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TWI801668B - 多孔層結構體及其製造方法 - Google Patents

多孔層結構體及其製造方法 Download PDF

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Publication number
TWI801668B
TWI801668B TW108134384A TW108134384A TWI801668B TW I801668 B TWI801668 B TW I801668B TW 108134384 A TW108134384 A TW 108134384A TW 108134384 A TW108134384 A TW 108134384A TW I801668 B TWI801668 B TW I801668B
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Taiwan
Prior art keywords
substrate
mentioned
urethane
urethane prepolymer
polyol
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TW108134384A
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English (en)
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TW202023808A (zh
Inventor
河村亮
山田利樹
佐佐木一弥
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日商大日精化工業股份有限公司
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Abstract

本發明係一種多孔層結構體，其包含基材A及設置於該基材A上而成之胺基甲酸酯發泡層，上述胺基甲酸酯發泡層係使具有異氰酸酯基之胺基甲酸酯預聚物發泡而成之發泡層，上述胺基甲酸酯發泡層之密度為0.10～0.60 g/cm3 ，上述胺基甲酸酯預聚物實質上不含揮發成分，且滿足特定組成。

Description

多孔層結構體及其製造方法
本發明係關於一種多孔層結構體及其製造方法。
胺基甲酸酯預聚物用於接著劑、塗料、密封材料等，尤其是濕氣硬化型胺基甲酸酯預聚物具有由空氣中之水分硬化故而可單獨使用之優點。此種胺基甲酸酯預聚物於分子內具有可與空氣中或塗佈該預聚物之基材中存在之水(濕氣)反應而形成交聯構造之官能基(例如異氰酸酯基)。並且，未硬化且於常溫下為液體或固體狀之各種各樣之胺基甲酸酯預聚物根據用途進行開發。
又，因與水(濕氣)反應而發泡，故有時亦會作為聚胺基甲酸酯發泡體片材使用。聚胺基甲酸酯發泡體片材因具有優異之柔軟性、伸縮性、緩衝性，故藉由與各種布料之組合應用於衣料、靴子、護體等用途。一直以來，於該聚胺基甲酸酯發泡體片材之製造中使用有機溶劑，但近年來因對於人體之有害性或環境問題而限制或禁止其使用，當務之急係轉變為於不使用有機溶劑之情形下製造聚胺基甲酸酯發泡體片材之方法。
例如，於專利文獻1中揭示有未使用有害之有機溶劑，無需有機溶劑之乾燥步驟及萃取步驟，而將溶劑之蒸發去除所需要之能量消耗量降低化之製造方法。
[先前技術文獻] [專利文獻]
[專利文獻1]日本專利第3776428號公報
專利文獻1中記載之方法之特徵在於，使水蒸氣接觸片狀之液狀混合物而使液狀混合物被水發泡，但於該方法中因發泡後與基材片貼合，故與基材片之密接性降低。於要求良好之柔軟性之胺基甲酸酯用途中，就耐久性之觀點而言亦需要發泡層與基材層之良好之密接性，但專利文獻1中所獲得之片材難以滿足該要求。
根據以上，本發明之目的在於，提供一種能夠於未使用有機溶劑之情形下製造、且能夠發揮良好之柔軟性及耐久性之多孔層結構體及其製造方法。
