TWI782129B - 發泡胺基甲酸酯薄片、及合成皮革 - Google Patents

發泡胺基甲酸酯薄片、及合成皮革 Download PDF

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Publication number
TWI782129B
TWI782129B TW107139261A TW107139261A TWI782129B TW I782129 B TWI782129 B TW I782129B TW 107139261 A TW107139261 A TW 107139261A TW 107139261 A TW107139261 A TW 107139261A TW I782129 B TWI782129 B TW I782129B
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Taiwan
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mass
urethane resin
parts
aforementioned
urethane
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TW107139261A
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English (en)
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TW201922923A (zh
Inventor
鐵井智博
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日商迪愛生股份有限公司
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/0047—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by incorporating air, i.e. froth
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Abstract

本發明提供一種發泡胺基甲酸酯薄片，其特徵為藉由含有胺基甲酸酯樹脂(A)、水性介質(B)、及碳原子數為10以上之界面活性劑(C)的水性胺基甲酸酯樹脂組成物形成，密度為200~1,000kg/m3。又，本發明提供一種合成皮革，其係前述至少具有基材(i)、及聚胺基甲酸酯層(ii)之合成皮革，特徵為該聚胺基甲酸酯層(ii)為藉由如請求項1至4中任一項之發泡胺基甲酸酯薄片形成者。前述聚胺基甲酸酯層(ii)，亦可為進行壓印加工者。前述界面活性劑(C)，較佳為硬脂酸鹽，前述胺基甲酸酯樹脂(A)為具有陰離子性基者，且較佳為使用流動起始溫度為80℃以上者。

Description

發泡胺基甲酸酯薄片、及合成皮革
本發明係關於一種發泡胺基甲酸酯薄片。
聚胺基甲酸酯樹脂，因為具有優異的機械強度、及柔軟性，所以至今為止係於塗布劑、接著劑等各式各樣的用途使用。其中，至今為止係廣泛利用含有二甲基甲醯胺(DMF)的溶劑系胺基甲酸酯樹脂，但DMF的法律限制逐年變嚴格，弱溶劑化、水系化、無溶劑化等環境對應製品之開發已成為當務之急。
其中，將胺基甲酸酯樹脂分散於水中的水系胺基甲酸酯(PUD)係最積極地被進行研究。在將該水系胺基甲酸酯利用於各式各樣的用途之際，以提升質地等為目的，作為發泡體成型的需求也多。作為藉由水系胺基甲酸酯將發泡體成型的方法，探討例如，摻合微膠囊、使二氧化碳等氣體分散於PUD摻合液的機械發泡等(例如參照專利文獻1)。然而，摻合微膠囊的方法，所得到的發泡體之質地變不佳，微膠囊的膨脹所致之平滑性不佳係成為問題。又，使氣體分散的方法，在製造發泡體的過程，由於夾雜於摻合液的氣泡消失等，因此氣泡尺寸等的控制為困難，且難以穩定地得到質地良好的發泡體。
先前技術文獻 專利文獻
專利文獻1 日本特開2007-191810號公報
本發明欲解決之課題，在於提供一種使用含有水的胺基甲酸酯樹脂組成物，質地及拉伸強度優異之發泡胺基甲酸酯薄片。
本發明提供一種發泡胺基甲酸酯薄片，其特徵為藉由含有胺基甲酸酯樹脂(A)、水(B)、及碳原子數為10以上之界面活性劑(C)的胺基甲酸酯樹脂組成物形成，密度為200~1,000kg/m3。
