CN113767195A - 氨基甲酸酯树脂组合物、发泡氨基甲酸酯片以及合成皮革 - Google Patents
氨基甲酸酯树脂组合物、发泡氨基甲酸酯片以及合成皮革 Download PDFInfo
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- CN113767195A CN113767195A CN202080029291.0A CN202080029291A CN113767195A CN 113767195 A CN113767195 A CN 113767195A CN 202080029291 A CN202080029291 A CN 202080029291A CN 113767195 A CN113767195 A CN 113767195A
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- Prior art keywords
- urethane resin
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- resin composition
- urethane
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- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 131
- 239000011342 resin composition Substances 0.000 title claims abstract description 39
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- 239000002649 leather substitute Substances 0.000 title claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 16
- 125000005587 carbonate group Chemical group 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
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- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
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Abstract
本发明提供一种氨基甲酸酯树脂组合物,其特征在于,其含有氨基甲酸酯树脂(A)、水(B)和表面活性剂(C),所述表面活性剂(C)不具有芳香环且具有碳原子数为10以上的疏水部,上述氨基甲酸酯树脂组合物具有来自于氨基甲酸酯树脂(A)的碳酸酯结构(X)和氧亚烷基结构(Y)。另外,本发明提供一种发泡氨基甲酸酯片,其特征在于,其由氨基甲酸酯树脂组合物形成,且密度为200~1,000kg/m3。根据技术方案1所述的氨基甲酸酯树脂组合物,其中,上述碳酸酯结构(X)与上述氧亚烷基结构(Y)的质量比[X/Y]为10/90~90/10的范围。
Description
技术领域
本发明涉及氨基甲酸酯树脂组合物、发泡氨基甲酸酯片以及合成皮革。
背景技术
聚氨酯树脂由于具有优异的机械强度和柔软性,所以迄今为止被用于涂布剂、粘接剂等各种用途。其中,迄今为止广泛利用了含有二甲基甲酰胺(DMF)的溶剂系氨基甲酸酯树脂,但DMF的法律规定逐年严格,弱溶剂化、水系化、无溶剂化等应对环境的制品的开发成为当务之急。
其中,使氨基甲酸酯树脂分散于水中而成的水系氨基甲酸酯(PUD)的研究最盛行。在将该水系氨基甲酸酯用于各种用途时,以提高手感等为目的而成型为发泡体的需求也多。作为利用水系氨基甲酸酯来成型发泡体的方法,例如研究了配合微胶囊、或使二氧化碳等气体分散于PUD配合液中的机械发泡等(例如,参照专利文献1。)。然而,在配合微胶囊的方法中,所得到的发泡体的手感变得不良、或因微胶囊的膨胀而导致的平滑性不良成为问题。另外,在使气体分散的方法中,在制造发泡体的过程中混入配合液中的气泡消失等,因此难以控制泡尺寸等,难以稳定地得到手感良好的发泡体。
另外,除了手感以外,近年来针对人的皮脂中所含的油酸的耐性、还能够耐受低温时的实际使用的低温弯曲性的需求也高,难以满足这些处于权衡关系的要求特性。
