CN1288033A - 低散发生物降解胶粘剂 - Google Patents
低散发生物降解胶粘剂 Download PDFInfo
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- CN1288033A CN1288033A CN00128743A CN00128743A CN1288033A CN 1288033 A CN1288033 A CN 1288033A CN 00128743 A CN00128743 A CN 00128743A CN 00128743 A CN00128743 A CN 00128743A CN 1288033 A CN1288033 A CN 1288033A
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
本发明涉及基于聚天冬氨酸或其盐和/或其衍生物及天然增粘剂树脂的水溶性低散发胶粘剂混合物,并涉及其应用。
Description
本发明涉及基于聚天冬氨酸或其盐和/或衍生物与天然增粘剂树脂的混合物的水溶性低散发胶粘剂，并涉及其应用。
聚天冬氨酸、其盐及其衍生物的制备和应用长期以来一直是各种出版物的主题。
适宜的聚天冬氨酸的实例为EP-A-0 650 995中所述的聚合物及衍生物，在此将该专利内容收入本说明书。聚天冬氨酸的有机或无机盐均可作为本发明胶粘剂混合物的成分。下面将聚天冬氨酸、其盐和/或其衍生物统称为PASP。PASP在自然界是广泛分布的。
许多出版物以各种形式描述了其制备方法。生物技术方法是已知的，如湿化学合成路线。此处仅列举：US-A 839 461(=EP-A 0 256366)，US-A 4 590 260和US-A 5 288 783。
根据现有技术，基于天然原料的胶粘剂与基于合成原料的胶粘剂是有差别的，这些基料的混合物也是可以的。
合成基材料的数目几乎是无穷无尽的，并且由于其它的组合可能性，故难以分成区别鲜明的类别。胶粘剂通常如下分类：
1．聚氨酯
2．环氧树脂
3．脲醛树脂
4．聚氯丁二烯
5．聚乙酸乙烯酯均聚物
6．聚丙烯酸酯
7．聚合物分散胶—一般称作上述两组聚合物的水溶液分散体。在多数情况下它们实际上是不含溶剂和其它挥发性有机组分的。
术语“聚羧酸酯”一般理解为不仅包括聚天冬氨酸及其衍生物，而且具体包括聚天冬氨酸、其均聚物和共聚物及其盐。因此聚丙烯酸酯一般为丙烯酸均聚物或基于丙烯酸和马来酸或基于马来酸和甲基乙烯基醚的共聚物。它们可以是酸性、中性或碱性的。
聚天冬氨酸和聚丙烯酸在物理化学行为方面有许多不同。丙烯酸酯胶粘剂是基于丙烯酸单体，特别是丙烯酸酯和甲基丙烯酸酯的胶粘剂。它们或者以单体形式作为在粘接期间聚合的反应性胶粘剂使用，或者以已经聚合的形式(聚丙烯酸酯或聚甲基丙烯酸酯)作为溶液胶粘剂或分散液胶粘剂使用。
第一组包括甲基丙烯酸酯，在无空气存在下固化；氰基丙烯酸酯，暴露在潮气中聚合；及较窄范围内的丙烯酸酯胶粘剂。后者由(甲基)丙烯酸单体、起增稠剂和弹性增强剂作用的聚合物、及一种加聚反应引发剂优选氧化还原引发剂组成。它们与活化剂溶液一起作为双组分胶粘剂使用，并且可用于粘接相当多底材(包括金属、玻璃、塑料、弹性体和木材)。由它们产生的粘接力在很宽温度范围内有如此高强度是引人注目的。另一方面，作为溶液和分散液胶粘剂使用的丙烯酸酯胶粘剂在许多情况下是基于聚合的丙烯酸乙酯和/或丁酯，其机械性能和粘接性能在某些情况下可通过加入含有另外官能团如羧基或羟基的适宜共聚单体进行设计。它们适于作为粘接织物、皮革、塑料和金属的压敏胶粘剂而被广泛应用。
基于聚丙烯酸酯的水性分散压敏胶粘剂是已知的。例如，WO98/56867及其中所引的EP 0 490 191 A2描述了基于聚丙烯酸酯并加入了增粘剂树脂、增塑剂和其它组分的低散发水性分散胶粘剂。
但是，基于聚丙烯酸酯的胶粘剂通常显示了一系列缺点：
1．为了改进粘接性，它们一般含有乙酸乙烯酯。但是乙酸乙烯酯具有易于放出乙醛并因此会是臭味的缺点。
2．其不充分的生物降解性，限制了其在医学领域，特别是在整形外科和骨外科的应用。
3．除了医学应用外，基于天然和合成聚合物的生物降解胶粘剂在现代环境相容技术方面，例如在包装领域也引起了日益增长的兴趣。基于聚丙烯酸酯的传统胶粘剂在这部分市场方面是派不上用场的。