又，本發明提供一種合成皮革，其係至少具有基材(i)、及聚胺基甲酸酯層(ii)之合成皮革，特徵為前述聚胺基甲酸酯層(ii)為藉由前述發泡胺基甲酸酯薄片形成者。
本發明的發泡胺基甲酸酯薄片為質地及拉伸強度優異者。
又，在將前述發泡胺基甲酸酯薄片應用於合成皮革之際，其係進一步為剝離強度亦優異、且能在其表面上均勻地製作外觀設計性優異的壓印加工者。
用以實施發明之形態
本發明的發泡胺基甲酸酯薄片為藉由含有胺基甲酸酯樹脂(A)、水(B)、及未具有芳香環且具有碳原子數為10以上的疏水部之界面活性劑(C)的胺基甲酸酯樹脂組成物形成，密度為200~1,000kg/m3者。
前述胺基甲酸酯樹脂(A)為可分散於後述的水(B)中等者，且可使用例如：具有陰離子性基、陽離子性基、非離子性基等親水性基的胺基甲酸酯樹脂；以乳化劑強制地分散於水(B)中的胺基甲酸酯樹脂等。該等之胺基甲酸酯樹脂(A)，可單獨使用，亦可併用2種以上。從製造穩定性之觀點而言，該等中，較佳為使用具有親水性基的胺基甲酸酯樹脂，更佳為具有陰離子性基的水性胺基甲酸酯樹脂。
作為得到前述具有陰離子性基的胺基甲酸酯樹脂之方法，可舉出例如，將選自包含具有羧基的二醇化合物、及具有磺醯基的化合物的群組之1種以上的化合物作為原料使用之方法。
作為前述具有羧基的二醇化合物，可使用例如：2,2-二羥甲基丙酸、2,2-二羥甲基丁酸、2,2-二羥甲基酪酸、2,2-二羥甲基丙酸、2,2-戊酸等。該等之化合物，可單獨使用，亦可併用2種以上。
作為前述具有磺醯基的化合物，可使用例如：3,4-二胺基丁烷磺酸、3,6-二胺基-2-甲苯磺酸、2,6-二胺基苯磺酸、N-(2-胺乙基)-2-胺乙基磺酸等。該等之化合物，可單獨使用，亦可併用2種以上。
從得到更優異的水分散穩定性之觀點而言，作為使用為了製造前述具有陰離子性基的胺基甲酸酯樹脂而使用的原料時的使用量，較佳為胺基甲酸酯樹脂(A)的原料之合計質量中0.1~4.8質量%的範圍，更佳為0.5~4質量%的範圍，進一步更佳為1~3質量%的範圍。
前述羧基及磺醯基，在胺基甲酸酯樹脂組成物中，也可一部分或全部被鹼性化合物中和。作為前述鹼性化合物，可使用例如：氨、三乙胺、吡啶、
Figure 107139261-A0202-12-0004-6
啉等有機胺；單乙醇胺、二甲基乙醇胺等烷醇胺；包含鈉、鉀、鋰、鈣等之金屬鹼化合物等。
作為得到前述具有陽離子性基的胺基甲酸酯樹脂之方法，可舉出例如，使用具有胺基的化合物之1種或2種以上作為原料的方法。
作為前述具有胺基的化合物，可使用例如：三伸乙四胺、二伸乙三胺等具有1級及2級胺基的化合物；N-甲基二乙醇胺、N-乙基二乙醇胺等N-烷基二烷醇胺、N-甲基二胺基乙胺、N-乙基二胺基乙胺等之N-烷基二胺基烷胺等具有3級胺基的化合物等。該等之化合物，可單獨使用，亦可併用2種以上。
作為前述胺基甲酸酯樹脂(A)，具體而言，可使用例如，為了製造多異氰酸酯(a1)、多元醇(a2)、及前述具有親水性基的水性胺基甲酸酯樹脂而使用的原料之反應物。
作為前述多異氰酸酯(a1)，可使用例如：苯二異氰酸酯、甲苯二異氰酸酯、二苯甲烷二異氰酸酯、苯二甲基二異氰酸酯、萘二異氰酸酯、多亞甲基多苯基多異氰酸酯、碳二亞胺化二苯甲烷多異氰酸酯等芳香族多異氰酸酯；六亞甲基二異氰酸酯、離胺酸二異氰酸酯、環己烷二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷二異氰酸酯、苯二甲基二異氰酸酯、四甲基苯二甲基二異氰酸酯、二聚酸二異氰酸酯、降莰烯二異氰酸酯等脂肪族或脂環式多異氰酸酯等。該等之多異氰酸酯，可單獨使用，亦可併用2種以上。
從製造穩定性、及得到之皮膜的機械物性之觀點而言，作為前述多異氰酸酯(a1)的使用量，較佳為前述胺基甲酸酯樹脂(A)的原料之合計質量中5~40質量%的範圍，更佳為10~30質量%的範圍。
作為前述多元醇(a2)，可使用例如：聚醚多元醇、聚酯多元醇、聚丙烯酸多元醇、聚碳酸酯多元醇、聚丁二烯多元醇等。該等之多元醇，可單獨使用，亦可併用2種以上。
從得到之皮膜的機械強度之觀點而言，作為前述多元醇(a2)的數量平均分子量，較佳為500~8,000的範圍，更佳為800~4,000的範圍。再者，前述多元醇 (a2)的數量平均分子量係表示利用凝膠滲透管柱層析(GPC)法測定的數值。