现有技术文献
专利文献
专利文献1:日本特开2007-191810号公报
发明内容
发明要解决的课题
本发明要解决的课题在于使用含有水的氨基甲酸酯树脂组合物,提供手感、耐油酸性和低温弯曲性优异的氨基甲酸酯树脂组合物。
用于解决课题的手段
本发明提供一种氨基甲酸酯树脂组合物,其特征在于,其含有氨基甲酸酯树脂(A)、水(B)和表面活性剂(C),所述表面活性剂(C)不具有芳香环且具有碳原子数为10以上的疏水部,上述氨基甲酸酯树脂组合物具有来自于氨基甲酸酯树脂(A)的碳酸酯结构(X)和氧亚烷基结构(Y)。
另外,本发明提供一种发泡氨基甲酸酯片,其特征在于,其由氨基甲酸酯树脂组合物形成,且密度为200~1,000kg/m3。另外,本发明提供一种合成皮革,其特征在于,其为至少具有基材(i)和聚氨酯层(ii)的合成皮革,上述聚氨酯层(ii)由上述发泡氨基甲酸酯片形成。
发明的效果
本发明的氨基甲酸酯树脂组合物使用含有水的氨基甲酸酯树脂组合物,手感、耐油酸性和低温弯曲性优异。
具体实施方式
本发明的氨基甲酸酯树脂组合物含有氨基甲酸酯树脂(A)、水(B)和表面活性剂(C),所述表面活性剂(C)不具有芳香环且具有碳原子数为10以上的疏水部,所述氨基甲酸酯树脂组合物具有来自于氨基甲酸酯树脂(A)的碳酸酯结构(X)和氧亚烷基结构(Y)。
上述氨基甲酸酯树脂(A)能够在后述的水(B)中分散等,例如可以使用具有阴离子性基团、阳离子性基团、非离子性基团等亲水性基团的氨基甲酸酯树脂;用乳化剂强制性地分散于水(B)中的氨基甲酸酯树脂等。这些氨基甲酸酯树脂(A)可以单独使用,也可以组合使用2种以上。其中,从制造稳定性的方面出发,优选使用具有亲水性基团的氨基甲酸酯树脂,更优选具有阴离子性基团的氨基甲酸酯树脂。
作为得到上述具有阴离子性基团的氨基甲酸酯树脂的方法,例如可举出使用选自具有羧基的二醇化合物和具有磺酰基的化合物中的1种以上化合物作为原料的方法。
作为上述具有羧基的二醇化合物,例如可以使用2,2-二羟甲基丙酸、2,2-二羟甲基丁酸、2,2-二羟甲基酪酸、2,2-二羟甲基丙酸、2,2-二羟甲基戊酸等。这些化合物可以单独使用,也可以组合使用2种以上。
作为上述具有磺酰基的化合物,例如可以使用3,4-二氨基丁磺酸、3,6-二氨基-2-甲苯磺酸、2,6-二氨基苯磺酸、N-(2-氨基乙基)-2-氨基乙基磺酸等。这些化合物可以单独使用,也可以组合使用2种以上。
作为使用为了制造上述具有阴离子性基团的氨基甲酸酯树脂而使用的原料时的使用量,从得到更优异的水分散稳定性的方面出发,在氨基甲酸酯树脂(A)的原料的合计质量中优选为0.1~4.8质量%的范围,更优选为0.5~4质量%的范围,进一步优选为1~3质量%的范围。
上述羧基和磺酰基在氨基甲酸酯树脂组合物中可以一部分或全部被碱性化合物中和。作为上述碱性化合物,例如可以使用氨、三乙胺、吡啶、吗啉等有机胺;单乙醇胺、二甲基乙醇胺等烷醇胺;包含钠、钾、锂、钙等的金属碱化合物等。
作为得到上述具有阳离子性基团的氨基甲酸酯树脂的方法,例如可举出使用具有氨基的化合物中的1种或2种以上作为原料的方法。
作为上述具有氨基的化合物,例如可以使用三亚乙基四胺、二亚乙基三胺等具有伯氨基和仲氨基的化合物;N-甲基二乙醇胺、N-乙基二乙醇胺等N-烷基二烷醇胺、N-甲基二氨基乙胺、N-乙基二氨基乙胺等N-烷基二氨基烷基胺等具有叔氨基的化合物等。这些化合物可以单独使用,也可以组合使用2种以上。
本发明的氨基甲酸酯树脂组合物通过具有来自于上述氨基甲酸酯树脂(A)的碳酸酯结构(X)和氧亚烷基结构(Y),能够得到优异的耐油酸性和低温弯曲性。上述碳酸酯结构(X)和氧亚烷基结构(Y)可以由1种氨基甲酸酯树脂(A)供给,也可以由2种以上的氨基甲酸酯树脂(A)分别供给。需要说明的是,上述碳酸酯结构(X)[O-CO-O]来自于后述的聚碳酸酯多元醇(a2-1),上述氧亚烷基结构(Y)[O-CH2-CH2]来自于后述的聚醚多元醇(a2-2)。
从能够维持优异的手感、以高水平兼顾耐油酸性和低温弯曲性的方面出发,上述碳酸酯结构(X)与上述氧亚烷基结构(Y)的质量比[X/Y]优选为10/90~90/10的范围,更优选为10/90~60/40的范围。
另外,作为上述质量比[X/Y],在上述碳酸酯结构(X)和氧亚烷基结构(Y)由1种氨基甲酸酯树脂(A)供给的情况下,优选为10/90~90/10的范围,更优选为10/90~60/40的范围。
另外,作为上述质量比[X/Y],在上述碳酸酯结构(X)和氧亚烷基结构(Y)由2种以上的氨基甲酸酯树脂(A)分别供给的情况下,优选为10/90~90/10的范围,更优选为10/90~60/40的范围。需要说明的是,在该情况下,上述碳酸酯结构(X)和氧亚烷基结构(Y)表示由2种以上的氨基甲酸酯树脂(A)供给的总和。
