CN102510887A - 用于粘附于低表面能基底的丙烯酸组合物 - Google Patents
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Abstract
一般而言,本发明特征在于包含以下物质的反应产物的压敏粘合剂:(a)约25至约95重量份的至少一种一元醇的丙烯酸酯,其均聚物的Tg小于0℃,(b)0至约75重量份的至少一种非极性烯键式不饱和单体,其均聚物的溶解度参数不大于10.50和Tg大于15℃;和(c)约5至约35重量份的至少一种极性烯键式不饱和单体,其均聚物的溶解度参数大于10.50和Tg大于15℃。压敏粘合剂粘附于具有低表面能和/或高表面能的基底。
Description
相关申请的交叉参考
本申请要求2009年9月24日提交的美国临时申请号61/245,431的优先权,在此通过引用将其全部并入本文。
发明领域
本发明涉及压敏粘合剂(PSA)。具体地,本发明涉及粘附到具有低表面能和/或高表面能的基底的压敏粘合剂。
背景技术的描述
丙烯酸酯压敏粘合剂在本领域中是熟知的。这些粘合剂中的许多是丙烯酸的烷基酯与较小部分的极性共聚单体的共聚物。由于存在极性共聚单体,这些粘合剂通常不能很好地粘附于低能和油性表面(例如,临界润湿表面张力不大于约35达因/cm的表面)。
发明内容
通常,本发明特征在于包含以下物质的反应产物的压敏粘合剂:
(a)约25至约95重量份(parts by weight)的至少一种一元醇的丙烯酸酯,其均聚物的Tg小于0℃,
(b)0至约75重量份的至少一种非极性烯键式不饱和单体,其均聚物的溶解度参数不大于10.50和Tg大于15℃;和
(c)约5至约35重量份的至少一种极性烯键式不饱和单体,其均聚物的溶解度参数大于10.50和Tg大于15℃。
在另外的实施方式中,所述压敏粘合剂包含以下物质的反应产物:
(a)约25至约95重量份的至少一种一元醇的丙烯酸酯,其均聚物的Tg小于0℃,
(b)0至约75重量份的至少一种非极性烯键式不饱和单体,其均聚物的溶解度参数不大于10.50和Tg大于15℃;和
(c)约5至约35重量份的至少一种极性烯键式不饱和单体,其均聚物的溶解度参数从大于10.50至约13.5和Tg大于15℃。在另一个实施方式中,所述压敏粘合剂包含以下物质的反应产物:
(a)约25至约95重量份的至少一种一元醇的丙烯酸酯,其均聚物的Tg小于0℃,
(b)0至约75重量份的至少一种非极性烯键式不饱和单体,其均聚物的溶解度参数不大于10.50和Tg大于15℃;和
(c)约5至约35重量份的至少一种极性烯键式不饱和单体,其具有式I的一般结构
其中,在式I的结构中,
R1=H或C1-C4烷基,
X=N或O
R2=苯基或C3-C6环烷基。
在另外的实施方式中,压敏粘合剂包含以下物质的反应产物:(a)约25至约95重量份的至少一种一元醇的丙烯酸酯,其均聚物的Tg小于0℃,(b)0至约75重量份的至少一种另外的烯键式不饱和单体,(c)约5至约35重量份的至少一种极性烯键式不饱和单体,其具有式I的一般结构:
其中,在式I的结构中,
R1=H或CH3
X=O或N
R2=式II
其中,R4是选自以下的成员:氢、甲基、乙基、氯甲基、羟甲基、苯基、甲氧苯基、甲氧丁基和甲氧烯丙基。P是从约0到3的整数。q是从1到3的整数;R3是2-4个碳原子的不饱和二价烷基或取代的烷基基团或4-9个碳原子,优选5-6个碳原子的饱和或不饱和二价碳环脂族环;并且A是选自以下的成员:O、NH或NR1,其中R1如上所限定。
本文涉及的溶解度参数是根据Fedors,Polym.Eng.and Sci.,14:147(1974)中描述的技术来计算的。在根据Fedors的技术测量时其均聚物的溶解度参数大于10.50的单体在本文中被称为极性单体,而在根据Fedors的技术测量时其均聚物的溶解度参数为10.50或更小的单体在本文中被称为非极性单体。
本发明提供压敏粘合剂,所述压敏粘合剂由于掺入非极性烯键式不饱和单体(组分(b))和约5-35份量的极性烯键式不饱和单体(组分(c))而显示对低能(例如,塑料,如聚烯烃塑料)表面优良的附着力。该粘合剂对高能表面,如不锈钢也显示优良的附着力。
