CN100338164C - 以聚氯丁二烯分散体为基础的粘合剂组合物 - Google Patents
以聚氯丁二烯分散体为基础的粘合剂组合物 Download PDFInfo
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- CN100338164C CN100338164C CNB018159133A CN01815913A CN100338164C CN 100338164 C CN100338164 C CN 100338164C CN B018159133 A CNB018159133 A CN B018159133A CN 01815913 A CN01815913 A CN 01815913A CN 100338164 C CN100338164 C CN 100338164C
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Classifications
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Abstract
本发明涉及以聚氯丁二烯分散体为基础和具有改进粘合性能的粘合剂组合物，生产所述组合物的方法，和它们作为无机和有机基材的接触粘合剂的用途。
Description
本发明涉及具有改进粘合性能的以聚氯丁二烯分散体为基础的粘合剂组合物，它们的制备方法，以及它们作为有机或无机基材的压敏接触粘合剂的用途。
聚氯丁二烯的制备很早就是已知的，它们通过在碱性水介质中的乳液聚合来制备；参阅“Ullmanns Encyclopedie der technischenChemie”，第9卷，第366页，Urban und Schwarzenberg出版社，München-Berlin 1957；“Encyclopedia of Polymer Science andTechnology”，第3卷，705-730页，John Wiley，New York 1965；“Methoden der Organischen Chemie”(Houben-Weyl)XIV/1，738及随后页，Georg Thieme Verlag Stuttgart 1961。
适合的乳化剂原则上包括充分稳定乳液的所有化合物和它们的混合物，例如长链脂肪酸的水溶性盐，尤其钠、钾和铵盐，松香和松香的衍生物，相对高分子量醇硫酸盐，芳基磺酸，芳基磺酸的甲醛缩合物，基于聚环氧乙烷和聚环氧丙烷的非离子乳化剂，以及具有乳化作用的聚合物，如聚乙烯醇(DE-A 2 307 811，DE-A 2 426 012，DE-A 2 514 666，DE-A 2 527 320，DE-A 2 755 074，DE-A 3 246 748，DE-A 1 271 405，1 301 502，US-P 2 234 215，JP-A 60-31510(＝07.28.1983的58-136 824))。
聚氯丁二烯要么进行适当配混和硫化，以用于生产工业橡胶制品，要么作为接触粘合剂的原材料(“Handbook of Adhesives”，21章，Van Nostrand Reinhold出版社，New York，第2版1977)。
以聚氯丁二烯为基础的接触粘合剂主要是溶剂型粘合剂，将它施涂于两件粘合体上并干燥。通过随后在压力下连接两个部件，获得了高强度的粘结物。用这些溶剂型接触粘合剂，粘合剂在室温下可以在长时间内粘结(“露置时间”)被认为是特别有利的。
由于经济和环保的原因，对于能够加工成相应的水性粘合剂配制料的适合聚氯丁二烯水分散体存在着增长的需求。然而，缺点是在水的蒸发之后，与溶剂型粘合剂相比，“露置时间”是更短的。尤其当添加增加粘结的耐热性的高熔点树脂时，获得所要粘结的基材的良好而可重复的接触仅能够通过干燥粘合剂薄膜的预先热活化来实现，尤其在不良吸收或非吸收性基材的情况下(H.W.Lucas，in“AdhesivesAge”，1992，第2册，28页)。
“露置时间”在本说明书中定义为在所施涂的粘合剂充分干燥，使基材可以粘结的时刻和在室温下只通过施加压力不再可能获得令人满意的粘结的时刻之间的时间间隔。
因此目的是提供以聚氯丁二烯水分散体为基础和在蒸发水之后拥有长“露置时间”(在该时间内，在室温下，不用热活化的情况下可以进行粘结)的水性粘合剂组合物。而且，通过将高熔点树脂加入到粘合剂组合物中，有可能获得压敏接触粘合剂的耐热性的改进。
