TWI823985B - 積層體 - Google Patents

積層體 Download PDF

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Publication number
TWI823985B
TWI823985B TW108129416A TW108129416A TWI823985B TW I823985 B TWI823985 B TW I823985B TW 108129416 A TW108129416 A TW 108129416A TW 108129416 A TW108129416 A TW 108129416A TW I823985 B TWI823985 B TW I823985B
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TW
Taiwan
Prior art keywords
urethane resin
resin composition
group
aforementioned
acid ester
Prior art date
Application number
TW108129416A
Other languages
English (en)
Other versions
TW202020046A (zh
Inventor
藤下章惠
千千和宏之
Original Assignee
日商Ｄｉｃ股份有限公司
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Publication of TW202020046A publication Critical patent/TW202020046A/zh
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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Abstract

本發明提供一種胺基甲酸酯樹脂組成物，其為含有胺基甲酸酯樹脂(A)、水(B)、及成膜助劑(C)之胺基甲酸酯樹脂組成物，其特徵為前述成膜助劑(C)係選自包含聚氧乙烯烷基醚(c-1)、聚氧乙烯山梨醇酐脂肪酸酯(c-2)、及聚甘油脂肪酸酯(c-3)之群組的1種以上。又，本發明提供一種積層體，其特徵為至少具有基材(i)、及藉由前述胺基甲酸酯樹脂組成物所形成的發泡層(ii)。

Description

積層體
本發明係關於胺基甲酸酯樹脂組成物。
胺基甲酸酯樹脂，由於其機械強度、質地良好，廣泛地被利用於合成皮革(包含人工皮革含)之製造。在此用途中，迄今係以含有N,N-二甲基甲醯胺(DMF)之溶劑系胺基甲酸酯樹脂為主流。然而，在歐洲之DMF管制、在中國、台灣之VOC排出管制的強化、主導服裝製造商之DMF管制等背景下，尋求構成合成皮革之各層用胺基甲酸酯樹脂組成物的去DMF化。
在此種環境下，胺基甲酸酯樹脂分散於水中之胺基甲酸酯分散液(PUD)，係作為使習知之溶劑系胺基甲酸酯樹脂進行濕式凝固所形成之中間多孔層的代替原料而開始被檢討。此代替中，為了賦予與濕式成膜品同等之質地等，而紛紛進行作成PUD之發泡體的檢討。
就得到前述PUD之發泡體的方法而言，例如，已有檢討摻合微膠囊，或使二氧化碳等氣體分散於PUD摻合液中的機械發泡等(例如，參照專利文獻1)。然而，在摻合微膠囊之方法中，產生「所得到的發泡體之質地變得不良，或因微膠囊之膨脹而造成平滑性不良」的問題。又，在使氣體分散之方法中，由於在製造發泡體之過程中摻合液所捕捉之氣泡消失等，氣泡尺寸等之控制有困難，使安定地得到質地良好之合成皮革變得困難。