為了解決上述問題而進行銳意研究，結果本發明者等發現，能夠藉由包含使特定之胺基甲酸酯預聚物發泡而成之胺基甲酸酯發泡層之多孔層結構體解決該問題，從而想到了本發明。即，本發明如下所述。
[1]一種多孔層結構體，其包含基材A及設置於該基材A上而成之胺基甲酸酯發泡層，上述胺基甲酸酯發泡層為使具有異氰酸酯基之胺基甲酸酯預聚物發泡而成之發泡層，上述胺基甲酸酯發泡層之密度為0.10~0.60g/cm3，上述胺基甲酸酯預聚物實質上不含揮發成分，且滿足下述(A)~(C)之至少任一種組成： (A)包含於所有多元醇成分中佔50質量%以上之凝膠化點為20ml以上且未達30ml之多元醇成分(a)之組成；(B)包含於所有多元醇成分中佔30質量%以上之凝膠化點為30ml以上且未達50ml之多元醇成分(b)之組成；(C)包含於所有多元醇成分中佔10質量%以上之凝膠化點為50ml以上之多元醇成分(c)之組成。
[2]如[1]之多孔層結構體，其中設置上述胺基甲酸酯發泡層前之上述基材A為含水基材A。
[3]如[1]或[2]之多孔層結構體，其中於上述基材A為聚酯基布、胺基甲酸酯發泡層之厚度為200μm時之用以自基材A剝離胺基甲酸酯發泡層之剝離力為1.5kgf/inch以上。
[4]如[1]至[3]中任一項之多孔層結構體，其中上述胺基甲酸酯預聚物包含於所有多元醇成分中佔50質量%以上之聚碳酸酯多元醇成分。
[5]如[1]至[4]中任一項之多孔層結構體，其中於上述胺基甲酸酯預聚物中，聚異氰酸酯成分之異氰酸酯基當量相對於上述所有多元醇成分之羥基當量之比為1.33~5.0。
[6]一種多孔層結構體之製造方法，其係如[1]至[5]中任一項之多孔層結構體之製造方法，其包含：基材含水處理步驟，其對基材A實施含水處理而製成含水基材A；胺基甲酸酯預聚物塗佈步驟，其將具有異氰酸酯基之胺基甲酸酯預聚物塗佈於基材B上而形成胺基甲酸酯預聚物塗膜；塗膜結構體製作步驟，其貼合上述含水基材A與於上述基材B上形成之上述胺基甲酸酯預聚物塗膜而製作塗膜結構體；及 時效處理步驟，其對上述塗膜結構體實施時效處理；上述胺基甲酸酯預聚物實質上不含揮發成分，且滿足下述(a)~(c)之至少任一種組成：(A)包含於所有多元醇成分中佔50質量%以上之凝膠化點為20ml以上且未達30ml之多元醇成分(a)之組成；(B)包含於所有多元醇成分中佔30質量%以上之凝膠化點為30ml以上且未達50ml之多元醇成分(b)之組成；(C)包含於所有多元醇成分中佔10質量%以上之凝膠化點為50ml以上之多元醇成分(c)之組成。
[7]如[6]之多孔層結構體之製造方法，其包含於上述塗膜結構體製作步驟與上述時效處理步驟之間，使水蒸氣接觸上述塗膜結構體之水蒸氣接觸步驟。
根據本發明，能夠提供一種能夠於未使用有機溶劑之情形下製造、且能夠發揮良好之柔軟性及耐久性之多孔層結構體及其製造方法。
10:多孔層結構體
12:基材A
14:胺基甲酸酯發泡層
14A:胺基甲酸酯發泡層之下表面
16:基材B
20:多孔層結構體
22:基材A
24:胺基甲酸酯發泡層
24A:胺基甲酸酯發泡層之下表面
26:基材B
圖1係表示本實施形態之多孔層結構體之模式之剖視圖。
圖2係表示先前之多孔層結構體之模式之剖視圖。
以下，詳細地對本發明之實施形態(本實施形態)進行說明，但本發明並不限定於該實施形態。
[1.多孔層結構體]
本實施形態之多孔層結構體包含基材A及設置於該基材A上而成之胺基甲酸酯發泡層。胺基甲酸酯發泡層係使具有異氰酸酯基之胺基甲酸酯預聚物發泡而成之發泡層。即，該胺基甲酸酯發泡層成為包含具有異氰酸酯基之胺基甲酸酯預聚物之發泡物之發泡層。
上述胺基甲酸酯發泡層以其一部分浸入基材A之內部之方式存在。其結果為，基材A與胺基甲酸酯發泡層之密接性提高，該等於未剝離之情形下發揮優異之耐久性。又，因發泡而維持優異之耐久性並具有良好之柔軟性。
為了兼具浸入基材A之內部及良好之柔軟性，於本發明中，將胺基甲酸酯發泡層之密度設為0.10~0.60g/cm3，且使用具有異氰酸酯基之特定之胺基甲酸酯預聚物作為用以形成該胺基甲酸酯發泡層之胺基甲酸酯預聚物。