该粘合剂比含有,例如极性杂原子丙烯酸酯的其它常规粘合剂毒性小。该粘合剂进一步在低温和高温下均显示良好的剪切性能——尤其在包含少量的极性共聚单体时。
该粘合剂还提供降低对水分的敏感性和减小腐蚀金属,如铜的趋势的优势。
通过以下对其优选实施方式的描述和权利要求书,本发明的其它特征和优势将变得显而易见。
优选实施方式的描述
根本地,PSA要求粘性性能和弹性性能的精确平衡,导致附着力、粘结性、拉伸性和弹性的四重平衡。本质上,PSA产品具有足够的粘结性和弹性,以便——尽管它们的干粘性——它们可以用手指操作并从光滑表面去除而不留残留物。一般的商业习惯并不仅仅因为它们是“粘性的”或者粘附于特殊类型的表面而认可术语PSA延伸包括带和粘合剂。
本发明的压敏粘合剂对低能表面,如聚丙烯和高能表面,如不锈钢均显示良好的附着力。在两种情况下,在72小时停留后,根据以下测试程序B所测量的90°剥离强度为至少2lbs/0.5in.,优选为至少2.5lbs/0.5in.(英寸),更优选为至少3lbs/0.5in。如由剪切强度所测量的,该粘合剂也显示良好的粘结强度特性。优选地,根据以下测试程序C所测量的室温和70℃下的剪切强度均大于50分钟,更优选大于1,000分钟,甚至更优选大于10,000分钟。这些特性通过控制单体组合物达到适当的极性(如通过根据Fedors技术测定的单个单体的均聚物溶解度参数所测量的)和流变性质(如由粘合聚合物的1弧度/秒tanΔ最高温度所测量的Tg)来实现。几种常见单体及其各自的Fedors溶解度参数的列表显示在表1中。表1被分成四部分:低Tg丙烯酸酯单体,高Tg丙烯酸酯单体,高Tg甲基丙烯酸酯单体和乙烯基单体。
表1
粘合聚合物的流变特征可以通过由1弧度/秒tanΔ最高温度所测量的Tg来部分但有用地进行描述。优选由聚合物的1弧度/秒tanΔ最高值所测量的Tg值在-45℃和15℃之间,更优选在-25℃和0℃之间,甚至更优选在-20℃和-5℃之间。
根据本发明的粘合剂——具有必要的极性和流变性质——含有约25至约95份(更优选约40至约85份)的丙烯酸酯,其均聚物的Tg小于0℃(更优选小于-20℃);0至约75份(更优选约15至约60份)的非极性烯键式不饱和单体,其均聚物的Tg大于15℃;和约5至约35份的极性烯键式不饱和单体,其均聚物的Tg大于15℃。
丙烯酸酯是在醇部分中具有约4至约18个碳原子的一元醇的单官能丙烯酸酯,其均聚物的Tg小于0℃。这类丙烯酸酯包括:丙烯酸异辛酯、丙烯酸-2-乙基己酯、丙烯酸异壬酯、丙烯酸异癸酯、丙烯酸癸酯、丙烯酸月桂酯、丙酯酸己酯、丙烯酸丁酯和丙烯酸十八酯、丙烯酸-2-丙基庚酯或其组合。在丙烯酸十八酯的情况下,其量被选择以便在室温下不发生侧链结晶。
非极性烯键式不饱和单体是这样的单体:由Fedors方法测量的其均聚物的溶解度参数不大于10.50,其Tg大于15℃。该单体的非极性性质提高粘合剂的低能表面附着力。相对于上述丙烯酸酯的均聚物,它也提高粘合剂的结构性能(例如,粘结强度)。合适的非极性单体的实例包括丙烯酸-3,3,5-三甲基环己酯、丙烯酸环己酯、丙烯酸异冰片酯、N-辛基丙烯酰胺、丙烯酸叔丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯和甲基丙烯酸丙酯或其组合。
粘合剂还包含极性烯键式不饱和单体——由Fedors方法测量的其均聚物的溶解度参数大于10.50,其Tg大于15℃——以提高结构性能(例如,粘结强度)。合适的极性单体的实例包括丙烯酸、衣康酸、某些取代的丙烯酰胺,如N,N二甲基丙烯酸酰胺、N-乙烯基-2-吡咯烷酮、N-乙烯基己内酰胺、丙烯腈、丙烯酸四氢糠基酯、丙烯酸缩水甘油酯、丙烯酸-2-苯氧乙基酯和丙烯酸苄酯或其组合。