從此種背景，近年，就簡便地得到發泡體之方法而言，已有檢討將PUD以機械方式攪打而起泡的機械發泡手法。然而，機械發泡方法方面，在將PUD之水乾燥途中，會有胺基甲酸酯皮膜上發生龜裂(crack)，或由於發泡操作後之泡沫彼此合一、消泡，而有質地、剝離強度等物性表現不安定的大問題。 [先前技術文獻] [專利文獻]
[專利文獻1]日本特開2007-191810號公報
[發明所欲解決之課題]
本發明所欲解決之課題，為提供一種含有水之胺基甲酸酯樹脂組成物，其即使進行機械發泡，亦可形成具有優良耐龜裂性及質地之皮膜。 [用於解決課題之手段]
本發明提供一種胺基甲酸酯樹脂組成物，其為含有胺基甲酸酯樹脂(A)、水(B)、及成膜助劑(C)之胺基甲酸酯樹脂組成物，其特徵為前述成膜助劑(C)係選自包含聚氧乙烯烷基醚(c-1)、聚氧乙烯山梨醇酐脂肪酸酯(c-2)、及聚甘油脂肪酸酯(c-3)之群組的1種以上。又，本發明提供一種積層體，其特徵為至少具有基材(i)、及藉由前述胺基甲酸酯樹脂組成物形成之發泡層(ii)。 [發明之效果]
本發明之胺基甲酸酯樹脂組成物，為含有水者，為環境保護型者。又，本發明之胺基甲酸酯樹脂組成物即使進行機械發泡，亦可形成具有優良耐龜裂性及質地之皮膜。因此，本發明之胺基甲酸酯樹脂組成物，可適合使用作為合成皮革之材料，尤其可適合使用作為合成皮革之發泡層。
[用於實施發明之態樣]
本發明之胺基甲酸酯樹脂組成物，為含有胺基甲酸酯樹脂(A)、水(B)、及特定之成膜助劑(C)者。
在本發明中，必須含有前述特定之成膜助劑(C)。推測藉由使用特定之成膜助劑(C)，即使在使胺基甲酸酯樹脂組成物進行機械發泡後，由於系統中之泡保持性變得良好，故可抑制皮膜之龜裂，得到質地優良之皮膜。
就前述成膜助劑(C)而言，必須使用選自包含聚氧乙烯烷基醚(c-1)、聚氧乙烯山梨醇酐脂肪酸酯(c-2)、及聚甘油脂肪酸酯(c-3)之群組的1種以上之化合物。
就前述聚氧乙烯烷基醚(c-1)而言，例如，可使用：聚氧乙烯月桂基醚、聚氧乙烯鯨蠟基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚等。此等化合物可單獨使用，亦可將2種以上併用。此等中，從能得到親水性高，更優良的泡保持性、耐龜裂性及質地之觀點而言，下述式(1)所示之結構的加成莫耳數，以30以上為較佳，以50以上為更佳，以80以上為進一步更佳。又，其上限以200以下為較佳，以150以下為更佳，以130以下為進一步更佳。就前述(c-1)中之下述式(1)所示之結構的加成莫耳數而言，以30～200之範圍為較佳，以50～150之範圍為更佳，以80～130之範圍為進一步更佳。
就前述聚氧乙烯山梨醇酐脂肪酸酯(c-2)而言，例如，可使用：聚氧乙烯山梨醇酐單椰子油脂肪酸酯、聚氧乙烯山梨醇酐單棕櫚酸酯、聚氧乙烯山梨醇酐單硬脂酸酯、聚氧乙烯山梨醇酐單月桂酸酯、聚氧乙烯山梨醇酐單月桂酸酯三硬脂酸酯、聚氧乙烯山梨醇酐單月桂酸酯單油酸酯等。此等化合物可單獨使用，亦可將2種以上併用。此等中，從親水性高，可得到更優良的泡保持性、耐龜裂性及質地之觀點而言，式(1)所示之結構之加成莫耳數，以30以上為較佳，以50以上為更佳，以70以上為進一步更佳。又，其上限以200以下為較佳，以150以下為更佳，以100以下為進一步更佳。就前述(c-2)中之下述式(1)所示之結構的加成莫耳數而言，以30～200之範圍為較佳，以50～150之範圍為更佳，以70～100之範圍為進一步更佳。