胺基甲酸酯發泡層之密度與發泡層之發泡率相關，密度愈低發泡率愈高。並且，由於胺基甲酸酯發泡層之密度為0.10~0.60g/cm3，因此可維持其與基材A等之密接性，並可獲得良好之柔軟性。
又，本實施形態之胺基甲酸酯預聚物實質上不含揮發成分。即，於未使用有機溶劑之情形下製造多孔質結構體，因此不會產生有害性之問題或環境問題。
此處，於本發明中，所謂「實質上不含揮發成分」，意指刻意地不含有機溶劑等揮發成分，更具體而言係指不存在有機溶劑。
本發明之具有異氰酸酯基之胺基甲酸酯預聚物滿足下述(A)~(C)之至少任一種組成： (A)包含於所有多元醇成分中佔50質量%以上之凝膠化點為20ml以上且未達30ml之多元醇成分(a)之組成；(B)包含於所有多元醇成分中佔30質量%以上之凝膠化點為30ml以上且未達50ml之多元醇成分(b)之組成；(C)包含於所有多元醇成分中佔10質量%以上之凝膠化點為50ml以上之多元醇成分(c)之組成。
此處，凝膠化點能夠以下述方式求出。
首先，準備包含1質量%多元醇成分之N,N'-二甲基甲醯胺(DMF)溶液。之後，一面藉由螺旋槳攪拌器充分攪拌使其均一，一面使蒸餾水滴至該溶液中，於25±1℃之溫度條件下多元醇開始凝固，求出微白濁時之滴水量(ml)。
再者，測定中使用之DMF需要使用水分0.03質量%以下者，於DMF溶液已預先微白濁之情形時，可將凝固開始而白濁程度變化時之滴水量視作凝膠化點。
所謂多元醇成分(a)~(c)中之凝膠化點，係指表示親水性之程度者，凝膠化點為20ml以上且未達30ml之多元醇成分(a)於多元醇成分(a)~(c)中親水性之程度最低，因此為了獲得可成為具有良好之柔軟性、特別柔軟之質感之合成人造皮革之發泡層，較佳為包含於所有多元醇成分中佔50質量%以上。
成為多元醇成分(a)之多元醇係滿足上述凝膠化點範圍之聚酯多元醇，具體而言，作為聚酯多元醇之醇成分，可列舉：乙二醇、二乙二醇、三乙二醇、丙二醇、1,2-丙二醇、正丙二醇、1,3-丁二醇、1,4-丁二醇、1,3-戊二醇、1,5-戊二醇、1,6-己二醇、己二醇、3-甲基-1,5-戊二 醇、2-乙基-1,3-己二醇、1,9-壬二醇、新戊二醇等；作為酸成分，可列舉：對苯二甲酸、間苯二甲酸、丙二酸、戊二酸、庚二酸、辛二酸、丁二酸、己二酸、壬二酸、癸二酸、十二烷二酸等二元酸。該等二醇成分與二元酸之組合可列舉單獨使用或使用2種以上各個成分之聚酯二醇等，較佳為包含乙二醇、二乙二醇、1,2-丙二醇、正丙二醇之內之至少1種以上作為醇成分，或包含丁二酸等作為酸成分。關於上述多元醇之數量平均分子量，並無特別限定，較佳為500~3000。
又，凝膠化點為30ml以上且未達50ml之多元醇成分(b)於多元醇成分(a)~(c)中，親水性之程度為中等程度，因此為了獲得可成為具有良好之柔軟性、特別柔軟之質感之合成人造皮革之發泡層，較佳為包含於所有多元醇成分中佔30質量%以上。
成為多元醇成分(b)之多元醇係滿足上述凝膠化點範圍之聚酯多元醇，具體而言，作為聚酯多元醇之醇成分，可列舉：乙二醇、二乙二醇、三乙二醇、丙二醇、1,2-丙二醇、正丙二醇、1,3-丁二醇、1,4-丁二醇、1,3-戊二醇、1,5-戊二醇、1,6-己二醇、己二醇、3-甲基-1,5-戊二醇、2-乙基-1,3-己二醇、1,9-壬二醇、新戊二醇等；作為酸成分，可列舉：對苯二甲酸、間苯二甲酸、丙二酸、戊二酸、庚二酸、辛二酸、丁二酸、己二酸、壬二酸、癸二酸、十二烷二酸等二元酸。該等二醇成分與二元酸之組合可列舉單獨使用或使用2種以上各個成分之聚酯二醇等，較佳為包含乙二醇、二乙二醇、1,2-丙二醇、正丙二醇之內之至少1種以上作為醇成分，或包含丁二酸作為酸成分。關於上述多元醇之數量平均分子量，並無特別限定，較佳為500~未達2000。
進而，凝膠化點為50ml以上之多元醇成分(c)於多元醇成 分(a)~(c)中親水性之程度最高，因此為了獲得可成為具有良好之柔軟性、特別柔軟之質感之合成人造皮革之發泡層，較佳為包含於所有多元醇成分中佔10質量%以上。