前述多元醇(a2)中，視需要，也可併用數量平均分子量為50~450的鏈伸長劑(a2’)。作為前述鏈伸長劑(a2’)，可使用例如：乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、六亞甲二醇、蔗糖、甲二醇、丙三醇、山梨糖醇、雙酚A、4,4’-二羥基聯苯、4,4’-二羥基二苯醚、三羥甲基丙烷等具有羥基的鏈伸長劑；乙二胺、1,2-丙二胺、1,6-六亞甲二胺、哌
Figure 107139261-A0305-02-0008-5
、2,5-二甲基哌
Figure 107139261-A0305-02-0008-6
、異佛爾酮二胺、1,2-環己二胺、1,3-環己二胺、1,4-環己二胺、4,4’-二環己基甲烷二胺、3,3’-二甲基-4,4’-二環己基甲烷二胺、1,4-環己二胺、聯胺等具有胺基的鏈伸長劑等。該等之鏈伸長劑，可單獨使用，亦可併用2種以上。
從容易調整所得到之胺基甲酸酯樹脂(A)的流動起始溫度，得到更優異的拉伸強度之觀點而言，作為使用前述鏈伸長劑(a2’)時的使用量，較佳為胺基甲酸酯樹脂(A)的原料之合計質量中0.8~4.3質量%的範圍，更佳為1~3.5質量%的範圍，進一步更佳為1.5~3.2質量%的範圍。
作為前述胺基甲酸酯樹脂(A)之製造方法，可舉出例如：將為了製造前述多元醇(a2)、前述具有親水性基的胺基甲酸酯樹脂而使用的原料、前述鏈伸長劑(a2’)、及前述多異氰酸酯(a1)一次性投入，並進行反應的方法。該等之反應，可舉出例如，在50~100℃進行3~10小時。
作為製造前述胺基甲酸酯樹脂(A)之際的前述多元醇(a2)所具有之羥基、用以製造前述具有親水性基的胺基甲酸酯樹脂之原料所具有的羥基及胺基、以及前述鏈伸長劑(a2’)所具有的羥基及胺基之合計與前述多異氰酸酯(a1)具有的異氰酸酯基之莫耳比[異氰酸酯基/(羥基及胺基)]，較佳為0.8~1.2的範圍，更佳為0.9~1.1的範圍。
在製造前述胺基甲酸酯樹脂(A)之際，較佳為使殘存於前述胺基甲酸酯樹脂(A)的異氰酸酯基喪失活性。在使前述異氰酸酯基喪失活性時，較佳為使用甲醇等具有1個羥基的醇。作為前述醇的使用量，較佳為相對於胺基甲酸酯樹脂(A)100質量份為0.001~10質量份的範圍。
又，在製造前述胺基甲酸酯樹脂(A)之際，亦可使用有機溶劑。作為前述有機溶劑，可使用例如：丙酮、甲基乙基酮等酮化合物；四氫呋喃、二
Figure 107139261-A0305-02-0009-7
烷等醚化合物；乙酸乙酯、乙酸丁酯等乙酸酯化合物；乙腈等腈化合物；二甲基甲醯胺、N-甲基吡咯啶酮等醯胺化合物等。該等之有機溶媒，可單獨使用，亦可併用2種以上。再者，前述有機溶劑，較佳為在得到最後的胺基甲酸酯樹脂組成物之際，藉由蒸餾法等去除。
從可將利用後述的起泡步驟產生的氣泡穩定地保持(尤其在乾燥步驟中)，穩定地使發泡胺基甲酸酯薄片的密度成為200~1,000kg/m3的範圍之觀點而言，作為前述胺基甲酸酯樹脂(A)的流動起始溫度，較佳為80℃以上，更佳為80~220℃的範圍。
作為調整前述胺基甲酸酯樹脂(A)的流動起始溫度之方法，主要可舉出根據後述之為胺基甲酸酯樹脂(A)的原料之多元醇(a2)的種類、鏈伸長劑(a2’)的使用量、及多異氰酸酯(a1)的種類進行調整的方法。作為將前述流動起始溫度調高的方法，可舉出例如：使用如聚碳酸酯多元醇般結晶性高的多元醇作為多元醇(a2)、增加鏈伸長劑(a2’)的使用量、及使用如二環己基甲烷二異氰酸酯或4,4’-二苯甲烷二異氰酸酯般結晶性高的多異氰酸酯作為多異氰酸酯(a1)等。又，作為將前述流動起始溫度調低的方法，可舉出例如：使用如聚氧基丙二醇般結晶性低的多元醇作為多元醇(a2)、減少鏈伸長劑(a2’)的使用量、及使用如異佛爾酮二異氰酸酯或甲苯二異氰酸酯般結晶性低的多異氰酸酯作為多異氰酸酯(a1)等。因此，藉由適當選擇該等之方法，可調整前述胺基甲酸酯樹脂(A)的流動起始溫度。再者，前述胺基甲酸酯樹脂(A)的流動起始溫度之測定方法係於後述的實施例中記載。
在使用具有陰離子性基的胺基甲酸酯樹脂作為前述胺基甲酸酯樹脂(A)時，從容易調整流動起始溫度，得到更優異的氣泡保持性、質地、及拉伸強度之觀點而言，較佳為使用為含有選自包含4,4’-二苯甲烷二異氰酸酯、甲苯二異氰酸酯、環己基甲烷二異氰酸酯、及異佛爾酮二異氰酸酯的群組之1種以上的多異氰酸酯、多元醇(a2)、具有羧基的二醇化合物、以及具有羥基的鏈伸長劑(a2’)之鏈伸長劑的反應物之具有陰離子性基的胺基甲酸酯樹脂(A-A-1)。