该目的通过制备以聚氯丁二烯分散体为基础的水性粘合剂组合物来实现，所述分散体通过氯丁二烯在水乳液中在作为乳化剂的非改性树脂酸的存在下的连续聚合来获得。该粘合剂原材料的水分散体然后能够用现有技术粘合剂助剂和添加剂加工，获得拥有足够长“露置时间”的粘合剂组合物，在该时间内，在室温下不用热活化就可以进行粘结。
本发明因此提供了以包含具有每分子中至少两个共轭C＝C双键的三环二萜烯羧酸的聚氯丁二烯分散体为基础的粘合剂组合物。
优选的粘合剂组合物包括100重量份的聚氯丁二烯分散体(该分散体包括作为乳化剂的具有每分子中至少两个共轭C＝C双键的三环二萜烯羧酸)，15-75重量份的增粘树脂，1-10重量份的选自氧化锌和氧化镁中的金属氧化物，以及任选其它助剂和添加剂，所有物质以分散体的形式存在。
本发明进一步提供了通过将聚氯丁二烯分散体与常用粘合剂助剂和添加剂混合来制备粘合剂组合物的方法，其特征在于聚氯丁二烯分散体包括每分子中具有至少两个共轭C＝C双键的三环二萜烯羧酸。
存在于本发明的粘合剂组合物中的聚氯丁二烯分散体通过氯丁二烯和2-20重量份的与氯丁二烯可共聚的烯属不饱和单体在碱性介质中在1-10重量份的作为乳化剂的每分子中具有至少两个共轭C＝C双键的三环二萜烯羧酸的存在下的乳液聚合来获得，所有数字以100重量份的两种单体为基础计。
存在于本发明的粘合剂组合物中的聚氯丁二烯分散体在蒸发水之后具有在4-15天范围内的“露置时间”。
适合的可共聚的单体例如描述在“Methoden der OrganischenChemie”(Houben-Weyl)XIV/1；738及以后页，Georg Thieme VerlagStuttgart 1961中。优选的化合物是每分子中具有3-12个碳原子和1或2个可共聚的C＝C双键的那些。优选的可共聚的单体的实例是2，3-二氯丁二烯和1-氯丁二烯。
在本发明的方法中使用的聚氯丁二烯分散体通过在0-70℃，优选5-50℃，和在10-14，优选11-13的pH值下的乳液聚合来制备。活化通过常用活化剂和/或活化剂体系来完成。
可提及的实例包括以下：甲脒磺酸，过二硫酸钾，基于过二硫酸钾和任选的银盐(蒽醌-β-磺酸的Na盐)与例如甲脒亚磺酸、羟基甲烷亚磺酸的Na盐，亚硫酸钠和连二亚硫酸钠作为氧化还原伙伴的氧化还原体系。还适合的是以过氧化物和氢过氧化物为基础的氧化还原体系。本发明的聚氯丁二烯可连续或间歇制备。
为了调节本发明的聚氯丁二烯的粘度，可使用常用链转移剂如硫醇，如在DE-A 3 002 711，GB-PS 1 048 235，FR-PS2 703 106中所述，或例如黄原二硫化物，如在DE-A 1 186 215，DE-A 2 156 453，2 306 610和3 044 811，EP-A 53 319，GB-PS 512 458和952 156，以及US-A 2 321 693和2 567 117中所述。
尤其优选的链转移剂是正十二烷基硫醇和在DE-A 3 044 811，DE-A2 306 610和DE-A 2 156 453中的黄原二硫化物。
在聚合已进行至所需转化率(在可溶性聚氯丁二烯的情况下，一般是在50和80％之间，及在聚氯丁二烯凝胶的情况下高于80％)之后，有利的是通过添加已知的终止剂如叔丁基焦儿茶酚、吩噻嗪和二乙基羟基胺来终止反应。未反应的单体可用蒸汽和真空去除。
在本发明的方法的一个优选实施方案中，在其中聚氯丁二烯分散体通过乳液聚合制备的情况下，氯丁二烯与5-9重量份的2，3-二氯丁二烯在2.0-6.0重量份的作为乳化剂的每分子中具有至少两个共轭C＝C双键的三环二萜烯羧酸的存在下反应，所有数字以所使用的可聚合的单体为基准计。
根据本发明使用的三环二萜烯羧酸可以原始未改性树脂酸的形式使用(S.W.Barendrecht，L.T.Lees in Ullmanns Encyclopdieder Technischen Chemie，第4版第12卷528-538，Verlag Chemie，Weinheim-New York 1976)，它们由妥尔油、松树香脂或根树脂获得，只要它们不含松节油的可馏出的成分。
如果三环二萜烯羧酸本身容易获得，那么它们还可以以纯形式使用。
适合的三环二萜烯羧酸包括例如松香酸，长叶松酸，新松香酸和左旋海松酸。
可以通过气相色谱法由树脂酸的混合物测定含有共轭不饱和键的三环二萜烯羧酸的性质和量；例如，根据J.Amer.Oil Chem.Soc.54，289(1977)或用与之类似的方法。
在使用由妥尔油、松树香脂或根树脂获得的非改性树脂酸的场合，它不仅天然含有共轭不饱和的三环二萜烯羧酸，而且还有其它成分。非限制性地可提及适合的商购非改性树脂酸的实例是具有以下组成的由妥尔油获得的树脂酸：
| 组分，％ | |
| 松香酸 | 40 |
| 新松香酸 | 4 |