从得到更优异的低温弯曲性的方面出发,上述碳酸酯结构(X)和氧亚烷基结构(Y)优选由1种氨基甲酸酯树脂(A)供给。
作为上述氨基甲酸酯树脂(A),具体而言,例如可以使用多异氰酸酯(a1)、多元醇(a2)和为了制造上述具有亲水性基团的氨基甲酸酯树脂的原料的反应物。
作为上述多异氰酸酯(a1),例如可以使用苯二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、萘二异氰酸酯、多亚甲基多苯基多异氰酸酯、碳二亚胺化二苯基甲烷多异氰酸酯等芳香族多异氰酸酯;六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、环己烷二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、二聚酸二异氰酸酯、降冰片烯二异氰酸酯等脂肪族或脂环式多异氰酸酯等。这些多异氰酸酯可以单独使用,也可以组合使用2种以上。
作为上述多异氰酸酯(a1)的使用量,从制造稳定性和所得到的被膜的机械物性的方面出发,在上述氨基甲酸酯树脂(A)的原料的合计质量中优选为5~40质量%的范围,更优选为10~30质量%的范围。
作为上述多元醇(a2),聚碳酸酯多元醇(a2-1)和聚醚多元醇(a2-2)是必须的材料。另外,除此以外,例如可以使用聚酯多元醇、聚丙烯酸多元醇、聚丁二烯多元醇等。这些多元醇可以单独使用,也可以组合使用2种以上。
作为上述聚碳酸酯多元醇(a2-1),例如可以使用碳酸酯和/或碳酰氯与具有2个以上羟基的化合物的反应物。
作为上述碳酸酯,例如可以使用碳酸二甲酯、碳酸二乙酯、碳酸二苯酯、碳酸亚乙酯、碳酸亚丙酯等。这些化合物可以单独使用,也可以组合使用2种以上。
作为上述具有2个以上羟基的化合物,例如可以使用乙二醇、丙二醇、1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、1,2-丁二醇、2-甲基-1,3-丙二醇、1,5-戊二醇、新戊二醇、1,6-己二醇、1,5-己二醇、3-甲基-1,5-戊二醇、1,7-庚二醇、1,8-辛二醇、1,9-壬二醇、1,8-壬二醇、2-乙基-2-丁基-1,3-丙二醇、1,10-癸二醇、1,12-十二烷二醇、1,4-环己烷二甲醇、1,3-环己烷二甲醇、三羟甲基丙烷、三羟甲基乙烷、甘油等。这些化合物可以单独使用,也可以组合使用2种以上。
作为上述聚醚多元醇(a2-2),可以使用聚氧亚烷基多元醇;使用具有2个以上活性氢原子的化合物中的1种或2种以上作为引发剂,使环氧烷等环状醚开环聚合而得到的物质等。
作为上述聚氧亚烷基多元醇,例如可以使用聚氧乙二醇、聚氧丙二醇、聚氧四亚甲基二醇、聚氧乙烯聚氧丙烯二醇、聚氧乙烯聚氧四亚甲基二醇、聚氧丙烯聚氧四亚甲基二醇等。其中,从得到更优异的低温弯曲性的方面出发,优选聚氧丙二醇和/或聚氧四亚甲基二醇,更优选聚氧四亚甲基二醇。
上述环状醚的碳原子数优选为2~10,更优选为2~6,进一步优选为2~4。上述环状醚中所含的氢原子可以被卤素原子取代。作为上述环状醚,可以使用1种或2种以上,例如可以使用环氧乙烷、环氧丙烷、1,2-环氧丁烷、2,3-环氧丁烷、氧化苯乙烯、环氧氯丙烷、四氢呋喃、烷基化四氢呋喃等。
作为上述引发剂,可以使用1种或2种以上,例如可以使用乙二醇、二乙二醇、丙二醇、三亚甲基二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、新戊二醇、水等具有2个活性氢原子的化合物;甘油、二甘油、三羟甲基乙烷、三羟甲基丙烷、己三醇、单乙醇胺、二乙醇胺、三乙醇胺、乙二胺、季戊四醇、糖类等具有3个以上活性氢原子的化合物等。
另外,作为上述聚醚多元醇(a2-2),只要含有氧亚烷基结构(Y)即可,可以使用导入有酯键的聚醚聚酯多元醇。
作为上述多元醇(a2)的数均分子量,从所得到的被膜的机械强度的方面出发,优选为500~8,000的范围,更优选为800~4,000的范围。需要说明的是,上述多元醇(a2)的数均分子量表示通过凝胶渗透柱色谱(GPC)法测定的值。