作為前述水(B)，可使用例如離子交換水、蒸餾水等。該等之水，可單獨使用，亦可使用2種以上。
從水分散穩定性、及作業性之觀點而言，作為前述胺基甲酸酯樹脂(A)與前述水(B)之質量比[(A)/(B)]，較佳為10/80~70/30的範圍，更佳為20/80~60/40的範圍。
前述界面活性劑(C)，為了防止利用起泡產生的泡消失，必須使用未具有芳香環且具有碳原子數為10以上之疏水部者。
作為前述界面活性劑(C)，可使用例如：下述通式(1)所示之界面活性劑；脂肪酸鹽、琥珀酸鹽、磺基琥珀酸鹽、十八基磺基琥珀酸鹽、磺基琥珀酸酯等。該等之界面活性劑，可單獨使用，亦可併用2種以上。
RCO 2 - X + (1)
(式(1)中，R表示具有碳原子數為10~20之直鏈或分支結構的烷基，X表示Na、K、NH4、
Figure 107139261-A0202-12-0009-11
啉、乙醇胺、或三乙醇胺。)
從具有更優異的氣泡保持性之觀點而言，作為前述界面活性劑(C)，前述者之中，較佳為使用前述通式(1)所示之界面活性劑，更佳為使用表示碳原子數為13~19之直鏈的烷基者，進一步更佳為硬脂酸鹽。
從得到更優異的氣泡保持性之觀點而言，作為前述界面活性劑(C)的使用量，相對於前述胺基甲酸酯樹脂(A)(=固體成分)100質量份，較佳為0.01~10質量份的範圍，更佳為0.1~5質量份的範圍。
前述胺基甲酸酯樹脂組成物含有前述胺基甲酸酯樹脂(A)、水(B)、及界面活性劑(C)作為必要成分，但視需要亦可含有其它的添加劑。
作為前述其它的添加劑，可使用例如：交聯劑、中和劑、增黏劑、胺基甲酸酯化觸媒、填充劑、顏料、染料、阻燃劑、均染劑、抗黏結劑等。該等之添加劑，可單獨使用，亦可併用2種以上。
作為前述交聯劑，以發泡胺基甲酸酯薄片的機械強度之提升等為目的而使用，且可使用例如，多異氰酸酯交聯劑、環氧交聯劑、三聚氰胺交聯劑、
Figure 107139261-A0305-02-0012-8
唑啉交聯劑等。該等之交聯劑，可單獨使用，亦可併用2種以上。作為使用前述交聯劑時的使用量，例如，相對於前述胺基甲酸酯樹脂(A)(=固體成分)100質量份，較佳為0.01~100質量份的範圍，更佳為0.1~50質量份的範圍，進一步更佳為0.5~30質量份的範圍，特佳為1~10質量份。
接著，針對本發明的發泡胺基甲酸酯薄片之製造方法進行說明。
前述發泡胺基甲酸酯薄片係使前述胺基甲酸酯樹脂組成物起泡，得到起泡液，將該起泡液塗布於基材，並進行乾燥，得到200~1,000kg/m3的密度，藉以製造。
作為使前述胺基甲酸酯樹脂組成物起泡，得到起泡液之方法，可舉出例如，利用手之攪拌、或使用機械式混拌機等混合機之方法。在使用混合機時，可舉出例如，以500~3,000rpm進行10秒鐘~3分鐘攪拌的方法。此時，從容易將發泡胺基甲酸酯薄片的密度調整為本發明所界定的範圍之觀點而言，在起泡之前後，較佳為成為1.3~7倍之體積，更佳為成為1.2~2倍之體積，進一步更佳為成為1.3~1.7倍之體積。
作為將得到的起泡液塗布於脫模紙等基材的方法，可舉出例如，使用輥塗機、刀塗機、缺角輪塗機、塗抹器等的方法。
作為前述塗布物的乾燥方法，可舉出例如，在60~130℃的溫度進行30秒鐘~10分鐘乾燥的方法。
作為利用以上的方法得到的發泡胺基甲酸酯薄片之厚度，例如為5~200μm。
前述發泡胺基甲酸酯薄片的密度，必須為200~1,000kg/m3。若前述密度為該範圍，則成為兼具優異的質地與拉伸強度之薄片。從可作為發泡胺基甲酸酯薄片利用於各式各樣的用途之觀點而言，作為前述密度，較佳為300~900kg/m3的範圍，更佳為400~800kg/m3的範圍。再者，前述發泡胺基甲酸酯薄片的密度係表示藉由將發泡胺基甲酸酯薄片的質量除以體積而算出的數值。
接著，對於本發明之合成皮革進行說明。
本發明之合成皮革，其係至少具有基材(i)、及聚胺基甲酸酯層(ii)之合成皮革，前述聚胺基甲酸酯層(ii)為藉由前述發泡胺基甲酸酯薄片形成者。
作為前述合成皮革之製造方法，可舉出例如：(X)使前述胺基甲酸酯樹脂組成物起泡，得到起泡液，將該起泡液塗布於脫模紙上，並進行乾燥，與前述基材(i)貼合的方法；(Y)使前述胺基甲酸酯樹脂組成物起泡，得到起泡液，將該起泡液，塗布於在脫模紙上製作的表皮層上，並進行乾燥，與前述基材(i)貼合的方法；及(Z)使前述胺基甲酸酯樹脂組成物起泡，得到起泡液，將該起泡液塗布於前述基材(i)上，並進行乾燥，且視需要，於其上貼合在脫模紙上製作的表皮層(iii)之方法等。
