CN114057987A - 合成皮革用水分散聚氨酯-脲树脂组合物及其制备方法 - Google Patents

合成皮革用水分散聚氨酯-脲树脂组合物及其制备方法 Download PDF

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CN114057987A
CN114057987A CN202110886736.3A CN202110886736A CN114057987A CN 114057987 A CN114057987 A CN 114057987A CN 202110886736 A CN202110886736 A CN 202110886736A CN 114057987 A CN114057987 A CN 114057987A
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water
resin composition
synthetic leather
urea resin
dispersible polyurethane
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金泰雄
金周日
金度勋
申钟燮
权容得
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Dongcheng Chemical Co ltd
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Dongcheng Chemical Co ltd
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Abstract

本发明涉及合成皮革用水分散聚氨酯‑脲树脂组合物及其制备方法，更详细地，提供如下的合成皮革用水分散聚氨酯‑脲树脂组合物及其制备方法：包含具有磺酸基的离子化合物，不包含中和剂，由此具有优秀的树脂稳定性、耐热性及审美性。并且，本发明的合成皮革用水分散聚氨酯‑脲树脂组合物可通过调节具有磺酸基的离子化合物的含量来将聚氨酯‑脲的粒子大小控制成所要的大小，由此能够以各种用途适用。

Description

合成皮革用水分散聚氨酯-脲树脂组合物及其制备方法
相关申请
本申请要求于2020年8月3日提交的韩国专利申请10-2020-0096801的优先权，其公开内容通过引用全部并入本文。
技术领域
本发明涉及合成皮革用水分散聚氨酯-脲树脂组合物，更详细地，涉及如下的合成皮革用聚氨酯-脲树脂及其制备方法：代替羧酸类离子化合物，使用具有磺酸基的离子化合物，不包含中和剂，由此具有优秀的树脂稳定性。
背景技术
作为用于解决在现有的溶剂型树脂中使用的各种有机溶剂引起的环境问题等的代替方案，正在研发水分散聚氨酯-脲树脂。尤其，当进行溶剂型树脂的生产工序时，为了防止因使用有机溶剂而引起的对于人体的有害性，对于有机溶剂的规定逐渐增加，为此，正在研发无溶剂型聚氨酯或水分散聚氨酯-脲树脂等。
当制备水分散聚氨酯-脲树脂时，为了使疏水性的预聚物水分散，使用离子化合物。在以往，使用羧酸盐作为离子化合物，在此情况下，一同使用中和剂。用作中和剂的三乙胺等的物质促进作为预聚物的一成分的聚酯多元醇的水解，因此，具有可用于制备聚氨酯-脲树脂的多元醇受限、树脂稳定性降低的问题。
在韩国公开专利公报第10-2011-0029111号，提出了如下的水性聚氨酯-脲分散液的制备方法：为了将预聚物分散在水中，主要使用二羟甲基丙酸作为离子化合物，为了提高预聚物的分散率，还使用三乙胺。