上述多元醇(a2)中,可以根据需要组合使用数均分子量为50~450的扩链剂(a2’)。作为上述扩链剂(a2’),例如可以使用乙二醇、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、六亚甲基二醇、蔗糖、亚甲基二醇、甘油、山梨糖醇、双酚A、4,4’-二羟基联苯、4,4’-二羟基二苯基醚、三羟甲基丙烷等具有羟基的扩链剂;乙二胺、1,2-丙二胺、1,6-六亚甲基二胺、哌嗪、2,5-二甲基哌嗪、异佛尔酮二胺、1,2-环己二胺、1,3-环己二胺、1,4-环己二胺、4,4’-二环己基甲烷二胺、3,3’-二甲基-4,4’-二环己基甲烷二胺、1,4-环己二胺、肼等具有氨基的扩链剂等。这些扩链剂可以单独使用,也可以组合使用2种以上。
作为使用上述扩链剂(a2’)时的使用量,从容易调整所得到的氨基甲酸酯树脂(A)的流动起始温度、可以得到更优异的拉伸强度的方面出发,在氨基甲酸酯树脂(A)的原料的合计质量中优选为0.5~10质量%的范围,更优选为1~5质量%的范围,进一步优选为1.5~4质量%的范围。
作为上述氨基甲酸酯树脂(A)的制造方法,例如可举出将上述多元醇(a2)、用于制造上述具有亲水性基团的氨基甲酸酯树脂的原料、上述扩链剂(a2’)和上述多异氰酸酯(a1)一并投入并使其反应的方法。这些反应例如可举出在50~100℃下进行3~10小时。
作为制造上述氨基甲酸酯树脂(A)时的、上述多元醇(a2)所具有的羟基、用于制造上述具有亲水性基团的氨基甲酸酯树脂的原料所具有的羟基和氨基、以及上述扩链剂(a2’)所具有的羟基和氨基的合计与上述多异氰酸酯(a1)所具有的异氰酸酯基的摩尔比[异氰酸酯基/(羟基和氨基)]优选为0.8~1.2的范围,更优选为0.9~1.1的范围。
在制造上述氨基甲酸酯树脂(A)时,优选使残留于上述氨基甲酸酯树脂(A)的异氰酸酯基失活。在使上述异氰酸酯基失活的情况下,优选使用甲醇等具有1个羟基的醇。作为上述醇的使用量,相对于氨基甲酸酯树脂(A)100质量份,优选为0.001~10质量份的范围。
另外,在制造上述氨基甲酸酯树脂(A)时,可以使用有机溶剂。作为上述有机溶剂,例如可以使用丙酮、甲乙酮等酮化合物;四氢呋喃、二氧六环等醚化合物;乙酸乙酯、乙酸丁酯等乙酸酯化合物;乙腈等腈化合物;二甲基甲酰胺、N-甲基吡咯烷酮等酰胺化合物等。这些有机溶剂可以单独使用,也可以组合使用2种以上。需要说明的是,上述有机溶剂优选在得到最终的氨基甲酸酯树脂组合物时通过蒸馏法等除去。
作为上述氨基甲酸酯树脂(A)的流动起始温度,从能够稳定地保持通过后述的起泡工序产生的泡(特别是在干燥工序中)、稳定地使发泡氨基甲酸酯片的密度为优选的范围的方面出发,优选为80℃以上,更优选为80~220℃的范围。
作为调整上述氨基甲酸酯树脂(A)的流动起始温度的方法,主要可举出根据作为后述的氨基甲酸酯树脂(A)的原料的多元醇(a2)的种类、扩链剂(a2’)的使用量、以及多异氰酸酯(a1)的种类进行调整的方法。作为将上述流动起始温度调整得较高的方法,例如可举出使用聚碳酸酯多元醇之类的结晶性高的多元醇作为多元醇(a2)、增多扩链剂(a2’)的使用量、使用二环己基甲烷二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯之类的结晶性高的多异氰酸酯作为多异氰酸酯(a1)等。另外,作为将上述流动起始温度调整得较低的方法,例如可举出使用聚氧丙二醇之类的结晶性低的多元醇作为多元醇(a2)、减少扩链剂(a2’)的使用量、使用异佛尔酮二异氰酸酯、甲苯二异氰酸酯之类的结晶性低的多异氰酸酯作为多异氰酸酯(a1)等。因此,通过适当选择这些方法,能够调整上述氨基甲酸酯树脂(A)的流动起始温度。需要说明的是,上述氨基甲酸酯树脂(A)的流动起始温度的测定方法记载于后述的实施例中。
在使用具有阴离子性基团的氨基甲酸酯树脂作为上述氨基甲酸酯树脂(A)情况下,从容易调整流动起始温度、得到更优异的泡保持性和手感的方面出发,优选使用具有阴离子性基团的氨基甲酸酯树脂(A-A-1),所述具有阴离子性基团的氨基甲酸酯树脂(A-A-1)是选自4,4’-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、环己基甲烷二异氰酸酯和异佛尔酮二异氰酸酯中的1种以上的多异氰酸酯、多元醇(a2)、具有羧基的二醇化合物、以及包含具有羟基的扩链剂(a2’)的扩链剂的反应物。
作为上述水(B),例如可以使用离子交换水、蒸馏水等。这些水可以单独使用,也可以使用2种以上。
作为上述氨基甲酸酯树脂(A)与上述水(B)的质量比[(A)/(B)],从水分散稳定性和作业性的方面出发,优选为10/80~70/30的范围,更优选为20/80~60/40的范围。
为了防止因起泡而产生的泡消失(泡保持)、得到优异的手感,上述表面活性剂(C)必须使用不具有芳香环、且具有碳原子数为10以上的疏水部的表面活性剂。