作為前述基材(i)，可使用例如：利用聚酯纖維、聚乙烯纖維、尼龍纖維、丙烯酸系纖維、聚胺基甲酸酯纖維、乙酸酯纖維、嫘縈纖維、聚乳酸纖維、棉、麻、絲綢、羊毛、玻璃纖維、碳纖維、此等之混紡纖維等所得的不織布、織布、編織物等纖維基材；對前述不織布含浸聚胺基甲酸酯樹脂等樹脂者；進一步於前述不織布設置多孔質層者；熱塑性胺基甲酸酯(TPU)等樹脂基材等。
前述聚胺基甲酸酯層(ii)為藉由前述發泡薄片形成者，從可得到兼具更優異的質地與剝離強度的合 成皮革之觀點而言，作為其密度，較佳為300~900kg/m3的範圍，更佳為400~800kg/m3的範圍。再者，前述聚胺基甲酸酯層(ii)的密度係表示將自每邊10cm的合成皮革之重量減去每邊10cm的基材(i)之重量的數值，除以聚胺基甲酸酯層(ii)之厚度而得的數值。再者，前述聚胺基甲酸酯層(ii)的密度，可藉由將前述胺基甲酸酯樹脂組成物起泡狀況調整。
作為前述表皮層(iii)，可利用周知的材料以周知的方法形成，可使用例如：溶劑系胺基甲酸酯樹脂、水系胺基甲酸酯樹脂、矽酮樹脂、聚丙烯樹脂、聚酯樹脂等。重視柔軟的質地、及耐熱性、耐水解性時，較佳為使用聚碳酸酯系胺基甲酸酯樹脂。又，為了在環境對應下之DMF減少化，更佳為使用水系聚碳酸酯系胺基甲酸酯樹脂。
在前述表皮層(iii)上，視需要，以耐擦傷性提升等為目的，也可設置表面處理層(iv)。作為前述表面處理層(iv)，可利用周知的材料以周知的方法形成。
如上述，本發明之合成皮革為係藉由使用前述的質地及拉伸強度優異之發泡胺基甲酸酯薄片，而進一步為剝離強度亦優異、且能在其表面上均勻地製作外觀設計性優異的壓印加工者。
作為在前述聚胺基甲酸酯層(ii)上進行壓印加工的方法，可舉出例如：在合成皮革的聚胺基甲酸酯層(ii)上，載置施加有凹凸花紋等外觀設計性的脫模紙，以經預熱的輥等進行熱加壓的方法；及使用施加有凹凸 花紋等外觀設計性的輥塗機，進行熱加壓的方法。在前述熱加壓時，例如，可在50~200℃將輥進行加熱。
[實施例]
以下使用實施例，更詳細地說明本發明。
[合成例1]胺基甲酸酯樹脂(A-1)之調製
在甲基乙基酮3,281質量份及辛酸亞錫0.1質量份之存在下，於70℃使聚碳酸酯多元醇(「NIPPOLLAN 980R」Nippon Polyurethane Industry Co.,Ltd.製、數量平均分子量：2,000)1,000質量份、2,2-二羥甲基丙酸17質量份、乙二醇47質量份、及二苯甲烷二異氰酸酯(以下簡記為「MDI」)344質量份進行反應至溶液黏度達到20,000mPa‧s後，加入甲醇3質量份，使反應停止，得到胺基甲酸酯樹脂的甲基乙基酮溶液。在於該胺基甲酸酯樹脂溶液中混合聚氧乙烯二苯乙烯化苯醚(Hydrophile-Lipophile Balance(以下簡記為「HLB」)：14)70質量份、及三乙胺13質量份後，加入離子交換水800質量份，進行相轉變乳化(phase-transfer emulsification)，藉以得到前述胺基甲酸酯樹脂(A-1)分散於水的乳化液。
接著，藉由自前述乳化液餾去甲基乙基酮，得到包含胺基甲酸酯樹脂(A-1)50質量%之胺基甲酸酯樹脂組成物。
[合成例2]胺基甲酸酯樹脂(A-2)之調製
在甲基乙基酮3,281質量份及辛酸亞錫0.1質量份之存在下，於70℃使聚醚多元醇(「PTMG2000」三菱化學股份有限公司製、數量平均分子量：2,000)1,000質量份、2,2-二羥甲基丙酸17質量份、乙二醇47質量份、及MDI 344質量份進行反應至溶液黏度達到20,000mPa‧s後，加入甲醇3質量份，使反應停止，得到胺基甲酸酯樹脂的甲基乙基酮溶液。在於該胺基甲酸酯樹脂溶液中混合聚氧乙烯二苯乙烯化苯醚(HLB：14)70質量份、及三乙胺13質量份後，加入離子交換水800質量份，進行相轉變乳化，藉以得到前述胺基甲酸酯樹脂(A-2)分散於水的乳化液。
接著，藉由自前述乳化液餾去甲基乙基酮，得到包含胺基甲酸酯樹脂(A-2)50質量%之胺基甲酸酯樹脂組成物。
[合成例3]胺基甲酸酯樹脂(A-3)之調製