可以通过各种技术来聚合单体混合物,优选光引发本体聚合。优选加入引发剂以助于单体的聚合。所使用的引发剂的类型取决于聚合方法。对于聚合丙烯酸酯单体有用的光敏引发剂包括苯偶姻醚,如苯偶姻甲醚或苯偶姻异丙基醚、取代的苯偶姻醚,如2-甲基-2-羟基苯基·乙基酮、芳族磺酰氯,如2-萘磺酰氯和光敏氧化物,如1-苯基-1,2-丙二酮-2-(邻-乙氧羰基)肟。商业上可得的光敏引发剂的一个实例是IrgacureTM 651——可从Ciba-Geigy Corporation得到,其具有式2,2-二甲氧基-1,2-二苯乙烷-1-酮)。通常,光敏引发剂以基于单体重量约0.005至1重量百分比的量存在。合适的热引发剂的实例包括AIBN和过氧化物。
可聚合单体的混合物也可以含有交联剂或交联剂的组合,以增强粘合剂的剪切强度。以下是可用于本发明的交联剂类型的列表。
表2
在更具体的实施方式中,有用的交联剂包括取代的三嗪,如2,4,-双(三氯甲基)-6-(4-甲氧苯基)-仲-三嗪、2,4-双(三氯甲基)-6-(3,4-二甲氧苯基)-仲-三嗪和美国专利号4,329,384和4,330,590(Vesley)中公开的特定生色团-取代的卤-仲-三嗪,所述美国专利通过引用被并入本文。其它有用的交联剂包括多官能丙烯酸烷基酯单体,如三羟甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯、1,2乙二醇二丙烯酸酯、1,4丁二醇二丙烯酸酯、1,6己二醇二丙烯酸酯和1,12十二烷醇二丙烯酸酯。在(甲基)丙烯酸酯官能度之间具有不同分子量的各种其它交联剂,如美国公布号2010/0120931A1——通过引用其全部被并入本文——中所公开的那些也将是有用的。通常,基于单体的组合重量,交联剂以约0.005至1重量百分比的量存在。
压敏粘合剂可以用于粘合剂制品,如标签、带、印刷品(sheets)、装饰贴花等等。合适的基底——其充当可以施用粘合剂的粘合剂载体或面材——包括非编织材料,如例如纸、塑料、金属或泡沫;编织材料,如例如编织棉织物或编织合成聚合物。合成聚合物的非限制性实例包括聚乙烯、聚丙烯、聚氯乙烯、聚酯和聚酰胺。粘合剂可以通过任何常规方法施用到基底,所述常规方法包括挤压、喷涂、滚涂、幕帘涂布等。
除了压敏粘合剂以外,组合物还可以用于形成泡沫制品,如泡沫载体和带以及泡沫粘合剂。在一个实施方式中,泡沫制品由掺和物形成,所述掺和物包含(a)丙烯酸聚合物(b)液态低聚物和(d)可膨胀微球体或发泡剂;其中(a)和(b)中至少一种在另一种存在的情况下是交联的。
在需要泡沫状压敏粘合剂带的情况下,可以使用含有微球体的单体掺和物。合适的微球体可从Kema Nord Plastics以商品名″Expancel″和从Matsumoto Yushi Seiyaku以商品名″Micropearl″商购。当膨胀时,微球体的比重为约0.02-0.036g/cc。当处理恰当时,在压敏粘合剂组合物中包含未膨胀的微球体并且随后将它们加热以促使膨胀是有可能的,但通常优选将膨胀的微球体混合到粘合剂中。该方法更容易确保最终的粘合剂中的中空微球体被至少一薄层粘合剂充分围绕。
平均直径为10至200微米的聚合物微球体可以以体积计约15%至约75%的量在涂覆之前掺入到可聚合组合物中。同样有用的是玻璃微球体,其平均直径为5至200微米,优选约20至80微米。这样的微球体可以占压敏粘合剂的以体积计5%至65%。聚合物微球体和玻璃微球体在本领域中均是已知的。带的压敏粘合剂层的厚度应该是微球体直径的至少3倍,优选为至少7倍。
根据本发明的压敏粘合剂在其中有用的其它带结构物包括机械紧固件,如Dual-LockTM牌紧固件(Minnesota Mining and ManufacturingCo.,St.Paul,Minn.)和ScotchmateTM牌紧固件(Minnesota Mining andManufacturing Co.,St.Paul,Minn.)。压敏粘合剂在减震应用中也是有用的。
在涂覆之前可以与可聚合单体掺和的其它材料包括增塑剂、增粘剂、着色剂、增强剂、阻燃剂、发泡剂、导热剂、导电剂、后固化剂和后固化剂固定剂(post-curing agent curatives)及其加速剂等等。这些类型材料的实例可以在美国公布号2010/0120931A1中找到,其公开内容在此通过引用其全部被并入本文。
