CN106520052A - 高固含低粘度水性聚氨酯胶粘剂及制备方法 - Google Patents
高固含低粘度水性聚氨酯胶粘剂及制备方法 Download PDFInfo
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Abstract
本发明涉及一种高固含低粘度水性聚氨酯胶粘剂及制备方法,包括聚酯多元醇,聚酯多元醇在亲水扩链剂、催化剂作用下与多异氰酸酯反应形成聚酯多元醇‑多异氰酸酯预聚体,该预聚体加入氨基磺酸盐、去离子水、助剂、小分子扩链剂后形成水性聚氨酯分散体或乳液;主要是聚酯多元醇采用叔碳酸缩水甘油酯单体与多元酸、二元酸酐、含环氧基单体在触媒、阻聚剂、抗氧化剂的作用下聚合形成。通过选择不同单体与叔碳酸缩水甘油酯单体聚合或通过改变各单体组分的分量,可以获得不同分子量的聚酯多元醇树脂,满足各领域产品上的使用要求;在水性聚氨酯乳化前,无需加入溶剂进行稀释。具有配制灵活、适应性广、使用范围大、乳液粘度低、高含量高、无污染等优点。
Description
技术领域
本发明属于高分子树脂材料领域,具体的说是关于一种水性聚氨酯胶粘剂。本发明适用于鞋革、汽车、木质家具等产品的粘合剂。
背景技术
传统的胶粘剂,如氯丁橡胶胶粘剂、聚氨酯胶、接枝胶等,基本上都是溶剂挥发性胶粘剂,通过低沸点、极性溶剂的挥发,形成最终的粘合层,这种溶剂挥发性胶粘剂,在使用时产品的挥发性气体造成环境污染和侵害操作人员的身体健康。水性聚氨酯树脂合成与乳化技术的发展,使胶粘剂水性化成为了可能,如专利号为CN201410713630.3的一种新型高固含量水性聚氨酯鞋用胶粘剂的制备方法,使用聚己内酯二元醇、异佛尔酮二异氰酸酯原料,以桂酸二丁基锡为催化剂,二羟甲基丙酸的N-甲基吡咯烷酮乳化剂,在少量丁酮溶剂体系中合成用高固含量鞋用水性聚氨酯胶粘剂;专利号为CN201310117407.8的一种高固含量的磺酸型水性聚氨酯胶粘剂的制备方法,使用自制含磺酸盐的聚酯树脂制备固含量50%的胶粘剂;专利号为CN201310157763.2的磺酸型聚酯多元醇、磺酸型水性聚氨酯及其制备方法,以自制含磺酸盐的聚酯多元醇制备用于建筑、木器涂料和纺织、纸张胶粘剂。以上专利仅在合成路线上形成基本的50%固含量的水性聚氨酯分散体或乳液,但在工业化生产和满足庞大的胶粘剂等领域不同性能需求方面,与溶剂型的胶粘剂仍然有很大的差距。而且,在水性聚氨酯分散体和乳液的制备过程中,为了将高分子量的预聚体很好地分散在水中,通常使用丙酮或丁酮进行大分子稀释,制成乳液后再通过蒸除的方式脱去丙酮或丁酮,造成能源损耗和环境污染。德国的Bayer在市场上推广Dispercoll,U54等系列产品,基本可以达到50%以上的固体含量,用于鞋面和皮化等工业领域。此类产品是以聚酯多元醇、聚醚多元醇为原料,以赢创Evonik的氨基磺酸钠盐为乳化剂和增链剂,以替代或部分替代亲水性扩链剂,形成在50%固含和合适粘度的水性分散体或乳液。目前,聚酯多元醇和聚醚多元醇一般为己二酸系聚酯多元醇、芳香族聚酯多元醇、聚碳酸酯聚酯二元醇、脂肪族聚醚多元醇、聚四氢呋喃醚、以及弹性体或固态聚酯多元醇等,其分子结构和性能已经确定,不能通过单体配制组成满足各种应用场合的不同分子结构,产品适应性差、使用范围小。
发明内容
本发明的目的是针对现有技术存在的不足,提供一种可通过不同结构分子量和活性的单体配制组成满足各种应用场合使用要求的不同分子结构产品,产品配制灵活、适应性广、使用范围大、固含量高、环保性好的高固含低粘度水性聚氨酯胶粘剂及制备方法。