就前述聚甘油脂肪酸酯(c-3)而言，例如，可使用：聚甘油單癸酸酯、聚甘油單月桂酸酯、聚甘油單肉豆蔻酸酯、聚甘油單油酸酯、聚甘油單硬脂酸酯、聚甘油二油酸酯、聚甘油二硬脂酸酯、聚甘油五油酸酯等。此等化合物可單獨使用，亦可將2種以上併用。此等中，從親水性高，可得到更優良的泡保持性、耐龜裂性及質地的觀點而言，其HLB值(親水-親油平衡值(Hydrophilic-Lipophilic Balance))，以5以上為較佳，以10以上為更佳，以14以上為進一步更佳。又，上限以25以下為較佳，以20以下為更佳，以18以下為進一步更佳。就前述聚甘油脂肪酸酯(c-3)之HLB值而言，以5～25之範圍為較佳，以10～20之範圍為更佳，以14～18之範圍為進一步更佳。
前述(c-1)～(c-3)可單獨使用，亦可將2種以上併用。前述成膜助劑(C)之使用量，相對於後述之胺基甲酸酯樹脂(A)(=固形分)100質量份，以0.05～50質量份之範圍為較佳，以0.1～20質量份之範圍為更佳。
前述胺基甲酸酯樹脂(A)為能分散於後述之水(B)中者，例如，可使用：具有陰離子性基、陽離子性基、非離子性基等親水性基之胺基甲酸酯樹脂；藉由乳化劑強制地分散於水(B)中之胺基甲酸酯樹脂等。此等胺基甲酸酯樹脂可單獨使用，亦可將2種以上併用。此等中，從製造安定性及水分散安定性之點而言，以使用具有親水性基之胺基甲酸酯樹脂為較佳，以具有陰離子性基之胺基甲酸酯樹脂為更佳。
就得到前述具有陰離子性基之胺基甲酸酯樹脂的方法而言，例如，可列舉使用選自包含具有羧基之二醇化合物、及具有磺醯基之化合物之群組的1種以上之化合物作為原料的方法。
就前述具有羧基之二醇化合物而言，例如，可使用：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-纈草酸等。此等化合物可單獨使用，亦可將2種以上併用。
就前述具有磺醯基之化合物而言，例如，可使用：3,4-二胺基丁磺酸、3,6-二胺基-2-甲苯磺酸、2,6-二胺基苯磺酸、N-(2-胺基乙基)-2-胺基磺酸、N-(2-胺基乙基)-2-胺基乙基磺酸、N-2-胺基乙-2-胺基磺酸、N-(2-胺基乙基)-β-丙胺酸；此等之鹽等。此等化合物可單獨使用，亦可將2種以上併用。
在使用製造前述具有陰離子性基之胺基甲酸酯樹脂所用之原料之情況的使用量，從可得到更進一步優良的水分散安定性之觀點而言，較佳為胺基甲酸酯樹脂之原料合計質量中0.1～5質量%之範圍，更佳為0.5～4質量%之範圍，進一步更佳為1～3質量%之範圍。
前述羧基及磺醯基，在胺基甲酸酯樹脂組成物中可以部分或全部被鹼性化合物所中和。就前述鹼性化合物而言，例如，可使用：氨、三乙基胺、吡啶、啉等之有機胺；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。
就得到前述具有陽離子性基之胺基甲酸酯樹脂的方法而言，例如，可列舉使用1種或2種以上具有胺基之化合物作為原料的方法。
就前述具有胺基之化合物而言，例如，可使用：三伸乙基四胺、二伸乙基三胺等具有1級及2級胺基之化合物；N-甲基二乙醇胺、N-乙基二乙醇胺等N-烷基二烷醇胺、N-甲基二胺基乙基胺、N-乙基二胺基乙基胺等N-烷基二胺基烷基胺等具有3級胺基之化合物等。此等化合物可單獨使用，亦可將2種以上併用。
就要得到前述強制分散於水(B)中之胺基甲酸酯樹脂時可使用的乳化劑而言，例如，可使用：聚氧乙烯壬基苯基醚、聚氧乙烯月桂基醚、聚氧乙烯苯乙烯基苯基醚、聚氧乙烯山梨糖醇四油酸酯、聚氧乙烯・聚氧丙烯共聚物等非離子性乳化劑；油酸鈉等脂肪酸鹽、烷基硫酸酯鹽、烷基苯磺酸鹽、烷基磺酸基琥珀酸鹽、萘磺酸鹽、聚氧乙烯烷基硫酸鹽、烷磺酸酯鈉鹽、烷基二苯基醚磺酸鈉鹽等陰離子性乳化劑；烷基胺鹽、烷基三甲基銨鹽、烷基二甲基苄基銨鹽等陽離子性乳化劑等。此等乳化劑可單獨使用，亦可將2種以上併用。