成為多元醇成分(c)之多元醇具體而言為滿足上述凝膠化點範圍之聚醚多元醇，具體而言可列舉聚氧乙二醇(PEG)、EO/PO(ethylene oxide/propylene oxide，環氧乙烷/環氧丙烷)共聚物、EO/THF(ethylene oxide/tetrahydrofuran，環氧乙烷/四氫呋喃)共聚物等。關於上述多元醇之數量平均分子量，並無特別限定，較佳為500~6000。
以下，更詳細地對本實施形態之胺基甲酸酯預聚物、基材、胺基甲酸酯發泡層等進行說明。
<胺基甲酸酯預聚物>
胺基甲酸酯預聚物如上所述，由滿足(A)~(C)之至少任一種組成之多元醇成分、異氰酸酯成分、及適當其他成分構成。即，本實施形態之具有異氰酸酯基之胺基甲酸酯預聚物為可由多元醇成分與聚異氰酸酯成分獲得之胺基甲酸酯預聚物。尤其是，該胺基甲酸酯預聚物為濕氣硬化型胺基甲酸酯預聚物，可利用其於濕氣硬化時發泡，獲得本發明之多孔層結構體。
(多元醇成分)
只要胺基甲酸酯預聚物滿足既述之(A)~(C)之至少任一種組成，也可包含除多元醇成分(a)~(c)以外之多元醇成分。
例如，亦可設為多元醇成分(a)~(c)之各者與於凝膠化點測定中未達20ml之多元醇成分(x)之組合。若為該等之組合，則例如能夠確保發泡性，並能夠進行初始接著強度之提高或可撓性之提高、耐化學品 性或耐久性之賦予、黏度調整等。
關於成為多元醇成分(x)之多元醇，具體而言可列舉：作為聚醚多元醇之聚氧四亞甲基二醇(PTMG)、聚氧化丙烯二醇(PPG)、凝膠化點未達20ml之聚酯多元醇、己內酯系多元醇、聚碳酸酯系多元醇等。
尤其是，為了提高耐水解性而獲得良好之耐久性，亦可含有聚碳酸酯多元醇成分。於含有聚碳酸酯多元醇成分之情形時，較佳為於所有多元醇成分中包含50質量%以上，更佳為包含70~90質量%。
作為成為聚碳酸酯多元醇成分之聚碳酸酯多元醇，只要係藉由烷二醇與碳酸二烷基酯、碳酸伸烷酯、碳酸二苯酯等碳酸酯化合物反應所獲得之先前公知之聚碳酸酯多元醇，即無特別限定。
(異氰酸酯成分)
本實施形態之作為胺基甲酸酯預聚物之合成成分使用之異氰酸酯並無特別限定，但較佳為脂肪族二異氰酸酯、脂環族二異氰酸酯、芳香族二異氰酸酯等2官能基之聚異氰酸酯。
作為成為異氰酸酯成分之聚異氰酸酯之具體例，為：甲苯二異氰酸酯、4-甲氧基-1,3-苯二異氰酸酯、4-異丙基-1,3-苯二異氰酸酯、4-氯-1,3-苯二異氰酸酯、4-丁氧基-1,3-苯二異氰酸酯、2,4-二異氰酸酯-二苯醚、均三甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、伸四甲苯基二異氰酸酯、1,5-萘二異氰酸酯、聯苯胺二異氰酸酯、鄰硝基聯苯胺二異氰酸酯、4,4-二異氰酸二苄基酯、1,4-四亞甲基二異氰酸酯、1,5-五亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯、1,10-十亞甲基二異氰酸酯、1,4-環己二異氰酸酯、二甲苯二異氰酸酯、4,4'-亞甲基雙(環己基異氰酸酯)、1,5-四氫化萘二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷4,4'-二異氰酸酯 等。其中，較佳為至少包含4,4'-二苯基甲烷二異氰酸酯(MDI)。
於如車輛用途或淡色系用途等需要耐光性之情形時，較佳為併用4,4'-二苯基甲烷二異氰酸酯、及脂肪族二異氰酸酯或脂環族二異氰酸酯。
又，作為聚異氰酸酯，係碳數4~10之直鏈型脂肪族二異氰酸酯，較佳為包含10~50莫耳%之該碳數4~10之直鏈型脂肪族二異氰酸酯，更佳為包含20~40莫耳%。能夠藉由包含10~50莫耳%之碳數4~10之直鏈型脂肪族二異氰酸酯，發揮更良好之硬化性。作為碳數4~10之直鏈型脂肪族二異氰酸酯，較佳為1,5-五亞甲基二異氰酸酯、1,6-六亞甲基二異氰酸酯。
關於製成本實施形態之胺基甲酸酯預聚物時之多元醇與聚異氰酸酯之比率，聚異氰酸酯成分之異氰酸酯基當量相對於所有多元醇成分之羥基當量之比較佳為1.33~5.0，更佳為1.5~3.0。若NCO/OH為1.33~5.0，則柔軟性及與基材A之剝離強度皆更為良好。
關於本實施形態之胺基甲酸酯預聚物，可調配具有官能基數3~5之末端異氰酸酯基之聚異氰酸酯交聯劑作為調配成分。就硬化性及與基材之密接性之觀點而言，相對於胺基甲酸酯預聚物100質量份，較佳為含有30質量%以下之該聚異氰酸酯交聯劑，更佳為含有2~20質量%。
