CN103497725A - 一种纺织品用湿固化反应型聚氨酯热熔胶的制备方法 - Google Patents

一种纺织品用湿固化反应型聚氨酯热熔胶的制备方法 Download PDF

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CN103497725A
CN103497725A CN201310469047.8A CN201310469047A CN103497725A CN 103497725 A CN103497725 A CN 103497725A CN 201310469047 A CN201310469047 A CN 201310469047A CN 103497725 A CN103497725 A CN 103497725A
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hot melt
polyester polyol
curing reaction
antioxidant
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CN103497725B (zh
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李哲龙
朱万育
肖虎鹏
马洪伟
曾作祥
沈艳
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Kunshan Tianyang New Material Co ltd
Tianyang New Material Shanghai Technology Co ltd
East China University of Science and Technology
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Shanghai Tianyang Hotmelt Adhesives Co ltd
KUNSHAN TIANYANG HOT MELT ADHESIVE CO LTD
East China University of Science and Technology
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Abstract

本发明公开了一种纺织品用湿固化反应型聚氨酯热熔胶的制备方法，主要包括如下步骤：（1）将聚醚多元醇4000E、聚酯多元醇3000H、抗氧剂搅拌混合，加热升温至120℃左右，在真空度小于100Pa下，脱水0.5h；（2）加入增粘树脂，继续升温至135-140℃，在真空度小于100Pa下，脱水1.5h；（3）降温至87℃，加入4,4’-二苯基甲烷二异氰酸酯、催化剂，搅拌，在真空度小于100Pa下反应2h；（4）解除真空，加入白炭黑，快速搅拌，混匀，在真空度小于100Pa下继续搅拌10min；（5）保持出料温度在85-100℃，快速出料并封装，然后在80-85℃的条件下熟化4h，得标的产物。该产品用于纺织品复合，具有优异的剥离强度、较短的开放时间、良好的耐水解性能及良好的储存稳定性。