就前述胺基甲酸酯樹脂(A)而言，具體言之，例如，可使用聚異氰酸酯(a1)、多元醇(a2)、及製造前述具有親水性基之胺基甲酸酯樹脂所用之原料的反應物。
就前述聚異氰酸酯(a1)而言，例如，可使用：苯二異氰酸酯、甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、二甲苯二異氰酸酯、萘二異氰酸酯、聚亞甲基聚苯基聚異氰酸酯、碳化二亞胺化二苯基甲烷聚異氰酸酯等芳香族聚異氰酸酯；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、二甲苯二異氰酸酯、四甲基二甲苯二異氰酸酯、二聚酸二異氰酸酯、降莰烯二異氰酸酯等脂肪族聚異氰酸酯或脂環式聚異氰酸酯等。此等聚異氰酸酯可單獨使用，亦可將2種以上併用。
就前述聚異氰酸酯(a1)之使用量而言，從製造安定性、及所得到的皮膜之機械物性的觀點，較佳為前述胺基甲酸酯樹脂(A)之原料的合計質量中5～40質量%之範圍，更佳為10～30質量%之範圍。
就前述多元醇(a2)而言，例如，可使用聚醚多元醇、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。此等多元醇可單獨使用，亦可將2種以上併用。
就前述多元醇(a2)之數平均分子量而言，從所得到的皮膜之機械強度的觀點，以500～50,000之範圍為較佳，以800～10,000之範圍為更佳。再者，前述多元醇(a2)之數平均分子量，表示藉由凝膠滲透管柱層析(GPC)法測定之值。
前述多元醇(a2)中，視需要可併用數平均分子量小於500(較佳為50～450之範圍)之鏈伸長劑(a2-1)。就前述鏈伸長劑(a2-1)而言，例如，可使用：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、六亞甲基二醇、蔗糖、亞甲基二醇、甘油、山梨糖醇、雙酚A、4,4’-二羥基聯苯、4,4’-二羥基二苯基醚、三羥甲基丙烷等具有羥基的鏈伸長劑；乙二胺、1,2-丙二胺、1,6-六亞甲基二胺、哌、2,5-二甲基哌、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、肼等具有胺基的鏈伸長劑等。此等鏈伸長劑可單獨使用，亦可將2種以上併用。
使用前述鏈伸長劑(a2-1)之情況的使用量，從所得到之皮膜之機械強度的觀點而言，較佳為胺基甲酸酯樹脂(A)之原料之合計質量中0.5～5質量%之範圍，更佳為1～3質量%之範圍。
就前述胺基甲酸酯樹脂(A)之製造方法而言，例如，可列舉將前述多元醇(a2)、前述製造具有親水性基之胺基甲酸酯樹脂用的原料、前述鏈伸長劑(a2-1)、及前述聚異氰酸酯(a1)一併進料，使其反應的方法。此等反應可列舉例如於50～100℃進行3～10小時。
就製造前述胺基甲酸酯樹脂(A)時之前述多元醇(a2)具有的羥基、前述製造具有親水性基之胺基甲酸酯樹脂所用之原料具有的羥基及胺基、以及前述鏈伸長劑(a2-1)具有之羥基及胺基的合計，與前述聚異氰酸酯(a1)具有之異氰酸酯基的莫耳比[異氰酸酯基/(羥基及胺基)]而言，以0.8～1.2之範圍為較佳，以0.9～1.1之範圍為更佳。
在製造前述胺基甲酸酯樹脂(A)時，以使前述胺基甲酸酯樹脂(A)所殘存的異氰酸酯基失活為較佳。在使前述異氰酸酯基失活之情況中，較佳為使用甲醇等具有1個羥基之醇。就前述醇之使用量而言，相對於100質量份之胺基甲酸酯樹脂(A)，以0.001～10質量份之範圍為較佳。