4．作为水性聚丙烯酸酯分散体的另一个缺点，WO 98/56867提到了具有高潜伏毒性的其它可能成分，如甲醛或防腐剂如苯并异噻唑啉酮和氯甲基异噻唑啉酮。
此外，EP 0 810 323描述了共聚物在用于处理单独由单体(甲基)丙烯酸和马来酸酐(MAA)制备的纸面方面的应用。在某些环境中，MAA可用醇或胺改性。此共聚物具有粘接性能。
WO 97/38633描述了各种氨基酸的共聚物作为胶粘剂在整形外科中粘接损伤组织的应用。在该情况下特别使用了天冬氨酸的聚合物。
从此现有技术出发，本发明的目的是开发一种低散发水性胶粘剂，该胶粘剂包含一种或多种除具有可比的粘接性能外还可生物降解并且是毒理学上可接受的成分。
本发明提供了基于聚天冬氨酸、其盐和/或其衍生物并含有天然增粘剂树脂的生物降解胶粘剂混合物，并且还提供了其在医学、技术和工业领域的应用。
基于PASP和天然增粘剂树脂的本发明胶粘剂混合物不仅满足生物降解性、毒理性能和令人赞许的散发特性方面的严格要求，而且还在下列方面惊人般地引人注目：
1．有利的流变学特性，
2．显著改进的可涂布性，及
3．卓越的粘结力(内部强度)。
而且，非常可能不经微生物处理胶粘剂。
满足本发明目的的适宜PASP是根据EP 0 650 995的PASP。本发明优选提供包含聚天冬氨酸(PASP)和天然增粘剂树脂的胶粘剂混合物作为水性分散体，其特征在于水含量为3wt％-90wt％，优选为3wt％-60wt％，特别优选为3wt％-50wt％。平均分子量Mn优选大于400，特别为500-100，000。
除了PASP，本发明的胶粘剂混合物还包含例如从Polym.Mater.Sci.Eng.，61(1989)，588-592页原理上已知的天然增粘剂树脂。这些天然增粘剂特别为存在于分散体中的例如基于双萜、三萜或倍半萜烯的天然树脂酸或其酯。本发明PASP与增粘剂的平衡比优选为5∶1-1∶5。
优选的增粘剂树脂为天然树脂。例如，可以使用禾木树脂、来自澳大利亚黄胶木属物种的黄色或红色树脂、安息香树脂、加拿大香脂、中国或日本天然漆、达玛树脂、龙血树脂、榄香脂、岩蔷薇胶、乳香、没药树脂、秘鲁香脂、山达脂、苏合香脂、吐鲁香脂、威尼斯松节油或松香。根据其获得方式可将后者再分为香脂松香、木蒸松香和妥尔油树脂。
作为年龄增长过程中发生的树脂化过程的结果，天然树脂的溶解性随年龄的增长而变化。根据其溶解性能它们还可分成下列种类：油溶性的-例如__树脂和琥珀；及醇溶性的，包括香脂和松树树脂(松香、达玛树脂、山达脂、马尼拉__脂和乳香)。
天然树脂是液态或固态的无定形和非晶产品，平均分子质量小于2000g/mol。
它们的密度为0.9-1.3 kg/l。坚硬的天然树脂在约40℃(阿魏胶)至360℃(琥珀)的温度范围内熔融。
在化学方面，天然树脂是非常不同的物质如树脂酸(树脂酸)、树脂醇(树脂醇)、及树脂酸和树脂醇的酯的混合物。
树脂酸易于转变为树脂酯和树脂皂，或转变为硬树脂，其对树脂涂敷材料更有意义。大部分含有树脂酸如松香的松柏树脂根据其组成，可用二烯、亲二烯体、醇或酚改性，得到例如马来酸酯树脂或所谓的合成__树脂。不饱和树脂酸的氢化导致得到具有粘接性或增塑性的产品。
市售称作松脂制品的天然树脂多数来源于松树。它们可再分为香脂树脂(来自活树的松香和松节油)、木树脂(从树桩提取的树脂)和从妥尔油中获得的妥尔油树脂，它们是在纤维素蒸煮过程中产生的。
本发明的水性分散液可包括常规量的增稠剂、润湿剂、消泡剂、成膜剂或颜料作为另外的添加剂。其它可用的可能添加剂为胶粘剂中用的常规填料，特别是有机或无机填料。
其它适宜的添加剂包括水溶性生物降解溶剂，例如乙醇、二醇、二醇醚、由甘油醛、甘油酸及其酯、甘油酯、甘油二醋酸酯和甘油一醋酸酯衍生的水溶性甘油衍生物。
为了生产压敏胶粘剂产品，可用常规方法，例如通过喷涂、刮涂、辊涂、倾注、辊涂或浸涂将分散液涂到适当的底材上。
根据本发明制备的并基于PASP和天然树脂的胶粘剂混合物，惊人地特别适于粘接硬、软或弹性表面。
它们可用于纸张工业、木材工业、织物工业、汽车工业、塑料工业、金属工业、电气工业、包装工业、皮革工业、建筑工业或化妆品工业。
根据本发明制备的胶粘剂混合物可用于例如粘接瓶签、粘性便条、信封或邮票。它们适于粘接塑料、弹性体和柔性泡沫，或作为尿布及其它卫生用品如卫生巾中的组分。
也可以用它们粘接玻璃、金属、再生纸板或胶合板。还可以粘接陶瓷、软木、橡胶或毡制品。根据本发明制备的胶粘剂混合物可用于生产胶带的组装粘接、胶接木建筑、镶盖、生产木地板、木板接合、剥芯胶接或支架、框架和榫钉的胶接。