作为上述表面活性剂(C),例如可以使用下述通式(1)所示的表面活性剂;脂肪酸盐、琥珀酸盐、磺基琥珀酸盐、十八烷基磺基琥珀酸盐、磺基琥珀酸酯等。这些表面活性剂可以单独使用,也可以组合使用2种以上。
RCO2·X+ (1)
(式(1)中,R表示碳原子数为10~20的具有直链或支链结构的烷基,X表示Na、K、NH4、吗啉、乙醇胺、或三乙醇胺。)
作为上述表面活性剂(C),上述中,从具有更优异的泡保持性的方面出发,优选使用上述通式(1)所示的表面活性剂,更优选使用显示碳原子数为13~19的直链烷基的表面活性剂,进一步优选硬脂酸盐。
作为上述表面活性剂(C)的使用量,从得到更优异的泡保持性的方面出发,相对于上述氨基甲酸酯树脂(A)(=固体成分)100质量份,优选为0.01~10质量份的范围,更优选为0.1~5质量份的范围。
上述氨基甲酸酯树脂组合物含有上述氨基甲酸酯树脂(A)、水(B)和表面活性剂(C)作为必须成分,但也可以根据需要含有其他添加剂。
作为上述其他添加剂,例如可以使用交联剂、中和剂、增稠剂、氨基甲酸酯化催化剂、填充剂、颜料、染料、阻燃剂、流平剂、抗粘连剂等。这些添加剂可以单独使用,也可以组合使用2种以上。
作为上述交联剂,是出于提高发泡氨基甲酸酯片的机械强度等目的而使用的,例如可以使用多异氰酸酯交联剂、环氧交联剂、三聚氰胺交联剂、噁唑啉交联剂等。这些交联剂可以单独使用,也可以组合使用2种以上。作为使用上述交联剂时的使用量,例如,相对于上述氨基甲酸酯树脂(A)(=固体成分)100质量份,优选为0.01~100质量份的范围,更优选为0.1~50质量份的范围,进一步优选为0.5~30质量份的范围,特别优选为1~10质量份。
接下来,对本发明的发泡氨基甲酸酯片的制造方法进行说明。
上述发泡氨基甲酸酯片是通过使上述氨基甲酸酯树脂组合物起泡而得到起泡液,将该起泡液涂布于基材,使其干燥,得到优选的密度而制造的。
作为使上述氨基甲酸酯树脂组合物起泡而得到起泡液的方法,例如可举出利用手的搅拌、使用机械混合器等混合器的方法。在使用混合器的情况下,例如可举出以500~3,000rpm搅拌10秒~3分钟的方法。此时,从容易将发泡氨基甲酸酯片的密度调整为优选的范围的方面出发,在起泡前后,优选设为1.3~7倍的体积,更优选设为1.2~2倍的体积,进一步优选设为1.3~1.7倍的体积。
作为将所得到的起泡液涂布于脱模纸等基材的方法,例如可举出使用辊涂机、刮刀涂布机、逗号涂布机、涂抹器等的方法。
作为上述涂布物的干燥方法,例如可举出在60~130℃的温度下干燥30秒~10分钟的方法。
作为通过以上的方法得到的发泡氨基甲酸酯片的厚度,例如为5~200μm。
作为上述发泡氨基甲酸酯片的密度,从得到更优选的手感和拉伸强度的方面出发,优选为200~1,000kg/m3,更优选为300~900kg/m3的范围,进一步优选为400~800kg/m3的范围。需要说明的是,上述发泡氨基甲酸酯片的密度表示通过将发泡氨基甲酸酯片的质量除以体积而算出的值。
接下来,对本发明的合成皮革进行说明。
本发明的合成皮革是至少具有基材(i)和聚氨酯层(ii)的合成皮革,上述聚氨酯层(ii)由上述发泡氨基甲酸酯片形成。
作为上述合成皮革的制造方法,例如可举出:
(X)使上述氨基甲酸酯树脂组合物起泡而得到起泡液,将该起泡液涂布于脱模纸上,使其干燥,与上述基材(i)贴合的方法,
(Y)使上述氨基甲酸酯树脂组合物起泡而得到起泡液,将该起泡液涂布于在脱模纸上制作的表皮层上,使其干燥,与上述基材(i)贴合的方法,
(Z)使上述氨基甲酸酯树脂组合物起泡而得到起泡液,将该起泡液涂布于上述基材(i)上,使其干燥,根据需要在其上贴合在脱模纸上制作的表皮层(iii)的方法等。
作为上述基材(i),例如可以使用聚酯纤维、聚乙烯纤维、尼龙纤维、丙烯酸系纤维、聚氨酯纤维、乙酸酯纤维、人造丝纤维、聚乳酸纤维、棉、麻、丝、羊毛、玻璃纤维、碳纤维、基于它们的混纺纤维等的无纺布、机织物、针织物等纤维基材;使聚氨酯树脂等树脂浸渗于上述无纺布而得到的无纺布;在上述无纺布上进一步设置有多孔质层的无纺布;热塑性氨基甲酸酯(TPU)等树脂基材等。
上述聚氨酯层(ii)由上述发泡片形成,作为其密度,从能够得到兼顾了更优异的手感和剥离强度的合成皮革的方面出发,优选为300~900kg/m3的范围,更优选为400~800kg/m3的范围。需要说明的是,上述聚氨酯层(ii)的密度表示用从每10cm见方的合成皮革的重量中减去每10cm见方的基材(i)的重量而得到的值除以聚氨酯层(ii)的厚度而得到的值。需要说明的是,上述聚氨酯层(ii)的密度可以通过上述氨基甲酸酯树脂组合物的起泡情况来调整。