根据论文[H.Honarkar,M.Barmar*,and M.Barikani,Fibers and Polymers2015,Vol.16,No.4,718-725]，公开了根据具有羧酸类和磺酸基的离子化合物的使用量的水性聚氨酯分散液的物性。但是，当使用在上述论文中使用的多元醇和异氰酸酯等的情况下，具有产品的成本高、所制备的水性聚氨酯分散液的物性不合适用作合成皮革用聚氨酯的问题。
发明内容
本发明所解决的问题在于，提供如下的合成皮革用聚氨酯-脲树脂组合物及其制备方法：作为合成皮革用水分散聚氨酯-脲树脂组合物的一成分，代替现有的羧酸盐，使用具有磺酸基的离子化合物，不包含中和剂，由此具有优秀的树脂稳定性、耐热性及审美性。
并且，本发明所解决的问题在于，提供如下的合成皮革用聚氨酯-脲树脂组合物及其制备方法：可通过调节具有磺酸基的离子化合物的含量来控制聚氨酯-脲粒子大小，由此可适用于各种材料。
为了实现上述技术问题，本发明提供合成皮革用水分散聚氨酯-脲树脂组合物，其包含多元醇、异氰酸酯及具有磺酸基的离子化合物，上述多元醇包含聚酯多元醇、聚醚多元醇或它们的混合物。
并且，本发明提供上述合成皮革用水分散聚氨酯-脲树脂组合物的制备方法。
附图说明
图1为示出实施例1的聚氨酯-脲粒子的大小分布的图。
具体实施方式
以下，对本发明进行说明。
除非具有其他定义，否则在本说明书中使用的所有术语(包括技术术语及科学术语)具有本发明所属技术领域的普通技术人员共同理解的含义。并且，除非明确的特别定义，否则不应理想地或过度地解释被通常使用的词典定义的术语。
合成皮革用水分散聚氨酯-脲树脂组合物
在以往，当制备聚氨酯-脲树脂组合物时，为了使具有疏水性的预聚物水分散，使用了如二羟甲基丙酸或二羟甲基丁酸的具有羧酸盐的化合物，为了提高预聚物的分散性，还添加了中和剂。若在聚氨酯-脲树脂组合物使用聚酯多元醇，则不仅可在粘结力等的物理物性方面期待优秀的效果，还可在表面触感、表面异色等的审美性部分期待优秀的效果。但是，中和剂起到聚酯多元醇的水解促进剂作用，因此，具有如下的问题：当使用具有羧酸盐的化合物时，聚酯多元醇的适用受限，由于添加中和剂，树脂稳定性降低。
本发明的合成皮革用水分散聚氨酯-脲树脂组合物与现有的合成皮革用水分散聚氨酯-脲树脂组合物的差异在于，代替羧酸盐，包含具有磺酸基的离子化合物，不包含中和剂。具体地，上述组合物包含多元醇、异氰酸酯及具有磺酸基的离子化合物，上述多元醇包含聚酯多元醇、聚醚多元醇或它们的混合物，不包含中和剂，由此可同时确保优秀的树脂稳定性及审美性。
本发明的合成皮革用水分散聚氨酯-脲树脂组合物包含具有磺酸基的离子化合物。
具有磺酸基的离子化合物起到向通过使多元醇与异氰酸酯进行反应来制备的预聚物赋予亲水基的作用。
以上述多元醇的总重量(例，100重量份)为基准，上述具有磺酸基的离子化合物的含量可以为1重量份至15重量份，更优选为3重量份至10重量份。例如，具有磺酸基的离子化合物可包含N-(2-氨基乙基)氨基乙磺酸钠、3-[(2-氨基乙基)氨基]丙砜钠、2-[(2-氨基乙基)氨基]乙磺酸钠或它们的混合物。
本发明的合成皮革用水分散聚氨酯-脲树脂组合物可不包含中和剂。
以往，中和剂为了在制备聚氨酯-脲树脂组合物时使疏水性的预聚物水分散而使用，在本发明中，代替羧酸盐，使用具有磺酸基的离子化合物，因此，即使不包含中和剂，也可使预聚物水分散。