根据本发明制备的基于PASP和天然增粘剂树脂的胶粘剂混合物可用于处理伤口和人体组织及骨头的粘接以及兽医学。
此外，根据本发明制备的基于PASP和天然胶粘剂的胶粘剂混合物惊人地特别适于建造诸如木材、织物或塑料等材料的结构。例如，本发明的胶粘剂混合物可用于压制再生纸板和聚合物片。
胶粘剂配方的实施例
| 序列号 | 组分 | 比例(%) |
| (1) | 聚天冬氨酸钠盐 | 45 |
| (2) | 白垩 | 7 |
| (3) | 乙二醇 | 7 |
| (4) | 天然树脂酸酯 | 15 |
| (5) | 水 | 加至100% |
制备说明
根据实施例1的胶粘剂
1．将固体(1)放入混合容器中并接通搅拌器。
2．加入(2)和(3)，短暂搅拌。
3．加入一半准备加入的水(5)，并搅拌直至均匀。
4．剧烈搅拌下将加热至80℃的树脂(4)加入到混合物中并使之均匀。
根据实施例1制备的胶粘剂显示了本发明所指出的优点。
Claims (11)
1．水溶性生物降解胶粘剂混合物，其特征在于它们包含聚天冬氨酸、其盐和/或其衍生物(PASP)和天然增粘剂树脂。
2．根据权利要求1的水溶性胶粘剂混合物，其特征在于水含量为3wt％-90wt％。
3．根据权利要求1和2的水溶性胶粘剂混合物，其特征在于使用了水溶性生物降解溶剂作为其它添加剂。
4．根据权利要求1的水溶性胶粘剂混合物，其特征在于使用天然树脂酸或其酯作为天然增粘剂树脂。
5．根据权利要求4的水溶性胶粘剂混合物，其特征在于使用禾木树脂、来自澳大利亚黄胶木属物种的黄色或红色树脂、安息香树脂、加拿大香脂、中国或日本天然漆、达玛树脂、龙血树脂、榄香脂、岩蔷薇胶、乳香、没药树脂、秘鲁香脂、山达脂、苏合香脂、吐鲁香脂、威尼斯松节油或松香作为天然树脂酸或其酯。
6．根据权利要求1的胶粘剂混合物作为尿布及其它卫生用品如卫生巾中组分的应用。
7．PASP和天然增粘剂树脂在制备胶粘剂混合物方面的应用，所述胶粘剂混合物用于伤口处理及处理人体组织和骨头以及兽医学。
8．PASP和天然增粘剂树脂在制备胶粘剂混合物方面的应用，所述胶粘剂混合物用于建造材料结构。
9．基于PASP和天然增粘剂树脂的胶粘剂混合物在纸张工业、织物工业、木材工业、汽车工业、塑料工业、金属工业、电气工业、包装工业、皮革工业、建筑工业或化妆品工业中的应用。
10．粘接硬、软或弹性表面的方法，其特征在于所用胶粘剂混合物包含PASP和天然增粘剂树脂。
11．制备基于PASP和天然增粘剂树脂的胶粘剂混合物的方法，其特征在于加入PASP，助剂与水一起在搅拌下加入，最后向混合物中加入天然增粘剂树脂并搅匀。
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| Application Number | Priority Date | Filing Date | Title |
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| DE19944159.6 | 1999-09-15 | ||
| DE19944159A DE19944159A1 (de) | 1999-09-15 | 1999-09-15 | Emissionsarmer, biologisch abbaubarer Klebstoff |
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| KR (1) | KR20010039883A (zh) |
| CN (1) | CN1288033A (zh) |
| DE (1) | DE19944159A1 (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242763A (zh) * | 2013-05-31 | 2013-08-14 | 苏州华周胶带有限公司 | 一种以聚酸亚胺薄膜为基材的胶带的制造方法 |
| CN107033833A (zh) * | 2017-03-15 | 2017-08-11 | 中国科学院长春应用化学研究所 | 一种聚氨基酸组合物及其制备方法和应用 |
| CN108559442A (zh) * | 2018-05-09 | 2018-09-21 | 佛山市三水日邦化工有限公司 | 一种高粘性eva热熔胶及其制备方法 |