Description

一种纺织品用湿固化反应型聚氨酯热熔胶的制备方法
技术领域
本发明涉及一种纺织品复合用湿固化反应型聚氨酯热熔胶的制备方法。
背景技术
热熔胶因其粘接迅速、无污染、无毒、低有机挥发物(VOC)等特点而得到越来越多的重视。传统热熔胶一般是以热塑性树脂为主组分，虽能快速固化粘接，但固化后胶层不耐高温，且易溶于有机溶剂，粘接强度不高，因而热塑性热熔胶的使用受到了限制。为克服上述缺点，开发出一种新型的湿固化聚氨酯热熔胶，这类热熔胶不仅具有传统热熔胶的较高初粘性、可快速固化定位的优点，而且胶层物理固化后，在体系内部产生化学交联，使胶层粘接强度，耐水性、耐溶剂性等都能得到明显改善，兼有传统溶剂型胶粘剂和热塑性热熔胶的优点。
湿固化反应型聚氨酯热熔胶是一类含端-NCO基团的聚氨酯胶粘剂。使用时，加热熔融施胶，待胶层冷却物理固化产生初步的粘接力后，胶层中的端NCO再与空气中的湿气或被粘物表面的活泼氢化合物反应，产生化学交联固化。湿固化反应型聚氨酯热熔胶不仅具有传统热塑性热熔胶快速粘接定位、提供较高的初粘强度优点，也能进一步固化交联，使胶层的粘接力、内聚强度等都能得到明显的提高。因此，湿固化反应型聚氨酯热熔胶广泛应用于纺织品复合、橡胶、塑料、金属与汽车制造、纺织业、制鞋业、书刊装订、木材工业及家具行业、电子行业等的粘接 。本发明制备的湿固化反应型聚氨酯热熔胶主要用于纺织品复合。
湿固化反应型聚氨酯热熔胶有全聚醚型预聚体类和全聚酯型预聚体类两种。全聚醚型的聚氨酯热熔性胶粘剂具有熔融粘度低、熔体粘度稳定性好、耐水性好、成本低等优点,但初粘和终粘强度较低；而全聚酯的聚氨酯热熔性胶粘剂具有很好的初粘和终粘强度，但是耐水解性能差、柔韧性差。本发明制备的湿固化反应型聚氨酯热熔胶主要优势在于，采用聚醚多元醇和聚酯多元醇的混合多元醇原料，兼有聚醚型湿固化反应型聚氨酯热熔胶和聚酯型湿固化反应性聚氨酯热熔胶两者的优点。
发明内容
本发明的目的之一是为了解决上述的技术问题而提供了一种纺织品复合用湿固化反应型聚氨酯热熔胶。
本发明的目的之二是提供上述的一种纺织品复合用湿固化反应型聚氨酯热熔胶的制备方法。
本发明的技术方案
一种纺织品复合用湿固化反应型聚氨酯热熔胶的制备方法，其特征在于它包括如下步骤：
（1）将聚醚多元醇4000E、聚酯多元醇3000H、聚酯多元醇2000N、抗氧剂搅拌混合，加热升温至120℃左右，在真空度小于100Pa下，脱水0.5h；
（2）加入增粘树脂，继续升温至135-140℃，在真空度小于100Pa下，脱水1.5h；
（3）降温至87℃，加入MDI、催化剂，搅拌，在85-95℃、真空度小于100Pa条件下反应2h；
（4）解除真空，加入白炭黑，快速搅拌，混匀，在真空度小于100Pa下继续搅拌10min；
（5）保持温度在85-100 ℃，快速出料、封装，然后在80-85℃的烘箱中熟化4h，得标的产品；
所述的聚酯多元醇3000H是分子量为3000的聚己二酸-1,6己二醇酯二醇，所述的聚酯多元醇2000N是分子量为2000的聚己二酸新戊二醇酯二醇；所述的增粘树脂为丙烯酸树脂；所述的聚醚多元醇4000E是分子量为4000的聚氧化丙烯二醇；所述抗氧剂为抗氧剂1010和抗氧剂1076的混合物；所述MDI为4,4’-二苯基甲烷二异氰酸酯； 
    以100份质量产品计，所述各物质的质量份数分别为：MDI为11-13份，聚醚多元醇4000E 为 37 - 51份，聚酯多元醇3000H为8 -13份，聚酯多元醇2000N为8 - 13份，抗氧剂1010为0.22份，抗氧剂1076为0.22份，增粘树脂为19 - 20份，催化剂为0.14份，白炭黑为0.5份。
所述的催化剂为辛酸亚锡和双(2，2-吗啉乙基)醚的混合物，两者的质量比为1:1。
本发明的有益效果
本发明制备的湿固化反应型聚氨酯热熔胶主要优势在于，由于为湿固化反应型粘接原理，使得本发明制备的湿固化反应型聚氨酯热熔胶不仅具有传统热塑性热熔胶快速粘接定位、提供较高的初粘强度优点，也能进一步固化交联，使胶层的粘接力、内聚强度等都能得到明显的提高；采用聚醚多元醇和聚酯多元醇的混合多元醇原料，这样使得本发明制备的湿固化反应型聚氨酯热熔胶兼有聚醚型湿固化反应型聚氨酯热熔胶和聚酯型湿固化反应性聚氨酯热熔胶两者的优点——熔体粘度稳定性好、耐水性好、成本低、初粘和终粘强度好、柔韧性较好。本发明制备的湿固化反应型聚氨酯热熔胶，应用于纺织品复合中，平均剥离强度为20N/2.5cm（克重为15g/cm2）左右，耐水解性能较好，具体结果见表1，从而达到纺织品复合行业对湿固化反应型聚氨酯热熔胶的要求。
具体实施方式
下面通过实施例对本发明进一步阐述，但并不限制本发明。
实施例1
（1）将51g聚醚多元醇4000E，8g聚酯多元醇3000H聚、8g酯多元醇2000N，0.22g抗氧剂1010和0.22g抗氧剂1076放入三口烧瓶中搅拌混合并加热升温至120℃左右，在真空度小于100Pa下，脱水0.5h；