上述中和剂包括本领域公知的所有常规中和剂，例如，可以为氨、碳酸铵或碳酸氢铵、三甲胺、三乙胺、三丁胺、二异丙基乙胺、二甲基乙醇胺、二乙基乙醇胺、三乙醇胺、氢氧化钾和碳酸钠中的一种以上，具体地，可以为三乙胺、三乙醇胺、二甲基乙醇胺或二异丙基乙胺或它们的混合物。
构成本发明的合成皮革用水分散聚氨酯-脲树脂组合物的多元醇包含聚酯多元醇、聚醚多元醇或它们的混合物，具体地，可包含聚酯多元醇及聚醚多元醇两种。
多元醇为构成水分散聚氨酯-脲树脂的软链段的物质。在本发明中，作为多元醇的一组成成分适用聚酯多元醇，可提高成型体的表面触感、革皮的调色剂相容性等的审美性。
例如，上述聚酯多元醇可包含聚己二酸乙二醇丁二醇酯二醇、聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚己二酸己二醇酯二醇和聚己内酯二醇中的一种以上。
并且，例如，上述聚醚多元醇可包含聚丁二醇、聚乙二醇、聚丙二醇和聚氧丙烯醚二醇中的一种以上。
为了制备具有优秀的机械物性的成型体，上述聚酯多元醇和聚醚多元醇的重均分子量可以为1000至4000，更具体为1500至2500。
并且，本发明的多元醇可包含本领域公知的常规二醇类多元醇。例如，可使用的二醇类多元醇可包含乙二醇、1,4-丁二醇、1,6-己二醇和1,3-丙二醇中的一种以上。
考虑所制备的合成革皮的物性，以聚氨酯-脲树脂组合物的总重量(例，100重量份)为基准，上述多元醇的含量可以为15重量份至25重量份，优选为18重量份至23重量份。若多元醇的含量小于15重量份，则合成革皮的固化度增加，可降低物性，若多元醇的含量大于25重量份，则合成革皮的柔软度增加，由此作为革皮适用时具有问题。
上述聚酯多元醇与聚醚多元醇的混合比例可以为1∶0.25重量比至1∶2重量比。
并且，包含异氰酸酯化合物作为构成本发明的预聚物的另一成分。这种异氰酸酯与多元醇进行反应来合成氨基甲酸酯基，为构成硬链段的物质。
异氰酸酯可包含脂肪族异氰酸酯、芳香族异氰酸酯或其混合物，脂肪族异氰酸酯与芳香族异氰酸酯的混合比例可以为1∶0.5重量比至1∶2重量比。
作为非限制性例，可使用的异氰酸酯可包含二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、1,6-六亚甲基二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯、对苯二异氰酸酯、间苯二异氰酸酯、六亚甲基二异氰酸酯三聚体、4,4’-二环己基甲烷二异氰酸酯、4,4-二甲基苯基甲烷二异氰酸酯、双-4-(异氰酸酯环己基)甲烷、聚亚甲基二苯基二异氰酸酯、二甲苯二异氰酸酯、赖氨酸二异氰酸酯、甲苯二异氰酸酯、四亚甲基二异氰酸酯、反式-1,4-环己烷二异氰酸酯、四甲基-1,3-二甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二异氰酸酯、1,1,6,6,-四氢氟六亚甲基二异氰酸酯、三甲基六亚甲基二异氰酸酯、二甲基二苯基二异氰酸酯、三苯甲烷三异氰酸酯或它们的混合物。
并且，以上述多元醇的总重量为基准，异氰酸酯的含量优选为20重量份至70重量份，更优选为30重量份至60重量份。若异氰酸酯的含量小于20重量份，可降低合成革皮的强度，若大于70重量份，则由于快速反应而产生副反应，可发生聚合物的稳定性和物性降低的问题。
并且，本发明还可包含增链剂作为形成树脂的成分。可通过使用增链剂来加强分子之间的结合。