实现本发明目的的高固含低粘度水性聚氨酯胶粘剂,包括聚酯多元醇,聚酯多元醇在亲水扩链剂、催化剂作用下与多异氰酸酯反应形成聚酯多元醇-多异氰酸酯预聚体,该预聚体加入氨基磺酸盐、去离子水、助剂、小分子扩链剂后形成水性聚氨酯分散体或乳液;主要是聚酯多元醇采用叔碳酸缩水甘油酯单体与多元酸、二元酸酐、含环氧基单体在触媒、阻聚剂、抗氧化剂的作用下聚合形成。
在以上技术方案中,催化剂采用三氟化硼-葵酸二甲酯或钛酸四丁酯。
在以上技术方案中,叔碳酸缩水甘油酯采用总碳数为7~10的叔碳酸缩水甘油酯,环氧当量为240g/mol,沸程为251~278℃,在23℃常温时粘度7.1mPa/s;多元酸采用脂肪二元酸和芳香族二酸中的一种或多种;二元酸酐采用丁二酸酐、戊二酸酐、马来酸酐、邻苯二甲酸酐中的一种或多种;含环氧基单体采用环氧环己烷、甲基丙烯酸缩水甘油酯、缩水甘油基环氧树脂、双酚A型低粘度环氧树脂、总碳数为7~10的叔碳酸缩水甘油酯中的一种或多种;小分子扩链剂采用乙二醇、1,4-丁二醇等小分子二醇或乙二胺。
在以上技术方案中,多异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯中的一种或多种。
在以上技术方案中,触媒采用三氟化硼-葵酸二甲酯,以及钛酸四丁酯、钛酸四异丙酯中的一种。
本发明高固含低粘度水性聚氨酯胶粘剂的制备方法,包括制备预制聚酯多元醇和制备水性聚氨酯分散体或乳液,主要是采用以下工艺步骤:
1.制备预制聚酯多元醇
1)将多元酸40~120份、抗氧化剂0.1~0.2份,投料入1000L反应釜,升温至152±2℃,加热熔融后抽真空脱水0.5小时;
2)预先混合叔碳酸缩水甘油酯150~450份、钛酸四丁酯或钛酸四异丙酯0.01~0.05份、三氟化硼-葵酸二甲酯0.01~0.05份、阻聚剂0.01~0.05份,通入氮气,并打开冷凝装置回流,中速搅拌下在30~40分钟内滴加入以上反应釜,常压反应1~2小时;
3)中速搅拌下,投料二元酸酐200~300份入以上反应釜,反应2~3小时;
4)预先混合环氧基单体200~500份、三氟化硼-葵酸二甲酯0.01~0.05份、阻聚剂0.01~0.05份,中速搅拌下在30~40分钟内滴加入以上反应釜,反应3~4小时;
5)测试酸值≤1.0mgKOH/g为合格,用200kg/桶过滤包装备用;
2.制备水性聚氨酯分散体或乳液
1)投料预制聚酯多元醇500~1000份入6000L反应釜,升温至115℃,抽真空脱水0.5小时,打开回流冷凝阀,通入氮气保护;
2)降温至80℃,中速搅拌下,30~40分钟内滴加多异氰酸酯300~600份入以上反应釜,反应1~1.5小时;
3)投料小分子二醇20~50份入以上反应釜,继续反应1小时;降温至70℃,投催化剂1~5份、助剂100~200份,继续反应2小时;
4)降温至60℃,在分散盘边缘线速度为12m/s以上的高速剪切下,快速加入氨基磺酸钠盐60~150份,然后高速搅拌30分钟;
5)高速搅拌下,缓慢滴加去离子水500~1500份,进行乳化,乳化结束持续搅拌30分钟;
6)加入乙二胺:去离子水为1∶5的混合溶液100~300份,慢速搅拌1.5小时;
7)调整PH值在6~7之间,加入助剂0.2~0.5份,经检测合格后,用80目过滤网过滤包装。
本发明的优点是:以叔碳酸缩水甘油酯一次或多次形成酯键的结构为根基,与多元酸、二元酸酐、含环氧基单体聚合形成聚酯多元醇,通过选择不同单体与叔碳酸缩水甘油酯单体聚合或通过改变各单体组分的分量,可以获得不同分子量的聚酯多元醇树脂,满足各领域产品上的使用要求,配制灵活、适应性广、使用范围大;利用叔碳酸缩水甘油酯基团的疏水特性和高度支化的结构具有低粘度特征,可以将聚氨酯预聚体的粘度控制在普通聚酯多元醇或聚醚多元醇预聚物粘度的1/10以下,预聚物的低粘度特性,在水性聚氨酯乳化前,无需加入丙酮、丁酮等低沸点溶剂进行稀释,避免了溶剂浪费与环境污染;采用三氟化硼-葵酸二甲酯为主催化剂,具有极高的反应催化特性,副反应小,对树脂造成氧化、变色小,重金属污染小,反应结束后无需去除催化剂,减少了后处理程序;采用氨基磺酸钠盐作为亲水扩链剂,可以使产品固含达到70%,又具有较低的乳液粘度。