在甲基乙基酮3,281質量份及辛酸亞錫0.1質量份之存在下，於70℃使聚酯多元醇(「PLACCEL 220」Daicel股份有限公司製、數量平均分子量：2,000)1,000質量份、2,2-二羥甲基丙酸17質量份、乙二醇47質量份、及MDI 344質量份進行反應至溶液黏度達到20,000mPa‧s後，加入甲醇3質量份，使反應停止，得到胺基甲酸酯樹脂的甲基乙基酮溶液。在於該胺基甲酸酯樹脂溶液中混合聚氧乙烯二苯乙烯化苯醚(HLB：14)70質量份、及三乙胺13質量份後，加入離子交換水800質量份，進行相轉 變乳化，藉以得到前述胺基甲酸酯樹脂(A-3)分散於水的乳化液。
接著，藉由自前述乳化液餾去甲基乙基酮，得到包含胺基甲酸酯樹脂(A-3)50質量%之胺基甲酸酯樹脂組成物。
[合成例4]胺基甲酸酯樹脂(A-4)之調製
在甲基乙基酮1,279質量份及辛酸亞錫0.1質量份之存在下，於70℃使聚碳酸酯多元醇(「NIPPOLLAN 980R」Nippon Polyurethane Industry Co.,Ltd.製、數量平均分子量：2,000)1,000質量份、2,2-二羥甲基丙酸17質量份、及二環己基甲烷二異氰酸酯(以下、簡記為「H12MDI」)262質量份進行反應至異氰酸酯濃度達到1.2質量%，得到胺基甲酸酯預聚物的甲基乙基酮溶液。在於該胺基甲酸酯樹脂溶液中混合聚氧乙烯二苯乙烯化苯醚(Hydrophile-Lipophile Balance(以下簡記為「HLB」)：14)64質量份、及三乙胺28質量份後，加入離子交換水2,650質量份，進行相轉變乳化，藉以得到前述胺基甲酸酯預聚物分散於水的乳化液。在得到的乳化液混合乙二胺21質量份與離子交換水189份，進行鏈伸長反應，藉以得到胺基甲酸酯樹脂組成物。
接著，藉由自胺基甲酸酯樹脂組成物餾去甲基乙基酮與水分，得到包含胺基甲酸酯樹脂(A-4)50質量%之胺基甲酸酯樹脂組成物。
[合成例5]胺基甲酸酯樹脂(A-5)之調製
在甲基乙基酮1,279質量份及辛酸亞錫0.1質量份之存在下，於70℃使聚醚多元醇(「PTMG2000」三菱化學股份有限公司製、數量平均分子量：2,000)1,000質量份、2,2-二羥甲基丙酸17質量份、及H12MDI 262質量份進行反應至異氰酸酯濃度達到1.2質量%，得到胺基甲酸酯樹脂預聚物(A‘-2)的甲基乙基酮溶液。在於該胺基甲酸酯樹脂溶液中混合聚氧乙烯二苯乙烯化苯醚(Hydrophile-Lipophile Balance(以下簡記為「HLB」)：14)64質量份、及三乙胺28質量份後，加入離子交換水2,650質量份，進行相轉變乳化，藉以得到前述胺基甲酸酯預聚物分散於水的乳化液。在得到的乳化液混合乙二胺21質量份與離子交換水189份，進行鏈伸長反應，藉以得到胺基甲酸酯樹脂組成物。
接著，藉由自胺基甲酸酯樹脂組成物餾去甲基乙基酮與水分，得到包含胺基甲酸酯樹脂(A-5)50質量%之胺基甲酸酯樹脂組成物。
[合成例6]胺基甲酸酯樹脂(A-6)之調製
在甲基乙基酮1,279質量份及辛酸亞錫0.1質量份之存在下，於70℃使聚酯多元醇(「PLACCEL 220」Daicel股份有限公司製、數量平均分子量：2,000)1,000質量份、2,2-二羥甲基丙酸17質量份、及H12MDI 262質量份進行反應至異氰酸酯濃度達到1.2質量%，得到胺基甲酸酯樹脂預聚物的甲基乙基酮溶液。在於該胺基甲酸酯樹脂 溶液中混合聚氧乙烯二苯乙烯化苯醚(Hydrophile-Lipophile Balance(以下簡記為「HLB」)：14)64質量份、及三乙胺28質量份後，加入離子交換水2,650質量份，進行相轉變乳化，藉以得到前述胺基甲酸酯預聚物分散於水的乳化液。在得到的乳化液混合乙二胺21質量份與離子交換水189份，進行鏈伸長反應，藉以得到胺基甲酸酯樹脂組成物。
接著，藉由自胺基甲酸酯樹脂組成物餾去甲基乙基酮與水分，得到包含胺基甲酸酯樹脂(A-6)50質量%之胺基甲酸酯樹脂組成物。
[實施例1]
在合成例1所得之胺基甲酸酯樹脂組成物100質量份，加入增黏劑(Borchers公司製「Borchi Gel ALA」)2質量份、硬脂酸銨0.5質量份、及交聯劑(日本觸媒股份有限公司製「EPOCROS WS-700」)4質量份，使用機械式混拌機，以2,000rpm攪拌1分鐘，進行起泡，得到成為1.5倍之體積的起泡液。
將前述塗布於脫模紙，在80℃乾燥3分鐘，進一步在120℃乾燥2分鐘，藉以製造發泡胺基甲酸酯薄片。
[實施例2~8]
將使用的水性胺基甲酸酯樹脂組成物之種類、及硬脂酸銨之使用量，如表1~3所示進行變更，除此以外係與實施例1同樣進行，得到發泡胺基甲酸酯薄片。
[比較例1]