上述增链剂可以为二胺类或二醇类增链剂。例如，可使用的增链剂可包含异佛尔酮二胺、乙二胺、二乙烯三胺、三乙烯四胺、二环己基亚甲基二胺、1,6-己二胺或哌嗪、乙二醇、二甘醇、三乙二醇、丙二醇、二丙二醇、丁二醇、1,3-丁二醇、1,4-丁二醇、2-甲基戊二醇、1,5-戊二醇、1,6-己二醇、己二醇、新戊二醇、4-环己烷二甲醇、三羟甲基丙烷和季戊四醇中的一种以上。
以上述多元醇的总重量为基准，上述增链剂的含量可以为2重量份至15重量份，但并不特别局限于此。
并且，若需要，则本发明的合成皮革用水分散聚氨酯-脲树脂组合物可使用催化剂等。催化剂可在反应的任意阶段添加。但是，其添加量也并不特别受限。
例如，上述催化剂可包含以乙酸钾、硬脂酸锌、辛酸锡等为代表的各种金属盐和以二丁基二月桂酸锡等为代表的各种有机金属化合物中的一种以上的物质。
并且，本发明的合成皮革用水分散聚氨酯-脲树脂组合物不包含中和剂，树脂稳定性优秀，具体地，当在70℃的温度下保存14天以上时，可不发生分层现象。
合成皮革用水分散聚氨酯-脲树脂组合物的制备方法
以下，对本发明一实施方式的制备方法进行说明。但是，并不是限定于下述制备方法，可根据需求改变各个工序的步骤或选择性混合来使用。
本发明的合成皮革用水分散聚氨酯-脲树脂组合物可包括下述步骤来制备：预聚物制备步骤，使包含聚酯多元醇、聚醚多元醇或它们的混合物的多元醇与异氰酸酯进行反应来制备预聚物；组合物制备步骤，向上述预聚物中加入极性溶剂后，加入具有磺酸基的离子化合物来制备组合物；以及增链剂混合步骤，向上述组合物中加入水来分散后，混合增链剂。
首先，通过使包含聚酯多元醇、聚醚多元醇或它们的混合物的多元醇与异氰酸酯来制备预聚物。在此情况下，多元醇与异氰酸酯的混合比例可以为1∶0.2至1∶0.8重量比。
在此情况下，预聚物反应的完成基于滴定异氰酸酯的NCO含量而小于理论值且没有变化的情况。
之后，向预聚物中加入极性溶剂后，加入具有磺酸基的离子化合物来制备组合物。
在本发明中使用的极性溶剂只要是本领域通常使用的溶剂，就不会特别受限，只要是可分散预聚物且萃取时容易去除的溶剂就可使用。
根据聚氨酯-脲树脂的用途，以聚合物的总重量为基准，极性溶剂的含量可以为50重量份至200重量份，可在反应的开始、反应过程中或反应结束时的任意阶段加入。
具有磺酸基的离子化合物如上所述。优选地，如二羟甲基丙酸和二羟甲基丁酸的羧酸盐在制备预聚物的步骤中使用，相反，具有胺官能团及磺酸基的离子化合物在预聚物反应后使用。
以多元醇的总重量为基准，具有磺酸基的离子化合物的含量可以为1重量份至15重量份，更优选为3重量份至10重量份。在此情况下，可通过调节具有磺酸基的离子化合物的含量来自由控制包含在聚氨酯-脲树脂组合物的聚氨酯-脲粒子的大小。
之后，通过向上述组合物中加入水并分散来制备水分散液，并混合增链剂。混合增链剂后，去除极性溶剂来制备合成皮革用聚氨酯-脲树脂组合物。
在根据上述制备方法中制备的合成皮革用水分散聚氨酯-脲树脂组合物中，分散在水中的聚氨酯-脲粒子的大小可以为500nm至1500nm。
以下，通过实施例对本发明进行更详细的说明。但是，以下实施例仅用于例示本发明，本发明的范围并不限定于实施例。
实施例1
1-1.预聚物合成
向设置搅拌器、温度计、冷凝器的4颈瓶加入83.4g的聚己二酸乙二醇酯二醇(Mw2500)、6g的1,4-丁二醇(Mw 90.12)、66.7g的聚丁二醇(Mw 2000)后，在60℃的温度下搅拌30分钟。之后，在相同条件下，加入32.6g的异佛尔酮二异氰酸酯后，加入30g的4,4-亚甲基二苯基二异氰酸酯，在90℃至100℃的温度下反应4小时来合成预聚物。加入295.8g的丙酮来溶解预聚物，预聚物反应完成基于滴定NCO含量而小于理论值且没有变化的情况。
1-2.合成皮革用水分散聚氨酯-脲树脂组合物的制备