具体实施方式
本发明的高固含低粘度水性聚氨酯胶粘剂,包括聚酯多元醇,聚酯多元醇在亲水扩链剂、催化剂作用下与多异氰酸酯反应形成聚酯多元醇-多异氰酸酯预聚体,该预聚体加入该预聚体加入氨基磺酸盐、去离子水、助剂、小分子扩链剂后形成水性聚氨酯分散体或乳液;聚酯多元醇采用叔碳酸缩水甘油酯单体与多元酸、二元酸酐、环氧基单体在触媒、阻聚剂、抗氧化剂的作用下聚合形成,获得含叔碳酸缩水甘油酯单体的聚酯多元醇-多异氰酸酯聚氨酯树脂,选择不同单体与叔碳酸缩水甘油酯单体聚合或通过改变各单体组分分量的设计,可以获得不同分子量的低粘度、高分子量的聚酯多元醇树脂,满足各使用领域对产品的不同性能要求,同时,叔碳酸缩水甘油酯基团的低粘度特征,在水性聚氨酯乳化前,无需加入丙酮、丁酮等低沸点溶剂进行稀释,避免了生产过程中溶剂浪费与环境污染。
催化剂采用三氟化硼-葵酸二甲酯和钛酸四丁酯。三氟化硼-葵酸二甲酯具有极高的反应催化特性,副反应小,对树脂造成氧化、变色小,重金属污染小,反应结束后无需去除催化剂,减少了后处理程序。
叔碳酸缩水甘油酯的总碳数为7~10,环氧当量为240g/mol,沸程为251~278℃,23℃常温下粘度为7.1mPa/s,环氧当量值可以在240g/mol±10%范围内选择;多元酸采用脂肪二元酸和芳香族二酸中的一种或多种;二元酸酐采用丁二酸酐、戊二酸酐、马来酸酐、邻苯二甲酸酐中的一种或多种;环氧基单体采用环氧环己烷、甲基丙烯酸缩水甘油酯、缩水甘油基环氧树脂、双酚A型低粘度环氧树脂、总碳数为7~10的叔碳酸缩水甘油酯中的一种或多种;触媒为三氟化硼-葵酸二甲酯,以及钛酸四丁酯和钛酸四异丙酯中的一种;阻聚剂为对苯二酚、对苯醌、吩噻嗪、二叔丁基苯二酚中的一种;抗氧化剂为亚磷酸三苯酯、亚磷酸三酯、亚磷酸三正壬基苯中的一种;脂肪二元酸为丁二酸、戊二酸、己二酸、葵二酸、辛二酸、环己二酸,芳香族二酸为对苯二甲酸、邻苯二甲酸、间苯二甲酸、卤代苯二甲酸。依据产品的性能要求选择不同单体的多元酸、二元酸酐、环氧基与叔碳酸缩水甘油酯单体聚合或通过各单体的分量设计,获得不同分子量的聚酯多元醇树脂。
多异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯中的一种或多种。
本发明高固含低粘度水性聚氨酯胶粘剂的制备方法,包括制备预制聚酯多元醇和制备水性聚氨酯分散体或乳液,其工艺步骤为:
1.制备预制聚酯多元醇
1)将多元酸40~120份、抗氧化剂0.1~0.2份,投料入1000L反应釜,升温至152±2℃,加热熔融后抽真空脱水0.5小时;
2)预先混合叔碳酸缩水甘油酯150~450份、钛酸四丁酯或钛酸四异丙酯0.01~0.05份、三氟化硼-葵酸二甲酯0.01~0.05份、阻聚剂0.01~0.05份,通入氮气,并打开冷凝装置回流,中速搅拌下在30~40分钟内滴加入以上反应釜,常压反应1~2小时;
3)中速搅拌下,投料二元酸酐200~300份入以上反应釜,反应2~3小时;
4)预先含混合环氧基单体200~500份、三氟化硼-葵酸二甲酯0.01~0.05份、阻聚剂0.01~0.05份,中速搅拌下在30~40分钟内滴加入以上反应釜,反应3~4小时;
5)测试酸值≤1.0mgKOH/g为合格,用200kg/桶过滤包装备用;
2.制备水性聚氨酯分散体或乳液
1)投料预制聚酯多元醇500~1000份入6000L反应釜,升温至115℃,抽真空脱水0.5小时,打开回流冷凝阀,通入氮气保护;