| 长叶松酸 | 7 |
| 海松酸 | 3 |
| 异海松酸 | 6 |
| 脱氢松香酸 | 23 |
| 其它树脂酸 | 12 |
| 全部树脂酸的总和 | 95 |
| 脂肪酸 | 2 |
| 结合酸 | 1 |
| 不可皂化组分 | 2 |
| (来自Bergvik Kemi AB，Sderhamn，Sweden的公司小册子) | |
作为其它实例，可以提及由松树香脂获得的非改性树脂酸的组合物：
| 组分，％ | |
| 松香酸 | 46 |
| 新松香酸 | 16 |
| 长叶松酸 | 18 |
| 海松酸 | 8 |
| 异海松酸 | 1 |
| 其它树脂酸 | 10 |
除了共轭不饱和的三环二萜烯羧酸以外，还可使用其它乳化物质，如萘磺酸和甲醛的缩合产物的水溶性盐。
本发明的粘合剂组合物无有机溶剂或有机溶剂含量低。“低”在本文中表示低于30重量％的量(有机溶剂)，基于成品粘合剂计。
除了聚氯丁二烯分散体以外，本发明的粘合剂组合物任选包括其它粘合剂助剂和添加剂。作为例子，可添加填料如石英粉，石英砂，高度分散硅石，重晶石，碳酸钙，白垩，白云石或滑石，任选与润湿剂，例如多磷酸盐(如六偏磷酸钠)，萘磺酸，聚丙烯酸的铵或钠盐一起使用，填料一般以10-60wt％，优选20-50重量％的量添加，基于粘合剂计，以及润湿剂一般以0.2-0.6重量％的量添加，基于填料计。
尤其重要的添加剂是作为可以由聚合物排出的少量氯化氢的接受体的氧化锌。
其它适合的助剂例如是以0.01-1重量％(基于粘合剂)使用的有机增稠剂，如纤维素衍生物，海藻酸盐，淀粉，淀粉衍生物或聚丙烯酸，或以0.05-5重量％(基于粘合剂)使用的无机增稠剂，如膨润土。
为了保存，还可将杀真菌剂加入到本发明的粘合剂组合物中。它们一般以0.02-1.0重量％的量使用，基于粘合剂计。适合的杀真菌剂的实例是苯酚或甲酚的衍生物，或有机锡化合物。
增粘树脂，如非改性或改性天然树脂，例如松香树脂，烃树脂或合成树脂如邻苯二甲酸酯树脂也可任选以分散形式加入到粘合剂组合物中；参阅“Klebharze”R.Jordan，R.Hinterwaldner，75-115页，Hinterwaldner Verlag München 1994。优选的是具有110℃以上的软化点的烷基酚树脂分散体，尤其优选的是具有110℃以上的软化点的萜烯酚醛树脂(Terpenphenolharz)。
任选可以将有机溶剂，例如甲苯、二甲苯、乙酸丁酯、甲基乙基酮、乙酸乙酯、二烷或它们的混合物或增塑剂，例如以己二酸酯、邻苯二甲酸酯或磷酸酯为基础的那些加入到聚氯丁二烯分散体中。
本发明的粘合剂能够用于粘结相同或不同类型的任何基材，例如木材，纸张，塑料，纺织品，皮革，橡胶和无机材料，如陶瓷，陶器或石棉水泥。
本发明的水性粘合剂组合物另外可以使难以粘结的基材粘结，例如热塑性烯烃(TPO)，或具有高乙烯含量的乙烯-乙酸乙烯酯共聚物(EVA)，要不然，它们在表面不用底漆(Primer)预处理的情况下不能粘结。难以粘结的基材是具有低于35mN/m的表面张力的材料。该表面张力的测定例如描述在“Handbook of adhesive”，第1章，第12页，Van Nostrand Reinhold出版社，New York，第2版1977，或在“Strukturelles Kleben und Dichten”，Schindel-Bidinelli，第1卷，第191页，Hinterwaldner出版社，München 1988中。
实施例
A)聚氯丁二烯分散体的制备
聚合通过如在EP-A 0 032 977中所述的连续方法进行。
实施例1(对比实施例)
在由各自具有50L体积的7个相同的反应器组成的聚合级联的第一个反应器中引入水相(W)和单体相(M)以及活化剂相(A)，以连续恒定比率由测量和控制装置引入。每个反应器的平均停留时间是25分钟。反应器对应于在DE-A 2 650 714中所述的那些(数字按重量份/100重量份的所用单体)。
(M)＝单体相：
氯丁二烯 93.0重量份
2，3-二氯-1，3-丁二烯 7.0重量份
正十二烷基硫醇 0.22重量份
吩噻嗪 0.015重量份
(W)＝水相：
去离子水 115.0重量份
歧化松香酸的钠盐 2.6重量份
萘磺酸和甲醛的缩合产物的钠盐 0.7重量份
氢氧化钾 1.0重量份
(A)＝活化剂相：
1％甲脒亚磺酸水溶液 0.05重量份
在40℃的内部温度下，反应缓慢进行。通过外部冷却除去聚合产生的热，将聚合温度保持在45℃下。在66％的单体转化率下，反应通过添加吩噻嗪来终止。通过水蒸汽蒸馏从聚合物中除去残留单体，如在“Neoprene Latices，John C.Carl，E.I.DuPont 1964，第13页”中所述，聚合物胶乳再通过添加海藻酸盐来沉降。