又，在製造前述胺基甲酸酯樹脂(A)時，亦可使用有機溶劑。就前述有機溶劑而言，例如，可使用：丙酮、甲基乙基酮等酮化合物；四氫呋喃、二烷等醚化合物；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。此等有機溶劑可單獨使用，亦可將2種以上併用。再者，前述有機溶劑以最後藉由蒸餾法等去除為較佳。
就前述胺基甲酸酯樹脂(A)之流動開始溫度而言，從安定地保持藉由後述之機械發泡所產生之泡，將發泡層(ii)之密度調至較佳範圍，可安定地得到優良質地的觀點，以80℃以上為較佳，以80～220℃之範圍為更佳。
就調整前述胺基甲酸酯樹脂(A)之流動開始溫度的方法而言，主要可列舉：藉由為後述之胺基甲酸酯樹脂(A)之原料的多元醇(a2)之種類、鏈伸長劑(a2-1)之使用量、及聚異氰酸酯(a1)之種類而調整的方法。就將前述流動開始溫度調高之方法而言，例如，可列舉：使用如聚碳酸酯多元醇之結晶性高的多元醇來作為多元醇(a2)；增多鏈伸長劑(a2-1)之使用量；使用如4,4’-二苯基甲烷二異氰酸酯、二環己基甲烷二異氰酸酯之結晶性高的聚異氰酸酯來作為聚異氰酸酯(a1)等。又，就將前述流動開始溫度調低之方法而言，例如，可列舉：使用如聚氧丙二醇之結晶性低的多元醇來作為多元醇(a2)；減少鏈伸長劑(a2-1)之使用量；使用如甲苯二異氰酸酯、異佛爾酮二異氰酸酯之結晶性低的聚異氰酸酯來作為聚異氰酸酯(a1)等。因此，藉由適宜選擇此等方法，可調整前述胺基甲酸酯樹脂(A)之流動開始溫度。
再者，就前述胺基甲酸酯樹脂(A)之流動開始溫度的測定方法而言，例如，可列舉：將胺基甲酸酯樹脂組成物塗布於離型紙上(塗布厚度150μm)，藉由熱風乾燥機，於70℃乾燥4分鐘，繼而於120℃乾燥2分鐘，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量測試儀「CFT-500A」(使用口徑1mm、長度1mm之模頭，荷重98N，升溫速度3℃/分鐘)予以測定的方法。
就前述水(B)而言，例如，可使用離子交換水、蒸餾水、自來水等。此等中，以使用雜質少之離子交換水為較佳。就前述水(B)之含量而言，從作業性、塗布性、及保存安定性之觀點，較佳為胺基甲酸酯樹脂組成物中20～90質量%之範圍，更佳為40～80質量%之範圍。
就前述胺基甲酸酯樹脂(A)與前述水(B)之質量比[(A)/(B)]而言，從水分散安定性、及作業性之觀點，以5/95～70/30之範圍為較佳，以10/90～60/40之範圍為更佳。
本發明之胺基甲酸酯樹脂組成物，雖含有前述胺基甲酸酯樹脂(A)、水(B)、及成膜助劑(C)作為必須成分，然而視需要亦可含有其他添加劑。
就前述其他添加劑而言，例如，可使用界面活性劑、交聯劑、中和劑、增黏劑、胺基甲酸酯化觸媒、充填劑、顏料、染料、阻燃劑、調平劑、防結塊劑等。此等添加劑可單獨使用，亦可將2種以上併用。
就前述界面活性劑而言，從防止藉由機械發泡所產生之泡消失，得到更優良耐龜裂性及質地的觀點，較佳為使用具有碳原子數10以上之疏水部分的界面活性劑(D)。
就前述界面活性劑(D)而言，例如，可使用：下述式(2)所示之界面活性劑；脂肪酸鹽、琥珀酸鹽、磺酸基琥珀酸鹽、十八基磺酸基琥珀酸鹽、磺酸基琥珀酸酯等。此等界面活性劑可單獨使用，亦可將2種以上併用。
(式(2)中，R表示碳原子數10～20之直鏈或分支狀的烷基，X表示Na、K、NH4 、啉、乙醇胺、三乙醇胺)
就前述界面活性劑(D)而言，在前述者之中，從得到更進一步優良的泡保持性的觀點，以使用前述式(2)所示之界面活性劑為較佳，以表示碳原子數為13～19之直鏈之烷基者為更佳，以使用硬脂酸鹽為特佳。
就使用前述界面活性劑(D)之情況的使用量而言，從得到更進一步優良的泡保持性的觀點，相對於100質量份之前述胺基甲酸酯樹脂(A)(=固體成分)，以0.01～30質量份之範圍為較佳，以0.1～20質量份之範圍為更佳。