对于发明粘合剂(invertive adhesive)有用的增粘剂与丙烯酸聚合物基本上是相容的。增粘剂与丙烯酸聚合物基本上是相容的。如本文中所使用的,术语“基本上相容的”意为当增粘剂与丙烯酸聚合物组合时,产生的干燥膜形式的组合物对于正常视力基本上是透明的而不是不透明的。可以使用很多种增粘剂以增强粘合剂的粘着性和剥离,并且所述增粘剂可以单独或组合使用。这些包括松香和松香衍生物——包括在松树的含油树脂中天然产生的松香材料以及其衍生物——包括松香酯、改性松香,如分馏的、氢化的、脱氢的和聚合的松香、改性松香酯等等。
也可以应用萜烯树脂,其是具有式C10H16的烃,产生在大部分植物精油和含油树脂以及苯酚改性的萜烯树脂中,如α蒎烯、β蒎烯、二戊烯、苧烯、月桂烯、冰片烯、莰烯等等。也可以使用各种脂族烃类树脂,如Escorez 1304——由Exxon Chemical Co.制造,和基于C9、C5、二环戊二烯、苯并呋喃、茚、苯乙烯、取代的苯乙烯和苯乙烯衍生物等等的芳族烃类树脂。
可以使用氢化树脂和部分氢化树脂,如Regalrez 1018、Regalrez1033、Regalrez 1078、Regalrez 1094、Regalrez 1126、Regalrez 3102、Regalrez 6108等——由Eastman Chemical Company生产。各种类型的萜烯酚醛树脂SP 560和SP 553——由Schenectady Chemical Inc.制造和销售、Nirez 1100——由Reichold Chemical Inc.制造和销售、以及Piccolyte S-100——由Hercules Corporation制造和销售,对于本发明是特别有用的增粘剂。可以使用各种混合的脂族和芳族树脂,如HercotexAD 1100——由Hercules Corporation制造和销售。
针对给定配方选择的具体增粘树脂和/或量可以取决于被增粘的丙烯酸聚合物的类型。现有技术中已知的对于增粘丙烯酸基压敏粘合剂有用的许多树脂可以有效地用于实施本发明,尽管本发明的范围并不仅仅局限于这样的树脂。可以使用在Satas,Handbook of PresureSensitive Adhesive Technology(压敏粘合剂技术手册),Von NostrandReinhold,Co,Chap.20,第527-584页(1989)(通过引用被并入本文)中描述的树脂。
本发明中使用的增粘剂的量取决于使用的丙烯酸酯/低聚物掺和物和增粘剂。通常,根据本发明制备的压敏粘合剂组合物将包含按重量计总计5至约60%的一种或多种增粘剂。
根据本发明的压敏粘合剂优选根据在Martens等,美国专利号4,181,752中描述的技术通过光引发本体聚合被制备,所述美国专利通过引用被并入本文。可聚合单体和光敏引发剂在溶剂不存在的情况下被混合在一起,并被部分地聚合至粘度范围为约500cps至约50,000cps,以得到可涂覆的浆。可选地,单体可以与触变剂,如蒸气沉积(fumed)亲水性二氧化硅混合,以达到可涂覆的厚度。然后,将交联剂和任何其它成分加入到预聚合的浆中。可选地,这些成分(除交联剂意为)可以在预聚合之前直接加入到单体混合物中。
得到的组合物被涂覆到基底(其对紫外线辐射可以是透明的)上,并在惰性(即,不含氧)气氛,例如,氮气氛下通过暴露于紫外线辐射而被聚合。合适的基底的实例包括剥离衬垫(例如,聚硅氧烷剥离衬垫)和带背衬(tape backings)(其可以是涂底料的(primed)或未涂底料的纸或塑料)。也可以通过用对紫外线辐射基本上透明的塑料薄膜覆盖可聚合涂覆层,并如上述Martens等的专利中描述地利用紫外线灯通过该膜在空气中照射来实现充分的惰性气氛。可选地,不覆盖可聚合涂层,而是可以将可氧化锡化合物加入到可聚合的浆中,以提高浆的耐氧性——如在美国专利号4,303,485(Levens)中所描述地。紫外线光源优选90%的发射在280和400nm之间(更优选在300和400nm之间),其中最大值在351nm处。