胶乳的粘度是100mPas，固体含量58％。
在120小时的聚合时间之后，聚合生产线停止。
实施例2(本发明实施例)
重复实施例1的工序，但用等量的以妥尔油为基础的非改性树脂酸代替水相中的歧化松香酸。
胶乳的粘度是104mPas，固体含量58％。
实施例3(对比实施例)
重复在实施例1中所述的工序，但用氯丁二烯代替7重量份的2，3-二氯丁二烯和使转化率增加到85％。在沉降操作之后，获得了具有56％的固体含量和105mPas的粘度的分散体。聚合物的60％凝胶化。
实施例4(对比实施例)
聚合如在实施例1中所述，但是在10℃下和不用2，3-二氯丁二烯。
(M)＝单体相：
氯丁二烯 100.0重量份
正十二烷基硫醇 0.13重量份
吩噻嗪 0.015重量份
(W)＝水相：
去离子水 115.0重量份
歧化松香酸的钠盐 2.6重量份
萘磺酸和甲醛的缩合产物的钠盐 0.7重量份
氢氧化钾 1.0重量份
(A)＝活化剂相
1重量％甲脒亚磺酸水溶液 0.07重量份
过硫酸钾 0.05重量份
蒽醌-2-磺酸钠 0.005重量份
在15℃的内部温度下，反应在级联的第一个反应器中开始。通过外部冷却除去聚合释放的热，并将聚合温度降低到10℃。在80％的单体转化率下，通过添加吩噻嗪来终止反应。通过水蒸汽蒸馏从聚合物中除去残留单体，并沉降聚合物胶乳。
在4天的聚合时间之后，停止聚合生产线。
获得了具有56％固体含量和98mPas粘度的分散体。
B)测量方法
1)凝胶含量的测定
将分散体施涂于玻璃板，在室温下在氮气氛围下干燥3天，形成了薄膜。将250mg样品在室温下在封闭容器中于25ml的THF(已添加了1g的聚合抑制剂/L的THF)中溶解或溶胀24小时。将该混合物在20000转/分下超离心1小时，再在干燥后测定通过离心除去的物料的重量百分率。
2)剥离强度的测定
试验根据EN 1392进行。
将100um厚的分散体的湿膜施涂于2件试验样品上(Nora橡胶，粗糙化，100×30mm)和在室温下通风1小时。然后在4巴下将试验样品接合10秒钟。在室温下用普通工业拉伸试验机进行撕裂试验。在粘结之后的1天和9天之后立即测定强度值。
3)在聚酯上的接触粘结时间的测量(“露置时间”)
提供聚酯薄膜(Hostaphan RN 75/0，厚度：0.075mm)，使用具有0.2mm的刮刀孔的薄膜拉制仪器以5mm的宽度施涂分散体。将带有粘合剂分散体的聚酯条在空调室中在23℃和50％相对湿度下储存。在12小时的间隔后，将两件薄板条在各种情况下相互交叉，再加载50g的重量10秒钟。当在用手分离的试验中，不再可能接触薄膜时，就超过了接触粘结时间的界限。
C)以聚氯丁二烯分散体为基础的粘合剂的本发明制备方法
为了制备配制料，将聚氯丁二烯分散体引入到玻璃烧杯中，在搅拌下，添加稳定剂、老化抑制剂、ZnO和树脂。
表1用于比较研究的配制料的制备
| 产物 | 功能 | 添加的形式 | 固体含量(％) | 重量份 |
| 聚氯丁二烯分散体 | 聚合物 | 分散体 | 55-58 | 70 |
| Rhenofit DDA-EM50(1) | 老化抑制剂 | 分散体 | 50 | 2 |
| Emulvin W(2) | 稳定剂 | 溶液 | 20 | 2 |
| Akrosperse W-9804(3) | ZnO | 分散体 | 50 | 4 |
| Alresen VPT 1550(4) | 树脂 | 分散体 | 50 | 30 |
来源：(1)，(2)＝Bayer AG，(3)＝Akrochem，Akron/Ohio USA，(4)＝Vianova Resins Mainz-Kastel，Germany
“露置时间”的测量
表2在聚酯薄膜上的接触粘结时间的测量
| 接触粘结时间 | 12h | 24h | 32h | 3d | 6d | 9d | 12d | 24d | 25d |
| 分散体4 | 有 | 无 | |||||||
| 分散体3 | 有 | 有 | 无 | ||||||
| 分散体1 | 有 | 有 | 有 | 有 | 有 | 无 | |||
| 分散体2*) | 有 | 有 | 有 | 有 | 有 | 有 | 有 | 有 | 无 |
*)本发明实施例
剥离强度的测量
表3根据露置时间测量泡沫/金属结合强度(在ST37钢材上粘结PU泡沫)
| 分散体号 | 4 | 3 | 1 | 2*) | |
| 在粘结之前的储存时间，小时 | |||||
| 1 | N/mm | 0.8 | 1.0 | 0.5 | 0.7 |