2)降温至80℃,中速搅拌下,30~40分钟内滴加多异氰酸酯300~600份入以上反应釜,反应1~1.5小时;
3)投料小分子二醇20~50份入以上反应釜,继续反应1小时;降温至70℃,投催化剂1~5份、助剂100~200份,继续反应2小时;
4)降温至60℃,在分散盘边缘线速度为12m/s以上的高速剪切下,快速加入氨基磺酸钠盐60~150份,然后高速搅拌30分钟;
5)高速搅拌下,缓慢滴加去离子水500~1500份,进行乳化,乳化结束持续搅拌30分钟;
6)加入乙二胺:去离子水为1∶5的混合溶液100~300份,慢速搅拌1.5小时;
7)调整PH值在6~7之间,加入助剂0.2~0.5份,经检测合格后,用80目过滤网过滤包装。
该制备方法按照设计分子量为1000的聚酯多元醇投料。通过调整各单体投料量的设计,采用同样的制备方法,可获得分子量为2000、3000的聚酯多元醇。
本发明的制备方法中,在水性聚氨酯乳化前,无需加入丙酮等低沸点溶剂进行稀释,但要在相转变过程中缓慢滴加去离子水,并通过高速剪切乳化的过程中不断将已加入的去离子水在体系中均匀混合,获得完全没有丙酮的乳液,免除了后续的丙酮脱除等步骤,VOC含量≤50.0g/L。
本发明在产品性能设计上,采用引入不同基团进行分子聚合,达到不同树脂混拼的效果,以满足不同产品的使用需求,具有很大的灵活性。
本发明各组成物质的占比以份为计量单位,每1份以质量为计量单位,在批量产生时,一般每1份为1Kg。每1份物质重量可根据每批产量来调整确定。
Claims (8)
1.一种高固含低粘度水性聚氨酯胶粘剂,包括聚酯多元醇,聚酯多元醇在亲水扩链剂、催化剂作用下与多异氰酸酯反应形成聚酯多元醇-多异氰酸酯预聚体,该预聚体加入氨基磺酸钠盐、去离子水、助剂、小分子扩链剂后形成水性聚氨酯分散体或乳液;其特征是聚酯多元醇采用叔碳酸缩水甘油酯单体与多元酸、二元酸酐、环氧基单体在触媒、阻聚剂、抗氧化剂的作用下聚合形成。
2.根据权利要求1所述的高固含低粘度水性聚氨酯胶粘剂,其特征是催化剂采用三氟化硼-葵酸二甲酯或钛酸四丁酯。
3.根据权利要求1或2所述的高固含低粘度水性聚氨酯胶粘剂,其特征是叔碳酸缩水甘油酯采用总碳数为7~10的叔碳酸缩水甘油酯,环氧当量为240g/mol,沸程为251~278℃,在23℃常温下粘度7.1mPa/s;多元酸采用脂肪二元酸和芳香族二酸中的一种或多种;二元酸酐采用丁二酸酐、戊二酸酐、马来酸酐、邻苯二甲酸酐中的一种或多种;环氧基单体采用环氧环己烷、甲基丙烯酸缩水甘油酯、缩水甘油基环氧树脂、双酚A型低粘度环氧树脂、总碳数为7~10的叔碳酸缩水甘油酯中的一种或多种;小分子扩链剂采用乙二醇、1,4-丁二醇等小分子二醇或乙二胺。
4.根据权利要求1或2所述的高固含低粘度水性聚氨酯胶粘剂,其特征是多异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯中的一种或多种。
5.根据权利要求1或2所述的高固含低粘度水性聚氨酯胶粘剂,其特征是触媒采用三氟化硼-葵酸二甲酯,以及钛酸四丁酯和钛酸四异丙酯中的一种。
6.根据权利要求3所述的高固含低粘度水性聚氨酯胶粘剂,其特征是多异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异氟尔酮二异氰酸酯中的一种或多种。
7.根据权利要求3所述的高固含低粘度水性聚氨酯胶粘剂,其特征是触媒采用三氟化硼-葵酸二甲酯,以及钛酸四丁酯和钛酸四异丙酯中的一种。
8.一种高固含低粘度水性聚氨酯胶粘剂的制备方法,包括制备预制聚酯多元醇和制备水性聚氨酯分散体或乳液两个步骤,其特征是采用以下工艺步骤:
一、制备预制聚酯多元醇