本實施形態之胺基甲酸酯預聚物之製造方法並無特別限定。例如，能夠以NCO/OH成為1.33~5.0之方式將聚異氰酸酯混合於既述之多元醇，於80~120℃下使其等反應60~120分鐘左右而製造。
再者，於胺基甲酸酯預聚物中，視需要可適量調配多官能基聚異氰酸酯、熱塑性聚合物、黏著賦予樹脂、觸媒、顏料、抗氧化劑、 紫外線吸收劑、界面活性劑、阻燃劑、填充劑、發泡劑等。
(基材)
作為基材A，可使用先前公知之合成人造皮革之基材，例如可列舉：包含斜紋織物、平紋織物等之織物、機械地使該織物之棉布料起毛所獲得之起毛布、嫘縈布、尼龍布、聚酯布、克維拉布、不織布(聚酯、尼龍、各種乳膠)、各種膜、片材等。
設置胺基甲酸酯發泡層前之基材A較佳為含水基材A。即，藉由基材A預先含水，易形成胺基甲酸酯發泡層，並且易控制浸入胺基甲酸酯發泡層之基材之程度，更為提高該等之密接性。
含水基材A之含水率較佳為10~70質量%，更佳為15~50質量%。藉由含水率為10~70質量%，能夠控制發泡速度與發泡密度，並能夠製作柔軟性良好且具有優異之與基材之密接性之合成人造皮革。
於基材A為厚度1000μm之聚酯基布、胺基甲酸酯發泡層之厚度為200μm時之用以自基材A剝離胺基甲酸酯發泡層之剝離力較佳為1.5kgf/inch以上，更佳為2.0kgf/inch以上。藉由為1.5kgf/inch以上，可使例如發泡合成人造皮革與基材A之密接性(剝離強度)超過可實用之水準。剝離力之測定能夠藉由實施例之「剝離強度試驗」中所記載之方法進行測定。
又，於多孔質結構體之胺基甲酸酯發泡層中，較佳為於未形成基材A之側設置有基材B。該情形之基材B例如相當於表皮層，可列舉藉由溶劑系聚胺基甲酸酯、水系聚胺基甲酸酯、TPU(thermoplastic polyurethane，熱塑性聚胺酯)等表皮層形成用塗料形成者，但並無特別限定。
基材A只要係由能夠進行含水處理之素材構成者即可，關於厚度並無特別限定。又，基材B之厚度亦無特別限定，但作為不破壞製作出之合成人造皮革之質感之厚度，較佳為0.01~0.2mm，更佳為0.02~0.1mm。
(胺基甲酸酯發泡層)
關於上述使具有異氰酸酯基之胺基甲酸酯預聚物發泡而成之胺基甲酸酯發泡層之密度，就兼具良好之柔軟性與較大之剝離強度之觀點而言，設為0.10g/cm3~0.60g/cm3，較佳為0.2g/cm3~0.5g/cm3。發泡層之密度能夠藉由實施例中所記載之方法進行測定。
胺基甲酸酯發泡層之厚度較佳為0.05~1.0mm，更佳為0.1~0.8mm。
如上所述，具有藉由本實施形態之胺基甲酸酯預聚物(濕氣硬化型胺基甲酸酯預聚物)於濕氣硬化時發泡而形成之胺基甲酸酯發泡層之本實施形態之多孔層結構體，適用於鞋子、衣物、包、傢俱、車輛內飾材料(例如儀錶面板、車門、控制台、座椅)、隔熱材料、吸音材料、衝擊吸收材料等。
[2.多孔層結構體之製造方法]
本實施形態之多孔層結構體之製造方法包含：基材含水處理步驟，其對基材A實施含水處理而製成含水基材A；胺基甲酸酯預聚物塗佈步驟，其形成將具有異氰酸酯基之胺基甲酸酯預聚物塗佈於基材B上而成之胺基甲酸酯預聚物塗膜；塗膜結構體製作步驟，其貼合含水基材A與於上述基材B上形成之胺基甲酸酯預聚物塗膜而製作塗膜結構體；及時效處理步驟，其對塗膜結構體實施時效處理。
以下，對各步驟進行說明。
(基材含水處理步驟)
例如，於利用卷對卷方法製作多孔層結構體之情形時，作為含水處理步驟，一面捲出卷狀之基材A，一面使其通過裝有水之含浸槽之水中。藉此，將基材A浸漬於水。於含浸槽含浸之時間根據基材A之材質而不同，作為於該基材中充分地吸收水分之時間，例如較佳為5~60秒左右。之後，藉由通過兩個輥間去除不必要之水，製成含水基材A。此時，能夠藉由調整兩個輥間之間隙，調整含水率。之後，為了與塗佈有胺基甲酸酯預聚物之基材B進行貼合，將含水基材A捲出至位於下游之例如層壓輥側。
再者，關於含水處理步驟，除使基材A通過裝有水之含浸槽之水中之方法以外，亦可為使其與蒸汽或噴霧接觸之方法。
(胺基甲酸酯預聚物塗佈步驟)