在期望多层带结构物的情况下,一种构造方法是利用常规技术的多层涂覆法。例如,可以同时施用涂层(例如,通过模压涂机),然后,将整个多层结构同时进行固化。也可以相继施用涂层,由此,每个单独的层在施用下一个层之前被部分地或完全地固化。
测试程序
用于评价压敏粘合剂的测试程序包括以下:
单体转化实验(测试程序A)
单体转化通过重量分析进行测定。涂覆粘合剂样品后将其称重,随后在120℃下干燥3小时,然后再次称重。采用挥发物的百分比作为单体转化的指示。
90°剥离附着力实验(测试程序B)
仔细切割半英寸宽的粘合剂样品条,放到感兴趣的基底上。粘合剂厚度为5mil。然后,将5mil阳极化的铝背衬(0.625 in,宽)层压到约5英寸长的粘合剂上。感兴趣的测试基底包括低能表面,如聚丙烯(2″×5″×3/16天然聚丙烯板——来自Precision Punch and Plastic,Minneapolis,Minn.,其两侧均有罩,该罩在清洗和测试前被去掉)和聚碳酸酯(LexanTM,来自General Electric Co.)和高能表面,如不锈钢(304-2BA 28规格不锈钢,表面粗糙度为2.0.±1.0微英寸)。粘合剂层压到其上的背衬的自由端延伸超出基底,以便其可以夹到测力传感器(load cell)上以测定剥离强度。
用2kg硬橡胶辊来回滚动样品两次,以确保粘合剂与测试基底之间的接触。然后,在给定的停留时间(通常为72小时,除非另有说明)之后,以12”/分钟,按90℃剥离模式去除粘合剂。
在测试前,用丙酮洗涤不锈钢基底1次和用50/50异丙醇/水混合物洗涤3次。在测试前,用庚烷洗涤塑料基底3次。结果通常以lbs/0.5in.宽度作为两次测试的平均值进行报告。所有测试均在室温下进行。
剪切测试(测试程序C)
将0.5英寸的带条粘贴到不锈钢(304-2BA 28规格不锈钢,表面粗糙度为2.0±1.0微英寸)片上,该不锈钢片已经用丙酮洗涤不锈钢基底1次和用50/50异丙醇/水混合物洗涤3次,以便完成半平方英寸的重叠。然后,将5mil阳极化的铝片(0.625 in.,宽)层压到压敏粘合剂的整个区域,留下可以施加载荷的另外的区域。粘合剂厚度为5mil。然后,用15磅辊来回滚动样品两次,并允许停留4小时。70℃样品允许多停留10分钟。在停留之后,在室温下或者70℃下测试样品。在室温下,将1kg载荷施加到粘合剂上,并记录载荷落下之前的时间。在70℃下,将500g载荷施加到粘合剂上,并记录载荷落下之前的时间。结果通常被报告为2次测试的平均值。
显然地,可以对上文阐释的本发明进行许多修饰和变化而不背离其精神和范围,因此仅如在所附权利要求书中指明的才应该被强加限制。
Claims (18)
1.压敏粘合剂,其包含以下物质的反应产物:
(a)约25至约95重量份的至少一种一元醇的丙烯酸酯,其均聚物的Tg小于0℃,
(b)0至约75重量份的至少一种另外的烯键式不饱和单体,
(c)约5至约35重量份的至少一种极性烯键式不饱和单体,其具有式I的一般结构
其中,在式I的结构中,
R1=H或CH3
X=O或N
R2=式II
其中,R4是选自以下的成员:氢、甲基、乙基、氯甲基、羟甲基、苯基、甲氧苯基、甲氧丁基和甲氧烯丙基;P是从约0到3的整数,q是从1到3的整数;R3是2-4个碳原子的不饱和二价烷基或取代的烷基基团或4-9个碳原子,优选5-6个碳原子的饱和或不饱和二价碳环脂族环;并且A是选自以下的成员:O、NH或NR1,其中R1如上所限定。
2.权利要求1所述的压敏粘合剂,其中,组分(b)是至少一种非极性烯键式不饱和单体,其均聚物的溶解度参数不大于10.50和Tg大于15℃。
3.根据权利要求1或2所述的压敏粘合剂,其中,组分(a)是在醇部分上具有约4至约18个碳原子的一元醇的单官能丙烯酸酯。
4.根据权利要求1-3任一项所述的压敏粘合剂,其中,组分(a)选自:丙烯酸异辛酯、丙烯酸-2-乙基己酯、丙烯酸异壬酯、丙烯酸异癸酯、丙烯酸癸酯、丙烯酸月桂酯、丙酯酸己酯、丙烯酸丁酯和丙烯酸十八酯、丙烯酸-2-丙基庚酯或其组合。