（2）将20g增粘树脂加入上述烧瓶中，继续升温至135-140℃，在真空度小于100Pa下，脱水1.5h；
（3）降温至87℃，加入12g MDI、0.07辛酸亚锡和0.07g DMDEE，搅拌，在85-95℃、真空度小于100Pa下反应2h；
（4）解除真空，加人0.5g白炭黑，快速搅拌，混匀，在真空度小于100Pa下继续搅拌10min；
（5）保持出料温度在85-100 ℃，快速出料，氮气保护封装于铝箔袋中后在80-85℃的烘箱中熟化4h，得产品A。
实施例2
（1）将46g聚醚多元醇4000E，10g聚酯多元醇3000H聚、10g酯多元醇2000N，0.22g抗氧剂1010和0.22g抗氧剂1076放入三口烧瓶中搅拌混合并加热升温至120℃左右，在真空度小于100Pa下，脱水0.5h；
（2）将19g增粘树脂加入上述烧瓶中，继续升温至135-140℃，在真空度小于100Pa下，脱水1.5h；
（3）降温至87℃，加入12g MDI、0.07辛酸亚锡和0.07g DMDEE，搅拌，在85-95℃、真空度小于100Pa下反应2h；
（4）解除真空，加人0.5g白炭黑，快速搅拌，混匀，在真空度小于100Pa下继续搅拌10min；
（5）保持出料温度在85-100 ℃，快速出料，氮气保护封装于铝箔袋中后在80-85℃的烘箱中熟化4h，得产品B。
实施例3
（1）将44g聚醚多元醇4000E，11g聚酯多元醇3000H聚、11g酯多元醇2000N，0.22g抗氧剂1010和0.22g抗氧剂1076放入三口烧瓶中搅拌混合并加热升温至120℃左右，在真空度小于100Pa下，脱水0.5h；
（2）将19g增粘树脂加入上述烧瓶中，继续升温至135-140℃，在真空度小于100Pa下，脱水1.5h；
（3）降温至87℃，加入11g MDI、0.07辛酸亚锡和0.07g DMDEE，搅拌，在85-95℃、真空度小于100Pa下反应2h；
（4）解除真空，加人0.5g白炭黑，快速搅拌，混匀，在真空度小于100Pa下继续搅拌10min；
（5）保持出料温度在85-100 ℃，快速出料，氮气保护封装于铝箔袋中后在80-85℃的烘箱中熟化4h，得产品C。
实施例4
（1）将37g聚醚多元醇4000E，13g聚酯多元醇3000H聚、13g酯多元醇2000N，0.22g抗氧剂1010和0.22g抗氧剂1076放入三口烧瓶中搅拌混合并加热升温至120℃左右，在真空度小于100Pa下，脱水0.5h；
（2）将19g增粘树脂加入上述烧瓶中，继续升温至135-140℃，在真空度小于100Pa下，脱水1.5h；
（3）降温至87℃，加入13g MDI、0.07辛酸亚锡和0.07g DMDEE，搅拌，在85-95℃、真空度小于100Pa下反应2h；
（4）解除真空，加人0.5g白炭黑，快速搅拌，混匀，在真空度小于100Pa下继续搅拌10min；
（5）保持出料温度在85-100 ℃，快速出料，氮气保护封装于铝箔袋中后在80-85℃的烘箱中熟化4h，得产品D。
应用实施例
上述的实施例1-4所得的纺织品复合用湿固化反应型聚氨酯热熔胶A、纺织品复合用湿固化反应型聚氨酯热熔胶A、纺织品复合用湿固化反应型聚氨酯热熔胶C、纺织品复合用湿固化反应型聚氨酯热熔胶D的技术参数见表1，纺织品复合用湿固化反应型聚氨酯热熔胶A、B、C、D在纺织品复合中的应用，其应用方法包括如下步骤：
分别将上述实施例1-4所得的纺织品复合用湿固化反应型聚氨酯热熔胶产品A、B、C、D在120℃的温度下进行加热然后用0.45μm孔径的圆网进行涂布，对涤棉进行复合，然后将涂布后的涤棉布料在80℃、3kgf/cm2压力下进行烫压，至于20℃、湿度70%的恒温恒湿环境中放置24h。然后将布料剪成宽2.5cm、长20cm的布条，检测其克重（单位面积布料所含胶的质量），测试其剥离强度，经泡水后再测试其剥离强度，具体结果见表1。
表1  纺织品复合用湿固化反应型聚氨酯热熔胶的技术参数及应用玻璃强度试验结果
Figure 87948DEST_PATH_IMAGE002
从表1中的数据可以看出本发明提供的纺织品复合用湿固化反应型聚氨酯热熔胶在120℃下的黏度为5000mPa·s左右，用于纺织品复合中，不易渗胶，易涂布，15g/m2的克重下玻璃强度为19.92 N/2.5cm，且经水洗后玻璃强度下降不大，表明其玻璃强度好、耐水解性能优良。本发明提供的纺织品复合用湿固化反应型聚氨酯热熔胶A、B、C、D耐水解性能依次下降，但是其耐水解性能依然很好，产品B在的剥离强度最好（单位克重的玻璃强度最大），黏度适中，故优选产品B的实施例2为最佳实施例，产品B的配方为最佳配方。
以上所述内容仅为本发明构思下的基本说明，而依据本发明的技术方案所作的任何等效变换，均应属于本发明的保护范围。