作为上述表皮层(iii),可以利用公知的材料并通过公知的方法形成,例如可以使用溶剂系氨基甲酸酯树脂、水系氨基甲酸酯树脂、有机硅树脂、聚丙烯树脂、聚酯树脂等。在重视柔软的手感和耐热性、耐水解性的情况下,优选使用聚碳酸酯系氨基甲酸酯树脂。另外,为了环境应对中的DMF减少化,更优选使用水系聚碳酸酯系氨基甲酸酯树脂。
在上述表皮层(iii)上,可以根据需要以提高耐擦伤性等为目的而设置表面处理层(iv)。作为上述表面处理层(iv),可以利用公知的材料并通过公知的方法形成。
以上,本发明的合成皮革通过使用上述手感和拉伸强度优异的发泡氨基甲酸酯片,从而剥离强度也进一步优异,并且能够在其表面上均匀地制作设计性优异的压花加工。
作为在上述聚氨酯层(ii)上进行压花加工的方法,例如可举出如下方法:在合成皮革的聚氨酯层(ii)上载置实施了凹凸图案等设计性的脱模纸,用经预热的辊等进行热压的方法;使用实施了凹凸图案等设计性的辊涂机进行热压的方法。上述热压时,例如可以在50~200℃下对辊进行加热。
实施例
以下,使用实施例更详细地说明本发明。
[合成例1]氨基甲酸酯树脂(A-1)组合物的制备
在甲乙酮3,281质量份和辛酸亚锡0.1质量份的存在下,使聚碳酸酯多元醇(以1,6-己二醇为原料,数均分子量:2,000)1,000质量份、2,2-二羟甲基丙酸17质量份、乙二醇47质量份和二苯基甲烷二异氰酸酯344质量份在70℃下反应直至溶液粘度达到20,000mPa·s后,加入甲醇3质量份使反应停止,得到氨基甲酸酯树脂的甲乙酮溶液。在该氨基甲酸酯树脂溶液中混合聚氧乙烯二苯乙烯化苯基醚(Hydrophile-Lipophile Balance(以下,简记为“HLB”);14)70质量份和三乙胺13质量份后,加入离子交换水800质量份,进行转相乳化,由此得到在水中分散有上述氨基甲酸酯树脂(A-1)的乳化液。
接下来,从上述乳化液中蒸馏除去甲乙酮,由此得到包含50质量%的氨基甲酸酯树脂(A-1)的氨基甲酸酯树脂组合物。
[合成例2]氨基甲酸酯树脂(A-2)组合物的制备
在甲乙酮3,281质量份和辛酸亚锡0.1质量份的存在下,使聚氧四亚甲基二醇(数均分子量:2,000)1,000质量份、2,2-二羟甲基丙酸17质量份、乙二醇47质量份和344质量份的MDI在70℃下反应直至溶液粘度达到20,000mPa·s后,加入甲醇3质量份使反应停止,得到氨基甲酸酯树脂的甲乙酮溶液。在该氨基甲酸酯树脂溶液中混合聚氧乙烯二苯乙烯化苯基醚(HLB:14)70质量份和三乙胺13质量份后,加入离子交换水800质量份进行转相乳化,由此得到上述氨基甲酸酯树脂(A-2)分散于水中的乳化液。
接下来,从上述乳化液中蒸馏除去甲乙酮,由此得到包含50质量%的氨基甲酸酯树脂(A-2)的氨基甲酸酯树脂组合物。
[合成例3]氨基甲酸酯树脂(A-3)组合物的制备
在甲乙酮3,281质量份和辛酸亚锡0.1质量份的存在下,使聚碳酸酯多元醇(以1,6-己二醇作为原料,数均分子量:2,000)300质量份、聚氧四亚甲基二醇(数均分子量:2,000)700质量份、2,2-二羟甲基丙酸17质量份、乙二醇47质量份和344质量份的MDI在70℃下反应直至溶液粘度达到20,000mPa·s后,加入甲醇3质量份使其反应停止,得到氨基甲酸酯树脂的甲乙酮溶液。在该氨基甲酸酯树脂溶液中混合聚氧乙烯二苯乙烯化苯基醚(HLB:14)70质量份和三乙胺13质量份后,加入离子交换水800质量份进行转相乳化,由此得到上述氨基甲酸酯树脂(A-3)分散于水中的乳化液。
接下来,从上述乳化液中蒸馏除去甲乙酮,由此得到包含50质量%的氨基甲酸酯树脂(A-3)的氨基甲酸酯树脂组合物。
[合成例4]氨基甲酸酯树脂(A-4)组合物的制备
在甲乙酮3,281质量份和辛酸亚锡0.1质量份的存在下,使聚碳酸酯多元醇(以1,6-己二醇作为原料,数均分子量:2,000)500质量份、聚氧四亚甲基二醇(数均分子量:2,000)500质量份、2,2-二羟甲基丙酸17质量份、乙二醇47质量份和344质量份的MDI在70℃下反应直至溶液粘度达到20,000mPa·s后,加入甲醇3质量份使反应停止,得到氨基甲酸酯树脂的甲乙酮溶液。在该氨基甲酸酯树脂溶液中混合聚氧乙烯二苯乙烯化苯基醚(HLB:14)70质量份和三乙胺13质量份后,加入离子交换水800质量份进行转相乳化,由此得到上述氨基甲酸酯树脂(A-4)分散于水中的乳化液。
接下来,从上述乳化液中蒸馏除去甲乙酮,由此得到包含50质量%的氨基甲酸酯树脂(A-4)的氨基甲酸酯树脂组合物。