5.根据权利要求1-4任一项所述的压敏粘合剂,其中,组分(b)选自:丙烯酸、衣康酸、取代的丙烯酰胺、丙烯酸酯、N,N二甲基丙烯酸酰胺、N-乙烯基-2-吡咯烷酮、N-乙烯基己内酰胺、丙烯腈、丙烯酸四氢糠基酯、丙烯酸缩水甘油酯、丙烯酸-2-苯氧乙基酯和丙烯酸苄酯或其组合。
6.根据权利要求1-5任一项所述的压敏粘合剂,其中,组分(b)选自丙烯酸-3,3,5-三甲基环己酯、丙烯酸环己酯、丙烯酸异冰片酯、N-辛基丙烯酰胺、丙烯酸叔丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯和甲基丙烯酸丙酯或其组合。
7.根据权利要求1-6任一项所述的压敏粘合剂,进一步包含至少一种交联剂。
8.根据权利要求7所述的压敏粘合剂,其中,所述交联剂选自三嗪和多官能丙烯酸烷基酯单体。
9.根据权利要求1-8任一项所述的压敏粘合剂,进一步包含至少一种增粘剂。
10.根据权利要求9所述的压敏粘合剂,其中,所述增粘剂选自烃类树脂、木树脂、松香、松香衍生物和其两种或更多种的组合。
11.标签,其包含面材和权利要求1-10任一项的PSA。
12.标签,其粘附于临界润湿表面张力不大于约35达因/cm的表面。
13.根据权利要求11-12任一项所述的标签,其粘附于聚烯烃表面和金属表面。
14.根据权利要求11-13任一项所述的标签,其粘附于聚丙烯和不锈钢。
15.带,其包含基材和权利要求1-10任一项的PSA。
16.根据权利要求15所述的带,其中,所述基材是泡沫。
17.根据权利要求15或16所述的带,其中,所述基材是微孔泡沫。
18.根据权利要求15所述的带,其中,所述基材是非编织材料。
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US11802224B2 (en) | 2021-03-22 | 2023-10-31 | Sekisui Chemical Co., Ltd. | Adhesive tape, method for fixing electronic device component or on-board device component, and method for producing electronic device or on-board device |
CN113736398A (zh) * | 2021-08-20 | 2021-12-03 | 广东弘擎电子材料科技有限公司 | 一种耐电解液溶剂型丙烯酸酯压敏胶以及制备方法 |
WO2023175033A1 (en) | 2022-03-17 | 2023-09-21 | Zephyros, Inc. | Autonomously curable and foamable two-component acrylic adhesive |
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US5602221A (en) | 1993-11-10 | 1997-02-11 | Minnesota Mining And Manufacturing Company | Pressure sensitive adhesives with good low energy surface adhesion |
US20030099780A1 (en) * | 2001-03-29 | 2003-05-29 | 3M Innovative Properties Company | Methods for making glass fiber reinforced materials |
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- 2010-09-24 KR KR20127010522A patent/KR20120074298A/ko active IP Right Grant
- 2010-09-24 US US13/395,497 patent/US8916485B2/en active Active