例如一面捲出成為表皮之卷狀基材B，一面將收容於熔化器等之胺基甲酸酯預聚物塗佈於該基材B，形成胺基甲酸酯預聚物塗膜。此處，因胺基甲酸酯預聚物不含水分，故幾乎不會於塗膜形成後發泡。又，就適用期之方面而言亦為有效。
再者，胺基甲酸酯預聚物如上所述，具有異氰酸酯基、實質上不含揮發成分、且滿足既述之(a)~(c)之至少任一種組成。該胺基甲酸酯預聚物收容於熔化器等，備用於胺基甲酸酯預聚物塗佈步驟中之塗佈。
胺基甲酸酯預聚物塗膜之厚度亦視胺基甲酸酯預聚物之黏度或組成而定，但較佳為設為50~500μm，更佳為設為100~300μm。
形成有胺基甲酸酯預聚物塗膜之基材B為了與含水基材A進行貼合，例如捲出至層壓輥側。
(塗膜結構體製作步驟)
為了將於基材B上形成之胺基甲酸酯預聚物塗膜貼合於基材A，例如將含水基材A與基材B捲出至包含1對輥之層壓輥，並於此處進行層壓，藉此製作塗膜結構體。之後，卷狀地進行捲取，送至用以進行發泡處理之時效處理步驟。
(時效處理步驟)
於時效處理步驟中，於15~80℃下，並於40~95%RH之狀態下將卷狀之塗膜結構體保持48~120小時，從而完成時效處理。藉由該時效處理，產生發泡，從而製作本實施形態之多孔層結構體。
(水蒸氣接觸步驟)
又，於本製造方法中，較佳為於塗膜結構體製作步驟與時效處理步驟之間包含使水蒸氣接觸塗膜結構體之水蒸氣接觸步驟。於水蒸氣接觸步驟中，將環境設為30~60℃(較佳為35~55℃)、80%RH以上(較佳為85%RH以上)，關於該環境下之時間，雖視溫度條件或濕度條件而定，但較佳為設為20秒以上(較佳為25~60秒)。
能夠藉由水蒸氣接觸步驟提高塗膜結構體之含水率，因此易於之後之時效處理步驟中獲得良好之發泡率。即，能夠良好地控制發泡程度。
於如以上之步驟中，不會於胺基甲酸酯預聚物之塗膜形成後產生發泡。因此，可於無發泡(即泡沫)之狀態下進行之後之貼合。其結果為，能夠於基材與胺基甲酸酯發泡層之間達成較高之密接性。並且，因可藉由時效處理步驟進行充分之發泡，故可形成維持較高之密接性、且柔 軟性良好之胺基甲酸酯發泡層。
如上所述，本實施形態之多孔層結構體能夠發揮良好之柔軟性及與基材A之密接性(剝離力)，認為其係由如下述之構成所致。
即，首先，關於未藉由本發明之製造方法製作之先前之多孔層結構體20，如圖2所示般位於基材A22與基材B26之間之胺基甲酸酯發泡層24之下表面24A幾乎未浸入基材A22側。其原因在於，於先前之方法中，於塗佈經發泡之胺基甲酸酯預聚物後貼合未特別進行事先處理(例如含水處理)之基布，因此，胺基甲酸酯發泡層24與基材A22之密接性小於本發明。
另一方面，關於藉由本發明之製造方法製作之多孔層結構體10，如圖1所示般位於基材A12與基材B16之間之胺基甲酸酯發泡層14之下表面14A恰好地浸入基材A12側，因此認為由於投錨效應而使胺基甲酸酯發泡層14與基材A12之密接性變得非常大。
就獲得由投錨效應所帶來之良好之密接性之觀點而言，作為發泡層浸入基材A之程度，較佳為發泡層自表面含浸至少相對於基材A之厚度約10%以上。若浸入程度小於10%，則難以充分展現密接性。但是，於如含浸至發泡層占基材A之厚度之大半之程度之情形時，會產生破壞柔軟性或未充分展現密接性等異常。合適之含浸程度因基材A之種類而不同，但該等可藉由貼合步驟前之基材A之含水處理進行控制。
再者，多孔層結構體能夠以原本之狀態用作合成人造皮革，亦可適當進行例如表面處理劑之塗佈或與其他基材之貼合等處理。
[實施例]
其次，進而詳細地利用實施例及比較例對本發明進行說 明。但是，本發明並不限定於實施例等。再者，數量平均分子量藉由GPC(gel permeation chromatography，凝膠層析儀)(聚苯乙烯換算)進行測定。
[實施例1~41、比較例1~34]
(胺基甲酸酯預聚物之合成)
以表2~10所示之各調配量將下述表1所示之多元醇放入賦予了攪拌機、溫度計、氣體導入口等之500毫升之玻璃製反應容器，進行加熱、減壓之脫水處理後，封入氮氣，將內溫設為100℃並進行攪拌後，以特定量(NCO/OH=1.3~5.0)放入MDI，使其攪拌反應120分鐘，獲得胺基甲酸酯預聚物。