在丙酮中溶解预聚物后，将烧瓶内部温度调节成40℃以下，在20分钟的时间内分批加入9.8g(基于固体含量的3.97％)的N-(2-氨基乙基)氨基乙磺酸钠(Mw 190.19)。60分钟后，缓慢加入457.8g的水，并通过高速搅拌进行水分散。之后，在水中混合13.6g的异佛尔酮二胺(Mw 170.25)后，在10分钟的时间内滴注3次，追加搅拌1小时后终止反应。通过适用FT-IR，终止点基于NCO峰(peak)的消失。反应完成后，真空去除丙酮。
实施例2
2-1.预聚物合成
向设置搅拌器、温度计、冷凝器的4颈瓶加入84.2g的聚己二酸乙二醇酯二醇(Mw2500)、6.1g的1,4-丁二醇(Mw 90.12)、67.3g的聚丁二醇(Mw 2000)后，在60℃的温度下搅拌30分钟。之后，在相同条件下，加入32.9g的异佛尔酮二异氰酸酯后，加入30.3g的4,4-亚甲基二苯基二异氰酸酯，在90℃至100℃的温度下反应4小时来合成预聚物。加入295.8g的丙酮来溶解预聚物，预聚物反应完成基于滴定NCO含量而小于理论值且没有变化的情况。
2-2.合成皮革用水分散聚氨酯-脲树脂组合物的制备
除使用8.3g(基于固体含量的3.37％)的N-(2-氨基乙基)氨基乙磺酸钠(Mw190.19)之外，通过与实施例1-2相同的方式执行来制备合成皮革用水分散聚氨酯-脲树脂组合物。
实施例3
3-1.预聚物合成
向设置搅拌器、温度计、冷凝器的4颈瓶加入82.7g的聚己二酸乙二醇酯二醇(Mw2500)、6g的1,4-丁二醇(Mw 90.12)、66.1g的聚丁二醇(Mw 2000)后，在60℃的温度下搅拌30分钟。之后，在相同条件下，加入32.3g的异佛尔酮二异氰酸酯后，加入29.8g的4,4-亚甲基二苯基二异氰酸酯，在90℃至100℃的温度下反应4小时来合成预聚物。加入295.8g的丙酮来溶解预聚物，预聚物反应完成基于滴定NCO含量而小于理论值且没有变化的情况。
3-2.合成皮革用水分散聚氨酯-脲树脂组合物的制备
除使用11.3g(基于固体含量的4.57％)的N-(2-氨基乙基)氨基乙磺酸钠(Mw190.19)之外，通过与实施例1-2相同的方式执行来制备合成皮革用水分散聚氨酯-脲树脂组合物。
实施例4
通过与上述实施例1相同的方法和条件进行合成，使用所制备的上述合成皮革用水分散聚氨酯-脲树脂组合物，在商用化生产系统中制备合成皮革用水分散聚氨酯-脲。当进行预聚物反应且加入丙酮时，适用锚式搅拌器，在第一反应器中进行。之后，移动至第二反应器后，制备合成皮革用水分散聚氨酯树脂组合物，并适用盘形搅拌器。在第二反应器中完成反应后，真空去除丙酮。
比较例1
1-1.预聚物合成
向设置搅拌器、温度计、冷凝器的4颈瓶加入82.3g的聚己二酸乙二醇酯二醇(Mw2500)、5.9g的1,4-丁二醇(Mw 90.12)、65.9g的聚丁二醇(Mw 2000)及9.72g的二羟甲基丁烷酸(Mw148.18)(基于固体含量的3.94％)后，在90℃至95℃的温度下反应1小时。之后，在相同条件下，向烧瓶加入32.2g的异佛尔酮二异氰酸酯后，加入29.7g的4,4’-亚甲基二苯基二异氰酸酯，在90℃至100℃的温度下反应4小时来合成预聚物。加入295.8g的丙酮来溶解预聚物，预聚物反应完成基于滴定NCO含量而小于理论值且没有变化的情况。
1-2.合成皮革用水分散聚氨酯-脲树脂组合物的制备