1)将多元酸40~120份、抗氧化剂0.1~0.2份,投料入1000L反应釜,升温至152±2℃,加热熔融后抽真空脱水0.5小时;
2)预先混合叔碳酸缩水甘油酯150~450份、钛酸四丁酯或钛酸四异丙酯0.01~0.05份、三氟化硼-葵酸二甲酯0.01~0.05份、阻聚剂0.01~0.05份,通入氮气,并打开冷凝装置回流,中速搅拌下在30~40分钟内滴加入以上反应釜,常压反应1~2小时;
3)中速搅拌下,投料二元酸酐200~300份入以上反应釜,反应2~3小时;
4)预先混合环氧基单体200~500份、三氟化硼-葵酸二甲酯0.01~0.05份、阻聚剂0.01~0.05份,中速搅拌下在30~40分钟内滴加入以上反应釜,反应3~4小时;
5)测试酸值≤1.0mgKOH/g为合格,用200kg/桶过滤包装备用;
二、制备水性聚氨酯分散体或乳液
1)投料预制聚酯多元醇500~1000份入6000L反应釜,升温至115℃,抽真空脱水0.5小时,打开回流冷凝阀,通入氮气保护;
2)降温至80℃,中速搅拌下,30~40分钟内滴加多异氰酸酯300~600份入以上反应釜,反应1~1.5小时;
3)投料小分子二醇20~50份入以上反应釜,继续反应1小时;降温至70℃,投催化剂1~5份、助剂100~200份,继续反应2小时;
4)降温至60℃,在分散盘边缘线速度为12m/s以上的转速剪切下,快速加入氨基磺酸钠盐60~150份,然后高速搅拌30分钟;
5)高速搅拌下,缓慢滴加去离子水500~1500份,乳化结束持续搅拌30分钟;
6)加入乙二胺比去离子水为1比5的混合溶液100~300份,慢速搅拌1.5小时;
7)调整PH值在6~7之间,加入助剂0.2~0.5份,经检测合格后,用80目过滤网过滤包装。
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108641657A (zh) * | 2018-04-28 | 2018-10-12 | 安徽富煌门窗幕墙有限公司 | 一种聚氨酯双组份窗角胶 |
CN113150259A (zh) * | 2020-12-28 | 2021-07-23 | 上海汇得科技股份有限公司 | 一种支化聚酯多元醇及其制备方法和应用 |
CN114364745A (zh) * | 2019-10-28 | 2022-04-15 | Dic株式会社 | 发泡片及合成皮革 |
CN114437307A (zh) * | 2020-10-30 | 2022-05-06 | 长兴化学工业(中国)有限公司 | 水性聚氨酯分散体、涂料组合物及其应用 |
CN115785881A (zh) * | 2022-12-14 | 2023-03-14 | 佛山市精信汇明科技有限公司 | 一种制鞋用水性聚氨酯胶粘剂及其应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090018254A1 (en) * | 2006-02-10 | 2009-01-15 | Basf Coatings Ag | Aqueous multicomponent systems, their preparation and use |
CN101649039A (zh) * | 2008-08-15 | 2010-02-17 | 段友芦 | 高固体含量、低活化温度的水性聚氨酯分散液,制备方法及其用途 |
CN102875945A (zh) * | 2012-09-08 | 2013-01-16 | 佛山市科富科技有限公司 | 聚酯丙烯酸酯杂混水分散体的制备方法 |
CN105061716A (zh) * | 2015-07-22 | 2015-11-18 | 四川大学 | 一种水性聚氨酯乳液及其制备方法 |