| 12 | N/mm | 0.4 | 1.2 | 1.2 | 1.3 |
| 24 | N/mm | 0 | 0.8 | 0.9 | 1.3 |
| 96 | N/mm | 0 | 0.2 | 0.5 | 1.2 |
| 144 | N/mm | 0 | 0 | 0 | 1.2 |
*)本发明实施例
本发明的聚氯丁二烯分散体的非常长的“露置时间”在表2的实施例2中得到证明。与以其它聚氯丁二烯分散体为基础的粘合剂配制料相比，对非吸收性基材如钢材的粘合力(表3，No.2)也是优异的，即使在6天的储存时间之后。
对在TPO上的粘合力的评价
在施涂粘合剂分散体之后，将所述材料在RT下干燥24小时，再测试粘合剂薄膜在该TPO基材(DOW Engage类)上的粘合力。
表4对TPO的粘合力的测量
| 分散体号 | 4 | 3 | 1 | 2*) |
| 对在TPO上的粘合力的评价 | 粘合剂薄膜干燥，容易从基材上去除 | 粘合剂薄膜干燥，容易从基材上去除 | 粘合剂薄膜发粘，但粘合剂对TPO的粘合力的水平低 | 粘合剂薄膜发粘，对TPO的粘合力强 |
在对比实验3和4的情况下，干燥粘合剂薄膜能够毫无问题地从TPO基材上剥离(对TPO无粘合力)。在对比实验1的情况下，干燥粘合剂薄膜对TPO基材的粘合力弱，只有用本发明的粘合剂组合物，获得了具有优异粘合力的粘合剂薄膜。在试图从TPO上剥离干燥粘合剂薄膜时，粘合剂薄膜撕裂，因为对TPO的粘合力太强。
Claims (15)
1、以聚氯丁二烯分散体为基础的粘合剂组合物，所述分散体中包括每分子中具有至少两个共轭C＝C双键三环二萜烯羧酸作为乳化剂，其中所述三环二萜烯羧酸以原始未改性树脂酸的形式或以纯形式使用。
2、如权利要求1的粘合剂组合物，包括100重量份的聚氯丁二烯分散体，15-75重量份的增粘树脂，1-10重量份的选自氧化锌和氧化镁的金属氧化物，以及任选的其它助剂和添加剂，其中所述聚氯丁二烯分散体包含作为乳化剂的每分子中具有至少两个共轭C＝C双键的三环二萜烯羧酸。
3、如权利要求1的粘合剂组合物，其特征在于在水的蒸发之后，它具有在4-15天范围内的“露置时间”。
4、如权利要求2的粘合剂组合物，其特征在于所用增粘树脂是具有110℃以上软化点的萜烯酚醛树脂。
5、通过将聚氯丁二烯分散体与常用粘合剂助剂和添加剂混合来制备粘合剂组合物的方法，特征在于所述聚氯丁二烯分散体包括每分子中具有至少两个共轭C＝C双键的三环二萜烯羧酸，其中所述三环二萜烯羧酸以原始未改性树脂酸的形式或以纯形式使用。
6、如权利要求5的方法，特征在于在通过乳液聚合制备聚氯丁二烯分散体的过程中，氯丁二烯和2-20重量份的2，3-二氯丁二烯在1-10重量份的作为乳化剂的每分子中具有至少两个共轭C＝C双键的三环二萜烯羧酸的存在下反应，所有数字以所使用的可聚合的单体为100重量份为基础计。
7、权利要求1的粘合剂组合物作为有机或无机基材用压敏接触粘合剂的用途。
8、如权利要求7的用途，其特征在于该粘合剂组合物用于粘结相同或不同类型的基材。
9、如权利要求7的用途，其中所述有机或无机基材选自木材、纸张、塑料、纺织品、皮革、橡胶、陶瓷、陶器和石棉水泥。
10、如权利要求7的用途，其中所述有机或无机基材选自热塑性烯烃、具有高乙烯含量的乙烯-乙酸乙烯酯共聚物和具有低于35mN/m的表面张力的材料。
11、用于粘结有机或无机基材的压敏接触粘合剂，它包含权利要求1的粘合剂组合物。
12、如权利要求11的粘合剂，其特征在于该粘合剂组合物用于粘结相同或不同类型的基材。
13、如权利要求11的粘合剂，其中所述有机或无机基材选自木材、纸张、塑料、纺织品、皮革、橡胶、陶瓷、陶器和石棉水泥。
14、如权利要求11的用途，其中所述有机或无机基材选自热塑性烯烃、具有高乙烯含量的乙烯-乙酸乙烯酯共聚物和具有低于35mN/m的表面张力的材料。
15.用权利要求11-14中任一项的压敏接触粘合剂粘结的有机或无机基材。
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| DE10046545A DE10046545A1 (de) | 2000-09-19 | 2000-09-19 | Klebstoffzusammensetzung auf Basis von Polychloropren-Dispersionen |
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| DE10046545A1 (de) * | 2000-09-19 | 2002-03-28 | Bayer Ag | Klebstoffzusammensetzung auf Basis von Polychloropren-Dispersionen |