就前述交聯劑而言，其係以發泡層(ii)之機械強度提高等為目的而使用者，例如，可使用聚異氰酸酯交聯劑、環氧交聯劑、三聚氰胺交聯劑、唑啉交聯劑等。此等交聯劑可單獨使用，亦可將2種以上併用。就使用前述交聯劑之情況的使用量而言，例如，相對於100質量份之前述胺基甲酸酯樹脂(A)(=固體成分)，以0.01～100質量份之範圍為較佳，以0.1～50質量份之範圍為更佳，以0.5～30質量份之範圍為進一步更佳。
繼而，對於本發明之積層體加以說明。
前述積層體為至少具有基材(i)、及藉由前述胺基甲酸酯樹脂組成物形成之發泡層(ii)者。
就前述基材(i)而言，例如，可使用：藉由聚酯纖維、聚乙烯纖維、尼龍纖維、丙烯酸纖維、聚胺基甲酸酯纖維、乙酸酯纖維、嫘縈纖維、聚乳酸纖維、棉、麻、絹、羊毛、玻璃纖維、碳纖維、彼等之混紡纖維等所製成之不織布、織布、編結物等纖維基材；使前述不織布含浸聚胺基甲酸酯樹脂等樹脂者；在前述不織布進一步設置多孔質層者；熱塑性胺基甲酸酯(TPU)等樹脂基材等。
繼而，針對本發明之積層體的製造方法加以說明。
就前述積層體之製造方法而言，例如，可列舉： (X)使前述胺基甲酸酯樹脂組成物起泡，得到起泡液，將該起泡液塗布於離型紙上，使其乾燥並與前述基材(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，將該起泡液塗布於離型紙上所製作的表皮層上，使其乾燥並與前述基材(i)貼合的方法， (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，使其乾燥，視需要於其上貼合離型紙上所製作之表皮層(iii)的方法等。
就使前述胺基甲酸酯樹脂組成物起泡，得到起泡液之方法而言，例如，可列舉藉由手攪拌、使用機械混合機等之混合機的機械發泡等。此等中，從能簡便地得到起泡液的觀點，以使用混合機之方法為較佳。在使用混合機之情況，例如，可列舉以500～3,000rpm攪拌10秒～10分鐘的方法。此時，從可得到質地良好之發泡層(ii)的觀點而言，起泡前後以形成1.3～7倍之體積為較佳，以形成1.2～2倍之體積為更佳。
就將所得到之起泡液塗布於基材(i)等的方法而言，例如，可列舉使用滾筒塗布機、刮刀塗布機、逗點式塗布機、塗抹器等之方法。
就前述塗布物之乾燥方法而言，例如，可列舉於60～130℃之溫度下乾燥30秒～10分鐘的方法。
就依照以上之方法所得到的發泡層(ii)之厚度而言，例如，為5～300μm。
就前述發泡層(ii)之密度而言，從可得到更進一步優良質地的觀點，以200～1,000kg/m3 為較佳，以400～800kg/m3 之範圍為更佳。再者，前述發泡層(ii)之密度表示每10cm見方之積層體之重量減去每10cm見方之基材(i)之重量的值，除以發泡層(ii)之厚度而得的值。
就前述表皮層(iii)而言，可藉由周知之材料，以周知之方法形成，例如，可使用溶劑系胺基甲酸酯樹脂、水系胺基甲酸酯樹脂、聚矽氧樹脂、聚丙烯樹脂、聚酯樹脂等。在重視柔軟質地、及耐熱性、耐水解性之情況，以使用聚碳酸酯系胺基甲酸酯樹脂為較佳。又，為了環境保護之DMF減量化，以使用水系聚碳酸酯系胺基甲酸酯樹脂為更佳。
前述表皮層(iii)上，視需要為了提高耐擦傷性、賦予光澤性等之目的，可進一步設置表面處理層(iv)。就前述表面處理層(iv)而言，可藉由周知之材料，以周知之方法形成。
以上，本發明之胺基甲酸酯樹脂組成物，為含有水者，為環境保護型者。又，本發明之胺基甲酸酯樹脂組成物，即使進行機械發泡，亦可形成具有優良耐龜裂性及質地之皮膜。因此，本發明之胺基甲酸酯樹脂組成物，可適合使用作為合成皮革之材料，尤其可適合使用作為合成皮革之發泡層。 [實施例]