CN105085854A (zh) * | 2014-05-09 | 2015-11-25 | 武汉强力荷新材料有限公司 | 一种无溶剂、多元粒径分布高固含量低粘度环保型水性聚氨酯乳液的制备方法 |
-
2016
- 2016-10-27 CN CN201610957233.XA patent/CN106520052A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090018254A1 (en) * | 2006-02-10 | 2009-01-15 | Basf Coatings Ag | Aqueous multicomponent systems, their preparation and use |
CN101649039A (zh) * | 2008-08-15 | 2010-02-17 | 段友芦 | 高固体含量、低活化温度的水性聚氨酯分散液,制备方法及其用途 |
CN102875945A (zh) * | 2012-09-08 | 2013-01-16 | 佛山市科富科技有限公司 | 聚酯丙烯酸酯杂混水分散体的制备方法 |
CN105085854A (zh) * | 2014-05-09 | 2015-11-25 | 武汉强力荷新材料有限公司 | 一种无溶剂、多元粒径分布高固含量低粘度环保型水性聚氨酯乳液的制备方法 |
CN105061716A (zh) * | 2015-07-22 | 2015-11-18 | 四川大学 | 一种水性聚氨酯乳液及其制备方法 |
Non-Patent Citations (2)
Title |
---|
任娜娜,等: "新型聚酯多元醇水分散体的制备", 《涂料工业》 * |
张剑飞,等: "高固体分、高羟值聚酯树脂的合成及性能研究", 《涂料工业》 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108641657A (zh) * | 2018-04-28 | 2018-10-12 | 安徽富煌门窗幕墙有限公司 | 一种聚氨酯双组份窗角胶 |
CN114364745A (zh) * | 2019-10-28 | 2022-04-15 | Dic株式会社 | 发泡片及合成皮革 |
CN114437307A (zh) * | 2020-10-30 | 2022-05-06 | 长兴化学工业(中国)有限公司 | 水性聚氨酯分散体、涂料组合物及其应用 |
CN114437307B (zh) * | 2020-10-30 | 2024-01-26 | 长兴化学工业(中国)有限公司 | 水性聚氨酯分散体、涂料组合物及其应用 |
CN113150259A (zh) * | 2020-12-28 | 2021-07-23 | 上海汇得科技股份有限公司 | 一种支化聚酯多元醇及其制备方法和应用 |
CN113150259B (zh) * | 2020-12-28 | 2022-07-29 | 上海汇得科技股份有限公司 | 一种支化聚酯多元醇及其制备方法和应用 |
CN115785881A (zh) * | 2022-12-14 | 2023-03-14 | 佛山市精信汇明科技有限公司 | 一种制鞋用水性聚氨酯胶粘剂及其应用 |
CN115785881B (zh) * | 2022-12-14 | 2024-03-12 | 佛山市精信汇明科技有限公司 | 一种制鞋用水性聚氨酯胶粘剂及其应用 |
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