Figure 108134384-A0305-02-0018-1
再者，凝膠化點以如下方式測定。
首先，確認試樣(多元醇)之非揮發成分後，以於DMF(水分0.03質量%以下)中成為10質量%溶液之方式進行調整，藉由螺旋槳攪拌器進行攪拌，獲得均一之DMF溶液。
將該DMF 10g放入300ml之錐形燒瓶，進而添加90g DMF，利用磁攪拌器均一地攪拌，獲得1質量% DMF溶液100g。一面於25±1℃之溫度條件下持續攪拌該溶液，一面藉由滴定管滴加蒸餾水，將白濁不再消失之滴水量(微白濁時之滴水量：ml)設為凝膠化點。
再者，將DMF設為1級品試劑，使用以不吸收水分之方式保管者。
(表皮之製作)
將用於合成人造皮革之溶劑型聚胺酯樹脂之Resamine NE-8875-30(大日精化工業股份有限公司)、用於合成人造皮革之著色劑之Seikaseven BS-780(大日精化工業股份有限公司)與作為稀釋溶劑之甲基乙基酮及二甲基甲醯胺混合，利用棒式塗佈機以250μm/wet之塗佈量均一地塗佈於離型紙上後，使其於120℃下乾燥5分鐘，獲得膜厚40~50μm之附有表皮之膜(基材B)。
(合成人造皮革之製作)
以形成塗佈膜厚100μm之塗膜之方式將加熱至100℃之胺基甲酸酯預聚物塗佈於上述離型紙上形成之表皮，利用層壓輥加熱壓接經含水處理或未經含水處理之基布(基材A)，製作塗膜結構體。作為時效處理步驟，於溫度25℃、相對濕度65%之環境下保持120小時，使塗膜結構體熟成。剝離離型紙而製成評估用合成人造皮革。對其進行下述評估。將結果示於下述表。
再者，基布使用織物(聚酯之圓編之聚胺基甲酸酯基布、厚度1.0mm)。關於含水處理，藉由如下操作進行：使基布含浸於水後，利用適當調整了輥間距之壓液機均一地擠榨。又，藉由調整壓液機之輥間距，獲得所期望之含水率。
(發泡程度評估：發泡層之密度)
利用各胺基甲酸酯預聚物製作評估用合成人造皮革後，將該合成人造皮革切割為10cm×10cm見方，另外，將含水處理前之基材A切割為10cm×10cm、將離型紙上形成之表皮切割為10cm×10cm，並自離型紙剝離，藉由下述式計算發泡層之密度。
(1)合成人造皮革之重量測定、計算：根據合成人造皮革整體之重量：u、基材A之重量：v、表皮層之重量：w，藉由下述式求出發泡層之重量。
發泡層之重量：s=u-v-w
(2)合成人造皮革之厚度測定、計算：根據合成人造皮革整體之厚度：l、基材A之厚度：m、表皮層之厚度：n，藉由下述式求出發泡層之厚度。
發泡層之厚度：t=l-m-n
(3)發泡層之密度計算：藉由下述式求出發泡層之密度。
發泡層之密度=s÷t×10×10(g/cm3)
再者，能夠藉由發泡層之密度為0.10g/cm3~0.60g/cm3，兼具良好之柔軟性與較大之剝離強度。
(剝離強度試驗)
將寬度17mm之胺基甲酸酯系HM(Hot Melt，熱熔)膠帶熱壓接於評估用合成人造皮革後，製作寬度25mm之短條狀之測定試樣，藉由AGS-J(島津製作所)以200mm/min之速度拉伸，測定接著強度，為1.5kgf/inch以上，藉此判斷出發泡合成人造皮革與基材A之密接性(剝離強度)超過可實用之水準。
(耐水解試驗)
以膜厚成為40~50μm之方式將胺基甲酸酯預聚物塗佈於離型紙上，於25℃/60RH%之環境下使其熟成120小時，製成耐水解試驗中使用之膜。將剝離了離型紙之膜置於70℃/95RH%之環境下，每週進行耐久試驗，直至進行7週，使用AGS-J(島津製作所)進行拉伸強度試驗。評估指標如下。
維持斷裂強度保持率50%以上之時間：1~4週 ×
維持斷裂強度保持率50%以上之時間：5~6週 ○
維持斷裂強度保持率50%以上之時間：7週以上 ◎
再者，○及◎為合格。
[關於判定合格與否]
於各表中，將發泡層之密度為0.1~0.6g/cm3、且符合剝離強度之基準(1.5kgf/inch以上)者記為○，將發泡層之密度並非0.1~0.6g/cm3、或不符合剝離強度之基準者記為×，而表示判定之結果。
Figure 108134384-A0305-02-0022-2
Figure 108134384-A0305-02-0023-11