- 2010-09-24 RU RU2012116264/05A patent/RU2559456C2/ru not_active IP Right Cessation
- 2010-09-24 PL PL10762815T patent/PL2480617T3/pl unknown
- 2010-09-24 ES ES10762815T patent/ES2453978T3/es active Active
- 2010-09-24 CN CN201080041723.6A patent/CN102510887B/zh active Active
- 2010-09-24 WO PCT/US2010/050158 patent/WO2011038202A1/en active Application Filing
- 2010-09-24 AU AU2010298113A patent/AU2010298113A1/en not_active Abandoned
- 2010-09-24 EP EP20100762815 patent/EP2480617B1/en active Active
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US5708109A (en) * | 1993-11-10 | 1998-01-13 | Minnesota Mining And Manufacturing Company | Pressure sensitive adhesives with good oily surface adhesion |
US20030091815A1 (en) * | 1996-12-04 | 2003-05-15 | 3M Innovative Properties Company | Pavement marking article and raised pavement marker that uses pressure sensitive adhesive |
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CN104812861A (zh) * | 2012-11-23 | 2015-07-29 | 3M创新有限公司 | 多层压敏粘合剂组件 |
CN110283549A (zh) * | 2012-11-23 | 2019-09-27 | 3M创新有限公司 | 多层压敏粘合剂组件 |
CN110283549B (zh) * | 2012-11-23 | 2022-01-11 | 3M创新有限公司 | 多层压敏粘合剂组件 |
Also Published As
Publication number | Publication date |
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US20120171915A1 (en) | 2012-07-05 |
RU2559456C2 (ru) | 2015-08-10 |
PL2480617T3 (pl) | 2014-08-29 |
KR20120074298A (ko) | 2012-07-05 |
EP2480617A1 (en) | 2012-08-01 |
RU2012116264A (ru) | 2013-10-27 |
ES2453978T3 (es) | 2014-04-09 |
CN102510887B (zh) | 2015-10-14 |
US8916485B2 (en) | 2014-12-23 |
EP2480617B1 (en) | 2014-03-19 |
WO2011038202A1 (en) | 2011-03-31 |
AU2010298113A1 (en) | 2012-04-12 |
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