在丙酮中溶解预聚物后，将烧瓶内部温度调节成40℃以下，在20分钟的时间内加入7.3g的三乙胺来进行中和反应。之后，缓慢加入457g的水，并通过高速搅拌进行水分散。之后，在水混合异佛尔酮二胺(Mw 170.25)后，在10分钟的时间内滴注3次，追加搅拌1小时后终止反应。通过适用FT-IR，终止点基于NCO峰(peak)的消失。反应完成后，真空去除丙酮。
评价例1合成皮革用水分散聚氨酯-脲树脂组合物的物性评价
通过下述方式评价在实施例1至4、比较例1中制备的合成皮革用水分散聚氨酯-脲树脂组合物地物性。
1)粒子大小：粒度分析仪(Particle size analyzer)(Zetasizer Nano ZS)
2)软化点：KS M 6634法
3)100％模量：ASTM D638法
4)粘结力：KS MISO36
5)树脂稳定性：在70℃的温度下保存树脂原液(例如未稀释的溶液)后，发生分层或沉淀的时间
表1
实施例1 实施例2 实施例3 实施例4 比较例1
粒子大小(nm) 888 1030 724 800 115
软化点(℃) 165 167 164 167 162
100％模量(Modulus)(kgf/cm<sup>2</sup>) 28 26 29 29 27
粘结力(kgf/inch) 3.5至4.5 3.5至4.5 3.5至4.5 3.5至4.5 3.5至4.5
树脂稳定性 14天以上 14天以上 14天以上 14天以上 7天
1)粒子大小：示出根据具有磺酸基的离子化合物的含量的粒子大小分析结果。若具有磺酸基的离子化合物的含量增加，则阴离子性亲水基的含量增加，因此，减少聚氨酯-脲的粒子大小(实施例1至4)。在比较例1中，代替具有磺酸基的离子化合物，使用羧酸盐，粒子大小与实施例1至4相比小，经推测，这为具有磺酸基的离子化合物与羧酸盐的亲水基活性度及反应性差异引起的结果。图1为根据实施例1的聚氨酯-脲的粒子大小分析结果。
2)软化点，100％模量：示出聚氨酯-脲膜的物理特性结果。在代替羧酸盐而使用具有磺酸基的离子化合物的情况下，耐热性和100％模量等的物性并无显著差异。由此可确认，通过多元醇、异氰酸酯及增链剂示出物性值，具有磺酸基的离子化合物影响组合物的分散性及稳定性。
测定时使用的膜通过如下方式制备：以0.2mm的厚度涂敷聚氨酯-脲树脂，在110℃的温度下干燥2分钟后，在70℃的温度下熟成12小时。
3)粘结力：制备合成革皮后确认了与封口胶带的表面粘结力，确认了因适用聚酯多元醇，在所有树脂均示出优秀的粘结力结果。
测定粘结性(例如粘结力)时所使用的成革皮通过如下方式制备：将配合调色剂的聚氨酯-脲树脂以0.15mm的厚度涂敷后，在110℃的温度下干燥2分钟，上述干燥工序进行2次。之后，在革皮上端涂敷粘结剂后，通过使用层压背衬(backing)层的试片来测定粘结性。
4)树脂稳定性：在70℃的温度下评价合成皮革用水分散聚氨酯-脲树脂的稳定性。在实施例1至4中，具有14天以上的稳定性。在比较例1中，在经过7天的时间点，产生分层现象，这被认为是作为中和剂适用的三乙胺引起的。
如上述表1，包含具有磺酸基的离子化合物的合成皮革用水分散聚氨酯-脲树脂组合物具有优秀的稳定性，利用其来制备的膜示出优秀的物性。并且，在实施例4中，确认了本发明的合成皮革用聚氨酯-脲树脂组合物可在商用化生产系统中生产及制备。并且，实施例1至4的合成皮革用水分散聚氨酯树脂组合物适用聚酯多元醇，不包含中和剂，从而提高表面触感、革皮的调色剂相容性等审美性。
如上文所述，根据本公开的一个或多个实施例，合成皮革用水分散聚氨酯-脲树脂组合物通过包含具有磺酸基的离子化合物代替现有的羧酸盐作为树脂组合物的组分，并且不包含中和剂，从而具有优异的树脂稳定性、耐热性和审美性。