在合成例1所得之胺基甲酸酯樹脂組成物100質量份，加入增黏劑(Borchers公司製「Borchi Gel ALA」)2質量份、十二基苯磺酸鈉1.5質量份、及交聯劑(日本觸媒股份有限公司製「EPOCROS WS-700」)4質量份，使用機械式混拌機，以2,000rpm攪拌1分鐘，進行起泡，得到成為1.5倍之體積的起泡液。
將前述塗布於脫模紙，在80℃乾燥3分鐘，進一步在120℃乾燥2分鐘，藉以製造薄片。
[比較例2]
在合成例1所得之胺基甲酸酯樹脂組成物100質量份，加入增黏劑(Borchers公司製「Borchi Gel ALA」)2質量份、及交聯劑(日本觸媒股份有限公司製「EPOCROS WS-700」)4質量份，使用機械式混拌機，以2,000rpm攪拌1分鐘，進行起泡，得到成為1.5倍之體積的起泡液。
將前述塗布於脫模紙，在80℃乾燥3分鐘，進一步在120℃乾燥2分鐘後，由於氣泡在乾燥步驟中消失，因此形成幾乎無孔的薄片。
[比較例3]
在合成例1所得之胺基甲酸酯樹脂組成物100質量份，加入增黏劑(Borchers公司製「Borchi Gel ALA」)2 質量份、十二基苯磺酸鈉1.5質量份、硬脂酸銨1質量份、及交聯劑(日本觸媒股份有限公司製「EPOCROS WS-700」)4質量份，使用機械式混拌機，以2,000rpm攪拌1分鐘，進行起泡，得到成為7倍之體積的起泡液。
將前述塗布於脫模紙，在80℃乾燥3分鐘，進一步在120℃乾燥2分鐘，藉以製造薄片。
[數量平均分子量之測定方法]
合成例所使用之多元醇等的數量平均分子量係利用凝膠滲透管柱層析(GPC)法，以下述的條件進行測定。
測定裝置：高速GPC裝置(Tosoh股份有限公司製「HLC-8220GPC」)
管柱：將Tosoh股份有限公司製之下述的管柱串聯使用。
「TSKgel G5000」(7.8mmI.D.×30cm)×1支
「TSKgel G4000」(7.8mmI.D.×30cm)×1支
「TSKgel G3000」(7.8mmI.D.×30cm)×1支
「TSKgel G2000」(7.8mmI.D.×30cm)×1支
檢測器：RI(示差折射計)
管柱溫度：40℃
溶離液：四氫呋喃(THF)
流速：1.0mL/分鐘
注入量：100μL(試料濃度0.4質量%的四氫呋喃溶液)
標準試料：使用下述的標準聚苯乙烯，作成檢量線。
(標準聚苯乙烯)
Tosoh股份有限公司製「TSKgel標準聚苯乙烯A-500」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯A-1000」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯A-2500」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯A-5000」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-1」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-2」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-4」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-10」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-20」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-40」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-80」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-128」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-288」
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-550」
[胺基甲酸酯樹脂(A)的流動起始溫度之測定方法]