[实施例1]
向合成例1中得到的氨基甲酸酯树脂(A-1)组合物30质量份和合成例2中得到的氨基甲酸酯树脂(A-2)组合物70质量份中加入增稠剂(Borchers公司制“Borchi Gel ALA”)2质量份、硬脂酸铵0.5质量份、交联剂(日本触媒株式会社制“EPOCROS WS-700”)4质量份,使用机械混合器以2,000rpm搅拌1分钟,使其起泡,得到体积为1.5倍的起泡液。
将其涂布于脱模纸,在80℃下干燥3分钟,进一步在120℃下干燥2分钟,由此制造发泡氨基甲酸酯片。
[实施例2]
在实施例1的基础上,将氨基甲酸酯树脂(A-1)的配合量变更为50质量份,将氨基甲酸酯树脂(A-2)的配合量变更为50质量份,除此以外,与实施例1同样地操作,得到发泡氨基甲酸酯片。
[实施例3]
在实施例1的基础上,将氨基甲酸酯树脂(A-1)的配合量变更为80质量份,将氨基甲酸酯树脂(A-2)的配合量变更为20质量份,除此以外,与实施例1同样地操作,得到发泡氨基甲酸酯片。
[实施例4]
在合成例3中得到的氨基甲酸酯树脂(A-3)组合物100质量份中加入增稠剂(Borchers公司制“Borchi Gel ALA”)2质量份,硬脂酸铵0.5质量份,交联剂(日本触媒株式会社制“EPOCROS WS-700”)4质量份,使用机械混合器以2,000rpm搅拌1分钟,使其起泡,得到体积为1.5倍的起泡液。
将其涂布于脱模纸,在80℃下干燥3分钟,进一步在120℃下干燥2分钟,由此制造发泡氨基甲酸酯片。
[实施例5]
向合成例4中得到的氨基甲酸酯树脂(A-4)组合物100质量份中加入增稠剂(Borchers公司制“Borchi Gel ALA”)2质量份、硬脂酸铵0.5质量份、交联剂(日本触媒株式会社制“EPOCROS WS-700”)4质量份,使用机械混合器以2,000rpm搅拌1分钟,使其起泡,得到体积为1.5倍的起泡液。
将其涂布于脱模纸,在80℃下干燥3分钟,进一步在120℃下干燥2分钟,由此制造发泡氨基甲酸酯片。
[比较例1]
向合成例1中得到的氨基甲酸酯树脂(A-1)组合物30质量份和合成例2中得到的氨基甲酸酯树脂(A-2)组合物70质量份中加入增稠剂(Borchers公司制“Borchi Gel ALA”)2质量份、十二烷基苯磺酸钠1.5质量份、交联剂(日本触媒株式会社制“EPOCROS WS-700”)4质量份,使用机械混合器以2,000rpm搅拌1分钟,使其起泡,得到体积为1.5倍的起泡液。
将其涂布于脱模纸,在80℃下干燥3分钟,进一步在120℃下干燥2分钟,由此制造片材。
[比较例2]
向合成例1中得到的氨基甲酸酯树脂(A-1)组合物100质量份中加入增稠剂(Borchers公司制“Borchi Gel ALA”)2质量份,硬脂酸铵0.5质量份、交联剂(日本触媒株式会社制“EPOCROS WS-700”)4质量份,使用机械混合器以2,000rpm搅拌1分钟,使其起泡,得到体积为1.5倍的起泡液。
将其涂布于脱模纸,在80℃下干燥3分钟,进一步在120℃下干燥2分钟,由此制造发泡氨基甲酸酯片。
[比较例3]
向合成例2中得到的氨基甲酸酯树脂(A-2)组合物100质量份中加入增稠剂(Borchers公司制“Borchi Gel ALA”)2质量份、硬脂酸铵0.5质量份、交联剂(日本触媒株式会社制“EPOCROS WS-700”)4质量份,使用机械混合器以2,000rpm搅拌1分钟,使其起泡,得到体积为1.5倍的起泡液。
将其涂布于脱模纸,在80℃下干燥3分钟,进一步在120℃下干燥2分钟,由此制造发泡氨基甲酸酯片。
[数均分子量的测定方法]
合成例中使用的多元醇等数均分子量通过凝胶渗透柱色谱(GPC)法,在下述条件下测定。
测定装置:高速GPC装置(东曹株式会社制“HLC-8220GPC”)柱:将东曹株式会社制的下述柱串联连接而使用。
“TSKgel G5000”(7.8mmI.D.×30cm)×1根
“TSKgel G4000”(7.8mmI.D.×30cm)×1根
“TSKgel G3000”(7.8mmI.D.×30cm)×1根
“TSKgel G2000”(7.8mmI.D.×30cm)×1根
检测器:RI(差示折射计)
柱温:40℃
洗脱液:四氢呋喃(THF)
流速:1.0mL/分钟
注入量:100μL(试样浓度0.4质量%的四氢呋喃溶液)
标准试样:使用下述的标准聚苯乙烯制作标准曲线。
(标准聚苯乙烯)
东曹株式会社制“TSKgel标准聚苯乙烯A-500”
东曹株式会社制“TSKgel标准聚苯乙烯A-1000”
东曹株式会社制“TSKgel标准聚苯乙烯A-2500”