Claims (2)

1.一种纺织品用湿固化反应型聚氨酯热熔胶的制备方法，其特征在于它包括如下步骤：
（1）将聚醚多元醇4000E、聚酯多元醇3000H、聚酯多元醇2000N、抗氧剂搅拌混合，加热升温至120℃左右，在真空度小于100Pa下，脱水0.5h；
（2）加入增粘树脂，继续升温至135-140℃，在真空度小于100Pa下，脱水1.5h；
（3）降温至87℃，加入MDI、催化剂，搅拌，在85-95℃、真空度小于100Pa条件下反应2h；
（4）解除真空，加入白炭黑，快速搅拌，混匀，在真空度小于100Pa下继续搅拌10min；
（5）保持温度在85-100 ℃，快速出料、封装，然后在80-85℃的烘箱中熟化4h，得标的产品；
所述的聚酯多元醇3000H是分子量为3000的聚己二酸-1,6己二醇酯二醇，所述的聚酯多元醇2000N是分子量为2000的聚己二酸新戊二醇酯二醇；所述的增粘树脂为丙烯酸树脂；所述的聚醚多元醇4000E是分子量为4000的聚氧化丙烯二醇；所述抗氧剂为抗氧剂1010和抗氧剂1076的混合物；所述MDI为4,4’-二苯基甲烷二异氰酸酯； 
    以100份质量产品计，所述各物质的质量份数分别为：MDI为11-13份，聚醚多元醇4000E 为 37 - 51份，聚酯多元醇3000H为8 -13份，聚酯多元醇2000N为8 - 13份，抗氧剂1010为0.22份，抗氧剂1076为0.22份，增粘树脂为19 - 20份，催化剂为0.14份，白炭黑为0.5份。
2.如权利要求1所述的方法，其特征在于所述的催化剂为辛酸亚锡和双(2，2-吗啉乙基)醚的混合物，两者的质量比为1:1。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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Families Citing this family (11)

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JP6525023B2 (ja) * 2017-04-25 2019-06-05 横浜ゴム株式会社 反応性ホットメルト接着剤
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JP2022152669A (ja) * 2021-03-29 2022-10-12 昭和電工マテリアルズ株式会社 反応性ホットメルト接着剤、接着体及びその製造方法、並びに衣類
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CN115651595A (zh) * 2022-11-03 2023-01-31 深圳市优宝新材料科技有限公司 聚氨酯热熔胶及其制备方法
CN117089312B (zh) * 2023-09-15 2024-01-26 广东中粘新材料科技有限公司 一种应用于汽车行业的单组份聚氨酯结构胶及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030024639A1 (en) * 2001-04-12 2003-02-06 Paulsen Evelyn Jennifer Lin Controlled structure polyurethane prepolymers for polyurethane structural adhesives
CN102977838A (zh) * 2012-12-22 2013-03-20 昆山天洋热熔胶有限公司 一种衬布用湿固化聚氨酯热熔胶及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040214978A1 (en) * 2003-04-22 2004-10-28 Rosin Michael L. Moisture-curing, hot-melt polyurethane adhesive
CN101613586A (zh) * 2009-07-16 2009-12-30 烟台德邦科技有限公司 一种反应型聚氨酯热熔胶及其制备方法
CN102336883B (zh) * 2011-07-14 2012-09-26 无锡市万力粘合材料有限公司 面料复合用反应型聚氨酯热熔胶的制备方法
CN103497725B (zh) * 2013-09-26 2014-09-17 昆山天洋热熔胶有限公司 一种纺织品用湿固化反应型聚氨酯热熔胶的制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030024639A1 (en) * 2001-04-12 2003-02-06 Paulsen Evelyn Jennifer Lin Controlled structure polyurethane prepolymers for polyurethane structural adhesives
CN102977838A (zh) * 2012-12-22 2013-03-20 昆山天洋热熔胶有限公司 一种衬布用湿固化聚氨酯热熔胶及其制备方法

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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