將合成例所得之水性胺基甲酸酯樹脂組成物塗布於脫模紙(塗布厚度150μm)，並以熱風乾燥機，在70℃乾燥4分鐘，接著在120℃乾燥2分鐘，藉以得到乾燥物。將該乾燥物，使用島津製作所股份有限公司製流動試驗機「CFT-500A」(使用口徑1mm、長度1mm的模具、荷重98N、升溫速度3℃/分鐘)，測定流動起始溫度。
[質地之評價方法]
以手觸摸得到的發泡胺基甲酸酯薄片，並如以下進行評價。
「A」：富有柔軟性。
「B」：稍微有柔軟性。
「C」：柔軟性差。
「D」：硬。
[拉伸強度之測定方法]
將裁切所得到的胺基甲酸酯薄片為寬10mm、長度60mm者作為試驗片。將該試驗片之兩端以夾具夾持，使用拉伸試驗機「Autograph AG-I」(島津製作所股份有限公司製)，在溫度23℃、濕度60%的環境下，以十字頭速度300mm/分鐘拉伸，測定100%伸長時之拉伸強度，並如以下進行評價。
「T」：10N/cm2以上
「F」：小於10N/cm2
Figure 107139261-A0305-02-0025-1
Figure 107139261-A0305-02-0025-2
Figure 107139261-A0305-02-0025-3
為本發明之發泡胺基甲酸酯薄片的實施例1~8，可知：具有優異的質地及拉伸強度。
另一方面，比較例1為使用具有芳香環的十二基苯磺酸鈉代替界面活性劑(C)的態樣，但氣泡保持性不良，薄片之質地硬而為不良。
比較例2為未使用界面活性劑(C)的態樣，但氣泡保持性不良，薄片之質地硬而為不良。
比較例3為使發泡倍率變過剩，密度低於本發明所界定之範圍的態樣，但拉伸強度不良。
[實施例9]
在合成例1所得之胺基甲酸酯樹脂組成物100質量份，加入增黏劑(Borchers公司製「Borchi Gel ALA」)2質量份、硬脂酸銨1.5質量份、及交聯劑(日本觸媒股份有限公司製「EPOCROS WS-700」)4質量份，使用機械式混拌機，以2,000rpm攪拌1分鐘，進行起泡，得到成為1.5倍之體積的起泡液。
將前述塗布於聚酯纖維不織布，在80℃乾燥3分鐘，進一步在120℃乾燥2分鐘，藉以形成聚胺基甲酸酯層。接著，在得到的聚胺基甲酸酯層上，載置施加有凹凸圖案的脫模紙，並施加預熱為180℃的輥加壓，藉以得到壓印加工的合成皮革。
[實施例10~12]
將使用的胺基甲酸酯樹脂組成物之種類、及硬脂酸銨之使用量，如表4所示進行變更，除此以外係與實施例9同樣進行，得到合成皮革。
[質地之評價方法]
以手觸摸得到的合成皮革，並如以下進行評價。
「A」：富有柔軟性。
「B」：稍微有柔軟性。
「C」：柔軟性差。
「D」：硬。
[剝離強度之測定方法]
將實施例及比較例所得到的合成皮革，使用島津Autograph「AG-1」(島津製作所股份有限公司製)，以滿刻度5kg、測試頭20mm/分鐘的條件，測定剝離強度，並如以下進行評價。
「A」：0.15MPa以上
「B」：0.1MPa以上、小於0.15MPa
「C」：小於0.1MPa
[壓印加工性之評價方法]
以目視觀察實施例及比較例所得到的合成皮革，並如以下進行評價。
「T」：藉由壓印加工形成的表面上之皺褶可均勻地製作。
「F」：藉由壓印加工形成的表面上之皺褶不均勻。
Figure 107139261-A0305-02-0028-4
為本發明之合成皮革的實施例9~12，可知：具有優異的質地、剝離強度、及壓印加工性。

Claims (5)

  1. 一種發泡胺基甲酸酯薄片，其特徵為藉由含有胺基甲酸酯樹脂(A)、水(B)、及未具有芳香環且具有碳原子數為10以上的疏水部之界面活性劑(C)的胺基甲酸酯樹脂組成物形成，密度為200~1,000kg/m3，該胺基甲酸酯樹脂(A)係以選自包含4,4’-二苯甲烷二異氰酸酯、甲苯二異氰酸酯、二環己基甲烷二異氰酸酯、及異佛爾酮二異氰酸酯的群組之1種以上的多異氰酸酯、與具有羥基的鏈伸長劑為必要成分，該胺基甲酸酯樹脂(A)的流動起始溫度為80℃以上。
  2. 如請求項1之發泡胺基甲酸酯薄片，其中該界面活性劑(C)為硬脂酸鹽。
  3. 如請求項1或2之發泡胺基甲酸酯薄片，其中該胺基甲酸酯樹脂(A)為具有陰離子性基者。
  4. 一種合成皮革，其係至少具有基材(i)、及聚胺基甲酸酯層(ii)之合成皮革，特徵為該聚胺基甲酸酯層(ii)為藉由如請求項1至3中任一項之發泡胺基甲酸酯薄片形成者。
  5. 如請求項4之合成皮革，其中該聚胺基甲酸酯層(ii)為進行壓印加工者。
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