivity is improved. The obtained leather swatches were aged for 35 hours under the conditions of a temperature of 40 ° C and a relative humidity of 60%. After the aging, the obtained leather piece "peel release paper" was cut only for a predetermined area, and the interlayer adhesion was evaluated by the same method as in Example 1. As a result, the peel strength of the leather piece was 6.5 kg/25 mm, and the layer formed of the hot-melt type moisture-cured polyurethane a and the hot-melt type moisture-cured polyurethane B were used. The interface of the layer has been peeled off. -29-201037125 As shown by the results of the above examples, the leather samples obtained in Examples 1 to 4 of the application of the present invention were high in peel strength regardless of the peeling strength. Further, in Examples 1 to 2 and 4, no peeling was observed at the interface between the polyurethane layers. This is considered to be because the two types of hot-melt moisture-curing polyurethane are laminated in a molten state, and the interface becomes unclear, and the crosslinked structure is sufficiently formed at the interface. Further, in Example 3, although the polyurethane layer formed of the hot-melt type moisture-cured polyurethane A and the hot-melt type moisture-cured polyurethane C At the interface of the formed f) I polyurethane layer, some slight peeling was observed, but the peel strength was sufficiently high. On the other hand, as shown in Comparative Example 1, when the hot-melt type moisture-cured polyurethane A was applied and re-solidified, in the case where the adhesiveness remained, the passability was poor, and the continuous production system was difficult. . Further, as shown in Comparative Example 2, when the hot-melt type moisture-cured polyurethane A was applied and produced by a low-speed line which was cured to the extent that the adhesion was eliminated, the Q peel strength was remarkably lowered. This is considered to be because the interface in the two-layer polyurethane layer was made clear, and that a sufficient cross-linking structure was not formed between the two layers. As described above, the "method of manufacturing a leather sheet" includes the first hot-melt type moisture-cured polyurethane coated on the surface of the first sheet. a coating step; in the state in which the first hot-melt type moisture-curable polyurethane is applied in a state of melting or softening, the second heat-melt type moisture-hardened type -30-201037125 a second coating step in which the polyurethane is applied to the surface thereof; and the second sheet is in a state in which the second hot-melt moisture-curable polyurethane is applied in a state of melting or softening A lamination step that fits over its surface. According to such a manufacturing method, the interface at the interface is formed by the interface at which the first hot-melt type moisture-cured polyurethane and the second hot-melt type moisture-curable polyurethane are cross-linked. The intensity will become higher. Further, since it is difficult to form a clear interface formed by the above-described conventional manufacturing method, the interface becomes unclear, and the peel strength at the interface is made higher. In addition, the first hot-melt type moisture-cured polyurethane having a molten or softened state is coated with the second hot-melt type moisture-curable polyurethane before the curing reaction proceeds sufficiently. A structure capable of forming a sufficient crosslink between a layer formed of the first hot-melt moisture-curable polyurethane and a layer formed of the second hot-melt moisture-curable polyurethane . In addition, in the continuous production, the layer formed by the first hot-melt type moisture-curing polyurethane and the second hot-melt type moisture-curing type polyurethane are formed. The surface of the layer was covered by the first sheet and the second sheet, respectively, and the adhesion due to the unhardened hot-melt moisture-cured polyurethane did not occur. Therefore, it also has excellent step passability. Further, in the second coating step, the melt viscosity of the first hot-melt moisture-curable polyurethane is higher than the melt viscosity of the second hot-melt moisture-curable polyurethane. Further, the melt viscosity of the first hot-melt moisture-curable polyurethane is preferably 1.5 to 2 times the melt viscosity of the second hot-melt moisture-curable polyurethane. When the first hot-melt type moisture-cured polyurethane has a low melt viscosity when the second heat-31 - 201037125 melt-type moisture-curable polyurethane is applied, the previously coated The first hot-melt type moisture-cured polyurethane layer is mixed with the newly applied second heat-melt type moisture-cured polyurethane, and the layer properties tend not to be sufficiently maintained. In addition, in the case where the first hot-melt type moisture-cured polyurethane and/or the second hot-melt type moisture-curable polyurethane contain a foaming agent, it can be easily formed as An elastic polyurethane layer for the intermediate layer. Further, the leather sample obtained by any of the above production methods is a first polyurethane layer formed of a first hot-melt type moisture-cured polyurethane and a second hot-melt type The second polyurethane layer formed by the gas-hardening polyurethane maintains high adhesion and a sense of unity. Therefore, the obtained leather sample has a wrinkle which is fine, and has excellent uniformity of appearance or touch. [Probability of Industrial Applicability] According to the present invention, there is provided a method of producing a leather plaque capable of sufficiently improving a two-layer polyurethane laminate portion formed by a hot-melt type moisture-cured polyurethane The peel strength of the interface. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing the [Fig. 3] disclosed in Patent Document 1. Fig. 2 is a schematic view showing the method of manufacturing the leather piece of the first embodiment. -32- 201037125 Fig. 3 is a schematic view showing a manufacturing method of a modification of the first embodiment. Fig. 4 is a schematic cross-sectional view showing a leather piece obtained by the procedure of the first embodiment. [Main component symbol description] 1 2 2 a 2b 3 3 a 3b 4 10 11 12 13
22a 22b 23a 23b 25 脫模紙 第1熱熔融型濕氣硬化聚胺基甲酸醋 刮刀塗布器 具備加熱器之樹脂進料器 第2熱熔融型濕氣硬化型聚胺基甲酸酉旨 輥塗布器 具備加熱器之樹脂進料器 基布 皮革樣片 脫模紙1之導出捲軸 基布4之導出捲軸 捲取捲軸 刮刀塗布器 樹脂供應部 刮刀塗布器 樹脂供應部 塗布機構 導出捲軸 -33- 30 201037125 31、 32 、 33a 、 33b 、 34 、 35 輥 36 導出捲軸 37 基材 3 8 捲取捲軸 CR 壓延輥 R 主輥 301 剝離紙（脫模紙） 303 、 305 刮刀塗布器 304 水蒸氣噴霧器 3 12 熱熔融型濕氣硬化聚胺基甲酸酯 3 13 熱熔融型濕氣硬化聚胺基甲酸酯22a 22b 23a 23b 25 Release paper first hot-melt type moisture-cured polyurethane squeegee applicator resin feeder with heater 2nd hot-melt type moisture-curing polyurethane urethane roll coater Resin feeder with heater base cloth leather sample release paper 1 derivation reel base fabric 4 export reel take-up reel blade applicator resin supply blade applicator resin supply part coating mechanism export reel -33- 30 201037125 31 , 32 , 33a , 33b , 34 , 35 Roll 36 Export reel 37 Substrate 3 8 Take-up reel CR Calender roll R Main roll 301 Release paper (release paper) 303, 305 Scraper applicator 304 Water sprayer 3 12 Hot melt Type moisture hardening polyurethane 3 13 hot melt type moisture hardening polyurethane