此外，根据本公开的一个或多个实施例，合成皮革用水分散聚氨酯-脲树脂组合物可通过控制具有磺酸基的离子化合物的含量来控制聚氨酯-脲的粒子大小。

Claims (13)

1.一种合成皮革用水分散聚氨酯-脲树脂组合物，其特征在于，包含多元醇、异氰酸酯及具有磺酸基的离子化合物，上述多元醇包含聚酯多元醇、聚醚多元醇或它们的混合物。
2.根据权利要求1所述的合成皮革用水分散聚氨酯-脲树脂组合物，其特征在于，上述组合物不包含中和剂。
3.根据权利要求1所述的合成皮革用水分散聚氨酯-脲树脂组合物，其特征在于，以上述多元醇的总重量为基准，上述具有磺酸基的离子化合物的含量为1重量份至15重量份。
4.根据权利要求1所述的合成皮革用水分散聚氨酯-脲树脂组合物，其特征在于，上述具有磺酸基的离子化合物包含N-(2-氨基乙基)氨基乙磺酸钠、3-[(2-氨基乙基)氨基]丙砜钠、2-[(2-氨基乙基)氨基]乙磺酸钠或它们的混合物。
5.根据权利要求1所述的合成皮革用水分散聚氨酯-脲树脂组合物，其特征在于，上述聚酯多元醇与上述聚醚多元醇的混合比例为1∶0.25重量比至1∶2重量比。
6.根据权利要求1所述的合成皮革用水分散聚氨酯-脲树脂组合物，其特征在于，上述多元醇包括聚丁二醇、聚乙二醇、聚丙二醇、聚氧丙烯醚二醇、聚己二酸乙二醇丁二醇酯二醇、聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚己二酸己二醇酯二醇及聚己内酯二醇中的一种以上。
7.根据权利要求1所述的合成皮革用水分散聚氨酯-脲树脂组合物，其特征在于，上述异氰酸酯包含脂肪族异氰酸酯、芳香族异氰酸酯或其混合物。
8.根据权利要求7所述的合成皮革用水分散聚氨酯-脲树脂组合物，其特征在于，上述脂肪族异氰酸酯与上述芳香族异氰酸酯的混合比例为1∶0.5重量比至1∶2重量比。
9.根据权利要求1所述的合成皮革用水分散聚氨酯-脲树脂组合物，其特征在于，上述异氰酸酯包括二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯、1,6-六亚甲基二异氰酸酯、2,4-甲苯二异氰酸酯、2,6-甲苯二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、1,5-萘二异氰酸酯、对苯二异氰酸酯和间苯二异氰酸酯中的一种以上。
10.根据权利要求1所述的合成皮革用水分散聚氨酯-脲树脂组合物，其特征在于，以上述多元醇的总重量为基准，包含20重量份至70重量份的上述异氰酸酯，包含1重量份至15重量份的上述具有磺酸基的离子化合物。
11.根据权利要求1所述的合成皮革用水分散聚氨酯-脲树脂组合物，其特征在于，当在70℃的温度下保存14天以上时，上述合成皮革用水分散聚氨酯-脲树脂组合物不发生分层现象。
12.一种合成皮革用水分散聚氨酯-脲树脂组合物的制备方法，其特征在于，包括：
预聚物制备步骤，使包含聚酯多元醇、聚醚多元醇或它们的混合物的多元醇与异氰酸酯进行反应来制备预聚物；
组合物制备步骤，向上述预聚物中加入极性溶剂后，加入具有磺酸基的离子化合物来制备组合物；以及
混合步骤，向上述组合物中加入水来分散后，混合增链剂。
13.根据权利要求12所述的合成皮革用水分散聚氨酯-脲树脂组合物的制备方法，其特征在于，分散在水中的上述聚氨酯-脲粒子的大小为500nm至1500nm。
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Application publication date: 20220218