Figure 108134384-A0305-02-0024-4
根據表2~4可知本實施例具有良好之發泡程度。
Figure 108134384-A0305-02-0025-5
Figure 108134384-A0305-02-0026-6
根據表5、6，藉由基材之含水率為15~50質量%，可獲得良好之發泡程度及剝離強度。
Figure 108134384-A0305-02-0027-7
Figure 108134384-A0305-02-0028-8
根據表7、8可知藉由貼合後之水蒸氣處理(水蒸氣接觸步驟)發泡程度提高。但是，即便為最易發泡且親水性等級較高之基布，若不含水，則貼合後進行水蒸氣處理時亦不會充分地發泡。
Figure 108134384-A0305-02-0029-9
根據表9，可知藉由胺基甲酸酯預聚物包含於所有多元醇成分中佔50質量%以上之聚碳酸酯多元醇成分，耐水解性變得良好。
Figure 108134384-A0305-02-0030-10
根據表10，即便基材之含水率相同，藉由NCO/OH比為1.33~5，亦可獲得良好之發泡程度及剝離強度。
10:多孔層結構體
12:基材A
14:胺基甲酸酯發泡層
14A:胺基甲酸酯發泡層之下表面
16:基材B

Claims (7)

  1. 一種多孔層結構體，其包含基材A及設置於該基材A上而成之胺基甲酸酯發泡層，設置上述胺基甲酸酯發泡層前之上述基材A為含水基材A，該含水基材A之含水率為10~70質量%，上述胺基甲酸酯發泡層為使具有異氰酸酯基之胺基甲酸酯預聚物發泡而成之發泡層，上述胺基甲酸酯發泡層之密度為0.10~0.60g/cm3，上述胺基甲酸酯預聚物實質上不含揮發成分，且滿足下述(A)~(C)之至少任一種組成：(A)包含於所有多元醇成分中佔50質量%以上之凝膠化點為20ml以上且未達30ml之多元醇成分(a)之組成；(B)包含於所有多元醇成分中佔30質量%以上之凝膠化點為30ml以上且未達50ml之多元醇成分(b)之組成；(C)包含於所有多元醇成分中佔10質量%以上之凝膠化點為50ml以上之多元醇成分(c)之組成。
  2. 如請求項1之多孔層結構體，其中於上述基材A為聚酯基布、胺基甲酸酯發泡層之厚度為200μm時之用以自基材A剝離胺基甲酸酯發泡層之剝離力為1.5kgf/inch以上。
  3. 如請求項1之多孔層結構體，其中上述胺基甲酸酯預聚物包含於所有 多元醇成分中佔50質量%以上之聚碳酸酯多元醇成分。
  4. 如請求項2之多孔層結構體，其中上述胺基甲酸酯預聚物包含於所有多元醇成分中佔50質量%以上之聚碳酸酯多元醇成分。
  5. 如請求項1至4中任一項之多孔層結構體，其中於上述胺基甲酸酯預聚物中，聚異氰酸酯成分之異氰酸酯基當量相對於上述所有多元醇成分之羥基當量之比為1.33~5.0。
  6. 一種多孔層結構體之製造方法，其係如請求項1至5中任一項之多孔層結構體之製造方法，其包含：基材含水處理步驟，其對基材A實施含水處理而製成含水率為10~70質量%之含水基材A；胺基甲酸酯預聚物塗佈步驟，其形成將具有異氰酸酯基之胺基甲酸酯預聚物塗佈於基材B上而成之胺基甲酸酯預聚物塗膜；塗膜結構體製作步驟，其貼合上述含水基材A與於上述基材B上形成之上述胺基甲酸酯預聚物塗膜而製作塗膜結構體；及時效處理步驟，其以使上述胺基甲酸酯預聚物塗膜發泡形成胺基甲酸酯發泡層之方式對上述塗膜結構體實施時效處理；上述胺基甲酸酯預聚物實質上不含揮發成分，且滿足下述(A)~(C)之至少任一種組成：(A)包含於所有多元醇成分中佔50質量%以上之凝膠化點為20ml以上且未達30ml之多元醇成分(a)之組成； (B)包含於所有多元醇成分中佔30質量%以上之凝膠化點為30ml以上且未達50ml之多元醇成分(b)之組成；(C)包含於所有多元醇成分中佔10質量%以上之凝膠化點為50ml以上之多元醇成分(c)之組成。
  7. 如請求項6之多孔層結構體之製造方法，其包含於上述塗膜結構體製作步驟與上述時效處理步驟之間，使水蒸氣接觸上述塗膜結構體之水蒸氣接觸步驟。
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