以下，使用實施例，更詳細地說明本發明。
[實施例1] 添加100質量份之聚醚系聚胺基甲酸酯分散液(DIC股份有限公司製「Hydran WLS-120AR」，固體成分50質量%，以下簡稱為「PUD(A-1)」)、2質量份之增黏劑(Borchers公司製「Borch Gel ALA」)、3質量份之硬脂酸銨、4質量份之交聯劑(日清紡化學股份有限公司製「Carbodilite SV-02」)、3質量份之聚氧乙烯月桂基醚(式(1)所示之結構的加成莫耳數：100)，使用機械式混合機，以3,000rpm攪拌，使其包含空氣，得到體積相當於初期體積之1.5倍的起泡液。 將其塗布於離型紙上，於80℃乾燥3分鐘，形成厚度300μm之胺基甲酸酯發泡層，將其與聚酯纖維不織布貼合，得到合成皮革。
[實施例2～7、比較例1] 除了將所用之胺基甲酸酯樹脂(A)的種類、以及成膜助劑(C)之種類及/或使用量如表1～2所示變更以外，以與實施例1同樣之方式，得到合成皮革。
[泡保持性之評價方法] 在實施例及比較例中，將得到起泡液後放置2小時左右之起泡液，藉由掃描電子顯微鏡(SEM)觀察，確認泡之形狀，並如以下之方式評價。 「T」：泡之尺寸的變化小，泡之體積・密度的變化少。 「F」：泡之尺寸變得非常大，或泡消失而密度變高。
[耐龜裂性之評價方法] 觀察實施例及比較例中所得到的合成皮革之外觀，確認有無龜裂。將無龜裂者評價為「T」，將確認到龜裂者評價為「F」。
[質地之評價方法]
以手觸摸實施例及比較例中所得到之合成皮革，並如以下之方式評價。
「T」：有柔軟性及彈力
「F」：柔軟性差，僵硬。
Figure 108129416-A0305-02-0017-1
[表2]
表1～2中之簡稱為以下者。 「PUD(A-2)」：聚碳酸酯系聚胺基甲酸酯分散液(DIC股份有限公司製「Hydran WLS-110AR」，固體成分50質量%) 「PUD(A-3)」：酯系聚胺基甲酸酯分散液(DIC股份有限公司製「Hydran ADS-110」，固體成分50質量%)
可知為本發明之胺基甲酸酯樹脂組成物的實施例1～7，可得到具有優良的泡保持性、耐龜裂性及質地之合成皮革。
另一方面，比較例1為不使用成膜助劑(C)之態樣，而泡保持性、耐龜裂性、質地均不良。
無。

Claims (4)

  1. 一種積層體，其特徵為至少具有基材(i)、及藉由胺基甲酸酯樹脂組成物所形成的發泡層(ii)，該胺基甲酸酯樹脂組成物係含有胺基甲酸酯樹脂(A)、水(B)、及成膜助劑(C)者，該成膜助劑(C)係選自包含聚氧乙烯烷基醚(c-1)、聚氧乙烯山梨醇酐脂肪酸酯(c-2)、及聚甘油脂肪酸酯(c-3)之群組的1種以上，該聚氧乙烯烷基醚(c-1)中的下述式(1)所示之結構的加成莫耳數為50以上，
    Figure 108129416-A0305-02-0019-3
     該聚氧乙烯山梨醇酐脂肪酸酯(c-2)中的上述式(1)所示之結構的加成莫耳數為30以上，該聚甘油脂肪酸酯(c-3)之親水-親油平衡(HLB)值為5以上，該胺基甲酸酯樹脂組成物係進一步含有具有碳原子數為10以上之疏水部分的界面活性劑(D)者。
  2. 如請求項1之積層體，其中該胺基甲酸酯樹脂(A)為具有陰離子性基者。
  3. 如請求項1之積層體，其中該界面活性劑(D)為硬脂酸鹽。
  4. 如請求項1之積層體，其中該發泡層(ii)為藉由將該胺基甲酸酯樹脂組成物進行機械發泡而形成者。
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