| DE10224898A1 (de) * | 2002-06-04 | 2003-12-18 | Bayer Ag | Wässrige Klebstoff-Dispersionen |
| US7205986B2 (en) * | 2002-12-18 | 2007-04-17 | Semiconductor Energy Laboratory Co., Ltd. | Image display device and testing method of the same |
| DE10318107A1 (de) * | 2003-04-22 | 2004-11-11 | Bayer Materialscience Ag | Wässrige Klebstoff-Dispersionen |
| WO2004106422A1 (de) * | 2003-05-30 | 2004-12-09 | Lanxess Deutschland Gmbh | Wässrige zusammensetzungen auf basis von polychloropren |
| DE10360368A1 (de) * | 2003-12-22 | 2005-07-21 | Bayer Materialscience Ag | Dispersionen |
| CN100415781C (zh) * | 2004-10-14 | 2008-09-03 | 兰爱克谢斯德国有限责任公司 | 含水的粘合剂分散体 |
| DE102006016608A1 (de) * | 2006-04-06 | 2007-10-11 | Bayer Materialscience Ag | Zubereitungen für den Einsatz in Beton |
| US8118969B2 (en) * | 2006-11-30 | 2012-02-21 | Illinois Tool Works Inc. | Water-based polychloroprene adhesive |
| DE102007018661A1 (de) | 2007-04-20 | 2008-10-23 | Bayer Materialscience Ag | Nanoharnstoffe zur Stabilisierung von CR-Latices sowie Verklebungen und Beschichtungen |
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| EP3406140A1 (de) | 2017-05-24 | 2018-11-28 | Bayer CropScience AG | Wässrige zusammensetzung geeignet zum schutz von setzlingen oder bäumen |
| EP3874081B1 (de) | 2018-10-31 | 2023-02-08 | Covestro Intellectual Property GmbH & Co. KG | Kompositbauteil enthaltend ein polychloropren- und/oder polyurethan-bindemittel |
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2000
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- 2001-09-06 CN CNB018159133A patent/CN100338164C/zh not_active Expired - Fee Related
- 2001-09-06 AU AU2001293796A patent/AU2001293796A1/en not_active Abandoned
- 2001-09-06 AT AT01974229T patent/ATE366294T1/de active
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- 2001-09-06 CA CA002422387A patent/CA2422387C/en not_active Expired - Fee Related