东曹株式会社制“TSKgel标准聚苯乙烯A-5000”
东曹株式会社制“TSKgel标准聚苯乙烯F-1”
东曹株式会社制“TSKgel标准聚苯乙烯F-2”
东曹株式会社制“TSKgel标准聚苯乙烯F-4”
东曹株式会社制“TSKgel标准聚苯乙烯F-10”
东曹株式会社制“TSKgel标准聚苯乙烯F-20”
东曹株式会社制“TSKgel标准聚苯乙烯F-40”
东曹株式会社制“TSKgel标准聚苯乙烯F-80”
东曹株式会社制“TSKgel标准聚苯乙烯F-128”
东曹株式会社制“TSKgel标准聚苯乙烯F-288”
东曹株式会社制“TSKgel标准聚苯乙烯F-550”
[氨基甲酸酯树脂(A)的流动起始温度的测定方法]
将合成例中得到的氨基甲酸酯树脂组合物涂布于脱模纸(涂布厚度150μm),用热风干燥机在70℃干燥4分钟,接下来在120℃干燥2分钟,由此得到干燥物。对于该干燥物,使用株式会社岛津制作所制流动试验仪“CFT-500A”(使用口径1mm、长度1mm的模具,载荷98N,升温速度3℃/分钟),测定流动起始温度。
[手感的评价方法]
用手触摸所得到的发泡氨基甲酸酯片,如下进行评价。
“A”:富有柔软性。
“B”:稍有柔软性。
“C”:柔软性差。
“D”:硬。
[耐油酸性的方法]
将实施例和比较例中得到的发泡氨基甲酸酯片贴合于无纺布,由此得到合成皮革。将所得到的合成皮革裁切成宽度50mm、长度50mm,将其作为试验片。将该试验片在80℃下在油酸中浸渍24小时后取出,用纸巾轻轻地擦去附着于表面的油酸。目视观察油酸浸渍前后的外观变化,如下进行评价。
“T”:无外观变化。
“F”:合成皮革膨胀和/或变形。
[低温弯曲性的方法]
将实施例和比较例中得到的发泡氨基甲酸酯片贴合于无纺布,由此得到合成皮革。利用柔度计(株式会社安田精机制“低温柔度计”)对所得到的合成皮革进行弯曲性试验(-30℃,100次/每分钟),测定直至在合成皮革的表面产生磨损为止的次数,如下进行评价。
“A”:15,000次以上
“B”:10,000次以上且小于15,000次
“C”:小于10,000次
[表1]
[表2]
可知本发明的氨基甲酸酯树脂组合物具有优异的手感、耐油酸性和低温弯曲性。
另一方面,比较例1是使用具有芳香环的十二烷基苯磺酸钠来代替表面活性剂(C)的方式,泡保持性不良,手感硬且不良。
比较例2是使用了不含氧亚烷基结构(Y)的氨基甲酸酯树脂组合物的方式,低温弯曲性不良。
比较例3是使用了不含碳酸酯结构(X)的氨基甲酸酯树脂组合物的方式,耐油酸性不良。
Claims (6)
1.一种氨基甲酸酯树脂组合物,其特征在于,其含有氨基甲酸酯树脂(A)、水(B)和表面活性剂(C),所述表面活性剂(C)不具有芳香环且具有碳原子数为10以上的疏水部,所述氨基甲酸酯树脂组合物具有来自于氨基甲酸酯树脂(A)的碳酸酯结构(X)和氧亚烷基结构(Y)。
2.根据权利要求1所述的氨基甲酸酯树脂组合物,其中,所述碳酸酯结构(X)与所述氧亚烷基结构(Y)的质量比[X/Y]为10/90~90/10的范围。
3.根据权利要求1或2所述的氨基甲酸酯树脂组合物,其中,所述表面活性剂(C)为硬脂酸盐。
4.根据权利要求1~3中任一项所述的氨基甲酸酯树脂组合物,其中,所述氨基甲酸酯树脂(A)具有阴离子性基团。
5.一种发泡氨基甲酸酯片,其特征在于,其由权利要求1~4中任一项所述的氨基甲酸酯树脂组合物形成,且密度为200kg/m3~1,000kg/m3。
6.一种合成皮革,其特征在于,其至少具有基材(i)和聚氨酯层(ii),
所述聚氨酯层(ii)由权利要求5所述的发泡氨基甲酸酯片形成。
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TW202104327A (zh) | 2021-02-01 |
WO2020217813A1 (ja) | 2020-10-29 |
JPWO2020217813A1 (ja) | 2021-05-06 |
EP3936659A1 (en) | 2022-01-12 |
JP6904485B2 (ja) | 2021-07-14 |
EP3936659A4 (en) | 2022-07-06 |
KR20210129162A (ko) | 2021-10-27 |
CN113767195B (zh) | 2024-03-15 |
US20220220250A1 (en) | 2022-07-14 |
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