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| JP2002212474A (ja) * | 2001-01-18 | 2002-07-31 | Tsukioka:Kk | 可食性インキおよび食品包装印刷物 |
| DE102013004909A1 (de) | 2013-03-22 | 2014-10-09 | Jowat Ag | Neue Klebstoffzusammensetzungen auf Basis nachwachsender Rohstoffe und deren Verwendung |
| CN103834010B (zh) * | 2014-03-21 | 2016-05-25 | 山东泰和水处理科技股份有限公司 | 一种松香基接枝聚天冬氨酸及其制备方法 |
| CN105505266B (zh) * | 2016-01-15 | 2017-07-07 | 上海嘉好胶粘制品有限公司 | 一种输液贴胶及其制备方法 |
| CN105670445A (zh) * | 2016-02-26 | 2016-06-15 | 蚌埠赛尔时代工贸有限公司 | 一种塑料桶制造用的外层的保护涂料 |
| FR3114769B1 (fr) | 2020-10-07 | 2023-12-01 | RTFACT Brands | Tissu biodégradable en liège |
| WO2022075030A1 (ja) * | 2020-10-08 | 2022-04-14 | Dic株式会社 | 樹脂組成物、成形体、積層体、ガスバリア材、コーティング材及び接着剤 |
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1999
- 1999-09-15 DE DE19944159A patent/DE19944159A1/de not_active Withdrawn
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- 2000-09-05 JP JP2000268470A patent/JP2001098249A/ja active Pending
- 2000-09-14 KR KR1020000053940A patent/KR20010039883A/ko not_active Application Discontinuation
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242763A (zh) * | 2013-05-31 | 2013-08-14 | 苏州华周胶带有限公司 | 一种以聚酸亚胺薄膜为基材的胶带的制造方法 |
| CN103242763B (zh) * | 2013-05-31 | 2014-10-29 | 苏州华周胶带有限公司 | 一种以聚酸亚胺薄膜为基材的胶带的制造方法 |
| CN107033833A (zh) * | 2017-03-15 | 2017-08-11 | 中国科学院长春应用化学研究所 | 一种聚氨基酸组合物及其制备方法和应用 |
| CN108559442A (zh) * | 2018-05-09 | 2018-09-21 | 佛山市三水日邦化工有限公司 | 一种高粘性eva热熔胶及其制备方法 |
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| Publication number | Publication date |
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| JP2001098249A (ja) | 2001-04-10 |
| DE19944159A1 (de) | 2001-03-22 |
| EP1085072A2 (de) | 2001-03-21 |
| EP1085072A3 (de) | 2002-07-24 |
| KR20010039883A (ko) | 2001-05-15 |
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