- 2001-09-06 BR BRPI0113964-9A patent/BR0113964B1/pt not_active IP Right Cessation
- 2001-09-06 MX MXPA03002332A patent/MXPA03002332A/es active IP Right Grant
- 2001-09-06 EP EP01974229A patent/EP1322720B1/de not_active Expired - Lifetime
- 2001-09-06 DE DE50112696T patent/DE50112696D1/de not_active Expired - Lifetime
- 2001-09-14 US US09/954,767 patent/US6767947B2/en not_active Expired - Lifetime
-
2004
- 2004-05-19 HK HK04103549A patent/HK1060590A1/xx not_active IP Right Cessation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1427727A (en) * | 1972-07-04 | 1976-03-10 | Distugil | Production of polychloroprene |
| US5298580A (en) * | 1991-09-30 | 1994-03-29 | Bayer Ag | Process for the production of vulcanizable mercaptan-and/or xanthogen disulfide-regulated polychloroprene rubbers with minimal mold fouling |
| US5332771A (en) * | 1992-12-07 | 1994-07-26 | E. I. Du Pont De Nemours And Company | High-performance water-based chloroprene polymer adhesive composition |
| US5527846A (en) * | 1995-03-27 | 1996-06-18 | E. I. Du Pont De Nemours And Company | Polychloroprene adhesive latex composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20040030410A (ko) | 2004-04-09 |
| EP1322720B1 (de) | 2007-07-04 |
| CA2422387C (en) | 2009-11-24 |
| ATE366294T1 (de) | 2007-07-15 |
| US6767947B2 (en) | 2004-07-27 |
| JP5183852B2 (ja) | 2013-04-17 |
| CA2422387A1 (en) | 2003-03-13 |
| MXPA03002332A (es) | 2003-10-15 |
| ES2288992T3 (es) | 2008-02-01 |
| DE50112696D1 (de) | 2007-08-16 |
| BR0113964A (pt) | 2003-07-29 |
| JP2004525991A (ja) | 2004-08-26 |
| KR100861608B1 (ko) | 2008-10-07 |
| DE10046545A1 (de) | 2002-03-28 |
| HK1060590A1 (en) | 2004-08-13 |
| DK1322720T3 (da) | 2007-09-24 |
| AU2001293796A1 (en) | 2002-04-02 |
| WO2002024825A1 (de) | 2002-03-28 |
| CN1460119A (zh) | 2003-12-03 |
| BR0113964B1 (pt) | 2012-06-12 |
| US20020120045A1 (en) | 2002-08-29 |
| EP1322720A1 (de) | 2003-07-02 |
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